This is a modern-English version of Elements of Chemistry,: In a New Systematic Order, Containing all the Modern Discoveries, originally written by Lavoisier, Antoine Laurent.
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ELEMENTS
OF
CHEMISTRY,
IN A
NEW SYSTEMATIC ORDER,
CONTAINING ALL THE
MODERN DISCOVERIES.
ILLUSTRATED WITH THIRTEEN COPPERPLATES.
By Mr. Lavoisier,
Member of the Academy of Sciences, Royal Society of Medicine, and Agricultural Society of Paris, of the Royal Society of London, and Philosophical Societies of Orleans, Bologna, Basil, Philadelphia, Haerlem, Manchester, &c. &c.
Member of the Academy of Sciences, Royal Society of Medicine, and Agricultural Society of Paris, the Royal Society of London, and Philosophical Societies of Orleans, Bologna, Basel, Philadelphia, Haarlem, Manchester, etc. etc.
TRANSLATED FROM THE FRENCH,
By ROBERT KERR, F.R. & A.SS.E.
Member of the Royal College of Surgeons, and Surgeon to the Orphan
Hospital of Edinburgh.
EDINBURGH: printed for WILLIAM CREECH, and sold in london by g. g. and
j. j. robinsons.
MDCCXC.
Member of the Royal College of Surgeons and Surgeon to the Orphan Hospital of Edinburgh.
EDINBURGH: printed for WILLIAM CREECH, and sold in London by G. G. and J. J. Robinsons.
1790.
[Pg v]
[Pg v]
ADVERTISEMENT OF THE TRANSLATOR.
The very high character of Mr Lavoisier as a chemical philosopher, and the great revolution which, in the opinion of many excellent chemists, he has effected in the theory of chemistry, has long made it much desired to have a connected account of his discoveries, and of the new theory he has founded upon the modern experiments written by himself. This is now accomplished by the publication of his Elements of Chemistry; therefore no excuse can be at all necessary for giving the following work to the public in an English dress; and the only hesitation of the Translator is with regard to his own abilities for the task. He is most ready to confess, that his knowledge of the composition [Pg vi]of language fit for publication is far inferior to his attachment to the subject, and to his desire of appearing decently before the judgment of the world.
The high regard for Mr. Lavoisier as a chemical philosopher and the significant changes he has brought to chemistry, according to many esteemed chemists, has long created a desire for a complete account of his discoveries and the new theory he has developed based on modern experiments, written by him. This is now achieved with the publication of his Elements of Chemistry; therefore, there’s no need for any excuse to present the following work to the public in English. The only uncertainty the Translator has is about his own abilities for this task. He readily admits that his knowledge of the proper use of language for publication is much less than his passion for the subject and his wish to present himself well before the judgment of the world.
He has earnestly endeavoured to give the meaning of the Author with the most scrupulous fidelity, having paid infinitely greater attention to accuracy of translation than to elegance of stile. This last indeed, had he even, by proper labour, been capable of attaining, he has been obliged, for very obvious reasons, to neglect, far more than accorded with his wishes. The French copy did not reach his hands before the middle of September; and it was judged necessary by the Publisher that the Translation should be ready by the commencement of the University Session at the end of October.
He has worked hard to convey the author's meaning with the utmost accuracy, focusing much more on getting the translation right than on making it sound polished. Even if he could have achieved a more refined style with some effort, he had to put that aside for clear reasons. He didn't receive the French version until the middle of September, and the Publisher deemed it essential for the Translation to be finished by the start of the University Session at the end of October.
He at first intended to have changed all the weights and measures used by Mr Lavoisier into their correspondent English denominations, but, upon trial, the task was found infinitely too great for the time allowed; and to have executed this part of the work inaccurately, must have been both useless and misleading to the reader. All that has been attempted in this way is adding, between brackets ( ), the degrees of Fahrenheit's[Pg vii] scale corresponding with those of Reaumeur's thermometer, which is used by the Author. Rules are added, however, in the Appendix, for converting the French weights and measures into English, by which means the reader may at any time calculate such quantities as occur, when desirous of comparing Mr Lavoisier's experiments with those of British authors.
He initially planned to convert all the weights and measurements used by Mr. Lavoisier into their equivalent English units, but during the process, he realized that the task was way too big for the time available. Doing this part of the work incorrectly would have been both pointless and confusing for the reader. What has been done instead is to add, in brackets ( ), the degrees from Fahrenheit's[Pg vii] scale that correspond to the readings of Reaumeur's thermometer, which the Author uses. However, rules have been included in the Appendix for converting French weights and measures into English, so readers can easily calculate any quantities they come across when they want to compare Mr. Lavoisier's experiments with those of British writers.
By an oversight, the first part of the translation went to press without any distinction being preserved between charcoal and its simple elementary part, which enters into chemical combinations, especially with oxygen or the acidifying principle, forming carbonic acid. This pure element, which exists in great plenty in well made charcoal, is named by Mr Lavoisier carbone, and ought to have been so in the translation; but the attentive reader can very easily rectify the mistake. There is an error in Plate XI. which the engraver copied strictly from the original, and which was not discovered until the plate was worked off at press, when that part of the Elements which treats of the apparatus there represented came to be translated. The two tubes 21. and 24. by which the gas is conveyed[Pg viii] into the bottles of alkaline solution 22. 25. should have been made to dip into the liquor, while the other tubes 23. and 26. which carry off the gas, ought to have been cut off some way above the surface of the liquor in the bottles.
By an oversight, the first part of the translation was published without any distinction between charcoal and its simple elemental part, which combines chemically, especially with oxygen or the acidifying principle, forming carbonic acid. This pure element, which is found abundantly in well-made charcoal, is referred to by Mr. Lavoisier as carbone, and it should have been used this way in the translation; however, the attentive reader can easily correct the mistake. There is an error in Plate XI. that the engraver copied precisely from the original, which wasn't discovered until the plate was printed off, when the section of the Elements discussing the apparatus depicted there was translated. The two tubes 21. and 24. that carry the gas[Pg viii] into the bottles of alkaline solution 22. and 25. should have been designed to dip into the liquid, while the other tubes 23. and 26. that remove the gas should have ended above the surface of the liquid in the bottles.
A few explanatory notes are added; and indeed, from the perspicuity of the Author, very few were found necessary. In a very small number of places, the liberty has been taken of throwing to the bottom of the page, in notes, some parenthetical expressions, only relative to the subject, which, in their original place, tended to confuse the sense. These, and the original notes of the Author, are distinguished by the letter A, and to the few which the Translator has ventured to add, the letter E is subjoined.
A few explanatory notes have been added; and honestly, thanks to the clarity of the Author, very few were needed. In a few instances, we've placed some parenthetical remarks at the bottom of the page in notes, as they were relevant to the subject but made the original text confusing. These notes, along with the Author's original ones, are marked with the letter A, and the few added by the Translator are marked with the letter E.
Mr Lavoisier has added, in an Appendix, several very useful Tables for facilitating the calculations now necessary in the advanced state of modern chemistry, wherein the most scrupulous accuracy is required. It is proper to give some account of these, and of the reasons for omitting several of them.[Pg ix]
Mr. Lavoisier has included several very useful tables in an appendix to help with the calculations that are now essential in the advanced field of modern chemistry, which demands the highest level of accuracy. It’s important to provide some information about these tables and the reasons for leaving out some of them.[Pg ix]
No. I. of the French Appendix is a Table for converting ounces, gros, and grains, into the decimal fractions of the French pound; and No. II. for reducing these decimal fractions again into the vulgar subdivisions. No. III. contains the number of French cubical inches and decimals which correspond to a determinate weight of water.
No. I. of the French Appendix is a table for converting ounces, gros, and grains into decimal fractions of the French pound; and No. II. is for converting these decimal fractions back into the usual subdivisions. No. III. shows the number of French cubic inches and decimals that correspond to a specific weight of water.
The Translator would most readily have converted these Tables into English weights and measures; but the necessary calculations must have occupied a great deal more time than could have been spared in the period limited for publication. They are therefore omitted, as altogether useless, in their present state, to the British chemist.
The Translator would have easily converted these Tables into English weights and measures, but the necessary calculations would have taken much more time than could be allowed within the publication deadline. They are therefore left out, as they are completely useless in their current form for the British chemist.
No. IV. is a Table for converting lines or twelfth parts of the inch, and twelfth parts of lines, into decimal fractions, chiefly for the purpose of making the necessary corrections upon the quantities of gasses according to their barometrical pressure. This can hardly be at all useful or necessary, as the barometers used in Britain are graduated in decimal fractions of the inch, but, being referred to by the Author in[Pg x] the text, it has been retained, and is No. I. of the Appendix to this Translation.
No. IV. is a table for converting lines or twelfth parts of an inch and twelfth parts of lines into decimal fractions, mainly for correcting the amounts of gases based on their barometric pressure. This is probably not very useful or necessary since the barometers used in Britain are marked in decimal fractions of an inch, but since the Author mentions it in [Pg x] the text, it has been kept and is No. I. of the Appendix to this Translation.
No. V. Is a Table for converting the observed heights of water within the jars used in pneumato-chemical experiments into correspondent heights of mercury for correcting the volume of gasses. This, in Mr Lavoisier's Work, is expressed for the water in lines, and for the mercury in decimals of the inch, and consequently, for the reasons given respecting the Fourth Table, must have been of no use. The Translator has therefore calculated a Table for this correction, in which the water is expressed in decimals, as well as the mercury. This Table is No. II. of the English Appendix.
No. V. Is a table for converting the measured heights of water in the jars used in pneumatic-chemical experiments into equivalent heights of mercury to correct the volume of gases. In Mr. Lavoisier's work, the water is represented in lines and the mercury in decimal inches, which, for the reasons outlined regarding the Fourth Table, must have been impractical. The Translator has therefore created a table for this correction, with both water and mercury expressed in decimals. This table is No. II. of the English Appendix.
No. VI. contains the number of French cubical inches and decimals contained in the corresponding ounce-measures used in the experiments of our celebrated countryman Dr Priestley. This Table, which forms No. III. of the English Appendix, is retained, with the addition of a column, in which the corresponding English cubical inches and decimals are expressed.[Pg xi]
No. VI. shows the number of French cubic inches and decimals found in the corresponding ounce-measures used in the experiments of our renowned countryman Dr. Priestley. This Table, which is No. III. in the English Appendix, is kept with an additional column that displays the corresponding English cubic inches and decimals.[Pg xi]
No. VII. Is a Table of the weights of a cubical foot and inch, French measure, of the different gasses expressed in French ounces, gros, grains, and decimals. This, which forms No. VI. of the English Appendix, has been, with considerable labour, calculated into English weight and measure.
No. VII. Is a Table of the weights of a cubic foot and inch, in French measurement, of the different gases expressed in French ounces, gros, grains, and decimals. This, which is No. VI. of the English Appendix, has been meticulously converted into English weight and measurement.
No. VIII. Gives the specific gravities of a great number of bodies, with columns, containing the weights of a cubical foot and inch, French measure, of all the substances. The specific gravities of this Table, which is No. VII. of the English Appendix, are retained, but the additional columns, as useless to the British philosopher, are omitted; and to have converted these into English denominations must have required very long and painful calculations.
No. VIII. Provides the specific gravities of many materials, along with columns showing the weights of a cubic foot and inch in French measurement for all the substances. The specific gravities in this table, which is No. VII. of the English Appendix, are kept, but the extra columns, being unnecessary for the British scholar, are removed; converting these into English measurements would have needed extensive and tedious calculations.
Rules are subjoined, in the Appendix to this translation, for converting all the weights and measures used by Mr Lavoisier into corresponding English denominations; and the Translator is proud to acknowledge his obligation to the learned Professor of Natural Philosophy in the University of Edinburgh, who kindly supplied him with the necessary information for this purpose. A Table is likewise added, No. IV. of[Pg xii] the English Appendix, for converting the degrees of Reaumeur's scale used by Mr Lavoisier into the corresponding degrees of Fahrenheit, which is universally employed in Britain[1].
Rules are included in the Appendix of this translation for converting all the weights and measures used by Mr. Lavoisier into their equivalent English units. The Translator is proud to acknowledge his gratitude to the esteemed Professor of Natural Philosophy at the University of Edinburgh, who generously provided the necessary information for this task. A Table is also included, No. IV. of[Pg xii] the English Appendix, for converting the degrees of Reaumur's scale used by Mr. Lavoisier into the corresponding degrees of Fahrenheit, which is commonly used in Britain[1].
This Translation is sent into the world with the utmost diffidence, tempered, however, with this consolation, that, though it must fall greatly short of the elegance, or even propriety of language, which every writer ought to endeavour to attain, it cannot fail of advancing the interests of true chemical science, by disseminating the accurate mode of analysis adopted by its justly celebrated Author. Should the public call for a second edition, every care shall be taken to correct the forced imperfections of the present translation, and to improve the work by valuable additional matter from other authors of reputation in the several subjects treated of.
This translation is released into the world with a lot of hesitation, but it offers some comfort in knowing that, although it may not meet the standards of elegance or even proper language that every writer should strive for, it will definitely help advance the cause of true chemical science by sharing the accurate analysis method created by its well-respected author. If there’s a demand for a second edition, we will make sure to correct the unavoidable flaws in this translation and enhance the work with valuable additional content from other reputable authors on the various topics covered.
Edinburgh, }
Oct. 23. 1789. }
Edinburgh, }
Oct. 23, 1789. }
FOOTNOTES:
[1] The Translator has since been enabled, by the kind assistance of the gentleman above alluded to, to give Tables, of the same nature with those of Mr Lavoisier, for facilitating the calculations of the results of chemical experiments.
[1] The Translator has since been able, thanks to the generous help of the gentleman mentioned above, to provide tables similar to those of Mr. Lavoisier, to make it easier to calculate the results of chemical experiments.
[Pg xiii]
[Pg xiii]
PREFACE OF THE AUTHOR.
When I began the following Work, my only object was to extend and explain more fully the Memoir which I read at the public meeting of the Academy of Sciences in the month of April 1787, on the necessity of reforming and completing the Nomenclature of Chemistry. While engaged in this employment, I perceived, better than I had ever done before, the justice of the following maxims of the Abbé de Condillac, in his System of Logic, and some other of his works.
When I started this work, my only aim was to elaborate on and clarify the memoir I presented at the public meeting of the Academy of Sciences in April 1787, concerning the need to reform and finalize the nomenclature of chemistry. While working on this, I realized more clearly than ever the validity of the following principles from Abbé de Condillac in his System of Logic and some of his other writings.
"We think only through the medium of words.—Languages are true analytical methods.—Algebra,[Pg xiv] which is adapted to its purpose in every species of expression, in the most simple, most exact, and best manner possible, is at the same time a language and an analytical method.—The art of reasoning is nothing more than a language well arranged."
"We only think through words. Languages are genuine analytical tools. Algebra,[Pg xiv] which is tailored for its purpose in every type of expression, is the simplest, most precise, and most effective way to communicate, serving as both a language and an analytical method. The art of reasoning is simply a well-organized language."
Thus, while I thought myself employed only in forming a Nomenclature, and while I proposed to myself nothing more than to improve the chemical language, my work transformed itself by degrees, without my being able to prevent it, into a treatise upon the Elements of Chemistry.
Thus, while I believed I was just creating a naming system, and while I aimed only to enhance the chemical terminology, my work gradually evolved, without my control, into a comprehensive study on the Basics of Chemistry.
The impossibility of separating the nomenclature of a science from the science itself, is owing to this, that every branch of physical science must consist of three things; the series of facts which are the objects of the science, the ideas which represent these facts, and the words by which these ideas are expressed. Like three impressions of the same seal, the word ought to produce the idea, and the idea to be a picture of the fact. And, as ideas are preserved and communicated by means of words, it necessarily follows[Pg xv] that we cannot improve the language of any science without at the same time improving the science itself; neither can we, on the other hand, improve a science, without improving the language or nomenclature which belongs to it. However certain the facts of any science may be, and, however just the ideas we may have formed of these facts, we can only communicate false impressions to others, while we want words by which these may be properly expressed.
The inability to separate the terminology of a science from the science itself is due to the fact that every branch of physical science consists of three elements: the set of facts that the science studies, the ideas that represent these facts, and the words that express these ideas. Like three impressions from the same seal, the word should evoke the idea, and the idea should reflect the fact. Since ideas are preserved and shared through words, it follows[Pg xv] that we cannot enhance the language of any science without simultaneously improving the science itself; likewise, we cannot improve a science without enhancing the language or terminology associated with it. Regardless of how certain the facts of any science may be, and however accurate the ideas we have formed about these facts, we can only convey misleading impressions to others if we lack the words to express them accurately.
To those who will consider it with attention, the first part of this treatise will afford frequent proofs of the truth of the above observations. But as, in the conduct of my work, I have been obliged to observe an order of arrangement essentially differing from what has been adopted in any other chemical work yet published, it is proper that I should explain the motives which have led me to do so.
To anyone who thinks about it carefully, the first part of this treatise will provide plenty of evidence supporting the above observations. However, since I've had to follow a different order in my work compared to any other published chemical texts, I should explain the reasons that led me to this choice.
It is a maxim universally admitted in geometry, and indeed in every branch of knowledge, that, in the progress of investigation, we should proceed from known facts to what is unknown. In early infancy, our ideas spring from our wants; the sensation of want excites the idea of[Pg xvi] the object by which it is to be gratified. In this manner, from a series of sensations, observations, and analyses, a successive train of ideas arises, so linked together, that an attentive observer may trace back to a certain point the order and connection of the whole sum of human knowledge.
It’s a widely accepted principle in geometry and really in all areas of knowledge that, as we explore and investigate, we should start with what we know before moving on to what we don't. In early childhood, our thoughts come from our needs; the feeling of needing something triggers the idea of the object that will satisfy that need. In this way, a continuous flow of ideas develops from a series of sensations, observations, and analyses, all linked together, so that a careful observer can trace back to a certain point the order and connections that make up the entire body of human knowledge.
When we begin the study of any science, we are in a situation, respecting that science, similar to that of children; and the course by which we have to advance is precisely the same which Nature follows in the formation of their ideas. In a child, the idea is merely an effect produced by a sensation; and, in the same manner, in commencing the study of a physical science, we ought to form no idea but what is a necessary consequence, and immediate effect, of an experiment or observation. Besides, he that enters upon the career of science, is in a less advantageous situation than a child who is acquiring his first ideas. To the child, Nature gives various means of rectifying any mistakes he may commit respecting the salutary or hurtful qualities of the objects which surround him. On every occasion his judgments are corrected by experience; want and pain are the necessary[Pg xvii] consequences arising from false judgment; gratification and pleasure are produced by judging aright. Under such masters, we cannot fail to become well informed; and we soon learn to reason justly, when want and pain are the necessary consequences of a contrary conduct.
When we start studying any science, we're in a position similar to that of children regarding that science; the path we need to follow is exactly the same one that Nature uses to shape their ideas. In a child, an idea is just a result of a sensation. Similarly, when starting to learn a physical science, we should only form ideas that are direct results of experiments or observations. Moreover, someone diving into the world of science is in a less favorable position than a child who is gaining their first concepts. Nature provides the child with various ways to correct any mistakes they might make about the helpful or harmful qualities of the things around them. Each time, their judgments are refined through experience; need and discomfort are the necessary consequences of incorrect judgments, while satisfaction and pleasure come from making the right calls. With such guidance, we can't help but become well-informed, and we quickly learn to reason correctly when need and discomfort are the inevitable outcomes of acting otherwise.
In the study and practice of the sciences it is quite different; the false judgments we form neither affect our existence nor our welfare; and we are not forced by any physical necessity to correct them. Imagination, on the contrary, which is ever wandering beyond the bounds of truth, joined to self-love and that self-confidence we are so apt to indulge, prompt us to draw conclusions which are not immediately derived from facts; so that we become in some measure interested in deceiving ourselves. Hence it is by no means to be wondered, that, in the science of physics in general, men have often made suppositions, instead of forming conclusions. These suppositions, handed down from one age to another, acquire additional weight from the authorities by which they are supported, till at last they are received, even by men of genius, as fundamental truths.[Pg xviii]
In the study and practice of the sciences, things are quite different; the wrong judgments we make don’t impact our lives or well-being, and there’s no physical need to correct them. On the other hand, imagination, which constantly wanders beyond the limits of truth, combined with self-love and the self-confidence we tend to indulge in, leads us to make conclusions that aren't directly based on facts. This means we can end up deceiving ourselves to some extent. Therefore, it's not surprising that in the field of physics, people have often made assumptions instead of drawing conclusions. These assumptions, passed down through generations, gain more weight due to the authorities that back them until they are ultimately accepted—even by brilliant minds—as fundamental truths.[Pg xviii]
The only method of preventing such errors from taking place, and of correcting them when formed, is to restrain and simplify our reasoning as much as possible. This depends entirely upon ourselves, and the neglect of it is the only source of our mistakes. We must trust to nothing but facts: These are presented to us by Nature, and cannot deceive. We ought, in every instance, to submit our reasoning to the test of experiment, and never to search for truth but by the natural road of experiment and observation. Thus mathematicians obtain the solution of a problem by the mere arrangement of data, and by reducing their reasoning to such simple steps, to conclusions so very obvious, as never to lose sight of the evidence which guides them.
The only way to prevent errors from happening and to correct them once they occur is to simplify and control our reasoning as much as possible. This is up to us, and ignoring it is the main source of our mistakes. We should only rely on facts: These are provided to us by nature and can't mislead us. In every case, we should test our reasoning through experiments and only seek the truth through the natural process of experimentation and observation. This is how mathematicians solve problems, by organizing data and breaking down their reasoning into simple steps, reaching conclusions that are so clear, they never lose sight of the evidence guiding them.
Thoroughly convinced of these truths, I have imposed upon myself, as a law, never to advance but from what is known to what is unknown; never to form any conclusion which is not an immediate consequence necessarily flowing from observation and experiment; and always to arrange the facts, and the conclusions which are drawn from them, in such an order as shall render it most easy for beginners in the[Pg xix] study of chemistry thoroughly to understand them. Hence I have been obliged to depart from the usual order of courses of lectures and of treatises upon chemistry, which always assume the first principles of the science, as known, when the pupil or the reader should never be supposed to know them till they have been explained in subsequent lessons. In almost every instance, these begin by treating of the elements of matter, and by explaining the table of affinities, without considering, that, in so doing, they must bring the principal phenomena of chemistry into view at the very outset: They make use of terms which have not been defined, and suppose the science to be understood by the very persons they are only beginning to teach. It ought likewise to be considered, that very little of chemistry can be learned in a first course, which is hardly sufficient to make the language of the science familiar to the ears, or the apparatus familiar to the eyes. It is almost impossible to become a chemist in less than three or four years of constant application.
Completely convinced of these truths, I have made it my rule to always progress from what is known to what is unknown; never to draw any conclusions that don’t directly follow from observation and experimentation; and to organize the facts and the conclusions drawn from them in a way that makes it easiest for beginners in the[Pg xix] study of chemistry to fully grasp them. Because of this, I’ve had to break away from the typical structure of chemistry lectures and textbooks, which usually start with the foundational principles of the science assumed as known, even though students or readers shouldn't be expected to know them until they’ve been explained in later lessons. In almost every case, these materials begin by discussing the elements of matter and explaining the affinity table, without realizing that they are essentially presenting the main chemical phenomena right at the start: They use terms that haven’t been defined yet and assume the audience understands the science while they’re still in the early stages of learning. It’s also important to note that very little of chemistry can be grasped in a first course, which is barely enough to make the language of the science familiar to the ears or the equipment familiar to the eyes. It's nearly impossible to become a chemist in less than three or four years of dedicated study.
These inconveniencies are occasioned not so much by the nature of the subject, as by the method of teaching it; and, to avoid them, I[Pg xx] was chiefly induced to adopt a new arrangement of chemistry, which appeared to me more consonant to the order of Nature. I acknowledge, however, that in thus endeavouring to avoid difficulties of one kind, I have found myself involved in others of a different species, some of which I have not been able to remove; but I am persuaded, that such as remain do not arise from the nature of the order I have adopted, but are rather consequences of the imperfection under which chemistry still labours. This science still has many chasms, which interrupt the series of facts, and often render it extremely difficult to reconcile them with each other: It has not, like the elements of geometry, the advantage of being a complete science, the parts of which are all closely connected together: Its actual progress, however, is so rapid, and the facts, under the modern doctrine, have assumed so happy an arrangement, that we have ground to hope, even in our own times, to see it approach near to the highest state of perfection of which it is susceptible.
These inconveniences are caused not so much by the subject itself, but by the teaching method used; and to avoid them, I[Pg xx] was mainly motivated to create a new arrangement of chemistry that seemed more aligned with the natural order. I admit, however, that in trying to avoid one set of challenges, I’ve found myself facing other ones, some of which I haven’t been able to eliminate; but I believe that the remaining issues don’t stem from the order I’ve chosen, but rather from the imperfections that chemistry still faces. This science still has many gaps that disrupt the flow of facts and often make it very hard to connect them with one another: it doesn’t have, like the elements of geometry, the benefit of being a complete science, where all parts are tightly linked. Nevertheless, its current progress is so fast, and the facts, under modern theories, have taken on such a favorable arrangement, that we have reason to hope, even in our time, to see it come close to the highest level of perfection it can achieve.
The rigorous law from which I have never deviated, of forming no conclusions which are not fully warranted by experiment, and of never[Pg xxi] supplying the absence of facts, has prevented me from comprehending in this work the branch of chemistry which treats of affinities, although it is perhaps the best calculated of any part of chemistry for being reduced into a completely systematic body. Messrs Geoffroy, Gellert, Bergman, Scheele, De Morveau, Kirwan, and many others, have collected a number of particular facts upon this subject, which only wait for a proper arrangement; but the principal data are still wanting, or, at least, those we have are either not sufficiently defined, or not sufficiently proved, to become the foundation upon which to build so very important a branch of chemistry. This science of affinities, or elective attractions, holds the same place with regard to the other branches of chemistry, as the higher or transcendental geometry does with respect to the simpler and elementary part; and I thought it improper to involve those simple and plain elements, which I flatter myself the greatest part of my readers will easily understand, in the obscurities and difficulties which still attend that other very useful and necessary branch of chemical science.
The strict rule I’ve always followed—never drawing conclusions that aren't fully backed by experiments and never filling in gaps where facts are missing—has kept me from including the area of chemistry that deals with affinities in this work, even though it’s probably the part of chemistry most suited to being organized into a systematic framework. Mr. Geoffroy, Gellert, Bergman, Scheele, De Morveau, Kirwan, and many others have gathered various specific facts on this topic, which just need proper organization. However, the main data is still lacking, or at least, the data we have isn’t clearly defined or proven enough to serve as a solid foundation for such an important area of chemistry. This science of affinities, or elective attractions, is to the other branches of chemistry what higher or transcendental geometry is to the simpler and more basic parts; I believed it was inappropriate to mix those straightforward and clear elements, which I think most of my readers will easily grasp, with the complexities and challenges that still surround this very useful and essential branch of chemical science.
Perhaps a sentiment of self-love may, without my perceiving it, have given additional force to[Pg xxii] these reflections. Mr de Morveau is at present engaged in publishing the article Affinity in the Methodical Encyclopædia; and I had more reasons than one to decline entering upon a work in which he is employed.
Perhaps a feeling of self-love may, without me realizing it, have given extra weight to[Pg xxii] these thoughts. Mr. de Morveau is currently working on publishing the article Affinity in the Methodical Encyclopedia, and I had several reasons to turn down participating in a project he is involved in.
It will, no doubt, be a matter of surprise, that in a treatise upon the elements of chemistry, there should be no chapter on the constituent and elementary parts of matter; but I shall take occasion, in this place, to remark, that the fondness for reducing all the bodies in nature to three or four elements, proceeds from a prejudice which has descended to us from the Greek Philosophers. The notion of four elements, which, by the variety of their proportions, compose all the known substances in nature, is a mere hypothesis, assumed long before the first principles of experimental philosophy or of chemistry had any existence. In those days, without possessing facts, they framed systems; while we, who have collected facts, seem determined to reject them, when they do not agree with our prejudices. The authority of these fathers of human philosophy still carry great weight, and there is reason to fear that it will even bear hard upon generations yet to come.[Pg xxiii]
It will likely be surprising that in a discussion about the basics of chemistry, there is no section on the basic and fundamental components of matter; however, I'll take this opportunity to point out that the tendency to reduce all natural substances to three or four elements comes from a bias that has been passed down from the Greek philosophers. The idea of four elements, which mix in different proportions to create all known substances, is just a theory that was proposed long before the foundations of experimental science or chemistry were established. Back then, lacking actual facts, they created systems; meanwhile, we, who have gathered facts, seem intent on dismissing them when they conflict with our biases. The influence of these early thinkers in philosophy still holds significant power, and there's concern that it will continue to weigh heavily on future generations.[Pg xxiii]
It is very remarkable, that, notwithstanding of the number of philosophical chemists who have supported the doctrine of the four elements, there is not one who has not been led by the evidence of facts to admit a greater number of elements into their theory. The first chemists that wrote after the revival of letters, considered sulphur and salt as elementary substances entering into the composition of a great number of substances; hence, instead of four, they admitted the existence of six elements. Beccher assumes the existence of three kinds of earth, from the combination of which, in different proportions, he supposed all the varieties of metallic substances to be produced. Stahl gave a new modification to this system; and succeeding chemists have taken the liberty to make or to imagine changes and additions of a similar nature. All these chemists were carried along by the influence of the genius of the age in which they lived, which contented itself with assertions without proofs; or, at least, often admitted as proofs the slighted degrees of probability, unsupported by that strictly rigorous analysis required by modern philosophy.[Pg xxiv]
It's quite remarkable that despite the number of philosophical chemists who have supported the idea of four elements, every single one has been convinced by the evidence to accept that there are actually more elements in their theories. The first chemists who wrote after the Renaissance considered sulfur and salt as fundamental substances that combined to create many other materials; as a result, instead of just four, they recognized six elements. Beccher proposed that there are three types of earth, from which he believed all kinds of metals were produced in different combinations. Stahl modified this idea, and later chemists have taken the liberty to make changes and additions of a similar nature. All these chemists were influenced by the spirit of their time, which often accepted claims without strong evidence or, at the very least, relied on weak probabilities that wouldn't hold up to the rigorous analysis demanded by modern philosophy.[Pg xxiv]
All that can be said upon the number and nature of elements is, in my opinion, confined to discussions entirely of a metaphysical nature. The subject only furnishes us with indefinite problems, which may be solved in a thousand different ways, not one of which, in all probability, is consistent with nature. I shall therefore only add upon this subject, that if, by the term elements, we mean to express those simple and indivisible atoms of which matter is composed, it is extremely probable we know nothing at all about them; but, if we apply the term elements, or principles of bodies, to express our idea of the last point which analysis is capable of reaching, we must admit, as elements, all the substances into which we are capable, by any means, to reduce bodies by decomposition. Not that we are entitled to affirm, that these substances we consider as simple may not be compounded of two, or even of a greater number of principles; but, since these principles cannot be separated, or rather since we have not hitherto discovered the means of separating them, they act with regard to us as simple substances, and we ought never to suppose them compounded until experiment and observation has proved them to be so.[Pg xxv]
All that can be said about the number and nature of elements is, in my opinion, limited to discussions that are entirely metaphysical. The topic only presents us with unclear problems, which can be solved in countless different ways, none of which are likely consistent with nature. Therefore, I will only add that if, by the term elements, we mean to refer to the simple and indivisible atoms that make up matter, it’s very probable we know nothing about them at all. However, if we use the term elements or principles of bodies to express our idea of the final point that analysis can reach, we must include as elements all the substances into which we can reduce bodies by decomposition in any way. Not that we are entitled to claim that these substances we consider simple might not be made of two or even more principles; but since we cannot separate these principles, or rather since we have not yet found a way to separate them, they behave as simple substances with respect to us, and we should never assume they are compounded until experiments and observations prove otherwise.[Pg xxv]
The foregoing reflections upon the progress of chemical ideas naturally apply to the words by which these ideas are to be expressed. Guided by the work which, in the year 1787, Messrs de Morveau, Berthollet, de Fourcroy, and I composed upon the Nomenclature of Chemistry, I have endeavoured, as much as possible, to denominate simple bodies by simple terms, and I was naturally led to name these first. It will be recollected, that we were obliged to retain that name of any substance by which it had been long known in the world, and that in two cases only we took the liberty of making alterations; first, in the case of those which were but newly discovered, and had not yet obtained names, or at least which had been known but for a short time, and the names of which had not yet received the sanction of the public; and, secondly, when the names which had been adopted, whether by the ancients or the moderns, appeared to us to express evidently false ideas, when they confounded the substances, to which they were applied, with others possessed of different, or perhaps opposite qualities. We made no scruple, in this case, of substituting other names in their room, and the greatest number of these were borrowed from the Greek language. We[Pg xxvi] endeavoured to frame them in such a manner as to express the most general and the most characteristic quality of the substances; and this was attended with the additional advantage both of assisting the memory of beginners, who find it difficult to remember a new word which has no meaning, and of accustoming them early to admit no word without connecting with it some determinate idea.
The reflections on the evolution of chemical concepts naturally relate to the terminology used to express these ideas. Based on the work that in 1787, Messrs de Morveau, Berthollet, de Fourcroy, and I created about the Nomenclature of Chemistry, I have tried as much as possible to name simple substances with straightforward terms, and I instinctively focused on naming these first. It’s important to remember that we had to keep the traditional name of any substance that was already well-known in the world, and we only made changes in two specific situations: first, with substances that were newly discovered and had not yet been given names, or that had only recently been known and whose names had not yet been widely accepted; and second, when the names that had been chosen, whether by ancient or modern sources, seemed to convey clearly incorrect ideas by mixing up the substances they referred to with others that had different or even opposite qualities. In these cases, we had no hesitation in replacing those names, with most of the new names coming from Greek. We aimed to create them in a way that highlighted the most general and distinctive characteristics of the substances; this not only helped beginners remember new words that might not have any inherent meaning, but also taught them early on to ensure that every word was linked to a specific idea.
To those bodies which are formed by the union of several simple substances we gave new names, compounded in such a manner as the nature of the substances directed; but, as the number of double combinations is already very considerable, the only method by which we could avoid confusion, was to divide them into classes. In the natural order of ideas, the name of the class or genus is that which expresses a quality common to a great number of individuals: The name of the species, on the contrary, expresses a quality peculiar to certain individuals only.
To the groups formed by combining several simple substances, we assigned new names, crafted according to the characteristics of the substances involved. Since there are already quite a few double combinations, the best way to prevent confusion was to sort them into categories. In terms of logical organization, the name of the class or genus refers to a quality shared by many individuals, while the name of the species highlights a quality that is specific to certain individuals only.
These distinctions are not, as some may imagine, merely metaphysical, but are established by Nature. "A child," says the Abbé de Condillac,[Pg xxvii] "is taught to give the name tree to the first one which is pointed out to him. The next one he sees presents the same idea, and he gives it the same name. This he does likewise to a third and a fourth, till at last the word tree, which he first applied to an individual, comes to be employed by him as the name of a class or a genus, an abstract idea, which comprehends all trees in general. But, when he learns that all trees serve not the same purpose, that they do not all produce the same kind of fruit, he will soon learn to distinguish them by specific and particular names." This is the logic of all the sciences, and is naturally applied to chemistry.
These distinctions aren’t just abstract ideas, as some might think, but are established by nature. “A child,” says Abbé de Condillac,[Pg xxvii] “is taught to call the first tree he sees a tree. The next one he sees brings the same idea to mind, so he gives it the same name. He does this with a third and a fourth tree until finally, the word tree, which he originally used for one specific tree, becomes a general term he uses to categorize all trees. However, when he learns that not all trees serve the same function and that they don’t all produce the same type of fruit, he will quickly start to differentiate them using specific names.” This is the reasoning behind all sciences, and it naturally applies to chemistry.
The acids, for example, are compounded of two substances, of the order of those which we consider as simple; the one constitutes acidity, and is common to all acids, and, from this substance, the name of the class or the genus ought to be taken; the other is peculiar to each acid, and distinguishes it from the rest, and from this substance is to be taken the name of the species. But, in the greatest number of acids, the two constituent elements, the acidifying principle,[Pg xxviii] and that which it acidifies, may exist in different proportions, constituting all the possible points of equilibrium or of saturation. This is the case in the sulphuric and the sulphurous acids; and these two states of the same acid we have marked by varying the termination of the specific name.
Acids, for instance, are made up of two substances similar to those we regard as simple. One of these substances creates acidity and is found in all acids, and from this substance, the name of the class or genus should be derived. The other substance is unique to each acid, setting it apart from others, and from this substance, the name of the species is determined. However, in most acids, the two parts—the acidifying principle, [Pg xxviii] and what it acidifies—can exist in different amounts, creating various points of balance or saturation. This is true for both sulphuric and sulphurous acids; we denote these two forms of the same acid by changing the ending of the specific name.
Metallic substances which have been exposed to the joint action of the air and of fire, lose their metallic lustre, increase in weight, and assume an earthy appearance. In this state, like the acids, they are compounded of a principle which is common to all, and one which is peculiar to each. In the same way, therefore, we have thought proper to class them under a generic name, derived from the common principle; for which purpose, we adopted the term oxyd; and we distinguish them from each other by the particular name of the metal to which each belongs.
Metal substances that have been exposed to both air and fire lose their metallic shine, gain weight, and take on a dusty look. In this state, similar to acids, they are made up of a common principle that unites them all, along with one that is unique to each. Therefore, we decided to categorize them under a general name based on the common principle; for this, we chose the term oxyd; and we differentiate them from each other by the specific name of the metal they belong to.
Combustible substances, which in acids and metallic oxyds are a specific and particular principle, are capable of becoming, in their turn, common principles of a great number of substances. The sulphurous combinations have[Pg xxix] been long the only known ones in this kind. Now, however, we know, from the experiments of Messrs Vandermonde, Monge, and Berthollet, that charcoal may be combined with iron, and perhaps with several other metals; and that, from this combination, according to the proportions, may be produced steel, plumbago, &c. We know likewise, from the experiments of M. Pelletier, that phosphorus may be combined with a great number of metallic substances. These different combinations we have classed under generic names taken from the common substance, with a termination which marks this analogy, specifying them by another name taken from that substance which is proper to each.
Combustible substances, which serve as a specific and unique principle in acids and metallic oxides, can also become common principles in many other substances. For a long time, sulphurous compounds were the only known examples of this kind. However, thanks to the experiments conducted by Messrs Vandermonde, Monge, and Berthollet, we now know that charcoal can combine with iron and possibly with several other metals. Depending on the proportions used in this combination, materials like steel and graphite can be produced. Additionally, experiments by M. Pelletier have shown that phosphorus can be combined with a wide range of metallic substances. We have categorized these different combinations using generic names derived from the common substance, with a suffix that indicates this similarity, while specifying them with another name according to the particular substance involved.
The nomenclature of bodies compounded of three simple substances was attended with still greater difficulty, not only on account of their number, but, particularly, because we cannot express the nature of their constituent principles without employing more compound names. In the bodies which form this class, such as the neutral salts, for instance, we had to consider, 1st, The acidifying principle, which is common to them all; 2d, The acidifiable principle which constitutes their peculiar acid; 3d, The saline,[Pg xxx] earthy, or metallic basis, which determines the particular species of salt. Here we derived the name of each class of salts from the name of the acidifiable principle common to all the individuals of that class; and distinguished each species by the name of the saline, earthy, or metallic basis, which is peculiar to it.
The naming of substances made up of three simple materials was even more complicated, not just because of their quantity, but especially because we can't describe the nature of their basic components without using more complex names. In this category of substances, like neutral salts, we had to look at: 1st, the acidifying principle that all of them share; 2nd, the acidifiable principle that gives them their specific acid; and 3rd, the saline, earthy, or metallic foundation that identifies the specific type of salt. We based the name of each class of salts on the name of the acidifiable principle that is common to all members of that class, and we identified each type by the name of the saline, earthy, or metallic foundation that is unique to it.[Pg xxx]
A salt, though compounded of the same three principles, may, nevertheless, by the mere difference of their proportion, be in three different states. The nomenclature we have adopted would have been defective, had it not expressed these different states; and this we attained chiefly by changes of termination uniformly applied to the same state of the different salts.
A salt, although made up of the same three components, can still exist in three different forms just by changing their proportions. The naming system we've chosen would be lacking if it didn't represent these different forms; we achieved this mainly by consistently changing the endings applied to the same form of the different salts.
In short, we have advanced so far, that from the name alone may be instantly found what the combustible substance is which enters into any combination; whether that combustible substance be combined with the acidifying principle, and in what proportion; what is the state of the acid; with what basis it is united; whether the saturation be exact, or whether the acid or the basis be in excess.[Pg xxxi]
In short, we've come so far that just from the name, we can immediately identify the combustible substance involved in any combination; whether that substance is mixed with the acidifying principle and in what amount; what the state of the acid is; what it's combined with; and whether the saturation is complete, or if there's either too much acid or too much base.[Pg xxxi]
It may be easily supposed that it was not possible to attain all these different objects without departing, in some instances, from established custom, and adopting terms which at first sight will appear uncouth and barbarous. But we considered that the ear is soon habituated to new words, especially when they are connected with a general and rational system. The names, besides, which were formerly employed, such as powder of algaroth, salt of alembroth, pompholix, phagadenic water, turbith mineral, colcathar, and many others, were neither less barbarous nor less uncommon. It required a great deal of practice, and no small degree of memory, to recollect the substances to which they were applied, much more to recollect the genus of combination to which they belonged. The names of oil of tartar per deliquium, oil of vitriol, butter of arsenic and of antimony, flowers of zinc, &c. were still more improper, because they suggested false ideas: For, in the whole mineral kingdom, and particularly in the metallic class, there exists no such thing as butters, oils, or flowers; and, in short, the substances to which they give these fallacious names, are nothing less than rank poisons.[Pg xxxii]
It’s easy to think that achieving all these different goals required us to stray from established practices and use terms that might seem awkward and strange at first. But we figured that people quickly get used to new words, especially when they relate to a clear and logical system. The names used before, like powder of algaroth, salt of alembroth, pompholix, phagadenic water, turbith mineral, colcathar, and others, were just as awkward and uncommon. It took a lot of practice and a good memory to remember what these substances referred to, let alone the type of combination they belonged to. The names oil of tartar per deliquium, oil of vitriol, butter of arsenic and of antimony, flowers of zinc, etc., were even more misleading because they created false notions: In the entire mineral world, especially in the metallic category, there’s no such thing as butters, oils, or flowers; in fact, the substances those misleading names refer to are nothing short of toxic poisons.[Pg xxxii]
When we published our essay on the nomenclature of chemistry, we were reproached for having changed the language which was spoken by our masters, which they distinguished by their authority, and handed down to us. But those who reproach us on this account, have forgotten that it was Bergman and Macquer themselves who urged us to make this reformation. In a letter which the learned Professor of Upsal, M. Bergman, wrote, a short time before he died, to M. de Morveau, he bids him spare no improper names; those who are learned, will always be learned, and those who are ignorant will thus learn sooner.
When we published our essay on the naming conventions in chemistry, we faced criticism for changing the language that our predecessors used, which they regarded as authoritative and passed down to us. However, those who criticize us for this have forgotten that it was Bergman and Macquer themselves who encouraged this reform. In a letter that the esteemed Professor Bergman from Upsal wrote to M. de Morveau shortly before his death, he urged him to eliminate any improper names; those who are knowledgeable will always be knowledgeable, and those who are not will learn more quickly this way.
There is an objection to the work which I am going to present to the public, which is perhaps better founded, that I have given no account of the opinion of those who have gone before me; that I have stated only my own opinion, without examining that of others. By this I have been prevented from doing that justice to my associates, and more especially to foreign chemists, which I wished to render them. But I beseech the reader to consider, that, if I had filled an elementary work with a multitude of quotations; if I had allowed myself to enter into[Pg xxxiii] long dissertations on the history of the science, and the works of those who have studied it, I must have lost sight of the true object I had in view, and produced a work, the reading of which must have been extremely tiresome to beginners. It is not to the history of the science, or of the human mind, that we are to attend in an elementary treatise: Our only aim ought to be ease and perspicuity, and with the utmost care to keep every thing out of view which might draw aside the attention of the student; it is a road which we should be continually rendering more smooth, and from which we should endeavour to remove every obstacle which can occasion delay. The sciences, from their own nature, present a sufficient number of difficulties, though we add not those which are foreign to them. But, besides this, chemists will easily perceive, that, in the first part of my work, I make very little use of any experiments but those which were made by myself: If at any time I have adopted, without acknowledgment, the experiments or the opinions of M. Berthollet, M. Fourcroy, M. de la Place, M. Monge, or, in general, of any of those whose principles are the same with my own, it is owing to this circumstance, that frequent intercourse, and the habit of communicating our[Pg xxxiv] ideas, our observations, and our way of thinking to each other, has established between us a sort of community of opinions, in which it is often difficult for every one to know his own.
There’s an objection to the work I’m about to share with the public, which is probably valid, that I haven’t included the views of those who came before me; that I’ve only presented my own perspective without looking into others. Because of this, I haven’t given my colleagues, especially foreign chemists, the recognition I wanted to. However, I ask the reader to consider that if I had filled this elementary work with countless quotes; if I had allowed myself to get into long discussions about the history of the science and the work of those who have studied it, I would have lost sight of my true goal, creating a work that would likely be very boring for beginners. An elementary treatise shouldn't focus on the history of the science or human thought: our main goal should be clarity and simplicity, making sure to keep anything that might distract the student out of the way; it’s a path we should constantly strive to smooth out, removing every obstacle that could cause delays. The sciences, by their very nature, already present enough challenges without adding unrelated ones. Moreover, chemists will easily notice that in the first part of my work, I rely very little on experiments done by others: If at any point I’ve used, without credit, the experiments or opinions of M. Berthollet, M. Fourcroy, M. de la Place, M. Monge, or others with similar principles, it’s because the frequent interactions and the habit of sharing our ideas, observations, and ways of thinking have created a kind of community of opinions among us, making it often difficult for anyone to recognize their own.
The remarks I have made on the order which I thought myself obliged to follow in the arrangement of proofs and ideas, are to be applied only to the first part of this work. It is the only one which contains the general sum of the doctrine I have adopted, and to which I wished to give a form completely elementary.
The comments I've made about the order I felt I needed to follow in arranging proofs and ideas apply only to the first part of this work. It's the only section that contains the overall summary of the doctrine I've embraced and that I aimed to present in a completely basic form.
The second part is composed chiefly of tables of the nomenclature of the neutral salts. To these I have only added general explanations, the object of which was to point out the most simple processes for obtaining the different kinds of known acids. This part contains nothing which I can call my own, and presents only a very short abridgment of the results of these processes, extracted from the works of different authors.
The second part mainly includes tables listing the names of neutral salts. I've added only general explanations to help highlight the simplest methods for obtaining the various known acids. This section doesn’t contain anything I can claim as my own, and it only offers a brief summary of the results from these methods, taken from the works of various authors.
In the third part, I have given a description, in detail, of all the operations connected with modern chemistry. I have long thought that a[Pg xxxv] work of this kind was much wanted, and I am convinced it will not be without use. The method of performing experiments, and particularly those of modern chemistry, is not so generally known as it ought to be; and had I, in the different memoirs which I have presented to the Academy, been more particular in the detail of the manipulations of my experiments, it is probable I should have made myself better understood, and the science might have made a more rapid progress. The order of the different matters contained in this third part appeared to me to be almost arbitrary; and the only one I have observed was to class together, in each of the chapters of which it is composed, those operations which are most connected with one another. I need hardly mention that this part could not be borrowed from any other work, and that, in the principal articles it contains, I could not derive assistance from any thing but the experiments which I have made myself.
In the third part, I’ve provided a detailed description of all the procedures related to modern chemistry. I've long felt that a work like this was greatly needed, and I'm sure it will be useful. The way to conduct experiments, especially in modern chemistry, isn’t as widely known as it should be; and had I been more specific about the techniques in the various papers I've submitted to the Academy, I likely would have communicated my ideas more clearly, and the science could have advanced more quickly. The organization of the topics in this third part seemed almost random to me; the only guideline I followed was to group related operations together in each chapter. I should emphasize that this part couldn’t be borrowed from any other source, and for the main topics it covers, I could only rely on the experiments I've conducted myself.
I shall conclude this preface by transcribing, literally, some observations of the Abbé de Condillac, which I think describe, with a good deal of truth, the state of chemistry at a period not far distant from our own. These observations[Pg xxxvi] were made on a different subject; but they will not, on this account, have less force, if the application of them be thought just.
I’ll wrap up this preface by quoting some remarks from Abbé de Condillac that I believe accurately reflect the state of chemistry not long ago. These comments[Pg xxxvi] were made on a different topic, but they still hold value if applied correctly.
'Instead of applying observation to the things we wished to know, we have chosen rather to imagine them. Advancing from one ill founded supposition to another, we have at last bewildered ourselves amidst a multitude of errors. These errors becoming prejudices, are, of course, adopted as principles, and we thus bewilder ourselves more and more. The method, too, by which we conduct our reasonings is as absurd; we abuse words which we do not understand, and call this the art of reasoning. When matters have been brought this length, when errors have been thus accumulated, there is but one remedy by which order can be restored to the faculty of thinking; this is, to forget all that we have learned, to trace back our ideas to their source, to follow the train in which they rise, and, as my Lord Bacon says, to frame the human understanding anew.
'Instead of using observation to learn about the things we wanted to know, we chose to just imagine them. Moving from one poorly thought-out belief to another, we eventually got lost in a sea of mistakes. These mistakes turned into biases, which we then accepted as principles, causing us to confuse ourselves even more. The way we reason is just as ridiculous; we misuse words we don’t really understand and call this reasoning. When we reach this point, with so many errors piling up, there's only one way to bring order back to our thinking: we must forget everything we’ve learned, trace our ideas back to their sources, follow the path they take as they form, and, as my Lord Bacon says, reconstruct human understanding from scratch.'
'This remedy becomes the more difficult in proportion as we think ourselves more learned.[Pg xxxvii] Might it not be thought that works which treated of the sciences with the utmost perspicuity, with great precision and order, must be understood by every body? The fact is, those who have never studied any thing will understand them better than those who have studied a great deal, and especially than those who have written a great deal.'
'This remedy becomes more challenging the more we believe we know. [Pg xxxvii] Could it be assumed that works discussing the sciences clearly, precisely, and in an organized manner should be understood by everyone? In reality, those who have never studied anything will grasp them better than those who have studied a lot, particularly more than those who have written extensively.'
At the end of the fifth chapter, the Abbé de Condillac adds: 'But, after all, the sciences have made progress, because philosophers have applied themselves with more attention to observe, and have communicated to their language that precision and accuracy which they have employed in their observations: In correcting their language they reason better.'
At the end of the fifth chapter, Abbé de Condillac adds: 'But, in the end, the sciences have advanced because philosophers have focused more on observation and have brought the same precision and accuracy to their language that they use in their observations: By refining their language, they reason better.'
CONTENTS.
PART FIRST.
Of the Formation and Decomposition of
Aëriform Fluids,
—of the Combustion
of Simple Bodies, and the Formation
of Acids, Page 1
CHAP. I.—Of the Combinations of Caloric, and
the Formation of Elastic Aëriform Fluids or
Gasses, ibid.
CHAP. II.—General Views relative to the Formation
and Composition of our Atmosphere, 26
CHAP. III.—Analysis of Atmospheric Air, and its
Division into two Elastic Fluids;
one fit for
Respiration, the other incapable of being respired, 32
CHAP. IV.—Nomenclature of the several constituent
Parts of Atmospheric Air, 48
CHAP. V.—Of the Decomposition of Oxygen
Gas by Sulphur,
Phosphorus, and Charcoal, and
[Pg xl]of the Formation of Acids in general, 54
CHAP. VI.—Of the Nomenclature of Acids in general,
and particularly of those drawn from
Nitre and Sea Salt, 66
CHAP. VII.—Of the Decomposition of Oxygen
Gas
by means of Metals, and the Formation of
Metallic Oxyds, 78
CHAP. VIII.—Of the Radical Principle of Water,
and of its Decomposition by Charcoal and
Iron, 83
CHAP. IX.—Of the Quantities of Caloric disengaged
from different Species of Combustion, 97
Combustion of Phosphorus, 100
SECT. I.—Combustion of Charcoal, 101
SECT. II.—Combustion of Hydrogen Gas, 102
SECT. III.—Formation of Nitric Acid, 102
SECT. IV.—Combustion of Wax, 105
SECT. V.—Combustion of Olive Oil, 106
CHAP. X.—Of the Combustion of Combustible
Substances with each other, 109
CHAP. XI.—Observations upon Oxyds and Acids
with several Bases,
and upon the Composition
of Animal and Vegetable Substances, 115
CHAP. XII.—Of the Decomposition of Vegetable
and Animal Substances by the Action of Fire, 123
CHAP. XIII.—Of the Decomposition of Vegetable
Oxyds by the Vinous Fermentation, 129
CHAP. XIV.—Of the Putrefactive Fermentation, 141
CHAP. XV.—Of the Acetous Fermentation, 146
CHAP. XVI.—Of the Formation of Neutral Salts,
and of their Bases, 149
[Pg xli]
SECT. I.—Of Potash, 151
SECT. II.—Of Soda, 155
SECT. III.—Of Ammoniac, 156
SECT. IV.—Of Lime, Magnesia, Barytes, and Argill, 157
SECT. V.—Of Metallic Bodies, 159
CHAP. XVII.—Continuation of the Observations
upon Salifiable Bases, and the Formation
of Neutral Salts, 161
PART II.
Of the Combinations of Acids with Salifiable
Bases, and of the Formation
of Neutral Salts, 175
INTRODUCTION, ibid.
TABLE of Simple Substances, 175
SECT. I.—Observations upon simple Substances, 176
TABLE of Compound Oxydable and Acidifiable
Bases, 179
SECT. II.—Observations upon Compound Radicals, 180
SECT. III.—Observations upon the Combinations
of Light and Caloric with different Substances, 182
[Pg xlii]
TABLE of the Combinations of Oxygen with the
Simple Substances, to face 185
SECT. IV.—Observations upon these Combinations, 185
TABLE of the Combinations of Oxygen with Compound
Radicals, 190
SECT. V.—Observations upon these Combinations, 191
TABLE of the Combinations of Azote with the
Simple Substances, 194
SECT VI.—Observations upon these Combinations
of Azote, 195
TABLE of the Combinations of Hydrogen with
Simple Substances, 198
SECT. VII.—Observations upon Hydrogen, and its
Combinations, 199
TABLE of the Binary Combinations of Sulphur
with the Simple Substances, 202
SECT. VIII.—Observations upon Sulphur, and its
Combinations, 203
TABLE of the Combinations of Phosphorus with
Simple Substances, 204
SECT. IX.—Observations upon Phosphorus and its
Combinations, 205
TABLE of the Binary Combinations of Charcoal, 207
SECT. X.—Observations upon Charcoal, and its
Combinations, 208
SECT. XI.—Observations upon the Muriatic, Fluoric,
and Boracic Radicals, and their Combinations, 209
[Pg xliii]
SECT. XII.—Observations upon the Combinations
of Metals with each other, 219
TABLE of the Combinations of Azote, in the State
of Nitrous Acid, with the Salifiable Bases, 212
TABLE of the Combinations of Azote, in the State
of Nitric Acid, with the Salifiable Bases, 213
SECT. XIII.—Observations upon Nitrous and Nitric
Acids, and their Combinations with Salifiable
Bases, 214
TABLE of the Combinations of Sulphuric Acid
with the Salifiable Bases, 218
SECT. XIV.—Observations upon Sulphuric Acid,
and its Combinations, 219
TABLE of the Combinations of Sulphurous Acid, 222
SECT. XV.—Observations upon Sulphurous Acid,
and its Combinations with Salifiable Bases, 223
TABLE of the Combinations of Phosphorous and
Phosphoric Acids, 225
SECT. XVI.—Observations upon Phosphorous and
Phosphoric Acids, and their Combinations
with Salifiable Bases, 226
TABLE of the Combinations of Carbonic Acid, 228
SECT. XVII.—Observations upon Carbonic Acid,
and its Combinations with Salifiable Bases, 229
TABLE of the Combinations of Muriatic Acid, 231
TABLE of the Combinations of Oxygenated Muriatic Acid, 232
[Pg xliv]
SECT. XVIII.—Observations upon Muriatic and
Oxygenated Muriatic Acid,
and their Combinations
with Salifiable Bases, 233
TABLE of the Combinations of Nitro-Muriatic Acid, 236
SECT. XIX.—Observations upon Nitro-muriatic
Acid, and its Combinations with Salifiable
Bases, 237
TABLE of the Combinations of Fluoric Acid, 239
SECT. XX.—Observations upon Fluoric Acid, and
its Combinations with Salifiable Bases, 240
TABLE of the Combinations of Boracic Acid, 242
SECT. XXI.—Observations upon Boracic Acid,
and its Combinations with Salifiable Bases, 243
TABLE of the Combinations of Arseniac Acid, 246
SECT. XXII.—Observations upon Arseniac Acid,
and its Combinations with Salifiable Bases, 247
SECT. XXIII.—Observations upon Molibdic Acid,
and its Combinations with Salifiable Bases, 249
SECT. XXIV.—Observations upon Tungstic Acid,
and its Combinations with Salifiable Bases,
and
a Table of these in the order of their Affinity, 251
TABLE of the Combinations of Tartarous Acid, 253
SECT. XXV.—Observations upon Tartarous Acid,
and its Combinations with Salifiable Bases, 254
SECT. XXVI.—Observations upon Mallic Acid,
and its Combinations with Salifiable Bases, 256
TABLE of the Combinations of Citric Acid, 258
SECT. XXVII.—Observations upon Citric Acid,
and its Combinations with Salifiable Bases, 259
[Pg xlv]
TABLE of the Combinations of Pyro-lignous Acid, 260
SECT. XXVIII.—Observations upon Pyro-lignous
Acid, and its Combinations with Salifiable Bases, 261
SECT. XXIX.—Observations upon Pyro-tartarous
Acid, and its Combinations with Salifiable
Bases, ibid.
TABLE of the Combinations of Pyro-mucous Acid, 263
SECT. XXX.—Observations upon Pyro-mucous
Acid, and its Combinations with Salifiable Bases, 264
TABLE of the Combinations of Oxalic Acid, 265
SECT. XXXI.—Observations upon Oxalic Acid,
and its Combinations with Salifiable Bases, 266
TABLE of the Combinations of Acetous Acid, to
face 267
SECT. XXXII.—Observations upon Acetous Acid,
and its Combinations with the Salifiable Bases, 267
TABLE of the Combinations of Acetic Acid, 271
SECT. XXXIII.—Observations upon Acetic Acid,
and its Combinations with Salifiable Bases, 272
TABLE of the Combinations of Succinic Acid, 273
SECT. XXXIV.—Observations upon Succinic Acid,
and its Combinations with Salifiable Bases, 274
SECT. XXXV.—Observations upon Benzoic Acid,
and its Combinations with Salifiable Bases, 275
SECT. XXXVI.—Observations upon Camphoric
Acid, and its Combinations with Salifiable
[Pg xlvi]Bases, 276
SECT. XXXVII.—Observations upon Gallic Acid,
and its Combinations with Salifiable Bases, 277
SECT. XXXVIII.—Observations upon Lactic Acid,
and its Combinations with Salifiable Bases, 278
TABLE of the Combinations of Saccholactic Acid, 280
SECT. XXXIX.—Observations upon Saccholactic
Acid, and its Combination with Salifiable Bases, 281
TABLE of the Combinations of Formic Acid, 282
SECT. XL.—Observations upon Formic Acid, and
its Combinations with the Salifiable Bases, 283
SECT. XLI.—Observations upon the Bombic Acid,
and its Combinations with the Salifiable Bases, 284
TABLE of the Combinations of the Sebacic Acid, 285
SECT. XLII.—Observations upon the Sebacic Acid,
and its Combinations with the Salifiable Bases, 286
SECT. XLIII.—Observations upon the Lithic Acid,
and its Combinations with the Salifiable Bases, 287
TABLE of the Combinations of the Prussic Acid, 288
SECT. XLIV.—Observations upon the Prussic Acid,
and its Combinations with the Salifiable Bases, 289
PART III.
[Pg xlvii]
Description of the Instruments and Operations
of Chemistry, 291
INTRODUCTION, 291
CHAP. I.—Of the Instruments necessary for determining
the Absolute and Specific Gravities of
Solid and Liquid Bodies, 295
CHAP. II.—Of Gazometry, or the Measurement
of the Weight and Volume of Aëriform Substances, 304
SECT. I.—Of the Pneumato-chemical Apparatus, ibid.
SECT. II.—Of the Gazometer, 308
SECT. III.—Some other methods for Measuring
the Volume of Gasses, 319
SECT. IV.—Of the method of Separating the different
Gasses from each other, 323
SECT. V.—Of the necessary Corrections of the Volume
of Gasses,
according to the Pressure of
the Atmosphere, 328
SECT. VI.—Of the Correction relative to the Degrees
of the Thermometer, 335
SECT. VII.—Example for Calculating the Corrections
relative to the Variations of Pressure and
Temperature, 337
SECT. VIII.—Method of determining the Weight
of the different Gasses, 340
CHAP. III.—Description of the Calorimeter, or
Apparatus for measuring Caloric, 343
CHAP. IV.—Of the Mechanical Operations for
Division of Bodies, 357
[Pg xlviii]
SECT. I.—Of Trituration, Levigation, and Pulverization, ibid.
SECT. II.—Of Sifting and Washing Powdered
Substances, 361
SECT. III.—Of Filtration, 363
SECT. IV.—Of Decantation, 365
CHAP. V.—Of Chemical means for Separating the
Particles of Bodies
from each other without
Decomposition, and for Uniting them again, 367
SECT. I.—Of the Solution of Salts, 368
SECT. II.—Of Lixiviation, 373
SECT. III.—Of Evaporation, 375
SECT. IV.—Of Cristallization, 379
SECT. V.—Of Simple Distillation, 384
SECT. VI.—Of Sublimation, 388
CHAP. VI.—Of Pneumato-chemical Distillations,
Metallic Dissolutions,
and some other operations
which require very complicated instruments, 390
SECT. I.—Of Compound and Pneumato-chemical
Distillations, ibid.
SECT. II.—Of Metallic Dissolutions, 398
SECT. III.—Apparatus necessary in Experiments
upon Vinous and Putrefactive Fermentations, 401
SECT. IV.—Apparatus for the Decomposition of
Water, 404
CHAP. VII.—Of the Composition and Use of
Lutes, 407
CHAP. VIII.—Of Operations upon Combustion
and Deflagration, 414
SECT. I.—Of Combustion in general, ibid.
SECT. II.—Of the Combustion of Phosphorus, 418
[Pg xlix]
SECT. III.—Of the Combustion of Charcoal, 422
SECT. IV.—Of the Combustion of Oils, 426
SECT. V.—Of the Combustion of Alkohol, 433
SECT. VI.—Of the Combustion of Ether, 435
SECT. VII.—Of the Combustion of Hydrogen
Gas, and the Formation of Water, 437
SECT. VIII.—Of the Oxydation of Metals, 441
CHAP. IX.—Of Deflagration, 452
CHAP. X.—Of the Instruments necessary for Operating
upon Bodies in very high Temperatures, 460
SECT. I.—Of Fusion, ibid.
SECT. II.—Of Furnaces, 462
SECT. III.—Of increasing the Action of Fire, by
using Oxygen Gas instead of Atmospheric Air, 474
APPENDIX.
No. I.—Table for Converting Lines, or Twelfth
Parts of an Inch,
and Fractions of Lines, into
Decimal Fractions of the Inch, 481
No. II.—Table for Converting the Observed
Heighth of Water in the Jars of the Pneumato-Chemical
Apparatus, expressed in Inches and
Decimals, into Corresponding Heighths of Mercury, 482
No. III.—Table for Converting the Ounce
Measures used
by Dr Priestley into French and
English Cubical Inches, 483
[Pg l]
No. IV.—Table for Reducing the Degrees of
Reaumeur's Thermometer into its corresponding
Degrees of Fahrenheit's Scale, 484
No. V.—Additional.—Rules for Converting
French Weights
and Measures into correspondent
English Denominations, 485
No. VI.—Table of the Weights of the different
Gasses, at 28 French inches,
or 29.84 English
inches barometrical pressure, and at 10° (54.5°)
of temperature,
expressed in English measure
and English Troy weight, 490
No. VII.—Tables of the Specific Gravities of
different bodies, 491
No. VIII.—Additional.—Rules for Calculating
the Absolute Gravity in English Troy
Weight of a
Cubic Foot and Inch, English
Measure, of any Substance whose Specific Gravity
is known, 505
No. IX.—Tables for Converting Ounces, Drams,
and Grains, Troy, into
Decimals of the Troy
Pound of 12 Ounces, and for Converting Decimals
of the Pound Troy
into Ounces, &c. 508
No. X.—Table of the English Cubical Inches and
Decimals corresponding to a determinate Troy
Weight of Distilled Water at the Temperature
of 55°, calculated from Everard's experiment, 511
PART ONE.
On the Formation and Breakdown of
Gaseous Fluids,
—on the Combustion
of Simple Substances, and the Creation
of Acids, Page 1
CHAP. I.—On the Combinations of Heat, and
the Formation of Elastic Gaseous Fluids, ibid.
CHAP. II.—Overall Perspective on the Formation
and Composition of Our Atmosphere, 26
CHAP. III.—Analysis of Atmospheric Air, and its
Division into two Elastic Fluids;
one suitable for
Breathing, the other unsuitable for respiration, 32
CHAP. IV.—Naming the various components
of Atmospheric Air, 48
CHAP. V.—On the Breakdown of Oxygen
Gas by Sulfur,
Phosphorus, and Charcoal, and
[Pg xl]the Formation of Acids in general, 54
CHAP. VI.—On the Naming of Acids in general,
and especially those derived from
Nitrate and Sea Salt, 66
CHAP. VII.—On the Breakdown of Oxygen
Gas
using Metals, and the Creation of
Metallic Oxides, 78
CHAP. VIII.—On the Fundamental Principle of Water,
and its Breakdown by Charcoal and
Iron, 83
CHAP. IX.—On the Amounts of Heat released
from various Types of Combustion, 97
Combustion of Phosphorus, 100
SECT. I.—Combustion of Charcoal, 101
SECT. II.—Combustion of Hydrogen Gas, 102
SECT. III.—Formation of Nitric Acid, 102
SECT. IV.—Combustion of Wax, 105
SECT. V.—Combustion of Olive Oil, 106
CHAP. X.—On the Combustion of Combustible
Substances with one another, 109
CHAP. XI.—Observations on Oxides and Acids
with various Bases,
and on the Composition
of Animal and Plant Substances, 115
CHAP. XII.—On the Breakdown of Plant
and Animal Substances through Fire, 123
CHAP. XIII.—On the Breakdown of Plant
Oxides through Vinous Fermentation, 129
CHAP. XIV.—On the Putrefactive Fermentation, 141
CHAP. XV.—On the Acetic Fermentation, 146
CHAP. XVI.—On the Formation of Neutral Salts,
and their Bases, 149
[Pg xli]
SECT. I.—On Potash, 151
SECT. II.—On Soda, 155
SECT. III.—On Ammonia, 156
SECT. IV.—On Lime, Magnesia, Barium, and Clay, 157
SECT. V.—On Metallic Substances, 159
CHAP. XVII.—Continuing the Observations
on Salifiable Bases, and the Formation
of Neutral Salts, 161
PART TWO.
On the Combinations of Acids with Salifiable
Bases, and the Formation
of Neutral Salts, 175
INTRODUCTION, ibid.
TABLE of Simple Substances, 175
SECT. I.—Observations on Simple Substances, 176
TABLE of Compound Oxidizable and Acidifiable
Bases, 179
SECT. II.—Observations on Compound Radicals, 180
SECT. III.—Observations on the Combinations
of Light and Heat with different Substances, 182
[Pg xlii]
TABLE of the Combinations of Oxygen with the
Simple Substances, 185
SECT. IV.—Observations on these Combinations, 185
TABLE of the Combinations of Oxygen with Compound
Radicals, 190
SECT. V.—Observations on these Combinations, 191
TABLE of the Combinations of Nitrogen with the
Simple Substances, 194
SECT VI.—Observations on these Combinations
of Nitrogen, 195
TABLE of the Combinations of Hydrogen with
Simple Substances, 198
SECT. VII.—Observations on Hydrogen, and its
Combinations, 199
TABLE of the Binary Combinations of Sulfur
with the Simple Substances, 202
SECT. VIII.—Observations on Sulfur, and its
Combinations, 203
TABLE of the Combinations of Phosphorus with
Simple Substances, 204
SECT. IX.—Observations on Phosphorus and its
Combinations, 205
TABLE of the Binary Combinations of Charcoal, 207
SECT. X.—Observations on Charcoal, and its
Combinations, 208
SECT. XI.—Observations on the Hydrochloric, Fluoric,
and Boracic Radicals, and their Combinations, 209
[Pg xliii]
SECT. XII.—Observations on the Combinations
of Metals with one another, 219
TABLE of the Combinations of Nitrogen, in the State
of Nitrous Acid, with the Salifiable Bases, 212
TABLE of the Combinations of Nitrogen, in the State
of Nitric Acid, with the Salifiable Bases, 213
SECT. XIII.—Observations on Nitrous and Nitric
Acids, and their Combinations with Salifiable
Bases, 214
TABLE of the Combinations of Sulfuric Acid
with the Salifiable Bases, 218
SECT. XIV.—Observations on Sulfuric Acid,
and its Combinations, 219
TABLE of the Combinations of Sulfurous Acid, 222
SECT. XV.—Observations on Sulfurous Acid,
and its Combinations with Salifiable Bases, 223
TABLE of the Combinations of Phosphorous and
Phosphoric Acids, 225
SECT. XVI.—Observations on Phosphorous and
Phosphoric Acids, and their Combinations
with Salifiable Bases, 226
TABLE of the Combinations of Carbonic Acid, 228
SECT. XVII.—Observations on Carbonic Acid,
and its Combinations with Salifiable Bases, 229
TABLE of the Combinations of Hydrochloric Acid, 231
TABLE of the Combinations of Oxygenated Hydrochloric Acid, 232
[Pg xliv]
SECT. XVIII.—Observations on Hydrochloric and
Oxygenated Hydrochloric Acid,
and their Combinations
with Salifiable Bases, 233
TABLE of the Combinations of Nitric Hydrochloric Acid, 236
SECT. XIX.—Observations on Nitric Hydrochloric
Acid, and its Combinations with Salifiable
Bases, 237
TABLE of the Combinations of Fluoric Acid, 239
SECT. XX.—Observations on Fluoric Acid, and
its Combinations with Salifiable Bases, 240
TABLE of the Combinations of Boracic Acid, 242
SECT. XXI.—Observations on Boracic Acid,
and its Combinations with Salifiable Bases, 243
TABLE of the Combinations of Arsenic Acid, 246
SECT. XXII.—Observations on Arsenic Acid,
and its Combinations with Salifiable Bases, 247
SECT. XXIII.—Observations on Molybdic Acid,
and its Combinations with Salifiable Bases, 249
SECT. XXIV.—Observations on Tungstic Acid,
and its Combinations with Salifiable Bases,
and
a Table of these in the order of their Affinity, 251
TABLE of the Combinations of Tartaric Acid, 253
SECT. XXV.—Observations on Tartaric Acid,
and its Combinations with Salifiable Bases, 254
SECT. XXVI.—Observations on Malic Acid,
and its Combinations with Salifiable Bases, 256
TABLE of the Combinations of Citric Acid, 258
SECT. XXVII.—Observations on Citric Acid,
and its Combinations with Salifiable Bases, 259
[Pg xlv]
TABLE of the Combinations of Pyrolignous Acid, 260
SECT. XXVIII.—Observations on Pyrolignous
Acid, and its Combinations with Salifiable Bases, 261
SECT. XXIX.—Observations on Pyrotartaric
Acid, and its Combinations with Salifiable
Bases, ibid.
TABLE of the Combinations of Pyromucous Acid, 263
SECT. XXX.—Observations on Pyromucous
Acid, and its Combinations with Salifiable Bases, 264
TABLE of the Combinations of Oxalic Acid, 265
SECT. XXXI.—Observations on Oxalic Acid,
and its Combinations with Salifiable Bases, 266
TABLE of the Combinations of Acetic Acid, to
face 267
SECT. XXXII.—Observations on Acetic Acid,
and its Combinations with the Salifiable Bases, 267
TABLE of the Combinations of Acetic Acid, 271
SECT. XXXIII.—Observations on Acetic Acid,
and its Combinations with Salifiable Bases, 272
TABLE of the Combinations of Succinic Acid, 273
SECT. XXXIV.—Observations on Succinic Acid,
and its Combinations with Salifiable Bases, 274
SECT. XXXV.—Observations on Benzoic Acid,
and its Combinations with Salifiable Bases, 275
SECT. XXXVI.—Observations on Camphoric
Acid, and its Combinations with Salifiable
[Pg xlvi]Bases, 276
SECT. XXXVII.—Observations on Gallic Acid,
and its Combinations with Salifiable Bases, 277
SECT. XXXVIII.—Observations on Lactic Acid,
and its Combinations with Salifiable Bases, 278
TABLE of the Combinations of Saccholactic Acid, 280
SECT. XXXIX.—Observations on Saccholactic
Acid, and its Combination with Salifiable Bases, 281
TABLE of the Combinations of Formic Acid, 282
SECT. XL.—Observations on Formic Acid, and
its Combinations with the Salifiable Bases, 283
SECT. XLI.—Observations on Bombic Acid,
and its Combinations with the Salifiable Bases, 284
TABLE of the Combinations of Sebacic Acid, 285
SECT. XLII.—Observations on Sebacic Acid,
and its Combinations with the Salifiable Bases, 286
SECT. XLIII.—Observations on Lithic Acid,
and its Combinations with the Salifiable Bases, 287
TABLE of the Combinations of Prussic Acid, 288
SECT. XLIV.—Observations on Prussic Acid,
and its Combinations with the Salifiable Bases, 289
PART THREE.
[Pg xlvii]
Description of the Instruments and Operations
of Chemistry, 291
INTRODUCTION, 291
CHAP. I.—On the Tools needed to determine
the Absolute and Specific Densities of
Solid and Liquid Bodies, 295
CHAP. II.—On Gas Measurement, or the Calculation
of the Weight and Volume of Gaseous Substances, 304
SECT. I.—On the Pneumato-chemical Equipment, ibid.
SECT. II.—On the Gas Meter, 308
SECT. III.—Other methods for Measuring
the Volume of Gases, 319
SECT. IV.—On the method of Separating different
Gases from each other, 323
SECT. V.—On the Necessary Adjustments of the Volume
of Gases,
considering the Pressure of
the Atmosphere, 328
SECT. VI.—On the Adjustment regarding the Degrees
of the Thermometer, 335
SECT. VII.—Example for Calculating the Adjustments
based on Changes in Pressure and
Temperature, 337
SECT. VIII.—Method for determining the Weight
of different Gases, 340
CHAP. III.—Description of the Calorimeter, or
Device for measuring Heat, 343
CHAP. IV.—On the Mechanical Processes for
Dividing Bodies, 357
[Pg xlviii]
SECT. I.—On Grinding, Levigation, and Pulverization, ibid.
SECT. II.—On Sifting and Washing Powdered
Substances, 361
SECT. III.—On Filtration, 363
SECT. IV.—On Decantation, 365
CHAP. V.—On Chemical methods for Separating the
Particles of Bodies
from each other without
Decomposition, and for Reuniting them, 367
SECT. I.—On the Dissolution of Salts, 368
SECT. II.—On Leaching, 373
SECT. III.—On Evaporation, 375
SECT. IV.—On Crystallization, 379
SECT. V.—On Simple Distillation, 384
SECT. VI.—On Sublimation, 388
CHAP. VI.—On Pneumato-chemical Distillations,
Metallic Dissolutions,
and some other operations
that require very complex instruments, 390
SECT. I.—On Compound and Pneumato-chemical
Distillations, ibid.
SECT. II.—On Metallic Dissolutions, 398
SECT. III.—Apparatus necessary in Experiments
on Fermentations due to Wine and Decay, 401
SECT. IV.—Apparatus for the Breakdown of
Water, 404
CHAP. VII.—On the Composition and Use of
Lutes, 407
CHAP. VIII.—On Operations involving Combustion
and Deflagration, 414
SECT. I.—On Combustion in general, ibid.
SECT. II.—On the Combustion of Phosphorus, 418
[Pg xlix]
SECT. III.—On the Combustion of Charcoal, 422
SECT. IV.—On the Combustion of Oils, 426
SECT. V.—On the Combustion of Alcohol, 433
SECT. VI.—On the Combustion of Ether, 435
SECT. VII.—On the Combustion of Hydrogen
Gas, and the Creation of Water, 437
SECT. VIII.—On the Oxidation of Metals, 441
CHAP. IX.—On Deflagration, 452
CHAP. X.—On the Tools needed for Working
with Materials at very high Temperatures, 460
SECT. I.—On Melting, ibid.
SECT. II.—On Furnaces, 462
SECT. III.—On enhancing the Action of Fire by
using Oxygen Gas instead of Air, 474
APPENDIX.
No. I.—Table for Converting Lines, or Twelfths
of an Inch,
and Fractions of Lines, into
Decimal Fractions of the Inch, 481
No. II.—Table for Converting the Recorded
Height of Water in the Jars of the Pneumato-Chemical
Apparatus, expressed in Inches and
Decimals, into Corresponding Heights of Mercury, 482
No. III.—Table for Converting the Ounce
Measures used
by Dr. Priestley into French and
English Cubic Inches, 483
[Pg l]
No. IV.—Table for Converting the Degrees of
Réaumur's Thermometer into its corresponding
Degrees of Fahrenheit's Scale, 484
No. V.—Extra.—Guidelines for Converting
French Weights
and Measures into Corresponding
English Units, 485
No. VI.—Table of the Weights of the different
Gases, at 28 French inches,
or 29.84 English
inches barometric pressure, and at 10° (54.5°)
of temperature,
expressed in English measures
and English Troy weight, 490
No. VII.—Tables of the Specific Densities of
various bodies, 491
No. VIII.—Additional info.—Rules for Calculating
the Absolute Density in English Troy
Weight of a
Cubic Foot and Inch, English
Measure, of any Substance whose Specific Density
is known, 505
No. IX.—Tables for Converting Ounces, Drams,
and Grains, Troy, into
Decimals of the Troy
Pound of 12 Ounces, and for Converting Decimals
of the Pound Troy
into Ounces, &c. 508
No. X.—Table of the English Cubic Inches and
Decimals corresponding to a definite Troy
Weight of Distilled Water at the Temperature
of 55°, calculated from Everard's experiment, 511
ELEMENTS
OF
CHEMISTRY.
PART I.
Of the Formation and Decomposition of Aëriform Fluids—of the Combustion of Simple Bodies—and the Formation of Acids.
Of the Creation and Breakdown of Gaseous Fluids—of the Burning of Simple Substances—and the Creation of Acids.
CHAP. I.
Of the Combinations of Caloric, and the Formation of Elastic Aëriform Fluids.
That every body, whether solid or fluid, is augmented in all its dimensions by any increase of its sensible heat, was long ago fully established as a physical axiom, or universal proposition, by the celebrated Boerhaave. Such facts as have been adduced for controverting the[Pg 2] generality of this principle offer only fallacious results, or, at least, such as are so complicated with foreign circumstances as to mislead the judgment: But, when we separately consider the effects, so as to deduce each from the cause to which they separately belong, it is easy to perceive that the separation of particles by heat is a constant and general law of nature.
That everything, whether solid or liquid, expands in every dimension when its temperature rises was previously established as a fundamental principle by the renowned Boerhaave. Any evidence put forward to challenge the universality of this principle only presents misleading outcomes, or at the very least, results that are so intertwined with external factors that they can confuse our understanding. However, when we examine the effects individually, tracing each back to its specific cause, it becomes clear that the expansion of particles due to heat is a consistent and universal law of nature.
When we have heated a solid body to a certain degree, and have thereby caused its particles to separate from each other, if we allow the body to cool, its particles again approach each other in the same proportion in which they were separated by the increased temperature; the body returns through the same degrees of expansion which it before extended through; and, if it be brought back to the same temperature from which we set out at the commencement of the experiment, it recovers exactly the same dimensions which it formerly occupied. But, as we are still very far from being able to arrive at the degree of absolute cold, or deprivation of all heat, being unacquainted with any degree of coldness which we cannot suppose capable of still farther augmentation, it follows, that we are still incapable of causing the ultimate particles of bodies to approach each other as near as is possible; and, consequently, that the particles of all bodies do not touch each other in any state hitherto known, which, tho'[Pg 3] a very singular conclusion, is yet impossible to be denied.
When we heat a solid object to a certain temperature and cause its particles to move apart, if we let the object cool down, its particles will move back together in the same way they were separated by the heat. The object returns through the same levels of expansion that it went through before; and if we bring it back to the same temperature we started at, it will have exactly the same size it had before. However, since we are still far from reaching absolute zero, or the complete absence of heat, we do not know of any temperature that we can't imagine could still get colder. This means we can’t bring the ultimate particles of materials as close together as possible; therefore, the particles of all materials never actually touch each other in any known state, which, though a very unusual conclusion, is impossible to deny.
It is supposed, that, since the particles of bodies are thus continually impelled by heat to separate from each other, they would have no connection between themselves; and, of consequence, that there could be no solidity in nature, unless they were held together by some other power which tends to unite them, and, so to speak, to chain them together; which power, whatever be its cause, or manner of operation, we name Attraction.
It is assumed that since the particles of matter are constantly pushed apart by heat, they wouldn’t be connected to each other. As a result, there would be no solidity in nature unless they were held together by some other force that brings them together, so to speak, chaining them together. This force, regardless of its cause or how it works, is what we call Attraction.
Thus the particles of all bodies may be considered as subjected to the action of two opposite powers, the one repulsive, the other attractive, between which they remain in equilibrio. So long as the attractive force remains stronger, the body must continue in a state of solidity; but if, on the contrary, heat has so far removed these particles from each other, as to place them beyond the sphere of attraction, they lose the adhesion they before had with each other, and the body ceases to be solid.
Thus, the particles of all bodies can be seen as affected by two opposing forces, one pushing them apart and the other pulling them together, keeping them in balance. As long as the attractive force is stronger, the body will stay solid; however, if heat has separated these particles enough to push them beyond the range of attraction, they lose the connection they had with each other, and the body stops being solid.
Water gives us a regular and constant example of these facts; whilst below Zero[2] of the French thermometer, or 32° of Fahrenheit,[Pg 4] it remains solid, and is called ice. Above that degree of temperature, its particles being no longer held together by reciprocal attraction, it becomes liquid; and, when we raise its temperature above 80°, (212°) its particles, giving way to the repulsion caused by the heat, assume the state of vapour or gas, and the water is changed into an aëriform fluid.
Water gives us a clear and consistent example of these facts. Below zero degrees on the French thermometer, or 32°F, it stays solid and is known as ice. When the temperature rises above that, its particles can't hold together anymore due to a lack of attraction, and it turns into liquid. If we heat it to over 80° (212°F), the particles overcome the heat's repulsion and transform into vapor or gas, changing the water into an airy fluid.
The same may be affirmed of all bodies in nature: They are either solid or liquid, or in the state of elastic aëriform vapour, according to the proportion which takes place between the attractive force inherent in their particles, and the repulsive power of the heat acting upon these; or, what amounts to the same thing, in proportion to the degree of heat to which they are exposed.
The same can be said for all bodies in nature: They are either solid or liquid, or in the form of elastic vapor, depending on the balance between the attractive force within their particles and the repulsive power of the heat acting on them; or, essentially, in relation to the level of heat they are exposed to.
It is difficult to comprehend these phenomena, without admitting them as the effects of a real and material substance, or very subtile fluid, which, insinuating itself between the particles of bodies, separates them from each other; and, even allowing the existence of this fluid to be hypothetical, we shall see in the sequel, that it explains the phenomena of nature in a very satisfactory manner.
It’s hard to understand these phenomena without acknowledging them as the results of a real and material substance, or a very subtle fluid, which, by embedding itself between the particles of matter, separates them from one another. Even if we consider the existence of this fluid as hypothetical, we will see later that it provides a very satisfactory explanation for the phenomena of nature.
This substance, whatever it is, being the cause of heat, or, in other words, the sensation which we call warmth being caused by the accumulation of this substance, we cannot, in strict language,[Pg 5] distinguish it by the term heat; because the same name would then very improperly express both cause and effect. For this reason, in the memoir which I published in 1777[3], I gave it the names of igneous fluid and matter of heat. And, since that time, in the work[4] published by Mr de Morveau, Mr Berthollet, Mr de Fourcroy, and myself, upon the reformation of chemical nomenclature, we thought it necessary to banish all periphrastic expressions, which both lengthen physical language, and render it more tedious and less distinct, and which even frequently does not convey sufficiently just ideas of the subject intended. Wherefore, we have distinguished the cause of heat, or that exquisitely elastic fluid which produces it, by the term of caloric. Besides, that this expression fulfils our object in the system which we have adopted, it possesses this farther advantage, that it accords with every species of opinion, since, strictly speaking, we are not obliged to suppose this to be a real substance; it being sufficient, as will more clearly appear in the sequel of this work, that it be considered as the repulsive cause, whatever that may be, which separates the particles of matter from each other; so that[Pg 6] we are still at liberty to investigate its effects in an abstract and mathematical manner.
This substance, whatever it is, causes heat, or in other words, the sensation we call warmth comes from the buildup of this substance. Therefore, we can't accurately refer to it as heat, since the same name would improperly label both the cause and the effect. For this reason, in the paper I published in 1777[3], I named it igneous fluid and matter of heat. Since then, in the work[4] published by Mr de Morveau, Mr Berthollet, Mr de Fourcroy, and me, on revising chemical terminology, we decided to eliminate all roundabout expressions that make scientific language longer, more tedious, and less clear, and often fail to accurately convey the intended ideas. Therefore, we have referred to the cause of heat, or that highly elastic fluid that produces it, as caloric. Besides fulfilling our purpose in the system we've adopted, this term also has the advantage of being compatible with all types of theories, since technically, we’re not required to assume it’s a real substance; it’s sufficient, as will be clearer later in this work, to see it as the repulsive cause, whatever that might be, that separates particles of matter from each other. This way, we can still investigate its effects in an abstract and mathematical way.
In the present state of our knowledge, we are unable to determine whether light be a modification of caloric, or if caloric be, on the contrary, a modification of light. This, however, is indisputable, that, in a system where only decided facts are admissible, and where we avoid, as far as possible, to suppose any thing to be that is not really known to exist, we ought provisionally to distinguish, by distinct terms, such things as are known to produce different effects. We therefore distinguish light from caloric; though we do not therefore deny that these have certain qualities in common, and that, in certain circumstances, they combine with other bodies almost in the same manner, and produce, in part, the same effects.
In today's understanding, we can't say for sure whether light is a form of heat, or if heat is actually a form of light. However, it's clear that in a system that only accepts established facts, and where we try our best to avoid assuming things that aren't actually known to exist, we should temporarily use different terms to identify things that produce different effects. So, we make a distinction between light and heat; although this doesn't mean we deny that they share some qualities and, under certain conditions, can interact with other substances similarly and produce some of the same effects.
What I have already said may suffice to determine the idea affixed to the word caloric; but there remains a more difficult attempt, which is, to give a just conception of the manner in which caloric acts upon other bodies. Since this subtile matter penetrates through the pores of all known substances; since there are no vessels through which it cannot escape, and, consequently, as there are none which are capable of retaining it, we can only come at the knowledge of its properties by effects which are fleeting, and difficultly ascertainable. It is in[Pg 7] these things which we neither see nor feel, that it is especially necessary to guard against the extravagancy of our imagination, which forever inclines to step beyond the bounds of truth, and is very difficultly restrained within the narrow line of facts.
What I've already said should be enough to clarify the idea attached to the word caloric, but there's a more challenging task ahead, which is to accurately explain how caloric interacts with other bodies. Since this subtle matter seeps through the pores of all known substances, and since there are no containers that can hold it in, we can only understand its properties through effects that are temporary and hard to measure. In[Pg 7] these aspects that we neither see nor feel, it's especially important to be cautious about the wildness of our imagination, which tends to go beyond the limits of reality and is very hard to keep in line with actual facts.
We have already seen, that the same body becomes solid, or fluid, or aëriform, according to the quantity of caloric by which it is penetrated; or, to speak more strictly, according as the repulsive force exerted by the caloric is equal to, stronger, or weaker, than the attraction of the particles of the body it acts upon.
We have already seen that the same substance can be solid, liquid, or gas, depending on the amount of heat it contains; or, to be more precise, based on whether the repulsive force of the heat is equal to, stronger than, or weaker than the attraction between the particles of the substance it affects.
But, if these two powers only existed, bodies would become liquid at an indivisible degree of the thermometer, and would almost instantaneously pass from the solid state of aggregation to that of aëriform elasticity. Thus water, for instance, at the very moment when it ceases to be ice, would begin to boil, and would be transformed into an aëriform fluid, having its particles scattered indefinitely through the surrounding space. That this does not happen, must depend upon the action of some third power. The pressure of the atmosphere prevents this separation, and causes the water to remain in the liquid state till it be raised to 80° of temperature (212°) above zero of the French thermometer, the quantity of caloric which it receives in the lowest temperature being insufficient[Pg 8] to overcome the pressure of the atmosphere.
But if these two forces were the only ones at play, substances would turn into liquid at a single point on the thermometer, instantly shifting from a solid state to a gaseous state. For example, water, at the moment it stops being ice, would start to boil and be converted into a gas, with its particles spreading out indefinitely in the surrounding space. The fact that this doesn't happen must be due to the influence of a third force. Atmospheric pressure keeps this separation from occurring, allowing the water to stay in a liquid form until it reaches 80° Celsius (212° Fahrenheit), as the amount of heat it gains at the lowest temperature isn't enough[Pg 8] to overcome atmospheric pressure.
Whence it appears that, without this atmospheric pressure, we should not have any permanent liquid, and should only be able to see bodies in that state of existence in the very instant of melting, as the smallest additional caloric would instantly separate their particles, and dissipate them through the surrounding medium. Besides, without this atmospheric pressure, we should not even have any aëriform fluids, strictly speaking, because the moment the force of attraction is overcome by the repulsive power of the caloric, the particles would separate themselves indefinitely, having nothing to give limits to their expansion, unless their own gravity might collect them together, so as to form an atmosphere.
It seems that without atmospheric pressure, we wouldn't have any permanent liquids, and we would only observe substances in that state for a fleeting moment when they melt. Any slight increase in heat would quickly cause their particles to separate and disperse into the surrounding environment. Moreover, without atmospheric pressure, we wouldn’t even have gaseous substances, because once the force of attraction is overtaken by the repulsive energy of heat, the particles would spread out infinitely, lacking any limits to their expansion unless their own gravity could pull them together to create an atmosphere.
Simple reflection upon the most common experiments is sufficient to evince the truth of these positions. They are more particularly proved by the following experiment, which I published in the Memoirs of the French Academy for 1777, p. 426.
Simple reflection on the most common experiments is enough to reveal the truth of these points. They are especially demonstrated by the following experiment, which I published in the Memoirs of the French Academy for 1777, p. 426.
Having filled with sulphuric ether[5] a small narrow glass vessel, A, (Plate VII. Fig. 17.), standing[Pg 9] upon its stalk P, the vessel, which is from twelve to fifteen lines diameter, is to be covered by a wet bladder, tied round its neck with several turns of strong thread; for greater security, fix a second bladder over the first. The vessel should be filled in such a manner with the ether, as not to leave the smallest portion of air between the liquor and the bladder. It is now to be placed under the recipient BCD of an air-pump, of which the upper part B ought to be fitted with a leathern lid, through which passes a wire EF, having its point F very sharp; and in the same receiver there ought to be placed the barometer GH. The whole being thus disposed, let the recipient be exhausted, and then, by pushing down the wire EF, we make a hole in the bladder. Immediately the ether begins to boil with great violence, and is changed into an elastic aëriform fluid, which fills the receiver. If the quantity of ether be sufficient to leave a few drops in the phial after the evaporation is finished, the elastic fluid produced will sustain the mercury in the barometer attached to the air-pump, at eight or ten inches in winter, and from[Pg 10] twenty to twenty-five in summer[6]. To render this experiment more complete, we may introduce a small thermometer into the phial A, containing the ether, which will descend considerably during the evaporation.
Having filled a small narrow glass vessel, A, with sulfuric ether (Plate VII. Fig. 17.), which stands on its stalk P and has a diameter of about twelve to fifteen lines, cover the vessel with a wet bladder, securing it around the neck with several turns of strong thread. For added security, place a second bladder over the first. Fill the vessel with ether in such a way that no air remains between the liquid and the bladder. Next, place it under the receiver BCD of an air pump, ensuring that the upper part B is fitted with a leather lid, through which a sharp wire EF passes, with its point F being very sharp. Also, place a barometer GH in the same receiver. Once everything is set up, let the receiver be exhausted, and then push down the wire EF to puncture the bladder. Immediately, the ether will start boiling vigorously and convert into an elastic gas that fills the receiver. If there is enough ether left in the vial after evaporation, the produced gas will cause the mercury in the barometer attached to the air pump to rise to eight or ten inches in winter and from twenty to twenty-five in summer. To make this experiment even more thorough, you can insert a small thermometer into the vial A containing the ether, which will show a significant drop in temperature during the evaporation process.
The only effect produced in this experiment is, the taking away the weight of the atmosphere, which, in its ordinary state, presses on the surface of the ether; and the effects resulting from this removal evidently prove, that, in the ordinary temperature of the earth, ether would always exist in an aëriform state, but for the pressure of the atmosphere, and that the passing of the ether from the liquid to the aëriform state is accompanied by a considerable lessening of heat; because, during the evaporation, a part of the caloric, which was before in a free state, or at least in equilibrio in the surrounding bodies, combines with the ether, and causes it to assume the aëriform state.
The only effect produced in this experiment is the removal of the weight of the atmosphere, which, in its normal state, presses down on the surface of the ether; and the results from this removal clearly show that, at the typical temperature of the earth, ether would always exist in a gaseous state if it weren't for the pressure of the atmosphere. Additionally, the transition of ether from a liquid to a gaseous state is accompanied by a significant decrease in heat because, during evaporation, part of the heat that was previously free, or at least balanced with surrounding bodies, combines with the ether and causes it to become gaseous.
The same experiment succeeds with all evaporable fluids, such as alkohol, water, and even mercury; with this difference, that the atmosphere formed in the receiver by alkohol only[Pg 11] supports the attached barometer about one inch in winter, and about four or five inches in summer; that formed by water, in the same situation, raises the mercury only a few lines, and that by quicksilver but a few fractions of a line. There is therefore less fluid evaporated from alkohol than from ether, less from water than from alkohol, and still less from mercury than from either; consequently there is less caloric employed, and less cold produced, which quadrates exactly with the results of these experiments.
The same experiment works with all evaporating liquids like alcohol, water, and even mercury, but with this difference: the atmosphere created in the receiver by alcohol only[Pg 11] supports the attached barometer by about one inch in winter and about four or five inches in summer. The atmosphere created by water, in the same situation, raises the mercury by only a few lines, and that created by mercury only raises it by a tiny fraction of a line. Therefore, less fluid evaporates from alcohol than from ether, less from water than from alcohol, and even less from mercury than from either. As a result, less heat is used, and less cold is generated, which aligns perfectly with the outcomes of these experiments.
Another species of experiment proves very evidently that the aëriform state is a modification of bodies dependent on the degree of temperature, and on the pressure which these bodies undergo. In a Memoir read by Mr de la Place and me to the Academy in 1777, which has not been printed, we have shown, that, when ether is subjected to a pressure equal to twenty-eight inches of the barometer, or about the medium pressure of the atmosphere, it boils at the temperature of about 32° (104°), or 33° (106.25°), of the thermometer. Mr de Luc, who has made similar experiments with spirit of wine, finds it boils at 67° (182.75°). And all the world knows that water boils at 80° (212°). Now, boiling being only the evaporation of a liquid, or the moment of its passing from the fluid to the aëriform state, it is evident that, if we keep[Pg 12] ether continually at the temperature of 33° (106.25°), and under the common pressure of the atmosphere, we shall have it always in an elastic aëriform state; and that the same thing will happen with alkohol when above 67° (182.75°), and with water when above 80° (212°); all which are perfectly conformable to the following experiment[7].
Another type of experiment clearly shows that the gaseous state is a change in matter dependent on the temperature and the pressure these substances are under. In a paper presented by Mr. de la Place and me to the Academy in 1777, which hasn’t been published, we demonstrated that when ether is subjected to a pressure of twenty-eight inches of mercury, or about the average atmospheric pressure, it boils at a temperature of around 32° (104°) or 33° (106.25°) on the thermometer. Mr. de Luc, who has conducted similar experiments with alcohol, found that it boils at 67° (182.75°). And everyone knows that water boils at 80° (212°). Since boiling is simply the evaporation of a liquid or the point at which it changes from a liquid to a gaseous state, it’s clear that if we keep ether consistently at a temperature of 33° (106.25°) and under normal atmospheric pressure, it will always remain in an elastic gaseous state; the same goes for alcohol above 67° (182.75°) and for water above 80° (212°); all of this is perfectly consistent with the following experiment[Pg 12][7].
I filled a large vessel ABCD (Plate VII. Fig. 16.) with water, at 35° (110.75°), or 36° (113°); I suppose the vessel transparent, that we may see what takes place in the experiment; and we can easily hold the hands in water at that temperature without inconvenience. Into it I plunged some narrow necked bottles F, G, which were filled with the water, after which they were turned up, so as to rest on their mouths on the bottom of the vessel. Having next put some ether into a very small matrass, with its neck a b c, twice bent as in the Plate, I plunged this matrass into the water, so as to have its neck inserted into the mouth of one of the bottles F. Immediately upon feeling the effects of the heat communicated to it by the water in the vessel ABCD it began to boil; and the caloric entering into combination with it, changed it into elastic aëriform fluid, with which I filled several bottles successively, F, G, &c.
I filled a large container ABCD (Plate VII. Fig. 16.) with water at 35° (110.75°) or 36° (113°); I assume the container is transparent so we can see what happens in the experiment, and we can easily keep our hands in water at that temperature without discomfort. I then submerged some narrow-necked bottles F and G, which were filled with water, and turned them upside down so their mouths rested on the bottom of the container. Next, I poured some ether into a very small flask, with its neck a b c bent twice as shown in the Plate, and plunged this flask into the water, inserting its neck into the mouth of one of the bottles F. As soon as it started to feel the heat from the water in the container ABCD, it began to boil; and the heat combined with it, turning it into an elastic gas, which I used to fill several bottles in succession, F, G, etc.
This is not the place to enter upon the examination of the nature and properties of this aëriform fluid, which is extremely inflammable; but, confining myself to the object at present in view, without anticipating circumstances, which I am not to suppose the reader to know, I shall only observe, that the ether, from this experiment, is almost only capable of existing in the aëriform state in our world; for, if the weight of our atmosphere was only equal to between 20 and 24 inches of the barometer, instead of 28 inches, we should never be able to obtain ether in the liquid state, at least in summer; and the formation of ether would consequently be impossible upon mountains of a moderate degree of elevation, as it would be converted into gas immediately upon being produced, unless we employed recipients of extraordinary strength, together with refrigeration and compression. And, lastly, the temperature of the blood being nearly that at which ether passes from the liquid to the aëriform state, it must evaporate in the primae viae, and consequently it is very probable the medical properties of this fluid depend chiefly upon its mechanical effect.
This isn’t the place to discuss the nature and properties of this flammable gas, but focusing on the current topic without assuming prior knowledge, I’ll simply note that ether, based on this experiment, can almost only exist as a gas in our world. If our atmosphere’s pressure were only between 20 and 24 inches on the barometer, instead of 28 inches, we would never be able to get ether in a liquid state, at least not in summer. This means that ether couldn’t form on moderately high mountains, as it would turn into gas right after being produced unless we used containers of extraordinary strength with cooling and compression. Finally, since the temperature of blood is about the same as the point at which ether transitions from liquid to gas, it must evaporate in the digestive tract. Therefore, it’s likely that the medicinal properties of this substance mainly rely on its mechanical effects.
These experiments succeed better with nitrous ether, because it evaporates in a lower temperature than sulphuric ether. It is more difficult to obtain alkohol in the aëriform state; because, as it requires 67° (182.75°) to reduce it to vapour,[Pg 14] the water of the bath must be almost boiling, and consequently it is impossible to plunge the hands into it at that temperature.
These experiments work better with nitrous ether because it evaporates at a lower temperature than sulfuric ether. It’s harder to obtain alcohol in the gas state since it needs to reach 67° (182.75°) to turn into vapor,[Pg 14] meaning the water in the bath has to be nearly boiling, making it impossible to dip your hands in at that temperature.
It is evident that, if water were used in the foregoing experiment, it would be changed into gas, when exposed to a temperature superior to that at which it boils. Although thoroughly convinced of this, Mr de la Place and myself judged it necessary to confirm it by the following direct experiment. We filled a glass jar A, (Plate VII. Fig. 5.) with mercury, and placed it with its mouth downwards in a dish B, likewise filled with mercury, and having introduced about two gross of water into the jar, which rose to the top of the mercury at CD; we then plunged the whole apparatus into an iron boiler EFGH, full of boiling sea-water of the temperature of 85° (123.25°), placed upon the furnace GHIK. Immediately upon the water over the mercury attaining the temperature of 80° (212°), it began to boil; and, instead of only filling the small space ACD, it was converted into an aëriform fluid, which filled the whole jar; the mercury even descended below the surface of that in the dish B; and the jar must have been overturned, if it had not been very thick and heavy, and fixed to the dish by means of iron-wire. Immediately after withdrawing the apparatus from the boiler, the vapour in the jar began to condense, and the[Pg 15] mercury rose to its former station; but it returned again to the aëriform state a few seconds after replacing the apparatus in the boiler.
It’s clear that if water were used in the experiment mentioned earlier, it would turn into gas when exposed to a temperature higher than its boiling point. Though Mr. de la Place and I were completely convinced of this, we thought it was necessary to confirm it with the following direct experiment. We filled a glass jar A (Plate VII. Fig. 5.) with mercury and placed it upside down in a dish B, which was also filled with mercury. We introduced about two gross of water into the jar, which rose to the top of the mercury at CD. We then placed the entire setup into an iron boiler EFGH, filled with boiling seawater at a temperature of 85° (123.25°), situated over the furnace GHIK. As soon as the water over the mercury reached a temperature of 80° (212°), it started to boil. Instead of only filling the small space ACD, it transformed into a gas that filled the whole jar; the mercury even dropped below the level of that in dish B. The jar would have fallen over if it hadn’t been very thick and heavy, and secured to the dish with iron wire. Right after we pulled the apparatus from the boiler, the vapor in the jar began to condense, and the[Pg 15] mercury rose back to its original level, but it shifted back to the gaseous state a few seconds after we put the apparatus back in the boiler.
We have thus a certain number of substances, which are convertible into elastic aëriform fluids by degrees of temperature, not much superior to that of our atmosphere. We shall afterwards find that there are several others which undergo the same change in similar circumstances, such as muriatic or marine acid, ammoniac or volatile alkali, the carbonic acid or fixed air, the sulphurous acid, &c. All of these are permanently elastic in or about the mean temperature of the atmosphere, and under its common pressure.
We have a number of substances that can be turned into elastic gases at temperatures not far above that of our atmosphere. Later, we will see that there are several others that change in similar situations, such as hydrochloric acid, ammonia, carbon dioxide, sulfur dioxide, and so on. All of these gases remain elastic at or around the average temperature of the atmosphere and under its usual pressure.
All these facts, which could be easily multiplied if necessary, give me full right to assume, as a general principle, that almost every body in nature is susceptible of three several states of existence, solid, liquid, and aëriform, and that these three states of existence depend upon the quantity of caloric combined with the body. Henceforwards I shall express these elastic aëriform fluids by the generic term gas; and in each species of gas I shall distinguish between the caloric, which in some measure serves the purpose of a solvent, and the substance, which in combination with the caloric, forms the base of the gas.[Pg 16]
All these facts, which could easily be expanded if needed, give me every reason to believe that almost everything in nature can exist in three different states: solid, liquid, and gas. These three states depend on the amount of heat, or caloric, that is combined with the matter. From now on, I’ll refer to these elastic gases simply as gas; and for each type of gas, I’ll differentiate between the heat, which acts like a solvent to some extent, and the substance that, when combined with the heat, forms the foundation of the gas.[Pg 16]
To these bases of the different gases, which are hitherto but little known, we have been obliged to assign names; these I shall point out in Chap. IV. of this work, when I have previously given an account of the phenomena attendant upon the heating and cooling of bodies, and when I have established precise ideas concerning the composition of our atmosphere.
To these foundations of the different gases, which are still not well understood, we have had to give names; I will highlight these in Chap. IV of this work after I have explained the phenomena related to the heating and cooling of substances, and after I have clarified what our atmosphere is made of.
We have already shown, that the particles of every substance in nature exist in a certain state of equilibrium, between that attraction which tends to unite and keep the particles together, and the effects of the caloric which tends to separate them. Hence the caloric not only surrounds the particles of all bodies on every side, but fills up every interval which the particles of bodies leave between each other. We may form an idea of this, by supposing a vessel filled with small spherical leaden bullets, into which a quantity of fine sand is poured, which, insinuating into the intervals between the bullets, will fill up every void. The balls, in this comparison, are to the sand which surrounds them exactly in the same situation as the particles of bodies are with respect to the caloric; with this difference only, that the balls are supposed to touch each other, whereas the particles of bodies are not in contact, being retained at a small distance from each other, by the caloric.[Pg 17]
We've already shown that the particles of every substance in nature exist in a certain state of balance between the attraction that brings them together and the effects of heat that push them apart. Therefore, heat not only surrounds the particles of all bodies but also fills every space left between them. To visualize this, imagine a container filled with small spherical lead pellets, into which fine sand is poured. The sand fills in the gaps between the pellets, taking up all the empty space. In this comparison, the pellets are like the particles of matter, and the sand represents the heat that surrounds them, with one key difference: the pellets are assumed to touch each other, while the particles of matter are not in contact, as they are held apart by heat.[Pg 17]
If, instead of spherical balls, we substitute solid bodies of a hexahedral, octohedral, or any other regular figure, the capacity of the intervals between them will be lessened, and consequently will no longer contain the same quantity of sand. The same thing takes place, with respect to natural bodies; the intervals left between their particles are not of equal capacity, but vary in consequence of the different figures and magnitude of their particles, and of the distance at which these particles are maintained, according to the existing proportion between their inherent attraction, and the repulsive force exerted upon them by the caloric.
If we replace spherical balls with solid shapes like cubes or octahedrons, the gaps between them will decrease, so they won’t hold the same amount of sand. The same applies to natural substances; the spaces between their particles aren’t all the same size but change based on the various shapes and sizes of the particles, as well as the distances that these particles are kept apart. This is influenced by the balance between their natural attraction and the repulsive force from heat.
In this manner we must understand the following expression, introduced by the English philosophers, who have given us the first precise ideas upon this subject; the capacity of bodies for containing the matter of heat. As comparisons with sensible objects are of great use in assisting us to form distinct notions of abstract ideas, we shall endeavour to illustrate this, by instancing the phenomena which take place between water and bodies which are wetted and penetrated by it, with a few reflections.
In this way, we need to understand the following concept introduced by English philosophers, who provided us with the first clear ideas on this topic: the ability of substances to hold heat. Since comparisons with tangible objects help us form clear ideas about abstract concepts, we will try to illustrate this by looking at the effects that occur between water and objects that it wets and soaks, along with a few thoughts.
If we immerge equal pieces of different kinds of wood, suppose cubes of one foot each, into water, the fluid gradually insinuates itself into their pores, and the pieces of wood are augmented both in weight and magnitude: But[Pg 18] each species of wood will imbibe a different quantity of water; the lighter and more porous woods will admit a larger, the compact and closer grained will admit of a lesser quantity; for the proportional quantities of water imbibed by the pieces will depend upon the nature of the constituent particles of the wood, and upon the greater or lesser affinity subsisting between them and water. Very resinous wood, for instance, though it may be at the same time very porous, will admit but little water. We may therefore say, that the different kinds of wood possess different capacities for receiving water; we may even determine, by means of the augmentation of their weights, what quantity of water they have actually absorbed; but, as we are ignorant how much water they contained, previous to immersion, we cannot determine the absolute quantity they contain, after being taken out of the water.
If we submerge equal pieces of different types of wood, say one-foot cubes, in water, the liquid slowly seeps into their pores, and the wood gains weight and size. However, each type of wood will absorb a different amount of water; lighter and more porous woods will take in more, while denser and tightly grained woods will absorb less. The amount of water absorbed by each piece depends on the specific nature of the wood’s fibers and their affinity for water. For example, very resinous wood, even if it is quite porous, will absorb very little water. We can say that different types of wood have different abilities to hold water; we can even figure out how much water they’ve absorbed by measuring the increase in their weight. But, since we don’t know how much water they held before being submerged, we can’t determine the exact amount they contain after being taken out of the water.
The same circumstances undoubtedly take place, with bodies that are immersed in caloric; taking into consideration, however, that water is an incompressible fluid, whereas caloric is, on the contrary, endowed with very great elasticity; or, in other words, the particles of caloric have a great tendency to separate from each other, when forced by any other power to approach; this difference must of necessity occasion[Pg 19] very considerable diversities in the results of experiments made upon these two substances.
The same situations undoubtedly occur, with bodies immersed in heat; however, it's important to note that water is an incompressible fluid, while heat is extremely elastic. In other words, the particles of heat have a strong tendency to move apart from each other when pressured to come together by another force. This difference must inevitably lead to significant variations in the results of experiments conducted on these two substances.[Pg 19]
Having established these clear and simple propositions, it will be very easy to explain the ideas which ought to be affixed to the following expressions, which are by no means synonimous, but possess each a strict and determinate meaning, as in the following definitions:
Having set out these clear and straightforward points, it will be really easy to explain the ideas that should be attached to the following expressions. These terms are not synonymous; each has a specific and defined meaning, as shown in the following definitions:
Free caloric, is that which is not combined in any manner with any other body. But, as we live in a system to which caloric has a very strong adhesion, it follows that we are never able to obtain it in the state of absolute freedom.
Free caloric is that which is not combined in any way with any other substance. However, since we exist in a system where caloric is strongly attached, it means we can never truly obtain it in a state of absolute freedom.
Combined caloric, is that which is fixed in bodies by affinity or elective attraction, so as to form part of the substance of the body, even part of its solidity.
Combined caloric is the heat that's stored in bodies due to attraction or affinity, making it a part of the body's substance, even contributing to its solidity.
By the expression specific caloric of bodies, we understand the respective quantities of caloric requisite for raising a number of bodies of the same weight to an equal degree of temperature. This proportional quantity of caloric depends upon the distance between the constituent particles of bodies, and their greater or lesser degrees of cohesion; and this distance, or rather the space or void resulting from it, is, as I have already observed, called the capacity of bodies for containing caloric.[Pg 20]
By the term specific caloric of substances, we mean the specific amounts of heat needed to raise a number of substances of the same weight to the same temperature. This proportional amount of heat depends on the distance between the particles that make up the substances, as well as their varying degrees of cohesion; and this distance, or the space or gap it creates, is what I previously referred to as the capacity of substances to hold heat.[Pg 20]
Heat, considered as a sensation, or, in other words, sensible heat, is only the effect produced upon our sentient organs, by the motion or passage of caloric, disengaged from the surrounding bodies. In general, we receive impressions only in consequence of motion, and we might establish it as an axiom, That, without motion, there is no sensation. This general principle applies very accurately to the sensations of heat and cold: When we touch a cold body, the caloric which always tends to become in equilibrio in all bodies, passes from our hand into the body we touch, which gives us the feeling or sensation of cold. The direct contrary happens, when we touch a warm body, the caloric then passing from the body into our hand, produces the sensation of heat. If the hand and the body touched be of the same temperature, or very nearly so, we receive no impression, either of heat or cold, because there is no motion or passage of caloric; and thus no sensation can take place, without some correspondent motion to occasion it.
Heat is seen as a sensation, or in other words, sensible heat, and it’s simply the effect produced on our sensory organs by the movement or transfer of caloric from surrounding bodies. Generally, we only receive impressions due to movement, and we could say as a rule, That, Without movement, there is no feeling.. This principle applies quite well to the sensations of heat and cold: when we touch a cold object, the caloric that always aims to balance out among all bodies moves from our hand into the object, giving us the feeling of cold. The opposite occurs when we touch a warm object; the caloric then moves from the object into our hand, producing the sensation of heat. If our hand and the object we touch are at the same temperature, or very close to it, we don’t feel either heat or cold because there’s no movement or transfer of caloric; thus, no sensation can occur without some corresponding motion to trigger it.
When the thermometer rises, it shows, that free caloric is entering into the surrounding bodies: The thermometer, which is one of these, receives its share in proportion to its mass, and to the capacity which it possesses for containing caloric. The change therefore which takes place upon the thermometer, only announces a[Pg 21] change of place of the caloric in those bodies, of which the thermometer forms one part; it only indicates the portion of caloric received, without being a measure of the whole quantity disengaged, displaced, or absorbed.
When the thermometer goes up, it indicates that free heat is entering the surrounding objects. The thermometer, being one of these objects, takes in heat based on its mass and its ability to hold heat. Therefore, the change that occurs in the thermometer simply signals a change in the location of the heat in those objects, of which the thermometer is a part; it only shows the amount of heat received, without measuring the total amount that has been released, shifted, or absorbed.
The most simple and most exact method for determining this latter point, is that described by Mr de la Place, in the Memoirs of the Academy, No. 1780, p. 364; a summary explanation of which will be found towards the conclusion of this work. This method consists in placing a body, or a combination of bodies, from which caloric is disengaging, in the midst of a hollow sphere of ice; and the quantity of ice melted becomes an exact measure of the quantity of caloric disengaged. It is possible, by means of the apparatus which we have caused to be constructed upon this plan, to determine, not as has been pretended, the capacity of bodies for containing heat, but the ratio of the increase or diminution of capacity produced by determinate degrees of temperature. It is easy with the same apparatus, by means of divers combinations of experiments, to determine the quantity of caloric requisite for converting solid substances into liquids, and liquids into elastic aëriform fluids; and, vice versa, what quantity of caloric escapes from elastic vapours in changing to liquids, and what quantity escapes from liquids during their conversion into solids. Perhaps,[Pg 22] when experiments have been made with sufficient accuracy, we may one day be able to determine the proportional quantity of caloric, necessary for producing the several species of gasses. I shall hereafter, in a separate chapter, give an account of the principal results of such experiments as have been made upon this head.
The simplest and most precise method for figuring out this point is the one described by Mr. de la Place in the Memoirs of the Academy, No. 1780, p. 364; a summary explanation of it can be found toward the end of this work. This method involves placing a body, or a group of bodies, that is releasing heat in the center of a hollow sphere of ice; the amount of ice that melts serves as an exact measure of the heat released. With the apparatus we’ve built based on this plan, we can determine, not as previously claimed, the capacity of bodies to hold heat, but rather the ratio of increase or decrease in capacity caused by specific temperature changes. Using the same apparatus, we can also determine how much heat is needed to turn solids into liquids and liquids into gases, and conversely, how much heat is released from gases when they turn into liquids, and how much escapes from liquids when they solidify. Perhaps, [Pg 22] once experiments have been conducted with enough precision, we will one day be able to figure out the proportional amount of heat necessary to create different types of gases. I will provide, in a separate chapter, a summary of the main results from the experiments conducted on this topic.
It remains, before finishing this article, to say a few words relative to the cause of the elasticity of gasses, and of fluids in the state of vapour. It is by no means difficult to perceive that this elasticity depends upon that of caloric, which seems to be the most eminently elastic body in nature. Nothing is more readily conceived, than that one body should become elastic by entering into combination with another body possessed of that quality. We must allow that this is only an explanation of elasticity, by an assumption of elasticity, and that we thus only remove the difficulty one step farther, and that the nature of elasticity, and the reason for caloric being elastic, remains still unexplained. Elasticity in the abstract is nothing more than that quality of the particles of bodies by which they recede from each other when forced together. This tendency in the particles of caloric to separate, takes place even at considerable distances. We shall be satisfied of this, when we consider that air is susceptible of undergoing great compression, which supposes that its particles[Pg 23] were previously very distant from each other; for the power of approaching together certainly supposes a previous distance, at least equal to the degree of approach. Consequently, those particles of the air, which are already considerably distant from each other, tend to separate still farther. In fact, if we produce Boyle's vacuum in a large receiver, the very last portion of air which remains spreads itself uniformly through the whole capacity of the vessel, however large, fills it completely throughout, and presses every where against its sides: We cannot, however, explain this effect, without supposing that the particles make an effort to separate themselves on every side, and we are quite ignorant at what distance, or what degree of rarefaction, this effort ceases to act.
It’s important to say a few words about why gases and vapors are elastic before we wrap up this article. It’s not hard to see that this elasticity comes from heat, which seems to be the most elastic substance in nature. It makes sense that one material can become elastic when combined with another that has that property. However, this just shifts the explanation of elasticity to one based on another form of elasticity, and we still don’t understand what elasticity really is or why heat is elastic. In simple terms, elasticity refers to the property of particles in materials that makes them pull apart when they’re pushed together. This tendency of heat particles to separate occurs even at significant distances. We realize this when we consider how air can be compressed greatly, implying its particles were initially quite far apart; the ability to come closer implies they were at least that far apart before. Therefore, the air particles, which are already fairly distant from each other, naturally want to move apart even more. In fact, if we create a vacuum in a large container, the last bit of air left spreads out evenly within the entire space, no matter how large it is, filling it completely and pressing against all sides. Yet, we can’t explain this effect without assuming that the particles are trying to push away from each other in all directions, and we have no idea at what distance or level of rarefaction this effort stops working.
Here, therefore, exists a true repulsion between the particles of elastic fluids; at least, circumstances take place exactly as if such a repulsion actually existed; and we have very good right to conclude, that the particles of caloric mutually repel each other. When we are once permitted to suppose this repelling force, the rationale of the formation of gasses, or aëriform fluids, becomes perfectly simple; tho' we must, at the same time, allow, that it is extremely difficult to form an accurate conception of this repulsive force acting upon very minute[Pg 24] particles placed at great distances from each other.
Here, there is a real repulsion between the particles of elastic fluids; in fact, the situation unfolds just as if such a repulsion truly existed. We can reasonably conclude that the particles of heat (caloric) push each other away. Once we accept the idea of this repelling force, the explanation for the formation of gases, or air-like fluids, becomes completely straightforward. However, we must also acknowledge that it's extremely challenging to form a clear understanding of this repulsive force acting on very tiny particles that are far apart from one another.
It is, perhaps, more natural to suppose, that the particles of caloric have a stronger mutual attraction than those of any other substance, and that these latter particles are forced asunder in consequence of this superior attraction between the particles of the caloric, which forces them between the particles of other bodies, that they may be able to reunite with each other. We have somewhat analogous to this idea in the phenomena which occur when a dry sponge is dipt into water: The sponge swells; its particles separate from each other; and all its intervals are filled up by the water. It is evident, that the sponge, in the act of swelling, has acquired a greater capacity for containing water than it had when dry. But we cannot certainly maintain, that the introduction of water between the particles of the sponge has endowed them with a repulsive power, which tends to separate them from each other; on the contrary, the whole phenomena are produced by means of attractive powers; and these are, first, The gravity of the water, and the power which it exerts on every side, in common with all other fluids; 2dly, The force of attraction which takes place between the particles of the water, causing them to unite together; 3dly, The mutual attraction of the particles of the sponge with each other;[Pg 25] and, lastly, The reciprocal attraction which exists between the particles of the sponge and those of the water. It is easy to understand, that the explanation of this fact depends upon properly appreciating the intensity of, and connection between, these several powers. It is probable, that the separation of the particles of bodies, occasioned by caloric, depends in a similar manner upon a certain combination of different attractive powers, which, in conformity with the imperfection of our knowledge, we endeavour to express by saying, that caloric communicates a power of repulsion to the particles of bodies.
It seems more logical to think that the particles of heat have a stronger attraction to each other than the particles of any other substance, and that those other particles are pushed apart because of this stronger attraction between the heat particles, which forces them in between the particles of other materials so they can come back together. We can see something similar to this idea in what happens when a dry sponge is dipped in water: the sponge expands; its particles move apart, and all the spaces in between are filled with water. It's clear that as the sponge expands, it has developed a greater capacity to hold water than it did when it was dry. However, we can't say for sure that the water being introduced between the sponge's particles gives them a repelling force that makes them separate from one another; on the contrary, all of these effects are caused by attractive forces: first, the weight of the water and the force it exerts from all sides, like all other fluids; second, the attraction between the water particles that makes them stick together; third, the mutual attraction of the sponge particles to each other;[Pg 25] and lastly, the attraction between the sponge particles and the water particles. It's easy to see that understanding this situation hinges on accurately assessing the strength and relationship between these different forces. It's likely that the way heat causes particles to separate is similarly based on a specific combination of different attractive forces. Due to the limitations of our knowledge, we try to express this by saying that heat gives a repelling power to the particles of bodies.
FOOTNOTES:
[2] Whenever the degree of heat occurs in this work, it is stated by the author according to Reaumur's scale. The degrees within brackets are the correspondent degrees of Fahrenheit's scale, added by the translator. E.
[2] Whenever heat is mentioned in this work, the author uses Reaumur's scale. The degrees in brackets represent the equivalent degrees in Fahrenheit, added by the translator. E.
[4] Chemical Nomenclature.
__A_TAG_PLACEHOLDER_0__ Chemistry Naming.
[5] As I shall afterwards give a definition, and explain the properties of the liquor called ether, I shall only premise here, that it is a very volatile inflammable liquor, having a considerably smaller specific gravity than water, or even spirit of wine.—A.
[5] I will later provide a definition and explain the properties of the substance known as ether. For now, I’ll just say that it is a highly volatile, flammable liquid with a much lower specific gravity than water or even alcohol.—A.
[6] It would have been more satisfactory if the Author had specified the degrees of the thermometer at which these heights of the mercury in the barometer are produced.
[6] It would have been more helpful if the Author had mentioned the temperature readings at which these levels of mercury in the barometer occur.
CHAP. II.
General Views relative to the Formation and Composition of our Atmosphere.
These views which I have taken of the formation of elastic aëriform fluids or gasses, throw great light upon the original formation of the atmospheres of the planets, and particularly that of our earth. We readily conceive, that it must necessarily consist of a mixture of the following substances: First, Of all bodies that are susceptible of evaporation, or, more strictly speaking, which are capable of retaining the state of aëriform elasticity in the temperature of our atmosphere, and under a pressure equal to that of a column of twenty-eight inches of quicksilver in the barometer; and, secondly, Of all substances, whether liquid or solid, which are capable of being dissolved by this mixture of different gasses.
These views I've taken on the formation of elastic gaseous fluids shed significant light on the original formation of planetary atmospheres, especially that of Earth. We can easily understand that it must consist of a mixture of the following substances: First, all bodies that can evaporate, or, to be more precise, those that can maintain a gaseous state at the temperature of our atmosphere and under pressure equal to that of a column of twenty-eight inches of mercury in the barometer; and, secondly, all substances, whether liquid or solid, that can be dissolved by this mixture of different gases.
The better to determine our ideas relating to this subject, which has not hitherto been sufficiently considered, let us, for a moment, conceive what change would take place in the various[Pg 27] substances which compose our earth, if its temperature were suddenly altered. If, for instance, we were suddenly transported into the region of the planet Mercury, where probably the common temperature is much superior to that of boiling water, the water of the earth, and all the other fluids which are susceptible of the gasseous state, at a temperature near to that of boiling water, even quicksilver itself, would become rarified; and all these substances would be changed into permanent aëriform fluids or gasses, which would become part of the new atmosphere. These new species of airs or gasses would mix with those already existing, and certain reciprocal decompositions and new combinations would take place, until such time as all the elective attractions or affinities subsisting amongst all these new and old gasseous substances had operated fully; after which, the elementary principles composing these gasses, being saturated, would remain at rest. We must attend to this, however, that, even in the above hypothetical situation, certain bounds would occur to the evaporation of these substances, produced by that very evaporation itself; for as, in proportion to the increase of elastic fluids, the pressure of the atmosphere would be augmented, as every degree of pressure tends, in some measure, to prevent evaporation, and as even the most evaporable[Pg 28] fluids can resist the operation of a very high temperature without evaporating, if prevented by a proportionally stronger compression, water and all other liquids being able to sustain a red heat in Papin's digester; we must admit, that the new atmosphere would at last arrive at such a degree of weight, that the water which had not hitherto evaporated would cease to boil, and, of consequence, would remain liquid; so that, even upon this supposition, as in all others of the same nature, the increasing gravity of the atmosphere would find certain limits which it could not exceed. We might even extend these reflections greatly farther, and examine what change might be produced in such situations upon stones, salts, and the greater part of the fusible substances which compose the mass of our earth. These would be softened, fused, and changed into fluids, &c.: But these speculations carry me from my object, to which I hasten to return.
To better understand our ideas about this topic, which hasn't been sufficiently explored until now, let's imagine what would happen to the various [Pg 27] substances that make up our Earth if its temperature suddenly changed. For example, if we were suddenly transported to Mercury, where the average temperature is much higher than boiling water, the water on Earth and all other fluids that can turn into gas at temperatures close to boiling would become vaporized. Even mercury itself would become less dense, and all these substances would turn into permanent gases that would mix with the existing atmosphere. These new types of gases would interact with the existing ones, leading to various decompositions and new combinations until all the attractions and affinities between the new and old gaseous substances have fully acted out; after that, the fundamental elements of these gases would reach a stable state. However, we must note that, even in this hypothetical situation, there would be limits to the evaporation of these substances caused by evaporation itself. As the amount of gas increases, the atmospheric pressure would also rise, and since higher pressure tends to hinder evaporation—just like how even the most evaporative [Pg 28] liquids can withstand very high temperatures without evaporating if there’s enough compression—water and other liquids could endure red heat in Papin's digester. We must conclude that the new atmosphere would eventually become so heavy that the water that hasn't evaporated would stop boiling and, consequently, remain liquid. Thus, even under this assumption, as in similar cases, the increasing density of the atmosphere would reach certain limits it couldn't exceed. We could even elaborate further and consider what changes might occur to rocks, salts, and most of the fusible substances that make up the Earth. These would soften, melt, and become liquid, etc.: But these thoughts divert me from my main point, which I quickly return to.
By a contrary supposition to the one we have been forming, if the earth were suddenly transported into a very cold region, the water which at present composes our seas, rivers, and springs, and probably the greater number of the fluids we are acquainted with, would be converted into solid mountains and hard rocks, at first diaphanous[Pg 29] and homogeneous, like rock crystal, but which, in time, becoming mixed with foreign and heterogeneous substances, would become opake stones of various colours. In this case, the air, or at least some part of the aëriform fluids which now compose the mass of our atmosphere, would doubtless lose its elasticity for want of a sufficient temperature to retain them in that state: They would return to the liquid state of existence, and new liquids would be formed, of whose properties we cannot, at present, form the most distant idea.
By a different assumption than the one we've been discussing, if the earth were suddenly moved to a very cold area, the water that currently makes up our seas, rivers, and springs—and probably most of the fluids we're familiar with—would turn into solid mountains and hard rocks. Initially, these would be transparent[Pg 29] and uniform, like rock crystal, but over time, they would mix with foreign and varied substances and become opaque stones of different colors. In this scenario, the air—or at least some part of the gases that now make up our atmosphere—would likely lose its elasticity due to the lack of a temperature sufficient to keep them in that state: they would revert to liquid form, and new liquids would emerge, the properties of which we can't even begin to imagine right now.
These two opposite suppositions give a distinct proof of the following corollaries: First, That solidity, liquidity, and aëriform elasticity, are only three different states of existence of the same matter, or three particular modifications which almost all substances are susceptible of assuming successively, and which solely depend upon the degree of temperature to which they are exposed; or, in other words, upon the quantity of caloric with which they are penetrated[8]. 2dly, That it is extremely probable that air is a fluid naturally existing in a state of vapour; or, as we may better express it, that our atmosphere is a compound of all the fluids[Pg 30] which are susceptible of the vaporous or permanently elastic state, in the usual temperature, and under the common pressure. 3dly, That it is not impossible we may discover, in our atmosphere, certain substances naturally very compact, even metals themselves; as a metallic substance, for instance, only a little more volatile than mercury, might exist in that situation.
These two opposing ideas provide clear evidence for the following conclusions: First, that solidity, liquidity, and gaseous elasticity are just three different states of the same matter, or three specific forms that almost all substances can take on in succession, depending entirely on the temperature they are subjected to; in other words, on the amount of heat they contain[8]. Second, it is highly likely that air is a fluid that naturally exists in a vaporous state; or, to phrase it more clearly, our atmosphere is a mixture of all the fluids[Pg 30] that can exist in a vaporous or permanently gaseous form at normal temperatures and under typical pressure. Third, it is not impossible that we may find certain substances in our atmosphere that are naturally very dense, even metals themselves; for example, a metallic substance that is just a bit more volatile than mercury might exist in that environment.
Amongst the fluids with which we are acquainted, some, as water and alkohol, are susceptible of mixing with each other in all proportions; whereas others, on the contrary, as quicksilver, water, and oil, can only form a momentary union; and, after being mixed together, separate and arrange themselves according to their specific gravities. The same thing ought to, or at least may, take place in the atmosphere. It is possible, and even extremely probable, that, both at the first creation, and every day, gasses are formed, which are difficultly miscible with atmospheric air, and are continually separating from it. If these gasses be specifically lighter than the general atmospheric mass, they must, of course, gather in the higher regions, and form strata that float upon the common air. The phenomena which accompany igneous meteors induce me to believe, that there exists in the upper parts[Pg 31] of our atmosphere a stratum of inflammable fluid in contact with those strata of air which produce the phenomena of the aurora borealis and other fiery meteors.—I mean hereafter to pursue this subject in a separate treatise.
Among the fluids we're familiar with, some, like water and alcohol, can mix together in any amount; while others, such as mercury, water, and oil, can only temporarily combine and will eventually separate based on their specific weights. The same might happen in the atmosphere. It's possible, and even very likely, that gases are created both at the beginning of time and every day that don't mix easily with the air and are constantly separating from it. If these gases are lighter than the overall atmospheric mass, they will rise and form layers that float above the common air. The events associated with shooting stars lead me to believe that there is a layer of flammable gas in the upper regions[Pg 31] of our atmosphere, in contact with the layers of air that cause the aurora borealis and other fiery phenomena. I plan to explore this topic in a separate study.
FOOTNOTES:
CHAP. III.
Analysis of Atmospheric Air, and its Division into two Elastic Fluids; the one fit for Respiration, the other incapable of being respired.
From what has been premised, it follows, that our atmosphere is composed of a mixture of every substance capable of retaining the gasseous or aëriform state in the common temperature, and under the usual pressure which it experiences. These fluids constitute a mass, in some measure homogeneous, extending from the surface of the earth to the greatest height hitherto attained, of which the density continually decreases in the inverse ratio of the superincumbent weight. But, as I have before observed, it is possible that this first stratum is surmounted by several others consisting of very different fluids.
From what has been established, it follows that our atmosphere is made up of a mix of every substance that can remain in a gaseous state at normal temperatures and under the usual pressure it experiences. These gases form a mostly uniform mass, stretching from the earth's surface to the highest point reached so far, with the density continuously decreasing in relation to the weight above it. However, as I have mentioned before, it's possible that this initial layer is topped by several others made up of very different gases.
Our business, in this place, is to endeavour to determine, by experiments, the nature of the elastic fluids which compose the inferior stratum of air which we inhabit. Modern chemistry has made great advances in this research; and it will appear by the following details that the analysis of atmospherical air has been more[Pg 33] rigorously determined than that of any other substance of the class. Chemistry affords two general methods of determining the constituent principles of bodies, the method of analysis, and that of synthesis. When, for instance, by combining water with alkohol, we form the species of liquor called, in commercial language, brandy or spirit of wine, we certainly have a right to conclude, that brandy, or spirit of wine, is composed of alkohol combined with water. We can produce the same result by the analytical method; and in general it ought to be considered as a principle in chemical science, never to rest satisfied without both these species of proofs.
Our business here is to try to figure out, through experiments, what the elastic gases are that make up the lower layer of air we breathe. Modern chemistry has made significant progress in this area, and the following details will show that the analysis of atmospheric air has been more[Pg 33] thoroughly determined than that of any other substance in this category. Chemistry offers two main ways to identify the basic components of substances: the analytical method and the synthetic method. For example, when we combine water with alcohol, we create a type of drink known in commercial terms as brandy or spirit of wine. We can confidently conclude that brandy or spirit of wine is made up of alcohol combined with water. We can reach the same conclusion using the analytical method; and as a general rule in chemical science, it should be seen as a principle to not be satisfied with only one of these types of evidence.
We have this advantage in the analysis of atmospherical air, being able both to decompound it, and to form it a new in the most satisfactory manner. I shall, however, at present confine myself to recount such experiments as are most conclusive upon this head; and I may consider most of these as my own, having either first invented them, or having repeated those of others, with the intention of analysing atmospherical air, in perfectly new points of view.
We have an advantage in analyzing atmospheric air, as we can both break it down and recreate it in a very effective way. For now, I'll focus on sharing the experiments that provide the most decisive results on this topic; I can claim most of these as my own since I either invented them or repeated others' experiments with the goal of analyzing atmospheric air from completely new perspectives.
I took a matrass (A, fig. 14. plate II.) of about 36 cubical inches capacity, having a long neck B C D E, of six or seven lines internal diameter, and having bent the neck as in Plate IV. Fig. 2. so as to allow of its being placed in[Pg 34] the furnace M M N N, in such a manner that the extremity of its neck E might be inserted under a bell-glass F G, placed in a trough of quicksilver R R S S; I introduced four ounces of pure mercury into the matrass, and, by means of a syphon, exhausted the air in the receiver F G, so as to raise the quicksilver to L L, and I carefully marked the height at which it stood by pasting on a slip of paper. Having accurately noted the height of the thermometer and barometer, I lighted a fire in the furnace M M N N, which I kept up almost continually during twelve days, so as to keep the quicksilver always almost at its boiling point. Nothing remarkable took place during the first day: The Mercury, though not boiling, was continually evaporating, and covered the interior surface of the vessels with small drops, at first very minute, which gradually augmenting to a sufficient size, fell back into the mass at the bottom of the vessel. On the second day, small red particles began to appear on the surface of the mercury, which, during the four or five following days, gradually increased in size and number; after which they ceased to increase in either respect. At the end of twelve days, seeing that the calcination of the mercury did not at all increase, I extinguished the fire, and allowed the vessels to cool. The bulk of air in the body and neck of the matrass, and in the bell-glass, reduced to[Pg 35] a medium of 28 inches of the barometer and 10° (54.5°) of the thermometer, at the commencement of the experiment was about 50 cubical inches. At the end of the experiment the remaining air, reduced to the same medium pressure and temperature, was only between 42 and 43 cubical inches; consequently it had lost about 1/6 of its bulk. Afterwards, having collected all the red particles, formed during the experiment, from the running mercury in which they floated, I found these to amount to 45 grains.
I used a flask (A, fig. 14. plate II.) with a capacity of about 36 cubic inches, featuring a long neck B C D E, with an internal diameter of six or seven lines. I bent the neck as shown in Plate IV. Fig. 2, so I could place it in[Pg 34] the furnace M M N N, allowing the end of the neck E to fit under a bell jar F G, which was set in a trough of mercury R R S S. I poured four ounces of pure mercury into the flask and used a siphon to remove the air from the receiver F G, raising the mercury to L L, at which point I carefully marked its height by affixing a slip of paper. After accurately recording the thermometer and barometer readings, I lit a fire in the furnace M M N N, maintaining it almost constantly for twelve days to keep the mercury nearly at its boiling point. Nothing significant occurred on the first day: the mercury, although not boiling, was consistently evaporating and forming tiny drops on the inner surfaces of the vessels, which gradually grew large enough to fall back into the main body at the bottom. On the second day, small red particles began to appear on the surface of the mercury, and over the next four or five days, their size and number increased, then they stopped growing altogether. After twelve days, seeing that the mercury's calcination wasn't progressing, I extinguished the fire and let the vessels cool. The air volume in the flask's body and neck, as well as in the bell jar, measured at[Pg 35] a medium pressure of 28 inches on the barometer and 10° (54.5°) on the thermometer, was about 50 cubic inches at the start of the experiment. By the end, the remaining air, measured at the same pressure and temperature, was only between 42 and 43 cubic inches; thus, it had lost about 1/6 of its volume. Afterward, I collected all the red particles that formed during the experiment from the bubbling mercury, and I found their total weight to be 45 grains.
I was obliged to repeat this experiment several times, as it is difficult in one experiment both to preserve the whole air upon which we operate, and to collect the whole of the red particles, or calx of mercury, which is formed during the calcination. It will often happen in the sequel, that I shall, in this manner, give in one detail the results of two or three experiments of the same nature.
I had to perform this experiment multiple times because it’s hard to maintain all the air we’re working with in one experiment and also collect all the red particles, or calx of mercury, that form during the calcination. Often, I will end up combining the results of two or three similar experiments into one detail.
The air which remained after the calcination of the mercury in this experiment, and which was reduced to 5/6 of its former bulk, was no longer fit either for respiration or for combustion; animals being introduced into it were suffocated in a few seconds, and when a taper was plunged into it, it was extinguished as if it had been immersed into water.[Pg 36]
The air left after heating the mercury in this experiment, which shrank to 5/6 of its original size, was no longer suitable for breathing or burning; animals placed in it suffocated within seconds, and when a candle was dipped into it, it went out as if it had been put into water.[Pg 36]
In the next place, I took the 45 grains of red matter formed during this experiment, which I put into a small glass retort, having a proper apparatus for receiving such liquid, or gasseous product, as might be extracted: Having applied a fire to the retort in a furnace, I observed that, in proportion as the red matter became heated, the intensity of its colour augmented. When the retort was almost red hot, the red matter began gradually to decrease in bulk, and in a few minutes after it disappeared altogether; at the same time 41-1/2 grains of running mercury were collected in the recipient, and 7 or 8 cubical inches of elastic fluid, greatly more capable of supporting both respiration and combustion than atmospherical air, were collected in the bell-glass.
Next, I took the 45 grains of red substance created during this experiment and placed it into a small glass retort, equipped with the appropriate apparatus to capture any liquid or gas that might be released. After heating the retort in a furnace, I noticed that as the red substance got hotter, its color became more intense. When the retort was almost red hot, the red substance started to gradually shrink, and a few minutes later, it completely vanished. At the same time, 41.5 grains of liquid mercury were collected in the recipient, along with 7 or 8 cubic inches of gas that was much better at supporting both breathing and combustion than regular air, which was gathered in the bell jar.
A part of this air being put into a glass tube of about an inch diameter, showed the following properties: A taper burned in it with a dazzling splendour, and charcoal, instead of consuming quietly as it does in common air, burnt with a flame, attended with a decrepitating noise, like phosphorus, and threw out such a brilliant light that the eyes could hardly endure it. This species of air was discovered almost at the same time by Mr Priestley, Mr Scheele, and myself. Mr Priestley gave it the name of dephlogisticated air, Mr Scheele called it empyreal air. At first I named it highly respirable air, to[Pg 37] which has since been substituted the term of vital air. We shall presently see what we ought to think of these denominations.
A portion of this air was put into a glass tube about an inch in diameter, and it exhibited the following properties: A taper burned in it with a dazzling brightness, and charcoal, instead of burning quietly as it does in regular air, ignited with a flame accompanied by a crackling noise, similar to phosphorus, and emitted such a bright light that the eyes could barely tolerate it. This type of air was discovered almost simultaneously by Mr. Priestley, Mr. Scheele, and me. Mr. Priestley named it dephlogisticated air, while Mr. Scheele referred to it as empyreal air. Initially, I called it highly respirable air, but the term vital air has since replaced it[Pg 37]. We will soon explore how we should view these names.
In reflecting upon the circumstances of this experiment, we readily perceive, that the mercury, during its calcination, absorbs the salubrious and respirable part of the air, or, to speak more strictly, the base of this respirable part; that the remaining air is a species of mephitis, incapable of supporting combustion or respiration; and consequently that atmospheric air is composed of two elastic fluids of different and opposite qualities. As a proof of this important truth, if we recombine these two elastic fluids, which we have separately obtained in the above experiment, viz. the 42 cubical inches of mephitis, with the 8 cubical inches of respirable air, we reproduce an air precisely similar to that of the atmosphere, and possessing nearly the same power of supporting combustion and respiration, and of contributing to the calcination of metals.
In reflecting on the circumstances of this experiment, we clearly see that mercury, during its heating process, absorbs the beneficial and breathable part of the air, or more specifically, the base of this breathable part; that the leftover air is a kind of toxic gas, incapable of supporting combustion or respiration; and therefore, that atmospheric air consists of two elastic gases with different and opposing qualities. To prove this important point, if we recombine these two elastic gases, which we obtained separately in the experiment mentioned above, specifically the 42 cubic inches of toxic gas and the 8 cubic inches of breathable air, we recreate air that is exactly like that of the atmosphere, with nearly the same ability to support combustion and respiration, as well as to aid in the calcination of metals.
Although this experiment furnishes us with a very simple means of obtaining the two principal elastic fluids which compose our atmosphere, separate from each other, yet it does not give us an exact idea of the proportion in which these two enter into its composition: For the attraction of mercury to the respirable part of the air, or rather to its base, is not sufficiently strong to overcome all the circumstances which[Pg 38] oppose this union. These obstacles are the mutual adhesion of the two constituent parts of the atmosphere for each other, and the elective attraction which unites the base of vital air with caloric; in consequence of these, when the calcination ends, or is at least carried as far as is possible, in a determinate quantity of atmospheric air, there still remains a portion of respirable air united to the mephitis, which the mercury cannot separate. I shall afterwards show, that, at least in our climate, the atmospheric air is composed of respirable and mephitic airs, in the proportion of 27 and 73; and I shall then discuss the causes of the uncertainty which still exists with respect to the exactness of that proportion.
Although this experiment provides us with a straightforward way to obtain the two main gases that make up our atmosphere separately, it doesn’t give us a precise idea of the ratio in which they contribute to its composition. The attraction of mercury to the breathable part of the air, or more accurately, to its base, isn't strong enough to overcome all the factors that hinder this combination. These factors include the mutual attraction between the two main components of the atmosphere and the specific attraction that bonds the base of vital air to heat. As a result, when the combustion is finished, or at least taken as far as it can go with a certain amount of atmospheric air, a portion of breathable air remains attached to the noxious gas, which the mercury can’t separate. I will later demonstrate that, at least in our climate, atmospheric air consists of breathable and noxious gases in the ratio of 27 to 73; I will then discuss the reasons for the uncertainty that still surrounds the accuracy of that ratio.
Since, during the calcination of mercury, air is decomposed, and the base of its respirable part is fixed and combined with the mercury, it follows, from the principles already established, that caloric and light must be disengaged during the process: But the two following causes prevent us from being sensible of this taking place: As the calcination lasts during several days, the disengagement of caloric and light, spread out in a considerable space of time, becomes extremely small for each particular moment of that time, so as not to be perceptible; and, in the next place, the operation being carried on by means of fire in a furnace, the heat[Pg 39] produced by the calcination itself becomes confounded with that proceeding from the furnace. I might add the respirable part of the air, or rather its base, in entering into combination with the mercury, does not part with all the caloric which it contained, but still retains a part of it after forming the new compound; but the discussion of this point, and its proofs from experiment, do not belong to this part of our subject.
Since the calcination of mercury breaks down air, and the breathable part combines with the mercury, it follows from the principles already established that heat and light must be released during the process. However, two factors prevent us from noticing this. First, since the calcination takes several days, the release of heat and light, spread out over a long time, becomes so small at each specific moment that it is imperceptible. Second, since the process uses fire in a furnace, the heat[Pg 39] generated by the calcination mixes with the heat coming from the furnace. Additionally, the breathable part of the air, or rather its base, when combining with the mercury, doesn’t release all the heat it contained but retains some of it after forming the new compound. However, discussing this point and providing experimental evidence for it isn’t relevant to this part of our topic.
It is, however, easy to render this disengagement of caloric and light evident to the senses, by causing the decomposition of air to take place in a more rapid manner. And for this purpose, iron is excellently adapted, as it possesses a much stronger affinity for the base of respirable air than mercury. The elegant experiment of Mr Ingenhouz, upon the combustion of iron, is well known. Take a piece of fine iron wire, twisted into a spiral, (BC, Plate IV. Fig. 17.) fix one of its extremities B into the cork A, adapted to the neck of the bottle DEFG, and fix to the other extremity of the wire C, a small morsel of tinder. Matters being thus prepared, fill the bottle DEFG with air deprived of its mephitic part; then light the tinder, and introduce it quickly with the wire upon which it is fixed, into the bottle which you stop up with the cork A, as is shown in the figure (17 Plate IV.) The instant the[Pg 40] tinder comes into contact with the vital air it begins to burn with great intensity; and, communicating the inflammation to the iron-wire, it too takes fire, and burns rapidly, throwing out brilliant sparks, which fall to the bottom of the vessel in rounded globules, which become black in cooling, but retain a degree of metallic splendour. The iron thus burnt is more brittle even than glass, and is easily reduced into powder, and is still attractable by the magnet, though not so powerfully as it was before combustion. As Mr Ingenhouz has neither examined the change produced on iron, nor upon the air by this operation, I have repeated the experiment under different circumstances, in an apparatus adapted to answer my particular views, as follows.
It’s pretty simple to show how the separation of heat and light is noticeable to our senses by speeding up the decomposition of air. For this, iron works really well since it has a much stronger attraction to the breathable part of air than mercury. The impressive experiment by Mr. Ingenhouz on burning iron is quite famous. Take a piece of fine iron wire twisted into a spiral (BC, Plate IV. Fig. 17), attach one end B to the cork A, which fits the neck of the bottle DEFG, and attach a small piece of tinder to the other end of the wire C. Once you have everything set up, fill the bottle DEFG with air that doesn’t have its harmful component. Next, light the tinder and quickly place it, along with the wire, into the bottle, sealing it with cork A, as shown in figure 17 (Plate IV). The moment the tinder contacts the vital air, it ignites intensely and transfers the flame to the iron wire, causing it to catch fire and burn rapidly, producing brilliant sparks that fall to the bottom of the vessel in rounded droplets. These droplets turn black as they cool but still keep some metallic shine. The iron that has burned becomes even more brittle than glass and can easily be turned into powder. It is still attracted by a magnet, though not as strongly as it was before burning. Since Mr. Ingenhouz didn’t investigate the changes in iron or air from this process, I have repeated the experiment under different conditions using a setup tailored to my specific goals, as follows.
Having filled a bell-glass (A, Plate IV. Fig. 3.) of about six pints measure, with pure air, or the highly respirable part of air, I transported this jar by means of a very flat vessel, into a quicksilver bath in the bason BC, and I took care to render the surface of the mercury perfectly dry both within and without the jar with blotting paper. I then provided a small capsule of china-ware D, very flat and open, in which I placed some small pieces of iron, turned spirally, and arranged in such a way as seemed most favourable for the combustion being communicated to every part. To the end of one of these pieces of iron was[Pg 41] fixed a small morsel of tinder, to which was added about the sixteenth part of a grain of phosphorus, and, by raising the bell-glass a little, the china capsule, with its contents, were introduced into the pure air. I know that, by this means, some common air must mix with the pure air in the glass; but this, when it is done dexterously, is so very trifling, as not to injure the success of the experiment. This being done, a part of the air is sucked out from the bell-glass, by means of a syphon GHI, so as to raise the mercury within the glass to EF; and, to prevent the mercury from getting into the syphon, a small piece of paper is twisted round its extremity. In sucking out the air, if the motion of the lungs only be used, we cannot make the mercury rise above an inch or an inch and a half; but, by properly using the muscles of the mouth, we can, without difficulty, cause it to rise six or seven inches.
Having filled a bell jar (A, Plate IV. Fig. 3.) with about six pints of pure air, or the most breathable part of air, I carefully transported this jar using a very flat vessel into a mercury bath in the basin BC. I made sure to dry the surface of the mercury completely, both inside and outside the jar, with blotting paper. Next, I prepared a small, flat, open china capsule D, where I placed some small spirally turned pieces of iron, arranged in a way that seemed most effective for ensuring combustion spread throughout the entire setup. At one end of one of these iron pieces, I attached a small piece of tinder and added about a sixteenth of a grain of phosphorus. By lifting the bell jar slightly, I introduced the china capsule and its contents into the pure air. I know that using this method, some common air will mix with the pure air in the jar; however, if done carefully, this contamination is so minimal that it won’t affect the outcome of the experiment. Once that was done, part of the air was removed from the bell jar using a siphon GHI, raising the mercury inside the jar to EF. To stop the mercury from entering the siphon, I twisted a small piece of paper around its end. When sucking out the air, if I only use my lung motion, I can't raise the mercury more than an inch or an inch and a half, but by properly using my mouth muscles, I can easily make it rise six or seven inches.
I next took an iron wire, (MN, Plate IV. Fig. 16.) properly bent for the purpose, and making it red hot in the fire, passed it through the mercury into the receiver, and brought it in contact with the small piece of phosphorus attached to the tinder. The phosphorus instantly takes fire, which communicates to the tinder, and from that to the iron. When the pieces have been properly arranged, the whole iron burns, even to the last particle,[Pg 42] throwing out a white brilliant light similar to that of Chinese fireworks. The great heat produced by this combustion melts the iron into round globules of different sizes, most of which fall into the China cup; but some are thrown out of it, and swim upon the surface of the mercury. At the beginning of the combustion, there is a slight augmentation in the volume of the air in the bell-glass, from the dilatation caused by the heat; but, presently afterwards, a rapid diminution of the air takes place, and the mercury rises in the glass; insomuch that, when the quantity of iron is sufficient, and the air operated upon is very pure, almost the whole air employed is absorbed.
I then took an iron wire, (MN, Plate IV. Fig. 16.) shaped for the purpose, heated it until it was red hot in the fire, then inserted it through the mercury into the receiver, where it touched a small piece of phosphorus attached to the tinder. The phosphorus instantly ignites, which sets the tinder on fire, and from there, it ignites the iron. Once the pieces are arranged properly, the entire iron burns completely, even down to the last fragment, [Pg 42] producing a bright white light similar to that seen in Chinese fireworks. The intense heat from this combustion melts the iron into round droplets of various sizes, most of which fall into the China cup, though some get ejected and float on the surface of the mercury. At the start of the combustion, there is a slight increase in the air volume inside the bell jar due to the heat causing expansion; however, soon after, there is a rapid decrease in the air, and the mercury level rises in the glass. If there is enough iron and the air being used is very pure, nearly all of the air gets absorbed.
It is proper to remark in this place, that, unless in making experiments for the purpose of discovery, it is better to be contented with burning a moderate quantity of iron; for, when this experiment is pushed too far, so as to absorb much of the air, the cup D, which floats upon the quicksilver, approaches too near the bottom of the bell-glass; and the great heat produced, which is followed by a very sudden cooling, occasioned by the contact of the cold mercury, is apt to break the glass. In which case, the sudden fall of the column of mercury, which happens the moment the least flaw is produced in the glass, causes such a wave, as throws a great part of the quicksilver from the bason. To avoid[Pg 43] this inconvenience, and to ensure success to the experiment, one gross and a half of iron is sufficient to burn in a bell-glass, which holds about eight pints of air. The glass ought likewise to be strong, that it may be able to bear the weight of the column of mercury which it has to support.
It’s important to note here that, unless you're conducting experiments for discovery, it's better to only burn a moderate amount of iron. If you push this experiment too far and absorb too much air, the cup D, which sits on the mercury, gets too close to the bottom of the bell jar. The intense heat generated, followed by a rapid cooling from the cold mercury, can easily break the glass. If the glass does break, the sudden drop in the mercury column at the slightest crack sends a wave that can splash a significant amount of the mercury out of the basin. To prevent[Pg 43] this issue and ensure the success of the experiment, using one and a half gross of iron is enough to burn in a bell jar that holds about eight pints of air. The glass also needs to be sturdy enough to support the weight of the mercury column it has to hold.
By this experiment, it is not possible to determine, at one time, both the additional weight acquired by the iron, and the changes which have taken place in the air. If it is wished to ascertain what additional weight has been gained by the iron, and the proportion between that and the air absorbed, we must carefully mark upon the bell-glass, with a diamond, the height of the mercury, both before and after the experiment[9]. After this, the syphon (GH, Pl. IV. fig. 3.) guarded, as before, with a bit of paper, to prevent its filling with mercury, is to be introduced under the bell-glass, having the thumb placed upon the extremity, G, of the syphon, to regulate the passage of the air; and by this means the air is gradually admitted, so as to let the mercury fall to its level. This being done, the bell-glass is to be carefully removed, the[Pg 44] globules of melted iron contained in the cup, and those which have been scattered about, and swim upon the mercury, are to be accurately collected, and the whole is to be weighed. The iron will be found in that state called martial ethiops by the old chemists, possessing a degree of metallic brilliancy, very friable, and readily reducible into powder, under the hammer, or with a pestle and mortar. If the experiment has succeeded well, from 100 grains of iron will be obtained 135 or 136 grains of ethiops, which is an augmentation of 35 per cent.
By this experiment, you can't determine both the extra weight gained by the iron and the changes in the air all at once. If you want to find out how much extra weight the iron has gained and the ratio of that to the air it absorbed, you need to carefully mark the height of the mercury on the bell jar with a diamond, before and after the experiment[9]. Next, the syphon (GH, Pl. IV. fig. 3.), which is protected with a piece of paper to keep it from filling with mercury, should be placed under the bell jar, with your thumb on the end, G, of the syphon to control the air flow. This allows the air to slowly enter, letting the mercury drop to its level. Once that’s done, carefully take off the bell jar, and collect the globules of melted iron from the cup, as well as those that are scattered and floating on the mercury, and weigh them all together. The iron will be found in a state called martial ethiops by the old chemists, which has a certain metallic shine, is quite brittle, and can easily be turned into powder with a hammer or pestle and mortar. If the experiment goes well, you should get 135 or 136 grains of ethiops from 100 grains of iron, which is a 35 percent increase.
If all the attention has been paid to this experiment which it deserves, the air will be found diminished in weight exactly equal to what the iron has gained. Having therefore burnt 100 grains of iron, which has acquired an additional weight of 35 grains, the diminution of air will be found exactly 70 cubical inches; and it will be found, in the sequel, that the weight of vital air is pretty nearly half a grain for each cubical inch; so that, in effect, the augmentation of weight in the one exactly coincides with the loss of it in the other.
If all the attention this experiment deserves has been given, the air will be found to weigh less by an amount exactly equal to the weight gained by the iron. So, after burning 100 grains of iron, which has gained an additional 35 grains, the reduction in air will be exactly 70 cubic inches; and it will be established later that the weight of vital air is about half a grain for each cubic inch. Therefore, the increase in weight of one matches the decrease in weight of the other exactly.
I shall observe here, once for all, that, in every experiment of this kind, the pressure and temperature of the air, both before and after the experiment, must be reduced, by calculation, to a common standard of 10° (54.5°) of the thermometer, and 28 inches of the barometer.[Pg 45] Towards the end of this work, the manner of performing this very necessary reduction will be found accurately detailed.
I want to point out that in every experiment of this kind, the air pressure and temperature, both before and after the experiment, must be adjusted mathematically to a common standard of 10° (54.5°) on the thermometer and 28 inches on the barometer.[Pg 45] Towards the end of this work, you will find detailed instructions on how to perform this essential adjustment.
If it be required to examine the nature of the air which remains after this experiment, we must operate in a somewhat different manner. After the combustion is finished, and the vessels have cooled, we first take out the cup, and the burnt iron, by introducing the hand through the quicksilver, under the bell-glass; we next introduce some solution of potash, or caustic alkali, or of the sulphuret of potash, or such other substance as is judged proper for examining their action upon the residuum of air. I shall, in the sequel, give an account of these methods of analysing air, when I have explained the nature of these different substances, which are only here in a manner accidentally mentioned. After this examination, so much water must be let into the glass as will displace the quicksilver, and then, by means of a shallow dish placed below the bell-glass, it is to be removed into the common water pneumato-chemical apparatus, where the air remaining may be examined at large, and with great facility.
If we need to take a look at the air left over after this experiment, we have to do it a bit differently. Once the burning is done and the containers have cooled down, we first pull out the cup and the burnt iron by reaching in through the mercury under the bell jar. Next, we add a solution of potash, caustic alkali, or potash sulfide, or any other suitable substance deemed appropriate for testing their effect on the remaining air. I will later explain these methods for analyzing air after I cover the nature of these different substances, which I've only mentioned here briefly. After this examination, we need to let in enough water to push out the mercury, and then, using a shallow dish placed under the bell jar, we can transfer it to the regular water pneumato-chemical setup, where we can easily analyze the remaining air in detail.
When very soft and very pure iron has been employed in this experiment, and, if the combustion has been performed in the purest respirable or vital air, free from all admixture of the noxious or mephitic part, the air which remains[Pg 46] after the combustion will be found as pure as it was before; but it is difficult to find iron entirely free from a small portion of charry matter, which is chiefly abundant in steel. It is likewise exceedingly difficult to procure the pure air perfectly free from some admixture of mephitis, with which it is almost always contaminated; but this species of noxious air does not, in the smallest degree, disturb the result of the experiment, as it is always found at the end exactly in the same proportion as at the beginning.
When very soft and very pure iron has been used in this experiment, and if the combustion has been carried out in the cleanest breathable or vital air, free from any mix of harmful or foul components, the air that remains[Pg 46] after the combustion will be just as pure as it was before. However, it's hard to find iron that is completely free from even a small amount of charry material, which is mainly found in steel. It is also quite challenging to obtain pure air that is perfectly free from any mix of foul substances, as it is almost always tainted; however, this type of harmful air does not affect the outcome of the experiment at all, as it is always found at the end in the same proportion as at the beginning.
I mentioned before, that we have two ways of determining the constituent parts of atmospheric air, the method of analysis, and that by synthesis. The calcination of mercury has furnished us with an example of each of these methods, since, after having robbed the respirable part of its base, by means of the mercury, we have restored it, so as to recompose an air precisely similar to that of the atmosphere. But we can equally accomplish this synthetic composition of atmospheric air, by borrowing the materials of which it is composed from different kingdoms of nature. We shall see hereafter that, when animal substances are dissolved in the nitric acid, a great quantity of gas is disengaged, which extinguishes light, and is unfit for animal respiration, being exactly similar to the noxious or mephitic part of atmospheric air. And, if we take 73 parts, by weight, of this elastic[Pg 47] fluid, and mix it with 27 parts of highly respirable air, procured from calcined mercury, we will form an elastic fluid precisely similar to atmospheric air in all its properties.
I mentioned earlier that we have two ways to figure out the components of air: through analysis and synthesis. The calcination of mercury gives us examples of both methods. After using mercury to remove the breathable part, we can restore it to recreate an air that closely resembles atmospheric air. We can also achieve this synthetic composition of atmospheric air by taking materials from different areas of nature. Later, we will see that when animal substances dissolve in nitric acid, a large amount of gas is released, which extinguishes light and isn't suitable for breathing, resembling the harmful or toxic parts of atmospheric air. If we take 73 parts by weight of this gas and mix it with 27 parts of breathable air from calcined mercury, we will create a gas that is exactly like atmospheric air in all its properties.
There are many other methods of separating the respirable from the noxious part of the atmospheric air, which cannot be taken notice of in this part, without anticipating information, which properly belongs to the subsequent chapters. The experiments already adduced may suffice for an elementary treatise; and, in matters of this nature, the choice of our evidences is of far greater consequence than their number.
There are many other ways to separate the breathable air from the harmful parts of the atmosphere that can't be discussed here without giving away information meant for the later chapters. The experiments mentioned so far may be enough for a basic overview; in topics like this, the quality of our evidence is much more important than the quantity.
I shall close this article, by pointing out the property which atmospheric air, and all the known gasses, possess of dissolving water, which is of great consequence to be attended to in all experiments of this nature. Mr Saussure found, by experiment, that a cubical foot of atmospheric air is capable of holding 12 grains of water in solution: Other gasses, as the carbonic acid, appear capable of dissolving a greater quantity; but experiments are still wanting by which to determine their several proportions. This water, held in solution by gasses, gives rise to particular phenomena in many experiments, which require great attention, and which has frequently proved the source of great errors to chemists in determining the results of their experiments.
I will end this article by highlighting the ability of atmospheric air and all known gases to dissolve water, which is very important to consider in all experiments of this kind. Mr. Saussure discovered through experimentation that a cubic foot of atmospheric air can hold 12 grains of water in solution. Other gases, like carbonic acid, seem to be able to dissolve a larger amount, but more experiments are needed to determine their specific proportions. This water, dissolved by gases, leads to unique phenomena in many experiments that require careful attention and has often caused significant errors for chemists when figuring out the results of their experiments.
FOOTNOTES:
[9] It will likewise be necessary to take care that the air contained in the glass, both before and after the experiment, be reduced to a common temperature and pressure, otherwise the results of the following calculations will be fallacious.—E.
[9] It will also be important to ensure that the air inside the glass, both before and after the experiment, is at a consistent temperature and pressure; otherwise, the results of the calculations that follow will be inaccurate.—E.
CHAP. IV.
Nomenclature of the several Constituent Parts of Atmospheric Air.
Hitherto I have been obliged to make use of circumlocution, to express the nature of the several substances which constitute our atmosphere, having provisionally used the terms of respirable and noxious, or non-respirable parts of the air. But the investigations I mean to undertake require a more direct mode of expression; and, having now endeavoured to give simple and distinct ideas of the different substances which enter into the composition of the atmosphere, I shall henceforth express these ideas by words equally simple.
So far, I've had to use indirect language to describe the different substances that make up our atmosphere, temporarily referring to them as respirable and noxious, or non-respirable parts of the air. However, the research I'm planning to conduct needs a more straightforward way of communicating. After trying to provide clear and simple ideas about the various substances in the atmosphere, I will now express these ideas using equally straightforward words.
The temperature of our earth being very near to that at which water becomes solid, and reciprocally changes from solid to fluid, and as this phenomenon takes place frequently under our observation, it has very naturally followed, that, in the languages of at least every climate subjected to any degree of winter, a term has been used for signifying water in the state of solidity, when deprived of its caloric. The same, however, has not been found necessary[Pg 49] with respect to water reduced to the state of vapour by an additional dose of caloric; since those persons who do not make a particular study of objects of this kind, are still ignorant that water, when in a temperature only a little above the boiling heat, is changed into an elastic aëriform fluid, susceptible, like all other gasses, of being received and contained in vessels, and preserving its gasseous form so long as it remains at the temperature of 80° (212°), and under a pressure not exceeding 28 inches of the mercurial barometer. As this phenomenon has not been generally observed, no language has used a particular term for expressing water in this state[10]; and the same thing occurs with all fluids, and all substances, which do not evaporate in the common temperature, and under the usual pressure of our atmosphere.
The temperature of our planet is very close to the point where water freezes and can also change back from solid to liquid. Because we often see this happening, it's only natural that in the languages of regions that experience any winter, there’s a term used to describe water in its solid form when it has lost heat. However, there hasn't been the same need for a term to describe water when it has turned into vapor due to added heat. Many people who don't specifically study this kind of thing are unaware that water, at temperatures slightly above boiling, turns into an elastic gas that can be contained in vessels and maintains its gaseous state as long as it stays at 80° (212°) and under a pressure not exceeding 28 inches on the mercury barometer. Since this phenomenon isn't commonly observed, no language has developed a specific term for water in this state, and the same applies to all fluids and other substances that do not evaporate at normal temperatures and under our usual atmospheric pressure.[Pg 49]
For similar reasons, names have not been given to the liquid or concrete states of most of the aëriform fluids: These were not known to arise from the combination of caloric with certain bases; and, as they had not been seen either in the liquid or solid states, their existence, under these forms, was even unknown to natural philosophers.[Pg 50]
For similar reasons, names haven't been assigned to the liquid or solid forms of most gases: it wasn't understood that they came from the combination of heat with certain substances; and since they hadn't been observed in liquid or solid states, their existence in these forms was even unknown to scientists.[Pg 50]
We have not pretended to make any alteration upon such terms as are sanctified by ancient custom; and, therefore, continue to use the words water and ice in their common acceptation: We likewise retain the word air, to express that collection of elastic fluids which composes our atmosphere; but we have not thought it necessary to preserve the same respect for modern terms, adopted by latter philosophers, having considered ourselves as at liberty to reject such as appeared liable to occasion erroneous ideas of the substances they are meant to express, and either to substitute new terms, or to employ the old ones, after modifying them in such a manner as to convey more determinate ideas. New words have been drawn, chiefly from the Greek language, in such a manner as to make their etymology convey some idea of what was meant to be represented; and these we have always endeavoured to make short, and of such a nature as to be changeable into adjectives and verbs.
We haven't tried to change any terms that are established by tradition, so we continue to use the words water and ice in their common sense. We also keep the word air to describe the collection of gases that make up our atmosphere. However, we didn’t feel it was necessary to maintain the same regard for modern terms introduced by later thinkers. We believed we were free to discard those that might lead to misunderstandings about the substances they describe, and instead, we either introduced new terms or modified the old ones to convey clearer meanings. New words have largely been created from Greek, designed so that their origins give some insight into what they represent. We have always tried to keep these words short and suited for conversion into adjectives and verbs.
Following these principles, we have, after Mr Macquer's example, retained the term gas, employed by Vanhelmont, having arranged the numerous class of elastic aëriform fluids under that name, excepting only atmospheric air. Gas, therefore, in our nomenclature, becomes a generic term, expressing the fullest degree of saturation in any body with caloric; being, in[Pg 51] fact, a term expressive of a mode of existence. To distinguish each species of gas, we employ a second term from the name of the base, which, saturated with caloric, forms each particular gas. Thus, we name water combined to saturation with caloric, so as to form an elastic fluid, aqueous gas; ether, combined in the same manner, etherial gas; the combination of alkohol with caloric, becomes alkoholic gas; and, following the same principles, we have muriatic acid gas, ammoniacal gas, and so on of every substance susceptible of being combined with caloric, in such a manner as to assume the gasseous or elastic aëriform state.
Following these principles, we have, after Mr. Macquer's example, kept the term gas, used by Vanhelmont, and classified the various types of elastic air-like fluids under that name, except for atmospheric air. Gas, therefore, in our terminology, becomes a general term that indicates the highest level of saturation in any substance with heat; it truly represents a way of existing. To identify each type of gas, we use a second term derived from the name of the base, which, saturated with heat, creates each specific gas. For example, we refer to water combined with heat to create an elastic fluid as aqueous gas; ether, similarly combined, is called etherial gas; the combination of alcohol with heat yields alkoholic gas; and, following the same principles, we have muriatic acid gas, ammoniacal gas, and so forth for every substance that can be combined with heat in such a way that it takes on a gaseous or elastic air-like state.
We have already seen, that the atmospheric air is composed of two gasses, or aëriform fluids, one of which is capable, by respiration, of contributing to animal life, and in which metals are calcinable, and combustible bodies may burn; the other, on the contrary, is endowed with directly opposite qualities; it cannot be breathed by animals, neither will it admit of the combustion of inflammable bodies, nor of the calcination of metals. We have given to the base of the former, or respirable portion of the air, the name of oxygen, from οξυς acidum, and γεινομας, gignor; because, in reality, one of the most general properties of this base is to form acids, by combining with many different substances. The union of this base with caloric[Pg 52] we term oxygen gas, which is the same with what was formerly called pure, or vital air. The weight of this gas, at the temperature of 10° (54.50), and under a pressure equal to 28 inches of the barometer, is half a grain for each cubical inch, or one ounce and a half to each cubical foot.
We have already seen that the air is made up of two gases, or airy substances. One of these is essential for animal life and supports respiration; it's also the medium in which metals can be burned and combustible materials can ignite. The other, on the other hand, has completely opposite properties—it cannot be breathed by animals, nor does it allow for the burning of flammable materials or the oxidation of metals. We refer to the first, breathable part of the air as oxygen, derived from οξυς acidum and γεινομας, gignor; because one of its key characteristics is its ability to form acids by reacting with various substances. When this base combines with heat[Pg 52], we call it oxygen gas, which is what used to be known as pure or vital air. The weight of this gas at 10° (54.50) and a pressure of 28 inches of mercury is half a grain per cubic inch, or one and a half ounces per cubic foot.
The chemical properties of the noxious portion of atmospheric air being hitherto but little known, we have been satisfied to derive the name of its base from its known quality of killing such animals as are forced to breathe it, giving it the name of azote, from the Greek privitive particle α and ξαη, vita; hence the name of the noxious part of atmospheric air is azotic gas; the weight of which, in the same temperature, and under the same pressure, is 1 oz. 2 gros. and 48 grs. to the cubical foot, or 0.4444 of a grain to the cubical inch. We cannot deny that this name appears somewhat extraordinary; but this must be the case with all new terms, which cannot be expected to become familiar until they have been some time in use. We long endeavoured to find a more proper designation without success; it was at first proposed to call it alkaligen gas, as, from the experiments of Mr Berthollet, it appears to enter into the composition of ammoniac, or volatile alkali; but then, we have as yet no proof of its making one of the constituent elements of[Pg 53] the other alkalies; beside, it is proved to compose a part of the nitric acid, which gives as good reason to have called it nitrigen. For these reasons, finding it necessary to reject any name upon systematic principles, we have considered that we run no risk of mistake in adopting the terms of azote, and azotic gas, which only express a matter of fact, or that property which it possesses, of depriving such animals as breathe it of their lives.
The chemical properties of the harmful part of the air have not been well understood until now, so we've chosen to name its base according to its known ability to kill animals that have to breathe it. We call it azote, which comes from the Greek prefix α and ξαη, meaning life; therefore, the harmful part of the air is known as azotic gas. Its weight is 1 oz. 2 gros. and 48 grs. per cubic foot, or 0.4444 of a grain per cubic inch. While this name may seem unusual, that's typical for new terms, which generally take time to become familiar. We tried for a long time to find a more suitable name but didn't succeed. At first, we considered calling it alkaligen gas, since Mr. Berthollet's experiments show it contributes to the composition of ammonia or volatile alkali; however, we still lack proof that it is one of the building blocks of the other alkalis. Moreover, it has been demonstrated to be a component of nitric acid, which gives us good reason to call it nitrigen. For these reasons, since we found it necessary to discard any name based on systematic principles, we feel safe adopting the terms azote and azotic gas, which simply describe the fact that it kills animals that breathe it.
I should anticipate subjects more properly reserved for the subsequent chapters, were I in this place to enter upon the nomenclature of the several species of gasses: It is sufficient, in this part of the work, to establish the principles upon which their denominations are founded. The principal merit of the nomenclature we have adopted is, that, when once the simple elementary substance is distinguished by an appropriate term, the names of all its compounds derive readily, and necessarily, from this first denomination.
I should expect topics that are better suited for the following chapters, if I were to discuss the naming of the different types of gases here. For now, it’s enough to establish the basic principles behind their names. The main advantage of the naming system we've chosen is that, once the simple element is identified by a specific term, the names of all its compounds naturally come from this original name.
FOOTNOTES:
CHAP. V.
Of the Decomposition of Oxygen Gas by Sulphur, Phosphorus, and Charcoal—and of the Formation of Acids in general.
In performing experiments, it is a necessary principle, which ought never to be deviated from, that they be simplified as much as possible, and that every circumstance capable of rendering their results complicated be carefully removed. Wherefore, in the experiments which form the object of this chapter, we have never employed atmospheric air, which is not a simple substance. It is true, that the azotic gas, which forms a part of its mixture, appears to be merely passive during combustion and calcination; but, besides that it retards these operations very considerably, we are not certain but it may even alter their results in some circumstances; for which reason, I have thought it necessary to remove even this possible cause of doubt, by only making use of pure oxygen gas in the following experiments, which show the effects produced by combustion in that gas; and I shall advert to such differences as take place in the results of these, when the oxygen gas, or pure[Pg 55] vital air, is mixed, in different proportions, with azotic gas.
In conducting experiments, it’s essential to follow the principle of keeping them as simple as possible and eliminating any factors that could complicate the results. Therefore, in the experiments described in this chapter, we have avoided using atmospheric air, since it’s not a simple substance. While it's true that nitrogen gas, which is part of the air mixture, seems mostly passive during combustion and calcination, it significantly slows down these processes, and we’re not entirely sure it doesn’t change the results under certain conditions. For this reason, I deemed it necessary to eliminate any potential doubts by using only pure oxygen gas in the following experiments, which demonstrate the effects of combustion in that gas. I will also note the differences in the results when pure oxygen, or "vital air," is mixed in varying amounts with nitrogen gas.
Having filled a bell-glass (A. Pl. iv. fig. 3), of between five and six pints measure, with oxygen gas, I removed it from the water trough, where it was filled, into the quicksilver bath, by means of a shallow glass dish slipped underneath, and having dried the mercury, I introduced 61-1/4 grains of Kunkel's phosphorus in two little China cups, like that represented at D, fig. 3. under the glass A; and that I might set fire to each of the portions of phosphorus separately, and to prevent the one from catching fire from the other, one of the dishes was covered with a piece of flat glass. I next raised the quicksilver in the bell-glass up to E F, by sucking out a sufficient portion of the gas by means of the syphon G H I. After this, by means of the crooked iron wire (fig. 16.), made red hot, I set fire to the two portions of phosphorus successively, first burning that portion which was not covered with the piece of glass. The combustion was extremely rapid, attended with a very brilliant flame, and considerable disengagement of light and heat. In consequence of the great heat induced, the gas was at first much dilated, but soon after the mercury returned to its level, and a considerable absorption of gas took place; at the same time, the[Pg 56] whole inside of the glass became covered with white light flakes of concrete phosphoric acid.
Having filled a bell jar (A. Pl. iv. fig. 3) with about five to six pints of oxygen gas, I took it out of the water trough where it was filled and placed it in a mercury bath using a shallow glass dish underneath. After drying the mercury, I added 61.25 grains of Kunkel's phosphorus in two small china cups, like the ones shown at D, fig. 3, under the jar A. To ignite each portion of phosphorus separately and avoid them catching fire from each other, I covered one of the dishes with a flat piece of glass. I then raised the mercury inside the bell jar to E F by using a siphon G H I to suck out a sufficient amount of gas. Next, I used a bent iron wire (fig. 16) heated red hot to ignite the two portions of phosphorus one after the other, starting with the one that wasn’t covered by the glass. The combustion was extremely fast, producing a very bright flame and a significant amount of light and heat. Because of the intense heat, the gas expanded a lot at first, but soon the mercury returned to its original level, and a considerable amount of gas was absorbed. At the same time, the entire inside of the jar was covered with white, glittering flakes of solid phosphoric acid.
At the beginning of the experiment, the quantity of oxygen gas, reduced, as above directed, to a common standard, amounted to 162 cubical inches; and, after the combustion was finished, only 23-1/4 cubical inches, likewise reduced to the standard, remained; so that the quantity of oxygen gas absorbed during the combustion was 138-3/4 cubical inches, equal to 69.375 grains.
At the start of the experiment, the amount of oxygen gas, adjusted to a common standard as mentioned earlier, was 162 cubic inches. After the combustion was complete, only 23.25 cubic inches, also adjusted to the standard, remained; which means the amount of oxygen gas absorbed during the combustion was 138.75 cubic inches, equivalent to 69.375 grains.
A part of the phosphorus remained unconsumed in the bottom of the cups, which being washed on purpose to separate the acid, weighed about 16-1/4 grains; so that about 45 grains of phosphorus had been burned: But, as it is hardly possible to avoid an error of one or two grains, I leave the quantity so far qualified. Hence, as nearly 45 grains of phosphorus had, in this experiment, united with 69.375 grains of oxygen, and as no gravitating matter could have escaped through the glass, we have a right to conclude, that the weight of the substance resulting from the combustion in form of white flakes, must equal that of the phosphorus and oxygen employed, which amounts to 114.375 grains. And we shall presently find, that these flakes consisted entirely of a solid or concrete acid. When we reduce these weights to hundredth parts, it will be found, that 100 parts of[Pg 57] phosphorus require 154 parts of oxygen for saturation, and that this combination will produce 254 parts of concrete phosphoric acid, in form of white fleecy flakes.
A portion of the phosphorus stayed unconsumed at the bottom of the cups, which were specifically washed to separate the acid, weighing about 16.25 grains. Therefore, around 45 grains of phosphorus had been burned. However, since it's nearly impossible to avoid an error of one or two grains, I'll note the quantity as such. Thus, since nearly 45 grains of phosphorus combined with 69.375 grains of oxygen in this experiment, and no gravitational matter could have escaped through the glass, we can conclude that the weight of the substance resulting from the combustion in the form of white flakes must equal the combined weight of the phosphorus and oxygen used, which totals 114.375 grains. We will soon discover that these flakes were entirely made up of a solid or concrete acid. When we convert these weights to hundredths, it will be found that 100 parts of[Pg 57] phosphorus require 154 parts of oxygen for saturation, and that this combination will produce 254 parts of concrete phosphoric acid in the form of white, fluffy flakes.
This experiment proves, in the most convincing manner, that, at a certain degree of temperature, oxygen possesses a stronger elective attraction, or affinity, for phosphorus than for caloric; that, in consequence of this, the phosphorus attracts the base of oxygen gas from the caloric, which, being set free, spreads itself over the surrounding bodies. But, though this experiment be so far perfectly conclusive, it is not sufficiently rigorous, as, in the apparatus described, it is impossible to ascertain the weight of the flakes of concrete acid which are formed; we can therefore only determine this by calculating the weights of oxygen and phosphorus employed; but as, in physics, and in chemistry, it is not allowable to suppose what is capable of being ascertained by direct experiment, I thought it necessary to rep at this experiment, as follows, upon a larger scale, and by means of a different apparatus.
This experiment clearly shows that at a certain temperature, oxygen has a stronger attraction or affinity for phosphorus than for heat. As a result, the phosphorus pulls the oxygen gas away from the heat, which then spreads out into the surrounding materials. However, even though this experiment is convincing, it's not completely rigorous because the setup makes it impossible to measure the weight of the solid acid formed. We can only figure this out by calculating the weights of oxygen and phosphorus used. Since it's not acceptable in physics or chemistry to rely on assumptions when direct measurements can be made, I thought it necessary to repeat this experiment on a larger scale using different equipment.
I took a large glass baloon (A. Pl. iv. fig. 4.) with an opening three inches diameter, to which was fitted a crystal stopper ground with emery, and pierced with two holes for the tubes yyy, xxx. Before shutting the baloon with its stopper, I introduced the support BC, surmounted[Pg 58] by the china cup D, containing 150 grs. of phosphorus; the stopper was then fitted to the opening of the baloon, luted with fat lute, and covered with slips of linen spread with quick-lime and white of eggs: When the lute was perfectly dry, the weight of the whole apparatus was determined to within a grain, or a grain and a half. I next exhausted the baloon, by means of an air pump applied to the tube xxx, and then introduced oxygen gas by means of the tube yyy, having a stop cock adapted to it. This kind of experiment is most readily and most exactly performed by means of the hydro-pneumatic machine described by Mr Meusnier and me in the Memoirs of the Academy for 1782, pag. 466. and explained in the latter part of this work, with several important additions and corrections since made to it by Mr Meusnier. With this instrument we can readily ascertain, in the most exact manner, both the quantity of oxygen gas introduced into the baloon, and the quantity consumed during the course of the experiment.
I took a large glass balloon (A. Pl. iv. fig. 4.) with a three-inch diameter opening, which was fitted with a crystal stopper that had been ground with emery and had two holes for the tubes yyy and xxx. Before sealing the balloon with its stopper, I placed the support BC, topped with the china cup D that contained 150 grams of phosphorus. The stopper was then secured onto the opening of the balloon, sealed with a fat lute, and covered with strips of linen smeared with quicklime and egg whites. Once the lute was completely dry, the total weight of the entire apparatus was measured to within a grain or a grain and a half. I then evacuated the balloon using an air pump connected to the tube xxx, and subsequently introduced oxygen gas through the tube yyy, which had a stopcock attached. This type of experiment is most easily and accurately conducted using the hydro-pneumatic machine detailed by Mr. Meusnier and myself in the Memoirs of the Academy for 1782, page 466, and further explained in the later sections of this work, with several crucial updates and corrections made by Mr. Meusnier. With this instrument, we can easily and precisely determine both the amount of oxygen gas introduced into the balloon and the amount consumed during the experiment.
When all things were properly disposed, I set fire to the phosphorus with a burning glass. The combustion was extremely rapid, accompanied with a bright flame, and much heat; as the operation went on, large quantities of white flakes attached themselves to the inner surface of the baloon, so that at last it was rendered[Pg 59] quite opake. The quantity of these flakes at last became so abundant, that, although fresh oxygen gas was continually supplied, which ought to have supported the combustion, yet the phosphorus was soon extinguished. Having allowed the apparatus to cool completely, I first ascertained the quantity of oxygen gas employed, and weighed the baloon accurately, before it was opened. I next washed, dried, and weighed the small quantity of phosphorus remaining in the cup, on purpose to determine the whole quantity of phosphorus consumed in the experiment; this residuum of the phosphorus was of a yellow ochrey colour. It is evident, that by these several precautions, I could easily determine, 1st, the weight of the phosphorus consumed; 2d, the weight of the flakes produced by the combustion; and, 3d, the weight of the oxygen which had combined with the phosphorus. This experiment gave very nearly the same results with the former, as it proved that the phosphorus, during its combustion, had absorbed a little more than one and a half its weight of oxygen; and I learned with more certainty, that the weight of the new substance, produced in the experiment, exactly equalled the sum of the weights of the phosphorus consumed, and oxygen absorbed, which indeed was easily determinable a priori. If the oxygen gas employed be pure, the residuum after combustion[Pg 60] is as pure as the gas employed; this proves that nothing escapes from the phosphorus, capable of altering the purity of the oxygen gas, and that the only action of the phosphorus is to separate the oxygen from the caloric, with which it was before united.
When everything was set up properly, I ignited the phosphorus using a magnifying glass. The combustion was very quick, producing a bright flame and a lot of heat; as the process continued, large amounts of white flakes stuck to the inner surface of the balloon, making it eventually become[Pg 59] completely opaque. The buildup of these flakes became so significant that, even though fresh oxygen gas was constantly being supplied—enough to support the combustion—the phosphorus was soon put out. After allowing the apparatus to cool completely, I first measured the amount of oxygen gas used and weighed the balloon accurately before opening it. I then washed, dried, and weighed the small amount of phosphorus left in the cup to determine the total quantity of phosphorus consumed during the experiment; this leftover phosphorus was a yellowish ochre color. Clearly, through these precautions, I could easily find out: 1st, the weight of the phosphorus consumed; 2nd, the weight of the flakes created by the combustion; and 3rd, the weight of the oxygen that combined with the phosphorus. This experiment yielded results very close to the previous one, showing that the phosphorus, while it burned, absorbed a little over one and a half times its weight of oxygen; and I learned more reliably that the weight of the new substance produced in the experiment exactly matched the total weights of the phosphorus consumed and the oxygen absorbed, which was easy to determine a priori. If the oxygen gas used is pure, the residue after combustion[Pg 60] is just as pure as the gas used; this demonstrates that nothing escapes from the phosphorus that could change the purity of the oxygen gas, and that the only effect of the phosphorus is to separate the oxygen from the heat it was previously combined with.
I mentioned above, that when any combustible body is burnt in a hollow sphere of ice, or in an apparatus properly constructed upon that principle, the quantity of ice melted during the combustion is an exact measure of the quantity of caloric disengaged. Upon this head, the memoir given by M. de la Place and me, Aº. 1780, p. 355, may be consulted. Having submitted the combustion of phosphorus to this trial, we found that one pound of phosphorus melted a little more than 100 pounds of ice during its combustion.
I mentioned earlier that when any combustible material is burned in a hollow sphere of ice, or in a device designed based on that principle, the amount of ice melted during the combustion directly measures the amount of heat released. For more on this, you can refer to the paper by M. de la Place and me, Aº. 1780, p. 355. When we tested the combustion of phosphorus, we discovered that one pound of phosphorus melted slightly over 100 pounds of ice during its burn.
The combustion of phosphorus succeeds equally well in atmospheric air as in oxygen gas, with this difference, that the combustion is vastly slower, being retarded by the large proportion of azotic gas mixed with the oxygen gas, and that only about one-fifth part of the air employed is absorbed, because as the oxygen gas only is absorbed, the proportion of the azotic gas becomes so great toward the close of the experiment, as to put an end to the combustion.[Pg 61]
The combustion of phosphorus works just as well in atmospheric air as it does in oxygen gas, but the process is much slower due to the high amount of nitrogen gas mixed with the oxygen. Only about one-fifth of the air used is absorbed because only the oxygen is absorbed. As the experiment progresses, the increasing proportion of nitrogen gas eventually stops the combustion.[Pg 61]
I have already shown, that phosphorus is changed by combustion into an extremely light, white, flakey matter; and its properties are entirely altered by this transformation: From being insoluble in water, it becomes not only soluble, but so greedy of moisture, as to attract the humidity of the air with astonishing rapidity; by this means it is converted into a liquid, considerably more dense, and of more specific gravity than water. In the state of phosphorus before combustion, it had scarcely any sensible taste, by its union with oxygen it acquires an extremely sharp and sour taste: in a word, from one of the class of combustible bodies, it is changed into an incombustible substance, and becomes one of those bodies called acids.
I’ve already shown that when phosphorus burns, it turns into a very light, white, flaky substance; and its properties completely change with this transformation. Instead of being insoluble in water, it becomes soluble and so eager for moisture that it rapidly absorbs humidity from the air. This process turns it into a liquid that is significantly denser and has a higher specific gravity than water. Before combustion, phosphorus had almost no noticeable taste, but after it combines with oxygen, it takes on a very sharp and sour flavor. In short, it shifts from being a combustible material to becoming an incombustible substance, joining the group of materials known as acids.
This property of a combustible substance to be converted into an acid, by the addition of oxygen, we shall presently find belongs to a great number of bodies: Wherefore, strict logic requires that we should adopt a common term for indicating all these operations which produce analogous results; this is the true way to simplify the study of science, as it would be quite impossible to bear all its specifical details in the memory, if they were not classically arranged. For this reason, we shall distinguish this conversion of phosphorus into an acid, by its union with oxygen, and in general every combination of oxygen with a combustible substance,[Pg 62] by the term of oxygenation: from which I shall adopt the verb to oxygenate, and of consequence shall say, that in oxygenating phosphorus we convert it into an acid.
This property of a combustible substance to turn into an acid when it combines with oxygen is something we will find applies to many materials. Therefore, it makes sense to use a common term for all these processes that produce similar results; this is truly the best way to simplify the study of science since it's impossible to remember all the specific details if they aren't organized properly. For this reason, we will refer to the conversion of phosphorus into an acid through its combination with oxygen, and generally any reaction of oxygen with a combustible substance, as oxygenation: and I will use the verb oxygenate, meaning that when we oxygenate phosphorus, we turn it into an acid.[Pg 62]
Sulphur is likewise a combustible body, or, in other words, it is a body which possesses the power of decomposing oxygen gas, by attracting the oxygen from the caloric with which it was combined. This can very easily be proved, by means of experiments quite similar to those we have given with phosphorus; but it is necessary to premise, that in these operations with sulphur, the same accuracy of result is not to be expected as with phosphorus; because the acid which is formed by the combustion of sulphur is difficultly condensible, and because sulphur burns with more difficulty, and is soluble in the different gasses. But I can safely assert, from my own experiments, that sulphur in burning absorbs oxygen gas; that the resulting acid is considerably heavier than the sulphur burnt; that its weight is equal to the sum of the weights of the sulphur which has been burnt, and of the oxygen absorbed; and, lastly that this acid is weighty, incombustible, and miscible with water in all proportions: The only uncertainty remaining upon this head, is with regard to the proportions of sulphur and of oxygen which enter into the composition of the acid.[Pg 63]
Sulfur is also a combustible substance, meaning it has the ability to decompose oxygen gas by attracting the oxygen from the heat it was combined with. This can easily be demonstrated through experiments similar to those we conducted with phosphorus; however, it's important to note that we shouldn't expect the same level of accuracy with sulfur as with phosphorus. This is because the acid produced from burning sulfur is hard to condense, sulfur burns more slowly, and it can dissolve in various gases. Nevertheless, I can confidently say from my experiments that sulfur absorbs oxygen gas when it burns; the resulting acid is significantly heavier than the sulfur that burned; its weight equals the combined weight of the burned sulfur and the absorbed oxygen; and finally, this acid is heavy, non-flammable, and mixes with water in any ratio. The only remaining uncertainty is concerning the proportions of sulfur and oxygen that make up the acid.[Pg 63]
Charcoal, which, from all our present knowledge regarding it, must be considered as a simple combustible body, has likewise the property of decomposing oxygen gas, by absorbing its base from the caloric: But the acid resulting from this combustion does not condense in the common temperature; under the pressure of our atmosphere, it remains in the state of gas, and requires a large proportion of water to combine with or be dissolved in. This acid has, however, all the known properties of other acids, though in a weaker degree, and combines, like them, with all the bases which are susceptible of forming neutral salts.
Charcoal, based on everything we currently know about it, is essentially a simple combustible material. It also has the ability to break down oxygen gas by taking its base from heat. However, the acid produced from this combustion doesn’t condense at normal temperatures; under atmospheric pressure, it stays gaseous and needs a significant amount of water to combine with or dissolve in. This acid does have all the recognized properties of other acids, but to a lesser extent, and it combines, like them, with all the bases that can form neutral salts.
The combustion of charcoal in oxygen gas, may be effected like that of phosphorus in the bell-glass, (A. Pl. IV. fig. 3.) placed over mercury: but, as the heat of red hot iron is not sufficient to set fire to the charcoal, we must add a small morsel of tinder, with a minute particle of phosphorus, in the same manner as directed in the experiment for the combustion of iron. A detailed account of this experiment will be found in the memoirs of the academy for 1781, p. 448. By that experiment it appears, that 28 parts by weight of charcoal require 72 parts of oxygen for saturation, and that the aëriform acid produced is precisely equal in weight to the sum of the weights of the charcoal and oxygen gas employed.[Pg 64] This aëriform acid was called fixed or fixable air by the chemists who first discovered it; they did not then know whether it was air resembling that of the atmosphere, or some other elastic fluid, vitiated and corrupted by combustion; but since it is now ascertained to be an acid, formed like all others by the oxygenation of its peculiar base, it is obvious that the name of fixed air is quite ineligible[11].
The burning of charcoal in oxygen gas can be done similarly to that of phosphorus in the bell jar (A. Pl. IV. fig. 3.) placed over mercury: however, since the heat of red-hot iron isn’t enough to ignite the charcoal, we need to add a small piece of tinder along with a tiny amount of phosphorus, just like in the experiment for burning iron. A detailed description of this experiment can be found in the academy's memoirs from 1781, p. 448. From that experiment, it’s clear that 28 parts by weight of charcoal need 72 parts of oxygen to fully react, and the resulting gas produced weighs exactly the same as the combined weights of the charcoal and oxygen used.[Pg 64] This gas was originally called fixed or fixable air by the chemists who first found it; they didn’t know at the time if it was similar to atmospheric air or some other altered gas corrupted by burning. Now that we know it’s an acid formed like all others by the oxygenation of its specific base, it’s evident that the term fixed air is no longer appropriate.[11]
By burning charcoal in the apparatus mentioned p. 60, Mr de la Place and I found that one lib. of charcoal melted 96 libs. 6 oz. of ice; that, during the combustion, 2 libs. 9 oz. 1 gros. 10 grs. of oxygen were absorbed, and that 3 libs. 9 oz. 1 gros. 10 grs. of acid gas were formed. This gas weighs 0.695 parts of a grain for each cubical inch, in the common standard temperature and pressure mentioned above, so that 34,242 cubical inches of acid gas are produced by the combustion of one pound of charcoal.
By burning charcoal in the apparatus mentioned on page 60, Mr. de la Place and I found that one pound of charcoal melted 96 pounds and 6 ounces of ice; during the combustion, 2 pounds, 9 ounces, 1 gros, and 10 grains of oxygen were absorbed, and 3 pounds, 9 ounces, 1 gros, and 10 grains of acid gas were produced. This gas weighs 0.695 grains for each cubic inch at the common standard temperature and pressure mentioned above, so that 34,242 cubic inches of acid gas are produced by the combustion of one pound of charcoal.
I might multiply these experiments, and show by a numerous succession of facts, that all acids are formed by the combustion of certain substances; but I am prevented from doing so in[Pg 65] place, by the plan which I have laid down, of proceeding only from facts already ascertained, to such as are unknown, and of drawing my examples only from circumstances already explained. In the mean time, however, the three examples above cited may suffice for giving a clear and accurate conception of the manner in which acids are formed. By these it may be clearly seen, that oxygen is an element common to them all, which constitutes their acidity; and that they differ from each other, according to the nature of the oxygenated or acidified substance. We must therefore, in every acid, carefully distinguish between the acidifiable, base, which Mr de Morveau calls the radical, and the acidifiing principle or oxygen.
I could expand on these experiments and demonstrate through many examples that all acids are produced by burning specific substances. However, I’m held back from doing that in[Pg 65] this section because I’ve decided to move only from established facts to unknown ones and to base my examples solely on already explained circumstances. In the meantime, the three examples mentioned above are enough to provide a clear and accurate understanding of how acids are formed. From these, it’s clear that oxygen is a common element in all of them that contributes to their acidity, and they differ based on the type of oxygenated or acidified substance. Therefore, in any acid, we need to carefully differentiate between the acidifiable base, which Mr. de Morveau refers to as the radical, and the acidifying principle or oxygen.
FOOTNOTES:
[11] It may be proper to remark, though here omitted by the author, that, in conformity with the general principles of the new nomenclature, this acid is by Mr Lavoisier and his coleagues called the carbonic acid, and when in the aëriform state carbonic acid gas. E.
[11] It’s worth mentioning, although the author left it out, that according to the new naming conventions, this acid is referred to as carbonic acid by Mr. Lavoisier and his colleagues, and in its gaseous form, it’s called carbonic acid gas. E.
CHAP. VI.
Of the Nomenclature of Acids in general, and particularly of those drawn from Nitre and Sea-Salt.
It becomes extremely easy, from the principles laid down in the preceding chapter, to establish a systematic nomenclature for the acids: The word acid, being used as a generic term, each acid falls to be distinguished in language, as in nature, by the name of its base or radical. Thus, we give the generic name of acids to the products of the combustion or oxygenation of phosphorus, of sulphur, and of charcoal; and these products are respectively named, the phosphoric acid, the sulphuric acid, and the carbonic acid.
It becomes very easy, based on the principles set out in the previous chapter, to create a systematic naming system for acids: The term acid is used as a general label, so each acid can be identified in language and in nature by the name of its base or radical. Therefore, we refer to the products of the combustion or oxidation of phosphorus, sulfur, and charcoal as acids; these products are called phosphoric acid, sulphuric acid, and carbonic acid, respectively.
There is however, a remarkable circumstance in the oxygenation of combustible bodies, and of a part of such bodies as are convertible into acids, that they are susceptible of different degrees of saturation with oxygen, and that the resulting acids, though formed by the union of the same elements, are possessed of different properties, depending upon that difference of proportion. Of this, the phosphoric acid, and more especially the sulphuric, furnishes us with examples.[Pg 67] When sulphur is combined with a small proportion of oxygen, it forms, in this first or lower degree of oxygenation, a volatile acid, having a penetrating odour, and possessed of very particular qualities. By a larger proportion of oxygen, it is changed into a fixed, heavy acid, without any odour, and which, by combination with other bodies, gives products quite different from those furnished by the former. In this instance, the principles of our nomenclature seem to fail; and it seems difficult to derive such terms from the name of the acidifiable base, as shall distinctly express these two degrees of saturation, or oxygenation, without circumlocution. By reflection, however, upon the subject, or perhaps rather from the necessity of the case, we have thought it allowable to express these varieties in the oxygenation of the acids, by simply varying the termination of their specific names. The volatile acid produced from sulphur was anciently known to Stahl under the name of sulphurous acid[12]. We have[Pg 68] preserved that term for this acid from sulphur under-saturated with oxygen; and distinguish the other, or completely saturated or oxygenated acid, by the name of sulphuric acid. We shall therefore say, in this new chemical language, that sulphur, in combining with oxygen, is susceptible of two degrees of saturation; that the first, or lesser degree, constitutes sulphurous acid, which is volatile and penetrating; whilst the second, or higher degree of saturation, produces sulphuric acid, which is fixed and inodorous. We shall adopt this difference of termination for all the acids which assume several degrees of saturation. Hence we have a phosphorous and a phosphoric acid, an acetous and an acetic acid; and so on, for others in similar circumstances.
However, there is a notable situation in the oxygenation of combustible substances and parts of those substances that can turn into acids: they can be saturated with different amounts of oxygen, and the resulting acids, even though made up of the same elements, have different properties based on that variation in proportion. For example, phosphoric acid, and especially sulphuric acid, illustrate this point. When sulphur combines with a small amount of oxygen, it forms, at this initial or lower level of oxygenation, a volatile acid with a penetrating smell and very specific qualities. With a larger amount of oxygen, it transforms into a fixed, heavy acid that has no odor and, when combined with other substances, produces results that are quite different from those yielded by the former. In this situation, our naming system seems inadequate; it’s challenging to derive terms from the name of the acid-forming base that clearly express these two levels of saturation or oxygenation without lengthy explanations. However, upon reflection on the topic, or perhaps driven by necessity, we’ve deemed it acceptable to express these variations in acid oxygenation by simply altering the ending of their specific names. The volatile acid produced from sulphur was historically known to Stahl as sulphurous acid. We have kept that term for this acid derived from sulphur with insufficient oxygen, while we refer to the other, or fully saturated, acid as sulphuric acid. Therefore, in this updated chemical terminology, we will say that sulphur, when combining with oxygen, can take on two degrees of saturation: the first, or lower degree, constitutes sulphurous acid, which is volatile and penetrating; while the second, or higher degree of saturation, produces sulphuric acid, which is fixed and odorless. We will apply this change in name endings to all acids that have multiple degrees of saturation. Thus, we have phosphorous and phosphoric acid, acetous and acetic acid, and so on for others in similar situations.[Pg 67][Pg 68]
This part of chemical science would have been extremely simple, and the nomenclature of the acids would not have been at all perplexed, as it is now in the old nomenclature, if the base or radical of each acid had been known when the acid itself was discovered. Thus, for instance, phosphorus being a known substance before the discovery of its acid, this latter was rightly distinguished by a term drawn from the name of its acidifiable base. But when, on the contrary, an acid happened to be discovered before its base, or rather, when the acidifiable base from which it was formed remained unknown,[Pg 69] names were adopted for the two, which have not the smallest connection; and thus, not only the memory became burthened with useless appellations, but even the minds of students, nay even of experienced chemists, became filled with false ideas, which time and reflection alone is capable of eradicating. We may give an instance of this confusion with respect to the acid sulphur: The former chemists having procured this acid from the vitriol of iron, gave it the name of the vitriolic acid from the name of the substance which produced it; and they were then ignorant that the acid procured from sulphur by combustion was exactly the same.
This area of chemical science would have been really straightforward, and the naming of the acids wouldn’t have been confusing at all, unlike the old system, if the base or radical of each acid had been known when the acid was first discovered. For example, phosphorus was already known before its acid was found, so that acid was rightly named based on the name of its base. However, when an acid was discovered before its base, or more precisely, when the base it was derived from was still unknown, names were chosen for the two that have no real connection. This not only burdened memory with unnecessary terms but also led to misconceptions in the minds of students and even experienced chemists, which only time and reflection can clear up. An example of this confusion is with sulfuric acid: earlier chemists obtained this acid from iron vitriol and named it the vitriolic acid based on the substance that produced it, without realizing that the acid obtained from burning sulfur was actually the same.
The same thing happened with the aëriform acid formerly called fixed air; it not being known that this acid was the result of combining charcoal with oxygen, a variety of denominations have been given to it, not one of which conveys just ideas of its nature or origin. We have found it extremely easy to correct and modify the ancient language with respect to these acids proceeding from known bases, having converted the name of vitriolic acid into that of sulphuric, and the name of fixed air into that of carbonic acid; but it is impossible to follow this plan with the acids whose bases are still unknown; with these we have been obliged to use a contrary plan, and, instead of forming the name of the acid from that of its[Pg 70] base, have been forced to denominate the unknown base from the name of the known acid, as happens in the case of the acid which is procured from sea salt.
The same thing happened with the gas previously known as fixed air; since it wasn't understood that this gas resulted from combining charcoal with oxygen, it was given a variety of names, none of which accurately describe its nature or origin. We have found it quite simple to update the old terminology regarding these acids derived from known bases, changing vitriolic acid to sulphuric and fixed air to carbonic acid; however, it's impossible to apply this method to the acids whose bases are still unknown. For these, we’ve had to take the opposite approach, and instead of naming the acid after its[Pg 70] base, we’ve had to name the unknown base after the known acid, as seen with the acid obtained from sea salt.
To disengage this acid from the alkaline base with which it is combined, we have only to pour sulphuric acid upon sea-salt, immediately a brisk effervescence takes place, white vapours arise, of a very penetrating odour, and, by only gently heating the mixture, all the acid is driven off. As, in the common temperature and pressure of our atmosphere, this acid is naturally in the state of gas, we must use particular precautions for retaining it in proper vessels. For small experiments, the most simple and most commodious apparatus consists of a small retort G, (Pl. V. Fig. 5.), into which the sea-salt is introduced, well dried[13], we then pour on some concentrated sulphuric acid, and immediately introduce the beak of the retort under little jars or bell-glasses A, (same Plate and Fig.), previously filled with quicksilver. In proportion as the acid gas is disengaged, it passes into the jar, and gets to the top of the quicksilver, which it displaces. When the disengagement[Pg 71] of the gas slackens, a gentle heat is applied to the retort, and gradually increased till nothing more passes over. This acid gas has a very strong affinity with water, which absorbs an enormous quantity of it, as is proved by introducing a very thin layer of water into the glass which contains the gas; for, in an instant, the whole acid gas disappears, and combines with the water.
To separate this acid from the alkaline base it’s mixed with, we just need to pour sulfuric acid over sea salt. Right away, a lively fizz starts, white vapors rise with a strong, sharp odor, and by gently heating the mixture, all the acid is released. Since this acid naturally exists as a gas in our normal atmospheric conditions, we have to take special care to keep it in suitable containers. For small experiments, the easiest and most convenient setup consists of a small retort G, (Pl. V. Fig. 5.), where we place well-dried sea salt[13]. Then, we pour some concentrated sulfuric acid on it and quickly put the spout of the retort under small jars or bell glasses A, (same Plate and Fig.), that are filled with quicksilver. As the acid gas is released, it moves into the jar and rises to the top of the quicksilver, pushing it down. When the gas release slows down, we apply gentle heat to the retort and gradually increase it until nothing more comes out. This acid gas has a strong attraction to water, which absorbs a huge amount of it. This is demonstrated by adding a very thin layer of water into the glass containing the gas; in an instant, all the acid gas disappears and combines with the water.
This latter circumstance is taken advantage of in laboratories and manufactures, on purpose to obtain the acid of sea-salt in a liquid form; and for this purpose the apparatus (Pl. IV. Fig. 1.) is employed. It consists, 1st, of a tubulated retort A, into which the sea-salt, and after it the sulphuric acid, are introduced through the opening H; 2d, of the baloon or recipient c, b, intended for containing the small quantity of liquid which passes over during the process; and, 3d, of a set of bottles, with two mouths, L, L, L, L, half filled with water, intended for absorbing the gas disengaged by the distillation. This apparatus will be more amply described in the latter part of this work.
This situation is utilized in labs and factories to extract liquid sea salt acid. For this purpose, the apparatus (Pl. IV. Fig. 1.) is used. It includes, first, a tubulated retort A where sea salt is added, followed by sulfuric acid through the opening H; second, the balloon or recipient c, b, which holds the small amount of liquid that comes over during the process; and third, a set of bottles with two openings, L, L, L, L, partially filled with water to absorb the gas released during distillation. This apparatus will be described in more detail later in this work.
Although we have not yet been able, either to compose or to decompound this acid of sea-salt, we cannot have the smallest doubt that it, like all other acids, is composed by the union of oxygen with an acidifiable base. We have therefore called this unknown substance the[Pg 72] muriatic base, or muriatic radical, deriving this name, after the example of Mr Bergman and Mr de Morveau, from the Latin word muria, which was anciently used to signify sea-salt. Thus, without being able exactly to determine the component parts of muriatic acid, we design, by that term, a volatile acid, which retains the form of gas in the common temperature and pressure of our atmosphere, which combines with great facility, and in great quantity, with water, and whose acidifiable base adheres so very intimately with oxygen, that no method has hitherto been devised for separating them. If ever this acidifiable base of the muriatic acid is discovered to be a known substance, though now unknown in that capacity, it will be requisite to change its present denomination for one analogous with that of its base.
Although we haven't been able to break down or analyze this sea salt acid yet, we have no doubt that, like all other acids, it is made up of oxygen combined with an acidifiable base. We have therefore referred to this unknown substance as the[Pg 72] muriatic base or muriatic radical, taking this name from the Latin word muria, which was historically used to refer to sea salt. Thus, even though we can’t precisely identify the components of muriatic acid, we define it as a volatile acid that exists as a gas under normal temperature and pressure, combines readily and in significant amounts with water, and whose acidifiable base is so closely bonded with oxygen that no method has yet been found to separate them. If this acidifiable base of muriatic acid is ever identified as a known substance, despite currently being unknown in that context, its name will need to be changed to align with that of its base.
In common with sulphuric acid, and several other acids, the muriatic is capable of different degrees of oxygenation; but the excess of oxygen produces quite contrary effects upon it from what the same circumstance produces upon the acid of sulphur. The lower degree of oxygenation converts sulphur into a volatile gasseous acid, which only mixes in small proportions with water, whilst a higher oxygenation forms an acid possessing much stronger acid properties, which is very fixed and cannot remain in the state of gas but in a very high temperature, which has[Pg 73] no smell, and which mixes in large proportion with water. With muriatic acid, the direct reverse takes place; an additional saturation with oxygen renders it more volatile, of a more penetrating odour, less miscible with water, and diminishes its acid properties. We were at first inclined to have denominated these two degrees of saturation in the same manner as we had done with the acid of sulphur, calling the less oxygenated muriatous acid, and that which is more saturated with oxygen muriatic acid: But, as this latter gives very particular results in its combinations, and as nothing analogous to it is yet known in chemistry, we have left the name of muriatic acid to the less saturated, and give the latter the more compounded appellation of oxygenated muriatic acid.
Like sulfuric acid and several other acids, hydrochloric acid can have different levels of oxygenation; however, the extra oxygen affects it very differently than it does sulfuric acid. A lower level of oxygenation turns sulfur into a volatile gaseous acid, which only mixes in small amounts with water, while a higher level creates a much stronger acid that is very stable and can only exist as a gas at extremely high temperatures, which has[Pg 73] no smell and mixes well with water. With hydrochloric acid, the opposite happens; an additional saturation with oxygen makes it more volatile, gives it a stronger odor, makes it less mixable with water, and reduces its acidity. Initially, we thought about naming these two saturation levels similarly to how we did with sulfuric acid, calling the less oxygenated muriatous acid and the more oxygenated muriatic acid: However, since this latter form produces very specific results in its combinations and nothing similar is known in chemistry yet, we decided to keep the name muriatic acid for the less saturated version and give the more saturated one the more complex name of oxygenated muriatic acid.
Although the base or radical of the acid which is extracted from nitre or saltpetre be better known, we have judged proper only to modify its name in the same manner with that of the muriatic acid. It is drawn from nitre, by the intervention of sulphuric acid, by a process similar to that described for extracting the muriatic acid, and by means of the same apparatus (Pl. IV. Fig. 1.). In proportion as the acid passes over, it is in part condensed in the baloon or recipient, and the rest is absorbed by the water contained in the bottles L,L,L,L; the water becomes first green,[Pg 74] then blue, and at last yellow, in proportion to the concentration of the acid. During this operation, a large quantity of oxygen gas, mixed with a small proportion of azotic gas, is disengaged.
Although the base or radical of the acid extracted from nitre or saltpetre is better understood, we have decided to only slightly change its name, similar to that of muriatic acid. It is obtained from nitre using sulphuric acid, through a process like the one described for extracting muriatic acid, and using the same equipment (Pl. IV. Fig. 1.). As the acid evaporates, some of it condenses in the balloon or recipient, while the rest is absorbed by the water in bottles L,L,L,L; the water changes from green,[Pg 74] to blue, and finally to yellow, depending on the acid's concentration. During this process, a significant amount of oxygen gas, mixed with a small amount of nitrogen gas, is released.
This acid, like all others, is composed of oxygen, united to an acidifiable base, and is even the first acid in which the existence of oxygen was well ascertained. Its two constituent elements are but weakly united, and are easily separated, by presenting any substance with which oxygen has a stronger affinity than with the acidifiable base peculiar to this acid. By some experiments of this kind, it was first discovered that azote, or the base of mephitis or azotic gas, constituted its acidifiable base or radical; and consequently that the acid of nitre was really an azotic acid, having azote for its base, combined with oxygen. For these reasons, that we might be consistent with our principles, it appeared necessary, either to call the acid by the name of azotic, or to name the base nitric radical; but from either of these we were dissuaded, by the following considerations. In the first place, it seemed difficult to change the name of nitre or saltpetre, which has been universally adopted in society, in manufactures, and in chemistry; and, on the other hand, azote having been discovered by Mr Berthollet to be the base of volatile alkali, or ammoniac, as well as of this acid,[Pg 75] we thought it improper to call it nitric radical. We have therefore continued the term of azote to the base of that part of atmospheric air which is likewise the nitric and ammoniacal radical; and we have named the acid of nitre, in its lower and higher degrees of oxygenation, nitrous acid in the former, and nitric acid in the latter state; thus preserving its former appellation properly modified.
This acid, like all others, is made up of oxygen combined with an acidifiable base, and it's actually the first acid where the existence of oxygen was clearly confirmed. Its two main elements are only weakly bonded and can be easily separated by introducing any substance that has a stronger attraction to oxygen than the acidifiable base specific to this acid. Through some experiments like this, it was initially discovered that nitrogen, or the base of mephitic or nitrogen gas, made up its acidifiable base or radical; thus, the acid of nitre was truly an azotic acid, with nitrogen as its base, combined with oxygen. For these reasons, to stay consistent with our principles, it seemed necessary to either call the acid azotic or refer to the base as nitric radical; however, we were discouraged from either option for the following reasons. First, it seemed challenging to change the name of nitre or saltpetre, which has been widely accepted in society, manufacturing, and chemistry; and on the other hand, since Mr. Berthollet discovered that nitrogen is the base of volatile alkali or ammonia, as well as of this acid,[Pg 75] we thought it inappropriate to call it nitric radical. Therefore, we have retained the term nitrogen for the base of that portion of atmospheric air which is also the nitrogen and ammonium radical; and we have named the acid of nitre, in its lower and higher degrees of oxygenation, nitrous acid for the former and nitric acid for the latter, thus keeping its original name properly modified.
Several very respectable chemists have disapproved of this deference for the old terms, and wished us to have persevered in perfecting a new chemical language, without paying any respect for ancient usage; so that, by thus steering a kind of middle course, we have exposed ourselves to the censures of one sect of chemists, and to the expostulations of the opposite party.
Several highly regarded chemists have criticized our respect for the old terminology and have encouraged us to continue developing a new chemical language without regard for traditional usage. By trying to find a balance, we have subjected ourselves to the criticism of one group of chemists and the protests of the other side.
The acid of nitre is susceptible of assuming a great number of separate states, depending upon its degree of oxygenation, or upon the proportions in which azote and oxygen enter into its composition. By a first or lowest degree of oxygenation, it forms a particular species of gas, which we shall continue to name nitrous gas; this is composed nearly of two parts, by weight, of oxygen combined with one part of azote; and in this state it is not miscible with water. In this gas, the azote is by no means saturated with oxygen, but, on the contrary, has[Pg 76] still a very great affinity for that element, and even attracts it from atmospheric air, immediately upon getting into contact with it. This combination of nitrous gas with atmospheric air has even become one of the methods for determining the quantity of oxygen contained in air, and consequently for ascertaining its degree of salubrity.
The acid of nitre can take on many different states, depending on how much oxygen it contains and the proportions of nitrogen and oxygen in its makeup. At its lowest level of oxygenation, it forms a specific type of gas that we will continue to call nitrous gas; this gas is made up of roughly two parts oxygen combined with one part nitrogen by weight, and in this state, it does not mix with water. In this gas, nitrogen is not fully saturated with oxygen; instead, it has a strong attraction to oxygen and will pull it from the surrounding air as soon as it comes into contact with it. This reaction between nitrous gas and atmospheric air has become a method for measuring the amount of oxygen in the air, and thus determining its quality for health.
This addition of oxygen converts the nitrous gas into a powerful acid, which has a strong affinity with water, and which is itself susceptible of various additional degrees of oxygenation. When the proportions of oxygen and azote is below three parts, by weight, of the former, to one of the latter, the acid is red coloured, and emits copious fumes. In this state, by the application of a gentle heat, it gives out nitrous gas; and we term it, in this degree of oxygenation, nitrous acid. When four parts, by weight, of oxygen, are combined with one part of azote, the acid is clear and colourless, more fixed in the fire than the nitrous acid, has less odour, and its constituent elements are more firmly united. This species of acid, in conformity with our principles of nomenclature, is called nitric acid.
This addition of oxygen turns nitrous gas into a powerful acid that strongly interacts with water and can undergo various additional levels of oxygenation. When the ratio of oxygen to nitrogen is less than three parts by weight of the former to one of the latter, the acid is red and gives off a lot of fumes. In this state, when gently heated, it releases nitrous gas; we call it, at this level of oxygenation, nitrous acid. When four parts by weight of oxygen are mixed with one part of nitrogen, the acid is clear and colorless, more stable in heat than nitrous acid, has a milder smell, and its component elements are more tightly bonded. This type of acid, according to our naming conventions, is referred to as nitric acid.
Thus, nitric acid is the acid of nitre, surcharged with oxygen; nitrous acid is the acid of nitre surcharged with azote; or, what is the same thing, with nitrous gas; and this latter is[Pg 77] azote not sufficiently saturated with oxygen to possess the properties of an acid. To this degree of oxygenation, we have afterwards, in the course of this work, given the generical name of oxyd[14].
Thus, nitric acid is the acid from saltpeter that has a lot of oxygen; nitrous acid is the acid from saltpeter that has nitrogen oxide, or in other words, nitrous gas; and this last one is nitrogen that doesn’t have enough oxygen to have the properties of an acid. To this level of oxygenation, we have later in this work, given the general name of oxide[14].
FOOTNOTES:
[12] The term formerly used by the English chemists for this acid was written sulphureous; but we have thought proper to spell it as above, that it may better conform with the similar terminations of nitrous, carbonous, &c. to be used hereafter. In general, we have used the English terminations ic and ous to translate the terms of the Author which end with ique and cux, with hardly any other alterations.—E.
[12] The term previously used by English chemists for this acid was written sulphureous; however, we have chosen to spell it as above to better align with similar endings like nitrous, carbonous, etc., that will be used later. In general, we have used the English endings ic and ous to translate the Author's terms that end with ique and cux, with very few other changes.—E.
[13] For this purpose, the operation called decrepitation is used, which consists in subjecting it to nearly a red heat, in a proper vessel, so as to evaporate all its water of crystallization.—E.
[13] For this purpose, the process called decrepitation is used, which involves heating it to almost a red heat in a suitable container to evaporate all its water of crystallization.—E.
[14] In strict conformity with the principles of the new nomenclature, but which the Author has given his reasons for deviating from in this instance, the following ought to have been the terms for azote, in its several degrees of oxygenation: Azote, azotic gas, (azote combined with caloric), azotic oxyd gas, nitrous acid, and nitric acid.—E.
[14] Following the strict guidelines of the new naming system, which the Author has explained why he chose to depart from in this case, the terms for nitrogen, in its various degrees of oxidation, should have been: Nitrogen, nitrous gas (nitrogen combined with heat), nitrous oxide gas, nitrous acid, and nitric acid.—E.
CHAP. VII.
Of the Decomposition of Oxygen Gas by means of Metals, and the Formation of Metallic Oxyds.
Oxygen has a stronger affinity with metals heated to a certain degree than with caloric; in consequence of which, all metallic bodies, excepting gold, silver, and platina, have the property of decomposing oxygen gas, by attracting its base from the caloric with which it was combined. We have already shown in what manner this decomposition takes place, by means of mercury and iron; having observed, that, in the case of the first, it must be considered as a kind of gradual combustion, whilst, in the latter, the combustion is extremely rapid, and attended with a brilliant flame. The use of the heat employed in these operations is to separate the particles of the metal from each other, and to diminish their attraction of cohesion or aggregation, or, what is the same thing, their mutual attraction for each other.
Oxygen has a stronger attraction to metals when heated to a certain temperature than to heat energy (caloric); as a result, all metals, except for gold, silver, and platinum, can break down oxygen gas by pulling its base away from the heat it was combined with. We have already explained how this breakdown happens using mercury and iron; we noted that, in the case of mercury, it should be seen as a type of slow combustion, while in the case of iron, the combustion is very quick and produces a bright flame. The purpose of the heat used in these processes is to separate the metal particles from one another and reduce their cohesive attraction or, in other words, their mutual attraction to each other.
The absolute weight of metallic substances is augmented in proportion to the quantity of oxygen they absorb; they, at the same time, lose their metallic splendour, and are reduced into[Pg 79] an earthy pulverulent matter. In this state metals must not be considered as entirely saturated with oxygen, because their action upon this element is counterbalanced by the power of affinity between it and caloric. During the calcination of metals, the oxygen is therefore acted upon by two separate and opposite powers, that of its attraction for caloric, and that exerted by the metal, and only tends to unite with the latter in consequence of the excess of the latter over the former, which is, in general, very inconsiderable. Wherefore, when metallic substances are oxygenated in atmospheric air, or in oxygen gas, they are not converted into acids like sulphur, phosphorus, and charcoal, but are only changed into intermediate substances, which, though approaching to the nature of salts, have not acquired all the saline properties. The old chemists have affixed the name of calx not only to metals in this state, but to every body which has been long exposed to the action of fire without being melted. They have converted this word calx into a generical term, under which they confound calcareous earth, which, from a neutral salt, which it really was before calcination, has been changed by fire into an earthy alkali, by losing half of its weight, with metals which, by the same means, have joined themselves to a new substance, whose quantity often exceeds half their weight, and by which they[Pg 80] have been changed almost into the nature of acids. This mode of classifying substances of so very opposite natures, under the same generic name, would have been quite contrary to our principles of nomenclature, especially as, by retaining the above term for this state of metallic substances, we must have conveyed very false ideas of its nature. We have, therefore, laid aside the expression metallic calx altogether, and have substituted in its place the term oxyd, from the Greek word οξυς.
The weight of metal substances increases based on how much oxygen they take in; at the same time, they lose their metallic shine and turn into[Pg 79] a powdery, earthy substance. In this condition, metals shouldn't be viewed as completely saturated with oxygen because their interaction with oxygen is balanced by its attraction to heat. During the heating of metals, oxygen is affected by two opposing forces: its pull towards heat, and the force exerted by the metal itself, which usually is just slightly stronger. Therefore, when metals combine with oxygen in the air or in oxygen gas, they don’t become acids like sulfur, phosphorus, and charcoal; instead, they become intermediate substances that are somewhat similar to salts but don't have all the properties of salts. Early chemists called metals in this state calx, as well as anything that had been subjected to high heat without melting. They turned the word calx into a general term that included calcareous earth, which, after being neutral before heating, had turned into an earthy alkali by losing half of its weight, and metals that had bonded with another substance that often exceeds half their weight, nearly transforming them into acidic substances. This way of classifying such different materials under the same term would have been completely against our naming principles, especially since keeping the original term for this state of metals would create very misleading ideas about their nature. Consequently, we have completely removed the term metallic calx and replaced it with the term oxyd, derived from the Greek word οξυς.
By this may be seen, that the language we have adopted is both copious and expressive. The first or lowest degree of oxygenation in bodies, converts them into oxyds; a second degree of additional oxygenation constitutes the class of acids, of which the specific names, drawn from their particular bases, terminate in ous, as the nitrous and sulphurous acids; the third degree of oxygenation changes these into the species of acids distinguished by the termination in ic, as the nitric and sulphuric acids; and, lastly, we can express a fourth, or highest degree of oxygenation, by adding the word oxygenated to the name of the acid, as has been already done with the oxygenated muriatic acid.
This shows that the language we use is both rich and expressive. The first or lowest level of oxygenation in substances turns them into oxides; a second level of added oxygenation creates a class of acids, with specific names based on their particular bases that end in ous, like nitrous and sulphurous acids. The third level of oxygenation transforms these into a type of acid identified by names ending in ic, such as nitric and sulphuric acids; finally, we can indicate a fourth, or highest level of oxygenation by adding the word oxygenated to the name of the acid, as we have already done with oxygenated muriatic acid.
We have not confined the term oxyd to expressing the combinations of metals with oxygen, but have extended it to signify that first degree of oxygenation in all bodies, which,[Pg 81] without converting them into acids, causes them to approach to the nature of salts. Thus, we give the name of oxyd of sulphur to that soft substance into which sulphur is converted by incipient combustion; and we call the yellow matter left by phosphorus, after combustion, by the name of oxyd of phosphorus. In the same manner, nitrous gas, which is azote in its first degree of oxygenation, is the oxyd of azote. We have likewise oxyds in great numbers from the vegetable and animal kingdoms; and I shall show, in the sequel, that this new language throws great light upon all the operations of art and nature.
We haven't limited the term oxide to just the combinations of metals with oxygen; we've broadened it to mean the first level of oxygenation in all substances, which, [Pg 81] without turning them into acids, makes them more similar to salts. For instance, we refer to the soft substance that sulfur turns into during initial combustion as oxide of sulfur; and we call the yellow residue left by phosphorus after combustion oxide of phosphorus. Similarly, nitrous gas, which is nitrogen in its first level of oxygenation, is known as oxide of nitrogen. We also have many oxides from both the plant and animal kingdoms; I'll demonstrate later that this new terminology significantly clarifies all the processes of art and nature.
We have already observed, that almost all the metallic oxyds have peculiar and permanent colours. These vary not only in the different species of metals, but even according to the various degrees of oxygenation in the same metal. Hence we are under the necessity of adding two epithets to each oxyd, one of which indicates the metal oxydated[15], while the other indicates[Pg 82] the peculiar colour of the oxyd. Thus, we have the black oxyd of iron, the red oxyd of iron, and the yellow oxyd of iron; which expressions respectively answer to the old unmeaning terms of martial ethiops, colcothar, and rust of iron, or ochre. We have likewise the gray, yellow, and red oxyds of lead, which answer to the equally false or insignificant terms, ashes of lead, massicot, and minium.
We've already noticed that almost all metallic oxides have distinct and lasting colors. These colors vary not only among different types of metals but also according to different levels of oxygenation within the same metal. Therefore, we need to use two descriptors for each oxide: one indicating the metal being oxidized, while the other describes the specific color of the oxide. For example, we refer to the black oxide of iron, the red oxide of iron, and the yellow oxide of iron; these phrases correspond to the outdated and meaningless terms of martial ethiops, colcothar, and rust of iron, or ochre. We also have the gray, yellow, and red oxides of lead, which relate to the equally vague or nonsensical terms ashes of lead, massicot, and minium.
These denominations sometimes become rather long, especially when we mean to indicate whether the metal has been oxydated in the air, by detonation with nitre, or by means of acids; but then they always convey just and accurate ideas of the corresponding object which we wish to express by their use. All this will be rendered perfectly clear and distinct by means of the tables which are added to this work.
These terms can sometimes be quite lengthy, especially when we want to specify whether the metal has oxidized in the air, through detonation with nitrate, or using acids. However, they always communicate clear and precise ideas about the object we want to describe. Everything will be made perfectly clear and straightforward with the tables included in this work.
FOOTNOTES:
[15] Here we see the word oxyd converted into the verb to oxydate, oxydated, oxydating, after the same manner with the derivation of the verb to oxygenate, oxygenated, oxygenating, from the word oxygen. I am not clear of the absolute necessity of this second verb here first introduced, but think, in a work of this nature, that it is the duty of the translator to neglect every other consideration for the sake of strict fidelity to the ideas of his author.—E.
[15] Here we see the word oxid changed into the verb to oxidate, oxidated, oxidating, in the same way as the verb to oxygenate, oxygenated, oxygenating, comes from the word oxygen. I'm not sure why this second verb is necessary, but I believe that in a work like this, it's the translator's job to prioritize strict adherence to the original author's ideas over any other considerations.—E.
CHAP. VIII.
Of the Radical Principle of Water, and of its Decomposition by Charcoal and Iron.
Until very lately, water has always been thought a simple substance, insomuch that the older chemists considered it as an element. Such it undoubtedly was to them, as they were unable to decompose it; or, at least, since the decomposition which took place daily before their eyes was entirely unnoticed. But we mean to prove, that water is by no means a simple or elementary substance. I shall not here pretend to give the history of this recent, and hitherto contested discovery, which is detailed in the Memoirs of the Academy for 1781, but shall only bring forwards the principal proofs of the decomposition and composition of water; and, I may venture to say, that these will be convincing to such as consider them impartially.
Until recently, water was always thought to be a simple substance, so much so that older chemists considered it an element. To them, it was undoubtedly an element since they couldn’t break it down; or at least, the decomposition happening right before their eyes went totally unnoticed. But we aim to show that water is definitely not a simple or elemental substance. I won’t attempt to give the history of this recent, and still debated, discovery, which is detailed in the Memoirs of the Academy for 1781, but I will present the main evidence for the decomposition and composition of water. I dare say that these will be convincing to anyone who considers them fairly.
Experiment First.
Having fixed the glass tube EF, (Pl. vii. fig. 11.) of from 8 to 12 lines diameter, across a furnace, with a small inclination from E to F,[Pg 84] lute the superior extremity E to the glass retort A, containing a determinate quantity of distilled water, and to the inferior extremity F, the worm SS fixed into the neck of the doubly tubulated bottle H, which has the bent tube KK adapted to one of its openings, in such a manner as to convey such aëriform fluids or gasses as may be disengaged, during the experiment, into a proper apparatus for determining their quantity and nature.
Having set up the glass tube EF (Pl. vii. fig. 11), which has a diameter of 8 to 12 lines, across a furnace with a slight tilt from E to F,[Pg 84] seal the top end E to the glass retort A, which contains a specific amount of distilled water, and attach the bottom end F to the worm SS fixed into the neck of the doubly tubulated bottle H. This bottle has the bent tube KK connected to one of its openings, designed to direct any gaseous substances that are released during the experiment into the appropriate apparatus for measuring their quantity and nature.
To render the success of this experiment certain, it is necessary that the tube EF be made of well annealed and difficultly fusible glass, and that it be coated with a lute composed of clay mixed with powdered stone-ware; besides which, it must be supported about its middle by means of an iron bar passed through the furnace, lest it should soften and bend during the experiment. A tube of China-ware, or porcellain, would answer better than one of glass for this experiment, were it not difficult to procure one so entirely free from pores as to prevent the passage of air or of vapours.
To ensure the success of this experiment, the tube EF needs to be made from well-annealed and difficult-to-melt glass, and it should be coated with a sealant made of clay mixed with powdered stoneware. Additionally, it must be supported in the middle by an iron bar that goes through the furnace, to prevent it from softening and bending during the experiment. A tube made of china or porcelain would work better than glass for this experiment, if only it weren't so hard to find one that is completely free of pores to stop the passage of air or vapors.
When things are thus arranged, a fire is lighted in the furnace EFCD, which is supported of such a strength as to keep the tube EF red hot, but not to make it melt; and, at the same time, such a fire is kept up in the furnace VVXX, as to keep the water in the retort A continually boiling.[Pg 85]
When everything is set up this way, a fire is lit in the furnace EFCD, which is strong enough to keep the tube EF red hot but not so strong that it melts. At the same time, a fire is maintained in the furnace VVXX to keep the water in the retort A continuously boiling.[Pg 85]
In proportion as the water in the retort A is evaporated, it fills the tube EF, and drives out the air it contained by the tube KK; the aqueous gas formed by evaporation is condensed by cooling in the worm SS, and falls, drop by drop, into the tubulated bottle H. Having continued this operation until all the water be evaporated from the retort, and having carefully emptied all the vessels employed, we find that a quantity of water has passed over into the bottle H, exactly equal to what was before contained in the retort A, without any disengagement of gas whatsoever: So that this experiment turns out to be a simple distillation; and the result would have been exactly the same, if the water had been run from one vessel into the other, through the tube EF, without having undergone the intermediate incandescence.
As the water in retort A evaporates, it fills the tube EF and pushes out the air it contained through the tube KK. The vapor created by evaporation is cooled and condensed in the worm SS, and it drips into the tubulated bottle H. After continuing this process until all the water has evaporated from the retort and thoroughly emptying all the equipment used, we find that the amount of water collected in bottle H is exactly equal to the amount that was originally in retort A, without any gas being released at all. This experiment effectively demonstrates simple distillation, and the outcome would have been the same if the water had been poured directly from one vessel to the other through tube EF, without being heated in between.
Experiment Second.
The apparatus being disposed, as in the former experiment, 28 grs. of charcoal, broken into moderately small parts, and which has previously been exposed for a long time to a red heat in close vessels, are introduced into the tube EF. Every thing else is managed as in the preceding experiment.
The setup is the same as in the previous experiment. 28 grs. of charcoal, broken into moderately small pieces and previously heated for a long time in sealed containers, are placed into the tube EF. Everything else is handled just like in the last experiment.
The water contained in the retort A is distilled, as in the former experiment, and, being[Pg 86] condensed in the worm, falls into the bottle H; but, at the same time, a considerable quantity of gas is disengaged, which, escaping by the tube KK, is received in a convenient apparatus for that purpose. After the operation is finished, we find nothing but a few atoms of ashes remaining in the tube EF; the 28 grs. of charcoal having entirely disappeared.
The water in retort A is distilled like in the previous experiment, and, being[Pg 86] condensed in the worm, drips into bottle H; meanwhile, a significant amount of gas is released, which escapes through tube KK and is collected in a suitable device for that purpose. Once the process is complete, we see that only a few particles of ash are left in tube EF; the 28 grs. of charcoal have completely vanished.
When the disengaged gasses are carefully examined, they are sound to weigh 113.7 grs.[16]; these are of two kinds, viz. 144 cubical inches of carbonic acid gas, weighing 100 grs. and 380 cubical inches of a very light gas, weighing only 13.7 grs. which takes fire when in contact with air, by the approach of a lighted body; and, when the water which has passed over into the bottle H is carefully examined, it is found to have lost 85.7 grs. of its weight. Thus, in this experiment, 85.7 grs. of water, joined to 28 grs. of charcoal, have combined in such a way as to form 100 grs. of carbonic acid, and 13.7 grs. of a particular gas capable of being burnt.
When the released gases are closely examined, they weigh a total of 113.7 grs.[16]; these consist of two types: 144 cubic inches of carbon dioxide, weighing 100 grs., and 380 cubic inches of a very light gas, weighing only 13.7 grs., which ignites upon contact with air when exposed to a flame; and when the water that has flowed into bottle H is carefully analyzed, it is found to have lost 85.7 grs. of its weight. Thus, in this experiment, 85.7 grs. of water, combined with 28 grs. of charcoal, have formed 100 grs. of carbon dioxide and 13.7 grs. of a specific flammable gas.
I have already shown, that 100 grs. of carbonic acid gas consists of 72 grs. of oxygen, combined with 28 grs. of charcoal; hence the 28[Pg 87] grs. of charcoal placed in the glass tube have acquired 72 grs. of oxygen from the water; and it follows, that 85.7 grs. of water are composed of 72 grs. of oxygen, combined with 13.7 grs. of a gas susceptible of combustion. We shall see presently that this gas cannot possibly have been disengaged from the charcoal, and must, consequently, have been produced from the water.
I've already demonstrated that 100 grs. of carbon dioxide is made up of 72 grs. of oxygen combined with 28 grs. of carbon; therefore, the 28 [Pg 87] grs. of carbon in the glass tube have taken in 72 grs. of oxygen from the water. This means that 85.7 grs. of water consists of 72 grs. of oxygen combined with 13.7 grs. of a combustive gas. We will see shortly that this gas could not possibly have been released from the carbon and must have come from the water.
I have suppressed some circumstances in the above account of this experiment, which would only have complicated and obscured its results in the minds of the reader. For instance, the inflammable gas dissolves a very small part of the charcoal, by which means its weight is somewhat augmented, and that of the carbonic gas proportionally diminished. Altho' the alteration produced by this circumstance is very inconsiderable; yet I have thought it necessary to determine its effects by rigid calculation, and to report, as above, the results of the experiment in its simplified state, as if this circumstance had not happened. At any rate, should any doubts remain respecting the consequences I have drawn from this experiment, they will be fully dissipated by the following experiments, which I am going to adduce in support of my opinion.[Pg 88]
I’ve left out some details in the above explanation of this experiment that would just complicate and confuse the results for the reader. For example, the flammable gas absorbs a tiny bit of the charcoal, which slightly increases its weight and decreases the weight of the carbon dioxide proportionally. Although the change from this is quite minor, I felt it was necessary to calculate its effects accurately and to present the results of the experiment in a simplified manner, as if this issue hadn’t occurred. In any case, if there are still any doubts about the conclusions I’ve drawn from this experiment, they will be completely clarified by the upcoming experiments that I will present to support my viewpoint.[Pg 88]
Experiment Third.
The apparatus being disposed exactly as in the former experiment, with this difference, that instead of the 28 grs. of charcoal, the tube EF is filled with 274 grs. of soft iron in thin plates, rolled up spirally. The tube is made red hot by means of its furnace, and the water in the retort A is kept constantly boiling till it be all evaporated, and has passed through the tube EF, so as to be condensed in the bottle H.
The setup is arranged just like in the previous experiment, except that instead of 28 grams of charcoal, the tube EF is filled with 274 grams of thin plates of soft iron, rolled up in a spiral. The tube is heated to a red-hot temperature using its furnace, and the water in the retort A is kept boiling constantly until it completely evaporates and passes through the tube EF, where it is condensed in the bottle H.
No carbonic acid gas is disengaged in this experiment, instead of which we obtain 416 cubical inches, or 15 grs. of inflammable gas, thirteen times lighter than atmospheric air. By examining the water which has been distilled, it is found to have lost 100 grs. and the 274 grs. of iron confined in the tube are found to have acquired 85 grs. additional weight, and its magnitude is considerably augmented. The iron is now hardly at all attractable by the magnet; it dissolves in acids without effervescence; and, in short, it is converted into a black oxyd, precisely similar to that which has been burnt in oxygen gas.
No carbon dioxide is released in this experiment; instead, we end up with 416 cubic inches, or 15 grams, of flammable gas, which is thirteen times lighter than air. When examining the distilled water, it shows a loss of 100 grams, and the 274 grams of iron in the tube are found to have gained an additional 85 grams in weight, and its size has significantly increased. The iron is now barely magnetic; it dissolves in acids without bubbling; and, in short, it has turned into a black oxide, exactly like the one that has been burned in oxygen.
In this experiment we have a true oxydation of iron, by means of water, exactly similar to that produced in air by the assistance of heat. One hundred grains of water having been decomposed,[Pg 89] 85 grs. of oxygen have combined with the iron, so as to convert it into the state of black oxyd, and 15 grs. of a peculiar inflammable gas are disengaged: From all this it clearly follows, that water is composed of oxygen combined with the base of an inflammable gas, in the respective proportions of 85 parts, by weight of the former, to 15 parts of the latter.
In this experiment, we see a true oxidation of iron, similar to what happens in air when heat is involved. After decomposing one hundred grains of water,[Pg 89] 85 grs. of oxygen have combined with the iron, turning it into black oxide, and 15 grs. of a specific flammable gas are released. From this, it’s clear that water is made up of oxygen combined with the base of a flammable gas, in the proportions of 85 parts by weight of oxygen to 15 parts of the gas.
Thus water, besides the oxygen, which is one of its elements in common with many other substances, contains another element as its constituent base or radical, and for which we must find an appropriate term. None that we could think of seemed better adapted than the word hydrogen, which signifies the generative principle of water, from υδορ aqua, and γεινομας gignor[17]. We call the combination of this element with caloric hydrogen gas; and the term hydrogen expresses the base of that gas, or the radical of water.
So, water, in addition to oxygen, which it shares with many other substances, has another element as its main component, and we need to find a fitting term for it. None that we considered seemed better suited than the word hydrogen, which means the generative principle of water, derived from υδορ aqua, and γεινομας gignor[17]. We refer to the combination of this element with heat as hydrogen gas; and the term hydrogen represents the base of that gas or the core component of water.
This experiment furnishes us with a new combustible body, or, in other words, a body which has so much affinity with oxygen as to draw it from its connection with caloric, and to decompose air or oxygen gas. This combustible body has itself so great affinity with caloric, that, unless when engaged in a combination with some other body, it always subsists in the aëriform or gasseous state, in the usual temperature and pressure of our atmosphere. In this state of gas it is about 1/13 of the weight of an equal bulk of atmospheric air; it is not absorbed by water, though it is capable of holding a small quantity of that fluid in solution, and it is incapable of being used for respiration.
This experiment gives us a new flammable substance, or in other words, a substance that has such a strong attraction to oxygen that it can pull it away from its combination with heat and break down air or oxygen gas. This flammable substance has such a strong attraction to heat that, unless it's combined with another substance, it always exists in a gas form at the typical temperature and pressure of our atmosphere. In this gas state, it weighs about 1/13 of the weight of the same volume of atmospheric air; it doesn't dissolve in water, although it can hold a small amount of that liquid in solution, and it cannot be used for breathing.
As the property this gas possesses, in common with all other combustible bodies, is nothing more than the power of decomposing air, and carrying off its oxygen from the caloric with which it was combined, it is easily understood that it cannot burn, unless in contact with air or oxygen gas. Hence, when we set fire to a bottle full of this gas, it burns gently, first at the neck of the bottle, and then in the inside of it, in proportion as the external air gets in: This combustion is slow and successive, and only takes place at the surface of contact between the two gasses. It is quite different when the two gasses are mixed before they are set on fire: If, for instance, after having introduced one part of[Pg 91] oxygen gas into a narrow mouthed bottle, we fill it up with two parts of hydrogen gas, and bring a lighted taper, or other burning body, to the mouth of the bottle, the combustion of the two gasses takes place instantaneously with a violent explosion. This experiment ought only to be made in a bottle of very strong green glass, holding not more than a pint, and wrapped round with twine, otherwise the operator will be exposed to great danger from the rupture of the bottle, of which the fragments will be thrown about with great force.
As the property this gas has, similar to all other flammable substances, is simply the ability to decompose air and remove its oxygen from the heat it was combined with, it's easy to see that it won't ignite unless it's in contact with air or oxygen gas. So, when we ignite a bottle filled with this gas, it burns slowly, starting at the neck of the bottle and then inside it, depending on how much outside air can enter: This combustion is gradual and occurs only at the surface where the two gases meet. It’s totally different when the two gases are mixed before ignition: For instance, if we put one part of [Pg 91] oxygen gas into a narrow-necked bottle, fill it up with two parts of hydrogen gas, and bring a lit taper or another burning object to the mouth of the bottle, the combustion of the two gases happens instantaneously with a violent explosion. This experiment should only be conducted in a very strong green glass bottle, holding no more than a pint, and wrapped with twine, or else the person performing it risks significant danger from the bottle breaking, with the shards being propelled violently.
If all that has been related above, concerning the decomposition of water, be exactly conformable to truth;—if, as I have endeavoured to prove, that substance be really composed of hydrogen, as its proper constituent element, combined with oxygen, it ought to follow, that, by reuniting these two elements together, we should recompose water; and that this actually happens may be judged of by the following experiment.
If everything mentioned above about the breakdown of water is accurate—if, as I have tried to show, that substance is really made up of hydrogen as its main component combined with oxygen—it should follow that by bringing these two elements back together, we should recreate water. The following experiment can demonstrate that this actually occurs.
Experiment Fourth.
I took a large cristal baloon, A, Pl. iv. fig. 5. holding about 30 pints, having a large opening, to which was cemented the plate of copper BC, pierced with four holes, in which four tubes terminate. The first tube, H h, is intended to[Pg 92] be adapted to an air pump, by which the baloon is to be exhausted of its air. The second tube gg, communicates, by its extremity MM, with a reservoir of oxygen gas, with which the baloon is to be filled. The third tube d D d', communicates, by its extremity d NN, with a reservoir of hydrogen gas. The extremity d' of this tube terminates in a capillary opening, through which the hydrogen gas contained in the reservoir is forced, with a moderate degree of quickness, by the pressure of one or two inches of water. The fourth tube contains a metallic wire GL, having a knob at its extremity L, intended for giving an electrical spark from L to d', on purpose to set fire to the hydrogen gas: This wire is moveable in the tube, that we may be able to separate the knob L from the extremity d' of the tube D d'. The three tubes d D d', gg, and H h, are all provided with stop-cocks.
I took a large crystal balloon, A, Pl. iv. fig. 5, that holds about 30 pints, with a big opening. A copper plate BC was attached to it, featuring four holes where four tubes connect. The first tube, H h, is meant to connect to an air pump to evacuate the balloon of air. The second tube, gg, connects at its end, MM, to a reservoir of oxygen gas that will fill the balloon. The third tube, d D d', connects at its end, d NN, to a reservoir of hydrogen gas. The end d' of this tube has a small opening that allows the hydrogen gas to flow from the reservoir at a moderate speed, using the pressure of one or two inches of water. The fourth tube has a metal wire GL with a knob at the end, L, which is used to create an electrical spark from L to d' to ignite the hydrogen gas. This wire can move within the tube so we can separate the knob L from the end d' of the tube D d'. The three tubes d D d', gg, and H h all have stopcocks.
That the hydrogen gas and oxygen gas may be as much as possible deprived of water, they are made to pass, in their way to the baloon A, through the tubes MM, NN, of about an inch diameter, and filled with salts, which, from their deliquescent nature, greedily attract the moisture of the air: Such are the acetite of potash, and the muriat or nitrat of lime[18]. These salts[Pg 93] must only be reduced to a coarse powder, lest they run into lumps, and prevent the gasses from geting through their interstices.
To remove as much water as possible from the hydrogen and oxygen gases before they reach the balloon A, they are directed through the tubes MM and NN, which are about an inch in diameter and filled with salts. These salts, due to their ability to absorb moisture from the air, include potassium acetate and either calcium chloride or calcium nitrate[18]. The salts[Pg 93] should be ground to a coarse powder to avoid clumping, which would block the gases from passing through.
We must be provided before hand with a sufficient quantity of oxygen gas, carefully purified from all admixture of carbonic acid, by long contact with a solution of potash[19].
We need to have enough pure oxygen gas ready in advance, thoroughly cleaned of any carbon dioxide, by being in contact with a potash solution.[19].
We must likewise have a double quantity of hydrogen gas, carefully purified in the same manner by long contact with a solution of potash in water. The best way of obtaining this gas free from mixture is, by decomposing water with very pure soft iron, as directed in Exp. 3. of this chapter.
We also need double the amount of hydrogen gas, carefully purified in the same way by prolonged contact with a potash solution in water. The best method to obtain this gas free from impurities is by breaking down water with very pure soft iron, as described in Exp. 3 of this chapter.
Having adjusted every thing properly, as above directed, the tube H h is adapted to an air-pump, and the baloon A is exhausted of its air. We next admit the oxygen gas so as to fill the baloon, and then, by means of pressure, as is before mentioned, force a small stream of hydrogen gas through its tube D d', which we immediately set on fire by an electric spark. By means of the above described apparatus, we can[Pg 94] continue the mutual combustion of these two gasses for a long time, as we have the power of supplying them to the baloon from their reservoirs, in proportion as they are consumed. I have in another place[20] given a description of the apparatus used in this experiment, and have explained the manner of ascertaining the quantities of the gasses consumed with the most scrupulous exactitude.
Having properly adjusted everything as directed, the tube H h is connected to an air pump, and the balloon A is vacuumed of air. Next, we let oxygen gas into the balloon to fill it, and then, by applying pressure as mentioned earlier, we force a small stream of hydrogen gas through its tube D d', which we immediately ignite with an electric spark. With the apparatus described above, we can[Pg 94] continuously allow these two gases to combust for a long time since we can supply them to the balloon from their reservoirs as they are consumed. I have previously[20] provided a description of the apparatus used in this experiment and explained how to precisely determine the quantities of the gases consumed.
In proportion to the advancement of the combustion, there is a deposition of water upon the inner surface of the baloon or matrass A: The water gradually increases in quantity, and, gathering into large drops, runs down to the bottom of the vessel. It is easy to ascertain the quantity of water collected, by weighing the baloon both before and after the experiment. Thus we have a twofold verification of our experiment, by ascertaining both the quantities of the gasses employed, and of the water formed by their combustion: These two quantities must be equal to each other. By an operation of this kind, Mr Meusnier and I ascertained that it required 85 parts, by weight, of oxygen, united to 15 parts of hydrogen, to compose 100 parts of water. This experiment, which has not hitherto been published, was made in presence of a numerous committee from the Royal Academy.[Pg 95] We exerted the most scrupulous attention to its accuracy; and have reason to believe that the above propositions cannot vary a two hundredth part from absolute truth.
As combustion progresses, water collects on the inner surface of the balloon or flask A. The amount of water gradually increases, and when it forms large droplets, it runs down to the bottom of the vessel. You can easily determine the amount of water collected by weighing the balloon before and after the experiment. This gives us two ways to verify our experiment by checking the amounts of gases used and the water produced from their combustion. These two amounts should be equal to each other. In this way, Mr. Meusnier and I found that it required 85 parts by weight of oxygen combined with 15 parts of hydrogen to create 100 parts of water. This experiment, which hasn't been published before, took place in front of a large committee from the Royal Academy. We were very careful about ensuring its accuracy and believe that the above results are accurate to within two hundredths of a part from the absolute truth.[Pg 95]
From these experiments, both analytical and synthetic, we may now affirm that we have ascertained, with as much certainty as is possible in physical or chemical subjects, that water is not a simple elementary substance, but is composed of two elements, oxygen and hydrogen; which elements, when existing separately, have so strong affinity for caloric, as only to subsist under the form of gas in the common temperature and pressure of our atmosphere.
From these experiments, both analytical and synthetic, we can now confidently say that we have determined, as clearly as possible in physical or chemical matters, that water is not a simple elemental substance, but is made up of two elements, oxygen and hydrogen. These elements, when they exist separately, have such a strong attraction for heat that they can only exist as gas under the normal temperature and pressure of our atmosphere.
This decomposition and recomposition of water is perpetually operating before our eyes, in the temperature of the atmosphere, by means of compound elective attraction. We shall presently see that the phenomena attendant upon vinous fermentation, putrefaction, and even vegetation, are produced, at least in a certain degree, by decomposition of water. It is very extraordinary that this fact should have hitherto been overlooked by natural philosophers and chemists: Indeed, it strongly proves, that, in chemistry, as in moral philosophy, it is extremely difficult to overcome prejudices imbibed in early education, and to search for truth in any other road than the one we have been accustomed to follow.[Pg 96]
This breaking down and reassembling of water happens continuously right in front of us, influenced by the temperature of the atmosphere and through selective attraction. We'll soon see that the processes involved in wine fermentation, decay, and even plant growth are caused, at least to some extent, by the breakdown of water. It’s quite remarkable that this fact has been overlooked by scientists and chemists until now: it really shows that, in chemistry, just like in moral philosophy, it's very hard to shake off the biases learned in early education and to seek the truth through paths other than the ones we’ve always followed.[Pg 96]
I shall finish this chapter by an experiment much less demonstrative than those already related, but which has appeared to make more impression than any other upon the minds of many people. When 16 ounces of alkohol are burnt in an apparatus[21] properly adapted for collecting all the water disengaged during the combustion, we obtain from 17 to 18 ounces of water. As no substance can furnish a product larger than its original bulk, it follows, that something else has united with the alkohol during its combustion; and I have already shown that this must be oxygen, or the base of air. Thus alkohol contains hydrogen, which is one of the elements of water; and the atmospheric air contains oxygen, which is the other element necessary to the composition of water. This experiment is a new proof that water is a compound substance.
I’ll wrap up this chapter with an experiment that’s less flashy than the ones I’ve already shared, but it seems to leave a bigger impact on many people. When you burn 16 ounces of alcohol in a properly set-up apparatus[21], you get about 17 to 18 ounces of water. Since no substance can produce a product greater than its original amount, this means that something else must have combined with the alcohol during combustion; and I’ve already explained that this must be oxygen, or the component of air. So, alcohol contains hydrogen, which is one of the elements of water, and the air contains oxygen, which is the other element needed to make water. This experiment provides further evidence that water is a compound substance.
FOOTNOTES:
[16] In the latter part of this work will be found a particular account of the processes necessary for separating the different kinds of gasses, and for determining their quantities.—A.
[16] In the later sections of this work, you'll find a detailed description of the methods used to separate different types of gases and measure their quantities.—A.
[17] This expression Hydrogen has been very severely criticised by some, who pretend that it signifies engendered by water, and not that which engenders water. The experiments related in this chapter prove, that, when water is decomposed, hydrogen is produced, and that, when hydrogen is combined with oxygen, water is produced: So that we may say, with equal truth, that water is produced from hydrogen, or hydrogen is produced from water.—A.
[17] The term Hydrogen has faced harsh criticism from some people, who argue that it means something created by water, rather than that which creates water. The experiments discussed in this chapter demonstrate that when water is broken down, hydrogen is generated, and when hydrogen combines with oxygen, water is formed. Therefore, we can accurately say that water comes from hydrogen, or hydrogen comes from water.—A.
[19] By potash is here meant, pure or caustic alkali, deprived of carbonic acid by means of quick-lime: In general, we may observe here, that all the alkalies and earths must invariably be considered as in their pure or caustic state, unless otherwise expressed.—E. The method of obtaining this pure alkali of potash will be given in the sequel.—A.
[19] By potash, we mean pure or caustic alkali, free of carbonic acid through the use of quicklime. Generally, we should note that all alkalies and earths should always be regarded as being in their pure or caustic form, unless stated otherwise.—E. The process for obtaining this pure alkali of potash will be provided later.—A.
CHAP. IX.
Of the quantities of Caloric disengaged from different species of Combustion.
We have already mentioned, that, when any body is burnt in the center of a hollow sphere of ice and supplied with air at the temperature of zero (32°), the quantity of ice melted from the inside of the sphere becomes a measure of the relative quantities of caloric disengaged. Mr de la Place and I gave a description of the apparatus employed for this kind of experiment in the Memoirs of the Academy for 1780, p. 355; and a description and plate of the same apparatus will be found in the third part of this work. With this apparatus, phosphorus, charcoal, and hydrogen gas, gave the following results:
We already mentioned that when something is burned in the center of a hollow ice sphere and supplied with air at zero degrees (32°F), the amount of ice melted from the inside of the sphere becomes a measure of the relative quantities of heat released. Mr. de la Place and I described the apparatus used for this type of experiment in the Memoirs of the Academy for 1780, p. 355; and a description and illustration of the same apparatus can be found in the third part of this work. Using this apparatus, phosphorus, charcoal, and hydrogen gas produced the following results:
One pound of phosphorus melted 100 libs. of ice.
One pound of phosphorus melted 100 lbs. of ice.
One pound of charcoal melted 96 libs. 8 oz.
One pound of charcoal melted 96 lbs. 8 oz.
One pound of hydrogen gas melted 295 libs. 9 oz. 3-1/2 gros.
One pound of hydrogen gas weighed 295 lbs. 9 oz. 3-1/2 gros.
As a concrete acid is formed by the combustion of phosphorus, it is probable that very little caloric remains in the acid, and, consequently,[Pg 98] that the above experiment gives us very nearly the whole quantity of caloric contained in the oxygen gas. Even if we suppose the phosphoric acid to contain a good deal of caloric, yet, as the phosphorus must have contained nearly an equal quantity before combustion, the error must be very small, as it will only consist of the difference between what was contained in the phosphorus before, and in the phosphoric acid after combustion.
As a concrete acid forms from burning phosphorus, it's likely that very little heat is left in the acid. Therefore,[Pg 98] the experiment mentioned above likely accounts for almost all the heat present in the oxygen gas. Even if we assume that phosphoric acid holds a significant amount of heat, since the phosphorus must have had almost the same amount before it was burned, the discrepancy should be minimal. It will only reflect the difference between what was in the phosphorus beforehand and what is in the phosphoric acid afterward.
I have already shown in Chap. V. that one pound of phosphorus absorbs one pound eight ounces of oxygen during combustion; and since, by the same operation, 100 lib. of ice are melted, it follows, that the quantity of caloric contained in one pound of oxygen gas is capable of melting 66 libs. 10 oz. 5 gros 24 grs. of ice.
I already demonstrated in Chapter V that one pound of phosphorus absorbs one pound eight ounces of oxygen when it burns; and since this same process melts 100 pounds of ice, it follows that the amount of heat contained in one pound of oxygen gas can melt 66 pounds 10 ounces 5 gros 24 grains of ice.
One pound of charcoal during combustion melts only 96 libs. 8 oz. of ice, whilst it absorbs 2 libs. 9 oz. 1 gros 10 grs. of oxygen. By the experiment with phosphorus, this quantity of oxygen gas ought to disengage a quantity of caloric sufficient to melt 171 libs. 6 oz. 5 gros of ice; consequently, during this experiment, a quantity of caloric, sufficient to melt 74 libs. 14 oz. 5 gros of ice disappears. Carbonic acid is not, like phosphoric acid, in a concrete state after combustion but in the state of gas, and requires to be united with caloric to enable it to[Pg 99] subsist in that state; the quantity of caloric missing in the last experiment is evidently employed for that purpose. When we divide that quantity by the weight of carbonic acid, formed by the combustion of one pound of charcoal, we find that the quantity of caloric necessary for changing one pound of carbonic acid from the concrete to the gasseous state, would be capable of melting 20 libs. 15 oz. 5 gros of ice.
One pound of charcoal, when burned, melts only 96 lbs. 8 oz. of ice, while it absorbs 2 lbs. 9 oz. 1 gros 10 grs. of oxygen. According to the experiment with phosphorus, this amount of oxygen gas should release enough heat to melt 171 lbs. 6 oz. 5 gros of ice; therefore, during this experiment, a quantity of heat sufficient to melt 74 lbs. 14 oz. 5 gros of ice is lost. Carbonic acid, unlike phosphoric acid, is not solid after burning but exists as a gas and needs heat to remain in that state; the amount of heat missing in the last experiment is clearly used for that purpose. When we divide that amount by the weight of carbonic acid formed by burning one pound of charcoal, we find that the heat required to change one pound of carbonic acid from solid to gas would be enough to melt 20 lbs. 15 oz. 5 gros of ice.
We may make a similar calculation with the combustion of hydrogen gas and the consequent formation of water. During the combustion of one pound of hydrogen gas, 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas are absorbed, and 295 libs. 9 oz. 3-1/2 gros of ice are melted. But 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas, in changing from the aëriform to the solid state, loses, according to the experiment with phosphorus, enough of caloric to have melted 377 libs. 12 oz. 3 gros of ice. There is only disengaged, from the same quantity of oxygen, during its combustion with hydrogen gas, as much caloric as melts 295 libs. 2 oz. 3-1/2 gros; wherefore there remains in the water at Zero (32°), formed, during this experiment, as much caloric as would melt 82 libs. 9 oz. 7-1/2 gros of ice.
We can make a similar calculation with the burning of hydrogen gas and the resulting formation of water. During the burning of one pound of hydrogen gas, 5 lbs. 10 oz. 5 grains 24 gr. of oxygen gas are used up, and 295 lbs. 9 oz. 3-1/2 grains of ice are melted. However, 5 lbs. 10 oz. 5 grains 24 gr. of oxygen gas, when changing from gas to solid, loses, according to the experiment with phosphorus, enough heat to melt 377 lbs. 12 oz. 3 grains of ice. During its combustion with hydrogen gas, the same amount of oxygen releases enough heat to melt only 295 lbs. 2 oz. 3-1/2 grains; therefore, there is in the water at Zero (32°), created during this experiment, enough heat to melt 82 lbs. 9 oz. 7-1/2 grains of ice.
Hence, as 6 libs. 10 oz. 5 gros 24 grs. of water are formed from the combustion of one pound of hydrogen gas with 5 libs. 10 oz. 5 gros 24 grs. of oxygen, it follows that, in each[Pg 100] pound of water, at the temperature of Zero, (32°), there exists as much caloric as would melt 12 libs. 5 oz. 2 gros 48 grs. of ice, without taking into account the quantity originally contained in the hydrogen gas, which we have been obliged to omit, for want of data to calculate its quantity. From this it appears that water, even in the state of ice, contains a considerable quantity of caloric, and that oxygen, in entering into that combination, retains likewise a good proportion.
Hence, since 6 lbs. 10 oz. 5 gros 24 grs. of water are produced from the combustion of one pound of hydrogen gas with 5 lbs. 10 oz. 5 gros 24 grs. of oxygen, it follows that in each [Pg 100] pound of water, at a temperature of Zero (32°), there is enough heat to melt 12 lbs. 5 oz. 2 gros 48 grs. of ice, not including the amount originally contained in the hydrogen gas, which we have had to leave out due to lack of data to calculate its quantity. This shows that water, even in its ice form, holds a significant amount of heat, and that oxygen, when forming that combination, also retains a good amount.
From these experiments, we may assume the following results as sufficiently established.
From these experiments, we can assume the following results are firmly established.
Combustion of Phosphorus.
From the combustion of phosphorus, as related in the foregoing experiments, it appears, that one pound of phosphorus requires 1 lib. 8 oz. of oxygen gas for its combustion, and that 2 libs. 8 oz. of concrete phosphoric acid are produced.
From the burning of phosphorus, as described in the earlier experiments, it seems that one pound of phosphorus needs 1 lb. 8 oz. of oxygen gas to burn, and that 2 lbs. 8 oz. of solid phosphoric acid are produced.
The quantity of caloric disengaged by the combustion of one pound of phosphorus, expressed by the number of pounds of ice melted during that operation, is | 100.00000. |
The quantity disengaged from each pound of oxygen, during the combustion of phosphorus, expressed in the same manner, is | 66.66667. |
The quantity disengaged during the formation of one pound of phosphoric acid, | 40.00000. |
The quantity remaining in each pound of phosphoric acid, | 0.00000(A). |
[Note A: We here suppose the phosphoric acid not to contain any caloric, which is not strictly true; but, as I have before observed, the quantity it really contains is probably very small, and we have not given it a value, for want of a sufficient data to go upon.—A.][Pg 101]
[Note A: We assume that the phosphoric acid doesn’t contain any heat energy, which isn’t entirely accurate; however, as mentioned earlier, the amount it actually contains is likely minimal, and we haven’t assigned it a value due to insufficient data.—A.][Pg 101]
Combustion of Charcoal.
In the combustion of one pound of charcoal, 2 libs. 9 oz. 1 gros 10 grs. of oxygen gas are absorbed, and 3 libs. 9 oz. 1 gros 10 grs. of carbonic acid gas are formed.
In the burning of one pound of charcoal, 2 lbs. 9 oz. 1 gros 10 grs. of oxygen gas are taken in, and 3 lbs. 9 oz. 1 gros 10 grs. of carbon dioxide are produced.
Caloric, disengaged daring the combustion of one pound of charcoal, | 96.50000(A). |
Caloric disengaged during the combustion of charcoal, from each pound of oxygen gas absorbed, | 37.52823. |
Caloric disengaged during the formation of one pound of carbonic acid gas, | 27.02024. |
Caloric retained by each pound of oxygen after the combustion, | 29.13844. |
Caloric necessary for supporting one pound of carbonic acid in the state of gas, | 20.97960. |
[Note A: All these relative quantities of caloric are expressed by the number of pounds of ice, and decimal parts, melted during the several operations.—E.][Pg 102]
[Note A: All these quantities of heat are measured in pounds of ice, including decimal parts, that are melted during the various processes.—E.][Pg 102]
Combustion of Hydrogen Gas.
In the combustion of one pound of hydrogen gas, 5 libs. 10 oz. 5 gros 24 grs. of oxygen gas are absorbed, and 6 libs. 10 oz. 5 gros 24 grs. of water are formed.
In the combustion of one pound of hydrogen gas, 5 lbs. 10 oz. 5 gros 24 grs. of oxygen gas are absorbed, and 6 lbs. 10 oz. 5 gros 24 grs. of water are formed.
Caloric from each lib. of hydrogen gas, | 295.58950. |
Caloric from each lib. of oxygen gas, | 52.16280. |
Caloric disengaged during the formation of each pound of water, | 44.33840. |
Caloric retained by each lib. of oxygen after combustion with hydrogen, | 14.50386. |
Caloric retained by each lib. of water at the temperature of Zero (32°), | 12.32823. |
Of the Formation of Nitric Acid.
When we combine nitrous gas with oxygen gas, so as to form nitric or nitrous acid a degree of heat is produced, which is much less considerable than what is evolved during the other combinations of oxygen; whence it follows that oxygen, when it becomes fixed in nitric acid, retains a great part of the heat which it possessed[Pg 103] in the state of gas. It is certainly possible to determine the quantity of caloric which is disengaged during the combination of these two gasses, and consequently to determine what quantity remains after the combination takes place. The first of these quantities might be ascertained, by making the combination of the two gasses in an apparatus surrounded by ice; but, as the quantity of caloric disengaged is very inconsiderable, it would be necessary to operate upon a large quantity of the two gasses in a very troublesome and complicated apparatus. By this consideration, Mr de la Place and I have hitherto been prevented from making the attempt. In the mean time, the place of such an experiment may be supplied by calculations, the results of which cannot be very far from truth.
When we mix nitrous gas with oxygen gas to create nitric or nitrous acid, a small amount of heat is released, which is much less than what is produced in other oxygen combinations. This indicates that when oxygen becomes part of nitric acid, it keeps a significant amount of the heat it had as a gas[Pg 103]. It's definitely possible to measure the amount of heat released during the combination of these two gases, allowing us to figure out how much heat remains after they combine. We could measure the heat released by combining the gases in an ice-cooled setup, but since the amount of heat emitted is quite small, we'd need to work with a large volume of both gases in a complex and cumbersome apparatus. Because of this, Mr. de la Place and I have not yet attempted the experiment. In the meantime, we can use calculations to replace the experiment, and the results should be fairly accurate.
Mr de la Place and I deflagrated a convenient quantity of nitre and charcoal in an ice apparatus, and found that twelve pounds of ice were melted by the deflagration of one pound of nitre. We shall see, in the sequel, that one pound of nitre is composed, as under, of
Mr. de la Place and I ignited a suitable amount of saltpeter and charcoal in an ice setup, and discovered that twelve pounds of ice melted when one pound of saltpeter was ignited. We will see later that one pound of saltpeter is made up, as follows, of
Potash | 7 oz. | 6 gros | 51.84 grs. | = | 4515.84 grs. |
Dry acid | 8 | 1 | 21.16 | = | 4700.16. |
The above quantity of dry acid is composed of[Pg 104]
The amount of dry acid mentioned above is made up of[Pg 104]
Oxygen | 6 oz. | 3 gros | 66.34 grs. | = | 3738.34 grs. |
Azote | 1 | 5 | 25.82 | = | 961.82. |
By this we find that, during the above deflagration, 2 gros 1-1/3 gr. of charcoal have suffered combustion, alongst with 3738.34 grs. or 6 oz. 3 gros 66.34 grs. of oxygen. Hence, since 12 libs. of ice were melted during the combustion, it follows, that one pound of oxygen burnt in the same manner would have melted 29.58320 libs. of ice. To which the quantity of caloric, retained by a pound of oxygen after combining with charcoal to form carbonic acid gas, being added, which was already ascertained to be capable of melting 29.13844 libs. of ice, we have for the total quantity of caloric remaining in a pound of oxygen, when combined with nitrous gas in the nitric acid 58.72164; which is the number of pounds of ice the caloric remaining in the oxygen in that state is capable of melting.
By this, we find that during the above explosion, 2 gros 1-1/3 gr. of charcoal burned, along with 3738.34 grs. or 6 oz. 3 gros 66.34 grs. of oxygen. Since 12 libs. of ice melted during the combustion, it follows that one pound of oxygen burned in the same way would have melted 29.58320 libs. of ice. When we add the amount of heat retained by a pound of oxygen after it combines with charcoal to form carbonic acid gas, which has already been determined to melt 29.13844 libs. of ice, we find that the total amount of heat remaining in a pound of oxygen, when combined with nitrous gas in nitric acid, is 58.72164; this represents the number of pounds of ice the heat remaining in the oxygen in that state can melt.
We have before seen that, in the state of oxygen gas, it contained at least 66.66667; wherefore it follows that, in combining with azote to form nitric acid, it only loses 7.94502. Farther experiments upon this subject are necessary to ascertain how far the results of this calculation may agree with direct fact. This enormous quantity of caloric retained by oxygen in its combination into nitric acid, explains the[Pg 105] cause of the great disengagement of caloric during the deflagrations of nitre; or, more strictly speaking, upon all occasions of the decomposition of nitric acid.
We've seen before that in the state of oxygen gas, it contained at least 66.66667; therefore, it follows that when it combines with nitrogen to form nitric acid, it only loses 7.94502. Further experiments on this subject are needed to determine how closely the results of this calculation match direct evidence. This huge amount of heat retained by oxygen when it combines into nitric acid explains the[Pg 105] reason for the significant release of heat during the combustion of saltpeter; or, more accurately, during all instances of nitric acid decomposition.
Of the Combustion of Wax.
Having examined several cases of simple combustion, I mean now to give a few examples of a more complex nature. One pound of wax-taper being allowed to burn slowly in an ice apparatus, melted 133 libs. 2 oz. 5-1/3 gros of ice. According to my experiments in the Memoirs of the Academy for 1784, p. 606, one pound of wax-taper consists of 13 oz. 1 gros 23 grs. of charcoal, and 2 oz. 6 gros 49 grs. of hydrogen.
Having looked at several cases of simple combustion, I now want to provide a few examples that are more complex. One pound of wax candle, when allowed to burn slowly in an ice apparatus, melted 133 lbs. 2 oz. 5-1/3 gros of ice. According to my experiments published in the Memoirs of the Academy for 1784, p. 606, one pound of wax candle contains 13 oz. 1 gros 23 grs. of charcoal, and 2 oz. 6 gros 49 grs. of hydrogen.
By the foregoing experiments, the above quantity of charcoal ought to melt | 79.39390 libs. of ice; |
and the hydrogen should melt | 52.37605 |
———— | |
In all | 131.76995 libs. |
Thus, we see the quantity of caloric disengaged from a burning taper, is pretty exactly conformable to what was obtained by burning separately a quantity of charcoal and hydrogen[Pg 106] equal to what enters into its composition. These experiments with the taper were several times repeated, so that I have reason to believe them accurate.
Thus, we see that the amount of heat released from a burning candle is closely aligned with what was measured by separately burning the same amount of charcoal and hydrogen that make up its composition. These experiments with the candle were repeated several times, so I have reason to believe they are accurate.[Pg 106]
Combustion of Olive Oil.
We included a burning lamp, containing a determinate quantity of olive-oil, in the ordinary apparatus, and, when the experiment was finished, we ascertained exactly the quantities of oil consumed, and of ice melted; the result was, that, during the combustion of one pound of olive-oil, 148 libs. 14 oz. 1 gros of ice were melted. By my experiments in the Memoirs of the Academy for 1784, and of which the following Chapter contains an abstract, it appears that one pound of olive-oil consists of 12 oz. 5 gros 5 grs. of charcoal, and 3 oz. 2 gros 67 grs. of hydrogen. By the foregoing experiments, that quantity of charcoal should melt 76.18723 libs. of ice, and the quantity of hydrogen in a pound of the oil should melt 62.15053 libs. The sum of these two gives 138.33776 libs. of ice, which the two constituent elements of the oil would have melted, had they separately suffered combustion, whereas the oil really melted 148.88330 libs. which gives an excess of 10.54554 in the result of the experiment[Pg 107] above the calculated result, from data furnished by former experiments.
We added a burning lamp filled with a specific amount of olive oil to the regular setup, and after finishing the experiment, we measured exactly how much oil was used and how much ice melted. The result showed that burning one pound of olive oil melted 148 libs. 14 oz. 1 gros of ice. According to my experiments published in the Memoirs of the Academy for 1784, summarized in the following chapter, one pound of olive oil contains 12 oz. 5 gros 5 grs. of charcoal and 3 oz. 2 gros 67 grs. of hydrogen. Based on these experiments, that amount of charcoal should melt 76.18723 libs. of ice, and the hydrogen in one pound of oil should melt 62.15053 libs.. Adding these two amounts gives a total of 138.33776 libs. of ice that the individual elements of the oil would have melted if they burned separately. However, the oil actually melted 148.88330 libs., resulting in an excess of 10.54554 above the calculated amount based on previous experiments.[Pg 107]
This difference, which is by no means very considerable, may arise from errors which are unavoidable in experiments of this nature, or it may be owing to the composition of oil not being as yet exactly ascertained. It proves, however, that there is a great agreement between the results of our experiments, respecting the combination of caloric, and those which regard its disengagement.
This difference, although not very significant, may come from unavoidable errors in experiments like this, or it could be due to the composition of oil not being precisely determined yet. However, it shows that there is a strong consistency between our experimental results regarding the combination of heat and those concerning its release.
The following desiderata still remain to be determined, viz. What quantity of caloric is retained by oxygen, after combining with metals, so as to convert them into oxyds; What quantity is contained by hydrogen, in its different states of existence; and to ascertain, with more precision than is hitherto attained, how much caloric is disengaged during the formation of water, as there still remain considerable doubts with respect to our present determination of this point, which can only be removed by farther experiments. We are at present occupied with this inquiry; and, when once these several points are well ascertained, which we hope they will soon be, we shall probably be under the necessity of making considerable corrections upon most of the results of the experiments and calculations in this Chapter. I did not, however, consider this as a sufficient reason for withholding[Pg 108] so much as is already known from such as may be inclined to labour upon the same subject. It is difficult, in our endeavours to discover the principles of a new science, to avoid beginning by guess-work; and it is rarely possible to arrive at perfection from the first setting out.
The following questions still need to be answered: How much heat is retained by oxygen after it reacts with metals to form oxides? What amount is found in hydrogen in its various states? And we need to determine more accurately than we currently can how much heat is released during the formation of water, as there are still significant uncertainties regarding our current understanding of this, which can only be resolved through further experiments. We are currently focused on this inquiry, and once we clarify these points, which we hope will happen soon, we will likely need to make significant corrections to most of the results from the experiments and calculations in this chapter. However, I didn't think this was a good reason to hold back[Pg 108] what is already known from those who might be interested in working on the same topic. It’s challenging, in our efforts to uncover the principles of a new science, to avoid starting with guesswork, and it’s rarely possible to achieve perfection right from the beginning.
CHAP. X.
Of the Combination of Combustible Substances with each other.
As combustible substances in general have a great affinity for oxygen, they ought likewise to attract, or tend to combine with each other; quae sunt eadem uni tertio, sunt eadem inter se; and the axiom is found to be true. Almost all the metals, for instance, are capable of uniting with each other, and forming what are called alloys[22], in common language. Most of these, like all combinations, are susceptible of several degrees of saturation; the greater number of these alloys are more brittle than the pure metals of which they are composed, especially when the metals alloyed together are considerably different in their degrees of fusibility. To this difference in fusibility, part of the phenomena attendant upon alloyage are owing, particularly the property of iron, called by workmen[Pg 110] hotshort. This kind of iron must be considered as an alloy, or mixture of pure iron, which is almost infusible, with a small portion of some other metal which fuses in a much lower degree of heat. So long as this alloy remains cold, and both metals are in the solid state, the mixture is malleable; but, if heated to a sufficient degree to liquify the more fusible metal, the particles of the liquid metal, which are interposed between the particles of the metal remaining solid, must destroy their continuity, and occasion the alloy to become brittle. The alloys of mercury, with the other metals, have usually been called amalgams, and we see no inconvenience from continuing the use of that term.
As flammable substances generally have a strong attraction to oxygen, they also tend to attract or combine with one another; quae sunt eadem uni tertio, sunt eadem inter se; and this principle holds true. Almost all metals, for example, can unite with one another to form what are commonly known as alloys[22]. Most of these, like all combinations, can vary in their saturation levels; many of these alloys are more brittle than the pure metals they are made from, especially when the metals being combined have significantly different melting points. This difference in melting points partly explains some of the behaviors observed in alloyage, particularly the property of iron known by workers as[Pg 110] hotshort. This type of iron should be regarded as an alloy, or a mixture of nearly infusible pure iron with a small amount of another metal that melts at a much lower temperature. As long as this alloy remains cold and both metals are solid, the mixture is malleable; however, if it’s heated enough to melt the more fusible metal, the liquid metal particles will disrupt the continuity of the solid particles, causing the alloy to become brittle. Alloys of mercury with other metals have typically been referred to as amalgams, and we see no issue with continuing to use that term.
Sulphur, phosphorus, and charcoal, readily unite with metals. Combinations of sulphur with metals are usually named pyrites. Their combinations with phosphorus and charcoal are either not yet named, or have received new names only of late; so that we have not scrupled to change them according to our principles. The combinations of metal and sulphur we call sulphurets, those with phosphorus phosphurets, and those formed with charcoal carburets. These denominations are extended to all the combinations into which the above three substances enter, without being previously oxygenated.[Pg 111] Thus, the combination of sulphur with potash, or fixed vegetable alkali, is called sulphuret of potash; that which it forms with ammoniac, or volatile alkali, is termed sulphuret of ammoniac.
Sulfur, phosphorus, and charcoal easily bond with metals. Combinations of sulfur with metals are usually called pyrites. Their combinations with phosphorus and charcoal are either unnamed so far or have only recently been given new names, so we haven't hesitated to rename them based on our principles. We refer to the combinations of metal and sulfur as sulfur compounds, those with phosphorus as phosphorus compounds, and those made with charcoal as carbon compounds. These names apply to all combinations involving these three substances that haven't been oxygenated first.[Pg 111] For example, the combination of sulfur with potash, or fixed vegetable alkali, is called sulfur potash; the one it creates with ammonia, or volatile alkali, is called sulfur ammonia.
Hydrogen is likewise capable of combining with many combustible substances. In the state of gas, it dissolves charcoal, sulphur, phosphorus, and several metals; we distinguish these combinations by the terms, carbonated hydrogen gas, sulphurated hydrogen gas, and phosphorated hydrogen gas. The sulphurated hydrogen gas was called hepatic air by former chemists, or foetid air from sulphur, by Mr Scheele. The virtues of several mineral waters, and the foetid smell of animal excrements, chiefly arise from the presence of this gas. The phosphorated hydrogen gas is remarkable for the property, discovered by Mr Gengembre, of taking fire spontaneously upon getting into contact with atmospheric air, or, what is better, with oxygen gas. This gas has a strong flavour, resembling that of putrid fish; and it is very probable that the phosphorescent quality of fish, in the state of putrefaction, arises from the escape of this species of gas. When hydrogen and charcoal are combined together, without the intervention of caloric, to bring the hydrogen into the state of gas, they form oil, which is either fixed or volatile, according to the proportions of hydrogen and[Pg 112] charcoal in its composition. The chief difference between fixed or fat oils drawn from vegetables by expression, and volatile or essential oils, is, that the former contains an excess of charcoal, which is separated when the oils are heated above the degree of boiling water; whereas the volatile oils, containing a just proportion of these two constituent ingredients, are not liable to be decomposed by that heat, but, uniting with caloric into the gasseous state, pass over in distillation unchanged.
Hydrogen can also combine with various flammable substances. In its gas state, it dissolves charcoal, sulfur, phosphorus, and several metals; we refer to these combinations as carbonated hydrogen gas, sulphurated hydrogen gas, and phosphorated hydrogen gas. Sulphurated hydrogen gas was previously known as hepatic air by earlier chemists, or foetid air from sulphur, according to Mr. Scheele. The benefits of some mineral waters and the unpleasant smell of animal waste mainly come from this gas. Phosphorated hydrogen gas is notable for its ability, discovered by Mr. Gengembre, to ignite spontaneously upon contact with atmospheric air, or even better, with oxygen gas. This gas has a strong odor that resembles rotten fish, and it's highly likely that the phosphorescent quality found in decaying fish comes from the release of this type of gas. When hydrogen and charcoal are combined without heat being applied to turn hydrogen into gas, they create oil, which can be either fixed or volatile depending on the hydrogen and charcoal proportions in its makeup. The main difference between fixed or fatty oils extracted from plants and volatile or essential oils is that the former contains more charcoal, which gets separated when the oils are heated beyond the boiling point of water; while the volatile oils, which have the right proportions of these two components, do not break down under that heat. Instead, they combine with heat to become gaseous and pass over unchanged during distillation.
In the Memoirs of the Academy for 1784, p. 593. I gave an account of my experiments upon the composition of oil and alkohol, by the union of hydrogen with charcoal, and of their combination with oxygen. By these experiments, it appears that fixed oils combine with oxygen during combustion, and are thereby converted into water and carbonic acid. By means of calculation applied to the products of these experiments, we find that fixed oil is composed of 21 parts, by weight, of hydrogen combined with 79 parts of charcoal. Perhaps the solid substances of an oily nature, such as wax, contain a proportion of oxygen, to which they owe their state of solidity. I am at present engaged in a series of experiments, which I hope will throw great light upon this subject.
In the Memoirs of the Academy for 1784, p. 593, I discussed my experiments on the makeup of oil and alcohol, focusing on how hydrogen joins with charcoal and their reaction with oxygen. These experiments show that fixed oils react with oxygen during combustion, turning into water and carbon dioxide. Through calculations based on the results of these experiments, we find that fixed oil consists of 21 parts by weight of hydrogen combined with 79 parts of charcoal. It's possible that solid substances with oily qualities, like wax, contain some oxygen, which contributes to their solidity. I'm currently working on a series of experiments that I believe will provide significant insights into this topic.
It is worthy of being examined, whether hydrogen in its concrete state, uncombined with[Pg 113] caloric, be susceptible of combination with sulphur, phosphorus, and the metals. There is nothing that we know of, which, a priori, should render these combinations impossible; for combustible bodies being in general susceptible of combination with each other, there is no evident reason for hydrogen being an exception to the rule: However, no direct experiment as yet establishes either the possibility or impossibility of this union. Iron and zinc are the most likely, of all the metals, for entering into combination with hydrogen; but, as these have the property of decomposing water, and as it is very difficult to get entirely free from moisture in chemical experiments, it is hardly possible to determine whether the small portions of hydrogen gas, obtained in certain experiments with these metals, were previously combined with the metal in the state of solid hydrogen, or if they were produced by the decomposition of a minute quantity of water. The more care we take to prevent the presence of water in these experiments, the less is the quantity of hydrogen gas procured; and, when very accurate precautions are employed, even that quantity becomes hardly sensible.
It's worth investigating whether hydrogen in its pure form, without being combined with[Pg 113] heat, can combine with sulfur, phosphorus, and the metals. There's nothing we know that should make these combinations impossible because combustible substances generally tend to combine with one another, so there's no clear reason why hydrogen would be an exception. However, no direct experiment has yet shown whether this combination is possible or impossible. Iron and zinc are the most likely metals to combine with hydrogen, but since these metals can break down water, and it's very hard to completely eliminate moisture in chemical experiments, it’s difficult to determine whether the small amounts of hydrogen gas obtained from certain experiments with these metals were previously combined with the metal as solid hydrogen or produced by breaking down a tiny amount of water. The more effort we make to eliminate water from these experiments, the less hydrogen gas we obtain; and when very precise precautions are taken, even that amount becomes hardly noticeable.
However this inquiry may turn out respecting the power of combustible bodies, as sulphur, phosphorus, and metals, to absorb hydrogen, we are certain that they only absorb a very small[Pg 114] portion; and that this combination, instead of being essential to their constitution, can only be considered as a foreign substance, which contaminates their purity. It is the province of the advocates[23] for this system to prove, by decisive experiments, the real existence of this combined hydrogen, which they have hitherto only done by conjectures founded upon suppositions.
However this inquiry turns out regarding the ability of combustible materials, like sulfur, phosphorus, and metals, to absorb hydrogen, we know that they only take in a very small[Pg 114] amount; and that this combination, instead of being essential to their nature, should be seen as an external substance that compromises their purity. It is up to the supporters[23] of this system to demonstrate, through conclusive experiments, the actual existence of this combined hydrogen, which they have so far only suggested through theories based on assumptions.
FOOTNOTES:
[22] This term alloy, which we have from the language of the arts, serves exceedingly well for distinguishing all the combinations or intimate unions of metals with each other, and is adopted in our new nomenclature for that purpose.—A.
[22] The term alloy, which comes from the language of the arts, is perfect for identifying all the combinations or close unions of metals with one another, and it has been used in our new naming system for that purpose.—A.
[23] By these are meant the supporters of the phlogistic theory, who at present consider hydrogen, or the base of inflammable air, as the phlogiston of the celebrated Stahl.—E.
[23] This refers to the proponents of the phlogistic theory, who currently view hydrogen, or the base of flammable gas, as the phlogiston described by the famous Stahl.—E.
CHAP. XI.
Observations upon Oxyds and Acids with several Bases—and upon the Composition of Animal and Vegetable Substances.
We have, in Chap. V. and VIII. examined the products resulting from the combustion of the four simple combustible substances, sulphur, phosphorus, charcoal, and hydrogen: We have shown, in Chap. X that the simple combustible substances are capable of combining with each other into compound combustible substances, and have observed that oils in general, and particularly the fixed vegetable oils, belong to this class, being composed of hydrogen and charcoal. It remains, in this chapter, to treat of the oxygenation of these compound combustible substances, and to show that there exist acids and oxyds having double and triple bases. Nature furnishes us with numerous examples of this kind of combinations, by means of which, chiefly, she is enabled to produce a vast variety of compounds from a very limited number of elements, or simple substances.[Pg 116]
In Chapters V and VIII, we've looked into the products generated from burning four basic flammable substances: sulfur, phosphorus, charcoal, and hydrogen. We've demonstrated in Chapter X that these simple flammable substances can combine with each other to form compound flammable substances. We've noted that oils, especially fixed vegetable oils, fall into this category, as they are made up of hydrogen and charcoal. In this chapter, we will discuss the oxygenation of these compound flammable substances and show that there are acids and oxides with double and triple bases. Nature provides us with many examples of this type of combination, which allows her to create a wide variety of compounds from a small number of elements or simple substances.[Pg 116]
It was long ago well known, that, when muriatic and nitric acids were mixed together, a compound acid was formed, having properties quite distinct from those of either of the acids taken separately. This acid was called aqua regia, from its most celebrated property of dissolving gold, called king of metals by the alchymists. Mr Berthollet has distinctly proved that the peculiar properties of this acid arise from the combined action of its two acidifiable bases; and for this reason we have judged it necessary to distinguish it by an appropriate name: That of nitro-muriatic acid appears extremely applicable, from its expressing the nature of the two substances which enter into its composition.
It has been well known for a long time that when muriatic and nitric acids are mixed together, they create a compound acid with properties that are quite different from those of each acid on its own. This acid is called aqua regia, named for its well-known ability to dissolve gold, referred to as the king of metals by alchemists. Mr. Berthollet has clearly demonstrated that the unique properties of this acid result from the combined action of its two acidifying components; for this reason, we believe it’s important to give it a suitable name: nitro-muriatic acid seems very fitting, as it reflects the nature of the two substances that make up its composition.
This phenomenon of a double base in one acid, which had formerly been observed only in the nitro-muriatic acid, occurs continually in the vegetable kingdom, in which a simple acid, or one possessed of a single acidifiable base, is very rarely found. Almost all the acids procurable from this kingdom have bases composed of charcoal and hydrogen, or of charcoal, hydrogen, and phosphorus, combined with more or less oxygen. All these bases, whether double or triple, are likewise formed into oxyds, having less oxygen than is necessary to give them the properties of acids. The acids and oxyds from the animal kingdom are still more compound, as their bases generally consist of a combination[Pg 117] of charcoal, phosphorus, hydrogen, and azote.
This phenomenon of having two bases in one acid, which was previously noted only in nitro-muriatic acid, frequently occurs in the plant kingdom, where a simple acid or one with just a single base is rarely found. Almost all the acids obtained from this realm have bases made up of carbon and hydrogen, or carbon, hydrogen, and phosphorus, combined with varying amounts of oxygen. All these bases, whether double or triple, are also formed into oxides, having less oxygen than what’s needed to give them the properties of acids. The acids and oxides from the animal kingdom are even more complex, as their bases typically consist of a combination[Pg 117] of carbon, phosphorus, hydrogen, and nitrogen.
As it is but of late that I have acquired any clear and distinct notions of these substances, I shall not, in this place, enlarge much upon the subject, which I mean to treat of very fully in some memoirs I am preparing to lay before the Academy. Most of my experiments are already performed; but, to be able to give exact reports of the resulting quantities, it is necessary that they be carefully repeated, and increased in number: Wherefore, I shall only give a short enumeration of the vegetable and animal acids and oxyds, and terminate this article by a few reflections upon the composition of vegetable and animal bodies.
Since I have only recently gained a clear understanding of these substances, I won’t go into great detail about the topic here. I plan to discuss it thoroughly in some papers I’m preparing to present to the Academy. Most of my experiments are already done; however, to provide accurate reports of the resulting quantities, I need to repeat them carefully and increase their number. Therefore, I will only provide a brief list of the vegetable and animal acids and oxides, and I’ll conclude this article with a few thoughts on the composition of plant and animal bodies.
Sugar, mucus, under which term we include the different kinds of gums, and starch, are vegetable oxyds, having hydrogen and charcoal combined, in different proportions, as their radicals or bases, and united with oxygen, so as to bring them to the state of oxyds. From the state of oxyds they are capable of being changed into acids by the addition of a fresh quantity of oxygen; and, according to the degrees of oxygenation, and the proportion of hydrogen and charcoal in their bases, they form the several kinds of vegetable acids.
Sugar, mucus—which includes various types of gums—and starch are plant-based compounds made up of hydrogen and carbon in different amounts, combined with oxygen to form oxides. These oxides can be converted into acids by adding more oxygen, leading to different types of plant acids based on the level of oxygenation and the ratio of hydrogen and carbon in their structures.
It would be easy to apply the principles of our nomenclature to give names to these vegetable[Pg 118] acids and oxyds, by using the names of the two substances which compose their bases: They would thus become hydro-carbonous acids and oxyds: In this method we might indicate which of their elements existed in excess, without circumlocution, after the manner used by Mr Rouelle for naming vegetable extracts: He calls these extracto-resinous when the extractive matter prevails in their composition, and resino-extractive when they contain a larger proportion of resinous matter. Upon that plan, and by varying the terminations according to the formerly established rules of our nomenclature, we have the following denominations: Hydro-carbonous, hydro-carbonic; carbono-hydrous, and carbono-hydric oxyds. And for the acids: Hydro-carbonous, hydro carbonic, oxygenated hydro-carbonic; carbono-hydrous, carbono-hydric, and oxygenated carbono-hydric. It is probable that the above terms would suffice for indicating all the varieties in nature, and that, in proportion as the vegetable acids become well understood, they will naturally arrange themselves under these denominations. But, though we know the elements of which these are composed, we are as yet ignorant of the proportions of these ingredients, and are still far from being able to class them in the above methodical manner; wherefore, we have determined to retain[Pg 119] the ancient names provisionally. I am somewhat farther advanced in this inquiry than at the time of publishing our conjunct essay upon chemical nomenclature; yet it would be improper to draw decided consequences from experiments not yet sufficiently precise: Though I acknowledge that this part of chemistry still remains in some degree obscure, I must express my expectations of its being very soon elucidated.
It would be easy to apply our naming principles to give names to these plant-based[Pg 118] acids and oxides by using the names of the two substances that make up their bases. They would then be called hydro-carbonous acids and oxides. This method would allow us to indicate which of their elements was in excess, straightforwardly, similar to how Mr. Rouelle names plant extracts: He calls them extracto-resinous when the extractive matter is dominant and resino-extractive when they have more resinous matter. Following that plan and adjusting the endings according to our established naming rules, we arrive at the following names: Hydro-carbonous, hydro-carbonic; carbono-hydrous, and carbono-hydric oxides. For the acids, we have: Hydro-carbonous, hydro-carbonic, oxygenated hydro-carbonic; carbono-hydrous, carbono-hydric, and oxygenated carbono-hydric. These terms would likely be enough to describe all the varieties found in nature, and as we better understand vegetable acids, they will naturally fall into these categories. However, even though we know the elements that make them up, we still don't know the proportions of these components and are far from being able to categorize them methodically. Therefore, we've decided to keep[Pg 119] the old names for now. I am somewhat further along in this inquiry than I was when we published our joint essay on chemical nomenclature, yet it would be inappropriate to draw firm conclusions from experiments that aren’t precise enough. While I recognize that this area of chemistry is still somewhat unclear, I do expect it will soon be clarified.
I am still more forcibly necessitated to follow the same plan in naming the acids, which have three or four elements combined in their bases; of these we have a considerable number from the animal kingdom, and some even from vegetable substances. Azote, for instance, joined to hydrogen and charcoal, form the base or radical of the Prussic acid; we have reason to believe that the same happens with the base of the Gallic acid; and almost all the animal acids have their bases composed of azote, phosphorus, hydrogen, and charcoal. Were we to endeavour to express at once all these four component parts of the bases, our nomenclature would undoubtedly be methodical; it would have the property of being clear and determinate; but this assemblage of Greek and Latin substantives and adjectives, which are not yet universally admitted by chemists, would have the appearance of a[Pg 120] barbarous language, difficult both to pronounce and to be remembered. Besides, this part of chemistry being still far from that accuracy it must arrive to, the perfection of the science ought certainly to precede that of its language; and we must still, for some time, retain the old names for the animal oxyds and acids. We have only ventured to make a few slight modifications of these names, by changing the termination into ous, when we have reason to suppose the base to be in excess, and into ic, when we suspect the oxygen predominates.
I am still more strongly compelled to follow the same approach in naming the acids that have three or four elements combined in their bases; we have many of these from the animal kingdom, and some even from plant sources. For example, nitrogen combined with hydrogen and carbon forms the base or radical of prussic acid; we believe the same is true for gallic acid's base; and almost all animal acids have bases made up of nitrogen, phosphorus, hydrogen, and carbon. If we tried to express all these four components of the bases at once, our naming system would certainly be systematic; it would be clear and specific. However, this mix of Greek and Latin nouns and adjectives, which chemists do not yet universally accept, would come off as a[Pg 120] confusing language, hard to pronounce and remember. Moreover, since this part of chemistry is still far from the accuracy it needs to achieve, the advancement of the science should certainly come before the refinement of its language; and for now, we must continue to use the old names for the animal oxides and acids. We have only made a few slight changes to these names, by changing the ending to ous when we believe the base is in excess, and to ic when we suspect the oxygen is predominant.
The following are all the vegetable acids hitherto known:
The following are all the vegetable acids that have been known so far:
3. Oxalic acid. Tartaric acid.
5. Pyro-tartaric acid.
6. Citric acid. 7. Malic acid. 8. Pyro-mucous acid.
9. Pyroligneous acid.
10. Gallic acid. 11. Benzoic acid. 12. Camphor acid.
Succinic acid.
Though all these acids, as has been already said, are chiefly, and almost entirely, composed of hydrogen, charcoal, and oxygen, yet, properly speaking, they contain neither water carbonic acid nor oil, but only the elements necessary for forming these substances. The power of affinity reciprocally exerted by the hydrogen, charcoal, and oxygen, in these acids, is in a state[Pg 121] of equilibrium only capable of existing in the ordinary temperature of the atmosphere; for, when they are heated but a very little above the temperature of boiling water, this equilibrium is destroyed, part of the oxygen and hydrogen unite, and form water; part of the charcoal and hydrogen combine into oil; part of the charcoal and oxygen unite to form carbonic acid; and, lastly, there generally remains a small portion of charcoal, which, being in excess with respect to the other ingredients, is left free. I mean to explain this subject somewhat farther in the succeeding chapter.
Though all these acids, as mentioned earlier, are mainly made up of hydrogen, carbon, and oxygen, they do not actually contain water, carbonic acid, or oil, but only the elements needed to create these substances. The attractive forces between the hydrogen, carbon, and oxygen in these acids are in a state[Pg 121] of balance that only exists at normal atmospheric temperatures. When heated just a little above the boiling point of water, this balance is disrupted; some of the oxygen and hydrogen combine to form water, some of the carbon and hydrogen form oil, some of the carbon and oxygen create carbonic acid, and finally, a small amount of carbon usually remains, which is in excess compared to the other components and is left free. I plan to explain this topic in more detail in the next chapter.
The oxyds of the animal kingdom are hitherto less known than those from the vegetable kingdom, and their number is as yet not at all determined. The red part of the blood, lymph, and most of the secretions, are true oxyds, under which point of view it is very important to consider them. We are only acquainted with six animal acids, several of which, it is probable, approach very near each other in their nature, or, at least, differ only in a scarcely sensible degree. I do not include the phosphoric acid amongst these, because it is found in all the kingdoms of nature. They are,
The oxides of the animal kingdom are still less understood than those from the plant kingdom, and we have yet to determine their number. The red component of blood, lymph, and most secretions are true oxides, which makes it very important to consider them in this context. We only know of six animal acids, several of which probably have very similar characteristics or differ only minimally. I do not include phosphoric acid in this list because it is found across all kingdoms of nature. They are,
The connection between the constituent elements of the animal oxyds and acids is not more permanent than in those from the vegetable kingdom, as a small increase of temperature is sufficient to overturn it. I hope to render this subject more distinct than has been done hitherto in the following chapter.
The relationship between the main components of animal oxides and acids isn’t any more stable than that of those in the plant kingdom, as even a slight rise in temperature can disrupt it. I aim to clarify this topic more than has been done so far in the following chapter.
CHAP. XII.
Of the Decomposition of Vegetable and Animal Substances by the Action of Fire.
Before we can thoroughly comprehend what takes place during the decomposition of vegetable substances by fire, we must take into consideration the nature of the elements which enter into their composition, and the different affinities which the particles of these elements exert upon each other, and the affinity which caloric possesses with them. The true constituent elements of vegetables are hydrogen, oxygen, and charcoal: These are common to all vegetables, and no vegetable can exist without them: Such other substances as exist in particular vegetables are only essential to the composition of those in which they are found, and do not belong to vegetables in general.
Before we can fully understand what happens during the decomposition of plant materials by fire, we need to consider the nature of the elements that make them up and the different attractions between the particles of these elements, as well as the attraction that heat has with them. The key elements in plants are hydrogen, oxygen, and carbon: these are found in all plants, and no plant can exist without them. Other substances that are present in specific plants are only necessary for the makeup of those particular plants and don't apply to plants in general.
Of these elements, hydrogen and oxygen have a strong tendency to unite with caloric, and be converted into gas, whilst charcoal is a fixed element, having but little affinity with caloric. On the other hand, oxygen, which, in the usual temperature, tends nearly equally to unite with hydrogen and with charcoal, has a much stronger[Pg 124] affinity with charcoal when at the red heat[24], and then unites with it to form carbonic acid.
Of these elements, hydrogen and oxygen easily combine with heat to become gas, while charcoal is a solid element that has little attraction to heat. However, oxygen, which normally tends to bond equally with hydrogen and charcoal at room temperature, has a much stronger affinity for charcoal when it's heated to red-hot temperatures. At that point, it combines with charcoal to create carbon dioxide.[Pg 124]
Although we are far from being able to appreciate all these powers of affinity, or to express their proportional energy by numbers, we are certain, that, however variable they may be when considered in relation to the quantity of caloric with which they are combined, they are all nearly in equilibrium in the usual temperature of the atmosphere; hence vegetables neither contain oil[25], water, nor carbonic acid, tho' they contain all the elements of these substances. The hydrogen is neither combined with the oxygen nor with the charcoal, and reciprocally; the particles of these three substances form a triple combination, which remains in equilibrium[Pg 125] whilst undisturbed by caloric but a very slight increase of temperature is sufficient to overturn this structure of combination.
Although we still can't fully understand all these forces of attraction or quantify their energy with numbers, we know that, despite how much they can change based on the amount of heat they have, they are all pretty much balanced at the typical temperature of the atmosphere. That's why plants don’t have oil[25], water, or carbon dioxide, even though they have all the elements that make up those substances. The hydrogen isn’t combined with the oxygen or the carbon, and vice versa; the particles of these three substances form a triple bond that stays balanced[Pg 125] unless disturbed by heat, but just a small increase in temperature can disrupt this combination.
If the increased temperature to which the vegetable is exposed does not exceed the heat of boiling water, one part of the hydrogen combines with the oxygen, and forms water, the rest of the hydrogen combines with a part of the charcoal, and forms volatile oil, whilst the remainder of the charcoal, being set free from its combination with the other elements, remains fixed in the bottom of the distilling vessel.
If the temperature that the vegetable is subjected to doesn’t go beyond the boiling point of water, one part of the hydrogen mixes with the oxygen to create water, while the rest of the hydrogen combines with some of the charcoal to form volatile oil. Meanwhile, the leftover charcoal, freed from its bonds with the other elements, stays at the bottom of the distilling vessel.
When, on the contrary, we employ a red heat, no water is formed, or, at least, any that may have been produced by the first application of the heat is decomposed, the oxygen having a greater affinity with the charcoal at this degree of heat, combines with it to form carbonic acid, and the hydrogen being left free from combination with the other elements, unites with caloric, and escapes in the state of hydrogen gas. In this high temperature, either no oil is formed, or, if any was produced during the lower temperature at the beginning of the experiment, it is decomposed by the action of the red heat. Thus the decomposition of vegetable matter, under a high temperature, is produced by the action of double and triple affinities; while the charcoal attracts the oxygen,[Pg 126] on purpose to form carbonic acid, the caloric attracts the hydrogen, and converts it into hydrogen gas.
When we use a red heat, no water is produced, or if any was created at the start when the heat was applied, it breaks down since oxygen has a stronger attraction to charcoal at this temperature. It combines with the charcoal to create carbon dioxide, while the hydrogen is freed from combining with the other elements, joins with heat, and escapes as hydrogen gas. At this high temperature, either no oil is formed, or if any was produced at the lower temperature earlier in the process, it gets broken down by the red heat. Therefore, the breakdown of plant matter at high temperatures occurs due to the actions of double and triple affinities; while the charcoal pulls in the oxygen on purpose to create carbon dioxide, the heat attracts the hydrogen and turns it into hydrogen gas.
The distillation of every species of vegetable substance confirms the truth of this theory, if we can give that name to a simple relation of facts. When sugar is submitted to distillation, so long as we only employ a heat but a little below that of boiling water, it only loses its water of cristallization, it still remains sugar, and retains all its properties; but, immediately upon raising the heat only a little above that degree, it becomes blackened, a part of the charcoal separates from the combination, water slightly acidulated passes over accompanied by a little oil, and the charcoal which remains in the retort is nearly a third part of the original weight of the sugar.
The distillation of every type of plant material supports the validity of this theory, if we can call it that in reference to a straightforward relationship of facts. When sugar is distilled, as long as we use heat just below the boiling point of water, it only loses its water of crystallization and remains sugar, keeping all its properties. However, as soon as we increase the heat slightly above that point, it starts to blacken; some of the charcoal separates from the mixture, a bit of slightly acidic water is produced along with a small amount of oil, and the charcoal left in the distillation vessel is about one-third of the original weight of the sugar.
The operation of affinities which take place during the decomposition, by fire, of vegetables which contain azote, such as the cruciferous plants, and of those containing phosphorus, is more complicated; but, as these substances only enter into the composition of vegetables in very small quantities, they only, apparently, produce slight changes upon the products of distillation; the phosphorus seems to combine with the charcoal, and, acquiring fixity from that union, remains behind in the retort, while the[Pg 127] azote, combining with a part of the hydrogen, forms ammoniac, or volatile alkali.
The way affinities work during the decomposition of plants containing nitrogen, like cruciferous vegetables, and those with phosphorus is more complex. However, since these substances are present in very small amounts in plants, their impact on the distillation products is minimal. Phosphorus appears to combine with charcoal, and through that bond, it becomes stable and is left behind in the retort, while the [Pg 127] nitrogen combines with some of the hydrogen to form ammonia, or volatile alkali.
Animal substances, being composed nearly of the same elements with cruciferous plants, give the same products in distillation, with this difference, that, as they contain a greater quantity of hydrogen and azote, they produce more oil and more ammoniac. I shall only produce one fact as a proof of the exactness with which this theory explains all the phenomena which occur during the distillation of animal substances, which is the rectification and total decomposition of volatile animal oil, commonly known by the name of Dippel's oil. When these oils are procured by a first distillation in a naked fire they are brown, from containing a little charcoal almost in a free state; but they become quite colourless by rectification. Even in this state the charcoal in their composition has so slight a connection with the other elements as to separate by mere exposure to the air. If we put a quantity of this animal oil, well rectified, and consequently clear, limpid, and transparent, into a bell-glass filled with oxygen gas over mercury, in a short time the gas is much diminished, being absorbed by the oil, the oxygen combining with the hydrogen of the oil forms water, which sinks to the bottom, at the same time the charcoal which was combined with the hydrogen being set free, manifests itself[Pg 128] by rendering the oil black. Hence the only way of preserving these oils colourless and transparent, is by keeping them in bottles perfectly full and accurately corked, to hinder the contact of air, which always discolours them.
Animal substances, made up of nearly the same elements as cruciferous plants, yield similar products when distilled. The difference is that since they have a higher amount of hydrogen and nitrogen, they produce more oil and ammonia. I’ll mention one fact that demonstrates how accurately this theory explains all the phenomena involved in the distillation of animal substances: the purification and complete breakdown of volatile animal oil, commonly known as Dippel's oil. When these oils are obtained from a first distillation using an open flame, they appear brown due to containing some charcoal in a nearly free state; however, they become completely colorless when purified. Even in this pure state, the charcoal in their composition is only loosely bonded with the other elements, allowing it to separate with just exposure to air. If we place a quantity of this well-purified animal oil, which is clear, transparent, and limpid, into a bell jar filled with oxygen gas over mercury, the gas level decreases significantly in a short time as it is absorbed by the oil. The oxygen combines with the hydrogen in the oil to form water, which settles at the bottom, while the charcoal that was combined with the hydrogen is freed and turns the oil black. Therefore, the only way to keep these oils colorless and transparent is to store them in bottles that are completely full and tightly corked to prevent contact with air, which always causes discoloration.
Successive rectifications of this oil furnish another phenomenon confirming our theory. In each distillation a small quantity of charcoal remains in the retort, and a little water is formed by the union of the oxygen contained in the air of the distilling vessels with the hydrogen of the oil. As this takes place in each successive distillation, if we make use of large vessels and a considerable degree of heat, we at last decompose the whole of the oil, and change it entirely into water and charcoal. When we use small vessels, and especially when we employ a slow fire, or degree of heat little above that of boiling water, the total decomposition of these oils, by repeated distillation, is greatly more tedious, and more difficultly accomplished. I shall give a particular detail to the Academy, in a separate memoir, of all my experiments upon the decomposition of oil; but what I have related above may suffice to give just ideas of the composition of animal and vegetable substances, and of their decomposition by the action of fire.
Successive refinements of this oil reveal another phenomenon that supports our theory. In each distillation, a small amount of charcoal is left in the retort, and a bit of water is produced from the combination of the oxygen in the air of the distilling vessels with the hydrogen from the oil. As this happens in each successive distillation, if we use larger vessels and apply a high level of heat, we eventually break down the entire oil, converting it completely into water and charcoal. When we work with smaller vessels, and especially when we use a low flame or a heat level just above boiling water, the complete breakdown of these oils through repeated distillation is much more tedious and challenging to achieve. I will provide detailed information to the Academy in a separate report about all my experiments on oil decomposition; however, what I’ve described above should be sufficient to give a clear understanding of the composition of animal and vegetable substances and how they decompose through the action of fire.
FOOTNOTES:
[24] Though this term, red heat, does not indicate any absolutely determinate degree of temperature, I shall use it sometimes to express a temperature considerably above that of boiling water.—A.
[24] While the term "red heat" doesn't specify an exact temperature, I will occasionally use it to refer to a temperature significantly higher than that of boiling water.—A.
[25] I must be understood here to speak of vegetables reduced to a perfectly dry state; and, with respect to oil, I do not mean that which is procured by expression either in the cold, or in a temperature not exceeding that of boiling water; I only allude to the empyreumatic oil procured by distillation with a naked fire, in a heat superior to the temperature of boiling water; which is the only oil declared to be produced by the operation of fire. What I have published upon this subject in the Memoirs of the Academy for 1786 may be consulted.—A.
[25] I need to clarify that I’m talking about vegetables that have been completely dried out. Also, when I refer to oil, I’m not talking about the kind that’s extracted through cold pressing or at temperatures that don’t exceed boiling water. I’m specifically referring to the empyreumatic oil obtained through distillation with an open flame, at temperatures higher than boiling water, which is the only oil said to be created by fire. You can refer to what I published on this topic in the Memoirs of the Academy for 1786.—A.
CHAP. XIII.
Of the Decomposition of Vegetable Oxyds by the Vinous Fermentation.
The manner in which wine, cyder, mead, and all the liquors formed by the spiritous fermentation, are produced, is well known to every one. The juice of grapes or of apples being expressed, and the latter being diluted with water, they are put into large vats, which are kept in a temperature of at least 10° (54.5°) of the thermometer. A rapid intestine motion, or fermentation, very soon takes place, numerous globules of gas form in the liquid and burst at the surface; when the fermentation is at its height, the quantity of gas disengaged is so great as to make the liquor appear as if boiling violently over a fire. When this gas is carefully gathered, it is found to be carbonic acid perfectly pure, and free from admixture with any other species of air or gas whatever.
The way wine, cider, mead, and all the drinks made through fermentation are made is well known to everyone. The juice from grapes or apples is pressed, and the apple juice is mixed with water. They are placed in large vats, which are kept at a temperature of at least 10° (54.5° on the thermometer). A rapid internal motion, or fermentation, soon occurs, causing numerous bubbles of gas to form in the liquid and burst at the surface. When fermentation is at its peak, the amount of gas released is so great that the liquid looks like it’s boiling vigorously. When this gas is carefully collected, it is found to be pure carbon dioxide, completely free from any other type of air or gas.
When the fermentation is completed, the juice of grapes is changed from being sweet, and full of sugar, into a vinous liquor which no longer contains any sugar, and from which we procure, by distillation, an inflammable liquor,[Pg 130] known in commerce under the name of Spirit of Wine. As this liquor is produced by the fermentation of any saccharine matter whatever diluted with water, it must have been contrary to the principles of our nomenclature to call it spirit of wine rather than spirit of cyder, or of fermented sugar; wherefore, we have adopted a more general term, and the Arabic word alkohol seems extremely proper for the purpose.
When fermentation is done, grape juice transforms from sweet and sugary to a wine-like liquid that has no sugar left. From this, we obtain an inflammable liquid through distillation,[Pg 130] which is commercially known as Spirit of Wine. Since this liquid can be generated through the fermentation of any sugary substance mixed with water, it would have been against our naming conventions to call it spirit of wine instead of spirit of cider or fermented sugar. Therefore, we’ve chosen a more general term, and the Arabic word alkohol seems quite fitting for this purpose.
This operation is one of the most extraordinary in chemistry: We must examine whence proceed the disengaged carbonic acid and the inflammable liquor produced, and in what manner a sweet vegetable oxyd becomes thus converted into two such opposite substances, whereof one is combustible, and the other eminently the contrary. To solve these two questions, it is necessary to be previously acquainted with the analysis of the fermentable substance, and of the products of the fermentation. We may lay it down as an incontestible axiom, that, in all the operations of art and nature, nothing is created; an equal quantity of matter exists both before and after the experiment; the quality and quantity of the elements remain precisely the same; and nothing takes place beyond changes and modifications in the combination of these elements. Upon this principle the whole art of performing chemical experiments[Pg 131] depends: We must always suppose an exact equality between the elements of the body examined and those of the products of its analysis.
This process is one of the most remarkable in chemistry: We need to investigate where the released carbon dioxide and the flammable liquid come from, and how a sweet plant-derived oxide gets transformed into two completely different substances, one of which is combustible while the other is the exact opposite. To answer these questions, we must first understand the analysis of the fermentable substance and the products of fermentation. We can establish as an undeniable truth that, in all processes of art and nature, nothing is created; the same amount of matter exists before and after the experiment; the quality and quantity of the elements remain exactly the same; and what occurs is simply changes and modifications in the combinations of those elements. The entire practice of conducting chemical experiments[Pg 131] hinges on this principle: We must always assume perfect equality between the elements of the substance being examined and those of its analysis products.
Hence, since from must of grapes we procure alkohol and carbonic acid, I have an undoubted right to suppose that must consists of carbonic acid and alkohol. From these premises, we have two methods of ascertaining what passes during vinous fermentation, by determining the nature of, and the elements which compose, the fermentable substances, or by accurately examining the produces resulting from fermentation; and it is evident that the knowledge of either of these must lead to accurate conclusions concerning the nature and composition of the other. From these considerations, it became necessary accurately to determine the constituent elements of the fermentable substances; and, for this purpose, I did not make use of the compound juices of fruits, the rigorous analysis of which is perhaps impossible, but made choice of sugar, which is easily analysed, and the nature of which I have already explained. This substance is a true vegetable oxyd with two bases, composed of hydrogen and charcoal brought to the state of an oxyd, by a certain proportion of oxygen; and these three elements are combined in such a way, that a very slight force is sufficient to destroy the equilibrium of their connection. By[Pg 132] a long train of experiments, made in various ways, and often repeated, I ascertained that the proportion in which these ingredients exist in sugar, are nearly eight parts of hydrogen, 64 parts of oxygen, and 28 parts of charcoal, all by weight, forming 100 parts of sugar.
Therefore, since we obtain alcohol and carbon dioxide from grape must, I have every reason to believe that must consists of carbon dioxide and alcohol. Based on this, we have two ways to understand what happens during fermentation: by determining the nature and elements of the fermentable substances, or by accurately examining the products of fermentation. It's clear that knowing one of these will provide accurate insights about the other. Given this, it became essential to accurately identify the elements in the fermentable substances. For this, I chose to use sugar instead of the complex juices from fruits, which are difficult to analyze, and I have already explained the nature of sugar. This substance is a true vegetable oxide with two bases, made up of hydrogen and carbon that have been oxidized by a certain amount of oxygen. These three elements are combined in such a way that a slight force can easily disrupt their connection. Through a long series of experiments conducted in various ways and often repeated, I found that the proportions of these ingredients in sugar are roughly eight parts hydrogen, 64 parts oxygen, and 28 parts carbon, all by weight, making up a total of 100 parts of sugar.
Sugar must be mixed with about four times its weight of water, to render it susceptible of fermentation; and even then the equilibrium of its elements would remain undisturbed, without the assistance of some substance, to give a commencement to the fermentation. This is accomplished by means of a little yeast from beer; and, when the fermentation is once excited, it continues of itself until completed. I shall, in another place, give an account of the effects of yeast, and other ferments, upon fermentable substances. I have usually employed 10 libs. of yeast, in the state of paste, for each 100 libs. of sugar, with as much water as is four times the weight of the sugar. I shall give the results of my experiments exactly as they were obtained, preserving even the fractions produced by calculation.[Pg 133]
Sugar needs to be mixed with about four times its weight in water to be able to ferment; and even then, the balance of its elements stays unchanged without some substance to kickstart the fermentation process. This is done using a bit of yeast from beer; once the fermentation is initiated, it continues on its own until it’s complete. I will discuss the effects of yeast and other ferments on fermentable substances elsewhere. I typically use 10 lbs. of yeast in paste form for every 100 lbs. of sugar, with enough water that is four times the weight of the sugar. I will present the results of my experiments exactly as I obtained them, including all the fractions from my calculations.[Pg 133]
Table 1. Materials of Fermentation.
libs. | oz. | gros | grs. | ||
Water | 400 | 0 | 0 | 0 | |
Sugar | 100 | 0 | 0 | 0 | |
Yeast in paste, 10 libs. composed of | { Water | 7 | 3 | 6 | 44 |
{ Dry yeast | 2 | 12 | 1 | 28 | |
—— | —— | —— | —— | ||
Total | 510 |
Table 2. Constituent Elements of the Materials of Fermentation.
libs. | oz. | gros | grs. | ||
407 libs, 3 oz. 6 gros 44 grs. of water, composed of | {Hydrogen | 61 | 1 | 2 | 71.40 |
{ Oxygen | 346 | 2 | 3 | 44.60 | |
{Hydrogen | 8 | 0 | 0 | 0 | |
100 libs. sugar, composed of | {Oxygen | 64 | 0 | 0 | 0 |
{Charcoal | 28 | 0 | 0 | 0 | |
{Hydrogen | 0 | 4 | 5 | 9.30 | |
2 libs. 12 oz. 1 gros 28 grs. of dry yeast, composed of | {Oxygen | 1 | 10 | 2 | 28.76 |
{ Charcoal | 0 | 12 | 4 | 59 | |
{ Azote | 0 | 0 | 5 | 2.94 | |
——— | ——— | —— | ——— | ||
Total weight | 510 | 0 | 0 | 0 |
Table 3. Recapitulation of these Elements.
libs. | oz. | gros | grs. | |||||
Oxygen: | ||||||||
of the water | 340 | 0 | 0 | 0} | libs. | oz. | gros | grs. |
of the water in the yeast | 6 | 2 | 3 | 44.60} | 411 | 12 | 6 | 1.36 |
of the sugar | 64 | 0 | 0 | 0} | ||||
of the dry yeast | 1 | 10 | 2 | 28.76} | ||||
Hydrogen: | ||||||||
of the water | 60 | 0 | 0 | 0} | ||||
of the water in the yeast | 1 | 1 | 2 | 71.40} | 69 | 6 | 0 | 8.70 |
of the sugar | 8 | 0 | 0 | 0} | ||||
of the dry yeast | 0 | 4 | 5 | 9.30} | ||||
Charcoal: | ||||||||
of the sugar | 28 | 0 | 0 | 0} | ||||
of the yeast | 0 | 12 | 4 | 59.00} | 28 | 12 | 4 | 59.00 |
Azote of the yeast | - | - | - | - } | 0 | 0 | 5 | 2.94 |
—— | ——— | ——— | ——— | |||||
In all | 510 | 0 | 0 | 0 |
Having thus accurately determined the nature and quantity of the constituent elements of the materials submitted to fermentation, we have next to examine the products resulting from that process. For this purpose, I placed the above 510 libs. of fermentable liquor in a proper[26] apparatus, by means of which I could accurately determine the quantity and quality of gas disengaged during the fermentation, and could even weigh every one of the products[Pg 135] separately, at any period of the process I judged proper. An hour or two after the substances are mixed together, especially if they are kept in a temperature of from 15° (65.75°) to 18° (72.5°) of the thermometer, the first marks of fermentation commence; the liquor turns thick and frothy, little globules of air are disengaged, which rise and burst at the surface; the quantity of these globules quickly increases, and there is a rapid and abundant production of very pure carbonic acid, accompanied with a scum, which is the yeast separating from the mixture. After some days, less or more according to the degree of heat, the intestine motion and disengagement of gas diminish; but these do not cease entirely, nor is the fermentation completed for a considerable time. During the process, 35 libs. 5 oz. 4 gros 19 grs. of dry carbonic acid are disengaged, which carry alongst with them 13 libs. 14 oz. 5 gros of water. There remains in the vessel 460 libs. 11 oz. 6 gros 53 grs. of vinous liquor, slightly acidulous. This is at first muddy, but clears of itself, and deposits a portion of yeast. When we separately analise all these substances, which is effected by very troublesome processes, we have the results as given in the following Tables. This process, with all the subordinate calculations and analyses, will be detailed at large in the Memoirs of the Academy.
Having accurately determined the nature and amount of the elements in the materials we used for fermentation, the next step is to examine the products that come from that process. For this, I placed the 510 lbs. of fermentable liquid in suitable[26] equipment, which allowed me to accurately measure the quantity and quality of gas released during fermentation, and I could even weigh each of the products[Pg 135] separately at any time I deemed appropriate. An hour or two after mixing the substances, particularly if kept at a temperature between 15° (65.75°) and 18° (72.5°), the first signs of fermentation begin; the liquid becomes thick and frothy, with small bubbles of air that rise and burst at the surface. The number of these bubbles quickly increases, and there is a rapid production of very pure carbon dioxide, accompanied by a scum that is yeast separating from the mixture. After a few days, depending on the heat, the bubbling and gas release slow down; however, they do not completely stop, and fermentation continues for a significant time. During this process, 35 lbs. 5 oz. 4 dr. 19 gr. of dry carbon dioxide are released, taking along with it 13 lbs. 14 oz. 5 dr. of water. There remains in the vessel 460 lbs. 11 oz. 6 dr. 53 gr. of slightly acidic wine. Initially, this is cloudy but eventually clears up on its own, leaving behind some yeast. When we analyze all these substances separately, which involves a rather complex process, we get the results shown in the following tables. This process, along with all the related calculations and analyses, will be explained in detail in the Academy's Memoirs.
Table 4. Product of Fermentation.
libs. | oz. | gros | grs. | ||
35 libs. 5 oz. 4 gros 19 grs. of carbonic acid, composed of | {Oxygen | 25 | 7 | 1 | 34 |
{Charcoal | 9 | 14 | 2 | 57 | |
408 libs. 15 oz. 5 gros 14 grs. of water, composed of | {Oxygen | 347 | 10 | 0 | 59 |
{Hydrogen | 61 | 5 | 4 | 27 | |
{Oxygen, combined with hydrogen | 31 | 6 | 1 | 64 | |
57 libs. 11 oz. 1 gros 58 grs. of dry alkohol, composed of | {Hydrogen, combined with oxygen | 5 | 8 | 5 | 3 |
{Hydrogen, combined with charcoal | 4 | 0 | 5 | 0 | |
{Charcoal, combined with hydrogen | 16 | 11 | 5 | 63 | |
2 libs. 8 oz. of dry acetous acid, composed of | {Hydrogen | 0 | 2 | 4 | 0 |
{Oxygen | 1 | 11 | 4 | 0 | |
{Charcoal | 0 | 10 | 0 | 0 | |
4 libs. 1 oz. 4 gros 3 grs. of residuum of sugar, composed of | {Hydrogen | 0 | 5 | 1 | 67 |
{Oxygen | 2 | 9 | 7 | 27 | |
{Charcoal | 1 | 2 | 2 | 53 | |
{Hydrogen | 0 | 2 | 2 | 41 | |
1 lib. 6 oz. 0 gros 5 grs. of dry yeast, composed of | {Oxygen | 0 | 13 | 1 | 14 |
{ Charcoal | 0 | 6 | 2 | 30 | |
{Azote | 0 | 0 | 2 | 37 | |
—— | —— | —— | —— | ||
510 libs. | Total | 510 | 0 | 0 | 0 |
Table 5. Recapitulation of the Products.
libs. | oz. | gros | grs. | ||
409 libs. 10 oz. 0 gros 54 grs. of oxygen contained in the | Water | 347 | 10 | 0 | 59 |
Carbonic acid | 25 | 7 | 1 | 34 | |
Alkohol | 31 | 6 | 1 | 64 | |
Acetous acid | 1 | 11 | 4 | 0 | |
Residuum of sugar | 2 | 9 | 7 | 27 | |
Yeast | 0 | 13 | 1 | 14 | |
28 libs. 12 oz. 5 gros 59 grs. of charcoal contained in the | Carbonic acid | 9 | 14 | 2 | 57 |
Alkohol | 16 | 11 | 5 | 63 | |
Acetous acid | 0 | 10 | 0 | 0 | |
Residuum of sugar | 1 | 2 | 2 | 53 | |
Yeast | 0 | 6 | 2 | 30 | |
71 libs. 8 oz. 6 gros 66 grs. of hydrogen contained in the | Water | 61 | 5 | 4 | 27 |
Water of the alkohol | 5 | 8 | 5 | 3 | |
Combined with the charcoal of the alko. | 4 | 0 | 5 | 0 | |
Acetous acid | 0 | 2 | 4 | 0 | |
Residuum of sugar | 0 | 5 | 1 | 67 | |
Yeast | 0 | 2 | 2 | 41 | |
2 gros 37 grs. of azote in the yeast | 0 | 0 | 2 | 37 | |
—— | ——— | ——— | ——— | ——— | |
510 libs. | Total | 510 | 0 | 0 | 0 |
In these results, I have been exact, even to grains; not that it is possible, in experiments of this nature, to carry our accuracy so far, but as the experiments were made only with a few pounds of sugar, and as, for the sake of comparison, I reduced the results of the actual experiments to the quintal or imaginary hundred[Pg 138] pounds, I thought it necessary to leave the fractional parts precisely as produced by calculation.
In these results, I have been precise, even down to the last detail; it isn’t really possible, in experiments like these, to be that exact, but since the experiments were conducted with only a few pounds of sugar, and for comparison’s sake, I converted the results of the actual experiments to the quintal or an imaginary hundred[Pg 138] pounds, I felt it was important to keep the fractional parts exactly as calculated.
When we consider the results presented by these tables with attention, it is easy to discover exactly what occurs during fermentation. In the first place, out of the 100 libs. of sugar employed, 4 libs. 1 oz. 4 gros 3 grs. remain, without having suffered decomposition; so that, in reality, we have only operated upon 95 libs. 14 oz. 3 gros 69 grs. of sugar; that is to say, upon 61 libs. 6 oz. 45 grs. of oxygen, 7 libs. 10 oz. 6 gros 6 grs. of hydrogen, and 26 libs. 13 oz. 5 gros 19 grs. of charcoal. By comparing these quantities, we find that they are fully sufficient for forming the whole of the alkohol, carbonic acid and acetous acid produced by the fermentation. It is not, therefore, necessary to suppose that any water has been decomposed during the experiment, unless it be pretended that the oxygen and hydrogen exist in the sugar in that state. On the contrary, I have already made it evident that hydrogen, oxygen and charcoal, the three constituent elements of vegetables, remain in a state of equilibrium or mutual union with each other which subsists so long as this union remains undisturbed by increased temperature, or by some new compound attraction; and that then[Pg 139] only these elements combine, two and two together, to form water and carbonic acid.
When we closely examine the results shown in these tables, it becomes clear what happens during fermentation. First, out of the 100 lbs. of sugar used, 4 lbs. 1 oz. 4 gros 3 grs. remain unchanged; so, in reality, we have only acted on 95 lbs. 14 oz. 3 gros 69 grs. of sugar. This means we've worked with 61 lbs. 6 oz. 45 grs. of oxygen, 7 lbs. 10 oz. 6 gros 6 grs. of hydrogen, and 26 lbs. 13 oz. 5 gros 19 grs. of carbon. By comparing these amounts, we find they are more than enough to produce all the alcohol, carbon dioxide, and acetic acid generated by the fermentation process. Therefore, we don't need to assume that any water has been broken down during the experiment, unless it's claimed that the oxygen and hydrogen exist in the sugar in that form. On the contrary, I've already shown that hydrogen, oxygen, and carbon—the three main elements in plants—remain balanced and united as long as this combination isn't disturbed by higher temperatures or new chemical attractions; and then[Pg 139] only these elements come together, two by two, to form water and carbon dioxide.
The effects of the vinous fermentation upon sugar is thus reduced to the mere separation of its elements into two portions; one part is oxygenated at the expence of the other, so as to form carbonic acid, whilst the other part, being deoxygenated in favour of the former, is converted into the combustible substance alkohol; therefore, if it were possible to reunite alkohol and carbonic acid together, we ought to form sugar. It is evident that the charcoal and hydrogen in the alkohol do not exist in the state of oil, they are combined with a portion of oxygen, which renders them miscible with water; wherefore these three substances, oxygen, hydrogen, and charcoal, exist here likewise in a species of equilibrium or reciprocal combination; and in fact, when they are made to pass through a red hot tube of glass or porcelain, this union or equilibrium is destroyed, the elements become combined, two and two, and water and carbonic acid are formed.
The effects of wine fermentation on sugar can be simplified to the separation of its components into two parts; one part gains oxygen at the expense of the other, creating carbon dioxide, while the other part loses oxygen to the first part and transforms into the flammable substance alcohol. Therefore, if we could somehow combine alcohol and carbon dioxide, we would end up with sugar. It's clear that the carbon and hydrogen in alcohol aren’t in the form of oil; they are combined with some oxygen, which makes them mixable with water. Thus, these three substances—oxygen, hydrogen, and carbon—also exist in a kind of balance or combined state here. In fact, when they are forced through a red-hot glass or porcelain tube, this balance is disrupted, and the elements combine in pairs to form water and carbon dioxide.
I had formally advanced, in my first Memoirs upon the formation of water, that it was decomposed in a great number of chemical experiments, and particularly during the vinous fermentation. I then supposed that water existed ready formed in sugar, though I am now convinced that sugar only contains the elements[Pg 140] proper for composing it. It may be readily conceived, that it must have cost me a good deal to abandon my first notions, but by several years reflection, and after a great number of experiments and observations upon vegetable substances, I have fixed my ideas as above.
I had previously stated in my first memoirs about the formation of water that it was broken down in many chemical experiments, especially during the fermentation of wine. I initially thought that water was already present in sugar, but now I realize that sugar only contains the elements[Pg 140] necessary to make it. It’s easy to understand that it was difficult for me to let go of my initial ideas, but after several years of reflection and many experiments and observations on plant substances, I have solidified my understanding as mentioned above.
I shall finish what I have to say upon vinous fermentation, by observing, that it furnishes us with the means of analysing sugar and every vegetable fermentable matter. We may consider the substances submitted to fermentation, and the products resulting from that operation, as forming an algebraic equation; and, by successively supposing each of the elements in this equation unknown, we can calculate their values in succession, and thus verify our experiments by calculation, and our calculation by experiment reciprocally. I have often successfully employed this method for correcting the first results of my experiments, and to direct me in the proper road for repeating them to advantage. I have explained myself at large upon this subject, in a Memoir upon vinous fermentation already presented to the Academy, and which will speedily be published.
I will wrap up my discussion on wine fermentation by noting that it gives us a way to analyze sugar and all kinds of plant-based fermentable materials. We can think of the substances that undergo fermentation and the products that come from it as an algebraic equation. By treating each element in this equation as unknown one by one, we can calculate their values step by step, allowing us to verify our experiments through calculations and our calculations through experiments in return. I have often used this method successfully to correct initial results of my experiments and guide me on the best way to repeat them effectively. I have explained this topic in detail in a paper about wine fermentation that I have already submitted to the Academy, which will be published shortly.
FOOTNOTES:
CHAP. XIV.
Of the Putrefactive Fermentation.
The phenomena of putrefaction are caused, like those of vinous fermentation, by the operation of very complicated affinities. The constituent elements of the bodies submitted to this process cease to continue in equilibrium in the threefold combination, and form themselves anew into binary combinations[27], or compounds, consisting of two elements only; but these are entirely different from the results produced by the vinous fermentation. Instead of one part of the hydrogen remaining united with part of the water and charcoal to form alkohol, as in the vinous fermentation, the whole of the hydrogen is dissipated, during putrefaction, in the form of hydrogen gas, whilst, at the same time, the oxygen and charcoal, uniting with caloric, escape in the form of carbonic acid gas; so that, when the whole process is finished, especially[Pg 142] if the materials have been mixed with a sufficient quantity of water, nothing remains but the earth of the vegetable mixed with a small portion of charcoal and iron. Thus putrefaction is nothing more than a complete analysis of vegetable substance, during which the whole of the constituent elements is disengaged in form of gas, except the earth, which remains in the state of mould[28].
The process of decay is caused, like the process of alcoholic fermentation, by complex chemical interactions. The components of the matter going through this process stop balancing in their three-way combination and instead reform into two-element combinations or compounds. However, these are completely different from what happens in alcoholic fermentation. Instead of part of the hydrogen staying bonded with some of the water and carbon to create alcohol, as seen in fermentation, all the hydrogen is released during decay as hydrogen gas. At the same time, the oxygen and carbon, combined with heat, escape as carbon dioxide gas. So, when the whole process is done, especially if the materials have been mixed with enough water, what’s left is just the earth of the plant mixed with a little bit of carbon and iron. Therefore, decay is simply a complete breakdown of plant matter, during which all the original elements are released as gas, except for the earth, which remains as mold.
Such is the result of putrefaction when the substances submitted to it contain only oxygen, hydrogen, charcoal and a little earth. But this case is rare, and these substances putrify imperfectly and with difficulty, and require a considerable time to complete their putrefaction. It is otherwise with substances containing azote, which indeed exists in all animal matters, and even in a considerable number of vegetable substances. This additional element is remarkably favourable to putrefaction; and for this reason animal matter is mixed with vegetable, when the putrefaction of these is wished to be hastened. The whole art of forming composts and dunghills, for the purposes of agriculture, consists in the proper application of this admixture.
This is what happens during decay when the substances involved only have oxygen, hydrogen, carbon, and a bit of earth. However, this situation is rare, and these substances rot slowly and with difficulty, taking a significant amount of time to fully decay. The situation is different for substances that contain nitrogen, which is found in all animal matter and even in many plant substances. This extra element greatly speeds up the decay process; that's why animal matter is combined with plant matter when faster decomposition is desired. The entire practice of making compost and manure piles for agricultural purposes hinges on the right mix of these materials.
The addition of azote to the materials of putrefaction not only accelerates the process,[Pg 143] that element likewise combines with part of the hydrogen, and forms a new substance called volatile alkali or ammoniac. The results obtained by analysing animal matters, by different processes, leave no room for doubt with regard to the constituent elements of ammoniac; whenever the azote has been previously separated from these substances, no ammoniac is produced; and in all cases they furnish ammoniac only in proportion to the azote they contain. This composition of ammoniac is likewise fully proved by Mr Berthollet, in the Memoirs of the Academy for 1785, p. 316. where he gives a variety of analytical processes by which ammoniac is decomposed, and its two elements, azote and hydrogen, procured separately.
The addition of nitrogen to decaying materials not only speeds up the process,[Pg 143] but it also combines with some of the hydrogen to create a new substance called volatile alkali or ammonia. The results from analyzing animal matter through various methods clearly show the elements that make up ammonia; whenever nitrogen has been removed from these substances, no ammonia is produced, and in all instances, they only provide ammonia in proportion to the nitrogen they contain. This composition of ammonia is further supported by Mr. Berthollet in the Memoirs of the Academy for 1785, p. 316, where he details various analytical methods for decomposing ammonia and obtaining its two elements, nitrogen and hydrogen, separately.
I already mentioned in Chap. X. that almost all combustible bodies were capable of combining with each other; hydrogen gas possesses this quality in an eminent degree, it dissolves charcoal, sulphur, and phosphorus, producing the compounds named carbonated hydrogen gas, sulphurated hydrogen gas, and phosphorated hydrogen gas. The two latter of these gasses have a peculiarly disagreeable flavour; the sulphurated hydrogen gas has a strong resemblance to the smell of rotten eggs, and the phosphorated smells exactly like putrid fish. Ammoniac has likewise a peculiar odour, not less penetrating, or less disagreeable, than these other gasses. From[Pg 144] the mixture of these different flavours proceeds the fetor which accompanies the putrefaction of animal substances. Sometimes ammoniac predominates, which is easily perceived by its sharpness upon the eyes; sometimes, as in feculent matters, the sulphurated gas is most prevalent; and sometimes, as in putrid herrings, the phosphorated hydrogen gas is most abundant.
I already mentioned in Chap. X that almost all combustible materials can combine with each other. Hydrogen gas has this ability to a great extent; it dissolves charcoal, sulfur, and phosphorus, creating compounds known as carbonated hydrogen gas, sulphurated hydrogen gas, and phosphorated hydrogen gas. The latter two gases have a uniquely unpleasant taste; the sulphurated hydrogen gas smells a lot like rotten eggs, while the phosphorated hydrogen gas smells exactly like rotten fish. Ammonia also has a strong odor, just as penetrating and unpleasant as these other gases. From[Pg 144] the combination of these different smells comes the foul odor associated with the decay of animal matter. Sometimes ammonia is the most dominant, which is easily noticed by its sharpness to the eyes; other times, like in feces, the sulphurated gas is most present; and sometimes, as in rotten herring, the phosphorated hydrogen gas is the most abundant.
I long supposed that nothing could derange or interrupt the course of putrefaction; but Mr Fourcroy and Mr Thouret have observed some peculiar phenomena in dead bodies, buried at a certain depth, and preserved to a certain degree, from contact with air; having found the muscular flesh frequently converted into true animal fat. This must have arisen from the disengagement of the azote, naturally contained in the animal substance, by some unknown cause, leaving only the hydrogen and charcoal remaining, which are the elements proper for producing fat or oil. This observation upon the possibility of converting animal substances into fat may some time or other lead to discoveries of great importance to society. The faeces of animals, and other excrementitious matters, are chiefly composed of charcoal and hydrogen, and approach considerably to the nature of oil, of which they furnish a considerable quantity by distillation with a naked fire; but the intolerable foetor which accompanies all the products[Pg 145] of these substances prevents our expecting that, at least for a long time, they can be rendered useful in any other way than as manures.
I used to think that nothing could disrupt or change the process of decay; however, Mr. Fourcroy and Mr. Thouret have noticed some unusual phenomena in dead bodies buried at a certain depth and kept from air contact to some extent, often finding that the muscle tissue is transformed into actual animal fat. This must have happened due to the release of nitrogen, which is naturally found in animal matter, for some unknown reason, leaving only hydrogen and carbon behind, which are the necessary elements for creating fat or oil. This observation about the potential to turn animal substances into fat might someday lead to significant discoveries that could benefit society. Animal feces and other waste materials are mainly made up of carbon and hydrogen and are quite similar to oil, from which we can obtain a considerable amount through distillation with an open flame; however, the unbearable odor that comes with all the products[Pg 145] of these substances makes it unlikely that, at least for a long time, they can be used for anything other than fertilizer.
I have only given conjectural approximations in this Chapter upon the composition of animal substances, which is hitherto but imperfectly understood. We know that they are composed of hydrogen, charcoal, azote, phosphorus, and sulphur, all of which, in a state of quintuple combination, are brought to the state of oxyd by a larger or smaller quantity of oxygen. We are, however, still unacquainted with the proportions in which these substances are combined, and must leave it to time to complete this part of chemical analysis, as it has already done with several others.
I’ve only provided some educated guesses in this chapter about the makeup of animal substances, which is still not fully understood. We know they consist of hydrogen, carbon, nitrogen, phosphorus, and sulfur, all of which, in a combination of five elements, are transformed into oxides by varying amounts of oxygen. However, we still don’t know the specific ratios in which these substances combine, and we’ll have to wait for time to finalize this aspect of chemical analysis, just as it has done with several other topics.
FOOTNOTES:
[27] Binary combinations are such as consist of two simple elements combined together. Ternary, and quaternary, consist of three and four elements.—E.
[27] Binary combinations consist of two simple elements combined together. Ternary combinations have three elements, while quaternary ones have four. —E.
CHAP. XV.
Of the Acetous Fermentation.
The acetous fermentation is nothing more than the acidification or oxygenation of wine[29], produced in the open air by means of the absorption of oxygen. The resulting acid is the acetous acid, commonly called Vinegar, which is composed of hydrogen and charcoal united together in proportions not yet ascertained, and changed into the acid state by oxygen. As vinegar is an acid, we might conclude from analogy that it contains oxygen, but this is put beyond doubt by direct experiments: In the first place, we cannot change wine into vinegar without the contact of air containing oxygen; secondly, this process is accompanied by a diminution of the volume of the air in which it is carried on from the absorption of its oxygen; and, thirdly, wine may be changed into vinegar by any other means of oxygenation.
The acetous fermentation is simply the process of turning wine into vinegar through acidification or oxygenation, taking place in the open air as it absorbs oxygen. The resulting acid is acetic acid, commonly known as vinegar, which is made up of hydrogen and carbon bonded together in proportions that have not yet been determined, transformed into an acidic state by oxygen. Since vinegar is acidic, we might assume it contains oxygen, but this is confirmed by direct experiments: first, we can't convert wine into vinegar without exposing it to air that contains oxygen; second, this process results in a decrease in the volume of air as it absorbs oxygen; and third, wine can also be turned into vinegar through other methods of oxygenation.
Independent of the proofs which these facts furnish of the acetous acid being produced by the oxygenation of wine, an experiment made by Mr Chaptal, Professor of Chemistry at Montpellier, gives us a distinct view of what takes place in this process. He impregnated water with about its own bulk of carbonic acid from fermenting beer, and placed this water in a cellar in vessels communicating with the air, and in a short time the whole was converted into acetous acid. The carbonic acid gas procured from beer vats in fermentation is not perfectly pure, but contains a small quantity of alkohol in solution, wherefore water impregnated with it contains all the materials necessary for forming the acetous acid. The alkohol furnishes hydrogen and one portion of charcoal, the carbonic acid furnishes oxygen and the rest of the charcoal, and the air of the atmosphere furnishes the rest of the oxygen necessary for changing the mixture into acetous acid. From this observation it follows, that nothing but hydrogen is wanting to convert carbonic acid into acetous acid; or more generally, that, by means of hydrogen, and according to the degree of oxygenation, carbonic acid may be changed into all the vegetable acids; and, on the contrary, that, by depriving any of the vegetable acids of their hydrogen, they may be converted into carbonic acid.[Pg 148]
Regardless of the evidence these facts provide about acetic acid being produced through the oxygenation of wine, an experiment conducted by Mr. Chaptal, a Chemistry Professor at Montpellier, gives us a clear understanding of what happens in this process. He infused water with about its own volume of carbonic acid from fermenting beer and placed this water in a cellar in containers connected to the air. Soon after, the entire mixture transformed into acetic acid. The carbonic acid gas obtained from fermenting beer is not completely pure and contains a small amount of alcohol in solution; therefore, water treated with it has all the necessary components to create acetic acid. The alcohol supplies hydrogen and one part of carbon, the carbonic acid provides oxygen and the remainder of the carbon, and the air gives the extra oxygen needed to convert the mixture into acetic acid. This observation leads us to conclude that only hydrogen is needed to turn carbonic acid into acetic acid; or, more broadly, that with hydrogen and depending on the level of oxygenation, carbonic acid can be transformed into any of the plant acids; conversely, by removing hydrogen from any of the plant acids, they can be changed back into carbonic acid.[Pg 148]
Although the principal facts relating to the acetous acid are well known, yet numerical exactitude is still wanting, till furnished by more exact experiments than any hitherto performed; wherefore I shall not enlarge any farther upon the subject. It is sufficiently shown by what has been said, that the constitution of all the vegetable acids and oxyds is exactly conformable to the formation of vinegar; but farther experiments are necessary to teach us the proportion of the constituent elements in all these acids and oxyds. We may easily perceive, however, that this part of chemistry, like all the rest of its divisions, makes rapid progress towards perfection, and that it is already rendered greatly more simple than was formerly believed.
Although the main facts about acetic acid are well established, we still lack precise numerical data until more accurate experiments are conducted than those done so far; therefore, I won't delve further into the topic. It's clear from what has been discussed that the structure of all plant acids and oxides aligns perfectly with the formation of vinegar, but additional experiments are needed to determine the ratios of the constituent elements in these acids and oxides. However, it's easy to see that this aspect of chemistry, like its other branches, is advancing quickly towards greater understanding and is already much simpler than was previously thought.
FOOTNOTES:
[29] The word Wine, in this chapter, is used to signify the liquor produced by the vinous fermentation, whatever vegetable substance may have been used for obtaining it.—E.
[29] In this chapter, the term Wine refers to the drink created through the fermentation of grapes, regardless of the plant material used to produce it.—E.
CHAP. XVI.
Of the Formation of Neutral Salts, and of their different Bases.
We have just seen that all the oxyds and acids from the animal and vegetable kingdoms are formed by means of a small number of simple elements, or at least of such as have not hitherto been susceptible of decomposition, by means of combination with oxygen; these are azote, sulphur, phosphorus, charcoal, hydrogen, and the muriatic radical[30]. We may justly admire the simplicity of the means employed by nature to multiply qualities and forms, whether by combining three or four acidifiable bases in different proportions, or by altering the dose of oxygen employed for oxydating or acidifying them. We shall find the means no less simple and diversified, and as abundantly productive of forms and qualities, in the order of bodies we are now about to treat of.
We have just seen that all the oxides and acids from the animal and vegetable kingdoms are created using a small number of simple elements, or at least those that have not yet been shown to decompose, through their combination with oxygen. These elements include nitrogen, sulfur, phosphorus, carbon, hydrogen, and the hydrochloric radical[30]. We can truly appreciate the simplicity of the methods used by nature to create a variety of qualities and forms, whether by combining three or four acid-forming bases in different proportions or by changing the amount of oxygen used for oxidation or acidification. We will find similarly simple and diverse methods, which are just as effective in producing different forms and qualities, in the category of substances we are about to discuss.
Acidifiable substances, by combining with oxygen, and their consequent conversion into acids, acquire great susceptibility of farther combination; they become capable of uniting with earthy and metallic bodies, by which means neutral salts are formed. Acids may therefore be considered as true salifying principles, and the substances with which they unite to form neutral salts may be called salifiable bases: The nature of the union which these two principles form with each other is meant as the subject of the present chapter.
Acidic substances, when they combine with oxygen and turn into acids, become very reactive and can easily join with earthy and metallic materials, leading to the creation of neutral salts. Therefore, acids can be viewed as true salifying agents, and the substances they combine with to create neutral salts can be referred to as salifiable bases. The kind of connection these two principles make with one another is what this chapter will discuss.
This view of the acids prevents me from considering them as salts, though they are possessed of many of the principal properties of saline bodies, as solubility in water, &c. I have already observed that they are the result of a first order of combination, being composed of two simple elements, or at least of elements which act as if they were simple, and we may therefore rank them, to use the language of Stahl, in the order of mixts. The neutral salts, on the contrary, are of a secondary order of combination, being formed by the union of two mixts with each other, and may therefore be termed compounds. Hence I shall not arrange the alkalies[31] or earths in the class of salts, to which I[Pg 151] allot only such as are composed of an oxygenated substance united to a base.
This perspective on acids stops me from seeing them as salts, even though they share many key characteristics of saline substances, like being soluble in water, etc. I've already noted that they result from a primary type of combination, made up of two simple elements, or at least elements that function as if they were simple, so we can categorize them, to use Stahl's terminology, as mixts. In contrast, neutral salts come from a secondary type of combination, formed by the joining of two mixts together, and can therefore be called compounds. For this reason, I won’t classify the alkalis[31] or earths as salts, which I reserve solely for those made of an oxygenated substance combined with a base.
I have already enlarged sufficiently upon the formation of acids in the preceding chapter, and shall not add any thing farther upon that subject; but having as yet given no account of the salifiable bases which are capable of uniting with them to form neutral salts, I mean, in this chapter, to give an account of the nature and origin of each of these bases. These are potash, soda, ammoniac, lime, magnesia, barytes, argill[32], and all the metallic bodies.
I’ve already covered the formation of acids enough in the previous chapter, so I won’t go into that topic any further. However, since I haven't yet discussed the bases that can combine with acids to form neutral salts, in this chapter, I will explain the nature and origin of each of these bases. These include potash, soda, ammonium, lime, magnesia, barytes, clay, and all the metals.
§ 1. Of Potash.
We have already shown, that, when a vegetable substance is submitted to the action of fire in distilling vessels, its component elements, oxygen, hydrogen, and charcoal, which formed a threefold combination in a state of equilibrium, unite, two and two, in obedience to affinities which act conformable to the degree of heat[Pg 152] employed. Thus, at the first application of the fire, whenever the heat produced exceeds the temperature of boiling water, part of the oxygen and hydrogen unite to form water; soon after the rest of the hydrogen, and part of the charcoal, combine into oil; and, lastly, when the fire is pushed to the red heat, the oil and water, which had been formed in the early part of the process, become again decomposed, the oxygen and charcoal unite to form carbonic acid, a large quantity of hydrogen gas is set free, and nothing but charcoal remains in the retort.
We have already demonstrated that when a plant material is heated in distillation vessels, its main elements—oxygen, hydrogen, and carbon—work together in a balanced way. They combine in pairs based on their affinities, which change according to the level of heat[Pg 152] used. So, when the heat first exceeds the boiling point of water, some of the oxygen and hydrogen combine to create water. Shortly after, the remaining hydrogen and some of the carbon come together to form oil. Finally, when the heat reaches a red-hot level, the previously formed oil and water break down again; oxygen and carbon unite to create carbon dioxide, a large amount of hydrogen gas is released, and only carbon is left in the retort.
A great part of these phenomena occur during the combustion of vegetables in the open air; but, in this case, the presence of the air introduces three new substances, the oxygen and azote of the air and caloric, of which two at least produce considerable changes in the results of the operation. In proportion as the hydrogen of the vegetable, or that which results from the decomposition of the water, is forced out in the form of hydrogen gas by the progress of the fire, it is set on fire immediately upon getting in contact with the air, water is again formed, and the greater part of the caloric of the two gasses becoming free produces flame. When all the hydrogen gas is driven out, burnt, and again reduced to water, the remaining charcoal continues to burn, but without flame; it is[Pg 153] formed into carbonic acid, which carries off a portion of caloric sufficient to give it the gasseous form; the rest of the caloric, from the oxygen of the air, being set free, produces the heat and light observed during the combustion of charcoal. The whole vegetable is thus reduced into water and carbonic acid, and nothing remains but a small portion of gray earthy matter called ashes, being the only really fixed principles which enter into the constitution of vegetables.
A large part of these phenomena occurs when plants burn in the open air; however, in this situation, the presence of air introduces three new elements: the oxygen and nitrogen from the air and heat, at least two of which significantly impact the results of the process. As the hydrogen from the plant, or that which comes from the breakdown of water, is pushed out as hydrogen gas due to the fire's intensity, it ignites as soon as it contacts the air, forming water again, and much of the heat from the two gases is released, creating a flame. Once all the hydrogen gas is expelled, burned, and turned back into water, the leftover charcoal continues to burn but without a flame; it turns into carbon dioxide, which takes away enough heat to become gas; the remaining heat from the oxygen in the air is released and creates the heat and light we see when charcoal burns. Ultimately, the entire plant is reduced to water and carbon dioxide, leaving just a small amount of gray, earthy material known as ash, which is the only truly stable component that makes up plants.
The earth, or rather ashes, which seldom exceeds a twentieth part of the weight of the vegetable, contains a substance of a particular nature, known under the name of fixed vegetable alkali, or potash. To obtain it, water is poured upon the ashes, which dissolves the potash, and leaves the ashes which are insoluble; by afterwards evaporating the water, we obtain the potash in a white concrete form: It is very fixed even in a very high degree of heat. I do not mean here to describe the art of preparing potash, or the method of procuring it in a state of purity, but have entered upon the above detail that I might not use any word not previously explained.
The earth, or rather the ashes, which rarely make up more than one-twentieth of the weight of the plant material, contains a specific substance known as fixed vegetable alkali or potash. To extract it, water is poured over the ashes, dissolving the potash and leaving behind the insoluble ashes; by evaporating the water afterward, we obtain the potash in a solid white form. It remains stable even at very high temperatures. I'm not here to explain the process of making potash or how to obtain it in pure form, but I included this detail to ensure that I don't use any terms that haven't been previously defined.
The potash obtained by this process is always less or more saturated with carbonic acid, which is easily accounted for: As the potash does not form, or at least is not set free, but in proportion[Pg 154] as the charcoal of the vegetable is converted into carbonic acid by the addition of oxygen, either from the air or the water, it follows, that each particle of potash, at the instant of its formation, or at least of its liberation, is in contact with a particle of carbonic acid, and, as there is a considerable affinity between these two substances, they naturally combine together. Although the carbonic acid has less affinity with potash than any other acid, yet it is difficult to separate the last portions from it. The most usual method of accomplishing this is to dissolve the potash in water; to this solution add two or three times its weight of quick-lime, then filtrate the liquor and evaporate it in close vessels; the saline substance left by the evaporation is potash almost entirely deprived of carbonic acid. In this state it is soluble in an equal weight of water, and even attracts the moisture of the air with great avidity; by this property it furnishes us with an excellent means of rendering air or gas dry by exposing them to its action. In this state it is soluble in alkohol, though not when combined with carbonic acid; and Mr Berthollet employs this property as a method of procuring potash in the state of perfect purity.
The potash produced by this process is always somewhat saturated with carbonic acid, which makes sense: Since potash is not formed, or at least not released, except in proportion[Pg 154] to the charcoal from the vegetable being converted into carbonic acid through the addition of oxygen, either from the air or water, it follows that each particle of potash, at the moment of its formation or at least its release, is in contact with a particle of carbonic acid. There’s a significant affinity between these two substances, so they naturally combine. Although carbonic acid has less affinity for potash than other acids do, it’s still hard to separate the last bits from it. The most common method to achieve this is to dissolve the potash in water, add two or three times its weight of quick-lime to this solution, then filter the liquid and evaporate it in sealed containers; the residue left from the evaporation is potash that is mostly free of carbonic acid. In this form, it dissolves in an equal weight of water and even absorbs moisture from the air eagerly; this characteristic provides a great way to dry air or gas by exposing them to its effect. It is soluble in alcohol in this state, but not when mixed with carbonic acid; Mr. Berthollet uses this property to obtain potash in a state of perfect purity.
All vegetables yield less or more of potash in consequence of combustion, but it is furnished in various degrees of purity by different vegetables; usually, indeed, from all of them it is[Pg 155] mixed with different salts from which it is easily separable. We can hardly entertain a doubt that the ashes, or earth which is left by vegetables in combustion, pre-existed in them before they were burnt, forming what may be called the skeleton, or osseous part of the vegetable. But it is quite otherwise with potash; this substance has never yet been procured from vegetables but by means of processes or intermedia capable of furnishing oxygen and azote, such as combustion, or by means of nitric acid; so that it is not yet demonstrated that potash may not be a produce from these operations. I have begun a series of experiments upon this object, and hope soon to be able to give an account of their results.
All vegetables produce varying amounts of potash as a result of burning, but different vegetables provide it in different levels of purity; generally, from all of them it is[Pg 155] combined with various salts from which it can be easily separated. We can hardly doubt that the ashes or residue left by vegetables during combustion existed in them before they were burned, forming what can be called the framework or hard part of the vegetable. However, potash is different; this substance has only been obtained from vegetables through processes or intermediates capable of supplying oxygen and nitrogen, like combustion or nitric acid. Thus, it has not yet been proven that potash isn’t a product of these processes. I've started a series of experiments on this topic and hope to provide an account of the results soon.
§ 2. Of Soda.
Soda, like potash, is an alkali procured by lixiviation from the ashes of burnt plants, but only from those which grow upon the sea-side, and especially from the herb kali, whence is derived the name alkali, given to this substance by the Arabians. It has some properties in common with potash, and others which are entirely different: In general, these two substances have peculiar characters in their saline combinations which are proper to each, and consequently distinguish them from each other; thus soda,[Pg 156] which, as obtained from marine plants, is usually entirely saturated with carbonic acid, does not attract the humidity of the atmosphere like potash, but, on the contrary, desiccates, its cristals effloresce, and are converted into a white powder having all the properties of soda, which it really is, having only lost its water of cristallization.
Soda, like potash, is an alkali obtained by leaching the ashes of burnt plants, but only from those that grow by the sea, especially from the herb kali, which is where the name alkali comes from, given by the Arabs. It shares some properties with potash, but has others that are completely different. Generally, these two substances have unique characteristics in their salt combinations that set them apart; for instance, soda,[Pg 156] which is sourced from marine plants, is usually fully saturated with carbonic acid and does not attract moisture from the air like potash does. Instead, it dries out, its crystals effloresce, and turn into a white powder that retains all the properties of soda, having only lost its water of crystallization.
Hitherto we are not better acquainted with the constituent elements of soda than with those of potash, being equally uncertain whether it previously existed ready formed in the vegetable or is a combination of elements effected by combustion. Analogy leads us to suspect that azote is a constituent element of all the alkalies, as is the case with ammoniac; but we have only slight presumptions, unconfirmed by any decisive experiments, respecting the composition of potash and soda.
So far, we don't know more about the basic components of soda than we do about potash. We're equally unsure whether it existed in its complete form in plants or if it's made up of elements that combine through burning. By analogy, we suspect that nitrogen is a fundamental part of all the alkalis, as it is with ammonia. However, we only have limited evidence, which hasn't been confirmed by any definite experiments, about the makeup of potash and soda.
§ 3. Of Ammoniac.
We have, however, very accurate knowledge of the composition of ammoniac, or volatile alkali, as it is called by the old chemists. Mr Berthollet, in the Memoirs of the Academy for 1784, p. 316. has proved by analysis, that 1000 parts of this substance consist of about 807 parts of azote combined with 193 parts of hydrogen.[Pg 157]
We do, however, have very precise knowledge of what ammonia, or volatile alkali as the old chemists called it, is made of. Mr. Berthollet, in the Memoirs of the Academy for 1784, p. 316, demonstrated through analysis that 1000 parts of this substance are made up of about 807 parts of nitrogen combined with 193 parts of hydrogen.[Pg 157]
Ammoniac is chiefly procurable from animal substances by distillation, during which process the azote and hydrogen necessary to its formation unite in proper proportions; it is not, however, procured pure by this process, being mixed with oil and water, and mostly saturated with carbonic acid. To separate these substances it is first combined with an acid, the muriatic for instance, and then disengaged from that combination by the addition of lime or potash. When ammoniac is thus produced in its greatest degree of purity it can only exist under the gasseous form, at least in the usual temperature of the atmosphere, it has an excessively penetrating smell, is absorbed in large quantities by water, especially if cold and assisted by compression. Water thus saturated with ammoniac has usually been termed volatile alkaline fluor; we shall call it either simply ammoniac, or liquid ammoniac, and ammoniacal gas when it exists in the aëriform state.
Ammoniac is mainly obtained from animal materials through distillation, where nitrogen and hydrogen join together in the right proportions to form it. However, this process doesn’t yield pure ammoniac, as it ends up mixed with oil and water and is mostly saturated with carbonic acid. To separate these substances, it is first mixed with an acid, like hydrochloric acid, and then released from that combination by adding lime or potash. When ammoniac is produced in its purest form, it can only exist as a gas at normal atmospheric temperatures. It has a very strong smell and is absorbed in large amounts by water, especially if it's cold and under pressure. Water that becomes saturated with ammoniac is often referred to as volatile alkaline fluor; we’ll refer to it simply as ammoniac, or liquid ammoniac, and ammoniacal gas when it’s in gaseous form.
§ 4. Of Lime, Magnesia, Barytes, and Argill.
The composition of these four earths is totally unknown, and, until by new discoveries their constituent elements are ascertained, we are certainly authorised to consider them as simple bodies. Art has no share in the production of these earths, as they are all procured ready formed[Pg 158] from nature; but, as they have all, especially the three first, great tendency to combination, they are never found pure. Lime is usually saturated with carbonic acid in the state of chalk, calcarious spars, most of the marbles, &c.; sometimes with sulphuric acid, as in gypsum and plaster stones; at other times with fluoric acid forming vitreous or fluor spars; and, lastly, it is found in the waters of the sea, and of saline springs, combined with muriatic acid. Of all the salifiable bases it is the most universally spread through nature.
The makeup of these four types of earth is completely unknown, and until new discoveries can identify their elements, we are definitely justified in viewing them as simple substances. Art plays no role in creating these earths, as they are all found ready-made from nature; however, since they have a strong tendency to combine—especially the first three—they are never found in a pure form. Lime is usually mixed with carbonic acid in the form of chalk, limestone, most marbles, etc.; sometimes it's combined with sulfuric acid, as seen in gypsum and plaster stones; at other times, it binds with fluorine to form fluorite or fluor spar; and finally, it can be found in seawater and saline springs, combined with hydrochloric acid. Of all salifiable bases, lime is the most widely distributed in nature.[Pg 158]
Magnesia is found in mineral waters, for the most part combined with sulphuric acid; it is likewise abundant in sea-water, united with muriatic acid; and it exists in a great number of stones of different kinds.
Magnesia is mostly found in mineral waters, mostly combined with sulfuric acid; it is also plentiful in seawater, combined with hydrochloric acid; and it exists in many different types of stones.
Barytes is much less common than the three preceding earths; it is found in the mineral kingdom, combined with sulphuric acid, forming heavy spars, and sometimes, though rarely, united to carbonic acid.
Barytes is much less common than the three earths mentioned before; it occurs in the mineral kingdom, combined with sulfuric acid, forming heavy spars, and sometimes, although rarely, combined with carbonic acid.
Argill, or the base of alum, having less tendency to combination than the other earths, is often found in the state of argill, uncombined with any acid. It is chiefly procurable from clays, of which, properly speaking, it is the base, or chief ingredient.[Pg 159]
Argill, or alum's base, is less likely to combine with other substances compared to other earths, and is often found as argill, not combined with any acid. It is mainly sourced from clays, which, more accurately, it serves as the base or main component.[Pg 159]
§ 5. Of Metallic Bodies.
The metals, except gold, and sometimes silver, are rarely found in the mineral kingdom in their metallic state, being usually less or more saturated with oxygen, or combined with sulphur, arsenic, sulphuric acid, muriatic acid, carbonic acid, or phosphoric acid. Metallurgy, or the docimastic art, teaches the means of separating them from these foreign matters; and for this purpose we refer to such chemical books as treat upon these operations.
The metals, except for gold and occasionally silver, are seldom found in their pure metallic form in nature. They are usually combined with oxygen, or with substances like sulfur, arsenic, sulfuric acid, hydrochloric acid, carbonic acid, or phosphoric acid. Metallurgy, or the science of metal processing, provides the methods to separate these metals from these impurities. For this, we recommend consulting chemical texts that cover these processes.
We are probably only acquainted as yet with a part of the metallic substances existing in nature, as all those which have a stronger affinity to oxygen, than charcoal possesses, are incapable of being reduced to the metallic state, and, consequently, being only presented to our observation under the form of oxyds, are confounded with earths. It is extremely probable that barytes, which we have just now arranged with earths, is in this situation; for in many experiments it exhibits properties nearly approaching to those of metallic bodies. It is even possible that all the substances we call earths may be only metallic oxyds, irreducible by any hitherto known process.
We probably only know a portion of the metallic substances that exist in nature, as those with a stronger attraction to oxygen than charcoal cannot be reduced to a metallic state. Therefore, they are only observed in the form of oxides and are often confused with earths. It's highly likely that barytes, which we just categorized with earths, falls into this category; because in many experiments, it shows properties that are quite similar to those of metals. It’s even possible that all the substances we refer to as earths are merely metallic oxides that can't be reduced by any process currently known.
Those metallic bodies we are at present acquainted with, and which we can reduce to the[Pg 160] metallic or reguline state, are the following seventeen:
Those metal bodies we know today, which we can reduce to the[Pg 160] metallic or pure state, are the following seventeen:
3. Tungsten.
4. Manganese. Nickel. Cobalt. 7. Bismuth. Antimony. Zinc. 10. Iron. Tin. 12. Guide. Copper. 14. Mercury. 15. Silver. 16. Platinum.
17. Gold.
I only mean to consider these as salifiable bases, without entering at all upon the consideration of their properties in the arts, and for the uses of society. In these points of view each metal would require a complete treatise, which would lead me far beyond the bounds I have prescribed for this work.
I just want to look at these as things that can be sold, without getting into their properties in art or their usefulness to society. From this perspective, each metal would need a whole detailed study, which would take me way beyond the limits I've set for this work.
FOOTNOTES:
[30] I have not ventured to omit this element, as here enumerated with the other principles of animal and vegetable substances, though it is not at all taken notice of in the preceding chapters as entering into the composition of these bodies.—E.
[30] I haven't dared to leave this element out, as it's listed along with the other principles of animal and plant substances, even though it's not mentioned in the previous chapters as part of the makeup of these bodies.—E.
[31] Perhaps my thus rejecting the alkalies from the class of salts may be considered as a capital defect in the method I have adopted, and I am ready to admit the charge; but this inconvenience is compensated by so many advantages, that I could not think it of sufficient consequence to make me alter my plan.—A.
[31] Maybe my decision to exclude alkalis from the salt category could be seen as a major flaw in the method I've chosen, and I'm willing to accept that criticism; however, this downside is outweighed by numerous benefits, so I don't believe it's significant enough to change my approach.—A.
[32] Called Alumine by Mr Lavoisier; but as Argill has been in a manner naturalized to the language for this substance by Mr Kirwan, I have ventured to use it in preference.—E.
[32] Lavoisier referred to it as Alumine, but since Kirwan has sort of established "Argill" in the language for this substance, I chose to use it instead.—E.
CHAP. XVII.
Continuation of the Observations upon Salifiable Bases, and the Formation of Neutral Salts.
It is necessary to remark, that earths and alkalies unite with acids to form neutral salts without the intervention of any medium, whereas metallic substances are incapable of forming this combination without being previously less or more oxygenated; strictly speaking, therefore, metals are not soluble in acids, but only metallic oxyds. Hence, when we put a metal into an acid for solution, it is necessary, in the first place, that it become oxygenated, either by attracting oxygen from the acid or from the water; or, in other words, that a metal cannot be dissolved in an acid unless the oxygen, either of the acid, or of the water mixed with it, has a stronger affinity to the metal than to the hydrogen or the acidifiable base; or, what amounts to the same thing, that no metallic solution can take place without a previous decomposition of the water, or the acid in which it is made. The explanation of the principal phenomena of metallic solution depends entirely[Pg 162] upon this simple observation, which was overlooked even by the illustrious Bergman.
It’s important to note that earths and alkalis combine with acids to create neutral salts without needing any intermediary, while metallic substances can’t form this combination unless they are oxidized to some extent first. Strictly speaking, metals aren’t soluble in acids; only metallic oxides are. So, when a metal is placed in an acid to dissolve, it must first become oxygenated, either by pulling oxygen from the acid or from water. In other words, a metal can’t dissolve in an acid unless the oxygen from the acid or the water mixed with it has a stronger attraction to the metal than to the hydrogen or the acidifiable base. Essentially, this means that no metallic solution can occur without first decomposing the water or the acid it’s in. The explanation for the main phenomena of metallic dissolution entirely[Pg 162] relies on this simple observation, which was missed even by the renowned Bergman.
The first and most striking of these is the effervescence, or, to speak less equivocally, the disengagement of gas which takes place during the solution; in the solutions made in nitric acid this effervescence is produced by the disengagement of nitrous gas; in solutions with sulphuric acid it is either sulphurous acid gas or hydrogen gas, according as the oxydation of the metal happens to be made at the expence of the sulphuric acid or of the water. As both nitric acid and water are composed of elements which, when separate, can only exist in the gasseous form, at least in the common temperature of the atmosphere, it is evident that, whenever either of these is deprived of its oxygen, the remaining element must instantly expand and assume the state of gas; the effervescence is occasioned by this sudden conversion from the liquid to the gasseous state. The same decomposition, and consequent formation of gas, takes place when solutions of metals are made in sulphuric acid: In general, especially by the humid way, metals do not attract all the oxygen it contains; they therefore reduce it, not into sulphur, but into sulphurous acid, and as this acid can only exist as gas in the usual temperature, it is disengaged, and occasions effervescence.[Pg 163]
The first and most noticeable thing here is the bubbling, or to put it more clearly, the release of gas that happens during the solution process. In solutions made with nitric acid, this bubbling is caused by the release of nitrous gas; in solutions with sulfuric acid, it can either be sulfurous acid gas or hydrogen gas, depending on whether the oxidation of the metal occurs due to the sulfuric acid or the water. Since both nitric acid and water are made up of elements that can only exist as gases when separated, especially at regular atmospheric temperatures, it’s clear that whenever one of these loses its oxygen, the remaining element will immediately expand and turn into gas. The bubbling happens because of this quick change from liquid to gas. The same breakdown and resulting gas formation occurs when metals are dissolved in sulfuric acid. Generally, especially through the wet method, metals don’t take in all the oxygen it has; they reduce it, not into sulfur, but into sulfurous acid, and since this acid can only exist as a gas at normal temperatures, it gets released and causes bubbling.[Pg 163]
The second phenomenon is, that, when the metals have been previously oxydated, they all dissolve in acids without effervescence: This is easily explained; because, not having now any occasion for combining with oxygen, they neither decompose the acid nor the water by which, in the former case, the effervescence is occasioned.
The second phenomenon is that when the metals have already been oxidized, they all dissolve in acids without fizzing. This is easy to understand because, not needing to combine with oxygen anymore, they don't break down the acid or the water, which is what caused the fizzing in the previous case.
A third phenomenon, which requires particular consideration, is, that none of the metals produce effervescence by solution in oxygenated muriatic acid. During this process the metal, in the first place, carries off the excess of oxygen from the oxygenated muriatic acid, by which it becomes oxydated, and reduces the acid to the state of ordinary muriatic acid. In this case there is no production of gas, not that the muriatic acid does not tend to exist in the gasseous state in the common temperature, which it does equally with the acids formerly mentioned, but because this acid, which otherwise would expand into gas, finds more water combined with the oxygenated muriatic acid than is necessary to retain it in the liquid form; hence it does not disengage like the sulphurous acid, but remains, and quietly dissolves and combines with the metallic oxyd previously formed from its superabundant oxygen.
A third phenomenon that needs special attention is that none of the metals create bubbles when dissolved in oxygenated hydrochloric acid. In this process, the metal first removes the excess oxygen from the oxygenated hydrochloric acid, which oxidizes the metal and reduces the acid to regular hydrochloric acid. There’s no gas produced, not because hydrochloric acid doesn’t tend to exist as a gas at normal temperatures—it does, just like the acids mentioned earlier—but because this acid, which would otherwise turn into gas, has more water combined with the oxygenated hydrochloric acid than needed to keep it liquid. As a result, it doesn’t release gas like sulfurous acid does; instead, it stays dissolved and combines with the metallic oxide formed from the excess oxygen.
The fourth phenomenon is, that metals are absolutely insoluble in such acids as have their[Pg 164] bases joined to oxygen by a stronger affinity than these metals are capable of exerting upon that acidifying principle. Hence silver, mercury, and lead, in their metallic states, are insoluble in muriatic acid, but, when previously oxydated, they become readily soluble without effervescence.
The fourth phenomenon is that metals are completely insoluble in acids where their[Pg 164] bases are bonded to oxygen with a stronger attraction than the metals can exert on that acidifying agent. Therefore, silver, mercury, and lead, in their metallic forms, do not dissolve in muriatic acid, but once they are oxidized, they easily dissolve without bubbling.
From these phenomena it appears that oxygen is the bond of union between metals and acids; and from this we are led to suppose that oxygen is contained in all substances which have a strong affinity with acids: Hence it is very probable the four eminently salifiable earths contain oxygen, and their capability of uniting with acids is produced by the intermediation of that element. What I have formerly noticed relative to these earths is considerably strengthened by the above considerations, viz. that they may very possibly be metallic oxyds, with which oxygen has a stronger affinity than with charcoal, and consequently not reducible by any known means.
From these phenomena, it seems that oxygen is the connection between metals and acids; and this leads us to believe that oxygen is present in all substances that have a strong attraction to acids. Therefore, it's very likely that the four highly reactive earths contain oxygen, and their ability to combine with acids is due to the presence of that element. What I've previously mentioned about these earths is significantly supported by the above ideas, namely that they could very well be metallic oxides, which have a stronger bond with oxygen than with carbon, and therefore can't be reduced by any known methods.
All the acids hitherto known are enumerated in the following table, the first column of which contains the names of the acids according to the new nomenclature, and in the second column are placed the bases or radicals of these acids, with observations.[Pg 165]
All the acids known so far are listed in the following table. The first column shows the names of the acids according to the new naming system, and the second column contains the bases or radicals of these acids, along with comments.[Pg 165]
Names of the Acids. | Names of the Bases, with Observations. |
1. Sulphurous | }Sulphur. |
2. Sulphuric | } |
3. Phosphorous | }Phosphorus. |
4. Phosphoric | } |
5. Muriatic | }Muriatic radical or base, hitherto unknown. |
6. Oxygenated muriatic | } |
7. Nitrous | } |
8. Nitric | }Azote. |
9. Oxygenated nitric | } |
10. Carbonic | Charcoal |
}The bases or radicals of all these acids | |
11. Acetous | }seem to be formed by a combination |
12. Acetic | }of charcoal and hydrogen; |
13. Oxalic | }and the only difference seems to be |
14. Tartarous | }owing to the different proportions in |
15. Pyro-tartarous | }which these elements combine to form |
16. Citric | }their bases, and to the different doses |
17. Malic | }of oxygen in their acidification. A |
18. Pyro-lignous | }connected series of accurate experiments |
19. Pyro-mucous | }is still wanted upon this subject. |
20. Gallic | }Our knowledge of the bases of |
21. Prussic | }these acids is hitherto imperfect; we |
22. Benzoic | }only know that they contain hydrogen |
23. Succinic | }and charcoal as principal elements, |
24. Camphoric | }and that the prussic acid contains |
25. Lactic | }azote. |
26. Saccholactic | } |
27. Bombic | }The base of these and all acids |
28. Formic | }procured from animal substances seems |
29. Sebacic | }to consist of charcoal, hydrogen, |
}phosphorous, and azote. | |
30. Boracic | }The bases of these two are hitherto |
31. Fluoric | }entirely unknown. |
32. Antimonic | Antimony. |
33. Argentic | Silver. |
34. Arseniac(A) | Arsenic. |
[Pg 166] | |
35. Bismuthic | Bismuth. |
36. Cobaltic | Cobalt. |
37. Cupric | Copper. |
38. Stannic | Tin. |
39. Ferric | Iron. |
40. Manganic | Manganese. |
41. Mercuric(B) | Mercury. |
42. Molybdic | Molybdena. |
43. Nickolic | Nickel. |
44. Auric | Gold. |
45. Platinic | Platina. |
46. Plumbic | Lead. |
47. Tungstic | Tungstein. |
48. Zincic | Zinc. |
[Note A: This term swerves a little from the rule in making the name of this acid terminate in ac instead of ic. The base and acid are distinguished in French by arsenic and arsenique; but, having chosen the English termination ic to translate the French ique, I was obliged to use this small deviation.—E.]
[Note A: This term deviates slightly from the standard by ending the name of this acid with ac instead of ic. In French, the base and acid are differentiated as arsenic and arsenique; however, after opting for the English ending ic to translate the French ique, I had to make this minor exception.—E.]
[Note B: Mr Lavoisier has hydrargirique; but mercurius being used for the base or metal, the name of the acid, as above, is equally regular, and less harsh.—E.]
[Note B: Mr. Lavoisier has hydrargirique; but since mercurius is used for the base or metal, the name of the acid, as mentioned above, is equally correct and less harsh.—E.]
In this list, which contains 48 acids, I have enumerated 17 metallic acids hitherto very imperfectly known, but upon which Mr Berthollet is about to publish a very important work. It cannot be pretended that all the acids which exist in nature, or rather all the acidifiable bases, are yet discovered; but, on the other hand, there are considerable grounds for supposing that a more accurate investigation than has hitherto been attempted will diminish the number of the vegetable acids, by showing that several of these, at present considered as distinct acids, are only[Pg 167] modifications of others. All that can be done in the present state of our knowledge is, to give a view of chemistry as it really is, and to establish fundamental principles, by which such bodies as may be discovered in future may receive names, in conformity with one uniform system.
In this list, which includes 48 acids, I've listed 17 metallic acids that are not very well known so far, but Mr. Berthollet is about to publish an important work on them. We can't claim that all the acids that exist in nature, or rather all the acidifiable bases, have been discovered yet; however, there is strong reason to believe that a more thorough investigation than what has been done so far will reduce the number of vegetable acids by showing that several currently regarded as distinct acids are just[Pg 167] variations of others. All we can do at this point in our understanding is to present a view of chemistry as it truly is and to establish fundamental principles, so that any substances discovered in the future can be named in accordance with a consistent system.
The known salifiable bases, or substances capable of being converted into neutral salts by union with acids, amount to 24; viz. 3 alkalies, 4 earths, and 17 metallic substances; so that, in the present state of chemical knowledge, the whole possible number of neutral salts amounts to 1152[33]. This number is upon the supposition that the metallic acids are capable of dissolving other metals, which is a new branch of chemistry not hitherto investigated, upon which depends all the metallic combinations named vitreous. There is reason to believe that many of these supposable saline combinations are not capable of being formed, which must greatly reduce the real number of neutral salts producible by nature and art. Even if we suppose the real number to amount only to five or six hundred species of possible neutral salts, it is evident that, were we to distinguish them, after[Pg 168] the manner of the ancients, either by the names of their first discoverers, or by terms derived from the substances from which they are procured, we should at last have such a confusion of arbitrary designations, as no memory could possibly retain. This method might be tolerable in the early ages of chemistry, or even till within these twenty years, when only about thirty species of salts were known; but, in the present times, when the number is augmenting daily, when every new acid gives us 24 or 48 new salts, according as it is capable of one or two degrees of oxygenation, a new method is certainly necessary. The method we have adopted, drawn from the nomenclature of the acids, is perfectly analogical, and, following nature in the simplicity of her operations, gives a natural and easy nomenclature applicable to every possible neutral salt.
The known bases that can form neutral salts when combined with acids total 24: 3 alkalis, 4 earths, and 17 metallic substances. Based on current chemical knowledge, the total possible number of neutral salts is 1152.[33]. This assumes that metallic acids can dissolve other metals, which is a new area of chemistry that hasn't been explored yet, and it’s crucial for understanding all the metallic combinations called vitreous. There's good reason to think that many of these theoretical salt combinations can't actually be formed, which would significantly lower the actual number of neutral salts that nature and human creation can produce. Even if we consider the actual number to be only five or six hundred types of possible neutral salts, it’s clear that if we tried to classify them like the ancients did—with names based on their first discoverers or terms derived from their source substances—we would end up with so many arbitrary names that no one could remember them all. This approach might have worked in the early days of chemistry or even up until twenty years ago, when only about thirty types of salts were known. But now, with the number of salts increasing daily, where every new acid can give us 24 or 48 new salts depending on its level of oxygenation, a new system is definitely needed. The system we've chosen, based on the naming of acids, is completely logical and aligns with the simplicity of nature’s processes, providing a straightforward and effective naming system for every possible neutral salt.
In giving names to the different acids, we express the common property by the generical term acid, and distinguish each species by the name of its peculiar acidifiable base. Hence the acids formed by the oxygenation of sulphur, phosphorus, charcoal, &c. are called sulphuric acid, phosphoric acid, carbonic acid, &c. We thought it likewise proper to indicate the different degrees of saturation with oxygen, by different terminations of the same specific names.[Pg 169] Hence we distinguish between sulphurous and sulphuric, and between phosphorous and phosphoric acids, &c.
When naming the different acids, we use the general term acid to express the common property and specify each type by the name of its unique acidifying base. Therefore, the acids created from the oxidation of sulfur, phosphorus, charcoal, etc., are referred to as sulphuric acid, phosphoric acid, carbonic acid, etc. We also deemed it appropriate to show the various levels of oxygen saturation by using different endings for the same specific names.[Pg 169] Thus, we differentiate between sulfurous and sulfuric, as well as phosphorous and phosphoric acids, etc.
By applying these principles to the nomenclature of neutral salts, we give a common term to all the neutral salts arising from the combination of one acid, and distinguish the species by adding the name of the salifiable base. Thus, all the neutral salts having sulphuric acid in their composition are named sulphats; those formed by the phosphoric acid, phosphats, &c. The species being distinguished by the names of the salifiable bases gives us sulphat of potash, sulphat of soda, sulphat of ammoniac, sulphat of lime, sulphat of iron, &c. As we are acquainted with 24 salifiable bases, alkaline, earthy, and metallic, we have consequently 24 sulphats, as many phosphats, and so on through all the acids. Sulphur is, however, susceptible of two degrees of oxygenation, the first of which produces sulphurous, and the second, sulphuric acid; and, as the neutral salts produced by these two acids, have different properties, and are in fact different salts, it becomes necessary to distinguish these by peculiar terminations; we have therefore distinguished the neutral salts formed by the acids in the first or lesser degree of oxygenation, by changing the termination at into ite, as sulphites, phosphites[34], &c. Thus, oxygenated[Pg 170] or acidified sulphur, in its two degrees of oxygenation is capable of forming 48 neutral salts, 24 of which are sulphites, and as many sulphats; which is likewise the case with all the acids capable of two degrees of oxygenation[35].
By applying these principles to the naming of neutral salts, we provide a common term for all the neutral salts formed by one acid, and we distinguish the types by adding the name of the basic compound. Therefore, all the neutral salts containing sulfuric acid are called sulfates; those made with phosphoric acid are phosphates, etc. The species identified by the names of the basic compounds includes sulfate of potash, sulfate of soda, sulfate of ammonia, sulfate of lime, sulfate of iron, and so on. Since we know of 24 basic compounds, whether they are alkaline, earthy, or metallic, we have 24 sulfates, just as many phosphates, and this extends to all acids. However, sulfur can exist in two states of oxygenation, the first resulting in sulfurous acid and the second in sulfuric acid; since the neutral salts produced by these two acids have different properties and are, in fact, different salts, it’s necessary to differentiate these by specific endings. Therefore, we have designated the neutral salts formed by acids in the first or lower degree of oxygenation by changing the ending ate to ite, such as sulfites, phosphites[34], etc. Thus, oxygenated[Pg 170] or acidified sulfur, at its two levels of oxygenation, can create 48 neutral salts, 24 of which are sulfites, and the same applies to all acids capable of two levels of oxygenation[35].
It were both tiresome and unnecessary to follow these denominations through all the varieties of their possible application; it is enough to have given the method of naming the various salts, which, when once well understood, is easily applied to every possible combination. The name of the combustible and acidifiable body being once known, the names of the acid it is capable of forming, and of all the neutral combinations[Pg 171] the acid is susceptible of entering into, are most readily remembered. Such as require a more complete illustration of the methods in which the new nomenclature is applied will, in the Second Part of this book, find Tables which contain a full enumeration of all the neutral salts, and, in general, all the possible chemical combinations, so far as is consistent with the present state of our knowledge. To these I shall subjoin short explanations, containing the best and most simple means of procuring the different species of acids, and some account of the general properties of the neutral salts they produce.
It would be both tedious and unnecessary to go through all the different ways these names can be applied; it’s enough to explain the method for naming the various salts, which, once clearly understood, can be easily applied to any combination. Once you know the name of the flammable and acidic substance, it’s easy to remember the names of the acids it can form and all the neutral combinations that can occur with that acid[Pg 171]. Those who need a more detailed illustration of how the new naming system works will find Tables in the Second Part of this book that list all the neutral salts and, generally, all the possible chemical combinations based on our current understanding. I will also add brief explanations with the best and simplest methods for obtaining the different types of acids and an overview of the general properties of the neutral salts they create.
I shall not deny, that, to render this work more complete, it would have been necessary to add particular observations upon each species of salt, its solubility in water and alkohol, the proportions of acid and of salifiable base in its composition, the quantity of its water of cristallization, the different degrees of saturation it is susceptible of, and, finally, the degree of force or affinity with which the acid adheres to the base. This immense work has been already begun by Messrs Bergman, Morveau, Kirwan, and other celebrated chemists, but is hitherto only in a moderate state of advancement, even the principles upon which it is founded are not perhaps sufficiently accurate.[Pg 172]
I won't deny that, to make this work more complete, it would have been necessary to include specific details about each type of salt, such as its solubility in water and alcohol, the ratios of acid and basic components in its makeup, the amount of water it contains in crystal form, the different levels of saturation it can achieve, and finally, the strength or affinity with which the acid bonds to the base. This extensive project has already been started by Messrs Bergman, Morveau, Kirwan, and other well-known chemists, but it is still only moderately advanced, and even the principles it’s based on may not be entirely accurate.[Pg 172]
These numerous details would have swelled this elementary treatise to much too great a size; besides that, to have gathered the necessary materials, and to have completed all the series of experiments requisite, must have retarded the publication of this book for many years. This is a vast field for employing the zeal and abilities of young chemists, whom I would advise to endeavour rather to do well than to do much, and to ascertain, in the first place, the composition of the acids, before entering upon that of the neutral salts. Every edifice which is intended to resist the ravages of time should be built upon a sure foundation; and, in the present state of chemistry, to attempt discoveries by experiments, either not perfectly exact, or not sufficiently rigorous, will serve only to interrupt its progress, instead of contributing to its advancement.
These many details would have made this basic treatise much too long; moreover, collecting the necessary materials and completing all the required experiments would have delayed the publication of this book by several years. This is a huge area for young chemists to channel their passion and skills, and I would suggest they focus on doing quality work rather than a lot of it, starting by determining the composition of acids before tackling neutral salts. Any structure intended to stand the test of time needs a solid foundation; and in the current state of chemistry, trying to make discoveries through experiments that are either not entirely precise or not rigorous enough will only hinder progress instead of helping it grow.
FOOTNOTES:
[33] This number excludes all triple salts, or such as contain more than one salifiable base, all the salts whose bases are over or under saturated with acid, and those formed by the nitro-muriatic acid.—E.
[33] This number does not include any triple salts, or those that have more than one base that can react with an acid, nor the salts with bases that are either oversaturated or undersaturated with acid, and those made with nitro-muriatic acid.—E.
[34] As all the specific names of the acids in the new nomenclature are adjectives, they would have applied severally to the various salifiable bases, without the invention of other terms, with perfect distinctness. Thus, sulphurous potash, and sulphuric potash, are equally distinct as sulphite of potash, and sulphat of potash; and have the advantage of being more easily retained in the memory, because more naturally arising from the acids themselves, than the arbitrary terminations adopted by Mr Lavoisier.—E.
[34] Since all the specific names of the acids in the new naming system are adjectives, they could clearly be applied to the different salifiable bases without needing to create additional terms. For example, sulphurous potash and sulphuric potash are just as clear as sulphite of potash and sulphat of potash; and they’re easier to remember because they come more naturally from the acids themselves than the arbitrary endings introduced by Mr. Lavoisier.—E.
[35] There is yet a third degree of oxygenation of acids, as the oxygenated muriatic and oxygenated nitric acids. The terms applicable to the neutral salts resulting from the union of these acids with salifiable bases is supplied by the Author in the Second Part of this Work. These are formed by prefixing the word oxygenated to the name of the salt produced by the second degree of oxygenation. Thus, oxygenated muriat of potash, oxygenated nitrat of soda, &c.—E.
[35] There is also a third level of oxygenation for acids, which includes oxygenated muriatic and oxygenated nitric acids. The terminology for the neutral salts formed when these acids combine with salifiable bases is provided by the Author in the Second Part of this Work. These salts are named by adding the word oxygenated before the name of the salt created from the second level of oxygenation. For example, oxygenated muriat of potash, oxygenated nitrat of soda, etc.—E.
PART II.
Of the Combination of Acids with Salifiable Bases, and of the Formation of Neutral Salts.
INTRODUCTION.
If I had strictly followed the plan I at first laid down for the conduct of this work, I would have confined myself, in the Tables and accompanying observations which compose this Second Part, to short definitions of the several known acids, and abridged accounts of the processes by which they are obtainable, with a mere nomenclature or enumeration of the neutral salts which result from the combination of these acids with the various salifiable bases. But I afterwards found that the addition of similar Tables of all the simple substances which enter[Pg 174] into the composition of the acids and oxyds, together with the various possible combinations of these elements, would add greatly to the utility of this work, without being any great increase to its size. These additions, which are all contained in the twelve first sections of this Part, and the Tables annexed to these, form a kind of recapitulation of the first fifteen Chapters of the First Part: The rest of the Tables and Sections contain all the saline combinations.
If I had strictly followed the plan I initially set out for this work, I would have limited myself, in the Tables and the accompanying observations that make up this Second Part, to brief definitions of the various known acids and summarized descriptions of the processes used to obtain them, along with just a list of the neutral salts that result from the combination of these acids with different salifiable bases. However, I later realized that adding similar Tables of all the simple substances that compose the acids and oxides, along with the various possible combinations of these elements, would greatly enhance the usefulness of this work without significantly increasing its length. These additions, which are included in the first twelve sections of this Part, and the Tables attached to them, serve as a kind of recap of the first fifteen Chapters of the First Part: The remaining Tables and Sections include all the saline combinations.
It must be very apparent that, in this Part of the Work, I have borrowed greatly from what has been already published by Mr de Morveau in the First Volume of the Encyclopedie par ordre des Matières. I could hardly have discovered a better source of information, especially when the difficulty of consulting books in foreign languages is considered. I make this general acknowledgment on purpose to save the trouble of references to Mr de Morveau's work in the course of the following part of mine.[Pg 175]
It should be clear that in this part of my work, I have heavily referenced what Mr. de Morveau published in the first volume of the Encyclopédie par ordre des Matières. It’s tough to find a better source of information, especially considering how hard it is to consult books in other languages. I’m making this general acknowledgment so I won’t have to repeatedly reference Mr. de Morveau’s work throughout this part.[Pg 175]
TABLE OF SIMPLE SUBSTANCES.
Simple substances belonging to all the kingdoms of nature, which may be considered as the elements of bodies.
Simple substances from all parts of nature, which can be viewed as the building blocks of matter.
New Names. | Correspondent old Names. |
Light | Light. |
Caloric | {Heat. |
{Principle or element of heat. | |
{Fire. Igneous fluid. | |
{Matter of fire and of heat. | |
Oxygen | {Dephlogisticated air. |
{Empyreal air. | |
{Vital air, or | |
{Base of vital air. | |
Azote | {Phlogisticated air or gas. |
{Mephitis, or its base. | |
Hydrogen | {Inflammable air or gas, |
{or the base of inflammable air. |
Oxydable and Acidifiable simple Substance not Metallic.
New Names. | Correspondent old names. |
Sulphur | } |
Phosphorous | }The same names. |
Charcoal | } |
Muriatic radical | } |
Fluoric radical | }Still unknown. |
Boracic radical | } |
Oxydable and Acidifiable simple Metallic Bodies
New Names. | Correspondent Old Names. | |||
Antimony | } | { | Antimony. | |
Arsenic | } | { | Arsenic. | |
Bismuth | } | { | Bismuth. | |
Cobalt | } | { | Cobalt. | |
Copper | } | { | Copper. | |
Gold | } | { | Gold. | |
Iron | } | { | Iron. | |
Lead | } Regulus of | { | Lead. | |
Manganese | } | { | Manganese. | |
Mercury | } | { | Mercury. | |
Molybdena | } | { | Molybdena. | |
Nickel | } | { | Nickel. | |
Platina | } | { | Platina. | |
Silver | } | { | Silver. | |
Tin | } | { | Tin. | |
Tungstein | } | { | Tungstein. | |
Zinc | } | { | Zinc. |
Salifiable simple Earthy Substances.
New Names. | Correspondent old Names. |
Lime | {Chalk, calcareous earth. |
{Quicklime. | |
Magnesia | {Magnesia, base of Epsom salt. |
{Calcined or caustic magnesia. | |
Barytes | Barytes, or heavy earth. |
Argill | Clay, earth of alum. |
Silex | Siliceous or vitrifiable earth. |
Sec. I.—Observations upon the Table of Simple Substances.
The principle object of chemical experiments is to decompose natural bodies, so as separately to examine the different substances which enter into their composition. By consulting chemical systems, it will be found that this science of chemical analysis has made rapid progress in our own times. Formerly oil and salt were considered as elements of bodies, whereas later observation and experiment have shown that all salts, instead of being simple, are composed of an acid united to a base. The bounds of analysis have been greatly enlarged by modern discoveries[36]; the acids are shown to be composed of oxygen, as an acidifying principle common to all, united in each to a particular base. I have proved what Mr Haffenfratz had[Pg 177] before advanced, that these radicals of the acids are not all simple elements, many of them being, like the oily principle, composed of hydrogen and charcoal. Even the bases of neutral salts have been proved by Mr Berthollet to be compounds, as he has shown that ammoniac is composed of azote and hydrogen.
The main goal of chemical experiments is to break down natural substances so we can closely examine the different materials that make them up. If you look at chemical theories, you'll see that the science of chemical analysis has advanced quickly in recent times. In the past, oil and salt were thought to be basic elements; however, more recent observations and experiments have revealed that all salts, instead of being simple, are made up of an acid combined with a base. The scope of analysis has expanded significantly due to modern discoveries[36]; it has been shown that acids consist of oxygen, which acts as a common acidifying agent, combined with specific bases. I have demonstrated what Mr. Haffenfratz previously noted, that the radicals of acids are not all simple elements; many of them, like the oily principle, are made of hydrogen and carbon. Mr. Berthollet has also shown that even the bases of neutral salts are compounds, revealing that ammonia is made up of nitrogen and hydrogen.
Thus, as chemistry advances towards perfection, by dividing and subdividing, it is impossible to say where it is to end; and these things we at present suppose simple may soon be found quite otherwise. All we dare venture to affirm of any substance is, that it must be considered as simple in the present state of our knowledge, and so far as chemical analysis has hitherto been able to show. We may even presume that the earths must soon cease to be considered as simple bodies; they are the only bodies of the salifiable class which have no tendency to unite with oxygen; and I am much inclined to believe that this proceeds from their being already saturated with that element. If so, they will fall to be considered as compounds consisting of simple substances, perhaps metallic, oxydated to a certain degree. This is only hazarded as a conjecture; and I trust the reader will take care not to confound what I have related as truths, fixed on the firm basis of observation and experiment, with mere hypothetical conjectures.[Pg 178]
As chemistry progresses towards perfection through continuous division and subdivision, it’s impossible to predict where it will finally end. What we currently consider simple might soon be understood quite differently. The only thing we can confidently say about any substance is that, based on our current knowledge and what chemical analysis has shown so far, it should be regarded as simple. We may even speculate that the earths will soon no longer be viewed as simple substances; they are the only materials in the salifiable class that don’t tend to combine with oxygen, and I believe this might be because they are already saturated with that element. If that’s the case, they should be regarded as compounds made up of simpler substances, possibly metallic, oxidized to some extent. This is just a guess, and I hope the reader will be careful not to confuse what I’ve presented as established truths based on observation and experiment with mere hypothetical ideas.[Pg 178]
The fixed alkalies, potash, and soda, are omitted in the foregoing Table, because they are evidently compound substances, though we are ignorant as yet what are the elements they are composed of.[Pg 179]
The fixed alkalis, potash, and soda, are not included in the previous Table because they are clearly compound substances, although we still don’t know what elements they are made of.[Pg 179]
Table of compound oxydable and acidifiable bases.
Names of the radicals. | ||
Oxydable or acidifiable | { Nitro-muriatic radical or | |
base, from the mineral | { base of the acid formerly | |
kingdom. | { called aqua regia. | |
{ Tartarous radical or base. | ||
{ Malic. | } | |
{ Citric. | } | |
{ Pyro-lignous. | } | |
Oxydable or acidifiable | { Pyro-mucous. | } |
hydro-carbonous or | { Pyro-tartarous. | } |
carbono-hydrous radicals | { Oxalic. | } |
from the vegetable | { Acetous. | } |
kingdom. | { Succinic. | } Radicals |
{ Benzoic. | } | |
{ Camphoric. | } | |
{ Gallic. | } | |
} | ||
Oxydable or acidifiable | { Lactic. | } |
radicals from the animal | { Saccholactic. | } |
kingdom, which | { Formic. | } |
mostly contain azote, | { Bombic. | } |
and frequently phosphorus. | { Sebacic. | } |
{ Lithic. | } | |
{ Prussic. | } |
Note.—The radicals from the vegetable kingdom are converted by a first degree of oxygenation into vegetable oxyds, such as sugar, starch, and gum or mucus: Those of the animal kingdom by the same means form animal oxyds, as lymph, &c.—A.[Pg 180]
Note.—The compounds derived from plants are transformed through the initial stage of oxidation into plant oxides, like sugar, starch, and gum or mucus. Similarly, compounds from the animal kingdom undergo the same process to create animal oxides, such as lymph, etc.—A.[Pg 180]
Sect. 2.—Observations upon the Table of Compound Radicals.
The older chemists being unacquainted with the composition of acids, and not suspecting them to be formed by a peculiar radical or base for each, united to an acidifying principle or element common to all, could not consequently give any name to substances of which they had not the most distant idea. We had therefore to invent a new nomenclature for this subject, though we were at the same time sensible that this nomenclature must be susceptible of great modification when the nature of the compound radicals shall be better understood[37].
The older chemists, unfamiliar with the makeup of acids and unaware that each one is made up of a specific radical or base combined with a common acidifying element, were unable to name substances they had no clear concept of. As a result, we had to create a new naming system for this topic, though we recognized that this system would likely need significant changes as we gain a better understanding of the nature of the compound radicals.[37]
The compound oxydable and acidifiable radicals from the vegetable and animal kingdoms, enumerated in the foregoing table, are not hitherto reducible to systematic nomenclature, because their exact analysis is as yet unknown. We only know in general, by some experiments of my own, and some made by Mr Hassenfratz, that most of the vegetable acids, such as the tartarous, oxalic, citric, malic, acetous, pyro-tartarous, and pyromucous, have radicals composed of hydrogen and charcoal, combined in[Pg 181] such a way as to form single bases, and that these acids only differ from each other by the proportions in which these two substances enter into the composition of their bases, and by the degree of oxygenation which these bases have received. We know farther, chiefly from the experiments of Mr Berthollet, that the radicals from the animal kingdom, and even some of those from vegetables, are of a more compound nature, and, besides hydrogen and charcoal, that they often contain azote, and sometimes phosphorus; but we are not hitherto possessed of sufficiently accurate experiments for calculating the proportions of these several substances. We are therefore forced, in the manner of the older chemists, still to name these acids after the substances from which they are procured. There can be little doubt that these names will be laid aside when our knowledge of these substances becomes more accurate and extensive; the terms hydro-carbonous, hydro-carbonic, carbono-hydrous, and carbono hydric[38], will then become substituted for those we now employ, which will then only remain as testimonies of the imperfect state in which this part of chemistry was transmitted to us by our predecessors.
The oxidizable and acidifiable radicals from plants and animals listed in the previous table can't yet be classified systematically because we don't fully understand their composition. From my own experiments and those of Mr. Hassenfratz, we know that most vegetable acids—like tartaric, oxalic, citric, malic, acetic, pyro-tartaric, and pyromucic acids—have radicals made up of hydrogen and carbon arranged to form single bases. These acids only differ from each other in the amounts of these two elements in their bases and the level of oxygenation those bases have undergone. Additionally, from Mr. Berthollet's experiments, we've learned that the radicals from animal sources, and some from plants, are more complex and often contain nitrogen and sometimes phosphorus, but we still lack precise experiments to determine the proportions of these substances. Therefore, like the earlier chemists, we still name these acids based on the materials they come from. It's likely that these names will be replaced as our understanding of these substances improves and expands; terms like hydro-carbonous, hydro-carbonic, carbono-hydrous, and carbono hydric[38] will eventually take over the names we currently use, which will then serve as a reminder of how incomplete our knowledge of this area of chemistry was as handed down by previous researchers.
It is evident that the oils, being composed of hydrogen and charcoal combined, are true carbono-hydrous or hydro-carbonous radicals; and, indeed, by adding oxygen, they are convertible into vegetable oxyds and acids, according to their degrees of oxygenation. We cannot, however, affirm that oils enter in their entire state into the composition of vegetable oxyds and acids; it is possible that they previously lose a part either of their hydrogen or charcoal, and that the remaining ingredients no longer exist in the proportions necessary to constitute oils. We still require farther experiments to elucidate these points.
It’s clear that oils, made up of hydrogen and carbon combined, are true hydrocarbons. By adding oxygen, they can be transformed into vegetable oxides and acids, depending on how much oxygen is added. However, we can’t say that oils are fully incorporated into the composition of vegetable oxides and acids; it’s possible that they lose some of their hydrogen or carbon first, and what’s left may not be in the right proportions to be considered oils. We still need more experiments to clarify these points.
Properly speaking, we are only acquainted with one compound radical from the mineral kingdom, the nitro-muriatic, which is formed by the combination of azote with the muriatic radical. The other compound mineral acids have been much less attended to, from their producing less striking phenomena.
Properly speaking, we only know of one compound radical from the mineral kingdom, the nitro-muriatic, which is created by combining nitrogen with the muriatic radical. The other compound mineral acids have been given much less attention because they produce less noticeable effects.
Sect. 3.—Observations upon the Combinations of Light and Caloric with different Substances.
I have not constructed any table of the combinations of light and caloric with the various simple and compound substances, because our conceptions of the nature of these combinations are not hitherto sufficiently accurate. We[Pg 183] know, in general, that all bodies in nature are imbued, surrounded, and penetrated in every way with caloric, which fills up every interval left between their particles; that, in certain cases, caloric becomes fixed in bodies, so as to constitute a part even of their solid substance, though it more frequently acts upon them with a repulsive force, from which, or from its accumulation in bodies to a greater or lesser degree, the transformation of solids into fluids, and of fluids to aëriform elasticity, is entirely owing. We have employed the generic name gas to indicate this aëriform state of bodies produced by a sufficient accumulation of caloric; so that, when we wish to express the aëriform state of muriatic acid, carbonic acid, hydrogen, water, alkohol, &c. we do it by adding the word gas to their names; thus muriatic acid gas, carbonic acid gas, hydrogen gas, aqueous gas, alkoholic gas, &c.
I haven't created any table outlining the combinations of light and heat with various simple and compound substances because our understanding of these combinations isn't quite accurate yet. We[Pg 183] generally know that all bodies in nature are filled, surrounded, and permeated with heat, which occupies every space between their particles; in some cases, heat becomes fixed in substances, making up part of their solid structure. However, it more often acts on them with a repulsive force, which, along with its accumulation to varying degrees in substances, is responsible for the transformation of solids into liquids and liquids into gaseous states. We use the term gas to refer to this gaseous state of substances created by significant heat accumulation; hence, when we want to describe the gaseous state of muriatic acid, carbonic acid, hydrogen, water, alcohol, etc., we simply add the word gas to their names, like muriatic acid gas, carbonic acid gas, hydrogen gas, aqueous gas, alcohol gas, etc.
The combinations of light, and its mode of acting upon different bodies, is still less known. By the experiments of Mr Berthollet, it appears to have great affinity with oxygen, is susceptible of combining with it, and contributes alongst with caloric to change it into the state of gas. Experiments upon vegetation give reason to believe that light combines with certain parts of vegetables, and that the green of their leaves, and the various colours of their flowers, is chiefly[Pg 184] owing to this combination. This much is certain, that plants which grow in darkness are perfectly white, languid, and unhealthy, and that to make them recover vigour, and to acquire their natural colours, the direct influence of light is absolutely necessary. Somewhat similar takes place even upon animals: Mankind degenerate to a certain degree when employed in sedentary manufactures, or from living in crowded houses, or in the narrow lanes of large cities; whereas they improve in their nature and constitution in most of the country labours which are carried on in the open air. Organization, sensation, spontaneous motion, and all the operations of life, only exist at the surface of the earth, and in places exposed to the influence of light. Without it nature itself would be lifeless and inanimate. By means of light, the benevolence of the Deity hath filled the surface of the earth with organization, sensation, and intelligence. The fable of Promotheus might perhaps be considered as giving a hint of this philosophical truth, which had even presented itself to the knowledge of the ancients. I have intentionally avoided any disquisitions relative to organized bodies in this work, for which reason the phenomena of respiration, sanguification, and animal heat, are not considered; but I hope, at some future time, to be able to elucidate these curious subjects.
The ways that light interacts with different substances are still not fully understood. Experiments by Mr. Berthollet show that light has a strong connection with oxygen, can combine with it, and works with heat to change it into gas. Research on plants suggests that light interacts with specific parts of vegetables, and that the green color of leaves and the various colors of flowers are mainly[Pg 184] due to this interaction. It’s clear that plants growing in darkness are completely white, weak, and unhealthy, and they need direct light to regain strength and their natural colors. A similar effect occurs in animals: humans tend to become less vibrant when engaged in sedentary jobs or when living in crowded spaces or narrow alleys of big cities, while they tend to thrive in most outdoor country work. Life processes—like organization, sensation, and movement—only happen at the earth's surface and in places exposed to light. Without light, nature itself would be lifeless and inanimate. Light allows the goodness of the divine to fill the earth’s surface with life, sensitivity, and intelligence. The myth of Prometheus might hint at this philosophical truth, which even the ancients recognized. I have intentionally avoided discussing organized life in this work, which is why topics like respiration, blood formation, and body heat are not covered; however, I hope to explore these fascinating subjects in the future.
[Trancriber's note: The following table has been split into four sections ease reading]
TABLE of the binary Combinations of Oxygen with simple Substances
Combinations of oxygen with simple non-metallic substances. | Names of the simple substances. | First degree of oxygenation. | |
New Names. | Ancient Names. | ||
Caloric | Oxygen gas | Vital or dephlogisticated air | |
Hydrogen. | Water(A). | ||
Azote | Nitrous oxyd, or base of nitrous gas | Nitrous gas or air | |
Charcoal | Oxyd of charcoal, or carbonic oxyd | Unknown | |
Sulphur | Oxyd of sulphur | Soft sulphur | |
Phosphorus | Oxyd of phosphorus {Residuum from the combustion of phosphorus | ||
Muriatic radical | Muriatic oxyd | Unknown | |
Fluoric radical | Fluoric oxyd | Unknown | |
Boracic radical | Boracic oxyd | Unknown | |
Combinations of oxygen with the simple metallic substances. | Antimony | Grey oxyd of antimony | Grey calx of antimony |
Silver | Oxyd of silver | Calx of silver | |
Arsenic | Grey oxyd of arsenic | Grey calx of arsenic | |
Bismuth | Grey oxyd of bismuth | Grey calx of bismuth | |
Cobalt | Grey oxyd of cobalt | Grey calx of cobalt | |
Copper | Brown oxyd of copper | Brown calx of copper | |
Tin | Grey oxyd of tin | Grey calx of tin | |
Iron | Black oxyd of iron | Martial ethiops | |
Manganese | Black oxyd of manganese | Black calx of manganese | |
Mercury | Black oxyd of mercury | Ethiops mineral(B) | |
Molybdena | Oxyd of molybdena | Calx of molybdena | |
Nickel | Oxyd of nickel | Calx of nickel | |
Gold | Yellow oxyd of gold | Yellow calx of gold | |
Platina | Yellow oxyd of platina | Yellow calx of platina | |
Lead | Grey oxyd of lead | Grey calx of lead | |
Tungstein | Oxyd of Tungstein | Calx of Tungstein | |
Zinc | Grey oxyd of zinc | Grey calx of zinc |
Combinations of oxygen with simple non-metallic substances. | Names of the simple substances. | Second degree of oxygenation. | |
New Names. | Ancient Names. | ||
Caloric | |||
Hydrogen. | |||
Azote | Nitrous acid | Smoaking nitrous acid | |
Charcoal | Carbonous acid | Unknown | |
Sulphur | Sulphurous acid | Sulphureous acid | |
Phosphorus | Phosphorous acid | Volatile acid of phosphorus | |
Muriatic radical | Muriatous acid | Unknown | |
Fluoric radical | Fluorous acid | Unknown | |
Boracic radical | Boracous acid | Unknown | |
Combinations of oxygen with the simple metallic substances. | Antimony | White oxyd of antimony | White calx of antimony, diaphoretic antimony |
Silver | |||
Arsenic | White oxyd of arsenic | White calx of arsenic | |
Bismuth | White oxyd of bismuth | White calx of bismuth | |
Cobalt | |||
Copper | Blue and green oxyds of copper | Blue and green calces of copper | |
Tin | White oxyd of tin | White calx of tin, or putty of tin | |
Iron | Yellow and red oxyds of iron | Ochre and rust of iron | |
Manganese | White oxyd of manganese | White calx of manganese | |
Mercury | Yellow and red oxyds of mercury | Turbith mineral, red precipitate, calcinated mercury, precipitate per se | |
Molybdena | |||
Nickel | |||
Gold | Red oxyd of gold | Red calx of gold, purple precipitate of cassius | |
Platina | |||
Lead | Yellow and red oxyds of lead | Massicot and minium | |
Tungstein | |||
Zinc | White oxyd of zinc | White calx of zinc, pompholix |
Combinations of oxygen with simple non-metallic substances. | Names of the simple substances. | Third degree of oxygenation. | |
New Names. | Ancient Names. | ||
Caloric | |||
Hydrogen. | |||
Azote | Nitric acid | Pale, or not smoaking nitrous acid | |
Charcoal | Carbonic acid | Fixed air | |
Sulphur | Sulphuric acid | Vitriolic acid | |
Phosphorus | Phosphoric acid | Phosphoric acid | |
Muriatic radical | Muriatic acid | Marine acid | |
Fluoric radical | Fluoric acid | Unknown till lately | |
Boracic radical | Boracic acid | Homberg's sedative salt | |
Combinations of oxygen with the simple metallic substances. | Antimony | Antimonic acid | |
Silver | Argentic acid | ||
Arsenic | Arseniac acid | Acid of arsenic | |
Bismuth | Bismuthic acid | ||
Cobalt | Cobaltic acid | ||
Copper | Cupric acid | ||
Tin | Stannic acid | ||
Iron | Ferric acid | ||
Manganese | Manganesic acid | ||
Mercury | Mercuric acid | ||
Molybdena | Molybdic acid | Acid of molybdena | |
Nickel | Nickelic acid | ||
Gold | Auric acid | ||
Platina | Platinic acid | ||
Lead | Plumbic acid | ||
Tungstein | Tungstic acid | Acid of Tungstein | |
Zinc | Zincic acid |
Combinations of oxygen with simple non-metallic substances. | Names of the simple substances. | Fourth degree of oxygenation. | |
New Names. | Ancient Names. | ||
Caloric | |||
Hydrogen. | |||
Azote | Oxygenated nitric | Unknown acid | |
Charcoal | Oxygenated carbonic acid | Unknown | |
Sulphur | Oxygenated sulphuric acid | Unknown | |
Phosphorus | Oxygenated phosphoric acid | Unknown | |
Muriatic radical | Oxygenated muriatic acid | Dephlogisticated marine acid | |
Fluoric radical | |||
Boracic radical | |||
Combinations of oxygen with the simple metallic substances. | Antimony | ||
Silver | |||
Arsenic | Oxygenated arseniac acid | Unknown | |
Bismuth | |||
Cobalt | |||
Copper | |||
Tin | |||
Iron | |||
Manganese | |||
Mercury | |||
Molybdena | Oxygenated molybdic acid | Unknown | |
Nickel | |||
Gold | |||
Platina | |||
Lead | |||
Tungstein | Oxygenated Tungstic acid | Unknown | |
Zinc |
[Note A: Only one degree of oxygenation of hydrogen is hitherto known.—A.]
[Note A: Only one level of hydrogen oxygenation is known so far.—A.]
[Note B: Ethiops mineral is the sulphuret of mercury; this should have been called black precipitate of mercury.—E.][Pg 185]
[Note B: Ethiops mineral is the sulfide of mercury; this should have been called black precipitate of mercury.—E.][Pg 185]
Sect. 4.—Observations upon the Combinations of Oxygen with the simple Substances.
Oxygen forms almost a third of the mass of our atmosphere, and is consequently one of the most plentiful substances in nature. All the animals and vegetables live and grow in this immense magazine of oxygen gas, and from it we procure the greatest part of what we employ in experiments. So great is the reciprocal affinity between this element and other substances, that we cannot procure it disengaged from all combination. In the atmosphere it is united with caloric, in the state of oxygen gas, and this again is mixed with about two thirds of its weight of azotic gas.
Oxygen makes up nearly a third of the mass of our atmosphere, making it one of the most abundant substances in nature. All animals and plants thrive and develop in this vast supply of oxygen gas, and we source most of what we use in experiments from it. The strong attraction between this element and others means we can't obtain it completely free from any combination. In the atmosphere, it exists combined with heat as oxygen gas, which is also mixed with about two-thirds of its weight in nitrogen gas.
Several conditions are requisite to enable a body to become oxygenated, or to permit oxygen to enter into combination with it. In the first place, it is necessary that the particles of the body to be oxygenated shall have less reciprocal attraction with each other than they have for the oxygen, which otherwise cannot possibly combine with them. Nature, in this case, may be assisted by art, as we have it in our power to diminish the attraction of the particles of bodies almost at will by heating them, or, in other words, by introducing caloric into the interstices[Pg 186] between their particles; and, as the attraction of these particles for each other is diminished in the inverse ratio of their distance, it is evident that there must be a certain point of distance of particles when the affinity they possess with each other becomes less than that they have for oxygen, and at which oxygenation must necessarily take place if oxygen be present.
Several conditions are necessary for a substance to become oxygenated, or to allow oxygen to combine with it. First, the particles of the substance that needs oxygen must be less attracted to each other than they are to the oxygen; otherwise, they won't be able to combine. Nature can be assisted by human intervention since we can reduce the attraction between the particles almost at will by heating them, or in other words, by introducing heat into the spaces[Pg 186] between their particles. Since the attraction between these particles decreases as they move apart, it's clear that there is a specific distance at which the attraction they have for each other is weaker than their attraction to oxygen, and at this point, oxygenation will occur if oxygen is present.
We can readily conceive that the degree of heat at which this phenomenon begins must be different in different bodies. Hence, on purpose to oxygenate most bodies, especially the greater part of the simple substances, it is only necessary to expose them to the influence of the air of the atmosphere in a convenient degree of temperature. With respect to lead, mercury, and tin, this needs be but little higher than the medium temperature of the earth; but it requires a more considerable degree of heat to oxygenate iron, copper, &c. by the dry way, or when this operation is not assisted by moisture. Sometimes oxygenation takes place with great rapidity, and is accompanied by great sensible heat, light, and flame; such is the combustion of phosphorus in atmospheric air, and of iron in oxygen gas. That of sulphur is less rapid; and the oxygenation of lead, tin, and most of the metals, takes place vastly slower, and consequently the disengagement of caloric, and more especially of light, is hardly sensible.[Pg 187]
We can easily understand that the temperature at which this process starts can vary between different materials. Therefore, to oxygenate most substances, especially many of the basic elements, we just need to expose them to the air at a suitable temperature. For lead, mercury, and tin, this temperature needs to be just slightly above the average temperature of the Earth; however, for iron, copper, and similar materials, a significantly higher temperature is needed to oxygenate them without moisture. Sometimes, oxygenation happens very quickly and produces a lot of heat, light, and flames; for instance, when phosphorus burns in air, or when iron reacts in oxygen gas. Sulfur reacts more slowly, and the oxygenation of lead, tin, and most metals happens much more gradually, so the release of heat, and especially light, is barely noticeable.[Pg 187]
Some substances have so strong an affinity with oxygen, and combine with it in such low degrees of temperature, that we cannot procure them in their unoxygenated state; such is the muriatic acid, which has not hitherto been decomposed by art, perhaps even not by nature, and which consequently has only been found in the state of acid. It is probable that many other substances of the mineral kingdom are necessarily oxygenated in the common temperature of the atmosphere, and that being already saturated with oxygen, prevents their farther action upon that element.
Some substances have such a strong attraction to oxygen and combine with it at such low temperatures that we can’t obtain them without oxygen. Muriatic acid is one example; it hasn’t been broken down by science, and possibly not even by nature, so it’s only been found in its acidic form. It’s likely that many other substances in the mineral kingdom are naturally oxygenated at the regular temperature of the atmosphere, and since they are already saturated with oxygen, they can't react further with it.
There are other means of oxygenating simple substances besides exposure to air in a certain degree of temperature, such as by placing them in contact with metals combined with oxygen, and which have little affinity with that element. The red oxyd of mercury is one of the best substances for this purpose, especially with bodies which do not combine with that metal. In this oxyd the oxygen is united with very little force to the metal, and can be driven out by a degree of heat only sufficient to make glass red hot; wherefore such bodies as are capable of uniting with oxygen are readily oxygenated, by means of being mixed with red oxyd of mercury, and moderately heated. The same effect may be, to a certain degree, produced by means of the black oxyd of manganese, the red oxyd of lead,[Pg 188] the oxyds of silver, and by most of the metallic oxyds, if we only take care to choose such as have less affinity with oxygen than the bodies they are meant to oxygenate. All the metallic reductions and revivifications belong to this class of operations, being nothing more than oxygenations of charcoal, by means of the several metallic oxyds. The charcoal combines with the oxygen and with caloric, and escapes in form of carbonic acid gas, while the metal remains pure and revivified, or deprived of the oxygen which before combined with it in the form of oxyd.
There are other ways to oxygenate simple substances besides exposing them to air at a certain temperature, like putting them in contact with metals that are combined with oxygen and have low affinity for that element. Red mercury oxide is one of the best substances for this purpose, especially for materials that don’t react with that metal. In this oxide, the oxygen is only weakly bonded to the metal, and it can be released with just enough heat to make glass glow red. Therefore, substances that can bond with oxygen are easily oxygenated by mixing them with red mercury oxide and heating them moderately. A similar effect can be achieved to some extent with black manganese oxide, red lead oxide,[Pg 188] silver oxides, and most other metallic oxides, as long as we choose ones that have less affinity for oxygen than the materials we want to oxygenate. All metallic reductions and revivifications fall under this category of processes, being simply the oxygenation of charcoal using various metallic oxides. The charcoal combines with the oxygen and heat, escaping as carbon dioxide gas, while the metal remains pure and revived, or free from the oxygen that previously bonded with it as oxide.
All combustible substances may likewise be oxygenated by means of mixing them with nitrat of potash or of soda, or with oxygenated muriat of potash, and subjecting the mixture to a certain degree of heat; the oxygen, in this case, quits the nitrat or the muriat, and combines with the combustible body. This species of oxygenation requires to be performed with extreme caution, and only with very small quantities; because, as the oxygen enters into the composition of nitrats, and more especially of oxygenated muriats, combined with almost as much caloric as is necessary for converting it into oxygen gas, this immense quantity of caloric becomes suddenly free the instant of the combination of the oxygen with the combustible[Pg 189] body, and produces such violent explosions as are perfectly irresistible.
All combustible substances can also be oxygenated by mixing them with potassium nitrate or sodium nitrate, or with potassium chlorate, and applying a certain amount of heat. In this case, the oxygen separates from the nitrate or the chlorate and combines with the combustible material. This type of oxygenation needs to be done with extreme caution and only in very small quantities because, as the oxygen is part of the nitrates, and especially in the case of oxygenated chlorates, combined with nearly as much heat as is needed to turn it into oxygen gas, this enormous amount of heat is suddenly released the moment the oxygen combines with the combustible body, which can create extremely violent explosions that are completely uncontrollable.[Pg 189]
By the humid way we can oxygenate most combustible bodies, and convert most of the oxyds of the three kingdoms of nature into acids. For this purpose we chiefly employ the nitric acid, which has a very slight hold of oxygen, and quits it readily to a great number of bodies by the assistance of a gentle heat. The oxygenated muriatic acid may be used for several operations of this kind, but not in them all.
By the humid method, we can oxygenate most combustible substances and turn many of the oxides from the three kingdoms of nature into acids. For this, we mainly use nitric acid, which has a weak bond with oxygen and easily releases it to many substances when heated gently. Oxygenated muriatic acid can be used for several processes like this, but not for all of them.
I give the name of binary to the combinations of oxygen with the simple substances, because in these only two elements are combined. When three substances are united in one combination I call it ternary, and quaternary when the combination consists of four substances united.[Pg 190]
I refer to combinations of oxygen with simple substances as binary because they involve only two elements. When three substances join together in one combination, I call it ternary, and I use quaternary for combinations made up of four substances. [Pg 190]
Table of the combinations of Oxygen with the compound radicals.
Names of the radicals. | Names of the resulting acids. | |
New nomenclature. | Old nomenclature. | |
Nitro muriatic radical | Nitro muriatic acid | Aqua regia. |
(A) | ||
Tartaric | Tartarous acid | Unknown till lately. |
Malic | Malic acid | Ditto. |
Citric | Citric acid | Acid of lemons. |
Pyro-lignous | Pyro-lignous acid | Empyreumatic acid of wood. |
Pyro-mucous | Pyro-mucous acid | Empyr. acid of sugar. |
Pyro-tartarous | Pyro-tartarous acid | Empyr. acid of tartar. |
Oxalic | Oxalic acid | Acid of sorel. |
Acetic | {Acetous acid | Vinegar, or acid of vinegar. |
{Acetic acid | Radical vinegar. | |
Succinic | Succinic acid | Volatile salt of amber. |
Benzoic | Benzotic acid | Flowers of benzoin. |
Camphoric | Camphoric acid | Unknown till lately. |
Gallic | Gallic acid | The astringent principle of vegetables. |
(B) | ||
Lactic | Lactic acid | Acid of sour whey. |
Saccholactic | Saccholactic acid | Unknown till lately. |
Formic | Formic acid | Acid of ants. |
Bombic | Bombic acid | Unknown till lately. |
Sebacic | Sebacic acid | Ditto. |
Lithic | Lithic acid | Urinary calculus. |
Prussic | Prussic acid | Colouring matter of Prussian blue. |
[Note A: These radicals by a first degree of oxygenation form vegetable oxyds, as sugar, starch, mucus, &c.—A.]
[Note A: These radicals, when oxygenated once, create vegetable oxides like sugar, starch, mucus, etc.—A.]
[Note B: These radicals by a first degree of oxygenation form the animal oxyds, as lymph, red part of the blood, animal secretions, &c.—A.][Pg 191]
[Note B: These radicals, with a basic level of oxygenation, create animal oxides like lymph, the red component of blood, animal secretions, etc.—A.][Pg 191]
Sec. V.—Observations upon the Combinations of Oxygen with the Compound Radicals.
I published a new theory of the nature and formation of acids in the Memoirs of the Academy for 1776, p. 671. and 1778, p. 535. in which I concluded, that the number of acids must be greatly larger than was till then supposed. Since that time, a new field of inquiry has been opened to chemists; and, instead of five or six acids which were then known, near thirty new acids have been discovered, by which means the number of known neutral salts have been increased in the same proportion. The nature of the acidifiable bases, or radicals of the acids, and the degrees of oxygenation they are susceptible of, still remain to be inquired into. I have already shown, that almost all the oxydable and acidifiable radicals from the mineral kingdom are simple, and that, on the contrary, there hardly exists any radical in the vegetable, and more especially in the animal kingdom, but is composed of at least two substances, hydrogen and charcoal, and that azote and phosphorus are frequently united to these, by which we have compound radicals of two, three, and four bases or simple elements united.[Pg 192]
I published a new theory about the nature and formation of acids in the Memoirs of the Academy for 1776, p. 671, and 1778, p. 535, where I concluded that the number of acids must be much larger than previously thought. Since then, chemists have opened up a new area of research, and instead of the five or six acids that were known back then, nearly thirty new acids have been discovered, which has also increased the number of known neutral salts correspondingly. The nature of the acidifiable bases, or radicals of the acids, as well as the levels of oxygenation they can undergo, still need to be explored. I have already demonstrated that almost all the oxidizable and acidifiable radicals from the mineral kingdom are simple, whereas hardly any radical in the plant kingdom, and especially in the animal kingdom, is made up of fewer than two substances, hydrogen and carbon. Additionally, nitrogen and phosphorus often combine with these, leading to compound radicals with two, three, and four bases or simple elements combined.[Pg 192]
From these observations, it appears that the vegetable and animal oxyds and acids may differ from each other in three several ways: 1st, According to the number of simple acidifiable elements of which their radicals are composed: 2dly, According to the proportions in which these are combined together: And, 3dly, According to their different degrees of oxygenation: Which circumstances are more than sufficient to explain the great variety which nature produces in these substances. It is not at all surprising, after this, that most of the vegetable acids are convertible into each other, nothing more being requisite than to change the proportions of the hydrogen and charcoal in their composition, and to oxygenate them in a greater or lesser degree. This has been done by Mr Crell in some very ingenious experiments, which have been verified and extended by Mr Hassenfratz. From these it appears, that charcoal and hydrogen, by a first oxygenation, produce tartarous acid, oxalic acid by a second degree, and acetous or acetic acid by a third, or higher oxygenation; only, that charcoal seems to exist in a rather smaller proportion in the acetous and acetic acids. The citric and malic acids differ little from the preceding acids.
From these observations, it seems that plant and animal oxides and acids can differ from each other in three main ways: 1st, based on the number of basic elements that make up their radicals; 2nd, based on the ratios in which these elements are combined; and 3rd, based on their varying degrees of oxygenation. These factors are more than enough to explain the wide variety that nature produces in these substances. Therefore, it’s not surprising that most organic acids can be converted into one another, requiring only a change in the ratios of hydrogen and carbon in their makeup and adjusting their oxygen levels. Mr. Crell performed some very clever experiments demonstrating this, which Mr. Hassenfratz has confirmed and expanded upon. From these experiments, it appears that carbon and hydrogen, when first oxygenated, produce tartaric acid; with a second oxidation they yield oxalic acid; and with a third, they create acetic acid. The only note is that carbon seems to exist in a slightly smaller amount in the acetic acid. Citric and malic acids are quite similar to the acids mentioned earlier.
Ought we then to conclude that the oils are the radicals of the vegetable and animal acids? I have already expressed my doubts upon this[Pg 193] subject: 1st, Although the oils appear to be formed of nothing but hydrogen and charcoal, we do not know if these are in the precise proportion necessary for constituting the radicals of the acids: 2dly, Since oxygen enters into the composition of these acids equally with hydrogen and charcoal, there is no more reason for supposing them to be composed of oil rather than of water or of carbonic acid. It is true that they contain the materials necessary for all these combinations, but then these do not take place in the common temperature of the atmosphere; all the three elements remain combined in a state of equilibrium, which is readily destroyed by a temperature only a little above that of boiling water[39].
Should we then conclude that oils are the fundamental components of vegetable and animal acids? I’ve already shared my doubts on this[Pg 193] topic: First, although oils seem to be made up of only hydrogen and carbon, we don’t know if they’re in the exact proportions needed to form the radicals of the acids. Second, because oxygen is also part of these acids along with hydrogen and carbon, there’s no more reason to think they are made of oil rather than water or carbonic acid. It’s true that they have the necessary materials for all these combinations, but these don't occur at the average temperature of the atmosphere. All three elements stay combined in a balanced state, which can easily be disrupted by a temperature just slightly above boiling water[39].
Table of the Binary Combinations of Azote with the Simple Substances.
Simple Substances. | Results of the Combinations. | |
New Nomenclature. | Old Nomenclature. | |
Caloric | Azotic gas | Phlogisticated air, or Mephitis. |
Hydrogen | Ammoniac | Volatile alkali. |
{Nitrous oxyd | Base of Nitrous gas. | |
{Nitrous acid | Smoaking nitrous acid. | |
Oxygen | {Nitric acid | Pale nitrous acid. |
{Oxygenated nitric acid | Unknown. | |
{This combination is hitherto unknown; should it | ||
{ever be discovered, it will be called, according to | ||
Charcoal | {the principles of our nomenclature, Azuret of | |
{Charcoal. Charcoal dissolves in azotic gas, and | ||
{forms carbonated azotic gas. | ||
Phosphorus. | Azuret of phosphorus. | Still unknown. |
{Azuret of sulphur. | Still unknown. We know | |
Sulphur | {that sulphur dissolves in azotic gas, forming | |
{sulphurated azotic gas. | ||
{Azote combines with charcoal and hydrogen, and | ||
Compound | {sometimes with phosphorus, in the compound | |
radicals | {oxydable and acidifiable bases, and is generally | |
{contained in the radicals of the animal acids. | ||
{Such combinations are hitherto unknown; if ever | ||
Metallic | {discovered, they will form metallic azurets, as | |
substances | {azuret of gold, of silver, &c. | |
Lime | { | |
Magnesia | { | |
Barytes | {Entirely unknown. If ever discovered, they will | |
Argill | {form azuret of lime, azuret of magnesia, &c. | |
Potash | { | |
Soda | { |
Section. VI.—Observations upon the Combinations of Azote with the Simple Substances.
Azote is one of the most abundant elements; combined with caloric it forms azotic gas, or mephitis, which composes nearly two thirds of the atmosphere. This element is always in the state of gas in the ordinary pressure and temperature, and no degree of compression or of cold has been hitherto capable of reducing it either to a solid or liquid form. This is likewise one of the essential constituent elements of animal bodies, in which it is combined with charcoal and hydrogen, and sometimes with phosphorus; these are united together by a certain portion of oxygen, by which they are formed into oxyds or acids according to the degree of oxygenation. Hence the animal substances may be varied, in the same way with vegetables, in three different manners: 1st, According to the number of elements which enter into the composition of the base or radical: 2dly, According to the proportions of these elements: 3dly, According to the degree of oxygenation.
Azote is one of the most abundant elements; when combined with caloric, it forms azotic gas, or mephitis, which makes up nearly two-thirds of the atmosphere. This element is always a gas under normal pressure and temperature, and no amount of compression or cold has been able to turn it into a solid or liquid form so far. It is also one of the essential building blocks of animal bodies, where it combines with carbon and hydrogen, and sometimes with phosphorus; these elements are connected by a certain amount of oxygen, which allows them to form oxides or acids depending on the level of oxygenation. Therefore, animal substances can vary, just like plant substances, in three different ways: 1st, based on the number of elements that make up the base or radical; 2nd, based on the ratios of these elements; 3rd, based on the level of oxygenation.
When combined with oxygen, azote forms the nitrous and nitric oxyds and acids; when with hydrogen, ammoniac is produced. Its combinations with the other simple elements[Pg 196] are very little known; to these we give the name of Azurets, preserving the termination in uret for all nonoxygenated compounds. It is extremely probable that all the alkaline substances may hereafter be found to belong to this genus of azurets.
When azote mixes with oxygen, it creates nitrous and nitric oxides and acids; when it combines with hydrogen, it produces ammonia. Its combinations with other simple elements[Pg 196] are mostly unknown; we refer to these as Azurets, keeping the suffix in uret for all non-oxygenated compounds. It's highly likely that all alkaline substances will eventually be classified under this group of azurets.
The azotic gas may be procured from atmospheric air, by absorbing the oxygen gas which is mixed with it by means of a solution of sulphuret of potash, or sulphuret of lime. It requires twelve or fifteen days to complete this process, during which time the surface in contact must be frequently renewed by agitation, and by breaking the pellicle which forms on the top of the solution. It may likewise be procured by dissolving animal substances in dilute nitric acid very little heated. In this operation, the azote is disengaged in form of gas, which we receive under bell glasses filled with water in the pneumato-chemical apparatus. We may procure this gas by deflagrating nitre with charcoal, or any other combustible substance; when with charcoal, the azotic gas is mixed with carbonic acid gas, which may be absorbed by a solution of caustic alkali, or by lime water, after which the azotic gas remains pure. We can procure it in a fourth manner from combinations of ammoniac with metallic oxyds, as pointed out by Mr de Fourcroy: The hydrogen of the ammoniac combines with the oxygen of the[Pg 197] oxyd, and forms water, whilst the azote being left free escapes in form of gas.
The nitrogen gas can be obtained from the air by removing the oxygen mixed with it using a solution of potassium sulfide or calcium sulfide. This process takes about twelve to fifteen days, during which the surface in contact needs to be refreshed by stirring and breaking the film that forms on top of the solution. It can also be obtained by dissolving animal materials in slightly heated dilute nitric acid. In this process, nitrogen is released as gas, which we collect under bell jars filled with water in the pneumatic chemical setup. We can also get this gas by burning saltpeter with charcoal or any other combustible material; when using charcoal, the nitrogen gas mixes with carbon dioxide, which can be absorbed by a solution of caustic soda or lime water, leaving behind pure nitrogen. Lastly, as noted by Mr. de Fourcroy, we can derive it from compounds of ammonia and metal oxides: the hydrogen from the ammonia reacts with the oxygen from the oxide, forming water, while the nitrogen is freed and escapes as gas.
The combinations of azote were but lately discovered: Mr Cavendish first observed it in nitrous gas and acid, and Mr Berthollet in ammoniac and the prussic acid. As no evidence of its decomposition has hitherto appeared, we are fully entitled to consider azote as a simple elementary substance.[Pg 198]
The combinations of nitrogen were only recently discovered: Mr. Cavendish first noticed it in nitrous gas and acid, and Mr. Berthollet in ammonia and prussic acid. Since there has been no evidence of its breakdown so far, we can confidently treat nitrogen as a simple elemental substance.[Pg 198]
Table of the Binary Combinations of Hydrogen with Simple Substances.
Simple Substances. | Resulting Compounds. | |
New Nomenclature. | Old Names. | |
Caloric | Hydrogen gas | Inflammable air. |
Azote | Ammoniac | Volatile Alkali. |
Oxygen | Water | Water. |
Sulphur | {Hydruret of sulphur, or } | |
{sulphuret of hydrogen } | Hitherto unknown (A). | |
Phosphorus | {Hydruret of phosphorus, or } | |
{phosphuret of hydrogen } | ||
Charcoal | {Hydro-carbonous, or } | Not known till lately. |
{carbono-hydrous radicals(B)} | ||
Metallic | {Metallic hydrurets(C), as} | Hitherto unknown. |
substances, as | {hydruret of iron, &c.} | |
iron, &c. | { | } |
[Note A: These combinations take place in the state of gas, and form, respectively, sulphurated and phosphorated oxygen gas—A.]
[Note A: These combinations occur in the gaseous state and create, respectively, sulfurated and phosphorated oxygen gas—A.]
[Note B: This combination of hydrogen with charcoal includes the fixed and volatile oils, and forms the radicals of a considerable part of the vegetable and animal oxyds and acids. When it takes place in the state of gas it forms carbonated hydrogen gas.—A.]
[Note B: This combination of hydrogen with charcoal includes the fixed and volatile oils and creates the radicals for a significant portion of vegetable and animal oxides and acids. When it occurs in a gaseous state, it forms carbonated hydrogen gas.—A.]
[Note C: None of these combinations are known, and it is probable that they cannot exist, at least in the usual temperature of the atmosphere, owing to the great affinity of hydrogen for caloric.—A.][Pg 199]
[Note C: None of these combinations are known, and it’s likely that they can’t exist, at least under normal atmospheric temperatures, due to hydrogen's strong attraction to heat.—A.][Pg 199]
Sect. 7.—Observations upon Hydrogen, and its Combinations with Simple Substances.
Hydrogen, as its name expresses, is one of the constituent elements of water, of which it forms fifteen hundredth parts by weight, combined with eighty-five hundredth parts of oxygen. This substance, the properties and even existence of which was unknown till lately, is very plentifully distributed in nature, and acts a very considerable part in the processes of the animal and vegetable kingdoms. As it possesses so great affinity with caloric as only to exist in the state of gas, it is consequently impossible to procure it in the concrete or liquid state, independent of combination.
Hydrogen, as its name suggests, is one of the elements that make up water, constituting fifteen hundredths of its weight, paired with eighty-five hundredths of oxygen. This substance, which was largely unknown in terms of its properties and even its existence until recently, is widely found in nature and plays a significant role in the processes of both the animal and plant kingdoms. Because it has such a strong affinity for heat, it only exists as a gas, making it impossible to obtain it in solid or liquid form without combining it with other elements.
To procure hydrogen, or rather hydrogen gas, we have only to subject water to the action of a substance with which oxygen has greater affinity than it has to hydrogen; by this means the hydrogen is set free, and, by uniting with caloric, assumes the form of hydrogen gas. Red hot iron is usually employed for this purpose: The iron, during the process, becomes oxydated, and is changed into a substance resembling the iron ore from the island of Elba. In this state of oxyd it is much less attractible by[Pg 200] the magnet, and dissolves in acids without effervescence.
To obtain hydrogen, or hydrogen gas, we just need to expose water to a substance that has a stronger attraction to oxygen than hydrogen does; this way, the hydrogen is released, and when it combines with heat, it takes on the form of hydrogen gas. Red-hot iron is usually used for this process: the iron, during this process, gets oxidized and turns into a substance similar to the iron ore from the island of Elba. In this oxidized state, it is much less attracted by[Pg 200] magnets and dissolves in acids without bubbling.
Charcoal, in a red heat, has the same power of decomposing water, by attracting the oxygen from its combination with hydrogen. In this process carbonic acid gas is formed, and mixes with the hydrogen gas, but is easily separated by means of water or alkalies, which absorb the carbonic acid, and leave the hydrogen gas pure. We may likewise obtain hydrogen gas by dissolving iron or zinc in dilute sulphuric acid. These two metals decompose water very slowly, and with great difficulty, when alone, but do it with great ease and rapidity when assisted by sulphuric acid; the hydrogen unites with caloric during the process, and is disengaged in form of hydrogen gas, while the oxygen of the water unites with the metal in the form of oxyd, which is immediately dissolved in the acid, forming a sulphat of iron or of zinc.
Charcoal, when heated to a red glow, can break down water by pulling the oxygen out of its combination with hydrogen. This creates carbonic acid gas, which mixes with the hydrogen gas but can easily be separated using water or alkalis that absorb the carbonic acid, leaving the hydrogen gas pure. We can also obtain hydrogen gas by dissolving iron or zinc in diluted sulfuric acid. These two metals slowly decompose water on their own, but they do so much more quickly and easily when combined with sulfuric acid. During this process, the hydrogen binds with heat and is released as hydrogen gas, while the oxygen from the water combines with the metal to form an oxide, which immediately dissolves in the acid, creating a sulfate of iron or zinc.
Some very distinguished chemists consider hydrogen as the phlogiston of Stahl; and as that celebrated chemist admitted the existence of phlogiston in sulphur, charcoal, metals, &c. they are of course obliged to suppose that hydrogen exists in all these substances, though they cannot prove their supposition; even if they could, it would not avail much, since this disengagement of hydrogen is quite insufficient to explain the phenomena of calcination and combustion.[Pg 201] We must always recur to the examination of this question, "Are the heat and light, which are disengaged during the different species of combustion, furnished by the burning body, or by the oxygen which combines in all these operations?" And certainly the supposition of hydrogen being disengaged throws no light whatever upon this question. Besides, it belongs to those who make suppositions to prove them; and, doubtless, a doctrine which without any supposition explains the phenomena as well, and as naturally, as theirs does by supposition, has at least the advantage of greater simplicity[40].
Some well-known chemists see hydrogen as the phlogiston of Stahl; since that famous chemist acknowledged the presence of phlogiston in substances like sulfur, charcoal, metals, etc., they feel obligated to believe that hydrogen is present in all these materials, even though they can't prove that claim. Even if they could, it wouldn't matter much, as the release of hydrogen alone doesn't adequately explain the processes of calcination and combustion.[Pg 201] We always need to revisit the question, "Do the heat and light released during various types of combustion come from the burning material, or from the oxygen that reacts in all these processes?" And clearly, the idea of hydrogen being released offers no insight into this question. Furthermore, those who make claims should be the ones to support them; a theory that explains phenomena as effectively and naturally as theirs does—without requiring any assumptions—has the clear advantage of being simpler.[40].
Table of the Binary Combinations of Sulphur with Simple Substances.
Simple Substances. | Resulting Compounds. | |
New Nomenclature. | Old Nomenclature. | |
Caloric | Sulphuric gas | |
{Oxyd of sulphur | Soft sulphur. | |
Oxygen | {Sulphurous acid | Sulphureous acid. |
{Sulphuric acid | Vitriolic acid. | |
Hydrogen | Sulphuret of hydrogen} | |
Azote | azote} | Unknown Combinations. |
Phosphorus | phosphorus} | |
Charcoal | charcoal} | |
Antimony | antimony | Crude antimony. |
Silver | silver | |
Arsenic | arsenic | Orpiment, realgar. |
Bismuth | bismuth | |
Cobalt | cobalt | |
Copper | copper | Copper pyrites. |
Tin | tin | |
Iron | iron | Iron pyrites. |
Manganese | manganese | |
Mercury | mercury | Ethiops mineral, cinnabar. |
Molybdena | molybdena | |
Nickel | nickel | |
Gold | gold | |
Platina | platina | |
Lead | lead | Galena. |
Tungstein | tungstein | |
Zinc | zinc | Blende. |
Potash | potash | Alkaline liver of sulphur with fixed vegetable alkali. |
Soda | soda | Alkaline liver of sulphur with fixed mineral alkali. |
Ammoniac | ammoniac | Volatile liver of sulphur, smoaking liquor of Boyle. |
Lime | lime | Calcareous liver of sulphur. |
Magnesia | magnesia | Magnesian liver of sulphur. |
Barytes | barytes | Barytic liver of sulphur. |
Argill | argill | Yet unknown. |
Sect. 8.—Observations on Sulphur, and its Combinations.
Sulphur is a combustible substance, having a very great tendency to combination; it is naturally in a solid state in the ordinary temperature, and requires a heat somewhat higher than boiling water to make it liquify. Sulphur is formed by nature in a considerable degree of purity in the neighbourhood of volcanos; we find it likewise, chiefly in the state of sulphuric acid, combined with argill in aluminous schistus, with lime in gypsum, &c. From these combinations it may be procured in the state of sulphur, by carrying off its oxygen by means of charcoal in a red heat; carbonic acid is formed, and escapes in the state of gas; the sulphur remains combined with the clay, lime, &c. in the state of sulphuret, which is decomposed by acids; the acid unites with the earth into a neutral salt, and the sulphur is precipitated.[Pg 204]
Sulfur is a flammable substance that has a strong tendency to combine with other elements. It naturally exists as a solid at normal temperatures and requires heat slightly above boiling water to melt. Sulfur is found in nature in a fairly pure form near volcanoes; it also exists mainly as sulfuric acid, combined with clay in alum shales, with lime in gypsum, and so on. From these combinations, sulfur can be obtained by removing its oxygen with charcoal at a red heat; carbon dioxide is produced and escapes as a gas, while sulfur remains combined with the clay, lime, etc., as sulfide, which can be broken down by acids. The acid reacts with the earth to form a neutral salt, and sulfur is then separated.[Pg 204]
Table of the Binary Combinations of Phosphorus with the Simple Substances.
Simple Substances. | Resulting Compounds. |
Caloric | Phosphoric gas. |
{ Oxyd of phosphorus. | |
Oxygen | { Phosphorous acid. |
{ Phosphoric acid. | |
Hydrogen | Phosphuret of hydrogen. |
Azote | Phosphuret of azote. |
Sulphur | Phosphuret of Sulphur. |
Charcoal | Phosphuret of charcoal. |
Metallic substances | Phosphuret of metals(A). |
Potash} | |
Soda} | |
Ammoniac} | Phosphuret of Potash, Soda, &c.(B) |
Lime} | |
Barytes} | |
Magnesia} | |
Argill} |
[Note A: Of all these combinations of phosphorus with metals, that with iron only is hitherto known, forming the substance formerly called Siderite; neither is it yet ascertained whether, in this combination, the phosphorus be oxygenated or not.—A.]
[Note A: Of all these combinations of phosphorus with metals, only the one with iron is known so far, creating the substance that was previously called Siderite; it’s also not yet confirmed whether, in this combination, the phosphorus is oxygenated or not.—A.]
[Note B: These combinations of phosphorus with the alkalies and earths are not yet known; and, from the experiments of Mr Gengembre, they appear to be impossible—A.][Pg 205]
[Note B: These combinations of phosphorus with alkalis and earths are still unknown; and based on Mr. Gengembre's experiments, they seem to be impossible—A.][Pg 205]
Sect. 9.—Observations upon Phosphorus, and its Combinations.
Phosphorus is a simple combustible substance, which was unknown to chemists till 1667, when it was discovered by Brandt, who kept the process secret; soon after Kunkel found out Brandt's method of preparation, and made it public. It has been ever since known by the name of Kunkel's phosphorus. It was for a long time procured only from urine; and, though Homberg gave an account of the process in the Memoirs of the Academy for 1692, all the philosophers of Europe were supplied with it from England. It was first made in France in 1737, before a committee of the Academy at the Royal Garden. At present it is procured in a more commodious and more oeconomical manner from animal bones, which are real calcareous phosphats, according to the process of Messrs Gahn, Scheele, Rouelle, &c. The bones of adult animals being calcined to whiteness, are pounded, and passed through a fine silk sieve; pour upon the fine powder a quantity of dilute sulphuric acid, less than is sufficient for dissolving the whole. This acid unites with the calcareous earth of the bones into a sulphat of lime, and the phosphoric acid remains free in the liquor. The liquid[Pg 206] is decanted off, and the residuum washed with boiling water; this water which has been used to wash out the adhering acid is joined with what was before decanted off, and the whole is gradually evaporated; the dissolved sulphat of lime cristallizes in form of silky threads, which are removed, and by continuing the evaporation we procure the phosphoric acid under the appearance of a white pellucid glass. When this is powdered, and mixed with one third its weight of charcoal, we procure very pure phosphorus by sublimation. The phosphoric acid, as procured by the above process, is never so pure as that obtained by oxygenating pure phosphorus either by combustion or by means of nitric acid; wherefore this latter should always be employed in experiments of research.
Phosphorus is a basic flammable substance that chemists didn’t know about until 1667, when it was discovered by Brandt, who kept the discovery a secret. Shortly after, Kunkel figured out Brandt's method and made it public. Ever since, it's been called Kunkel's phosphorus. For a long time, it was only sourced from urine, and although Homberg described the process in the Memoirs of the Academy for 1692, all of Europe was supplied from England. It was first produced in France in 1737, in front of a committee of the Academy at the Royal Garden. Today, it is obtained more easily and economically from animal bones, which are essentially calcium phosphates, based on the method of Messrs Gahn, Scheele, Rouelle, etc. The bones of adult animals are calcined until they’re completely white, then ground up and sifted through a fine silk mesh. A diluted sulfuric acid solution, less than what’s needed to totally dissolve everything, is poured over the fine powder. This acid combines with the calcium from the bones to create calcium sulfate, leaving the phosphoric acid free in the solution. The liquid[Pg 206] is poured off, and the leftover material is washed with boiling water; this washing water, which contains the leftover acid, is combined with the previously decanted liquid, and everything is gradually evaporated. The dissolved calcium sulfate crystallizes into silky strands, which are removed, and by continuing the evaporation, we obtain phosphoric acid in the form of a clear white glass. When this is powdered and mixed with one third of its weight in charcoal, we can obtain very pure phosphorus through sublimation. The phosphoric acid produced through this method is never as pure as that obtained by oxygenating pure phosphorus, either through combustion or by using nitric acid; therefore, the latter should always be used in research experiments.
Phosphorus is found in almost all animal substances, and in some plants which give a kind of animal analysis. In all these it is usually combined with charcoal, hydrogen, and azote, forming very compound radicals, which are, for the most part, in the state of oxyds by a first degree of union with oxygen. The discovery of Mr Hassenfratz, of phosphorus being contained in charcoal, gives reason to suspect that it is more common in the vegetable kingdom than has generally been supposed: It is certain, that, by proper processes, it may be procured from every individual of some of the families of plants.[Pg 207]
Phosphorus is present in almost all animal substances and in some plants that provide a type of animal analysis. In these cases, it’s typically combined with carbon, hydrogen, and nitrogen, forming complex radicals that are mostly in an oxidized state due to a basic union with oxygen. Mr. Hassenfratz's discovery that phosphorus is found in charcoal suggests that it’s more common in the plant kingdom than previously thought. It’s clear that with the right processes, it can be extracted from every member of certain plant families.[Pg 207]
As no experiment has hitherto given reason to suspect that phosphorus is a compound body, I have arranged it with the simple or elementary substances. It takes fire at the temperature of 32° (104°) of the thermometer.
As no experiment has yet suggested that phosphorus is a compound substance, I have categorized it with the simple or basic elements. It ignites at a temperature of 32° (104°) on the thermometer.
Table of the Binary Combinations of Charcoal.
Simple Substances. | Resulting Compounds. | |
{Oxyd of charcoal | Unknown. | |
Oxygen | {Carbonic acid | Fixed air, chalky acid. |
Sulphur | Carburet of sulphur} | |
Phosphorus | Carburet of phosphorus} | Unknown. |
Azote | Carburet of azote} | |
{Carbono-hydrous radical | ||
Hydrogen | {Fixed and volatile oils | |
{Of these only the carburets of | ||
Metallic substances | Carburets of metals | {iron and zinc are known, and |
{were formerly called Plumbago. | ||
Alkalies and earths | Carburet of potash, &c. | Unknown. |
Sect. X.—Observations upon Charcoal, and its Combinations with Simple Substances.
As charcoal has not been hitherto decomposed, it must, in the present state of our knowledge, be considered as a simple substance. By modern experiments it appears to exist ready formed in vegetables; and I have already remarked, that, in these, it is combined with hydrogen, sometimes with azote and phosphorus, forming compound radicals, which may be changed into oxyds or acids according to their degree of oxygenation.
As charcoal has not been broken down until now, it must, based on our current understanding, be considered a simple substance. Modern experiments suggest it occurs naturally in plants, and I have already noted that in these plants, it is combined with hydrogen, and sometimes with nitrogen and phosphorus, forming compound radicals that can be converted into oxides or acids depending on their level of oxygenation.
To obtain the charcoal contained in vegetable or animal substances, we subject them to the action of fire, at first moderate, and afterwards very strong, on purpose to drive off the last portions of water, which adhere very obstinately to the charcoal. For chemical purposes, this is usually done in retorts of stone-ware or porcellain, into which the wood, or other matter, is introduced, and then placed in a reverberatory furnace, raised gradually to its greatest heat: The heat volatilizes, or changes into gas, all the parts of the body susceptible of combining with caloric into that form, and the charcoal, being more fixed in its nature, remains in the retort[Pg 209] combined with a little earth and some fixed salts.
To get the charcoal from plant or animal materials, we first expose them to moderate fire, and then increase the heat significantly to remove the last bits of moisture that stubbornly cling to the charcoal. For chemical purposes, this is typically done in stoneware or porcelain retorts, where the wood or other material is placed and then heated gradually in a reverberatory furnace to its maximum temperature. The heat causes all components that can turn into gas when exposed to heat to evaporate, while the more stable charcoal remains in the retort[Pg 209], mixed with some earth and fixed salts.
In the business of charring wood, this is done by a less expensive process. The wood is disposed in heaps, and covered with earth, so as to prevent the access of any more air than is absolutely necessary for supporting the fire, which is kept up till all the water and oil is driven off, after which the fire is extinguished by shutting up all the air-holes.
In the business of charring wood, this is done using a more affordable process. The wood is stacked in piles and covered with soil to minimize the airflow to only what’s necessary to keep the fire going. This continues until all the moisture and oil are burned off, after which the fire is put out by sealing all the air holes.
We may analyse charcoal either by combustion in air, or rather in oxygen gas, or by means of nitric acid. In either case we convert it into carbonic acid, and sometimes a little potash and some neutral salts remain. This analysis has hitherto been but little attended to by chemists; and we are not even certain if potash exists in charcoal before combustion, or whether it be formed by means of some unknown combination during that process.
We can analyze charcoal either by burning it in air, or more specifically in oxygen gas, or by using nitric acid. In either method, we turn it into carbon dioxide, and occasionally a small amount of potash and some neutral salts are left over. So far, chemists have paid little attention to this analysis, and we’re not even sure if potash is present in charcoal before burning, or if it is created through some unknown reaction during the process.
Sect. 11.—Observations upon the Muriatic, Fluoric, and Boracic Radicals, and their Combinations.
As the combinations of these substances, either with each other, or with the other combustible bodies, are hitherto entirely unknown, we have[Pg 210] not attempted to form any table for their nomenclature. We only know that these radicals are susceptible of oxygenation, and of forming the muriatic, fluoric, and boracic acids, and that in the acid state they enter into a number of combinations, to be afterwards detailed. Chemistry has hitherto been unable to disoxygenate any of them, so as to produce them in a simple state. For this purpose, some substance must be employed to which oxygen has a stronger affinity than to their radicals, either by means of single affinity, or by double elective attraction. All that is known relative to the origin of the radicals of these acids will be mentioned in the sections set apart for considering their combinations with the salifiable bases.
Since the combinations of these substances, whether with each other or with other combustible materials, are still completely unknown, we have[Pg 210] not tried to create any table for their naming. We only know that these radicals can be oxidized and can form hydrochloric, fluorine, and boric acids, and that in their acidic form they enter into various combinations, which will be detailed later. Up to now, chemistry has not been able to remove oxygen from any of them to produce them in their simple form. To do this, some substance must be used that has a stronger attraction to oxygen than their radicals do, either through single affinity or double elective attraction. Everything known about the origin of the radicals of these acids will be discussed in the sections dedicated to their combinations with salifiable bases.
Sect. 12.—Observations upon the Combinations of Metals with each other.
Before closing our account of the simple or elementary substances, it might be supposed necessary to give a table of alloys or combinations of metals with each other; but, as such a table would be both exceedingly voluminous and very unsatisfactory, without going into a series of experiments not yet attempted, I have thought it adviseable to omit it altogether. All[Pg 211] that is necessary to be mentioned is, that these alloys should be named according to the metal in largest proportion in the mixture or combination; thus the term alloy of gold and silver, or gold alloyed with silver, indicates that gold is the predominating metal.
Before wrapping up our discussion on simple or basic substances, it might seem necessary to provide a table of alloys or combinations of metals. However, since such a table would be both extremely lengthy and quite unsatisfactory without delving into a series of experiments that haven't been conducted yet, I've decided to leave it out completely. All[Pg 211] that needs to be noted is that these alloys should be named based on the metal that makes up the largest portion of the mixture or combination; for instance, the term alloy of gold and silver, or gold mixed with silver, indicates that gold is the main metal.
Metallic alloys, like all other combinations, have a point of saturation. It would even appear, from the experiments of Mr de la Briche, that they have two perfectly distinct degrees of saturation.[Pg 212]
Metallic alloys, like any other combinations, have a saturation point. It also seems, based on Mr. de la Briche's experiments, that they have two completely different degrees of saturation.[Pg 212]
Table of the Combinations of Azote in the state of Nitrous Acid with the Salifiable Bases, arranged according to the affinities of these Bases with the Acid.
Names of the bases. | Names of the neutral salts. | |
New nomenclature. | Notes. | |
Barytes | Nitrite of barytes. | { |
Potash | potash. | {These salts are only |
Soda | soda. | {known of late, and |
Lime | lime. | {have received no particular |
Magnesia | magnesia. | {name in the old |
Ammoniac | ammoniac. | {nomenclature. |
Argill | argill. | { |
{As metals dissolve both in nitrous and | ||
Oxyd of zinc | zinc. | {nitric acids, metallic salts must of |
iron | iron. | {consequence be formed having |
manganese | manganese. | {different degrees of oxygenation. |
cobalt | cobalt. | {Those wherein the metal is |
nickel | nickel. | {least oxygenated must be |
lead | lead. | {called Nitrites, when more so, |
tin | tin. | {Nitrats; but the limits of this |
copper | copper. | {distinction are difficultly |
bismuth | bismuth. | {ascertainable. The older |
antimony | antimony. | {chemists were not acquainted |
arsenic | arsenic. | {with any of these salts. |
mercury | mercury. | { |
silver | {It is extremely probable that gold, silver | |
gold | {and platina only form nitrats, and cannot subsist | |
platina | {in the state of nitrites. |
Table of the Combinations of Azote, completely saturated with Oxygen, in the state of Nitric Acid, with the Salifiable Bases, in the order of the affinity with the Acid.
Bases. | Names of the resulting neutral salts. | |||
New nomenclature. | Old nomenclature. | |||
Barytes | Nitrat of | barytes | Nitre, with a base of heavy earth. | |
Potash | potash | Nitre, saltpetre. Nitre with base of potash. | ||
Soda | soda | Quadrangular nitre. Nitre with base of mineral alkali. | ||
Lime | lime | Calcareous nitre. Nitre with calcareous base. Mother water of nitre, or saltpetre. | ||
Magnesia | magnesia | Magnesian nitre. Nitre with base of magnesia. | ||
Ammoniac | ammoniac | Ammoniacal nitre. | ||
Argill | argill | Nitrous alum. Argillaceous nitre. Nitre with base of earth of alum. | ||
Oxyd of | zinc | zinc | Nitre of zinc. | |
iron | iron | Nitre of iron. Martial nitre. Nitrated iron. | ||
manganese | manganese | Nitre of manganese. | ||
cobalt | cobalt | Nitre of cobalt. | ||
nickel | nickel | Nitre of nickel. | ||
lead | lead | Saturnine nitre. Nitre of lead. | ||
tin | tin | Nitre of tin. | ||
copper | copper | Nitre of copper or of Venus. | ||
bismuth | bismuth | Nitre of bismuth. | ||
antimony | antimony | Nitre of antimony. | ||
arsenic | arsenic | Arsenical nitre. | ||
mercury | mercury | Mercurial nitre. | ||
silver | silver | Nitre of silver or luna. Lunar caustic. | ||
gold | gold | Nitre of gold. | ||
platina | platina | Nitre of platina. |
Sect. 13.—Observations upon the Nitrous and Nitric Acids, and their Combinations.
The nitrous and nitric acids are procured from a neutral salt long known in the arts under the name of saltpetre. This salt is extracted by lixiviation from the rubbish of old buildings, from the earth of cellars, stables, or barns, and in general of all inhabited places. In these earths the nitric acid is usually combined with lime and magnesia, sometimes with potash, and rarely with argill. As all these salts, excepting the nitrat of potash, attract the moisture of the air, and consequently would be difficultly preserved, advantage is taken, in the manufactures of saltpetre and the royal refining house, of the greater affinity of the nitric acid to potash than these other bases, by which means the lime, magnesia, and argill, are precipitated, and all these nitrats are reduced to the nitrat of potash or saltpetre[41].
The nitrous and nitric acids are obtained from a neutral salt commonly known as saltpetre. This salt is extracted through leaching from the debris of old buildings, from the soil in cellars, stables, or barns, and generally from any inhabited places. In these soils, nitric acid is usually combined with lime and magnesia, sometimes with potash, and rarely with clay. Since all these salts, except for potassium nitrate, attract moisture from the air and would therefore be hard to keep, the manufacturing of saltpetre and in the royal refining house takes advantage of nitric acid's stronger attraction to potash compared to these other bases. This process causes the lime, magnesia, and clay to precipitate, reducing all these nitrates to potassium nitrate or saltpetre[41].
The nitric acid is procured from this salt by distillation, from three parts of pure saltpetre decomposed by one part of concentrated sulphuric[Pg 215] acid, in a retort with Woulfe's apparatus, (Pl. IV. fig. 1.) having its bottles half filled with water, and all its joints carefully luted. The nitrous acid passes over in form of red vapours surcharged with nitrous gas, or, in other words, not saturated with oxygen. Part of the acid condenses in the recipient in form of a dark orange red liquid, while the rest combines with the water in the bottles. During the distillation, a large quantity of oxygen gas escapes, owing to the greater affinity of oxygen to caloric, in a high temperature, than to nitrous acid, though in the usual temperature of the atmosphere this affinity is reversed. It is from the disengagement of oxygen that the nitric acid of the neutral salt is in this operation converted into nitrous acid. It is brought back to the state of nitric acid by heating over a gentle fire, which drives off the superabundant nitrous gas, and leaves the nitric acid much diluted with water.
The nitric acid is obtained from this salt through distillation, using three parts of pure saltpeter decomposed by one part of concentrated sulfuric acid in a retort with Woulfe's apparatus, (Pl. IV. fig. 1.) where the bottles are half filled with water and all joints are carefully sealed. The nitrous acid is released as red vapors filled with nitrous gas, or in other words, not saturated with oxygen. Some of the acid condenses in the receiver as a dark orange-red liquid, while the rest mixes with the water in the bottles. During distillation, a large amount of oxygen gas escapes because oxygen has a stronger attraction to heat at higher temperatures than to nitrous acid, although this attraction is reversed at normal atmospheric temperatures. It’s this release of oxygen that turns the nitric acid in the neutral salt into nitrous acid during the process. The nitrous acid is restored to nitric acid by gently heating it, which removes the excess nitrous gas and results in nitric acid that is much diluted with water.
Nitric acid is procurable in a more concentrated state, and with much less loss, by mixing very dry clay with saltpetre. This mixture is put into an earthern retort, and distilled with a strong fire. The clay combines with the potash, for which it has great affinity, and the nitric acid passes over, slightly impregnated with nitrous gas. This is easily disengaged by heating the acid gently in a retort, a small quantity[Pg 216] of nitrous gas passes over into the recipient, and very pure concentrated nitric acid remains in the retort.
Nitric acid can be obtained in a more concentrated form and with less wastage by mixing very dry clay with saltpeter. This mixture is placed in an earthen retort and distilled with a strong heat. The clay bonds with the potash, which it has a strong attraction for, while the nitric acid evaporates, slightly mixed with nitrous gas. This gas can easily be released by gently heating the acid in a retort, allowing a small amount[Pg 216] of nitrous gas to transfer into the receiving container, leaving very pure concentrated nitric acid behind in the retort.
We have already seen that azote is the nitric radical. If to 20-1/2 parts, by weight, of azote 43-1/2 parts of oxygen be added, 64 parts of nitrous gas are formed; and, if to this we join 36 additional parts of oxygen, 100 parts of nitric acid result from the combination. Intermediate quantities of oxygen between these two extremes of oxygenation produce different species of nitrous acid, or, in other words, nitric acid less or more impregnated with nitrous gas. I ascertained the above proportions by means of decomposition; and, though I cannot answer for their absolute accuracy, they cannot be far removed from truth. Mr Cavendish, who first showed by synthetic experiments that azote is the base of nitric acid, gives the proportions of azote a little larger than I have done; but, as it is not improbable that he produced the nitrous acid and not the nitric, that circumstance explains in some degree the difference in the results of our experiments.
We have already established that azote is the nitric radical. If you add 20.5 parts, by weight, of azote to 43.5 parts of oxygen, you'll get 64 parts of nitrous gas; and if you then add 36 more parts of oxygen, you will obtain 100 parts of nitric acid from that combination. Intermediate amounts of oxygen between these two extremes of oxygenation yield different types of nitrous acid, or in other words, nitric acid that is more or less saturated with nitrous gas. I determined these proportions through decomposition; and while I can't guarantee their absolute accuracy, they must be close to the truth. Mr. Cavendish, who first demonstrated through synthetic experiments that azote is the base of nitric acid, provides slightly larger proportions of azote than I have; however, since it’s possible that he produced nitrous acid instead of nitric acid, that may explain some of the differences in our experimental results.
As, in all experiments of a philosophical nature, the utmost possible degree of accuracy is required, we must procure the nitric acid for experimental purposes, from nitre which has been previously purified from all foreign matter. If, after distillation, any sulphuric acid is suspected[Pg 217] in the nitric acid, it is easily separated by dropping in a little nitrat of barytes, so long as any precipitation takes place; the sulphuric acid, from its greater affinity, attracts the barytes, and forms with it an insoluble neutral salt, which falls to the bottom. It may be purified in the same manner from muriatic acid, by dropping in a little nitrat of silver so long as any precipitation of muriat of silver is produced. When these two precipitations are finished, distill off about seven-eighths of the acid by a gentle heat, and what comes over is in the most perfect degree of purity.
As in all philosophical experiments, we need the highest level of accuracy, so we must obtain the nitric acid for our experiments from nitrate that has been thoroughly purified of any impurities. If there is any concern that sulfuric acid is present in the nitric acid after distillation, we can easily separate it by adding a bit of barium nitrate as long as we see any precipitation. The sulfuric acid will attract the barium due to its stronger affinity, forming an insoluble neutral salt that settles at the bottom. We can purify it in the same way from hydrochloric acid by adding a small amount of silver nitrate until we produce a precipitate of silver chloride. Once these two precipitations are complete, we can distill off about seven-eighths of the acid using gentle heat, and what remains will be extremely pure.
The nitric acid is one of the most prone to combination, and is at the same time very easily decomposed. Almost all the simple substances, with the exception of gold, silver, and platina, rob it less or more of its oxygen; some of them even decompose it altogether. It was very anciently known, and its combinations have been more studied by chemists than those of any other acid. These combinations were named nitres by Messrs Macquer and Beaumé; but we have changed their names to nitrats and nitrites, according as they are formed by nitric or by nitrous acid, and have added the specific name of each particular base, to distinguish the several combinations from each other.[Pg 218]
Nitric acid is one of the most reactive acids and is also very easily broken down. Almost all simple substances, except for gold, silver, and platinum, can take away some of its oxygen; some can even completely break it down. It has been known since ancient times, and chemists have studied its compounds more than those of any other acid. These compounds were called nitres by Macquer and Beaumé, but we've renamed them to nitrates and nitrites, depending on whether they're formed by nitric or nitrous acid, and we've added the specific name of each base to differentiate the various compounds from one another.[Pg 218]
Table of the Combinations of Sulphuric Acid with the Salifiable Bases, in the order of affinity.
Names of the bases. | Resulting compounds. | |||
New nomenclature. | Old nomenclature. | |||
Barytes | Sulphat of | barytes | Heavy spar. Vitriol of heavy earth. | |
Potash | potash | Vitriolated tartar. Sal de duobus. Arcanum duplicatam. | ||
Soda | soda | Glauber's salt. | ||
Lime | lime | Selenite, gypsum, calcareous vitriol. | ||
Magnesia | magnesia | Epsom salt, sedlitz salt, magnesian vitriol. | ||
Ammoniac | ammoniac | Glauber's secret sal ammoniac. | ||
Argill | argill | Alum. | ||
Oxyd of | zinc | zinc | White vitriol, goslar vitriol, white coperas, vitriol of zinc. | |
iron | iron | Green coperas, green vitriol, martial vitriol, vitriol of iron. | ||
manganese | manganese | Vitriol of manganese. | ||
cobalt | cobalt | Vitriol of cobalt. | ||
nickel | nickel | Vitriol of nickel. | ||
lead | lead | Vitriol of lead. | ||
tin | tin | Vitriol of tin. | ||
copper | copper | Blue coperas, blue vitriol, Roman vitriol, vitriol of copper. | ||
bismuth | bismuth | Vitriol of bismuth. | ||
antimony | antimony | Vitriol of antimony. | ||
arsenic | arsenic | Vitriol of arsenic. | ||
mercury | mercury | Vitriol of mercury. | ||
silver | silver | Vitriol of silver. | ||
gold | gold | Vitriol of gold. | ||
platina | platina | Vitriol of platina. |
Sect. 14.—Observations upon Sulphuric Acid and its Combinations.
For a long time this acid was procured by distillation from sulphat of iron, in which sulphuric acid and oxyd of iron are combined, according to the process described by Basil Valentine in the fifteenth century; but, in modern times, it is procured more oeconomically by the combustion of sulphur in proper vessels. Both to facilitate the combustion, and to assist the oxygenation of the sulphur, a little powdered saltpetre, nitrat of potash, is mixed with it; the nitre is decomposed, and gives out its oxygen to the sulphur, which contributes to its conversion into acid. Notwithstanding this addition, the sulphur will only continue to burn in close vessels for a limited time; the combination ceases, because the oxygen is exhausted, and the air of the vessels reduced almost to pure azotic gas, and because the acid itself remains long in the state of vapour, and hinders the progress of combustion.
For a long time, this acid was obtained by distilling iron sulfate, which involves a combination of sulfuric acid and iron oxide, following the method described by Basil Valentine in the fifteenth century. However, nowadays, it's produced more economically by burning sulfur in the right containers. To help with the combustion and to aid the oxidation of the sulfur, a small amount of powdered saltpeter, or potassium nitrate, is added. The saltpeter breaks down and releases oxygen, which helps convert sulfur into acid. Despite this addition, the sulfur can only burn in closed containers for a limited time; the reaction stops because the oxygen runs out, and the air inside the containers becomes almost pure nitrogen gas. Additionally, the acid itself remains in vapor form for a long time, which impedes the burning process.
In the manufactories for making sulphuric acid in the large way, the mixture of nitre and sulphur is burnt in large close built chambers lined with lead, having a little water at the bottom for facilitating the condensation of the vapours.[Pg 220] Afterwards, by distillation in large retorts with a gentle heat, the water passes over, slightly impregnated with acid, and the sulphuric acid remains behind in a concentrated state. It is then pellucid, without any flavour, and nearly double the weight of an equal bulk of water. This process would be greatly facilitated, and the combustion much prolonged, by introducing fresh air into the chambers, by means of several pairs of bellows directed towards the flame of the sulphur, and by allowing the nitrous gas to escape through long serpentine canals, in contact with water, to absorb any sulphuric or sulphurous acid gas it might contain.
In large-scale factories producing sulfuric acid, a mixture of saltpeter and sulfur is burned in large, sealed chambers lined with lead, containing a bit of water at the bottom to help condense the vapors.[Pg 220] Afterward, through distillation in large retorts with gentle heat, the water is collected, slightly infused with acid, while the sulfuric acid remains concentrated behind. The resulting acid is clear, without any taste, and weighs nearly twice as much as an equal volume of water. This process could be greatly improved and the combustion extended by introducing fresh air into the chambers using several pairs of bellows aimed at the sulfur flame and allowing the nitrous gas to escape through long, winding pipes that come in contact with water to absorb any sulfuric or sulfurous acid gas it may contain.
By one experiment, Mr Berthollet found that 69 parts of sulphur in combustion, united with 31 parts of oxygen, to form 100 parts of sulphuric acid; and, by another experiment, made in a different manner, he calculates that 100 parts of sulphuric acid consists of 72 parts sulphur, combined with 28 parts of oxygen, all by weight.
In one experiment, Mr. Berthollet discovered that 69 parts of sulfur combined with 31 parts of oxygen during combustion to create 100 parts of sulfuric acid. In another experiment, conducted differently, he calculated that 100 parts of sulfuric acid is made up of 72 parts sulfur and 28 parts oxygen, all by weight.
This acid, in common with every other, can only dissolve metals when they have been previously oxydated; but most of the metals are capable of decomposing a part of the acid, so as to carry off a sufficient quantity of oxygen, to render themselves soluble in the part of the acid which remains undecomposed. This happens with silver, mercury, iron, and zinc, in boiling[Pg 221] concentrated sulphuric acid; they become first oxydated by decomposing part of the acid, and then dissolve in the other part; but they do not sufficiently disoxygenate the decomposed part of the acid to reconvert it into sulphur; it is only reduced to the state of sulphurous acid, which, being volatilised by the heat, flies off in form of sulphurous acid gas.
This acid, like all others, can only dissolve metals after they’ve been oxidized first. However, most metals can break down some of the acid, allowing them to release enough oxygen to become soluble in the portion of the acid that hasn’t been decomposed. This occurs with silver, mercury, iron, and zinc when placed in boiling[Pg 221] concentrated sulfuric acid; they first get oxidized by breaking down part of the acid and then dissolve in the remaining part. However, they don’t remove enough oxygen from the decomposed part of the acid to convert it back into sulfur; it only gets reduced to sulfurous acid, which evaporates due to the heat and escapes as sulfurous acid gas.
Silver, mercury, and all the other metals except iron and zinc, are insoluble in diluted sulphuric acid, because they have not sufficient affinity with oxygen to draw it off from its combination either with the sulphur, the sulphurous acid, or the hydrogen; but iron and zinc, being assisted by the action of the acid, decompose the water, and become oxydated at its expence, without the help of heat.[Pg 222]
Silver, mercury, and all the other metals except for iron and zinc don’t dissolve in diluted sulfuric acid because they lack enough attraction to oxygen to break it away from its bonds with sulfur, sulfurous acid, or hydrogen. However, iron and zinc, with the help of the acid, break down the water and become oxidized using it, without needing heat.[Pg 222]
Table of the Combinations of the Sulphurous Acid with the Salifiable Bases, in the order of affinity.
Names of the Bases. | Names of the Neutral Salts. | ||
Barytes | Sulphite of | barytes. | |
Potash | potash. | ||
Soda | soda. | ||
Lime | lime. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd of | zinc | zinc. | |
iron | iron. | ||
manganese | manganese. | ||
cobalt | cobalt. | ||
nickel | nickel. | ||
lead | lead. | ||
tin | tin. | ||
copper | copper. | ||
bismuth | bismuth. | ||
antimony | antimony. | ||
arsenic | arsenic. | ||
mercury | mercury. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. |
Note.—The only one of these salts known to the old chemists was the sulphite of potash, under the name of Stahl's sulphureous salt. So that, before our new nomenclature, these compounds must have been named Stahl's sulphureous salt, having base of fixed vegetable alkali, and so of the rest.
Note.—The only salt that the old chemists recognized was the potash sulphite, referred to as Stahl's sulphureous salt. So, before we had our new naming system, these compounds would have been called Stahl's sulphureous salt, which has a base of fixed vegetable alkali, and similarly for the others.
In this Table we have followed Bergman's order of affinity of the sulphuric acid, which is the same in regard to the earths and alkalies, but it is not certain if the order be the same for the metallic oxyds.—A.[Pg 223]
In this Table, we've followed Bergman's arrangement of the affinity of sulfuric acid, which is similar when it comes to the earths and alkalis, but it's unclear if the order applies to the metallic oxides.—A.[Pg 223]
Sect. 15.—Observations upon Sulphurous Acid, and its Combinations.
The sulphurous acid is formed by the union of oxygen with sulphur by a lesser degree of oxygenation than the sulphuric acid. It is procurable either by burning sulphur slowly, or by distilling sulphuric acid from silver, antimony, lead, mercury, or charcoal; by which operation a part of the oxygen quits the acid, and unites to these oxydable bases, and the acid passes over in the sulphurous state of oxygenation. This acid, in the common pressure and temperature of the air, can only exist in form of gas; but it appears, from the experiments of Mr Clouet, that, in a very low temperature, it condenses, and becomes fluid. Water absorbs a great deal more of this gas than of carbonic acid gas, but much less than it does of muriatic acid gas.
Sulphurous acid is created when oxygen combines with sulfur, but with less oxygen than what’s found in sulfuric acid. You can get it by burning sulfur slowly or by distilling sulfuric acid from metals like silver, antimony, lead, mercury, or charcoal. During this process, some of the oxygen leaves the acid and bonds with these oxidizable bases, resulting in the acid transitioning to a sulphurous state of oxygenation. Under normal atmospheric pressure and temperature, this acid only exists as a gas. However, experiments by Mr. Clouet show that at very low temperatures, it condenses and becomes liquid. Water absorbs much more of this gas than it does carbon dioxide but significantly less than it absorbs hydrochloric acid gas.
That the metals cannot be dissolved in acids without being previously oxydated, or by procuring oxygen, for that purpose, from the acids during solution, is a general and well established fact, which I have perhaps repeated too often. Hence, as sulphurous acid is already deprived of great part of the oxygen necessary for forming the sulphuric acid, it is more disposed[Pg 224] to recover oxygen, than to furnish it to the greatest part of the metals; and, for this reason, it cannot dissolve them, unless previously oxydated by other means. From the same principle it is that the metallic oxyds dissolve without effervescence, and with great facility, in sulphurous acid. This acid, like the muriatic, has even the property of dissolving metallic oxyds surcharged with oxygen, and consequently insoluble in sulphuric acid, and in this way forms true sulphats. Hence we might be led to conclude that there are no metallic sulphites, were it not that the phenomena which accompany the solution of iron, mercury, and some other metals, convince us that these metallic substances are susceptible of two degrees of oxydation, during their solution in acids. Hence the neutral salt in which the metal is least oxydated must be named sulphite, and that in which it is fully oxydated must be called sulphat. It is yet unknown whether this distinction is applicable to any of the metallic sulphats, except those of iron and mercury.[Pg 225]
That metals can't be dissolved in acids without first being oxidized, or obtaining oxygen from the acids during the process, is a well-known fact that I've probably mentioned too often. Therefore, since sulfurous acid already has much of the oxygen required to form sulfuric acid removed, it's more likely to recover oxygen than to provide it to most metals. For this reason, it can't dissolve metals unless they are oxidized by other methods first. This same principle explains why metallic oxides dissolve easily and without fizzing in sulfurous acid. This acid, like hydrochloric acid, can even dissolve metallic oxides that are over-oxygenated and therefore insoluble in sulfuric acid, leading to the formation of true sulfates. This might make us think there are no metallic sulfites, but the reactions that happen during the dissolution of iron, mercury, and a few other metals show that these metals can be oxidized in two stages when dissolving in acids. Thus, the neutral salt for the least oxidized metal should be called a sulfite, while the one for the fully oxidized metal should be known as a sulfate. It's still unclear whether this distinction applies to any of the metallic sulfates, aside from those of iron and mercury.[Pg 225]
Table of the Combinations of Phosphorous and Phosphoric Acids, with the Salifiable Bases, in the Order of Affinity.
Names of the Bases. | Names of the Neutral Salts formed by | |
Phosphorous Acid, | Phosphoric Acid. | |
Phosphites of(B) | Phosphats of(C) | |
Lime | lime | lime. |
Barytes | barytes | barytes. |
Magnesia | magnesia | magnesia. |
Potash | potash | potash. |
Soda | soda | soda. |
Ammoniac | ammoniac | ammoniac. |
Argill | argill | argill. |
Oxyds of(A) | ||
zinc | zinc | zinc. |
iron | iron | iron. |
manganese | manganese | manganese. |
cobalt | cobalt | cobalt. |
nickel | nickel | nickel. |
lead | lead | lead. |
tin | tin | tin. |
copper | copper | copper. |
bismuth | bismuth | bismuth. |
antimony | antimony | antimony. |
arsenic | arsenic | arsenic. |
mercury | mercury | mercury. |
silver | silver | silver. |
gold | gold | gold. |
platina | platina | platina. |
[Note A: The existence of metallic phosphites supposes that metals are susceptible of solution in phosphoric acid at different degrees of oxygenation, which is not yet ascertained.—A.]
[Note A: The existence of metallic phosphites suggests that metals can dissolve in phosphoric acid to varying extents of oxidation, which is not yet confirmed.—A.]
[Note B: All the phosphites were unknown till lately, and consequently have not hitherto received names.—A.]
[Note B: All the phosphites were unknown until recently, so they haven't been named until now.—A.]
[Note C: The greater part of the phosphats were only discovered of late, and have not yet been named.—A.][Pg 226]
[Note C: Most of the phosphates were only discovered recently and haven’t been named yet.—A.][Pg 226]
Group. XVI.—Observations upon Phosphorous and Phosphoric Acids, and their Combinations.
Under the article Phosphorus, Part II. Sect. X. we have already given a history of the discovery of that singular substance, with some observations upon the mode of its existence in vegetable and animal bodies. The best method of obtaining this acid in a state of purity is by burning well purified phosphorus under bell-glasses, moistened on the inside with distilled water; during combustion it absorbs twice and a half its weight of oxygen; so that 100 parts of phosphoric acid is composed of 28-1/2 parts of phosphorus united to 71-1/2 parts of oxygen. This acid may be obtained concrete, in form of white flakes, which greedily attract the moisture of the air, by burning phosphorus in a dry glass over mercury.
Under the article Phosphorus, Part II. Sect. X., we have already discussed the history of the discovery of this unique substance and made some observations about how it exists in plants and animals. The best way to obtain this acid in a pure state is by burning well-purified phosphorus under bell jars that have been moistened on the inside with distilled water; during combustion, it absorbs two and a half times its weight in oxygen. Therefore, 100 parts of phosphoric acid consist of 28.5 parts of phosphorus combined with 71.5 parts of oxygen. This acid can be obtained as a solid in the form of white flakes, which readily attract moisture from the air, by burning phosphorus in a dry glass over mercury.
To obtain phosphorous acid, which is phosphorus less oxygenated than in the state of phosphoric acid, the phosphorus must be burnt by a very slow spontaneous combustion over a glass-funnel leading into a crystal phial; after a few days, the phosphorus is found oxygenated, and the phosphorous acid, in proportion as it forms, has attracted moisture from the air, and dropped into the phial. The phosphorous[Pg 227] acid is readily changed into phosphoric acid by exposure for a long time to the free air; it absorbs oxygen from the air, and becomes fully oxygenated.
To get phosphorous acid, which has less oxygen than phosphoric acid, you need to burn phosphorus through a very slow spontaneous combustion process using a glass funnel that leads into a crystal vial. After a few days, the phosphorus will have reacted with oxygen, and the phosphorous acid will have drawn moisture from the air, collecting in the vial. The phosphorous [Pg 227] acid easily transforms into phosphoric acid if exposed to open air for a long time; it absorbs oxygen and becomes fully oxygenated.
As phosphorus has a sufficient affinity for oxygen to attract it from the nitric and muriatic acids, we may form phosphoric acid, by means of these acids, in a very simple and cheap manner. Fill a tubulated receiver, half full of concentrated nitric acid, and heat it gently, then throw in small pieces of phosphorus through the tube, these are dissolved with effervescence and red fumes of nitrous gas fly off; add phosphorus so long as it will dissolve, and then increase the fire under the retort to drive off the last particles of nitric acid; phosphoric acid, partly fluid and partly concrete, remains in the retort.[Pg 228]
As phosphorus readily attracts oxygen from nitric and muriatic acids, we can easily and cheaply make phosphoric acid using these acids. Fill a tubulated receiver halfway with concentrated nitric acid and heat it gently. Then, add small pieces of phosphorus through the tube; it will dissolve with bubbles, and red fumes of nitrous gas will be released. Keep adding phosphorus until it stops dissolving, then increase the heat under the retort to remove the remaining nitric acid. You'll be left with phosphoric acid, which will be a mix of liquid and solid in the retort.[Pg 228]
Table of the Combinations of Carbonic Acid, with the Salifiable Bases, in the Order of Affinity.
Names of Bases | Resulting Neutral Salts. | ||
New Nomenclature. | Old Nomenclature. | ||
Barytes | Carbonates of | barytes(A) | Aërated or effervescent heavy earth. |
Lime | lime | Chalk, calcareous spar, Aërated calcareous earth. | |
Potash | potash | Effervescing or aërated fixed vegetable alkali, mephitis of potash. | |
Soda | soda | Aërated or effervescing fixed mineral alkali, mephitic soda. | |
Magnesia | magnesia | Aërated, effervescing, mild, or mephitic magnesia. | |
Ammoniac | ammoniac | Aërated, effervescing, mild, or mephitic volatile alkali. | |
Argill | argill | Aërated or effervescing argillaceous earth, or earth of alum. | |
Oxyds of | |||
zinc | zinc | Zinc spar, mephitic or aërated zinc. | |
iron | iron | Sparry iron-ore, mephitic or aërated iron. | |
manganese | manganese | Aërated manganese. | |
cobalt | cobalt | Aërated cobalt. | |
nickel | nickel | Aërated nickel. | |
lead | lead | Sparry lead-ore, or aërated lead. | |
tin | tin | Aërated tin. | |
copper | copper | Aërated copper. | |
bismuth | bismuth | Aërated bismuth. | |
antimony | antimony | Aërated antimony. | |
arsenic | arsenic | Aërated arsenic. | |
mercury | mercury | Aërated mercury. | |
silver | silver | Aërated silver. | |
gold | gold | Aërated gold. | |
platina | platina | Aërated platina. |
[Note A: As these salts have only been understood of late, they have not, properly speaking, any old names. Mr Morveau, in the First Volume of the Encyclopedia, calls them Mephites; Mr Bergman gives them the name of aërated; and Mr de Fourcroy, who calls the carbonic acid chalky acid, gives them the name of chalks.—A][Pg 229]
[Note A: Since these salts have only recently been understood, they don't really have any old names. Mr. Morveau, in the First Volume of the Encyclopedia, calls them Mephites; Mr. Bergman refers to them as aërated; and Mr. de Fourcroy, who calls carbonic acid chalky acid, names them chalks.—A][Pg 229]
Group. XVII.—Observations upon Carbonic Acid, and its Combinations.
Of all the known acids, the carbonic is the most abundant in nature; it exists ready formed in chalk, marble, and all the calcareous stones, in which it is neutralized by a particular earth called lime. To disengage it from this combination, nothing more is requisite than to add some sulphuric acid, or any other which has a stronger affinity for lime; a brisk effervescence ensues, which is produced by the disengagement of the carbonic acid which assumes the state of gas immediately upon being set free. This gas, incapable of being condensed into the solid or liquid form by any degree of cold or of pressure hitherto known, unites to about its own bulk of water, and thereby forms a very weak acid. It may likewise be obtained in great abundance from saccharine matter in fermentation, but is then contaminated by a small portion of alkohol which it holds in solution.
Of all the known acids, carbonic acid is the most common in nature; it can be found naturally in chalk, marble, and all calcareous stones, where it is neutralized by a specific substance called lime. To separate it from this combination, all you need to do is add some sulfuric acid, or any other acid that has a stronger attraction to lime; this causes a vigorous fizzing as the carbonic acid is released and turns into gas immediately upon being freed. This gas cannot be condensed into solid or liquid form by any known level of cold or pressure and combines with about its own volume of water to form a very weak acid. It can also be produced in large amounts from sugary substances during fermentation, but it will then be mixed with a small amount of alcohol that it dissolves.
As charcoal is the radical of this acid, we may form it artificially, by burning charcoal in oxygen gas, or by combining charcoal and metallic oxyds in proper proportions; the oxygen of the oxyd combines with the charcoal, forming[Pg 230] carbonic acid gas, and the metal being left free, recovers its metallic or reguline form.
As charcoal is the base of this acid, we can create it artificially by burning charcoal in oxygen gas or by mixing charcoal and metal oxides in the right amounts; the oxygen from the oxide combines with the charcoal, forming[Pg 230] carbonic acid gas, while the metal is left free and returns to its metallic form.
We are indebted for our first knowledge of this acid to Dr Black, before whose time its property of remaining always in the state of gas had made it to elude the researches of chemistry.
We owe our initial understanding of this acid to Dr. Black, whose work came at a time when its tendency to always exist as a gas had caused it to evade the studies of chemistry.
It would be a most valuable discovery to society, if we could decompose this gas by any cheap process, as by that means we might obtain, for economical purposes, the immense store of charcoal contained in calcareous earths, marbles, limestones, &c. This cannot be effected by single affinity, because, to decompose the carbonic acid, it requires a substance as combustible as charcoal itself, so that we should only make an exchange of one combustible body for another not more valuable; but it may possibly be accomplished by double affinity, since this process is so readily performed by Nature, during vegetation, from the most common materials.[Pg 231]
It would be a significant breakthrough for society if we could break down this gas using an inexpensive method. That way, we could access the vast amount of charcoal found in calcareous soil, marbles, limestones, and so on for economical uses. This can't be done through a single affinity because decomposing carbonic acid requires a substance as flammable as charcoal itself, which would just swap one combustible material for another that's no more useful. However, it might be possible through double affinity, as this process is often carried out by Nature during plant growth using very common materials.[Pg 231]
Table of the Combinations of Muriatic Acid, with the Salifiable Bases, in the Order of Affinity.
Names of the bases. | Resulting Neutral Salts. | |
New nomenclature. | Old nomenclature. | |
Barytes. | Muriat of | |
barytes | Sea-salt, having base of heavy earth. | |
Potash | potash | Febrifuge salt of Sylvius: Muriated vegetable fixed alkali. |
Soda | soda | Sea-salt. |
Lime | lime | Muriated lime. Oil of lime. |
Magnesia | magnesia | Marine Epsom salt. Muriated magnesia. |
Ammoniac | ammoniac | Sal ammoniac. |
Argill | argill | {Muriated alum, sea-salt with base of earth of alum. |
Oxyd of | ||
zinc | zinc | Sea-salt of, or muriatic zinc. |
iron | iron | Salt of iron, Martial sea-salt. |
manganese | manganese | Sea-salt of manganese. |
cobalt | cobalt | Sea-salt of cobalt. |
nickel | nickel | Sea-salt of nickel. |
lead | lead | Horny-lead. Plumbum corneum. |
tin | smoaking of tin solid of tin | Smoaking liquor of Libavius. Solid butter of tin. |
copper | copper | Sea-salt of copper. |
bismuth | bismuth | Sea-salt of bismuth. |
antimony | antimony | Sea-salt of antimony. |
arsenic | arsenic | Sea-salt of arsenic. |
mercury | {sweet of mercury | Sweet sublimate of mercury, calomel, aquila alba. |
{corrosive of mercury | Corrosive sublimate of mercury. | |
silver | silver | Horny silver, argentum corneum, luna cornea. |
gold | gold | Sea-salt of gold. |
platina | platina | Sea-salt of platina. |
Table Of the Combinations of Oxygenated Muriatic Acid, with the Salifiable Bases, in the Order of Affinity.
Names of the Bases. | Names of the Neutral Salts by the new Nomenclature. |
Oxygenated muriat of | |
Barytes | barytes. |
Potash | potash. |
Soda | soda. |
Lime | lime. |
Magnesia | magnesia. |
Argill | argill. |
Oxyd of | |
zinc | zinc. |
iron | iron. |
manganese | manganese. |
cobalt | cobalt. |
nickel | nickel. |
lead | lead. |
tin | tin. |
copper | copper. |
bismuth | bismuth. |
antimony | antimony. |
arsenic | arsenic. |
mercury | mercury. |
silver | silver. |
gold | gold. |
platina | platina. |
This order of salts, entirely unknown to the ancient chemists, was discovered in 1786 by Mr Berthollet.—A.[Pg 233]
This type of salt, completely unknown to ancient chemists, was discovered in 1786 by Mr. Berthollet.—A.[Pg 233]
Group. XIX.—Observations upon Muriatic and Oxygenated Muriatic Acids, and their Combinations.
Muriatic acid is very abundant in the mineral kingdom naturally combined with different salifiable bases, especially with soda, lime, and magnesia. In sea-water, and the water of several lakes, it is combined with these three bases, and in mines of rock-salt it is chiefly united to soda. This acid does not appear to have been hitherto decomposed in any chemical experiment; so that we have no idea whatever of the nature of its radical, and only conclude, from analogy with the other acids, that it contains oxygen as its acidifying principle. Mr Berthollet suspects the radical to be of a metallic nature; but, as Nature appears to form this acid daily, in inhabited places, by combining miasmata with aëriform fluids, this must necessarily suppose a metallic gas to exist in the atmosphere, which is certainly not impossible, but cannot be admitted without proof.
Muriatic acid is very common in the mineral world, usually found combined with different bases, especially soda, lime, and magnesia. In seawater and the water from several lakes, it combines with these three bases, and in rock salt mines, it mainly joins with soda. This acid has not been broken down in any chemical experiments so far, so we really have no idea what its core component is. We can only assume, based on other acids, that it contains oxygen as its acidifying element. Mr. Berthollet thinks the core component might be metallic, but since nature seems to produce this acid regularly in populated areas by mixing miasma with air, it implies that a metallic gas exists in the atmosphere. While this isn't impossible, it can't be accepted without evidence.
The muriatic acid has only a moderate adherence to the salifiable bases, and can readily be driven from its combination with these by sulphuric acid. Other acids, as the nitric, for instance, may answer the same purpose; but nitric acid being volatile, would mix, during distillation,[Pg 234] with the muriatic. About one part of sulphuric acid is sufficient to decompose two parts of decrepitated sea-salt. This operation is performed in a tubulated retort, having Woulfe's apparatus, (Pl. IV. Fig. 1.), adapted to it. When all the junctures are properly lured, the sea-salt is put into the retort through the tube, the sulphuric acid is poured on, and the opening immediately closed with its ground crystal stopper. As the muriatic acid can only subsist in the gaseous form in the ordinary temperature, we could not condense it without the presence of water. Hence the use of the water with which the bottles in Woulfe's apparatus are half filled; the muriatic acid gas, driven off from the sea-salt in the retort, combines with the water, and forms what the old chemists called smoaking spirit of salt, or Glauber's spirit of sea-salt, which we now name muriatic acid.
Muriatic acid has only a moderate attraction to alkaline bases and can easily be removed from its combination with these by using sulfuric acid. Other acids, like nitric acid, can serve the same purpose; however, since nitric acid is volatile, it would mix with muriatic acid during distillation.[Pg 234] About one part of sulfuric acid is enough to break down two parts of decrepitated sea salt. This process is carried out in a tubulated retort with Woulfe's apparatus (Pl. IV. Fig. 1.) attached. Once all the connections are secure, the sea salt is added to the retort through the tube, sulfuric acid is poured in, and the opening is immediately sealed with a ground glass stopper. Since muriatic acid can only exist as a gas at normal temperatures, we cannot condense it without water. This is why the bottles in Woulfe's apparatus are half-filled with water; the muriatic acid gas released from the sea salt in the retort combines with the water to form what old chemists called smoaking spirit of salt or Glauber's spirit of sea-salt, which we now refer to as muriatic acid.
The acid obtained by the above process is still capable of combining with a farther dose of oxygen, by being distilled from the oxyds of manganese, lead, or mercury, and the resulting acid, which we name oxygenated muriatic acid, can only, like the former, exist in the gasseous form, and is absorbed, in a much smaller quantity by water. When the impregnation of water with this gas is pushed beyond a certain point, the superabundant acid precipitates to the bottom of the vessels in a concrete form. Mr Berthollet has[Pg 235] shown that this acid is capable of combining with a great number of the salifiable bases; the neutral salts which result from this union are susceptible of deflagrating with charcoal, and many of the metallic substances; these deflagrations are very violent and dangerous, owing to the great quantity of caloric which the oxygen carries alongst with it into the composition of oxygenated muriatic acid.[Pg 236]
The acid produced by the process described above can still combine with more oxygen when distilled from manganese, lead, or mercury oxides. The resulting acid, which we call oxygenated muriatic acid, can only exist in a gaseous form, and is absorbed by water in much smaller amounts. When water is saturated with this gas beyond a certain level, the excess acid precipitates at the bottom of the container in a solid form. Mr. Berthollet has[Pg 235] shown that this acid can combine with many salifiable bases; the neutral salts that result from this reaction can ignite with charcoal and various metals. These ignitions are very violent and dangerous because of the large amount of heat that the oxygen brings with it in the composition of oxygenated muriatic acid.[Pg 236]
Table of the Combinations of Nitro-muriatic Acid with the Salifiable Bases, in the Order of Affinity, so far as is known.
Names of the Bases. | Names of the Neutral Salts. | ||
Argill | Nitro-muriat of | argill. | |
Ammoniac | ammoniac. | ||
Oxyd of | |||
antimony | antimony. | ||
silver | silver. | ||
arsenic | arsenic. | ||
Barytes | barytes. | ||
Oxyd of | bismuth | bismuth. | |
Lime | lime. | ||
Oxyd of | |||
cobalt | cobalt. | ||
copper | copper. | ||
tin | tin. | ||
iron | iron. | ||
Magnesia | magnesia. | ||
Oxyd of | |||
manganese | manganese. | ||
mercury | mercury. | ||
molybdena | molybdena. | ||
nickel | nickel. | ||
gold | gold. | ||
platina | platina. | ||
lead | lead. | ||
Potash | potash. | ||
Soda | soda. | ||
Oxyd of | |||
tungstein | tungstein. | ||
zinc | zinc. |
Note.—Most of these combinations, especially those with the earths and alkalies, have been little examined, and we are yet to learn whether they form a mixed salt in which the compound radical remains combined, or if the two acids separate, to form two distinct neutral salts.—A.[Pg 237]
Note.—Most of these combinations, especially those with the earths and alkalis, haven't been studied much, and we still need to find out whether they create a mixed salt where the compound radical stays combined or if the two acids separate to form two different neutral salts.—A.[Pg 237]
Sect. XX.—Observations upon the Nitro-Muriatic Acid, and its Combinations.
The nitro-muriatic acid, formerly called aqua regia, is formed by a mixture of nitric and muriatic acids; the radicals of these two acids combine together, and form a compound base, from which an acid is produced, having properties peculiar to itself, and distinct from those of all other acids, especially the property of dissolving gold and platina.
The nitro-muriatic acid, once known as aqua regia, is created by mixing nitric and muriatic acids. The radicals of these two acids come together to form a compound base, which produces an acid with unique properties, particularly its ability to dissolve gold and platinum, unlike any other acid.
In dissolutions of metals in this acid, as in all other acids, the metals are first oxydated by attracting a part of the oxygen from the compound radical. This occasions a disengagement of a particular species of gas not hitherto described, which may be called nitro-muriatic gas; it has a very disagreeable smell, and is fatal to animal life when respired; it attacks iron, and causes it to rust; it is absorbed in considerable quantity by water, which thereby acquires some slight characters of acidity. I had occasion to make these remarks during a course of experiments upon platina, in which I dissolved a considerable quantity of that metal in nitro-muriatic acid.
In the process of dissolving metals in this acid, just like with all other acids, the metals are first oxidized by drawing a portion of the oxygen from the compound radical. This leads to the release of a type of gas that hasn't been described before, which can be called nitro-muriatic gas; it has a very unpleasant odor and is deadly to animal life if inhaled. It corrodes iron, causing it to rust, and it is absorbed in significant amounts by water, which then takes on some mild acidic properties. I noted these observations during a series of experiments on platinum, where I dissolved a substantial amount of that metal in nitro-muriatic acid.
I at first suspected that, in the mixture of nitric and muriatic acids, the latter attracted a[Pg 238] part of the oxygen from the former, and became converted into oxygenated muriatic acid, which gave it the property of dissolving gold; but several facts remain inexplicable upon this supposition. Were it so, we must be able to disengage nitrous gas by heating this acid, which however does not sensibly happen. From these considerations, I am led to adopt the opinion of Mr Berthollet, and to consider nitro-muriatic acid as a single acid, with a compound base or radical.[Pg 239]
I initially thought that in the mix of nitric and hydrochloric acids, the hydrochloric acid pulled some oxygen from the nitric acid and turned into oxygenated hydrochloric acid, which allowed it to dissolve gold. However, there are several facts that don’t make sense with this idea. If that were true, we should be able to produce nitrous gas by heating this acid, but that doesn't really happen. Based on these points, I lean towards Mr. Berthollet's view and see nitro-hydrochloric acid as a single acid with a combined base or radical.
Table of the Combinations of Fluoric Acid, with the Salifiable Bases, in the Order of Affinity.
Names of the Bases. | Names of the Neutral Salts. | ||
Lime | Fluat of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. | ||
And by the dry way, | |||
Argill | Fluat of | argill. |
Note.—These combinations were entirely unknown to the old chemists, and consequently have no names in the old nomenclature.—A.[Pg 240]
Note.—These combinations were completely unknown to the early chemists, and as a result, they don’t have names in the old naming system.—A.[Pg 240]
Section. XXI.—Observations upon the Fluoric Acid, and its Combinations.
Fluoric exists ready formed by Nature in the fluoric spars[42], combined with calcareous earth, so as to form an insoluble neutral salt. To obtain it disengaged from that combination, fluor spar, or fluat of lime, is put into a leaden retort, with a proper quantity of sulphuric acid, a recipient likewise of lead, half full of water, is adapted, and fire is applied to the retort. The sulphuric acid, from its greater affinity, expels the fluoric acid which passes over and is absorbed by the water in the receiver. As fluoric acid is naturally in the gasseous form in the ordinary temperature, we can receive it in a pneumato-chemical apparatus over mercury. We are obliged to employ metallic vessels in this process, because fluoric acid dissolves glass and silicious earth, and even renders these bodies volatile, carrying them over with itself in distillation in the gasseous form.
Fluoric is naturally found in fluoric spar[42], which is a combination with calcareous earth that forms an insoluble neutral salt. To separate it from that combination, fluor spar, or fluat of lime, is placed in a lead retort with a proper amount of sulfuric acid. A lead container, half full of water, is also set up, and heat is applied to the retort. The sulfuric acid, having a stronger affinity, drives out the fluoric acid, which then moves over and is absorbed by the water in the receiver. Since fluoric acid is naturally a gas at normal temperature, we can collect it in a pneumatochemical apparatus over mercury. We have to use metal containers in this process because fluoric acid dissolves glass and silica, even causing these materials to vaporize and carry them over during distillation in gaseous form.
We are indebted to Mr Margraff for our first acquaintance with this acid, though, as he could never procure it free from combination with a considerable quantity of silicious earth, he was[Pg 241] ignorant of its being an acid sui generis. The Duke de Liancourt, under the name of Mr Boulanger, considerably increased our knowledge of its properties; and Mr Scheele seems to have exhausted the subject. The only thing remaining is to endeavour to discover the nature of the fluoric radical, of which we cannot hitherto form any ideas, as the acid does not appear to have been decomposed in any experiment. It is only by means of compound affinity that experiments ought to be made with this view, with any probability of success.[Pg 242]
We owe our first introduction to this acid to Mr. Margraff, even though he could never obtain it without a significant amount of silicious earth mixed in, so he was unaware that it was a unique acid. The Duke de Liancourt, under the alias Mr. Boulanger, greatly enhanced our understanding of its properties, and Mr. Scheele seems to have covered the topic thoroughly. The only thing left is to try to uncover the nature of the fluoric radical, about which we currently have no clear ideas, as the acid does not seem to have been broken down in any experiment. Experiments should focus on compound affinity to have any chance of success.[Pg 242]
Table of the Combinations of Boracic Acid, with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Lime | Borat of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
mercury | mercury. | ||
Argill | argill. |
Note.—Most of these combinations were neither known nor named by the old chemists. The boracic acid was formerly called sedative salt, and its compounds borax, with base of fixed vegetable alkali, &c.—A.[Pg 243]
Note.—Most of these combinations were neither recognized nor named by the early chemists. Boracic acid used to be called sedative salt, and its compounds borax, with a base of fixed vegetable alkali, etc.—A.[Pg 243]
Section. XXII.—Observations upon Boracic Add and its Combinations.
This is a concrete acid, extracted from a salt procured from India called borax or tincall. Although borax has been very long employed in the arts, we have as yet very imperfect knowledge of its origin, and of the methods by which it is extracted and purified; there is reason to believe it to be a native salt, found in the earth in certain parts of the east, and in the water of some lakes. The whole trade of borax is in the hands of the Dutch, who have been exclusively possessed of the art of purifying it till very lately, that Messrs L'Eguillier of Paris have rivalled them in the manufacture; but the process still remains a secret to the world.
This is a concrete acid, extracted from a salt obtained from India called borax or tincall. Although borax has been used in various arts for a long time, we still have an incomplete understanding of its origin and the methods used to extract and purify it. There is reason to believe it is a natural salt found in the earth in certain parts of the East and in the waters of some lakes. The entire borax trade is controlled by the Dutch, who have had the exclusive skill of purifying it until very recently when Messrs L'Eguillier of Paris began to compete with them in production; however, the process still remains a secret to the world.
By chemical analysis we learn that borax is a neutral salt with excess of base, consisting of soda, partly saturated with a peculiar acid long called Homberg's sedative salt, now the boracic acid. This acid is found in an uncombined state in the waters of certain lakes. That of Cherchiais in Italy contains 94-1/2 grains in each pint of water.
By chemical analysis, we find that borax is a neutral salt with an excess of base, made up of soda that is partly saturated with a unique acid previously known as Homberg's sedative salt, now called boric acid. This acid occurs in its uncombined form in the waters of certain lakes. For example, the lake Cherchiais in Italy contains 94.5 grains of it in each pint of water.
To obtain boracic acid, dissolve some borax in boiling water, filtrate the solution, and add sulphuric acid, or any other having greater affinity[Pg 244] to soda than the boracic acid; this latter acid is separated, and is procured in a crystalline form by cooling. This acid was long considered as being formed during the process by which it is obtained, and was consequently supposed to differ according to the nature of the acid employed in separating it from the soda; but it is now universally acknowledged that it is identically the same acid, in whatever way procured, provided it be properly purified from mixture of other acids, by warning, and by repeated solution and cristallization. It is soluble both in water and alkohol, and has the property of communicating a green colour to the flame of that spirit. This circumstance led to a suspicion of its containing copper, which is not confirmed by any decisive experiment. On the contrary, if it contain any of that metal, it must only be considered as an accidental mixture. It combines with the salifiable bases in the humid way; and though, in this manner, it is incapable of dissolving any of the metals directly, this combination is readily affected by compound affinity.
To get boracic acid, dissolve some borax in boiling water, filter the solution, and add sulfuric acid or any other acid that has a stronger attraction to soda than boracic acid does. The boracic acid separates out and can be collected in crystalline form by cooling. For a long time, it was thought that this acid was formed during the process of extraction and was believed to vary based on the type of acid used to separate it from soda. However, it's now widely accepted that it is the same acid regardless of how it's obtained, as long as it's properly purified from other acid mixtures through heating, dissolving, and recrystallization. It dissolves in both water and alcohol, and it gives off a green color when burned in an alcohol flame. This raised suspicions that it might contain copper, but no conclusive experiments have supported that idea. In fact, if it does contain any copper, it's likely just an accidental mixture. It reacts with salifiable bases in a wet way, and while it cannot dissolve metals directly this way, this combination can be affected by compound affinities.
The Table presents its combinations in the order of affinity in the humid way; but there is a considerable change in the order when we operate via sicca; for, in that case, argill, though the last in our list, must be placed immediately after soda.[Pg 245]
The Table shows its combinations based on their affinity in a wet way; however, the order changes significantly when we work in a dry way, because in that situation, clay, although last on our list, should be placed right after soda.[Pg 245]
The boracic radical is hitherto unknown; no experiments having as yet been able to decompose the acid; We conclude, from analogy with the other acids, that oxygen exists in its composition as the acidifying principle.[Pg 246]
The boracic radical is still unknown; no experiments have been able to break down the acid yet. Based on similarities with other acids, we conclude that oxygen is part of its composition as the acidifying element.[Pg 246]
Table of the Combinations of Arseniac Acid, with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Lime | Arseniat of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. | ||
Argill | argill. |
Note.—This order of salts was entirely unknown to the antient chemists. Mr Macquer, in 1746, discovered the combinations of arseniac acid with potash and soda, to which he gave the name of arsenical neutral salts.—A.[Pg 247]
Note.—This type of salt was completely unknown to ancient chemists. Mr. Macquer discovered the combinations of arsenic acid with potash and soda in 1746, and he named them arsenical neutral salts.—A.[Pg 247]
Section. XXIII.—Observations upon Arseniac Acid, and its Combinations.
In the Collections of the Academy for 1746, Mr Macquer shows that, when a mixture of white oxyd of arsenic and nitre are subjected to the action of a strong fire, a neutral salt is obtained, which he calls neutral salt of arsenic. At that time, the cause of this singular phenomenon, in which a metal acts the part of an acid, was quite unknown; but more modern experiments teach that, during this process, the arsenic becomes oxygenated, by carrying off the oxygen of the nitric acid; it is thus converted into a real acid, and combines with the potash. There are other methods now known for oxygenating arsenic, and obtaining its acid free from combination. The most simple and most effectual of these is as follows: Dissolve white oxyd of arsenic in three parts, by weight, of muriatic acid; to this solution, in a boiling state, add two parts of nitric acid, and evaporate to dryness. In this process the nitric acid is decomposed, its oxygen unites with the oxyd of arsenic, and converts it into an acid, and the nitrous radical flies off in the state of nitrous gas; whilst the muriatic acid is converted by the heat into muriatic acid gas, and may be collected in proper vessels. The arseniac acid is entirely[Pg 248] freed from the other acids employed during the process by heating it in a crucible till it begins to grow red; what remains is pure concrete arseniac acid.
In the Collections of the Academy for 1746, Mr. Macquer demonstrates that when a mixture of white arsenic oxide and saltpeter is exposed to intense heat, a neutral salt forms, which he refers to as neutral salt of arsenic. At that time, the reason for this unusual occurrence, where a metal behaves like an acid, was completely unknown; however, more recent experiments reveal that, during this process, the arsenic gets oxygenated by taking oxygen from the nitric acid, thus turning into a true acid that combines with potash. There are now other recognized methods for oxygenating arsenic and obtaining its acid in a pure form. The simplest and most effective method is as follows: Dissolve white arsenic oxide in three parts by weight of hydrochloric acid; then, while the solution is boiling, add two parts of nitric acid and evaporate it to dryness. In this process, the nitric acid breaks down, its oxygen bonds with the arsenic oxide and transforms it into an acid, while the nitrous radical escapes as nitrous gas; meanwhile, the hydrochloric acid turns into hydrochloric acid gas due to the heat and can be collected in suitable containers. The arsenic acid is completely[Pg 248] separated from the other acids used in the process by heating it in a crucible until it starts to glow red; what remains is pure solid arsenic acid.
Mr Scheele's process, which was repeated with great success by Mr Morveau, in the laboratory at Dijon, is as follows: Distil muriatic acid from the black oxyd of manganese, this converts it into oxygenated muriatic acid, by carrying off the oxygen from the manganese, receive this in a recipient containing white oxyd of arsenic, covered by a little distilled water; the arsenic decomposes the oxygenated muriatic acid, by carrying off its supersaturation of oxygen, the arsenic is converted into arseniac acid, and the oxygenated muriatic acid is brought back to the state of common muriatic acid. The two acids are separated by distillation, with a gentle heat increased towards the end of the operation, the muriatic acid passes over, and the arseniac acid remains behind in a white concrete form.
Mr. Scheele's process, which Mr. Morveau successfully repeated in the laboratory in Dijon, is as follows: Distill hydrochloric acid from black manganese oxide, which converts it into oxygenated hydrochloric acid by removing oxygen from the manganese. Capture this in a container with white arsenic oxide, topped with a little distilled water; the arsenic decomposes the oxygenated hydrochloric acid by removing its excess oxygen, turning the arsenic into arsenic acid, and reverting the oxygenated hydrochloric acid back to regular hydrochloric acid. The two acids are separated by distillation, using gentle heat that increases towards the end of the process; hydrochloric acid vaporizes, while arsenic acid stays behind in a solid white form.
The arseniac acid is considerably less volatile than white oxyd of arsenic; it often contains white oxyd of arsenic in solution, owing to its not being sufficiently oxygenated; this is prevented by continuing to add nitrous acid, as in the former process, till no more nitrous gas is produced. From all these observations I would give the following definition of[Pg 249] arseniac acid. It is a white concrete metallic acid, formed by the combination of arsenic with oxygen, fixed in a red heat, soluble in water, and capable of combining with many of the salifiable bases.
The arsenic acid is much less volatile than white arsenic oxide; it often contains white arsenic oxide in solution because it isn’t fully oxygenated. This can be avoided by continuing to add nitrous acid, as in the previous method, until no more nitrous gas is produced. Based on all these observations, I would define [Pg 249] arsenic acid as a white solid metallic acid formed by the combination of arsenic with oxygen, fixed at a red heat, soluble in water, and capable of combining with many salifiable bases.
Sect. 24.—Observations upon Molybdic Acid, and its Combinations with Acidifiable Bases[43].
Molybdena is a particular metallic body, capable of being oxygenated, so far as to become a true concrete acid[44]. For this purpose, one part ore of molybdena, which is a natural sulphuret of that metal, is put into a retort, with five or six parts nitric acid, diluted with a quarter of its weight of water, and heat is applied to the retort; the oxygen of the nitric acid acts both upon the molybdena and the sulphur, converting the one into molybdic, and the other into sulphuric acid; pour on fresh quantities of nitric acid so long as any red fumes of nitrous[Pg 250] gas escape; the molydbena is then oxygenated as far as is possible, and is found at the bottom of the retort in a pulverulent form, resembling chalk. It must be washed in warm water, to separate any adhering particles of sulphuric acid; and, as it is hardly soluble, we lose very little of it in this operation. All its combinations with salifiable bases were unknown to the ancient chemists.
Molybdenum is a specific metallic substance that can be oxidized enough to form a true concrete acid[44]. To do this, you take one part molybdenum ore, which is a natural sulfide of that metal, and place it in a retort with five or six parts diluted nitric acid (mixed with a quarter of its weight in water), then heat the retort. The oxygen from the nitric acid reacts with both the molybdenum and the sulfur, turning molybdenum into molybdic acid and sulfur into sulfuric acid. Continue adding fresh nitric acid as long as red fumes of nitrous[Pg 250] gas are released; at that point, the molybdenum is as oxidized as possible and appears at the bottom of the retort in a powdery form, similar to chalk. It should be washed in warm water to remove any lingering sulfuric acid particles, and since it is barely soluble, we lose very little during this process. Ancient chemists were unaware of all its combinations with basic salts.
Table of the Combinations of Tungstic Acid with the Salifiable Bases.
Bases. | Neutral Salts. | |
Lime | Tungstat of | lime. |
Barytes | barytes. | |
Magnesia | magnesia. | |
Potash | potash. | |
Soda | soda. | |
Ammoniac | ammoniac. | |
Argill | argill. | |
Oxyd of antimony(A), &c. | antimony(B), &c. |
[Note A: The combinations with metallic oxyds were set down by Mr Lavoisier in alphabetical order; their order of affinity being unknown, I have omitted them, as serving no purpose.—E.]
[Note A: The combinations with metallic oxides were listed by Mr. Lavoisier in alphabetical order; since their order of affinity is unknown, I have left them out, as they serve no purpose.—E.]
[Note B: All these salts were unknown to the ancient chemists.—A.]
[Note B: All these salts were unknown to the ancient chemists.—A.]
Sect. 25.—Observations upon Tungstic Acid, and its Combinations.
Tungstein is a particular metal, the ore of which has frequently been confounded with that of tin. The specific gravity of this ore is to water as 6 to 1; in its form of cristallization it resembles[Pg 252] the garnet, and varies in colour from a pearl-white to yellow and reddish; it is found in several parts of Saxony and Bohemia. The mineral called Wolfram, which is frequent in the mines of Cornwal, is likewise an ore of this metal. In all these ores the metal is oxydated; and, in some of them, it appears even to be oxygenated to the state of acid, being combined with lime into a true tungstat of lime.
Tungsten is a specific metal whose ore has often been confused with tin. The specific gravity of this ore is 6 times that of water; in its crystallization, it looks like [Pg 252] garnet and varies in color from pearl white to yellow and reddish. It can be found in several regions of Saxony and Bohemia. The mineral known as Wolfram, which is common in the mines of Cornwall, is also an ore of this metal. In all these ores, the metal is oxidized, and in some of them, it seems to be oxygenated to the point of becoming acidic, as it combines with lime to form a true tungstate of lime.
To obtain the acid free, mix one part of ore of tungstein with four parts of carbonat of potash, and melt the mixture in a crucible, then powder and pour on twelve parts of boiling water, add nitric acid, and the tungstic acid precipitates in a concrete form. Afterwards, to insure the complete oxygenation of the metal, add more nitric acid, and evaporate to dryness, repeating this operation so long as red fumes of nitrous gas are produced. To procure tungstic acid perfectly pure, the fusion of the ore with carbonat of potash must be made in a crucible of platina, otherwise the earth of the common crucibles will mix with the products, and adulterate the acid.[Pg 253]
To get the acid free, mix one part tungsten ore with four parts potassium carbonate and melt the mixture in a crucible. Then grind it and pour it into twelve parts of boiling water, add nitric acid, and the tungstic acid will precipitate in a solid form. Next, to ensure the metal is completely oxygenated, add more nitric acid and evaporate to dryness, repeating this process until red fumes of nitrous gas are produced. To obtain perfectly pure tungstic acid, the fusion of the ore with potassium carbonate must be done in a platinum crucible; otherwise, the material from regular crucibles will mix with the products and contaminate the acid.[Pg 253]
Table of the Combinations of Tartarous Acid, with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Lime | Tartarite of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd of | |||
zinc | zinc. | ||
iron | iron. | ||
manganese | manganese. | ||
cobalt | cobalt. | ||
nickel | nickel. | ||
lead | lead. | ||
tin | tin. | ||
copper | copper. | ||
bismuth | bismuth. | ||
antimony | antimony. | ||
arsenic | arsenic. | ||
silver | silver. | ||
mercury | mercury. | ||
gold | gold. | ||
platina | platina. |
Sect. 26.—Observations upon Tartarous Acid, and its Combinations.
Tartar, or the concretion which fixes to the inside of vessels in which the fermentation of wine is completed, is a well known salt, composed of a peculiar acid, united in considerable excess to potash. Mr Scheele first pointed out the method of obtaining this acid pure. Having observed that it has a greater affinity to lime than to potash, he directs us to proceed in the following manner. Dissolve purified tartar in boiling water, and add a sufficient quantity of lime till the acid be completely saturated. The tartarite of lime which is formed, being almost insoluble in cold water, falls to the bottom, and is separated from the solution of potash by decantation; it is afterwards washed in cold water, and dried; then pour on some sulphuric acid, diluted with eight or nine parts of water, digest for twelve hours in a gentle heat, frequently stirring the mixture; the sulphuric acid combines with the lime, and the tartarous acid is left free. A small quantity of gas, not hitherto examined, is disengaged during this process. At the end of twelve hours, having decanted off the clear liquor, wash the sulphat of lime in cold water, which add to the decanted[Pg 255] liquor, then evaporate the whole, and the tartarous acid is obtained in a concrete form. Two pounds of purified tartar, by means of from eight to ten ounces of sulphuric acid, yield about eleven ounces of tartarous acid.
Tartar, or the substance that forms inside containers where wine fermentation takes place, is a well-known salt made up of a unique acid combined with a significant amount of potash. Mr. Scheele first described how to obtain this acid in its pure form. He noted that the acid has a stronger attraction to lime than to potash and instructed us to follow this process. Dissolve purified tartar in boiling water, and add enough lime until the acid is fully saturated. The lime tartar formed is nearly insoluble in cold water, so it settles to the bottom and can be separated from the potash solution by decantation; it is then washed in cold water and dried. Next, pour some sulfuric acid, diluted with eight or nine parts of water, onto the substance, let it sit for twelve hours with gentle heat while stirring the mixture regularly; the sulfuric acid reacts with the lime, leaving the tartarous acid free. A small amount of gas, which hasn’t been studied yet, is released during this process. After twelve hours, decant the clear liquid, wash the sulfate of lime with cold water, and add this to the decanted[Pg 255] liquid; then evaporate the entire mixture to obtain tartarous acid in a solid form. Two pounds of purified tartar, using eight to ten ounces of sulfuric acid, yield about eleven ounces of tartarous acid.
As the combustible radical exists in excess, or as the acid from tartar is not fully saturated with oxygen, we call it tartarous acid, and the neutral salts formed by its combinations with salifiable bases tartarites. The base of the tartarous acid is a carbono-hydrous or hydro-carbonous radical, less oxygenated than in the oxalic acid; and it would appear, from the experiments of Mr Hassenfratz, that azote enters into the composition of the tartarous radical, even in considerable quantity. By oxygenating the tartarous acid, it is convertible into oxalic, malic, and acetous acids; but it is probable the proportions of hydrogen and charcoal in the radical are changed during these conversions, and that the difference between these acids does not alone consist in the different degrees of oxygenation.
As the flammable radical is present in excess, or as the acid from tartar isn’t fully saturated with oxygen, we refer to it as tartarous acid, and the neutral salts formed by its combinations with bases as tartarites. The base of the tartarous acid is a carbon-hydrogen or hydrocarbon radical, which has less oxygen than in oxalic acid. According to experiments by Mr. Hassenfratz, nitrogen is also part of the composition of the tartarous radical, possibly in significant amounts. By adding oxygen to the tartarous acid, it can be converted into oxalic, malic, and acetic acids; however, it’s likely that the ratios of hydrogen and carbon in the radical change during these conversions, and that the differences between these acids aren’t solely due to varying degrees of oxygenation.
The tartarous acid is susceptible of two degrees of saturation in its combinations with the fixed alkalies; by one of these a salt is formed with excess of acid, improperly called cream of tartar, which in our new nomenclature is named acidulous tartarite of potash; by a second or equal degree of saturation a perfectly neutral salt is formed, formerly called vegetable salt,[Pg 256] which we name tartarite of potash. With soda this acid forms tartarite of soda, formerly called sal de Seignette, or sal polychrest of Rochell.
The tartaric acid can combine with fixed alkalies in two different ways; one creates a salt with an excess of acid, incorrectly known as cream of tartar, which we now call acidic tartarite of potash; the other creates a perfectly neutral salt, previously known as vegetable salt,[Pg 256] which we refer to as tartarite of potash. With soda, this acid forms tartarite of soda, which was once called sal de Seignette or sal polychrest of Rochell.
Sect. 27.—Observations upon Malic Acid, and its Combinations with the Salifiable Bases[45].
The malic acid exists ready formed in the sour juice of ripe and unripe apples, and many other fruits, and is obtained as follows: Saturate the juice of apples with potash or soda, and add a proper proportion of acetite of lead dissolved in water; a double decomposition takes place, the malic acid combines with the oxyd of lead and precipitates, being almost insoluble, and the acetite of potash or soda remains in the liquor. The malat of lead being separated by decantation, is washed with cold water, and some dilute sulphuric acid is added; this unites with the lead into an insoluble sulphat, and the malic acid remains free in the liquor.
The malic acid is naturally found in the sour juice of both ripe and unripe apples, as well as many other fruits, and can be obtained using the following method: Saturate the juice of apples with potassium or sodium carbonate, and add the right amount of lead acetate dissolved in water; a double reaction occurs, where malic acid combines with lead oxide and precipitates, since it's almost insoluble, while the potassium or sodium acetate stays in the liquid. The lead malate is then separated by decantation, washed with cold water, and a bit of dilute sulfuric acid is added; this reacts with the lead to form an insoluble sulfate, leaving the malic acid free in the liquid.
This acid, which is found mixed with citric and tartarous acid in a great number of fruits, is a kind of medium between oxalic and acetous[Pg 257] acids being more oxygenated than the former, and less so than the latter. From this circumstance, Mr Hermbstadt calls it imperfect vinegar; but it differs likewise from acetous acid, by having rather more charcoal, and less hydrogen, in the composition of its radical.
This acid, which is found combined with citric and tartaric acid in many fruits, acts as a middle ground between oxalic and acetic acids, being more oxygenated than the former and less so than the latter. Because of this, Mr. Hermbstadt refers to it as imperfect vinegar; however, it also differs from acetic acid in having somewhat more carbon and less hydrogen in its radical composition.[Pg 257]
When an acid much diluted has been used in the foregoing process, the liquor contains oxalic as well as malic acid, and probably a little tartarous, these are separated by mixing lime-water with the acids, oxalat, tartarite, and malat of lime are produced; the two former, being insoluble, are precipitated, and the malat of lime remains dissolved; from this the pure malic acid is separated by the acetite of lead, and afterwards by sulphuric acid, as directed above.[Pg 258]
When a highly diluted acid has been used in the process described earlier, the liquid contains both oxalic and malic acid, and likely a small amount of tartaric acid as well. These are separated by mixing lime water with the acids, resulting in the formation of oxalate, tartrate, and malate of lime; the first two are insoluble and will precipitate, while the malate of lime stays dissolved. From this solution, pure malic acid is extracted using lead acetate, and then further purified with sulfuric acid, as previously outlined.[Pg 258]
Table of the Combinations of Citric Acid, with the Salifiable Bases, in the Order of Affinity(A).
Bases. | Neutral Salts. | ||
Barytes | Citrat of | barytes. | |
Lime | lime. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
cobalt | cobalt. | ||
copper | copper. | ||
arsenic | arsenic. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. | ||
Argill | argill. |
[Note A: These combinations were unknown to the ancient chemists. The order of affinity of the salifiable bases with this acid was determined by Mr Bergman and by Mr de Breney of the Dijon Academy.—A.][Pg 259]
[Note A: These combinations were unknown to the ancient chemists. The order of affinity of the basic substances that can form salts with this acid was determined by Mr. Bergman and Mr. de Breney of the Dijon Academy.—A.][Pg 259]
Sect. 28.—Observations upon Citric Acid, and its Combinations.
The citric acid is procured by expression from lemons, and is found in the juices of many other fruits mixed with malic acid. To obtain it pure and concentrated, it is first allowed to depurate from the mucous part of the fruit by long rest in a cool cellar, and is afterwards concentrated by exposing it to the temperature of 4 or 5 degrees below Zero, from 21° to 23° of Fahrenheit, the water is frozen, and the acid remains liquid, reduced to about an eighth part of its original bulk. A lower degree of cold would occasion the acid to be engaged amongst the ice, and render it difficultly separable. This process was pointed out by Mr Georgius.
The citric acid is extracted from lemons and is also found in the juices of many other fruits along with malic acid. To get it pure and concentrated, it’s first allowed to settle out the mucous parts of the fruit by resting in a cool cellar for a long time, and then it’s concentrated by cooling it to about 4 or 5 degrees below zero, around 21° to 23° Fahrenheit. The water freezes, leaving the acid in a liquid state, reduced to about an eighth of its original volume. If it gets any colder, the acid would mix with the ice, making it hard to separate. This process was described by Mr. Georgius.
It is more easily obtained by saturating the lemon-juice with lime, so as to form a citrat of lime, which is insoluble in water; wash this salt, and pour on a proper quantity of sulphuric acid; this forms a sulphat of lime, which precipitates and leaves the citric acid free in the liquor.[Pg 260]
It can be obtained more easily by mixing lemon juice with lime to create lime citrate, which doesn't dissolve in water. Rinse this salt and add the right amount of sulfuric acid; this will create calcium sulfate, which will settle out and leave citric acid free in the liquid.[Pg 260]
Table of the Combinations of Pyro-lignous Acid with the Salifiable Bases, in the Order of Affinity(A).
Bases. | Neutral Salts. | ||
Lime | Pyro-mucite of | lime. | |
Barytes | barytes. | ||
Potash | potash. | ||
Soda | soda. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. | ||
Argill | argill. |
[Note A: The above affinities were determined by Messrs de Morveau and EloI Boursier de Clervaux. These combinations were entirely unknown till lately.—A.][Pg 261]
[Note A: The affinities mentioned above were identified by Messrs de Morveau and EloI Boursier de Clervaux. These combinations were completely unknown until recently.—A.][Pg 261]
Sect. 29.—Observations upon Pyro-lignous Acid, and its Combinations.
The ancient chemists observed that most of the woods, especially the more heavy and compact ones, gave out a particular acid spirit, by distillation, in a naked fire; but, before Mr Goetling, who gives an account of his experiments upon this subject in Crell's Chemical Journal for 1779, no one had ever made any inquiry into its nature and properties. This acid appears to be the same, whatever be the wood it is procured from. When first distilled, it is of a brown colour, and considerably impregnated with charcoal and oil; it is purified from these by a second distillation. The pyro-lignous radical is chiefly composed of hydrogen and charcoal.
The early chemists noted that most types of wood, especially the denser and more compact ones, released a specific acidic vapor when distilled over an open flame. However, it wasn’t until Mr. Goetling detailed his experiments in Crell's Chemical Journal in 1779 that anyone really investigated its nature and properties. This acid seems to be consistent regardless of the type of wood it comes from. During the first distillation, it appears brown and is significantly mixed with charcoal and oil, which are removed in a second distillation. The pyro-lignous component mainly consists of hydrogen and charcoal.
Sect. XXX.—Observations upon Pyro-tartarous Acid, and its Combinations with the Salifiable Bases[46].
The name of Pyro-tartarous acid is given to a dilute empyreumatic acid obtained from purified[Pg 262] acidulous tartarite of potash by distillation in a naked fire. To obtain it, let a retort be half filled with powdered tartar, adapt a tubulated recipient, having a bent tube communicating with a bell-glass in a pneumato-chemical apparatus; by gradually raising the fire under the retort, we obtain the pyro-tartarous acid mixed with oil, which is separated by means of a funnel. A vast quantity of carbonic acid gas is disengaged during the distillation. The acid obtained by the above process is much contaminated with oil, which ought to be separated from it. Some authors advise to do this by a second distillation; but the Dijon academicians inform us, that this is attended with great danger from explosions which take place during the process.[Pg 263]
The name Pyro-tartarous acid refers to a dilute empyreumatic acid derived from purified[Pg 262] acidulous tartarite of potash through distillation over an open flame. To make it, fill a retort halfway with powdered tartar, and attach a tubulated container, ensuring that it has a bent tube connecting to a bell jar in a pneumatic chemical setup; by gradually heating the retort, we obtain pyro-tartarous acid mixed with oil, which we can separate using a funnel. A large amount of carbonic acid gas is released during the distillation. The acid produced by this method is often contaminated with oil, which should be removed. Some experts suggest separating it through a second distillation, but the academicians from Dijon warn that this process carries a significant risk of explosions occurring.[Pg 263]
Table of the Combinations of Pyro-mucous Acid, with the Salifiable Bases, in the Order of Affinity(A).
Bases. | Neutral Salts. | ||
Potash | Pyro-mucite of | potash. | |
Soda | soda. | ||
Barytes | barytes. | ||
Lime | lime. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
antimony | antimony. |
[Note A: All these combinations were unknown to the ancient chemists.—A.][Pg 264]
[Note A: All these combinations were unknown to the ancient chemists.—A.][Pg 264]
Sect. XXXI.—Observations upon Pyro-mucous Acid, and its Combinations.
This acid is obtained by distillation in a naked fire from sugar, and all the saccharine bodies; and, as these substances swell greatly in the fire, it is necessary to leave seven-eighths of the retort empty. It is of a yellow colour, verging to red, and leaves a mark upon the skin, which will not remove but alongst with the epidermis. It may be procured less coloured, by means of a second distillation, and is concentrated by freezing, as is directed for the citric acid. It is chiefly composed of water and oil slightly oxygenated, and is convertible into oxalic and malic acids by farther oxygenation with the nitric acid.
This acid is made by distilling sugar and all sugary substances over an open flame, and since these materials expand significantly when heated, it's important to leave seven-eighths of the retort empty. It has a yellow color with a reddish hue and leaves a stain on the skin that can only be removed along with the outer skin layer. You can get a less colored version by doing a second distillation, and it can be concentrated by freezing, similar to citric acid. Its main components are water and slightly oxygenated oil, and it can be converted into oxalic and malic acids through further oxygenation with nitric acid.
It has been pretended that a large quantity of gas is disengaged during the distillation of this acid, which is not the case if it be conducted slowly, by means of moderate heat.[Pg 265]
It has been claimed that a lot of gas is released during the distillation of this acid, but that's not true if it's done slowly with moderate heat.[Pg 265]
Table of the Combinations of the Oxalic Acid, with the Salifiable Bases, in the Order of Affinity(A).
Bases. | Neutral Salts. | ||
Lime | Oxalat of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd of | |||
zinc | zinc. | ||
iron | iron. | ||
manganese | manganese. | ||
cobalt | cobalt. | ||
nickel | nickel. | ||
lead | lead. | ||
copper | copper. | ||
bismuth | bismuth. | ||
antimony | antimony. | ||
arsenic | arsenic. | ||
mercury | mercury. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. |
[Note A: All unknown to the ancient chemists.—A.][Pg 266]
[Note A: All unknown to the ancient chemists.—A.][Pg 266]
Sect. XXXII.—Observations upon Oxalic Acid, and its Combinations.
The oxalic acid is mostly prepared in Switzerland and Germany from the expressed juice of sorrel, from which it cristallizes by being left long at rest; in this state it is partly saturated with potash, forming a true acidulous oxalat of potash, or salt with excess of acid. To obtain it pure, it must be formed artificially by oxygenating sugar, which seems to be the true oxalic radical. Upon one part of sugar pour six or eight parts of nitric acid, and apply a gentle heat; a considerable effervescence takes place, and a great quantity of nitrous gas is disengaged; the nitric acid is decomposed, and its oxygen unites to the sugar: By allowing the liquor to stand at rest, cristals of pure oxalic acid are formed, which must be dried upon blotting paper, to separate any remaining portions of nitric acid; and, to ensure the purity of the acid, dissolve the cristals in distilled water, and cristallize them afresh.
Oxalic acid is primarily produced in Switzerland and Germany from the pressed juice of sorrel, which crystallizes if left to sit for a long time; in this state, it is partly saturated with potash, forming an acidic potassium oxalate or a salt with excess acid. To obtain it in pure form, it must be synthesized artificially by oxidizing sugar, which appears to be the true oxalic radical. Pour six to eight parts of nitric acid over one part of sugar, then apply gentle heat; this will cause considerable fizzing and release a significant amount of nitrous gas. The nitric acid breaks down, and its oxygen combines with the sugar. By letting the mixture sit undisturbed, crystals of pure oxalic acid will form, which should be dried on blotting paper to remove any residual nitric acid. To ensure the purity of the acid, dissolve the crystals in distilled water and re-crystallize them.
Bases. | Neutral salts. | Names of the resulting neutral salts according to the old nomenclature. |
Barytes | Acetite of barytes | Unknown to the ancients. Discovered by Mr de Morveau, who calls it barotic acéte. |
Potash | —— potash | Secret terra foliata tartari of Muller. Arcanum tartari of Basil Valentin and Paracelsus. Purgative magistery of tartar of Schroëder. Essential salt of wine of Zwelfer. Regenerated tartar of Tachenius. Diuretic salt of Sylvius and Wilson. |
Soda | —— soda | Foliated earth with base of mineral alkali. Mineral or crystallisable foliated earth. Mineral acetous salt. |
Lime | —— lime | Salt of chalk, coral, or crabs eyes; mentioned by Hartman. |
Magnesia | —— magnesia | First mentioned by Mr Wenzel. |
Ammoniac | —— ammoniac | Spiritus Mindereri. Ammoniacal acetous salt. |
Oxyd of zinc | —— zinc | Known to Glauber, Schwedemberg, Respour, Pott, de Lassone, and Wenzel, but not named. |
—— manganese | —— manganese | Unknown to the ancients. |
—— iron | —— iron | Martial vinegar. Described by Monnet, Wenzel, and the Duke d'Ayen. |
—— lead | —— lead | Sugar, vinegar, and salt of lead or Saturn. |
—— tin | —— tin | Known to Lemery, Margraff, Monnet, Weslendorf, and Wenzel, but not named. |
—— cobalt | —— cobalt | Sympathetic ink of Mr Cadet. |
—— copper | —— copper | Verdigris, crystals of verditer, verditer, distilled verdigris, crystals of Venus or of copper. |
—— nickel | —— nickel | Unknown to the ancients. |
—— arsenic | —— arsenic | Arsenico-acetous fuming liquor, liquid phosphorus of Mr Cadet. |
—— bismuth | —— bismuth | Sugar of bismuth of Mr Geoffroi. Known to Gellert, Pott, Weslendorf, Bergman, and de Morveau. |
—— mercury | —— mercury | Mercurial foliated earth, Keyser's famous antivenereal remedy. Mentioned by Gebaver in 1748; known to Helot, Margraff, Baumé, Bergman, and de Morveau. |
—— antimony | —— antimony | Unknown. |
—— silver | —— silver | Described by Margraff, Monnet, and Wenzel; unknown to the ancients. |
—— gold | —— gold | Little known, mentioned by Schroëder and Juncker. |
—— platina | —— platina | Unknown. |
Argill | —— argill | According to Mr Wenzel, vinegar dissolves only a very small proportion of argill. |
From the liquor remaining after the first cristallization of the oxalic acid we may obtain malic acid by refrigeration: This acid is more oxygenated than the oxalic; and, by a further oxygenation, the sugar is convertible into acetous acid, or vinegar.
From the leftover liquid after the first crystallization of oxalic acid, we can get malic acid by cooling it down. This acid has more oxygen than oxalic acid; and with additional oxygenation, sugar can be turned into acetic acid, or vinegar.
The oxalic acid, combined with a small quantity of soda or potash, has the property, like the tartarous acid, of entering into a number of combinations without suffering decomposition: These combinations form triple salts, or neutral salts with double bases, which ought to have proper names. The salt of sorrel, which is potash having oxalic acid combined in excess, is named acidulous oxalat of potash in our new nomenclature.
The oxalic acid, mixed with a small amount of soda or potash, has the ability, like tartaric acid, to form several combinations without breaking down: These combinations create triple salts or neutral salts with two bases, which should have specific names. The salt of sorrel, which is potash combined with an excess of oxalic acid, is called acidulous oxalate of potash in our new naming system.
The acid procured from sorrel has been known to chemists for more than a century, being mentioned by Mr Duclos in the Memoirs of the Academy for 1688, and was pretty accurately described by Boerhaave; but Mr Scheele first showed that it contained potash, and demonstrated its identity with the acid formed by the oxygenation of sugar.
The acid derived from sorrel has been recognized by chemists for over a century, with Mr. Duclos mentioning it in the Memoirs of the Academy in 1688, and it was fairly accurately described by Boerhaave. However, it was Mr. Scheele who first revealed that it contained potash and proved that it was the same as the acid produced by the oxygenation of sugar.
Sect. 33.—Observations upon Acetous Acid, and its Combinations.
This acid is composed of charcoal and hydrogen united together, and brought to the state of an acid by the addition of oxygen; it is consequently formed by the same elements with[Pg 268] the tartarous oxalic, citric, malic acids, and others, but the elements exist in different proportions in each of these; and it would appear that the acetous acid is in a higher state of oxygenation than these other acids. I have some reason to believe that the acetous radical contains a small portion of azote; and, as this element is not contained in the radicals of any vegetable acid except the tartarous, this circumstance is one of the causes of difference. The acetous acid, or vinegar, is produced by exposing wine to a gentle heat, with the addition of some ferment: This is usually the ley, or mother, which has separated from other vinegar during fermentation, or some similar matter. The spiritous part of the wine, which consists of charcoal and hydrogen, is oxygenated, and converted into vinegar: This operation can only take place with free access of air, and is always attended by a diminution of the air employed in consequence of the absorption of oxygen; wherefore, it ought always to be carried on in vessels only half filled with the vinous liquor submitted to the acetous fermentation. The acid formed during this process is very volatile, is mixed with a large proportion of water, and with many foreign substances; and, to obtain it pure, it is distilled in stone or glass vessels by a gentle fire. The acid which passes over in distillation is somewhat changed by the[Pg 269] process, and is not exactly of the same nature with what remains in the alembic, but seems less oxygenated: This circumstance has not been formerly observed by chemists.
This acid is made up of charcoal and hydrogen combined, and is turned into an acid by adding oxygen. It's formed from the same elements as the tartaric, oxalic, citric, malic acids, and others, but the proportions of these elements differ in each one. It appears that acetic acid is more oxygenated than these other acids. I have some reason to think that the acetic radical contains a small amount of nitrogen; since this element isn't present in the radicals of any other plant acids except tartaric, this is one of the reasons for the differences. Acetic acid, or vinegar, is produced by gently heating wine and adding some ferment: usually this is the lees, or mother, that separates from other vinegar during fermentation, or something similar. The alcoholic part of the wine, which consists of charcoal and hydrogen, gets oxygenated and turns into vinegar: this process can only happen with a good supply of air, and always leads to a decrease in the air used due to oxygen absorption. Therefore, it should always be done in containers that are only half full of the wine undergoing acetic fermentation. The acid produced during this process is very volatile, mixed with a lot of water and other substances; to get it pure, it is distilled in stone or glass containers over a gentle heat. The acid that comes out during distillation changes slightly due to the process, and is not exactly the same as what remains in the alembic, but seems to be less oxygenated: this fact has not been noted by chemists before.
Distillation is not sufficient for depriving this acid of all its unnecessary water; and, for this purpose, the best way is by exposing it to a degree of cold from 4° to 6° below the freezing point, from 19° to 23° of Fahrenheit; by this means the aqueous part becomes frozen, and leaves the acid in a liquid state, and considerably concentrated. In the usual temperature of the air, this acid can only exist in the gasseous form, and can only be retained by combination with a large proportion of water. There are other chemical processes for obtaining the acetous acid, which consist in oxygenating the tartarous, oxalic, or malic acids, by means of nitric acid; but there is reason to believe the proportions of the elements of the radical are changed during this process. Mr Hassenfratz is at present engaged in repeating the experiments by which these conversions are said to be produced.
Distillation alone isn't enough to remove all the excess water from this acid. The best method for that is to expose it to temperatures between 4° and 6° below freezing, or 19° to 23° Fahrenheit. This causes the water to freeze, leaving the acid in a liquid state and making it much more concentrated. At normal air temperatures, this acid only exists as a gas and can only be kept in that state by combining it with a lot of water. There are other chemical methods to obtain acetic acid, which involve oxidizing tartaric, oxalic, or malic acids using nitric acid; however, it's believed that the proportions of the elements in the radical change during this process. Mr. Hassenfratz is currently working on repeating the experiments that are said to produce these conversions.
The combinations of acetous acid with the various salifiable bases are very readily formed; but most of the resulting neutral salts are not cristallizable, whereas those produced by the tartarous and oxalic acids are, in general, hardly soluble. Tartarite and oxalat of lime are[Pg 270] not soluble in any sensible degree: The malats are a medium between the oxalats and acetites, with respect to solubility, and the malic acid is in the middle degree of saturation between the oxalic and acetous acids. With this, as with all the acids, the metals require to be oxydated previous to solution.
The combinations of acetic acid with various bases are formed quite easily; however, most of the resulting neutral salts are not crystal-forming, while those produced by tartaric and oxalic acids are generally poorly soluble. Calcium tartrate and calcium oxalate are[Pg 270] not soluble to any significant extent. Malates fall between oxalates and acetates in terms of solubility, and malic acid is moderately saturated between oxalic and acetic acids. Like all acids, metals need to be oxidized before they can dissolve.
The ancient chemists knew hardly any of the salts formed by the combinations of acetous acid with the salifiable bases, except the acetites of potash, soda, ammoniac, copper, and lead. Mr Cadet discovered the acetite of arsenic[47]; Mr Wenzel, the Dijon academicians Mr de Lassone, and Mr Proust, made us acquainted with the properties of the other acetites. From the property which acetite of potash possesses, of giving out ammoniac in distillation, there is some reason to suppose, that, besides charcoal and hydrogen, the acetous radical contains a small proportion of azote, though it is not impossible but the above production of ammoniac may be occasioned by the decomposition of the potash.
The ancient chemists hardly knew any of the salts created by mixing acetic acid with bases, except for the acetates of potash, soda, ammonia, copper, and lead. Mr. Cadet discovered the acetate of arsenic[47]; Mr. Wenzel, the Dijon academics, Mr. de Lassone, and Mr. Proust introduced us to the properties of the other acetates. Due to the property of potassium acetate to release ammonia during distillation, there’s reason to believe that, besides charcoal and hydrogen, the acetic radical might contain a small amount of nitrogen, although it’s also possible that the ammonia is produced from the breakdown of the potash.
Table of the Combinations of Acetic Acid with the Salifiable Bases, in the order of affinity.
Bases. | Neutral Salts. | ||
Barytes | Acetat of | barytes. | |
Potash | potash. | ||
Soda | soda. | ||
Lime | lime. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Oxyd of | zinc | zinc. | |
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. | ||
Argill | argill. |
Note.—All these salts were unknown to the ancients; and even those chemists who are most versant in modern discoveries, are yet at a lose whether the greater part of the salts produced by the oxygenated acetic radical belong properly to the class of acetites, or to that of acetats.—A.[Pg 272]
Note.—All these salts were unknown to ancient people; and even those chemists who are most knowledgeable about modern discoveries still aren’t sure whether most of the salts produced by the oxygenated acetic radical should be categorized as acetites or acetates.—A.[Pg 272]
Sect. 34.—Observations upon Acetic Acid, and its Combinations.
We have given to radical vinegar the name of acetic acid, from supposing that it consists of the same radical with that of the acetous acid, but more highly saturated with oxygen. According to this idea, acetic acid is the highest degree of oxygenation of which the hydro-carbonous radical is susceptible; but, although this circumstance be extremely probable, it requires to be confirmed by farther, and more decisive experiments, before it be adopted as an absolute chemical truth. We procure this acid as follows: Upon three parts acetite of potash or of copper, pour one part of concentrated sulphuric acid, and, by distillation, a very highly concentrated vinegar is obtained, which we call acetic acid, formerly named radical vinegar. It is not hitherto rigorously proved that this acid is more highly oxygenated than the acetous acid, nor that the difference between them may not consist in a different proportion between the elements of the radical or base.[Pg 273]
We call radical vinegar acetic acid because we assume it contains the same radical as acetous acid but is more saturated with oxygen. Based on this idea, acetic acid represents the highest level of oxygenation that this hydrocarbon radical can achieve; however, while this seems very likely, it needs to be validated by further, more definitive experiments before it is accepted as an absolute chemical fact. We produce this acid as follows: pour one part of concentrated sulfuric acid over three parts of potassium or copper acetate, and through distillation, a very concentrated vinegar is obtained, which we refer to as acetic acid, previously known as radical vinegar. It has not yet been strictly proven that this acid is more oxygenated than acetous acid, nor is it certain that the difference between them doesn't result from a different ratio of the elements in the radical or base.[Pg 273]
Table of the Combinations of Succinic Acid with the Salifiable Bases, in the order of Affinity.
Bases. | Neutral Salts. | ||
Barytes | Succinat of | barytes. | |
Lime | lime. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Magnesia | magnesia. | ||
Argill | argill. | ||
Oxyd | of zinc | zinc. | |
iron | iron. | ||
manganese | manganese. | ||
cobalt | cobalt. | ||
nickel | nickel. | ||
lead | lead. | ||
tin | tin. | ||
copper | copper. | ||
bismuth | bismuth. | ||
antimony | antimony. | ||
arsenic | arsenic. | ||
mercury | mercury. | ||
silver | silver. | ||
gold | gold. | ||
platina | platina. |
Note.—All the succinats were unknown to the ancient chemists.—A.[Pg 274]
Note.—All the succinates were unknown to ancient chemists.—A.[Pg 274]
Sect. 35.—Observations upon Succinic Acid, and its Combinations.
The succinic acid is drawn from amber by sublimation in a gentle heat, and rises in a concrete form into the neck of the subliming vessel. The operation must not be pushed too far, or by too strong a fire, otherwise the oil of the amber rises alongst with the acid. The salt is dried upon blotting paper, and purified by repeated solution and crystallization.
Succinic acid is extracted from amber through sublimation at a gentle heat, and it condenses in solid form in the neck of the sublimation vessel. The process shouldn't be rushed or done with too much heat, or else the oil from the amber will come up with the acid. The salt is dried on blotting paper and purified through repeated solutions and crystallizations.
This acid is soluble in twenty-four times its weight of cold water, and in a much smaller quantity of hot water. It possesses the qualities of an acid in a very small degree, and only affects the blue vegetable colours very slightly. The affinities of this acid, with the salifiable bases, are taken from Mr de Morveau, who is the first chemist that has endeavoured to ascertain them.[Pg 275]
This acid dissolves in twenty-four times its weight of cold water and in a much smaller amount of hot water. It has only a weak acidic quality and only slightly affects blue plant colors. The relationships of this acid with the basic compounds were noted by Mr. de Morveau, who was the first chemist to try to determine them.[Pg 275]
Section. XXXVI.—Observations upon Benzoic Acid, and its Combinations with Salifiable Bases[48].
This acid was known to the ancient chemists under the name of Flowers of Benjamin, or of Benzoin, and was procured, by sublimation, from the gum or resin called Benzoin: The means of procuring it, via humida, was discovered by Mr Geoffroy, and perfected by Mr Scheele. Upon benzoin, reduced to powder, pour strong lime-water, having rather an excess of lime; keep the mixture continually stirring, and, after half an hour's digestion, pour off the liquor, and use fresh portions of lime-water in the same manner, so long as there is any appearance of neutralization. Join all the decanted liquors, and evaporate, as far as possible, without occasioning cristallization, and, when the liquor is cold, drop in muriatic acid till no more precipitate is formed. By the former part of the process a benzoat of lime is formed, and, by the latter, the muriatic acid combines with the lime, forming muriat of lime, which remains[Pg 276] dissolved, while the benzoic acid, being insoluble, precipitates in a concrete state.
This acid was known to ancient chemists as Flowers of Benjamin or Benzoin, and it was obtained through sublimation from the gum or resin called Benzoin. The method for obtaining it, via humida, was discovered by Mr. Geoffroy and refined by Mr. Scheele. Take powdered benzoin and pour strong lime-water over it, ensuring there's a bit of excess lime. Keep stirring the mixture continuously, and after half an hour, pour off the liquid. Use fresh lime-water in the same way until there are no signs of neutralization. Combine all the poured-off liquids and evaporate them as much as possible without causing crystallization. When the liquid is cold, add muriatic acid until no more precipitate forms. The first part of the process creates benzoate of lime, and in the second part, the muriatic acid reacts with the lime to form muriate of lime, which stays dissolved, while the benzoic acid, being insoluble, precipitates out in a solid form.[Pg 276]
Group. XXXVII.—Observations upon Camphoric Acid, and its Combinations with Salifiable Bases[49].
Camphor is a concrete essential oil, obtained, by sublimation, from a species of laurus which grows in China and Japan. By distilling nitric acid eight times from camphor, Mr Kosegarten converted it into an acid analogous to the oxalic; but, as it differs from that acid in some circumstances, we have thought necessary to give it a particular name, till its nature be more completely ascertained by farther experiment.
Camphor is a solid essential oil, extracted through sublimation from a type of laurel that grows in China and Japan. By distilling nitric acid eight times from camphor, Mr. Kosegarten turned it into an acid similar to oxalic acid; however, since it differs from that acid in some ways, we felt it was necessary to give it a specific name until its properties are better determined through further experiments.
As camphor is a carbono-hydrous or hydro-carbonous radical, it is easily conceived, that, by oxygenation, it should form oxalic, malic, and several other vegetable acids: This conjecture is rendered not improbable by the experiments of Mr Kosegarten; and the principal phenomena exhibited in the combinations of camphoric acid with the salifiable bases, being[Pg 277] very similar to those of the oxalic and malic acids, lead me to believe that it consists of a mixture of these two acids.
As camphor is a carbon-hydrogen compound, it's easy to understand that when it undergoes oxidation, it can create oxalic, malic, and various other plant-based acids. This idea is supported by Mr. Kosegarten's experiments. The main outcomes observed in the combinations of camphoric acid with basic substances are[Pg 277] quite similar to those of oxalic and malic acids, which makes me think that it is a blend of these two acids.
Section. XXXVIII.—Observations upon Gallic Acid, and its Combinations with Salifiable Bases[50].
The Gallic acid, formerly called Principle of Astringency, is obtained from gall nuts, either by infusion or decoction with water, or by distillation with a very gentle heat. This acid has only been attended to within these few years. The Committee of the Dijon Academy have followed it through all its combinations, and give the best account of it hitherto produced. Its acid properties are very weak; it reddens the tincture of turnsol, decomposes sulphurets, and unites to all the metals when they have been previously dissolved in some other acid. Iron, by this combination, is precipitated of a very deep blue or violet colour. The radical of this acid, if it deserves the name of one, is hitherto entirely unknown; it is contained in[Pg 278] oak willow, marsh iris, the strawberry, nymphea, Peruvian bark, the flowers and bark of pomgranate, and in many other woods and barks.
The Gallic acid, once known as the Principle of Astringency, is extracted from gall nuts through infusion or boiling with water, or by gentle distillation. This acid has only gained attention in recent years. The Committee of the Dijon Academy has examined all its combinations and provides the best explanation produced so far. Its acidic properties are quite weak; it turns the tincture of litmus red, breaks down sulfides, and binds with all metals that have been dissolved in another acid first. When combined with iron, it results in a very deep blue or violet precipitate. The core component of this acid, if it can be considered one, is still completely unknown; it can be found in oak, willow, marsh iris, strawberries, water lilies, Peruvian bark, as well as the flowers and bark of pomegranate, and many other types of wood and bark.
Section. XXXIX.—Observations upon Lactic Acid, and its Combinations with Salifiable Bases[51].
The only accurate knowledge we have of this acid is from the works of Mr Scheele. It is contained in whey, united to a small quantity of earth, and is obtained as follows: Reduce whey to one eighth part of its bulk by evaporation, and filtrate, to separate all its cheesy matter; then add as much lime as is necessary to combine with the acid; the lime is afterwards disengaged by the addition of oxalic acid, which combines with it into an insoluble neutral salt. When the oxalat of lime has been separated by decantation, evaporate the remaining liquor to the consistence of honey; the lactic acid is dissolved by alkohol, which does not unite with the sugar of milk and other foreign matters;[Pg 279] these are separated by filtration from the alkohol and acid; and the alkohol being evaporated, or distilled off, leaves the lactic acid behind.
The only accurate knowledge we have about this acid comes from the work of Mr. Scheele. It's found in whey, combined with a small amount of earth, and you can obtain it like this: Reduce whey to one-eighth of its original volume by evaporation, and filter it to separate all the cheesy material. Then, add enough lime to react with the acid; the lime is later removed by adding oxalic acid, which reacts with it to form an insoluble neutral salt. Once the calcium oxalate has been separated by decantation, evaporate the remaining liquid until it reaches a honey-like consistency. The lactic acid is dissolved in alcohol, which doesn’t mix with the milk sugar and other impurities; these are filtered out from the alcohol and acid. Finally, evaporating or distilling the alcohol leaves the lactic acid behind.[Pg 279]
This acid unites with all the salifiable bases forming salts which do not cristallize; and it seems considerably to resemble the acetous acid.[Pg 280]
This acid combines with all the basic substances to create salts that don't crystallize, and it seems quite similar to acetic acid.[Pg 280]
Table of the Combinations of Saccholactic Acid with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Lime | Saccholat of | lime. | |
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Potash | potash. | ||
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd | of zinc | zinc. | |
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. |
Note.—All these were unknown to the ancient chemists.—A.[Pg 281]
Note.—All these were unknown to the ancient chemists.—A.[Pg 281]
Section. XL.—Observations upon Saccholactic Acid, and its Combinations.
A species of sugar may be extracted, by evaporation, from whey, which has long been known in pharmacy, and which has a considerable resemblance to that procured from sugar canes. This saccharine matter, like ordinary sugar, may be oxygenated by means of nitric acid: For this purpose, several portions of nitric acid are distilled from it; the remaining liquid is evaporated, and set to cristallize, by which means cristals of oxalic acid are procured; at the same time a very fine white powder precipitates, which is the saccholactic acid discovered by Scheele. It is susceptible of combining with the alkalies, ammoniac, the earths, and even with the metals: Its action upon the latter is hitherto but little known, except that, with them, it forms difficultly soluble salts. The order of affinity in the table is taken from Bergman.[Pg 282]
A type of sugar can be extracted from whey through evaporation, which has been well-known in pharmacy for a long time and resembles the sugar obtained from sugarcane. This sugary substance, like regular sugar, can be oxidized using nitric acid. For this process, several amounts of nitric acid are distilled from it; the leftover liquid is evaporated and allowed to crystallize, resulting in crystals of oxalic acid. At the same time, a very fine white powder settles out, which is the saccholactic acid discovered by Scheele. It can combine with alkalis, ammonia, earths, and even metals. Its effects on metals are still not well understood, other than that it forms salts that are hard to dissolve. The order of affinity in the table is taken from Bergman.[Pg 282]
Table of the Combinations of Formic Acid, with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Barytes | Formiat of | barytes. | |
Potash | potash. | ||
Soda | soda. | ||
Lime | lime. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
bismuth | bismuth. | ||
silver | silver. | ||
Argill | argill. |
Note.—All unknown to the ancient chemists.—A.[Pg 283]
Note.—All unknown to the ancient chemists.—A.[Pg 283]
Section. XLI.—Observations upon Formic Acid, and its Combinations.
This acid was first obtained by distillation from ants, in the last century, by Samuel Fisher. The subject was treated of by Margraff in 1749, and by Messrs Ardwisson and Ochrn of Leipsic in 1777. The formic acid is drawn from a large species of red ants, formica rufa, Lin. which form large ant hills in woody places. It is procured, either by distilling the ants with a gentle heat in a glass retort or an alembic; or, after having washed the ants in cold water, and dried them upon a cloth, by pouring on boiling water, which dissolves the acid; or the acid may be procured by gentle expression from the insects, in which case it is stronger than in any of the former ways. To obtain it pure, we must rectify, by means of distillation, which separates it from the uncombined oily and charry matter; and it may be concentrated by freezing, in the manner recommended for treating the acetous acid.[Pg 284]
This acid was first extracted by distillation from ants in the last century by Samuel Fisher. The topic was addressed by Margraff in 1749, and by Messrs. Ardwisson and Ochrn from Leipzig in 1777. Formic acid is sourced from a large species of red ants, formica rufa, Lin., which build large ant hills in wooded areas. It can be obtained either by gently distilling the ants in a glass retort or alembic, or by washing the ants in cold water, drying them on a cloth, and then pouring boiling water over them to dissolve the acid. The acid can also be acquired by gently pressing the insects, which produces a stronger yield than the previous methods. To obtain it in pure form, it needs to be distilled, separating it from the uncombined oily and charred substances, and it can be concentrated by freezing, as recommended for acetous acid.[Pg 284]
Section. XLII.—Observations upon Bombic Acid, and its Combinations with Acidifiable Bases[52].
The juices of the silk worm seem to assume an acid quality when that insect changes from a larva to a chrysalis. At the moment of its escape from the latter to the butterfly form, it emits a reddish liquor which reddens blue paper, and which was first attentively observed by Mr Chaussier of the Dijon academy, who obtains the acid by infusing silk worm chrysalids in alkohol, which dissolves their acid without being charged with any of the gummy parts of the insect; and, by evaporating the alkohol, the acid remains tollerably pure. The properties and affinities of this acid are not hitherto ascertained with any precision; and we have reason to believe that analogous acids may be procured from other insects. The radical of this acid is probably, like that of the other acids from the animal kingdom, composed of charcoal, hydrogen, and azote, with the addition, perhaps, of phosphorus.
The juices of the silkworm seem to take on an acidic quality when the insect transforms from a larva to a chrysalis. At the moment it breaks free from the chrysalis and becomes a butterfly, it releases a reddish liquid that turns blue paper red. This was first carefully noted by Mr. Chaussier of the Dijon Academy, who extracts the acid by soaking silkworm chrysalids in alcohol. This process dissolves the acid without incorporating any of the gummy parts of the insect; and by evaporating the alcohol, the acid remains fairly pure. The properties and characteristics of this acid aren't fully understood yet, and we believe that similar acids could be obtained from other insects. The base of this acid is likely composed of carbon, hydrogen, and nitrogen, possibly with the addition of phosphorus, similar to other acids found in the animal kingdom.
Table of the Combinations of Sebacic Acid, with the Salifiable Bases, in the Order of Affinity.
Bases. | Neutral Salts. | ||
Barytes | Sebat of | barytes. | |
Potash | potash. | ||
Soda | soda. | ||
Lime | lime. | ||
Magnesia | magnesia. | ||
Ammoniac | ammoniac. | ||
Argill | argill. | ||
Oxyd of | |||
zinc | zinc. | ||
manganese | manganese. | ||
iron | iron. | ||
lead | lead. | ||
tin | tin. | ||
cobalt | cobalt. | ||
copper | copper. | ||
nickel | nickel. | ||
arsenic | arsenic. | ||
bismuth | bismuth. | ||
mercury | mercury. | ||
antimony | antimony. | ||
silver | silver. |
Note.—All these were unknown to the ancient chemists.—A.[Pg 286]
Note.—All these were unknown to the ancient chemists.—A.[Pg 286]
Section. XLIII.—Observations upon Sebacid Acid, and its Combinations.
To obtain the sebacic acid, let some suet be melted in a skillet over the fire, alongst with some quick-lime in fine powder, and constantly stirred, raising the fire towards the end of the operation, and taking care to avoid the vapours, which are very offensive. By this process the sebacic acid unites with the lime into a sebat of lime, which is difficultly soluble in water; it is, however, separated from the fatty matters with which it is mixed by solution in a large quantity of boiling water. From this the neutral salt is separated by evaporation; and, to render it pure, is calcined, redissolved, and again cristallized. After this we pour on a proper quantity of sulphuric acid, and the sebacic acid passes over by distillation.[Pg 287]
To get the sebacic acid, melt some animal fat in a skillet over the fire, along with some powdered quicklime, and keep stirring it constantly. Towards the end of the process, raise the heat while being careful to avoid the fumes, which can be quite unpleasant. This method causes the sebacic acid to combine with the lime into a lime sebate, which is not easily soluble in water. However, it can be separated from the fatty substances it’s mixed with by dissolving it in a large amount of boiling water. From this solution, the neutral salt is obtained through evaporation, and to purify it, it is calcined, redissolved, and crystallized again. After that, we add the right amount of sulfuric acid, and the sebacic acid is collected through distillation.[Pg 287]
Sect. 44.—Observations upon the Lithic Acid, and its Combinations with the Salifiable Bases[53].
From the later experiments of Bergman and Scheele, the urinary calculus appears to be a species of salt with an earthy basis; it is slightly acidulous, and requires a large quantity of water for solution, three grains being scarcely soluble in a thousand grains of boiling water, and the greater part again cristallizes when cold. To this concrete acid, which Mr de Morveau calls Lithiasic Acid, we give the name of Lithic Acid, the nature and properties of which are hitherto very little known. There is some appearance that it is an acidulous neutral salt, or acid combined in excess with a salifiable base; and I have reason to believe that it really is an acidulous phosphat of lime; if so, it must be excluded from the class of peculiar acids.
From the later experiments of Bergman and Scheele, urinary stones seem to be a type of salt with an earthy base; they are slightly acidic and need a lot of water to dissolve. Three grains barely dissolve in a thousand grains of boiling water, and most of it crystallizes again when cooled. To this concrete acid, which Mr. de Morveau refers to as Lithiasic Acid, we call Lithic Acid, the nature and properties of which are still very little known. It seems to be an acidic neutral salt or an acid combined in excess with a basic substance; I believe it is actually an acidic phosphate of lime; if that's the case, it should be excluded from the category of specific acids.
Table of the Combinations of the Prussic Acid with the Salifiable Bases, in the order of affinity.
Bases. | Neutral Salts. | ||
Potash | Prussiat of | potash. | |
Soda | soda. | ||
Ammoniac | ammoniac. | ||
Lime | lime. | ||
Barytes | barytes. | ||
Magnesia | magnesia. | ||
Oxyd | of zinc | zinc. | |
iron | iron. | ||
manganese | manganese. | ||
cobalt | cobalt. | ||
nickel | nickel. | ||
lead | lead. | ||
tin | tin. | ||
copper | copper. | ||
bismuth | bismuth. | ||
antimony | antimony. | ||
arsenic | arsenic. | ||
silver | silver. | ||
mercury | mercury. | ||
gold | gold. | ||
platina | platina. |
Note.—-All these were unknown to former chemists.—A.
Note.—All these were unknown to earlier chemists.—A.
Observations upon the Prussic Acid, and its Combinations.
As the experiments which have been made hitherto upon this acid seem still to leave a considerable degree of uncertainty with regard to its nature, I shall not enlarge upon its properties, and the means of procuring it pure and dissengaged from combination. It combines with iron, to which it communicates a blue colour, and is equally susceptible of entering into combination with most of the other metals, which are precipitated from it by the alkalies, ammoniac, and lime, in consequence of greater affinity. The Prussic radical, from the experiments of Scheele, and especially from those of Mr Berthollet, seems composed of charcoal and azote; hence it is an acid with a double base. The phosphorus which has been found combined with it appears, from the experiments of Mr Hassenfratz, to be only accidental.
As the experiments done so far on this acid still leave a lot of uncertainty about its nature, I won't go into detail about its properties or how to obtain it in a pure form. It combines with iron, giving it a blue color, and it can also form compounds with most other metals, which are precipitated from it by alkalis, ammonia, and lime due to stronger attraction. The prussic radical, based on the experiments by Scheele and especially those by Mr. Berthollet, seems to be made up of carbon and nitrogen; therefore, it’s an acid with a dual base. The phosphorus that has been found combined with it appears to be only incidental, according to Mr. Hassenfratz's experiments.
Although this acid combines with alkalies, earths, and metals, in the same way with other acids, it possesses only some of the properties we have been in use to attribute to acids, and it may consequently be improperly ranked here in[Pg 290] the class of acids; but, as I have already observed, it is difficult to form a decided opinion upon the nature of this substance until the subject has been farther elucidated by a greater number of experiments.
Although this acid reacts with bases, earths, and metals just like other acids, it only has some of the properties we usually associate with acids. Therefore, it might not be appropriate to classify it as an acid in[Pg 290]. However, as I've mentioned before, it's hard to have a clear opinion about the nature of this substance until more experiments shed light on the topic.
FOOTNOTES:
[40] Those who wish to see what has been said upon this great chemical question by Messrs de Morveau, Berthollet, De Fourcroy, and myself, may consult our translation of Mr Kirwan's Essay upon Phlogiston.—A.
[40] If you want to check out what has been discussed about this major chemical issue by Messrs de Morveau, Berthollet, De Fourcroy, and me, you can look at our translation of Mr. Kirwan's Essay on Phlogiston.—A.
[42] Commonly called Derbyshire spars.—E.
__A_TAG_PLACEHOLDER_0__ Commonly called Derbyshire spars.—E.
[43] I have not added the Table of these combinations, as the order of their affinity is entirely unknown; they are called molybdats of argil, antimony, potash, &c.—E.
[43] I didn't include the table of these combinations since the order of their affinity is completely unknown; they are referred to as molybdates of clay, antimony, potash, etc.—E.
[45] I have omitted the Table, as the order of affinity is unknown, and is given by Mr Lavoisier only in alphabetical order. All the combinations of malic acid with salifiable bases, which are named malats, were unknown to the ancient chemists.—E.
[45] I left out the Table since the order of affinity is unknown, and Mr. Lavoisier only presents it in alphabetical order. All the combinations of malic acid with basic substances, referred to as malats, were not known to ancient chemists.—E.
[46] The order of affinity of the salifiable bases with this acid is hitherto unknown. Mr Lavoisier, from its similarity to pyro-lignous acid, supposes the order to be the same in both; but, as this is not ascertained by experiment, the table is omitted. All these combinations, called Pyro-tartarites, were unknown till lately—E.
[46] The order in which the basic substances can react with this acid is still unknown. Mr. Lavoisier thinks that it’s the same as with pyro-lignous acid because they are similar, but since this hasn’t been confirmed by experiments, the table has been left out. All of these combinations, known as Pyro-tartarites, were not recognized until recently—E.
[47] Savans Etrangers, Vol. III.
__A_TAG_PLACEHOLDER_0__ Foreign Scholars, Vol. III.
[48] These combinations are called Benzoats of Lime, Potash, Zinc, &c.; but, as the order of affinity is unknown, the alphabetical table is omitted, as unnecessary.—E.
[48] These mixtures are referred to as Benzoates of Lime, Potash, Zinc, etc.; however, since the order of affinity is unclear, the alphabetical table has been left out as it's deemed unnecessary.—E.
[49] These combinations, which were all unknown to the ancients, are called Camphorats. The table is omitted, as being only in alphabetical order.—E.
[49] These combinations, which the ancients were unaware of, are known as Camphorats. The table is not included, as it is simply in alphabetical order.—E.
[50] These combinations, which are called Gallats, were all unknown to the ancients; and the order of their affinity is not hitherto established.—A.
[50] These combinations, known as Gallats, were completely unknown to ancient people; and the way they are related to each other hasn’t been determined yet.—A.
[52] These combinations named Bombats were unknown to the ancient chemists; and the affinities of the salifiable bases with the bombic acid are hitherto undetermined.—A.
[52] These combinations called Bombats were unknown to the ancient chemists, and the connections between the salifiable bases and bombic acid are still not determined.—A.
[53] All the combinations of this acid, should it finally turn out to be one, were unknown to the ancient chemists, and its affinities with the salifiable bases have not been hitherto determined.—A.
[53] All the combinations of this acid, if it turns out to be one, were unknown to the ancient chemists, and its interactions with the basic substances have not been determined up to this point.—A.
PART III.
Description of the Instruments and Operations of Chemistry.
INTRODUCTION.
In the two former parts of this work I designedly avoided being particular in describing the manual operations of chemistry, because I had found from experience, that, in a work appropriated to reasoning, minute descriptions of processes and of plates interrupt the chain of ideas, and render the attention necessary both difficult and tedious to the reader. On the other hand, if I had confined myself to the summary descriptions hitherto given, beginners could have only acquired very vague conceptions of practical chemistry from my work, and must have wanted both confidence and interest in operations they could neither repeat nor[Pg 292] thoroughly comprehend. This want could not have been supplied from books; for, besides that there are not any which describe the modern instruments and experiments sufficiently at large, any work that could have been consulted would have presented these things under a very different order of arrangement, and in a different chemical language, which must greatly tend to injure the main object of my performance.
In the first two parts of this work, I intentionally avoided going into detail about the manual operations of chemistry because I found from experience that, in a work focused on reasoning, detailed descriptions of processes and illustrations disrupt the flow of ideas and make it hard and tedious for the reader to stay focused. On the other hand, if I had only provided the summary descriptions given so far, beginners would have gained only a vague understanding of practical chemistry from my work, lacking both confidence and interest in operations they couldn’t replicate or fully grasp. This gap couldn’t be filled by other books; aside from there being none that sufficiently cover modern instruments and experiments in detail, any work that could be consulted would present this information in a very different structure and with different chemical terminology, which would likely undermine the primary goal of my writing.
Influenced by these motives, I determined to reserve, for a third part of my work, a summary description of all the instruments and manipulations relative to elementary chemistry. I considered it as better placed at the end, rather than at the beginning of the book, because I must have been obliged to suppose the reader acquainted with circumstances which a beginner cannot know, and must therefore have read the elementary part to become acquainted with. The whole of this third part may therefore be considered as resembling the explanations of plates which are usually placed at the end of academic memoirs, that they may not interrupt the connection of the text by lengthened description. Though I have taken great pains to render this part clear and methodical, and have not omitted any essential instrument or apparatus, I am far from pretending by it to set aside the necessity of attendance upon lectures and laboratories,[Pg 293] for such as wish to acquire accurate knowledge of the science of chemistry. These should familiarise themselves to the employment of apparatus, and to the performance of experiments by actual experience. Nihil est in intellectu quod non prius fuerit in sensu, the motto which the celebrated Rouelle caused to be painted in large characters in a conspicuous part of his laboratory, is an important truth never to be lost sight of either by teachers or students of chemistry.
Driven by these reasons, I decided to set aside a third part of my work for a summary description of all the instruments and techniques related to basic chemistry. I felt it was better to place this at the end of the book rather than at the beginning, as I would have to assume the reader is familiar with concepts that a beginner wouldn’t know, and they would need to read the foundational section first to learn about them. Therefore, this entire third part can be viewed as akin to the explanations of illustrations typically included at the end of academic papers, so they don’t disrupt the flow of the text with lengthy descriptions. Although I’ve worked hard to make this section clear and systematic, ensuring no essential instrument or equipment is left out, I do not claim that it replaces the need for attending lectures and labs for those who want to fully understand the science of chemistry. They should become accustomed to using equipment and conducting experiments through hands-on experience. Nihil est in intellectu quod non prius fuerit in sensu, the motto that the famous Rouelle had painted in large letters in a prominent place in his lab, is an important truth that should never be overlooked by either chemistry teachers or students.
Chemical operations may be naturally divided into several classes, according to the purposes they are intended for performing. Some may be considered as purely mechanical, such as the determination of the weight and bulk of bodies, trituration, levigation, searching, washing, filtration, &c. Others may be considered as real chemical operations, because they are performed by means of chemical powers and agents; such are solution, fusion, &c. Some of these are intended for separating the elements of bodies from each other, some for reuniting these elements together; and some, as combustion, produce both these effects during the same process.
Chemical operations can be naturally categorized into several types based on their intended purposes. Some are purely mechanical, like measuring the weight and volume of materials, grinding, levigating, sifting, washing, filtering, etc. Others are genuine chemical operations since they rely on chemical forces and agents; these include dissolving and melting, among others. Some of these operations aim to separate the components of substances from one another, while others focus on rejoining these components, and some, like combustion, achieve both results in the same process.
Without rigorously endeavouring to follow the above method, I mean to give a detail of the chemical operations in such order of arrangement as seemed best calculated for conveying[Pg 294] instruction. I shall be more particular in describing the apparatus connected with modern chemistry, because these are hitherto little known by men who have devoted much of their time to chemistry, and even by many professors of the science.
Without strictly trying to follow the above method, I intend to provide a detailed account of the chemical operations in an order that I believe will best convey[Pg 294] instruction. I will focus more on describing the equipment related to modern chemistry, as this is still not well known among those who have dedicated significant time to chemistry, including many professors of the subject.
CHAP. I.
Of the Instruments necessary for determining the Absolute and Specific Gravities of Solid and Liquid Bodies.
The best method hitherto known for determining the quantities of substances submitted to chemical experiment, or resulting from them, is by means of an accurately constructed beam and scales, with properly regulated weights, which well known operation is called weighing. The denomination and quantity of the weights used as an unit or standard for this purpose are extremely arbitrary, and vary not only in different kingdoms, but even in different provinces of the same kingdom, and in different cities of the same province. This variation is of infinite consequence to be well understood in commerce and in the arts; but, in chemistry, it is of no moment what particular denomination of weight be employed, provided the results of experiments be expressed in convenient fractions of the same denomination. For this purpose, until all the weights used in society be reduced to the same standard, it will be sufficient for chemists in different parts to use the common[Pg 296] pound of their own country as the unit or standard, and to express all its fractional parts in decimals, instead of the arbitrary divisions now in use. By this means the chemists of all countries will be thoroughly understood by each other, as, although the absolute weights of the ingredients and products cannot be known, they will readily, and without calculation, be able to determine the relative proportions of these to each other with the utmost accuracy; so that in this way we shall be possessed of an universal language for this part of chemistry.
The best method known so far for measuring the quantities of substances used in chemical experiments or produced by them is through an accurately made balance and scales with properly calibrated weights, a process commonly known as weighing. The names and amounts of the weights used as a unit or standard for this purpose are quite arbitrary and vary not only between different countries but also within different regions of the same country and different cities of the same region. This variation is crucial to understand in commerce and the arts, but in chemistry, it doesn't really matter what specific weight denomination is used, as long as the results of experiments are expressed in convenient fractions of the same weight denomination. Therefore, until all weights in society are standardized, it is sufficient for chemists in different regions to use the common[Pg 296] pound from their own country as the unit or standard and express all its fractional parts in decimals rather than the arbitrary divisions currently in use. This way, chemists from all countries will understand each other clearly, as although the exact weights of the ingredients and products may not be known, they will be able to determine the relative proportions of these substances to each other accurately and effortlessly, providing us with a universal language for this aspect of chemistry.
With this view I have long projected to have the pound divided into decimal fractions, and I have of late succeeded through the assistance of Mr Fourche balance-maker at Paris, who has executed it for me with great accuracy and judgment. I recommend to all who carry on experiments to procure similar divisions of the pound, which they will find both easy and simple in its application, with a very small knowledge of decimal fractions[54].
With this in mind, I've long envisioned dividing the pound into decimal fractions, and recently I've succeeded with the help of Mr. Fourche, a balance-maker in Paris, who did it for me with great precision and skill. I recommend that everyone who conducts experiments get similar divisions of the pound, which they will find easy and straightforward to apply, requiring only a minimal understanding of decimal fractions[54].
As the usefulness and accuracy of chemistry depends entirely upon the determination of the weights of the ingredients and products both before and after experiments, too much precision cannot be employed in this part of the subject; and, for this purpose, we must be provided with good instruments. As we are often obliged, in chemical processes, to ascertain, within a grain or less, the tare or weight of large and heavy instruments, we must have beams made with peculiar niceness by accurate workmen, and these must always be kept apart from the laboratory in some place where the vapours of acids, or other corrosive liquors, cannot have access, otherwise the steel will rust, and the accuracy of the balance be destroyed. I have three sets, of different sizes, made by Mr Fontin with the utmost nicety, and, excepting those made by Mr Ramsden of London, I do not think any can compare with them for precision and sensibility. The largest of these is about three feet long in the beam for large weights, up to fifteen or twenty pounds; the second, for weights of eighteen or twenty ounces, is exact to a tenth part of a grain; and the smallest, calculated only for weighing about one gros, is sensibly affected by the five hundredth part of a grain.
As the usefulness and accuracy of chemistry depend entirely on determining the weights of the ingredients and products both before and after experiments, we can't be too precise in this part of the subject; for this reason, we need to have good instruments. Since we often need to measure, within a grain or less, the weight of large and heavy items during chemical processes, we require beams crafted with exceptional precision by skilled workers. These must always be kept separate from the laboratory in a place where the vapors of acids or other corrosive liquids can't reach them; otherwise, the steel will rust and compromise the accuracy of the balance. I have three sets of different sizes, made by Mr. Fontin with the greatest precision, and aside from those made by Mr. Ramsden in London, I don’t think any can match them in terms of precision and sensitivity. The largest of these is about three feet long and is designed for weights of up to fifteen or twenty pounds; the second, for weights of eighteen or twenty ounces, is accurate to a tenth of a grain; and the smallest, intended only for weighing about one gros, is noticeably affected by the five-hundredth of a grain.
Besides these nicer balances, which are only used for experiments of research, we must have[Pg 298] others of less value for the ordinary purposes of the laboratory. A large iron balance, capable of weighing forty or fifty pounds within half a dram, one of a middle size, which may ascertain eight or ten pounds, within ten or twelve grains, and a small one, by which about a pound may be determined, within one grain.
Besides these nicer balances, which are only used for research experiments, we need[Pg 298] others of lesser quality for regular lab purposes. A large iron balance can weigh forty or fifty pounds accurately to within half a dram, a medium-sized balance can measure eight or ten pounds within ten or twelve grains, and a small one can determine about a pound within one grain.
We must likewise be provided with weights divided into their several fractions, both vulgar and decimal, with the utmost nicety, and verified by means of repeated and accurate trials in the nicest scales; and it requires some experience, and to be accurately acquainted with the different weights, to be able to use them properly. The best way of precisely ascertaining the weight of any particular substance is to weigh it twice, once with the decimal divisions of the pound, and another time with the common subdivisions or vulgar fractions, and, by comparing these, we attain the utmost accuracy.
We also need to have weights divided into different fractions, both regular and decimal, with the highest precision, and validated through numerous accurate tests on sensitive scales. It takes some experience and a good understanding of the various weights to use them correctly. The best way to accurately determine the weight of a specific substance is to weigh it twice: first using the decimal divisions of the pound, and then again with the regular fractions. By comparing these results, we achieve the greatest accuracy.
By the specific gravity of any substance is understood the quotient of its absolute weight divided by its magnitude, or, what is the same, the weight of a determinate bulk of any body. The weight of a determinate magnitude of water has been generally assumed as unity for this purpose; and we express the specific gravity of gold, sulphuric acid, &c. by saying, that gold is nineteen times, and sulphuric acid twice the weight of water, and so of other bodies.[Pg 299]
Specific gravity refers to the ratio of a substance's weight to its volume, or, in other words, the weight of a specific amount of a substance. For this purpose, the weight of a certain volume of water is typically considered to be one. We express the specific gravity of materials like gold and sulfuric acid by stating that gold is nineteen times heavier than water, and sulfuric acid is twice as heavy, and so on for other substances.[Pg 299]
It is the more convenient to assume water as unity in specific gravities, that those substances whose specific gravity we wish to determine, are most commonly weighed in water for that purpose. Thus, if we wish to determine the specific gravity of gold flattened under the hammer, and supposing the piece of gold to weigh 8 oz. 4 gros 2-1/2 grs. in the air[55], it is suspended by means of a fine metallic wire under the scale of a hydrostatic balance, so as to be entirely immersed in water, and again weighed. The piece of gold in Mr Brisson's experiment lost by this means 3 gros 37 grs.; and, as it is evident that the weight lost by a body weighed in water is precisely equal to the weight of the water displaced, or to that of an equal volume of water, we may conclude, that, in equal magnitudes, gold weighs 4893-1/2 grs. and water 253 grs. which, reduced to unity, gives 1.0000 as the specific gravity of water, and 19.3617 for that of gold. We may operate in the same manner with all solid substances. We have rarely any occasion, in chemistry, to determine the specific gravity of solid bodies, unless when operating upon alloys or metallic glasses; but we have very frequent necessity to ascertain that of fluids, as it is often the only means of judging of their purity or degree of concentration.
It’s more convenient to take water as the standard for specific gravities since we usually weigh the substances whose specific gravity we want to determine in water. For example, if we want to find out the specific gravity of gold that's been flattened with a hammer, and we assume that the piece of gold weighs 8 oz. 4 gros 2-1/2 grs. in air[55], it’s suspended using a fine metal wire under the scale of a hydrostatic balance, fully submerged in water, and weighed again. In Mr. Brisson's experiment, the piece of gold lost 3 gros 37 grs.; and since it’s clear that the weight lost by an object weighed in water equals the weight of the displaced water, or that of an equal volume of water, we can conclude that, for equal volumes, gold weighs 4893-1/2 grs. and water 253 grs.. This, when simplified, gives us 1.0000 as the specific gravity of water and 19.3617 for gold. We can use this same method with all solid substances. In chemistry, we rarely need to determine the specific gravity of solid bodies unless we’re dealing with alloys or metallic glasses; however, it’s often essential to know the specific gravity of fluids, as it can be the only way to assess their purity or concentration level.
This object may be very fully accomplished with the hydrostatic balance, by weighing a solid body; such, for example, as a little ball of rock cristal suspended by a very fine gold wire, first in the air, and afterwards in the fluid whose specific gravity we wish to discover. The weight lost by the cristal, when weighed in the liquor, is equal to that of an equal bulk of the liquid. By repeating this operation successively in water and different fluids, we can very readily ascertain, by a simple and easy calculation, the relative specific gravities of these fluids, either with respect to each other or to water. This method is not, however, sufficiently exact, or, at least, is rather troublesome, from its extreme delicacy, when used for liquids differing but little in specific gravity from water; such, for instance, as mineral waters, or any other water containing very small portions of salt in solution.
This task can be effectively done using a hydrostatic balance by weighing a solid object, like a small ball made of crystal suspended by a fine gold wire, first in the air and then in the fluid whose specific gravity we want to measure. The weight lost by the crystal when weighed in the liquid equals the weight of the same volume of the liquid. By repeating this process in water and various other fluids, we can easily determine the relative specific gravities of these fluids either in comparison to each other or to water through simple calculations. However, this method isn't very precise and can be somewhat tricky due to its extreme sensitivity, especially when dealing with liquids that have specific gravities close to that of water, such as mineral waters or any water with small amounts of dissolved salt.
In some operations of this nature, which have not hitherto been made public, I employed an instrument of great sensibility for this purpose with great advantage. It consists of a hollow cylinder, A b c f, Pl. vii. fig. 6. of brass, or rather of silver, loaded at its bottom, b c f, with tin, as represented swimming in a jug of water, l m n o. To the upper part of the cylinder is attached a stalk of silver wire, not more than three fourths of a line diameter, surmounted by[Pg 301] a little cup d, intended for containing weights; upon the stalk a mark is made at g, the use of which we shall presently explain. This cylinder may be made of any size; but, to be accurate, ought at least to displace four pounds of water. The weight of tin with which this instrument is loaded ought to be such as will make it remain almost in equilibrium in distilled water, and should not require more than half a dram, or a dram at most, to make it sink to g.
In some operations like this, which haven't been publicly shared before, I used a very sensitive instrument to great effect. It's made up of a hollow cylinder, A b c f, Pl. vii. fig. 6, made of brass or even silver, weighted at the bottom, b c f, and floating in a jug of water, l m n o. Attached to the top of the cylinder is a silver wire stalk, not thicker than three-fourths of a line in diameter, topped with[Pg 301] a small cup d designed to hold weights; there's a mark at g on the stalk, which we'll explain shortly. This cylinder can be made in any size; however, to be precise, it should at least displace four pounds of water. The tin weight used for this instrument should be enough to keep it nearly balanced in distilled water, and it shouldn't take more than half a dram, or at most a full dram, to make it sink to g.
We must first determine, with great precision, the exact weight of the instrument, and the number of additional grains requisite for making it sink, in distilled water of a determinate temperature, to the mark: We then perform the same experiment upon all the fluids of which we wish to ascertain the specific gravity, and, by means of calculation, reduce the observed differences to a common standard of cubic feet, pints or pounds, or of decimal fractions, comparing them with water. This method, joined to experiments with certain reagents[56], is one of the best for determining the quality of waters, and is even capable of pointing out differences which escape the most accurate chemical analysis. I shall, at some future[Pg 302] period, give an account of a very extensive set of experiments which I have made upon this subject.
We first need to accurately determine the exact weight of the instrument and how many extra grains are needed to make it sink to the mark in distilled water at a specific temperature. Next, we perform the same experiment with all the fluids we want to measure the specific gravity of, and through calculations, we convert the observed differences to a common standard like cubic feet, pints, pounds, or decimal fractions, comparing them to water. This method, along with tests using certain reagents[56], is one of the best for assessing water quality and can even reveal differences that the most precise chemical analysis might miss. I will, at a later[Pg 302] time, provide a detailed account of a wide range of experiments I have conducted on this topic.
These metallic hydrometers are only to be used for determining the specific gravities of such waters as contain only neutral salts or alkaline substances; and they may be constructed with different degrees of ballast for alkohol and other spiritous liquors. When the specific gravities of acid liquors are to be ascertained, we must use a glass hydrometer, as represented Pl. vii. fig. 14[57]. This consists of a hollow cylinder of glass, a b c f, hermetically sealed at its lower end, and drawn out at the upper into a capillary tube a, ending in the little cup or bason d. This instrument is ballasted with more or less mercury, at the bottom of the cylinder introduced through the tube, in proportion to the weight of the liquor intended to be examined: We may introduce a small graduated slip of paper into the tube a d; and, though these degrees do not exactly correspond to the fractions of grains in the different liquors, they may be rendered very useful in calculation.
These metal hydrometers are meant only for measuring the specific gravities of waters that contain only neutral salts or alkaline substances; they can be made with different weights for alcohol and other spirits. When we need to measure the specific gravities of acidic liquids, we should use a glass hydrometer, as shown in Pl. vii. fig. 14[57]. This consists of a hollow glass cylinder, a b c f, sealed at the bottom and tapered into a capillary tube a, which ends in a small cup or basin d. This instrument is weighted with varying amounts of mercury at the bottom of the cylinder, added through the tube, depending on the weight of the liquid being tested. We can insert a small graduated strip of paper into the tube a d; and while these measurements don't precisely match the fractions of grains in different liquids, they can still be quite useful for calculations.
What is said in this chapter may suffice, without farther enlargement, for indicating the[Pg 303] means of ascertaining the absolute and specific gravities of solids and fluids, as the necessary instruments are generally known, and may easily be procured: But, as the instruments I have used for measuring the gasses are not any where described, I shall give a more detailed account of these in the following chapter.
What’s discussed in this chapter should be enough to indicate the[Pg 303] methods for determining the absolute and specific gravities of solids and liquids, since the necessary tools are typically known and can be easily obtained. However, because the instruments I've used to measure gases aren’t described anywhere, I will provide a more detailed explanation of these in the next chapter.
FOOTNOTES:
[54] Mr Lavoisier gives, in this part of his work, very accurate directions for reducing the common subdivisions of the French pound into decimal fractions, and vice versa, by means of tables subjoined to this 3d part. As these instructions, and the table, would be useless to the British chemist, from the difference between the subdivisions of the French and Troy pounds, I have omitted them, but have subjoined in the appendix accurate rules for converting the one into the other.—E.
[54] Mr. Lavoisier provides very clear instructions in this section of his work for converting the common subdivisions of the French pound into decimal fractions, and vice versa, using the tables included in this third part. Since these instructions and the table would not be helpful to British chemists due to the differences between the subdivisions of the French and Troy pounds, I have left them out but included accurate rules for converting between the two in the appendix.—E.
CHAP. II.
Of Gazometry, or the Measurement of the Weight and Volume of Aëriform Substances.
SECT. I.
Description of the Pneumato-chemical Apparatus.
The French chemists have of late applied the name of pneumato-chemical apparatus to the very simple and ingenious contrivance, invented by Dr Priestley, which is now indispensibly necessary to every laboratory. This consists of a wooden trough, of larger or smaller dimensions as is thought convenient, lined with plate-lead or tinned copper, as represented in perspective, Pl. V. In Fig. 1. the same trough or cistern is supposed to have two of its sides cut away, to show its interior construction more distinctly. In this apparatus, we distinguish between the shelf ABCD Fig. 1. and 2. and the bottom or body of the cistern FGHI Fig. 2.[Pg 305] The jars or bell-glasses are filled with water in this deep part, and, being turned with their mouths downwards, are afterwards set upon the shelf ABCD, as shown Plate X. Fig. 1. F. The upper parts of the sides of the cistern above the level of the shelf are called the rim or borders.
The French chemists have recently referred to the simple yet clever device invented by Dr. Priestley as a pneumato-chemical apparatus, which is now essential in every laboratory. This consists of a wooden trough, varying in size as needed, lined with lead or tinned copper, as shown in perspective, Pl. V. In Fig. 1, this trough or cistern has two of its sides removed to clearly display its interior structure. In this apparatus, we identify the shelf ABCD in Fig. 1 and 2, as well as the bottom or body of the cistern FGHI in Fig. 2.[Pg 305] The jars or bell glasses are filled with water in this deeper section, then inverted with their openings facing down, and placed on the shelf ABCD, as illustrated in Plate X, Fig. 1 F. The upper parts of the sides of the cistern that rise above the shelf level are termed the rim or borders.
The cistern ought to be filled with water, so as to stand at least an inch and a half deep upon the shelf, and it should be of such dimensions as to admit of at least one foot of water in every direction in the well. This size is sufficient for ordinary occasions; but it is often convenient, and even necessary, to have more room; I would therefore advise such as intend to employ themselves usefully in chemical experiments, to have this apparatus made of considerable magnitude, where their place of operating will allow. The well of my principal cistern holds four cubical feet of water, and its shelf has a surface of fourteen square feet; yet, in spite of this size, which I at first thought immoderate, I am often straitened for room.
The cistern should be filled with water to at least an inch and a half deep on the shelf, and it needs to be big enough to hold at least one foot of water in every direction in the well. This size is adequate for regular use; however, it can be useful, and sometimes necessary, to have more space. Therefore, I recommend that anyone planning to do useful chemical experiments should have this equipment made larger, if their workspace allows. The well of my main cistern holds four cubic feet of water, and its shelf has a surface area of fourteen square feet; yet, despite this size, which I initially thought was excessive, I often find myself short on space.
In laboratories, where a considerable number of experiments are performed, it is necessary to have several lesser cisterns, besides the large one, which may be called the general magazine; and even some portable ones, which may be moved when necessary, near a furnace, or wherever they may be wanted. There are likewise some operations which dirty the water of the apparatus,[Pg 306] and therefore require to be carried on in cisterns by themselves.
In labs, where a lot of experiments take place, it’s important to have several smaller tanks in addition to the large one, which can be called the general magazine; and even some portable ones that can be moved as needed, close to a furnace or wherever else they might be needed. There are also some processes that contaminate the water in the equipment,[Pg 306] so they need to be done in separate tanks.
It were doubtless considerably cheaper to use cisterns, or iron-bound tubs, of wood simply dove-tailed, instead of being lined with lead or copper; and in my first experiments I used them made in that way; but I soon discovered their inconvenience. If the water be not always kept at the same level, such of the dovetails as are left dry shrink, and, when more water is added, it escapes through the joints, and runs out.
It was definitely a lot cheaper to use cisterns or iron-bound tubs made of simply joined wood instead of lining them with lead or copper; and in my initial experiments, I used them that way. However, I quickly realized their downsides. If the water isn't always kept at the same level, the dry joints can shrink, and when more water is added, it leaks through the joints and spills out.
We employ cristal jars or bell glasses, Pl. V. Fig. 9. A. for containing the gasses in this apparatus; and, for transporting these, when full of gas, from one cistern to another, or for keeping them in reserve when the cistern is too full, we make use of a flat dish BC, surrounded by a standing up rim or border, with two handles DE for carrying it by.
We use crystal jars or bell glasses, Pl. V. Fig. 9. A., to hold the gases in this setup. To move these jars full of gas from one tank to another, or to store them when the tank is too full, we use a flat dish BC with a raised edge or rim and two handles DE for easy carrying.
After several trials of different materials, I have found marble the best substance for constructing the mercurial pneumato-chemical apparatus, as it is perfectly impenetrable by mercury, and is not liable, like wood, to separate at the junctures, or to allow the mercury to escape through chinks; neither does it run the risk of breaking, like glass, stone-ware, or porcelain. Take a block of marble BCDE, Plate V. Fig. 3. and 4. about two feet long, 15 or 18 inches[Pg 307] broad, and ten inches thick, and cause it to be hollowed out as at m n Fig. 5. about four inches deep, as a reservoir for the mercury; and, to be able more conveniently to fill the jars, cut the gutter T V, Fig. 3. 4. and 5. at least four inches deeper; and, as this trench may sometimes prove troublesome, it is made capable of being covered at pleasure by thin boards, which slip into the grooves x y, Fig. 5. I have two marble cisterns upon this construction, of different sizes, by which I can always employ one of them as a reservoir of mercury, which it preserves with more safety than any other vessel, being neither subject to overturn, nor to any other accident. We operate with mercury in this apparatus exactly as with water in the one before described; but the bell-glasses must be of smaller diameter, and much stronger; or we may use glass tubes, having their mouths widened, as in Fig. 7.; these are called eudiometers by the glass-men who sell them. One of the bell-glasses is represented Fig. 5. A. standing in its place, and what is called a jar is engraved Fig. 6.
After trying out various materials, I've found that marble is the best choice for building the mercury pneumatic-chemical apparatus. It's completely impermeable to mercury and unlike wood, it won't separate at the joints or let the mercury leak through cracks; it also doesn't risk breaking like glass, stoneware, or porcelain. Take a block of marble BCDE, Plate V. Fig. 3. and 4. about two feet long, 15 or 18 inches[Pg 307] wide, and ten inches thick, and hollow it out as shown at m n Fig. 5., about four inches deep, to serve as a reservoir for the mercury. To make it easier to fill the jars, cut the channel T V, Fig. 3. 4. and 5. at least four inches deeper. Since this trench can sometimes be a nuisance, it can be covered with thin boards that slide into the grooves x y, Fig. 5. I have two marble cisterns made this way, in different sizes, so I can always use one as a mercury reservoir, which it holds more safely than any other container, as it won't tip over or face any other accidents. We handle mercury in this apparatus just like we do with water in the previous design; however, the bell glasses need to be narrower and much sturdier. Alternatively, we can use glass tubes with flared openings, as shown in Fig. 7.; these are referred to as eudiometers by the glass merchants. One of the bell glasses is shown in Fig. 5. A, positioned correctly, and what's known as a jar is depicted in Fig. 6.
The mercurial pneumato-chemical apparatus is necessary in all experiments wherein the disengaged gasses are capable of being absorbed by water, as is frequently the case, especially in all combinations, excepting those of metals, in fermentation, [Pg 308]&c.
The quick-changing pneumatic chemical device is essential in all experiments where the released gases can be absorbed by water, which is often the case, especially in all combinations, except for those involving metals, in fermentation, [Pg 308]&c.
SECT. II.
Of the Gazometer.
I give the name of gazometer to an instrument which I invented, and caused construct, for the purpose of a kind of bellows, which might furnish an uniform and continued stream of oxygen gas in experiments of fusion. Mr Meusnier and I have since made very considerable corrections and additions, having converted it into what may be called an universal instrument, without which it is hardly possible to perform most of the very exact experiments. The name we have given the instrument indicates its intention for measuring the volume or quantity of gas submitted to it for examination.
I call the device gazometer, which I invented and had built, to serve as a type of bellows that provides a steady and consistent flow of oxygen gas for fusion experiments. Since then, Mr. Meusnier and I have made significant improvements and additions, turning it into what we can call a universal instrument, which is essential for conducting most precise experiments. The name we've chosen for the instrument reflects its purpose of measuring the volume or amount of gas it tests.
It consists of a strong iron beam, DE, Pl. VIII. Fig. 1. three feet long, having at each end, D and E, a segment of a circle, likewise strongly constructed of iron, and very firmly joined. Instead of being poised as in ordinary balances, this beam rests, by means of a cylindrical axis of polished steel, F, Fig. 9. upon two large moveable brass friction-wheels, by which the resistance to its motion from friction is considerably diminished, being converted into friction[Pg 309] of the second order. As an additional precaution, the parts of these wheels which support the axis of the beam are covered with plates of polished rock-cristal. The whole of this machinery is fixed to the top of the solid column of wood BC, Fig. 1. To one extremity D of the beam, a scale P for holding weights is suspended by a flat chain, which applies to the curvature of the arc nDo, in a groove made for the purpose. To the other extremity E of the beam is applied another flat chain, i k m, so constructed, as to be incapable of lengthening or shortening, by being less or more charged with weight; to this chain, an iron trivet, with three branches, a i, c i, and h i, is strongly fixed at i, and these branches support a large inverted jar A, of hammered copper, of about 18 inches diameter, and 20 inches deep. The whole of this machine is represented in perspective, Pl. VIII. Fig. 1. and Pl. IX. Fig. 2. and 4. give perpendicular sections, which show its interior structure.
It features a strong iron beam, DE, Pl. VIII. Fig. 1, three feet long, with a circular segment at each end, D and E, also made of robust iron and securely attached. Instead of being balanced like regular scales, this beam sits on a polished steel cylindrical axis, F, Fig. 9, on two large movable brass friction wheels, which greatly reduce the resistance to its movement due to friction, converting it into second-order friction[Pg 309]. As an extra measure, the parts of these wheels that support the beam's axis are covered with polished rock crystal. This entire setup is mounted on top of a solid wooden column, BC, Fig. 1. At one end, D, of the beam, a scale, P, for holding weights hangs from a flat chain that fits into a groove along the curved arc nDo. At the other end, E, of the beam is another flat chain, i k m, designed not to stretch or shrink regardless of the weight applied. An iron trivet with three branches, a i, c i, and h i, is securely attached at i, and these branches support a large inverted jar A made of hammered copper, approximately 18 inches in diameter and 20 inches deep. The whole mechanism is illustrated in perspective in Pl. VIII. Fig. 1, and Pl. IX. Figs. 2 and 4 provide vertical sections that reveal its internal structure.
Round the bottom of the jar, on its outside, is fixed (Pl. IX. Fig. 2.) a border divided into compartments 1, 2, 3, 4, &c. intended to receive leaden weights separately represented 1, 2, 3, Fig. 3. These are intended for increasing the weight of the jar when a considerable pressure is requisite, as will be afterwards explained, though such necessity seldom occurs.[Pg 310] The cylindrical jar A is entirely open below, de, Pl. IX. Fig. 4.; but is closed above with a copper lid, a b c, open at b f, and capable of being shut by the cock g. This lid, as may be seen by inspecting the figures, is placed a few inches within the top of the jar to prevent the jar from being ever entirely immersed in the water, and covered over. Were I to have this instrument made over again, I should cause the lid to be considerably more flattened, so as to be almost level. This jar or reservoir of air is contained in the cylindrical copper vessel, LMNO, Pl. VIII. Fig. 1. filled with water.
At the bottom of the jar, on the outside, is a border divided into compartments 1, 2, 3, 4, etc., designed to hold lead weights that are represented separately as 1, 2, 3. These weights are meant to increase the jar's weight when significant pressure is needed, although such a need rarely occurs.[Pg 310] The cylindrical jar A is completely open at the bottom, but it has a copper lid on top, which is open at one side and can be closed with a valve. This lid is positioned a few inches inside the top of the jar to prevent it from being fully submerged in water. If I were to have this instrument made again, I would make the lid much flatter, almost level. This jar or air reservoir is housed within the cylindrical copper vessel, LMNO, filled with water.
In the middle of the cylindrical vessel LMNO, Pl. IX. Fig. 4. are placed two tubes st, xy, which are made to approach each other at their upper extremities t y; these are made of such a length as to rise a little above the upper edge LM of the vessel LMNO, and when the jar abcde touches the bottom NO, their upper ends enter about half an inch into the conical hollow b, leading to the stop-cock g.
In the center of the cylindrical container LMNO, Pl. IX. Fig. 4, there are two tubes st, xy, which are designed to come close together at their upper ends t y; they are long enough to extend slightly above the top edge LM of the container LMNO, and when the jar abcde touches the bottom NO, their upper ends dip about half an inch into the conical hollow b, leading to the stop-cock g.
The bottom of the vessel LMNO is represented Pl. IX. Fig. 3. in the middle of which a small hollow semispherical cap is soldered, which may be considered as the broad end of a funnel reversed; the two tubes st, xy, Fig. 4. are adapted to this cap at s and x, and by this means communicate with the tubes mm, nn, oo, pp, Fig. 3. which are fixed horizontally upon the[Pg 311] bottom of the vessel, and all of which terminate in, and are united by, the spherical cap sx. Three of these tubes are continued out of the vessel, as in Pl. VIII. Fig. 1. The first marked in that figure 1, 2, 3, is inserted at its extremity 3, by means of an intermediate stop-cock 4, to the jar V. which stands upon the shelf of a small pneumato-chemical apparatus GHIK, the inside of which is shown Pl. IX. Fig. 1. The second tube is applied against the outside of the vessel LMNO from 6 to 7, is continued at 8, 9, 10, and at 11 is engaged below the jar V. The former of these tubes is intended for conveying gas into the machine, and the latter for conducting small quantities for trials under jars. The gas is made either to flow into or out of the machine, according to the degree of pressure it receives; and this pressure is varied at pleasure, by loading the scale P less or more, by means of weights. When gas is to be introduced into the machine, the pressure is taken off, or even rendered negative; but, when gas is to be expelled, a pressure is made with such degree of force as is found necessary.
The bottom of the vessel LMNO is shown in Pl. IX. Fig. 3, where a small hollow semicircular cap is soldered in the center. This cap can be thought of as the wide end of an upside-down funnel. The two tubes st, xy, Fig. 4, connect to this cap at s and x, allowing them to link with the tubes mm, nn, oo, pp, Fig. 3, which are fixed horizontally on the[Pg 311] bottom of the vessel. All these tubes end in and connect with the spherical cap sx. Three of these tubes extend out of the vessel, as shown in Pl. VIII. Fig. 1. The first, marked in that figure as 1, 2, 3, is attached at its end 3 through an intermediate stop-cock 4 to the jar V, which rests on the shelf of a small pneumatic-chemical apparatus GHIK, with its interior depicted in Pl. IX. Fig. 1. The second tube runs along the outside of the vessel LMNO from 6 to 7, continues at 8, 9, 10, and at 11 connects below the jar V. The first of these tubes is designed to bring gas into the machine, while the second one is for directing small amounts for experiments under jars. The gas can flow into or out of the machine, depending on the pressure it receives, which can be adjusted by adding or removing weights from the scale P. When gas needs to be introduced into the machine, the pressure is reduced or even made negative; but when gas needs to be expelled, pressure is applied with whatever force is necessary.
The third tube 12, 13, 14, 15, is intended for conveying air or gas to any necessary place or apparatus for combustions, combinations, or any other experiment in which it is required.
The third tube 12, 13, 14, 15, is meant for carrying air or gas to any required location or device for combustion, mixtures, or any other experiment that needs it.
To explain the use of the fourth tube, I must enter into some discussions. Suppose the vessel[Pg 312] LMNO, Pl. VIII. Fig. 1. full of water, and the jar A partly filled with gas, and partly with water; it is evident that the weights in the bason P may be so adjusted, as to occasion an exact equilibrium between the weight of the bason and of the jar, so that the external air shall not tend to enter into the jar, nor the gas to escape from it; and in this case the water will stand exactly at the same level both within and without the jar. On the contrary, if the weight in the bason P be diminished, the jar will then press downwards from its own gravity, and the water will stand lower within the jar than it does without; in this case, the included air or gas will suffer a degree of compression above that experienced by the external air, exactly proportioned to the weight of a column of water, equal to the difference of the external and internal surfaces of the water. From these reflections, Mr Meusnier contrived a method of determining the exact degree of pressure to which the gas contained in the jar is at any time exposed. For this purpose, he employs a double glass syphon 19, 20, 21, 22, 23, firmly cemented at 19 and 23. The extremity 19 of this syphon communicates freely with the water in the external vessel of the machine, and the extremity 23 communicates with the fourth tube at the bottom of the cylindrical vessel, and consequently, by means of the perpendicular[Pg 313] tube st, Pl. IX. Fig. 4. with the air contained in the jar. He likewise cements, at 16, Pl. VIII. Fig. 1. another glass tube 16, 17, 18, which communicates at 16 with the water in the exterior vessel LMNO, and, at its upper end 18, is open to the external air.
To explain how the fourth tube is used, I need to go into some detail. Imagine the vessel [Pg 312] LMNO, Pl. VIII. Fig. 1. filled with water, and the jar A partially filled with gas and partially with water; it’s clear that the weights in the basin P can be adjusted to create a perfect balance between the weight of the basin and the jar, so that the outside air won't push into the jar, nor will the gas escape from it; in this situation, the water will be at the same level inside and outside the jar. On the other hand, if the weight in the basin P is reduced, the jar will then move downwards due to its own weight, and the water will be lower inside the jar than outside; in this case, the air or gas inside will be compressed more than the external air, with the difference being exactly equal to the weight of a column of water that corresponds to the difference in height between the internal and external water surfaces. From these observations, Mr. Meusnier developed a method to measure the exact pressure the gas in the jar is under at any given time. To do this, he uses a double glass syphon 19, 20, 21, 22, 23, securely attached at 19 and 23. The end 19 of this syphon connects freely to the water in the external vessel of the machine, while end 23 connects to the fourth tube at the bottom of the cylindrical vessel, and therefore, through the vertical [Pg 313] tube st, Pl. IX. Fig. 4., to the air inside the jar. He also attaches, at 16, Pl. VIII. Fig. 1., another glass tube 16, 17, 18, which connects at 16 with the water in the external vessel LMNO and is open to the external air at its upper end 18.
By these several contrivances, it is evident that the water must stand in the tube 16, 17, 18, at the same level with that in the cistern LMNO; and, on the contrary, that, in the branch 19, 20, 21, it must stand higher or lower, according as the air in the jar is subjected to a greater or lesser pressure than the external air. To ascertain these differences, a brass scale divided into inches and lines is fixed between these two tubes. It is readily conceived that, as air, and all other elastic fluids, must increase in weight by compression, it is necessary to know their degree of condensation to be enabled to calculate their quantities, and to convert the measure of their volumes into correspondent weights; and this object is intended to be fulfilled by the contrivance now described.
By these various methods, it's clear that the water must be at the same level in tubes 16, 17, and 18 as it is in the cistern LMNO. Conversely, in branch 19, 20, and 21, the water level will be higher or lower depending on whether the air in the jar is under greater or lesser pressure than the outside air. To measure these differences, a brass scale marked in inches and fractions is fixed between the two tubes. It's easy to understand that, since air and all other gases increase in weight when compressed, we need to know their level of compression to calculate their quantities and convert their volume measurements into corresponding weights. This is the purpose of the setup described here.
But, to determine the specific gravity of air or of gasses, and to ascertain their weight in a known volume, it is necessary to know their temperature, as well as the degree of pressure under which they subsist; and this is accomplished by means of a small thermometer, strongly cemented into a brass collet, which screws[Pg 314] into the lid of the jar A. This thermometer is represented separately, Pl. VIII. Fig. 10. and in its place 24, 25, Fig. 1. and Pl. IX. Fig. 4. The bulb is in the inside of the jar A, and its graduated stalk rises on the outside of the lid.
But to figure out the specific gravity of air or gases and to determine their weight in a specific volume, you need to know their temperature and the amount of pressure they are under. This is done using a small thermometer that is securely attached to a brass collet, which screws[Pg 314] into the lid of jar A. This thermometer is shown separately in Pl. VIII. Fig. 10, and in its position in 24, 25, Fig. 1, and Pl. IX. Fig. 4. The bulb is located inside jar A, and its graduated stem extends outside the lid.
The practice of gazometry would still have laboured under great difficulties, without farther precautions than those above described. When the jar A sinks in the water of the cistern LMNO, it must lose a weight equal to that of the water which it displaces; and consequently the compression which it makes upon the contained air or gas must be proportionally diminished. Hence the gas furnished, during experiments from the machine, will not have the same density towards the end that it had at the beginning, as its specific gravity is continually diminishing. This difference may, it is true, be determined by calculation; but this would have occasioned such mathematical investigations as must have rendered the use of this apparatus both troublesome and difficult. Mr Meusnier has remedied this inconvenience by the following contrivance. A square rod of iron, 26, 27, Pl. VIII. Fig. 1. is raised perpendicular to the middle of the beam DE. This rod passes through a hollow box of brass 28, which opens, and may be filled with lead; and this box is made to slide alongst the rod, by means of a toothed pinion playing in a rack, so as to raise[Pg 315] or lower the box, and to fix it at such places as is judged proper.
The practice of measuring gas would still have faced significant challenges without the additional precautions mentioned earlier. When jar A sinks in the water of the cistern LMNO, it loses weight equal to the amount of water it displaces; consequently, the pressure it exerts on the air or gas inside it decreases proportionally. Thus, the gas produced during experiments from the machine will not have the same density at the end as it did at the beginning, since its specific gravity keeps dropping. This difference can be calculated, but doing so would lead to complicated mathematical investigations, making the use of this apparatus both annoying and challenging. Mr. Meusnier has addressed this issue with the following design. A square iron rod, 26, 27, Pl. VIII. Fig. 1, is positioned vertically in the middle of the beam DE. This rod goes through a hollow brass box 28, which can open and be filled with lead; the box can slide along the rod using a toothed pinion engaging with a rack, allowing it to raise or lower the box and set it at whatever position is deemed appropriate.
When the lever or beam DE stands horizontal, this box gravitates to neither side; but, when the jar A sinks into the cistern LMNO, so as to make the beam incline to that side, it is evident the loaded box 28, which then passes beyond the center of suspension, must gravitate to the side of the jar, and augment its pressure upon the included air. This is increased in proportion as the box is raised towards 27, because the same weight exerts a greater power in proportion to the length of the lever by which it acts. Hence, by moving the box 28 alongst the rod 26, 27, we can augment or diminish the correction it is intended to make upon the pressure of the jar; and both experience and calculation show that this may be made to compensate very exactly for the loss of weight in the jar at all degrees of pressure.
When the lever or beam DE is level, the box doesn't lean to either side. However, when the jar A sinks into the cistern LMNO, making the beam tilt to that side, it’s clear that the loaded box 28, which then moves past the center of suspension, must lean toward the jar, increasing the pressure on the air inside. This pressure rises as the box is lifted toward 27 because the same weight exerts more force based on the length of the lever it's acting on. So, by moving the box 28 along the rod 26, 27, we can increase or decrease the adjustment it’s supposed to make on the jar's pressure; both experience and calculations indicate that this can be finely tuned to offset the loss of weight in the jar at all pressure levels.
I have not hitherto explained the most important part of the use of this machine, which is the manner of employing it for ascertaining the quantities of the air or gas furnished during experiments. To determine this with the most rigorous precision, and likewise the quantity supplied to the machine from experiments, we fixed to the arc which terminates the arm of the beam E, Pl. VIII. Fig. 1. the brass sector l m, divided into degrees and half degrees,[Pg 316] which consequently moves in common with the beam; and the lowering of this end of the beam is measured by the fixed index 29, 30, which has a Nonius giving hundredth parts of a degree at its extremity 30.
I haven't yet explained the most crucial part of how to use this machine, which is how to measure the amounts of air or gas produced during experiments. To determine this with the highest precision, as well as the quantity supplied to the machine during experiments, we attached a brass sector l m, marked in degrees and half-degrees, to the arc at the end of the beam E, Pl. VIII. Fig. 1. This sector moves along with the beam, and the lowering of this end of the beam is measured by the fixed index 29, 30, which features a Nonius that gives measurements to the hundredth of a degree at its end 30.
The whole particulars of the different parts of the above described machine are represented in Plate VIII. as follow.
The complete details of the various parts of the machine described above are shown in Plate VIII as follows.
Fig. 2. Is the flat chain invented by Mr Vaucanson, and employed for suspending the scale or bason P, Fig. 1; but, as this lengthens or shortens according as it is more or less loaded, it would not have answered for suspending the jar A, Fig. 1.
Fig. 2. This is the flat chain created by Mr. Vaucanson, used for hanging the scale or basin P, Fig. 1; however, since it stretches or shrinks depending on how much weight it carries, it wouldn't have worked for supporting the jar A, Fig. 1.
Fig. 5. Is the chain i k m, which in Fig. 1. sustains the jar A. This is entirely formed of plates of polished iron interlaced into each other, and held together by iron pins. This chain does not lengthen in any sensible degree, by any weight it is capable of supporting.
Fig. 5. This is the chain i k m, which in Fig. 1 supports the jar A. It is entirely made of polished iron plates woven together and secured with iron pins. This chain doesn't stretch noticeably with any weight it can hold.
Fig. 6. The trivet, or three branched stirrup, by which the jar A is hung to the balance, with the screw by which it is fixed in an accurately vertical position.
Fig. 6. The trivet, or three-branched stirrup, used to hang jar A onto the balance, along with the screw that secures it in a perfectly vertical position.
Fig. 3. The iron rod 26, 27, which is fixed perpendicular to the center of the beam, with its box 28.
Fig. 3. The iron rod 26, 27, which is secured upright at the center of the beam, along with its box 28.
Fig. 7. & 8. The friction-wheels, with the plates of rock-cristal Z, as points of contact[Pg 317] by which the friction of the axis of the lever of the balance is avoided.
Fig. 7. & 8. The friction wheels, with the plates of rock crystal Z, serve as contact points[Pg 317] to prevent friction on the axis of the balance lever.
Fig. 4. The piece of metal which supports the axis of the friction-wheels.
Fig. 4. The metal part that holds the axis of the friction wheels.
Fig. 9. The middle of the lever or beam, with the axis upon which it moves.
Fig. 9. The center of the lever or beam, featuring the axle it rotates around.
Fig. 10. The thermometer for determining the temperature of the air or gas contained in the jar.
Fig. 10. The thermometer for measuring the temperature of the air or gas inside the jar.
When this gazometer is to be used, the cistern or external vessel, LMNO, Pl. VIII. Fig. 1. is to be filled with water to a determinate height, which should be the same in all experiments. The level of the water should be taken when the beam of the balance stands horizontal; this level, when the jar is at the bottom of the cistern, is increased by all the water which it displaces, and is diminished in proportion as the jar rises to its highest elevation. We next endeavour, by repeated trials, to discover at what elevation the box 28 must be fixed, to render the pressure equal in all situations of the beam. I should have said nearly, because this correction is not absolutely rigorous; and differences of a quarter, or even of half a line, are not of any consequence. This height of the box 28 is not the same for every degree of pressure, but varies according as this is of one, two, three, or more inches. All these should be registered with great order and precision.[Pg 318]
When using this gas meter, fill the cistern or external vessel, LMNO, Pl. VIII. Fig. 1, with water to a specific height, which should be consistent across all experiments. The water level should be measured when the balance beam is horizontal; this level increases with the water displaced by the jar when it’s at the bottom of the cistern and decreases as the jar rises to its highest point. Next, we try multiple times to determine the height at which the box 28 should be positioned to ensure equal pressure in all beam positions. I should say "almost," because this correction isn't completely exact; differences of a quarter or even half a line don't matter. The height for box 28 isn’t the same for every pressure level; it changes depending on whether the pressure is one, two, three, or more inches. All these measurements should be recorded systematically and accurately.[Pg 318]
We next take a bottle which holds eight or ten pints, the capacity of which is very accurately determined by weighing the water it is capable of containing. This bottle is turned bottom upwards, full of water, in the cistern of the pneumato chemical apparatus GHIK, Fig. 1. and is set on its mouth upon the shelf of the apparatus, instead of the glass jar V, having the extremity 11 of the tube 7, 8, 9, 10, 11, inserted into its mouth. The machine is fixed at zero of pressure, and the degree marked by the index 30 upon the sector m l is accurately observed; then, by opening the stop-cock 8, and pressing a little upon the jar A, as much air is forced into the bottle as fills it entirely. The degree marked by the index upon the sector is now observed, and we calculate what number of cubical inches correspond to each degree. We then fill a second and third bottle, and so on, in the same manner, with the same precautions, and even repeat the operation several times with bottles of different sizes, till at last, by accurate attention, we ascertain the exact gage or capacity of the jar A, in all its parts; but it is better to have it formed at first accurately cylindrical, by which we avoid these calculations and estimates.
Next, we take a bottle that holds eight or ten pints, and we determine its exact capacity by weighing the water it can hold. This bottle is turned upside down, filled with water, in the cistern of the pneumato-chemical apparatus GHIK, Fig. 1, and is placed mouth down on the shelf of the apparatus, replacing the glass jar V, with the end of tube 7, 8, 9, 10, 11 inserted into its mouth. The machine is set to zero pressure, and we carefully observe the degree marked by the index 30 on the sector m l; then, by opening the stop-cock 8 and applying a bit of pressure on jar A, we force enough air into the bottle to fill it completely. We then note the degree marked by the index on the sector and calculate how many cubic inches correspond to each degree. Next, we fill a second and third bottle in the same way, taking the same precautions, and even repeat the process several times with bottles of different sizes until we accurately determine the exact gauge or capacity of jar A in all its parts. However, it’s best to have it initially created as an accurate cylinder, which allows us to avoid these calculations and estimates.
The instrument I have been describing was constructed with great accuracy and uncommon skill by Mr Meignie junior, engineer and physical[Pg 319] instrument-maker. It is a most valuable instrument, from the great number of purposes to which it is applicable; and, indeed, there are many experiments which are almost impossible to be performed without it. It becomes expensive, because, in many experiments, such as the formation of water and of nitric acid, it is absolutely necessary to employ two of the same machines. In the present advanced state of chemistry, very expensive and complicated instruments are become indispensibly necessary for ascertaining the analysis and synthesis of bodies with the requisite precision as to quantity and proportion; it is certainly proper to endeavour to simplify these, and to render them less costly; but this ought by no means to be attempted at the expence of their conveniency of application, and much less of their accuracy.
The instrument I've been talking about was built with great precision and exceptional skill by Mr. Meignie junior, an engineer and physical instrument-maker. It's a very valuable tool because it can be used for a wide range of purposes, and there are many experiments that are nearly impossible to conduct without it. It becomes costly since, for many experiments, like creating water and nitric acid, you need to use two of the same machines. In today's advanced field of chemistry, expensive and complex instruments are essential for accurately analyzing and synthesizing substances in the right quantities and proportions. It's certainly important to try to simplify these instruments and make them more affordable, but this shouldn't be done at the expense of their ease of use or accuracy.
SECT. III.
Some other methods of measuring the volume of Gasses.
The gazometer described in the foregoing section is too costly and too complicated for being generally used in laboratories for measuring the gasses, and is not even applicable to every[Pg 320] circumstance of this kind. In numerous series of experiments, more simple and more readily applicable methods must be employed. For this purpose I shall describe the means I used before I was in possession of a gazometer, and which I still use in preference to it in the ordinary course of my experiments.
The gas meter mentioned in the previous section is too expensive and complicated to be widely used in labs for measuring gases, and it’s not suitable for every[Pg 320] situation of this type. In many experiments, simpler and more practical methods need to be used. For this reason, I will describe the methods I used before I had a gas meter, which I still prefer to use in my regular experiments.
Suppose that, after an experiment, there is a residuum of gas, neither absorbable by alkali nor water, contained in the upper part of the jar AEF, Pl. IV. Fig. 3. standing on the shelf of a pneumato-chemical apparatus, of which we wish to ascertain the quantity, we must first mark the height to which the mercury or water rises in the jar with great exactness, by means of slips of paper pasted in several parts round the jar. If we have been operating in mercury, we begin by displacing the mercury from the jar, by introducing water in its stead. This is readily done by filling a bottle quite full of water; having stopped it with your finger, turn it up, and introduce its mouth below the edge of the jar; then, turning down its body again, the mercury, by its gravity, falls into the bottle, and the water rises in the jar, and takes the place occupied by the mercury. When this is accomplished, pour so much water into the cistern ABCD as will stand about an inch over the surface of the mercury; then pass the dish BC, Pl. V. Fig. 9. under the jar, and carry it to the[Pg 321] water cistern, Fig. 1. and 2. We here exchange the gas into another jar, which has been previously graduated in the manner to be afterwards described; and we thus judge of the quantity or volume of the gas by means of the degrees which it occupies in the graduated jar.
Suppose that after an experiment, there's a leftover gas at the top of the jar AEF, Pl. IV. Fig. 3, which can't be absorbed by alkali or water, and we want to measure how much of it is there. First, we need to accurately mark how high the mercury or water rises in the jar by using slips of paper stuck to different parts around the jar. If we were working with mercury, we start by displacing it from the jar by filling a bottle completely with water. After capping the bottle with your finger, turn it upside down and place its opening below the edge of the jar. When you release your finger, the mercury will fall into the bottle, and the water will rise in the jar, taking the spot where the mercury was. Once that's done, pour enough water into the cistern ABCD so that it's about an inch above the surface of the mercury. Then, place the dish BC, Pl. V. Fig. 9 beneath the jar and move it to the [Pg 321] water cistern, Fig. 1. and 2. Here, we transfer the gas into another jar that has been measured beforehand, allowing us to assess the quantity or volume of the gas based on the scale marked on the graduated jar.
There is another method of determining the volume of gas, which may either be substituted in place of the one above described, or may be usefully employed as a correction or proof of that method. After the air or gas is exchanged from the first jar, marked with slips of paper, into the graduated jar, turn up the mouth of the marked jar, and fill it with water exactly to the marks EF, Pl. IV. Fig. 3. and by weighing the water we determine the volume of the air or gas it contained, allowing one cubical foot, or 1728 cubical inches, of water for each 70 pounds, French weight.
There’s another way to measure the volume of gas that can either replace the method described earlier or be used as a way to check or correct that method. After transferring the air or gas from the first jar, labeled with slips of paper, into the graduated jar, turn the labeled jar upside down and fill it with water up to the marks EF, Pl. IV. Fig. 3. By weighing the water, we can determine the volume of air or gas it held, using one cubic foot, or 1728 cubic inches, of water for every 70 pounds, French weight.
The manner of graduating jars for this purpose is very easy, and we ought to be provided with several of different sizes, and even several of each size, in case of accidents. Take a tall, narrow, and strong glass jar, and, having filled it with water in the cistern, Pl. V. Fig. 1. place it upon the shelf ABCD; we ought always to use the same place for this operation, that the level of the shelf may be always exactly similar, by which almost the only error to which this process is liable will be avoided. Then take a narrow[Pg 322] mouthed phial which holds exactly 6 oz. 3 gros 61 grs. of water, which corresponds to 10 cubical inches. If you have not one exactly of this dimension, choose one a little larger, and diminish its capacity to the size requisite, by dropping in a little melted wax and rosin. This bottle serves the purpose of a standard for gaging the jars. Make the air contained in this bottle pass into the jar, and mark exactly the place to which the water has descended; add another measure of air, and again mark the place of the water, and so on, till all the water be displaced. It is of great consequence that, during the course of this operation, the bottle and jar be kept at the same temperature with the water in the cistern; and, for this reason, we must avoid keeping the hands upon either as much as possible; or, if we suspect they have been heated, we must cool them by means of the water in the cistern. The height of the barometer and thermometer during this experiment is of no consequence.
The process for calibrating jars for this purpose is quite simple, and we should have several of different sizes, and even a few of each size, in case of accidents. Take a tall, narrow, and sturdy glass jar, fill it with water from the cistern, Pl. V. Fig. 1, and place it on the shelf ABCD. We should always use the same spot for this operation so that the shelf level remains consistent, which will help minimize errors in this process. Next, take a narrow-mouthed bottle that holds exactly 6 oz., 3 gros, and 61 grs. of water, which is equivalent to 10 cubic inches. If you don’t have one that’s exactly the right size, pick one that's slightly larger and reduce its capacity to the needed size by adding a bit of melted wax and rosin. This bottle will be our standard for measuring the jars. Let the air in the bottle enter the jar and mark exactly where the water level drops to; then add another measure of air and mark the new water level, and repeat this until all the water has been displaced. It’s crucial to keep the bottle and jar at the same temperature as the water in the cistern during this operation; for this reason, we should avoid touching either item as much as possible, or if we believe our hands have warmed them up, we should cool them with the cistern water. The height of the barometer and thermometer during this experiment doesn’t matter.
When the marks have been thus ascertained upon the jar for every ten cubical inches, we engrave a scale upon one of its sides, by means of a diamond pencil. Glass tubes are graduated in the same manner for using in the mercurial apparatus, only they must be divided into cubical inches, and tenths of a cubical inch. The bottle used for gaging these must hold[Pg 323] 8 oz. 6 gros 25 grs. of mercury, which exactly corresponds to a cubical inch of that metal.
When the marks have been determined on the jar for every ten cubic inches, we engrave a scale on one of its sides using a diamond pencil. Glass tubes are marked in the same way for use in the mercury apparatus, but they need to be divided into cubic inches and tenths of a cubic inch. The bottle used for measuring these must hold[Pg 323] 8 oz. 6 gros 25 grs. of mercury, which exactly equals one cubic inch of that metal.
The method of determining the volume of air or gas, by means of a graduated jar, has the advantage of not requiring any correction for the difference of height between the surface of the water within the jar, and in the cistern; but it requires corrections with respect to the height of the barometer and thermometer. But, when we ascertain the volume of air by weighing the water which the jar is capable of containing, up to the marks EF, it is necessary to make a farther correction, for the difference between the surface of the water in the cistern, and the height to which it rises within the jar. This will be explained in the fifth section of this chapter.
The method for measuring the volume of air or gas using a graduated jar has the advantage of not needing any adjustments for the difference in height between the water level inside the jar and in the cistern. However, it does require adjustments for the barometer and thermometer readings. When we find the volume of air by weighing the water the jar can hold up to the marks EF, we need to make an additional correction for the difference between the water level in the cistern and the height it reaches inside the jar. This will be explained in the fifth section of this chapter.
SECT. IV.
Of the method of Separating the different Gasses from each other.
As experiments often produce two, three, or more species of gas, it is necessary to be able to separate these from each other, that we may ascertain the quantity and species of each. Suppose that under the jar A, Pl. IV. Fig. 3. is[Pg 324] contained a quantity of different gasses mixed together, and standing over mercury, we begin by marking with slips of paper, as before directed, the height at which the mercury stands within the glass; then introduce about a cubical inch of water into the jar, which will swim over the surface of the mercury: If the mixture of gas contains any muriatic or sulphurous acid gas, a rapid and considerable absorption will instantly take place, from the strong tendency these two gasses have, especially the former, to combine with, or be absorbed by water. If the water only produces a slight absorption of gas hardly equal to its own bulk, we conclude, that the mixture neither contains muriatic acid, sulphuric acid, or ammoniacal gas, but that it contains carbonic acid gas, of which water only absorbs about its own bulk. To ascertain this conjecture, introduce some solution of caustic alkali, and the carbonic acid gas will be gradually absorbed in the course of a few hours; it combines with the caustic alkali or potash, and the remaining gas is left almost perfectly free from any sensible residuum of carbonic acid gas.
As experiments often produce two, three, or more types of gas, it's essential to separate them from one another so we can measure the amount and type of each. Let's say that under the jar A, Pl. IV. Fig. 3. is[Pg 324] a mix of different gases. We start by marking with slips of paper, as previously instructed, the height at which the mercury stands inside the glass. Then, we introduce about a cubic inch of water into the jar, which will float on the surface of the mercury. If the gas mixture contains muriatic or sulfurous acid gas, there will be rapid and significant absorption because these gases, especially muriatic acid, have a strong tendency to combine with or be absorbed by water. If the water only slightly absorbs gas, not much more than its own volume, we can conclude that the mixture doesn't contain muriatic acid, sulfuric acid, or ammoniacal gas, but has carbonic acid gas, which water only absorbs about its own volume. To verify this assumption, add a solution of caustic alkali, and the carbonic acid gas will be gradually absorbed over a few hours; it combines with the caustic alkali or potash, leaving the remaining gas almost completely free of any noticeable residue of carbonic acid gas.
After each experiment of this kind, we must carefully mark the height at which the mercury stands within the jar, by slips of paper pasted on, and varnished over when dry, that they may not be washed off when placed in the water apparatus.[Pg 325] It is likewise necessary to register the difference between the surface of the mercury in the cistern and that in the jar, and the height of the barometer and thermometer, at the end of each experiment.
After every experiment like this, we need to clearly mark the height of the mercury in the jar using strips of paper that are glued on and varnished once dry, so they don’t wash off when put in the water setup.[Pg 325] It's also important to record the difference between the mercury surface in the cistern and the one in the jar, along with the readings of the barometer and thermometer at the end of each experiment.
When all the gas or gasses absorbable by water and potash are absorbed, water is admitted into the jar to displace the mercury; and, as is described in the preceding section, the mercury in the cistern is to be covered by one or two inches of water. After this, the jar is to be transported by means of the flat dish BC, Pl. V. Fig. 9. into the water apparatus; and the quantity of gas remaining is to be ascertained by changing it into a graduated jar. After this, small trials of it are to be made by experiments in little jars, to ascertain nearly the nature of the gas in question. For instance, into a small jar full of the gas, Fig. 8. Pl. V. a lighted taper is introduced; if the taper is not immediately extinguished, we conclude the gas to contain oxygen gas; and, in proportion to the brightness of the flame, we may judge if it contain less or more oxygen gas than atmospheric air contains. If, on the contrary, the taper be instantly extinguished, we have strong reason to presume that the residuum is chiefly composed of azotic gas. If, upon the approach of the taper, the gas takes fire and burns quietly at the surface with a white flame, we conclude it to be[Pg 326] pure hydrogen gas; if this flame is blue, we judge it consists of carbonated hydrogen gas; and, if it takes fire with a sudden deflagration, that it is a mixture of oxygen and hydrogen gas. If, again, upon mixing a portion of the residuum with oxygen gas, red fumes are produced, we conclude that it contains nitrous gas.
When all the gases that can be absorbed by water and potash have been absorbed, water is added to the jar to push out the mercury. As mentioned in the previous section, the mercury in the cistern should be covered by one to two inches of water. After that, the jar is moved using the flat dish BC, Pl. V. Fig. 9 into the water apparatus, and the amount of gas left is measured by transferring it to a graduated jar. Following this, small tests should be conducted in smaller jars to estimate the type of gas in question. For example, if a lighted taper is placed into a small jar filled with the gas, as shown in Fig. 8. Pl. V, and the taper does not go out right away, we can conclude that the gas contains oxygen; the brightness of the flame can help us determine whether it has more or less oxygen than the air we breathe. Conversely, if the taper goes out instantly, we have good reason to believe that the leftover gas is mostly nitrogen. If the gas ignites and burns steadily at the surface with a white flame when the taper is brought near, we conclude it is[Pg 326] pure hydrogen gas; if the flame is blue, we can deduce that it contains carbonated hydrogen gas; and if it ignites with a loud bang, it indicates a mixture of oxygen and hydrogen gas. Lastly, if a portion of the leftover gas is mixed with oxygen gas and produces red fumes, we can conclude that it contains nitrous gas.
These preliminary trials give some general knowledge of the properties of the gas, and nature of the mixture, but are not sufficient to determine the proportions and quantities of the several gasses of which it is composed. For this purpose all the methods of analysis must be employed; and, to direct these properly, it is of great use to have a previous approximation by the above methods. Suppose, for instance, we know that the residuum consists of oxygen and azotic gas mixed together, put a determinate quantity, 100 parts, into a graduated tube of ten or twelve lines diameter, introduce a solution of sulphuret of potash in contact with the gas, and leave them together for some days; the sulphuret absorbs the whole oxygen gas, and leaves the azotic gas pure.
These initial tests provide some basic insights into the properties of the gas and the nature of the mixture, but they aren't enough to accurately determine the proportions and amounts of the different gases it contains. To do that, all analysis methods need to be used, and having a rough estimate from the earlier methods is very helpful for guiding this process. For example, if we know that the residue consists of a mix of oxygen and nitrogen gas, we can take a specific amount, like 100 parts, and put it into a graduated tube that’s about ten or twelve millimeters in diameter. Then, we introduce a solution of potassium sulfide in contact with the gas and let them sit together for several days; the potassium sulfide will absorb all the oxygen gas, leaving the nitrogen gas in its pure form.
If it is known to contain hydrogen gas, a determinate quantity is introduced into Volta's eudiometer alongst with a known proportion of hydrogen gas; these are deflagrated together by means of the electrical spark; fresh portions of oxygen gas are successively added, till no farther[Pg 327] deflagration takes place, and till the greatest possible diminution is produced. By this process water is formed, which is immediately absorbed by the water of the apparatus; but, if the hydrogen gas contain charcoal, carbonic acid is formed at the same time, which is not absorbed so quickly; the quantity of this is readily ascertained by assisting its absorption, by means of agitation. If the residuum contains nitrous gas, by adding oxygen gas, with which it combines into nitric acid, we can very nearly ascertain its quantity, from the diminution produced by this mixture.
If it’s known to contain hydrogen gas, a specific amount is added to Volta's eudiometer along with a known amount of oxygen gas; these are ignited together using an electrical spark. Fresh amounts of oxygen gas are then added one after another until no further reaction occurs and the maximum reduction is achieved. This process creates water, which is immediately absorbed by the water in the apparatus. However, if the hydrogen gas contains carbon, carbon dioxide is produced at the same time, which is absorbed more slowly; the amount of this can be easily measured by promoting its absorption through stirring. If the remaining gas contains nitric oxide, we can determine its quantity by adding oxygen gas, which combines to form nitric acid, based on the reduction observed from this mixture.
I confine myself to these general examples, which are sufficient to give an idea of this kind of operations; a whole volume would not serve to explain every possible case. It is necessary to become familiar with the analysis of gasses by long experience; we must even acknowledge that they mostly possess such powerful affinities to each other, that we are not always certain of having separated them completely. In these cases, we must vary our experiments in every possible point of view, add new agents to the combination, and keep out others, and continue our trials, till we are certain of the truth and exactitude of our conclusions.[Pg 328]
I stick to these general examples, which are enough to give an idea of this type of operation; a whole book wouldn’t cover every possible case. It’s essential to get used to analyzing gases through extensive experience; we have to recognize that they often have such strong affinities with one another that we can’t always be sure we’ve completely separated them. In these situations, we need to vary our experiments from every possible angle, add new agents to the mix, exclude others, and keep testing until we're confident in the accuracy and truth of our conclusions.[Pg 328]
SECT. V.
Of the necessary corrections upon the volume of the Gasses, according to the pressure of the Atmosphere.
All elastic fluids are compressible or condensible in proportion to the weight with which they are loaded. Perhaps this law, which is ascertained by general experience, may suffer some irregularity when these fluids are under a degree of condensation almost sufficient to reduce them to the liquid state, or when either in a state of extreme rarefaction or condensation; but we seldom approach either of these limits with most of the gasses which we submit to our experiments. I understand this proposition of gasses being compressible, in proportion to their superincumbent weights, as follows:
All elastic gases can be compressed or condensed based on the weight they're subjected to. This rule, which is supported by general experience, might show some inconsistencies when these gases are almost condensed enough to become liquid, or when they're extremely rarefied or condensed. However, we rarely reach either of these extremes with most of the gases we test. I interpret this idea of gases being compressible, in relation to the pressure above them, as follows:
A barometer, which is an instrument generally known, is, properly speaking, a species of syphon, ABCD, Pl. XII. Fig. 16. whose leg AB is filled with mercury, whilst the leg CD is full of air. If we suppose the branch CD indefinitely continued till it equals the height of our atmosphere, we can readily conceive that the barometer is, in reality, a sort of balance, in which[Pg 329] a column of mercury stands in equilibrium with a column of air of the same weight. But it is unnecessary to prolongate the branch CD to such a height, as it is evident that the barometer being immersed in air, the column of mercury AB will be equally in equilibrium with a column of air of the same diameter, though the leg CD be cut off at C, and the part CD be taken away altogether.
A barometer, which is a commonly known instrument, is essentially a type of siphon, ABCD, Pl. XII. Fig. 16. One leg, AB, is filled with mercury, while the other leg, CD, is filled with air. If we imagine the branch CD extended indefinitely until it matches the height of our atmosphere, we can easily understand that the barometer is essentially a balance where[Pg 329] a column of mercury is balanced by a column of air of the same weight. However, it's not necessary to extend branch CD to that height, as it's clear that since the barometer is in air, the mercury column AB will still be in equilibrium with a column of air of the same diameter, even if the leg CD is cut off at C and the segment CD is completely removed.
The medium height of mercury in equilibrium with the weight of a column of air, from the highest part of the atmosphere to the surface of the earth is about twenty-eight French inches in the lower parts of the city of Paris; or, in other words, the air at the surface of the earth at Paris is usually pressed upon by a weight equal to that of a column of mercury twenty-eight inches in height. I must be understood in this way in the several parts of this publication when talking of the different gasses, as, for instance, when the cubical foot of oxygen gas is said to weigh 1 oz. 4 gros, under 28 inches pressure. The height of this column of mercury, supported by the pressure of the air, diminishes in proportion as we are elevated above the surface of the earth, or rather above the level of the sea, because the mercury can only form an equilibrium with the column of air which is above it, and is not in the smallest[Pg 330] degree affected by the air which is below its level.
The average height of mercury in balance with the weight of a column of air, from the highest part of the atmosphere down to the Earth's surface, is about twenty-eight French inches in the lower parts of Paris. In other words, the air at sea level in Paris is typically pressed down by a weight equivalent to a twenty-eight-inch tall column of mercury. This is how I should be understood throughout this publication when discussing various gases—for instance, when we say that a cubic foot of oxygen gas weighs 1 oz. 4 gros under 28 inches of pressure. The height of this mercury column, supported by the air pressure, decreases as we rise above the Earth's surface or, more precisely, above sea level, because the mercury can only be in balance with the column of air above it and is not affected at all by the air below its level.
In what ratio does the mercury in the barometer descend in proportion to its elevation? or, what is the same thing, according to what law or ratio do the several strata of the atmosphere decrease in density? This question, which has exercised the ingenuity of natural philosophers during last century, is considerably elucidated by the following experiment.
In what ratio does the mercury in the barometer drop in relation to its height? Or, similarly, according to what law or ratio do the different layers of the atmosphere diminish in density? This question, which has challenged the creativity of natural philosophers over the last century, is significantly clarified by the following experiment.
If we take the glass syphon ABCDE, Pl. XII. Fig. 17. shut at E, and open at A, and introduce a few drops of mercury, so as to intercept the communication of air between the leg AB and the leg BE, it is evident that the air contained in BCDE is pressed upon, in common with the whole surrounding air, by a weight or column of air equal to 28 inches of mercury. But, if we pour 28 inches of mercury into the leg AB, it is plain the air in the branch BCDE will now be pressed upon by a weight equal to twice 28 inches of mercury, or twice the weight of the atmosphere; and experience shows, that, in this case, the included air, instead of filling the tube from B to E, only occupies from C to E, or exactly one half of the space it filled before. If to this first column of mercury we add two other portions of 28 inches each, in the branch AB, the air in the branch BCDE will be pressed upon by four times the weight of the[Pg 331] atmosphere, or four times the weight of 28 inches of mercury, and it will then only fill the space from D to E, or exactly one quarter of the space it occupied at the commencement of the experiment. From these experiments, which may be infinitely varied, has been deduced as a general law of nature, which seems applicable to all permanently elastic fluids, that they diminish in volume in proportion to the weights with which they are pressed upon; or, in other words, "the volume of all elastic fluids is in the inverse ratio of the weight by which they are compressed."
If we take the glass siphon ABCDE, Pl. XII. Fig. 17, closed at E and open at A, and add a few drops of mercury to block the air connection between leg AB and leg BE, it's clear that the air in BCDE is being compressed along with all the surrounding air by a weight or column of air equal to 28 inches of mercury. However, if we pour 28 inches of mercury into leg AB, it's obvious that the air in branch BCDE will now be compressed by a weight equal to twice 28 inches of mercury, or double the weight of the atmosphere. Experience shows that, in this scenario, the air inside only fills the tube from B to E and occupies space from C to E, which is exactly half of what it occupied before. If we then add two more columns of 28 inches each to branch AB, the air in branch BCDE will be compressed by four times the weight of the atmosphere, or four times the weight of 28 inches of mercury, and it will only fill the space from D to E, or one quarter of the space it initially occupied at the start of the experiment. From these experiments, which can be varied infinitely, a general law of nature has been derived, which seems to apply to all permanently elastic fluids: they decrease in volume relative to the weights they are subjected to; or, in other words, "the volume of all elastic fluids is inversely proportional to the weight by which they are compressed."
The experiments which have been made for measuring the heights of mountains by means of the barometer, confirm the truth of these deductions; and, even supposing them in some degree inaccurate, these differences are so extremely small, that they may be reckoned as nullities in chemical experiments. When this law of the compression of elastic fluids is once well understood, it becomes easily applicable to the corrections necessary in pneumato chemical experiments upon the volume of gas, in relation to its pressure. These corrections are of two kinds, the one relative to the variations of the barometer, and the other for the column of water or mercury contained in the jars. I shall endeavour to explain these by examples, beginning with the most simple case.[Pg 332]
The experiments done to measure the heights of mountains using a barometer confirm the validity of these conclusions. Even if there are some inaccuracies, the differences are so tiny that they can be considered negligible in chemical experiments. Once we fully understand the law of elastic fluid compression, it becomes easy to apply it to the necessary corrections in pneumatic chemical experiments regarding gas volume in relation to pressure. There are two types of corrections: one related to changes in the barometer and the other for the water or mercury column in the jars. I will try to explain these with examples, starting with the simplest case.[Pg 332]
Suppose that 100 cubical inches of oxygen gas are obtained at 10° (54.5°) of the thermometer, and at 28 inches 6 lines of the barometer, it is required to know what volume the 100 cubical inches of gas would occupy, under the pressure of 28 inches[58], and what is the exact weight of the 100 inches of oxygen gas? Let the unknown volume, or the number of inches this gas would occupy at 28 inches of the barometer, be expressed by x; and, since the volumes are in the inverse ratio of their superincumbent weights, we have the following statement: 100 cubical inches is to x inversely as 28.5 inches of pressure is to 28.0 inches; or directly 28 : 28.5 :: 100 : x = 101.786—cubical inches, at 28 inches barometrical pressure; that is to say, the same gas or air which at 28.5 inches of the barometer occupies 100 cubical inches of volume, will occupy 101.786 cubical inches when the barometer is at 28 inches. It is equally easy to calculate the weight of this gas, occupying 100 cubical inches, under 28.5 inches of barometrical pressure; for, as it corresponds[Pg 333] to 101.786 cubical inches at the pressure of 28, and as, at this pressure, and at 10° (54.5°) of temperature, each cubical inch of oxygen gas weighs half a grain, it follows, that 100 cubical inches, under 28.5 barometrical pressure, must weigh 50.893 grains. This conclusion might have been formed more directly, as, since the volume of elastic fluids is in the inverse ratio of their compression, their weights must be in the direct ratio of the same compression: Hence, since 100 cubical inches weigh 50 grains, under the pressure of 28 inches, we have the following statement to determine the weight of 100 cubical inches of the same gas as 28.5 barometrical pressure, 28 : 50 :: 28.5 : x, the unknown quantity, = 50.893.
Suppose we have 100 cubic inches of oxygen gas at 10° (54.5°) and 28 inches 6 lines on the barometer. We need to find out what volume the 100 cubic inches of gas would occupy under the pressure of 28 inches[58], and what the exact weight of that gas is. Let the unknown volume, or the number of inches this gas would take up at 28 inches of barometric pressure, be represented by x; since the volumes are inversely proportional to their weights, we have the following relationship: 100 cubic inches is to x inversely as 28.5 inches of pressure is to 28.0 inches; or directly, 28 : 28.5 :: 100 : x = 101.786 cubic inches at 28 inches barometric pressure. This means that the same gas that occupies 100 cubic inches at 28.5 inches of the barometer will take up 101.786 cubic inches at 28 inches. It’s also straightforward to calculate the weight of this gas occupying 100 cubic inches under 28.5 inches of barometric pressure; since it corresponds to 101.786 cubic inches at that pressure, and at 10° (54.5°), each cubic inch of oxygen gas weighs half a grain, we can conclude that 100 cubic inches under 28.5 inches of barometric pressure must weigh 50.893 grains. This result could have been reached more directly, because the volume of gases is inversely related to their compression, implying their weights are directly proportional to the same compression. Therefore, since 100 cubic inches weigh 50 grains under 28 inches pressure, we can set up this equation to find the weight of 100 cubic inches of the same gas at 28.5 inches of barometric pressure: 28 : 50 :: 28.5 : x, the unknown quantity, = 50.893.
The following case is more complicated: Suppose the jar A, Pl. XII. Fig. 18. to contain a quantity of gas in its upper part ACD, the rest of the jar below CD being full of mercury, and the whole standing in the mercurial bason or reservoir GHIK, filled with mercury up to EF, and that the difference between the surface CD of the mercury in the jar, and EF, that in the cistern, is six inches, while the barometer stands at 27.5 inches. It is evident from these data, that the air contained in ACD is pressed upon by the weight of the atmosphere, diminished by the weight of the column of mercury CE, or by 27.5 - 6 = 21.5 inches of barometrical[Pg 334] pressure. This air is therefore less compressed than the atmosphere at the mean height of the barometer, and consequently occupies more space than it would occupy at the mean pressure, the difference being exactly proportional to the difference between the compressing weights. If, then, upon measuring the space ACD, it is found to be 120 cubical inches, it must be reduced to the volume which it would occupy under the mean pressure of 28 inches. This is done by the following statement: 120 : x, the unknown volume, :: 21.5 : 28 inversely; this gives x = 120 × 21.5 / 28 = 92.143 cubical inches.
The following case is more complicated: Imagine jar A, Pl. XII. Fig. 18, contains a volume of gas in its upper section ACD, while the rest of the jar below CD is filled with mercury. The entire setup is positioned in the mercury basin or reservoir GHIK, which is filled with mercury up to EF. There is a six-inch difference between the surface CD of the mercury in the jar and EF, the level in the cistern, while the barometer reads 27.5 inches. From this information, we can see that the air in ACD is being compressed by the weight of the atmosphere, reduced by the weight of the mercury column CE, or by 27.5 - 6 = 21.5 inches of barometric pressure. This means the air is less compressed than the atmosphere at the average barometric height and therefore takes up more space than it would at that average pressure. The difference in volume is directly proportional to the difference in compressive weights. So, if measuring the volume of ACD reveals it to be 120 cubic inches, it should be adjusted to reflect the volume it would occupy under the average pressure of 28 inches. This can be calculated as follows: 120 : x, the unknown volume, :: 21.5 : 28 inversely; this results in x = 120 × 21.5 / 28 = 92.143 cubic inches.
In these calculations we may either reduce the height of the mercury in the barometer, and the difference of level in the jar and bason, into lines or decimal fractions of the inch; but I prefer the latter, as it is more readily calculated. As, in these operations, which frequently recur, it is of great use to have means of abbreviation, I have given a table in the appendix for reducing lines and fractions of lines into decimal fractions of the inch.
In these calculations, we can either convert the height of the mercury in the barometer and the difference in level between the jar and basin into lines or decimal fractions of an inch. I prefer the latter because it's easier to calculate. Since these operations come up often, it's really helpful to have a way to simplify things, so I've included a table in the appendix for converting lines and fractions of lines into decimal fractions of an inch.
In experiments performed in the water-apparatus, we must make similar corrections to procure rigorously exact results, by taking into account, and making allowances for the difference of height of the water within the jar above the surface of the water in the cistern. But, as the[Pg 335] pressure of the atmosphere is expressed in inches and lines of the mercurial barometer, and, as homogeneous quantities only can be calculated together, we must reduce the observed inches and lines of water into correspondent heights of the mercury. I have given a table in the appendix for this conversion, upon the supposition that mercury is 13.5681 times heavier than water.
In experiments conducted with the water apparatus, we need to make similar adjustments to obtain highly accurate results by considering and accounting for the height difference of the water in the jar above the surface of the water in the cistern. However, since atmospheric pressure is measured in inches and lines of the mercury barometer, and since only homogeneous quantities can be calculated together, we need to convert the observed inches and lines of water into equivalent mercury heights. I've included a table in the appendix for this conversion, based on the assumption that mercury is 13.5681 times heavier than water.
SECT. VI.
Of Corrections relative to the Degrees of the Thermometer.
In ascertaining the weight of gasses, besides reducing them to a mean of barometrical pressure, as directed in the preceding section, we must likewise reduce them to a standard thermometrical temperature; because, all elastic fluids being expanded by heat, and condensed by cold, their weight in any determinate volume is thereby liable to considerable alterations. As the temperature of 10° (54.5°) is a medium between the heat of summer and the cold of winter, being the temperature of subterraneous places, and that which is most easily approached to at all seasons, I have chosen that degree as a mean to which I reduce air or gas in this species of calculation.[Pg 336]
In measuring the weight of gases, in addition to adjusting them to an average barometric pressure as explained in the previous section, we also need to adjust them to a standard temperature. Since all gases expand when heated and contract when cooled, their weight in any given volume can change significantly. I've chosen a temperature of 10° (54.5°) as a standard because it’s a midway point between summer heat and winter cold, representing the temperature found underground, which is also the most consistently achievable at any time of year. This is the temperature to which I will reduce air or gas in these calculations.[Pg 336]
Mr de Luc found that atmospheric air was increased 1/215 part of its bulk, by each degree of a mercurial thermometer, divided into 81 degrees, between the freezing and boiling points; this gives 1/211 part for each degree of Reaumur's thermometer, which is divided into 80 degrees between these two points. The experiments of Mr Monge seem to make this dilatation less for hydrogen gas, which he thinks is only dilated 1/180. We have not any exact experiments hitherto published respecting the ratio of dilatation of the other gasses; but, from the trials which have been made, their dilatation seems to differ little from that of atmospheric air. Hence I may take for granted, till farther experiments give us better information upon this subject, that atmospherical air is dilated 1/210 part, and hydrogen gas 1/190 part for each degree of the thermometer; but, as there is still great uncertainty upon this point, we ought always to operate in a temperature as near as possible to the standard of 10°, (54.5°) by this means any errors in correcting the weight or volume of gasses by reducing them to the common standard, will become of little moment.
Mr. de Luc discovered that atmospheric air expands by 1/215 of its volume for each degree on a mercury thermometer, which is marked from 0 to 81 degrees between the freezing and boiling points. This translates to 1/211 for each degree on Reaumur's thermometer, which is marked from 0 to 80 degrees between the same two points. Mr. Monge's experiments suggest that hydrogen gas expands even less, at only 1/180. So far, there haven't been any precise experiments published on the expansion of other gases, but based on the tests that have been conducted, their expansion seems to be quite similar to that of atmospheric air. Therefore, I can assume, until further tests provide more accurate information, that atmospheric air expands by 1/210 and hydrogen gas by 1/190 for each degree on the thermometer. However, since there is still significant uncertainty on this topic, we should always conduct experiments at a temperature as close as possible to the standard of 10° (54.5°). This way, any errors in adjusting the weight or volume of gases to the common standard will be minimal.
The calculation for this correction is extremely easy. Divide the observed volume of air by 210, and multiply the quotient by the degrees of temperature above or below 10°[Pg 337] (54.5°). This correction is negative when the actual temperature is above the standard, and positive when below. By the use of logarithmical tables this calculation is much facilitated[59].
The calculation for this correction is really simple. Just divide the observed volume of air by 210, and then multiply the result by how many degrees the temperature is above or below 10°[Pg 337] (54.5°). This correction is negative when the actual temperature is above the standard and positive when it’s below. Using logarithm tables makes this calculation much easier[59].
SECT. VII.
Example for calculating the Corrections relative to the Variations of Pressure and Temperature.
CASE.
In the jar A, Pl. IV. Fig. 3. standing in a water apparatus, is contained 353 cubical inches of air; the surface of the water within the jar at EF is 4-1/2 inches above the water in the cistern, the barometer is at 27 inches 9-1/2 lines, and the thermometer at 15° (65.75°). Having burnt a quantity of phosphorus in the air, by which concrete phosphoric acid is produced, the air after the combustion occupies 295 cubical[Pg 338] inches, the water within the jar stands 7 inches above that in the cistern, the barometer is at 27 inches 9-1/4 lines, and the thermometer at 16° (68°). It is required from these data to determine the actual volume of air before and after combustion, and the quantity absorbed during the process.
In jar A, Pl. IV. Fig. 3, which is part of a water apparatus, there are 353 cubic inches of air. The water level in the jar at EF is 4.5 inches above the water in the cistern, the barometer measures 27 inches and 9.5 lines, and the thermometer reads 15° (65.75°). After burning some phosphorus in the air, which produces solid phosphoric acid, the air in the jar now takes up 295 cubic[Pg 338] inches, the water level in the jar is 7 inches above that in the cistern, the barometer shows 27 inches and 9.25 lines, and the thermometer reads 16° (68°). From this data, we need to determine the actual volume of air before and after combustion, as well as the amount absorbed during the process.
Calculation before Combustion.
The air in the jar before combustion was 353 cubical inches, but it was only under a barometrical pressure of 27 inches 9-1/2 lines; which, reduced to decimal fractions by Tab. I. of the Appendix, gives 27.79167 inches; and from this we must deduct the difference of 4-1/2 inches of water, which, by Tab. II. corresponds to 0.33166 inches of the barometer; hence the real pressure of the air in the jar is 27.46001. As the volume of elastic fluids diminish in the inverse ratio of the compressing weights, we have the following statement to reduce the 353 inches to the volume the air would occupy at 28 inches barometrical pressure.
The air in the jar before combustion was 353 cubic inches, but it was only at a barometric pressure of 27 inches 9-1/2 lines; which, when converted to decimal fractions using Table I of the Appendix, gives 27.79167 inches. From this, we need to subtract the difference of 4-1/2 inches of water, which, according to Table II, corresponds to 0.33166 inches on the barometer. Thus, the actual pressure of the air in the jar is 27.46001. Since the volume of gases decreases in the opposite ratio to the compressing weights, we can use the following statement to convert the 353 inches to the volume the air would occupy at a barometric pressure of 28 inches.
353 : x, the unknown volume, :: 27.46001 : 28. Hence, x = 353 × 27.46001 / 28 = 346.192 cubical inches, which is the volume the same quantity of air would have occupied at 28 inches of the barometer.[Pg 339]
353 : x, the unknown volume, :: 27.46001 : 28. So, x = 353 × 27.46001 / 28 = 346.192 cubic inches, which is the volume the same amount of air would have taken up at 28 inches on the barometer.[Pg 339]
The 210th part of this corrected volume is 1.65, which, for the five degrees of temperature above the standard gives 8.255 cubical inches; and, as this correction is subtractive, the real corrected volume of the air before combustion is 337.942 inches.
The 210th part of this corrected volume is 1.65, which, for the five degrees of temperature above the standard gives 8.255 cubic inches; and since this correction is subtractive, the actual corrected volume of the air before combustion is 337.942 inches.
Calculation after Combustion.
By a similar calculation upon the volume of air after combustion, we find its barometrical pressure 27.77083 - 0.51593 = 27.25490. Hence, to have the volume of air under the pressure of 28 inches, 295 : x :: 27.77083 : 28 inversely; or, x = 295 x 27.25490 / 28 = 287.150. The 210th part of this corrected volume is 1.368, which, multiplied by 6 degrees of thermometrical difference, gives the subtractive correction for temperature 8.208, leaving the actual corrected volume of air after combustion 278.942 inches.
By a similar calculation based on the volume of air after combustion, we find its barometric pressure to be 27.77083 - 0.51593 = 27.25490. Therefore, to determine the volume of air at a pressure of 28 inches, we set up the ratio 295 : x :: 27.77083 : 28 inversely; thus, x = 295 x 27.25490 / 28 = 287.150. The 210th part of this corrected volume is 1.368, which, when multiplied by a 6-degree temperature difference, results in a subtractive correction for temperature of 8.208, leaving the actual corrected volume of air after combustion at 278.942 inches.
Result.
The corrected volume before combustion | 337.942 |
Ditto remaining after combustion | 278.942 |
———— | |
Volume absorbed during combustion | 59.000. |
SECT. VIII.
Method of determining the Absolute Gravity of the different Gasses.
Take a large balloon A, Pl. V. Fig. 10. capable of holding 17 or 18 pints, or about half a cubical foot, having the brass cap bcde strongly cemented to its neck, and to which the tube and stop-cock f g is fixed by a tight screw. This apparatus is connected by the double screw represented separately at Fig. 12. to the jar BCD, Fig. 10. which must be some pints larger in dimensions than the balloon. This jar is open at top, and is furnished with the brass cap h i, and stop-cock l m. One of these slop-cocks is represented separately at Fig. 11.
Take a large balloon A, Pl. V. Fig. 10, that can hold 17 or 18 pints, or about half a cubic foot, with the brass cap bcde securely attached to its neck, and the tube and stop-cock f g connected by a tight screw. This setup is linked by the double screw shown separately in Fig. 12 to the jar BCD, Fig. 10, which needs to be a few pints larger than the balloon. This jar is open at the top and has the brass cap h i and stop-cock l m. One of these stop-cocks is shown separately in Fig. 11.
We first determine the exact capacity of the balloon by filling it with water, and weighing it both full and empty. When emptied of water, it is dried with a cloth introduced through its neck d e, and the last remains of moisture are removed by exhausting it once or twice in an air-pump.
We start by figuring out the exact capacity of the balloon by filling it with water and weighing it when it’s full and when it’s empty. After draining the water, we dry it with a cloth inserted through its neck d e, and the last bits of moisture are removed by using an air vacuum a couple of times.
When the weight of any gas is to be ascertained, this apparatus is used as follows: Fix the balloon A to the plate of an air-pump by means of the screw of the stop-cock f g, which is[Pg 341] left open; the balloon is to be exhausted as completely as possible, observing carefully the degree of exhaustion by means of the barometer attached to the air-pump. When the vacuum is formed, the stop-cock f g is shut, and the weight of the balloon determined with the most scrupulous exactitude. It is then fixed to the jar BCD, which we suppose placed in water in the shelf of the pneumato chemical apparatus Fig. 1.; the jar is to be filled with the gas we mean to weigh, and then, by opening the stop-cocks f g and l m, the gas ascends into the balloon, whilst the water of the cistern rises at the same time into the jar. To avoid very troublesome corrections, it is necessary, during this first part of the operation, to sink the jar in the cistern till the surfaces of the water within the jar and without exactly correspond. The stop-cocks are again shut, and the balloon being unscrewed from its connection with the jar, is to be carefully weighed; the difference between this weight and that of the exhausted balloon is the precise weight of the air or gas contained in the balloon. Multiply this weight by 1728, the number of cubical inches in a cubical foot, and divide the product by the number of cubical inches contained in the balloon, the quotient is the weight of a cubical foot of the gas or air submitted to experiment.[Pg 342]
When you need to determine the weight of any gas, use this apparatus as follows: Attach balloon A to the air pump's plate using the screw on stop-cock f g, which should be left open. Exhaust the balloon as completely as possible, carefully checking the level of exhaustion with the barometer attached to the air pump. Once the vacuum is created, close the stop-cock f g, and accurately weigh the balloon. Then, connect it to jar BCD, which we assume is placed in water on the shelf of the pneumato-chemical apparatus Fig. 1. Fill the jar with the gas you want to weigh, and then, by opening stop-cocks f g and l m, allow the gas to rise into the balloon while the water in the cistern simultaneously rises into the jar. To avoid complicated adjustments, it’s crucial during this first part of the process to lower the jar into the cistern until the water levels inside and outside the jar are exactly even. Close the stop-cocks again, and after unscrewing the balloon from its connection with the jar, weigh it carefully. The difference between this weight and that of the empty balloon gives you the exact weight of the air or gas in the balloon. Multiply this weight by 1728, the number of cubic inches in a cubic foot, and divide the result by the number of cubic inches in the balloon; the quotient will be the weight of a cubic foot of the gas or air being tested.[Pg 342]
Exact account must be kept of the barometrical height and temperature of the thermometer during the above experiment; and from these the resulting weight of a cubical foot is easily corrected to the standard of 28 inches and 10°, as directed in the preceding section. The small portion of air remaining in the balloon after forming the vacuum must likewise be attended to, which is easily determined by the barometer attached to the air-pump. If that barometer, for instance, remains at the hundredth part of the height it stood at before the vacuum was formed, we conclude that one hundredth part of the air originally contained remained in the balloon, and consequently that only 99/100 of gas was introduced from the jar into the balloon.
An accurate record must be kept of the barometric pressure and temperature of the thermometer during the above experiment; from this information, the resulting weight of a cubic foot can be easily adjusted to the standard of 28 inches and 10°, as outlined in the previous section. The small amount of air left in the balloon after creating the vacuum also needs to be monitored, which can be easily measured with the barometer attached to the air pump. For example, if that barometer reads at one-hundredth of the height it was at before the vacuum was created, we can conclude that one-hundredth of the air originally inside remained in the balloon, meaning that only 99/100 of the gas was transferred from the jar to the balloon.
FOOTNOTES:
[58] According to the proportion of 114 to 107, given between the French and English foot, 28 inches of the French barometer are equal to 29.83 inches of the English. Directions will be found in the appendix for converting all the French weights and measures used in this work into corresponding English denominations.—E.
[58] Based on the ratio of 114 to 107, which is used for the French and English foot, 28 inches of the French barometer equals 29.83 inches of the English one. You'll find instructions in the appendix for converting all the French weights and measures mentioned in this work into their English equivalents.—E.
[59] When Fahrenheit's thermometer is employed, the dilatation by each degree must be smaller, in the proportion of 1 to 2.25, because each degree of Reaumur's scale contains 2.25 degrees of Fahrenheit; hence we must divide by 472.5, and finish the rest of the calculation as above.—E.
[59] When using Fahrenheit's thermometer, the expansion for each degree must be smaller, in the ratio of 1 to 2.25, since each degree on Reaumur's scale is equivalent to 2.25 degrees on the Fahrenheit scale; therefore, we need to divide by 472.5 and complete the rest of the calculation as mentioned above.—E.
CHAP. III.
Description of the Calorimeter, or Apparatus for measuring Caloric.
The calorimeter, or apparatus for measuring the relative quantities of heat contained in bodies, was described by Mr de la Place and me in the Memoirs of the Academy for 1780, p. 355. and from that Essay the materials of this chapter are extracted.
The calorimeter, or device for measuring the relative amounts of heat in substances, was detailed by Mr. de la Place and me in the Memoirs of the Academy for 1780, p. 355. The materials for this chapter are taken from that essay.
If, after having cooled any body to the freezing point, it be exposed in an atmosphere of 25° (88.25°), the body will gradually become heated, from the surface inwards, till at last it acquire the same temperature with the surrounding air. But, if a piece of ice be placed in the same situation, the circumstances are quite different; it does not approach in the smallest degree towards the temperature of the circumambient air, but remains constantly at Zero (32°), or the temperature of melting ice, till the last portion of ice be completely melted.
If you cool something down to freezing and then expose it to air that's 25°C (88.25°F), the object will slowly warm up from the outside in until it matches the temperature of the surrounding air. However, if you put a piece of ice in the same situation, it behaves very differently; it doesn't warm up at all but stays at 0°C (32°F), the melting point of ice, until it's completely melted.
This phenomenon is readily explained; as, to melt ice, or reduce it to water, it requires to be combined with a certain portion of caloric;[Pg 344] the whole caloric attracted from the surrounding bodies, is arrested or fixed at the surface or external layer of ice which it is employed to dissolve, and combines with it to form water; the next quantity of caloric combines with the second layer to dissolve it into water, and so on successively till the whole ice be dissolved or converted into water by combination with caloric, the very last atom still remaining at its former temperature, because the caloric has never penetrated so far as long as any intermediate ice remained to melt.
This phenomenon is easy to explain. To melt ice or turn it into water, it needs to be combined with a certain amount of heat; [Pg 344] the total heat attracted from the surrounding bodies gets trapped or fixed at the surface or outer layer of ice that it's working to dissolve, and it combines with that layer to form water. The next amount of heat combines with the second layer to melt it into water, and this process continues successively until all the ice is turned into water through its combination with heat. The very last bit of ice stays at its original temperature because the heat hasn’t penetrated that far as long as there's still any ice left to melt.
Upon these principles, if we conceive a hollow sphere of ice at the temperature of Zero (32°) placed in an atmosphere 10° (54.5°), and containing a substance at any degree of temperature above freezing, it follows, 1st, That the heat of the external atmosphere cannot penetrate into the internal hollow of the sphere of ice; 2dly, That the heat of the body placed in the hollow of the sphere cannot penetrate outwards beyond it, but will be stopped at the internal surface, and continually employed to melt successive layers of ice, until the temperature of the body be reduced to Zero (32°), by having all its superabundant caloric above that temperature carried off by the ice. If the whole water, formed within the sphere of ice during the reduction of the temperature of the included body to Zero, be carefully collected, the weight[Pg 345] of the water will be exactly proportional to the quantity of caloric lost by the body in passing from its original temperature to that of melting ice; for it is evident that a double quantity of caloric would have melted twice the quantity of ice; hence the quantity of ice melted is a very exact measure of the quantity of caloric employed to produce that effect, and consequently of the quantity lost by the only substance that could possibly have supplied it.
Based on these principles, if we imagine a hollow sphere made of ice at a temperature of 32°F (0°C) placed in an atmosphere at 54.5°F (10°C), and it contains a substance at any temperature above freezing, it follows that: 1) the heat from the outside atmosphere cannot penetrate into the hollow part of the ice sphere; and 2) the heat from the object inside the hollow cannot escape outward beyond the internal surface of the sphere and will instead be absorbed to melt successive layers of ice until the temperature of the object is reduced to 32°F (0°C), as all the excess heat above that temperature is absorbed by the ice. If we carefully collect all the water formed within the ice sphere while the temperature of the object drops to 32°F, the weight[Pg 345] of that water will be directly proportional to the amount of heat lost by the object as it cools from its original temperature to that of melting ice; it’s clear that twice the amount of heat would melt twice the amount of ice, so the amount of ice melted is a precise measure of the heat used to achieve that, and consequently, of the heat lost by the only substance capable of providing it.
I have made this supposition of what would take place in a hollow sphere of ice, for the purpose of more readily explaining the method used in this species of experiment, which was first conceived by Mr de la Place. It would be difficult to procure such spheres of ices and inconvenient to make use of them when got; but, by means of the following apparatus, we have remedied that defect. I acknowledge the name of Calorimeter, which I have given it, as derived partly from Greek and partly from Latin, is in some degree open to criticism; but, in matters of science, a slight deviation from strict etymology, for the sake of giving distinctness of idea, is excusable; and I could not derive the name entirely from Greek without approaching too near to the names of known instruments employed for other purposes.
I’ve created this idea about what would happen in a hollow sphere of ice to make it easier to explain the method used in this type of experiment, which was first thought up by Mr. de la Place. It would be hard to get such ice spheres and inconvenient to use them once obtained; however, with the following equipment, we’ve addressed that issue. I acknowledge that the name Calorimeter, which I’ve chosen, is partly derived from Greek and partly from Latin, and it’s somewhat open to criticism; but in science, a slight departure from strict etymology for the sake of clarity is acceptable, and I couldn’t derive the name entirely from Greek without getting too close to the names of existing instruments used for different purposes.
The calorimeter is represented in Pl. VI. It is shown in perspective at Fig. 1. and its interior[Pg 346] structure is engraved in Fig. 2. and 3.; the former being a horizontal, and the latter a perpendicular section. Its capacity or cavity is divided into three parts, which, for better distinction, I shall name the interior, middle, and external cavities. The interior cavity f f f f, Fig. 4. into which the substances submitted to experiment are put, is composed of a grating or cage of iron wire, supported by several iron bars; its opening or mouth LM, is covered by the lid HG, of the same materials. The middle cavity b b b b, Fig. 2. and 3. is intended to contain the ice which surrounds the interior cavity, and which is to be melted by the caloric of the substance employed in the experiment. The ice is supported by the grate m m at the bottom of the cavity, under which is placed the sieve n n. These two are represented separately in Fig. 5. and 6.
The calorimeter is shown in Pl. VI. It's illustrated in perspective in Fig. 1, and its interior structure is detailed in Fig. 2 and 3; the first being a horizontal section and the second a vertical section. Its capacity or cavity is divided into three parts, which, for clarity, I will call the inner, middle, and outer cavities. The inner cavity f f f f, Fig. 4, where the materials for the experiment are placed, is made up of a grating or cage of iron wire, supported by several iron bars. Its opening or mouth LM is covered by the lid HG, which is made of the same materials. The middle cavity b b b b, Fig. 2 and 3, is designed to hold the ice that surrounds the inner cavity and is meant to be melted by the heat from the substance used in the experiment. The ice is supported by the grate m m at the bottom of the cavity, beneath which is a sieve n n. These two are shown separately in Fig. 5 and 6.
In proportion as the ice contained in the middle cavity is melted, by the caloric disengaged from the body placed in the interior cavity, the water runs through the grate and sieve, and falls through the conical funnel c c d, Fig. 3. and tube x y, into the receiver F, Fig. 1. This water may be retained or let out at pleasure, by means of the stop-cock u. The external cavity a a a a, Fig. 2. and 3. is filled with ice, to prevent any effect upon the ice in the middle cavity from the heat of the surrounding air, and[Pg 347] the water produced from it is carried off through the pipe ST, which shuts by means of the stop-cock r. The whole machine is covered by the lid FF, Fig. 7. made of tin painted with oil colour, to prevent rust.
As the ice in the middle cavity melts due to the heat released from the body inside, the water flows through the grate and sieve, falling through the conical funnel c c d, Fig. 3, and the tube x y into the receiver F, Fig. 1. This water can be held or released as needed using the stop-cock u. The outer cavity a a a a, Fig. 2 and 3, is filled with ice to shield the inner cavity from the heat of the surrounding air, and[Pg 347] the resulting water is drained through the pipe ST, which is closed off by the stop-cock r. The entire machine is topped with the lid FF, Fig. 7, made of tin painted with oil-based paint to prevent rust.
When this machine is to be employed, the middle cavity b b b b, Fig. 2. and 3., the lid GH, Fig. 4. of the interior cavity, the external cavity a a a a, Fig. 2. and 3. and the general lid FF, Fig. 7. are all filled with pounded ice, well rammed, so that no void spaces remain, and the ice of the middle cavity is allowed to drain. The machine is then opened, and the substance submitted to experiment being placed in the interior cavity, it is instantly closed. After waiting till the included body is completely cooled to the freezing point, and the whole melted ice has drained from the middle cavity, the water collected in the vessel F, Fig. 1. is accurately weighed. The weight of the water produced during the experiment is an exact measure of the caloric disengaged during the cooling of the included body, as this substance is evidently in a similar situation with the one formerly mentioned as included in a hollow sphere of ice; the whole caloric disengaged is stopped by the ice in the middle cavity, and that ice is preserved from being affected by any other heat by means of the ice contained in the general lid, Fig. 7. and in the external cavity. Experiments[Pg 348] of this kind last from fifteen to twenty hours; they are sometimes accelerated by covering up the substance in the interior cavity with well drained ice, which hastens its cooling.
When this machine is used, the middle cavity b b b b, Fig. 2 and 3, the lid GH, Fig. 4 of the inner cavity, the outer cavity a a a a, Fig. 2 and 3, and the main lid FF, Fig. 7, are all packed with crushed ice, tightly packed to eliminate any gaps, and the ice in the middle cavity is allowed to drain. The machine is then opened, and the material to be tested is placed in the inner cavity, which is immediately sealed. After waiting until the contained material is completely cooled to the freezing point, and all the melted ice has drained from the middle cavity, the water collected in vessel F, Fig. 1 is carefully weighed. The amount of water produced during the experiment accurately reflects the heat released during the cooling of the contained material, as this material is clearly in a similar situation to what was previously described as being encased in a hollow sphere of ice; all the heat released is captured by the ice in the middle cavity, and that ice remains unaffected by any additional heat due to the ice in the main lid, Fig. 7, and in the outer cavity. Experiments[Pg 348] like this last from fifteen to twenty hours; they can sometimes be sped up by covering the material in the inner cavity with well-drained ice, which helps it cool faster.
The substances to be operated upon are placed in the thin iron bucket, Fig. 8. the cover of which has an opening fitted with a cork, into which a small thermometer is fixed. When we use acids, or other fluids capable of injuring the metal of the instruments, they are contained in the matras, Fig. 10. which has a similar thermometer in a cork fitted to its mouth, and which stands in the interior cavity upon the small cylindrical support RS, Fig. 10.
The materials to be processed are put in the thin iron bucket, Fig. 8, which has a lid with an opening fitted with a cork, where a small thermometer is inserted. When we use acids or other liquids that could damage the metal instruments, they are held in the flasks, Fig. 10, which also has a thermometer in a cork fitted to its opening, and which rests in the inner cavity on the small cylindrical support RS, Fig. 10.
It is absolutely requisite that there be no communication between the external and middle cavities of the calorimeter, otherwise the ice melted by the influence of the surrounding air, in the external cavity, would mix with the water produced from the ice of the middle cavity, which would no longer be a measure of the caloric lost by the substance submitted to experiment.
It is essential that there is no communication between the external and middle cavities of the calorimeter; otherwise, the ice melted by the surrounding air in the external cavity would mix with the water created from the ice in the middle cavity, no longer providing an accurate measure of the heat lost by the substance being tested.
When the temperature of the atmosphere is only a few degrees above the freezing point, its heat can hardly reach the middle cavity, being arrested by the ice of the cover, Fig. 7. and of the external cavity; but, if the temperature of the air be under the degree of freezing, it might cool the ice contained in the middle cavity, by[Pg 349] causing the ice in the external cavity to fall, in the first place, below zero (32°). It is therefore essential that this experiment be carried on in a temperature somewhat above freezing: Hence, in time of frost, the calorimeter must be kept in an apartment carefully heated. It is likewise necessary that the ice employed be not under zero (32°); for which purpose it must be pounded, and spread out thin for some time, in a place of a higher temperature.
When the air temperature is just a few degrees above freezing, its heat hardly reaches the middle cavity, getting blocked by the ice on the cover, Fig. 7, and in the outer cavity. However, if the air temperature drops below freezing, it could cool the ice in the middle cavity, causing the ice in the outer cavity to drop below zero (32°) first. So, it's crucial to conduct this experiment at a temperature slightly above freezing. Therefore, during freezing weather, the calorimeter needs to be kept in a carefully heated room. It’s also necessary that the ice used isn't below zero (32°); to achieve this, it should be crushed and spread thin for a while in a warmer place.
The ice of the interior cavity always retains a certain quantity of water adhering to its surface, which may be supposed to belong to the result of the experiment; but as, at the beginning of each experiment, the ice is already saturated with as much water as it can contain, if any of the water produced by the caloric should remain attached to the ice, it is evident, that very nearly an equal quantity of what adhered to it before the experiment must have run down into the vessel F in its stead; for the inner surface of the ice in the middle cavity is very little changed during the experiment.
The ice in the inner cavity always has some water sticking to its surface, which we can assume is part of the experiment's outcome. However, since the ice is already completely soaked with as much water as it can hold at the start of each experiment, if any water generated by the heat stays on the ice, it's clear that almost the same amount of water that was on it before the experiment must have dripped down into the vessel F instead, because the inner surface of the ice in the middle cavity changes very little during the experiment.
By any contrivance that could be devised, we could not prevent the access of the external air into the interior cavity when the atmosphere was 9° or 10° (52° or 54°) above zero. The air confined in the cavity being in that case specifically heavier than the external air, escapes downwards through the pipe x y, Fig. 3, and is[Pg 350] replaced by the warmer external air, which, giving out its caloric to the ice, becomes heavier, and sinks in its turn; thus a current of air is formed through the machine, which is the more rapid in proportion as the external air exceeds the internal in temperature. This current of warm air must melt a part of the ice, and injure the accuracy of the experiment: We may, in a great degree, guard against this source of error by keeping the stop-cock u continually shut; but it is better to operate only when the temperature of the external air does not exceed 3°, or at most 4°, (39° to 41°); for we have observed, that, in this case, the melting of the interior ice by the atmospheric air is perfectly insensible; so that we may answer for the accuracy of our experiments upon the specific heat of bodies to a fortieth part.
No matter what we tried, we couldn't stop outside air from getting into the inner cavity when the temperature was 9° or 10° (52° or 54°) above zero. The air trapped inside the cavity was heavier than the outside air, causing it to escape downwards through the pipe x y, Fig. 3, and be replaced by warmer outside air. This outside air, losing its heat to the ice, becomes heavier and sinks as well; this creates a flow of air through the machine that gets faster as the outside air temperature increases compared to the inside. This flow of warm air will melt some of the ice and affect the accuracy of the experiment. We can largely prevent this error by keeping the stop-cock u tightly closed, but it's best to run the experiment only when the outside air temperature doesn't exceed 3° or at most 4° (39° to 41°). We have noticed that in this case, the melting of the inside ice by outside air is barely noticeable, allowing us to ensure the accuracy of our experiments on the specific heat of substances to within a fortieth of a part.
We have caused make two of the above described machines; one, which is intended for such experiments as do not require the interior air to be renewed, is precisely formed according to the description here given; the other, which answers for experiments upon combustion, respiration, &c. in which fresh quantities of air are indispensibly necessary, differs from the former in having two small tubes in the two lids, by which a current of atmospheric air may be blown into the interior cavity of the machine.[Pg 351]
We have built two of the machines described above; one is designed for experiments that don't need the air inside to be replaced and is made exactly as described here. The other one, which is suitable for experiments on combustion, respiration, etc., where fresh air is essential, has two small tubes in the lids that allow a flow of outside air to be introduced into the machine's interior.[Pg 351]
It is extremely easy, with this apparatus, to determine the phenomena which occur in operations where caloric is either disengaged or absorbed. If we wish, for instance, to ascertain the quantity of caloric which is disengaged from a solid body in cooling a certain number of degrees, let its temperature be raised to 80° (212°); it is then placed in the interior cavity f f f f, Fig. 2. and 3. of the calorimeter, and allowed to remain till we are certain that its temperature is reduced to zero (32°); the water produced by melting the ice during its cooling is collected, and carefully weighed; and this weight, divided by the volume of the body submitted to experiment, multiplied into the degrees of temperature which it had above zero at the commencement of the experiment, gives the proportion of what the English philosophers call specific heat.
It’s really easy, with this device, to figure out the phenomena that happen during processes where heat is either released or absorbed. For example, if we want to find out how much heat is released from a solid body when it cools down by a certain number of degrees, we raise its temperature to 80° (212°); then we place it in the interior cavity f f f f, Fig. 2. and 3. of the calorimeter, and let it sit until we confirm its temperature drops to zero (32°); we collect and carefully weigh the water produced from the melting ice during cooling; then, we divide this weight by the volume of the body being tested, and multiply it by the temperature in degrees above zero at the start of the experiment to get the specific heat, as the English philosophers call it.
Fluids are contained in proper vessels, whose specific heat has been previously ascertained, and operated upon in the machine in the same manner as directed for solids, taking care to deduct, from the quantity of water melted during the experiment, the proportion which belongs to the containing vessel.
Fluids are held in appropriate containers, whose specific heat has been determined beforehand, and processed in the machine just like solids, making sure to subtract from the amount of water melted during the experiment the portion that belongs to the container.
If the quantity of caloric disengaged during the combination of different substances is to be determined, these substances are to be previously reduced to the freezing degree by keeping[Pg 352] them a sufficient time surrounded with pounded ice; the mixture is then to be made in the inner cavity of the calorimeter, in a proper vessel likewise reduced to zero (32°); and they are kept inclosed till the temperature of the combination has returned to the same degree: The quantity of water produced is a measure of the caloric disengaged during the combination.
If you want to find out how much heat is released when different substances are combined, you first need to cool those substances down to freezing by leaving them in crushed ice for a while. Then, mix them in the inner chamber of the calorimeter, which should also be cooled to 32°F (0°C). Keep everything sealed until the temperature of the mixture returns to the same level. The amount of water produced will indicate how much heat was released during the combination.
To determine the quantity of caloric disengaged during combustion, and during animal respiration, the combustible bodies are burnt, or the animals are made to breathe in the interior cavity, and the water produced is carefully collected. Guinea pigs, which resist the effects of cold extremely well, are well adapted for this experiment. As the continual renewal of air is absolutely necessary in such experiments, we blow fresh air into the interior cavity of the calorimeter by means of a pipe destined for that purpose, and allow it to escape through another pipe of the same kind; and that the heat of this air may not produce errors in the results of the experiments, the tube which conveys it into the machine is made to pass through pounded ice, that it may be reduced to zero (32°) before it arrives at the calorimeter. The air which escapes must likewise be made to pass through a tube surrounded with ice, included in the interior cavity of the machine, and the water which is produced must make a part of what is[Pg 353] collected, because the caloric disengaged from this air is part of the product of the experiment.
To measure the amount of heat released during combustion and animal respiration, we burn the combustible materials or have the animals breathe inside a closed space, collecting the water produced. Guinea pigs, which handle cold very well, are particularly suited for this experiment. Since a constant supply of fresh air is crucial for these tests, we pump fresh air into the calorimeter using a dedicated pipe and let it exit through another similar pipe. To avoid inaccuracies in our results caused by the heat from this air, we run the tube that brings it into the system through crushed ice, cooling it down to zero (32°F) before it reaches the calorimeter. The air that exits also passes through a tube surrounded by ice, which is placed inside the apparatus, and the water produced must be included in the total amount collected, as the heat released from this air contributes to the overall results of the experiment.
It is somewhat more difficult to determine the specific caloric contained in the different gasses, on account of their small degree of density; for, if they are only placed in the calorimeter in vessels like other fluids, the quantity of ice melted is so small, that the result of the experiment becomes at best very uncertain. For this species of experiment we have contrived to make the air pass through two metallic worms, or spiral tubes; one of these, through which the air passes, and becomes heated in its way to the calorimeter, is contained in a vessel full of boiling water, and the other, through which the air circulates within the calorimeter to disengage its caloric, is placed in the interior cavity, f f f f, of that machine. By means of a small thermometer placed at one end of the second worm, the temperature of the air, as it enters the calorimeter, is determined, and its temperature in getting out of the interior cavity is found by another thermometer placed at the other end of the worm. By this contrivance we are enabled to ascertain the quantity of ice melted by determinate quantities of air or gas, while losing a certain number of degrees of temperature, and, consequently, to determine their several degrees of specific caloric. The[Pg 354] same apparatus, with some particular precautions, may be employed to ascertain the quantity of caloric disengaged by the condensation of the vapours of different liquids.
It's a bit trickier to figure out the exact heat content in different gases because they're not very dense. If we just put them in a calorimeter like we do with other liquids, the amount of ice that melts is so small that the results are pretty unreliable. For this kind of experiment, we designed a setup where air passes through two metal coils or spiral tubes. One of these coils, which heats the air on its way to the calorimeter, is placed in boiling water, while the other coil, which allows the air to cool down inside the calorimeter, is positioned in the inner cavity, f f f f, of the machine. A small thermometer at one end of the second coil measures the air temperature as it enters the calorimeter, and another thermometer at the other end of the coil measures the temperature when the air exits the inner cavity. This setup allows us to find out how much ice melts with specific amounts of air or gas as they lose a certain amount of heat, and therefore, we can determine their specific heat capacities. The[Pg 354] same apparatus, with some special precautions, can also be used to measure the amount of heat released during the condensation of vapor from different liquids.
The various experiments which may be made with the calorimeter do not afford absolute conclusions, but only give us the measure of relative quantities; we have therefore to fix a unit, or standard point, from whence to form a scale of the several results. The quantity of caloric necessary to melt a pound of ice has been chosen as this unit; and, as it requires a pound of water of the temperature of 60° (167°) to melt a pound of ice, the quantity of caloric expressed by our unit or standard point is what raises a pound of water from zero (32°) to 60° (167°). When this unit is once determined, we have only to express the quantities of caloric disengaged from different bodies by cooling a certain number of degrees, in analogous values: The following is an easy mode of calculation for this purpose, applied to one of our earliest experiments.
The different experiments that can be done with the calorimeter don’t provide absolute conclusions, but only give us a way to measure relative amounts. So, we need to establish a unit or standard point to create a scale for the various results. The amount of heat needed to melt a pound of ice has been chosen as this unit. Since it takes a pound of water at 60° (167°) to melt a pound of ice, the amount of heat represented by our unit or standard point is what raises a pound of water from 0° (32°) to 60° (167°). Once this unit is set, we can express the amounts of heat released from different substances by cooling a specific number of degrees in comparable values. Here’s an easy way to calculate this, using one of our earliest experiments.
We took 7 lib. 11 oz. 2 gros 36 grs. of plate-iron, cut into narrow slips, and rolled up, or expressing the quantity in decimals, 7.7070319. These, being heated in a bath of boiling water to about 78° (207.5°), were quickly introduced into the interior cavity of the calorimeter: At[Pg 355] the end of eleven hours, when the whole quantity of water melted from the ice had thoroughly drained off, we found that 1.109795 pounds of ice were melted. Hence, the caloric disengaged from the iron by cooling 78° (175.5°) having melted 1.109795 pounds of ice, how much would have been melted by cooling 60° (135°)? This question gives the following statement in direct proportion, 78 : 1.109795 :: 60 : x = 0.85369. Dividing this quantity by the weight of the whole iron employed, viz. 7.7070319, the quotient 0.110770 is the quantity of ice which would have been melted by one pound of iron whilst cooling through 60° (135°) of temperature.
We took 7 lib. 11 oz. 2 gros 36 grs. of plate iron, cut into narrow strips, and rolled up, or expressed in decimals, 7.7070319. These were heated in a bath of boiling water to about 78° (207.5°) and quickly placed into the inner cavity of the calorimeter. At[Pg 355] the end of eleven hours, when all the melted water from the ice had drained off, we found that 1.109795 pounds of ice had melted. Therefore, the heat released from the iron by cooling from 78° (175.5°), which melted 1.109795 pounds of ice, raises the question of how much ice would have melted by cooling from 60° (135°). This can be expressed in direct proportion as 78 : 1.109795 :: 60 : x = 0.85369. Dividing this amount by the total weight of the iron used, which is 7.7070319, gives a quotient of 0.110770, indicating the amount of ice that would be melted by one pound of iron cooling through 60° (135°).
Fluid substances, such as sulphuric and nitric acids, &c. are contained in a matras, Pl. VI. Fig. 9. having a thermometer adapted to the cork, with its bulb immersed in the liquid. The matras is placed in a bath of boiling water, and when, from the thermometer, we judge the liquid is raised to a proper temperature, the matras is placed in the calorimeter. The calculation of the products, to determine the specific caloric of these fluids, is made as above directed, taking care to deduct from the water obtained the quantity which would have been produced by the matras alone, which must be ascertained by a previous experiment. The[Pg 356] table of the results obtained by these experiments is omitted, because not yet sufficiently complete, different circumstances having occasioned the series to be interrupted; it is not, however, lost sight of; and we are less or more employed upon the subject every winter.
Fluid substances, like sulfuric and nitric acids, are contained in a flask, Pl. VI. Fig. 9, with a thermometer fitted to the cork, having its bulb immersed in the liquid. The flask is placed in a boiling water bath, and when the thermometer indicates that the liquid has reached the right temperature, the flask is moved to the calorimeter. The calculation of the products, to find the specific heat of these fluids, is done as described above, making sure to subtract from the water obtained the amount that would have been produced by the flask alone, which must be determined through a prior experiment. The[Pg 356] table of results from these experiments is not included because it is not yet complete; different circumstances have caused the series to be interrupted, but we are continuing to work on the subject every winter.
CHAP. IV.
Of Mechanical Operations for Division of Bodies.
SECT. I.
Of Trituration, Levigation, and Pulverization.
These are, properly speaking, only preliminary mechanical operations for dividing and separating the particles of bodies, and reducing them into very fine powder. These operations can never reduce substances into their primary, or elementary and ultimate particles; they do not even destroy the aggregation of bodies; for every particle, after the most accurate trituration, forms a small whole, resembling the original mass from which it was divided. The real chemical operations, on the contrary, such as solution, destroy the aggregation of bodies, and separate their constituent and integrant particles from each other.[Pg 358]
These are, to be precise, just initial mechanical processes for breaking down and separating the particles of substances and grinding them into very fine powder. These processes can never reduce materials to their basic, elemental, or ultimate particles; they don’t even eliminate the grouping of substances; because every particle, even after the most precise grinding, forms a small whole that resembles the original mass it came from. In contrast, real chemical processes, like dissolution, break apart the grouping of substances and separate their individual and component particles from one another.[Pg 358]
Brittle substances are reduced to powder by means of pestles and mortars. These are of brass or iron, Pl. I. Fig. 1.; of marble or granite, Fig. 2.; of lignum vitae, Fig. 3.; of glass, Fig. 4.; of agate, Fig. 5.; or of porcellain, Fig. 6. The pestles for each of these are represented in the plate, immediately below the mortars to which they respectively belong, and are made of hammered iron or brass, of wood, glass, porcellain, marble, granite, or agate, according to the nature of the substances they are intended to triturate. In every laboratory, it is requisite to have an assortment of these utensils, of various sizes and kinds: Those of porcellain and glass can only be used for rubbing substances to powder, by a dexterous use of the pestle round the sides of the mortar, as it would be easily broken by reiterated blows of the pestle.
Brittle materials are ground into powder using pestles and mortars. These can be made of brass or iron, as shown in Pl. I. Fig. 1; marble or granite, Fig. 2; lignum vitae, Fig. 3; glass, Fig. 4; agate, Fig. 5; or porcelain, Fig. 6. The pestles for each of these are illustrated in the plate, directly below the mortars they correspond to, and they’re made of hammered iron or brass, wood, glass, porcelain, marble, granite, or agate, depending on the materials they’re meant to grind. It's essential to have a variety of these tools in different sizes and types in every laboratory. Porcelain and glass ones should only be used for grinding substances to powder by carefully using the pestle around the edges of the mortar, as they can easily break if struck repeatedly with the pestle.
The bottom of mortars ought to be in the form of a hollow sphere, and their sides should have such a degree of inclination as to make the substances they contain fall back to the bottom when the pestle is lifted, but not so perpendicular as to collect them too much together, otherwise too large a quantity would get below the pestle, and prevent its operation. For this reason, likewise, too large a quantity of the substance to be powdered ought not to be put into the mortar at one time; and we must from[Pg 359] time to time get rid of the particles already reduced to powder, by means of sieves to be afterwards described.
The bottoms of mortars should be shaped like a hollow sphere, and their sides should be slanted enough to allow the materials inside to fall back to the bottom when the pestle is lifted, but not so vertical that it causes them to clump together. Otherwise, too much of the material would get under the pestle and hinder its function. For this reason, you shouldn't put too much of the substance to be ground into the mortar at once; we also need to periodically remove the particles that have already been ground into powder using sieves that will be described later.
The most usual method of levigation is by means of a flat table ABCD, Pl. 1. Fig. 7. of porphyry, or other stone of similar hardness, upon which the substance to be reduced to powder is spread, and is then bruised and rubbed by a muller M, of the same hard materials, the bottom of which is made a small portion of a large sphere; and, as the muller tends continually to drive the substances towards the sides of the table, a thin flexible knife, or spatula of iron, horn, wood, or ivory, is used for bringing them back to the middle of the stone.
The most common way to grind something down is using a flat table ABCD, Pl. 1. Fig. 7, made of porphyry or another tough stone. The material to be powdered is spread out on the table and then crushed and rubbed with a muller M, made from the same hard materials. The bottom of the muller is shaped like a small part of a large sphere. Since the muller constantly pushes the material toward the edges of the table, a thin, flexible knife or spatula made of iron, horn, wood, or ivory is used to move it back to the center of the stone.
In large works, this operation is performed by means of large rollers of hard stone, which turn upon each other, either horizontally, in the way of corn-mills, or by one vertical roller turning upon a flat stone. In the above operations, it is often requisite to moisten the substances a little, to prevent the fine powder from flying off.
In large projects, this process is done using big rollers made of hard stone that rotate against each other, either horizontally like in corn mills, or with one vertical roller spinning on a flat stone. During these operations, it’s often necessary to slightly dampen the materials to keep the fine powder from escaping.
There are many bodies which cannot be reduced to powder by any of the foregoing methods; such are fibrous substances, as woods; such as are tough and elastic, as the horns of animals, elastic gum, &c. and the malleable metals which flatten under the pestle, instead of being reduced to powder. For reducing the[Pg 360] woods to powder, rasps, as Pl. I. Fig. 8. are employed; files of a finer kind are used for horn, and still finer, Pl. 1. Fig. 9. and 10. for metals.
There are many materials that can't be ground into powder using any of the methods mentioned above. This includes fibrous substances like wood, tough and elastic materials like animal horns and elastic gum, and malleable metals that flatten out instead of turning to powder when crushed. To grind wood into powder, tools like rasps are used, as shown in Pl. I. Fig. 8. Finer files are used for horn, and even finer tools, shown in Pl. 1. Fig. 9. and 10., are used for metals.
Some of the metals, though not brittle enough to powder under the pestle, are too soft to be filed, as they clog the file, and prevent its operation. Zinc is one of these, but it may be powdered when hot in a heated iron mortar, or it may be rendered brittle, by alloying it with a small quantity of mercury. One or other of these methods is used by fire-work makers for producing a blue flame by means of zinc. Metals may be reduced into grains, by pouring them when melted into water, which serves very well when they are not wanted in fine powder.
Some metals, while not fragile enough to turn into powder with a pestle, are too soft to be filed since they clog the file and stop it from working. Zinc is one of these; however, it can be powdered when heated in a hot iron mortar, or it can be made brittle by mixing it with a small amount of mercury. Firework makers use one of these methods to create a blue flame with zinc. Metals can be broken into grains by pouring them into water while they’re melted, which works well when fine powder isn’t needed.
Fruits, potatoes, &c. of a pulpy and fibrous nature may be reduced to pulp by means of the grater, Pl. 1. Fig. 11.
Fruits, potatoes, etc., that have a pulpy and fibrous texture can be turned into pulp using the grater, Pl. 1. Fig. 11.
The choice of the different substances of which these instruments are made is a matter of importance; brass or copper are unfit for operations upon substances to be used as food or in pharmacy; and marble or metallic instruments must not be used for acid substances; hence mortars of very hard wood, and those of porcelain, granite, or glass, are of great utility in many operations.[Pg 361]
The choice of materials for these instruments is important; brass or copper aren’t suitable for working with substances used in food or medicine, and marble or metal instruments shouldn't be used for acidic substances. Therefore, mortars made of very hard wood, porcelain, granite, or glass are very useful for many tasks.[Pg 361]
SECT. II.
Of Sifting and Washing Powdered Substances.
None of the mechanical operations employed for reducing bodies to powder is capable of producing it of an equal degree of fineness throughout; the powder obtained by the longest and most accurate trituration being still an assemblage of particles of various sizes. The coarser of these are removed, so as only to leave the finer and more homogeneous particles by means of sieves, Pl. I. Fig. 12. 13. 14. 15. of different finenesses, adapted to the particular purposes they are intended for; all the powdered matter which is larger than the intestices of the sieve remains behind, and is again submitted to the pestle, while the finer pass through. The sieve Fig. 12. is made of hair-cloth, or of silk gauze; and the one represented Fig. 13. is of parchment pierced with round holes of a proper size; this latter is employed in the manufacture of gun-powder. When very subtile or valuable materials are to be sifted, which are easily dispersed, or when the finer parts of the powder may be hurtful, a compound sieve, Fig. 15. is made use of, which consists of the sieve ABCD, with a lid EF, and receiver GH; these three[Pg 362] parts are represented as joined together for use, Fig. 14.
None of the mechanical methods used to grind materials into powder can produce a consistent level of fineness throughout; even the powder created by the longest and most precise grinding still consists of particles of varying sizes. The larger particles are removed, leaving only the finer and more uniform particles using sieves, as shown in Pl. I. Fig. 12, 13, 14, 15, which are designed for specific purposes. Any powdered material that is larger than the openings of the sieve gets left behind and is ground again, while the finer particles pass through. The sieve in Fig. 12 is made of hair cloth or silk gauze, while the sieve in Fig. 13 is made of parchment with round holes of the appropriate size; the latter is used in making gunpowder. When very fine or valuable materials need to be sifted, which can easily scatter, or when the finer parts of the powder could be harmful, a compound sieve, shown in Fig. 15, is used, consisting of the sieve ABCD, with a lid EF and a receiver GH; these three parts are depicted as connected for use in Fig. 14.
There is a method of procuring powders of an uniform fineness, considerably more accurate than the sieve; but it can only be used with such substances as are not acted upon by water. The powdered substance is mixed and agitated with water, or other convenient fluid; the liquor is allowed to settle for a few moments, and is then decanted off; the coarsest powder remains at the bottom of the vessel, and the finer passes over with the liquid. By repeated decantations in this manner, various sediments are obtained of different degrees of fineness; the last sediment, or that which remains longed suspended in the liquor, being the finest. This process may likewise be used with advantage for separating substances of different degrees of specific gravity, though of the same fineness; this last is chiefly employed in mining, for separating the heavier metallic ores from the lighter earthy matters with which they are mixed.
There’s a method of getting powders of uniform fineness that’s way more accurate than using a sieve; however, it can only be used with substances that aren’t affected by water. The powdered substance is mixed and stirred with water or another suitable liquid; then, the mixture is allowed to settle for a few moments and is decanted. The coarsest powder settles at the bottom of the container, while the finer particles go along with the liquid. By repeating this decanting process, you can get various sediments with different levels of fineness; the last sediment, or the one that stays suspended in the liquid for the longest time, is the finest. This method can also be beneficial for separating substances with different specific gravities but the same fineness; this last application is mainly used in mining to separate heavier metallic ores from the lighter earthy materials they are mixed with.
In chemical laboratories, pans and jugs of glass or earthen ware are employed for this operation; sometimes, for decanting the liquor without disturbing the sediment, the glass syphon ABCHI, Pl. II. Fig. 11. is used, which may be supported by means of the perforated board DE, at the proper depth in the vessel FG, to draw off all the liquor required into the[Pg 363] receiver LM. The principles and application of this useful instrument are so well known as to need no explanation.
In chemical labs, glass or ceramic pans and jugs are used for this process. Sometimes, to pour off the liquid without disturbing the sediment, the glass siphon ABCHI, Pl. II. Fig. 11. is used, which can be held at the right depth in the vessel FG with the help of the perforated board DE, allowing all the liquid needed to be drawn into the[Pg 363] receiver LM. The principles and use of this practical tool are so widely understood that they don't require further explanation.
SECT. III.
Of Filtration.
A filtre is a species of very fine sieve, which is permeable to the particles of fluids, but through which the particles of the finest powdered solids are incapable of passing; hence its use in separating fine powders from suspension in fluids. In pharmacy, very close and fine woollen cloths are chiefly used for this operation; these are commonly formed in a conical shape, Pl. II. Fig. 2. which has the advantage of uniting all the liquor which drains through into a point A, where it may be readily collected in a narrow mouthed vessel. In large pharmaceutical laboratories, this filtring bag is streached upon a wooden stand, Pl. II. Fig. 1.
A filter is a type of very fine sieve that allows fluid particles to pass through while preventing the smallest powdered solids from getting through. This makes it useful for separating fine powders suspended in liquids. In pharmacy, very tightly woven wool cloths are mainly used for this process; these are usually shaped like a cone, as shown in Pl. II. Fig. 2. This shape helps collect all the liquid that drains through at a single point A, where it can be easily gathered into a narrow-mouthed container. In large pharmaceutical labs, this filtering bag is stretched over a wooden stand, as illustrated in Pl. II. Fig. 1.
For the purposes of chemistry, as it is requisite to have the filtres perfectly clean, unsized paper is substituted instead of cloth or flannel; through this substance, no solid body, however finely it be powdered, can penetrate, and fluids percolate through it with the greatest readiness.[Pg 364] As paper breaks easily when wet, various methods of supporting it are used according to circumstances. When a large quantity of fluid is to be filtrated, the paper is supported by the frame of wood, Pl. II. Fig. 3. ABCD, having a piece of coarse cloth stretched over it, by means of iron-hooks. This cloth must be well cleaned each time it is used, or even new cloth must be employed, if there is reason to suspect its being impregnated with any thing which can injure the subsequent operations. In ordinary operations, where moderate quantities of fluid are to be filtrated, different kinds of glass funnels are used for supporting the paper, as represented Pl. II. Fig. 5. 6. and 7. When several filtrations must be carried on at once, the board or shelf AB, Fig. 9. supported upon stands C and D, and pierced with round holes, is very convenient for containing the funnels.
For chemistry purposes, since it's essential to have completely clean filters, unsized paper is used instead of cloth or flannel; no solid particle, no matter how finely ground, can pass through this material, and liquids flow through it very easily.[Pg 364] Because paper tears easily when wet, various methods of supporting it are applied depending on the situation. When you need to filter a large amount of liquid, the paper is held up by a wooden frame, as shown in Pl. II. Fig. 3. ABCD, which has a piece of coarse cloth stretched over it using iron hooks. This cloth must be thoroughly cleaned every time it’s used, or even replaced with new cloth if there's any chance it has been contaminated with something that could affect the later processes. In standard operations where moderate amounts of liquid are to be filtered, different types of glass funnels are used to hold the paper, as shown in Pl. II. Fig. 5, 6, and 7. When multiple filtrations need to be done simultaneously, a board or shelf AB, Fig. 9, supported by stands C and D and having round holes drilled in it, is very helpful for holding the funnels.
Some liquors are so thick and clammy, as not to be able to penetrate through paper without some previous preparation, such as clarification by means of white of eggs, which being mixed with the liquor, coagulates when brought to boil, and, entangling the greater part of the impurities of the liquor, rises with them to the surface in the state of scum. Spiritous liquors may be clarified in the same manner by means of isinglass dissolved in water, which coagulates[Pg 365] by the action of the alkohol without the assistance of heat.
Some alcoholic beverages are so thick and sticky that they can't pass through paper without some prior treatment, like using egg whites for clarification. When mixed with the liquor and heated, the egg whites coagulate, trapping most of the impurities and rising to the surface as foam. Spirits can be clarified in the same way using isinglass dissolved in water, which coagulates by the action of the alcohol without needing heat.
As most of the acids are produced by distillation, and are consequently clear, we have rarely any occasion to filtrate them; but if, at any time, concentrated acids require this operation, it is impossible to employ paper, which would be corroded and destroyed by the acid. For this purpose, pounded glass, or rather quartz or rock-cristal, broke in pieces and grossly powdered, answers very well; a few of the larger pieces are put in the neck of the funnel; these are covered with the smaller pieces, the finer powder is placed over all, and the acid is poured on at top. For the ordinary purposes of society, river-water is frequently filtrated by means of clean washed sand, to separate its impurities.
As most acids are made through distillation and are therefore clear, we rarely need to filter them. However, if concentrated acids do require filtration, it's impossible to use paper, as it would be corroded and destroyed by the acid. Instead, crushed glass, or better yet, quartz or rock crystal, broken into pieces and coarsely powdered, works well; a few larger pieces are placed in the neck of the funnel, covered with smaller pieces, and the finer powder is added on top before pouring the acid over it. For everyday use, clean river water is often filtered through washed sand to remove impurities.
SECT. IV.
Of Decantation.
This operation is often substituted instead of filtration for separating solid particles which are diffused through liquors. These are allowed to settle in conical vessels, ABCDE, Pl. II. Fig. 10. the diffused matters gradually subside, and the[Pg 366] clear fluid is gently poured off. If the sediment be extremely light, and apt to mix again with the fluid by the slightest motion, the syphon, Fig. 11. is used, instead of decantation, for drawing off the clear fluid.
This process is often used as an alternative to filtration for separating solid particles that are mixed in liquids. These particles are allowed to settle in conical vessels, ABCDE, Pl. II. Fig. 10. The suspended particles gradually sink, and the[Pg 366] clear liquid is carefully poured off. If the sediment is very light and likely to mix back with the liquid at the slightest movement, a siphon, Fig. 11, is used instead of decantation to remove the clear liquid.
In experiments, where the weight of the precipitate must be rigorously ascertained, decantation is preferable to filtration, providing the precipitate be several times washed in a considerable proportion of water. The weight of the precipitate may indeed be ascertained, by carefully weighing the filtre before and after the operation; but, when the quantity of precipitate is small, the different proportions of moisture retained by the paper, in a greater or lesser degree of exsiccation, may prove a material source of error, which ought carefully to be guarded against.
In experiments where it's crucial to accurately determine the weight of the precipitate, decantation is better than filtration, as long as the precipitate is washed multiple times with a significant amount of water. You can find out the weight of the precipitate by carefully weighing the filter before and after the process. However, when the precipitate is small, the varying amounts of moisture trapped in the paper, due to different levels of drying, can lead to significant errors, which should be carefully avoided.
CHAP. V.
Of Chemical Means for separating the Particles of Bodies from each other; without Decomposition, and for uniting them again.
I have already shown that there are two methods of dividing the particles of bodies, the mechanical and chemical. The former only separates a solid mass into a great number of smaller masses; and for these purposes various species of forces are employed, according to circumstances, such as the strength of man or of animals, the weight of water applied through the means of hydraulic engines, the expansive power of steam, the force of the wind, &c. By all these mechanical powers, we can never reduce substances into powder beyond a certain degree of fineness; and the smallest particle produced in this way, though it seems very minute to our organs, is still in fact a mountain, when compared with the ultimate elementary particles of the pulverized substance.
I have already shown that there are two ways to break down the particles of materials: the mechanical and chemical. The first method simply divides a solid mass into many smaller pieces; for these purposes, different types of forces are used, depending on the situation, like the strength of humans or animals, the weight of water used with hydraulic machines, the power of steam, the force of the wind, etc. No matter what mechanical methods we use, we can never grind substances into powder finer than a certain level; and the tiniest particle made this way, while it may seem very small to us, is still actually a mountain compared to the ultimate basic particles of the ground substance.
The chemical agents, on the contrary, divide bodies into their primitive particles. If, for instance, a neutral salt be acted upon by these, it is divided, as far as is possible, without ceasing to be a neutral salt. In this Chapter, I mean to[Pg 368] give examples of this kind of division of bodies, to which I shall add some account of the relative operations.
The chemical agents, on the other hand, break down substances into their basic particles. For example, if a neutral salt is exposed to these agents, it is separated as much as possible without losing its status as a neutral salt. In this Chapter, I mean to[Pg 368] provide examples of this type of breakdown of substances, and I'll include some descriptions of the related processes.
SECT. I.
Of the Solution of Salts.
In chemical language, the terms of solution and dissolution have long been confounded, and have very improperly been indiscriminately employed for expressing both the division of the particles of a salt in a fluid, such as water, and the division of a metal in an acid. A few reflections upon the effects of these two operations will suffice to show that they ought not to be confounded together. In the solution of salts, the saline particles are only separated from each other, whilst neither the salt nor the water are at all decomposed; we are able to recover both the one and the other in the same quantity as before the operation. The same thing takes place in the solution of resins in alkohol. During metallic dissolutions, on the contrary, a decomposition, either of the acid, or of the water which dilutes it, always takes place; the metal combines with oxygen, and is changed into an oxyd, and a gasseous substance is disengaged; so that in reality none of the substances[Pg 369] employed remain, after the operation, in the same state they were in before. This article is entirely confined to the consideration of solution.
In chemistry, the terms solution and dissolution have often been confused and used interchangeably to describe both the separation of salt particles in a liquid like water and the breakdown of a metal in an acid. A brief look at the effects of these two processes shows that they shouldn't be mixed up. In the process of dissolving salts, the salt particles are simply separated from one another, while neither the salt nor the water is broken down; we can recover both in the same amounts as before the process. The same occurs with resins dissolving in alcohol. In contrast, during metallic dissolutions, decomposition always happens, either of the acid or of the water that dilutes it; the metal combines with oxygen and turns into an oxide, and a gas is produced. Therefore, none of the substances[Pg 369] used remain in the same state after the process. This article focuses solely on the topic of solution.
To understand properly what takes place during the solution of salts, it is necessary to know, that, in most of these operations, two distinct effects are complicated together, viz. solution by water, and solution by caloric; and, as the explanation of most of the phenomena of solution depends upon the distinction of these two circumstances, I shall enlarge a little upon their nature.
To properly understand what happens during the dissolving of salts, it’s important to know that in most of these processes, two different effects are combined: dissolving in water and dissolving through heat. Since the explanation of many solution phenomena relies on distinguishing between these two aspects, I will expand a bit on their nature.
Nitrat of potash, usually called nitre or saltpetre, contains very little water of cristallization, perhaps even none at all; yet this salt liquifies in a degree of heat very little superior to that of boiling water. This liquifaction cannot therefore be produced by means of the water of cristallization, but in consequence of the salt being very fusible in its nature, and from its passing from the solid to the liquid state of aggregation, when but a little raised above the temperature of boiling water. All salts are in this manner susceptible of being liquified by caloric, but in higher or lower degrees of temperature. Some of these, as the acetites of potash and soda, liquify with a very moderate heat, whilst others, as sulphat of potash, lime, &c. require the strongest fires we are capable of producing. This liquifaction[Pg 370] of salts by caloric produces exactly the same phenomena with the melting of ice; it is accomplished in each salt by a determinate degree of heat, which remains invariably the same during the whole time of the liquifaction. Caloric is employed, and becomes fixed during the melting of the salt, and is, on the contrary, disengaged when the salt coagulates. These are general phenomena which universally occur during the passage of every species of substance from the solid to the fluid state of aggregation, and from fluid to solid.
Potassium nitrate, commonly known as nitre or saltpetre, has very little or possibly no water of crystallization. However, this salt melts at a temperature slightly above that of boiling water. This melting is not caused by water of crystallization; it happens because the salt is very fusible and transitions from solid to liquid when it's just a bit above the boiling point of water. All salts can be melted by heat, but it requires different temperatures for each one. Some, like potassium and sodium acetates, melt at relatively low temperatures, while others, such as potassium and lime sulfates, need very high temperatures to melt. This melting[Pg 370] of salts due to heat resembles the melting of ice; each salt melts at a specific temperature that remains constant throughout the melting process. Heat is absorbed and fixed while the salt melts and is released when the salt solidifies. These are general phenomena that occur whenever any substance changes from solid to liquid and then back to solid.
These phenomena arising from solution by caloric are always less or more conjoined with those which take place during solutions in water. We cannot pour water upon a salt, on purpose to dissolve it, without employing a compound solvent, both water and caloric; hence we may distinguish several different cases of solution, according to the nature and mode of existence of each salt. If, for instance, a salt be difficultly soluble in water, and readily so by caloric, it evidently follows, that this salt will be difficultly soluble in cold water, and considerably in hot water; such is nitrat of potash, and more especially oxygenated muriat of potash. If another salt be little soluble both in water and caloric, the difference of its solubility in cold and warm water will be very inconsiderable; sulphat of lime is of this kind. From these considerations,[Pg 371] it follows, that there is a necessary relation between the following circumstances; the solubility of a salt in cold water, its solubility in boiling water, and the degree of temperature at which the same salt liquifies by caloric, unassisted by water; and that the difference of solubility in hot and cold water is so much greater in proportion to its ready solution in caloric, or in proportion to its susceptibility of liquifying in a low degree of temperature.
These phenomena that arise from dissolving substances with heat are always linked, more or less, to what happens when substances dissolve in water. We can't just pour water on a salt to dissolve it without using a mixed solvent, which includes both water and heat. Therefore, we can identify several different scenarios of dissolution, depending on the type of salt and how it exists. For example, if a salt is hard to dissolve in water but easily dissolved with heat, it clearly follows that this salt will be hard to dissolve in cold water and much easier in hot water; this is the case with potassium nitrate, especially the oxygenated potassium chloride. If another salt is not very soluble in either water or heat, the difference in its solubility in cold and warm water will be minor; calcium sulfate is one such example. Based on these points, [Pg 371] we can conclude that there is an essential relationship between the following factors: the solubility of a salt in cold water, its solubility in boiling water, and the temperature at which the same salt melts when heated without water. Additionally, the difference in solubility between hot and cold water becomes significantly larger in relation to its ease of dissolving with heat, or in relation to its ability to melt at a lower temperature.
The above is a general view of solution; but, for want of particular facts, and sufficiently exact experiments, it is still nothing more than an approximation towards a particular theory. The means of compleating this part of chemical science is extremely simple; we have only to ascertain how much of each salt is dissolved by a certain quantity of water at different degrees of temperature; and as, by the experiments published by Mr de la Place and me, the quantity of caloric contained in a pound of water at each degree of the thermometer is accurately known, it will be very easy to determine, by simple experiments, the proportion of water and caloric required for solution by each salt, what quantity of caloric is absorbed by each at the moment of liquifaction, and how much is disengaged at the moment of cristallization. Hence the reason why salts are more rapidly soluble in hot than in cold water is perfectly evident. In all solutions[Pg 372] of salts caloric is employed; when that is furnished intermediately from the surrounding bodies, it can only arrive slowly to the salt; whereas this is greatly accelerated when the requisite caloric exists ready combined with the water of solution.
The above is a general overview of the solution; however, due to a lack of specific facts and sufficiently accurate experiments, it remains just an approximation of a particular theory. The process of completing this aspect of chemical science is very straightforward; we simply need to find out how much of each salt dissolves in a given amount of water at different temperatures. Since the experiments published by Mr. de la Place and myself accurately determine the amount of heat contained in a pound of water at each degree of the thermometer, it will be quite easy to find out, through simple experiments, the ratio of water and heat needed for each salt to dissolve, how much heat is absorbed by each during melting, and how much is released during crystallization. This explains why salts dissolve more quickly in hot water than in cold. In all salt solutions[Pg 372], heat is utilized; when it is provided from surrounding sources, it can only reach the salt slowly, while this process is greatly sped up when the necessary heat is already combined with the water used for the solution.
In general, the specific gravity of water is augmented by holding salts in solution; but there are some exceptions to the rule. Some time hence, the quantities of radical, of oxygen, and of base, which constitute each neutral salt, the quantity of water and caloric necessary for solution, the increased specific gravity communicated to water, and the figure of the elementary particles of the cristals, will all be accurately known. From these all the circumstances and phenomena of cristallization will be explained, and by these means this part of chemistry will be compleated. Mr Seguin has formed the plan of a thorough investigation of this kind, which he is extremely capable of executing.
In general, the specific gravity of water increases when salts are dissolved in it, but there are some exceptions to this rule. In the future, we will have a clear understanding of the amounts of radicals, oxygen, and bases that make up each neutral salt, along with the amount of water and heat needed for dissolution, the increased specific gravity of water, and the shape of the elementary particles of the crystals. All the factors and processes of crystallization will then be explained, and this area of chemistry will be complete. Mr. Seguin has devised a plan for a comprehensive study of this kind, which he is well-equipped to carry out.
The solution of salts in water requires no particular apparatus; small glass phials of different sizes, Pl. II. Fig. 16. and 17. pans of earthern ware, A, Fig. 1. and 2. long-necked matrasses, Fig. 14. and pans or basons of copper or of silver, Fig. 13. and 15. answer very well for these operations.[Pg 373]
Dissolving salts in water doesn't need any special equipment; small glass bottles of various sizes, Pl. II. Fig. 16. and 17., clay dishes, A, Fig. 1. and 2., long-necked flasks, Fig. 14., and pans or bowls made of copper or silver, Fig. 13. and 15., work perfectly for these tasks.[Pg 373]
SECT. II.
Of Lixiviation.
This is an operation used in chemistry and manufactures for separating substances which are soluble in water from such as are insoluble. The large vat or tub, Pl. II. Fig. 12. having a hole D near its bottom, containing a wooden spiget and fosset or metallic stop-cock DE, is generally used for this purpose. A thin stratum of straw is placed at the bottom of the tub; over this, the substance to be lixiviated is laid and covered by a cloth, then hot or cold water, according to the degree of solubility of the saline matter, is poured on. When the water is supposed to have dissolved all the saline parts, it is let off by the stop-cock; and, as some of the water charged with salt necessarily adheres to the straw and insoluble matters, several fresh quantities of water are poured on. The straw serves to secure a proper passage for the water, and may be compared to the straws or glass rods used in filtrating, to keep the paper from touching the sides of the funnel. The cloth which is laid over the matters under lixiviation prevents the water from making a hollow in[Pg 374] these substances where it is poured on, through which it might escape without acting upon the whole mass.
This is a process used in chemistry and manufacturing to separate substances that dissolve in water from those that don’t. The large container, Pl. II. Fig. 12., has a hole D near its bottom with a wooden spigot and a metal stopcock DE, which is typically used for this purpose. A thin layer of straw is placed at the bottom of the container; on top of this, the substance to be leached is added and covered with a cloth. Then, hot or cold water is poured on it, depending on how soluble the salt is. Once the water has dissolved all the soluble parts, it is released through the stopcock. Since some of the salty water clings to the straw and the insoluble materials, several fresh amounts of water are poured on. The straw helps ensure good water flow and is similar to the straws or glass rods used in filtration to keep the paper from touching the sides of the funnel. The cloth laid over the substances being leached prevents the water from creating a depression in[Pg 374] those materials when it’s poured on, which could allow it to escape without affecting the entire mass.
This operation is less or more imitated in chemical experiments; but as in these, especially with analytical views, greater exactness is required, particular precautions must be employed, so as not to leave any saline or soluble part in the residuum. More water must be employed than in ordinary lixiviations, and the substances ought to be previously stirred up in the water before the clear liquor is drawn off, otherwise the whole mass might not be equally lixiviated, and some parts might even escape altogether from the action of the water. We must likewise employ fresh portions of water in considerable quantity, until it comes off entirely free from salt, which we may ascertain by means of the hydrometer formerly described.
This process is somewhat similar to procedures used in chemical experiments. However, since these experiments, especially for analytical purposes, require more precision, specific precautions must be taken to ensure that no saline or soluble materials are left in the residue. More water should be used than in regular leaching, and the substances should be thoroughly mixed in the water before the clear liquid is removed; otherwise, the entire mass might not be evenly leached, and some parts could completely miss the water's effect. We should also use fresh water in significant amounts until it is completely free of salt, which we can check using the hydrometer mentioned earlier.
In experiments with small quantities, this operation is conveniently performed in jugs or matrasses of glass, and by filtrating the liquor through paper in a glass funnel. When the substance is in larger quantity, it may be lixiviated in a kettle of boiling water, and filtrated through paper supported by cloth in the wooden frame, Pl. II. Fig. 3. and 4.; and in operations in the large way, the tub already mentioned must be used.[Pg 375]
In experiments with small amounts, this process is easily done in glass jugs or flasks, and by filtering the liquid through paper in a glass funnel. When the substance is in larger quantities, it can be leached in a kettle of boiling water and filtered through paper supported by cloth in a wooden frame, Pl. II. Fig. 3. and 4.; and for large-scale operations, the previously mentioned tub should be used.[Pg 375]
SECT. III.
Of Evaporation.
This operation is used for separating two substances from each other, of which one at least must be fluid, and whose degrees of volatility are considerably different. By this means we obtain a salt, which has been dissolved in water, in its concrete form; the water, by heating, becomes combined with caloric, which renders it volatile, while the particles of the salt being brought nearer to each other, and within the sphere of their mutual attraction, unite into the solid state.
This process is used to separate two substances from one another, at least one of which must be a liquid, and whose volatility levels are significantly different. Through this method, we obtain salt that has been dissolved in water in its solid form; when heated, the water combines with heat, making it evaporate, while the particles of the salt come closer together and, within the range of their mutual attraction, bond into a solid state.
As it was long thought that the air had great influence upon the quantity of fluid evaporated, it will be proper to point out the errors which this opinion has produced. There certainly is a constant slow evaporation from fluids exposed to the free air; and, though this species of evaporation may be considered in some degree as a solution in air, yet caloric has considerable influence in producing it, as is evident from the refrigeration which always accompanies this process; hence we may consider this gradual evaporation as a compound solution made partly in[Pg 376] air, and partly in caloric. But the evaporation which takes place from a fluid kept continually boiling, is quite different in its nature, and in it the evaporation produced by the action of the air is exceedingly inconsiderable in comparison with that which is occasioned by caloric. This latter species may be termed vaporization rather than evaporation. This process is not accelerated in proportion to the extent of evaporating surface, but in proportion to the quantities of caloric which combine with the fluid. Too free a current of cold air is often hurtful to this process, as it tends to carry off caloric from the water, and consequently retards its conversion into vapour. Hence there is no inconvenience produced by covering, in a certain degree, the vessels in which liquids are evaporated by continual boiling, provided the covering body be of such a nature as does not strongly draw off the caloric, or, to use an expression of Dr Franklin's, provided it be a bad conductor of heat. In this case, the vapours escape through such opening as is left, and at least as much is evaporated, frequently more than when free access is allowed to the external air.
As it was once believed that the air greatly affected the amount of fluid that evaporated, it's important to highlight the misconceptions this belief has caused. There is definitely a slow, constant evaporation from fluids exposed to open air; and while this type of evaporation can be seen as a sort of solution in air, heat plays a significant role in causing it, as shown by the cooling that always accompanies this process. Therefore, we can think of this gradual evaporation as a combined solution occurring partly in [Pg 376] air and partly in heat. However, the evaporation from a fluid that is kept boiling continuously is quite different, and the evaporation caused by air is minimal compared to that caused by heat. This latter process can be referred to as vaporization rather than evaporation. This process is not sped up by the size of the evaporating surface but by the amount of heat interacting with the fluid. A too-strong current of cold air can often harm this process, as it tends to carry heat away from the water and thus slows down its transformation into vapor. Therefore, there's no problem in partially covering the containers holding liquids that are evaporating through continuous boiling, as long as the covering material does not significantly draw off the heat, or, as Dr. Franklin put it, as long as it is a poor conductor of heat. In this situation, the vapors escape through any openings left, and often more is evaporated than when there's unrestricted access to outside air.
As during evaporation the fluid carried off by caloric is entirely lost, being sacrificed for the sake of the fixed substances with which it was combined, this process is only employed where the fluid is of small value, as water, for instance.[Pg 377] But, when the fluid is of more consequence, we have recourse to distillation, in which process we preserve both the fixed substance and the volatile fluid. The vessels employed for evaporation are basons or pans of copper, silver, or lead, Pl. II. Fig. 13. and 15. or capsules of glass, porcellain, or stone ware, Pl. II. A, Fig. 1. and 2. Pl. III. Fig. 3 and 4. The best utensils for this purpose are made of the bottoms of glass retorts and matrasses, as their equal thinness renders them more fit than any other kind of glass vessel for bearing a brisk fire and sudden alterations of heat and cold without breaking.
As evaporation occurs, the liquid that is taken away by heat is completely lost, sacrificed for the fixed substances it's mixed with. This method is only used when the liquid is of low value, like water, for example.[Pg 377] However, when the liquid has greater significance, we use distillation, a process that allows us to keep both the fixed substance and the volatile liquid. The containers used for evaporation are bowls or pans made of copper, silver, or lead, Pl. II. Fig. 13 and 15, or glass, porcelain, or stoneware capsules, Pl. II. A, Fig. 1 and 2, Pl. III. Fig. 3 and 4. The best tools for this purpose are made from the bottoms of glass retorts and flasks, as their uniform thinness makes them better than any other type of glass vessel for handling a strong fire and sudden changes in temperature without breaking.
As the method of cutting these glass vessels is no where described in books, I shall here give a description of it, that they may be made by chemists for themselves out of spoiled retorts, matrasses, and recipients, at a much cheaper rate than any which can be procured from glass manufacturers. The instrument, Pl. III. Fig. 5. consisting of an iron ring AC, fixed to the rod AB, having a wooden handle D, is employed as follows: Make the ring red hot in the fire, and put it upon the matrass G, Fig. 6. which is to be cut; when the glass is sufficiently heated, throw on a little cold water, and it will generally break exactly at the circular line heated by the ring.
As the method for cutting these glass vessels isn't described in any books, I will give an explanation here so that chemists can make them from damaged retorts, flasks, and containers at a much cheaper price than what they can buy from glass manufacturers. The tool, shown in Pl. III. Fig. 5, consists of an iron ring AC attached to a rod AB with a wooden handle D. Here's how to use it: Heat the ring until it’s red hot in the fire, then place it on the flask G, Fig. 6, that you want to cut. Once the glass is hot enough, splash a bit of cold water on it, and it will usually break right along the circular line heated by the ring.
Small flasks or phials of thin glass are exceeding good vessels for evaporating small quantities[Pg 378] of fluid; they are very cheap, and stand the fire remarkably. One or more of these may be placed upon a second grate above the furnace, Pl. III. Fig. 2. where they will only experience a gentle heat. By this means a great number of experiments may be carried on at one time. A glass retort, placed in a sand bath, and covered with a dome of baked earth, Pl. III. Fig. 1. answers pretty well for evaporations; but in this way it is always considerably slower, and is even liable to accidents; as the sand heats unequally, and the glass cannot dilate in the same unequal manner, the retort is very liable to break. Sometimes the sand serves exactly the office of the iron ring formerly mentioned; for, if a single drop of vapour, condensed into liquid, happens to fall upon the heated part of the vessel, it breaks circularly at that place. When a very intense fire is necessary, earthen crucibles may be used; but we generally use the word evaporation to express what is produced by the temperature of boiling water, or not much higher.[Pg 379]
Small flasks or thin glass vials are excellent for evaporating small amounts[Pg 378] of liquid; they are quite inexpensive and can handle heat well. You can place one or more of these on a second grate above the furnace, as shown in Pl. III. Fig. 2, where they will be exposed to gentle heat. This setup allows for many experiments to be conducted simultaneously. A glass retort placed in a sand bath and covered with a dome made of baked earth, as shown in Pl. III. Fig. 1, works fairly well for evaporation; however, it tends to be slower and can be prone to accidents because the sand heats unevenly. Since the glass can't expand at the same uneven rate, the retort is at a high risk of breaking. Sometimes, the sand acts like the iron ring mentioned earlier; if even a single drop of condensed vapor lands on the hot part of the vessel, it can cause it to break in a circular pattern. When a very high temperature is needed, earthen crucibles can be used, but we typically use the term evaporation to refer to what's produced at the boiling point of water or slightly above.[Pg 379]
SECT. IV.
Of Cristallization.
In this process the integrant parts of a solid body, separated from each other by the intervention of a fluid, are made to exert the mutual attraction of aggregation, so as to coalesce and reproduce a solid mass. When the particles of a body are only separated by caloric, and the substance is thereby retained in the liquid state, all that is necessary for making it cristallize, is to remove a part of the caloric which is lodged between its particles, or, in other words, to cool it. If this refrigeration be slow, and the body be at the same time left at rest, its particles assume a regular arrangement, and cristallization, properly so called, takes place; but, if the refrigeration is made rapidly, or if the liquor be agitated at the moment of its passage to the concrete state, the cristallization is irregular and confused.
In this process, the individual parts of a solid body, which are separated by a fluid, come together to exert a mutual attraction that causes them to merge and form a solid mass. When the particles of a body are only separated by heat, keeping the substance in a liquid state, all that's needed to make it crystallize is to remove some of the heat that’s between its particles, or in other words, to cool it down. If this cooling happens slowly and the body is left undisturbed, its particles will arrange themselves in an orderly way, resulting in proper crystallization. However, if the cooling occurs quickly or if the liquid is stirred while transitioning to a solid state, the crystallization will be irregular and messy.
The same phenomena occur with watery solutions, or rather in those made partly in water, and partly by caloric. So long as there remains a sufficiency of water and caloric to keep the particles of the body asunder beyond the sphere[Pg 380] of their mutual attraction, the salt remains in the fluid state; but, whenever either caloric or water is not present in sufficient quantity, and the attraction of the particles for each other becomes superior to the power which keeps them asunder, the salt recovers its concrete form, and the cristals produced are the more regular in proportion as the evaporation has been slower and more tranquilly performed.
The same phenomena happen with watery solutions, or rather with those made partly in water and partly with heat. As long as there is enough water and heat to keep the particles of the substance apart from each other, the salt stays in a fluid state. However, whenever there's not enough heat or water and the attraction between the particles becomes stronger than the force keeping them apart, the salt returns to its solid form, and the crystals formed are more regular the slower and more calmly the evaporation occurred.
All the phenomena we formerly mentioned as taking place during the solution of salts, occur in a contrary sense during their cristallization. Caloric is disengaged at the instant of their assuming the solid state, which furnishes an additional proof of salt being held in solution by the compound action of water and caloric. Hence, to cause salts to cristallize which readily liquify by means of caloric, it is not sufficient to carry off the water which held them in solution, but the caloric united to them must likewise be removed. Nitrat of potash, oxygenated muriat of potash, alum, sulphat of soda, &c. are examples of this circumstance, as, to make these salts cristallize, refrigeration must be added to evaporation. Such salts, on the contrary, as require little caloric for being kept in solution, and which, from that circumstance, are nearly equally soluble in cold and warm water, are cristallizable by simply carrying off the water which holds them in solution, and[Pg 381] even recover their solid state in boiling water; such are sulphat of lime, muriat of potash and of soda, and several others.
All the phenomena we previously mentioned that occur during the dissolution of salts happen in the opposite way during their crystallization. Heat is released the moment they turn into a solid, which provides additional evidence that salts are kept dissolved by the combined effects of water and heat. Therefore, to make salts crystallize that easily turn to liquid with heat, it's not enough to simply remove the water that dissolved them; the heat associated with them must also be removed. Potassium nitrate, potassium chlorate, alum, sodium sulfate, etc., are examples of this situation, as making these salts crystallize requires cooling in addition to evaporation. In contrast, salts that need little heat to stay dissolved, and are nearly equally soluble in both cold and warm water, can crystallize just by removing the water that keeps them dissolved, and[Pg 381] can even return to their solid form in boiling water; examples include calcium sulfate, potassium chloride, and sodium chloride, among others.
The art of refining saltpetre depends upon these properties of salts, and upon their different degrees of solubility in hot and cold water. This salt, as produced in the manufactories by the first operation, is composed of many different salts; some are deliquescent, and not susceptible of being cristallized, such as the nitrat and muriat of lime; others are almost equally soluble in hot and cold water, as the muriats of potash and of soda; and, lastly, the saltpetre, or nitrat of potash, is greatly more soluble in hot than it is in cold water. The operation is begun, by pouring upon this mixture of salts as much water as will hold even the least soluble, the muriats of soda and of potash, in solution; so long as it is hot, this quantity readily dissolves all the saltpetre, but, upon cooling, the greater part of this salt cristallizes, leaving about a sixth part remaining dissolved, and mixed with the nitrat of lime and the two muriats. The nitre obtained by this process is still somewhat impregnated with other salts, because it has been cristallized from water in which these abound: It is completely purified from these by a second solution in a small quantity of boiling water, and second cristallization. The water remaining after these cristallizations of nitre is still loaded with a mixture[Pg 382] of saltpetre, and other salts; by farther evaporation, crude saltpetre, or rough-petre, as the workmen call it, is procured from it, and this is purified by two fresh solutions and cristallizations.
The process of refining saltpetre relies on the properties of salts and their varying degrees of solubility in hot and cold water. The salt produced in factories during the initial stage consists of many different salts; some are deliquescent and can't be crystallized, like the nitrate and muriate of lime; others are almost equally soluble in both hot and cold water, such as the muriates of potash and soda; and finally, saltpetre, or nitrate of potash, is much more soluble in hot water than in cold. The process begins by adding enough water to this mixture of salts to dissolve even the least soluble ones, the muriates of soda and potash. While the water is hot, it dissolves all the saltpetre, but as it cools, most of this salt crystallizes out, leaving about a sixth part still dissolved and mixed with the nitrate of lime and the two muriates. The nitre obtained from this process still contains some other salts because it has crystallized from water rich in them. It is fully purified through a second dissolution in a small amount of boiling water and a second crystallization. The water left after these crystallizations of nitre still contains a mix of saltpetre and other salts; through further evaporation, crude saltpetre, or rough-petre as the workers call it, is obtained from it, which is then purified by two additional dissolutions and crystallizations.
The deliquescent earthy salts which do not contain the nitric acid are rejected in this manufacture; but those which consist of that acid neutralized by an earthy base are dissolved in water, the earth is precipitated by means of potash, and allowed to subside; the clear liquor is then decanted, evaporated, and allowed to cristallize. The above management for refining saltpetre may serve as a general rule for separating salts from each other which happen to be mixed together. The nature of each must be considered, the proportion in which each dissolves in given quantities of water, and the different solubility of each in hot and cold water. If to these we add the property which some salts possess, of being soluble in alkohol, or in a mixture of alkohol and water, we have many resources for separating salts from each other by means of cristallization, though it must be allowed that it is extremely difficult to render this separation perfectly complete.
The dissolvable earthy salts that don’t contain nitric acid are discarded in this process; however, those that consist of that acid neutralized by an earthy base are dissolved in water. The earth is then taken out using potash and allowed to settle. The clear liquid is then poured off, evaporated, and left to crystallize. This method for refining saltpeter can serve as a general guideline for separating mixed salts. Each salt's characteristics need to be considered, along with how much of each dissolves in specific amounts of water and their differing solubility in hot and cold water. Additionally, if we include the property of some salts being soluble in alcohol or a mix of alcohol and water, we have various methods for separating salts through crystallization, although it’s important to note that achieving a perfectly complete separation is extremely challenging.
The vessels used for cristallization are pans of earthen ware, A, Pl. II. Fig. 1. and 2. and large flat dishes, Pl. III. Fig. 7. When a saline solution is to be exposed to a slow evaporation[Pg 383] in the heat of the atmosphere, with free access of air, vessels of some depth, Pl. III. Fig. 3. must be employed, that there may be a considerable body of liquid; by this means the cristals produced are of considerable size, and remarkably regular in their figure.
The containers used for crystallization are earthenware pans, A, Pl. II. Fig. 1 and 2, and large flat dishes, Pl. III. Fig. 7. When a saline solution needs to be slowly evaporated[Pg 383] in the warm air, with plenty of airflow, you should use deeper vessels, Pl. III. Fig. 3. This allows for a larger volume of liquid; as a result, the crystals formed will be larger and have a more uniform shape.
Every species of salt cristallizes in a peculiar form, and even each salt varies in the form of its cristals according to circumstances, which take place during cristallization. We must not from thence conclude that the saline particles of each species are indeterminate in their figures: The primative particles of all bodies, especially of salts, are perfectly constant in their specific forms; but the cristals which form in our experiments are composed of congeries of minute particles, which, though perfectly equal in size and shape, may assume very dissimilar arrangements, and consequently produce a vast variety of regular forms, which have not the smallest apparent resemblance to each other, nor to the original cristal. This subject has been very ably treated by the Abbé Haüy, in several memoirs presented to the Academy, and in his work upon the structure of cristals: It is only necessary to extend generally to the class of salts the principles he has particularly applied to some cristalized stones.[Pg 384]
Every type of salt crystallizes in a unique shape, and even within the same salt, the form of its crystals can change depending on the conditions during crystallization. We shouldn't conclude that the salt particles of each type are random in shape. The basic particles of all substances, especially salts, are consistently defined in their specific forms; however, the crystals we form in our experiments consist of groups of tiny particles that, while equal in size and shape, can arrange themselves in very different ways. This leads to a wide variety of regular shapes that bear no resemblance to one another or to the original crystal. This topic has been skillfully addressed by Abbé Haüy in several papers he presented to the Academy, as well as in his work on the structure of crystals. It is only necessary to generally apply the principles he specifically used for some crystallized stones to the broader class of salts.[Pg 384]
SECT. V.
Of Simple Distillation.
As distillation has two distinct objects to accomplish, it is divisible into simple and compound; and, in this section, I mean to confine myself entirely to the former. When two bodies, of which one is more volatile than the other, or has more affinity to caloric, are submitted to distillation, our intention is to separate them from each other: The more volatile substance assumes the form of gas, and is afterwards condensed by refrigeration in proper vessels. In this case distillation, like evaporation, becomes a species of mechanical operation, which separates two substances from each other without decomposing or altering the nature of either. In evaporation, our only object is to preserve the fixed body, without paying any regard to the volatile matter; whereas, in distillation, our principal attention is generally paid to the volatile substance, unless when we intend to preserve both the one and the other. Hence, simple distillation is nothing more than evaporation produced in close vessels.
As distillation has two main goals, it can be divided into simple and compound types; in this section, I will focus only on the former. When two substances are distilled, and one is more volatile or has a stronger attraction to heat than the other, our goal is to separate them. The more volatile substance turns into gas and is later condensed by cooling in appropriate containers. In this instance, distillation, like evaporation, acts as a mechanical process that separates two substances without breaking down or changing the nature of either. In evaporation, our primary goal is to keep the non-volatile substance intact, without concern for the volatile matter; however, in distillation, we usually pay more attention to the volatile substance unless we want to preserve both. Thus, simple distillation is essentially evaporation that occurs in closed containers.
The most simple distilling vessel is a species of bottle or matrass, A, Pl. III. Fig. 8. which has[Pg 385] been bent from its original form BC to BD, and which is then called a retort; when used, it is placed either in a reverberatory furnace, Pl. XIII. Fig. 2. or in a sand bath under a dome of baked earth, Pl. III. Fig. 1. To receive and condense the products, we adapt a recipient, E, Pl. III. Fig. 9. which is luted to the retort. Sometimes, more especially in pharmaceutical operations, the glass or stone ware cucurbit, A, with its capital B, Pl. III. Fig. 12, or the glass alembic and capital, Fig. 13. of one piece, is employed. This latter is managed by means of a tubulated opening T, fitted with a ground stopper of cristal; the capital, both of the cucurbit and alembic, has a furrow or trench, r r, intended for conveying the condensed liquor into the beak RS, by which it runs out. As, in almost all distillations, expansive vapours are produced, which might burst the vessels employed, we are under the necessity of having a small hole, T, Fig. 9. in the balloon or recipient, through which these may find vent; hence, in this way of distilling, all the products which are permanently aëriform are entirely lost, and even such as difficultly lose that state have not sufficient space to condense in the balloon: This apparatus is not, therefore, proper for experiments of investigation, and can only be admitted in the ordinary operations of the laboratory or in pharmacy. In the article appropriated for compound[Pg 386] distillation, I shall explain the various methods which have been contrived for preserving the whole products from bodies in this process.
The simplest distilling vessel is a type of bottle or flask, A, Pl. III. Fig. 8, which has been shaped from its original form BC to BD, and is then called a retort. When in use, it is placed either in a reverberatory furnace, Pl. XIII. Fig. 2, or in a sand bath under a dome of baked earth, Pl. III. Fig. 1. To collect and condense the products, we use a container, E, Pl. III. Fig. 9, which is sealed to the retort. Sometimes, especially in pharmaceutical processes, the glass or stoneware cucurbit, A, with its lid B, Pl. III. Fig. 12, or the glass alembic and lid, Fig. 13, made from a single piece, is used. The latter is operated using a tubulated opening T, which is fitted with a ground glass stopper; the lid of both the cucurbit and alembic has a groove or channel, r r, designed to direct the condensed liquid into the spout RS, from which it flows out. Since, in almost all distillations, expanding vapors are produced that could break the vessels, we need to have a small hole, T, Fig. 9, in the container or receiver so that these vapors can escape. Therefore, in this method of distillation, all products that are permanently gaseous are completely lost, and even those that only slowly lose that state do not have enough space to condense in the container. This setup is not suitable for experimental research and can only be used for routine operations in the lab or pharmacy. In the section dedicated to compound distillation, I will explain the various methods that have been developed to capture all products from substances in this process.
As glass or earthen vessels are very brittle, and do not readily bear sudden alterations of heat and cold, every well regulated laboratory ought to have one or more alembics of metal for distilling water, spiritous liquors, essential oils, &c. This apparatus consists of a cucurbit and capital of tinned copper or brass, Pl. III. Fig. 15. and 16. which, when judged proper, may be placed in the water bath, D, Fig. 17. In distillations, especially of spiritous liquors, the capital must be furnished with a refrigetory, SS, Fig. 16. kept continually filled with cold water; when the water becomes heated, it is let off by the stop-cock, R, and renewed with a fresh supply of cold water. As the fluid distilled is converted into gas by means of caloric furnished by the fire of the furnace, it is evident that it could not condense, and, consequently, that no distillation, properly speaking, could take place, unless it is made to deposit in the capital all the caloric it received in the cucurbit; with this view, the sides of the capital must always be preserved at a lower temperature than is necessary for keeping the distilling substance in the state of gas, and the water in the refrigetory is intended for this purpose.[Pg 387] Water is converted into gas by the temperature of 80° (212°), alkohol by 67° (182.75°), ether by 32° (104°); hence these substances cannot be distilled, or, rather, they will fly off in the state of gas, unless the temperature of the refrigetory be kept under these respective degrees.
As glass or ceramic containers are very fragile and can’t handle sudden changes in temperature, every well-organized lab should have one or more metal alembics for distilling water, alcoholic drinks, essential oils, etc. This equipment includes a cupric and cap made of tinned copper or brass, as shown in Pl. III, Fig. 15 and 16, which can be placed in a water bath, D, Fig. 17 when necessary. During distillations, particularly with alcoholic beverages, the cap must be equipped with a cooler, SS, Fig. 16, that’s kept constantly filled with cold water; when the water heats up, it’s released through the stop-cock, R, and replaced with a fresh supply of cold water. Since the liquid being distilled turns into gas due to the heat provided by the furnace, it’s clear that it can’t condense, and therefore, proper distillation can’t occur unless it deposits all the heat it received in the cupric into the cap; for this reason, the sides of the cap must always be maintained at a lower temperature than what’s needed to keep the distilling substance in its gaseous state, and the water in the cooler serves this purpose.[Pg 387] Water turns into gas at 80° (212°), alcohol at 67° (182.75°), and ether at 32° (104°); thus, these substances can’t be distilled, or they will evaporate as gas unless the cooler’s temperature is kept below these specific degrees.
In the distillation of spiritous, and other expansive liquors, the above described refrigetory is not sufficient for condensing all the vapours which arise; in this case, therefore, instead of receiving the distilled liquor immediately from the beak, TU, of the capital into a recipient, a worm is interposed between them. This instrument is represented Pl. III. Fig. 18. contained in a worm tub of tinned copper, it consists of a metallic tube bent into a considerable number of spiral revolutions. The vessel which contains the worm is kept full of cold water, which is renewed as it grows warm. This contrivance is employed in all distilleries of spirits, without the intervention of a capital and refrigetory, properly so called. The one represented in the plate is furnished with two worms, one of them being particularly appropriated to distillations of odoriferous substances.
In the distillation of alcoholic and other volatile liquids, the refrigerator described above is not enough to condense all the vapors that are produced. In this case, instead of collecting the distilled liquid directly from the beak, TU, of the still into a container, a worm is placed between them. This device is shown in Pl. III. Fig. 18. It is housed in a tinned copper worm tub and consists of a metal tube bent into many spiral coils. The container holding the worm is filled with cold water, which is replaced as it warms up. This setup is used in all spirit distilleries, without needing a still and a properly named refrigerator. The one shown in the plate has two worms, with one specifically designed for distilling fragrant substances.
In some simple distillations it is necessary to interpose an adopter between the retort and receiver, as shown Pl. III. Fig, 11. This may[Pg 388] serve two different purposes, either to separate two products of different degrees of volatility, or to remove the receiver to a greater distance from the furnace, that it may be less heated. But these, and several other more complicated instruments of ancient contrivance, are far from producing the accuracy requisite in modern chemistry, as will be readily perceived when I come to treat of compound distillation.
In some simple distillations, it's necessary to place an adopter between the retort and receiver, as shown in Pl. III. Fig. 11. This can serve two different purposes: either to separate two products with different volatility levels or to move the receiver further away from the furnace so it heats less. However, these and several other more complicated devices from earlier times lack the precision needed in modern chemistry, which will become clear when I discuss compound distillation.
SECT. VI.
Of Sublimation.
This term is applied to the distillation of substances which condense in a concrete or solid form, such as the sublimation of sulphur, and of muriat of ammoniac, or sal ammoniac. These operations may be conveniently performed in the ordinary distilling vessels already described, though, in the sublimation of sulphur, a species of vessels, named Alludels, have been usually employed. These are vessels of stone or porcelain ware, which adjust to each other over a cucurbit containing the sulphur to be sublimed. One of the best subliming vessels, for substances which are not very volatile, is a flask,[Pg 389] or phial of glass, sunk about two thirds into a sand bath; but in this way we are apt to lose a part of the products. When these are wished to be entirely preserved, we must have recourse to the pneumato-chemical distilling apparatus, to be described in the following chapter.
This term refers to the distillation of substances that solidify or turn into a solid form, like the sublimation of sulfur and ammonium chloride, or sal ammoniac. These processes can be conveniently carried out in the regular distillation equipment already mentioned, although for the sublimation of sulfur, a type of vessel called Alludels is commonly used. These are containers made of stone or porcelain that fit together over a vessel containing the sulfur to be sublimated. One of the best vessels for sublimating substances that aren’t very volatile is a flask or glass vial, which is placed about two-thirds into a sand bath; however, this method can result in some of the products being lost. If we want to keep all the products, we need to use the pneumato-chemical distilling apparatus, which will be explained in the next chapter.
CHAP. VI.
Of Pneumato-chemical Distillations, Metallic Dissolutions, and some other operations which require very complicated instruments.
SECT. I.
Of Compound and Pneumato-chemical Distillations.
In the preceding chapter, I have only treated of distillation as a simple operation, by which two substances, differing in degrees of volatility, may be separated from each other; but distillation often actually decomposes the substances submitted to its action, and becomes one of the most complicated operations in chemistry. In every distillation, the substance distilled must be brought to the state of gas, in the cucurbit or retort, by combination with caloric: In simple distillation, this caloric is given out in the refrigeratory or in the worm, and the substance again recovers its liquid or solid form, but the substances submitted to compound distillation[Pg 391] are absolutely decompounded; one part, as for instance the charcoal they contain, remains fixed in the retort, and all the rest of the elements are reduced to gasses of different kinds. Some of these are susceptible of being condensed, and of recovering their solid or liquid forms, whilst others are permanently aëriform; one part of these are absorbable by water, some by the alkalies, and others are not susceptible of being absorbed at all. An ordinary distilling apparatus, such as has been described in the preceding chapter, is quite insufficient for retaining or for separating these diversified products, and we are obliged to have recourse, for this purpose, to methods of a more complicated nature.
In the previous chapter, I only discussed distillation as a straightforward process, where two substances with different boiling points are separated. However, distillation often actually breaks down the substances involved, making it one of the more complex operations in chemistry. During any distillation, the substance needs to be turned into gas in the flask or retort using heat. In basic distillation, this heat is released in the condenser or the cooling coil, causing the substance to return to its liquid or solid state. However, in complex distillation[Pg 391], the substances are completely broken down; one component, like the charcoal they contain, stays in the retort, while the rest are transformed into different gases. Some of these gases can be condensed back into solid or liquid forms, while others remain gaseous indefinitely. Some gases can be absorbed by water, some by alkalis, and others cannot be absorbed at all. A typical distillation setup, like the one described in the previous chapter, is not adequate for capturing or separating these various products, so we need to use more complicated methods for that purpose.
The apparatus I am about to describe is calculated for the most complicated distillations, and may be simplified according to circumstances. It consists of a tubulated glass retort A, Pl. IV. Fig. 1. having its beak fitted to a tubulated balloon or recipient BC; to the upper orifice D of the balloon a bent tube DEfg is adjusted, which, at its other extremity g, is plunged into the liquor contained in the bottle L, with three necks xxx. Three other similar bottles are connected with this first one, by means of three similar bent tubes disposed in the same manner; and the farthest neck of the last bottle is connected with a jar in a pneumato-chemical apparatus, by means of a bent[Pg 392] tube[60]. A determinate weight of distilled water is usually put into the first bottle, and the other three have each a solution of caustic potash in water. The weight of all these bottles, and of the water and alkaline solution they contain, must be accurately ascertained. Every thing being thus disposed, the junctures between the retort and recipient, and of the tube D of the latter, must be luted with fat lute, covered over with slips of linen, spread with lime and white of egg; all the other junctures are to be secured by a lute made of wax and rosin melted together.
The setup I'm about to describe is designed for the most complex distillations and can be simplified as needed. It consists of a glass retort A, Pl. IV. Fig. 1, with its spout connected to a tubulated balloon or vessel BC. A bent tube DEfg is attached to the top opening D of the balloon, with its other end g submerged in the liquid inside bottle L, which has three openings xxx. Three similar bottles are linked to the first one using three bent tubes arranged the same way, and the farthest spout of the last bottle connects to a jar in a pneumato-chemical setup via a bent[Pg 392] tube[60]. A specific amount of distilled water is usually placed in the first bottle, and each of the other three contains a solution of caustic potash in water. The weight of all the bottles along with the water and alkaline solution they hold must be precisely measured. Once everything is set up, the joints between the retort and the recipient, as well as the tube D of the latter, must be sealed with a thick lute and covered with strips of linen spread with lime and egg white; all other joints should be secured with a lute made from melted wax and rosin.
When all these dispositions are completed, and when, by means of heat applied to the retort A, the substance it contains becomes decomposed, it is evident that the least volatile products must condense or sublime in the beak or neck of the retort itself, where most of the concrete substances will fix themselves. The more volatile substances, as the lighter oils, ammoniac, and several others, will condense in the recipient GC, whilst the gasses, which are not susceptible of condensation by cold, will pass on by the tubes, and boil up through the liquors in the several bottles. Such as are absorbable[Pg 393] by water will remain in the first bottle, and those which caustic alkali can absorb will remain in the others; whilst such gasses as are not susceptible of absorption, either by water or alkalies, will escape by the tube RM, at the end of which they may be received into jars in a pneumato-chemical apparatus. The charcoal and fixed earth, &c. which form the substance or residuum, anciently called caput mortuum, remain behind in the retort.
When all these processes are finished, and when heat is applied to the retort A, causing the substance inside to decompose, it’s clear that the least volatile products will condense or sublime in the beak or neck of the retort itself, where most of the solid substances will settle. The more volatile substances, like lighter oils and ammonia, will condense in the recipient GC, while the gases that can’t condense with cold will pass through the tubes and bubble up through the liquids in the various bottles. Those that can be absorbed by water will stay in the first bottle, and those that caustic alkali can absorb will remain in the others; meanwhile, gases that can’t be absorbed, either by water or alkalies, will escape through the tube RM, where they can be collected in jars using a pneumatic-chemical setup. The charcoal and fixed earth, etc., which make up the residue, traditionally known as caput mortuum, remain in the retort.
In this manner of operating, we have always a very material proof of the accuracy of the analysis, as the whole weights of the products taken together, after the process is finished, must be exactly equal to the weight of the original substance submitted to distillation. Hence, for instance, if we have operated upon eight ounces of starch or gum arabic, the weight of the charry residuum in the retort, together with that of all the products gathered in its neck and the balloon, and of all the gas received into the jars by the tube RM added to the additional weight acquired by the bottles, must, when taken together, be exactly eight ounces. If the product be less or more, it proceeds from error, and the experiment must be repeated until a satisfactory result be procured, which ought not to differ more than six or eight grains in the pound from the weight of the substance submitted to experiment.[Pg 394]
In this way of working, we always have clear proof of the accuracy of the analysis, as the total weight of all the products combined, after the process is finished, must equal the weight of the original substance that was distilled. So, for example, if we start with eight ounces of starch or gum arabic, the weight of the leftover residue in the retort, plus the weight of all the products collected in its neck and the balloon, and the weight of all the gas collected in the jars via the tube RM, along with any extra weight gained by the bottles, must add up to exactly eight ounces. If the total is off by more or less, it's due to an error, and the experiment must be repeated until a satisfactory result is achieved, which should not differ by more than six or eight grains in a pound from the weight of the original substance being tested.[Pg 394]
In experiments of this kind, I for a long time met with an almost insurmountable difficulty, which must at last have obliged me to desist altogether, but for a very simple method of avoiding it, pointed out to me by Mr Hassenfratz. The smallest diminution in the heat of the furnace, and many other circumstances inseparable from this kind of experiments, cause frequent reabsorptions of gas; the water in the cistern of the pneumato-chemical apparatus rushes into the last bottle through the tube RM, the same circumstance happens from one bottle into another, and the fluid is often forced even into the recipient C. This accident is prevented by using bottles having three necks, as represented in the plate, into one of which, in each bottle, a capillary glass-tube St, st, st, st, is adapted, so as to have its lower extremity t immersed in the liquor. If any absorption takes place, either in the retort, or in any of the bottles, a sufficient quantity of external air enters, by means of these tubes, to fill up the void; and we get rid of the inconvenience at the price of having a small mixture of common air with the products of the experiment, which is thereby prevented from failing altogether. Though these tubes admit the external air, they cannot permit any of the gasseous substances to escape, as they are always shut below by the water of the bottles.[Pg 395]
In experiments like this, I faced a nearly impossible challenge for a long time, which would have forced me to give up completely if it weren't for a straightforward solution suggested by Mr. Hassenfratz. Even a slight drop in the furnace's heat and various other unavoidable factors associated with these experiments can lead to frequent gas reabsorption. The water in the cistern of the pneumatic-chemical apparatus rushes into the last bottle through the tube RM, and a similar process occurs from one bottle to another, often pushing the fluid into the recipient C. This issue is avoided by using bottles with three necks, as shown in the illustration, with a capillary glass tube St, st, st, st, attached to one neck in each bottle, whose lower end t is submerged in the liquid. If any absorption occurs, whether in the retort or any of the bottles, an adequate amount of external air enters through these tubes to fill the gap. This way, we eliminate the problem at the cost of having a slight mixture of regular air with the experiment's products, which prevents the process from failing completely. Although these tubes allow external air in, they prevent any gaseous substances from escaping since they are always sealed below by the water in the bottles.[Pg 395]
It is evident that, in the course of experiments with this apparatus, the liquor of the bottles must rise in these tubes in proportion to the pressure sustained by the gas or air contained in the bottles; and this pressure is determined by the height and gravity of the column of fluid contained in all the subsequent bottles. If we suppose that each bottle contains three inches of fluid, and that there are three inches of water in the cistern of the connected apparatus above the orifice of the tube RM, and allowing the gravity of the fluids to be only equal to that of water, it follows that the air in the first bottle must sustain a pressure equal to twelve inches of water; the water must therefore rise twelve inches in the tube S, connected with the first bottle, nine inches in that belonging to the second, six inches in the third, and three in the last; wherefore these tubes must be made somewhat more than twelve, nine, six, and three inches long respectively, allowance being made for oscillatory motions, which often take place in the liquids. It is sometimes necessary to introduce a similar tube between the retort and recipient; and, as the tube is not immersed in fluid at its lower extremity, until some has collected in the progress of the distillation, its upper end must be shut at first with a little lute, so as to be opened according to necessity, or after[Pg 396] there is sufficient liquid in the recipient to secure its lower extremity.
It's clear that during experiments with this setup, the liquid in the bottles needs to rise in these tubes in relation to the pressure from the gas or air inside the bottles. This pressure is determined by the height and weight of the fluid column in all the following bottles. If we assume each bottle holds three inches of fluid and there are three inches of water in the cistern of the connected setup above the opening of the tube RM, and considering the weight of the fluids is equivalent to that of water, the air in the first bottle must support a pressure equal to twelve inches of water. Therefore, the water must rise twelve inches in the tube S connected to the first bottle, nine inches in the second, six inches in the third, and three inches in the last. Thus, these tubes should be longer than twelve, nine, six, and three inches respectively, accounting for the oscillations that often occur in the liquids. Sometimes, it's necessary to add a similar tube between the retort and the recipient; and since the tube isn't submerged in fluid at its lower end until some has collected during distillation, its upper end should initially be sealed with a little lute, allowing it to be opened as needed, or after[Pg 396] there is enough liquid in the recipient to ensure its lower end is secure.
This apparatus cannot be used in very accurate experiments, when the substances intended to be operated upon have a very rapid action upon each other, or when one of them can only be introduced in small successive portions, as in such as produce violent effervescence when mixed together. In such cases, we employ a tubulated retort A, Pl. VII. Fig. 1. into which one of the substances is introduced, preferring always the solid body, if any such is to be treated, we then lute to the opening of the retort a bent tube BCDA, terminating at its upper extremity B in a funnel, and at its other end A in a capillary opening. The fluid material of the experiment is poured into the retort by means of this funnel, which must be made of such a length, from B to C, that the column of liquid introduced may counterbalance the resistance produced by the liquors contained in all the bottles, Pl. IV. Fig. 1.
This device can't be used in very precise experiments when the substances involved react quickly with each other, or when one can only be added in small, sequential amounts, especially if they create violent fizzing when combined. In these situations, we use a tubulated retort A, Pl. VII. Fig. 1. where one of the substances is added, always opting for the solid if one is available. Then, we seal the opening of the retort with a bent tube BCDA, ending at the upper end B with a funnel, and at the other end A with a narrow opening. The liquid for the experiment is poured into the retort through this funnel, which needs to be long enough, from B to C, to balance out the pressure created by the liquids in all the bottles, Pl. IV. Fig. 1.
Those who have not been accustomed to use the above described distilling apparatus may perhaps be startled at the great number of openings which require luting, and the time necessary for making all the previous preparations in experiments of this kind. It is very true that, if we take into account all the necessary weighings of materials and products, both before and[Pg 397] after the experiments, these preparatory and succeeding steps require much more time and attention than the experiment itself. But, when the experiment succeeds properly, we are well rewarded for all the time and trouble bestowed, as by one process carried on in this accurate manner much more just and extensive knowledge is acquired of the nature of the vegetable or animal substance thus submitted to investigation, than by many weeks assiduous labour in the ordinary method of proceeding.
Those who aren't used to the distilling setup described above might be taken aback by the number of connections that need sealing and the time it takes to prepare for these kinds of experiments. It's true that, when we consider all the necessary measurements of materials and products, both before and [Pg 397] after the experiments, these preparatory steps and follow-ups take much more time and attention than the experiment itself. However, when the experiment goes well, the payoff makes all the time and effort worthwhile, as this precise process provides a much deeper and broader understanding of the vegetable or animal substance being studied than many weeks of hard work using the usual methods.
When in want of bottles with three orifices, those with two may be used; it is even possible to introduce all the three tubes at one opening, so as to employ ordinary wide-mouthed bottles, provided the opening be sufficiently large. In this case we must carefully fit the bottles with corks very accurately cut, and boiled in a mixture of oil, wax, and turpentine. These corks are pierced with the necessary holes for receiving the tubes by means of a round file, as in Pl. IV. Fig. 8.[Pg 398]
When you need bottles with three openings, you can use those with two instead; it's even possible to fit all three tubes into one opening as long as you use regular wide-mouth bottles with a sufficiently large opening. In this case, you must carefully fit the bottles with corks that are precisely cut and boiled in a mixture of oil, wax, and turpentine. These corks should be pierced with the necessary holes for the tubes using a round file, as shown in Pl. IV. Fig. 8.[Pg 398]
SECT. II.
Of Metallic Dissolutions.
I have already pointed out the difference between solution of salts in water and metallic dissolutions. The former requires no particular vessels, whereas the latter requires very complicated vessels of late invention, that we may not lose any of the products of the experiment, and may thereby procure truly conclusive results of the phenomena which occur. The metals, in general, dissolve in acids with effervescence, which is only a motion excited in the solvent by the disengagement of a great number of bubbles of air or aëriform fluid, which proceed from the surface of the metal, and break at the surface of the liquid.
I’ve already pointed out the difference between salt solutions in water and metallic solutions. The former doesn’t need special containers, while the latter requires very complex vessels designed recently so we don’t lose any of the experiment's products, allowing us to get truly conclusive results about the phenomena that occur. Generally, metals dissolve in acids with bubbling, which is just a reaction in the solvent caused by a large number of bubbles of air or gas escaping from the surface of the metal and popping at the surface of the liquid.
Mr Cavendish and Dr Priestley were the first inventors of a proper apparatus for collecting these elastic fluids. That of Dr Priestley is extremely simple, and consists of a bottle A, Pl. VII. Fig. 2. with its cork B, through which passes the bent glass tube BC, which is engaged under a jar filled with water in the pneumato-chemical apparatus, or simply in a bason full of water. The metal is first introduced into the[Pg 399] bottle, the acid is then poured over it, and the bottle is instantly closed with its cork and tube, as represented in the plate. But this apparatus has its inconveniencies. When the acid is much concentrated, or the metal much divided, the effervescence begins before we have time to cork the bottle properly, and some gas escapes, by which we are prevented from ascertaining the quantity disengaged with rigorous exactness. In the next place, when we are obliged to employ heat, or when heat is produced by the process, a part of the acid distills, and mixes with the water of the pneumato-chemical apparatus, by which means we are deceived in our calculation of the quantity of acid decomposed. Besides these, the water in the cistern of the apparatus absorbs all the gas produced which is susceptible of absorption, and renders it impossible to collect these without loss.
Mr. Cavendish and Dr. Priestley were the first to create an effective apparatus for collecting these gases. Dr. Priestley’s design is very straightforward; it consists of a bottle A, Pl. VII. Fig. 2, with a cork B, through which a bent glass tube BC passes. This tube is placed under a jar filled with water in the pneumatic chemical apparatus or simply in a basin full of water. First, the metal is placed into the [Pg 399] bottle, then the acid is poured over it, and the bottle is quickly sealed with its cork and tube, as shown in the plate. However, this setup has its drawbacks. When the acid is highly concentrated or the metal is finely divided, the fizzing starts before we can properly seal the bottle, causing some gas to escape, which prevents us from accurately measuring the released amount. Additionally, when heat is necessary or generated during the process, some of the acid evaporates and mixes with the water in the pneumatic chemical apparatus, misleading us about the amount of acid that has been decomposed. Furthermore, the water in the apparatus's basin absorbs all of the gas produced that can be absorbed, making it impossible to collect everything without losing some of it.
To remedy these inconveniencies, I at first used a bottle with two necks, Pl. VII. Fig. 3. into one of which the glass funnel BC is luted so as to prevent any air escaping; a glass rod DE is fitted with emery to the funnel, so as to serve the purpose of a stopper. When it is used, the matter to be dissolved is first introduced into the bottle, and the acid is then permitted to pass in as slowly as we please, by raising the glass rod gently as often as is necessary until saturation is produced.[Pg 400]
To fix these issues, I initially used a bottle with two openings, Pl. VII. Fig. 3. One opening is sealed with a glass funnel BC to keep any air from escaping; a glass rod DE is attached with emery to the funnel, acting as a stopper. When using it, you first add the substance you want to dissolve into the bottle, and then you can slowly allow the acid to enter by gently lifting the glass rod as often as needed until saturation occurs.[Pg 400]
Another method has been since employed, which serves the same purpose, and is preferable to the last described in some instances. This consists in adapting to one of the mouths of the bottle A, Pl. VII. Fig. 4. a bent tube DEFG, having a capillary opening at D, and ending in a funnel at G. This tube is securely luted to the mouth C of the bottle. When any liquid is poured into the funnel, it falls down to F; and, if a sufficient quantity be added, it passes by the curvature E, and falls slowly into the bottle, so long as fresh liquor is supplied at the funnel. The liquor can never be forced out of the tube, and no gas can escape through it, because the weight of the liquid serves the purpose of an accurate cork.
Another method has been used that serves the same purpose and is sometimes better than the previous one described. This method involves fitting a bent tube DEFG to one of the openings of bottle A, Pl. VII. Fig. 4. The tube has a tiny opening at D and ends in a funnel at G. This tube is securely attached to the mouth C of the bottle. When any liquid is poured into the funnel, it flows down to F; and if enough liquid is added, it moves through the curve E and slowly enters the bottle as long as more liquid is poured into the funnel. The liquid can never be pushed out of the tube, and no gas can escape through it because the weight of the liquid acts like a perfect stopper.
To prevent any distillation of acid, especially in dissolutions accompanied with heat, this tube is adapted to the retort A, Pl. VII. Fig. 1. and a small tubulated recipient, M, is applied, in which any liquor which may distill is condensed. On purpose to separate any gas that is absorbable by water, we add the double necked bottle L, half filled with a solution of caustic potash; the alkali absorbs any carbonic acid gas, and usually only one or two other gasses pass into the jar of the connected pneumato-chemical apparatus through the tube NO. In the first chapter of this third part we have directed how these are to be separated and examined.[Pg 401] If one bottle of alkaline solution be not thought sufficient, two, three, or more, may be added.
To prevent any acid vapor from forming, especially in solutions that are heated, this tube connects to the retort A, Pl. VII. Fig. 1, and a small tubulated container, M, is used to condense any liquid that distills. To separate any gases that can be absorbed by water, we include the double-necked bottle L, which is half-filled with a solution of caustic potash; this alkaline solution absorbs any carbonic acid gas, and typically only one or two other gases pass into the jar of the connected pneumato-chemical setup through the tube NO. In the first chapter of this third part, we have outlined how to separate and analyze these gases. [Pg 401] If one bottle of alkaline solution is not enough, additional bottles can be added.
SECT. III.
Apparatus necessary in Experiments upon Vinous and Putrefactive Fermentations.
For these operations a peculiar apparatus, especially intended for this kind of experiment, is requisite. The one I am about to describe is finally adopted, as the best calculated for the purpose, after numerous corrections and improvements. It consists of a large matrass, A, Pl. X. fig. 1. holding about twelve pints, with a cap of brass a b, strongly cemented to its mouth, and into which is screwed a bent tube c d, furnished with a stop-cock e. To this tube is joined the glass recipient B, having three openings, one of which communicates with the bottle C, placed below it. To the posterior opening of this recipient is fitted a glass tube g h i, cemented at g and i to collets of brass, and intended to contain a very deliquescent concrete neutral salt, such as nitrat or muriat of lime, acetite of potash, &c. This tube communicates with two bottles D and E, filled to x and y with a solution of caustic potash.[Pg 402]
For these operations, a special piece of equipment designed for this kind of experiment is needed. The device I’m about to describe has been finalized as the most suitable after many adjustments and enhancements. It includes a large flask, A, Pl. X. fig. 1, holding about twelve pints, with a brass cap a b, securely attached to its opening, into which a bent tube c d with a stopcock e is screwed. This tube connects to the glass container B, which has three openings, one of which connects to the bottle C, located below it. The back opening of this container is fitted with a glass tube g h i, sealed at g and i to brass fittings, designed to hold a highly deliquescent neutral salt, such as nitrate or muriate of lime, potassium acetate, etc. This tube connects to two bottles D and E, which are filled to x and y with a caustic potash solution.[Pg 402]
All the parts of this machine are joined together by accurate screws, and the touching parts have greased leather interposed, to prevent any passage of air. Each piece is likewise furnished with two stop-cocks, by which its two extremities may be closed, so that we can weigh each separately at any period of the operation.
All the parts of this machine are connected by precise screws, and the areas that touch have greased leather between them to stop any airflow. Each piece also has two shut-off valves, which can close its ends, allowing us to weigh each part separately at any point during the process.
The fermentable matter, such as sugar, with a proper quantity of yeast, and diluted with water, is put into the matrass. Sometimes, when the fermentation is too rapid, a considerable quantity of froth is produced, which not only fills the neck of the matrass, but passes into the recipient, and from thence runs down into the bottle C. On purpose to collect this scum and must, and to prevent it from reaching the tube filled with deliquescent salts, the recipient and connected bottle are made of considerable capacity.
The fermentable materials, like sugar, along with the right amount of yeast and diluted with water, are placed into the flask. Occasionally, when the fermentation happens too quickly, a large amount of foam is generated, which not only fills the neck of the flask but also flows into the container and then down into bottle C. To collect this foam and liquid and to keep it from getting into the tube filled with hygroscopic salts, the container and the connected bottle are designed to hold a significant amount.
In the vinous fermentation, only carbonic acid gas is disengaged, carrying with it a small proportion of water in solution. A great part of this water is deposited in passing through the tube g h i, which is filled with a deliquescent salt in gross powder, and the quantity is ascertained by the augmentation of the weight of the salt. The carbonic acid gas bubbles up through the alkaline solution in the bottle D, to which it is conveyed by the tube k l m. Any small portion which may not be absorbed by this[Pg 403] first bottle is secured by the solution in the second bottle E, so that nothing, in general, passes into the jar F, except the common air contained in the vessels at the commencement of the experiment.
In the wine fermentation process, only carbon dioxide is released, taking a small amount of water with it. Much of this water is collected as it passes through the tube g h i, which is packed with a hygroscopic salt in coarse powder, and the amount is measured by the increase in the weight of the salt. The carbon dioxide bubbles up through the alkaline solution in bottle D, which it reaches via the tube k l m. Any small amount that isn't absorbed by this[Pg 403] first bottle is captured by the solution in the second bottle E, ensuring that generally, nothing else enters jar F except for the air that was in the vessels at the start of the experiment.
The same apparatus answers extremely well for experiments upon the putrefactive fermentation; but, in this case, a considerable quantity of hydrogen gas is disengaged through the tube q r s t u, by which it is conveyed into the jar F; and, as this disengagement is very rapid, especially in summer, the jar must be frequently changed. These putrefactive fermentations require constant attendance from the above circumstance, whereas the vinous fermentation hardly needs any. By means of this apparatus we can ascertain, with great precision, the weights of the substances submitted to fermentation, and of the liquid and aëriform products which are disengaged. What has been already said in Part I. Chap. XIII. upon the products of the vinous fermentation, may be consulted.[Pg 404]
The same setup works really well for experiments on putrefactive fermentation; however, in this case, a significant amount of hydrogen gas is released through the tube q r s t u, which then goes into the jar F. Since this release happens very quickly, especially in summer, the jar needs to be changed often. These putrefactive fermentations require constant monitoring due to this reason, while the vinous fermentation barely needs any attention. With this apparatus, we can precisely measure the weights of the substances undergoing fermentation, as well as the liquid and gas products that are released. For more information on the products of vinous fermentation, refer to what is discussed in Part I. Chap. XIII.[Pg 404]
SECT. IV.
Apparatus for the Decomposition of Water.
Having already given an account, in the first part of this work, of the experiments relative to the decomposition of water, I shall avoid any unnecessary repetitions, and only give a few summary observations upon the subject in this section. The principal substances which have the power of decomposing water are iron and charcoal; for which purpose, they require to be made red hot, otherwise the water is only reduced into vapours, and condenses afterwards by refrigeration, without sustaining the smallest alteration. In a red heat, on the contrary, iron or charcoal carry off the oxygen from its union with hydrogen; in the first case, black oxyd of iron is produced, and the hydrogen is disengaged pure in form of gas; in the other case, carbonic acid gas is formed, which disengages, mixed with the hydrogen gas; and this latter is commonly carbonated, or holds charcoal in solution.
Having already discussed the experiments related to the decomposition of water in the first part of this work, I’ll skip any unnecessary repetitions and only provide a few summary observations on the topic in this section. The main materials that can decompose water are iron and charcoal; to do this, they need to be heated to red hot. Otherwise, the water only turns into vapor and then condenses back when cooled, without any significant change. When heated to red hot, iron or charcoal remove the oxygen from its bond with hydrogen; in the case of iron, black iron oxide is produced, and hydrogen is released in its pure gaseous form. In the case of charcoal, carbonic acid gas is created, which is released along with the hydrogen gas; the latter is usually carbonated or contains charcoal dissolved in it.
A musket barrel, without its breach pin, answers exceedingly well for the decomposition of water, by means of iron, and one should be[Pg 405] chosen of considerable length, and pretty strong. When too short, so as to run the risk of heating the lute too much, a tube of copper is to be strongly soldered to one end. The barrel is placed in a long furnace, CDEF, Pl. VII. Fig. 11. so as to have a few degrees of inclination from E to F; a glass retort A, is luted to the upper extremity E, which contains water, and is placed upon the furnace VVXX. The lower extremity F is luted to a worm SS, which is connected with the tubulated bottle H, in which any water distilled without decomposition, during the operation, collects, and the disengaged gas is carried by the tube KK to jars in a pneumato-chemical apparatus. Instead of the retort a funnel may be employed, having its lower part shut by a stop-cock, through which the water is allowed to drop gradually into the gun-barrel. Immediately upon getting into contact with the heated part of the iron, the water is converted into steam, and the experiment proceeds in the same manner as if it were furnished in vapours from the retort.
A musket barrel, without its breach pin, works really well for breaking down water with iron, and you should choose one that’s fairly long and strong. If it’s too short and risks overheating the lute too much, you should strongly solder a copper tube to one end. The barrel is placed in a long furnace, CDEF, Pl. VII. Fig. 11, with a slight incline from E to F; a glass retort A is attached to the upper end E, which holds water, and is placed on the furnace VVXX. The lower end F is attached to a worm SS, which connects to the tubulated bottle H, where any water that’s distilled without breaking down during the process collects, and the released gas travels through the tube KK to jars in a pneumatic-chemical setup. Instead of the retort, you could use a funnel, with its lower part closed off by a stop-cock, allowing water to drip slowly into the gun-barrel. As soon as the water touches the heated part of the iron, it turns into steam and the experiment continues just like if the vapors were coming from the retort.
In the experiment made by Mr Meusnier and me before a committee of the Academy, we used every precaution to obtain the greatest possible precision in the result of our experiment, having even exhausted all the vessels employed before we began, so that the hydrogen gas obtained might be free from any mixture[Pg 406] of azotic gas. The results of that experiment will hereafter be given at large in a particular memoir.
In the experiment conducted by Mr. Meusnier and me in front of a committee from the Academy, we took every precaution to achieve the highest possible accuracy in our results. We even used up all the vessels beforehand to ensure that the hydrogen gas we collected was free from any mixture of nitrogen gas. The details of that experiment will be provided later in a separate paper.[Pg 406]
In numerous experiments, we are obliged to use tubes of glass, porcelain, or copper, instead of gun-barrels; but glass has the disadvantage of being easily melted and flattened, if the heat be in the smallest degree raised too high; and porcelain is mostly full of small minute pores, through which the gas escapes, especially when compressed by a column of water. For these reasons I procured a tube of brass, which Mr de la Briche got cast and bored out of the solid for me at Strasburg, under his own inspection. This tube is extremely convenient for decomposing alkohol, which resolves into charcoal, carbonic acid gas, and hydrogen gas; it may likewise be used with the same advantage for decomposing water by means of charcoal, and in a great number of experiments of this nature.[Pg 407]
In many experiments, we have to use tubes made of glass, porcelain, or copper instead of gun-barrels; however, glass can easily melt and flatten if the heat is raised even slightly. Porcelain mostly has tiny pores through which gas escapes, especially when compressed by a column of water. For these reasons, I got a brass tube made, which Mr. de la Briche had cast and bored from solid material for me in Strasbourg, overseeing the entire process. This tube is very useful for breaking down alcohol, which turns into charcoal, carbon dioxide, and hydrogen gas; it can also be effectively used to decompose water using charcoal, and for many other experiments of this kind.[Pg 407]
FOOTNOTES:
[60] The representation of this apparatus, Pl. IV. Fig. 1. will convey a much better idea of its disposition than can possibly be given by the most laboured description.—E.
[60] The illustration of this device, Pl. IV. Fig. 1, will provide a much clearer understanding of its layout than any detailed description could.—E.
CHAP. VII.
Of the Composition and Application of Lutes.
The necessity of properly securing the junctures of chemical vessels to prevent the escape of any of the products of experiments, must be sufficiently apparent; for this purpose lutes are employed, which ought to be of such a nature as to be equally impenetrable to the most subtile substances, as glass itself, through which only caloric can escape.
The need to securely seal the connections of chemical containers to stop any experimental products from leaking should be clear. For this reason, we use lutes that should be just as impermeable to the finest substances as glass itself, which only allows heat to escape.
This first object of lutes is very well accomplished by bees wax, melted with about an eighth part of turpentine. This lute is very easily managed, sticks very closely to glass, and is very difficultly penetrable; it may be rendered more consistent, and less or more hard or pliable, by adding different kinds of resinous matters. Though this species of lute answers extremely well for retaining gasses and vapours, there are many chemical experiments which produce considerable heat, by which this lute becomes liquified, and consequently the expansive vapours must very readily force through and escape.[Pg 408]
This first type of lute is effectively made from beeswax, melted with about one-eighth of turpentine. This lute is easy to work with, sticks tightly to glass, and is quite hard to penetrate; its consistency can be adjusted to be harder or softer by adding various kinds of resin. While this type of lute works extremely well for holding gases and vapors, there are many chemical experiments that generate significant heat, causing this lute to melt, and as a result, the expanding vapors can easily escape.[Pg 408]
For such cases, the following fat lute is the best hitherto discovered, though not without its disadvantages, which shall be pointed out. Take very pure and dry unbaked clay, reduced to a very fine powder, put this into a brass mortar, and beat it for several hours with a heavy iron pestle, dropping in slowly some boiled lintseed oil; this is oil which has been oxygenated, and has acquired a drying quality, by being boiled with litharge. This lute is more tenacious, and applies better, if amber varnish be used instead of the above oil. To make this varnish, melt some yellow amber in an iron laddle, by which operation it loses a part of its succinic acid, and essential oil, and mix it with lintseed oil. Though the lute prepared with this varnish is better than that made with boiled oil, yet, as its additional expence is hardly compensated by its superior quality, it is seldom used.
For these situations, the following fat lute is the best one discovered so far, though it has some drawbacks that will be pointed out. Take very pure and dry unbaked clay, ground into a fine powder, and place it in a brass mortar. Then, for several hours, beat it with a heavy iron pestle while gradually adding some boiled linseed oil; this oil has been oxygenated and has gained drying properties by being boiled with litharge. This lute is stickier and applies better if you use amber varnish instead of the oil. To make this varnish, melt some yellow amber in an iron ladle, which removes some of its succinic acid and essential oil, and mix it with linseed oil. Although the lute made with this varnish is better than the one made with boiled oil, its added cost hardly justifies the improved quality, so it is rarely used.
The above fat lute is capable of sustaining a very violent degree of heat, is impenetrable by acids and spiritous liquors, and adheres exceedingly well to metals, stone ware, or glass, providing they have been previously rendered perfectly dry. But if, unfortunately, any of the liquor in the course of an experiment gets through, either between the glass and the lute, or between the layers of the lute itself, so as to moisten the part, it is extremely difficult to close[Pg 409] the opening. This is the chief inconvenience which attends the use of fat lute, and perhaps the only one it is subject to. As it is apt to soften by heat, we must surround all the junctures with slips of wet bladder applied over the luting, and fixed on by pack-thread tied round both above and below the joint; the bladder, and consequently the lute below, must be farther secured by a number of turns of pack-thread all over it. By these precautions, we are free from every danger of accident; and the junctures secured in this manner may be considered, in experiments, as hermetically sealed.
The fat lute mentioned above can withstand extremely high temperatures, is resistant to acids and alcoholic liquids, and sticks very well to metals, stoneware, or glass, as long as they have been made completely dry beforehand. However, if any liquid seeps through during an experiment, either between the glass and the lute or between the layers of the lute itself, making that area damp, it becomes very challenging to seal the opening. This is the main drawback of using fat lute, and it's possibly the only one. Since it can soften with heat, we need to wrap all the joints with wet bladder placed over the luting, secured with pack-thread tied both above and below the joint. Additionally, the bladder, and thus the lute beneath it, must be further anchored with multiple turns of pack-thread all around it. By taking these precautions, we can avoid any accidents, and the joints secured this way can be considered hermetically sealed during experiments.
It frequently happens that the figure of the junctures prevents the application of ligatures, which is the case with the three-necked bottles formerly described; and it even requires great address to apply the twine without shaking the apparatus; so that, where a number of junctures require luting, we are apt to displace several while securing one. In these cases, we may substitute slips of linen, spread with white of egg and lime mixed together, instead of the wet bladder. These are applied while still moist, and very speedily dry and acquire considerable hardness. Strong glue dissolved in water may answer instead of white of egg. These fillets are usefully applied likewise over junctures luted together with wax and rosin.[Pg 410]
It often happens that the shape of the joints makes it difficult to use ligatures, like with the three-necked bottles mentioned earlier; and it takes a lot of skill to apply the twine without shaking the setup. So, when there are several joints that need sealing, we might accidentally move a few while trying to secure one. In these situations, we can use strips of linen coated with a mixture of egg white and lime instead of a wet bladder. These are applied while still damp and quickly dry to become quite hard. Strong glue mixed with water can also work instead of egg white. These strips are also useful over joints that have been sealed with wax and rosin.[Pg 410]
Before applying a lute, all the junctures of the vessels must be accurately and firmly fitted to each other, so as not to admit of being moved. If the beak of a retort is to be luted to the neck of a recipient, they ought to fit pretty accurately; otherwise we must fix them, by introducing short pieces of soft wood or of cork. If the disproportion between the two be very considerable, we must employ a cork which fits the neck of the recipient, having a circular hole of proper dimensions to admit the beak of the retort. The same precaution is necessary in adapting bent tubes to the necks of bottles in the apparatus represented Pl. IV. Fig. 1. and others of a similar nature. Each mouth of each bottle must be fitted with a cork, having a hole made with a round file of a proper size for containing the tube. And, when one mouth is intended to admit two or more tubes, which frequently happens when we have not a sufficient number of bottles with two or three necks, we must use a cork with two or three holes, Pl. IV. Fig. 8.
Before applying a lute, all the joints of the vessels must be accurately and securely fitted to each other, so they can’t be moved. If the spout of a retort is to be sealed to the neck of a container, they should fit quite snugly; otherwise, we need to secure them by inserting short pieces of soft wood or cork. If there’s a significant gap between the two, we should use a cork that fits the neck of the container, with a round hole appropriately sized to accommodate the spout of the retort. The same care is needed when attaching bent tubes to the necks of bottles, as shown in Pl. IV. Fig. 1, and in similar situations. Each opening of each bottle must be fitted with a cork that has a hole made with a round file of the right size to hold the tube. And when one opening is meant to hold two or more tubes, which often happens when we don’t have enough bottles with two or three necks, we need to use a cork with two or three holes, as shown in Pl. IV. Fig. 8.
When the whole apparatus is thus solidly joined, so that no part can play upon another, we begin to lute. The lute is softened by kneading and rolling it between the fingers, with the assistance of heat, if necessary. It is rolled into little cylindrical pieces, and applied to the junctures, taking great care to make it[Pg 411] apply close, and adhere firmly, in every part; a second roll is applied over the first, so as to pass it on each side, and so on till each juncture be sufficiently covered; after this, the slips of bladder, or of linen, as above directed, must be carefully applied over all. Though this operation may appear extremely simple, yet it requires peculiar delicacy and management; great care must be taken not to disturb one juncture whilst luting another, and more especially when applying the fillets and ligatures.
When all the parts are securely joined so that nothing can move against each other, we start the luting process. The lute is made softer by kneading and rolling it between our fingers, using heat if needed. It's shaped into small cylindrical pieces and placed at the joints, being careful to ensure it fits tightly and sticks well in every area. A second roll is put over the first, going around each side, and this continues until each joint is adequately covered. After that, the pieces of bladder or linen, as previously described, must be carefully laid over everything. While this process may seem very straightforward, it actually requires special care and skill; it's crucial not to disturb one joint while luting another, especially when applying the strips and ties.
Before beginning any experiment, the closeness of the luting ought always to be previously tried, either by slightly heating the retort A, Pl. IV. Fig. 1, or by blowing in a little air by some of the perpendicular tubes S s s s; the alteration of pressure causes a change in the level of the liquid in these tubes. If the apparatus be accurately luted, this alteration of level will be permanent; whereas, if there be the smallest, opening in any of the junctures, the liquid will very soon recover its former level. It must always be remembered, that the whole success of experiments in modern chemistry depends upon the exactness of this operation, which therefore requires the utmost patience, and most attentive accuracy.
Before starting any experiment, the seal should always be tested first, either by gently heating the retort A, Pl. IV. Fig. 1, or by blowing in a little air through some of the vertical tubes S s s s; the change in pressure will cause the liquid level in these tubes to shift. If the setup is sealed properly, this change in level will be permanent; however, if there’s even the tiniest opening at any of the joints, the liquid will quickly return to its original level. It's important to remember that the success of experiments in modern chemistry relies entirely on the precision of this process, which requires the greatest patience and utmost accuracy.
It would be of infinite service to enable chemists, especially those who are engaged in pneumatic processes, to dispense with the use of lutes,[Pg 412] or at least to diminish the number necessary in complicated instruments. I once thought of having my apparatus constructed so as to unite in all its parts by fitting with emery, in the way of bottles with cristal stoppers; but the execution of this plan was extremely difficult. I have since thought it preferable to substitute columns of a few lines of mercury in place of lutes, and have got an apparatus constructed upon this principle, which appears capable of very convenient application in a great number of circumstances.
It would be incredibly helpful to allow chemists, especially those working with gases, to eliminate the use of sealants,[Pg 412] or at least to reduce the amount needed in complex equipment. I once considered designing my apparatus to connect all its parts by fitting them together with emery, similar to how bottles with glass stoppers work; however, implementing this idea was extremely challenging. I have since decided that it's better to use columns filled with a few lines of mercury instead of sealants, and I’ve built an apparatus based on this concept, which seems to be very useful in a variety of situations.
It consists of a double necked bottle A, Pl. XII. Fig. 12.; the interior neck bc communicates with the inside of the bottle, and the exterior neck or rim de leaves an interval between the two necks, forming a deep gutter intended to contain the mercury. The cap or lid of glass B enters this gutter, and is properly fitted to it, having notches in its lower edge for the passage of the tubes which convey the gas. These tubes, instead of entering directly into the bottles as in the ordinary apparatus, have a double bend for making them enter the gutter, as represented in Fig. 13. and for making them fit the notches of the cap B; they rise again from the gutter to enter the inside of the bottle over the border of the inner mouth. When the tubes are disposed in their proper places, and the cap firmly fitted on, the gutter is filled with[Pg 413] mercury, by which means the bottle is completely excluded from any communication, excepting through the tubes. This apparatus may be very convenient in many operations in which the substances employed have no action upon Mercury. Pl. XII. Fig. 14. represents an apparatus upon this principle properly fitted together.
It consists of a double-necked bottle A, Pl. XII. Fig. 12.; the inner neck bc connects with the inside of the bottle, while the outer neck or rim de creates a gap between the two necks, forming a deep channel meant to hold the mercury. The glass cap or lid B fits into this channel, designed with notches along its bottom edge to allow the gas tubes to pass through. Instead of going directly into the bottles like in standard setups, these tubes have a double bend to make their way into the channel, as shown in Fig. 13, and fit into the notches of the cap B; they then rise again from the channel to enter the bottle's interior over the edge of the inner opening. Once the tubes are positioned correctly and the cap is securely in place, the channel is filled with[Pg 413] mercury, fully sealing the bottle from any communication except through the tubes. This apparatus can be extremely useful in many operations where the materials used don't react with mercury. Pl. XII. Fig. 14. shows an apparatus based on this principle, properly assembled.
Mr Seguin, to whose active and intelligent assistance I have been very frequently much indebted, has bespoken for me, at the glass-houses, some retorts hermetically united to their recipients, by which luting will be altogether unnecessary.
Mr. Seguin, whose helpful and smart assistance I have often relied on, has ordered for me, at the glasshouses, some retorts sealed tightly to their recipients, making luting completely unnecessary.
CHAP. VIII.
Of Operations upon Combustion and Deflagration.
SECT. I.
Of Combustion in general.
Combustion, according to what has been already said in the First Part of this Work, is the decomposition of oxygen gas produced by a combustible body. The oxygen which forms the base of this gas is absorbed by, and enters into, combination with the burning body, while the caloric and light are set free. Every combustion, therefore, necessarily supposes oxygenation; whereas, on the contrary, every oxygenation does not necessarily imply concomitant combustion; because combustion, properly so called, cannot take place without disengagement of caloric and light. Before combustion can take place, it is necessary that the base of oxygen gas should have greater affinity to the combustible body than it has to caloric;[Pg 415] and this elective attraction, to use Bergman's expression, can only take place at a certain degree of temperature, which is different for each combustible substance; hence the necessity of giving a first motion or beginning to every combustion by the approach of a heated body. This necessity of heating any body we mean to burn depends upon certain considerations, which have not hitherto been attended to by any natural philosopher, for which reason I shall enlarge a little upon the subject in this place.
Combustion, as explained in the First Part of this Work, is the breakdown of oxygen gas created by a flammable substance. The oxygen that makes up this gas is absorbed by and combines with the burning material, while heat and light are released. Thus, every combustion process requires oxygen; however, not every instance of oxygen combining means combustion is happening, since true combustion can't occur without the release of heat and light. For combustion to happen, the oxygen gas must have a stronger attraction to the flammable material than to heat;[Pg 415] and this selective attraction, as Bergman puts it, can only occur at a specific temperature, which varies for each combustible material. This is why you must initiate combustion by bringing in a heated object. The need to heat any material we intend to burn is based on certain factors that have not yet been addressed by any natural philosopher, so I will expand on this topic here.
Nature is at present in a state of equilibrium, which cannot have been attained until all the spontaneous combustions or oxygenations possible in the ordinary degrees of temperature had taken place. Hence, no new combustions or oxygenations can happen without destroying this equilibrium, and raising the combustible substances to a superior degree of temperature. To illustrate this abstract view of the matter by example: Let us suppose the usual temperature of the earth a little changed, and that it is raised only to the degree of boiling water; it is evident, that, in this case, phosphorus, which is combustible in a considerably lower degree of temperature, would no longer exist in nature in its pure and simple state, but would always be procured in its acid or oxygenated state, and its radical would become one of the substances unknown[Pg 416] to chemistry. By gradually increasing the temperature of the earth the same circumstance would successively happen to all the bodies capable of combustion; and, at last, every possible combustion having taken place, there would no longer exist any combustible body whatever, as every substance susceptible of that operation would be oxygenated, and consequently incombustible.
Nature is currently in a state of balance that could only have been achieved after all possible spontaneous combustions or oxidations at ordinary temperatures occurred. Therefore, no new combustions or oxidations can happen without disrupting this balance and raising the combustible materials to a higher temperature. To illustrate this abstract idea with an example: Suppose the Earth's usual temperature changes slightly and rises to the boiling point of water; it’s clear that, in this case, phosphorus, which ignites at a much lower temperature, would no longer exist in its pure form in nature, but would always be found as an acid or oxidized state, and its core would become an unknown substance to chemistry. By gradually increasing the Earth's temperature, the same situation would occur successively with all combustible materials; eventually, after all possible combustions have occurred, there would be no combustible materials left, since every substance that could undergo that process would be oxidized and, therefore, non-combustible.[Pg 416]
There cannot therefore exist, so far as relates to us, any combustible body, except such as are incombustible in the ordinary temperatures of the earth; or, what is the same thing, in other words, that it is essential to the nature of every combustible body not to possess the property of combustion, unless heated, or raised to the degree of temperature at which its combustion naturally takes place. When this degree is once produced, combustion commences, and the caloric which is disengaged by the decomposition of the oxygen gas keeps up the temperature necessary for continuing combustion. When this is not the case, that is, when the disengaged caloric is insufficient for keeping up the necessary temperature, the combustion ceases: This circumstance is expressed in common language by saying, that a body burns ill, or with difficulty.
There can't be any combustible material, as far as we’re concerned, except those that don’t burn at the usual temperatures on Earth; in other words, it's essential for every combustible material not to have the property of combustion unless it is heated or raised to the temperature at which it naturally ignites. Once that temperature is reached, combustion starts, and the heat released from the breakdown of oxygen gas maintains the temperature needed to keep the combustion going. If that heat is not enough to maintain the necessary temperature, the combustion stops. People commonly describe this situation by saying that something burns poorly or with difficulty.
Although combustion possesses some circumstances in common with distillation, especially[Pg 417] with the compound kind of that operation, they differ in a very material point. In distillation there is a separation of one part of the elements of the substance from each other, and a combination of these, in a new order, occasioned by the affinities which take place in the increased temperature produced during distillation: This likewise happens in combustion, but with this farther circumstance, that a new element, not originally in the body, is brought into action; oxygen is added to the substance submitted to the operation, and caloric is disengaged.
Although combustion has some similarities to distillation, especially[Pg 417] in the way that distillation operates with compounds, they differ significantly in one key aspect. In distillation, part of the elements of the substance are separated from each other and then recombined in a new order due to the affinities that occur as the temperature rises during the process. This also happens in combustion, but with the additional factor that a new element, not originally present in the material, is introduced; oxygen is added to the substance undergoing the process, and heat is released.
The necessity of employing oxygen in the state of gas in all experiments with combustion, and the rigorous determination of the quantities employed, render this kind of operations peculiarly troublesome. As almost all the products of combustion are disengaged in the state of gas, it is still more difficult to retain them than even those furnished during compound distillation; hence this precaution was entirely neglected by the ancient chemists; and this set of experiments exclusively belong to modern chemistry.
The need to use oxygen in its gaseous form for all combustion experiments, along with the precise measurement of the amounts used, makes these operations particularly challenging. Since almost all combustion byproducts are released as gases, capturing them is even harder than collecting those produced during compound distillation. Because of this, ancient chemists completely overlooked this precaution, and as a result, this series of experiments is solely part of modern chemistry.
Having thus pointed out, in a general way, the objects to be had in view in experiments upon combustion, I proceed, in the following sections of this chapter, to describe the different instruments I have used with this view. The following arrangement is formed, not upon the[Pg 418] nature of the combustible bodies, but upon that of the instruments necessary for combustion.
Having pointed out, in a general way, the goals of experiments on combustion, I will now describe the different instruments I have used for this purpose in the following sections of this chapter. The following arrangement is based not on the nature of the combustible materials but on the instruments needed for combustion.
SECT. II.
Of the Combustion of Phosphorus.
In these combustions we begin by filling a jar, capable at least of holding six pints, with oxygen gas in the water apparatus, Pl. V. Fig. 1.; when it is perfectly full, so that the gas begins to flow out below, the jar, A, is carried to the mercury apparatus, Pl. IV. Fig. 3. We then dry the surface of the mercury, both within and without the jar, by means of blotting-paper, taking care to keep the paper for some time entirely immersed in the mercury before it is introduced under the jar, lest we let in any common air, which sticks very obstinately to the surface of the paper. The body to be submitted to combustion, being first very accurately weighed in nice scales, is placed in a small flat shallow dish, D, of iron or porcelain; this is covered by the larger cup P, which serves the office of a diving bell, and the whole is passed through the mercury into the jar, after which the larger cup is retired. The difficulty of passing the materials of combustion in this manner[Pg 419] through the mercury may be avoided by raising one of the sides of the jar, A, for a moment, and slipping in the little cup, D, with the combustible body as quickly as possible. In this manner of operating, a small quantity of common air gets into the jar, but it is so very inconsiderable as not to injure either the progress or accuracy of the experiment in any sensible degree.
In these experiments, we start by filling a jar that can hold at least six pints with oxygen gas using the water apparatus, Pl. V. Fig. 1. When the jar is completely full and the gas starts to flow out at the bottom, we take the jar, A, to the mercury apparatus, Pl. IV. Fig. 3. We then dry the surface of the mercury, both inside and outside the jar, with blotting paper, making sure to keep the paper completely submerged in the mercury for a while before placing it under the jar, to avoid letting in any regular air that stubbornly clings to the paper's surface. The substance meant for combustion is first accurately weighed using precise scales and placed in a small flat dish, D, made of iron or porcelain; this is then covered by a larger cup, P, which acts like a diving bell, and the whole setup is submerged in the mercury before removing the larger cup. To make it easier to transfer the combustion material this way[Pg 419] through the mercury, one side of the jar, A, can be briefly lifted to quickly slip in the small cup, D, with the combustible material. Some regular air may enter the jar in this method, but the amount is so minimal that it doesn't significantly affect the experiment's progress or accuracy.
When the cup, D, is introduced under the jar, we suck out a part of the oxygen gas, so as to raise the mercury to EF, as formerly directed, Part I. Chap. V. otherwise, when the combustible body is set on fire, the gas becoming dilated would be in part forced out, and we should no longer be able to make any accurate calculation of the quantities before and after the experiment. A very convenient mode of drawing out the air is by means of an air-pump syringe adapted to the syphon, GHI, by which the mercury may be raised to any degree under twenty-eight inches. Very inflammable bodies, as phosphorus, are set on fire by means of the crooked iron wire, MN, Pl. IV. Fig. 16. made red hot, and passed quickly through the mercury. Such as are less easily set on fire have a small portion of tinder, upon which a minute particle of phosphorus is fixed, laid upon them before using the red hot iron.[Pg 420]
When we place cup D under the jar, we remove some of the oxygen gas to raise the mercury to EF, as previously explained in Part I, Chap. V. Otherwise, when the combustible material is ignited, the gas expands and gets pushed out, making it impossible to accurately measure the amounts before and after the experiment. A very convenient way to remove the air is by using an air-pump syringe connected to the siphon GHI, which allows the mercury to be raised to any level below twenty-eight inches. Highly flammable materials, like phosphorus, are ignited using the bent iron wire MN from Pl. IV, Fig. 16, which is heated until red hot and quickly passed through the mercury. Less flammable substances have a small piece of tinder with a tiny bit of phosphorus placed on them before using the heated iron.[Pg 420]
In the first moment of combustion the air, being heated, rarifies, and the mercury descends; but when, as in combustions of phosphorus and iron, no elastic fluid is formed, absorption becomes presently very sensible, and the mercury rises high into the jar. Great attention must be used not to burn too large a quantity of any substance in a given quantity of gas, otherwise, towards the end of the experiment, the cup would approach so near the top of the jar as to endanger breaking it by the great heat produced, and the sudden refrigeration from the cold mercury. For the methods of measuring the volume of the gasses, and for correcting the measures according to the heighth of the barometer and thermometer, &c. see Chap. II. Sect. V. and VI. of this part.
In the initial moment of combustion, the heated air expands, and the mercury level drops; however, when no gas is produced, as in the cases of phosphorus and iron combustion, absorption becomes quite noticeable, causing the mercury to rise high in the jar. Care must be taken not to burn too much of any substance in a specific volume of gas; otherwise, towards the end of the experiment, the cup may rise too close to the top of the jar, risking breakage due to the intense heat created and the sudden cooling from the cold mercury. For information on how to measure gas volumes and adjust measurements based on the barometer and thermometer readings, see Chap. II. Sect. V. and VI. of this part.
The above process answers very well for burning all the concrete substances, and even for the fixed oils: These last are burnt in lamps under the jar, and are readily set on fire by means of tinder, phosphorus, and hot iron. But it is dangerous for substances susceptible of evaporating in a moderate heat, such as ether, alkohol, and the essential oils; these substances dissolve in considerable quantity in oxygen gas; and, when set on fire, a dangerous and sudden explosion takes place, which carries up the jar to a great height, and dashes it in a thousand pieces. From two such explosions some of the[Pg 421] members of the Academy and myself escaped very narrowly. Besides, though this manner of operating is sufficient for determining pretty accurately the quantity of oxygen gas absorbed, and of carbonic acid produced, as water is likewise formed in all experiments upon vegetable and animal matters which contain an excess of hydrogen, this apparatus can neither collect it nor determine its quantity. The experiment with phosphorus is even incomplete in this way, as it is impossible to demonstrate that the weight of the phosphoric acid produced is equal to the sum of the weights of the phosphorus burnt and oxygen gas absorbed during the process. I have been therefore obliged to vary the instruments according to circumstances, and to employ several of different kinds, which I shall describe in their order, beginning with that used for burning phosphorus.
The process described works well for burning all solid substances, including fixed oils. These oils can be burned in lamps placed under the jar and are easily ignited using tinder, phosphorus, and hot iron. However, it's risky to handle substances that can evaporate at moderate temperatures, like ether, alcohol, and essential oils. These substances dissolve significantly in oxygen gas, and when ignited, they can cause a dangerous and sudden explosion that can send the jar flying high and smash it into countless pieces. From two such explosions, a few members of the[Pg 421] Academy and I barely escaped. Furthermore, while this method is good for accurately determining the amount of oxygen gas absorbed and carbon dioxide produced, it can't collect or measure the water formed in experiments involving plant and animal materials that have excess hydrogen. The experiment with phosphorus is also incomplete in this regard, as we can't demonstrate that the weight of the produced phosphoric acid equals the combined weight of the burned phosphorus and the absorbed oxygen gas. Therefore, I’ve had to adapt the instruments based on the circumstances and use several different types, starting with the one used for burning phosphorus.
Take a large balloon, A, Pl. IV. Fig. 4. of cristal or white glass, with an opening, EF, about two inches and a half, or three inches, diameter, to which a cap of brass is accurately fitted with emery, and which has two holes for the passage of the tubes xxx, yyy. Before shutting the balloon with its cover, place within it the stand, BC, supporting the cup of porcelain, D, which contains the phosphorus. Then lute on the cap with fat lute, and allow it to dry for some days, and weigh the whole accurately;[Pg 422] after this exhaust the balloon by means of an air-pump connected with the tube xxx, and fill it with oxygen gas by the tube yyy, from the gazometer, Pl. VIII. Fig. 1. described Chap. II. Sect II. of this part. The phosphorus is then set on fire by means of a burning-glass, and is allowed to burn till the cloud of concrete phosphoric acid stops the combustion, oxygen gas being continually supplied from the gazometer. When the apparatus has cooled, it is weighed and unluted; the tare of the instrument being allowed, the weight is that of the phosphoric acid contained. It is proper, for greater accuracy, to examine the air or gas contained in the balloon after combustion, as it may happen to be somewhat heavier or lighter than common air; and this difference of weight must be taken into account in the calculations upon the results of the experiment.
Take a large balloon, A, Pl. IV. Fig. 4, made of crystal or white glass, with an opening, EF, about two and a half to three inches in diameter. A brass cap is fitted to this opening using emery, and it has two holes for the passage of the tubes xxx and yyy. Before sealing the balloon with its cover, place inside the stand, BC, which supports the porcelain cup, D, containing the phosphorus. Then seal the cap with fat lute and let it dry for several days, ensuring to weigh the whole assembly accurately;[Pg 422] after this, evacuate the balloon using an air pump connected to tube xxx, and fill it with oxygen gas through tube yyy, from the gazometer, Pl. VIII. Fig. 1, described in Chap. II. Sect II of this part. The phosphorus is then ignited with a burning glass and allowed to burn until the cloud of solid phosphoric acid stops the combustion, with oxygen gas being continuously supplied from the gazometer. Once the apparatus has cooled, it is weighed and opened; taking into account the tare of the instrument, the weight reflects that of the phosphoric acid present. For greater accuracy, it is advisable to analyze the air or gas inside the balloon after combustion, as it may be slightly heavier or lighter than regular air; this weight difference should be considered in the calculations of the experiment's results.
SECT. III.
Of the Combustion of Charcoal.
The apparatus I have employed for this process consists of a small conical furnace of hammered copper, represented in perspective, Pl. XII. Fig. 9. and internally displayed Fig. 11. It is[Pg 423] divided into the furnace, ABC, where the charcoal is burnt, the grate, d e, and the ash-hole, F; the tube, GH, in the middle of the dome of the furnace serves to introduce the charcoal, and as a chimney for carrying off the air which has served for combustion. Through the tube, l m n, which communicates with the gazometer, the hydrogen gas, or air, intended for supporting the combustion, is conveyed into the ash-hole, F, whence it is forced, by the application of pressure to the gazometer, to pass through the grate, d e, and to blow upon the burning charcoal placed immediately above.
The equipment I used for this process includes a small conical furnace made of hammered copper, shown in perspective in Pl. XII. Fig. 9, and displayed internally in Fig. 11. It is[Pg 423] divided into the furnace, ABC, where the charcoal burns, the grate, d e, and the ash-hole, F. The tube, GH, in the center of the dome of the furnace is used to add the charcoal and acts as a chimney to vent the air that has been used for combustion. Through the tube, l m n, which connects to the gasometer, hydrogen gas or air intended to support combustion is sent into the ash-hole, F, where it is forced, by applying pressure to the gasometer, to flow through the grate, d e, and blow onto the burning charcoal positioned directly above.
Oxygen gas, which forms 28/100 of atmospheric air, is changed into carbonic acid gas during combustion with charcoal, whilst the azotic gas of the air is not altered at all. Hence, after the combustion of charcoal in atmospheric air, a mixture of carbonic acid gas and azotic gas must remain; to allow this mixture to pass off, the tube, o p, is adapted to the chimney, GH, by means of a screw at G, and conveys the gas into bottles half filled with solution of caustic potash. The carbonic acid gas is absorbed by the alkali, and the azotic gas is conveyed into a second gazometer, where its quantity is ascertained.
Oxygen gas, which makes up 28% of the air, is converted into carbon dioxide when it burns with charcoal, while the nitrogen gas in the air remains unchanged. Therefore, after burning charcoal in the air, a mixture of carbon dioxide and nitrogen gas is left over. To allow this mixture to escape, the tube, o p, is connected to the chimney, GH, using a screw at G, and directs the gas into bottles that are half filled with a caustic potash solution. The carbon dioxide is absorbed by the alkali, and the nitrogen gas is sent to a second gasometer, where its amount is measured.
The weight of the furnace, ABC, is first accurately determined, then introduce the tube RS, of known weight, by the chimney, GH,[Pg 424] till its lower end S, rests upon the grate, d e, which it occupies entirely; in the next place, fill the furnace with charcoal, and weigh the whole again, to know the exact quantity of charcoal submitted to experiment. The furnace is now put in its place, the tube, l m n, is screwed to that which communicates with the gazometer, and the tube, o p, to that which communicates with the bottles of alkaline solution. Every thing being in readiness, the stop-cock of the gazometer is opened, a small piece of burning charcoal is thrown into the tube, RS, which is instantly withdrawn, and the tube, o p, is screwed to the chimney, GH. The little piece of charcoal falls upon the grate, and in this manner gets below the whole charcoal, and is kept on fire by the stream of air from the gazometer. To be certain that the combustion is begun, and goes on properly, the tube, q r s, is fixed to the furnace, having a piece of glass cemented to its upper extremity, s, through which we can see if the charcoal be on fire.
The weight of the furnace, ABC, is first accurately measured, then the tube RS, which has a known weight, is introduced through the chimney, GH,[Pg 424] until its lower end S rests on the grate, d e, which it completely covers. Next, fill the furnace with charcoal and weigh the entire setup again to determine the exact amount of charcoal used in the experiment. The furnace is then placed in position, the tube, l m n, is connected to the one linked with the gazometer, and the tube, o p, is connected to the one that leads to the bottles of alkaline solution. Once everything is ready, the stop-cock of the gazometer is opened, and a small piece of burning charcoal is dropped into the tube, RS, which is quickly pulled out, and then the tube, o p, is attached to the chimney, GH. The small piece of charcoal lands on the grate, getting beneath all the other charcoal, and is kept burning by the airflow from the gazometer. To ensure that combustion has started and is proceeding correctly, the tube, q r s, is attached to the furnace, with a piece of glass sealed to its upper end, s, allowing us to see if the charcoal is ignited.
I neglected to observe above, that the furnace, and its appendages, are plunged in water in the cistern, TVXY, Fig. 11. Pl. XII. to which ice may be added to moderate the heat, if necessary; though the heat is by no means very considerable, as there is no air but what comes from the gazometer, and no more of the charcoal[Pg 425] burns at one time than what is immediately over the grate.
I neglected to mention earlier that the furnace and its parts are submerged in water in the cistern, TVXY, Fig. 11. Pl. XII. Ice can be added to reduce the heat if needed; however, the heat isn't very intense since there's no air apart from what comes from the gas meter, and only a small amount of charcoal[Pg 425] burns at a time, just enough for what sits directly over the grate.
As one piece of charcoal is consumed another falls down into its place, in consequence of the declivity of the sides of the furnace; this gets into the stream of air from the grate, d e, and is burnt; and so on, successively, till the whole charcoal is consumed. The air which has served the purpose of the combustion passes through the mass of charcoal, and is forced by the pressure of the gazometer to escape through the tube, o p, and to pass through the bottles of alkaline solution.
As one piece of charcoal burns out, another drops down into its place because of the slope of the furnace sides. This falls into the airflow from the grate, d e, and gets burned; this process continues until all the charcoal is gone. The air that was used for combustion flows through the charcoal and is pushed by the pressure of the gasometer to escape through the tube, o p, and pass through the bottles of alkaline solution.
This experiment furnishes all the necessary data for a complete analysis of atmospheric air and of charcoal. We know the weight of charcoal consumed; the gazometer gives us the measure of the air employed; the quantity and quality of gas remaining after combustion may be determined, as it is received, either in another gazometer, or in jars, in a pneumato-chemical apparatus; the weight of ashes remaining in the ash-hole is readily ascertained; and, finally, the additional weight acquired by the bottles of alkaline solution gives the exact quantity of carbonic acid formed during the process. By this experiment we may likewise determine, with sufficient accuracy, the proportions in which charcoal and oxygen enter into the composition of carbonic acid.[Pg 426]
This experiment provides all the necessary data for a complete analysis of atmospheric air and charcoal. We know the weight of the charcoal used; the gas meter tells us how much air was used; the quantity and quality of gas left over after combustion can be measured, either in another gas meter or in jars within a pneumatic chemical setup; the weight of the ashes left in the ash pit is easy to determine; and finally, the extra weight gained by the bottles of alkaline solution gives the precise amount of carbon dioxide produced during the process. Through this experiment, we can also determine, with enough accuracy, the proportions of charcoal and oxygen that combine to form carbon dioxide.[Pg 426]
In a future memoir I shall give an account to the Academy of a series of experiments I have undertaken, with this instrument, upon all the vegetable and animal charcoals. By some very slight alterations, this machine may be made to answer for observing the principal phenomena of respiration.
In a future memoir, I will report to the Academy about a series of experiments I've conducted with this instrument on all types of plant and animal charcoal. With just a few minor adjustments, this machine can be used to observe the main phenomena of respiration.
SECT. IV.
Of the Combustion of Oils.
Oils are more compound in their nature than charcoal, being formed by the combination of at least two elements, charcoal and hydrogen; of course, after their combustion in common air, water, carbonic acid gas, and azotic gas, remain. Hence the apparatus employed for their combustion requires to be adapted for collecting these three products, and is consequently more complicated than the charcoal furnace.
Oils are more complex than charcoal, as they are made up of at least two elements: charcoal and hydrogen. After they burn in regular air, they produce water, carbon dioxide, and nitrogen gas. Therefore, the equipment used for burning oils needs to be designed to collect these three products, making it more complicated than a charcoal furnace.
The apparatus I employ for this purpose is composed of a large jar or pitcher A, Pl. XII. Fig. 4. surrounded at its upper edge by a rim of iron properly cemented at DE, and receding from the jar at BC, so as to leave a furrow or gutter xx, between it and the outside of the jar,[Pg 427] somewhat more than two inches deep. The cover or lid of the jar, Fig. 5. is likewise surrounded by an iron rim f g, which adjusts into the gutter xx, Fig. 4. which being filled with mercury, has the effect of closing the jar hermetically in an instant, without using any lute; and, as the gutter will hold about two inches of mercury, the air in the jar may be made to sustain the pressure of more than two feet of water, without danger of its escaping.
The setup I use for this is made up of a large jar or pitcher A, Pl. XII. Fig. 4. It has an iron rim properly secured at DE around its upper edge and slopes away from the jar at BC, creating a groove or channel xx that’s over two inches deep between it and the outer edge of the jar,[Pg 427]. The lid of the jar, Fig. 5, is also fitted with an iron rim f g that fits into the channel xx, Fig. 4. When this channel is filled with mercury, it seals the jar airtight in an instant, without needing any paste; and since the channel can hold about two inches of mercury, the air inside the jar can withstand the pressure of more than two feet of water without the risk of leaking.
The lid has four holes, T h i k, for the passage of an equal number of tubes. The opening T is furnished with a leather box, through which passes the rod, Fig. 3. intended for raising and lowering the wick of the lamp, as will be afterwards directed. The three other holes are intended for the passage of three several tubes, one of which conveys the oil to the lamp, a second conveys air for keeping up the combustion, and the third carries off the air, after it has served for combustion. The lamp in which the oil is burnt is represented Fig. 2; a is the reservoir of oil, having a funnel by which it is filled; b c d e f g h is a syphon which conveys the oil to the lamp 11; 7, 8, 9, 10, is the tube which conveys the air for combustion from the gazometer to the same lamp. The tube b c is formed externally, at its lower end b, into a male screw, which turns in a female screw in the lid of the reservoir of oil a; so that, by turning[Pg 428] the reservoir one way or the other, it is made to rise or fall, by which the oil is kept at the necessary level.
The lid has four holes, T h i k, for four tubes to pass through. The opening T is equipped with a leather box that holds the rod, Fig. 3, which is used to raise and lower the wick of the lamp, as will be explained later. The other three holes are for three different tubes: one that brings oil to the lamp, a second that brings in air to maintain the flame, and the third that lets out air after it has been used for combustion. The lamp where the oil is burned is shown in Fig. 2; a is the oil reservoir, which has a funnel for filling it up; b c d e f g h is a siphon that transfers the oil to the lamp 11; 7, 8, 9, 10, is the tube that carries air for combustion from the gasometer to the lamp. The tube b c is designed externally with a male screw at its lower end b, which fits into a female screw in the lid of the oil reservoir a; by turning[Pg 428] the reservoir one way or another, it can be raised or lowered to keep the oil at the right level.
When the syphon is to be filled, and the communication formed between the reservoir of oil and the lamp, the stop-cock c is shut, and that at e opened, oil is poured in by the opening f at the top of the syphon, till it rises within three or four lines of the upper edge of the lamp, the stop-cock k is then shut, and that at c opened; the oil is then poured in at f, till the branch b c d of the syphon is filled, and then the stop-cock e is closed. The two branches of the syphon being now completely filled, a communication is fully established between the reservoir and the lamp.
When it's time to fill the siphon and connect the oil reservoir to the lamp, the stopcock c is closed, and the one at e is opened. Oil is poured in through the opening f at the top of the siphon until it rises within three or four lines of the upper edge of the lamp. Then, stopcock k is closed, and stopcock c is opened. More oil is added at f until the branch b c d of the siphon is filled, and afterward, stopcock e is closed. With both branches of the siphon now completely filled, a full connection is established between the reservoir and the lamp.
In Pl. XII. Fig. 1. all the parts of the lamp 11, Fig. 2. are represented magnified, to show them distinctly. The tube i k carries the oil from the reservoir to the cavity a a a a, which contains the wick; the tube 9, 10, brings the air from the gazometer for keeping up the combustion; this air spreads through the cavity d d d d, and, by means of the passages c c c c and b b b b, is distributed on each side of the wick, after the principles of the lamps constructed by Argand, Quinquet, and Lange.
In Pl. XII. Fig. 1, all the parts of the lamp 11, Fig. 2 are shown enlarged for clarity. The tube i k delivers oil from the reservoir to the cavity a a a a, which holds the wick. The tube 9, 10 brings air from the gas holder to support combustion; this air flows into the cavity d d d d, and, through the openings c c c c and b b b b, is distributed on either side of the wick, following the design principles made by Argand, Quinquet, and Lange.
To render the whole of this complicated apparatus more easily understood, and that its description may make all others of the same kind[Pg 429] more readily followed, it is represented, completely connected together for use, in Pl. XI. The gazometer P furnishes air for the combustion by the tube and stop-cock 1, 2; the tube 2, 3, communicates with a second gazometer, which is filled whilst the first one is emptying during the process, that there may be no interruption to the combustion; 4, 5, is a tube of glass filled with deliquescent salts, for drying the air as much as possible in its passage; and the weight of this tube and its contained salts, at the beginning of the experiment, being known, it is easy to determine the quantity of water absorbed by them from the air. From this deliquescent tube the air is conducted through the pipe 5, 6, 7, 8, 9, 10, to the lamp 11, where it spreads on both sides of the wick, as before described, and feeds the flame. One part of this air, which serves to keep up the combustion of the oil, forms carbonic acid gas and water, by oxygenating its elements. Part of this water condenses upon the sides of the pitcher A, and another part is held in solution in the air by means of caloric furnished by the combustion. This air is forced by the compression of the gazometer to pass through the tube 12, 13, 14, 15, into the bottle 16, and the worm 17, 18, where the water is fully condensed from the refrigeration of the air; and, if any water still remains[Pg 430] in solution, it is absorbed by deliquescent salts contained in the tube 19, 20.
To make this complex setup easier to understand and ensure that its description is easier to follow for similar devices[Pg 429], it is shown fully assembled for use in Pl. XI. The gasometer P provides air for combustion through the tube and stop-cock 1, 2; tube 2, 3 connects to a second gasometer that fills up while the first one is emptying during the process, preventing any interruptions in combustion; 4, 5 is a glass tube filled with hygroscopic salts to dry the air as much as possible as it passes through; knowing the weight of this tube and its salts at the start of the experiment allows for easy calculation of the amount of water they absorb from the air. From this drying tube, the air is directed through the pipe 5, 6, 7, 8, 9, 10 to the lamp 11, where it spreads on both sides of the wick, as previously described, and fuels the flame. Part of this air, which supports the combustion of the oil, produces carbon dioxide and water by oxygenating its components. Some of this water condenses on the sides of the pitcher A, and some of it remains dissolved in the air due to the heat produced by the combustion. This air is forced by the pressure of the gasometer to flow through tube 12, 13, 14, 15, into bottle 16, and the worm 17, 18, where water is completely condensed by cooling the air; and if any water still remains[Pg 430] dissolved, it is absorbed by hygroscopic salts in tube 19, 20.
All these precautions are solely intended for collecting and determining the quantity of water formed during the experiment; the carbonic acid and azotic gas remains to be ascertained. The former is absorbed by caustic alkaline solution in the bottles 22 and 25. I have only represented two of these in the figure, but nine at least are requisite; and the last of the series may be half filled with lime-water, which is the most certain reagent for indicating the presence of carbonic acid; if the lime-water is not rendered turbid, we may be certain that no sensible quantity of that acid remains in the air.
All these precautions are just meant to collect and measure the amount of water produced during the experiment; we still need to find out about the carbon dioxide and nitrogen gas. The carbon dioxide is absorbed by the caustic alkaline solution in bottles 22 and 25. I've only shown two of these in the figure, but at least nine are needed; and the last one in the series can be half filled with lime water, which is the most reliable solution for detecting carbon dioxide. If the lime water doesn’t become cloudy, we can be sure that there’s no significant amount of that gas left in the air.
The rest of the air which has served for combustion, and which chiefly consists of azotic gas, though still mixed with a considerable portion of oxygen gas, which has escaped unchanged from the combustion, is carried through a third tube 28, 29, of deliquescent salts, to deprive it of any moisture it may have acquired in the bottles of alkaline solution and lime-water, and from thence by the tube 29, 30, into a gazometer, where its quantity is ascertained. Small essays are then taken from it, which are exposed to a solution of sulphuret of potash, to ascertain the proportions of oxygen and azotic gas it contains.[Pg 431]
The remaining air used for combustion, which mainly consists of nitrogen gas but is still mixed with a significant amount of oxygen gas that has not changed from the combustion, is directed through a third tube 28, 29, containing deliquescent salts to remove any moisture it may have picked up in the bottles of alkaline solution and lime water. From there, it moves through tube 29, 30, into a gas meter, where its volume is measured. Small samples are then taken from it and exposed to a solution of potassium sulfide to determine the proportions of oxygen and nitrogen gas it contains.[Pg 431]
In the combustion of oils the wick becomes charred at last, and obstructs the rise of the oil; besides, if we raise the wick above a certain height, more oil rises through its capillary tubes than the stream of air is capable of consuming, and smoke is produced. Hence it is necessary to be able to lengthen or shorten the wick without opening the apparatus; this is accomplished by means of the rod 31, 32, 33, 34, which passes through a leather-box, and is connected with the support of the wick; and that the motion of this rod, and consequently of the wick, may be regulated with the utmost smoothness and facility; it is moved at pleasure by a pinnion which plays in a toothed rack. The rod, with its appendages, are represented Pl. XII. Fig. 3. It appeared to me, that the combustion would be assisted by surrounding the flame of the lamp with a small glass jar open at both ends, as represented in its place in Pl. XI.
In the burning of oils, the wick eventually gets charred, which blocks the flow of oil. Additionally, if we raise the wick above a certain height, more oil comes up through its tiny tubes than the air can burn, causing smoke. Therefore, it’s important to be able to adjust the wick’s height without opening the device. This is done using the rod 31, 32, 33, 34, which goes through a leather box and is connected to the wick support. The movement of this rod, and therefore the wick, can be controlled very smoothly and easily; it’s adjusted by a pinion that engages with a toothed rack. The rod and its components are shown in Pl. XII. Fig. 3. I thought that the combustion would improve by surrounding the lamp flame with a small glass jar that’s open at both ends, as depicted in its designated spot in Pl. XI.
I shall not enter into a more detailed description of the construction of this apparatus, which is still capable of being altered and modified in many respects, but shall only add, that when it is to be used in experiment, the lamp and reservoir with the contained oil must be accurately weighed, after which it is placed as before directed, and lighted; having then formed the connection between the air in the gazometer and the lamp, the external jar A, Pl. XI. is fixed[Pg 432] over all, and secured by means of the board BC and two rods of iron which connect this board with the lid, and are screwed to it. A small quantity of oil is burnt while the jar is adjusting to the lid, and the product of that combustion is lost; there is likewise a small portion of air from the gazometer lost at the same time. Both of these are of very inconsiderable consequence in extensive experiments, and they are even capable of being valued in our calculation of the results.
I won’t go into more detail about how this apparatus is built, which can still be changed or improved in many ways. I’ll just add that when it’s time for an experiment, the lamp and oil reservoir need to be weighed accurately. Then, as previously instructed, it should be positioned and lit. After establishing the connection between the air in the gasometer and the lamp, the external jar A, Pl. XI. is placed over everything and secured using the board BC and two iron rods that connect the board to the lid, which are screwed in. A small amount of oil is burned while the jar is being adjusted to the lid, and we lose the product of that combustion; a small amount of air from the gasometer is also lost at that time. Both losses are minor in large experiments and can even be factored into our results.
In a particular memoir, I shall give an account to the Academy of the difficulties inseparable from this kind of experiments: These are so insurmountable and troublesome, that I have not hitherto been able to obtain any rigorous determination of the quantities of the products. I have sufficient proof, however, that the fixed oils are entirely resolved during combustion into water and carbonic acid gas, and consequently that they are composed of hydrogen and charcoal; but I have no certain knowledge respecting the proportions of these ingredients.[Pg 433]
In a specific memoir, I will report to the Academy about the challenges that come with these kinds of experiments. These difficulties are so overwhelming and frustrating that I haven't been able to get any precise measurements of the product quantities so far. However, I have enough evidence to show that fixed oils completely break down during burning into water and carbon dioxide, which means they are made up of hydrogen and carbon; but I don't have clear information about the ratios of these components.[Pg 433]
SECT. V.
Of the Combustion of Alkohol.
The combustion of alkohol may be very readily performed in the apparatus already described for the combustion of charcoal and phosphorus. A lamp filled with alkohol is placed under the jar A, Pl. IV. Fig. 3. a small morsel of phosphorus is placed upon the wick of the lamp, which is set on fire by means of the hot iron, as before directed. This process is, however, liable to considerable inconveniency; it is dangerous to make use of oxygen gas at the beginning of the experiment for fear of deflagration, which is even liable to happen when common air is employed. An instance of this had very near proved fatal to myself, in presence of some members of the Academy. Instead of preparing the experiment, as usual, at the time it was to be performed, I had disposed every thing in order the evening before; the atmospheric air of the jar had thereby sufficient time to dissolve a good deal of the alkohol; and this evaporation had even been considerably promoted by the height of the column of mercury, which I had raised to EF, Pl. IV. Fig. 3. The moment I attempted[Pg 434] to set the little morsel of phosphorus on fire by means of the red hot iron, a violent explosion took place, which threw the jar with great violence against the floor of the laboratory, and dashed it in a thousand pieces.
The combustion of alcohol can be easily performed using the setup already described for burning charcoal and phosphorus. A lamp filled with alcohol is placed under jar A, Pl. IV. Fig. 3. A small piece of phosphorus is placed on the lamp's wick, which is ignited with a hot iron, as previously instructed. However, this method can be quite problematic; using oxygen gas at the start of the experiment is risky due to the potential for an explosion, and the same danger exists even when just using regular air. I almost had a serious accident in front of several members of the Academy because of this. Instead of preparing the experiment at the time I was supposed to, I set everything up the night before, allowing the air in the jar to dissolve a lot of the alcohol. This evaporation was further enhanced by the height of the mercury column I raised to EF, Pl. IV. Fig. 3. The moment I tried to ignite the small piece of phosphorus with the hot iron, a violent explosion occurred, sending the jar crashing to the laboratory floor and shattering it into a thousand pieces.
Hence we can only operate upon very small quantities, such as ten or twelve grains of alkohol, in this manner; and the errors which may be committed in experiments upon such small quantities prevents our placing any confidence in their results. I endeavoured to prolong the combustion, in the experiments contained in the Memoirs of the Academy for 1784, p. 593. by lighting the alkohol first in common air, and furnishing oxygen gas afterwards to the jar, in proportion as it consumed; but the carbonic acid gas produced by the process became a great hinderance to the combustion, the more so that alkohol is but difficultly combustible, especially in worse than common air; so that even in this way very small quantities only could be burnt.
Therefore, we can only work with very small amounts, like ten or twelve grains of alcohol, this way; and the mistakes that can happen in experiments with such small quantities prevent us from trusting the results. I tried to extend the combustion in the experiments published in the Memoirs of the Academy for 1784, p. 593, by first lighting the alcohol in regular air and then adding oxygen gas to the jar as it was used up; however, the carbon dioxide produced by the process significantly interfered with the combustion, particularly since alcohol is not very easily combustible, especially in air that is worse than normal; thus, even with this method, only very small amounts could be burned.
Perhaps this combustion might succeed better in the oil apparatus, Pl. XI.; but I have not hitherto ventured to try it. The jar A in which the combustion is performed is near 1400 cubical inches in dimension; and, were an explosion to take place in such a vessel, its consequences would be very terrible, and very difficult to guard against. I have not, however, despaired of making the attempt.[Pg 435]
Perhaps this combustion might work better in the oil apparatus, Pl. XI.; but I have not yet dared to try it. The jar A in which the combustion takes place is almost 1400 cubic inches in size; and if an explosion were to occur in such a container, the results would be quite severe and hard to prevent. However, I haven’t given up on trying it.[Pg 435]
From all these difficulties, I have been hitherto obliged to confine myself to experiments upon very small quantities of alkohol, or at least to combustions made in open vessels, such as that represented in Pl. IX. Fig. 5. which will be described in Section VII. of this chapter. If I am ever able to remove these difficulties, I shall resume this investigation.
From all these challenges, I've had to limit myself to experiments with very small amounts of alcohol, or at least to burnings conducted in open containers, like the one shown in Pl. IX. Fig. 5, which will be discussed in Section VII of this chapter. If I can ever overcome these obstacles, I will continue this investigation.
SECT. VI.
Of the Combustion of Ether.
Tho' the combustion of ether in close vessels does not present the same difficulties as that of alkohol, yet it involves some of a different kind, not more easily overcome, and which still prevent the progress of my experiments. I endeavoured to profit by the property which ether possesses of dissolving in atmospheric air, and rendering it inflammable without explosion. For this purpose, I constructed the reservoir of ether a b c d, Plate XII. Fig. 8. to which air is brought from the gazometer by the tube 1, 2, 3, 4. This air spreads, in the first place, in the double lid ac of the reservoir, from which it passes through seven tubes ef, gh, ik, &c. which descend to the bottom of the ether, and it is[Pg 436] forced by the pressure of the gazometer to boil up through the ether in the reservoir. We may replace the ether in this first reservoir, in proportion as it is dissolved and carried off by the air, by means of the supplementary reservoir E, connected by a brass tube fifteen or eighteen inches long, and shut by a stop-cock. This length of the connecting tube is to enable the descending ether to overcome the resistance occasioned by the pressure of the air from the gazometer.
Although burning ether in sealed containers isn't as challenging as burning alcohol, it still presents different difficulties that aren't any easier to overcome, which continue to hinder my experiments. I aimed to take advantage of ether's ability to dissolve in air and make it flammable without causing an explosion. To do this, I built the ether reservoir a b c d, Plate XII. Fig. 8, where air is supplied from the gasometer through the tube 1, 2, 3, 4. This air first fills the double lid ac of the reservoir, from which it moves through seven tubes ef, gh, ik, etc., that reach the bottom of the ether. It is[Pg 436] pushed by the gasometer's pressure to bubble up through the ether in the reservoir. We can replace the ether in this initial reservoir as it gets dissolved and carried away by the air, using the supplemental reservoir E, which is connected by a brass tube fifteen to eighteen inches long, and sealed with a stop-cock. This length of the connecting tube helps the descending ether overcome the resistance created by the air pressure from the gasometer.
The air, thus loaded with vapours of ether, is conducted by the tube 5, 6, 7, 8, 9, to the jar A, into which it is allowed to escape through a capillary opening, at the extremity of which it is set on fire. The air, when it has served the purpose of combustion, passes through the bottle 16, Pl. XI. the worm 17, 18, and the deliquescent tube 19, 20, after which it passes through the alkaline bottles; in these its carbonic acid gas is absorbed, the water formed during the experiment having been previously deposited in the former parts of the apparatus.
The air, filled with ether vapors, is channeled through the tube 5, 6, 7, 8, 9 into the jar A, where it escapes through a small opening that’s ignited at the end. After the air has been used for combustion, it travels through the bottle 16, Pl. XI, the worm 17, 18, and the deliquescent tube 19, 20, before moving through the alkaline bottles. In these bottles, carbon dioxide is absorbed, and the water produced during the experiment has already collected in earlier parts of the apparatus.
When I caused construct this apparatus, I supposed that the combination of atmospheric air and ether formed in the reservoir a b c d, Pl. XII. Fig. 8. was in proper proportion for supporting combustion; but in this I was mistaken; for there is a very considerable quantity of excess of ether; so that an additional quantity of atmospheric[Pg 437] air is necessary to enable it to burn fully. Hence a lamp constructed upon these principles will burn in common air, which furnishes the quantity of oxygen necessary for combustion, but will not burn in close vessels in which the air is not renewed. From this circumstance, my ether lamp went out soon after being lighted and shut up in the jar A, Pl. XII. Fig. 8. To remedy this defect, I endeavoured to bring atmospheric air to the lamp by the lateral tube 10, 11, 12, 13, 14, 15, which I distributed circularly round the flame; but the flame is so exceedingly rare, that it is blown out by the gentlest possible stream of air, so that I have not hitherto succeeded in burning ether. I do not, however, despair of being able to accomplish it by means of some changes I am about to have made upon this apparatus.
When I created this device, I thought that the mix of atmospheric air and ether in the reservoir a b c d, Pl. XII. Fig. 8. was in the right proportions to support combustion; but I was wrong. There is actually a significant excess of ether, which means that more atmospheric air [Pg 437] is needed for it to burn completely. As a result, a lamp designed with these principles will burn in regular air, which provides the necessary oxygen for combustion, but will not work in sealed containers where the air isn't replenished. Because of this, my ether lamp went out shortly after being lit and placed inside jar A, Pl. XII. Fig. 8. To solve this issue, I tried to supply atmospheric air to the lamp through the lateral tube 10, 11, 12, 13, 14, 15, which I arranged around the flame; but the flame is so fragile that even the slightest breeze extinguishes it, so I haven’t yet managed to burn ether. However, I am hopeful that I can achieve this with some modifications I plan to make to the device.
SECT. VII.
Of the Combustion of Hydrogen Gas, and the Formation of Water.
In the formation of water, two substances, hydrogen and oxygen, which are both in the aëriform state before combustion, are transformed into liquid or water by the operation.[Pg 438] This experiment would be very easy, and would require very simple instruments, if it were possible to procure the two gasses perfectly pure, so that they might burn without any residuum. We might, in that case, operate in very small vessels, and, by continually furnishing the two gasses in proper proportions, might continue the combustion indefinitely. But, hitherto, chemists have only employed oxygen gas, mixed with azotic gas; from which circumstance, they have only been able to keep up the combustion of hydrogen gas for a very limited time in close vessels, because, as the residuum of azotic gas is continually increasing, the air becomes at last so much contaminated, that the flame weakens and goes out. This inconvenience is so much the greater in proportion as the oxygen gas employed is less pure. From this circumstance, we must either be satisfied with operating upon small quantities, or must exhaust the vessels at intervals, to get rid of the residuum of azotic gas; but, in this case, a portion of the water formed during the experiment is evaporated by the exhaustion; and the resulting error is the more dangerous to the accuracy of the process, that we have no certain means of valuing it.
In the formation of water, two substances, hydrogen and oxygen, both in gas form before combustion, are transformed into liquid or water through the process. [Pg 438] This experiment would be quite simple and would require only basic equipment if we could obtain both gases in completely pure forms, allowing them to burn without any leftover residues. In that case, we could work with very small containers and, by constantly supplying the two gases in the right amounts, could continue the combustion indefinitely. However, so far, chemists have only used oxygen gas mixed with nitrogen gas; as a result, they can only sustain the combustion of hydrogen gas for a very limited time in sealed vessels. This is because the leftover nitrogen gas continuously increases, and the air becomes so contaminated that the flame weakens and eventually goes out. The problem worsens if the oxygen gas used is less pure. Because of this, we have to either settle for working with small quantities or periodically pump out the vessels to remove the nitrogen gas waste; however, this process leads to some of the water formed during the experiment evaporating and the resulting error significantly affects the accuracy of the experiment, as we have no reliable way to quantify it.
These considerations make me desirous to repeat the principal experiments of pneumatic chemistry with oxygen gas entirely free from[Pg 439] any admixture of azotic gas; and this may be procured from oxygenated muriat of potash. The oxygen gas extracted from this salt does not appear to contain azote, unless accidentally, so that, by proper precautions, it may be obtained perfectly pure. In the mean time, the apparatus employed by Mr Meusnier and me for the combustion of hydrogen gas, which is described in the experiment for recomposition of water, Part I. Chap. VIII. and need not be here repeated, will answer the purpose; when pure gasses are procured, this apparatus will require no alterations, except that the capacity of the vessels may then be diminished. See Pl. IV. Fig. 5.
These considerations make me eager to repeat the main experiments of pneumatic chemistry using oxygen gas that is completely free from[Pg 439] any mix of nitrogen gas; and this can be obtained from oxygenated muriate of potash. The oxygen gas extracted from this salt doesn’t seem to contain nitrogen, unless by accident, so with the right precautions, it can be obtained perfectly pure. In the meantime, the apparatus used by Mr. Meusnier and me for burning hydrogen gas, which is described in the experiment for the recomposition of water, Part I. Chap. VIII, doesn’t need to be restated here and will work for the purpose; when pure gases are obtained, this apparatus won’t need any changes, except that the volume of the vessels might then be reduced. See Pl. IV. Fig. 5.
The combustion, when once begun, continues for a considerable time, but weakens gradually, in proportion as the quantity of azotic gas remaining from the combustion increases, till at last the azotic gas is in such over proportion that the combustion can no longer be supported, and the flame goes out. This spontaneous extinction must be prevented, because, as the hydrogen gas is pressed upon in its reservoir, by an inch and a half of water, whilst the oxygen gas suffers a pressure only of three lines, a mixture of the two would take place in the balloon, which would at last be forced by the superior pressure into the reservoir of oxygen gas. Wherefore the combustion must be stopped,[Pg 440] by shutting the stop-cock of the tube dDd whenever the flame grows very feeble; for which purpose it must be attentively watched.
The combustion, once it starts, lasts for a significant amount of time but gradually weakens as the amount of nitrogen gas left from the combustion increases. Eventually, the nitrogen gas becomes so abundant that combustion can't continue, and the flame goes out. This spontaneous extinction needs to be prevented because, as the hydrogen gas is pushed in its reservoir by an inch and a half of water, the oxygen gas only experiences a pressure of three lines. This could lead to a mixture of the two gases inside the balloon, which would eventually be forced by the greater pressure into the reservoir of oxygen gas. Therefore, combustion must be stopped,[Pg 440] by closing the stop-cock of the tube dDd whenever the flame becomes very weak; this requires careful monitoring.
There is another apparatus for combustion, which, though we cannot with it perform experiments with the same scrupulous exactness as with the preceding instruments, gives very striking results that are extremely proper to be shewn in courses of philosophical chemistry. It consists of a worm EF, Pl. IX. Fig. 5. contained in a metallic cooller ABCD. To the upper part of this worm E, the chimney GH is fixed, which is composed of two tubes, the inner of which is a continuation of the worm, and the outer one is a case of tin-plate, which surrounds it at about an inch distance, and the interval is filled up with sand. At the inferior extremity K of the inner tube, a glass tube is fixed, to which we adopt the Argand lamp LM for burning alkohol, &c.
There’s another device for combustion that, while it doesn’t allow us to conduct experiments with the same level of precise accuracy as the previous instruments, produces very striking results that are ideal for demonstrating in chemistry courses. It consists of a coil EF, Pl. IX. Fig. 5, housed in a metal cooler ABCD. At the top of this coil E, there’s a chimney GH made up of two tubes. The inner tube continues from the coil, while the outer one is a tin-plate casing that surrounds it at about an inch distance, with the space in between filled with sand. At the bottom end K of the inner tube, a glass tube is attached, to which we connect the Argand lamp LM for burning alcohol, etc.
Things being thus disposed, and the lamp being filled with a determinate quantity of alkohol, it is set on fire; the water which is formed during the combustion rises in the chimney KE, and being condensed in the worm, runs out at its extremity F into the bottle P. The double tube of the chimney, filled with sand in the interstice, is to prevent the tube from cooling in its upper part, and condensing the water; otherwise,[Pg 441] it would fall back in the tube, and we should not be able to ascertain its quantity, and besides it might fall in drops upon the wick, and extinguish the flame. The intention of this construction, is to keep the chimney always hot, and the worm always cool, that the water may be preserved in the state of vapour whilst rising, and may be condensed immediately upon getting into the descending part of the apparatus. By this instrument, which was contrived by Mr Meusnier, and which is described by me in the Memoirs of the Academy for 1784, p. 593. we may, with attention to keep the worm always cold, collect nearly seventeen ounces of water from the combustion of sixteen ounces of alkohol.
With everything arranged, and the lamp filled with a specific amount of alcohol, it is ignited. The water produced during combustion rises in the chimney KE, and, after being condensed in the worm, flows out at its end F into the bottle P. The double tube of the chimney, filled with sand in the gap, is meant to prevent the upper part of the tube from cooling and condensing the water; otherwise,[Pg 441] it would fall back into the tube, making it impossible for us to measure its quantity, and it might drip onto the wick, extinguishing the flame. This design aims to keep the chimney always hot and the worm always cool, so the water remains in vapor form as it rises and condenses immediately upon reaching the downward section of the apparatus. With this device, invented by Mr. Meusnier and described in my writings in the Memoirs of the Academy for 1784, p. 593, we can, by carefully keeping the worm cold, collect nearly seventeen ounces of water from the combustion of sixteen ounces of alcohol.
SECT. VIII.
Of the Oxydation of Metals.
The term oxydation or calcination is chiefly used to signify the process by which metals exposed to a certain degree of heat are converted into oxyds, by absorbing oxygen from the air. This combination takes place in consequence of oxygen possessing a greater affinity to metals, at a certain temperature, than to caloric, which[Pg 442] becomes disengaged in its free state; but, as this disengagement, when made in common air, is slow and progressive, it is scarcely evident to the senses. It is quite otherwise, however, when oxydation takes place in oxygen gas; for, being produced with much greater rapidity, it is generally accompanied with heat and light, so as evidently to show that metallic substances are real combustible bodies.
The term oxidation or calcination mainly refers to the process where metals that are heated to a certain point are turned into oxides by absorbing oxygen from the air. This combination happens because oxygen has a stronger attraction to metals at a specific temperature than to heat, which[Pg 442] is released in its free form. However, since this release occurs slowly in open air, it's not very noticeable to our senses. In contrast, when oxidation happens in oxygen gas, it occurs much more quickly and is usually accompanied by heat and light, clearly indicating that metallic substances are indeed combustible materials.
All the metals have not the same degree of affinity to oxygen. Gold, silver, and platina, for instance, are incapable of taking it away from its combination with caloric, even in the greatest known heat; whereas the other metals absorb it in a larger or smaller quantity, until the affinities of the metal to oxygen, and of the latter to caloric, are in exact equilibrium. Indeed, this state of equilibrium of affinities may be assumed as a general law of nature in all combinations.
Not all metals have the same level of attraction to oxygen. For example, gold, silver, and platinum cannot separate oxygen from its bond with heat, even at the highest temperatures known. In contrast, other metals can absorb oxygen to varying degrees until the attraction between the metal and oxygen, and between oxygen and heat, is perfectly balanced. In fact, this balance of attractions can be considered a general principle of nature in all combinations.
In all operations of this nature, the oxydation of metals is accelerated by giving free access to the air; it is sometimes much assisted by joining the action of a bellows, which directs a stream of air over the surface of the metal. This process becomes greatly more rapid if a stream of oxygen gas be used, which is readily done by means of the gazometer formerly described. The metal, in this case, throws out a brilliant flame, and the oxydation is very quickly[Pg 443] accomplished; but this method can only be used in very confined experiments, on account of the expence of procuring oxygen gas. In the essay of ores, and in all the common operations of the laboratory, the calcination or oxydation of metals is usually performed in a dish of baked clay, Pl. IV. Fig. 6. commonly called a roasting test, placed in a strong furnace. The substances to be oxydated are frequently stirred, on purpose to present fresh surfaces to the air.
In all operations like this, the oxidation of metals speeds up when air can flow freely. It’s often helped by using a bellows that directs a stream of air over the metal's surface. This process quickens significantly when a stream of oxygen gas is used, easily achieved with the previously mentioned gasometer. In this situation, the metal produces a brilliant flame, and oxidation happens very quickly[Pg 443]; however, this method is only practical for small-scale experiments because of the cost of obtaining oxygen gas. In ore analysis and most common laboratory operations, the calcination or oxidation of metals is typically done in a dish made of baked clay, Pl. IV. Fig. 6, commonly referred to as a roasting test, which is placed in a strong furnace. The materials to be oxidized are often stirred to expose fresh surfaces to the air.
Whenever this operation is performed upon a metal which is not volatile, and from which nothing flies off into the surrounding air during the process, the metal acquires additional weight; but the cause of this increased weight during oxydation could never have been discovered by means of experiments performed in free air; and it is only since these operations have been performed in close vessels, and in determinate quantities of air, that any just conjectures have been formed concerning the cause of this phenomenon. The first method for this purpose is due to Dr Priestley, who exposes the metal to be calcined in a porcelain cup N, Pl. IV. Fig. 11. placed upon the stand IK, under a jar A, in the bason BCDE, full of water; the water is made to rise up to GH, by sucking out the air with a syphon, and the focus of a burning glass is made to fall upon the metal. In a few minutes the oxydation takes place,[Pg 444] a part of the oxygen contained in the air combines with the metal, and a proportional diminution of the volume of air is produced; what remains is nothing more than azotic gas, still however mixed with a small quantity of oxygen gas. I have given an account of a series of experiments made with this apparatus in my Physical and Chemical Essays, first published in 1773. Mercury may be used instead of water in this experiment, whereby the results are rendered still more conclusive.
Whenever this process is done on a metal that isn’t volatile, and nothing escapes into the surrounding air during the process, the metal gains extra weight. However, the reason for this weight increase during oxidation could never have been figured out by experiments done in open air. It’s only since these operations have been conducted in sealed containers, with specific amounts of air, that any accurate guesses have been made about the cause of this phenomenon. The first method for this was developed by Dr. Priestley, who places the metal to be calcined in a porcelain cup N, Pl. IV. Fig. 11. on the stand IK, beneath a jar A, in the basin BCDE filled with water. The water is raised to GH by pulling out the air with a siphon, and the focus of a burning glass is directed onto the metal. After a few minutes, oxidation occurs, [Pg 444] as part of the oxygen in the air combines with the metal, leading to a proportional decrease in the volume of air. What remains is just nitrogen gas, still mixed with a small amount of oxygen gas. I have detailed a series of experiments using this setup in my Physical and Chemical Essays, first published in 1773. Mercury can also be used instead of water in this experiment, which makes the results even more conclusive.
Another process for this purpose was invented by Mr Boyle, and of which I gave an account in the Memoirs of the Academy for 1774, p. 351. The metal is introduced into a retort, Pl. III. Fig. 20. the beak of which is hermetically sealed; the metal is then oxydated by means of heat applied with great precaution. The weight of the vessel, and its contained substances, is not at all changed by this process, until the extremity of the neck of the retort is broken; but, when that is done, the external air rushes in with a hissing noise. This operation is attended with danger, unless a part of the air is driven out of the retort, by means of heat, before it is hermetically sealed, as otherwise the retort would be apt to burst by the dilation of the air when placed in the furnace. The quantity of air driven out may be received under a jar in the pneumato-chemical apparatus,[Pg 445] by which its quantity, and that of the air remaining in the retort, is ascertained. I have not multiplied my experiments upon oxydation of metals so much as I could have wished; neither have I obtained satisfactory results with any metal except tin. It is much to be wished that some person would undertake a series of experiments upon oxydation of metals in the several gasses; the subject is important, and would fully repay any trouble which this kind of experiment might occasion.
Another process for this purpose was invented by Mr. Boyle, and I provided an account of it in the Memoirs of the Academy for 1774, p. 351. The metal is placed into a retort, Pl. III. Fig. 20, which is hermetically sealed at the neck. The metal is then oxidized using heat applied very carefully. The weight of the vessel and its contents doesn’t change at all during this process until the end of the neck of the retort is broken; at that point, external air rushes in with a hissing sound. This operation comes with risks unless some of the air is expelled from the retort through heat before sealing it. Otherwise, the retort could burst due to the expansion of the air when heated in the furnace. The amount of air expelled can be collected under a jar in the pneumatic-chemical apparatus,[Pg 445] which allows us to measure both its quantity and the amount of air left in the retort. I haven’t conducted as many experiments on the oxidation of metals as I would have liked; I also haven't gotten satisfactory results with any metal except for tin. It would be great if someone would carry out a series of experiments on the oxidation of metals in various gases; the topic is important and would definitely be worth the effort required for this kind of experimentation.
As all the oxyds of mercury are capable of revivifying without addition, and restore the oxygen gas they had before absorbed, this seemed to be the most proper metal for becoming the subject of conclusive experiments upon oxydation. I formerly endeavoured to accomplish the oxydation of mercury in close vessels, by filling a retort, containing a small quantity of mercury, with oxygen gas, and adapting a bladder half full of the same gas to its beak; See Pl. IV. Fig. 12. Afterwards, by heating the mercury in the retort for a very long time, I succeeded in oxydating a very small portion, so as to form a little red oxyd floating upon the surface of the running mercury; but the quantity was so small, that the smallest error committed in the determination of the quantities of oxygen gas before and after the operation must have thrown very great uncertainty upon the[Pg 446] results of the experiment. I was, besides, dissatisfied with this process, and not without cause, lest any air might have escaped through the pores of the bladder, more especially as it becomes shrivelled by the heat of the furnace, unless covered over with cloths kept constantly wet.
As all the mercury oxides can revive without any additions and restore the oxygen gas they previously absorbed, it seemed like the best metal to conduct definitive experiments on oxidation. I previously tried to oxidize mercury in sealed vessels by filling a retort with a small amount of mercury and oxygen gas, then attaching a bladder half full of the same gas to its neck; see Pl. IV. Fig. 12. Later, by heating the mercury in the retort for a very long time, I managed to oxidize a tiny portion, creating a small amount of red oxide floating on the surface of the liquid mercury. However, the quantity was so small that even the slightest error in measuring the amounts of oxygen gas before and after the process could have greatly affected the[Pg 446] results of the experiment. Additionally, I was unhappy with this method, and understandably so, as there was a risk of any air escaping through the bladder's pores, especially since it shrinks from the furnace's heat unless covered with cloths that are kept continually wet.
This experiment is performed with more certainty in the apparatus described in the Memoirs of the Academy for 1775, p. 580. This consists of a retort, A, Pl. IV. Fig. 2. having a crooked glass tube BCDE of ten or twelve lines internal diameter, melted on to its beak, and which is engaged under the bell glass FG, standing with its mouth downwards, in a bason filled with water or mercury. The retort is placed upon the bars of the furnace MMNN, Pl. IV. Fig. 2. or in a sand bath, and by means of this apparatus we may, in the course of several days, oxydate a small quantity of mercury in common air; the red oxyd floats upon the surface, from which it may be collected and revivified, so as to compare the quantity of oxygen gas obtained in revivification with the absorption which took place during oxydation. This kind of experiment can only be performed upon a small scale, so that no very certain conclusions can be drawn from them[61].
This experiment is conducted with more reliability using the apparatus described in the Memoirs of the Academy for 1775, p. 580. It consists of a retort, A, Pl. IV. Fig. 2, which has a bent glass tube BCDE with an internal diameter of ten or twelve lines fused onto its beak. This tube is placed under the bell jar FG, positioned upside down in a basin filled with water or mercury. The retort is set on the bars of the furnace MMNN, Pl. IV. Fig. 2, or in a sand bath. Using this setup, we can oxidize a small amount of mercury in regular air over several days; the red oxide floats on the surface, allowing it to be collected and revived, enabling a comparison between the amount of oxygen gas released during revival and the absorption that occurred during oxidation. This type of experiment can only be done on a small scale, so no very definitive conclusions can be drawn from them[61].
The combustion of iron in oxygen gas being a true oxydation of that metal, ought to be mentioned in this place. The apparatus employed by Mr Ingenhousz for this operation is represented in Pl. IV. Fig. 17.; but, having already described it sufficiently in Chap. III. I shall refer the reader to what is said of it in that place. Iron may likewise be oxydated by combustion in vessels filled with oxygen gas, in the way already directed for phosphorus and charcoal. This apparatus is represented Pl. IV. Fig. 3. and described in the fifth chapter of the first part of this work. We learn from Mr Ingenhousz, that all the metals, except gold, silver, and mercury, may be burnt or oxydated in the same manner, by reducing them into very fine wire, or very thin plates cut into narrow slips; these are twisted round with iron-wire, which communicates the property of burning to the other metals.
The burning of iron in oxygen gas is a true oxidation of that metal and should be noted here. The setup used by Mr. Ingenhousz for this process is shown in Pl. IV. Fig. 17.; however, since I’ve already described it in detail in Chap. III, I’ll direct the reader to that section for more information. Iron can also be oxidized by burning it in containers filled with oxygen gas, as outlined for phosphorus and charcoal. This setup is shown in Pl. IV. Fig. 3. and is explained in the fifth chapter of the first part of this work. According to Mr. Ingenhousz, all metals except gold, silver, and mercury can be burned or oxidized in the same way by turning them into very fine wire or very thin plates cut into narrow strips; these are then twisted together with iron wire, which allows the other metals to burn.
Mercury is even difficultly oxydated in free air. In chemical laboratories, this process is usually carried on in a matrass A, Pl. IV. Fig. having a very flat body, and a very long neck BC, which vessel is commonly called Boyle's bell. A quantity of mercury is introduced sufficient to cover the bottom, and it is placed in a sand-bath, which keeps up a constant heat approaching to that of boiling mercury. By continuing this operation with five or six similar matrasses during several months, and renewing[Pg 448] the mercury from time to time, a few ounces of red oxyd are at last obtained. The great slowness and inconvenience of this apparatus arises from the air not being sufficiently renewed; but if, on the other hand, too free a circulation were given to the external air, it would carry off the mercury in solution in the state of vapour, so that in a few days none would remain in the vessel.
Mercury is difficult to oxidize in open air. In chemical labs, this process is usually done in a flask A, Pl. IV. Fig., which has a very flat body and a long neck BC, commonly called Boyle's bell. A sufficient amount of mercury is added to cover the bottom, and it is placed in a sand bath, which maintains a constant heat close to that of boiling mercury. By continuing this process with five or six similar flasks for several months and periodically replacing the mercury, a few ounces of red oxide can eventually be collected. The slow progress and inconvenience of this setup is due to the air not being renewed adequately; however, if there is too much airflow from the outside, it would vaporize the mercury, leaving none behind in the vessel in just a few days.
As, of all the experiments upon the oxydation of metals, those with mercury are the most conclusive, it were much to be wished that a simple apparatus could be contrived by which this oxydation and its results might be demonstrated in public courses of chemistry. This might, in my opinion, be accomplished by methods similar to those I have already described for the combustion of charcoal and the oils; but, from other pursuits, I have not been able hitherto to resume this kind of experiment.
As the experiments on the oxidation of metals, particularly with mercury, are the most definitive, it would be great if a simple setup could be created to demonstrate this oxidation and its outcomes in public chemistry classes. In my view, this could be achieved using methods similar to those I've already described for burning charcoal and oils; however, due to other commitments, I haven't been able to return to this type of experiment yet.
The oxyd of mercury revives without addition, by being heated to a slightly red heat. In this degree of temperature, oxygen has greater affinity to caloric than to mercury, and forms oxygen gas. This is always mixed with a small portion of azotic gas, which indicates that the mercury absorbs a small portion of this latter gas during oxydation. It almost always contains a little carbonic acid gas, which must undoubtedly be attributed to the foulnesses of the[Pg 449] oxyd; these are charred by the heat, and convert a part of the oxygen gas into carbonic acid.
The mercury oxide comes back to life by just being heated to a slightly red heat. At this temperature, oxygen bonds more strongly with heat than with mercury, creating oxygen gas. This gas is usually mixed with a bit of nitrogen gas, showing that mercury absorbs some nitrogen during the oxidation process. It almost always contains a small amount of carbon dioxide, which is likely due to impurities in the[Pg 449] oxide; these impurities get charred by the heat and turn some of the oxygen gas into carbon dioxide.
If chemists were reduced to the necessity of procuring all the oxygen gas employed in their experiments from mercury oxydated by heat without addition, or, as it is called, calcined or precipitated per se, the excessive dearness of that preparation would render experiments, even upon a moderate scale, quite impracticable. But mercury may likewise be oxydated by means of nitric acid; and in this way we procure a red oxyd, even more pure than that produced by calcination. I have sometimes prepared this oxyd by dissolving mercury in nitric acid, evaporating to dryness, and calcining the salt, either in a retort, or in capsules formed of pieces of broken matrasses and retorts, in the manner formerly described; but I have never succeeded in making it equally beautiful with what is sold by the druggists, and which is, I believe, brought from Holland. In choosing this, we ought to prefer what is in solid lumps composed of soft adhering scales, as when in powder it is sometimes adulterated with red oxyd of lead.
If chemists had to get all the oxygen gas used in their experiments from mercury that’s been heated without any additives, known as calcined or precipitated by itself, the high cost of that process would make even moderate experiments completely impractical. However, mercury can also be oxidized using nitric acid, which allows us to obtain a red oxide that's even purer than the one made by calcination. I've sometimes made this oxide by dissolving mercury in nitric acid, evaporating it to dryness, and then calcining the salt either in a retort or in capsules made from broken pieces of flasks and retorts, as I've described before; but I've never managed to create one as beautiful as the kind sold by druggists, which I believe comes from Holland. When choosing this, we should prefer solid lumps made of soft, flaky scales, because when it's in powder form, it can sometimes be mixed with red lead oxide.
To obtain oxygen gas from the red oxyd of mercury, I usually employ a porcelain retort, having a long glass tube adapted to its beak, which is engaged under jars in the water pneumato-chemical[Pg 450] apparatus, and I place a bottle in the water, at the end of the tube, for receiving the mercury, in proportion as it revives and distils over. As the oxygen gas never appears till the retort becomes red, it seems to prove the principle established by Mr Berthollet, that an obscure heat can never form oxygen gas, and that light is one of its constituent elements. We must reject the first portion of gas which comes over, as being mixed with common air, from what was contained in the retort at the beginning of the experiment; but, even with this precaution, the oxygen gas procured is usually contaminated with a tenth part of azotic gas, and with a very small portion of carbonic acid gas. This latter is readily got rid of, by making the gas pass through a solution of caustic alkali; but we know of no method for separating the azotic gas; its proportions may however be ascertained, by leaving a known quantity of the oxygen gas contaminated with it for a fortnight, in contact with sulphuret of soda or potash, which absorbs the oxygen gas so as to convert the sulphur into sulphuric acid, and leaves the azotic gas remaining pure.
To obtain oxygen gas from mercuric oxide, I typically use a porcelain retort with a long glass tube attached to the opening, which is positioned under jars in a water pneumato-chemical apparatus. I place a bottle in the water at the end of the tube to collect the mercury as it evaporates and distills. Since oxygen gas only appears when the retort is red-hot, this supports Mr. Berthollet's principle that obscure heat won’t generate oxygen gas and that light is one of its essential components. We need to discard the first portion of gas that comes out because it’s mixed with the common air already in the retort at the start of the experiment. Even with this precaution, the oxygen gas obtained usually still contains about 10% nitrogen gas and a small amount of carbon dioxide. The latter can easily be eliminated by passing the gas through a solution of caustic alkali; however, we don't have a method to separate the nitrogen gas. Its proportion can, however, be determined by leaving a known amount of the contaminated oxygen gas in contact with sodium sulfide or potassium sulfide for two weeks, which absorbs the oxygen and converts the sulfur into sulfuric acid, leaving the nitrogen gas pure.
We may likewise procure oxygen gas from black oxyd of manganese or nitrat of potash, by exposing them to a red heat in the apparatus already described for operating upon red[Pg 451] oxyd of mercury; only, as it requires such a heat as is at least capable of softening glass, we must employ retorts of stone or of porcelain. But the purest and best oxygen gas is what is disengaged from oxygenated muriat of potash by simple heat. This operation is performed in a glass retort, and the gas obtained is perfectly pure, provided that the first portions, which are mixed with the common air of the vessels, be rejected.
We can also obtain oxygen gas from manganese dioxide or potassium nitrate by heating them to a red heat in the apparatus already described for working with red[Pg 451] mercury oxide. However, since it requires heat that's at least enough to soften glass, we need to use stone or porcelain retorts. The purest and best oxygen gas comes from potassium chlorate when simply heated. This process is done in a glass retort, and the gas produced is completely pure, as long as the initial portions mixed with the air in the vessels are discarded.
FOOTNOTES:
CHAP. IX.
Of Deflagration.
I have already shown, Part I. Chap. IX. that oxygen does not always part with the whole of the caloric it contained in the state of gas when it enters into combination with other bodies. It carries almost the whole of its caloric alongst with it in entering into the combinations which form nitric acid and oxygenated muriatic acid; so that in nitrats, and more especially in oxygenated muriats, the oxygen is, in a certain degree, in the state of oxygen gas, condensed, and reduced to the smallest volume it is capable of occupying.
I have already shown in Part I, Chapter IX, that oxygen doesn't always release all the heat it had in gas form when it combines with other substances. It retains nearly all of its heat when forming nitric acid and oxygenated muriatic acid; thus, in nitrates, and especially in oxygenated muriates, the oxygen is somewhat in the form of oxygen gas, compressed and reduced to the smallest volume it can occupy.
In these combinations, the caloric exerts a constant action upon the oxygen to bring it back to the state of gas; hence the oxygen adheres but very slightly, and the smallest additional force is capable of setting it free; and, when such force is applied, it often recovers the state of gas instantaneously. This rapid passage from the solid to the aëriform state is called detonation, or fulmination, because it is usually accompanied with noise and explosion. Deflagrations are commonly produced by means of combinations of charcoal either with nitre or[Pg 453] oxygenated muriat of potash; sometimes, to assist the inflammation, sulphur is added; and, upon the just proportion of these ingredients, and the proper manipulation of the mixture, depends the art of making gun-powder.
In these combinations, the caloric constantly acts on the oxygen to return it to a gaseous state; therefore, the oxygen barely sticks around, and even the smallest extra force can release it. When that force is applied, it often transforms back to gas instantly. This quick change from solid to gas is called detonation or fulmination because it usually comes with noise and explosions. Deflagrations are commonly created by mixing charcoal with either nitrate or[Pg 453] oxygenated potassium chloride; sometimes, sulfur is added to help with ignition, and the right balance of these ingredients along with the correct handling of the mixture is essential for making gunpowder.
As oxygen is changed, by deflagration with charcoal, into carbonic acid, instead of oxygen gas, carbonic acid gas is disengaged, at least when the mixture has been made in just proportions. In deflagration with nitre, azotic gas is likewise disengaged, because azote is one of the constituent elements of nitric acid.
As oxygen is transformed through combustion with charcoal into carbon dioxide, carbon dioxide gas is released instead of oxygen gas, at least when the mixture is made in the right proportions. In combustion with nitrate, nitrogen gas is also released, because nitrogen is one of the key elements of nitric acid.
The sudden and instantaneous disengagement and expansion of these gasses is not, however, sufficient for explaining all the phenomena of deflagration; because, if this were the sole operating power, gun powder would always be so much the stronger in proportion as the quantity of gas disengaged in a given time was the more considerable, which does not always accord with experiment. I have tried some kinds which produced almost double the effect of ordinary gun powder, although they gave out a sixth part less of gas during deflagration. It would appear that the quantity of caloric disengaged at the moment of detonation contributes considerably to the expansive effects produced; for, although caloric penetrates freely through the pores of every body in nature, it can only do so progressively, and in a given time; hence,[Pg 454] when the quantity disengaged at once is too large to get through the pores of the surrounding bodies, it must necessarily act in the same way with ordinary elastic fluids, and overturn every thing that opposes its passage. This must, at least in part, take place when gun-powder is set on fire in a cannon; as, although the metal is permeable to caloric, the quantity disengaged at once is too large to find its way through the pores of the metal, it must therefore make an effort to escape on every side; and, as the resistance all around, excepting towards the muzzle, is too great to be overcome, this effort is employed for expelling the bullet.
The sudden and instantaneous release and expansion of these gases, however, isn’t enough to explain all the phenomena of deflagration. If that were the only driving force, gunpowder would always be stronger the more gas it released in a given time, which doesn’t always match what experiments show. I have tested some types that produced almost double the effect of regular gunpowder, even though they released a sixth less gas during deflagration. It seems that the amount of heat released at the moment of detonation significantly contributes to the expansive effects; because while heat can easily pass through the pores of all materials in nature, it can only do so gradually and over time. Hence, when the amount released at once is too large to move through the pores of surrounding materials, it will behave similarly to ordinary gases and push against everything that blocks its path. This must happen, at least in part, when gunpowder ignites in a cannon. Even though the metal can absorb heat, the quantity being released at once is too great to be absorbed through the metal’s pores, so it has to push outward in every direction. Since the resistance all around—except towards the muzzle—is too strong to overcome, this force is used to drive the bullet out.
The caloric produces a second effect, by means of the repulsive force exerted between its particles; it causes the gasses, disengaged at the moment of deflagration, to expand with a degree of force proportioned to the temperature produced.
The caloric has a second effect due to the repulsive force between its particles; it makes the gases released during deflagration expand with a level of force proportional to the temperature generated.
It is very probable that water is decomposed during the deflagration of gun-powder, and that part of the oxygen furnished to the nascent carbonic acid gas is produced from it. If so, a considerable quantity of hydrogen gas must be disengaged in the instant of deflagration, which expands, and contributes to the force of the explosion. It may readily be conceived how greatly this circumstance must increase the effect of powder, if we consider that a pint of hydrogen[Pg 455] gas weighs only one grain and two thirds; hence a very small quantity in weight must occupy a very large space, and it must exert a prodigious expansive force in passing from the liquid to the aëriform state of existence.
It’s very likely that water breaks down during the explosion of gunpowder, and that some of the oxygen provided to create carbonic acid gas comes from it. If that’s the case, a significant amount of hydrogen gas must be released at the moment of explosion, which expands and adds to the force of the blast. It’s easy to see how much this factor can amplify the power of gunpowder if we think about the fact that a pint of hydrogen[Pg 455] gas only weighs one and two-thirds grains; therefore, a very small weight of it must take up a large volume, and it exerts an enormous expanding force as it transitions from a liquid to a gas.
In the last place, as a portion of undecomposed water is reduced to vapour during the deflagration of gun-powder, and as water, in the state of gas, occupies seventeen or eighteen hundred times more space than in its liquid state, this circumstance must likewise contribute largely to the explosive force of the powder.
In the end, as some unbroken water turns into vapor during the combustion of gunpowder, and since water in gas form takes up seventeen or eighteen hundred times more space than it does in liquid form, this factor must also significantly add to the explosive power of the powder.
I have already made a considerable series of experiments upon the nature of the elastic fluids disengaged during the deflagration of nitre with charcoal and sulphur; and have made some, likewise, with the oxygenated muriat of potash. This method of investigation leads to tollerably accurate conclusions with respect to the constituent elements of these salts. Some of the principal results of these experiments, and of the consequences drawn from them respecting the analysis of nitric acid, are reported in the collection of memoirs presented to the Academy by foreign philosophers, vol. xi. p. 625. Since then I have procured more convenient instruments, and I intend to repeat these experiments upon a larger scale, by which I shall procure more accurate precision in their results; the following, however, is the process I have hitherto[Pg 456] employed. I would very earnestly advise such as intend to repeat some of these experiments, to be very much upon their guard in operating upon any mixture which contains nitre, charcoal, and sulphur, and more especially with those in which oxygenated muriat of potash is mixed with these two materials.
I have already conducted a significant number of experiments on the nature of the gases produced during the burning of saltpeter with charcoal and sulfur; I've also done some with potassium chlorate. This investigative method leads to fairly accurate conclusions about the elements that make up these salts. Some of the main findings from these experiments and their implications for the analysis of nitric acid are detailed in the collection of papers submitted to the Academy by foreign scholars, vol. xi. p. 625. Since then, I've acquired better instruments, and I plan to repeat these experiments on a larger scale, which will give me more precise results; however, here is the method I have used so far[Pg 456]. I strongly advise anyone looking to repeat these experiments to be very cautious when working with any mixture that includes saltpeter, charcoal, and sulfur, especially those that combine potassium chlorate with these two materials.
I make use of pistol barrels, about six inches long, and of five or six lines diameter, having the touch-hole spiked up with an iron nail strongly driven in, and broken in the hole, and a little tin-smith's solder run in to prevent any possible issue for the air. These are charged with a mixture of known quantities of nitre and charcoal, or any other mixture capable of deflagration, reduced to an impalpable powder, and formed into a paste with a moderate quantity of water. Every portion of the materials introduced must be rammed down with a rammer nearly of the same caliber with the barrel, four or five lines at the muzzle must be left empty, and about two inches of quick match are added at the end of the charge. The only difficulty in this experiment, especially when sulphur is contained in the mixture, is to discover the proper degree of moistening; for, if the paste be too much wetted, it will not take fire, and if too dry, the deflagration is apt to become too rapid, and even dangerous.[Pg 457]
I use pistol barrels that are about six inches long and five or six lines in diameter. The touch-hole is sealed up with an iron nail that’s driven in tightly, then broken off inside, and I add a bit of tin-smith's solder to prevent any air from escaping. These barrels are loaded with a mixture of specific amounts of saltpeter and charcoal, or any other mix that can deflagrate, ground into a very fine powder and made into a paste with a moderate amount of water. Every part of the materials needs to be packed down with a rammer that’s nearly the same size as the barrel, leaving four or five lines empty at the muzzle, and about two inches of quick match is added at the end of the charge. The only tricky part of this experiment, especially when sulfur is included in the mix, is getting the right level of moisture; if the paste is too wet, it won’t ignite, and if it’s too dry, the deflagration can become too quick and even dangerous.[Pg 457]
When the experiment is not intended to be rigorously exact, we set fire to the match, and, when it is just about to communicate with the charge, we plunge the pistol below a large bell-glass full of water, in the pneumato chemical apparatus. The deflagration begins, and continues in the water, and gas is disengaged with less or more rapidity, in proportion as the mixture is more or less dry. So long as the deflagration continues, the muzzle of the pistol must be kept somewhat inclined downwards, to prevent the water from getting into its barrel. In this manner I have sometimes collected the gas produced from the deflagration of an ounce and half, or two ounces, of nitre.
When the experiment doesn't need to be super precise, we light the match, and when it’s about to ignite the charge, we lower the pistol under a large glass bell full of water in the pneumatic chemical setup. The reaction starts and continues underwater, releasing gas at a faster or slower rate depending on how dry the mixture is. As long as the reaction is ongoing, the muzzle of the pistol should be angled slightly down to keep water from entering the barrel. This way, I’ve been able to collect the gas produced from burning one and a half or two ounces of saltpeter.
In this manner of operating it is impossible to determine the quantity of carbonic acid gas disengaged, because a part of it is absorbed by the water while passing through it; but, when the carbonic acid is absorbed, the azotic gas remains; and, if it be agitated for a few minutes in caustic alkaline solution, we obtain it pure, and can easily determine its volume and weight. We may even, in this way, acquire a tollerably exact knowledge of the quantity of carbonic acid by repeating the experiment a great many times, and varying the proportions of charcoal, till we find the exact quantity requisite to deflagrate the whole nitre employed. Hence, by means of the weight of charcoal employed, we[Pg 458] determine the weight of oxygen necessary for saturation, and deduce the quantity of oxygen contained in a given weight of nitre.
In this way of working, it's impossible to figure out how much carbon dioxide is released because some of it gets absorbed by the water as it passes through. However, when carbon dioxide gets absorbed, the nitrogen gas stays behind; and if we agitate it for a few minutes in a strong alkaline solution, we can get it in pure form and easily measure its volume and weight. By doing this over and over again and changing the amounts of charcoal used, we can get a pretty accurate idea of how much carbon dioxide is involved until we find the exact amount needed to completely react with the nitre we used. Thus, by knowing the weight of charcoal used, we can determine the weight of oxygen necessary for a complete reaction and figure out the amount of oxygen contained in a specific weight of nitre.
I have used another process, by which the results of this experiment are considerably more accurate, which consists in receiving the disengaged gasses in bell-glasses filled with mercury. The mercurial apparatus I employ is large enough to contain jars of from twelve to fifteen pints in capacity, which are not very readily managed when full of mercury, and even require to be filled by a particular method. When the jar is placed in the cistern of mercury, a glass syphon is introduced, connected with a small air-pump, by means of which the air is exhausted, and the mercury rises so as to fill the jar. After this, the gas of the deflagration is made to pass into the jar in the same manner as directed when water is employed.
I’ve used a different method that makes the results of this experiment much more accurate. This method involves collecting the released gases in bell jars filled with mercury. The apparatus I use is large enough to hold jars with a capacity of twelve to fifteen pints, which can be quite tricky to handle when full of mercury and even need to be filled using a specific technique. When the jar is placed in the mercury cistern, a glass siphon is inserted, connected to a small air pump that evacuates the air, causing the mercury to rise and fill the jar. After that, the gas from the deflagration is directed into the jar in the same way as when using water.
I must again repeat, that this species of experiment requires to be performed with the greatest possible precautions. I have sometimes seen, when the disengagement of gas proceeded with too great rapidity, jars filled with more than an hundred and fifty pounds of mercury driven off by the force of the explosion, and broken to pieces, while the mercury was scattered about in great quantities.
I have to emphasize again that this type of experiment needs to be done with the utmost care. I've occasionally witnessed cases where gas was released too quickly, causing jars filled with more than one hundred and fifty pounds of mercury to be blown away by the force of the explosion and shatter, scattering mercury all over the place.
When the experiment has succeeded, and the gas is collected under the jar, its quantity in[Pg 459] general, and the nature and quantities of the several species of gasses of which the mixture is composed, are accurately ascertained by the methods already pointed out in the second chapter of this part of my work. I have been prevented from putting the last hand to the experiments I had begun upon deflagration, from their connection with the objects I am at present engaged in; and I am in hopes they will throw considerable light upon the operations belonging to the manufacture of gun-powder.
When the experiment is successful, and the gas is collected under the jar, the amount in[Pg 459] general, along with the types and amounts of the various gases that make up the mixture, will be accurately determined using the methods described in the second chapter of this part of my work. I haven't been able to complete the experiments I started on deflagration due to their connection with the current projects I'm working on; however, I hope they will provide significant insights into the processes involved in making gunpowder.
CHAP. X.
Of the Instruments necessary for Operating upon Bodies in very high Temperatures.
SECT. I.
Of Fusion.
We have already seen, that, by aqueous solution, in which the particles of bodies are separated from each other, neither the solvent nor the body held in solution are at all decomposed; so that, whenever the cause of separation ceases, the particles reunite, and the saline substance recovers precisely the same appearance and properties it possessed before solution. Real solutions are produced by fire, or by introducing and accumulating a great quantity of caloric between the particles of bodies; and this species of solution in caloric is usually called fusion.
We have already seen that in a liquid solution, where the particles of substances are separated from each other, neither the solvent nor the substance dissolved in it gets broken down. So, whenever the cause of separation stops, the particles come back together, and the dissolved substance regains exactly the same appearance and properties it had before it was dissolved. Real solutions are created by heat or by adding and accumulating a lot of heat energy between the particles of substances, and this type of solution due to heat is usually called fusion.
This operation is commonly performed in vessels called crucibles, which must necessarily[Pg 461] be less fusible than the bodies they are intended to contain. Hence, in all ages, chemists have been extremely solicitous to procure crucibles of very refractory materials, or such as are capable of resisting a very high degree of heat. The best are made of very pure clay or of porcelain earth; whereas such as are made of clay mixed with calcareous or silicious earth are very fusible. All the crucibles made in the neighbourhood of Paris are of this kind, and consequently unfit for most chemical experiments. The Hessian crucibles are tolerably good; but the best are made of Limoges earth, which seems absolutely infusible. We have, in France, a great many clays very fit for making crucibles; such, for instance, is the kind used for making melting pots at the glass-manufactory of St Gobin.
This process is usually done in containers called crucibles, which must be less likely to melt than the materials they hold. Therefore, throughout history, chemists have been very careful to find crucibles made from highly heat-resistant materials. The best ones are made from very pure clay or porcelain; however, those made from clay mixed with lime or silica are quite easy to melt. All the crucibles made around Paris fall into this category and are therefore unsuitable for most chemical experiments. Hessian crucibles are fairly good, but the best ones are made from Limoges clay, which appears to be completely non-melting. In France, we have many types of clay that are great for making crucibles; for example, the kind used for making melting pots at the St Gobin glass factory.
Crucibles are made of various forms, according to the operations they are intended to perform. Several of the most common kinds are represented Pl. VII. Fig. 7. 8. 9. and 10. the one represented at Fig. 9. is almost shut at its mouth.
Crucibles come in different shapes depending on the tasks they're meant to do. Some of the most common types are shown in Pl. VII. Fig. 7, 8, 9, and 10. The one shown in Fig. 9 is almost closed at the top.
Though fusion may often take place without changing the nature of the fused body, this operation is frequently employed as a chemical means of decomposing and recompounding bodies. In this way all the metals are extracted from their ores; and, by this process, they are revivified,[Pg 462] moulded, and alloyed with each other. By this process sand and alkali are combined to form glass, and by it likewise pastes, or coloured stones, enamels, &c. are formed.
Though fusion may often occur without altering the essence of the fused material, this process is commonly used as a chemical method for breaking down and recombining substances. This is how all metals are extracted from their ores, and through this method, they are revitalized,[Pg 462] shaped, and combined with one another. In this process, sand and alkali come together to create glass, and similarly, pastes, colored stones, enamels, etc., are produced.
The action of violent fire was much more frequently employed by the ancient chemists than it is in modern experiments. Since greater precision has been employed in philosophical researches, the humid has been preferred to the dry method of process, and fusion is seldom had recourse to until all the other means of analysis have failed.
The use of intense heat was much more common among ancient chemists than it is in modern experiments. With the increased precision in scientific research, the wet method has become more popular than the dry method, and melting is rarely used until all other analytical methods have been tried and failed.
SECT. II.
Of Furnaces.
These are instruments of most universal use in chemistry; and, as the success of a great number of experiments depends upon their being well or ill constructed, it is of great importance that a laboratory be well provided in this respect. A furnace is a kind of hollow cylindrical tower, sometimes widened above, Pl. XIII. Fig. 1. ABCD, which must have at least two lateral openings; one in its upper part F, which is the door of the fire-place, and one below, G, leading to the ash-hole. Between these the furnace[Pg 463] is divided by a horizontal grate, intended for supporting the fewel, the situation of which is marked in the figure by the line HI. Though this be the least complicated of all the chemical furnaces, yet it is applicable to a great number of purposes. By it lead, tin, bismuth, and, in general, every substance which does not require a very strong fire, may be melted in crucibles; it will serve for metallic oxydations, for evaporatory vessels, and for sand-baths, as in Pl. III. Fig. 1. and 2. To render it proper for these purposes, several notches, m m m m, Pl. XIII. Fig. 1. are made in its upper edge, as otherwise any pan which might be placed over the fire would stop the passage of the air, and prevent the fewel from burning. This furnace can only produce a moderate degree of heat, because the quantity of charcoal it is capable of consuming is limited by the quantity of air which is allowed to pass through the opening G of the ash-hole. Its power might be considerably augmented by enlarging this opening, but then the great stream of air which is convenient for some operations might be hurtful in others; wherefore we must have furnaces of different forms, constructed for different purposes, in our laboratories: There ought especially to be several of the kind now described of different sizes.
These are some of the most commonly used tools in chemistry, and since the success of many experiments relies on
The reverberatory furnace, Pl. XIII. Fig. 2. is perhaps more necessary. This, like the common[Pg 464] furnace, is composed of the ash-hole HIKL, the fire-place KLMN, the laboratory MNOP, and the dome RRSS, with its funnel or chimney TTVV; and to this last several additional tubes may be adapted, according to the nature of the different experiments. The retort A is placed in the division called the laboratory, and supported by two bars of iron which run across the furnace, and its beak comes out at a round hole in the side of the furnace, one half of which is cut in the piece called the laboratory, and the other in the dome. In most of the ready made reverberatory furnaces which are sold by the potters at Paris, the openings both above and below are too small: These do not allow a sufficient volume of air to pass through; hence, as the quantity of charcoal consumed, or, what is much the same thing, the quantity of caloric disengaged, is nearly in proportion to the quantity of air which passes through the furnace, these furnaces do not produce a sufficient effect in a great number of experiments. To remedy this defect, there ought to be two openings GG to the ash-hole; one of these is shut up when only a moderate fire is required; and both are kept open when the strongest power of the furnace is to be exerted. The opening of the dome SS ought likewise to be considerably larger than is usually made.[Pg 465]
The reverberatory furnace, Pl. XIII. Fig. 2, is probably more essential. This, like the standard [Pg 464] furnace, consists of the ash-hole HIKL, the fire-place KLMN, the laboratory MNOP, and the dome RRSS, with its funnel or chimney TTVV. Several additional tubes can be added to the funnel based on the nature of different experiments. The retort A is positioned in the section called the laboratory, supported by two iron bars that cross the furnace, and its nozzle extends through a round hole in the side of the furnace—half of which is cut into the piece called the laboratory, and the other half in the dome. In many of the prefabricated reverberatory furnaces sold by potters in Paris, the openings both above and below are too small. This restricts airflow, which means the amount of charcoal burned, or similarly, the amount of heat released, is nearly proportional to the airflow through the furnace. As a result, these furnaces often fail to produce adequate results in numerous experiments. To fix this issue, there should be two openings GG to the ash-hole; one can be closed when only a moderate fire is needed, and both should be open when the furnace is required to operate at full capacity. The opening of the dome SS should also be significantly larger than is usually designed. [Pg 465]
It is of great importance not to employ retorts of too large size in proportion to the furnace, as a sufficient space ought always to be allowed for the passage of the air between the sides of the furnace and the vessel. The retort A in the figure is too small for the size of the furnace, yet I find it more easy to point out the error than to correct it. The intention of the dome is to oblige the flame and heat to surround and strike back or reverberate upon every part of the retort, whence the furnace gets the name of reverberatory. Without this circumstance the retort would only be heated in its bottom, the vapours raised from the contained substance would condense in the upper part, and a continual cohabitation would take place without any thing passing over into the receiver, but, by means of the dome, the retort is equally heated in every part, and the vapours being forced out, can only condense in the neck of the retort, or in the recipient.
It’s really important not to use a retort that’s too large for the furnace because there needs to be enough space for air to flow between the furnace and the vessel. The retort A in the figure is too small for the furnace, but I find it easier to point out the mistake than to fix it. The purpose of the dome is to force the flame and heat to surround the retort and reflect back on every part of it, which is why the furnace is called reverberatory. Without this design, the retort would only get heated at the bottom, causing the vapors from the substance inside to condense at the top, leading to a constant buildup without any transfer to the receiver. However, with the dome, the retort heats evenly throughout, and the vapors are pushed out, so they can only condense in the neck of the retort or in the receiver.
To prevent the bottom of the retort from being either heated or coolled too suddenly, it is sometimes placed in a small sand-bath of baked clay, standing upon the cross bars of the furnace. Likewise, in many operations, the retorts are coated over with lutes, some of which are intended to preserve them from the too sudden influence of heat or of cold, while others are for sustaining the glass, or forming a kind of second[Pg 466] retort, which supports the glass one during operations wherein the strength of the fire might soften it. The former is made of brick-clay with a little cow's hair beat up alongst with it, into a paste or mortar, and spread over the glass or stone retorts. The latter is made of pure clay and pounded stone-ware mixed together, and used in the same manner. This dries and hardens by the fire, so as to form a true supplementary retort capable of retaining the materials, if the glass retort below should crack or soften. But, in experiments which are intended for collecting gasses, this lute, being porous, is of no manner of use.
To prevent the bottom of the retort from being heated or cooled too quickly, it’s sometimes placed in a small sand bath made of baked clay, resting on the cross bars of the furnace. Similarly, in many processes, the retorts are covered with lutes, some of which are meant to protect them from sudden changes in temperature, while others are designed to support the glass or create a sort of second[Pg 466] retort that helps hold the glass during processes where the heat could soften it. The first type is made of brick clay mixed with some cow's hair, turned into a paste or mortar, and applied to the glass or stone retorts. The second type is made from pure clay mixed with crushed stoneware and used in the same way. This dries and hardens in the fire, forming a true supplementary retort that can hold the materials if the glass retort below cracks or softens. However, in experiments designed to collect gases, this lute is not useful since it's porous.
In a great many experiments wherein very violent fire is not required, the reverberatory furnace may be used as a melting one, by leaving out the piece called the laboratory, and placing the dome immediately upon the fire-place, as represented Pl. XIII. Fig. 3. The furnace represented in Fig. 4. is very convenient for fusions; it is composed of the fire-place and ash-hole ABD, without a door, and having a hole E, which receives the muzzle of a pair of bellows strongly luted on, and the dome ABGH, which ought to be rather lower than is represented in the figure. This furnace is not capable of producing a very strong heat, but is sufficient for ordinary operations, and may be readily moved to any part of the laboratory[Pg 467] where it is wanted. Though these particular furnaces are very convenient, every laboratory must be provided with a forge furnace, having a good pair of bellows, or, what is more necessary, a powerful melting furnace. I shall describe the one I use, with the principles upon which it is constructed.
In many experiments where extreme heat isn't necessary, the reverberatory furnace can be used for melting by removing the part called the laboratory and placing the dome directly on the fire-place, as shown in Pl. XIII. Fig. 3. The furnace depicted in Fig. 4 is very handy for fusions; it consists of the fire-place and ash-hole ABD, without a door, and has a hole E that connects to a pair of bellows securely attached, along with the dome ABGH, which should be a bit lower than shown in the figure. This furnace doesn’t generate very intense heat, but it's adequate for regular tasks and can be easily moved to any part of the laboratory[Pg 467] where it's needed. While these specific furnaces are quite practical, every laboratory should have a forge furnace with a good pair of bellows, or, more importantly, a powerful melting furnace. I will explain the one I use and the principles behind its design.
The air circulates in a furnace in consequence of being heated in its passage through the burning coals; it dilates, and, becoming lighter than the surrounding air, is forced to rise upwards by the pressure of the lateral columns of air, and is replaced by fresh air from all sides, especially from below. This circulation of air even takes place when coals are burnt in a common chaffing dish; but we can readily conceive, that, in a furnace open on all sides, the mass of air which passes, all other circumstances being equal, cannot be so great as when it is obliged to pass through a furnace in the shape of a hollow tower, like most of the chemical furnaces, and consequently, that the combustion must be more rapid in a furnace of this latter construction. Suppose, for instance, the furnace ABCDEF open above, and filled with burning coals, the force with which the air passes through the coals will be in proportion to the difference between the specific gravity of two columns equal to AC, the one of cold air without, and the other of heated air within the furnace.[Pg 468] There must be some heated air above the opening AB, and the superior levity of this ought likewise to be taken into consideration; but, as this portion is continually coolled and carried off by the external air, it cannot produce any great effect.
The air moves through a furnace because it gets heated as it passes through the burning coals; it expands and becomes lighter than the surrounding air, causing it to rise due to the pressure from the air columns on the sides. This rising air is replaced by fresh air from all directions, especially from below. This air circulation also occurs when coals are burned in a regular chafing dish; however, it’s easy to see that in a furnace that’s open on all sides, the amount of air passing through, with all other conditions being equal, won't be as much as when it has to flow through a furnace shaped like a hollow tower, like most chemical furnaces. Thus, combustion will be faster in that type of furnace. For example, imagine the furnace ABCDEF is open at the top and filled with burning coals; the speed at which air moves through the coals will depend on the difference in weight between two equal columns, AC, one of the cold air outside and the other of the heated air inside the furnace. There needs to be some heated air above the opening AB, and the lighter weight of this air should also be considered; however, since this portion is constantly cooled and swept away by the outside air, it won’t have a significant effect.[Pg 468]
But, if we add to this furnace a large hollow tube GHAB of the same diameter, which preserves the air which has been heated by the burning coals from being coolled and dispersed by the surrounding air, the difference of specific gravity which causes the circulation will then be between two columns equal to GC. Hence, if GC be three times the length of AC, the circulation will have treble force. This is upon the supposition that the air in GHCD is as much heated as what is contained in ABCD, which is not strictly the case, because the heat must decrease between AB and GH; but, as the air in GHAB is much warmer than the external air, it follows, that the addition of the tube must increase the rapidity of the stream of air, that a larger quantity must pass through the coals, and consequently that a greater degree of combustion must take place.
But if we add a large hollow tube GHAB of the same diameter to this furnace, which prevents the heated air from the burning coals from cooling down and mixing with the surrounding air, the difference in specific gravity that causes the circulation will then be between two columns equal to GC. If GC is three times the length of AC, the circulation will be three times stronger. This assumes that the air in GHCD is heated the same as the air in ABCD, which isn't entirely accurate since the heat decreases between AB and GH; however, since the air in GHAB is much warmer than the outside air, we can conclude that adding the tube will increase the speed of the airflow, allowing more air to pass through the coals, and as a result, there will be a greater amount of combustion.
We must not, however, conclude from these principles, that the length of this tube ought to be indefinitely prolonged; for, since the heat of the air gradually diminishes in passing from AB to GH, even from the contact of the sides of the[Pg 469] tube, if the tube were prolonged to a certain degree, we would at last come to a point where the specific gravity of the included air would be equal to the air without; and, in this case, as the cool air would no longer tend to rise upwards, it would become a gravitating mass, resisting the ascension of the air below. Besides, as this air, which has served for combustion, is necessarily mixed with carbonic acid gas, which is considerably heavier than common air, if the tube were made long enough, the air might at last approach so near to the temperature of the external air as even to gravitate downwards; hence we must conclude, that the length of the tube added to a furnace must have some limit beyond which it weakens, instead of strengthening the force of the fire.
We shouldn't conclude from these principles that the length of this tube should be extended indefinitely. As the heat of the air decreases from AB to GH, even from the contact of the sides of the [Pg 469] tube, extending the tube too much would eventually reach a point where the specific gravity of the air inside equals that of the outside air. At that point, since the cool air would no longer rise, it would become a heavy mass, preventing the air below from rising. Moreover, the air used for combustion is mixed with carbon dioxide, which is significantly heavier than normal air. If the tube is long enough, the air might get close to the temperature of the outside air and even start to sink. Therefore, we must conclude that there must be a limit to how long the tube attached to a furnace can be, beyond which it weakens rather than enhances the fire's strength.
From these reflections it follows, that the first foot of tube added to a furnace produces more effect than the sixth, and the sixth more than the tenth; but we have no data to ascertain at what height we ought to stop. This limit of useful addition is so much the farther in proportion as the materials of the tube are weaker conductors of heat, because the air will thereby be so much less coolled; hence baked earth is much to be preferred to plate iron. It would be even of consequence to make the tube double, and to fill the interval with rammed charcoal, which is one of the worst conductors of heat[Pg 470] known; by this the refrigeration of the air will be retarded, and the rapidity of the stream of air consequently increased; and, by this means, the tube may be made so much the longer.
From these reflections, it follows that the first foot of a tube added to a furnace has a greater effect than the sixth, and the sixth has a greater effect than the tenth; however, we have no data to determine at what height we should stop. This limit for useful addition is further away in proportion to how poorly the materials of the tube conduct heat, since the air will therefore be cooled less. Hence, baked earth is much better than plate iron. It would also be beneficial to make the tube double and fill the space in between with compacted charcoal, which is one of the worst heat conductors known; this would slow down the cooling of the air and consequently increase the speed of the air flow, allowing the tube to be made significantly longer.[Pg 470]
As the fire-place is the hottest part of a furnace, and the part where the air is most dilated in its passage, this part ought to be made with a considerable widening or belly. This is the more necessary, as it is intended to contain the charcoal and crucible, as well as for the passage of the air which supports, or rather produces the combustion; hence we only allow the interstices between the coals for the passage of the air.
As the fireplace is the hottest part of a furnace and where the air expands the most during its passage, this area should be designed with a significant widening or belly. This is even more important, as it needs to hold the charcoal and crucible, as well as allow the air to flow through that fuels or actually creates the combustion; therefore, we only leave the spaces between the coals for the airflow.
From these principles my melting furnace is constructed, which I believe is at least equal in power to any hitherto made, though I by no means pretend that it possesses the greatest possible intensity that can be produced in chemical furnaces. The augmentation of the volume of air produced during its passage through a melting furnace not being hitherto ascertained from experiment, we are still unacquainted with the proportions which should exist between the inferior and superior apertures, and the absolute size of which these openings should be made is still less understood; hence data are wanting by which to proceed upon principle, and we can only accomplish the end in view by repeated trials.[Pg 471]
From these principles, I've built my melting furnace, which I believe is at least as powerful as any ever made, although I don't claim that it has the highest possible intensity achievable in chemical furnaces. Since the increase in the volume of air during its passage through a melting furnace hasn't been determined through experiments, we still don't know the right proportions between the lower and upper openings, and we understand even less about the size these openings should be. Because of this, we lack the necessary data to proceed based on principles, so we can only achieve our goal through repeated tests.[Pg 471]
This furnace, which, according to the above stated rules, is in form of an eliptical spheroid, is represented Pl. XIII. Fig. 6. ABCD; it is cut off at the two ends by two plains, which pass, perpendicular to the axis, through the foci of the elipse. From this shape it is capable of containing a considerable quantity of charcoal, while it leaves sufficient space in the intervals for the passage of the air. That no obstacle may oppose the free access of external air, it is perfectly open below, after the model of Mr Macquer's melting furnace, and stands upon an iron tripod. The grate is made of flat bars set on edge, and with considerable interstices. To the upper part is added a chimney, or tube, of baked earth, ABFG, about eighteen feet long, and almost half the diameter of the furnace. Though this furnace produces a greater heat than any hitherto employed by chemists, it is still susceptible of being considerably increased in power by the means already mentioned, the principal of which is to render the tube as bad a conductor of heat as possible, by making it double, and filling the interval with rammed charcoal.
This furnace, shaped like an elliptical spheroid according to the rules stated above, is shown in Pl. XIII. Fig. 6. ABCD; it is truncated at both ends by two planes that are perpendicular to the axis and pass through the foci of the ellipse. This design allows it to hold a significant amount of charcoal while still providing enough space for air to flow through. To ensure unobstructed access for outside air, it is fully open at the bottom, following the model of Mr. Macquer's melting furnace, and rests on an iron tripod. The grate is constructed from flat bars positioned vertically, with ample gaps between them. A chimney or tube made of baked earth, ABFG, approximately eighteen feet long and nearly half the diameter of the furnace, is attached to the upper section. Although this furnace generates more heat than any previously used by chemists, its power can still be significantly enhanced by the previously mentioned methods, the main one being to make the tube as poor a conductor of heat as possible by constructing it as a double tube and filling the space in between with compacted charcoal.
When it is required to know if lead contains any mixture of gold or silver, it is heated in a strong fire in capsules of calcined bones, which are called cuppels. The lead is oxydated, becomes vitrified, and sinks into the substance of[Pg 472] the cuppel, while the gold or silver, being incapable of oxydation, remain pure. As lead will not oxydate without free access of air, this operation cannot be performed in a crucible placed in the middle of the burning coals of a furnace, because the internal air, being mostly already reduced by the combustion into azotic and carbonic acid gas, is no longer fit for the oxydation of metals. It was therefore necessary to contrive a particular apparatus, in which the metal should be at the same time exposed to the influence of violent heat, and defended from contact with air rendered incombustible by its passage through burning coals. The furnace intended for answering this double purpose is called the cuppelling or essay furnace. It is usually made of a square form, as represented Pl. XIII. Fig. 8. and 10. having an ash-hole AABB, a fire-place BBCC, a laboratory CCDD, and a dome DDEE. The muffle or small oven of baked earth GH, Fig. 9. being placed in the laboratory of the furnace upon cross bars of iron, is adjusted to the opening GG, and luted with clay softened in water. The cuppels are placed in this oven or muffle, and charcoal is conveyed into the furnace through the openings of the dome and fire-place. The external air enters through the openings of the ash-hole for supporting the combustion, and escapes by the superior opening or chimney at EE; and air is[Pg 473] admitted through the door of the muffle GG for oxydating the contained metal.
When you need to find out if lead has any gold or silver mixed in, it’s heated in high-temperature fire inside capsules made from calcined bones, called cuppels. The lead gets oxidized, turns into a glass-like substance, and sinks into the bottom of[Pg 472] the cuppel, while the gold or silver, which can’t be oxidized, stays pure. Since lead won’t oxidize without access to air, this process can’t be done in a crucible sitting in the middle of a furnace’s burning coals, because the air inside becomes mostly carbon and nitrogen dioxide from the combustion and isn’t suitable for oxidizing metals anymore. Thus, a special setup was needed to keep the metal exposed to intense heat while shielding it from air that has passed through burning coals and become incombustible. The furnace designed for this dual purpose is called the cuppelling or assay furnace. It usually has a square shape, as shown in Pl. XIII. Fig. 8 and 10, with an ash-hole AABB, a fire-place BBCC, a laboratory CCDD, and a dome DDEE. The muffle, or small oven made from baked earth GH, Fig. 9, sits in the laboratory of the furnace on iron cross bars, aligns with the opening GG, and is sealed with clay mixed with water. The cuppels are placed inside this oven or muffle, and charcoal is fed into the furnace through the dome and fire-place openings. The external air enters through the ash-hole openings to support the combustion, and exits through the top opening or chimney at EE; air is[Pg 473] let in through the door of the muffle GG to oxidize the metal inside.
Very little reflection is sufficient to discover the erroneous principles upon which this furnace is constructed. When the opening GG is shut, the oxydation is produced slowly, and with difficulty, for want of air to carry it on; and, when this hole is open, the stream of cold air which is then admitted fixes the metal, and obstructs the process. These inconveniencies may be easily remedied, by constructing the muffle and furnace in such a manner that a stream of fresh external air should always play upon the surface of the metal, and this air should be made to pass through a pipe of clay kept continually red hot by the fire of the furnace. By this means the inside of the muffle will never be coolled, and processes will be finished in a few minutes, which at present require a considerable space of time.
It doesn’t take much thought to see the flawed principles behind this furnace's design. When the opening GG is closed, oxidation happens slowly and with difficulty due to a lack of air; when this hole is open, the incoming cold air solidifies the metal and interferes with the process. These issues can be easily fixed by designing the muffle and furnace so that a stream of fresh air constantly flows over the surface of the metal, and this air should travel through a clay pipe that stays red hot from the furnace's fire. This way, the inside of the muffle won’t cool down, and processes that currently take a long time can be completed in just a few minutes.
Mr Sage remedies these inconveniencies in a different manner; he places the cuppel containing lead, alloyed with gold or silver, amongst the charcoal of an ordinary furnace, and covered by a small porcelain muffle; when the whole is sufficiently heated, he directs the blast of a common pair of hand-bellows upon the surface of the metal, and completes the cuppellation in this way with great ease and exactness.[Pg 474]
Mr. Sage addresses these issues differently; he places the cup containing lead mixed with gold or silver among the charcoal of a regular furnace and covers it with a small porcelain muffle. Once everything is heated enough, he uses a standard pair of hand bellows to blow air onto the surface of the metal, finishing the cupellation process with great ease and precision.[Pg 474]
SECT. III.
Of increasing the Action of Fire, by using Oxygen Gas instead of Atmospheric Air.
By means of large burning glasses, such as those of Tchirnausen and Mr de Trudaine, a degree of heat is obtained somewhat greater than has hitherto been produced in chemical furnaces, or even in the ovens of furnaces used for baking hard porcelain. But these instruments are extremely expensive, and do not even produce heat sufficient to melt crude platina; so that their advantages are by no means sufficient to compensate for the difficulty of procuring, and even of using them. Concave mirrors produce somewhat more effect than burning glasses of the same diameter, as is proved by the experiments of Messrs Macquer and Beaumé with the speculum of the Abbé Bouriot; but, as the direction of the reflected rays is necessarily from below upwards, the substance to be operated upon must be placed in the air without any support, which renders most chemical experiments impossible to be performed with this instrument.[Pg 475]
Using large magnifying glasses, like those made by Tchirnausen and Mr. de Trudaine, a level of heat is achieved that is somewhat higher than what has been produced in chemical furnaces or even in the kilns for baking hard porcelain. However, these devices are very expensive and don't even generate enough heat to melt raw platinum; thus, their benefits do not outweigh the challenges of acquiring and using them. Concave mirrors are somewhat more effective than magnifying glasses of the same size, as demonstrated by the experiments of Messrs Macquer and Beaumé using the speculum of Abbé Bouriot. However, since the direction of the reflected rays is from below upwards, the material that needs to be heated must be suspended in the air without any support, making most chemical experiments impossible with this tool.[Pg 475]
For these reasons, I first endeavoured to employ oxygen gas for combustion, by filling large bladders with it, and making it pass through a tube capable of being shut by a stop-cock; and in this way I succeeded in causing it to support the combustion of lighted charcoal. The intensity of the heat produced, even in my first attempt, was so great as readily to melt a small quantity of crude platina. To the success of this attempt is owing the idea of the gazometer, described p. 308. et seq. which I substituted instead of the bladders; and, as we can give the oxygen gas any necessary degree of pressure, we can with this instrument keep up a continued stream, and give it even a very considerable force.
For these reasons, I first tried using oxygen gas for combustion by filling large bladders with it and directing it through a tube that can be closed with a stop-cock. This method allowed me to make it support the burning of charcoal. The heat generated, even during my first attempt, was so intense that it easily melted a small amount of raw platinum. This successful attempt led to the idea of the gazometer, described on p. 308. et seq. which I used instead of the bladders; and since we can apply any necessary pressure to the oxygen gas, this instrument allows us to maintain a continuous flow and even generate a substantial force.
The only apparatus necessary for experiments of this kind consists of a small table ABCD, Pl. XII. Fig. 15, with a hole F, through which passes a tube of copper or silver, ending in a very small opening at G, and capable of being opened or shut by the stop-cock H. This tube is continued below the table at l m n o, and is connected with the interior cavity of the gazometer. When we mean to operate, a hole of a few lines deep must be made with a chizel in a piece of charcoal, into which the substance to be treated is laid; the charcoal is set on fire by means of a candle and blow-pipe, after which it is exposed[Pg 476] to a rapid stream of oxygen gas from the extremity G of the tube FG.
The only equipment needed for experiments like this is a small table ABCD, Pl. XII. Fig. 15, with a hole F, through which a copper or silver tube passes. This tube ends in a very tiny opening at G and can be opened or closed by the stop-cock H. The tube continues below the table at l m n o and connects to the inner cavity of the gasometer. When we want to conduct the experiment, a small hole must be made with a chisel in a piece of charcoal, where the substance to be tested is placed. The charcoal is ignited using a candle and blow-pipe, after which it is exposed[Pg 476] to a fast flow of oxygen gas from the end G of the tube FG.
This manner of operating can only be used with such bodies as can be placed, without inconvenience, in contact with charcoal, such as metals, simple earths, &c. But, for bodies whose elements have affinity to charcoal, and which are consequently decomposed by that substance, such as sulphats, phosphats, and most of the neutral salts, metallic glasses, enamels, &c. we must use a lamp, and make the stream of oxygen gas pass through its flame. For this purpose, we use the elbowed blow-pipe ST, instead of the bent one FG, employed with charcoal. The heat produced in this second manner is by no means so intense as in the former way, and is very difficultly made to melt platina. In this manner of operating with the lamp, the substances are placed in cuppels of calcined bones, or little cups of porcelain, or even in metallic dishes. If these last are sufficiently large, they do not melt, because, metals being good conductors of heat, the caloric spreads rapidly through the whole mass, so that none of its parts are very much heated.
This method can only be used with materials that can be easily in contact with charcoal, like metals and simple earths. However, for materials that have an affinity for charcoal and are broken down by it, such as sulfates, phosphates, and most neutral salts, metallic glasses, and enamels, we need to use a lamp and let a stream of oxygen gas pass through its flame. For this, we use the elbowed blowpipe ST instead of the bent one FG used with charcoal. The heat generated this way is not as intense as in the previous method and is very hard to use to melt platinum. When using the lamp, substances are placed in cups made of calcined bones, small porcelain dishes, or even metal dishes. If these metal dishes are large enough, they won’t melt because metals are good heat conductors, allowing the heat to spread quickly through the entire mass and preventing any part from overheating.
In the Memoirs of the Academy for 1782, p. 476. and for 1783, p. 573. the series of experiments I have made with this apparatus may be seen at large. The following are some of the principal results.[Pg 477]
In the Academy's Memoirs for 1782, p. 476, and for 1783, p. 573, you can find a detailed account of the experiments I've conducted with this device. Here are some of the main results.[Pg 477]
1. Rock cristal, or pure silicious earth, is infusible, but becomes capable of being softened or fused when mixed with other substances.
1. Rock crystal, or pure silica, can't be melted on its own, but it can be softened or fused when combined with other materials.
2. Lime, magnesia, and barytes, are infusible, either when alone, or when combined together; but, especially lime, they assist the fusion of every other body.
2. Lime, magnesia, and barytes don't melt, whether they're on their own or combined; however, especially lime helps the melting of all other substances.
3. Argill, or pure base of alum, is completely fusible per se into a very hard opake vitreous substance, which scratches glass like the precious stones.
3. Argill, or pure alum base, can be fully melted on its own into a very hard, opaque glass-like substance that can scratch glass just like precious stones.
4. All the compound earths and stones are readily fused into a brownish glass.
4. All the compounds of earth and stones can easily be melted into a brownish glass.
5. All the saline substances, even fixed alkali, are volatilized in a few seconds.
5. All the salty substances, even fixed alkali, evaporate in just a few seconds.
6. Gold, silver, and probably platina, are slowly volatilized without any particular phenomenon.
6. Gold, silver, and probably platinum, are slowly vaporized without any specific phenomenon.
7. All other metallic substances, except mercury, become oxydated, though placed upon charcoal, and burn with different coloured flames, and at last dissipate altogether.
7. All other metallic substances, except mercury, get oxidized, even when placed on charcoal, and they burn with different colored flames, eventually disappearing completely.
8. The metallic oxyds likewise all burn with flames. This seems to form a distinctive character for these substances, and even leads me to believe, as was suspected by Bergman, that barytes is a metallic oxyd, though we have not hitherto been able to obtain the metal in its pure or reguline state.[Pg 478]
8. The metallic oxides also burn with flames. This seems to be a unique feature of these substances and makes me think, as Bergman suspected, that barytes is a metallic oxide, even though we haven't been able to obtain the metal in its pure or reguline form so far.[Pg 478]
9. Some of the precious stones, as rubies, are capable of being softened and soldered together, without injuring their colour, or even diminishing their weights. The hyacinth, tho' almost equally fixed with the ruby, loses its colour very readily. The Saxon and Brasilian topaz, and the Brasilian ruby, lose their colour very quickly, and lose about a fifth of their weight, leaving a white earth, resembling white quartz, or unglazed china. The emerald, chrysolite, and garnet, are almost instantly melted into an opake and coloured glass.
9. Some precious stones, like rubies, can be softened and soldered together without damaging their color or even reducing their weight. The hyacinth, although nearly as durable as the ruby, loses its color easily. The Saxon and Brazilian topaz, along with the Brazilian ruby, quickly lose their color and about a fifth of their weight, turning into a white residue that looks like white quartz or unglazed china. The emerald, chrysolite, and garnet almost immediately melt into an opaque colored glass.
10. The diamond presents a property peculiar to itself; it burns in the same manner with combustible bodies, and is entirely dissipated.
10. The diamond has a unique property; it burns like flammable materials and completely disappears.
There is yet another manner of employing oxygen gas for considerably increasing the force of fire, by using it to blow a furnace. Mr Achard first conceived this idea; but the process he employed, by which he thought to dephlogisticate, as it is called, atmospheric air, or to deprive it of azotic gas, is absolutely unsatisfactory. I propose to construct a very simple furnace, for this purpose, of very refractory earth, similar to the one represented Pl. XIII. Fig. 4. but smaller in all its dimensions. It is to have two openings, as at E, through one of which the nozle of a pair of bellows is to pass, by which the heat is to be raised as high as possible with common air; after which, the[Pg 479] stream of common air from the bellows being suddenly stopt, oxygen gas is to be admitted by a tube, at the other opening, communicating with a gazometer having the pressure of four or five inches of water. I can in this manner unite the oxygen gas from several gazometers, so as to make eight or nine cubical feet of gas pass through the furnace; and in this way I expect to produce a heat greatly more intense than any hitherto known. The upper orifice of the furnace must be carefully made of considerable dimensions, that the caloric produced may have free issue, lest the too sudden expansion of that highly elastic fluid should produce a dangerous explosion.
There's another way to use oxygen gas to significantly boost the fire's intensity by using it to blow into a furnace. Mr. Achard first came up with this idea, but the method he used to "dephlogisticate," or remove nitrogen from, atmospheric air is completely unsatisfactory. I intend to build a very simple furnace specifically for this purpose, made from highly heat-resistant material, similar to the one shown in Pl. XIII. Fig. 4, but smaller in all dimensions. It will have two openings, as shown at E, where one will allow the nozzle of a pair of bellows to enter, raising the heat as high as possible with normal air. After that, the stream of normal air from the bellows will be suddenly stopped, and oxygen gas will be introduced through a tube at the other opening, connected to a gasometer with a pressure of four or five inches of water. This way, I can combine the oxygen gas from several gasometers to send about eight or nine cubic feet of gas through the furnace, and I expect to generate a heat far more intense than anything known so far. The top opening of the furnace must be designed carefully and large enough to allow the heat generated to escape freely, to prevent any dangerous explosions from the rapid expansion of that highly elastic gas.
FINIS.
APPENDIX.
No. I.
Table for Converting Lines, or Twelfth Parts of an Inch, and Fractions of Lines, into Decimal Fractions of the Inch.
Twelfth Parts of a Line. | Decimal Fractions. | Lines. | Decimal Fractions. |
1 | 0.00694 | 1 | 0.08333 |
2 | 0.01389 | 2 | 0.16667 |
3 | 0.02083 | 3 | 0.25000 |
4 | 0.02778 | 4 | 0.33333 |
5 | 0.03472 | 5 | 0.41667 |
6 | 0.04167 | 6 | 0.50000 |
7 | 0.04861 | 7 | 0.58333 |
8 | 0.05556 | 8 | 0.66667 |
9 | 0.06250 | 9 | 0.75000 |
10 | 0.06944 | 10 | 0.83333 |
11 | 0.07639 | 11 | 0.91667 |
12 | 0.08333 | 12 | 1.00000 |
No. II.
Table for Converting the Observed Heighths of Water in the Jars of the Pneumato-Chemical Apparatus, expressed in Inches and Decimals, into Corresponding Heighths of Mercury.
Water. | Mercury. | Water. | Mercury. |
.1 | .00737 | 4. | .29480 |
.2 | .01474 | 5. | .36851 |
.3 | .02201 | 6. | .44221 |
.4 | .02948 | 7. | .51591 |
.5 | .03685 | 8. | .58961 |
.6 | .04422 | 9. | .66332 |
.7 | .05159 | 10. | .73702 |
.8 | .05896 | 11. | .81072 |
.9 | .06633 | 12. | .88442 |
1. | .07370 | 13. | .96812 |
2. | .14740 | 14. | 1.04182 |
3. | .22010 | 15. | 1.11525 |
No. III.
Table for Converting the Ounce Measures used by Dr Priestly into French and English Cubical Inches.
Ounce measures. | French cubical inches. | English cubical inches. |
1 | 1.567 | 1.898 |
2 | 3.134 | 3.796 |
3 | 4.701 | 5.694 |
4 | 6.268 | 7.592 |
5 | 7.835 | 9.490 |
6 | 9.402 | 11.388 |
7 | 10.969 | 13.286 |
8 | 12.536 | 15.184 |
9 | 14.103 | 17.082 |
10 | 15.670 | 18.980 |
20 | 31.340 | 37.960 |
30 | 47.010 | 56.940 |
40 | 62.680 | 75.920 |
50 | 78.350 | 94.900 |
60 | 94.020 | 113.880 |
70 | 109.690 | 132.860 |
80 | 125.360 | 151.840 |
90 | 141.030 | 170.820 |
100 | 156.700 | 189.800 |
1000 | 1567.000 | 1898.000 |
No. IV. Additional.
Table for Reducing the Degrees of Reaumeur's Thermometer into its corresponding Degrees of Fahrenheit's Scale.
R. | F. | R. | F. | R. | F. | R. | F. | ||||
0 | = | 32 | 21 | = | 79.25 | 41 | = | 124.25 | 61 | = | 169.25 |
1 | = | 34.25 | 22 | = | 81.5 | 42 | = | 126.5 | 62 | = | 171.5 |
2 | = | 36.5 | 23 | = | 83.75 | 43 | = | 128.75 | 63 | = | 173.75 |
3 | = | 38.75 | 24 | = | 86 | 44 | = | 131 | 64 | = | 176. |
4 | = | 41 | 25 | = | 88.25 | 45 | = | 133.25 | 65 | = | 178.25 |
5 | = | 43.25 | 26 | = | 90.5 | 46 | = | 135.5 | 66 | = | 180.5 |
6 | = | 45.5 | 27 | = | 92.75 | 47 | = | 137.75 | 67 | = | 182.75 |
7 | = | 47.75 | 28 | = | 95 | 48 | = | 140 | 68 | = | 185 |
8 | = | 50 | 29 | = | 97.25 | 49 | = | 142.25 | 69 | = | 187.25 |
9 | = | 52.25 | 30 | = | 99.5 | 50 | = | 144.5 | 70 | = | 189.5 |
10 | = | 54.5 | 31 | = | 101.75 | 51 | = | 146.75 | 71 | = | 191.75 |
11 | = | 56.75 | 32 | = | 104 | 52 | = | 149 | 72 | = | 194. |
12 | = | 59 | 33 | = | 106.25 | 53 | = | 151.25 | 73 | = | 196.25 |
13 | = | 61.25 | 34 | = | 108.5 | 54 | = | 153.5 | 74 | = | 198.5 |
14 | = | 63.5 | 35 | = | 110.75 | 55 | = | 155.75 | 75 | = | 200.75 |
15 | = | 65.75 | 36 | = | 113 | 56 | = | 158 | 76 | = | 203 |
16 | = | 68 | 37 | = | 115.25 | 57 | = | 160.25 | 77 | = | 205.25 |
17 | = | 70.25 | 38 | = | 117.5 | 58 | = | 162.5 | 78 | = | 207.5 |
18 | = | 72.5 | 39 | = | 119.75 | 59 | = | 164.75 | 79 | = | 209.75 |
19 | = | 74.75 | 40 | = | 122 | 60 | = | 167 | 80 | = | 212 |
20 | = | 77 |
Note—Any degree, either higher or lower, than what is contained in the above Table, may be at any time converted, by remembering that one degree of Reaumeur's scale is equal to 2.25° of Fahrenheit; or it may be done without the Table by the following formula, R × 9 / 4 + 32 = F; that is, multiply the degree of Reaumeur by 9, divide the product by 4, to the quotient add 32, and the sum is the degree of Fahrenheit.—E.[Pg 485]
Note—Any temperature, whether higher or lower than what’s shown in the table above, can be converted at any time by remembering that one degree on the Réaumur scale is equal to 2.25° Fahrenheit. Alternatively, you can do it without the table using this formula: R × 9 / 4 + 32 = F. This means you multiply the Réaumur degree by 9, divide the result by 4, add 32 to the quotient, and the total gives you the temperature in Fahrenheit.—E.[Pg 485]
No. V. Additional.
Rules for converting French Weights and Measures into correspondent English Denominations[62].
§ 1. Weights.
The Paris pound, poids de mark of Charlemagne, contains 9216 Paris grains; it is divided into 16 ounces, each ounce into 8 gros, and each gros into 72 grains. It is equal to 7561 English Troy grains.
The Paris pound, known as the poids de mark of Charlemagne, contains 9,216 Paris grains; it is divided into 16 ounces, each ounce into 8 gros, and each gros into 72 grains. It equals 7,561 English Troy grains.
The English Troy pound of 12 ounces contains 5760 English Troy grains, and is equal to 7021 Paris grains.
The English Troy pound weighs 12 ounces and has 5760 English Troy grains, which is equivalent to 7021 Paris grains.
The English averdupois pound of 16 ounces contains 7000 English Troy grains, and is equal to 8538 Paris grains.
The English avoirdupois pound, which has 16 ounces, contains 7000 English Troy grains and is equal to 8538 Paris grains.
To reduce Paris grs. to English Troy grs. divide by | 1.2189 |
To reduce English Troy grs. to Paris grs. multiply by | |
To reduce Paris ounces to English Troy, divide by | 1.015734 |
To reduce English Troy ounces to Paris, multiply by |
Or the conversion may be made by means of the following Tables.
Or the conversion can be done using the following tables.
I. To reduce French to English Troy Weight.
The Paris pound | = | 7561 | } |
The ounce | = | 472.5625 | }English. |
The gros | = | 59.0703 | }Troy. |
The grain | = | .8194 | }Grains. |
II. To Reduce English Troy to Paris Weight.
The English Troy pound of 12 ounces | = | 7021. | } |
The Troy ounce | = | 585.0830 | } |
The dram of 60 grs. | = | 73.1353 | }Paris |
The penny weight, or denier, of 24 grs. | = | 29.2540 | }grains. |
The scruple, of 20 grs. | = | 24.3784 | } |
III. To Reduce English Averdupois to Paris Weight.
The averdupois pound of 16 ounces, or 7000 Troy grains. | = | 8538. | } Paris grains. |
The ounce | = | 533.6250 |
§ 2. Long and Cubical Measures.
To reduce Paris feet or inches into English, multiply by | 1.065977 |
English feet or inches into Paris, divide by | |
To reduce Paris cubic feet or inches to English, multiply by | 1.211278 |
English cubic feet or inches to Paris, divide by |
Or by means of the following tables:
Or using these tables:
IV. To Reduce Paris Long Measure to English.
The Paris royal foot of 12 inches | = | 12.7977 | }English |
The inch | = | 1.0659 | } |
The line, or 1/12 of an inch | = | .0888 | }inches. |
The 1/12 of a line | = | .0074 | } |
V. To Reduce English Long Measure to French.
The English foot | = | 11.2596 | } |
The inch | = | .9383 | } |
The 1/8 of an inch | = | .1173 | }Paris inches. |
The 1/10 | = | .0938 | } |
The line, or 1/12 | = | .0782 | } |
VI. To Reduce French Cube Measure to English.
The Paris cube foot | = | 1.211278 | } | English cubical feet, or | {2093.088384 | } | inches. |
The cubic inch | = | .000700 | } | {1.211278 | } |
VII. To Reduce English Cube Measure to French.
The English cube foot, or 1728 cubical inches | = | 1427.4864 | }French |
The cubical inch | = | .8260 | }cubical |
The cube tenth | = | .0008 | }inches. |
§ 3. Measure of Capacity.
To reduce the Paris pint to the English, multiply by | 2.01508. |
To reduce the English pint to the Paris, divide by |
No. VI.
Table of the Weights of the different Gasses, at 28 French inches, or 29.84 English inches barometrical pressure, and at 10° (54.5°) of temperature, expressed in English measure and English Troy weight.
Names of the Gasses. | Weight of a cubical inch. | Weight of a cubical foot. | ||
(A) | qrs. | oz. | dr. | qrs. |
Atmospheric air | .32112 | 1 | 1 | 15 |
Azotic gas | .30064 | 1 | 0 | 39.5 |
Oxygen gas | .34211 | 1 | 1 | 51 |
Hydrogen gas | .02394 | 0 | 0 | 41.26 |
Carbonic acid gas | .44108 | 1 | 4 | 41 |
(B) | ||||
Nitrous gas | .37000 | 1 | 2 | 39 |
Ammoniacal gas | .18515 | 0 | 5 | 19.73 |
Sulphurous acid gas | .71580 | 2 | 4 | 38 |
[Note A: These five were ascertained by Mr Lavoisier himself.—E.]
[Note A: Mr. Lavoisier himself confirmed these five.—E.]
[Note B: The last three are inserted by Mr Lavoisier upon the authority of Mr Kirwan.—E.][Pg 491]
[Note B: The last three are added by Mr. Lavoisier based on Mr. Kirwan's authority.—E.][Pg 491]
No. VII.
Tables of the Specific Gravities of different bodies.
§ 1. Metallic Substances.
GOLD.
Pure gold of 24 carats melted but not hammered | 19.2581 |
The same hammered | 19.3617 |
Gold of the Parisian standard, 22 carats fine, not hammered(A) | 17.4863 |
The same hammered | 17.5894 |
Gold of the standard of French coin, 21-22/32 carats fine, not hammered | 17.4022 |
The same coined | 17.6474 |
Gold of the French trinket standard, 20 carats fine, not hammered | 15.7090 |
The same hammered | 15.7746 |
[Note A: The same with Sterling.]
[Note A: The same with Sterling.]
SILVER.
Pure or virgin silver, 24 deniers, not hammered | 10.4743 |
The same hammered | 10.5107 |
Silver of the Paris standard, 11 deniers 10 grains fine, not hammered(B) | 10.1752 |
The same hammered | 10.3765 |
[Pg 492] | |
Silver, standard of French coin, 10 deniers 21 grains fine, not hammered | 10.0476 |
The same coined | 10.4077 |
[Note B: This is 10 grs. finer than Sterling.]
[Note B: This is 10 grs. finer than Sterling.]
PLATINA.
Crude platina in grains | 15.6017 |
The same, after being treated with muriatic acid | 16.7521 |
Purified platina, not hammered | 19.5000 |
The same hammered | 20.3366 |
The same drawn into wire | 21.0417 |
The same passed through rollers | 22.0690 |
COPPER AND BRASS.
Copper, not hammered | 7.7880 |
The same wire drawn | 8.8785 |
Brass, not hammered | 8.3958 |
The same wire drawn | 8.5441 |
IRON AND STEEL.
Cast iron | 7.2070 |
Bar iron, either screwed or not | 7.7880 |
Steel neither tempered nor screwed | 7.8331 |
Steel screwed but not tempered | 7.8404 |
Steel tempered and screwed | 7.8180 |
Steel tempered and not screwed | 7.8163 |
[Pg 493] |
TIN.
Pure tin from Cornwall melted and not screwed | 7.2914 |
The same screwed | 7.2994 |
Malacca tin, not screwed | 7.2963 |
The same screwed | 7.3065 |
Molten lead | 11.3523 |
Molten zinc | 7.1908 |
Molten bismuth | 9.8227 |
Molten cobalt | 7.8119 |
Molten arsenic | 5.7633 |
Molten nickel | 7.8070 |
Molten antimony | 6.7021 |
Crude antimony | 4.0643 |
Glass of antimony | 4.9464 |
Molybdena | 4.7385 |
Tungstein | 6.0665 |
Mercury | 13.5681 |
§ 2. Precious Stones.
White Oriental diamond | 3.5212 |
Rose-coloured Oriental ditto | 3.5310 |
Oriental ruby | 4.2833 |
Spinell ditto | 3.7600 |
Ballas ditto | 3.6458 |
Brasillian ditto | 3.5311 |
Oriental topas | 4.0106 |
[Pg 494] | |
Ditto Pistachio ditto | 4.0615 |
Brasillian ditto | 3.5365 |
Saxon topas | 3.5640 |
Ditto white ditto | 3.5535 |
Oriental saphir | 3.9941 |
Ditto white ditto | 3.9911 |
Saphir of Puy | 4.0769 |
Ditto of Brasil | 3.1307 |
Girasol | 4.0000 |
Ceylon jargon | 4.4161 |
Hyacinth | 3.6873 |
Vermillion | 4.2299 |
Bohemian garnet | 4.1888 |
Dodecahedral ditto | 4.0627 |
Syrian ditto | 4.0000 |
Volcanic ditto, with 24 sides | 2.4684 |
Peruvian emerald | 2.7755 |
Crysolite of the jewellers | 2.7821 |
Ditto of Brasil | 2.6923 |
Beryl, or Oriental aqua marine | 3.5489 |
Occidental aqua marine | 2.7227 |
§ 3. Silicious Stones.
Pure rock cristal of Madagascar | 2.6530 |
Ditto of Brasil | 2.6526 |
Ditto of Europe, or gelatinous | 2.6548 |
Cristallized quartz | 2.6546 |
Amorphous ditto | 2.6471 |
[Pg 495] | |
Oriental agate | 2.5901 |
Agate onyx | 2.6375 |
Transparent calcedony | 2.6640 |
Carnelian | 2.6137 |
Sardonyx | 2.6025 |
Prase | 2.5805 |
Onyx pebble | 2.6644 |
Pebble of Rennes | 2.6538 |
White jade | 2.9502 |
Green jade | 2.9660 |
Red jasper | 2.6612 |
Brown ditto | 2.6911 |
Yellow ditto | 2.7101 |
Violet ditto | 2.7111 |
Gray ditto | 2.7640 |
Jasponyx | 2.8160 |
Black prismatic hexahedral schorl | 3.3852 |
Black spary ditto | 3.3852 |
Black amorphous schorl, called antique basaltes | 2.9225 |
Paving stone | 2.4158 |
Grind stone | 2.1429 |
Cutler's stone | 2.1113 |
Fountainbleau stone | 2.5616 |
Scyth stone of Auvergne | 2.5638 |
Ditto of Lorrain | 2.5298 |
Mill stone | 2.4835 |
White flint | 2.5941 |
Blackish ditto | 2.5817 |
[Pg 496] |
§ 4. Various Stones, &c.
Opake green Italian serpentine, or gabro of the Florentines | 2.4295 | |
Coarse Briancon chalk | 2.7274 | |
Spanish chalk | 2.7902 | |
Foliated lapis ollaris of Dauphiny | 2.7687 | |
Ditto ditto from Sweden | 2.8531 | |
Muscovy talc | 2.7917 | |
Black mica | 2.9004 | |
Common schistus or slate | 2.6718 | |
New slate | 2.8535 | |
White rasor hone | 2.8763 | |
Black and white hone | 3.1311 | |
Rhombic or Iceland cristal | 2.7151 | |
Pyramidal calcareous spar | 2.7141 | |
Oriental or white antique alabaster | 2.7302 | |
Green Campan marble | 2.7417 | |
Red Campan marble | 2.7242 | |
White Carara marble | 2.7168 | |
White Parian marble | 2.8376 | |
Various kinds of calcareous stones | }from | 1.3864 |
used in France for building. | }to | 2.3902 |
Heavy spar | 4.4300 | |
White fluor | 3.1555 | |
Red ditto | 3.1911 | |
Green ditto | 3.1817 | |
Blue ditto | 3.1688 | |
Violet ditto | 3.1757 | |
[Pg 497] | ||
Red scintilant zeolite from Edelfors | 2.4868 | |
White scintilant zeolite | 2.0739 | |
Cristallized zeolite | 2.0833 | |
Black pitch stone | 2.0499 | |
Yellow pitch stone | 2.0860 | |
Red ditto | 2.6695 | |
Blackish ditto | 2.3191 | |
Red porphyry | 2.7651 | |
Ditto of Dauphiny | 2.7033 | |
Green serpentine | 2.8960 | |
Black ditto of Dauphiny, called variolite | 2.9339 | |
Green ditto from Dauphiny | 2.9883 | |
Ophites | 2.9722 | |
Granitello | 3.0626 | |
Red Egyptian granite | 2.6541 | |
Beautiful red granite | 2.7609 | |
Granite of Girardmas | 2.7163 | |
Pumice stone | .9145 | |
Lapis obsidianus | 2.3480 | |
Pierre de Volvic | 2.3205 | |
Touch stone | 2.4153 | |
Basaltes from Giants Causeway | 2.8642 | |
Ditto prismatic from Auvergne | 2.4153 | |
Glass gall | 2.8548 | |
Bottle glass | 2.7325 | |
Green glass | 2.6423 | |
White glass | 2.8922 | |
St Gobin cristal | 2.4882 | |
Flint glass | 3.3293 | |
Borax glass | 2.6070 | |
[Pg 498] | ||
Seves porcelain | 2.1457 | |
Limoges ditto | 2.3410 | |
China ditto | 2.3847 | |
Native sulphur | 2.0332 | |
Melted sulphur | 1.9907 | |
Hard peat | 1.3290 | |
Ambergrease | .9263 | |
Yellow transparent amber | 1.0780 |
§ 5. Liquids.
Distilled water | 1.0000 | |||
Rain water | 1.0000 | |||
Filtered water of the Seine | 1.00015 | |||
Arcueil water | 1.00046 | |||
Avray water | 1.00043 | |||
Sea water | 1.0263 | |||
Water of the Dead Sea | 1.2403 | |||
Burgundy wine | .9915 | |||
Bourdeaux ditto | .9939 | |||
Malmsey Madeira | 1.0382 | |||
Red beer | 1.0338 | |||
White ditto | 1.0231 | |||
Cyder | 1.0181 | |||
Highly rectified alkohol | .8293 | |||
Common spirits of wine | .8371 | |||
[Pg 499] | ||||
Alkohol | 15 pts. | water | 1 part. | .8527 |
14 | 2 | .8674 | ||
13 | 3 | .8815 | ||
12 | 4 | .8947 | ||
11 | 5 | .9075 | ||
10 | 6 | .9199 | ||
9 | 7 | .9317 | ||
8 | 8 | .9427 | ||
7 | 9 | .9519 | ||
6 | 10 | .9594 | ||
5 | 11 | .9674 | ||
4 | 12 | .9733 | ||
3 | 13 | .9791 | ||
2 | 14 | .9852 | ||
1 | 15 | .9919 | ||
Sulphuric ether | .7394 | |||
Nitric ether | .9088 | |||
Muriatic ether | .7298 | |||
Acetic ether | .8664 | |||
Sulphuric acid | 1.8409 | |||
Nitric ditto | 1.2715 | |||
Muriatic ditto | 1.1940 | |||
Red acetous ditto | 1.0251 | |||
White acetous ditto | 1.0135 | |||
Distilled ditto ditto | 1.0095 | |||
Acetic ditto | 1.0626 | |||
Formic ditto | .9942 | |||
Solution of caustic ammoniac, | or volatil alkali fluor | .8970 | ||
[Pg 500] | ||||
Essential or volatile oil | of turpentine | .8697 | ||
Liquid turpentine | .9910 | |||
Volatile oil of lavender | .8938 | |||
Volatile oil of cloves | 1.0363 | |||
Volatile oil of cinnamon | 1.0439 | |||
Oil of olives | .9153 | |||
Oil of sweet almonds | .9170 | |||
Lintseed oil | .9403 | |||
Oil of poppy seed | .9288 | |||
Oil of beech mast | .9176 | |||
Whale oil | .9233 | |||
Womans milk | 1.0203 | |||
Mares milk | 1.0346 | |||
Ass milk | 1.0355 | |||
Goats milk | 1.0341 | |||
Ewe milk | 1.0409 | |||
Cows milk | 1.0324 | |||
Cow whey | 1.0193 | |||
Human urine | 1.0106 |
§ 6. Resins and Gums
Common yellow or white rosin | 1.0727 |
Arcanson | 1.0857 |
Galipot(A) | 1.0819 |
Baras(A) | 1.0441 |
[Pg 501] | |
Sandarac | 1.0920 |
Mastic | 1.0742 |
Storax | 1.1098 |
Opake copal | 1.1398 |
Transparent ditto | 1.0452 |
Madagascar ditto | 1.0600 |
Chinese ditto | 1.0628 |
Elemi | 1.0182 |
Oriental anime | 1.0284 |
Occidental ditto | 1.0426 |
Labdanum | 1.1862 |
Ditto in tortis | 2.4933 |
Resin of guaiac | 1.2289 |
Ditto of jallap | 1.2185 |
Dragons blood | 1.2045 |
Gum lac | 1.1390 |
Tacamahaca | 1.0463 |
Benzoin | 1.0924 |
Alouchi(B) | 1.0604 |
Caragna(C) | 1.1244 |
Elastic gum | .9335 |
Camphor | .9887 |
Gum ammoniac | 1.2071 |
Sagapenum | 1.2008 |
[Pg 502] | |
Ivy gum(D) | 1.2948 |
Gamboge | 1.2216 |
Euphorbium | 1.1244 |
Olibanum | 1.1732 |
Myrrh | 1.3600 |
Bdellium | 1.3717 |
Aleppo Scamony | 1.2354 |
Smyrna ditto | 1.2743 |
Galbanum | 1.2120 |
Assafoetida | 1.3275 |
Sarcocolla | 1.2684 |
Opoponax | 1.6226 |
Cherry tree gum | 1.4817 |
Gum Arabic | 1.4523 |
Tragacanth | 1.3161 |
Basora gum | 1.4346 |
Acajou gum(E) | 1.4456 |
Monbain gum(F) | 1.4206 |
Inspissated juice of liquorice | 1.7228 |
—— Acacia | 1.5153 |
—— Areca | 1.4573 |
Terra Japonica | 1.3980 |
Hepatic aloes | 1.3586 |
Socotrine aloes | 1.3795 |
Inspissated juice of St John's wort | 1.5263 |
[Pg 503] | |
Opium | 1.3366 |
Indigo | .7690 |
Arnotto | .5956 |
Yellow wax | .9648 |
White ditto | .9686 |
Ouarouchi ditto(G) | .8970 |
Cacao butter | .8916 |
Spermaceti | .9433 |
Beef fat | .9232 |
Veal fat | .9342 |
Mutton fat | .9235 |
Tallow | .9419 |
Hoggs fat | .9368 |
Lard | .9478 |
Butter | .9423 |
[Note A: Resinous juices extracted in France from the Pine. Vide Bomare's Dict.]
[Note A: Sticky juices taken from the Pine in France. See Bomare's Dictionary.]
[Note B: Odoriferous gum from the tree which produces the Cortex Winteranus. Bomare.]
[Note B: Fragrant gum from the tree that produces the Cortex Winteranus. Bomare.]
[Note C: Resin of the tree called in Mexico Caragna, or Tree of Madness. Ibid.]
[Note C: Resin from the tree known in Mexico as Caragna, or Tree of Madness. Ibid.]
[Note D: Extracted in Persia and the warm countries from Hedera terrestris.—Bomare.]
[Note D: Extracted in Persia and warm countries from Hedera terrestris.—Bomare.]
[Note E: From a Brasilian tree of this name.—Ibid.]
[Note E: From a Brazilian tree of this name.—Ibid.]
[Note F: From a tree of this name.—Ibid.]
[Note F: From a tree of this name.—Same source.]
[Note G: The produce of the Tallow Tree of Guayana. Vide Bomare's Dict.]
[Note G: The produce of the Tallow Tree of Guayana. See Bomare's Dict.]
§ 7. Woods.
Heart of oak 60 years old | 1.1700 |
Cork | .2400 |
Elm trunk | .6710 |
Ash ditto | .8450 |
Beech | .8520 |
Alder | .8000 |
Maple | .7550 |
Walnut | .6710 |
Willow | .5850 |
Linden | .6040 |
[Pg 504] | |
Male fir | .5500 |
Female ditto | .4980 |
Poplar | .3830 |
White Spanish ditto | .5294 |
Apple tree | .7930 |
Pear tree | .6610 |
Quince tree | .7050 |
Medlar | .9440 |
Plumb tree | .7850 |
Olive wood | .9270 |
Cherry tree | .7150 |
Filbert tree | .6000 |
French box | .9120 |
Dutch ditto | 1.3280 |
Dutch yew | .7880 |
Spanish ditto | .8070 |
Spanish cypress | .6440 |
American cedar | .5608 |
Pomgranate tree | 1.3540 |
Spanish mulberry tree | .8970 |
Lignum vitae | 1.3330 |
Orange tree | .7050 |
Note—The numbers in the above Table, if the Decimal point be carried three figures farther to the right hand, nearly express the absolute weight of an English cube foot of each substance in averdupois ounces. See No. VIII. of the Appendix.—E.[Pg 505]
Note—The numbers in the table above, if you move the decimal point three places to the right, almost represent the absolute weight of an English cubic foot of each substance in avoirdupois ounces. See No. VIII. of the Appendix.—E.[Pg 505]
No. VIII. ADDITIONAL.
Rules for Calculating the Absolute Gravity in English Troy Weight of a Cubic Foot and Inch, English Measure, of any Substance whose Specific Gravity is known[64].
Got it! Please provide the text you'd like me to modernize. for Calculating the Absolute Gravity in English Troy Weight of a Cubic Foot and Inch, English Measure, of any Substance with a Known Specific Gravity[64].
In 1696, Mr Everard, balance-maker to the Exchequer, weighed before the Commissioners of the House of Commons 2145.6 cubical inches, by the Exchequer standard foot, of distilled water, at the temperature of 55° of Fahrenheit, and found it to weigh 1131 oz. 14 dts. Troy, of the Exchequer standard. The beam turned with 6 grs. when loaded with 30 pounds in each scale. Hence, supposing the pound averdupois to weigh 7000 grs. Troy, a cubic foot of water weighs 62-1/2 pounds averdupois, or 1000 ounces averdupois, wanting 106 grains Troy. And hence, if the specific gravity of water be called 1000, the proportional specific gravities of all other bodies will nearly express the number of averdupois ounces in a cubic foot. Or more accurately, supposing the specific gravity of water expressed by 1. and of all other bodies in proportional numbers, as the[Pg 506] cubic foot of water weighs, at the above temperature, exactly 437489.4 grains Troy, and the cubic inch of water 253.175 grains, the absolute weight of a cubical foot or inch of any body in Troy grains may be found by multiplying their specific gravity by either of the above numbers respectively.
In 1696, Mr. Everard, the balance-maker for the Exchequer, weighed 2145.6 cubic inches of distilled water at a temperature of 55°F before the Commissioners of the House of Commons. He found it weighed 1131 ounces 14 dwt Troy, according to the Exchequer standard. The beam tipped with 6 grains when loaded with 30 pounds in each scale. Therefore, assuming the avoirdupois pound weighs 7000 grains Troy, a cubic foot of water weighs 62.5 pounds avoirdupois, or 1000 avoirdupois ounces, minus 106 grains Troy. Thus, if we call the specific gravity of water 1000, the proportional specific gravities of other substances will roughly represent the number of avoirdupois ounces in a cubic foot. More precisely, if the specific gravity of water is represented as 1, and all other substances are scaled proportionally, as the[Pg 506] cubic foot of water weighs exactly 437489.4 grains Troy at that temperature, and a cubic inch of water weighs 253.175 grains, the absolute weight of a cubic foot or inch of any substance in Troy grains can be calculated by multiplying its specific gravity by either of those numbers.
By Everard's experiment, and the proportions of the English and French foot, as established by the Royal Society and French Academy of Sciences, the following numbers are ascertained.
By Everard's experiment and the measurements of the English and French foot, as defined by the Royal Society and the French Academy of Sciences, the following numbers have been determined.
Paris grains in a Paris cube foot of water | = | 645511 |
English grains in a Paris cube foot of water | = | 529922 |
Paris grains in an English cube foot of water | = | 533247 |
English grains in an English cube foot of water | = | 437489.4 |
English grains in an English cube inch of water | = | 253.175 |
By an experiment of Picard with the measure and | ||
weight of the Chatelet, the Paris cube foot of | ||
water contains of Paris grains | = | 641326 |
By one of Du Hamel, made with great care | = | 641376 |
By Homberg | = | 641666 |
These show some uncertainty in measures or in weights; but the above computation from Everard's experiment may be relied on, because the comparison of the foot of England with that of France was made by the joint labours of the Royal Society of London and the French Academy of Sciences: It agrees likewise very nearly with the weight assigned by Mr Lavoisier, 70 Paris pounds to the cubical foot of water.[Pg 508]
These show some uncertainty in measurements or weights; however, the calculation from Everard's experiment can be trusted because the comparison of the English foot with the French foot was done through the combined efforts of the Royal Society of London and the French Academy of Sciences. It also closely matches the weight given by Mr. Lavoisier, which is 70 Paris pounds for a cubic foot of water.[Pg 508]
No. IX.
Tables for Converting Ounces, Drams, and Grains, Troy, into Decimals of the Troy Pound of 12 Ounces, and for Converting Decimals of the Pound Troy into Ounces, &c.
I. For Grains.
Grains | = Pound. |
1 | .0001736 |
2 | .0003472 |
3 | .0005208 |
4 | .0006944 |
5 | .0008681 |
6 | .0010417 |
7 | .0012153 |
8 | .0013889 |
9 | .0015625 |
10 | .0017361 |
20 | .0034722 |
30 | .0052083 |
40 | .0069444 |
50 | .0086806 |
60 | .0104167 |
70 | .0121528 |
80 | .0138889 |
90 | .0156250 |
100 | .0173611 |
200 | .0374222 |
300 | .0520833 |
400 | .0694444 |
500 | .0868055 |
600 | .1041666 |
700 | .1215277 |
800 | .1388888 |
900 | .1562499 |
1000 | .1736110 |
2000 | .3472220 |
3000 | .5208330 |
4000 | .6944440 |
5000 | .8680550 |
6000 | 1.0418660 |
7000 | 1.2152770 |
8000 | 1.3888880 |
9000 | 1.5624990 |
II. For Drams.
Drams | = Pound. |
1 | .0104167 |
2 | .0208333 |
3 | .0312500 |
4 | .0416667 |
5 | .0520833 |
6 | .0625000 |
7 | .0729167 |
8 | .0833333 |
III. For Ounces.
Ounces | = Pounds. |
1 | .0833333 |
2 | .1666667 |
3 | .2500000 |
4 | .3333333 |
5 | .4166667 |
6 | .5000000 |
7 | .5833333 |
8 | .6666667 |
9 | .7500000 |
10 | .8333333 |
11 | .9166667 |
12 | 1.0000000 |
IV. Decimals of the Pound into Ounces, &c.
Tenth parts. | |||
lib. = | oz. | dr. | gr. |
0.1 | 1 | 1 | 36 |
0.2 | 2 | 3 | 12 |
0.3 | 3 | 4 | 48 |
0.4 | 4 | 6 | 24 |
0.5 | 6 | 0 | 0 |
0.6 | 7 | 1 | 36 |
0.7 | 8 | 3 | 12 |
0.8 | 9 | 4 | 48 |
0.9 | 10 | 6 | 24 |
Hundredth parts. | |||
0.01 | 0 | 0 | 57.6 |
0.02 | 0 | 1 | 55.2 |
0.03 | 0 | 2 | 52.8 |
0.04 | 0 | 3 | 50.4 |
0.05 | 0 | 4 | 48.0 |
0.06 | 0 | 5 | 45.6 |
0.07 | 0 | 6 | 43.2 |
0.08 | 0 | 7 | 40.8 |
0.09 | 0 | 3 | 38.4 |
Thousandths. | |||
0.001 | 0 | 0 | 5.76 |
0.002 | 0 | 0 | 11.52 |
0.003 | 0 | 0 | 17.28 |
0.004 | 0 | 0 | 23.04 |
0.005 | 0 | 0 | 28.80 |
lib. = | grs. | ||
0.006 | 34.56 | ||
0.007 | 40.32 | ||
0.008 | 46.08 | ||
0.009 | 51.84 | ||
Ten thousandth parts. | |||
0.0001 | 0.576 | ||
0.0002 | 1.152 | ||
0.0003 | 1.728 | ||
0.0004 | 2.304 | ||
0.0005 | 2.880 | ||
0.0006 | 3.456 | ||
0.0007 | 4.032 | ||
0.0008 | 4.608 | ||
0.0009 | 5.184 | ||
Hundred thousandth parts. | |||
0.00001 | 0.052 | ||
0.00002 | 0.115 | ||
0.00003 | 0.173 | ||
0.00004 | 0.230 | ||
0.00005 | 0.288 | ||
0.00006 | 0.346 | ||
0.00007 | 0.403 | ||
0.00008 | 0.461 | ||
0.00009 | 0.518 |
No. X.
Table of the English Cubical Inches and Decimals corresponding to a determinate Troy Weight of Distilled Water at the Temperature of 55°, calculated from Everard's experiment.
Table of English Cubical Inches and Decimals corresponding to a specific Troy Weight of Distilled Water at a Temperature of 55°, calculated from Everard's experiment.
For Grains.
Grs. | Cubical inches. |
1 = | .0039 |
2 | .0078 |
3 | .0118 |
4 | .0157 |
5 | .0197 |
6 | .0236 |
7 | .0275 |
8 | .0315 |
9 | .0354 |
10 | .0394 |
20 | .0788 |
30 | .1182 |
40 | .1577 |
50 | .1971 |
For Drams.
Drams. | Cubical inches. |
1 = | .2365 |
2 | .4731 |
3 | .7094 |
4 | .9463 |
5 | 1.1829 |
6 | 1.4195 |
7 | 1.6561 |
For Ounces.
Oz. | Cubical inches. |
1 = | 1.8927 |
2 | 3.7855 |
3 | 5.6782 |
4 | 7.5710 |
5 | 9.4631 |
6 | 11.3565 |
7 | 13.2493 |
8 | 15.1420 |
9 | 17.0748 |
10 | 18.9276 |
11 | 20.8204 |
For Pounds.
Libs. | Cubical inches. |
1 = | 22.7131 |
2 | 45.4263 |
3 | 68.1394 |
4 | 90.8525 |
5 | 113.5657 |
6 | 136.2788 |
7 | 158.9919 |
8 | 181.7051 |
9 | 204.4183 |
10 | 227.1314 |
50 | 1135.6574 |
100 | 2271.3148 |
1000 | 22713.1488 |
THE END.
FOOTNOTES:
[63] It is said, Belidor Archit. Hydrog. to contain 31 oz. 64 grs. of water, which makes it 58.075 English inches; but, as there is considerable uncertainty in the determinations of the weight of the French cubical measure of water, owing to the uncertainty of the standards made use of, it is better to abide by Mr Everard's measure, which was with the Exchequer standards, and by the proportions of the English and French foot, as established by the French Academy and Royal Society.
[63] It's reported in Belidor Archit. Hydrog. that it holds 31 oz. 64 grs. of water, which equals 58.075 English inches. However, since there's significant uncertainty regarding the weight of the French cubic measure of water, due to inconsistencies in the standards used, it's better to rely on Mr. Everard's measure, which was based on the Exchequer standards, and the proportions of the English and French foot, as set by the French Academy and Royal Society.
THE PLATES
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