OF THE ATOMIC THEORY. I come now to the last improvement which chemistry has received—an improvement which has given a degree of accuracy to chemical experimenting almost approaching to mathematical precision, which has simplified prodigiously our views respecting chemical combinations; which has enabled manufacturers to introduce theoretical improvements into their processes, and to regulate with almost perfect precision the relative quantities of the various constituents necessary to produce the intended effects. The consequence of this is, that nothing is wasted, nothing is thrown away. Chemical products have become not only better in quality, but more abundant and much cheaper. I allude to the atomic theory still only in its infancy, but already productive of the most important benefits. It is destined one day to produce still more wonderful effects, and to render chemistry not only the most delightful, but the most useful and indispensable, of all the sciences. Like all other great improvements in science, the atomic theory developed itself by degrees, and several of the older chemists ascertained facts which might, had they been aware of their importance, have led them to conclusions similar to those of the The atomic theory in chemistry has many points of resemblance to the fluxionary calculus in mathematics. Both give us the ratios of quantities; both reduce investigations that would be otherwise extremely difficult, or almost impossible, to the utmost simplicity; and what is still more curious, both have been subjected to the same kind of ridicule by those who have not put themselves to the trouble of studying them with such attention as to understand them completely. The minute philosopher of Berkeley, mutatis mutandis, might be applied to the atomic theory with as much justice as to the fluxionary calculus; and I have heard more than one individual attempt to throw ridicule upon the atomic theory by nearly the same kind of arguments. The first chemists, then, who attempted to analyze the salts may be considered as contributing towards laying the foundation of the atomic theory, though they were not themselves aware of the importance of the structure which might have been raised upon Bergman was the first chemist who attempted regular analyses of salts. It was he that first tried to establish regular formulas for the analyses of mineral waters, stones, and ores, by the means of solution and precipitation. Hence a knowledge of the constituents of the salts was necessary, before his formulas could be applied to practice. It was to supply this requisite information that he set about analyzing the salts, and his results were long considered by chemists as exact, and employed by them to determine the results of their analyses. We now know that these analytical results of Bergman are far from accurate; they have accordingly been laid aside as useless: but this knowledge has been derived from the progress of the atomic theory. The first accurate set of experiments to analyze the salts was made by Wenzel, and published by him in 1777, in a small volume entitled "Lehre von der Verwandschaft der KÖrper," or, "Theory of the Affinities of Bodies." These analyses of Wenzel are infinitely more accurate than those of Bergman, and indeed in many cases are equally precise with the best which we have even at the present day. Yet the book fell almost dead-born from the press; Wenzel's results never obtained the confidence of chemists, nor is his name ever quoted as an authority. Wenzel was struck with a phenomenon, which had indeed been noticed by preceding chemists; but they had not drawn the advantages from it which it was capable of affording. There are several saline solutions which, when mixed with each other, completely decompose each other, so that two new salts are produced. Thus, if we mix together solutions of nitrate of lead and sulphate of soda in the requisite proportions, the sulphuric acid of the latter salt will Sulphate of soda we obtain the two new salts, Sulphate of lead If we mix the two salts in the requisite proportions, the decomposition will be complete; but if there be an excess of one of the salts, that excess will still remain in solution without affecting the result. If we suppose the two salts anhydrous, then the proportions necessary for complete decomposition are,
and the quantities of the new salts formed will be
We see that the absolute weights of the two sets of salts are the same: all that has happened is, that both the acids and both the bases have exchanged situations. Now if, instead of mixing these two salts together in the preceding proportions, we employ
That is to say, if we employ 5 parts of nitrate of Sulphate of lead 19 and there will remain in solution a mixture of
The phenomena are precisely the same as before; the additional 5 of nitrate of lead have occasioned no alteration; the decomposition has gone on just as if they had not been present. Now the phenomena which drew the particular attention of Wenzel is, that if the salts were neutral before being mixed, the neutrality was not affected by the decomposition which took place on their mixture.7 A salt is said to be neutral when it neither possesses the characters of an acid or an alkali. Acids redden vegetable blues, while alkalies render them green. A neutral salt produces no effect whatever upon vegetable blues. This observation of Wenzel is very important: it is obvious that the salts, after their decomposition, could not have remained neutral unless the elements of the two salts had been such that the bases in each just saturated the acids in either of the salts. The constituents of the two salts are as follows:
Now it is clear, that unless 5 sulphuric acid were just saturated by 4 soda and by 14 oxide of lead; and 6·75 of nitric acid by the same 4 soda and 14 oxide of lead, the salts, after their decomposition, could not have preserved their neutrality. Had 4 soda required only 5·75 of nitric acid, or had 14 oxide of lead required only 4 sulphuric acid, to saturate them, the liquid, after decomposition, would have contained an excess of acid. As no such excess exists, it is clear that in saturating an acid, 4 soda goes exactly as far as 14 oxide of lead; and that, in saturating a base, 5 sulphuric acid goes just as far as 6·75 nitric acid. Nothing can exhibit in a more striking point of view, the almost despotic power of fashion and authority over the minds even of men of science, and the small number of them that venture to think for themselves, than the fact, that this most important and luminous explanation of Wenzel, confirmed by much more accurate experiments than any which chemistry had yet seen, is scarcely noticed by any of his contemporaries, and seems not to have attracted the smallest attention. In science, it is as unfortunate for a man to get before the age in which he lives, as to continue behind it. The admirable explanation of combustion by Hooke, and the important experiments on combustion and respiration by Mayow, were lost upon their contemporaries, and procured them little or no reputation whatever; while the same theory, and the same experiments, advanced by Lavoisier and Priestley, a century later, when the minds of men of science were prepared to receive them, raised them to the very first rank among philosophers, and produced a revolution in chemistry. So much concern has fortune, not merely in the success of kings and conquerors, but in the reputation acquired by men of science. In the year 1792 another labourer, in the same department of chemistry, appeared: this was Jeremiah Benjamin Richter, a Prussian chemist, of whose history I know nothing more than that his publications were printed and published in Breslau, from which I infer that he was a native of, or at least resided in, Silesia. He calls himself Assessor of the Royal Prussian Mines and Smeltinghouses, and Arcanist of the Commission of Berlin Porcelain Manufacture. He died in the prime of life, on the 4th of May, 1807. In the year 1792 he published a work entitled "AnfansgrÜnde der Stochyometrie; oder, Messkunst Chymischer Elemente" (Elements of Stochiometry; or, the Mathematics of the Chemical Elements). A second and third volume of this work appeared in 1793, and a fourth volume in 1794. The object of this book was a rigid analysis of the different salts, founded on the fact just mentioned, that when two salts decompose each other, the salts newly formed are neutral as well as those which have been decomposed. He took up the subject nearly in the same way as Wenzel had done, but carried the subject much further; and endeavoured to determine the capacity of saturation of each acid and base, and to attach numbers to each, indicating the weights which mutually saturate each other. He gave the whole subject a mathematical dress, and endeavoured to show that the same relation existed, between the numbers representing the capacity of saturation of these bodies, as does between certain classes of figurate numbers. When we strip the subject of the mystical form under which he presented it, the labours of Richter may be exhibited under the two following tables, which represent the capacity of saturation of the acids and bases, according to his experiments.
To understand this table, it is only necessary to observe, that if we take the quantity of any of the acids placed after it in the table, that quantity will be exactly saturated by the weight of each base put after it in the second column: thus, 1000 of sulphuric acid will be just saturated by 525 alumina, 615 magnesia, 672 ammonia, 793 lime, and so on. On the other hand, the quantity of any base placed after its name in the second column, will be just saturated by the weight of each acid placed after its name in the first column: thus, 793 parts of lime will be just saturated by 427 of fluoric acid, 577 of carbonic acid, 706 of sebacic acid, and so on. This work of Richter was followed by a periodical work entitled "Ueber die neuern Gegenstande der Chymie" (On the New Objects of Chemistry). This work was begun in the year 1792, and continued in twelve different numbers, or volumes, to the time of his death in 1807.8 Richter's labours in this important field produced as little attention as those of Wenzel. Gehlen wrote a short panegyric upon him at his death, praising his views and pointing out their importance; but I am not aware of any individual, either in Germany or elsewhere, who adopted Richter's opinions during his lifetime, or even seemed aware of their importance, unless we are to except Berthollet, who mentions them with approbation in his Chemical Statics. This inattention was partly owing to the great want of accuracy which it is impossible not be sensible of in Richter's experiments. He operated upon too large quantities of matter, which indeed was the common defect of the times, and was first checked by Dr. Wollaston. The dispute between the phlogistians and the antiphlogistians, which was not fully settled in Richter's time, drew the attention of chemists to another branch of the subject. Richter in some measure went before the age in which he lived, and had his labours not been recalled to our recollection by the introduction of atomic theory, he would probably have been forgotten, like Hooke and Mayow, and only brought again under review after the new discoveries in the science had put it in the power of chemists in general to appreciate the value of his labours. It is to Mr. Dalton that we are indebted for the happy and simple idea from which the atomic theory originated. John Dalton, to whose lot it has fallen to produce such an alteration and improvement in chemistry, was born in Westmorland, and belongs to that small and virtuous sect known in this country by the name of Quakers. When very young he lived with Mr. Gough of Kendal, a blind philosopher, to whom he read, and whom he assisted in his philosophical investigations. It was here, probably, that he From a careful examination of all the circumstances, he considered himself as entitled to infer, that when two elastic fluids or gases, A and B, are mixed together, there is no mutual repulsion among their particles; that is, the particles of A do not repel those of B, as they do one another. Consequently, the pressure or whole weight upon any one particle arises solely from those of its own kind. This doctrine is of so startling a nature and so contrary to the opinions previously received, that chemists have not been much disposed to admit it. But at the same time it must be confessed, that no one has hitherto been able completely to refute it. The consequences of admitting it are obvious: we should be able to account for a fact which has been long known, though no very satisfactory reason for it had been assigned; namely, that if two gases be placed in two separate vessels, communicating by a narrow orifice, and left at perfect rest in a place where the temperature never varies, But the second of these essays is by far the most important. In it he establishes, by the most unexceptionable evidence, that water, when it evaporates, is always converted into an elastic fluid, similar in its properties to air. But that the distance between the particles is greater the lower the temperature is at which the water evaporates. The elasticity of this vapour increases as the temperature increases. At 32° it is capable of balancing a column of mercury about half an inch in height, and at 212° it balances a column thirty inches high, or it is then equal to the pressure of the atmosphere. He determined the elasticity of vapour at all temperatures from 32° to 212°, pointed out the method of determining the quantity of vapour that at any time exists in the atmosphere, the effect which it has upon the volume of air, and the mode of determining its quantity. Finally, he determined, experimentally, the rate of evaporation from the surface of water at all temperatures from 32° to 212°. These investigations have been of infinite use to chemists in all their investigations respecting the specific gravity of gases, and have enabled them to resolve various interesting problems, both respecting specific gravity, evaporation, rain and respiration, which, In the last essay contained in this paper he has shown that all elastic fluids expand the same quantity by the same addition of heat, and this expansion is very nearly 1-480th part for every degree of Fahrenheit's thermometer. In this last branch of the subject Mr. Dalton was followed by Gay-Lussac, who, about half a year after the appearance of his Essays, published a paper in the Annales de Chimie, showing that the expansion of all elastic fluids, when equally heated, is the same. Mr. Dalton concluded that the expansion of all elastic fluids by heat is equable. And this opinion has been since confirmed by the important experiments of Dulong and Petit, which have thrown much additional light on the subject. In the year 1804, on the 26th of August, I spent a day or two at Manchester, and was much with Mr. Dalton. At that time he explained to me his notions respecting the composition of bodies. I wrote down at the time the opinions which he offered, and the following account is taken literally from my journal of that date: The ultimate particles of all simple bodies are atoms incapable of further division. These atoms (at least viewed along with their atmospheres of heat) are all spheres, and are each of them possessed of particular weights, which may be denoted by numbers. For the greater clearness he represented the atoms of the simple bodies by symbols. The following are his symbols for four simple bodies, together with the numbers attached to them by him in 1804:
The following symbols represent the way in which he thought these atoms were combined to form certain binary compounds, with the weight of an integrant particle of each compound:
The following were the symbols by which he represented the composition of certain tertiary compounds:
A quaternary compound:
A quinquenary compound:
A sextenary compound:
These symbols are sufficient to give the reader an idea of the notions entertained by Dalton respecting the nature of compounds. Water is a compound of one atom oxygen and one atom hydrogen as is It was this happy idea of representing the atoms and constitution of bodies by symbols that gave Mr. Dalton's opinions so much clearness. I was delighted with the new light which immediately struck my mind, and saw at a glance the immense importance of such a theory, when fully developed. Mr. Dalton informed me that the atomic theory first occurred to him during his investigations of olefiant gas and carburetted hydrogen gases, at that time imperfectly understood, and the constitution of which was first fully developed by Mr. Dalton himself. It was obvious from the experiments which he made upon them, that the constituents of both were carbon and hydrogen, and nothing else. He found further, that if we reckon the carbon in each the same, then carburetted hydrogen gas contains exactly twice as much hydrogen as olefiant gas does. This determined him to state the ratios of these constituents in numbers, and to consider the olefiant gas as a compound of one atom of carbon and one atom of hydrogen; and carburetted hydrogen of one atom of carbon and two atoms of hydrogen. The idea thus conceived was applied to carbonic oxide, Let not the reader suppose that this was an easy task. Chemistry at that time did not possess a single analysis which could be considered as even approaching to accuracy. A vast number of facts had been ascertained, and a fine foundation laid for future investigation; but nothing, as far as weight and measure were concerned, deserving the least confidence, existed. We need not be surprised, then, that Mr. Dalton's first numbers were not exact. It required infinite sagacity, and not a little labour, to come so near the truth as he did. How could accurate analyses of gases be made when there was not a single gas whose specific gravity was known, with even an approach to accuracy; the preceding investigations of Dalton himself paved the way for accuracy in this indispensable department; but still accurate results had not yet been obtained. In the third edition of my System of Chemistry, published in 1807, I introduced a short sketch of Mr. Dalton's theory, and thus made it known to the chemical world. The same year a paper of mine on oxalic acid was published in the Philosophical Transactions, in which I showed that oxalic acid unites in two proportions with strontian, forming an oxalate and binoxalate; and that, supposing the strontian in both salts to be the same, the oxalic acid in the latter is exactly twice as much as in the former. About the same time, Dr. Wollaston showed that bicarbonate of potash contains just twice the quantity of carbonic acid that exists in carbonate of potash; and that there are three oxalates of potash; viz., oxalate, binoxalate, and quadroxalate; the weight of acids in each of which are as the numbers 1, 2, 4. In the year 1808 Mr. Dalton published the first volume of his New System of Chemical Philosophy. This volume consists chiefly of two chapters: the first, on heat, occupies 140 pages. In it he treats of all the effects of heat, and shows the same sagacity and originality which characterize all his writings. Even when his opinions on a subject are not correct, his reasoning is so ingenious and original, and the new facts which he contrives to bring forward so important, that we are always pleased and always instructed. The second chapter, on the constitution
He had made choice of hydrogen for unity, because it is the lightest of all bodies. He was of opinion that the atomic weights of all other bodies are multiples of hydrogen; and, accordingly, they are all expressed in whole numbers. He had raised the atomic weight of oxygen from 6·5 to 7, from a more careful examination of the experiments on the component parts of water. Davy, from a more accurate set of experiments, soon after raised the number for oxygen to 7·5: and Dr. Prout, from a still more careful investigation of the relative specific In 1810 appeared the second volume of Mr. Dalton's New System of Chemical Philosophy. In it he examines the elementary principles, or simple bodies, namely, oxygen, hydrogen, azote, carbon, sulphur, phosphorus, and the metals; and the compounds consisting of two elements, namely, the compounds of oxygen with hydrogen, azote, carbon, sulphur, phosphorus; of hydrogen with azote, carbon, sulphur, phosphorus. Finally he treats of the fixed alkalies and earths. All these combinations are treated of with infinite sagacity; and he endeavours to determine the atomic weights of the different elementary substances. Nothing can exceed the ingenuity of his reasoning. But unfortunately at that time very few accurate chemical analyses existed; and in chemistry no reasoning, however ingenious, can compensate for this indispensable datum. Accordingly his table of atomic weights at the end this second volume, though much more complete than that at the end of the first volume, is still exceedingly defective; indeed no one number can be considered as perfectly correct. The third volume of the New System of Chemical Philosophy was only published in 1827; but the greatest part of it had been printed nearly ten years before. It treats of the metallic oxides, the sulphurets, phosphurets, carburets, and alloys. Doubtless many of the facts contained in it were new when the sheets were put to the press; but during the interval between the printing and publication, almost the whole of them had not merely been anticipated, but the subject carried much further. By far the Mr. Dalton represented the weight of an atom of hydrogen by 1, because it is the lightest of bodies. In this he has been followed by the chemists of the Royal Institution, by Mr. Philips, Dr. Henry, and Dr. Turner, and perhaps some others whose names I do not at present recollect. Dr. Wollaston, in his paper on Chemical Equivalents, represented the atomic weight of oxygen by 1, because it enters into a greater number of combinations than any other substance; and this plan has been adopted by Berzelius, by myself, and by the greater number, if not the whole, of the chemists on the continent. Perhaps the advantage which Dr. Wollaston assigned for making the atom of oxygen unity will ultimately disappear: for there is no reason for believing that the other supporters of combustion are not capable of entering into as many compounds as oxygen. But, In the year 1809 Gay-Lussac published in the second volume of the MÉmoires d'Arcueil a paper on the union of the gaseous substances with each other. In this paper he shows that the proportions in which the gases unite with each other are of the simplest kind. One volume of one gas either combining with one volume of another, or with two volumes, or with half a volume. The atomic theory of Dalton had been opposed with considerable keenness by Berthollet in his Introduction to the French transla M. AmÉdÉe Berthollet had proved that ammonia is a compound of one volume of azotic, and three volumes of hydrogen gas. Gay-Lussac himself had shown that sulphuric acid is composed of one volume sulphurous acid gas, and a half-volume of oxygen gas. He showed further, that the compounds of azote and oxygen were composed as follows:
He showed also, that when the two gases after combining remained in the gaseous state, the diminution of volume was either 0, or ?, or ½. The constancy of these proportions left no doubt that the combinations of all gaseous bodies were definite. The theory of Dalton applied to them with great facility. We have only to consider a volume of gas to represent an atom, and then we see that in gases one atom of one gas combines either with one, two, or three atoms of another gas, and never with more. There is, indeed, a difficulty occasioned by the way in which we view the composition of water. If water be composed of one atom of oxygen and one atom of hydrogen, then it follows that a volume of oxygen contains twice as many atoms as a volume of hydrogen. Consequently, if a volume of hydrogen gas represent an atom, half a volume of oxygen gas must represent an atom. Dr. Prout soon after showed that there is an intimate connexion between the atomic weight of a gas and its specific gravity. This indeed is obvious at once.I afterwards showed that the specific gravity of a gas is either equal to its atomic weight multiplied by 1·111[.1] (the specific gravity of oxygen gas), or by 0·555[.5] (half the specific gravity of oxygen gas), or by O·277[.7] (1-4th of the specific gravity of oxygen gas),(1-4th of the specific gravity of oxygen gas), these differences depending upon the relative condensation which the gases undergo when their elements unite. The following table exhibits the atoms and specific gravity of these three sets of gases:
When Professor Berzelius, of Stockholm, thought of writing his Elementary Treatise on Chemistry, the first volume of which was published in the year 1808, he prepared himself for the task by reading several chemical works which do not commonly fall under the eye of those who compose elementary treatises. Among other books he read the Stochiometry of Richter, and was much struck with the explanations there given of the composition of salts, and the precipitation of metals by each other. It followed from the researches of Richter, that if we were in possession of good analyses of certain salts, we might by means of them calculate with accuracy the composition of all the rest. Berzelius formed immediately the project of analyzing a series of salts with the most minute attention to accuracy. While employed in putting this project in execution, Davy discovered the constituents of the alkalies and earths, Mr. Dalton gave to the world his notions respecting the atomic theory, and Gay-Lussac made known his theory of volumes. This greatly enlarged his views as he proceeded, and induced him to embrace a much wider field than he had originally contemplated. His first analyses were unsatisfactory; but by repeating them and varying the methods, he detected errors, improved his processes, and finally obtained results, which agreed exceedingly well with the theoretical calculations. These laborious investigations occupied him several years. The first outline of his experiments appeared in the 77th volume of the Annales de Chimie, in 1811, in a letter addressed by Berzelius to Berthollet. In this letter he gives an account of his methods of analyses together with the composition of forty-seven compound bodies. He shows that when a metallic protosulphuret is converted into a sulphate, the sulphate is neutral; that an atom of sulphur is twice
So that they consist of nine atoms. Now as these two acids are composed of the same number and the same kind of atoms, one would expect that their properties should be the same; but this is not the case: acetic acid has a strong and aromatic smell, succinic acid has no smell whatever. Acetic acid is so soluble in water that it is difficult to obtain it in crystals, and it cannot be procured in a separate state free from water; for the crystals of acetic acid are composed of one atom of acid and one atom of water united together; but succinic acid is not only easily obtained free from water, but it is not even very soluble in that liquid. The nature of the salts formed by these two acids is quite different; the action of heat upon each is quite different; the specific gravity of each differs. In short all their properties exhibit a striking contrast. Now how are we to account for this? Undoubtedly by the different ways in which the atoms are arranged in each. If the electro-chemical theory of combination be correct, we can only view atoms as combining two by two. A substance then, containing nine atoms, such as acetic acid, must be of a very complex nature. And it is obvious enough that these nine atoms might arrange themselves in a great variety of binary compounds, and the way in which these binary compounds unite may, and doubtless does, produce a considerable effect upon the nature of the compound formed. Thus, if we make use of Mr. Dalton's symbols to represent the atoms of hydrogen, carbon and oxygen, we may suppose the nine atoms constituting acetic and succinic acid to be arranged thus: Block showing hydrogen carbon hydrogen, 3 oxygens, 3 carbons. Or thus: Block showing carbon hydrogen carbon, 3 oxygens, carbon hydrogen carbon. Now, undoubtedly these two arrangements would produce a great change in the nature of the compound. There is something in the vegetable acids quite different from the acids of the inorganic kingdom, and which would lead to the suspicion that the electro-chemical theory will not apply to them as it does to the others. In the acids of carbon, sulphur, phosphorus, selenium, &c., we find one atom of a positive substance united to one, two, or three of a negative substance: we are not surprised, therefore, to find the acid formed negative also. But in acetic and succinic acids we find every atom of oxygen united with two electro-positive atoms: the wonder then is, that the acid should not only retain its electro-negative properties, but that it should possess considerable power as an acid. In benzoic acid, for every atom of oxygen, there are present no fewer than seven electro-positive atoms. Berzelius has returned to these analytical experiments repeatedly, so that at last he has brought his results very near the truth indeed. It is to his labours chiefly that the great progress which the atomic theory has made is owing. In the year 1814 there appeared in the Philosophical Transactions a description of a Synoptical Scale of Chemical Equivalents, by Dr. Wollaston. In this paper we have the equivalents or atomic weights of seventy-three different bodies, deduced chiefly from a sagacious comparison of the previous analytical experiments of others, and almost all of Perhaps the reader will excuse me if to the preceding historical details I add a few words to make him acquainted with my own attempts to render the atomic theory more accurate by new and careful analyses. I shall not say any thing respecting the experiments which I undertook to determine the specific gravity of the gases; though they were performed with much care, and at a considerable expense, and though I believe the results obtained approached accuracy as nearly as the present state of chemical apparatus enables us to go. In the year 1819 I began a set of experiments to determine the exact composition of the salts containing the different elementary bodies by means of double decomposition, as was done by Wenzel, conceiving that in that way the results would be very near the truth, while the experiments would be more easily I published the result of my numerous experiments in 1825, in a work entitled "An Attempt to establish the First Principles of Chemistry by Experiment." The most valuable part of this book is the account of the salts; about three hundred of which I subjected to actual analysis. Of these the worst executed are the phosphates; for with respect to them I was sometimes misled by my method of double decomposition. I was not aware at first, that, |