Mémoires de la Société d'Arcueil2, 207 (1809) [from Henry A. Boorse and Lloyd Motz, eds., The World of the Atom, vol. 1 (New York: Basic Books, 1966) (translation: Alembic Club Reprint No. 4)]
Substances, whether in the solid, liquid, or gaseous state, possess properties which are independent of the force of cohesion; but they also posses others which appear to be modified by this force (so variable in its intensity), and which no longer follow any regular law. The same pressure applied to all solid or liquid substances would produce a diminution of volume differing in each case, while it would be equal for all elastic fluids. Similarly, heat expands all substances; but the dilations of liquids and solids have hitherto presented no regularity, and it is only those of elastic fluids which are equal and independent of the nature of each gas. The attraction of the molecules in solids and liquids is, therefore, the cause which modifies their special properties; and it appears that it is only when the attraction is entirely destroyed, as in gases, that bodies under similar conditions obey simple and regular laws. At least, it is my intention to make known some new properties in gases, the effects of which are regular, by showing that these substances combine amongst themselves in very simple proportions, and that the contraction of volume which they experience on combination also follows a regular law. I hope by this means to give a proof of an idea advanced by several very distinguished chemists--that we are perhaps not far removed from the time when we shall be able to submit the bulk of chemical phenomena to calculation.
It is a very important question in itself, and one much discussed amongst chemists, to ascertain if compounds are formed in all sorts of proportions. M. Proust, who appears first to have fixed his attention on this subject, is of opinion that the metals are susceptible of only two degrees of oxidation, a minimum and a maximum; but led away by this seductive theory, he has seen himself forced to entertain principles contrary to physics in order to reduce to two oxides all those which the same metal sometimes presents. M. Berthollet thinks, on the other hand--reasoning from general considerations and his own experiments--that compounds are always formed in very variable proportions, unless they are determined by special causes, such as crystallisation, insolubility, or elasticity. Lastly, Dalton has advanced the idea that compounds of two bodies are formed in such a way that one atom of the one unites with one, two, three, or more atoms of the other. It would follow from this mode of looking at compounds that they are formed in constant proportions, the existence of intermediate bodies being excluded, and in this respect Dalton's theory would resemble that of M. Proust; but M. Berthollet has already strongly opposed it in the Introduction he has written to Thomson's Chemistry, and we shall see that in reality it is not entirely exact. Such is the state of the question now under discussion; it is still very far from receiving its solution, but I hope that the facts which I now proceed to set forth, facts which have entirely escaped the notice of chemists, will contribute to its elucidation.
Suspecting, from the exact ratio of 100 of oxygen to 200 of hydrogen, which M. Humboldt and I had determined for the proportions of water, that other gases might also combine in simple ratios, I have made the following experiments. I prepared fluoboric, muriatic, and carbonic gases, and made them combine successively with ammonia gas. 100 parts of muriatic gas saturate precisely 100 parts of ammonia gas, and the salt which is formed from them is perfectly neutral, whether one or the other of the gases is in excess. Fluoboric gas, on the contrary, unites in two proportions with ammonia gas. When the acid gas is put first into the graduated tube, and the other gas is then passed in, it is found that equal volumes of the two condense, and that the salt formed is neutral. But if we begin by first putting the ammonia gas into the tube, and then admitting the fluoboric gas in single bubbles, the first gas will then be in excess with regard to the second, and there will result a salt with excess of base, composed of 100 of fluoboric gas and 200 ammonia gas. If carbonic gas is brought into contact with ammonia gas, by passing it sometimes first, sometimes second, into the tube, there is always formed a sub-carbonate composed of 100 parts of carbonic gas and 200 of ammonia gas. It may, however, be proved that neutral carbonate of ammonia would be composed of equal volumes of each of these components. M. Berthollet, who has analysed this salt, obtained by passing carbonic gas into the sub-carbonate, found that it was composed of 73.34 parts by weight of carbonic gas and 26.66 of ammonia gas. Now, if we suppose it to be composed of equal volumes of its components, we find from their known specific gravity, that it contains by weight
|71.81||of carbonic acid|
a proportion differing only slightly from the preceding.
If the neutral carbonate of ammonia could be formed by the mixture of carbonic gas and ammonia gas, as much of one gas as of the other would be absorbed; and since we can only obtain it through the intervention of water, we must conclude that it is the affinity of this liquid which competes with that of the ammonia to overcome the elasticity of the carbonic acid, and that the neutral carbonate of ammonia can only exist through the medium of water.
Thus we may conclude that muriatic, fluoboric, and carbonic acids take exactly their own volume of ammonia gas to form neutral salts, and that the last two take twice as much to form sub-salts. It is very remarkable to see acids so different from one another neutralise a volume of ammonia gas equal to their own; and from this we may suspect that if all acids and all alkalis could be obtained in the gaseous state, neutrality would result from the combination of equal volumes of acid and alkali.
It is not less remarkable that, whether we obtain a neutral salt or a sub-salt, their elements combine in simple ratios which may be considered as limits to their proportions. Accordingly, if we accept the specific gravity of muriatic acid determined by M. Biot and myself, and those of carbonic gas and ammonia given by M. Biot and Arago, we find that dry muriate of ammonia is composed of
a proportion very far from that of M. Berthollet--
In the same way, we find that sub-carbonate of ammonia contains
and the neutral carbonate
It is easy from the preceding results to ascertain the ratios of the capacity of fluoboric, muriatic, and carbonic acids; for since these three gases saturate the same volume of ammonia gas, their relative capacities will be inversely as their densities, allowance having been made for the water contained in muriatic acid.
We might even now conclude that gases combine with each other in very simple ratios; but I shall still give some fresh proofs.
According to the experiments of M. Amédée Berthollet, ammonia is composed of
|100 of nitrogen|
|300 of hydrogen,|
I have found (1st vol. of the Société d'Arceuil) that sulphuric acid is composed of
|100 of sulphurous gas,|
|50 of oxygen gas.|
When a mixture of 50 parts of oxygen and 100 of carbonic oxide (formed by the distillation of oxide of zinc with strongly calcined charcoal) is inflamed, these two gases are destroyed and their place taken by 100 parts of carbonic acid gas. Consequently carbonic acid may be considered as being composed of
|100 of carbonic oxide gas,|
|50 of oxygen gas.|
Davy, from the analysis of various compounds of nitrogen with oxygen, has found the following proportions by weight:
Reducing these proportions to volumes we find--
The first and the last of these proportions differ only slightly from 100 to 50 and 100 to 200; it is only the second which diverges somewhat from 100 to 100. The difference, however, is not very great, and is such as we might expect in experiments of this sort; and I have assured myself that it is actually nil. On burning the new combustible substance from potash in 100 parts by volume of nitrous gas, there remained over exactly 50 parts of nitrogen, the weight of which, deducted from that of the nitrous gas (determined with great care by M. Berard at Arcueil), yields as a result that this gas is composed of equal parts by volume of nitrogen and oxygen.
We may then admit the following numbers for the proportions by volume of the compounds of nitrogen with oxygen:
From my experiments, which differ very little from those of M. Chenevix, oxygenated muriatic acid is composed by weight of
Converting these quantities into volumes, we find that oxygenated muriatic acid is formed of
a proportion very nearly
Thus it appears evident to me that gases always combine in the simplest proportions when they act on one another; and we have seen in reality in all the preceding examples that the ratio of combinations is 1 to 1, 1 to 2, or 1 to 3. It is very important to observe that in considering weights there is no simple and finite relation between the elements of any one compound; it is only when there is a second compound between the same elements that the new proportion of the element that has been added is a multiple of the first quantity. Gases, on the contrary, in whatever proportions they may combine, always give rise to compounds whose elements by volume are multiples of each other.
Not only, however, do gases combine in very simple proportions, as we have just seen, but the apparent contraction of volume which they experience on combination has also a simple relation to the volume of the gases, or at least to that of one of them.
I have said, following M. Berthollet, that 100 parts of carbonic oxide gas, prepared by distilling oxide of zinc and strongly calcined charcoal, produce 100 parts of carbonic gas on combining with 50 of oxygen. It follows from this that the apparent contraction of the two gases is precisely equal to the volume of oxygen gas added. The density of carbonic gas is thus equal to that of carbonic oxide gas plus half the density of oxygen gas; or, conversely, the density of carbonic oxide gas is equal to that of carbonic gas, minus half that of oxygen gas. Accordingly, taking the density of air as unity, we find the density of carbonic oxide gas to be 0.9678, instead of 0.9569 experimentally determined by Cruickshanks. We know, besides, that a given volume of oxygen produces an equal volume of carbonic acid; consequently oxygen gas doubles its volume on forming carbonic oxide gas with carbon, and so does carbonic gas on being passed over red-hot charcoal. Since oxygen produces an equal volume of carbonic gas, and the density of the latter is well known, it is easy to calculate the proportion of its elements. In this way we find that carbonic gas is composed of
27.38 of carbon,
72.62 of oxygen,
and carbonic oxide of
42.99 of carbon,
57.01 of oxygen.
Pursuing a similar course, we find that if sulphur takes 100 parts of oxygen to produce sulphurous acid, it takes 150 parts to produce sulphuric acid. As a matter of fact, we find that sulphuric acid, according to the experiments of MM. Klaproth, Bucholz, and Richter, is composed of 100 parts by weight of sulphur and 138 of oxygen.
On the other hand sulphuric acid is composed of 2 parts by volume of sulphurous gas, and 1 of oxygen gas. Consequently the weight of a certain quantity of sulphuric acid should be the same as that of 2 parts of sulphurous acid and 1 of oxygen gas, i.e., 2x2.265, plus 1.10359--5.63359; seeing that, according to Kirwan, sulphurous gas weighs 2.265, the density of air being taken as unity. But from the proportion of 100 of sulphur to 138 of oxygen, this quantity contains 3.26653 of oxygen, and if we subtract from it 1.10359 there will remain 2.16294 for the weight of oxygen in 2 parts of sulphurous acid, or 1.08147 for the weight of oxygen contained in 1 part.
Now as this last quantity only differs by 2 per cent. from 1.10359, which represents the weight of oxygen gas, it must be concluded that oxygen gas, in combining with sulphur to form sulphurous gas, only experiences a diminution of a fiftieth of its volume, and this would probably be nil if the data I have employed were more exact. On this last supposition, using Kirwan's value for the specific gravity of sulphurous gas, we should find that this acid is composed of
100.00 of sulphur,
95.02 of oxygen.
But, if, adopting the preceding proportions for sulphuric acid, we allow, as appears probable, that 100 of sulphurous gas contain 100 of oxygen gas, and that 50 have still to be added to convert it into sulphuric acid, we shall obtain for the proportions in sulphurous acid
100.00 of sulphur
92.0 of oxygen.
Its specific gravity calculated on the same suppositions, and referred to that of air, would be 2.30314, instead of 2.2650 as Kirwan found directly.
Phosphorus is very closely connected with sulphur, seeing that both have nearly the same specific gravity. Consequently phosphorus should take up twice as much oxygen to become phosphorous acid, as to pass from this state into phosphoric acid. Since the latter is composed, according to Rose, of
100.0 of phosphorus,
114.0 of oxygen,
it follows that phosphorous acid should contain
100.0 of phosphorus,
76.0 of oxygen.
We have seen that 100 parts of nitrogen gas take 50 parts of oxygen gas to form nitrous oxide, and 100 of oxygen gas to form nitrous gas. In the first case, the contraction is a little greater than the volume of oxygen added; for the specific gravity of nitrous oxide, calculated on this hypothesis, is 1.52092, while that given by Davy is 1.61414. But it is easy to show, from some of Davy's experiments, that the apparent contraction is precisely equal to the volume of oxygen gas added. On passing the electronic spark through a mixture of 100 parts of hydrogen and 97.5 of nitrous oxide the hydrogen is destroyed, and 102 parts of nitrogen remain, including that quantity which is almost always mixed with the hydrogen, and a little of the latter gas which has escaped combustion. The residue, after making all corrections, would be nearly equal in volume to the nitrous oxide employed. Similarly, on passing the electric spark through a mixture of 100 parts of phosphoretted hydrogen and 250 of nitrous oxide, water and phosphoric acid are formed, and exactly 250 parts of nitrogen remain,--another evident proof that the apparent contraction of the elements of nitrous oxide is equal to the whole volume of oxygen added. From this circumstance, its specific gravity referred to that of air should be 1.52092.
The apparent contraction of the elements of nitrous gas appears, on the other hand, to be nil. If we admit, as I have shown, that it is composed of equal parts of oxygen and nitrogen, we find that its density, calculated on the assumption that there is no contraction, is 1.036, while that determined directly is 1.038.
Ammonia gas is composed of three parts by volume of hydrogen and one of nitrogen, and its density compared to air is 0.596. But if we suppose the apparent contraction to be half of the whole volume, we find 0.594 for the density. Thus it is proved, by this almost perfect concordance, that the apparent contraction of its elements is precisely half the total volume or rather double the volume of the nitrogen.
I have already proved that oxygenated muriatic gas is composed of 300 parts of muriatic gas and 100 of oxygen gas. Admitting that the apparent contraction of the two gases is half the whole volume, we find 2.468 for its density, and by experiment 2.470. I have also assured myself by several experiments that the proportions of its elements are such that it forms neutral salts with the metals. For example, if we pass oxygenated muriatic gas over copper, there is formed a slightly acid green muriate, and a little oxide of copper is precipitated, because the salt cannot be obtained perfectly neutral. It follows from this that in all the muriates, as in oxygenated muriatic acid, the acid reduced to volume is thrice the oxygen. It would be the same for carbonates and fluorides, the acids of which have for equal volumes the same saturation capacity as muriatic acid.
We see, then, from these various examples, that the contraction experienced by two gases on combination is in almost exact relation with their volume, or rather with the volume of one of them. Only very slight differences exist between the densities of compounds obtained by calculation and those given by experiment, and it is probable that, on undertaking new researches, we shall see them vanish entirely.
Recalling the great law of chemical affinity, that every combination involves an approximation of the elementary molecules, it is difficult to conceive why carbonic oxide gas should be lighter than oxygen. Indeed, that is the principal reason which has led M. Berthollet to assume the existence of hydrogen in this gas, and thus explain its low density. But it seems to me that the difficulty arises from supposing that the approximation of the elementary molecules is represented in gases by the diminution of volume which they suffer on combination. This supposition is not always true, and we might cite several gaseous combinations, the constituent molecules of which would be brought very close together, although there is not only no diminution of volume, but even a dilation. Such, for example, is nitrous gas, whether we consider it as being formed directly from nitrogen and oxygen, or from nitrous oxide and oxygen. In the first case, there is no diminution of volume; and in the second, there would be dilation, for 100 parts of nitrous oxide and 50 of oxygen would produce 200 of nitrous gas. We know too that carbonic gas represents an exactly equal volume of oxygen, and that the affinity which unites its elements is very powerful. Nevertheless, if we admitted an immediate relation between the condensation of the elements and the condensation of volume, we should conclude, contrary to experiment, that there is no condensation. Otherwise it would be necessary to suppose that if carbon were in the gaseous state it would combine in equal volumes (or in any other proportion) with oxygen, and that the apparent condensation would then be equal to the whole volume of the gaseous carbon. But if we make this supposition for carbonic acid, we may also make it for carbonic oxide, by assuming, for instance, that 100 parts of the gaseous carbon would produce 100 parts of the gas on combining with 50 parts of oxygen. However it may stand with these suppositions, which only serve to make it conceivable that oxygen can produce a compound lighter than itself by combining with a solid substance, we must admit, as a truth founded on a great number of observations, that the condensation of the molecules of two combining substances, in particular of two gases, has no immediate relation to the condensation of volume, since we often see that whilst one is very great the other is very small or even nil.
According to Dalton's ingenious idea, that combinations are formed from atom to atom, the various compounds which two substances can form would be produced by the union of one molecule of the one with one molecule of the other, or with two, or with a greater number, but always without intermediate compounds. Thomson and Wollaston have indeed described experiments which appear to confirm this theory. Thomson has found that super-oxalate of potash contains twice as much acid as is necessary to saturate the alkali; and Wollaston, that the sub-carbonate of potash contains, on the other hand, twice as much alkali as is necessary to saturate the acid.
The numerous results I have brought forward in this Memoir are also very favorable to the theory. But M. Berthollet, who thinks that combinations are made continuously, cites in proof of his opinion the acid sulphates, glass alloys, mixtures of various liquids,--all of which are compounds with very variable proportions, and he insists principally on the identity of the force which produces chemical compounds and solutions.
Each of these two opinions has, therefore, a large number of facts in its favour; although they are apparently utterly opposed, it is easy to reconcile them.
We must first of all admit, with M. Berthollet, that chemical action is exercised indefinitely in a continuous manner between the molecules of substances, whatever their number and ratio may be, and that in general we can obtain compounds with very variable proportions. But then we must admit at the same time that,--apart from insolubility, cohesion, and elasticity, which tend to produce compounds in fixed proportions,--chemical action is exerted more powerfully when the elements are in simple ratios or in multiple proportions among themselves, and that compounds are thus produced which separate out more easily. In this way we reconcile the two opinions, and maintain the great chemical law, that whenever two substances are in presence of each other they act in their sphere of activity according to their masses, and give rise in general to compounds with very variable proportions, unless these proportions are determined by special circumstances.
I have shown in this Memoir that the compounds of gaseous substances with each other are always formed in very simple ratios, so that representing one of the terms by unity, the other is 1, or 2, or at most 3. These ratios by volume are not observed with solid or liquid substances, nor when we consider weights, and they form a new proof that it is only in the gaseous state that substances are in the same circumstances and obey regular laws. It is remarkable to see that ammonia gas neutralizes exactly its own volume of gaseous acids; and it is probable that if all acids and alkalies were in the elastic state, they would all combine in equal volumes to produce neutral salts. The capacity of saturation of acids and alkalies measured by volume would then be the same, and this might perhaps be the true manner of determining it. The apparent contraction of volume suffered by gases on combination is also very simply related to the volume of one of them, and this property likewise is peculiar to gaseous substances.
In order to remove these differences it would be necessary to make new experiments on the density of sulphurous gas, on the direct union of oxygen gas with sulphur to see if there is contraction, and on the union of sulphurous gas with ammonia gas. I have found, it is true, on heating cinnabar in oxygen gas, that 100 parts of this gas only produce 93 of sulphurous gas. It also appeared as if less sulphurous gas than ammonia gas was necessary to form a neutral salt. But these experiments were not made under suitable conditions--especially the last, which could only be made in presence of water, the sulphurous gas decomposing and precipitating sulphur immediately on being mixed with ammonia gas,--I intend to repeat them and determine exactly all the conditions before drawing any conclusion from them. This is all the more necessary, as sulphurous gas can be used to analyze sulphuretted hydrogen gas, if its proportions are well known.