translation from Alembic Club Reprints, No. 4, "Foundations of the Molecular Theory: Comprising Papers and Extracts by John Dalton, Joseph Louis Gay-Lussac, and Amadeo Avogadro, (1808-1811)"
Reader note: The words "atom" and "molecule" did not yet have their modern meaning. By "integral molecule" Avogadro meant one molecule of a compound; by "constituent molecule" a molecule of a gaseous element; and by "elementary molecule" (or "half molecule") an atom.
M. Gay-Lussac has shown in an interesting Memoir that gases always unite in a very simple proportion by volume, and that when the result of the union is a gas, its volume also is very simply related to those of its components. But the quantitative proportions of substances in compounds seem only to depend on the relative number of molecules which combine, and on the number of composite molecules which result. It must then be admitted that very simple relations also exist between the volumes of gaseous substances and the numbers of simple or compound molecules which form them. The first hypothesis to present itself in this connection, and apparently even the only admissible one, is the supposition that the number of integral molecules in any gases is always the same for equal volumes, or always proportional to the volumes. Indeed, if we were to suppose that the number of molecules contained in a given volume were different for different gases, it would scarcely be possible to conceive that the law regulating the distance of molecules could give in all cases relations so simple as those which the facts just detailed compel us to acknowledge between the volume and the number of molecules. On the other hand, it is very well conceivable that the molecules of gases being at such a distance that their mutual attraction cannot be exercised, their varying attraction for caloric may be limited to condensing a greater or smaller quantity around them, without the atmosphere formed by this fluid having any greater extent in the one case than in the other, and, consequently, without the distance between the molecules varying; or, in other words, without the number of molecules contained in a given volume being different. Dalton, it is true, has proposed a hypothesis directly opposed to this, namely, that the quantity of caloric is always the same for the molecules of all bodies whatsoever in the gaseous state, and that the greater or less attraction for caloric only results in producing a greater or less condensation of this quantity around the molecules, and thus varying the distance between the molecules themselves. But in our present ignorance of the manner in which this attraction for the molecules for caloric is exerted, there is nothing to decide us a priori in favour of the one of these hypotheses rather than the other; and we should rather be inclined to adopt a neutral hypothesis, which would make the distance between the molecules and the quantities of caloric vary according to unknown laws, were it not that the hypothesis we have just proposed is based on that simplicity of relation between the volumes of gases on combination, which would appear to be otherwise inexplicable.
Setting out from this hypothesis, it is apparent that we have the means of determining very easily the relative masses of the molecules of substances obtainable in the gaseous state, and the relative number of these molecules in compounds; for the ratios of the masses of the molecules are then the same as those of the densities of the different gases at equal temperature and pressure, and the relative number of molecules in a compound is given at once by the ratio of the volumes of the gases that form it. For example, since the numbers 1.10359 and 0.07321 express the densities of the two gases oxygen and hydrogen compared to that of atmospheric air as unity, and the ratio of the two numbers consequently represents the ratio between the masses of equal volumes of these two gases, it will also represent on our hypothesis the ratio of the masses of their molecules. Thus the mass of the molecule of oxygen will be about 15 times that of the molecule of hydrogen, or more exactly, as 15.074 to 1. In the same way the mass of the molecule of nitrogen will be to that of hydrogen as 0.96913 to 0.07321, that is, as 13, or more exactly 13.238, to 1. On the other hand, since we know that the ratio of the volumes of hydrogen and oxygen in the formation of water is 2 to 1, it follows that water results from the union of each molecule of oxygen with two molecules of hydrogen. Similarly, according to the proportions by volume established by M. Gay-Lussac for the elements of ammonia, nitrous oxide, nitrous gas, and nitric acid, ammonia will result from the union of one molecule of nitrogen with three of hydrogen, nitrous oxide from one molecule of oxygen with two of nitrogen, nitrous gas from one molecule of nitrogen with one of oxygen, and nitric acid from one of nitrogen with two of oxygen.
There is a consideration which appears at first sight to be opposed to the admission of our hypothesis with respect to compound substances. It seems that a molecule composed of two or more elementary molecules should have its mass equal to the sum of the masses of those molecules; and that in particular, if in a compound one molecule of one substance unites with two or more molecules of another substance, the number of compound molecules should remain the same as the number of molecules of the first substance. Accordingly, on our hypothesis when a gas combines with two or more times its volume of another gas, the resulting compound, if gaseous, must have a volume equal to that of the first of these gases. Now, in general, this is not actually the case. For instance, the volume of water in the gaseous state is, as M. Gay-Lussac has shown, twice as great as the volume of oxygen which enters into it, or, what comes to the same thing, equal to that of the hydrogen instead of being equal to that of the oxygen. But a means of explaining facts of this type in conformity with our hypothesis presents itself naturally enough: we suppose, namely, that the constituent molecules of any simple gas whatever (i.e., the molecules which are at such a distance from each other that they cannot exercise their mutual action) are not formed of a solitary elementary molecule, but are made up of a certain number of these molecules united by attraction to form a single one; and further, that when molecules of another substance unite with the former to form a compound molecule, the integral molecule which should result splits up into two or more parts (or integral molecules) composed of half, quarter, &c., the number of elementary molecules going to form the constituent molecule of the first substance, combined with half, quarter, &c., the number of constituent molecules of the second substance that ought to enter into combination with one constituent molecule of the first substance (or, what comes to the same thing, combined with a number equal to this last of half-molecules, quarter-molecules, &c., of the second substance); so that the number of integral molecules of the compound becomes double, quadruple, &c., what it would have been if there had been no splitting-up, and exactly what is necessary to satisfy the volume of the resulting gas.* [Thus, for example, the integral molecule of water will be composed of a half molecule of oxygen with one molecule, or, what is the same thing, two half-molecules of hydrogen.]
On reviewing the various compound gases most generally known, I only find examples of duplication of the volume relatively to the volume of that one of the constituents which combines with one or more volumes of the other. We have already seen this for water. In the same way, we know that the volume of ammonia gas is twice that of the nitrogen which enters into it. M. Gay-Lussac has also shown that the volume of nitrous oxide is equal to that of the nitrogen which forms part of it, and consequently is twice that of the oxygen. Finally, nitrous gas, which contains equal volumes of nitrogen and oxygen, has a volume equal to the sum of the two constituent gases, that is to say, double that of each of them. Thus in all these cases there must be a division of the molecule into two; but it is possible that in other cases the division might be into four, eight, &c. The possibility of this division of compound molecules might have been conjectured a priori; for otherwise the integral molecules of bodies composed of several substances with a relatively large number of molecules, would come to have a mass excessive in comparison with the molecules of simple substances. We might therefore imagine that nature had some means of bringing them back to the order of the latter, and the facts have pointed out to us the existence of such means. Besides, there is another consideration which would seem to make us admit in some cases the division in question; for how could one otherwise conceive a real combination between two gaseous substances uniting in equal volumes without condensation, such as takes place in the formation of nitrous gas? Supposing the molecules to remain at such a distance that the mutual attraction of those of each gas could not be exercised, we cannot imagine that a new attraction could take place between the molecules of one gas and those of the other. But on the hypothesis of division of the molecule, it is easy to see that the combination really reduces two different molecules to one, and that there would be contraction by the whole volume of one of the gases if each compound molecule did not split up into two molecules of the same nature. M. Gay-Lussac clearly saw that, according to the facts, the diminution of volume on the combination of gases cannot represent the approximation of their elementary molecules. The division of molecules on combination explains to us how these two things may be made independent of each other.
Dalton, on arbitrary suppositions as to the most likely relative number of molecules in compounds, has endeavoured to fix ratios between the masses of the molecules of simple substances. Our hypothesis, supposing it well-founded, puts us in a position to confirm or rectify his results from precise data, and, above all, to assign the magnitude of compound molecules according to the volumes of the gaseous compounds, which depend partly on the division of molecules entirely unsuspected by this physicist.
Thus Dalton supposes [In what follows I shall make use of the exposition of Dalton's ideas given in Thomson's "System of Chemistry."] that water is formed by the union of hydrogen and oxygen, molecule to molecule. From this, and from the ratio by weight of the two components, it would follow that the mass of the molecule of oxygen would be to that of hydrogen as 7 1/2 to 1 nearly, or, according to Dalton's evaluation, as 6 to 1. This ratio on our hypothesis is, as we saw, twice as great, namely, as 15 to 1. As for the molecule of water, its mass ought to be roughly expressed by 15 + 2 = 17 (taking for unity that of hydrogen), if there were no division of the molecule into two; but on account of this division it is reduced to half, 8 1/2, or more exactly 8.537, as may also be found directly by dividing the density of aqueous vapour 0.625 (Gay-Lussac) by the density of hydrogen 0.0732. This mass only differs from 7, that assigned to it by Dalton, by the difference in the values for the composition of water; so that in this respect Dalton's result is approximately correct from the combination of two compensating errors,-the error in the mass of the molecule of oxygen, and his neglect of the division of the molecule.
Dalton supposes that in nitrous gas the combination of nitrogen and oxygen is molecule to molecule; we have seen on our hypothesis that this is actually the case. Thus Dalton would have found the same molecular mass for nitrogen as we have, always supposing that of hydrogen to be unity, if he had not set out from a different value for that of oxygen, and if he had taken precisely the same value for the quantities of the elements in nitrous gas by weight. But by supposing the molecule of oxygen to be less than half what we find, he has been obliged to make that of nitrogen also equal to less than half the value we have assigned to it, viz., 5 instead of 13. As regards the molecule of nitrous gas itself, his neglect of the division of the molecule again makes his result approach ours; he has made it 6 + 5 = 11, whilst according to us it is about (15 + 13) / 2 = 14, or more exactly (15.074 + 13.238) / 2 = 14.156, as we also find by dividing 1.03636, the density of nitrous gas according to Gay-Lussac, by 0.07321. Dalton has likewise fixed in the same manner as the facts have given us, the relative number of molecules in nitrous oxide and in nitric acid, and in the first case the same circumstance has rectified his result for the magnitude of the molecule. He makes it 6 + 2 x 5 = 16, whilst according to our method it should be (15.074 + 2 x 13.238) / 2 = 20.775, a number which is also obtained by dividing 1.52092, Gay-Lussac's value for the density of nitrous oxide, by the density of hydrogen.
In the case of ammonia, Dalton's supposition as to the relative number of molecules in its composition is on our hypothesis entirely at fault. He supposes nitrogen and hydrogen to be united in it molecule to molecule, whereas we have seen that one molecule of nitrogen unites with three molecules of hydrogen. According to him the molecule of ammonia would be 5 + 1 = 6: according to us it should be (13 + 3) / 2 = 8, or more exactly 8.119, as may also be deduced directly from the density of ammonia gas. The division of the molecule, which does not enter into Dalton's calculations, partly corrects in this case also the error which would result from his other suppositions.
All the compounds we have just discussed are produced by the union of one molecule of one of the components with one or more molecules of the other. In nitrous acid we have another compound of two of the substances already spoken of, in which the terms of the ratio between the number of molecules both differ from unity. From Gay-Lussac's experiments, it appears that this acid is formed from 1 part by volume of oxygen and 3 of nitrous gas, or, what comes to the same thing, of 3 parts of nitrogen and 5 of oxygen; whence it would follow, on our hypothesis, that its molecules should be composed of 3 molecules of nitrogen and 5 of oxygen, leaving the possibility of division out of account. But this mode of combination can be referred to the preceding simpler forms by considering it as the result of the union of 1 molecule of oxygen with 3 of nitrous gas, i.e. with 3 molecules, each composed of a half-molecule of oxygen and a half-molecule of nitrogen, which thus already includes the division of some of the molecules of oxygen which enter into that of nitrous acid. Supposing there to be no other division, the mass of this last molecule would 57.542, that of hydrogen being taken as unity, and the density of nitrous acid gas would be 4.21267, the density of air being taken as unity. But it is probable that there is at least another division into two, and consequently a reduction of the density to half: we must wait until this density has been determined by experiment. . . .
It will have been in general remarked on reading this Memoir that there are many points of agreement between our special results and those of Dalton, although we set out from a general principle, and Dalton has only been guided by considerations of detail. This agreement is an argument in favour of our hypothesis, which is at bottom merely Dalton's system furnished with a new means of precision from the connection we have found between it and the general fact established by M. Gay-Lussac. Dalton's system supposes that compounds are made in general in fixed proportions, and this is what experiment shows with regard to the more stable compounds and those most interesting to the chemist. It would appear that it is only combinations of this sort that can take place amongst gases, on account of the enormous size of the molecules which would result from ratios expressed by larger numbers, in spite of the division of the molecules, which is in all probability confined within narrow limits. We perceive that the close packing of the molecules in solids and in liquids, which only leaves between the integral molecules distances of the same order as those between the elementary molecules, can give rise to more complicated ratios, and even to combinations in all proportions; but these compounds will be so to speak of a different type from those with which we have been concerned, and this distinction may serve to reconcile M. Berthollet's ideas as to compounds with the theory of fixed proportions.