Scientific American Supplement, No. 286, June 25, 1881

by Various

The impossibility of the correctness of the hypothesis is now revealed by the fact just demonstrated, that in the case of nitrogen the specific gravity does not coincide with the molecular weight. If equal volumes contain the same number of molecules, the specific gravities and the molecular weights must be the same; and if the specific gravities and molecular weights are not the same, equal volumes cannot contain the same number of molecules. The assumed molecular weight of nitrogen is twice as great as the specific gravity, but the molecular weight and the specific gravity of cyanogen are identical; the number of molecules contained in one volume of cyanogen must, therefore, necessarily be twice as great as the number contained in one of nitrogen, and this is fully and completely borne out by the chemical facts.

In saying that when cyanogen combines with chlorine there is naturally no condensation, Mr. Greene has no idea that this natural law is fatal to his artificial law of Avogadro and Ampere; "for," continues he, "the theory is fulfilled by the actual reaction." It is not. The theory requires two vols. of cyanogen and two vols. of chlorine, that is, the unit of numbers, to enter into reaction and to produce two vols. of the compound. But they produce four vols., and the non-condensation is therefore in opposition to the theory. It is true beyond doubt that the molecular weight of cyanogen chloride is contained in two volumes, in spite of the hypothesis, not on the ground of it; two vols. + two vols., producing four vols.; two vols. could, theoretically, contain only half the unit of numbers, and there seems to be no escape from the following general conclusions:

1. Two vols. of CNCl, representing the unit of numbers, the constituent weights, C=12, N=14, Cl=35.5, must each, likewise, represent the same number; the molecular weight is, therefore, contained in one vol. of N or Cl, but in two of CNCl and equal numbers are not contained in equal volumes.

2. The weights N=14, Cl=35.5 occupy in the free state one volume, but in the combination, CNCl, two volumes; their specific gravity is, therefore, by chemical action reduced to one half. The fact thus elicited of the variability and variation of the specific gravity is of fundamental importance and involves the irrelevancy of the mathematical demonstration of the hypothesis. In this demonstration the specific gravity is assumed to be constant, and this assumption not holding good, and the number of molecules in unit of volume being reduced to one half when the specific gravity is reduced to the same extent by chemical action, it is obvious that the mathematical proof must fail. Mr. Greene states that I have proceeded to demolish C. Clerk Maxwell's conclusion from mathematical reasoning. This is incorrect; I have found no fault with the conclusion of the celebrated mathematician, and consider his reasoning unimpeachable. I am also of opinion that he is entitled to great credit and respect for the prominent part he has taken in the development of the kinetic theory, and further think that it was for the chemists to produce the fact of the variability of the specific gravities, which they would probably not have failed to do but for the prevalence of Avogadro's hypothesis, which is virtually the assertion of the constancy of the specific gravities.

3. The unit of numbers being represented by Cl=35.5, it is likewise represented by H=1, and as the product of the union of the two elements is HCl, 36.5 = two vols., combination takes place by addition and not by substitution; consequently are

4. The elementary molecules not compounds of atoms? And the distinction between atoms and molecules is an artificial one, not justified by the natural facts.

5. Is the molecular weight not in every instance = two volumes?

These conclusions overthrow all the fundamental assumptions on which the hypothesis rests, and leave it, in the full meaning of the term, without support. Though Mr. Greene states that my arguments are based upon entirely erroneous premises, he has not even attempted to invalidate a single one of my premises.

As he considers the non-condensation to be natural in the case of cyanogen and chlorine, the condensation of two vols. of HCl + two vols. of H₃N to two vols. of NH₄Cl ought to appear to him unnatural. He, however, contends for it, and tries, on this solitary occasion, to strengthen his opinion by authority, though the proof, if it could be given, that ammonium chloride at the temperature of volatilization is decomposed into its two constituents, would be insufficient to uphold the theory.

The ground on which Mr. Greene assumes a partial decomposition at 350° C. is the slight excess of the observed density (14.43) over that corresponding to four vols. (13.375). There is, however, a similar slight excess in the case of the vapor of ammonium cyanide, the same values being respectively 11.4 and 11; and as this compound is volatile at 100° C and, at the same time, is capable to exist at a very high temperature, being formed by the union of carbon with ammonia, nobody has ever, as far as I am aware, maintained that it is completely or partially decomposed at volatilization. The excess of weight not being due, therefore, to such cause in this case, it cannot be due to it in the other.