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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 HN to two vols. of NHCl 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.
The question being whether the molecular weight of ammonium chloride is two vols. or four vols., an idea of the magnitude of the assumed decomposition is conveyed by the proportion of the volume of the decomposed salt to the volume of the non-decomposed, and Mr. Greene's quotation of the percentage of weight is irrelevant and misleading, and his number not even correct. A mixture containing
1.055 vols. of spec. gr. 26.75 = 28.22 and 12.32 " " " " 13.375 = 164.78 ------ ------ 13.375 " 193
has the spec. gr. 193 / 13.375 = 14.43. The proportion in one vol. of the undecomposed to the decomposed salt is, therefore, as 1 to 11.68 and the percentage of volume of the former 0.0789, and that of weight 28.22 / 193 = 0.146, and not 0.16.
It is not easy to imagine why a small fraction of the heavy molecules should be volatilized undecomposed, the temperature being sufficient to decompose the great bulk. Marignac assumes, indeed, partial decomposition, but the difficulties which he encountered in making the experiments, on the results of which his opinion rests, were so great that he himself accords to the numbers obtained by him only the value of a rough approximation.
The heat absorbed in volatilization will comprise the heat of combination as well as of aggregation, if decomposition takes place, and will therefore be the same as that set free at combination. Favre and Silbermann found this to be 743.5 at ordinary temperature, from which Marignac concludes that it would be 715 for the temperature 350°; he found as the heat of volatilization 706, but considers the probable exact value to be between 617 and 818.
[Footnote 1: See Comptes Rendus, t. lxvii., p. 877.]
An uncertainty within so wide a range does not justify the confidence of Mr. Greene which he expresses in these words: "It is, therefore, extremely probable that ammonium chloride is almost entirely dissociated, even at the temperature of volatilization." By Boettinger's apparatus a decomposition may possibly have been demonstrated, but it remains to be seen whether it is not due to some special cause.
When Mr. Greene says that the relations between the physical properties of solids and liquids and their molecular composition can in no manner affect the laws of gases, nobody is likely to dissent; but the conclusion that their discussion is foreign to the question of the number of molecules in unit of volume does by no means follow. If the specific gravity of a solid or the weight of unit of volume represents a certain number of molecules, and is found to occupy two volumes in a compound of the solid with another solid, the number of molecules in one volume is reduced to one half. This I have shown to be the case in a number of compounds, and the decrease of the specific gravity with increase of the complexity of composition appears to be a general law, as may be concluded from the very low specific gravity of the most highly organized compounds, for instance the fatty bodies, the molecules of which, being composed of very many constituents, are of heavy weight; and likewise the compounds which occur in combination with water and without it, the simpler compound having invariably a greater specific gravity than the one combined with water; for instance:
BaH_2O_2 sp. gr. 4.495 " " + 8H_2O " 1.656 S_2H_2O_2 " 3.625 " " + 8H_2O " 1.396 FeSO_4 " 3.138 " + 7H_2O " 1.857
and so in every other case. This is now a recurrence of what takes place in gases, and proves the fallacy of the hypothesis; for if these compounds could be volatilized the vapor densities would necessarily vary in the inverse proportion of the degree of composition.
The reproach that Berthelot has been endeavoring for nearly a quarter of a century to hold back the progress of scientific chemistry, is a great and unjustifiable misrepresentation of the distinguished chemist and member of the Institute of France, who has done so much for thermo-chemistry, and the more unfortunate as it seems to serve only the purpose of a prelude to the following sentences: "But Mr. Vogel cannot claim, as can Mr. Berthelot, any real work or experiment, however roughly performed, suggested by the desire to prove the truth of his own views. Let him not, then, bring forth old and long since explained discrepancies, ... but when he will have discovered new or overlooked facts ... chemists will gladly listen." ... Mr. Greene is here no longer occupied to investigate whether what I have said concerning Avogadro's hypothesis is true or false, but with myself he has become personal, and in noticing his remarks my sole object is to contend against an error which is much prevalent. If, according to Mr. Greene, the real work of science consists in experimenting, and conclusions unsupported by our own experiments have no value, it does not appear for what purpose he has published his answer to my paper; an experiment of his, settling Marignac's uncertain results, would have justified the reliance he places on them. The ground he takes is utterly untenable. Experiments are necessary to establish facts; without them there could be no science, and the highest credit is due to those who perform successfully difficult or costly experiments. Experimenting is, however, not the aim and object of science, but the means to arrive at the truth; and discoveries derived from accumulated and generally accepted facts are not the less valuable on account of not having been derived from new and special experiment.
It is, further, far from true that the real work of science consists in experimenting; mental work is not less required, and the greatest results have not been obtained by experimenters, but by the mental labor of those who have, from the study of established facts, arrived at conclusions which the experimenters had failed to draw. This is naturally so, because a great generalization must explain all the facts involved, and can be derived only from their study; but the attention of the experimenter is necessarily absorbed by the special work he undertakes. I refer to the three greatest events in science: the discovery of the Copernican system, the three laws of Kepler, and Newton's law of gravitation, none of which is due to direct and special experimentation. Copernicus was an astronomer, but the discovery of his system is due chiefly to his study of the complications of the Ptolemaic system. Kepler is a memorable witness of what can be accomplished by skillful and persistent mental labor. "His discoveries were secrets extorted from nature by the most profound and laborious research." The discovery of his third law is said to have occupied him seventeen years. Newton's great discovery is likewise the result of mental labor; he was enabled to accomplish it by means of the laws of Kepler, the laws of falling bodies established by Galileo, and Picard's exact measurement of a degree of a meridian.
If, then, mental work is as indispensable as experimental, it is not less true that there are men more specially fitted for the one, others for the other, and the best interests of science will be served when experiments are made by those specially adapted, skillful, and favorably situated, and the possibly greatest number of men, able and willing to do mental work, engage in extracting from the accumulated treasures of experimental science all the results which they are capable to yield. Any truth discovered by this means is clear gain, and saves the waste of time, labor, and money spent in unnecessary experiment. Mr. Greene's zeal for experiment and depreciation of mental work would be in order, if ways and means were to be found to render the advancement of science as difficult and slow as possible; they are decidedly not in the interest of science, and can not have been inspired by a desire for its promotion.
As the evidence of the specific heats of the fallacy of Avogadro's hypothesis involves lengthy explanations, the subject is reserved for another paper.
San Francisco, Cal., May, 1881.