Scientific American Supplement, No. 286, June 25, 1881Various
Science
Scientific American Supplement, No. 286, June 25, 1881
Various
Science -- Periodicals
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 H_3N to two vols. of NH_4Cl 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.
Public-domain text, read in full here on John Shaqi.
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