History, Modern -- 19th century; Nineteenth century
A certain number of exceptions have also been noticed to the law of
Gay-Lussac, which may be formulated: the molecular weight of a compound
in a gaseous state is twice its density referred to hydrogen. Thus
equal volumes of ammonia and hydrogen chloride unite to form ammonium
chloride. It was to be expected that the density should be half the
molecular weight, thus:
NH3 + HCl = NH4Cl; and 53.5 ÷ 2 = 26.75 = density.
(14+3) (1+35.5) 53.5
But the density actually found is only half that number, viz., 13.37;
and for long this and similar cases were supposed to be exceptions
to the law of Gay-Lussac, viz., that equal volumes of gases at the
same pressure expand equally for equal rise of temperature. In other
instances the gradual decrease in density with rise of temperature can
be followed, as with chloral hydrate, the products of which are chloral
and water.
It was recognized by St. Claire Deville (1857) that the decrease
in density of such mixtures of gases was due, not to their being
exceptions to Avogadro’s law, but to the gradual decomposition of the
compound body with rise of temperature. To this gradual decomposition
he gave the name _dissociation_. This conception has proved of the
utmost importance to the science, as will be seen in the sequel. To
take the above instance of ammonium chloride, its abnormal density is
due to its dissociation into ammonia and hydrogen chloride; and the gas
which is obtained on raising its temperature consists, not of gaseous
ammonium chloride, but of a mixture of ammonia and hydrogen chloride,
which, as is easily seen, occupy, when separate, twice the volume that
would be occupied by the gaseous compound. Of recent years it has been
shown by Brereton Baker that, if perfectly free from moisture, ammonium
chloride gasifies as such, and that its density in the state of vapor
is, in fact, 26.75.
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