The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
[22] The question of the molecular weight of calomel--that is, whether
the mercury in the salts of the suboxide is monatomic or
diatomic--long occupied the minds of chemists, although it is not
of very great importance. It is only recently (1894) that this
question can be considered as answered, thanks to the researches
of V. Meyer and Harris, in favour of diatomicity--that is, that
calomel is analogous to peroxide of hydrogen and contains
Hg_{2}Cl_{2} (like O_{2}H_{2}) in its molecule if corrosive
sublimate contains HgCl_{2} (like water OH_{2}). As a matter of
fact, direct experiment gives the vapour density of calomel as
about 118--that is, indicates that its molecule contains HgCl,
whilst the molecule of the sublimate, judging also by the vapour
density (nearly 136), contains HgCl_{2}; it might therefore be
concluded that the mercury in the suboxide is not only monovalent
(corresponding to H) but also monatomic, whilst in the oxide it is
divalent and diatomic. Instances of a variable atomicity, as shown
by the vapour density, are known in N_{2}O, NO, and NH_{3}, CO and
CO_{2}, PCl_{3} and PCl_{5}, and it might therefore be supposed
that the present was a similar instance. But there are also
instances of a variable equivalency which do not correspond to a
variation of atomicity--for example, OH_{2} (water) and OH
(peroxide of hydrogen), CH_{4} (methane), C_{2}H_{5} (ethyl), and
CH_{2} (ethylene), &c. Here, according to the law of substitution,
the residues of OH_{2} and CH_{4} combine together and give
molecules; OHOH = O_{2}H_{2} (peroxide of hydrogen) and
CH_{3}CH_{3} = C_{2}H_{6} (ethane), &c. The same may be assumed
also to be the relation of calomel to sublimate; the residue HgCl,
which is combined with Cl in sublimate, corresponds to HgCl_{2},
and in calomel it may be supposed that this residue is combined
with itself, forming the molecule Hg_{2}Cl_{2}. On this view of
the composition of the molecule of calomel it would follow that in
the state of vapour it breaks up into two molecules, HgCl_{2} and
Hg, when the vapour density would be about 118 (because that of
sublimate is about 136 and that of mercury about 100), and that in
cooling this mixture (like a mixture of HCl and NH_{3}) again
gives Hg_{2}Cl_{2}. It was therefore necessary to prove that
calomel is decomposed in the state of vapour. This was not
effected for a long time, although Odling, as far back as the
thirties, showed that gold becomes amalgamated (_i.e._ absorbs
metallic mercury) in the vapour of calomel, but not in the vapour
of sublimate. Recently, however, V. Meyer and Harris (1894) have
shown that a greater amount of the vapour of mercury than of
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