The Principles of Chemistry, Volume IMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume I
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
and contain also an excess of the volatile substance dissolved, which
exhibits a capacity to combine with water and form a hydrate, whose
vapour tension is less than that of aqueous vapour. On evaporating in
air, this dissolved substance meets the atmospheric moisture and forms
a visible vapour (fumes) with it, which consists of the above-mentioned
compound. The attraction or affinity which binds, for instance,
hydriodic acid with water is evinced not only in the evolution of heat
and the diminution of vapour tension (rise of boiling point), but also
in many purely chemical relations. Thus hydriodic acid is produced from
iodine and hydrogen sulphide in the presence of water, but unless water
is present this reaction does not take place.[62]
[60] For this reason (the want of entire constancy of the composition
of constant boiling solutions with a change of pressure), the
existence of definite hydrates formed by volatile substances--for
instance, by hydrochloric acid and water--is frequently denied.
It is generally argued as follows: If there did exist a constancy
of composition, then it would be unaltered by a change of
pressure. But the distillation of constant boiling hydrates
is undoubtedly accompanied (judging by the vapour densities
determined by Bineau), like the distillation of sal ammoniac,
sulphuric acid, &c., by a complete decomposition of the original
compound--that is, these substances do not exist in a state
of vapour, but their products of decomposition (hydrochloric
acid and water) are gases at the temperature of volatilisation,
which dissolve in the volatilised and condensed liquids; but
the solubility of gases in liquids depends on the pressure,
and, therefore, the composition of constant boiling solutions
may, and even ought to, vary with a change of pressure, and,
further, the smaller the pressure and the lower the temperature
of volatilisation, the more likely is a true compound to be
obtained. According to the researches of Roscoe and Dittmar
(1859), the constant boiling solution of hydrochloric acid
proved to contain 18 p.c. of hydrochloric acid at a pressure of
3 atmospheres, 20 p.c. at 1 atmosphere, and 23 p.c. at 1/10 of
an atmosphere. On passing air through the solution until its
composition became constant (_i.e._ forcing the excess of aqueous
vapour or of hydrochloric acid to pass away with the air),
then acid was obtained containing about 20 p.c. at 100°, about
23 p.c. at 50°, and about 25 p.c. at 0°. From this it is seen
that by decreasing the pressure and lowering the temperature of
evaporation one arrives at the same limit, where the composition
should be taken as HCl + 6H_{2}O, which requires 25·26 p.c. of
hydrochloric acid. Fuming hydrochloric acid contains more than
this.
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