The Phase Rule and Its ApplicationsFindlay, Alexander
Science
The Phase Rule and Its Applications
Findlay, Alexander
Chemistry, Physical and theoretical; Phase rule and equilibrium; Solution (Chemistry)
As already mentioned, the decomposition of copper calcium acetate into the
single salts and saturated solution is accompanied by a contraction, and it
was therefore to be expected that increase of pressure would _lower_ the
transition point. This expectation of theory was confirmed by experiment,
for van't Hoff and Spring found that although the transition point under
atmospheric pressure is about 75°, decomposition of the double salt took
place even at the ordinary temperature when the pressure was increased to
6000 atm.[345]
Solubility Curves at the Transition Point.--At the transition point, as has
already been shown, the double salt and the two constituent salts can exist
in equilibrium with the same solution. The transition point, therefore,
must be the point of intersection of two solubility curves; the solubility
curve of the double salt and the solubility curve of the mixtures of the
two constituent salts. It should be noted here that we are not dealing with
the solubility curves of the single salts separately, for since the systems
are composed of three components, a single solid phase can, at a given
temperature, be in equilibrium with solutions of different composition, and
two solid phases in contact with solution (and vapour) are therefore
necessary to give an univariant system. The same applies, of course, to the
solubility of the double salt; for a double salt also constitutes a single
phase, and can therefore exist in equilibrium with solutions of varying
composition. If, however, we make the restriction (which we do for the
present) that the double salt is not decomposed by water, then the solution
will contain the constituent salts in the same relative proportions as they
are contained in the double salt, and the system may therefore be regarded
as one of _two_ components, viz. double salt and water. In this case one
solid phase is sufficient, with solution and {265} vapour, to give an
univariant system; and at a given temperature, therefore, the solubility
will have a perfectly definite value.
Since in almost all cases the solubility is determined in open vessels, we
shall in the following discussion consider that the vapour phase is absent,
and that the system is under a constant pressure, that of the atmosphere.
With this restriction, therefore, four phases will constitute an invariant
system, three phases an univariant, and two phases a bivariant system.
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