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)
Partial or Limited Miscibility.--In accordance with the Phase Rule, a pure
liquid in contact with its vapour constitutes a univariant system. If,
however, a small quantity of a second substance is added, which is capable
of dissolving in the first, a bivariant system will be obtained; for there
are now two components and, as before, only two phases--the homogeneous
liquid solution and the vapour. At constant temperature, therefore, both
the composition of the solution and the pressure of the vapour can undergo
change; or, if the composition of the solution remains unchanged, the
pressure and the temperature can alter. If the second (liquid) component is
added in increasing amount, the liquid will at first remain homogeneous,
and its composition and pressure will undergo a continuous change; when,
however, the concentration has reached a definite value, solution no longer
takes place; two liquid phases are produced. Since there are now three
phases present, two liquids and vapour, the system is univariant; at a
given temperature, therefore, the concentration of the components in the
two liquid phases, as well as the vapour pressure, must have definite
values. Addition of one of the components, therefore, cannot alter the
concentrations or the pressure, but can only cause a change in the relative
amounts of the phases.
The two liquid phases can be regarded, the one as a solution of the
component I. in component II., the other as a solution of component II. in
component I. If the pressure is maintained constant, then to each
temperature there will correspond a definite concentration of the
components in the two liquid phases; and addition of excess of one will
merely alter the relative amounts of the two solutions. As the temperature
changes, the composition of the two solutions will change, and there will
therefore be obtained two solubility curves, one showing the solubility of
component I. in component II., the other showing the solubility of
component II. in component I. Since heat may be either evolved or absorbed
when one liquid dissolves in another, the solubility may diminish or
increase {97} with rise of temperature. The two solutions which at a given
temperature correspond to one another are known as _conjugate solutions_.
The solubility relations of partially miscible liquids have been studied by
Guthrie,[167] and more especially by Alexejeff[168] and by Rothmund.[169] A
considerable variety of curves have been obtained, and we shall therefore
discuss only a few of the different cases which may be taken as typical of
the rest.
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