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)
Non-formation of Double Salts.--In Fig. 102 are shown the solubility curves
of two salts, A and B, which at the given temperature do not form a double
salt.[355] The ordinates represent the amount of A, the abscissæ the amount
of B in a _constant amount_ of the third component, the solvent. The {273}
point A, therefore, represents the solubility of the salt A at the given
temperature; and similarly, point B represents the solubility of B. Since
we are dealing with a three-component system, one solid phase in contact
with solution will constitute a bivariant system (in the absence of the
vapour phase and under a constant pressure). At any given temperature,
therefore, the concentration of the solution in equilibrium with the solid
can undergo change. If, now, to a pure solution of A a small quantity of B
is added, the solubility of A will in general be altered; as a rule it is
diminished, but sometimes it is increased.[356] The curve AC represents the
varying composition of the solution in equilibrium with the solid component
A. Similarly, the curve BC represents the composition of the solutions in
contact with pure B as solid phase. At the point, C, where these two curves
intersect, there are two solid phases, viz. pure A and pure B, in
equilibrium with solution, and the system becomes invariant. At this point
the solution is saturated with respect to both A and B, and at a given
temperature must have a perfectly definite composition. To take an example,
if we suppose A to represent sodium sulphate decahydrate, and B, magnesium
sulphate heptahydrate, and the temperature to be 18.5° (_i.e._ below the
transition point), the point C would represent a solution containing 2.16
gm.-molecules Na_{2}SO_{4} and 4.57 gm.-molecules MgSO_{4} per 100
gm.-molecules of water (p. 268). The curve ACB is the boundary curve for
saturated solutions; solutions lying outside this curve are supersaturated,
those lying within the area ACBO, are unsaturated.
[Illustration: FIG. 102.]
[Illustration: FIG. 103.]
[Illustration: FIG. 104.]
Formation of Double Salt.--We have already learned in the preceding chapter
that if the temperature is outside[357] the {274} transition interval, it
is possible to prepare a pure saturated solution of the double salt. If,
now, we suppose the double salt to contain the two constituent salts in
equimolecular proportions, its saturated solution must be represented by a
point lying on the line which bisects the angle AOB; _e.g._ point D, Fig.
103. But a double salt constitutes only a single phase, and can exist,
therefore, in contact with solutions of varying concentration, as
represented by EDF.
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