of the double salt must, therefore, pass through the point C, as shown in Fig. 105.
From this figure, now, it is seen that a solution saturated with respect to double salt alone (point D), is supersaturated with respect to the component A. If, then, at the temperature of the transition point, excess of the double salt is brought in contact with water,[[358]] and if supersaturation is excluded, the double salt will undergo decomposition and the component A will be deposited. The relative concentration of the component B in the solution will, therefore, increase, and the composition of the solution will be thereby altered in the direction DC. When the solution has the composition of C, the single salt ceases to be deposited, for at this point the solution is saturated for both double and single salt; and the system becomes invariant.
This diagram explains very clearly the phenomenon of the decomposition of a double salt at the transition point. As is evident, this decomposition will occur when the solution which is saturated at the temperature of the transition point, with respect to the two single salts (point C), does not contain these salts in the same ratio in which they are present in the double salt. If point C lay on the dotted line bisecting the right angle, then the pure saturated solution of the double salt would not be supersaturated with respect to either of the single salts, and the double salt would, therefore, not be decomposed by water. As has already been mentioned, this behaviour is found in the case of optically active isomerides, the solubilities of which are identical.
At the transition point, therefore, the isothermal curve also consists of two branches; but the point of intersection of the two branches now represents a solution which is saturated not
only with respect to the single salts, but also for the double salt in presence of the single salts.
We have just seen that by a change of temperature the two solubility curves, that for the two single salts and that for the double salt, were made to approach one another (cf. Figs. 104 and 105). In the previous chapter, however, we found that on passing the transition point to the region of stability for the double salt, the solution which is saturated for a mixture of the two constituent salts, is supersaturated for the double salt. In this case, therefore, point C must lie above the solubility curve of the pure double salt (Fig. 106), and a solution of the composition C, if brought in contact with double salt, will deposit the latter. If the single salts were also present, then as the double salt separated out, the single salts would pass into solution, because so long as the two single salts are present, the composition of the solution must remain unaltered. If one of the single salts disappear before the other, there will be left double salt plus A or double salt plus B, according to which was in excess; and the composition of the solution will be either that represented by D (saturated for double salt plus A), or that of the point F (saturated for double salt plus B).
In connection with the isothermal represented in Fig. 106, it should be noted that at this particular temperature a solution saturated with respect to the pure double salt is no longer supersaturated for one of the single salts (point D); so that at the temperature of this isothermal the double salt is not decomposed by water. At this temperature, further, the boundary curve consists of three branches AD, DF, and FB, which give the composition of the solutions in equilibrium with pure A, double salt, and pure B respectively; while the points D and F represent solutions saturated for double salt plus A and double salt plus B.
On continuing to alter the temperature in the same direction
as before, the relative shifting of the solubility curves becomes more marked, as shown in Fig. 107. At the temperature of this isothermal, the solution saturated for the double salt now lies in a region of distinct unsaturation with respect to the single salts; and the double salt can now exist as solid phase in contact with solutions containing both relatively more of A (curve ED), and relatively more of B (curve DF), than is contained in the double salt itself.