The vapour pressure of the different systems of sodium sulphate and water can best be studied with the help of the diagram in Fig. 34.[[216]] The curve ABCD represents the vapour-pressure curve of the saturated solution of anhydrous sodium sulphate. GC is the pressure curve of decahydrate + anhydrous salt, which, as we have seen, cuts the curve ABCD at the transition temperature, 32.6°. Since at this point the solution is saturated with respect to both the anhydrous salt and the decahydrate, the vapour-pressure curve of the saturated solution of the latter must also pass through the point C.[[217]] As at temperatures below this point the solubility of the decahydrate is less than that of the anhydrous salt, the vapour pressure of the solution will, in accordance with Babo's law (p. [126]), be higher than that of the solution of the anhydrous salt; which was also found experimentally to be the case (curve HC).
In connection with the vapour pressure of the saturated solutions of the anhydrous salt and the decahydrate, attention must be drawn to a conspicuous deviation from what was found to hold in the case of one-component systems in which a vapour phase was present (p. [31]). There, it was seen that the vapour pressure of the more stable system was always lower than that of the less stable; in the present case, however, we find that this is no longer so. We have already learned that at temperatures below 32.5° the system decahydrate—solution—vapour is more stable than the system anhydrous salt—solution—vapour; but the vapour pressure of the latter system is, as has just been stated, lower than that of the former. At temperatures above the transition point the vapour pressure of the saturated solution of the decahydrate will be lower than that of the saturated solution of the anhydrous salt.
This behaviour depends on the fact that the less stable form is the more soluble, and that the diminution of the vapour pressure increases with the amount of salt dissolved.
With regard to sodium sulphate heptahydrate the same considerations will hold as in the case of the decahydrate. Since at 24° the four phases heptahydrate, anhydrous salt, solution, vapour can coexist, the vapour-pressure curves of the systems hydrate—anhydrous salt—vapour (curve EB) and hydrate—solution—vapour (curve FB) must cut the pressure curve of the saturated solution of the anhydrous salt at the above temperature, as represented in Fig. 34 by the point B. This constitutes, therefore, a second quadruple point, which is, however, metastable.
From the diagram it is also evident that the dissociation pressure of the heptahydrate is higher than that of the decahydrate, although it contains less water of crystallization. The system heptahydrate—anhydrous salt—vapour must be metastable with respect to the system decahydrate—anhydrous salt—vapour, and will pass into the latter.[[218]] Whether or not there is a temperature at which the vapour-pressure curves of the two systems intersect, and below which the heptahydrate becomes the more stable form, is not known.
In the case of sodium sulphate there is only one stable hydrate. Other salts are known which exhibit a similar behaviour; and we shall therefore expect that the solubility relationships will be represented by a diagram similar to that for sodium sulphate. A considerable number of such cases have, indeed, been found,[[219]] and in some cases there is more than one metastable hydrate. This is found, for example, in the case of nickel iodate,[[220]] the solubility curves for which are given in Fig. 35. As can be seen from the figure, suspended transformation occurs, the solubility curves having in some cases been followed to a considerable distance beyond the transition point. One of the most brilliant examples, however, of suspended transformation in the case of salt hydrates, and the sluggish transition from the less stable to the more stable form, is found in the case of the hydrates of calcium chromate.[[221]]
In the preceding cases, the dissociation-pressure curve of the hydrated salt cuts the vapour-pressure curve of the saturated