On continuing the investigation at higher temperatures, it was found that the solubility no longer increased, but decreased with rise of temperature. At the same time, it was observed that the solid phase was now different from that in contact with the solution at temperatures below 33°; for whereas in the latter case the solid phase was sodium sulphate decahydrate, at temperatures above 33° the solid phase was the anhydrous salt. The course of the solubility curve of anhydrous sodium sulphate is shown by BD, and the values of the solubility are given in the following table:—[[210]]
Solubility of Anhydrous Sodium Sulphate.
| Temperature. | Solubility. |
| 18° | 53.25 |
| 20° | 52.76 |
| 25° | 51.53 |
| 30° | 50.37 |
| 33° | 49.71 |
| 34° | 49.53 |
| 36° | 49.27 |
| 40.15° | 48.78 |
| 50.40° | 46.82 |
As is evident from the figure, the solubility curve which is obtained when anhydrous sodium sulphate is present as the solid phase, cuts the curve representing the solubility of the decahydrate, at a temperature of about 33°.
If a solution of sodium sulphate which has been saturated at a temperature of about 34° be cooled down to a temperature below 17°, while care is taken that the solution is protected against access of particles of Glauber's salt, crystals of a second hydrate of sodium sulphate, having the composition Na2SO4,7H2O, separate out. On determining the composition of the solutions in equilibrium with this hydrate at different temperatures, the following values were obtained, these values being represented by the curve FE (Fig. 33):—
Solubility of Na2SO4,7H2O.
| Temperature. | Solubility. |
| 0° | 19.62 |
| 10° | 30.49 |
| 15° | 37.43 |
| 18° | 41.63 |
| 20° | 44.73 |
| 25° | 52.94 |
| 26° | 54.97 |
Since, as has already been stated, each solid substance has its own solubility curve, there are three separate curves to be considered in the case of sodium sulphate and water. Where two curves cut, the solution must be saturated with respect to two solid phases; at the point B, therefore, the point of intersection of the solubility curve of anhydrous sodium sulphate with that of the decahydrate, the solution must be saturated with respect to these two solid substances. But a system of two components existing in four phases, anhydrous salt—hydrated salt—solution—vapour, is invariant; and this invariability will remain even if only three phases are present, provided that one of the factors, pressure, temperature, or concentration of components retains a constant value. This is the case when solubilities are determined in open vessels; the pressure is then equal to atmospheric pressure. Under these circumstances, then, the system, anhydrous sodium sulphate—decahydrate—solution, will possess no degree of freedom, and can exist, therefore, only at one definite temperature and when the solution has a certain definite composition. The temperature of this point is 32.482° on a mercury thermometer, or 32.379° on the hydrogen thermometer.[[211]]