Lastly, if the temperature is maintained constant, i.e. if heat can pass into or out of the system, then on changing the volume the same changes in the phases will take place as described above until one of the phases has disappeared. Continued increase of volume (decrease of pressure) will then cause the disappearance of a second phase, the system passing along the dotted line OE′ (Figs. 16, 17), so that ultimately there remains only the vapour phase. Conversely, diminution of volume (increase of pressure) will ultimately lead either to solid (Fig. 16) or to liquid alone (Fig. 17), the system passing along the dotted line OE.
In discussing the alterations which may take place at the triple point with change of temperature and pressure, we have considered only the triple point S-L-V. The same reasoning, however, applies, mutatis mutandis, to all other triple points, so that if the specific volumes of the phases are known, and the sign of the heat effects which accompany the transformation of one phase into the other, it is possible to predict (by means of the theorem of Le Chatelier) the changes which will be produced in the system by alteration of the pressure and temperature.
In all cases of transformation at the triple point, it should be noted that all three phases are involved in the change,[[107]] and not two only; the fact that in the case, say, of the transformation from solid to liquid, or liquid to solid, at the melting point with change of temperature, only these two phases appear to be affected, is due to there generally being a large excess of the vapour phase present and to the prior disappearance therefore of the solid or liquid phase.
In the case of triple points at which two solid phases are in equilibrium with liquid, other arrangements of the curves around the triple point are found. It is, however, unnecessary to give a general treatment of these here, since the principles which have been applied to the triple point S-L-V can also be applied to the other triple points.[[108]]
Triple Point Solid—Solid—Vapour.—The triple point solid—solid—vapour is one which is of considerable importance. Examples of such a triple point have already been given in sulphur and tin, and a list of other substances capable of yielding two solid phases is given below. The triple point S-S-V is not precisely the same as the transition point, but is very nearly so. The transition point is the temperature at which the relative stability of the two solid phases undergoes change, when the vapour phase is absent and the pressure is 1 atm.; whereas at the triple point the pressure is that of the system itself. The transition point, therefore, bears the same relation to the triple point S-S-V as the melting point to the triple point S-L-V.
In the following table is given a list of the most important polymorphous substances, and the temperatures of the transition point.[[109]]