liquid phases is less than that of each of the components is not possible.
With regard to the partial pressure of the components, the behaviour is more uniform. The partial pressure of one component is in all cases lowered by the addition of the other component, the diminution being approximately proportional to the amount added. If two liquid phases are present, the partial pressure of the components, as well as the total pressure, is constant, and is the same for both phases. That is to say, in the case of the two liquids, saturated solution of water in ether, and of ether in water, the partial pressure of the ether in the vapour in contact with the one solution is the same as that in the vapour over the other solution.[[177]]
Complete Miscibility.—Although the phenomena of complete miscibility are here treated under a separate heading, it must not be thought that there is any essential difference between those cases where the liquids exhibit limited miscibility and those in which only one homogeneous solution is formed. As has been already pointed out, the solubility relations alter with the temperature; and liquids which at one temperature can dissolve in one another only to a limited extent, are found at some other temperature to possess the property of complete miscibility. Conversely, we may expect that liquids which at one temperature, say at the ordinary temperature, are miscible in all proportions, will be found at some other temperature to be only partially miscible. Thus, for example, it was found by Guthrie that ethyl alcohol and carbon disulphide, which are miscible in all proportions at the ordinary temperature, possess only limited miscibility at temperatures below -14.4°.[[178]] Nevertheless, it is doubtful if the critical solution temperature is in all cases experimentally realizable.
Pressure-Concentration Diagram.—Since, in the cases of complete miscibility of two liquid components, there are never more than two phases present, the system must always be bivariant; and two of the variables pressure, temperature or concentration of the components, must be arbitrarily chosen
before the system becomes defined. For this reason the Phase Rule affords only a slight guidance in the study of such equilibria; and we shall therefore not enter in detail into the behaviour of these homogeneous mixtures. All that the Phase Rule can tell us in connection with these solutions, is that at constant temperature the vapour pressure of the solution varies with the composition of the liquid phase; and if the composition of the liquid phase remains unchanged, the pressure also must remain unchanged. This constancy of composition is exhibited not only by pure liquids, but also by liquid solutions in all cases where the vapour pressure of the solution reaches a maximum or minimum value. This is the case, for example, with mixtures of constant boiling point.[[179]]
CHAPTER VII
SOLUTIONS OF SOLIDS IN LIQUIDS, ONLY ONE OF THE COMPONENTS BEING VOLATILE
General.—When a solid is brought into contact with a liquid in which it can dissolve, a certain amount of it passes into solution; and the process continues until the concentration reaches a definite value independent of the amount of solid present. A condition of equilibrium is established between the solid and the solution; the solution becomes saturated. Since the number of components is two, and the number of phases three, viz. solid, liquid solution, vapour, the system is univariant. If, therefore, one of the factors, pressure, temperature, or concentration of the components (in the solution[[180]]), is arbitrarily fixed, the state of the system becomes perfectly defined. Thus, at any given temperature, the vapour pressure of the system and the concentration of the components have a definite value. If the temperature is altered, the vapour pressure and also, in general, the concentration will undergo change. Likewise, if the pressure varies, while the system is isolated so that no heat can pass between it and its surroundings, the concentration and the temperature must also undergo variation until they attain values corresponding to the particular pressure.