We shall now consider briefly the formation of mixed crystals by isomorphous substances; the consideration of the formation of mixed crystals of isodimorphous substances will, on account of the complexity of the relationships, not be undertaken here.[[266]]
Formation of Mixed Crystals of Isomorphous Substances.
For the purpose of representing the relationships found here we shall employ a temperature-concentration diagram,[[267]] in which the ordinates represent the temperature and the abscissæ the concentration of the components. Since there are two solutions, the liquid and the solid, and since the concentration of the components in these two phases is not, in general, the same, two curves will be required for each system, one relating to the liquid phase, the other relating to the solid. The temperature at which solid begins to be deposited from the liquid solution will be called the freezing point of the mixture, and the temperature at which the solid solution just begins to liquefy will be called the melting point of the solid solution. The temperature-concentration curve for the liquid phase will therefore be the freezing-point curve; that for the solid solution, the melting-point curve. The latter will be represented by a dotted line.[[268]]
I.—The Two Components can form an Unbroken Series of Mixed Crystals.
Since, as has already been pointed out (p. [176]), a mixed crystal (solid solution) constitutes only one phase, it is evident that if the two components are miscible with one another in all proportions in the solid state, there can never be more than one solid phase present, viz. the solid solution or mixed crystal. If the components are completely miscible in the solid state, they will also be completely miscible in the liquid state, and there can therefore be only one liquid phase. The system can at no point become invariant, because there can never be more than three phases present. When, therefore, the two components form a continuous series of mixed crystals, the equilibrium curve must also be continuous. Of these systems three types are found.
(a) The freezing points of all mixtures lie between the freezing points of the pure components (Curve I., Fig. 49).
Examples.—This type of curve is represented by the mixed crystals of naphthalene and β-naphthol.[[269]] The addition of β-naphthol to naphthalene raises the freezing point of the latter, and the rise is directly proportional to the amount of naphthol added. The freezing point curve is therefore a straight line joining the melting points of the two components. This behaviour, however, is rather exceptional, the freezing-point curve lying generally above, sometimes also below, the straight line joining the melting points of the pure components. Thus the freezing-point curve of mixtures of α-monochlorocinnamic aldehyde and α-monobromocinnamic aldehyde[[270]] lies above the
straight line joining the melting points of the pure components (31.22° and 69.56°), as is evident from the following table:—