takes place.
The decomposition of sodium potassium tartrate, or of copper dipotassium chloride, differs in so far from that of Glauber's salt that two new solid phases are formed; and in the case of copper dipotassium chloride, one of the decomposition products is itself a double salt.
In the two examples of double salt decomposition which have just been mentioned, sufficient water was yielded to cause a partial liquefaction; but other cases are known where this is not so. Thus, when copper calcium acetate is heated to a
temperature of 75°, although decomposition of the double salt into the two single salts occurs as represented by the equation[[339]]—
CuCa(C2H3O2)4,8H2O = Cu(C2H3O2)2,H2O + Ca(C2H3O2)2,H2O + 6H2O
the amount of water split off is insufficient to give the appearance of partial fusion, and, therefore, only a change in the crystals is observed.
The preceding examples, in which decomposition of the double salt was effected by a rise of temperature, were chosen for first consideration as being more analogous to the case of Glauber's salt; but not a few examples are known where the reverse change takes place, formation of the double salt occurring above the transition point, and decomposition into the constituent salts below it. Instances of this behaviour are found in the case of the formation of astracanite from sodium and magnesium sulphates, and of sodium ammonium racemate from the two sodium ammonium tartrates, to which reference will be made later. Between these various systems, however, there is no essential difference; and whether decomposition or formation of the double salt occurs at temperatures above the transition point, will of course depend on the heat of change at that point. For, in accordance with van't Hoff's law of movable equilibrium (p. [58]), that change will take place at the higher temperature which is accompanied by an absorption of heat. If, therefore, the formation of the double salt from the single salts is accompanied by an absorption of heat, the double salt will be formed from the single salts on raising the temperature; but if the reverse is the case, then the double salt on being heated will decompose into the constituent salts.[[340]]
In those cases, now, which have so far been studied, the change at the transition point is accompanied by a taking up or a splitting off of water; and in such cases the general rule can be given, that if the water of crystallization of the two constituent
salts together is greater than that of the double salt, the latter will be produced from the former on raising the temperature (e.g. astracanite from sodium and magnesium sulphates); but if the double salt contains more water of crystallization than the two single salts, increase of temperature will effect the decomposition of the double salt. When we seek for the connection between this rule and the law of van't Hoff, it is found in the fact that the heat effect involved in the hydration or dehydration of the salts is much greater than that of the other changes which occur, and determines, therefore, the sign of the total heat effect.[[341]]