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nydus/The Principles of Chemistry, Volume IPublic
Page 802 of 822
Table of Contents

The volume occupied by Na2SO4,10H2O in grams = 322/1·46 = 220·5 cubic centimetres, and by MgSO4,7H2O = 246/1·68 = 146·4 c.c.; hence their mixture in equivalent quantities occupies a volume of 366·9 c.c. The volume of astrakhanite = 334/2·22 = 150·5 c.c., and the volume of 13H2O = 234 c.c., hence their sum = 380·5 c.c., and therefore it is easy to follow the formation of the astrakhanite in a suitable apparatus (a kind of thermometer containing oil and a powdered mixture of sodium and magnesium sulphates), and to see by the variation in volume that below 22° it remains unchanged, and at higher temperatures proceeds the more quickly the higher the temperature. At the transition temperature the solubility of astrakhanite and of the mixture of the component salts is one and the same, whilst at higher temperatures a solution which is saturated for a mixture of the individual salts would be supersaturated for astrakhanite, and at lower temperatures the solution of astrakhanite will be supersaturated for the component salts, as has been shown with especial detail by Karsten, Deacon, and others.

Roozeboom showed that there are two limits to the composition of the solutions which can exist for a double salt; these limits are respectively obtained by dissolving a mixture of the double salt with each of its component simple salts. Van't Hoff demonstrated, besides this, that the tendency towards the formation of double salts has a distinct influence on the progress of double decomposition, for at temperatures above 31° the mixture 2MgSO4,7H2O + 2NaCl passes into MgNa2(SO4)2,4H2O + MgCl2,6H2O + 4H2O, whilst below 31° there is not this double decomposition, but it proceeds in the opposite direction, as may be demonstrated by the above-described methods. Van der Heyd obtained a potassium astrakhanite, K2SO4MgSO4,4H2O, from solutions of the component salts at 100°. From these experiments on double salts we see that there is as close a dependence between the temperature and the formation of substances as there is between the temperature and a change of state. It is a case of Deville's principles of dissociation, extended in the direction of the passage of a solid into a liquid.

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