CHAPTER V

SOLUTIONS AND ELECTROLYTIC DISSOCIATION

Sec. 1.  SOLUTION

Vaporization and fusion are not the only means by which the physical state of a body may be changed without modifying its chemical constitution.  From the most remote periods solution has also been known and studied, but only in the last twenty years have we obtained other than empirical information regarding this phenomenon.

It is natural to employ here also the methods which have allowed us to penetrate into the knowledge of other transformations.  The problem of solution may be approached by way of thermodynamics and of the hypotheses of kinetics.

As long ago as 1858, Kirchhoff, by attributing to saline solutions—­ that is to say, to mixtures of water and a non-volatile liquid like sulphuric acid—­the properties of internal energy, discovered a relation between the quantity of heat given out on the addition of a certain quantity of water to a solution and the variations to which condensation and temperature subject the vapour-tension of the solution.  He calculated for this purpose the variations of energy which are produced when passing from one state to another by two different series of transformations; and, by comparing the two expressions thus obtained, he established a relation between the various elements of the phenomenon.  But, for a long time afterwards, the question made little progress, because there seemed to be hardly any means of introducing into this study the second principle of thermodynamics.[14] It was the memoir of Gibbs which at last opened out this rich domain and enabled it to be rationally exploited.  As early as 1886, M. Duhem showed that the theory of the thermodynamic potential furnished precise information on solutions or liquid mixtures.  He thus discovered over again the famous law on the lowering of the congelation temperature of solvents which had just been established by M. Raoult after a long series of now classic researches.

[Footnote 14:  The “second principle” referred to has been thus enunciated:  “In every engine that produces work there is a fall of temperature, and the maximum output of a perfect engine—­i.e. the ratio between the heat consumed in work and the heat supplied—­depends only on the extreme temperatures between which the fluid is evolved.”—­Demanet, Notes de Physique Experimentale, Louvain, 1905, fasc. 2, p. 147.  Clausius put it in a negative form, as thus:  No engine can of itself, without the aid of external agency, transfer heat from a body at low temperature to a body at a high temperature.  Cf.  Ganot’s Physics, 17th English edition, Sec. 508.—­ED.]

In the minds of many persons, however, grave doubts persisted.  Solution appeared to be an essentially irreversible phenomenon.  It was therefore, in all strictness, impossible to calculate the entropy of a solution, and consequently to be certain of the value of the thermodynamic potential.  The objection would be serious even to-day, and, in calculations, what is called the paradox of Gibbs would be an obstacle.