Study of electrolytic solution process using the scaled-particle theory. Part 3.—Effects of thermal dilution on standard thermodynamic functions

Abstract

A unified approach consisting of the scaled-particle theory in conjunction with the Born charging equation, proposed earlier in this series, has been used to calculate theoretically the standard free energy and entropy of hydration of various electrolytes in the temperature range between the normal freezing point and the critical temperature of water. The theory appears to hold well for the prediction of the entropy of hydration of electrolytes at least up to 300 °C, the highest temperature for which experimental data are at present available for comparison. The values of the individual ionic hydration entropies at different temperatures calculated according to the present theory and as estimated from experimental results by earlier workers using some extrathermodynamic assumptions have, however, been found to be widely different, particularly at elevated temperatures.