The question of the measure of electrolytes in organic reactions. Calculation of activity coefficients of electrolytes in solvolytic media

Abstract

The use of the stoicheiometric concentration as a measure of electrolytes in the study of their effects in organic and particularly solvolytic reactions is considered and questioned. As an aid to information on this subject and as a better approximation to the proper measure of the active electrolyte, a practical approach to activity coefficients of 1 : 1 electrolytes in solvolytic media is proposed by calculation using Harned's rule. Test values are compared with experimentally available activity coefficients and the applicability of this approach as well as some of its limitations are discussed. The rule is applied to various salts in ethanol and dioxan. The features of the coefficients reported are discussed including the large deviation from proportionality between activity and concentration which they indicate. Some of the possible implications for solvolytic studies and the need for caution in this respect are pointed out.