A quantitative analysis of solvent effects on reaction constant

Abstract

Solvent effects on reaction constant ρ for the dissociation equilibria of several series of organic acids are analysed in terms of three factors, namely, (i) variation in the effective dielectric constant, (ii) variation in the hydrogen-bonding ability of solvents, and (iii) variation in the conformation of the acids. A fourth factor, variation in the charge developed in the transition state of the reaction, is included in the analysis of ρ for reactions between diazodiphenylmethane and several series of carboxylic acids. It is shown that the ρ values for the dissociation equilibria of series of acids in other solvents can be calculated from their ρ values in water.