Effects of added acetonitrile on the heat capacities of activation for the solvolysis of simple organic esters in water

Abstract

Kinetic data for the solvolysis of a range of simple organic esters in water and in water + acetonitrile mixtures are examined in terms of the two-stage Albery–Robinson mechanism. The analysis is directed at understanding the dependence of previously reported heat capacities of activation on the composition of solvent. This dependence is shown to stem from a dependence on composition of the kinetic parameters describing the two-stage mechanism and on the variation of the temperature range over which the kinetic data were measured.