Transition state volumes and solvolysis mechanisms

Abstract

The transition state partial molal volume behavior, [Formula: see text] as a function of binary solvent composition was obtained for three reactions by dissection of the activation volume, ΔV*, into initial and transition state components: [Formula: see text] The solvolyses of t-butyl chloride, benzyl chloride, and p-chlorobenzyl chloride represented a gradation of reaction type between SN1 and SN2 and the transition state partial molal volume behavior was found to be distinctly different in each case and in agreement with the mechanistic classification of these reactions.