Temperature dependence of the rates of hydrolytic reactions in concentrated perchloric acid solutions

Abstract

The rates of the acid catalysed hydrolyses of phenyl, ethyl, t-butyl, and 4-nitrophenyl acetates and of diethyl sulphite have been determined as a function of perchloric acid concentration and temperature. Enthalpies and entropies of activation, ΔH^‡ and ΔS^‡, were deduced for the hydrolytic reactions as a function of perchloric acid concentration. The concentration dependences of the thermodynamic data are discussed in terms of reaction mechanism and the influence of hydration phenomena on reaction rates in concentrated acid solutions.