Estimation of O-H bond dissociation energies in alcohols and acids from kinetic data

Abstract

The O-H bond dissociation energies (DO-H) in five alcohols and six acids have been determined from experimental data (rate constants of radical reactions). The ratio of the rate constants of the reactions R1O˙+RH→R1OH+R˙ and RiO˙+RH→RiOH+R˙ and the intersecting parabolas method are used in the estimation procedure. The DO-H values are used to calculate the activation energies and rate constants for hydrogen abstraction from 2-methylbutane, butene-1, and cumene by alkoxyl and carboxyl radicals. The geometric parameters of the transition state are calculated for these reactions.