Reasonable correlations have been demonstrated between the activation energies for epoxidation of alkenes by peroxyl radicals in the gas phase and the charge transfer that occurs during the formation of the peroxyalkyl adduct, or the corresponding energy decrease due to the charge transfer, or the difference between the ionisation energy of the alkene and the electron affinity of the peroxyl radical. This demonstrates a high degree of coherence among previously published works on gas phase epoxidation by peroxyl radicals, as well as providing a useful method for the estimation of epoxidation rate constants that have not yet been measured.

The author would like to thank Prof. B. T. Sutcliffe and especially Prof. D. J. Waddington for much helpful discussion and for reviewing the manuscript.