Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method

Alkoxy radicals are key intermediates in the atmospheric degradations of volatile organic compounds, and can typically undergo reaction with O2, unimolecular decomposition or unimolecular isomerization. Previous structure–reactivity relationships for the estimation of rate constants for these processes for alkoxy radicals [Atkinson, R., 1997. Atmospheric reactions of alkoxy and β-hydroxyalkoxy radicals. International Journal of Chemical Kinetics, 29, 99–111; Aschmann, S.M., Atkinson, R., 1999. Products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol: reactions of ROC(O )< radicals. International Journal of Chemical Kinetics, 31, 501–513] have been updated to incorporate recent kinetic data from absolute and relative rate studies. Temperature-dependent rate expressions are derived allowing rate constants for all three of these alkoxy radical reaction pathways to be calculated at atmospherically relevant temperatures.