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

摘要

Alkoxy radicals are key intermediates in the atmospheric degradations of volatile organic compounds, and can typically undergo reaction with O_2, 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.