Effects of an inhomogeneous concentration distribution on rate constants of radical reactions in liquids obtained by time-resolved and modulation spectroscopy

Abstract
Non-uniform concentration distributions caused by photochemical generation of radicals in solution affect kinetic responses observed in experiments using time-resolved or modulated detection. Formulas for the correct analysis of kinetic measurements are derived for various experimental conditions. It is shown that the effects are generally much smaller than stated previously by other authors, and this is verified by the results of experiments on self-termination reactions of t-butyl and benzyl radicals.

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