A kinetic study of the self-reaction of prop-2-ylperoxyl radicals in solution using ultraviolet absorption spectroscopy

Abstract

Overall rate constants for the self-reaction of prop-2-ylperoxyl radicals in the liquid phase (cyclohexane, decane and dodecane) have been measured over the temperature range 293–373 K using ultraviolet absorption spectroscopy to monitor the concentration of alkylperoxyl radicals. The Arrhenius constants for the self-reaction are E_t= 20 ± 3 kJ mol^–1 and 2A_t=(5 ± 2.5)× 10⁹ dm³ mol^–1 s^–1. Above 363 K there is evidence that reaction with the solvent becomes increasingly important.