Reactions of alkylperoxyl radicals in solution. Part 2.—A kinetic and product study of self-reactions of 2-propylperoxyl radicals between 253 and 323 K

Abstract

The self-reactions of 2-propylperoxyl radicals have been studied between 253 and 323 K in decane solution. The ratio of the major products, propanone and propan-2-ol, as a function of temperature is in good agreement with the behaviour of other secondary peroxyl radicals in solution. The roles played by the solvent are considered by comparison with previous studies of this radical in the gas phase. It is concluded that the increase in ketone production relative to the alcohol as the temperature is lowered is best explained by the inclusion of the bimolecular reaction of the peroxyl radical producing propanone and hydrogen peroxide. It is suggested that this reaction has Arrhenius parameters of A≈ 10⁶ dm³ mol^–1 s^–1 and E_a≈ 5 kJ mol^–1.