Reactions of oxygenated radicals in the gas phase. Part 15. Reactions of t-butylperoxyl radicals with alkenes

Abstract

The photo-oxidation of mixtures of trans-2,2′-azoisobutane and some aliphatic alkenes has been studied between 313 and 393 K. Rate constants for the reaction between t-butylperoxyl radicals with ethene, 2-methylpropene, 2-methylbut-1-ene, 2-methylbut-2-ene, and 2,3-dimethylbut-2-ene have been determined at 393 K. Arrhenius parameters for the reaction (22) have been determined for 2-methylbut [graphic omitted] +(CH₃)₃CO₂·→ [graphic omitted] +(CH₃)₃CO·(22) 2-ene and 2,3-dimethylbut-2-ene. They are log (A₂₂/dm³ mol^–1S^–1) of 8.16 ± 0.38 and 8.58 ± 0.61, and E₂₂/kJ mol^–1 of 56.6 ± 2.4 and 48.7 ± 4.1, respectively. The data obtained in this work are compared with that obtained for the series hydroperoxyl, methylperoxyl, and isopropylperoxyl radicals, and with rate data obtained for the addition reaction between alkenes and peracetyl radicals.