Reactions of oxygenated radicals in the gas phase. Part II. Reactions of peracetyl radicals and butenes

Abstract

In the co-oxidation of acetaldehyde and alkenes between 356.6 and 410.1 K, peracetic acid and peracetyl radicals (formed from acetaldehyde) react with the hydrocarbon to form the corresponding epoxide [reactions (1) and (2)]. [graphic omitted] [graphic omitted]. The relative proportion of the epoxidising agents changes with time, reaction (2) being predominant in the early stages of reaction. Arrhenius parameters for the reactions of but-1-ene and 2-methylpropene are given in relations (i) and (ii), and (iii) and (iv) respectively. log₁₀(k₁/dm³ mol^–1 s^–1)=(8.68 ± 1.40)–[(82 430 ± 10 320) J mol^–1/2.3RT](i) log₁₀(k₂/dm³ mol^–1 s^–1)=(7.94 ± 0.48)–[(28 930 ± 3 510) J mol^–1/2.3RT](ii) log₁₀(k₁/dm³ mol^–1 s^–1)=(7.63 ± 1.83)–[(66 000 ± 13 540) J mol^–1/2.3RT](iii) log₁₀(k₂/dm³ mol^–1 s^–1)=(8.29 ± 0.16)–[(25 040 ± 1 170) J mol^–1/2.3RT](iv)