Reactions of oxygenated radicals in the gas phase. Part 4. Reactions of methylperoxyl and methoxyl radicals

Abstract

The reactions of methylperoxyl radicals formed during the oxidation of di-t-butyl peroxide have been studied. Particular attention has been paid to the reactions (4a), (4b), and (16). The following rate data have been 2CH₃O₂˙→ CH₃OH + HCHO + O₂(4a), 2CH₃O₂˙→ 2CH₃O˙+ O₂(4b), CH₃O₂˙+ HCHO → CH₃O₂H +˙CHO (30) obtained: k_4a/k_4b= 0.69 ± 0.08 and k₁₆=ca. 1.2 × 10³ dm³ mol^–1 s^–1 at 410 K. From these results and from those of previous work, E_4b–E_4a= 9 ± 1 kJ mol^–1. Further, the oxidation of methoxyl radicals plays an important role in the overall reaction (5). CH₃O˙+ O₂→ HCHO + HO₂˙(5)