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

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: k4a/k4b= 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, E4b–E4a= 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)