Abstract
AbstractThe reaction of methyl radicals (Me) with hexafluoroacetone (HFA), generated from ditertiary butyl peroxide (dtBP), was studied over the temperature range of 402–433 K and the pressure range of 38–111 torr. The reaction resulted in the following displacement process taking place: magnified image where TFA refers to trifluoroacetone. The trifluoromethyl radicals that were generated abstract a hydrogen atom from the peroxide: equation image such that k6a is given by: where θ = 2.303RT kcal/mol. The interaction of methyl and trifluoromethyl radicals results in the following steps: equation image Product analysis shows that k17/kk = 2.0 ± 0.2 such that k17 = 1010.4±0.5M−1 · s−1. The rate constant k5 is given by: It is concluded that the preexponential factor for the addition of methyl radicals to ketones is lower than that for the addition of methyl radicals to olefins.
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