Abstract
The reactions of trifluoromethyl radicals, generated by the photolysis of hexafluoroacetone, with the aldehydes HCOCF3, HCOC2F5 and HCOC3F7 have been studied and the following Arrhenius parameters determined : [graphic omitted] The rate of hydrogen atom abstraction from the fluoroaldehydes at 164°C is independent of the size of the fluoroalkyl group. Direct photolysis of the aldehydes HCOCF3, HCOC2F5 and HCOC3F7 is complicated by the intramolecular elimination reactions : [graphic omitted] A value of 1.95, which is independent of temperature, has been obtained for the cross-combination of CF3 and C2F5 radicals.
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