Abstract
The kinetics of the photochemical addition of dibromodifluoromethane to vinyl fluoride, 1,1-difluoroethylene and tetrafluoroethylene has been examined in gas phase experiments. The mechanism involves the addition of CF2Br˙ radicals to the alkene in a chain reaction. In the accessible range of alkene concentrations the chains are terminated not only by dimerization of the CF2Br˙ radicals but also by cross-terminations involving CF2Br˙ radicals and adduct radicals. Relative rate constants and Arrhenius parameters for the addition of CF2Br˙ radicals to specific sites in the alkenes have been measured from competitive experiments with ethylene. An estimate of the absolute Arrhenius parameters for the addition of CF2Br˙ radicals to ethylene is also given.
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Schedule a callMore From: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
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