Free radical addition to olefins. Part 19.—Trifluoromethyl radical addition to fluoro-substituted propenes and its absolute rate of addition to ethylene

Abstract
The rates of addition of trifluoromethyl radicals to each end of propene, 1,1,1-trifluoropropene and hexafluoropropene have been determined using a competitive technique, taking as a standard the rate of addition to ethylene. The rate of addition of trifluoromethyl radicals to ethylene (2) has been compared with the rate of combination of trifluoromethyl radicals (6), and a value of k2/k½ 6=(1.6 ± 0.2)× 103 exp (–2 900 ± 500 cal mol–1/RT) dm½ mol–½ s–½ was determined (1 cal = 4.184 J). [graphic omitted] Since the value of k6 is now well established, a new value of the absolute rate of addition of trifluoromethyl radicals to ethylene and to the other olefins can be computed.

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