Free radical addition to olefins:Part 2. - Addition of trichloromethyl radicals to fluoroethylenes

Arrhenius parameters have been determined for the addition of trichloromethyl radicals to fluoroethylenes; for the unsymmfitric olefins the parameters have been determined for each end of the double bond. addition to CH2 addition to CHF addition to CF2 log A2 E2 log A2 E2 log A2 E2 CH2 = CH2 5.6 3.2 CFH = CH2 5.4 5.4 CF2 = CH 2 5.5 8.3 CH2 = CHF 5.5 3.3 CF2 = CHF 6.4 7.1 CH2 = CF2 5.7 4.6 CFH = CF2 6.3 6.1 CF 2 = CF2 7.1 6.1 (log A2 in 1. mole-1 sec-1; E2 in kcal mole-1) The determined activation energies are compared with localization energies, and with free valence as calculated from simple Hückel theory.