The kinetics of free radical chain reactions in solutions of trichlorofluorethylene in cyclohexane

Abstract

The kinetics of the gamma-radiation-induced free radical chain reaction in solutions of C2C13F in cyclohexane (RH) was investigated over a temperature range of 87.5-200°C. The following rate constants and rate constant ratios were determined for the reactions:log k2b/kza = (-0.03 f 0.15) -(2.39 f 0.28)/e log (k3a/k4a) (mole l.-l) = (6.17 f 0.10) -(10.14 f 0.18)/8In competitive experiments in ternary solutions of CzC14 and CZC13F in cyclohexane the rate constant ratio kz./kz,, was determined By comparing with previous data for the addition of cyclohexyl radicals to other chlorocthylenes it is shown that in certain cases the trends in activation energies for cyclohexyl radical addition can be correlated with the C-C1 bond dissociation energies in the adduct: radicals.