The reaction of trichloromethyl radicals with hydrogen chlorid and a new estimation of the rate of combination of trichloromethyl radicals

The effect of the addition of hydrogen chloride on the photolysis of carbon tetrachloride in the presence of cyclohexane has been investigated in a companion paper. The data enable the rate constant ratio k8/(k5)1/2 to be determined. Since k−8 is well established, k5 can be estimated from known thermochemical data. The validity of the thermochemical derivation is checked by applying it to trifluoromethyl radicals. The photolysis of bromotrichloromethane and carbon tetrachloride in the presence of hydrogen chloride has been investigated over a range of temperatures. From these results and assuming reaction (5) has no activation energy, Arrhenius parameters for reaction (8) have been determined: equation image The activation energies for the reaction of methyl, trichloromethyl, and trifluoromethyl radicals with hydrogen chloride are compared, and at first sight surprising results are rationalized in terms of relative electronegativity.