Kinetics of the reactions of halogens with 1,1,1-trichloroethane and bond dissociation energies in selected chloroethanes

Abstract

The gas phase kinetic of the "bromine catalyzed elimination of HC1 from 1,1,1-trichloroethane was studied over the temperature range 565 to 634 K. The experimental results were found consistent with the following mechanism: [Equation] A least squares analysis of the kinetic data yields: [Equation], where [theta] = 2.303 RT kcal/mol. The A-factor for this reaction was compared with the values obtained from similar reactions. This comparison indicated that a value lower by a factor of three namely 10¹¹.² M⁻¹s⁻¹ was in better agreement with the literature and still well with this experimental data so that our selected result is [Equation]. The latter value of E1 was combined with the assumption, [Equation] to yield: [Equation] which led to [Equation]. The kinetics of the iodine catalyzed elimination of HCl from 1,1,1-trichloroethane was studied over the temperature range 564 to 608 K.