Kinetics of the CH2CH2Cl⇆-C2H4+Cl reaction

The kinetics of the unimolecular decomposition of the CH2CH2Cl radical has been studied experimentally in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were determined in time-resolved experiments as a function of temperature (400-480 K) and bath gas density ([He] = (3-24) x 10(16) atoms cm(-3)). The rate constants are close to the low-pressure limit under the conditions of the experiments. Ab initio and master equation modeling are applied to analyze both the experimental data and literature data on the reverse reaction: the addition of Cl atom to ethylene, On the basis of the results of this modeling, parametrized expressions for the temperature and pressure dependencies of the rate constants for both the direct and the reverse reactions are provided.