Kinetic study of the reaction of chlorine atoms with chloroform in the gas phase

The kinetics of the gas-phase reactions of chlorine atoms with H-chloroform and D-chloroform was studied experimentally. The relative rate method was applied using Cl + CH3Br as the reference reaction. The rate constants for H-abstraction from CHCl3 (kH) and D-abstraction from CDCl3 (kD) were measured in the temperature range of 297–527 K and at total pressure of 100 Torr. The derived temperature dependencies of the rate constants are given by kH = (4.8 ± 0.5) × 10−12 × exp(−1160 ± 30/T) and kD = (6.4 ± 2.1) × 10−12 × exp(−1660 ± 110/T) cm3 molecule−1 s−1. The kinetic isotope effect described by the ratio kH/kD was (0.77 ± 0.25) × exp(500 ± 95/T).