Kinetic studies of the reaction of atomic chlorine with chlorobenzene

Abstract

The rate constant k 1 for Cl + C 6H 5Cl → products has been studied via the pulsed laser photolysis-time-resolved resonance fluorescence technique over 710–1030 K. The results may be summarized as k 1 = (1.36 ± 0.47) × 10 −10 cm 3 molecule −1 s −1 exp{−(42.5 ± 2.5) kJ mol −1/ RT}. The quoted uncertainties are ±1 σ, and the 95% confidence limit for k 1 is ±21%. The major pathway is proposed to be formation of HCl and chlorophenyl radicals. Density functional calculations suggest the most favorable product is 3-chlorophenyl arising from attack meta to the C–Cl bond.