Kinetic studies of the reaction of atomic chlorine with chlorobenzene

The rate constant k1 for Cl + C6H5Cl → products has been studied via the pulsed laser photolysis-time-resolved resonance fluorescence technique over 710–1030 K. The results may be summarized as k1 = (1.36 ± 0.47) × 10−10 cm3 molecule−1 s−1 exp{−(42.5 ± 2.5) kJ mol−1/RT}. The quoted uncertainties are ±1σ, and the 95% confidence limit for k1 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.