Kinetic studies of the reaction of atomic chlorine with chlorobenzene

The rate constant k(1) 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 k(1) = (1.36 +/- 0.47) x 10(10) cm(3) molecule(1) s(1) exp{-(42.5 +/- 2.5) kJ mol(1)/RT}. The quoted uncertainties are +/- 1 sigma, 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. (C) 2009 Elsevier B. V. All rights reserved.