Kinetics of reactions of CN with chlorinated methanes

The kinetics of reactions of CN with the chlorinated methanes CH(3)Cl, CH(2)Cl(2), CHCl(3) and CCl(4) were investigated over the temperature range 298-573 K, using laser induced fluorescence (LIF) spectroscopy. At 298 K, rate constants of 9.0 +/- 0.3 x 10(13), 8.8 +/- 0.4 x 10(13), 9.0 +/- 0.5 x 10(13) and 4.3 +/- 0.6 x 10(13) cm3 molecule (1) s(1) were measured, respectively. A small positive temperature dependence was observed, as well as kinetic isotope effects of k(H)/k(D) similar to 2.14-2.25. These data along with product detection experiments strongly suggest that hydrogen abstraction dominates these reactions. (C) 2008 Elsevier B. V. All rights reserved.