Kinetics of the Reaction of the CCl2 Biradical with Molecular Chlorine

Abstract

The kinetics of the reaction of CCl2 with molecular chlorine has been studied using the laser photolysis/photoionization mass spectrometry technique. Dichloromethylene biradicals were produced by the pulsed laser photolysis of carbon tetrachloride, and the kinetics of their decay due to reaction with Cl2 were monitored in direct time-resolved experiments. Rate constants were determined as a function of temperature (300−750 K) and can be described by the Arrhenius expression k1 = (1.3 ± 0.3) × 10-11 exp(−(281 ± 96) K/T) cm3 molecule-1 s-1. Rate constants of reaction 1 are independent of the bath gas density within the experimental range [He] = (3−12) × 1016 atoms cm-3. CCl3 was observed as a primary product of the reaction.