Kinetics and mechanism in the decomposition of CCl4 in a radio-frequency pulse discharge

In the decomposition of CCl₄ in an r.f. pulse discharge the observation of time-resolved absorption spectra of the CCl radical allowed concentration measurements and a kinetic and mechanistic investigation of the system. Kinetic spectroscopy and end product analysis, with computer simulation of proposed mechanisms, indicates that the major decomposition reaction is CCl₄»CCl+3Cl (Cl₂+Cl), with a minor contribution from CCl₄»CCl₂+2Cl. Radical concentrations were of the order of 10^–7 mol dm^–3 (10¹⁴ molec. cm^–3). CCl removal was kinetically second order with a rate coefficient value of (3.7±8)×10¹⁰ mol^–1 dm^–3 s^–1 at 295±3 K at gas pressure 0.1 torr.