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| - Kinetics of the CH2Cl + CH3 and CHCl2 + CH3 Radical−Radical Reactions
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| - The CH2Cl + CH3 (1) and CHCl2 + CH3 (2) cross-radical reactions were studied by laser photolysis/photoionization mass spectroscopy. Overall rate constants were obtained in direct real-time experiments inthe temperature region 301−800 K and bath gas (helium) density (6−12) × 1016 atom cm-3. The observedrate constant of reaction 1 can be represented by an Arrhenius expression k1 = 3.93 × 10-11 exp(91 K/T) cm3molecule-1 s-1 (±25%) or as an average temperature-independent value of k1 = (4.8 ± 0.7) × 10-11 cm3molecule-1 s-1. The rate constant of reaction 2 can be expressed as k2 = 1.66 × 10-11 exp(359 K/T) cm3molecule-1 s-1 (±25%). C2H4 and C2H3Cl were detected as the primary products of reactions 1 and 2,respectively. The experimental values of the rate constant are in reasonable agreement with the predictionbased on the “geometric mean rule.” A separate experimental attempt to determine the rate constants of thehigh-temperature CH2Cl + O2 (10) and CHCl2 + O2 (11) reaction resulted in an upper limit of 1.2 × 10-16cm3 molecule-1 s-1 for k10 and k11 at 800 K.
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