Kinetic and Product Study of the Cl-Initiated Oxidation of 1,2,3-Trichloropropane (CH2ClCHClCH2Cl)

Abstract

The kinetics and products of the Cl atom initiated oxidation of CH2ClCHClCH2Cl (1,2,3-trichloropropane) have been investigated at (295 ± 2) K in 700−760 Torr of air in a 405 L reaction chamber. The major oxidation product (in terms of carbon balance) was CH2ClC(O)CH2Cl with smaller amounts of HC(O)Cl and CH2ClC(O)Cl. It was observed that chemical activation effects play a significant role in the atmospheric fate of CH2ClCHClO(·) and CH2ClCO(·)ClCH2Cl radicals. Relative rate techniques were used to measure the following: k(Cl + CH2ClCHClCH2Cl) = (1.86 ± 0.32) × 10-12, k(Cl + CHClCHCH2Cl) = (1.67 ± 0.18) × 10-10, k(Cl + CH2CClCH2Cl) = (1.46 ± 0.15) × 10-10, and k(Cl + CH2ClC(O)CH2Cl) = (5.53 ± 0.63) × 10-13 cm3 molecule-1 s-1. The UV−visible spectrum of CH2ClC(O)CH2Cl was measured over the range 270−385 nm and has a maximum at 305 nm where σ = (1.6 ± 0.2) × 10-19 cm2 molecule-1 (base e). Assuming a photolysis quantum yield of 1.00−0.04, the lifetime of CH2ClC(O)CH2Cl with respect to photolysis on a summer ...