The high-temperature oxidation of 1,1,1-trichloroethane can, under certain conditions, form the highly toxic byproduct phosgene. Potential routes of phosgene formation during the high temperature post-flame oxidation of 1,1,1-trichloroethane are investigated. These include photolysis reactions, heterogenous wall reactions, reactions of carbon monoxide and molecular chlorine, and high temperature oxidation reactions. Experiments using both extractive and in situ measurement techniques, along with chemical kinetic studies, indicate that phosgene is formed directly in the gas phase as a product of 1,1,1-trichloroethane oxidation. We measured up to 29% conversion of 1,1,1-trichloroethane to phosgene at an injection temperature of 1160K and a residence time of 0.1 s. The chemical kinetic model suggests that 1,1,1-trichloroethane conversion to phosgene is strongly dependent on temperature and is weakly dependent on initial concentration, equivalence ratio, and residence time. © 1994.
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