Laser Photolysis/Laser Induced Fluorescence Study of Hydroxyl Radical-Chloromethane/Chloroethane Reaction Rates at Elevated Temperatures

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Under oxidative conditions, the hydroxyl radical is probably the dominant species responsible for initiation of the decomposition of organic molecules in high temperature combustion environments. Laboratory flow reactor and full scale emissions data have shown that chlorinated methanes and ethanes are among the prevalent high temperature by-products from the thermal oxidation of chlorinated hydrocarbons (CHCs). It is therefore proposed to measure the high temperature reaction rates of OH radicals with chloro-methanes and - ethanes using a laser photolysis/laser-induced fluorescence technique in conjunction with a specially fabricated high temperature, atmospheric pressure quartz test cell. In the absence of thermal decomposition, precise rate constant measurements may be obtained up to 1373 K. The rate data will be used to validate or modify currently available calculation techniques for the transition state theory of bimolecular reaction rates. The growing use of incinerators to dispose of toxic organic wastes has generated an interest in the combustion of CHCs, which appear to be kinetically controlled. Successful modelling of the process requires knowledge of the high temperature oxidation mechanism. The proposed research will supply some of the key data for OH/CHC reactions at temperatures above 480 K, where data are presently unavailable.