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

在氧化条件下，羟基自由基可能是 主要物种负责的分解开始， 高温燃烧环境中的有机分子。 实验室流动反应器和全规模排放数据表明， 氯代甲烷和乙烷是普遍存在的高浓度 氯化物热氧化产生的高温副产物 碳氢化合物（CHCs）。 因此，建议测量高 OH自由基与氯代甲烷和- 使用激光光解/激光诱导荧光技术的乙烷 与专门制造的高温结合， 大气压石英测试单元。 在没有热量的情况下， 分解，可以获得精确的速率常数测量， 到1373K。 当前将使用费率数据进行验证或修改 过渡态理论的可用计算技术 双分子反应速率 越来越多地使用焚化炉来处理有毒有机废物， 引起了对CHCs燃烧的兴趣，这似乎是 动力学控制。 成功的建模过程需要 了解高温氧化机理。 拟议 研究将为OH/CHC反应提供一些关键数据， 温度高于480 K，其中数据 目前还没有。

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.