Kinetics of the Gas Phase Reactions of Cl and H Atoms With Chlorinated Hydrocarbons

研究了氯和氢原子与氯代烃在300-800 K范围内的基本反应动力学和机理。为此，建立了放电流共振荧光（DF/RF）装置。选择共振荧光作为检测方法，是因为它在检测原子时具有灵敏度和选择性。使用RF/DF方法可以分离所研究的反应，并将它们与可能的并发症（如二次原子-自由基反应）分离开来。实验动力学结果采用过渡态/RRKM/主方程方法进行分析，以方便外推到实验无法获得的温度和压力。使用燃烧（焚烧）处理危险有机废物，包括氯化碳氢化合物（CHCs），激发了对这一过程的动力学和机制的兴趣。氯原子和氢原子与主要CHC化合物的反应-本研究的主题-是所涉及的最重要和最敏感的反应之一。这些反应也与化学加工和阻燃有关。

Abstract - Knyazev The kinetics and mechanisms of elementary reactions of chlorine and hydrogen atoms with chlorinated hydrocarbons is studied over a wide range of temperatures (300-800 K). A discharge flow - resonance fluorescence (DF/RF) apparatus is constructed for this purpose. Resonance fluorescence is chosen as the detection method because of its sensitivity and selectivity in detecting atoms. Use of the RF/DF method makes it possible to isolate the reactions under study and to separate them from possible complications such as secondary atom-radical reactions. The experimental kinetic results are analyzed using a transition-state/RRKM/master-equation approach to facilitate extrapolation to temperatures and pressures not accessible experimentally. Use of combustion (incineration) for disposal of hazardous organic waste, including chlorinated hydrocarbons (CHCs), has stimulated interest in the kinetics and mechanisms of this process. The reactions of chlorine atoms and hydrogen atoms with the principal CHC compounds - the subject of this study - are among the most important and sensitive reactions involved. These reactions have relevance to chemical processing and flame inhibition/fire retardancy as well.