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

Cl 和 H 原子与氯化烃的气相反应动力学

• 批准号: 9807136
• 负责人: Vadim Knyazev
• 金额: --
• 依托单位: Catholic University of America
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-09-01 至 2001-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9807136&HistoricalAwards=false
• 关键词: Kinetics; Gas; Phase; Reactions; Cl

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.

摘要- Knyazev氯和氢原子与氯代烃的基元反应的动力学和机理在很宽的温度范围内（300-800 K）进行了研究。为此，我们研制了一台放电流动共振荧光（DF/RF）装置.由于共振荧光在检测原子时具有灵敏度和选择性，因此选择共振荧光作为检测方法。使用RF/DF方法可以分离研究中的反应，并将其与可能的并发症（如二次原子-自由基反应）分开。使用过渡态/RRKM/主方程的方法，以方便外推到实验无法访问的温度和压力的实验动力学结果进行分析。利用燃烧（焚化）处置危险有机废物，包括氯化烃，激发了人们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/阻燃性相关。