Kinetics of Key Radical Reactions for Use in Chemical Models of Chlorinated Hydrocarbon Combustion

摘要CTS-0105239V。用激光光解/光电离质谱(LP/PIMS)技术研究了氯代烃自由基在较宽的温度和压力范围内的反应动力学和机理。所研究的特殊体系包括(1)氯化自由基(CH2、Cl、CHCl2、CCl3)与甲基(CH3)的反应；(2)氯化甲基自由基与分子氧(O2)在高温下的反应；(3)C2Cl3和离域氯代烃自由基的单分子分解，以及它们与O2、氧原子和氯(Cl2)的反应。用过渡态理论、RRKM和主方程方法对实验动力学结果进行了分析。这项工作产生的信息将导致氯代烃(CHC)燃烧模型的改进。这应该能够更有效地焚烧氯化甲烷废物并减少危险排放。该奖项由燃烧和等离子体系统计划和实验物理化学计划共同支持。

AbstractCTS-0105239V. Knyazev, Catholic UniversityIn this study the kinetics and mechanisms of reactions of chlorinated hydrocarbon radicals is studied over wide ranges of temperature and pressure using the laser photolysis/ photoionization mass spectrometry (LP/PIMS) technique. Particular systems investigated include (1) reactions of chlorinated radicals (CH2, Cl, CHCl2, CCl3) with methyl (CH3); (2) reactions of chlorinated methyl radicals with molecular oxygen (O2) at high temperatures; and (3) the unimolecular decompositions of C2Cl3 and delocalized chlorinated hydrocarbon radicals, as well as their reactions with O2, oxygen atoms, and chlorine (Cl2). Experimental kinetic results are analysis using transition-state theory, RRKM, and Master Equation approaches.The information generated in this effort will lead to improved models of combustion of chlorinated hydrocarbons (CHCs). This should enable more efficient incineration of CHC waste and reduction of hazardous emissions. This award is support jointly by the Combustion and Plasma Systems Program and the Experimental Physical Chemistry Program.