Heterogeneous Oxidations of Organic Molecules: Mechanisms & Dynamics

在化学系有机动力学项目的支持下，位于博尔德的科罗拉多大学的Barney Ellison教授将探索烃膜在固/气界面和液/气界面的反应性。这些实验旨在鉴定介导烃膜氧化的反应性自由基。将产生必须彻底表征的烷基过氧自由基ROO。埃里森计划使用超高温超音速射流来产生CH 3CH 2自由基的光束，并产生基质隔离的乙基过氧自由基CH 3CH 2 OO。将完全研究基质隔离的EtO自由基的偏振红外光谱。气溶胶结合的过氧自由基的一个重要命运将是与NO反应，然后裂解为NO2和烷氧基自由基，或异构化为硝酸烷基酯。因此，Ellison建议在基质中产生CH 3 OO-NO加合物，并使用FTIR来探索其性质。与D博士合作。在能源部的EMSL实验室，埃里森将使用钛：蓝宝石激光器，通过二次谐波产生（SGH）的非线性光学过程，在液体/大气压力界面检测表面结合的过氧自由基。SHG实验将在水溶液和空气之间的界面处寻找ROO自由基。与B教授合作。Ellison教授计划探索烯烃膜与O3的氧化，并研究烯烃与O3在界面处氧化的机理。在O3与烯烃薄膜的研究中，Ellison Koel将生产最简单的Criegee中间体CH 2 OO的样品，并使用FITR在基质中进行研究。这里提出的实验研究的排序将提供一个基础，理论家预测和模拟真实的气溶胶和了解碳氢化合物膜的氧化机制在环境中。有机和大分子化学计划支持教授巴尼埃里森在博尔德的科罗拉多大学谁有着悠久的历史，与其他化学家的联合研究工作。埃里森的实验室定期与NOAA的Aeronomy Labs和NSF的NCAR实验室的大气化学家合作。反胶束模型是与V. Vaida（科罗拉多大学）和A.塔克（NOAA），并受到NOAA的实地数据的启发。埃里森继续与化学家研究生物质燃烧在美国能源部的NREL实验室在戈尔登，CO和表面化学家在美国能源部的EMSL实验室在里士满，华盛顿州和南加州大学在加利福尼亚州。所有这些小组都在研究与对流层挥发性有机化合物（VOC）的命运，大气中有机气溶胶的化学分析和动力学，以及气/固和气/液界面的化学和光谱特性有关的超复杂化学问题。埃里森和他的学生为这些实验室提供了一个“有机化学观点”。"

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Barney Ellison at the University of Colorado at Boulder will explore the reactivity of hydrocarbon films at a solid/gas interface and at a liquid/gas interface. These experiments are aimed at the identification of reactive radicals that mediate the oxidation of hydrocarbon films. Alkylperoxyl radicals, ROO, will be produced that must be thoroughly characterized. Ellison plans to use hyperthermal supersonic jets to produce beams of the CH3CH2 radical and to generate matrix-isolated ethylperoxyl radicals, CH3CH2OO. The polarized infrared spectroscopy of matrix-isolated EtOO radicals will be completely studied. An important fate of aerosol-bound peroxyl radicals will be reaction with NO followed by either fragmentation to NO2 and an alkoxy radical, or isomerization to an alkyl nitrate. Consequently, Ellison proposes to produce the CH3OO-NO adduct in a matrix and use an FTIR to explore its properties. In collaboration with Dr. D. Ray at the DOE's EMSL labs, Ellison will use a Ti:Sapphire laser to detect surface-bound peroxyl radicals at a liquid/atmospheric pressure interface via the non-linear optical process of second harmonic generation (SGH). The SHG experiment will search for ROO radicals at an interface between an aqueous solution and air. In collaboration with Prof. B. Koel at USC, Professor Ellison plans to explore the oxidation of alkene films with O3 and to study the mechanisms of olefin oxidation with O3 at an interface. In the study of O3 with olefin films, Ellison & Koel will produce samples of the simplest Criegee intermediate, CH2OO, and study it in matrices using FITR. Experimental studies of the sort proposed here will provide a basis for theorists to predict and model real aerosols and to understand the oxidation mechanisms of hydrocarbon films in the environment.The Organic and Macromolecular Chemistry Program supports Professor Barney Ellison at the University of Colorado at Boulder who has a long history of joint research efforts with other chemists. Ellison's lab collaborates regularly with atmospheric chemists at NOAA's Aeronomy Labs and the NSF's NCAR labs. The inverted micelle model was a collaboration with V. Vaida (University of Colorado) and A. Tuck (NOAA) and was inspired by NOAA's field data. Ellison continually works with chemists studying biomass burning at the DOE's NREL labs in Golden, CO and with surface chemists at the DOE's EMSL labs in Richmond, WA and at USC in Calif. All of these groups are pursuing hypercomplex chemical problems having to do with the tropospheric fate of volatile organic compounds (VOCs), the chemical analysis and dynamics of organic aerosols in the atmosphere, and the chemical and spectroscopic properties of gas/solid and gas/liquid interfaces. Ellison and his students provide these labs with an "organic chemistry point-of-view."