Water Vapor Dependence of the Reaction Kinetics of the Methylperoxyl Radical with Hydroperoxyl and Itself

甲基过氧自由基与氢过氧及其本身的反应动力学的水蒸气依赖性

• 批准号: 0631167
• 负责人: Jaron Hansen
• 金额: $ 24.95万
• 依托单位: Brigham Young University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-10-01 至 2009-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0631167&HistoricalAwards=false
• 关键词: Water; Vapor; Dependence; Reaction; Kinetics

Experimental investigation of the kinetics of the methylperoxyl + hydoperoxyl (CH3O2 + HO2) and methylperoxyl self-reaction as a function of pressure and water vapor will be conducted. Laser Flash Photolysis/UV Time-Resolved/Near-IR Wavelength Modulated Diode Laser Spectroscopy will be utilized to measure the kinetics and products of the title reactions over a range of atmospherically relevant conditions (220-298 K, 50-760 Torr). The equilibrium constant for the formation of a CH3O2-H2O complex will be measured between 220 and 298 K and at pressures ranging between 50 and 760 Torr. Results of the water dependence on the reactions will be used to address discrepancies between modeled and measured values of HOx (OH, HO2 and H2O2) and organic peroxides in the upper troposphere. In addition, the work in this proposal will generate data about the role of water in the kinetics of atmospherically important reactions. Critical to the understanding of the atmospheric implications of hydrated CH3O2 is a measurement of its abundance in the atmosphere; data on the equilibrium constant will help to predict this abundance.This project will provide research and training opportunities for both graduate and undergraduate students. A gas phase kinetics experiment will be designed and introduced into the undergraduate physical chemistry curriculum.

将进行甲基过氧化氢 + 氢过氧化氢 (CH3O2 + HO2) 和甲基过氧化氢自反应动力学随压力和水蒸气变化的实验研究。激光闪光光解/紫外时间分辨/近红外波长调制二极管激光光谱将用于测量标题反应在一系列大气相关条件（220-298 K，50-760 Torr）下的动力学和产物。 CH3O2-H2O 复合物形成的平衡常数将在 220 至 298 K 之间以及 50 至 760 Torr 的压力范围内测量。水对反应的依赖性结果将用于解决对流层上层 HOx（OH、HO2 和 H2O2）和有机过氧化物的建模值和测量值之间的差异。此外，该提案中的工作将生成有关水在大气重要反应动力学中的作用的数据。要了解水合 CH3O2 对大气的影响，关键在于测量其在大气中的丰度；有关平衡常数的数据将有助于预测这种丰度。该项目将为研究生和本科生提供研究和培训机会。将设计气相动力学实验并将其引入本科生物理化学课程中。