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

将进行甲基过氧基+羟基过氧基（CH_3 O_2 + HO_2）和甲基过氧基自身反应作为压力和水蒸气的函数的动力学的实验研究。激光闪光光解/UV时间分辨/近红外波长调制二极管激光光谱法将用于测量在大气相关条件（220-298 K，50-760 Torr）范围内标题反应的动力学和产物。将在220和298 K之间以及在50和760 Torr之间的压力范围内测量形成CH 3 O2-H2O络合物的平衡常数。水依赖于反应的结果将被用来解决模拟和测量值之间的差异HOx（OH，HO 2和H2 O2）和有机过氧化物在对流层上部。此外，该提案中的工作将产生关于水在大气重要反应动力学中的作用的数据。对理解水合CH 3 O2的大气影响至关重要的是测量其在大气中的丰度;关于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。设计了一个气相动力学实验，并将其引入到本科物理化学课程中。

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.