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Effect of CH3OOH on the atmospheric concentration of OH radicals
作者姓名:WANG Caixia  CHEN Zhongming
作者单位:The State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, China
摘    要:Methyl hydroperoxide (CH3OOH, MHP) is known to be a significant sink and reservoir of HOx and ROx radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×105 Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O3 in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10-12 cm3?molecule-1?s-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.

关 键 词:OH  radicals    methyl  hydroperoxide    rate  coefficient    UV  photolysis    gas-phase  reaction    LP-FTIR

Effect of CH3OOH on the atmospheric concentration of OH radicals
Authors:WANG Caixia  CHEN Zhongming
Institution:The State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, China
Abstract:Methyl hydroperoxide (CH3OOH, MHP) is known to be a significant sink and reservoir of HOx and ROx radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×105 Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O3 in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10-12 cm3?molecule-1?s-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.
Keywords:OH radicals  methyl hydroperoxide  rate coefficient  UV photolysis  gas-phase reaction  LP-FTIR
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