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Role of Hydrogen Migrations in Carbonyl Peroxy Radicals in the Atmosphere
Sai-nan Wang1,2, Run-run Wu1, Li-ming Wang*1,3
1.School of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou 510640, China;2.State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Pro- tection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China;3.Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou 510006, China
Abstract:
Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and ∽0.58 s?1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process; while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.
Key words:  Carbonyl peroxy radical, H-migration, Atmospheric oxidation
FundProject:
大气酰基过氧自由基中氢迁移的作用
王赛男1,2, 吴润润1, 王黎明*1,3
1.华南理工大学化学与化工学院,广州 510640;2.中国科学院广州地球化学研究所有机地球化学国家重点实验室,广东省环境资源利用与保护重点实验室,广州 510640;3.广东省大气环境与污染控制重点实验室,广州 510006
摘要:
本文采用量子化学和反应动力学理论计算方法研究了酰基过氧自由基中单分子氢迁移的作用. 计算结果表明至少在CH3CH2CH2C(O)O2和(CH3)2CHCH2C(O)O2自由基中,氢迁移在298 K的速率为∽0.012和∽0.58 s-1,可以与它们在大气中的双分子反应相比较,具有较重要的意义. 在大气环境中,氢迁移生成的CH3CHCH2C(O)OOH自由基在随后的反应中生成具有多官能团的产物,可能影响大气气溶胶的形成;生成的另一个自由基(CH3)2CCH2C(O)OOH则转化为甲醛和丙酮.
关键词:  酰基过氧自由基,氢迁移,大气氧化机理
DOI:10.1063/1674-0068/cjcp1811265
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