Global S&T Development Trend Analysis Platform of Resources and Environment
DOI | 10.1073/pnas.1715540115 |
Atmospheric autoxidation is increasingly important in urban and suburban North America | |
Praske, Eric1; Otkjaer, Rasmus V.2; Crounse, John D.3; Hethcox, J. Caleb1; Stoltz, Brian M.1; Kjaergaard, Henrik G.2; Wennberg, Paul O.3,4 | |
2018-01-02 | |
发表期刊 | PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
![]() |
ISSN | 0027-8424 |
出版年 | 2018 |
卷号 | 115期号:1页码:64-69 |
文章类型 | Article |
语种 | 英语 |
国家 | USA; Denmark |
英文摘要 | Gas-phase autoxidation-regenerative peroxy radical formation following intramolecular hydrogen shifts-is known to be important in the combustion of organic materials. The relevance of this chemistry in the oxidation of organics in the atmosphere has received less attention due, in part, to the lack of kinetic data at relevant temperatures. Here, we combine computational and experimental approaches to investigate the rate of autoxidation for organic peroxy radicals (RO2) produced in the oxidation of a prototypical atmospheric pollutant, n-hexane. We find that the reaction rate depends critically on the molecular configuration of the RO2 radical undergoing hydrogen transfer (H-shift). RO2 H-shift rate coefficients via transition states involving six- and seven-membered rings (1,5 and 1,6 H-shifts, respectively) of alpha-OH hydrogens (HOC-H) formed in this system are of order 0.1 s(-1) at 296 K, while the 1,4 H-shift is calculated to be orders of magnitude slower. Consistent with H-shift reactions over a substantial energetic barrier, we find that the rate coefficients of these reactions increase rapidly with temperature and exhibit a large, primary, kinetic isotope effect. The observed H-shift rate coefficients are sufficiently fast that, as a result of ongoing NOx emission reductions, autoxidation is now competing with bimolecular chemistry even in the most polluted North American cities, particularly during summer afternoons when NO levels are low and temperatures are elevated. |
英文关键词 | atmospheric chemistry air pollution autoxidation |
领域 | 地球科学 ; 气候变化 ; 资源环境 |
收录类别 | SCI-E |
WOS记录号 | WOS:000419128700028 |
WOS关键词 | SECONDARY ORGANIC AEROSOL ; HYDROGEN SHIFT REACTIONS ; OXIDIZED RO2 RADICALS ; PEROXY-RADICALS ; ALPHA-PINENE ; PARTICLE FORMATION ; MULTIFUNCTIONAL COMPOUNDS ; NONMETHANE HYDROCARBONS ; OZONOLYSIS PRODUCTS ; MASS-SPECTROMETRY |
WOS类目 | Multidisciplinary Sciences |
WOS研究方向 | Science & Technology - Other Topics |
URL | 查看原文 |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/204870 |
专题 | 地球科学 资源环境科学 气候变化 |
作者单位 | 1.CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA; 2.Univ Copenhagen, Dept Chem, DK-2100 Copenhagen, Denmark; 3.CALTECH, Div Geol & Planetary Sci, Pasadena, CA 91125 USA; 4.CALTECH, Div Engn & Appl Sci, Pasadena, CA 91125 USA |
推荐引用方式 GB/T 7714 | Praske, Eric,Otkjaer, Rasmus V.,Crounse, John D.,et al. Atmospheric autoxidation is increasingly important in urban and suburban North America[J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,2018,115(1):64-69. |
APA | Praske, Eric.,Otkjaer, Rasmus V..,Crounse, John D..,Hethcox, J. Caleb.,Stoltz, Brian M..,...&Wennberg, Paul O..(2018).Atmospheric autoxidation is increasingly important in urban and suburban North America.PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA,115(1),64-69. |
MLA | Praske, Eric,et al."Atmospheric autoxidation is increasingly important in urban and suburban North America".PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 115.1(2018):64-69. |
条目包含的文件 | 条目无相关文件。 |
除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。
修改评论