GSTDTAP  > 地球科学
DOI10.1073/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
ISSN0027-8424
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
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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
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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.
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