| DOI: | 10.1016/j.atmosenv.2014.09.066
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| Scopus记录号: | 2-s2.0-84908008117
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| 论文题名: | Reaction kinetics of Cl atoms with limonene: An experimental and theoretical study |
| 作者: | Dash M; R; , Rajakumar B
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| 刊名: | Atmospheric Environment
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| ISSN: | 0168-2563
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| EISSN: | 1573-515X
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| 出版年: | 2014
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| 卷: | 99 | | 起始页码: | 183
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| 结束页码: | 195
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| 语种: | 英语
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| 英文关键词: | Atmospheric lifetime
; Cl atoms
; Conventional transition-state theory (CTST)
; Limonene
; Rate coefficient
; Relative rate technique
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| Scopus关键词: | Atmospheric lifetime
; Cl atoms
; Limonene
; Rate coefficients
; Relative rate techniques
; Transition state theories
; 1 pentene
; 1,3 butadiene
; chloride
; chlorine
; limonene
; nonane
; organic compound
; oxalyl chloride
; unclassified drug
; chlorine
; error analysis
; estimation method
; hydrocarbon
; reaction kinetics
; theoretical study
; uncertainty analysis
; ab initio calculation
; analytical equipment
; analytical error
; Article
; atom
; chemical reaction kinetics
; controlled study
; conventional transition state theory
; experimental study
; flame ionization detector
; gas chromatograph
; molecular size
; molecule
; photolysis
; quantitative analysis
; temperature
; theoretical study
; theory
; ultraviolet radiation
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| Scopus学科分类: | Environmental Science: Water Science and Technology
; Earth and Planetary Sciences: Earth-Surface Processes
; Environmental Science: Environmental Chemistry
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| 英文摘要: | Rate coefficients for the reaction of Cl atoms with limonene (C10H16) were measured between 278-350K and 800Torr of N2, using the relative rate technique, with 1,3-butadiene (C4H6), n-nonane (C9H20), and 1-pentene (C5H10) as reference compounds. Cl atoms were generated by UV photolysis of oxalyl chloride ((COCl)2) at 254nm. A gas chromatograph equipped with a flame ionization detector (GC-FID) was used for quantitative analysis of the organics. The rate coefficient for the reaction of Cl atoms with limonene at 298K was measured to be (8.65±2.44)×10-10cm3molecule-1s-1. The rate coefficient is an average value of the measurements, with two standard deviations as the quoted error, including uncertainties in the reference rate coefficients. The kinetic data obtained over the temperature range of 278-350K were used to derive the following Arrhenius expression: k(T)=(9.75±4.1)×10-11exp[(655±133)/T]cm3molecule-1s-1. Theoretical kinetic calculations were also performed for the title reaction using conventional transition state theory (CTST) in combination with G3(MP2) theory between 275 and 400K. The kinetic data obtained over the temperature range of 275-400K were used to derive an Arrhenius expression: k(T)=(7.92±0.82)×10-13exp[(2310±34)/T]cm3molecule-1s-1. The addition channels contributes maximum to the total reaction and H-abstraction channels can be neglected in the range of studied pressures. The Atmospheric lifetime (τ) of limonene due to its reaction with Cl atoms was estimated and concluded that the reaction with chlorine atoms can be an effective tropospheric loss pathway in the marine boundary layer and in coastal urban areas. © 2014. |
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| 资源类型: | 期刊论文
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| 标识符: | http://119.78.100.158/handle/2HF3EXSE/80608
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| Appears in Collections: | 气候变化事实与影响
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作者单位: | Department of Chemistry, Indian Institute of Technology Madras, Chennai, India
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| Recommended Citation: | |
Dash M,R,, Rajakumar B. Reaction kinetics of Cl atoms with limonene: An experimental and theoretical study[J]. Atmospheric Environment,2014-01-01,99
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