DOI: 10.1016/j.atmosenv.2013.10.009
Scopus记录号: 2-s2.0-84887207625
论文题名: Tropospheric oxidation of cyclic unsaturated ethers in the day-time: Comparison of the reactions with Cl, OH and O3 based on the determination of their rate coefficients at 298K
作者: Alwe H ; D ; , Walavalkar M ; P ; , Sharma A ; , Dhanya S ; , Naik P ; D
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2014
卷: 82 起始页码: 113
结束页码: 120
语种: 英语
英文关键词: Rate coefficients
; Reactions with OH, O3 and Cl
; Tropospheric lifetime
; Unsaturated cyclic ethers
Scopus关键词: Cyclic ether
; Dominant pathways
; Good correlations
; HOMO energies
; Marine boundary layers
; Rate coefficients
; Tropospheric lifetime
; Tropospheric oxidants
; Atoms
; Ethers
; Molecules
; Troposphere
; 2,3 dihydrofuran
; 3,4 dihydropyran
; acyclic hydrocarbon substituent
; alkene
; chlorine
; dihydrofuran
; ether derivative
; hydrocarbon
; hydroxide
; oxygen
; ozone
; unclassified drug
; boundary layer
; chlorine
; energy efficiency
; environmental degradation
; ether
; hydroxyl radical
; molecular analysis
; oxidation
; ozone
; troposphere
; article
; atom
; boundary layer
; chemical reaction kinetics
; circadian rhythm
; conjugation
; degradation
; energy
; enthalpy
; molecule
; oxidation
; priority journal
; troposphere
Scopus学科分类: Environmental Science: Water Science and Technology
; Earth and Planetary Sciences: Earth-Surface Processes
; Environmental Science: Environmental Chemistry
英文摘要: The rate coefficients of the reactions of three unsaturated cyclic ethers, 2,5-dihydrofuran (2,5-DHF), 2,3-dihydrofuran (2,3-DHF), and 3,4-dihydropyran (3,4-DHP), with the major day-time tropospheric oxidants - OH (kOH) and O3(kO3), and that of 3,4-DHP with Cl atom (kCl) are determined usingrelativeratemethod, at 298K. The values of kOH are (6.45±1.69), (11.95±2.79) and (11.38±2.64) × 10-11cm3molecule-1s-1 for 2,5-DHF, 2,3-DHF and 3,4-DHP, respectively and kO3 are (1.65±0.31), (443.20±79.0) and (31.36±5.80)×10-17cm3molecule-1s-1 for 2,5-DHF, 2,3-DHF and 3,4-DHP, respectively. The value of kCl for 3,4-DHP is (6.15±0.84)×10-10cm3molecule-1s-1. The dominant pathway of tropospheric degradation of 2,5-DHF is the reaction with OH, whereas that of 2,3-DHF is the reaction with O3. Reaction with both OH and O3 are equally important in the case of 3,4-DHP. Under the conditions of marine boundary layer, the reaction with Cl atom is important in the tropospheric degradation of 2,5-DHF and 3,4-DHP, but insignificant in the case of 2,3-DHF (only 1.8%). The estimated tropospheric lifetimes in the day-time are 2.0, 0.08 and 0.62hfor 2,5-DHF, 2,3-DHF and 3,4-DHP respectively. The presence of O atom, unsaturation, conjugation etc. influences the rate coefficients in a complex manner. However, there is a good correlation of kOH with HOMO energy, which further improves by treating the molecules separately, either as ethers and hydrocarbons, or as cyclic and acyclic molecules. The values of kO3 of these ethers fit very well with the straight line regression derived for simple alkenes with their HOMO energy, except 2,3-DHF, which has a high strain enthalpy. The values of kCl also show a similar trend of increase with HOMO energy, but the correlation is not as good as that of kOH. © 2013 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/81214
Appears in Collections: 气候变化事实与影响
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作者单位: Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India
Recommended Citation:
Alwe H,D,, Walavalkar M,et al. Tropospheric oxidation of cyclic unsaturated ethers in the day-time: Comparison of the reactions with Cl, OH and O3 based on the determination of their rate coefficients at 298K[J]. Atmospheric Environment,2014-01-01,82