DOI: 10.1016/j.atmosenv.2018.03.002
Scopus记录号: 2-s2.0-85042916717
论文题名: Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update
作者: Bedjanian Y ; , Morin J ; , Romanias M ; N
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2018
卷: 180 起始页码: 167
结束页码: 172
语种: 英语
英文关键词: Alkyl nitrates
; Atmospheric lifetime
; Kinetics
; OH
; Structure-activity relationship (SAR)
Scopus关键词: Abstracting
; Atmospheric structure
; Atoms
; Carbon
; Chemical reactions
; Enzyme kinetics
; Free radicals
; Kinetics
; Phase interfaces
; Rate constants
; Structures (built objects)
; Alkyl nitrates
; Atmospheric lifetime
; Gas-phase reactions
; H-atom abstraction
; Pseudo-first-order
; Quadrupole mass spectrometer
; Structure-activity relationships
; Tropospheric lifetime
; Nitrates
; 1 hexyl nitrate
; 2 methyl 1 butyl nitrate
; aldehyde
; helium
; hydrogen
; hydroxyl radical
; neopentyl nitrate
; nitrate
; nitric acid derivative
; trimethylacetaldehyde
; unclassified drug
; chemical compound
; chemical reaction
; data processing
; experimental study
; gas phase reaction
; hydroxyl radical
; reaction kinetics
; Article
; atmosphere
; decomposition
; gas
; priority journal
; rate constant
; structure activity relation
; temperature dependence
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 kinetics of the reactions 2-methyl-1-butyl (2M1BNT), neopentyl (NPTNT) and 1-hexyl nitrates (1HXNT) with OH radicals has been studied using a low pressure flow tube reactor combined with a quadrupole mass spectrometer. The rate constants of the title reactions were determined under pseudo-first order conditions from kinetics of OH consumption in excess of nitrates. The overall rate coefficients, k2M1BNT = 1.54 × 10−14 (T/298)4.85 exp (1463/T) (T = 278–538 K), kNPTNT = 1.39 × 10−14 (T/298)4.89 exp (1189/T) (T = 278–500 K) and k1HXNT = 2.23 × 10−13 (T/298)2.83 exp (853/T) cm3molecule−1s−1 (T = 306–538 K) (with conservative 15% uncertainty), were determined at a total pressure of 1 Torr of helium. The yield of trimethylacetaldehyde ((CH3)3CCHO), resulting from the abstraction by OH of an α-hydrogen atom in neopentyl nitrate, followed by α-substituted alkyl radical decomposition, was determined as 0.31 ± 0.06 at T = 298 K. The calculated tropospheric lifetimes of 2M1BNT, NPTNT and 1HXNT indicate that reaction of these nitrates with OH represents an important sink of these compounds in the atmosphere. Based on the available kinetic data, we have updated the structure-activity relationship (SAR) for reactions of alkyl nitrates with OH at T = 298 K. Good agreement (within 20%) is obtained between experimentally measured rate constants (total and that for H-atom abstraction from α carbon) and those calculated from SAR using new substituents factors for almost all the experimental data available. © 2018 Elsevier Ltd Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/82902
Appears in Collections: 气候变化事实与影响
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作者单位: Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS, Université D'Orléans, Orléans Cedex 2, France; Aix Marseille Universite, CNRS, LCE, Marseille, France; IMT Lille Douai, SAGE, Douai, France
Recommended Citation:
Bedjanian Y,, Morin J,, Romanias M,et al. Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update[J]. Atmospheric Environment,2018-01-01,180