DOI: 10.1016/j.atmosenv.2017.07.038
Scopus记录号: 2-s2.0-85026243281
论文题名: Experimental and theoretical investigations of the kinetics and mechanism of the Cl + 4-hydroxy-4-methyl-2-pentanone reaction
作者: Aslan L ; , Priya A ; M ; , Sleiman C ; , Zeineddine M ; N ; , Coddeville P ; , Fittschen C ; , Ballesteros B ; , Canosa A ; , Senthilkumar L ; , El Dib G ; , Tomas A
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2017
卷: 166 起始页码: 315
结束页码: 326
语种: 英语
英文关键词: Chlorine
; DFT method
; Hydroxyketone
; Lifetime
; Oxygenated
Scopus关键词: Abstracting
; Atoms
; Borosilicate glass
; Chlorine
; Environmental chambers
; Ketones
; Polyols
; Reaction kinetics
; 4-hydroxy-4-methyl-2-pentanone
; Density functional theory methods
; DFT method
; Hydroxyketone
; Lifetime
; Oxygenated
; Small-curvature tunneling methods
; Structure-reactivity relationships
; Density functional theory
; 4 hydroxy 4 methyl 2 pentanone
; 4 methyl 2 pentanone
; acetic acid
; chloride
; formaldehyde
; unclassified drug
; carbon monoxide
; chlorine
; experimental apparatus
; experimental study
; glass
; hydrogen
; ketone
; polymer
; quantum mechanics
; reaction kinetics
; theoretical study
; absorption
; Article
; atom
; calculation
; density functional theory
; kinetics
; measurement
; priority journal
; room temperature
; structure activity relation
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 reaction of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) with Cl atoms was studied for the first time experimentally and theoretically. Relative kinetic measurements were carried out at room temperature and 1 bar of synthetic air/N2 in two different environmental chambers: a 300 L Teflon bag and a 16 L borosilicate glass cell. Reactants, reference compounds and products were monitored either by IR absorption or by GC-FID. Theoretical calculations were performed using the density functional theory method at BH&HLYP level of theory for twelve hydrogen abstraction pathways. The individual rate coefficients for the most favorable H-abstraction pathways were calculated by canonical variational theory using small curvature tunneling method at 298 K. An average experimental rate coefficient of (7.4 ± 0.6) × 10−11 cm3 molecule−1 s−1 was obtained at 298 K, in good agreement with the theoretical rate coefficient. The branching ratios for each reaction channel were evaluated theoretically from the individual rate coefficients of the identified channels. The H-atom abstracted on the –CH2 group appeared to be the dominant channel with a small barrier height. Formaldehyde, acetic acid, HCl, CO2 and CO were identified by IR as the major primary products. The obtained results are presented and discussed in terms of structure-reactivity relationships. A mechanism is suggested for the formation of the observed products. The atmospheric implications of the studied reaction are presented and more particularly, the lifetime of 4H4M2P towards Cl atoms is evaluated to be about 3 days. © 2017 Elsevier Ltd
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资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/82704
Appears in Collections: 气候变化事实与影响
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作者单位: Institut Mines-Télécom (IMT) Lille Douai, Université de Lille, Département Sciences de l'Atmosphère et Génie de l'Environnement (SAGE), Lille, France; Department of Physics, Bharathiar University, Coimbatore, Tamil Nadu, India; Institut de Physique de Rennes, UMR 6251 du CNRS - Université de Rennes 1, Bat. 11C, Campus de Beaulieu, 263 Avenue du Général Leclerc, Rennes Cedex, France; Université de Lille, CNRS, UMR 8522 – PC2A, PhysicoChimie des Processus de Combustion et de l'Atmosphère, Lille, France; Departamento de Química Física, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla - La Mancha, Campus Universitario, Ciudad Real, Spain
Recommended Citation:
Aslan L,, Priya A,M,et al. Experimental and theoretical investigations of the kinetics and mechanism of the Cl + 4-hydroxy-4-methyl-2-pentanone reaction[J]. Atmospheric Environment,2017-01-01,166