DOI: 10.1016/j.atmosenv.2014.03.036
Scopus记录号: 2-s2.0-84897533288
论文题名: Estimation of gas-phase rate coefficients for the reactions of a series of α,β-unsaturated esters with OH, NO3, O3 and Cl
作者: Gallego-Iniesta M ; P ; , Cabañas B ; , Salgado S ; , Martínez E ; , Martín P
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2014
卷: 90 起始页码: 133
结束页码: 145
语种: 英语
英文关键词: Atmospheric oxidants
; Estimation methods
; Group-reactivity factors
; Rate coefficients
; SAR method
; α,β-Unsaturated esters
Scopus关键词: Atmospheric chemistry
; Atoms
; Chlorine
; Esterification
; Esters
; Free radicals
; Molecules
; Oxidants
; Atmospheric oxidants
; Estimation methods
; Group-reactivity factors
; Rate coefficients
; SAR method
; Unsaturated esters
; Estimation
; acrylic acid butyl ester
; acrylic acid ethyl ester
; acrylic acid methyl ester
; chlorine
; ester
; hydroxyl radical
; methacrylic acid methyl ester
; nitrate
; oxidizing agent
; ozone
; chloride
; estimation method
; gas phase reaction
; hydroxyl radical
; nitrate
; oxidant
; ozone
; physicochemical property
; article
; atmosphere
; atom
; chemical reaction kinetics
; gas
; physical chemistry
; priority journal
; 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: Rate coefficients for reactions of a series of α,β-unsaturated esters with OH and NO3 radicals, O3 and Cl atoms have been estimated using different methods: i.e., physico-chemical correlations and Structure Activity Relationships (SARs). In this study new correlations to estimate rate coefficients have been proposed (only for α,β-unsaturated esters): logkNO3=(13.9±2.8)+(2.75±0.26)×log (kOH); log (kOH)=(4.93±1.14)+(1.60±0.12)×log (kCl); ln(kOH/cm3molecule-1s-1)= (1.71±0.21)×EHOMO/eV-(6.25±2.24); ln(kNO3/cm3molecule-1s-1)=(5.94±0.35)×EHOMO/eV+(27.87±3.65); ln(kO3/cm3molecule-1s-1)=(2.20±0.63)×EHOMO/eV-(16.75±6.65) and ln(kCl/cm3molecule-1s-1)=(0.21±0.23)×(EHOMO)/eV-(19.8±2.4). The group reactivity factors necessary to estimate the rate coefficients by SAR methods have also been calculated for a series of α,β-unsaturated esters for the first time: f(-C(O)O(CH2)3CH3), f(-C(O)O(CH2)5CH3), f(-C(O)OCH2CH(CH2CH3)CH2CH2CH2CH3) for reactions with the NO3 radical, OH radical and O3. Furthermore, f(-C(O)OCH3), f(-C(O)OCH2CH3), f(-C(O)O(CH2)3CH3), f(-C(O)OCH2CH2CH2CH2CH2CH3), f(-C(O)OCH2CH(CH2CH3)CH2CH2CH2CH3) for reactions with chlorine atoms have been estimated.The results show that for NO3 and OH radicals these methods are generally satisfactory. In the case of Cl atoms, all methods used in this study reproduce the rate coefficient within a factor of 1.5. In general the best method for estimating the rate coefficient of α,β-unsaturated esters with the main atmospheric oxidants is the correlation of ln k versus EHOMO. © 2014 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/81137
Appears in Collections: 气候变化事实与影响
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作者单位: Departamento de Química Física, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla La Mancha, Avda. Camilo José Cela S/N, 13071Ciudad Real, Spain; Instituto de Combustión y Contaminación Atmosférica (ICCA), Universidad de Castilla La Mancha, Camino Moledores S/N, 13071 Ciudad Real, Spain
Recommended Citation:
Gallego-Iniesta M,P,, Cabañas B,et al. Estimation of gas-phase rate coefficients for the reactions of a series of α,β-unsaturated esters with OH, NO3, O3 and Cl[J]. Atmospheric Environment,2014-01-01,90