DOI: 10.1016/j.atmosenv.2014.03.061
Scopus记录号: 2-s2.0-84897945873
论文题名: Reactivity of hydrohaloethers with OH radicals and chlorine atoms: Correlation with molecular properties
作者: Dalmasso P ; R ; , Taccone R ; A ; , Nieto J ; D ; , Cometto P ; M ; , Cobos C ; J ; , Lane S ; I
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2014
卷: 91 起始页码: 104
结束页码: 109
语种: 英语
英文关键词: Bond dissociation energies
; Gas-phase rate coefficients
; Hydrochloroethers
; Ionization potentials
; Structure-reactivity correlation
; Tropospheric chemistry
Scopus关键词: Atoms
; Chemical bonds
; Chlorine
; Free radicals
; Halogenation
; Ionization potential
; Bond dissociation energies
; Hydrochloroethers
; Rate coefficients
; Structure reactivity
; Tropospheric chemistry
; Ethers
; chlorine
; ether derivative
; flurothyl
; hydrogen
; hydroxyl radical
; atmospheric chemistry
; chlorine
; ether
; hydroxyl radical
; ionization
; molecular analysis
; troposphere
; article
; chemical structure
; controlled study
; density functional theory
; dissociation
; hydrogen bond
; ionization
; molecular dynamics
; physical chemistry
; priority journal
; quantum chemistry
; room temperature
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 reactivity of halogenated ethers, especially hydrochloroethers, with hydroxyl radicals and chlorine atoms was studied by correlating the room-temperature rate coefficients with both the C-H bond dissociation energies and the vertical ionization potentials of the parent molecules. These molecular properties were estimated at the composite G3B3 level of theory. The results suggest that Cl-substituted ethyl-methyl-ethers and ethyl-ethyl-ethers at the β-position tend to raise the activating effect of the ether linkage -O- and to enhance the possibility of the abstraction of H atoms bonded to α-carbon. Derived relationships between the rate coefficients (in cm3molecule-1s-1) and ionization potentials (in eV): log kOH=-(1.248±0.065) IP+(1.06±0.73) and log kCl=-(1.46±0.12) IP+(4.5±1.3) allows, in average, to estimate rate coefficients within a factor of 2-3. The atmospheric implications of halogenated and hydrogenated ethers are briefly discussed on the basis of their estimated global lifetimes. © 2014 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/81260
Appears in Collections: 气候变化事实与影响
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作者单位: Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC) CONICET, Centro Láser de Ciencias Moleculares and Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CONICET and Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Casilla de Correo 16, Sucursal 4, 1900 La Plata, Argentina
Recommended Citation:
Dalmasso P,R,, Taccone R,et al. Reactivity of hydrohaloethers with OH radicals and chlorine atoms: Correlation with molecular properties[J]. Atmospheric Environment,2014-01-01,91