DOI: 10.1016/j.atmosenv.2017.08.011
Scopus记录号: 2-s2.0-85029353667
论文题名: Anthracene and phenanthrene tropospheric oxidation promoted by the nitrate radical in the gas-phase. Theoretical modelistic study
作者: Maranzana A ; , Ghigo G ; , Tonachini G
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2017
卷: 167 起始页码: 181
结束页码: 189
语种: 英语
英文关键词: Anthracene
; DFT
; Gas-phase
; Mechanism
; Nitrate radical
; NO3
; Phenanthrene
; Tropospheric oxidation
Scopus关键词: Anthracene
; Atmospheric chemistry
; Density functional theory
; Free energy
; Gases
; Ground state
; Ketones
; Mechanisms
; Nitrates
; Nitrogen compounds
; Nitrogen oxides
; Oxidation
; Polycyclic aromatic hydrocarbons
; Reaction intermediates
; Troposphere
; Bimolecular reaction
; Environmental pollutants
; Gasphase
; Nitrate radicals
; Oxidative degradation
; Phenanthrene
; Radical coupling
; Radical-adducts
; Aromatic hydrocarbons
; anthracene
; ketone
; nitrate
; nitric oxide
; oxygen
; peroxy radical
; phenanthrene
; aldehyde
; atmospheric chemistry
; chemical pollutant
; concentration (composition)
; gas phase reaction
; ketone
; nitrate
; oxidation
; PAH
; phenanthrene
; radical
; troposphere
; Article
; density functional theory
; gas
; oxidation
; priority journal
; theoretical model
; 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: Polycyclic aromatic hydrocarbons and their oxidized derivatives are ubiquitous environmental pollutants that are toxic to different degrees. The NO3 radical is known to be an important actor in fostering nighttime atmospheric chemistry; hence it could elicit some nocturnal PAH-loss processes. In this study the gas phase pathways open to the initial anthracene and phenanthrene NO3 π−radical adducts in the presence of O2, NO and NO2 are examined by Density Functional Theory to ascertain the mechanistic features of their NO3-initiated oxidative degradation. Unimolecular steps involving the initial adducts (ring closures or fragmentation) present rather high free energy barriers and seem unlikely. Regarding bimolecular reactions, any radical present in the tropospheric environment can give an intrinsically fast radical coupling with the initial adducts, thus producing bifunctional closed shell species. The addition of ground state dioxygen is a relatively fast step that is reversible in some cases, less so in others. It entails subsequent reaction steps, which involve the peroxyl radical intermediate and addition and loss of small species as NO, NO3, NO2 and O2. These steps can either trigger a β−fragmentation with formation of a closed shell dialdehyde or formation of a closed shell nitroxy ketone, bifunctional species that appear to be the most likely products when typical tropospheric concentrations are taken into account. © 2017 Elsevier Ltd Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/82699
Appears in Collections: 气候变化事实与影响
There are no files associated with this item.
作者单位: Dipartimento di Chimica, Università di Torino, Corso Massimo D'Azeglio 48, Torino, Italy
Recommended Citation:
Maranzana A,, Ghigo G,, Tonachini G. Anthracene and phenanthrene tropospheric oxidation promoted by the nitrate radical in the gas-phase. Theoretical modelistic study[J]. Atmospheric Environment,2017-01-01,167