DOI: 10.1016/j.atmosenv.2014.02.062
Scopus记录号: 2-s2.0-84895957659
论文题名: H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature
作者: Berndt T ; , Jokinen T ; , Sipilä M ; , Mauldin R ; L ; , Herrmann H ; , Stratmann F ; , Junninen H ; , Kulmala M
刊名: Atmospheric Environment
ISSN: 0168-2563
EISSN: 1573-515X
出版年: 2014
卷: 89 起始页码: 603
结束页码: 612
语种: 英语
英文关键词: CI-APi-TOF mass spectrometry
; Criegee Intermediate
; Gas-phase ozonolysis
; Stabilization
Scopus关键词: Acetaldehyde
; Acetone
; Atmospheric pressure
; Butenes
; Free radicals
; Mass spectrometry
; Ozone
; Phase interfaces
; Reaction kinetics
; Stabilization
; Sulfur dioxide
; Water vapor
; 2 ,3-dimethyl-2-butene
; Alkene ozonolysis
; Criegee intermediates
; Gas-phase ozonolysis
; Gas-phase reactions
; Influence of water
; Rate coefficients
; Rising temperatures
; Reaction intermediates
; 2,3 dimethyl 2 butene
; acetaldehyde oxide
; acetone oxide
; criegee intermediate
; hydroxyl radical
; nitrite
; oxide
; sulfur dioxide
; sulfuric acid
; trans 2 butene
; unclassified drug
; acetaldehyde
; acetone
; atmospheric pressure
; decomposition
; gas phase reaction
; hydroxyl radical
; mass spectrometry
; oxidation
; ozone
; stabilization
; sulfur dioxide
; water vapor
; article
; atmospheric pressure
; chemical ionization atmospheric pressure interface time of flight mass spectrometry
; chemical structure
; controlled study
; decomposition
; molecular stability
; ozonolysis
; priority journal
; reaction analysis
; temperature sensitivity
; time of flight mass spectrometry
; water temperature
; water vapor
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 importance of gas-phase products from alkene ozonolysis other than OH radicals, most likely stabilized Criegee Intermediates (sCI), for the process of atmospheric SO2 oxidation to H2SO4 has been recently discovered. Subjects of this work are investigations on H2SO4 formation as a function of water vapour content (RH=2-65%) and temperature (278-343K) starting from the ozonolysis of trans-2-butene and 2,3-dimethyl-2-butene (TME). H2SO4 production other than via the OH radical reaction was attributed to the reaction of SO2 with sCI, i.e. acetaldehyde oxide arising from trans-2-butene ozonolysis and acetone oxide from TME. Measurements have been conducted in an atmospheric pressure flow tube using NO3--CI-APi-TOF mass spectrometry for H2SO4 detection. The sCI yields derived from H2SO4 measurements at 293K were 0.49±0.22 for acetaldehyde oxide and 0.45±0.20 for acetone oxide. Our findings indicate a H2SO4 yield from sCI+SO2 of unity or close to unity. The deduced rate coefficient ratio for the reaction of sCI with H2O and SO2, k(sCI+H2O)/k(sCI+SO2), was found to be strongly dependent on the structure of the Criegee Intermediate, for acetaldehyde oxide at 293K: (8.8±0.4)·10-5 (syn- and anti-conformer in total) and for acetone oxide: <4·10-6. H2SO4 formation from sCI was pushed back with rising temperature in both reaction systems most probably due to an enhancement of sCI decomposition. The ratio k(dec)/k(sCI+SO2) increased by a factor of 34 (acetone oxide) increasing the temperature from 278 to 343K. In the case of acetaldehyde oxide the temperature effect is less pronounced. The relevance of atmospheric H2SO4 formation via sCI+SO2 is discussed in view of its dependence on the structure of the Criegee Intermediate. © 2014 Elsevier Ltd. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/80899
Appears in Collections: 气候变化事实与影响
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作者单位: Leibniz-Institute for Tropospheric Research (TROPOS), 4318 Leipzig, Germany; Department of Physics, University of Helsinki, Finland; University of Colorado at Boulder, Boulder, CO, United States
Recommended Citation:
Berndt T,, Jokinen T,, Sipilä M,et al. H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature[J]. Atmospheric Environment,2014-01-01,89