Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

被引:9
作者
Newland, Mike J. [1 ,7 ]
Mouchel-Vallon, Camille [1 ,8 ]
Valorso, Richard [2 ,3 ]
Aumont, Bernard [2 ,3 ]
Vereecken, Luc [4 ]
Jenkin, Michael E. [5 ]
Rickard, Andrew R. [1 ,6 ]
机构
[1] Univ York, Dept Chem, Wolfson Atmospher Chem Labs, York, N Yorkshire, England
[2] Univ Paris Est Creteil, F-94010 Creteil, France
[3] Univ Paris, CNRS, LISA, F-94010 Creteil, France
[4] Forschungszentrum Julich, Inst Energy & Climate, IEK 8 Troposphere, D-52428 Julich, Germany
[5] Atmospher Chem Serv, Okehampton EX20 4QB, Devon, England
[6] Univ York, Natl Ctr Atmospher Sci, Wolfson Atmospher Chem Labs, York, N Yorkshire, England
[7] ICARE CNRS, 1 C Ave Rech Sci, F-45071 Orleans 2, France
[8] Univ Toulouse, CNRS, Lab Aerol, UPS, Toulouse, France
基金
英国自然环境研究理事会;
关键词
OZONOLYSIS REACTION; PRODUCTS; KINETICS; O-3; OH; REACTIVITY; OXIDATION; ISOPRENE; CLEAVAGE; SERIES;
D O I
10.5194/acp-22-6167-2022
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely the primary carbonyl/CI yields from the primary ozonide fragmentation, the amount of stabilisation of the excited CI, the unimolecular decomposition pathways, rates and products of the CI, and the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene-ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates of OH, SCI and carbonyl yields with root mean square errors of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.
引用
收藏
页码:6167 / 6195
页数:29
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