Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction
<p>Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for the reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are req...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2018-07-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/18/9329/2018/acp-18-9329-2018.pdf |
| _version_ | 1819068128358825984 |
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| author | M. E. Jenkin M. E. Jenkin R. Valorso B. Aumont A. R. Rickard A. R. Rickard T. J. Wallington |
| author_facet | M. E. Jenkin M. E. Jenkin R. Valorso B. Aumont A. R. Rickard A. R. Rickard T. J. Wallington |
| author_sort | M. E. Jenkin |
| collection | DOAJ |
| description | <p>Reaction with the hydroxyl (OH) radical is the dominant removal process for
volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for
the reactions of OH with VOCs are therefore essential parameters for chemical
mechanisms used in chemistry transport
models, and are required more generally for impact assessments involving
estimation of atmospheric lifetimes or oxidation rates for VOCs. A
structure–activity relationship (SAR) method is presented for the reactions
of OH with aromatic organic compounds, with the reactions of aliphatic
organic compounds considered in the preceding companion paper. The SAR is
optimized using a preferred set of data including reactions of OH with 67
monocyclic aromatic hydrocarbons and oxygenated organic compounds. In each
case, the rate coefficient is defined in terms of a summation of partial rate
coefficients for H abstraction or OH addition at each relevant site in the
given organic compound, so that the attack distribution is defined. The SAR
can therefore guide the representation of the OH reactions in the next
generation of explicit detailed chemical mechanisms. Rules governing the
representation of the reactions of the product radicals under tropospheric
conditions are also summarized, specifically the rapid reaction sequences
initiated by their reactions with O<sub>2</sub>.</p> |
| first_indexed | 2024-12-21T16:29:13Z |
| format | Article |
| id | doaj.art-f33bde890f484d518153dcf466cee0a3 |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-21T16:29:13Z |
| publishDate | 2018-07-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-f33bde890f484d518153dcf466cee0a32022-12-21T18:57:23ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242018-07-01189329934910.5194/acp-18-9329-2018Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism constructionM. E. Jenkin0M. E. Jenkin1R. Valorso2B. Aumont3A. R. Rickard4A. R. Rickard5T. J. Wallington6Atmospheric Chemistry Services, Okehampton, Devon, EX20 4QB, UKSchool of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UKLISA, UMR CNRS 7583, Université Paris Est Créteil et Université Paris Diderot, Institut Pierre Simon Laplace, 94010 Créteil, FranceLISA, UMR CNRS 7583, Université Paris Est Créteil et Université Paris Diderot, Institut Pierre Simon Laplace, 94010 Créteil, FranceWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, York, YO10 5DD, UKNational Centre for Atmospheric Science, University of York, York, YO10 5DD, UKResearch and Advanced Engineering, Ford Motor Company, SRL-3083, P.O. Box 2053, Dearborn, MI 48121-2053, USA<p>Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for the reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are required more generally for impact assessments involving estimation of atmospheric lifetimes or oxidation rates for VOCs. A structure–activity relationship (SAR) method is presented for the reactions of OH with aromatic organic compounds, with the reactions of aliphatic organic compounds considered in the preceding companion paper. The SAR is optimized using a preferred set of data including reactions of OH with 67 monocyclic aromatic hydrocarbons and oxygenated organic compounds. In each case, the rate coefficient is defined in terms of a summation of partial rate coefficients for H abstraction or OH addition at each relevant site in the given organic compound, so that the attack distribution is defined. The SAR can therefore guide the representation of the OH reactions in the next generation of explicit detailed chemical mechanisms. Rules governing the representation of the reactions of the product radicals under tropospheric conditions are also summarized, specifically the rapid reaction sequences initiated by their reactions with O<sub>2</sub>.</p>https://www.atmos-chem-phys.net/18/9329/2018/acp-18-9329-2018.pdf |
| spellingShingle | M. E. Jenkin M. E. Jenkin R. Valorso B. Aumont A. R. Rickard A. R. Rickard T. J. Wallington Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction Atmospheric Chemistry and Physics |
| title | Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction |
| title_full | Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction |
| title_fullStr | Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction |
| title_full_unstemmed | Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction |
| title_short | Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aromatic organic compounds for use in automated mechanism construction |
| title_sort | estimation of rate coefficients and branching ratios for gas phase reactions of oh with aromatic organic compounds for use in automated mechanism construction |
| url | https://www.atmos-chem-phys.net/18/9329/2018/acp-18-9329-2018.pdf |
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