A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical
Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the s...
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2018-03-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/18/4039/2018/acp-18-4039-2018.pdf |
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| author | J. T. Shaw R. T. Lidster R. T. Lidster D. R. Cryer N. Ramirez F. C. Whiting G. A. Boustead L. K. Whalley L. K. Whalley T. Ingham T. Ingham A. R. Rickard A. R. Rickard R. E. Dunmore D. E. Heard D. E. Heard A. C. Lewis A. C. Lewis L. J. Carpenter J. F. Hamilton T. J. Dillon |
| author_facet | J. T. Shaw R. T. Lidster R. T. Lidster D. R. Cryer N. Ramirez F. C. Whiting G. A. Boustead L. K. Whalley L. K. Whalley T. Ingham T. Ingham A. R. Rickard A. R. Rickard R. E. Dunmore D. E. Heard D. E. Heard A. C. Lewis A. C. Lewis L. J. Carpenter J. F. Hamilton T. J. Dillon |
| author_sort | J. T. Shaw |
| collection | DOAJ |
| description | Gas-phase rate coefficients are fundamental to
understanding atmospheric chemistry, yet experimental data are not available
for the oxidation reactions of many of the thousands of volatile organic
compounds (VOCs) observed in the troposphere. Here, a new experimental method
is reported for the simultaneous study of reactions between multiple
different VOCs and OH, the most important daytime atmospheric radical
oxidant. This technique is based upon established relative rate concepts but
has the advantage of a much higher throughput of target VOCs. By evaluating
multiple VOCs in each experiment, and through measurement of the depletion
in each VOC after reaction with OH, the OH + VOC reaction rate
coefficients can be derived. Results from experiments conducted under
controlled laboratory conditions were in good agreement with the available
literature for the reaction of 19 VOCs, prepared in synthetic gas
mixtures, with OH. This approach was used to determine a rate coefficient
for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; <i>k</i> = 5.7 (±0.3) × 10<sup>−11</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>.
In addition, a further seven VOCs had only two, or fewer, individual OH rate
coefficient measurements available in the literature. The results from this
work were in good agreement with those measurements. A similar dataset, at
an elevated temperature of 323 (±10) K, was used to determine new OH
rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3
monoterpene VOC + OH reactions. In OH relative reactivity experiments that
used ambient air at the University of York, a large number of different VOCs
were observed, of which 23 were positively identified. Due to
difficulties with detection limits and fully resolving peaks, only 19
OH rate coefficients were derived from these ambient air samples, including
10 reactions for which data were previously unavailable at the elevated
reaction temperature of <i>T</i> = 323 (±10) K. |
| first_indexed | 2024-12-10T13:22:53Z |
| format | Article |
| id | doaj.art-1e6c82bb4b9449e5982492893c5892ba |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-10T13:22:53Z |
| publishDate | 2018-03-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-1e6c82bb4b9449e5982492893c5892ba2022-12-22T01:47:15ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242018-03-01184039405410.5194/acp-18-4039-2018A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radicalJ. T. Shaw0R. T. Lidster1R. T. Lidster2D. R. Cryer3N. Ramirez4F. C. Whiting5G. A. Boustead6L. K. Whalley7L. K. Whalley8T. Ingham9T. Ingham10A. R. Rickard11A. R. Rickard12R. E. Dunmore13D. E. Heard14D. E. Heard15A. C. Lewis16A. C. Lewis17L. J. Carpenter18J. F. Hamilton19T. J. Dillon20Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKnow at: DSTL, Porton Down, Salisbury, Wiltshire, SP4 0JQ, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKNational Centre for Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKNational Centre for Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKNational Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKSchool of Chemistry, University of Leeds, Leeds, LS2 9JT, UKNational Centre for Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKNational Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKWolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UKGas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; <i>k</i> = 5.7 (±0.3) × 10<sup>−11</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of <i>T</i> = 323 (±10) K.https://www.atmos-chem-phys.net/18/4039/2018/acp-18-4039-2018.pdf |
| spellingShingle | J. T. Shaw R. T. Lidster R. T. Lidster D. R. Cryer N. Ramirez F. C. Whiting G. A. Boustead L. K. Whalley L. K. Whalley T. Ingham T. Ingham A. R. Rickard A. R. Rickard R. E. Dunmore D. E. Heard D. E. Heard A. C. Lewis A. C. Lewis L. J. Carpenter J. F. Hamilton T. J. Dillon A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical Atmospheric Chemistry and Physics |
| title | A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical |
| title_full | A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical |
| title_fullStr | A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical |
| title_full_unstemmed | A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical |
| title_short | A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical |
| title_sort | self consistent multivariate method for the determination of gas phase rate coefficients applied to reactions of atmospheric vocs and the hydroxyl radical |
| url | https://www.atmos-chem-phys.net/18/4039/2018/acp-18-4039-2018.pdf |
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