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Volume 18, issue 6
Atmos. Chem. Phys., 18, 4039–4054, 2018
https://doi.org/10.5194/acp-18-4039-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
Atmos. Chem. Phys., 18, 4039–4054, 2018
https://doi.org/10.5194/acp-18-4039-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 22 Mar 2018

Research article | 22 Mar 2018

A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

Jacob T. Shaw1, Richard T. Lidster1,a, Danny R. Cryer2, Noelia Ramirez2, Fiona C. Whiting1, Graham A. Boustead2, Lisa K. Whalley2,3, Trevor Ingham2,3, Andrew R. Rickard1,4, Rachel E. Dunmore1, Dwayne E. Heard2,3, Ally C. Lewis1,4, Lucy J. Carpenter1, Jacqui F. Hamilton1, and Terry J. Dillon1 Jacob T. Shaw et al.
  • 1Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK
  • 2School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK
  • 3National Centre for Atmospheric Science, University of Leeds, Leeds, LS2 9JT, UK
  • 4National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD, UK
  • anow at: DSTL, Porton Down, Salisbury, Wiltshire, SP4 0JQ, UK

Abstract. 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; k =  5.7 (±0.3)  ×  10−11 cm3 molecule−1 s−1. 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 T =  323 (±10) K.

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The lifetime of a chemical in the atmosphere is largely governed by the rate of its reaction with the hydroxyl radical (OH). Measurements of rates for many of the thousands of identified volatile organic compounds (VOCs) have yet to be determined experimentally. We have developed a new technique for the rapid determination of gas-phase rate coefficients for the simultaneous reactions between multiple VOCs and OH. The method is tasted across a range of scenarios and is used to derive new values.
The lifetime of a chemical in the atmosphere is largely governed by the rate of its reaction...
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