Gas-phase rate coefficients for reactions of NO3, OH, O3 and O(3P) with unsaturated alcohols and ethers: Correlations and structure-activity relations (SARs)

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Christian Pfrang - , University of Oxford (Author)
  • Martin D. King - , Royal Holloway University of London (Author)
  • Mareike Braeckevelt - , Chair of Urban Water Management, University of Oxford (Author)
  • Carlos E. Canosa-Mas - , University of Oxford (Author)
  • Richard P. Wayne - , University of Oxford (Author)

Abstract

Experimental difficulties sometimes force modellers to use predicted rate coefficients for reactions of oxygenated volatile organic compounds (oVOCs). We examine here methods for making the predictions for reactions of atmospheric initiators of oxidation, NO3, OH, O3 and O(3P), with unsaturated alcohols and ethers. Logarithmic correlations are found between measured rate coefficients and calculated orbital energies, and these correlations may be used directly to estimate rate coefficients for compounds where measurements have not been performed. To provide a shortcut that obviates the need to calculate orbital energies, structure-activity relations (SARs) are developed. Our SARs are tested for predictive power against compounds for which experimental rate coefficients exist, and their accuracy is discussed. Estimated atmospheric lifetimes for oVOCs are presented. The SARs for alkenols successfully predict key rate coefficients, and thus can be used to enhance the scope of atmospheric models incorporating detailed chemistry. SARs for the ethers have more limited applicability, but can still be useful in improving tropospheric models.

Details

Original languageEnglish
Pages (from-to)3018-3034
Number of pages17
JournalAtmospheric Environment
Volume42
Issue number13
Publication statusPublished - Apr 2008
Peer-reviewedYes

External IDs

ORCID /0009-0001-5656-0053/work/145224078

Keywords

Keywords

  • Alkenol, Ether, Hydroxyl, Nitrate, Oxygenated VOCs, Ozone