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

Pfrang, C., King, M.D., Braeckevelt, M., Canosa-Mas, C.E. and Wayne, R.P. (2008) Gas-phase rate coefficients for reactions of NO3, OH, O-3 and O(P-3) with unsaturated alcohols and ethers: correlations and structure-activity relations (SARs). Atmospheric Environment, 42 (13). pp. 3018-3034. ISSN 1352-2310

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To link to this article DOI: 10.1016/j.atmosenv.2007.12.046

Abstract/Summary

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, O-3 and O(P-3), 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. (C) 2008 Elsevier Ltd. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11556
Uncontrolled Keywords:oxygenated VOCs, alkenol, ozone, hydroxyl, nitrate, ether , VOLATILE ORGANIC-COMPOUNDS, PREDICTING RATE CONSTANTS, ABSOLUTE RATE CONSTANTS, ETHYL VINYL ETHER, PEROXY-RADICALS, ALKENES, OZONE, CHEMISTRY, MECHANISM, EMISSIONS

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