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Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2

Johnson, D., Price, D.W. and Marston, G. (2004) Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2. Atmospheric Environment, 38 (10). pp. 1447-1458. ISSN 1352-2310

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To link to this item DOI: 10.1016/j.atmosenv.2003.12.003

Abstract/Summary

Structure activity relationships (SARs) are presented for the gas-phase reactions of RO2 with HO2, and the self- and cross-reactions of RO2. For RO2+HO2 the SAR is based upon a correlation between the logarithm of the measured rate coefficient and a calculated ionisation potential for the molecule R-CH=CH2, R being the same group in both the radical and molecular analogue. The correlation observed is strong and only for one RO2 species does the measured rate coefficient deviate by more than a factor of two from the linear least-squares regression line. For the self- and cross-reactions of RO2 radicals, the SAR is based upon a correlation between the logarithm of the measured rate coefficient and the calculated electrostatic potential (ESP) at the equivalent carbon atom in the RH molecule to which oxygen is attached in RO2, again R being the same group in the molecule and the radical. For cases where R is a simple alkyl-group, a strong linear correlation observed. For RO2 radicals which contain lone pair-bearing substituents and for which the calculated ESP<-0.05 self-reaction rate coefficients appear to be insensitive to the value of the ESP. For RO2 of this type with ESP>-0.05 a linear relationship between log k and the ESP is again observed. Using the relationships, 84 out of the 85 rate coefficients used to develop the SARs are predicted to within a factor of three of their measured values. A relationship is also presented that allows the prediction of the Arrhenius parameters for the self-reactions of simple alkyl RO2 radicals. On the basis of the correlations, predictions of room-temperature rate coefficients are made for a number of atmospherically important peroxyl-peroxyl radical reactions. (C) 2003 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:11370
Uncontrolled Keywords:correlation, structure activity relationship (SAR), peroxyl radicals, self-reaction, rate coefficients, ORGANIC PEROXY-RADICALS, RATE CONSTANTS, MECHANISM, ALKENES, OZONE, CHEMISTRY, OXIDATION, NO3, OH

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