Correlations for gas-phase reactions of NO3, OH and O 3 with alkenes: An update

C. Pfrang, M.D. King, C.E. Canosa-Mas, R.P. Wayne

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Methods are developed for predicting rate coefficients for reactions of initiators of tropospheric oxidation with unsaturated compounds that are abundant in the atmosphere; prognostic tools of this kind are essential for atmospheric chemists and modellers. To pursue the aim of exploring such tools, the kinetics of reactions of NO3, OH and O3 with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. A comparison of the values predicted by the correlations with experimental data (where the latter exist) allowed us to assess the reliability of our method. We used a series of theoretical methods to calculate the HOMO energies, and found that higher computational effort improves the agreement of the predicted rate coefficients with experimental values, especially for reactions of NO3 with alkenes that possess vinyllic halogen substituents. As a consequence, it is expedient to suggest new correlations to replace those presented by us and others that were based on the lower level of theory. We propose the following correlations for the reactions of NO3, OH and O3 with alkenes: ln(/cm3 molecule−1 s−1)=6.40(EHOMO/eV)+31.69, ln(kOH/cm3 molecule−1 s−1)=1.21(EHOMO/eV)−12.34 and ln(/cm3 molecule−1 s−1)=3.28(EHOMO/eV)−6.78. These new correlations have been developed using the larger experimental data sets now available, and the impact of the extended data on the quality of the correlations is examined in the paper. Atmospheric lifetimes have been calculated from both experimental and estimated rate coefficients to provide an overview of removal efficiencies for different classes of alkenes with respect to oxidative processes initiated by NO3, OH and O3. A figure is presented to show the spatial scales over which alkenes may survive transport in competition with attack by NO3, OH and O3. Removal by NO3 or OH is always more important than removal by O3, and reactions with NO3 dominate for scales up to a few hundred metres.
Original languageEnglish
Pages (from-to)1170-1179
JournalAtmospheric Environment
Issue number6
Publication statusPublished - 2006


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