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Issue 23, 2002
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The OH-initiated atmospheric oxidation of pinonaldehyde: Detailed theoretical study and mechanism construction

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Abstract

The pinonaldehyde + OH reaction proceeds via H-atom abstraction by OH, which can occur on six different carbon atoms. For each of these OH-attack/H-abstraction sites in pinonaldehyde, a detailed mechanism of product formation in atmospheric conditions is developed, based solely on quantitative structure activity relationships (SARs) and on theoretical quantum chemistry methods, combined with transition state theory calculations or RRKM. Invoking only “classical” alkyl-, alkylperoxy- and alkoxy chemistries, the objective fate of some 30 organic radical intermediates was in this way predicted. Total primary product yields were obtained by propagating the product fractions of each step in the mechanism. Overall predicted product molar yields for high-NO conditions are: 22.9% 4-hydroxynorpinonaldehyde, 9.9% acetone, 12.9% CH2O, 30.3% organic nitrates, 73.8% CO2, 11.4% HC(O)OH, 16.6% norpinonaldehyde and CO, and 16.6% other (hydroxy)(poly)carbonyls. In more realistic atmospheric conditions, at lower NO levels, our theoretically predicted yields differ only regarding 4-hydroxynorpinonaldehyde (38.2%), HC(O)OH (0.3%), and nitrates (26.2%). The classical radical chemistries adopted in this work fail to reproduce the very high yield of CH2O (∼150%) observed in a recent laboratory investigation.

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Publication details

The article was received on 19 Jun 2002, accepted on 26 Sep 2002 and first published on 17 Oct 2002


Article type: Paper
DOI: 10.1039/B205901K
Citation: Phys. Chem. Chem. Phys., 2002,4, 5795-5805

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    The OH-initiated atmospheric oxidation of pinonaldehyde: Detailed theoretical study and mechanism construction

    G. Fantechi, L. Vereecken and J. Peeters, Phys. Chem. Chem. Phys., 2002, 4, 5795
    DOI: 10.1039/B205901K

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