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Issue 6, 2015
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Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions

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Abstract

The removal of SO2 in the presence of alkene–ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene–ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10−5 for CH2OO, 26 (±10) × 10−5 for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10−5 for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10−5 for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are −2.3 (±3.5) × 1011 cm−3 for CH2OO, 13 (±43) × 1011 cm−3 for CH3CHOO derived from cis-but-2-ene, −14 (±31) × 1011 cm−3 for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 1011 cm−3 for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10−4 for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 1013 for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10−2. The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.

Graphical abstract: Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions

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Publication details

The article was received on 17 Sep 2014, accepted on 23 Dec 2014 and first published on 06 Jan 2015


Article type: Paper
DOI: 10.1039/C4CP04186K
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Citation: Phys. Chem. Chem. Phys., 2015,17, 4076-4088
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    Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions

    M. J. Newland, A. R. Rickard, M. S. Alam, L. Vereecken, A. Muñoz, M. Ródenas and W. J. Bloss, Phys. Chem. Chem. Phys., 2015, 17, 4076
    DOI: 10.1039/C4CP04186K

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