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Kinetic Studies of OH and O3 Reactions with Allyl and Isopropenyl Acetate

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Abstract

Rate coefficients have been measured for the gas phasereactions of hydroxyl (OH) radicals and ozone with twounsaturated esters, allyl acetate(CH3C(O)OCH2CH=CH2) and isopropenylacetate (CH3C(O)OC(CH3)=CH2). The OHexperiments were carried out using the pulsed laserphotolysis – laser induced fluorescence technique overthe temperature range 243–372 K and the kinetic dataused to derive the following Arrhenius expressions (inunits of cm3 molecule-1 s-1): allylacetate, k 1 = (2.33 ± 0.27) ×10-12 exp[(732 ± 34)/T]; and isopropenyl acetate,k 2 = (4.52 ± 0.62) × 10-12exp[(809 ± 39)/T]. At 298 K, the rate coefficients obtained (inunits of 10-12 cm3 molecule-1 s-1)are: k 1 = (27.1 ± 3.0) and k 2= (69.6± 9.4). The relative rate technique has been usedto determine rate coefficients for the reaction ofozone with the acetates. Using methyl vinyl ketone asthe reference compound and a value of4.8 × 10-18 cm3 molecule-1s-1 asthe rate coefficient for its reaction with O3,the following rate coefficients were derived at 298 ± 4 K (in units of10-18 cm3molecule-1 s-1): allyl acetate, (2.4 ± 0.7) andisopropenyl acetate (0.7 ± 0.2). Theresults are discussed in terms of structure-activityrelationships and used to derive atmospheric lifetimesfor the acetates.

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Authors and Affiliations

  1. Laboratoire de Combustion et Systèmes Réactifs, CNRS, 1C, Avenue de la recherche scientifique, 45071, Orléans Cedex 2, France

    S. Le Calvé, A. Mellouki & G. Le Bras

  2. Department of Chemistry, Dublin Institute of Technology, Kevin Steet, Dublin 8, Ireland

    J. Treacy

  3. Department of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

    J. Wenger & H. Sidebottom

Authors
  1. S. Le Calvé
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  2. A. Mellouki
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  3. G. Le Bras
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  4. J. Treacy
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  5. J. Wenger
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  6. H. Sidebottom
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Le Calvé, S., Mellouki, A., Le Bras, G. et al. Kinetic Studies of OH and O3 Reactions with Allyl and Isopropenyl Acetate. Journal of Atmospheric Chemistry 37, 161–172 (2000). https://doi.org/10.1023/A:1006499008759

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  • DOI: https://doi.org/10.1023/A:1006499008759

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