Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

Phys Chem Chem Phys. 2007 Aug 21;9(31):4142-54. doi: 10.1039/b706216h. Epub 2007 Jun 28.

Abstract

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Atmosphere
  • Catalysis
  • Chemistry, Physical / methods*
  • Electronics
  • Free Radicals
  • Helium / chemistry
  • Hydroxyl Radical / chemistry*
  • Ketones / chemistry*
  • Kinetics
  • Models, Chemical
  • Oxygen / chemistry*
  • Pressure
  • Quantum Theory
  • Temperature
  • Thermodynamics

Substances

  • Free Radicals
  • Ketones
  • Helium
  • Hydroxyl Radical
  • Oxygen