Elementary reactions of formyl (HCO) radical studied by laser photolysis-transient absorption spectroscopy

L. N. Krasnoperov, E. N. Chesnokov, H. Stark, A. R. Ravishankara

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36 Scopus citations

Abstract

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV-Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH3 → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8-100 bar and the temperature range 498-769 K. Reactions (2) and (3) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: κ1(He) = (0.8 ± 0.4) × 10-10exp(-(66.0 ± 3.4) kJ mol-1//RT) cm3 molecule-1 s-1. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) 10-18 cm2 molecule-1 at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2) and (3) are: κ2 = (3.6 ± 0.8) × 10-11 cm3 molecule-1 s-1 (298 K); κ3 = (9.3 ± 2.3) × 10-11 cm3 molecule-1 s-1(298 and 588 K).

Original languageEnglish (US)
Pages (from-to)935-943
Number of pages9
JournalProceedings of the Combustion Institute
Volume30
Issue number1
DOIs
StatePublished - 2005
Event30th International Symposium on Combustion - Chicago, IL, United States
Duration: Jul 25 2004Jul 30 2004

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Mechanical Engineering
  • Physical and Theoretical Chemistry

Keywords

  • Formyl radical
  • Kinetics
  • UV absorption
  • Unimolecular dissociation

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