Mechanism of the 1-C4H9 + O reaction and the kinetics of the intermediate radical 1-C4H9O

W. Hack, K. Hoyermann, C. Kersten, M. Olzmann, B. Viskolcz

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Abstract

The 1-C4H9 + O reaction has been investigated in two quasi-static reactors with different detection systems. From a time-resolved measurement of OH formation by laser induced fluorescence (T = 295 K, p = 21 mbar, bath gas: He) an inverted vibrational state distribution for OH X2∏ (v = 0, 1, 2) was observed. By using Fourier transform infrared spectroscopy, relative product yields of 0.55 ± 0.08 for 1-C4H8, 0.397 ± 0.05 for HCHO and 0.053 ± 0.02 for C3H7CHO were determined (T = 298 K, p = 2 mbar, bath gas: He). The results are explained in terms of the formation and subsequent decomposition of an intermediate chemically activated 1-C4H9O radical and a competing abstraction channel leading directly to OH + 1-C4H8. A modelling by statistical rate theory based on ab initio results for the stationary points of the potential energy surface of C4H9O allows the quantitative description of the product branching ratios. From this modeling, threshold energies of E06 = 55 ± 6 and E07 = 88 ± 6 kJ mol-1 for the β-C-C and the β-C-H bond dissociation, respectively, in 1-C4H9O are obtained. For the 1,5 H atom shift, a most probable value of E05 = 40 ± 5 kJ mol-1 follows from a comparison of our quantum chemical results with data from the literature.

Original languageEnglish
Pages (from-to)2365-2371
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume3
Issue number12
DOIs
Publication statusPublished - 2001

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baths
reaction kinetics
Gases
Potential energy surfaces
Kinetics
kinetics
products
Time measurement
gases
vibrational states
laser induced fluorescence
Fluorescence
potential energy
infrared spectroscopy
reactors
time measurement
dissociation
Decomposition
decomposition
Atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Mechanism of the 1-C4H9 + O reaction and the kinetics of the intermediate radical 1-C4H9O. / Hack, W.; Hoyermann, K.; Kersten, C.; Olzmann, M.; Viskolcz, B.

In: Physical Chemistry Chemical Physics, Vol. 3, No. 12, 2001, p. 2365-2371.

Research output: Contribution to journalArticle

Hack, W. ; Hoyermann, K. ; Kersten, C. ; Olzmann, M. ; Viskolcz, B. / Mechanism of the 1-C4H9 + O reaction and the kinetics of the intermediate radical 1-C4H9O. In: Physical Chemistry Chemical Physics. 2001 ; Vol. 3, No. 12. pp. 2365-2371.
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