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

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

doi:10.1039/B100149N

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

W. Hack,^a K. Hoyermann,*^b C. Kersten,^b M. Olzmann*^c and B. Viskolcz^d

Author affiliations

* Corresponding authors

^a Max-Planck-Institut für Strömungsforschung, Bunsenstraße 10, Göttingen, Germany

^b Institut für Physikalische Chemie der Uniersität Göttingen, Tammannstraße 6, Göttingen, Germany

^c Institut für Physikalische Chemie der Uniersität Karlsruhe, Fritz-Haber-Weg 4, Karlsruhe, Germany
E-mail: matthias.olzmann@chemie.uni-karlsruhe.de

^d Department of Chemistry, Gy. J. Teachers' Training College, P.O. Box 396, Szeged, Hungary

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 X²Π ( [italic v (to differentiate from Times ital nu)] = 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 modeling 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.

Article information

https://doi.org/10.1039/B100149N

Article type

Paper

Submitted

03 Jan 2001

Accepted

01 Mar 2001

First published

09 Apr 2001

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Phys. Chem. Chem. Phys., 2001,3, 2365-2371

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

W. Hack, K. Hoyermann, C. Kersten, M. Olzmann and B. Viskolcz, Phys. Chem. Chem. Phys., 2001, 3, 2365 DOI: 10.1039/B100149N

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