The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame

Hansen, N.; Li, W.; Law, M. E.; Kasper, T.; Westmoreland, P. R.; Yang, B.; Cool, T. A.; Lucassen, A.

doi:10.1039/c0cp00241k

The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame

Journal Article · Tue Aug 31 00:00:00 EDT 2010 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c0cp00241k· OSTI ID:1060503

Hansen, N. ^[1]; Li, W.; Law, M. E.; Kasper, T.; Westmoreland, P. R.; Yang, B.; Cool, T. A.; Lucassen, A.

Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551

Fuel decomposition and benzene formation processes in a premixed, laminar, low-pressure, fuel-rich flame of 1-hexene (C(6)H(12), CH(2)QCH-CH(2)-CH(2)-CH(2)-CH(3)) are investigated by comparing quantitative mole fraction profiles of flame species with kinetic modeling results. The premixed flame, which is stabilized on a flat-flame burner under a reduced pressure of 30 Torr (= 40 mbar), is analyzed by flame-sampling molecular-beam time-of-flight mass spectrometry which uses photoionization by tunable vacuum-ultraviolet synchrotron radiation. The temperature profile of the flame is measured by OH laser-induced fluorescence. The model calculations include the latest rate coefficients for 1-hexene decomposition (J. H. Kiefer et al., J. Phys. Chem. A, 2009, 113, 13570) and for the propargyl (C(3)H(3)) + allyl (a-C(3)H(5)) reaction (J. A. Miller et al., J. Phys. Chem. A, 2010, 114, 4881). The predicted mole fractions as a function of distance from the burner are acceptable and often even in very good agreement with the experimentally observed profiles, thus allowing an assessment of the importance of various fuel decomposition reactions and benzene formation routes. The results clearly indicate that in contrast to the normal reactions of fuel destruction by radical attack, 1-hexene is destroyed mainly by decomposition via unimolecular dissociation forming allyl (a-C(3)H(5)) and n-propyl (n-C(3)H(7)). Minor fuel-consumption pathways include H-abstraction reactions producing various isomeric C(6)H(11) radicals with subsequent beta-scissions into C(2), C(3), and C(4) intermediates. The reaction path analysis also highlights a significant contribution through the propargyl (C(3)H(3)) + allyl (a-C(3)H(5)) reaction to the formation of benzene. In this flame, benzene is dominantly formed through H-assisted isomerization of fulvene, which itself is almost exclusively produced by the C(3)H(3) + a-C(3)H(5) reaction.

Research Organization:: Cornell Univ., Ithaca, NY (United States)

Sponsoring Organization:: USDOE IG Office of Audit Services (IG-30); DOE Germantown Operations Office

DOE Contract Number:: FG02-01ER15180

OSTI ID:: 1060503

Report Number(s):: DOE-ER15180-9

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 38 Vol. 12; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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