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Title: Isomer-specific combustion chemistry in allene and propyne flames

Abstract

A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C{sub 3}H{sub 4} isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O{sub 2}/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C{sub 6} aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C{sub 3}H{sub 5} potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007)more » 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction. (author)« less

Authors:
;  [1];  [2];  [1];  [3];  [4]; ;  [5]
  1. Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551 (United States)
  2. Department of Chem. Engineering, University of Massachusetts, Amherst, MA 01003 (United States)
  3. (Germany)
  4. Department of Chemistry, Bielefeld University, D-33615 Bielefeld (Germany)
  5. School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853 (United States)
Publication Date:
OSTI Identifier:
21235982
Resource Type:
Journal Article
Resource Relation:
Journal Name: Combustion and Flame; Journal Volume: 156; Journal Issue: 11; Other Information: Elsevier Ltd. All rights reserved
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALLENE; PROPYNE; COMBUSTION KINETICS; FLAMES; BENZENE; OXYGEN; ARGON; ISOMERIZATION; SIMULATION; BURNERS; PEAKS; STOICHIOMETRY; PRESSURE RANGE KILO PA; Low-pressure flames; Flame modeling

Citation Formats

Hansen, Nils, Miller, James A., Westmoreland, Phillip R., Kasper, Tina, Department of Chemistry, Bielefeld University, D-33615 Bielefeld, Kohse-Hoeinghaus, Katharina, Wang, Juan, and Cool, Terrill A.. Isomer-specific combustion chemistry in allene and propyne flames. United States: N. p., 2009. Web. doi:10.1016/J.COMBUSTFLAME.2009.07.014.
Hansen, Nils, Miller, James A., Westmoreland, Phillip R., Kasper, Tina, Department of Chemistry, Bielefeld University, D-33615 Bielefeld, Kohse-Hoeinghaus, Katharina, Wang, Juan, & Cool, Terrill A.. Isomer-specific combustion chemistry in allene and propyne flames. United States. doi:10.1016/J.COMBUSTFLAME.2009.07.014.
Hansen, Nils, Miller, James A., Westmoreland, Phillip R., Kasper, Tina, Department of Chemistry, Bielefeld University, D-33615 Bielefeld, Kohse-Hoeinghaus, Katharina, Wang, Juan, and Cool, Terrill A.. 2009. "Isomer-specific combustion chemistry in allene and propyne flames". United States. doi:10.1016/J.COMBUSTFLAME.2009.07.014.
@article{osti_21235982,
title = {Isomer-specific combustion chemistry in allene and propyne flames},
author = {Hansen, Nils and Miller, James A. and Westmoreland, Phillip R. and Kasper, Tina and Department of Chemistry, Bielefeld University, D-33615 Bielefeld and Kohse-Hoeinghaus, Katharina and Wang, Juan and Cool, Terrill A.},
abstractNote = {A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C{sub 3}H{sub 4} isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O{sub 2}/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C{sub 6} aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C{sub 3}H{sub 5} potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007) 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction. (author)},
doi = {10.1016/J.COMBUSTFLAME.2009.07.014},
journal = {Combustion and Flame},
number = 11,
volume = 156,
place = {United States},
year = 2009,
month =
}
  • No abstract prepared.
  • The chemistry initiated by C{sub 60}{sup x+} (with x = 1, 2, and 3) in allene and propyne has been tracked in the gas phase. Reaction rate coefficients and product distributions were measured with the Selected-Ion Flow Tube (SIFT) technique operating at 294 {+-} 3 K and at a helium buffer-gas pressure of 0.35 {+-} 0.01 Torr. C{sub 60}{sup .+} does not react with allene and propyne under SIFT conditions, but multiple addition was observed with C{sub 60}{sup 2+}. Multiple addition was also observed in the reaction of propyne with C{sub 60}{sup 3+}, but allene reacted only by electron transfermore » with this cation. Up to 16 molecules of allene were observed to add to C{sub 60}{sup 2+} with a remarkable periodicity in reactivity: even-numbered adducts react approximately 10 times faster than odd-numbered adducts. Multi-collision induced dissociation (CID) experiments demonstrated that the observed multiple-adduct ions have a `ball-and-chain` structure. Mechanisms are proposed for the sequential addition reactions and for the formation of C{sub 6}H{sub 7}{sup +} and C{sub 9}H{sub 12}{sup +} which was seen to compete with multiple addition in the reactions of allene with C{sub 60}{sup 2+} and of propyne with C{sub 60}{sup 3+}. The multiple-addition reactions are proposed to occur by chain propagation. 38 refs., 8 figs., 1 tab.« less
  • The photodissociation dynamics of propyne and allene are investigated in two molecular beam/photodissociation instruments, one using electron impact ionization and the other using tunable vacuum ultraviolet (VUV) light to photoionize the photoproducts. The primary dissociation channels for both reactants are C{sub 3}H{sub 3}+H and C{sub 3}H{sub 2}+H{sub 2}. Measurement of the photoionization efficiency curves on the VUV instrument shows that the C{sub 3}H{sub 3} product from propyne is the propynyl (CH{sub 3}CC) radical, whereas the C{sub 3}H{sub 3} product from allene is the propargyl (CH{sub 2}CCH) radical. The dominant C{sub 3}H{sub 2} product from both reactants is the propadienylidene (H{submore » 2}CCC) radical. We also observe a small amount of secondary C{sub 3}H{sub 2} product from photodissociation of the C{sub 3}H{sub 3} radicals in both cases. {copyright} {ital 1999 American Institute of Physics.} thinsp« less
  • No abstract prepared.
  • No abstract prepared.