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Title: Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [2];  [1]
  1. Univ. of Rennes, Cedex (France). Inst. of Physics at Rennes
  2. West Virginia Univ., Morgantown, WV (United States). Dept. of Chemistry
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
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We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

Research Organization:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000; AC02-05CH11231
OSTI ID:
1338711
Report Number(s):
SAND2016-10088J; 649570
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 46; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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