Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 142, Issue 4, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4906156
Keywords
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Funding
- National Science Foundation [CHE-1112466, CBET-1403979]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy through the Chemical Sciences Division [DE-AC02-05CH11231]
- United States Department of Energy's Bioenergy Technology Office [DE-AC36-99GO10337]
- National Renewable Energy Laboratory
- Swiss Federal Office for Energy (BFE) [101969/152433]
- Directorate For Engineering
- Div Of Chem, Bioeng, Env, & Transp Sys [1403979] Funding Source: National Science Foundation
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The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C6H5CH2, as well as a set of isotopically labeled radicals: C6H5CD2, C6D5CH2, and (C6H5CH2)-C-13. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C5H4=C=CH2, H atom, C5H4-C CH, C5H5, HCCCH2, and HC CH. Pyrolysis of the C6H5CD2, C6D5CH2, and (C6H5CH2)-C-13 benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C6H5CH2 (sic) C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway. (C) 2015 AIP Publishing LLC.
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