The Thermal Decomposition of the Benzyl Radical in a Heated Micro-Reactor. I. Experimental Findings

Grant T. Buckingham, Thomas K. Ormond, Jessica P. Porterfield, Patrick Hemberger, Oleg Kostko, Musahid Ahmed, David J. Robichaud, Mark R. Nimlos, John W. Daily, G. Barney Ellison

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45 Scopus Citations

Abstract

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 C6H513CH2. 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 C6H513CH2 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: C6H5CH2â‡C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway.

Original languageAmerican English
Article numberArticle No. 044307
Number of pages13
JournalThe Journal of Chemical Physics
Volume142
Issue number4
DOIs
StatePublished - 28 Jan 2015

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NREL Publication Number

  • NREL/JA-5100-63858

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