The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings.
- Buckingham GT Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
- Ormond TK Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
- Porterfield JP Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
- Hemberger P Molecular Dynamics Group, Paul Scherrer Institut, CH-5232 Villigen-PSI, Switzerland.
- Kostko O Chemical Sciences Division, Lawrence Berkeley National Laboratories, Berkeley, California 94720, USA.
- Ahmed M Chemical Sciences Division, Lawrence Berkeley National Laboratories, Berkeley, California 94720, USA.
- Robichaud DJ National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, USA.
- Nimlos MR National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, USA.
- Daily JW Department of Mechanical Engineering, Center for Combustion and Environmental Research,University of Colorado, Boulder, Colorado 80309-0427, USA.
- Ellison GB Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
- 2015-02-02
Published in:
- The Journal of chemical physics. - 2015
English
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 C6H5 (13)CH2. 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 C6H5 (13)CH2 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⇋C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway.
- Language
-
- English
- Open access status
- green
- Identifiers
-
- DOI 10.1063/1.4906156
- PMID 25637987
- Persistent URL
- https://sonar.ch/global/documents/23910
Statistics
Document views: 77
File downloads:
- Full-text: 0