TY - JOUR
T1 - The Thermal Decomposition of the Benzyl Radical in a Heated Micro-Reactor. I. Experimental Findings
AU - Buckingham, Grant T.
AU - Ormond, Thomas K.
AU - Porterfield, Jessica P.
AU - Hemberger, Patrick
AU - Kostko, Oleg
AU - Ahmed, Musahid
AU - Robichaud, David J.
AU - Nimlos, Mark R.
AU - Daily, John W.
AU - Barney Ellison, G.
N1 - Publisher Copyright:
© 2015 AIP Publishing LLC.
PY - 2015/1/28
Y1 - 2015/1/28
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84923794572&partnerID=8YFLogxK
U2 - 10.1063/1.4906156
DO - 10.1063/1.4906156
M3 - Article
AN - SCOPUS:84923794572
SN - 0021-9606
VL - 142
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 4
M1 - Article No. 044307
ER -