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Title: Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems

Abstract

The reaction of the phenyl radical (C6H5) with molecular oxygen (O2) plays a central role in the degradation of poly- and monocyclic aromatic radicals in combustion systems which would otherwise react with fuel components to form polycyclic aromatic hydrocarbons (PAHs) and eventually soot. Despite intense theoretical and experimental scrutiny over half a century, the overall reaction channels have not all been experimentally identified. Tunable vacuum ultraviolet photoionization in conjunction with a combustion simulating chemical reactor uniquely provides the complete isomer specific product spectrum and branching ratios of this prototype reaction. In the reaction of phenyl radicals and molecular oxygen at 873 K and 1003 K, ortho-benzoquinone (o-C6H4O2), the phenoxy radical (C6H5O), and cyclopentadienyl radical (C5H5) were identified as primary products formed through emission of atomic hydrogen, atomic oxygen and carbon dioxide. Furan (C4H4O), acrolein (C3H4O), and ketene (C2H2O) were also identified as primary products formed through ring opening and fragmentation of the 7-membered ring 2-oxepinoxy radical. Secondary reaction products para-benzoquinone (p-C6H4O2), phenol (C6H5OH), cyclopentadiene (C5H6), 2,4-cyclopentadienone (C5H4O), vinylacetylene (C4H4), and acetylene (C2H2) were also identified. The pyranyl radical (C5H5O) was not detected; however, electronic structure calculations show that it is formed and isomerizes to 2,4-cyclopentadienone through atomic hydrogen emission. Inmore » combustion systems, barrierless phenyl-type radical oxidation reactions could even degrade more complex aromatic radicals. Lastly, an understanding of these elementary processes is expected to lead to a better understanding toward the elimination of carcinogenic, mutagenic, and environmentally hazardous byproducts of combustion systems such as PAHs.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [3]
+ Show Author Affiliations
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1602912
Grant/Contract Number:  
FG02-03ER15411; FG02-04ER15570; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 28; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxygen; Chemical reactions; Oxides; Inorganic carbon compounds; Carbon

Citation Formats

Parker, Dorian S. N., Kaiser, Ralf I., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, and Mebel, Alexander M. Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems. United States: N. p., 2014. Web. doi:10.1021/jp509170x.
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Parker, Dorian S. N., Kaiser, Ralf I., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, & Mebel, Alexander M. Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems. United States. https://doi.org/10.1021/jp509170x
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Parker, Dorian S. N., Kaiser, Ralf I., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, and Mebel, Alexander M. Thu . "Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems". United States. https://doi.org/10.1021/jp509170x. https://www.osti.gov/servlets/purl/1602912.
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@article{osti_1602912,
title = {Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems},
author = {Parker, Dorian S. N. and Kaiser, Ralf I. and Troy, Tyler P. and Kostko, Oleg and Ahmed, Musahid and Mebel, Alexander M.},
abstractNote = {The reaction of the phenyl radical (C6H5) with molecular oxygen (O2) plays a central role in the degradation of poly- and monocyclic aromatic radicals in combustion systems which would otherwise react with fuel components to form polycyclic aromatic hydrocarbons (PAHs) and eventually soot. Despite intense theoretical and experimental scrutiny over half a century, the overall reaction channels have not all been experimentally identified. Tunable vacuum ultraviolet photoionization in conjunction with a combustion simulating chemical reactor uniquely provides the complete isomer specific product spectrum and branching ratios of this prototype reaction. In the reaction of phenyl radicals and molecular oxygen at 873 K and 1003 K, ortho-benzoquinone (o-C6H4O2), the phenoxy radical (C6H5O), and cyclopentadienyl radical (C5H5) were identified as primary products formed through emission of atomic hydrogen, atomic oxygen and carbon dioxide. Furan (C4H4O), acrolein (C3H4O), and ketene (C2H2O) were also identified as primary products formed through ring opening and fragmentation of the 7-membered ring 2-oxepinoxy radical. Secondary reaction products para-benzoquinone (p-C6H4O2), phenol (C6H5OH), cyclopentadiene (C5H6), 2,4-cyclopentadienone (C5H4O), vinylacetylene (C4H4), and acetylene (C2H2) were also identified. The pyranyl radical (C5H5O) was not detected; however, electronic structure calculations show that it is formed and isomerizes to 2,4-cyclopentadienone through atomic hydrogen emission. In combustion systems, barrierless phenyl-type radical oxidation reactions could even degrade more complex aromatic radicals. Lastly, an understanding of these elementary processes is expected to lead to a better understanding toward the elimination of carcinogenic, mutagenic, and environmentally hazardous byproducts of combustion systems such as PAHs.},
doi = {10.1021/jp509170x},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 119,
place = {United States},
year = {Thu Nov 13 00:00:00 EST 2014},
month = {Thu Nov 13 00:00:00 EST 2014}
}
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Crossed beam reaction of the phenyl radical, (C6H5, X2A′) with molecular oxygen <mml:math altimg="si1.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:mo stretchy="false">(</mml:mo><mml:msub><mml:mrow><mml:mtext>O</mml:mtext></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:mtext>,</mml:mtext><mml:msup><mml:mrow><mml:mtext>X</mml:mtext></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msup><mml:msubsup><mml:mrow><mml:mi mathvariant="normal">Σ</mml:mi></mml:mrow><mml:mrow><mml:mtext>g</mml:mtext></mml:mrow><mml:mrow><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo stretchy="false">)</mml:mo></mml:mrow></mml:math>: Observation of the phenoxy radical, (C6H5O, X2A′)
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