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Title: Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)

Abstract

Oxidation of organic compounds in combustion and in Earth’s troposphere is mediated by reactive species formed by the addition of molecular oxygen (O 2 ) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted “QOOH.” These species and their reactions with O 2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1353295
Resource Type:
Published Article
Journal Name:
Science
Additional Journal Information:
Journal Name: Science Journal Volume: 347 Journal Issue: 6222; Journal ID: ISSN 0036-8075
Publisher:
American Association for the Advancement of Science (AAAS)
Country of Publication:
United States
Language:
English

Citation Formats

Savee, John D., Papajak, Ewa, Rotavera, Brandon, Huang, Haifeng, Eskola, Arkke J., Welz, Oliver, Sheps, Leonid, Taatjes, Craig A., Zádor, Judit, and Osborn, David L. Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH). United States: N. p., 2015. Web. doi:10.1126/science.aaa1495.
Savee, John D., Papajak, Ewa, Rotavera, Brandon, Huang, Haifeng, Eskola, Arkke J., Welz, Oliver, Sheps, Leonid, Taatjes, Craig A., Zádor, Judit, & Osborn, David L. Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH). United States. doi:10.1126/science.aaa1495.
Savee, John D., Papajak, Ewa, Rotavera, Brandon, Huang, Haifeng, Eskola, Arkke J., Welz, Oliver, Sheps, Leonid, Taatjes, Craig A., Zádor, Judit, and Osborn, David L. Thu . "Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)". United States. doi:10.1126/science.aaa1495.
@article{osti_1353295,
title = {Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)},
author = {Savee, John D. and Papajak, Ewa and Rotavera, Brandon and Huang, Haifeng and Eskola, Arkke J. and Welz, Oliver and Sheps, Leonid and Taatjes, Craig A. and Zádor, Judit and Osborn, David L.},
abstractNote = {Oxidation of organic compounds in combustion and in Earth’s troposphere is mediated by reactive species formed by the addition of molecular oxygen (O 2 ) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted “QOOH.” These species and their reactions with O 2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.},
doi = {10.1126/science.aaa1495},
journal = {Science},
number = 6222,
volume = 347,
place = {United States},
year = {2015},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1126/science.aaa1495

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Cited by: 57 works
Citation information provided by
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