DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

Catching a glimpse of the elusive QOOH It's straightforward to write down the net combustion reaction: Oxygen reacts with hydrocarbons to form water and carbon dioxide. The details of how all the bonds break and form in succession are a great deal more complicated. Savee et al. now report direct detection of a long-postulated piece of the puzzle, a so-called QOOH intermediate. This structure results from bound oxygen stripping a hydrogen atom from carbon, leaving a carbon-centered radical behind. The study explores the influence of the hydrocarbon's unsaturation on the stability of QOOH, which has implications for both combustion and tropospheric oxidation chemistry. Science , this issue p. 643

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Combustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, CA 94551-0969, USA.
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. https://doi.org/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. Fri . "Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)". United States. https://doi.org/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 = {Catching a glimpse of the elusive QOOH It's straightforward to write down the net combustion reaction: Oxygen reacts with hydrocarbons to form water and carbon dioxide. The details of how all the bonds break and form in succession are a great deal more complicated. Savee et al. now report direct detection of a long-postulated piece of the puzzle, a so-called QOOH intermediate. This structure results from bound oxygen stripping a hydrogen atom from carbon, leaving a carbon-centered radical behind. The study explores the influence of the hydrocarbon's unsaturation on the stability of QOOH, which has implications for both combustion and tropospheric oxidation chemistry. Science , this issue p. 643},
doi = {10.1126/science.aaa1495},
journal = {Science},
number = 6222,
volume = 347,
place = {United States},
year = {Fri Feb 06 00:00:00 EST 2015},
month = {Fri Feb 06 00:00:00 EST 2015}
}

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

Citation Metrics:
Cited by: 105 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance
journal, January 2012

  • Orlando, John J.; Tyndall, Geoffrey S.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35166h

Kinetics of the reactions of methyl, ethyl, isopropyl, and tert-butyl radicals with molecular chlorine
journal, June 1986

  • Timonen, Raimo S.; Gutman, David
  • The Journal of Physical Chemistry, Vol. 90, Issue 13
  • DOI: 10.1021/j100404a038

Quantum Chemical Study of the Acrolein (CH 2 CHCHO) + OH + O 2 Reactions
journal, July 2010

  • Asatryan, Rubik; da Silva, Gabriel; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 32
  • DOI: 10.1021/jp104828a

Alkylperoxy Radical Photochemistry in Organic Aerosol Formation Processes
journal, December 2013

  • Kalafut-Pettibone, Alicia J.; Klems, Joseph P.; Burgess, Donald R.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 51
  • DOI: 10.1021/jp4094996

Kinetics of the Self Reaction of Cyclohexyl Radicals
journal, August 2011

  • Loginova, Ksenia A.; Knyazev, Vadim D.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 31
  • DOI: 10.1021/jp204012w

Chain Branching and Termination in the Low-Temperature Combustion of n -Alkanes: 2-Pentyl Radical + O 2 , Isomerization and Association of the Second O 2
journal, July 2010

  • Asatryan, Rubik; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 29
  • DOI: 10.1021/jp101159h

Rate constants for the reactions of isobutyl, neopentyl, cyclopentyl, and cyclohexyl radicals with molecular oxygen
journal, May 1986

  • Wu, Dihua; Bayes, Kyle D.
  • International Journal of Chemical Kinetics, Vol. 18, Issue 5
  • DOI: 10.1002/kin.550180505

Directly measuring reaction kinetics of ˙QOOH – a crucial but elusive intermediate in hydrocarbon autoignition
journal, January 2013

  • Zádor, Judit; Huang, Haifeng; Welz, Oliver
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 26
  • DOI: 10.1039/c3cp51185e

Advanced compression-ignition engines—understanding the in-cylinder processes
journal, January 2009


Interception of Excited Vibrational Quantum States by O2 in Atmospheric Association Reactions
journal, August 2012


Kinetics of elementary reactions in low-temperature autoignition chemistry
journal, August 2011

  • Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X.
  • Progress in Energy and Combustion Science, Vol. 37, Issue 4
  • DOI: 10.1016/j.pecs.2010.06.006

HOx radical regeneration in the oxidation of isoprene
journal, January 2009

  • Peeters, J.; Nguyen, T. L.; Vereecken, L.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 28
  • DOI: 10.1039/b908511d

Optimized intermolecular potential functions for liquid hydrocarbons
journal, October 1984

  • Jorgensen, William L.; Madura, Jeffry D.; Swenson, Carol J.
  • Journal of the American Chemical Society, Vol. 106, Issue 22
  • DOI: 10.1021/ja00334a030

A theoretical study of the OH-initiated gas-phase oxidation mechanism of β-pinene (C10H16): first generation products
journal, January 2012

  • Vereecken, L.; Peeters, J.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 11
  • DOI: 10.1039/c2cp23711c

High Natural Aerosol Loading over Boreal Forests
journal, April 2006


A differentially pumped harmonic filter on the Chemical Dynamics Beamline at the Advanced Light Source
journal, October 1995

  • Suits, Arthur G.; Heimann, Philip; Yang, Xueming
  • Review of Scientific Instruments, Vol. 66, Issue 10
  • DOI: 10.1063/1.1146161

Peroxy radical isomerization in the oxidation of isoprene
journal, January 2011

  • Crounse, John D.; Paulot, Fabien; Kjaergaard, Henrik G.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 30
  • DOI: 10.1039/c1cp21330j

Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate
journal, May 2010


Rate constants and isomeric branching of the Cl–isoprene reaction
journal, May 2002


The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics
journal, October 2008

  • Osborn, David L.; Zou, Peng; Johnsen, Howard
  • Review of Scientific Instruments, Vol. 79, Issue 10
  • DOI: 10.1063/1.3000004

Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene
journal, February 2004


Kinetics of the reactions of unsaturated hydrocarbon free radicals (vinyl, allyl, and propargyl) with molecular chlorine
journal, March 1987

  • Timonen, Raimo S.; Russell, John J.; Sarzynski, Dariusz.
  • The Journal of Physical Chemistry, Vol. 91, Issue 7
  • DOI: 10.1021/j100291a037

A large source of low-volatility secondary organic aerosol
journal, February 2014

  • Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard
  • Nature, Vol. 506, Issue 7489
  • DOI: 10.1038/nature13032

Determination of the Equilibrium Constant and Thermodynamic Parameters for the Reaction of Pentadienyl Radicals with O 2
journal, March 2001

  • Zils, Régis; Inomata, Satoshi; Imamura, Takashi
  • The Journal of Physical Chemistry A, Vol. 105, Issue 8
  • DOI: 10.1021/jp0031505

Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure
journal, January 2009

  • Fernandes, Ravi X.; Zádor, Judit; Jusinski, Leonard E.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 9
  • DOI: 10.1039/b819825j

Autoxidation of Organic Compounds in the Atmosphere
journal, September 2013

  • Crounse, John D.; Nielsen, Lasse B.; Jørgensen, Solvejg
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 20
  • DOI: 10.1021/jz4019207

Hydroxyl Radical Recycling in Isoprene Oxidation Driven by Hydrogen Bonding and Hydrogen Tunneling: The Upgraded LIM1 Mechanism
journal, July 2014

  • Peeters, Jozef; Müller, Jean-François; Stavrakou, Trissevgeni
  • The Journal of Physical Chemistry A, Vol. 118, Issue 38
  • DOI: 10.1021/jp5033146

Kinetics of reactions of chlorine atoms with a series of alkenes at 1 atm and 298 K: structure and reactivity
journal, October 2002

  • Ezell, Michael J.; Wang, Weihong; Ezell, Alisa A.
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 23
  • DOI: 10.1039/b207529f

Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry
journal, January 2007

  • Vereecken, L.; Müller, J. -F.; Peeters, J.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 38
  • DOI: 10.1039/b708023a

Effects of Olefin Group and Its Position on the Kinetics for Intramolecular H-Shift and HO 2 Elimination of Alkenyl Peroxy Radicals
journal, February 2011

  • Zhang, Feng; Dibble, Theodore S.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 5
  • DOI: 10.1021/jp1111839

Experimental and modeling study of the oxidation of n-butylbenzene
journal, April 2012


Kinetics of the cyclohexadienyl radical self-reaction and oxidation reaction using cavity ring-down spectroscopy
journal, February 2009


First-principles-derived kinetics of the reactions involved in low-temperature dimethyl ether oxidation
journal, February 2008


Low-temperature combustion chemistry of novel biofuels: resonance-stabilized QOOH in the oxidation of diethyl ketone
journal, January 2014

  • Scheer, Adam M.; Welz, Oliver; Zádor, Judit
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 26
  • DOI: 10.1039/c3cp55468f

Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions
journal, May 2013

  • Georgievskii, Yuri; Miller, James A.; Burke, Michael P.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 46
  • DOI: 10.1021/jp4060704

Theoretical studies of atmospheric reaction mechanisms in the troposphere
journal, January 2012

  • Vereecken, Luc; Francisco, Joseph S.
  • Chemical Society Reviews, Vol. 41, Issue 19
  • DOI: 10.1039/c2cs35070j

Role of O 2 + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients
journal, March 2012

  • Goldsmith, C. Franklin; Green, William H.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 13
  • DOI: 10.1021/jp210722w

OH reactivity in a South East Asian tropical rainforest during the Oxidant and Particle Photochemical Processes (OP3) project
journal, January 2013

  • Edwards, P. M.; Evans, M. J.; Furneaux, K. L.
  • Atmospheric Chemistry and Physics, Vol. 13, Issue 18
  • DOI: 10.5194/acp-13-9497-2013

Atmospheric oxidation capacity sustained by a tropical forest
journal, April 2008

  • Lelieveld, J.; Butler, T. M.; Crowley, J. N.
  • Nature, Vol. 452, Issue 7188
  • DOI: 10.1038/nature06870

Performance of the vacuum ultraviolet high-resolution and high-flux beamline for chemical dynamics studies at the Advanced Light Source
journal, May 1997

  • Heimann, P. A.; Koike, M.; Hsu, C. W.
  • Review of Scientific Instruments, Vol. 68, Issue 5
  • DOI: 10.1063/1.1148082

Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene
journal, August 2009


Chemical dynamics, molecular energetics, and kinetics at the synchrotron
journal, January 2010

  • Leone, Stephen R.; Ahmed, Musahid; Wilson, Kevin R.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 25
  • DOI: 10.1039/c001707h

UV Absorption Spectrum and Self-Reaction Kinetics of the Cyclohexadienyl Radical, and Stability of a Series of Cyclohexadienyl-Type Radicals
journal, July 1999

  • Berho, Florence; Rayez, Marie-Thérèse; Lesclaux, Robert
  • The Journal of Physical Chemistry A, Vol. 103, Issue 28
  • DOI: 10.1021/jp9904318