Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah Y.; Wang, Heng; Sioud, Salim; Raji, Misjudeen A.; Kohse-Hoinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, S. Mani

doi:10.1073/pnas.1707564114

Title: Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

Journal Article · Tue Nov 28 00:00:00 EST 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1707564114· OSTI ID:1432232

^[1]; Popolan-Vaida, Denisia M. ^[2]; Chen, Bingjie ^[1]; Moshammer, Kai ^[3]; Mohamed, Samah Y. ^[1]; Wang, Heng ^[1]; Sioud, Salim ^[4]; Raji, Misjudeen A. ^[4]; Kohse-Hoinghaus, Katharina ^[5]; Hansen, Nils ^[6]; Dagaut, Philippe ^[7]; Leone, Stephen R. ^[8];

^[1]

King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia). Clean Combustion Research Center
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of Central Florida, Orlando, FL (United States). Dept. of Chemistry
Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility; Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)
King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia). Analytical Core Lab.
Bielefeld Univ., Bielefeld (Germany). Dept. of Chemistry
Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
Centre National de la Recherche Scientifique (CNRS), Orleans (France). Inst. National des Sciences de l'Ingenierie et des Systemes, Inst. de Combustion, Aerothermique, Reactivite et Environnement
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. In conclusion, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); King Abdullah University of Science and Technology, Office of Sponsored Research (OSR)

Grant/Contract Number:: AC02-05CH11231; 291049-2GCSafe

OSTI ID:: 1432232

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 50; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 103 works

Citation information provided by
Web of Science

References (44)

Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes Battin-Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre-Alexandre Angewandte Chemie International Edition, Vol. 49, Issue 18 https://doi.org/10.1002/anie.200906850	journal	April 2010
Additional chain-branching pathways in the low-temperature oxidation of branched alkanes Wang, Zhandong; Zhang, Lidong; Moshammer, Kai Combustion and Flame, Vol. 164 https://doi.org/10.1016/j.combustflame.2015.11.035	journal	February 2016
Intramolecular Hydrogen Migration in Alkylperoxy and Hydroperoxyalkylperoxy Radicals: Accurate Treatment of Hindered Rotors Sharma, Sandeep; Raman, Sumathy; Green, William H. The Journal of Physical Chemistry A, Vol. 114, Issue 18 https://doi.org/10.1021/jp9098792	journal	May 2010
New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides Jalan, Amrit; Alecu, Ionut M.; Meana-Pañeda, Rubén Journal of the American Chemical Society, Vol. 135, Issue 30 https://doi.org/10.1021/ja4034439	journal	July 2013
Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene Claeys, M. Science, Vol. 303, Issue 5661 https://doi.org/10.1126/science.1092805	journal	February 2004
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry Qi, Fei Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.09.002	journal	January 2013
n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine Wang, Zhandong; Chen, Bingjie; Moshammer, Kai Combustion and Flame, Vol. 187 https://doi.org/10.1016/j.combustflame.2017.09.003	journal	January 2018
New experimental evidences about the formation and consumption of ketohydroperoxides Battin-Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre-Alexandre Proceedings of the Combustion Institute, Vol. 33, Issue 1 https://doi.org/10.1016/j.proci.2010.05.001	journal	January 2011
Quantification of the Keto-Hydroperoxide (HOOCH ₂ OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether Moshammer, Kai; Jasper, Ahren W.; Popolan-Vaida, Denisia M. The Journal of Physical Chemistry A, Vol. 120, Issue 40 https://doi.org/10.1021/acs.jpca.6b06634	journal	September 2016
Multi-path variational transition state theory for chiral molecules: the site-dependent kinetics for abstraction of hydrogen from 2-butanol by hydroperoxyl radical, analysis of hydrogen bonding in the transition state, and dramatic temperature dependence of the activation energy Bao, Junwei Lucas; Meana-Pañeda, Rubén; Truhlar, Donald G. Chemical Science, Vol. 6, Issue 10 https://doi.org/10.1039/C5SC01848J	journal	January 2015
Products and Mechanism of Secondary Organic Aerosol Formation from Reactions of n -Alkanes with OH Radicals in the Presence of NO _x Lim, Yong Bin; Ziemann, Paul J. Environmental Science & Technology, Vol. 39, Issue 23 https://doi.org/10.1021/es051447g	journal	December 2005
A large source of low-volatility secondary organic aerosol Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard Nature, Vol. 506, Issue 7489 https://doi.org/10.1038/nature13032	journal	February 2014
Quantum Thermochemistry: Multistructural Method with Torsional Anharmonicity Based on a Coupled Torsional Potential Zheng, Jingjing; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 9, Issue 3 https://doi.org/10.1021/ct3010722	journal	February 2013
Low Temperature Oxidation, Engine Knock Warnatz, Jürgen; Maas, Ulrich; Dibble, Robert W. Combustion https://doi.org/10.1007/978-3-642-98027-5_16	book	January 1999
Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH) Savee, John D.; Papajak, Ewa; Rotavera, Brandon Science, Vol. 347, Issue 6222 https://doi.org/10.1126/science.aaa1495	journal	February 2015
Theoretical kinetic studies for low temperature oxidation of two typical methylcyclohexyl radicals Xing, Lili; Zhang, Lidong; Zhang, Feng Combustion and Flame, Vol. 182 https://doi.org/10.1016/j.combustflame.2017.03.025	journal	August 2017
Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes Wang, Zhandong; Sarathy, S. Mani Combustion and Flame, Vol. 165 https://doi.org/10.1016/j.combustflame.2015.12.020	journal	March 2016
Autoxidation of Organic Compounds in the Atmosphere Crounse, John D.; Nielsen, Lasse B.; Jørgensen, Solvejg The Journal of Physical Chemistry Letters, Vol. 4, Issue 20 https://doi.org/10.1021/jz4019207	journal	September 2013
The Orbitrap: a new mass spectrometer Hu, Qizhi; Noll, Robert J.; Li, Hongyan Journal of Mass Spectrometry, Vol. 40, Issue 4 https://doi.org/10.1002/jms.856	journal	January 2005
Inhibition of the Autoxidation of Organic Substances in the Liquid Phase. Ingold, K. U. Chemical Reviews, Vol. 61, Issue 6 https://doi.org/10.1021/cr60214a002	journal	December 1961
Chemical aspects of the autoignition of hydrocarbonair mixtures Cox, R. A.; Cole, J. A. Combustion and Flame, Vol. 60, Issue 2 https://doi.org/10.1016/0010-2180(85)90001-X	journal	May 1985
Detection and Identification of the Keto-Hydroperoxide (HOOCH ₂ OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether Moshammer, Kai; Jasper, Ahren W.; Popolan-Vaida, Denisia M. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b00101	journal	February 2015
Low- and intermediate-temperature oxidation of ethylcyclohexane: A theoretical study Ning, HongBo; Gong, ChunMing; Tan, NingXin Combustion and Flame, Vol. 162, Issue 11 https://doi.org/10.1016/j.combustflame.2015.08.004	journal	November 2015
Negative temperature-coefficient of reaction rate during hydrocarbon oxidation Griffiths, J. F. Journal of the Chemical Society D: Chemical Communications, Issue 9 https://doi.org/10.1039/c2969000483b	journal	January 1969
The ethylperoxy radical: its ultraviolet spectrum, self-reaction, and reaction with hydroperoxy, each studied as a function of temperature Fenter, Frederick F.; Catoire, Valery; Lesclaux, Robert The Journal of Physical Chemistry, Vol. 97, Issue 14 https://doi.org/10.1021/j100116a016	journal	April 1993
Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry Hansen, Nils; Cool, Terrill A.; Westmoreland, Phillip R. Progress in Energy and Combustion Science, Vol. 35, Issue 2 https://doi.org/10.1016/j.pecs.2008.10.001	journal	April 2009
Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D. Environmental Science & Technology, Vol. 51, Issue 9 https://doi.org/10.1021/acs.est.7b00460	journal	April 2017
Mechanisms for the autoxidation of polyunsaturated lipids Porter, Ned A. Accounts of Chemical Research, Vol. 19, Issue 9 https://doi.org/10.1021/ar00129a001	journal	September 1986
Biofuel Combustion Chemistry: From Ethanol to Biodiesel Kohse-Höinghaus, Katharina; Oßwald, Patrick; Cool, Terrill A. Angewandte Chemie International Edition, Vol. 49, Issue 21 https://doi.org/10.1002/anie.200905335	journal	May 2010
Flame extinction and low-temperature combustion of isolated fuel droplets of n-alkanes Cuoci, Alberto; Saufi, Abd E.; Frassoldati, Alessio Proceedings of the Combustion Institute, Vol. 36, Issue 2 https://doi.org/10.1016/j.proci.2016.08.019	journal	January 2017
Oxidation Products of Biogenic Emissions Contribute to Nucleation of Atmospheric Particles Riccobono, F.; Schobesberger, S.; Scott, C. E. Science, Vol. 344, Issue 6185 https://doi.org/10.1126/science.1243527	journal	May 2014
Rapid Autoxidation Forms Highly Oxidized RO ₂ Radicals in the Atmosphere Jokinen, Tuija; Sipilä, Mikko; Richters, Stefanie Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201408566	journal	October 2014
Kinetics of elementary reactions in low-temperature autoignition chemistry Zádor, Judit; Taatjes, Craig A.; Fernandes, Ravi X. Progress in Energy and Combustion Science, Vol. 37, Issue 4 https://doi.org/10.1016/j.pecs.2010.06.006	journal	August 2011
Improved Kinetic Model of the Low-Temperature Oxidation of n -Heptane Pelucchi, Matteo; Bissoli, Mattia; Cavallotti, Carlo Energy & Fuels, Vol. 28, Issue 11 https://doi.org/10.1021/ef501483f	journal	October 2014
Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation Rodriguez, Anne; Herbinet, Olivier; Wang, Zhandong Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.044	journal	January 2017
The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko Journal of the American Chemical Society, Vol. 136, Issue 44 https://doi.org/10.1021/ja507146s	journal	October 2014
Reactivity Trends within Alkoxy Radical Reactions Responsible for Chain Branching Davis, Alexander C.; Francisco, Joseph S. Journal of the American Chemical Society, Vol. 133, Issue 45 https://doi.org/10.1021/ja204806b	journal	November 2011
Hydroxyl radical-induced formation of highly oxidized organic compounds Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13677	journal	December 2016
Modelling n-dodecane spray and combustion with the transported probability density function method Pei, Yuanjiang; Hawkes, Evatt R.; Kook, Sanghoon Combustion and Flame, Vol. 162, Issue 5 https://doi.org/10.1016/j.combustflame.2014.12.019	journal	May 2015
Liquid-phase autoxidation of organic compounds at elevated temperatures. 1. The stirred flow reactor technique and analysis of primary products from n-hexadecane autoxidation at 120-180.degree.C Jensen, R. K.; Korcek, S.; Mahoney, L. R. Journal of the American Chemical Society, Vol. 101, Issue 25 https://doi.org/10.1021/ja00519a018	journal	December 1979
New insights into the low-temperature oxidation of 2-methylhexane Wang, Zhandong; Mohamed, Samah Y.; Zhang, Lidong Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.06.085	journal	January 2017
Atmospheric pressure photoionization mass spectrometry Raffaelli, Andrea; Saba, Alessandro Mass Spectrometry Reviews, Vol. 22, Issue 5 https://doi.org/10.1002/mas.10060	journal	August 2003
Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto Proceedings of the National Academy of Sciences, Vol. 112, Issue 23 https://doi.org/10.1073/pnas.1423977112	journal	May 2015
Low Temperature Oxidation, Engine Knock Warnatz, Jürgen; Maas, Ulrich; Dibble, Robert W. Combustion https://doi.org/10.1007/978-3-662-04508-4_16	book	January 2001

Cited By (3)

Kinetics in the real world: linking molecules, processes, and systems Kohse-Höinghaus, Katharina; Troe, Jürgen; Grabow, Jens-Uwe Physical Chemistry Chemical Physics, Vol. 20, Issue 16 https://doi.org/10.1039/c8cp90054j	journal	January 2018
Atmospheric autoxidation is increasingly important in urban and suburban North America Praske, Eric; Otkjær, Rasmus V.; Crounse, John D. Proceedings of the National Academy of Sciences, Vol. 115, Issue 1 https://doi.org/10.1073/pnas.1715540115	journal	December 2017
NO ₂ Suppression of Autoxidation–Inhibition of Gas-Phase Highly Oxidized Dimer Product Formation Rissanen, Matti P. ACS Earth and Space Chemistry, Vol. 2, Issue 11 https://doi.org/10.1021/acsearthspacechem.8b00123	journal	September 2018

Similar Records

Cool flame chemistry of diesel surrogate compounds: n-Decane, 2-methylnonane, 2,7-dimethyloctane, and n-butylcyclohexane

Journal Article · Tue Jun 23 00:00:00 EDT 2020 · Combustion and Flame · OSTI ID:1432232

Wang, Zhandong; Hansen, Nils; Jasper, Ahren W.; +6 more

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

Journal Article · Thu Dec 31 00:00:00 EST 2015 · Combustion and Flame · OSTI ID:1432232

Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; +10 more

A comprehensive combustion chemistry study of 2,5-dimethylhexane

Journal Article · Thu Jan 16 00:00:00 EST 2014 · Combustion and Flame · OSTI ID:1432232

Sarathy, S. Mani; Javed, Tamour; Karsenty, Florent; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

Citation Formats

References (44)

Cited By (3)

Similar Records

Related Subjects