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

Handle URI:
http://hdl.handle.net/10754/626247
Title:
Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds
Authors:
Wang, Zhandong ( 0000-0003-1535-2319 ) ; Popolan-Vaida, Denisia M.; Chen, Bingjie; Moshammer, Kai; Mohamed, Samah; Wang, Heng; Sioud, Salim; Raji, Misjudeen; Kohse-Höinghaus, Katharina; Hansen, Nils; Dagaut, Philippe; Leone, Stephen R.; Sarathy, Mani ( 0000-0002-3975-6206 )
Abstract:
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. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.
KAUST Department:
Clean Combustion Research Center; Analytical Core Lab
Citation:
Wang Z, Popolan-Vaida DM, Chen B, Moshammer K, Mohamed SY, et al. (2017) Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds. Proceedings of the National Academy of Sciences: 201707564. Available: http://dx.doi.org/10.1073/pnas.1707564114.
Publisher:
Proceedings of the National Academy of Sciences
Journal:
Proceedings of the National Academy of Sciences
KAUST Grant Number:
OSR-2016-CRG5-3022
Issue Date:
28-Nov-2017
DOI:
10.1073/pnas.1707564114
Type:
Article
ISSN:
0027-8424; 1091-6490
Sponsors:
The authors thank Elisabeth Lutanie, Virginia Unkefer, and Ivan Gromicho (Research Publication Services, KAUST) for editorial assistance; Dr. Mikael Ehn and Dr. Matti P. Rissanen (University of Helsinki) and Dr. William H. Green (Massachusetts Institute of Technology) for valuable discussions; and Paul Fugazzi for technical support. This work was supported by King Abdullah University of Science and Technology, Office of Sponsored Research (OSR) under Award OSR-2016-CRG5-3022, and Saudi Aramco under the FUELCOM program (to Z.W., B.C., S.Y.M., H.W., and S.M.S.); Director, Office of Energy Research, Office of Basic Energy Sciences (BES), Chemical Sciences Division of the US Department of Energy (USDOE), Gas Phase Chemical Physics Program, under Contract DE-AC02-05CH11231 (to D.M.P.-V. and S.R.L.); Division of Chemical Sciences, Geosciences and Biosciences, BES/USDOE (N.H. and K.M.); Deutsche Forschungsgemeinschaft Project KO1363/31-1 (to K.K.-H.); European Research Council (ERC) under FP7/2007-2013/ERC Grant 291049-2G-CSafe (to P.D.). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE’s National Nuclear Security Administration under Contract DE-NA0003525. The Advanced Light Source is supported by the Director, Office of BES, of the USDOE under Contract DE-AC02-05CH11231.
Additional Links:
http://www.pnas.org/content/early/2017/11/27/1707564114
Appears in Collections:
Articles; Analytical Core Lab; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorWang, Zhandongen
dc.contributor.authorPopolan-Vaida, Denisia M.en
dc.contributor.authorChen, Bingjieen
dc.contributor.authorMoshammer, Kaien
dc.contributor.authorMohamed, Samahen
dc.contributor.authorWang, Hengen
dc.contributor.authorSioud, Salimen
dc.contributor.authorRaji, Misjudeenen
dc.contributor.authorKohse-Höinghaus, Katharinaen
dc.contributor.authorHansen, Nilsen
dc.contributor.authorDagaut, Philippeen
dc.contributor.authorLeone, Stephen R.en
dc.contributor.authorSarathy, Manien
dc.date.accessioned2017-11-29T11:13:56Z-
dc.date.available2017-11-29T11:13:56Z-
dc.date.issued2017-11-28en
dc.identifier.citationWang Z, Popolan-Vaida DM, Chen B, Moshammer K, Mohamed SY, et al. (2017) Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds. Proceedings of the National Academy of Sciences: 201707564. Available: http://dx.doi.org/10.1073/pnas.1707564114.en
dc.identifier.issn0027-8424en
dc.identifier.issn1091-6490en
dc.identifier.doi10.1073/pnas.1707564114en
dc.identifier.urihttp://hdl.handle.net/10754/626247-
dc.description.abstractDecades 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. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.en
dc.description.sponsorshipThe authors thank Elisabeth Lutanie, Virginia Unkefer, and Ivan Gromicho (Research Publication Services, KAUST) for editorial assistance; Dr. Mikael Ehn and Dr. Matti P. Rissanen (University of Helsinki) and Dr. William H. Green (Massachusetts Institute of Technology) for valuable discussions; and Paul Fugazzi for technical support. This work was supported by King Abdullah University of Science and Technology, Office of Sponsored Research (OSR) under Award OSR-2016-CRG5-3022, and Saudi Aramco under the FUELCOM program (to Z.W., B.C., S.Y.M., H.W., and S.M.S.); Director, Office of Energy Research, Office of Basic Energy Sciences (BES), Chemical Sciences Division of the US Department of Energy (USDOE), Gas Phase Chemical Physics Program, under Contract DE-AC02-05CH11231 (to D.M.P.-V. and S.R.L.); Division of Chemical Sciences, Geosciences and Biosciences, BES/USDOE (N.H. and K.M.); Deutsche Forschungsgemeinschaft Project KO1363/31-1 (to K.K.-H.); European Research Council (ERC) under FP7/2007-2013/ERC Grant 291049-2G-CSafe (to P.D.). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the USDOE’s National Nuclear Security Administration under Contract DE-NA0003525. The Advanced Light Source is supported by the Director, Office of BES, of the USDOE under Contract DE-AC02-05CH11231.en
dc.publisherProceedings of the National Academy of Sciencesen
dc.relation.urlhttp://www.pnas.org/content/early/2017/11/27/1707564114en
dc.rightsThis open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).en
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectautooxidationen
dc.subjectperoxidesen
dc.subjectignitionen
dc.subjectsecondary organic aerosolen
dc.subjectmass spectrometryen
dc.titleUnraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compoundsen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentAnalytical Core Laben
dc.identifier.journalProceedings of the National Academy of Sciencesen
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionDepartment of Chemistry, University of Central Florida, Orlando, FL 32816-2450en
dc.contributor.institutionChemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720en
dc.contributor.institutionDepartment of Physics, University of California, Berkeley, CA 94720en
dc.contributor.institutionDepartment of Chemistry, University of California, Berkeley, CA 94720en
dc.contributor.institutionPhysikalisch-Technische Bundesanstalt, 38116 Braunschweig, Germanyen
dc.contributor.institutionCombustion Research Facility, Sandia National Laboratories, Livermore, CA 94551en
dc.contributor.institutionDepartment of Chemistry, Bielefeld University, D-33615 Bielefeld, Germanyen
dc.contributor.institutionCNRS, Institut National des Sciences de l’Ingénierie et des Systèmes, Institut de Combustion, Aérothermique, Réactivité et Environnement, 45071, Orléans, Cedex 2, Franceen
kaust.authorWang, Zhandongen
kaust.authorChen, Bingjieen
kaust.authorMohamed, Samahen
kaust.authorWang, Hengen
kaust.authorSioud, Salimen
kaust.authorRaji, Misjudeenen
kaust.authorSarathy, Manien
kaust.grant.numberOSR-2016-CRG5-3022en
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