Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds
Popolan-Vaida, Denisia M.
Leone, Stephen R.
KAUST DepartmentAnalytical Chemistry Core Lab
Chemical Engineering Program
Clean Combustion Research Center
Combustion and Pyrolysis Chemistry (CPC) Group
Physical Science and Engineering (PSE) Division
KAUST Grant NumberOSR-2016-CRG5-3022
Online Publication Date2017-11-28
Print Publication Date2017-12-12
Permanent link to this recordhttp://hdl.handle.net/10754/626247
MetadataShow full item record
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.
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.
SponsorsThe 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.
Except where otherwise noted, this item's license is described as This open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).
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