Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

Handle URI:
http://hdl.handle.net/10754/625904
Title:
Degradation of carbonyl hydroperoxides in the atmosphere and in combustion
Authors:
Xing, Lili; Bao, Junwei Lucas; Wang, Zhandong ( 0000-0003-1535-2319 ) ; Zhang, Feng; Truhlar, Donald G.
Abstract:
Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.
KAUST Department:
Clean Combustion Research Center
Citation:
Xing L, Bao JL, Wang Z, Zhang F, Truhlar DG (2017) Degradation of carbonyl hydroperoxides in the atmosphere and in combustion. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b08297.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
12-Oct-2017
DOI:
10.1021/jacs.7b08297
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
This work was supported in part by the U. S. Department of Energy, Office of Basic Energy Sciences, under Award Number DE-SC0015997, by National Key Research and Development Program of China (No. 2016YFC0202600), by National Natural Science Foundation of China (No. 91541112), and by the China Scholarship Fund. J. L. Bao acknowledges the financial support from doctor dissertation fellowship (DDF) provided by University of Minnesota.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.7b08297
Appears in Collections:
Articles; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorXing, Lilien
dc.contributor.authorBao, Junwei Lucasen
dc.contributor.authorWang, Zhandongen
dc.contributor.authorZhang, Fengen
dc.contributor.authorTruhlar, Donald G.en
dc.date.accessioned2017-10-19T07:10:41Z-
dc.date.available2017-10-19T07:10:41Z-
dc.date.issued2017-10-12en
dc.identifier.citationXing L, Bao JL, Wang Z, Zhang F, Truhlar DG (2017) Degradation of carbonyl hydroperoxides in the atmosphere and in combustion. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b08297.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.7b08297en
dc.identifier.urihttp://hdl.handle.net/10754/625904-
dc.description.abstractOxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.en
dc.description.sponsorshipThis work was supported in part by the U. S. Department of Energy, Office of Basic Energy Sciences, under Award Number DE-SC0015997, by National Key Research and Development Program of China (No. 2016YFC0202600), by National Natural Science Foundation of China (No. 91541112), and by the China Scholarship Fund. J. L. Bao acknowledges the financial support from doctor dissertation fellowship (DDF) provided by University of Minnesota.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.7b08297en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.7b08297.en
dc.titleDegradation of carbonyl hydroperoxides in the atmosphere and in combustionen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minnesota 55455-0431, USAen
dc.contributor.institutionNational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, Chinaen
kaust.authorWang, Zhandongen
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