Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling

Handle URI:
http://hdl.handle.net/10754/627025
Title:
Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling
Authors:
Rachidi, Mariam El ( 0000-0001-7392-6777 ) ; Thion, Sébastien; Togbé, Casimir; Dayma, Guillaume; Mehl, Marco; Dagaut, Philippe; Pitz, William J.; Zádor, Judit; Sarathy, Mani ( 0000-0002-3975-6206 )
Abstract:
This study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O/N mixture was maintained at 0.7s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850-1000K for ϕ = 2.0 and ϕ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl+O, as well as the C-C and C-H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C-C/C-H scission branching ratio of the cyclopentyl radical decomposition.
KAUST Department:
Clean Combustion Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Al Rashidi MJ, Thion S, Togbé C, Dayma G, Mehl M, et al. (2017) Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling. Proceedings of the Combustion Institute 36: 469–477. Available: http://dx.doi.org/10.1016/j.proci.2016.05.036.
Publisher:
Elsevier BV
Journal:
Proceedings of the Combustion Institute
Issue Date:
23-Jun-2016
DOI:
10.1016/j.proci.2016.05.036
Type:
Article
ISSN:
1540-7489
Sponsors:
This work was funded by King Abdullah University of Science and Technology (KAUST) and Saudi Aramco under the FUELCOM program. It was also supported by competitive research funding from KAUST. JZ was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration, under contract DE-AC04-94AL85000. The work at LLNL was supported by the U.S. Department of Energy, Vehicle Technologies Office, program managers Gurpreet Singh and Leo Breton and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratories under contract DE-AC52-07NA27344.
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorRachidi, Mariam Elen
dc.contributor.authorThion, Sébastienen
dc.contributor.authorTogbé, Casimiren
dc.contributor.authorDayma, Guillaumeen
dc.contributor.authorMehl, Marcoen
dc.contributor.authorDagaut, Philippeen
dc.contributor.authorPitz, William J.en
dc.contributor.authorZádor, Juditen
dc.contributor.authorSarathy, Manien
dc.date.accessioned2018-02-01T12:01:30Z-
dc.date.available2018-02-01T12:01:30Z-
dc.date.issued2016-06-23en
dc.identifier.citationAl Rashidi MJ, Thion S, Togbé C, Dayma G, Mehl M, et al. (2017) Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling. Proceedings of the Combustion Institute 36: 469–477. Available: http://dx.doi.org/10.1016/j.proci.2016.05.036.en
dc.identifier.issn1540-7489en
dc.identifier.doi10.1016/j.proci.2016.05.036en
dc.identifier.urihttp://hdl.handle.net/10754/627025-
dc.description.abstractThis study is concerned with the identification and quantification of species generated during the combustion of cyclopentane in a jet stirred reactor (JSR). Experiments were carried out for temperatures between 740 and 1250K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O/N mixture was maintained at 0.7s. The reactant, product, and intermediate species concentration profiles were measured using gas chromatography and Fourier transform infrared spectroscopy. The concentration profiles of cyclopentane indicate inhibition of reactivity between 850-1000K for ϕ = 2.0 and ϕ = 3.0. This behavior is interesting, as it has not been observed previously for other fuel molecules, cyclic or non-cyclic. A kinetic model including both low- and high-temperature reaction pathways was developed and used to simulate the JSR experiments. The pressure-dependent rate coefficients of all relevant reactions lying on the PES of cyclopentyl+O, as well as the C-C and C-H scission reactions of the cyclopentyl radical were calculated at the UCCSD(T)-F12b/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory. The simulations reproduced the unique reactivity trend of cyclopentane and the measured concentration profiles of intermediate and product species. Sensitivity and reaction path analyses indicate that this reactivity trend may be attributed to differences in the reactivity of allyl radical at different conditions, and it is highly sensitive to the C-C/C-H scission branching ratio of the cyclopentyl radical decomposition.en
dc.description.sponsorshipThis work was funded by King Abdullah University of Science and Technology (KAUST) and Saudi Aramco under the FUELCOM program. It was also supported by competitive research funding from KAUST. JZ was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the National Nuclear Security Administration, under contract DE-AC04-94AL85000. The work at LLNL was supported by the U.S. Department of Energy, Vehicle Technologies Office, program managers Gurpreet Singh and Leo Breton and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratories under contract DE-AC52-07NA27344.en
dc.publisherElsevier BVen
dc.subjectCyclopentaneen
dc.subjectJet stirred rectoren
dc.subjectModelingen
dc.subjectSpecies profilesen
dc.titleElucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modelingen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalProceedings of the Combustion Instituteen
dc.contributor.institutionC.N.R.S.-I.N.S.I.S., Institut de Combustion, Aérothermique, Réactivité et Environnement, 1C, Avenue de la Recherche Scientifique, 45071 Orléans Cedex 2, Franceen
dc.contributor.institutionLawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United Statesen
dc.contributor.institutionCombustion Research Facility, Mail Stop 9055, Sandia National Laboratories, Livermore, California 94551-0969, United Statesen
kaust.authorRachidi, Mariam Elen
kaust.authorSarathy, Manien
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