Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling
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 1250 K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10 atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O2/N2 mixture was maintained at 0.7 s. 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 850–1000 K 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 + O2, 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. Sensitivitymore »
- Authors:
-
- King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
- CNRS-INSIS, Orleans Cedex (France)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
- OSTI Identifier:
- 1259489
- Alternate Identifier(s):
- OSTI ID: 1378505; OSTI ID: 1397890
- Report Number(s):
- SAND-2016-4957J; LLNL-JRNL-680022
Journal ID: ISSN 1540-7489; 640736
- Grant/Contract Number:
- AC04-94AL85000; AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the Combustion Institute
- Additional Journal Information:
- Journal Volume: 36; Journal Issue: 1; Journal ID: ISSN 1540-7489
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cyclopentane; Jet stirred rector; Species profiles; Modeling; 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Citation Formats
Al Rashidi, Mariam J., Thion, Sebastien, Togbe, Casimir, Dayma, Guillaume, Mehl, Marco, Dagaut, Philippe, Pitz, William J., Zador, Judit, and Sarathy, S. Mani. Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling. United States: N. p., 2016.
Web. doi:10.1016/j.proci.2016.05.036.
Al Rashidi, Mariam J., Thion, Sebastien, Togbe, Casimir, Dayma, Guillaume, Mehl, Marco, Dagaut, Philippe, Pitz, William J., Zador, Judit, & Sarathy, S. Mani. Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling. United States. https://doi.org/10.1016/j.proci.2016.05.036
Al Rashidi, Mariam J., Thion, Sebastien, Togbe, Casimir, Dayma, Guillaume, Mehl, Marco, Dagaut, Philippe, Pitz, William J., Zador, Judit, and Sarathy, S. Mani. Wed .
"Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling". United States. https://doi.org/10.1016/j.proci.2016.05.036. https://www.osti.gov/servlets/purl/1259489.
@article{osti_1259489,
title = {Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling},
author = {Al Rashidi, Mariam J. and Thion, Sebastien and Togbe, Casimir and Dayma, Guillaume and Mehl, Marco and Dagaut, Philippe and Pitz, William J. and Zador, Judit and Sarathy, S. Mani},
abstractNote = {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 1250 K, equivalence ratios from 0.5 to 3.0, and at an operating pressure of 10 atm. The fuel concentration was kept at 0.1% and the residence time of the fuel/O2/N2 mixture was maintained at 0.7 s. 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 850–1000 K 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 + O2, 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.},
doi = {10.1016/j.proci.2016.05.036},
journal = {Proceedings of the Combustion Institute},
number = 1,
volume = 36,
place = {United States},
year = {Wed Jun 22 00:00:00 EDT 2016},
month = {Wed Jun 22 00:00:00 EDT 2016}
}
Web of Science
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Works referencing / citing this record:
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