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Title: 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/O 2/N 2 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 + O 2, 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. Furthermore, sensitivitymore » 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.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [3];  [2];  [3];  [4];  [1]
  1. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia)
  2. CNRS-INSIS, Orleans Cedex (France)
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  4. 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 Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
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:
Journal Article: 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. 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, and Sarathy, S. Mani. Wed . "Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling". United States. doi: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. Furthermore, 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}
}

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Cited by: 8works
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  • 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 φmore » = 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.« less
  • Cited by 8
  • The oxidation of propene was studied in a jet stirred flow reactor in the temperature range 900-1200 K at pressures extending from 1 to 8 atm for a wide range of fuel-oxygen equivalence ratios (0.15-4.0). A computer program has been developed to model the experimental data by using a chemical kinetic reaction mechanism. A direct method to determine the first-order sensitivities of the mole fraction of each species with respect to the rate constants was used to develop the kinetic scheme. The present chemical kinetic reaction mechanism is able to reproduce the experimental results, although some discrepancies are observed formore » the minor products.« less
  • A jet-stirred reactor study of ethyl propanoate, a model biodiesel molecule, has been carried out at 10 atm pressure, using 0.1% fuel at equivalence ratios of 0.3, 0.6, 1.0 and 2.0 and at temperatures in the range 750-1100 K with a constant residence time of 0.7 seconds. Concentration profiles of ethyl propanoate were measured together with those of major intermediates, ethylene, propanoic acid, methane and formaldehyde, and major products, water, carbon dioxide and carbon monoxide. This data was used to further validate a previously published detailed chemical kinetic mechanism, containing 139 species and 790 reversible reactions. It was found thatmore » this mechanism required a significant increase in the rate constant of the six-centered unimolecular elimination reaction which produces ethylene and propanoic acid in order to correctly reproduce the measured concentrations of propanoic acid. The revised mechanism was then used to re-simulate shock tube ignition delay data with good agreement observed. Rate of production and sensitivity analyses were carried out under the experimental conditions, highlighting the importance that ethylene chemistry has on the overall reactivity of the system. (author)« less
  • The kinetics of the reduction of nitric oxide (NO) by ethylene have been studied in a fused silica jet-stirred reactor at 1 atm and a temperatures from 900 to 1,400 K to simulate conditions in a reburning zone. The initial mole fraction of NO was 1,000 ppm, that or ethylene was 4,400 ppm. The equivalence ratio was varied from 0.75 to 2. It was found that the reduction of NO varies with temperature and that for a given temperature, the maximum reduction of NO occurs slightly fuel-rich of stoichiometric conditions. Thus, operating under optimal NO-reburning conditions is possible for particularmore » combinations of equivalence ratio and temperature. The results generally agree with previous studies involving simple hydrocarbons or natural gas as reburn fuel. Detailed chemical kinetic modeling of the experiments was performed using an updated and improved kinetic scheme (877 reversible reactions and 122 species). Overall, reasonable agreement was obtained between the present measurements and the modeling although improvements of the model are still necessary. Also, the proposed kinetic mechanism can be successfully used to model the reduction of NO by ethane, acetylene, a natural gas blend (methane-ethane 10:1) and HCN, as well as the low temperature interactions between NO and simple alkanes. According to this study, the main way of reducing NO by ethylene involves the ketenyl radical, HCCO.« less