Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics
Abstract
Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (Φ = 0.5), stoichiometric (Φ = 1.0), and fuel-rich (Φ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C–H bonds and allylic pentenylmore »
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. de Lorraine, Nancy (France). Lab. Réactions et Génie des Procédés, CNRS.
- Texas A & M Univ., College Station, TX (United States)
- National Univ. of Ireland, Galway (Ireland)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1785905
- Report Number(s):
- LLNL-JRNL-666494
Journal ID: ISSN 1089-5639; 787978
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 28; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrocarbons; organic reactions; chemical reactions; fuels; molecular structure; 2-methyl-2-butane; shock tube experiments; jet-stirred reactor experiments; chemical kinetic models; allylic radicals; octane sensitivity
Citation Formats
Westbrook, Charles K., Pitz, William J., Mehl, Marco, Glaude, Pierre-Alexandre, Herbinet, Olivier, Bax, Sarah, Battin-Leclerc, Frederique, Mathieu, Olivier, Petersen, Eric L., Bugler, John, and Curran, Henry J. Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics. United States: N. p., 2015.
Web. doi:10.1021/acs.jpca.5b00687.
Westbrook, Charles K., Pitz, William J., Mehl, Marco, Glaude, Pierre-Alexandre, Herbinet, Olivier, Bax, Sarah, Battin-Leclerc, Frederique, Mathieu, Olivier, Petersen, Eric L., Bugler, John, & Curran, Henry J. Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics. United States. https://doi.org/10.1021/acs.jpca.5b00687
Westbrook, Charles K., Pitz, William J., Mehl, Marco, Glaude, Pierre-Alexandre, Herbinet, Olivier, Bax, Sarah, Battin-Leclerc, Frederique, Mathieu, Olivier, Petersen, Eric L., Bugler, John, and Curran, Henry J. Tue .
"Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics". United States. https://doi.org/10.1021/acs.jpca.5b00687. https://www.osti.gov/servlets/purl/1785905.
@article{osti_1785905,
title = {Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics},
author = {Westbrook, Charles K. and Pitz, William J. and Mehl, Marco and Glaude, Pierre-Alexandre and Herbinet, Olivier and Bax, Sarah and Battin-Leclerc, Frederique and Mathieu, Olivier and Petersen, Eric L. and Bugler, John and Curran, Henry J.},
abstractNote = {Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (Φ = 0.5), stoichiometric (Φ = 1.0), and fuel-rich (Φ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C–H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce “cool flames” or negative temperature coefficient behavior. Furthermore, the connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low-temperature reactivity, and the gasoline engine concept of octane sensitivity are discussed.},
doi = {10.1021/acs.jpca.5b00687},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 119,
place = {United States},
year = {Tue Apr 14 00:00:00 EDT 2015},
month = {Tue Apr 14 00:00:00 EDT 2015}
}
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