Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

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.

doi:10.1021/acs.jpca.5b00687

Title: Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

Journal Article · Tue Apr 14 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b00687· OSTI ID:1785905

Westbrook, Charles K. ^[1]; Pitz, William J. ^[1]; Mehl, Marco ^[1]; Glaude, Pierre-Alexandre ^[2]; Herbinet, Olivier ^[2]; Bax, Sarah ^[2]; Battin-Leclerc, Frederique ^[2]; Mathieu, Olivier ^[3]; Petersen, Eric L. ^[3]; Bugler, John ^[4]; Curran, Henry J. ^[4]

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)

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.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1785905

Report Number(s):: LLNL-JRNL-666494; 787978

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 28; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Multi-fuel surrogate chemical kinetic mechanisms for real world applications Westbrook, Charles K.; Mehl, Marco; Pitz, William J. Physical Chemistry Chemical Physics, Vol. 20, Issue 16 https://doi.org/10.1039/c7cp07901j	journal	January 2018
Review of Oxidation of Gasoline Surrogates and Its Components Piehl, J. A.; Zyada, A.; Bravo, L. Journal of Combustion, Vol. 2018 https://doi.org/10.1155/2018/8406754	journal	December 2018
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
hydrocarbons
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2-methyl-2-butane
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Title: Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

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