Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method—combustion of methane

Frenklach, Michael; Wang, Shuangfeng; Rabinowitz, Martin J.

doi:10.1016/0360-1285(92)90032-v

Cited by 390 publications

(218 citation statements)

References 111 publications

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“…The proposed reaction sequence is shown in Figure 5. The system of coupled differential equations was solved numerically ( Frenklach et al 1992). The underlying rate constants found for each process are compiled in Table 5 and the resulting kinetic fits to the column densities of each species are shown in Figure 6.…”

Section: Reaction Schemementioning

confidence: 99%

Laboratory Studies on the Irradiation of Methane in Interstellar, Cometary, and Solar System Ices

Bennett

Jamieson

Osamura

et al. 2006

ApJ

157

168

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Pure methane ices (CH 4 ) were irradiated at 10 K with energetic electrons to mimic the energy transfer processes that occur in the track of the trajectories of MeV cosmic-ray particles. The experiments were monitored via an FTIR spectrometer (solid state) and a quadrupole mass spectrometer (gas phase). Combined with electronic structure calculations, this paper focuses on the identification of CH x (x ¼ 1Y4) and C 2 H x (x ¼ 2Y6) species and also investigates their formation pathways quantitatively. The primary reaction step is determined to be the cleavage of a carbonhydrogen bond of the methane molecule to form a methyl radical (CH 3 ) plus a hydrogen atom. Hydrogen atoms recombined to form molecular hydrogen, the sole species detected in the gas phase during the irradiation exposure. In the matrix two neighboring methyl radicals can recombine to form an internally excited ethane molecule (C 2 H 6 ), which either can be stabilized by the surrounding matrix or was found to decompose unimolecularly to the ethyl radical (C 2 H 5 ) plus atomic hydrogen and then to the ethylene molecule (C 2 H 4 ) plus molecular hydrogen. The initially synthesized ethane, ethyl, and ethylene molecules can be radiolyzed subsequently by the impinging electrons to yield the vinyl radical (C 2 H 3 ) and acetylene (C 2 H 2 ) as degradation products. Upon warming the ice sample after the irradiation, the new species are released into the gas phase, simulating the sublimation processes interstellar ices undergo during the hot core phase or comets approaching perihelion. Our investigations also aid the understanding of the synthesis of hydrocarbons likely to be formed in the aerosol particles and organic haze layers of hydrocarbon-rich atmospheres of planets and their moons such as Titan.

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Section: Reaction Schemementioning

confidence: 99%

Laboratory Studies on the Irradiation of Methane in Interstellar, Cometary, and Solar System Ices

Bennett

Jamieson

Osamura

et al. 2006

ApJ

157

168

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“…At temperatures above about 1200K, the dominant chain branching stepin hydrocarbonignition is reaction (7) [7][8][9][10][11][12], with H atoms that are produced thermal decomposition of radicals such as ethyl, vinyl, formyl, isopropyl and others. Activation energies of these reactions are quite large (e.g., 30 kcal/mol) and the activation energy of reaction (7) is also quite ¯large (16.8 kcal/mol), these reactions need high temperatures to proceed.…”

Section: High Temperature Ignition Shocl~ Tubes Detonations and Pulmentioning

confidence: 99%

“…High temperature (T > ~1200K) shock tube ignition is controlled by reaction (7). At shock tube temperatures, there is an initiation period for radical generation, followed by a period of explosive, exponential growth in radicals, dominated by reaction (7), consuming fuel and increasing the temperature.…”

Section: Shock Tubesmentioning

confidence: 99%

Chemical kinetics of hydrocarbon ignition in practical combustion systems

Westbrook

2000

Proceedings of the Combustion Institute

711

395

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Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignitio n in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be Used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical cOmbustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant.

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“…Figure 4.2 depicts the typical procedure that is followed for the development and validation of chemical kinetic models. The flowchart is adapted from a process that was initially outlined by Frenklach et al [79] and was summarized by Simmie [80]. It shows that the development and validation of a chemical kinetic mechanism is an iterative process until good agreement between experimental data and simulation results is achieved.…”

Section: Validating Chemical Kinetic Mechanismsmentioning

confidence: 99%

Experimental and kinetic modeling study of 1-hexanol combustion in an opposed-flow diffusion flame

Yeung

Thomson

2013

Proceedings of the Combustion Institute

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Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method—combustion of methane

Cited by 390 publications

References 111 publications

Laboratory Studies on the Irradiation of Methane in Interstellar, Cometary, and Solar System Ices

Laboratory Studies on the Irradiation of Methane in Interstellar, Cometary, and Solar System Ices

Chemical kinetics of hydrocarbon ignition in practical combustion systems

Experimental and kinetic modeling study of 1-hexanol combustion in an opposed-flow diffusion flame

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