Chemical Kinetic Data Base for Combustion Chemistry. Part 2. Methanol

Tsang, Wing

doi:10.1063/1.555802

Cited by 296 publications

(254 citation statements)

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“…28 However, CH 3 O formed from R3a has a large energy excess resulting from the exothermicity of this channel (ΔH°2 98 = −180.9 kJ mol −1 ), and should fall apart quickly: (R13) where CH 2 OH is a possible product from R1, is also exothermic enough to make CH 2 O( 1 A ″) and estimated to be fast 29 27 The decay of the chemiluminescence signal (inset in Fig. 5), which is proportional to the concentration of CH 2 O( 1 A″), is mostly determined by R1 and R10-R11 and the short lifetime of the excited state (k′ ~ 10 7 s −1 ).…”

Section: Plp-lif-low Temperature Reactormentioning

confidence: 99%

Low Temperature Kinetics of the CH₃OH + OH Reaction

et al. 2014

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The rate constant of the reaction between methanol and the hydroxyl radical has been studied in the temperature range 56-202 K by pulsed laser photolysis-laser induced fluorescence in two separate experiments using either a low temperature flow tube coupled to a time of flight mass spectrometer or a pulsed Laval nozzle apparatus. The two independent techniques yield rate constants which are in mutual agreement and consistent with the results reported previously below 82 K [Shannon et al., Nature Chemistry, 2013, 5, 745-749] and above 210 K [Dillon et al., Phys. Chem. Chem. 2005, 7, 349-355], showing a very sharp increase with decreasing temperature with an onset around 180 K. This onset is also signalled by strong chemiluminescence tentatively assigned to formaldehyde, which is consistent with the formation of the methoxy radical at low temperature by quantum tunnelling, and its subsequent reaction with H and OH. Our results add confidence to the previous low temperature rate constant measurements and consolidate the experimental reference dataset for further theoretical work required to describe quantitatively the tunnelling mechanism operating in this reaction. An additional measurement of the rate constant at 56 K yielded a value of (4.9 ± 0.8) × 10 −11 cm 3 molecule −1 s −1 (2σ), showing that the rate constant is increasing less rapidly at temperatures below 70 K.

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Section: Plp-lif-low Temperature Reactormentioning

confidence: 99%

Low Temperature Kinetics of the CH₃OH + OH Reaction

et al. 2014

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“…The reactions of ethylene and methanol are part of this base. Reactions of methanol are mainly taken from Tsang [22]. The pressure dependent rate coefficients are obtained using the formalism proposed by Troe [23].…”

Section: Mechanism For the Oxidation Of N-heptanementioning

confidence: 99%

Influence of EGR compounds on the oxidation of an HCCI-diesel surrogate

Anderlohr

Piperel²,

Cruz³

et al. 2009

Proceedings of the Combustion Institute

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This paper presents an experimental and numerical study of the impact of various additives on the oxidation of a typical automotive surrogate fuel blend, i.e. n-heptane and toluene. It examines the impact of engine re-cycled exhaust gas compounds on the control of a Homogeneous Charge Compression Ignition (HCCI) engine. A series of experiments were performed in a highly diluted Jet-Stirred Reactor (JSR) at pressures of 1 and 10atm (1atm = 101325Pa). The chosen thermo-chemical conditions were close to those characteristic of the pre-ignition period in an HCCI-engine. The influence of various additives, namely nitric oxide (NO), ethylene (C 2 H 4 ) and methanol (CH 3 OH), on the oxidation of a n-heptane/toluene blend was studied over a wide range of temperatures (550-1100K), including the zone of the Negative Temperature Coefficient (NTC).A new detailed chemical kinetic reaction mechanism is proposed for the oxidation of the surrogate fuel. It includes reactions of NO, methanol (CH 3 OH) and ethylene (C 2 H 4 ) and is used to explain the obtained experimental data. The mechanism is further used to theoretically study the impact of other Exhaust Gas Recirculation (EGR) compounds on the hydrocarbon oxidation, namely ethane (C 2 H 6 ), formaldehyde (HCHO) and carbon monoxide (CO).

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“…Activation energies and pre-exponential factors are reported in literature [10,14,20,23,57] in the range from 89.9 to 91.8 kcal/mol and 0.95-2.00 Â 10 þ16 s À1 , respectively. Our activation energies (ranging from 95.3 to 102.7 kcal/mol) and pre-exponential factors (ranging from 5.08 Â 10 þ16 to 4.02 Â 10 þ18 s À1 ) differ from those previously reported, being higher than literature data.…”

Section: Ohmentioning

confidence: 99%

“…Figure 6 shows a comparison of our calculated rate constants (obtained from MRPT(6,4)/ACCD//CAS(6,4)/ACCD data and related dissociation rate constants and equilibrium constants) and literature data. [57][58][59][60][61][62][63] These recombination rate constants (in cm 3 molecule À1 s À1 ) are best fitted to:…”

Section: Ohmentioning

confidence: 99%

Implementation of a variational code for the calculation of rate constants and application to barrierless dissociation and radical recombination reactions: CH₃OH = CH₃ + OH

Oliveira¹,

Bauerfeldt²

2012

Int J of Quantum Chemistry

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Here, a new implementation for calculating canonical variational rate constants is introduced and tested against methanol dissociation rate constants and the (high pressure) radical recombination reaction, CH 3 þ OH ! CH 3 OH. Reaction paths are described at the CASSCF level, with energy corrections at MRMP2. Molecular properties for both stationary and non-stationary points along the reaction path are used for the calculation of rate constants. Different models for the low vibrational frequencies are discussed: harmonic oscillator and free rotor models. The CH 3 þ OH ! CH 3 OH recombination rate constants are determined from dissociation rate constants and equilibrium constants. Our calculated rate constants agree with previously reported data for these reactions, suggesting the good performance of our implemented code in calculating canonical variational rate constants. The rate expressions are suggested: as: k dis (T) ¼ 8.42 Â 10 þ16 Â e À96.18/RT and k rec (T) ¼ 2.05 Â 10 À10 Â (T/298) À0.24 Â e À0.30/RT , in units s À1 and cm 3 molecule À1 s À1 , respectively, and over the temperature range 300-2000 K, with activation energies in kcal/mol.

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Chemical Kinetic Data Base for Combustion Chemistry. Part 2. Methanol

Cited by 296 publications

References 0 publications

Low Temperature Kinetics of the CH₃OH + OH Reaction

Low Temperature Kinetics of the CH₃OH + OH Reaction

Influence of EGR compounds on the oxidation of an HCCI-diesel surrogate

Implementation of a variational code for the calculation of rate constants and application to barrierless dissociation and radical recombination reactions: CH₃OH = CH₃ + OH

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Chemical Kinetic Data Base for Combustion Chemistry. Part 2. Methanol

Cited by 296 publications

References 0 publications

Low Temperature Kinetics of the CH3OH + OH Reaction

Low Temperature Kinetics of the CH3OH + OH Reaction

Influence of EGR compounds on the oxidation of an HCCI-diesel surrogate

Implementation of a variational code for the calculation of rate constants and application to barrierless dissociation and radical recombination reactions: CH3OH = CH3 + OH

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Product

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Low Temperature Kinetics of the CH₃OH + OH Reaction

Low Temperature Kinetics of the CH₃OH + OH Reaction

Implementation of a variational code for the calculation of rate constants and application to barrierless dissociation and radical recombination reactions: CH₃OH = CH₃ + OH