Evaluated Kinetic Data for Combustion Modeling: Supplement II

Baulch, D. L.; Bowman, Craig T.; Cobos, Carlos; Cox, R. A.; Just, Th.; Kerr, J. A.; Pilling, M. J.; Stocker, David; Troe, J.; Tsang, Wing; Walker, Raymond W.; Warnatz, Jürgen

doi:10.1063/1.1748524

Cited by 1,340 publications

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“…From experiments, Wantuck et al [42] reported a nonlinear Arrhenius behavior, with the rate constant increasing strongly above 600 K. However, their results have been questioned due to possible interference by thermal dissociation of CH 3 O (R19) at the higher temperatures. For this reason, Baulch et al [34] chose to disregard the data from Wantuck et al in their evaluation of k 19 . It is interesting to note that our theoretical rate constant (denoted by the solid line in Fig.…”

Section: Ab Initio Calculationsmentioning

confidence: 99%

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

Aranda

Christensen

Alzueta

et al. 2013

Int J of Chemical Kinetics

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A detailed chemical kinetic model for oxidation of CH 3 OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and RRKM analysis were used to obtain rate coefficients for key reactions of CH 2 OH and CH 3 O (dissociation, isomerization, reaction with O 2 ). The experiments, involving CH 3 OH/O 2 mixtures diluted in N 2 , were carried out in a high pressure flow reactor at 600-900 K and 20-100 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, while increasing pressure shifted the ignition temperature towards lower values. Model predictions of the present experimental results, as well as Rapid Compression Machine (RCM) data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation 2 pathways for CH 3 OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the CH 3 OH+HO 2 ⇌CH 2 OH+H 2 O 2 reaction.

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Section: Ab Initio Calculationsmentioning

confidence: 99%

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

Aranda

Christensen

Alzueta

et al. 2013

Int J of Chemical Kinetics

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“…HNC( 1  + ) 188 (Hansel et al 1998) HCN + ( 2 ) 1447 1440 (Baulch et al 2005, Lias et al 1988 This work (MRCI+Q/cc-pVQZ including ZPE) HNC + ( 2  + ) 1336 1349 (Kraemer et al 1992) This work (MRCI+Q/cc-pVQZ including ZPE)…”

mentioning

confidence: 98%

The interstellar gas-phase chemistry of HCN and HNC

Loison¹,

Wakelam²,

Hickson³

2014

Monthly Notices of the Royal Astronomical Society

108

109

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+ CH 2 reaction and two new reactions: H + CCN and C + HNC. We test the effect of the new rate constants and branching ratios on the predictions of gas-grain chemical models for dark cloud conditions. The rapid C + HNC reaction keeps the HCN/HNC ratio significantly above one as long as the carbon atom abundance remains high. However, the reaction of HCN with H 3 + followed by DR of HCNH + acts to isomerize HCN into HNC when carbon atoms and CO are depleted leading to a HCN/HNC ratio close to or slightly greater than 1. This agrees well with observations in TMC-1 and L134N taking into consideration the overestimation of HNC abundances through the use of the same rotational excitation rate constants for HNC as for HCN in many radiative transfer models.

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“…Figure 3 compares our calculated reaction rate constants of the three channels with the corresponding values deployed in kinetic models of Dagaut et al [9] and Gudiyella and Brezinsky [11]. These two models incorporate the kinetic parameters that were carried over from the system of n-propane + HO 2 based on the recommended values of Baulch et al [39], from primary and secondary sites and from the system of toluene + HO 2 for benzylic sites [39]. Comparison is also made with our theoretically-derived values for ethylbenzene [22].…”

Section: Abstraction Of Propyl H Atom By Ho 2 Radicalsmentioning

confidence: 99%

Reactions of HO2 with n-propylbenzene and its phenylpropyl radicals

Altarawneh

Dlugogorski

2015

Combustion and Flame

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Abstraction of an H atom from the propyl side chain by hydroperoxyl radicals (HO 2 ) constitutes a central reaction in the low-temperature oxidation of n-propylbenzene (nPB).Herein, we calculate reaction rate constants for H abstraction from primary, secondary and benzylic sites in nPB. Rate of abstraction of a benzylic H atom dominates that of a secondary H atom with negligible abstraction of the primary H atom at T ≥ 600 K. We present the reaction enthalpies for 1-phenyl-1-propyl (R1), 1-phenyl-2-propyl (R2) and 1-phenyl-3-propyl (R3) radicals, and compare the computed reaction rate constants and bond dissociation enthalpies with analogous scarce literature values. Addition of HO 2 radicals to radical sites in R1, R2 and R3 proceeds in a highly exothermic process and results in the formation of HO 2 -phenylpropyl adducts. Mapped potential energy surfaces illustrate all plausible exit channels of the three HO 2 -phenylpropyl adducts. Master equation calculations for the three phenylpropyl + HO 2 reactions indicate that direct O-OH bond fission and water elimination control the fate of the adducts leading to the formation of ketonic-type structures. Results from this study should be useful to update kinetic models for the low-temperature oxidation of alkylbenzenes in general.

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Evaluated Kinetic Data for Combustion Modeling: Supplement II

Cited by 1,340 publications

References 0 publications

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

The interstellar gas-phase chemistry of HCN and HNC

Reactions of HO2 with n-propylbenzene and its phenylpropyl radicals

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