High-Temperature Reactions of OH Radicals with Benzene and Toluene

Seta, Takahiro; Nakajima, Masakazu; Miyoshi, Akira

doi:10.1021/jp0575456

Cited by 128 publications

(153 citation statements)

References 52 publications

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“…They are abbreviated as CBS-QB3 E(0K), hereinafter. Although the CBS-QB3 method has been tested for many compounds and is also validated for some transition-state calculations [12], the validity of the method for the system investigated in this work was confirmed by comparing the calculated bond dissociation enthalpies of the relevant compounds and radicals with experimental values [13][14][15]. The results are summarized in Tables I and II.…”

Section: Methodsmentioning

confidence: 87%

Computational studies on the reactions of 3‐butenyl and 3‐butenylperoxy radicals

Miyoshi

2010

Int J of Chemical Kinetics

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The reactions of 3-butenyl ( • CH 2 CH 2 CH CH 2 ) radicals-unimolecular decomposition, isomerization, as well as reaction with O 2 -and the subsequent unimolecular rearrangement reactions of the 3-butenylperoxy radicals have been investigated and are compared to the analogous reactions of butyl ( • CH 2 CH 2 CH 2 CH 3 ) and butylperoxy radicals using transition-state theory based on the quantum chemical calculations at the CBS-QB3 level. For alkyl-analogue processes, the reactions of 3-butenyl and 3-butenylperoxy radicals can be well characterized by the decreased and increased bond dissociation energies at the allylic and vinylic sites, respectively. The intramolecular addition reactions of the radical center atoms to the double bonds were found to be important non-alkyl-analogue reactions of 3-butenyl and 3-butenylperoxy radicals. As a consequence, the thermal decomposition of 3-butenyl radicals was found to be slower than that of butyl radicals by one order of magnitude at temperature near 1000 K. Intramolecular addition reactions are suggested to be the predominant unimolecular rearrangement processes of 3-butenylperoxy radicals over the entire temperature range investigated (500-1200 K). The intramolecular addition reactions of the alkenyl peroxy radicals, which have not been included in combustion kinetic models, and their implications for the autoignition of alkenes are discussed. C 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: [273][274][275][276][277][278][279][280][281][282][283][284][285][286][287][288] 2010

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Section: Methodsmentioning

confidence: 87%

Computational studies on the reactions of 3‐butenyl and 3‐butenylperoxy radicals

Miyoshi

2010

Int J of Chemical Kinetics

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“…C-H fission and H· abstraction of methylbenzyl radicals in pyrolysis and oxidation of xylenes was examined [26] and good agreement was achieved with experiment. Both calculations and shock tube/pulsed laserinduced fluorescence methods were applied to the reaction [27] of OH· with benzene and toluene and found a barrier for H· extraction of some 3 kcal/mol, quite similar to the barrier to OH· addition.…”

Section: Introductionmentioning

confidence: 93%

“…As indicated above, there have been a number of studies of both the H· abstraction and the OH· addition process of benzene, using fairly high levels of theory [24,25,27,29,46]. In addition to various specific levels of theory, the results differ also in whether or not zero-point vibrational terms have been added to the electronic energies.…”

Section: Benchmarksmentioning

confidence: 99%

Evaluation of DFT methods to study reactions of benzene with OH radical

Scheiner

2011

Int J of Quantum Chemistry

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Several DFT methods are applied to two different reaction channels involving OH· + C 6 H 6 , and the results compared to high-level ab initio calculations. The OH· adds directly to one C atom in the first channel, first forming an encounter complex with the OH· poised above the aromatic plane. B3LYP, BH&HLYP, and MPW1K compute an accurate estimate of the overall exothermicity, while M05-2X, PBE0 and PBEPBE, overestimate this quantity to some degree. With the exceptions of PBEPBE and PBE0, the other methods produce an acceptable barrier to addition. All approaches except BH&HLYP correctly predict an exothermic H· abstraction, although PBEPBE is too exothermic. The BH&HLYP barrier to H· abstraction is too high while the MPW1K, PBE0, and B3LYP values are better, and M05-2X the best.

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“…The main kinetic study of toluene + OH of relevance to combustion temperatures is a transition state theory study from Seta et al [41]. There are likely to be large uncertainties in this system which will clearly impact on the robustness of TRF mechanisms.…”

Section: The Representation Of the Reference Gasoline Via The Trf Surmentioning

confidence: 99%

The influence of n -butanol blending on the ignition delay times of gasoline and its surrogate at high pressures

Agbro

Tomlin

Lawes

et al. 2017

Fuel

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The influence of blending n-butanol at 20% by volume on the ignition delay times for a reference gasoline was studied in a rapid compression machine (RCM) for stoichiometric fuel/air mixtures at 20 bar and 678 K-858 K. Delay times for the blend lay between those of stoichiometric gasoline and stoichiometric n-butanol across the temperature range studied. At lower temperatures, delays for the blend were however, much closer to those of n-butanol than gasoline despite n-butanol being only 20% of the mixture. Under these conditions n-butanol acted as an octane enhancer over and above what might be expected from a simple linear blending law. The ability of a gasoline surrogate, based on a toluene reference fuel (TRF), to capture the main trends of the gasoline/ n-butanol blending behaviour was also tested within the RCM. The 3-component TRF based on a mixture of toluene, n-heptane and iso-octane was able to capture the trends well across the temperature range studied. Simulations of ignition delay times were also performed using a detailed blended nbutanol/TRF mechanism based on the adiabatic core assumption and volume histories from the experimental data. Overall, the model captured the main features of the blending behaviour, although at the lowest temperatures, predicted ignition delays for stoichiometric n-butanol were longer than those observed. A bruteforce local sensitivity analysis was performed to evaluate the main chemical processes driving the ignition behaviour of the TRF, n-butanol and blended fuels. The reactions of fuel + OH dominated the sensitivities at lower temperatures, with H abstraction from nn-butanol and the blend. At higher temperatures the decomposition of H 2 O 2 and reactions of HO 2 and that of formaldehyde with OH became critical, in common with the ignition behaviour of other fuels. Remaining uncertainties in the rates of these key reactions are discussed.

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High-Temperature Reactions of OH Radicals with Benzene and Toluene

Cited by 128 publications

References 52 publications

Computational studies on the reactions of 3‐butenyl and 3‐butenylperoxy radicals

Computational studies on the reactions of 3‐butenyl and 3‐butenylperoxy radicals

Evaluation of DFT methods to study reactions of benzene with OH radical

The influence of n -butanol blending on the ignition delay times of gasoline and its surrogate at high pressures

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