Kinetics of the reaction of OH radicals with acetylene in 25–8000 torr of air at 296 K

Sørensen, Michael A.; Kaiser, E. W.; Hurley, M. D.; Wallington, Timothy J.; Nielsen, Ole John

doi:10.1002/kin.10119

Cited by 54 publications

(64 citation statements)

References 16 publications

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“…The recent study of confirms the earlier data of , Michael et al (1980), Perry and Williamson (1982), , , Wahner and Zetzsch (1985), , Arnts et al (1989) and Bohn et al (1996), all of which indicate a rate coefficient at room temperature and 1 bar of air or N 2 of ∼8 ×10 −13 cm 3 molecule −1 s −1 and a value of k ∞ ∼1.0 ×10 −12 cm 3 molecule −1 s −1 at 298 K. These data are, however, inconsistent with those from the study of Fulle et al (1997), for reasons which are presently not understood (at 298 K and 1 bar of He, the data of Fulle et al (1997) lead to k = 1.12 ×10 −12 cm 3 molecule −1 s −1 , with k ∞ = 1.8 ×10 −12 cm 3 molecule −1 s −1 at 298 K).…”

Section: Comments On Preferred Valuessupporting

confidence: 88%

“…This influences the construction of falloff curves and the extrapolation to k 0 . The recent study of confirms the earlier data of , Michael et al (1980), Perry and Williamson (1982), Hack et al (1983), , , Wahner and Zetzsch (1985), , , Arnts et al (1989) and Bohn et al (1996) (g) HO radicals were generated by the photolysis of CH 3 ONO in CH 3 ONO-NO-C 2 H 2 -cyclohexane-air mixtures at 1 bar total pressure. The concentrations of acetylene and cyclohexane (the reference compound) were measured by GC.…”

Section: Comments On Preferred Valuessupporting

confidence: 84%

“…A comparison of the data of , Michael et al (1980), Perry and Williamson (1982), Hack et al (1983), , , Wahner and Zetzsch (1985), , , Arnts et al (1989) and Bohn et al (1996) at pressures between 0.01-1 bar with the results from Fulle et al (1997) at 2-80 bar shows considerable discrepancies, with the data of Fulle et al (1997) leading to k ∞ considerably higher than the lower pressure data. This influences the construction of falloff curves and the extrapolation to k 0 .…”

Section: Comments On Preferred Valuesmentioning

confidence: 96%

“…The preferred rate coefficient at 298 K is based on the experimental data of , Wahner and Zetzsch (1985) and Bohn et al (1996) and the theoretical analysis of . The temperature dependence is based on the data of , Michael et al (1980) and Perry and Williamson (1982) as discussed and evaluated by Atkinson (1989).…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

“…The preferred values are based on the data of Perry and Williamson (1982), , , Wahner and Zetzsch (1985), , , Arnts et al (1989), Bohn et al (1996) and and are applicable to room temperature only. …”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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Abstract. This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002, and subsequently during the preparation of this article. The article consists of a summary table of the recommended rate coefficients, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices containing the data sheets, which provide information upon which the recommendations are made.

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Section: Comments On Preferred Valuessupporting

confidence: 88%

Section: Comments On Preferred Valuessupporting

confidence: 84%

Section: Comments On Preferred Valuesmentioning

confidence: 96%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

et al. 2006

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The hydroxyl radical reaction rate constant and products of 3,5‐dimethyl‐1‐hexyn‐3‐ol

Wells

2004

Int J of Chemical Kinetics

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A bimolecular rate constant, k DHO , of (29 ± 9) × 10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,5-dimethyl-1-hexyn-3-ol (DHO, HC CC(OH)(CH 3 )CH 2 CH(CH 3 ) 2 ) at (297 ± 3) K and 1 atm total pressure. To more clearly define DHO's indoor environment degradation mechanism, the products of the DHO + OH reaction were also investigated. The positively identified DHO/OH reaction products were acetone ((CH 3 ) 2 C O), 3-butyne-2-one (3B2O, HC CC( O)(CH 3 )), 2-methyl-propanal (2MP, H(O )CCH(CH 3 ) 2 ), 4-methyl-2-pentanone (MIBK, CH 3 C( O)CH 2 CH(CH 3 ) 2 ), ethanedial (GLY, HC( O)C( O)H), 2-oxopropanal (MGLY, CH 3 C( O)C( O)H), and 2,3-butanedione (23BD, CH 3 C( O)C( O)CH 3 ). The yields of 3B2O and MIBK from the DHO/OH reaction were (8.4 ± 0.3) and (26 ± 2)%, respectively. The use of derivatizing agents O- (2,3,4,5,6-pentalfluorobenzyl)hydroxylamine (PFBHA) and N,Obis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible DHO/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms. C

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Experimental and Kinetic Modeling Study of C₂H₂ Oxidation at High Pressure

Giménez-López

Rasmussen

Hashemi

et al. 2016

Int J of Chemical Kinetics

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A detailed chemical kinetic model for oxidation of C 2 H 4 in the intermediate temperature range and high pressure has been developed and validated experimentally. New ab initio calculations and RRKM analysis of the important C 2 H 3 + O 2 reaction was was used to obtain rate coefficients over a wide range of conditions (0.003-100 bar, 200-3000 K). The results indicate that at 60 bar vinyl peroxide, rather than CH 2 O and HCO, is the dominant product.The experiments, involving C 2 H 4 /O 2 mixtures diluted in N 2 , were carried out in a high pressure flow reactor at 600-900 K and 60 bar, varying the reaction stoichiometry from very lean to fuel-rich conditions. Model predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Under the investigated conditions the oxidation pathways for C 2 H 4 are more complex than those prevailing at higher temperatures and lower pressures. The major differences are the importance of the hydroxyethyl (CH 2 CH 2 OH) and 2-hydroperoxyethyl 1 (CH 2 CH 2 OOH) radicals, formed from addition of OH and HO 2 to C 2 H 4 , and vinyl peroxide, formed from C 2 H 3 + O 2 . Hydroxyethyl is oxidized through the peroxide HOCH 2 CH 2 OO (lean conditions) or through ethenol (low O 2 concentration), while 2-hydroperoxyethyl is converted through oxirane. [2][3][4][5][6][7], shock tubes [8][9][10][11][12] and premixed laminar flames [13][14][15][16][17], covering a wide range of stoichiometries and temperatures. Most of the reported work, however, have been carried out at near atmospheric pressure. A few results are available from flow reactor studies at 5-10 bar [6], but despite their relevance for the chemistry in engines, gas turbines, and gas-to-liquid processes, data at high pressures are limited.The objective of the present study is to obtain experimental results for the oxidation of C 2 H 4 at high pressure (60 bar) as functions of temperature (600-900 K) and stoichiometry (lean to fuel-rich) and analyze them in terms of a detailed chemical kinetic model. The oxidation pathways for C 2 H 4 under these conditions are different from those prevailing at higher temperatures and lower pressures and the results of the current work help to extend the validation range for chemical kinetic modeling of C 2 H 4 oxidation. This paper is part of a series investigating the high-pressure, medium temperature oxidation of simple fuels: previously work has been reported for CO/H 2 , CH 4 , and CH 4 /C 2 H 6 mixtures [18,19]. The present kinetic model draws on this work, as well as recent results in tropospheric chemistry. Furthermore, the important reaction of C 2 H 3 with O 2 was characterized from ab initio calculations over a wide range of pressure and temperature. 3 ExperimentalThe experimental setup is a laboratory-scale high pressure laminar flow reactor designed to approximate plug-flow. The setup is described in detail elsewhere [18] and only a brief description is provided here. The system enables well-defined investigations of...

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Kinetics of the reaction of OH radicals with acetylene in 25–8000 torr of air at 296 K

Cited by 54 publications

References 16 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

The hydroxyl radical reaction rate constant and products of 3,5‐dimethyl‐1‐hexyn‐3‐ol

Experimental and Kinetic Modeling Study of C₂H₂ Oxidation at High Pressure

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Kinetics of the reaction of OH radicals with acetylene in 25–8000 torr of air at 296 K

Cited by 54 publications

References 16 publications

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

The hydroxyl radical reaction rate constant and products of 3,5‐dimethyl‐1‐hexyn‐3‐ol

Experimental and Kinetic Modeling Study of C2H2 Oxidation at High Pressure

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Experimental and Kinetic Modeling Study of C₂H₂ Oxidation at High Pressure