Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase

Mellouki, Abdelwahid; Bras, G. Le; Sidebottom, Howard

doi:10.1021/cr020526x

Cited by 282 publications

(278 citation statements)

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“…The CH 2 CH 2 OH radical may decompose thermally, react with the O/H radical pool, or with stable species such as O 2 . The rates for reactions of unsaturated alcohols with a CH 2 =CHROH structure are generally somewhat faster than those of the corresponding alkenes [30], indicating that the ROH substituent activates the C=C bond [30,50,51]. However, the difference in rates are roughly within a factor of two at 298 K. By analogy with oxidation of C 2 H 5 under similar conditions [19], we would expect the reaction with O 2 to be the major consumption step for CH 2 CH 2 OH.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…The rate constant governing the path to C 2 H 3 +H 2 O shows a strong positive temperature dependence, which makes (R4) the predominant reaction channel above 1000 K. The addition channel (R8) has mostly drawn attention due to its role in atmospheric chem-istry [30,38], but results have been reported also at higher pressures and temperatures of up to 800 K [48]. Recently, Senosiain et al [44] did a thorough master equation study of the C 2 H 4 +OH reaction.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…However, while these early studies correctly identified important features of the system, they had to rely on rough estimates for several key reactions. In developing the present mechanism we have been able to draw on a number of recent experimental or high-level theoretical studies, mostly prompted by the interest in C 2 H 4 oxidation in the troposphere [30,38]. Furthermore, we conducted a theoretical study of C 2 H 3 + O 2 , as discussed below.…”

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Experimental and kinetic modeling study of C2H4 oxidation at high pressure

López

Rasmussen

Alzueta

et al. 2009

Proceedings of the Combustion Institute

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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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Section: Detailed Kinetic Modelmentioning

confidence: 99%

Section: Detailed Kinetic Modelmentioning

confidence: 99%

mentioning

confidence: 99%

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Experimental and kinetic modeling study of C2H4 oxidation at high pressure

López

Rasmussen

Alzueta

et al. 2009

Proceedings of the Combustion Institute

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“…This increase in the reactivity is due to the presence of the hydrogen atoms linked to the carbon atoms located in a -position with respect to the CO group [20,21]. In addition hydrogen atoms that are attached to secondary carbons are the most likely attack sites [22][23].…”

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confidence: 99%

UV–visible spectra and gas-phase rate coefficients for the reaction of 2,3-pentanedione and 2,4-pentanedione with OH radicals

Messaadia

Dib

Ferhati

et al. 2015

Chemical Physics Letters

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The UV absorption cross-sections of 2,3-pentanedione and 2,4-pentanedione were measured and their reactions with OH were investigated in the gas-phase using a relative rate method. A temperature dependence of the rate coefficients was observed for both reactions over the temperature range 298 -338 K. This work provides the first UV cross-section in the gas phase for 2,4-pentanedione and the first kinetic data for the reaction of 2,3-pentanedione with OH radicals as a function of temperature. The tropospheric lifetimes obtained in this work suggest that once emitted into the atmosphere, these species could be quickly degraded close to their emission sources.

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“…The low decomposition barrier for C-C bond breaking compared to the other pathways is in agreement with observations and calculations for non-fluorinated alkoxy radials. [39][40][41] F-abstraction by O 2 atoms, forming FO 2 radicals, is endothermic by over 20 kcal mol À1 .…”

Section: Oxidation Mechanismmentioning

confidence: 99%

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

Vereecken

Crowley

Amedro

2015

Phys. Chem. Chem. Phys.

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Product formation in the reaction of perfluorinated methyl vinyl ether, CF 3 OCFQCF 2 , with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable endproducts in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF 3 OCFO, and fluorinated glycolaldehyde, CFOCF 2 OH, both with CF 2 O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF 2 OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work.

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Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 282 publications

References 154 publications

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

UV–visible spectra and gas-phase rate coefficients for the reaction of 2,3-pentanedione and 2,4-pentanedione with OH radicals

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂

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Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 282 publications

References 154 publications

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

UV–visible spectra and gas-phase rate coefficients for the reaction of 2,3-pentanedione and 2,4-pentanedione with OH radicals

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCFCF2

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Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF₃OCFCF₂