Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols

Papagni, Christine; Arey, Janet; Atkinson, Roger

doi:10.1002/1097-4601(200102)33:2<142::aid-kin1007>3.0.co;2-f

Cited by 77 publications

(83 citation statements)

References 41 publications

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“…2) exhibits a very fast decay consistent with a reaction rate coefficient with OH similar to isoprene (1.0−1.2×10 −10 cm 3 molecule −1 s −1 ). This estimate is consistent with the fastest rate recently derived by Baker et al (2005) and ∼80% greater than the SAR estimate (k SAR OH =6.82×10 −11 cm 3 molecule −1 s −1 or 7.9×10 −11 cm 3 molecule −1 s −1 with the correction from Bethel et al, 2001;Papagni et al, 2001) . This discrepancy can be partly explained by the effect of the alcohol group α of the double bond which enhances the addition of OH (Papagni et al, 2001).…”

Section: Consequencessupporting

confidence: 91%

Isoprene photooxidation: new insights into the production of acids and organic nitrates

et al. 2009

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Abstract. We describe a nearly explicit chemical mechanism for isoprene photooxidation guided by chamber studies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the total isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chemistry of the δ-hydroxy channel with less than 5% of the carbon following the trans branch. The modelled yield of isoprene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NO x . Methacrolein nitrates (modelled yield 15±3% from methacrolein) and methylvinylketone nitrates (modelled yield 11±3% yield from methylvinylketone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived nitrate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summarized in a condensed scheme appropriate for use in global chemical transport models.

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Section: Consequencessupporting

confidence: 91%

Isoprene photooxidation: new insights into the production of acids and organic nitrates

et al. 2009

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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%

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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“…4 where the best fit “alkane” and “alkene” lines from the literature 16 are displayed. Included are some data for alcohols and esters that formally react through hydrogen atom abstraction 42–44. The deviation from the “abstraction” line is clear and in some cases systematic, just as in the aldehyde case 21.…”

Section: Resultsmentioning

confidence: 99%

“… Plot of log( k OH) vs. log( k NO 3 ) adapted from 19. In addition, open circles represent data for aldehyde from this work and 20, open triangles represent unsaturated alcohols from 32, 42, filled triangles represent saturated alcohols from 16, and crosses represent ethers from 43, 44. …”

Section: Resultsmentioning

confidence: 99%

Biomarkers, biometrics, and biology

Laskey

2002

Cathet Cardio Intervent

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Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols

Cited by 77 publications

References 41 publications

Isoprene photooxidation: new insights into the production of acids and organic nitrates

Isoprene photooxidation: new insights into the production of acids and organic nitrates

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

Biomarkers, biometrics, and biology

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