Rate constants for the reaction of OH radicals with ethylene over the temperature range 299–425 °K

Atkinson, Roger; Perry, R. A.; Pitts, James N.

doi:10.1063/1.434066

Cited by 76 publications

(65 citation statements)

References 20 publications

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“…Furthermore, the present rate constant rate ratios kl/kz are, with minor exceptions, in excellent agreement with the ratios derived from the absolute room-temperature rate constants determined by Atkinson and Pitts and co-workers [13,16,18,20,411 using a flash photolysis-resonance fluorescence technique. For 1-butene, truns-2-butene, and 1,3-butadiene these flash photolysis-resonance fluorescence data [13,181 yield somewhat higher ratios (by 18%, 14% and 8%, respectively), though they are in agreement within the combined experimental errors.…”

Section: Discussionsupporting

confidence: 82%

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Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K

Atkinson

Aschmann

1984

Int J of Chemical Kinetics

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Using a relative rate technique, rate constants for the gas phase reactions of the OH radical with n-butane, n-hexane, and a series of alkenes and dialkenes, relative to that for propene, have been determined in one atmosphere of air at 295 f 1 K. The rate constant ratios obtained were (propene = 1.00): ethene, 0.323 2 0.014; 1-butene, 1.19 i 0.06; 1-pentene, 1.19 2 0.05; 1-hexene, 1.40 0.04; 1-heptene, 1.51 2 0.06; 3-methyl-1-butene, 1.21 2 0.04; isobutene, 1.95 2 0.09; cis-2-butene, 2.13 2 0.05; trans-2-butene, 2.43 2 0.05; 2-methyl-2-butene, 3.30 2 0.13; 2,3-dimethyl-2-butene, 4.17 i 0.18; propadiene, 0.367 0.036; 1,3-butadiene, 2.53 2 0.08; 2-methyl-1,3-butadiene, 3.81 2 0.15; n-butane, 0.101 2 0.012; and n-hexane, 0.198 ? 0.017. From a least-squares fit of these relative rate data to the most reliable literature absolute flash photolysis rate constants, these relative rate constants can be placed on an absolute basis using a rate constant for the reaction of OH radicals with propene of 2.63 x lo-" cm3 molecule-' s-'. The resulting rate constant data, together with previous relative rate data from these and other laboratories, lead to a self-consistent data set for the reactions of OH radicals with a large number of organics at room temperature.

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Section: Discussionsupporting

confidence: 82%

“…1-25 torr and ca. 225-torr total pressures of argon diluent, respectively, for propene and ethene [13,16,191. Hence for the alkenes and dialkenes only rate constant data obtained in the limiting high-pressure regime are useful for lower tropospheric purposes.…”

Section: Introductionmentioning

confidence: 99%

Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K

Atkinson

Aschmann

1984

Int J of Chemical Kinetics

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“…36,37,51 The high-pressure addition rate constant for C 2 H 4 + OH was generally found to decrease slightly with increasing temperature in the 100-600 K range, with measured Arrhenius activation energies ranging from -2.3 to 0.0 kcal/ mol. 23,31,36,43,51,53 Lower-temperature studies have been limited to Leone and co-workers' 53 study over the temperature range from 96 to 296 K using the pulsed Laval nozzle technique. Although relatively low pressures were employed in this study (e.g., less than 1 Torr for the lower temperatures), it was argued that the results still pertained to the high-pressure limit due to the increase in the lifetime of the complex with decreasing temperature.…”

Section: Introductionmentioning

confidence: 99%

A Two Transition State Model for Radical−Molecule Reactions: Applications to Isomeric Branching in the OH−Isoprene Reaction

et al. 2007

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A two transition state model is applied to the study of the addition of hydroxyl radical to ethylene. This reaction serves as a prototypical example of a radical-molecule reaction with a negative activation energy in the high-pressure limit. The model incorporates variational treatments of both inner and outer transition states. The outer transition state is treated with a recently derived long-range transition state theory approach focusing on the longest-ranged term in the potential. High-level quantum chemical estimates are incorporated in a variational transition state theory treatment of the inner transition state. Anharmonic effects in the inner transition state region are explored with direct phase space integration. A two-dimensional master equation is employed in treating the pressure dependence of the addition process. An accurate treatment of the two separate transition state regions at the energy and angular momentum resolved level is essential to the prediction of the temperature dependence of the addition rate. The transition from a dominant outer transition state to a dominant inner transition state is predicted to occur at about 130 K, with significant effects from both transition states over the 10 to 400 K temperature range. Modest adjustment in the ab initio predicted inner saddle point energy yields theoretical predictions which are in quantitative agreement with the available experimental observations. The theoretically predicted capture rate is reproduced to within 10% by the expression [4.93 × 10 -12 (T/298) -2.488 exp(-107.9/RT) + 3.33 × 10 -12 (T/298) 0.451 exp(117.6/RT); with R ) 1.987 and T in K] cm 3 molecules -1 s -1 over the 10-600 K range.

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“…The relative importance of the three channels is a complex function of pressure and temperature. At atmospheric pressure and temperatures <500 K, the reaction almost exclusively proceeds via (R8) to form CH 2 CH 2 OH with a slight negative temperature dependence [45][46][47].…”

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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Rate constants for the reaction of OH radicals with ethylene over the temperature range 299–425 °K

Cited by 76 publications

References 20 publications

Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K

Rate constants for the reaction of OH radicals with a series of alkenes and dialkenes at 295 ± 1 K

A Two Transition State Model for Radical−Molecule Reactions: Applications to Isomeric Branching in the OH−Isoprene Reaction

Experimental and kinetic modeling study of C2H4 oxidation at high pressure

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