Kinetics of the reaction of ethyl radicals with molecular oxygen from 294 to 1002 K

Slagle, Irene R.; Feng, Qiao; Gutman, David

doi:10.1021/j150660a054

Cited by 107 publications

(134 citation statements)

References 7 publications

Supporting

Mentioning

124

Contrasting

Order By: Relevance

“…The description of peroxyl radical epoxidation given here, which also involves low lying excited states, can also be combined with the mechanism of Gutman et al 29,30 and Schaefer et al [62][63][64] figure 9) for the decomposition of the alkylperoxyl radical to the alkene, again shown schematically by the solid line in figure 9. figure 9) as suggested by Quelch et al 63 and…”

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 79%

“…reaction 4). 29,30 The discussion has tended to concentrated on the example of ethyl + O 2 , which has been the system most studied: + O 2 system is given by the solid line in figure 7. An important result was that the reaction of C 2 H 5 + O 2 was observed to have a negative activation energy, even at higher temperatures where production of the ethene was significant.…”

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 99%

“…Both came to the conclusion that their results were best explained by a mechanism in which the conjugate alkene was formed directly from the decomposition of the alkylperoxyl radical, and not via an isomerisation to the hydroperoxyalkyl radical. Clifford et al 40 recently suggested that the reaction of alkyl radicals with O 2 would lead to a proportion of the resultant chemically activated alkylperoxyl radical being in the first excited with the implication from the work of Gutman et al 29 radicals.…”

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 99%

See 2 more Smart Citations

Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals

Stark

2000

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The relatively low lying first electronic excited states of peroxyl radicals are suggested to play a direct role in determining the rate of their addition to alkenes, with there being, in the vicinity of the transition state, an unavoided crossing of C s symmetry of the ground and first excited states. If there is no charge transfer between radical and alkene during the formation of the adduct, then the barrier height is approximately equal to the energy required to excite an isolated peroxyl radical to its first excited state; with charge transfer, the activation energy for the addition is lowered in proportion to the energy released by the charge transfer. It is also suggested that for the specific case of hydroperoxyl radical addition to ethene, this description is compatible with the generally accepted mechanism for the reaction of ethyl radicals with molecular oxygen whereby the resulting ethylperoxyl radical can decompose to ethene and a hydroperoxyl radical via a cyclic 2 A transition state. Electron affinities, ionisation energies, absolute electronegativities and hardness of acetylperoxyl, hydroperoxyl, methylperoxyl, ethylperoxyl, iso-propylperoxyl and tertbutylperoxyl radicals have been calculated at the G2MP2 level.

show abstract

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 79%

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 99%

Section: The Reactions Of Alkyl + O 2 and Ho 2 + Alkenesmentioning

confidence: 99%

See 1 more Smart Citation

Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals

Stark

2000

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…(f) Photolysis of Cl 2 in the presence of C 2 H 6 , O 2 and M=He or N 2 at a pressure of 773 mbar. k ∞ was measured relative to the reaction C 2 H 5 + Cl 2 → C 2 H 5 Cl + Cl for which a rate coefficient of 1.04 × 10 −11 exp(300/T ) cm 3 molecule −1 s −1 was employed Timonen and Gutman, 1986). Reliability log k ∞ = ± 0.2 over the temperature range 200-300 K.…”

Section: Comments On Preferred Valuesmentioning

confidence: 99%

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

et al. 2006

View full text Add to dashboard Cite

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.

show abstract

“…These experiments employ a method pioneered by Gutman and coworkers [14][15][16], initiating reaction in a slow-flow reactor by pulsed-laser photolysis and following the reaction by mass spectrometric analysis of a nearlyeffusive flow out of a small orifice in the side of the reactor. The modification by Osborn and coworkers [12,17] uses photoionization by the tunable vacuum ultraviolet from the Chemical Dynamics Beamline of the Advanced Light Source (ALS) at LBNL.…”

Section: High-pressure Mbms Reactormentioning

confidence: 99%

Advanced fuel chemistry for advanced engines.

Taatjes¹,

Jusinski²,

Zádor³

et al. 2009

View full text Add to dashboard Cite

Autoignition chemistry is central to predictive modeling of many advanced engine designs that combine high efficiency and low inherent pollutant emissions. This chemistry, and especially its pressure dependence, is poorly known for fuels derived from heavy petroleum and for biofuels, both of which are becoming increasingly prominent in the nation's fuel stream. We have investigated the pressure dependence of key ignition reactions for a series of molecules representative of non-traditional and alternative fuels. These investigations combined experimental characterization of hydroxyl radical production in well-controlled photolytically initiated oxidation and a hybrid modeling strategy that linked detailed quantum chemistry and computational kinetics of critical reactions with rate-equation models of the global chemical system. Comprehensive mechanisms for autoignition generally ignore the pressure dependence of branching fractions in the important alkyl + O 2 reaction systems; however we have demonstrated that pressure-dependent "formally direct" pathways persist at in-cylinder pressures. 4 ACKNOWLEDGMENTSWe thank Dr. Ahren Jasper (8353) for assistance in quantum chemistry and fundamental computational kinetic methods; Dr. David Osborn (8353) and Dr. John T. Farrell (ExxonMobil) for assistance in the design of the high-pressure MBMS reactor. We also thank Prof. Giovanni Meloni (University of San Francisco) for his contributions to the experimental investigations.5

show abstract

Kinetics of the reaction of ethyl radicals with molecular oxygen from 294 to 1002 K

Cited by 107 publications

References 7 publications

Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals

Addition of Peroxyl Radicals to Alkenes and the Reaction of Oxygen with Alkyl Radicals

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

Advanced fuel chemistry for advanced engines.

Contact Info

Product

Resources

About