Detailed kinetic modeling of 1,3-butadiene oxidation at high temperatures

Laskin, Alexander; Hai, Wang; Law, Chung K.

doi:10.1002/1097-4601(2000)32:10<589::aid-kin2>3.0.co;2-u

Cited by 151 publications

(106 citation statements)

References 74 publications

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“…(G2//B3LYP calculations by Laskin, Wang and Law in 2000 mapped out two of these pathways but missed the third, and did not report the differing entrance channel barrier heights. 2 ) The difference in the three barriers for the addition reaction does not result from tightened modes at the transition states, as there is no significant difference in the zero-point energy at the three transition states. It is clear that the dominant products of the reaction of H + 1,2-butadiene at low temperature should be CH 3 + propyne, the lowest barrier decomposition products of the radical detected in the experiments presented in this paper, not vinyl + ethylene or H 2 + 1,2-butadienyl radical as suggested by Kern.…”

Section: Discussionmentioning

confidence: 99%

“…The 2-buten-2-yl radical is one of several straight-chain isomers of the C 4 H 7 unsaturated hydrocarbon radical species. Several groups [1][2][3] have sought to characterize the important dissociation and isomerization channels of the C 4 H 7 radical isomers. Previous electronic structure G3//B3LYP calculations in our group 3 have characterized the relative energies and isomerization barriers of the C 4 H 7 radical isomers, as well as the enthalpies and transition states for the available dissociation reactions of the radicals ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

et al. 2005

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This work investigates the unimolecular dissociation of the 2-buten-2-yl radical. This radical has three potentially competing reaction pathways: C-C fission to form CH 3 + propyne, C-H fission to form H + 1,2-butadiene, and C-H fission to produce H + 2-butyne. The experiments were designed to probe the branching to the three unimolecular dissociation pathways of the radical and to test theoretical predictions of the relevant dissociation barriers. Our crossed laser-molecular beam studies show that 193 nm photolysis of 2-chloro-2-butene produces 2-buten-2-yl in the initial photolytic step. A minor C-Cl bond fission channel forms electronically excited 2-buten-2-yl radicals and the dominant C-Cl bond fission channel produces groundstate 2-buten-2-yl radicals with a range of internal energies that spans the barriers to dissociation of the radical. Detection of the stable 2-buten-2-yl radicals allows a determination of the translational, and therefore internal, energy that marks the onset of dissociation of the radical. The experimental determination of the lowest-energy dissociation barrier gave 31 ( 2 kcal/mol, in agreement with the 32.8 ( 2 kcal/mol barrier to C-C fission at the G3//B3LYP level of theory. Our experiments detected products of all three dissociation channels of unstable 2-buten-2-yl as well as a competing HCl elimination channel in the photolysis of 2-chloro-2-butene. The results allow us to benchmark electronic structure calculations on the unimolecular dissociation reactions of the 2-buten-2-yl radical as well as the CH 3 + propyne and H + 1,2-butadiene bimolecular reactions. They also allow us to critique prior experimental work on the H + 1,2-butadiene reaction.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

et al. 2005

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“…4 This is because those authors included only those isomerizations that involve migration of an H between two adjacent C atoms, whereas we include the possibility of the migration of an H between nonadjacent C atoms.…”

Section: Isomerization Transition Statesmentioning

confidence: 99%

“…Isolated theoretical and experimental values for the energies of some C 4 H 7 radicals and transition states appear in the literature, 4,[13][14][15][16] and extensive computational studies have been performed on other four-carbon systems, [17][18][19] but thus far, there has been no complete theoretical study of the straight-chain C 4 H 7 radicals as has been done for the C 3 H 5 system. 3,11,12 It is such a study that we provide here.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Straight-Chain C₄H₇ Radical Isomers and Their Dissociation and Isomerization Transition States

Miller

2004

J. Phys. Chem. A

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We use the G3//B3LYP method to calculate structures, harmonic vibrational frequencies, and energies at selected local minima and saddle points on the C 4 H 7 potential energy surface. These include the straightchain C 4 H 7 radical isomers (of which there are twelve conformers of five structural isomers: 1-buten-1-yl, 2-buten-2-yl, 1-buten-2-yl, 1-methylallyl, and 3-buten-1-yl), sets of dissociation products, and dissociation, isomerization, and conformational transition states. Analogy with smaller hydrocarbon systems reveals why, for some reaction channels, more than one transition state may be accessed from the conformers of a structural isomer en route to the corresponding products. We compare results of the G3 and G3//B3LYP methods for selected C 4 H 7 species.

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“…The chemistry of some important unsaturated species including 1,3-butadiene, propene, and allene have also been updated, adopting the work of Laskin et al [18], which is primarily based on the earlier studies of Davis et al [19]. …”

Section: Chemical Kinetic Model and Calculationsmentioning

confidence: 99%

Oxidation of Ethylene—Air Mixtures at Elevated Pressures, Part 2: Chemical Kinetics

Kopp¹,

Petersen²,

Metcalfe³

et al. 2014

Journal of Propulsion and Power

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Detailed kinetic modeling of 1,3-butadiene oxidation at high temperatures

Cited by 151 publications

References 74 publications

A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

Theoretical Study of the Straight-Chain C₄H₇ Radical Isomers and Their Dissociation and Isomerization Transition States

Oxidation of Ethylene—Air Mixtures at Elevated Pressures, Part 2: Chemical Kinetics

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Detailed kinetic modeling of 1,3-butadiene oxidation at high temperatures

Cited by 151 publications

References 74 publications

A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

A Study of the Unimolecular Dissociation of the 2-Buten-2-yl Radical via the 193 nm Photodissociation of 2-Chloro-2-butene

Theoretical Study of the Straight-Chain C4H7 Radical Isomers and Their Dissociation and Isomerization Transition States

Oxidation of Ethylene—Air Mixtures at Elevated Pressures, Part 2: Chemical Kinetics

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Theoretical Study of the Straight-Chain C₄H₇ Radical Isomers and Their Dissociation and Isomerization Transition States