Homoallylic isomerization of 1-penten-4-yl and the critical energy for methyl + 1,3-butadiene

Carter, W. P. L.; Tardy, D. C.

doi:10.1021/j100606a001

Cited by 14 publications

(6 citation statements)

References 2 publications

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“…1-Penten-4-yl. The chemically activated decomposition of the 1-penten-4-yl radical was studied by Carter and Tardy 19 from experiments on the addition of hydrogen atoms to 1,4-pentadiene. The most interesting observation is the occurrence of a very fast isomerization process, the homoallylic rearrangement, at room temperature.…”

Section: Basis For Estimatesmentioning

confidence: 99%

Mechanism and Rate Constants for the Decomposition of 1-Pentenyl Radicals

Tsang

2005

J. Phys. Chem. A

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This paper is concerned with the mechanisms and rate constants for the decomposition of 1-penten-3-yl, 1-penten-4-yl, and 1-penten-5-yl radicals. They are formed from radical attack on 1-pentene, which is an important decomposition product of normal alkyl radicals with more than 6 carbon atoms in combustion systems. This work is based on related data in the literature. These involve rate constants for the reverse radical addition process under high-pressure conditions, chemical activation experiments, and more recent direct studies. The high-pressure rate constants are based on detailed balance. The energy transfer effects and the pressure dependences of the rate constants are determined through the solution of the master equation and are projected to cover combustion conditions. The low barriers to these reactions make it necessary to treat these thermal reactions as open systems, as in chemical activation studies. The multiple reaction channels make the nature of the pressure effects different from those usually described in standard texts. The order of stability is 1-penten-3-yl approximately 1-penten-4-yl > 1-penten-5-yl and straddles those for the n-alkyl radicals. A key feature in these reactions is the effects traceable to allylic resonance. However, the 50 kJ/mol allylic resonance energy is not fully manifested. The important unsaturated products are 1,3-butadiene, the pentadienes, allyl radicals, and vinyl radicals. The results are compared with the recommendations in the literature, and significant differences are noted. Extensions to larger radicals with similar structures are discussed.

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Section: Basis For Estimatesmentioning

confidence: 99%

Mechanism and Rate Constants for the Decomposition of 1-Pentenyl Radicals

Tsang

2005

J. Phys. Chem. A

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“…A polymer has been found to deposit onto the walls of the reaction vessel. Methane and 3-methyl-1-butene are formed in reactions of 1-penten-4-yl radical studied extensively by Carter and Tardy [9]. Methane is presumably accompanied by the equivalent amounts of 1,3-butadiene but this particular hydrocarbon is removed from our system in the effective reaction with SH radicals [lll.…”

Section: (3)mentioning

confidence: 99%

Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals

Gierczak

owski

Niedzielski

1986

Int. J. Chem. Kinet.

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Unimolecular reactions of mutual isomerization of cyclopentyl and 1‐penten‐5‐yl radicals have been investigated by chemical activation. The radicals were generated by adding energized hydrogen atoms (EH about 23 kcal mol−1) to the double bond of either cyclopentane or 1,4‐pentadiene. Based on the extensive steady‐state RRKM calculations employing the experimental data from this work as well as from the literature, the threshold energies for the cyclopentyl ring opening and closure are 32 ± 0.3 and 16.2 ± 0.3 kcal mol−1, respectively. The entropy of activation for the ring opening is close to zero.

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“…The treatment is similar to that for the heptyl radicals, except that the isomerization possibilities are much decreased. We have found that the literature data for the reverse radical addition reaction to dienes (Kerr & Parsonage, 1972) as well as chemical activation results ( Carter and Tardy, 1974) on the addition of hydrogen atom to pentadienes particularly useful in providing a fixed point for estimation. There are however similar problems regarding the presentation of results under conditions where rate constants are no longer constant.…”

Section: Pah and Sootmentioning

confidence: 99%

Progress in the development of combustion kinetics databases for liquid fuels

Tsang

2004

Data Sci. J.

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This paper describes the present situation regarding chemical kinetic databases for the simulation of the combustion of liquid fuels. Past work in the area is summarized. Much is known about the reactions of the smaller fragments from combustion processes. In order to describe real liquid fuels there is the need for an understanding of how the larger organic fuels are broken down to these fragments. The type of reactions that need to be considered are described and the breakdown of heptane is used as an example.

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Homoallylic isomerization of 1-penten-4-yl and the critical energy for methyl + 1,3-butadiene

Cited by 14 publications

References 2 publications

Mechanism and Rate Constants for the Decomposition of 1-Pentenyl Radicals

Mechanism and Rate Constants for the Decomposition of 1-Pentenyl Radicals

Mutual isomerization of cyclopentyl and 1-Penten-5-y1 radicals

Progress in the development of combustion kinetics databases for liquid fuels

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