Unimolecular decomposition rates of cyclobutanone, 3-oxetanone, and perfluorocyclobutanone. RRKM [Rice-Ramsperger-Kassel-Marcus] calculation of internally converted hot molecules

Breuer, G.; Lewis, Roger S.; Lee, Edward K. C.

doi:10.1021/j100586a001

Cited by 11 publications

(15 citation statements)

References 4 publications

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“…The first primary thermal decomposition channel of 3-oxetanone produces formaldehyde and ketene (Reaction 1), products previously indicated for photolysis. 19 Evidence for the formation of ketene is found in FTIR bands at 2142 ( …”

Section: ■ Results and Discussionmentioning

confidence: 99%

Pyrolysis Reactions of 3-Oxetanone

et al. 2015

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The pyrolysis products of gas-phase 3-oxetanone were identified via matrix-isolation Fourier transform infrared spectroscopy and photoionization mass spectrometry. Pyrolysis was conducted in a hyperthermal nozzle at temperatures from 100 to 1200 °C with the dissociation onset observed at ∼600 °C. The ring strain in the cyclic structure of 3-oxetanone causes the molecule to decompose at relatively low temperatures. Previously, only one dissociation channel, producing formaldehyde and ketene, was considered as significant in photolysis. This study presents the first experimental measurements of the thermal decomposition of 3-oxetanone demonstrating an additional dissociation channel that forms ethylene oxide and carbon monoxide. Major products include formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene, and methyl radical. The first four products stem from initial decomposition of 3-oxetanone, while the additional products, ethylene and methyl radical, are believed to be due to further reactions involving ethylene oxide.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Pyrolysis Reactions of 3-Oxetanone

et al. 2015

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“…In an earlier work, RRKM theory was used to investigate the ketene dissociation channel of 3-oxetanone. The rate constants were computed using the energy barrier of analogous cyclobutanone molecule as detailed electronic structure data were not available on the dissociation pathways of 3-oxetanone.…”

Section: Resultsmentioning

confidence: 99%

“…14,15 Several studies have been reported in the literature on the decomposition reactions of small heterocyclic molecules and their substituted variants. For the thermal decomposition of 3oxetanone, two different dissociation patterns 16,17 can be considered as shown in Figure 1. The first one involves the formation of ketene (CH 2 CO) + formaldehyde (HCHO), and the second one leads to ethylene oxide (oxirane, c-C 2 H 4 O) + carbon monoxide (CO).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Further, Rice−Ramsperger−Kassel−Marcus (RRKM) theory 26−28 calculations have predicted a reaction rate ∼2 orders of magnitude slower for the cyclopropane channel as compared to the ketene channel. 16 Only a limited number of studies are available in the literature on the decomposition of unsubstituted 3-oxetanone. Almost four decades ago, there was a paper published 16 wherein unimolecular dissociation rate of 3-oxetanone was investigated by RRKM theory.…”

Section: ■ Introductionmentioning

confidence: 99%

“…16 Only a limited number of studies are available in the literature on the decomposition of unsubstituted 3-oxetanone. Almost four decades ago, there was a paper published 16 wherein unimolecular dissociation rate of 3-oxetanone was investigated by RRKM theory. In this work, only the ketene pathway was taken into account, and the activation energy was approximated by that of cyclobutanone.…”

Section: ■ Introductionmentioning

confidence: 99%

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Dissociation Chemistry of 3-Oxetanone in the Gas Phase

2017

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3-Oxetanone is a strained cyclic molecule which plays an important role in synthetic chemistry. A few studies exist in the literature about the equilibrium properties of this molecule and the dissociation patterns of substituted 3-oxetanones. For the unsubstituted 3-oxetanone, formation of ketene (CHCO) and formaldehyde (HCHO) was considered to be the major dissociation pathway. In a recent work, pyrolysis products of 3-oxetanone molecule in the gas phase were investigated by Fourier transform infrared spectroscopy and photoionization mass spectrometry. In this study, an additional dissociation channel forming ethylene oxide (c-CHO) and carbon monoxide CO was reported. In the present work, gas phase dissociation chemistry of 3-oxetanone was investigated by electronic structure theory, ab initio classical chemical dynamics simulations, and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant calculations. The barrier height for the ethylene oxide channel was found to be much higher than the ketene pathway. The dynamics simulations were performed at three different total energies, viz., 150, 200, and 300 kcal/mol, and multiple reaction pathways and varying branching ratios observed. A new dissociation channel involving a ring-opened isomer of ethylene oxide was identified in the simulations. This pathway has a lower energy barrier and was dominant in our dynamics simulations.

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An Experimental Study on Unimolecular Reactions Induced by Infrared Multiple Photon Absorption

Tsuchiya

1980

Springer Series in Solid-State Sciences

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Unimolecular decomposition rates of cyclobutanone, 3-oxetanone, and perfluorocyclobutanone. RRKM [Rice-Ramsperger-Kassel-Marcus] calculation of internally converted hot molecules

Cited by 11 publications

References 4 publications

Pyrolysis Reactions of 3-Oxetanone

Pyrolysis Reactions of 3-Oxetanone

Dissociation Chemistry of 3-Oxetanone in the Gas Phase

An Experimental Study on Unimolecular Reactions Induced by Infrared Multiple Photon Absorption

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