Durán, R. P. and Amorebieta, V. T. and Colussi, A. J. (1988) Is the homogeneous thermal dimerization of acetylene a free-radical chain reaction? Kinetic and thermochemical analysis. Journal of Physical Chemistry, 92 (3). pp. 636-640. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154810574
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Abstract
Basic kinetic and thermochemical arguments incorporated into calculations modeling the initial stages of the homogeneous pyrolysis of acetylene reveal that the usual assumption of a free-radical mechanism is flawed. The key findings are that updated thermochemistry for ethynyl, vinyl, and propargyl radicals and the inclusion of falloff corrections in radical reactions lead to (1) exceedingly slow decomposition rates below 1300 K, (2) kinetic inert gas effects, and (3) the formation of benzene rather than vinylacetylene or diacetylene, all predictions at variance with experimental observations. On this basis the involvement of vinylidene is proposed.
| Item Type: | Article | |||||||||
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| Additional Information: | © 1988 American Chemical Society. (Received: September 23, 1986) | |||||||||
| Issue or Number: | 3 | |||||||||
| Record Number: | CaltechAUTHORS:20150623-154810574 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150623-154810574 | |||||||||
| Official Citation: | Is the homogeneous thermal dimerization of acetylene a free-radical chain reaction? Kinetic and thermochemical analysis R. P. Duran, V. T. Amorebieta, and A. J. Colussi The Journal of Physical Chemistry 1988 92 (3), 636-640 DOI: 10.1021/j100314a014 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 58531 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 24 Jun 2015 22:09 | |||||||||
| Last Modified: | 03 Oct 2019 08:37 |
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