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Is the homogeneous thermal dimerization of acetylene a free-radical chain reaction? Kinetic and thermochemical analysis

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 . http://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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URLURL TypeDescription
http://dx.doi.org/10.1021/j100314a014DOIArticle
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ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1988 American Chemical Society. (Received: September 23, 1986)
Record Number:CaltechAUTHORS:20150623-154810574
Persistent URL:http://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:24 Jun 2015 22:09

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