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Kinetics and thermochemistry of the equilibrium 2 acetylene ⇌ C_4H_4: direct evidence against a chain mechanism

Ghibaudi, E. and Colussi, A. J. (1988) Kinetics and thermochemistry of the equilibrium 2 acetylene ⇌ C_4H_4: direct evidence against a chain mechanism. Journal of Physical Chemistry, 92 (20). pp. 5839-5842. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150623-154809577

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Abstract

It is shown that recent real-time measurements of the initial rates of decomposition of vinylacetylene behind incident shock waves together with earlier kinetic data for acetylene dimerization closely satisfy detailed balance, i.e., k_1/2k_(-1) = K_1 (Hidaka, Y.; Tanaka, K.; Suga, M. Chem. Phys. Lett. 1986, 130, 195; Skinner, G. B.; Sokoloski, E. M. J. Phys. Chem. 1960,64, 1952). The short times involved (t < 20 µs) allow molecular species, or their isomers, to take part in reactions 1 and -1 but specifically exclude free monoradical chain mechanisms. Since a one-step concerted dimerization is otherwise untenable on kinetic grounds, the intermediacy of vinylidene (H_2C=C:) in reaction 1 is proposed on the basis of ab initio calculations.


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http://dx.doi.org/10.1021/j100331a058DOIArticle
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ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Alternate Title:Kinetics and thermochemistry of the equilibrium 2 acetylene ⇌ C4H4: direct evidence against a chain mechanism
Additional Information:© 1988 American Chemical Society. (Received: September 8, 1987)
Record Number:CaltechAUTHORS:20150623-154809577
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154809577
Official Citation:Kinetics and thermochemistry of the equilibrium 2 acetylene .dblharw. C4H4: direct evidence against a chain mechanism E. Ghibaudi and A. J. Colussi The Journal of Physical Chemistry 1988 92 (20), 5839-5842 DOI: 10.1021/j100331a058
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58527
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 22:36
Last Modified:24 Jun 2015 22:36

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