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. doi:10.1021/j100331a058. https://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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| 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) | |||||||||
| Issue or Number: | 20 | |||||||||
| DOI: | 10.1021/j100331a058 | |||||||||
| Record Number: | CaltechAUTHORS:20150623-154809577 | |||||||||
| Persistent URL: | https://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: | 10 Nov 2021 22:06 |
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