Grela, M. A. and Amorebieta, V. T. and Colussi, A. J. (1992) Pyrolysis of styrene: kinetics and mechanism of the equilibrium styrene ↔ benzene + acetylene. Journal of Physical Chemistry, 96 (24). pp. 9861-9865. ISSN 0022-3654. doi:10.1021/j100203a052. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154805745
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Abstract
The thermal unimolecular decomposition of styrene into benzene and acetylene, C_6H_CH=CH2 → C_6H_6 + HCCH (l), was investigated in a low pressure (≈10 mTorr) flow reactor by on-line mass spectrometry between 1180 and 1350 K. Measured rates can be calculated, via RRKM extrapolation, from the expression log (k_(1∞), s^(-1)) = 14.38 - 17 076/T, which was derived by detailed balance from high-pressure (≈50 Torr) low-temperature (878-973 K) kinetic data for the reverse reaction. This value of E(1∞) = 77.9 kcal/mol allows for the generation of vinylidene, H_2C=C, the carbene isomer of acetylene, as a primary product of the title reaction. A non-radical process involving the rate-determining extrusion of H_2C=C: from a [4.1.0]-7-methylene cyclohepta-2,4-diene intermediate in equilibrium with styrene is consistent with kinetic and thermochemical considerations.
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| Alternate Title: | Pyrolysis of styrene: kinetics and mechanism of the equilibrium styrene .tautm. benzene + acetylene | |||||||||
| Additional Information: | © 1992 American Chemical Society. (Received: June 16, 1992; In Final Form: August 3, 1992) This work was financially supported by CONICET of Argentina. Mr. O. Lopez carried out some of the pyrolytic experiments. | |||||||||
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| Issue or Number: | 24 | |||||||||
| DOI: | 10.1021/j100203a052 | |||||||||
| Record Number: | CaltechAUTHORS:20150623-154805745 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150623-154805745 | |||||||||
| Official Citation: | Pyrolysis of styrene: kinetics and mechanism of the equilibrium styrene .tautm. benzene + acetylene M. A. Grela, V. T. Amorebieta, and A. J. Colussi The Journal of Physical Chemistry 1992 96 (24), 9861-9865 DOI: 10.1021/j100203a052 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 58513 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 26 Jun 2015 15:05 | |||||||||
| Last Modified: | 10 Nov 2021 22:06 |
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