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The very low-pressure pyrolysis of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether and the enthalpy of formation of the phenoxy radical

Colussi, A. J. and Zabel, F. and Benson, S. W. (1977) The very low-pressure pyrolysis of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether and the enthalpy of formation of the phenoxy radical. International Journal of Chemical Kinetics, 9 (2). pp. 161-178. ISSN 0538-8066. https://resolver.caltech.edu/CaltechAUTHORS:20150803-155823941

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Abstract

A value of the enthalpy of formation of the phenoxy radical in the gas phase, ΔH°,298K (ϕO·, g) = 11.4 ± 2.0 kcal/mol, has been obtained from the kinetic study of the unimolecular decompositions of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether at very low pressures. Bond fission, producing phenoxy or benzyl radicals, respectively, is the only mode of decomposition in each case. The present value leads to a bond dissociation energy BDE(ϕO—H) = 86.5 ± 2 kcal/mol, in good agreement with recent estimates made on the basis of competitive oxidation steps in the liquid phase. A comparison with bond dissociation energies of aliphatic alcohols, BDE(RO—H) = 104 kcal/mol, reveals that the stabilization energy of the phenoxy radical (17.5 kcal/mol) is considerably greater than the one observed for the isoelectronic benzyl radical (13.2 kcal/mol). Decomposition of phenoxy radicals into cyclopentadienyl radicals and CO has been observed at temperatures above 1000°K, and a mechanism for this reaction is proposed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/kin.550090202DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550090202/abstractPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1977 John Wiley & Sons. Received May 12, 1976, Revised July 14, 1976. This work was supported in part by the National Science Foundation under Grant MPS74-18565 and by the Air Force Office of Scientific Research under Contract F44620-71-C-0103.
Funders:
Funding AgencyGrant Number
NSFMPS74-18565
Air Force Office of Scientific Research (AFOSR)F44620-71-C-0103
Issue or Number:2
Record Number:CaltechAUTHORS:20150803-155823941
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150803-155823941
Official Citation:Colussi, A. J., Zabel, F. and Benson, S. W. (1977), The very low-pressure pyrolysis of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether and the enthalpy of formation of the phenoxy radical. Int. J. Chem. Kinet., 9: 161–178. doi: 10.1002/kin.550090202
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59162
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:05 Aug 2015 22:49
Last Modified:03 Oct 2019 08:44

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