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The very low-pressure pyrolysis of phenyl methyl sulfide and benzyl methyl sulfide. The enthalpy of formation of the methylthio and phenylthio radicals

Colussi, A. J. and Benson, S. W. (1977) The very low-pressure pyrolysis of phenyl methyl sulfide and benzyl methyl sulfide. The enthalpy of formation of the methylthio and phenylthio radicals. International Journal of Chemical Kinetics, 9 (2). pp. 295-306. ISSN 0538-8066. http://resolver.caltech.edu/CaltechAUTHORS:20150623-154816179

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Abstract

The kinetics and mechanisms of the unimolecular decompositions of phenyl methyl sulfide (PhSCH_3) and benzyl methyl sulfide (PhCH_2SCH_3) have been studied at very low pressures (VLPP). Both reactions essentially proceed by simple carbon-sulfur bond fission into the stabilized phenylthio (PhS·) and benzyl (PhCH_2·) radicals, respectively. The bond dissociation energies BDE(PhS-CH_3) = 67.5 ± 2.0 kcal/mol and BDE(PhCH_2-SCH_3) = 59.4 ± 2 kcal/mol, and the enthalpies of formation of the phenylthio and methylthio radicals ΔH°, _(298K)(PhS·, g) = 56.8 ± 2.0 kcal/mol and ΔH°_f, _(298K)(CH_3S·, g) = 34.2 ± 2.0 kcal/mol have been derived from the kinetic data, and the results are compared with earlier work on the same systems. The present values reveal that the stabilization energy of the phenylthio radical (9.6 kcal/mol) is considerably smaller than that observed for the related benzyl (13.2 kcal/mol) and phenoxy (17.5 kcal/mol) radicals.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/kin.550090212DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/kin.550090212/abstractPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1977 John Wiley & Sons. Received: May 27, 1976, Revised September 7, 1976. This work was supported in part by the National Science Foundation under Grant No. MPS74-18565 and by the Environmental Protection Agency under Grant No. R802288.
Funders:
Funding AgencyGrant Number
NSFMPS74-18565
Environmental Protection Agency (EPA)R802288
Record Number:CaltechAUTHORS:20150623-154816179
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154816179
Official Citation:Colussi, A. J. and Benson, S. W. (1977), The very low-pressure pyrolysis of phenyl methyl sulfide and benzyl methyl sulfide. The enthalpy of formation of the methylthio and phenylthio radicals. Int. J. Chem. Kinet., 9: 295–306. doi: 10.1002/kin.550090212
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58552
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 17:08
Last Modified:13 Feb 2019 18:06

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