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Rates of termination of radicals in solution. VII. Allylic radicals

Hefter, Heinz J. and Wu, Chin-Hua S. and Hammond, George S. (1973) Rates of termination of radicals in solution. VII. Allylic radicals. Journal of the American Chemical Society, 95 (3). pp. 851-855. ISSN 0002-7863. doi:10.1021/ja00784a037. https://resolver.caltech.edu/CaltechAUTHORS:20150302-080925934

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Abstract

The rate constants for bimolecular decay of allyl, 2-methallyl, and cis- and trans-1-methallyl radicals in liquid propene, isobutene, and cis- and trans-2-butene, respectively, have been determined over a wide temperature range from near the boiling points of the solvents to about - 120° using the esr-rotating sector technique. The values, which range from 10^9 to 10^(10) M^(-1) sec^(-1), were compared with the encounter rate constants calculated from density and viscosity data. We conclude that the self-termination of allyl, 2-methallyl, and trans-1-methallyl radicals fits the diffusion-controlled model. However, the rate constant for the cis-1-methallyl radical is unexpectedly high at the higher temperatures. The viscosities of liquid propene, isobutene, and cis- and trans-2-butene between their boiling points and - 100° are reported.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00784a037 DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00784a037PublisherArticle
Additional Information:© 1973 American Chemical Society. Received June 30, 1972. This work was supported by Grant No. AFOSR-7-1958 from the Directorate of Chemical Science, Air Force Office of Scientific Research.
Funders:
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)AFOSR-7-1958
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory4486
Issue or Number:3
DOI:10.1021/ja00784a037
Record Number:CaltechAUTHORS:20150302-080925934
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150302-080925934
Official Citation:Rates of termination of radicals in solution. VII. Allylic radicals Heinz J. Hefter, Chin-Hau S. Wu, and George S. Hammond Journal of the American Chemical Society 1973 95 (3), 851-855 DOI: 10.1021/ja00784a037
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55387
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:03 Mar 2015 23:50
Last Modified:10 Nov 2021 20:45

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