Rate constants for reactions of perfluorobutylperoxyl radical with alkenes
Article first published online: 30 SEP 2004
Copyright © 1991 John Wiley & Sons, Inc.
International Journal of Chemical Kinetics
Volume 23, Issue 10, pages 941–946, October 1991
How to Cite
Nahor, G. S. and Neta, P. (1991), Rate constants for reactions of perfluorobutylperoxyl radical with alkenes. Int. J. Chem. Kinet., 23: 941–946. doi: 10.1002/kin.550231008
- Issue published online: 30 SEP 2004
- Article first published online: 30 SEP 2004
- Manuscript Accepted: 18 MAR 1991
- Manuscript Received: 3 JAN 1991
Perfluorobutylperoxyl radicals were produced by radiolytic reduction of perfluorobutyl iodide in aerated methanol solutions. Rate constants for the reactions of this peroxyl radical with various organic compounds were determined by kinetic spectrophotometric pulse radiolysis. The rate constants for alkanes and alkenes were determined by competition kinetics using chlorpromazine as a reference. The results indicate that hydrogen abstraction from aliphatic compounds takes place with a rate constant that is too slow to measure in our system (<105 M−1 s−1), and that abstraction of allylic and doubly allylic hydrogens is slow compared with addition. Addition to alkenes takes place with rate constants of the order of k = 106 − 108 M−1 s−1. Good correlation was obtained between log k and the Taft substituent constants σ* for the various substituents on the double bond. Perfluorobutylperoxyl radical is found to be more reactive than trichloromethylperoxyl and other peroxyl radicals.