Solvent Effect on the Rate of β-Scission of the tert-Butoxyl Radical
The Journal of Physical Chemistry A1998Vol. 102(41), pp. 7975–7980
Citations Over TimeTop 10% of 1998 papers
Abstract
The transient absorption spectrum of the tert-butoxyl radical in the UV region was obtained by the laser flash photolysis technique. The rate constants for β-scission and self-termination reactions of tert-butoxyl radicals were measured in five solvents; the Arrhenius parameters of the rate constant for β-scission kβ were determined. It was shown that both the solvent polarity and ability for hydrogen bonding accelerate the reaction of β-scission. The solvent effect on the rate constant of the β-scission reaction is discussed in terms of a simple Onzager−Betcher model, a point dipole model, and a model of the H-bonded complex of the radical with the solvent molecule.
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