Croatica Chemica Acta, Vol. 58 No. 2, 1985.
Review article
Application of the LFER in Organic Electrochemistry: Interpretation of the Hammett Reaction Constant (e) for Processes of Reversible Electroreduction in Aprotic Solvents
Marek K. Kalinowski
; Department of Chemistry, University of Warsaw, 02093 Warsaw, ul. Pasteura 1, Poland
Tadeusz M. Krygowski
; Department of Chemistry, University of Warsaw, 02093 Warsaw, ul. Pasteura 1, Poland
Abstract
The paper is an overview of the application of the concept
of linear free energy relationships (LFER), most notably through
the Hammett equation, to investigations of reversible organic electrochemical reactions in aprotic solvents. In sequence the following
topics are covered: the effect of solvent properties on the equilibrium,
ion pairing effects, the direct application of Hammett's equation on polarographic data, entropic and enthalpic contributions to substituent effects, and the quantum chemical interpretatation of the reaction rate constant in aprotic media. The application of polarographic techniques is advocated as more sensitive and easier to interpret than the techniques of homogeneous kinetics.
Keywords
Hrčak ID:
177746
URI
Publication date:
21.7.1985.
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