Homogeneous redox catalysis of a heterogeneous electron transfer reaction

Catalysis of the reduction of tert-nitrobutane by terephthalonitrile has been investigated as an illustration of the technique. The reaction was studied by cyclic voltammetry in acetonitrile solvent using a hanging mercury drop electrode. The rate and equilibrium constants for electron transfer from...

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Bibliographic Details
Published in:Journal of electroanalytical chemistry and interfacial electrochemistry 1989-08, Vol.267 (1), p.93-104
Main Authors: Gilicinski, Andrew G., Evans, Dennis H.
Format: Article
Language:English
Subjects:
Adsorption
Chemistry
Electrochemistry
Exact sciences and technology
General and physical chemistry
Study of interfaces
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Summary:Catalysis of the reduction of tert-nitrobutane by terephthalonitrile has been investigated as an illustration of the technique. The reaction was studied by cyclic voltammetry in acetonitrile solvent using a hanging mercury drop electrode. The rate and equilibrium constants for electron transfer from the radical anion of terephthalonitrile to neutral tert-nitrobutane were found to be 5.2 × 10 5 1 mol −1 s −1 and 0.027, respectively, at 25° C. The reaction was studied at temperatures between −15 and 45° C and the self-exchange rate constant for tert-nitrobutane and its radical anion was found to be 5 × 10 3 1 mol −1 s −1 at 25° C with an activation energy of 25–30 kJ/mol.
ISSN:0022-0728
DOI:10.1016/0022-0728(89)80240-2