Document Type


Date of Award



Electrochemical analysis, Diffusion, Twin-electrode thin-layer electrochemistry

Degree Name

Doctor of Philosophy (PhD)



First Advisor

Eugene E. Schrier

Second Advisor

Walter E. Kaskan

Third Advisor

Bruce McDuffie


Science and Mathematics


The method of measuring diffusion coefficients using the twin-electrode thin-layer micrometer cell has been critically evaluated using the ferri-ferrocyanide couple in aqueous KCl as a model system. It has been demonstrated that precise measurements of steady-state currents and coulometric slopes can be made leading to reliable values for diffusion coefficients of soluble redox systems.

The following other systems were studied: Cu(II)/Cu(I) in 0.25M tetraethylallnonium perchlorate(TEAP-acetonitrile medium; ferroceneferricinim in three different solvents (acidified acetonitrile, N,N-dimethylformamide, propylene carbonate) with 0.1M TEAP as supporting electrolyte. Diffusion coefficients for the electroactive species were obtained, and electron-transfer characteristics of the redox systems were observed.

The dependence of the diffusion coefficients on viscosity was found to be in general agreement with the Stokes-Einstein relationship for the systems examined.

The kinetics of the reaction of ferricinium ion with oxygen was studied in a preliminary fashion. A second-order dependence on ferrocene concentration was found, with fractional order of dependence on oxygen.