Document Type
Dissertation
Date of Award
1971
Keywords
Electrochemical analysis, Diffusion, Twin-electrode thin-layer electrochemistry
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Eugene E. Schrier
Second Advisor
Walter E. Kaskan
Third Advisor
Bruce McDuffie
Series
Science and Mathematics
Abstract
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.
Recommended Citation
Konopka, Stanley J., "Diffusion coefficient measurements and other investigations using the methods of twin-electrode thin-layer electrochemistry" (1971). Graduate Dissertations and Theses. 165.
https://orb.binghamton.edu/dissertation_and_theses/165