Diffusion coefficient measurements and other investigations using the methods of twin-electrode thin-layer electrochemistry

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

Name thesis:degree_name

Doctor of Philosophy (PhD)

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Year

1971

Author dc:creator

• Konopka, Stanley J.

Contributors dc:contributor

• Eugene E. Schrier
• Walter E. Kaskan
• Bruce McDuffie

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

Repository record dc:identifier

https://orb.binghamton.edu/dissertation_and_theses/165

OAI identifier oai:identifier

oai:orb.binghamton.edu:dissertation_and_theses-1171