Publication Date


Advisor(s) - Committee Chair

Robert Farna, Curtis Wilkins, John Riley

Degree Program

Department of Chemistry

Degree Type

Master of Science


Numerous studies have been made in recent years on electron transfer reactions of transition metal complexes which proceed by either an inner- or an outer-sphere mechanism. However, except for the Fe(II)/ Fe(III) isotopic electron exchange system, few of the studies have been conducted in other than aqueous media. This study was undertaken to examine solvent effects on redox reactions of transition metal complexes which proceed by an outer-sphere mechanism.

During this study, the electron exchange rate between the bis(2,2',2"-tripyridyl)cobalt(II) complex and the tris(2,2'-dipyridyl) cobalt(III) complex was measured in a number of nonaqueous solvents. Rate measurements were made at three or more temperatures in order to determine the activation parameters. The free energy drive for the electron transfer reaction in each solvent was evaluated from the equilibrium constant which was deternined by either spectral or kinetic methods. In the case of water, a third method was used to determine the equilibrium constant which involved measurements of the redox couple of each reactant.

The results of this kinetic study are discussed in terms of the theoretical predictions of Marcus.


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