Correlation of Electrode Kinetics with Surface Structure.
Final rept. Oct 77-Sep 80,
MICHIGAN STATE UNIV EAST LANSING DEPT OF CHEMISTRY
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The overall objective of this research is to develop an understanding of the relationships between the kinetics and mechanisms of some simple heterogeneous electron-transfer reactions and the molecular structure of the reactant and the electrode-solution interface. Emphasis is being placed on studies of transition-metal redox couples involving substitutionally inert complexes in aqueous media at a number of solid metals as well as at mercury electrodes. These reactions provide excellent model systems for studying structural effects in electron transfer, since they are mechanistically simple and either inner- or outer-sphere reaction mechanisms can be induced, depending on the ability of the coordinated ligands to bind to the electrode surface. Problems that were addressed included 1 the effects of varying the nature of the metal surface upon the rates of inner-and outer-sphere reactions 2 the influence of ionic specific adsorption upon the reactivities of outer-sphere pathways 3determination of the influence of reactant specific adsorption to the reorganization energy barrier for electron transfer, and 4 elucidation of the role of reactant-solvent interactions in redox kinetics and thermodynamics.
- Physical Chemistry