Fundamental Studies of Underpotential Metal Deposition and Trace Analysis Using Solid Electrodes.

One of the objectives of this research was to study and to interpret the be havior of films at solid electrodes. With a sound understanding of the characteristics of submonolayer, monolayer and thicker films and their effect on electrochemical processes, it should be possible to apply this knowledge to understanding important solution heterogeneous processes, such as corrosion and electrocatalyis by underpotential metal deposition. A second objective was to develop new approaches to studying electrochemical reactions at solid electrodes, particularly the use of controlled hydrodynamics, in order to provide new diagnostic criteria for elucidating complex electrode processes. Another goal was to apply solid electrode structures to analytically important problems. A study of the electrocatalysis of the oxidation of formic acid by the UPD of lead, bismuth of thallium on polycrystalline platinum has shown that the third body hypothesis is a satisfactory explanation. It is necessary, however, to take into account the selective UPD of these metals and the uncatalyzed oxidation process on the various cystal planes of platinum. The lack of catalysis of the formic acid oxidation process by UPD silver and copper has been shown to caused by the selective UPD of these metals on the platinum plane which contributes least to the uncatalyzed oxidation process.