Surface Environmental Effects in Electrochemical Kinetics: Outer-Sphere Chromium (III) Reductions at Mercury, Gallium, Lead, and Thallium Surfaces.
Abstract
Electrochemical rate parameters for the outer-sphere reduction of several Cr(III) aquo and ammine complexes and also for vanadium and europium aquo complexes are compared at aqueous-metal interfaces formed with mercury, liquid gallium, lead, and underpotential deposited lead and thallium monolayers on silver. For reactants containing aquo ligands, substantial decreases in the rate constants, both before and after electrostatic double-layer corrections, were observed at a given electrode potential when substituting mercury by the other surfaces, especially lead and gallium. The rate alterations are accompanied by marked decreases in the apparent activation entropies, although offset by corresponding decreases in the measured activation enthalpies. These results are interpreted in terms of the varying influence of these metal surfaces on the interfacial solvent structure.
Document Details
- Document Type
- Technical Report
- Publication Date
- Sep 01, 1984
- Accession Number
- ADA145607
Entities
People
- H. Y. Liu
- Joseph T. Hupp
- Michael J. Weaver
Organizations
- Purdue University