The Influence of Specific Reactant-Solvent Interactions on Intrinsic Activation Entropies for Outer-Sphere Electron Transfer Reactions.
Abstract
The physical basis of the solvent contribution to the intrinsic activation entropy, Delta S* Sub int, for outer-sphere electron-transfer reactions in homogeneous solution is examined in terms of the entropic parameters for the constituent electrochemical half reactions. A relationship for calculating Delta S* Sub int is derived which takes into account specific reactant-solvent interactions for the isolated redox centers by employing electrochemical reaction entropy data. This relation yields rather larger and more structure-sensitive values of Delta S* Sub int than those deduced on the basis of the usual dielectric continuum treatment. These considerations indicate that the more negative values of Delta S* Sub int typically extracted from experimental kinetic data arise largely from the modification to the specific reactant-solvent interactions within the precursor complex caused by the proximity of the other redox center. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Nov 01, 1983
- Accession Number
- ADA139081
Entities
People
- Joseph T. Hupp
- Michael J. Weaver
Organizations
- Purdue University