Accession Number:

ADA142406

Title:

The Prediction of Electrochemical Reactivities from Contemporary Theory: Some Comparisons with Experiment.

Descriptive Note:

Technical rept.,

Corporate Author:

PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY

Report Date:

1984-04-01

Pagination or Media Count:

36.0

Abstract:

The application of current theoretical treatments of electron transfer to outer-sphere electrochemical reactions are considered with regard to the numerical prediction of rate parameters from thermodynamic and structural data. Formalisms based on a semiclassical treatment for the Frank-Condon barrier together with an encounter preequilibrium model for the preexponential factor are summarized and related to the more widely considered treatments for homogeneous redox reactions. Comparisons are made between the theoretical predictions and experimental rate parameters for representative inorganic outer-sphere reactions at electrode surfaces, and with related reactions in homogeneous solution. The effects of altering the electrode material and the outer-shell solvent are also considered. Although the measured rate parameters for several reactions at mercury electrodes are in reasonable agreement with the theoretical predictions, significant and even large discrepancies are seen for a number of cases. Likely reasons for these findings are discussed, including nonadiabaticity and specific solvation effects. Author

Subject Categories:

  • Numerical Mathematics
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE