The Driving-Force Dependence of Electrochemical Rate Parameters: Origins of Anodic-Cathodic Asymmetries for Metal Aquo Redox Couples.

Abstract

The consequences of differences in the intramolecular force constants and the ionic entropies between the oxidized and reduced states of aquo redox couples upon their electrochemical kinetics are examined as a function of the driving force. A generalized harmonic oscillator model is utilized that involves estimating the activation barrier from the individual force constants in the oxidized and reduced states rather than employing average ('reduced') values. Noticeable asymmetry in the anodic and cathodic Tafel plots is predicted for redox couples having large (ca. twofold) differences in force constants, the plots being markedly more curved at anodic over-potentials.

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Document Details

Document Type
Technical Report
Publication Date
Sep 01, 1984
Accession Number
ADA145605

Entities

People

  • Joseph T. Hupp
  • Michael J. Weaver

Organizations

  • Purdue University

Tags

Communities of Interest

  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Acquisition
  • Chemical Compounds
  • Chemical Kinetics
  • Chemical Reactions
  • Chemistry
  • Curvature
  • Electrochemical Kinetics
  • Electrochemical Reactions
  • Electrochemistry
  • Electrodes
  • Electron Transfer
  • Exchange Reactions
  • Free Energy
  • Oxidation Reduction Reactions
  • Physical Chemistry
  • Shape
  • Transitions

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  • Electrochemical Surface Science