Solvent Isotope Effects Upon the Kinetics of some Simple Electrode Reactions.

Abstract

The effect of replacing H2O with D2O solvent upon the electrochemical kinetics of simple transition-metal redox couples containing aquo, ammine, or ethylenediamine ligands have been investigated at mercury electrodes as a means of exploring the possible contribution of ligand-aqueous solvent interactions to the activation barrier to outer-sphere electron transfer. Comparison of isotope rate ratios for corresponding electrochemical and homogeneous outer-sphere reactions involving cationic ammine and aquo complexes yields values of isotopic rate ratios of hydrogen and deuterium for the former processes that are typically markedly larger than those predicted by the Marcus model from the homogeneous rate ratios. These discrepancies appear to arise from differences in the solvent environments in the transition states for electrochemical and homogeneous reactions.

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Document Details

Document Type
Technical Report
Publication Date
Aug 15, 1980
Accession Number
ADA089387

Entities

People

  • Michael J. Weaver
  • Paul D. Tyma
  • Scott M. Nettles

Organizations

  • Michigan State University

Tags

Communities of Interest

  • Materials and Manufacturing Processes

DTIC Thesaurus Topics

  • Chemical Synthesis
  • Chemistry
  • Deuterium
  • Electrochemical Cells
  • Electrochemical Kinetics
  • Electrochemical Reactions
  • Electrochemistry
  • Electrodes
  • Electron Transfer
  • Free Energy
  • Heavy Water
  • Hydrogen
  • Military Research
  • Oxidation Reduction Reactions
  • Photoelectrochemical Cells
  • Transition Metals
  • Water

Fields of Study

  • Chemistry

Readers

  • Electrochemical Surface Science
  • Materials Science and Engineering.
  • Regression Analysis.

Technology Areas

  • Microelectronics