Electrochemical Activation Parameters for Surface-Attached Reactants Evaluation of Unimolecular Frequency Factors for Representative Ligand-Bridged Reactions.

Abstract

The temperature dependence of unimolecular rate constants are reported for the one-electron reduction of various Co(III) and Cr(III) reactants attached to mercury or silver surfaces via either thiocyanate or various thiophenecarboxylate ligands. Combining the ideal activation enthalpies obtained at a constant electrode potential using a nonisothermal cell arrangement with the corresponding activation entropies estimated from reaction entropy data enables values of the unimolecular frequency factor, A sub et, for the elementary electron-transfer step to be evaluated. Values of A sub et close to 10 to the 13th power/sec-01 were obtained in this manner for the thiocyanate-bridged reactions at mercury, indicating that the electronic transmission coefficient approaches unity, i.e., the reactions are adiabatic.

Open PDF

Document Details

Document Type
Technical Report
Publication Date
Apr 01, 1983
Accession Number
ADA142483

Entities

People

  • K. L. Guyer
  • Michael J. Weaver
  • S. W. Barr
  • T. T. T. Li

Organizations

  • Purdue University

Tags

DTIC Thesaurus Topics

  • Accuracy
  • Cells
  • Chemical Reaction Properties
  • Chemical Synthesis
  • Chemistry
  • Coefficients
  • Data Acquisition
  • Electrochemical Cells
  • Electrochemical Reactions
  • Electrodes
  • Electron Transfer
  • Electrons
  • Free Energy
  • Frequency
  • Measurement
  • Military Research
  • Test And Evaluation

Fields of Study

  • Chemistry

Readers

  • Electrochemical Surface Science

Technology Areas

  • Microelectronics