Evaluation of Unimolecular Rate Constants for Some Outer-Sphere Electrochemical Reactions.

Abstract

Unimolecular rate constants, K sub et (per sec -1 ), and transfer coefficients, alpha sub et, for the outer-sphere electroreduction of several Co(III) ammine and ethylenediamine complexes have been evaluated by electrostatically adsorbing the reactants at silver electrodes coated with chloride or bromide monolayers. Sufficiently strong diffuse-layer adsorption is thereby produced so to enable K sub et and alpha sub et to be determined by means of linear sweep voltammetry, employing sufficiently fast sweep rates (10-100V/sec) and dilute reactant concentrations (less than or = 50 micrometers) so that the bulk solution reactant contributes negligibly to the observed faradaic transients. Comparisons with corresponding rate constants and transfer coefficients for the solution reactants enables the influence of precursor-state stability upon the latter rate parameters to be assessed. Originator-supplied key words include: Precursor state, Electrostatic work term correction, and Surface excess.

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Document Details

Document Type
Technical Report
Publication Date
Jan 01, 1985
Accession Number
ADA150758

Entities

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  • M. A. Tadayyoni
  • Michael J. Weaver

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  • Purdue University

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  • Air Platforms

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  • Capacitance
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  • Chemical Reactions
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  • Crystal Structure
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  • Analytical Chemistry
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