Linear Free Energy Relations for Multielectron Transfer Kinetics: A brief Look at the Bronsted/Tafel Analogy
Abstract
A comparison is made between electrochemical and homogeneous redox reactivity for species involving the transfer of multiple electrons at a single thermodynamic potential. In the electrochemical case the co-reactant is the electrode; in the homogeneous case it is any of several members of a homologous series of one-electron reagents. In the latter case it is shown that the slope of a plot of the observed pseudo first order rate constant (one-electron reagent in excess) versus the thermodynamic driving force rate constant identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Bronsted plot) for mechanistic purpose is closely analogous to the well known Tafel approach (log current vs. potential) in electrochemical kinetics. (JHD)
Document Details
- Document Type
- Technical Report
- Publication Date
- Nov 01, 1989
- Accession Number
- ADA215078
Entities
People
- Joseph T. Hupp
- M. S. Ram
Organizations
- Northwestern University