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 coreactant 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 can be used to identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Brønsted plot) for mechanistic purposes is closely analogous to the well-known Tafel approach (log current versus potential) in electrochemical kinetics.
Original language | English (US) |
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Pages (from-to) | 2378-2380 |
Number of pages | 3 |
Journal | Journal of Physical Chemistry |
Volume | 94 |
Issue number | 6 |
State | Published - Dec 1 1990 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry