Open Circuit (Mixed) Potential Changes Upon Contact Between Different Inert Electrodes–Size and Kinetic Effects

Abstract

We investigate the principle of the open circuit potential (OCP) change upon a particle collision event based on mixed potential theory and confirmed by a mimic experiment in which we studied the changes in the OCP when two different electrodes (Pt and Au) are brought into contact in a solution that contains some irreversible redox couples. A micrometer-sized Au ultramicroelectrode, when connected in parallel to a Pt micro- or nanoelectrode, showed clearly measurable OCP changes whose magnitude matches well with that predicted by a simplified mixed potential theory for a pair of different electrode materials. On the basis of the study, each electrode establishes a different mixed potential involving two or more half reactions that have different heterogeneous electron transfer kinetics at different electrodes and the OCP changes are very sensitive to the relative ratio of the rate constant of the individual half reaction at different materials.

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“…However as discussed in ref 24, Φ ,0 and Φ ,0 may vary with the surface area of the electrodes. Many plots in the rest of the paper, including Figure 2, will be classified subject to the value of .…”

“…In principle, the area dependence of the open-circuit potential can be calculated 24 or measured. Its value will depend, i.e.…”

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