Reversible Cyclic Voltammetry and Non-Unity Stoichiometry: The Ag/AgBr/Br- Redox Couple

The voltammetry of electrochemically reversible couples in which a soluble reactant is converted into an insoluble product is investigated computationally via simulation and, in the context of the Ag/AgBr/Br(-)redox couple, experimentally. The voltammetric waveshape is characterized and, when analyzed via apparent transfer coefficient analysis, shown to give rise to apparent transfer coefficients very considerably in excess of unity, leading to the generic insight for the characterization of electrode reactions involving solution and solid phase reactants.

Automated summary

In this study, the voltammetry of electrochemically reversible couples, particularly the Ag/AgBr/Br(-) redox couple, was investigated computationally and experimentally. The voltammetric waveshape was characterized and analyzed to understand the electrode reactions involving solution and solid phase reactants, revealing the presence of apparent transfer coefficients significantly exceeding unity.