Similarity of Heterogeneous Kinetics to Delay of Double-Layer Capacitance Using Chronoamperometry

Chronoamperometric curves for the oxidation of a ferrocenyl derivative via a potential step, calculated using the Cottrell equation, showed less diffusion-controlled currents on a platinum wire electrode. This lower deviation cannot be explained via Butler–Volmer heterogeneous kinetics, but was ascribed to the negatively capacitive current associated with a redox reaction. The deviation in fully oxidized electrical potential corresponds to the non-zero concentration at the electrode surface, which cannot be predicted using the Nernst equation. This equation expresses the relationship between the electrical potential and activity at the electrode surface rather than the concentration. The diffusion equation determines the relationship between the current and surface concentration rather than activity. Negative capacitance or a non-zero concentration may arise from structure formation on the electrode owing to dipole–dipole interactions, which are similar to the generation of double-layer capacitance, including frequency dispersion. Following this concept, we derive expressions for a lowered diffusion-controlled current and time-dependent surface concentration. The negatively capacitive current shows the time dependence of t−0.9, which is similar to the decay of double-layer capacitive currents. The surface concentration decays with t−0.4-dependence.