A formal scan rate in staircase and square-wave voltammetry

Because of the fact that real measurements are sometimes described in terms of the (formal) scan rate, the functional relationships between this parameter and the peak current in staircase (SCV) and square-wave voltammetry (SWV) were investigated theoretically. The real SCV peak current is proportional to the square-root of the formal scan rate, v, and inversely proportional to ΔE0.0541: −ip = 0.1453 nFSc ox ∗ (D/π)½v½ΔE−0.0541. In SWV of a reversible electrode reaction the net peak current depends primarily on the frequency, while the influence of the formal scan rate is of minor importance: Δip = nFSc ox ∗ D½(0.7339f½ + 0.0026ΔE0.3118v½). On the other hand, in SWV of a totally irreversible electrode reaction, the real net peak current is a stronger function of the formal scan rate: Δip = 0.0942 nFSc ox ∗ D½ΔE−0.11 v½. Experimental results, obtained in perchlorate solutions of Eu3+, are in relatively good agreement with the theory.