Theory of Square-Wave Voltammetry of Two-Step Electrode Reaction Using an Inverse Scan Direction

Figure 1

Theoretical square-wave voltammograms of two-step electrode reaction (1) and (2). 𝐸⁰₂−𝐸⁰₁=0.1 V, 𝑐^∗_Ox/𝑐^∗_tot=1, 𝑐^∗_Int=0, 𝑐^∗_Red=0, 𝜆₁=100, 𝜆₂=0.1, 𝛼₁=0.5, 𝛼₂=0.5, 𝐸_sw=50 mV, ∣d𝐸∣=5 mV, and 𝐸_st−𝐸⁰₁=0.4 V (a) and −0.4 V (b). A dimensionless net current (ΔΦ) and its forward (Φ_f) and backward (Φ_b) components are shown.

(a)

(b)