An Extended Method for the Practical Evaluation of the Standard Rate Constant from Cyclic Voltammetric Data

The Nicholson's treatment for the evaluation of the heterogeneous standard rate constant k 0 of electron transfer from cyclic voltammetric (CV) data is combined with the Klingler and Kochi method suitable to totally irreversible systems in order to use very large Δ E p x n values, where n is the number of electrons involved in a simple electron‐transfer process O+ n e − ⇌R. An empirical relationship between the dimensionless parameter Ψ = k 0 [π DnvF/(RT )] −1/2 and Δ E p x n which practically replaces the Nicholson's working curve up to about 200 mV is reported.