Correction factors for the analysis of voltammetric peak currents measured using staircase voltammetry

•Staircase voltammetry of reversible species is sensitive to the step potential.•Large step sizes lead to smaller peak currents and larger peak-to-peak separations.•Expressions are provided allowing the quantitative analysis of staircase voltammetry.•‘Edge’ effects only need to be considered for cases where dimensionless σ < 3350.

The use of staircase voltammetry for the measurement of reversible diffusional redox species under a linear mass-transport regime leads to significant suppression of the peak currents (up to 20% for larger step sizes) and an increase in the peak-to-peak separation (cf. ∆ Epp ~ 70 mV at the reversible limit as opposed to 57 mV). These discrepancies between the voltammetric results of a staircase and true analogue voltammogram may lead to mis-interpretation of data. This work provides an overview of the differences between the two techniques in the macro-electrode reversible limit and provides new expressions which allow the peak current of a staircase voltammogram to be quantitatively analysed. Moreover, clear guidance is provided about which conditions the application of the provided equation is valid in the terms of mass-transport edge effects to the macro-electrode.