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

Journal article

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.

Authors: Batchelor-McAuley, C; Yang, M; Hall, E; Compton, R

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Elsevier
• Journal: Journal of Electroanalytical Chemistry
• Volume: 758
• Pages: 1-6
• Publication date: 2015-10-18
• Acceptance date: 2015-10-05
• DOI: 10.1016/j.jelechem.2015.10.004
• ISSN: 1572-6657
• Keywords: electrochemistry; diffusion coefficient; Randles–Ševčík equation; electron transfer kinetics