Double-Sampled Differential Square-Wave Voltammetry

Mirceski, Valentin and Stojanov, Leon and Gulaboski, Rubin (2020) Double-Sampled Differential Square-Wave Voltammetry. Journal of Electroanalytical Chemistry (Thomson Reuters), 877. pp. 1-7. ISSN 1572-6657 (In Press)

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A differential form of square-wave voltammetry (SWV) is proposed based on a double sampling current protocol
within the last quarter of the duration of each potential pulse. Differential forward (Id,f) and backward (Id,b)
current components are well defined peaks with precisely accessible peak characteristics, which is not the case
in conventional variant of the technique where most frequently one encounters asymmetric or sigmoid curves.
The proposed methodology is theoretically tested with a simple quasi-reversible electrode reaction of a dissolved
redox couple at a macroscopic planar electrode, as well as with the mechanism where the electrode reaction is
coupled with a follow-up chemical reaction (i.e. ECr mechanism). Besides expected advances in analytical context, the proposed methodology is promising for mechanistic and kinetic analysis by inspecting the features of the forward and backward current components for any degree of electrochemical reversibility. Thus, the common analysis of the net peak current in conventional SWV can be replaced with the peak current ratio of the forward-to-backward (Ip,f/Ip,b) current components in the differential variant of the technique. The peak current ratio is a dimensionless, relative parameter enabling a straightforward comparison to experimental data, which is not always the case with the net peak current of the conventional SWV.

Item Type: Article
Impact Factor Value: 3.807
Subjects: Natural sciences > Chemical sciences
Natural sciences > Matematics
Natural sciences > Physical sciences
Divisions: Faculty of Medical Science
Depositing User: Rubin Gulaboski
Date Deposited: 13 Aug 2020 08:17
Last Modified: 13 Aug 2020 08:17

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