The net peak splitting phenomenon in square-wave voltammetry – A simple diagnostic tool to distinguish between surface electrode mechanisms associated with different chemical reactions




surface CE mechanism, surface EC mechanism;, surface EC’ regenerative mechanism;, split square-wave voltammograms;


Utilizing pulse voltammetric techniques for the electrochemical analysis of lipophilic redox systems has proven to be an effective method for studying a diverse range of redox compounds, from simple molecules to intricate proteins. To extract relevant thermodynamic and kinetic data from electrochemical analysis of redox systems exhibiting strong surface activity, there's a crucial need to decipher the underlying electrochemical mechanism in the system being examined. The "split net peak" phenomenon, a defining characteristic observed in all surface-active redox systems featuring fast electron transfer under square-wave voltammetry conditions, has been investigated in this study to establish diagnostic criteria for identifying surface electrochemical mechanisms associated with preceding, subsequent, regenerative, and reactant-inactivating chemical reactions. This understanding can be achieved by tracking the influence of the chemical reaction rate on the split square-wave voltammetric peaks in a particular electrochemical mechanism. The approach reported in the current work enables a very simple and precise differentiation between the elaborated mechanisms frequently encountered in protein-film voltammetry methodologies.

Author Biography

Rubin Gulaboski, Faculty of Medical Sciences, Goce Delčev University, Štip, Macedonia

Department of Physical Chemistry and Bioelectrochemistry


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2023-12-01 — Updated on 2023-12-24


How to Cite

Gulaboski, R. (2023). The net peak splitting phenomenon in square-wave voltammetry – A simple diagnostic tool to distinguish between surface electrode mechanisms associated with different chemical reactions. Macedonian Journal of Chemistry and Chemical Engineering, 42(2), 237–247. (Original work published December 1, 2023)




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