Electrode kinetics from a single square-wave voltammogram


  • Valentin Mirčeski Department of Chemistry, Faculty of Natural Sciences and Mathematics, Ss Kiril i Metodij University, Skopje
  • Dariusz Guziejewski Department of Inorganic and Analytical Chemistry, University of Lodż, Tamka 12, Lodż
  • Rubin Gulaboski Faculty of Medical Sciences, Goce Delcev University, Štip




square-wave voltammetry, electrode kinetics, chronoamperometry, simulations


A novel methodological approach for processing electrochemical data measured under conditions of square-wave voltammetry (SWV) is proposed. The methodology takes advantage of the chronoamperometric characteristics of the electrochemical system observed in the course of the voltammetric experiment, which are commonly not considered in conventional SWV. The method requires processing of a single voltammogram only, measured under given set of the potential modulation parameters (i.e. SW frequency and height of the potential pulses). The core idea is to analyze the variation of the current with time, considering the last quarter time period of each potential pulse of the potential modulation, instead of measuring the single current value from the very end of the pulses. Hence, a single point current measurement is replaced with a multisampling current procedure, leading to a series of new SW voltammograms measured at different time increments of each potential pulse. The novel method is illustrated by the theoretical analysis of a quasireversible electrode reaction of a dissolved and surface confined redox couple, as well as a reversible electrode reaction preceded by a chemical equilibrium reaction (CrEr mechanism).


J. Osteryoung, J. J. O`Dea, Square-wave voltammetry, In: A. J. Bard (Ed.), Electroanalytical Chemistry, Marcel Dekker, New York, Vol 14, p. 209 (1986).

G. N. Eccles, Recent advances in pulse, cyclic and square-wave voltammetric analysis, Crit. Rev. Anal. Chem., 22, 345 (1991).

M. Lovrić, Square-wave voltammetry, In: F. Scholz (Ed.) Electroanalytical methods, Springer, Berlin, 2002.

D. de Souza, S. A. S. Machado, L. A. Avaca, Square-wave voltammetry, Quim. Nova, 26, 81–89 (2003).

V. Mirčeski, S. Komorsky-Lovrić, M. Lovrić, Square-wave Voltammetry: Theory and Application, (Ed.) F. Scholz. Springer Verlag, Heidelberg, 2007.

V. Mirčeski, R. Gulaboski, M. Lovrić, I. Bogeski, R. Kappl, M. Hoth, Square-wave voltammetry: A review on the recent progress, Electroanalysis, 25, 2411–2422 (2013).

M. Lovrić, D. Jadresko, Theory of square-wave volt-ammetry of quasireversible electrode reactions using an inverse scan direction, Electrochim. Acta, 55, 948–951 (2010).

A. Molina, M. M. Moreno, C. Serna, M. Lopez-Tenes, J. Gonzalez, N. Abenza, Study of multicenter redox molecules with square wave voltammetry, J. Phys. Chem. C, 111, 12446–12450 (2007).

E. Laborda, D. Suwatchara, N. V. Rees, M. C. Henstridge, A. Molina, R. G. Compton, Variable tem-perature study of electro-reduction of 3-nitrophenolate via cyclic and square wave voltammetry: Molecular insights into electron transfer processes based on the asymmetric Marcus-Hush model, Electrochim. Acta, 110, 772–779 (2013).

V. Mirčeski, A. Bobrowski, J. Zarebski, F. Spasovski, Electrocatalysis of the first and second kind: Theoretical and experimental study in conditions of square-wave voltammetry, Electrochim. Acta, 55, 8696–8703 (2010).

R. Gulaboski, Surface ECE mechanism in protein film voltammetry – A theoretical study under conditions of square-wave voltammetry, J. Solid State Electrochem., 13, 1015–1024 (2009).

J. Gonzalez, C. M. Soto, A. Molina, Square wave vol-tammetry and voltcoulometry applied to electrocatalytic reactions. Oxidation of ferrocyanide at a ferrocene modified gold electrode, J. Electroanal. Chem., 634, 90–97 (2009).

X. Huang, L. Wang, S. Liao, Method of evaluation of electron transfer kinetics of a surface-confined redox system by means of Fourier transformed square wave voltammetry, Anal. Chem., 80, 5666–5670 (2008).

V. Mirčeski, F. Quentel, M. L’Her, Chiral recognition based on the kinetics of ion transfers across liquid/liquid interface, Electrochem. Commun., 11, 1262–1264 (2009).

V. Mirčeski, E. Laborda, D. Guziejewski, R. G. Comp-ton, New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum, Anal. Chem., 85, 5586–5594 (2013).

V. Mirčeski, D. Guziejewski, K. Lisichkov, Electrode kinetic measurements with square-wave voltammetry at a constant scan rate, Electrochim. Acta, 114, 667–673 (2013).

J. Gonzalez, C. M. Soto, A. Molina, Square wave vol-tammetry and voltcoulometry applied to electrocatalytic reactions. Oxidation of ferrocyanide at a ferrocene modified gold electrode, J. Electroanal. Chem., 634, 90–97 (2009).

V. Mirčeski, Square-wave voltammetry of an EC reac-tion of a partly adsorbed redox couple, J. Electroanal. Chem., 508, 138–149 (2001).

V. Mirčeski, M. Lovrić, EC mechanism of an adsorbed redox couple. volume vs surface chemical reaction, J. Electroanal. Chem., 565, 191–202 (2004).

S. Komorsky-Lovrić, M. Lovrić, Square-wave voltam-metry of quasi-reversible surface redox reactions, J. Electroanal. Chem., 384, 115−122 (1995)

V. Mirčeski, M. Lovrić, Quasireversible maximum in cathodic stripping square-wave voltammetry, Electroanalysis, 11, 984–989 (1999).

M. Lovrić, S. Komorsky-Lovrić, R.W. Murry, Adsorp-tion effects in square-wave voltammetry of totally irreversible redox reactions, Electrochim. Acta, 33, 739–744 (1988)

M. Lovrić, S. Komorsky-Lovrić, Square-wave voltammetry of an adsorbed reactant, J. Electroanal. Chem., 248, 239−253 (1988).

V. Mirčeski, M. Lovrić, Square-wave voltammetry of a cathodic stripping reaction complicated by adsorption of the reacting ligand, Anal. Chim. Acta, 386, 47–62 (1999).

V. Mirčeski, M. Lovrić, Split square-wave voltammograms of surface redox reactions, Electroanalysis, 9, 1283–1287 (1997).

V. Mirčeski, Charge transfer kinetics in thin-film volt-ammetry. Theoretical study under conditions of square-wave voltammetry, J. Phys. Chem. B, 108, 13719–13725 (2004).

E. Laviron, General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems, J. Electroanal. Chem. Interfacial Electrochem., 101, 19–28 (1979).




How to Cite

Mirčeski, V., Guziejewski, D., & Gulaboski, R. (2015). Electrode kinetics from a single square-wave voltammogram. Macedonian Journal of Chemistry and Chemical Engineering, 34(1), 181–188. https://doi.org/10.20450/mjcce.2015.654




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