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known electrode systems. The position of amplitude-based quasireversible maximum

and the size of peak potential separation of SW components of conventional or
potential-corrected voltammograms can be used as different strategies for electron
transfer rate estimation. The newly introduced analysis with the critical value of SW
amplitude, ESW(x) and/or related to specific peak potential separation of SW
components, ΔE′p(x), that crosses the artificial blank line creates a unique application
of potential-corrected voltammograms. A brief summary is given in Supplementary
Material (Table S1) for each of the electrode mechanisms discussed herein. One can
also perform more time-consuming direct fitting of the experimental data with
theoretical models. The plethora of possible assessment procedures makes it reliable

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when working with real experimental systems as exemplified by kinetic studies of uric
acid. In conclusion, this paper confirms the exceptional potential of electrokinetic

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evaluations with alteration of SW amplitude alone, which is a unique possibility for
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performing constant scan rate studies during SW voltammetric experiments.
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Acknowledgements
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The support from the National Science Centre of Poland through the grant

2016/23/D/ST4/03225 is acknowledged with gratitude.

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Figure legends

Fig. 1. CE mechanism. The theoretical dependency of the amplitude-normalized net

current (A) and peak potential separation of components in classic (B) and potential-
corrected (C) square-wave voltammograms on the parameters of the preceding
chemical reaction: equilibrium constant (A) and dimensionless kinetic parameter (B,
C). Simulation conditions are as follows: electron transfer coefficient α = 0.5, n = 2, D
= 5 × 10−6 cm2 s−1, T = 293.15 K, f = 25 Hz, step potential = 1 mV, and electrode
kinetic parameter log(ω) = 0.5. In panel A, the dimensionless kinetic parameter was
set as log(ε) = 2, whereas the equilibrium constant was assumed to be log(K) = 0 in

of
panels B and C.
Fig. 2. Theoretical dependencies of the amplitude-normalized SW net current (A) and

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peak potential separation of SW components measured for classic (B) and potential-
-p
corrected (C) voltammograms on the SW amplitude for the different electrode kinetics
of CE mechanism. Simulation conditions are as follows: n = 2, electron transfer
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coefficient α = 0.5, D = 5 × 10−6 cm2 s−1, T = 293.15 K, step potential = 1 mV, log(ε) =
0, log(K) = 0, and the electrode kinetic parameter log(ω) (A): from −0.50 (a) to −3.25
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(l) with an interval of 0.25; (B): from −0.5 (a) to −4.00 (h) with an interval of 0.50; (C):
from −3.75 (a) to −0.25 (o) with an interval of 0.25. The inset of (A) shows the
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dependence of the amplitude-based quasireversible maximum on the electrode

kinetic parameter. The inset of (B) depicts the dependence of the amplitude with no
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peak potential separation of SW components on the electrode kinetic parameter. The

inset of (C) presents the dependence of the peak potential separation of SW
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components at a given crossing point with the so-called blank (dashed line) of
potential-corrected SW voltammograms on the logarithm of the electrode kinetic
parameter.
Fig. 3. EC mechanism. The theoretical dependency of the peak potential separation
of SW components in classic (A) and potential-corrected (B) SW voltammograms on
the parameters of the following chemical reaction: dimensionless kinetic parameter
(A) and equilibrium constant (B). Simulation conditions are as follows: electron
transfer coefficient α = 0.5, n = 1, D = 5 × 10−6 cm2 s−1, T = 293.15 K, f = 25 Hz, step
potential = 1 mV, and electrode kinetic parameter log(ω) = −0.5. In panel B, the
dimensionless kinetic parameter was set as log(ε) = 2, whereas the equilibrium
constant was assumed to be log(K) = 1 in panel A.

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Fig. 4. Theoretical dependencies of the amplitude-normalized net SWV peak current

(A) and peak potential separation of SW components (B, C) on the SW amplitude for
the different electrode kinetics of an EC mechanism. Panels (B) and (C) correspond
to classic and potential-corrected SW voltammograms, respectively. Simulation
conditions are as follows: n = 2, electron transfer coefficient α = 0.5, D = 5 × 10−6 cm2
s−1, T = 293.15 K, step potential = 1 mV, log(ε) = 2, log(K) = 1 and the electrode
kinetic parameter log(ω) = 1.00 (a); 0.50 (b); 0.25 (c); 0.00 (d); −0.25 (e); −0.50 (f);
−0.75 (g); −1.00 (h); −1.25 (i); −1.50 (j); −1.75 (k); −2.00 (l); −2.50 (m); and −3.00 (n).
The inset of (A) shows the dependence of the critical amplitude at the maximum
response on the electrode kinetic parameter. The inset of (B) shows the log-log

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dependence of the amplitude at a zero potential separation on the electrode kinetic
parameter. The inset of (C) presents the dependence of the specific SW amplitude at

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a crossing point with the so-called blank (dashed line) of potential-corrected SW
-p
voltammograms on the logarithm of the electrode kinetic parameter.
Fig. 5. EsurfCirr mechanism. Theoretical dependencies of the peak potential
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separation of SW components in classic (A) and potential-corrected (B) square-wave
voltammograms on the chemical reaction kinetic parameter εirr. Simulation conditions
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are as follows: electron transfer coefficient α = 0.5, n = 2, D = 5 × 10−6 cm2 s−1, T =

293.15 K, f = 25 Hz, step potential = 1 mV, and electrode kinetic parameter log(ω) =
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−1.5.
Fig. 6. Theoretical dependencies of the amplitude-normalized SW net current (A) and
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peak potential separation of SW components measured for classic (B) and potential-
corrected (C) voltammograms on the SW amplitude for the different electrode kinetics
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of EsurfCirr mechanism. Simulation conditions are as follows: n = 1, electron transfer

coefficient α = 0.5, D = 5 × 10−6 cm2 s−1, T = 293.15 K, step potential = 1 mV, log(εirr)
= −1, and the electrode kinetic parameter log(ωs) from 0.00 (a) to −3.00 (m) with an
interval of 0.25 in each panel. The inset of (A) shows the dependence of the
amplitude-based quasireversible maximum on the electrode kinetic parameter. The
left inset of (B) depicts the dependence of the amplitude with no peak potential
separation of SW components on the electrode kinetic parameter, whereas the right
inset of (B) shows the relationship between the size of peak potential separation of
SW components at the amplitude Esw = 100 mV and the electrode kinetic parameter.
The inset of (C) presents the dependence of the specific SW amplitude at which the
peak potential separation of SW components crosses the so-called blank (dashed

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line) of potential-corrected SW voltammograms on the logarithm of the electrode

kinetic parameter.

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CRediT author statement

Conceptualization
I am the sole author, responsible for all depicted to the left credits
Methodology
Software
Validation
Formal analysis
Investigation
Resources
Data Curation
Writing - Original Draft
Writing - Review & Editing
Visualization
Supervision
Project administration

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Funding acquisition

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Highlights
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- Analysis of mechanisms with coupled chemical reaction at a constant scan rate.

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- Estimation of electrode reaction kinetics with SW amplitude effect only.

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- Implementation of amplitude-based quasireversible maximum.

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- Application of SW components separation size.

- Introduction of new features related to the electrode kinetics.

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Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6