Journal Pre-proof

Electrode mechanisms with coupled chemical reaction —

Amplitude effect in square-wave voltammetry

Dariusz Guziejewski

PII: S1572-6657(20)30369-6
DOI: https://doi.org/10.1016/j.jelechem.2020.114186
Reference: JEAC 114186

To appear in: Journal of Electroanalytical Chemistry

Received date: 20 November 2019

Revised date: 21 April 2020
Accepted date: 22 April 2020

Please cite this article as: D. Guziejewski, Electrode mechanisms with coupled chemical
reaction — Amplitude effect in square-wave voltammetry, Journal of Electroanalytical
Chemistry (2020), https://doi.org/10.1016/j.jelechem.2020.114186

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
typesetting and review before it is published in its final form, but we are providing this
version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.

© 2020 Published by Elsevier.

 Journal Pre-proof

Electrode mechanisms with coupled chemical reaction —

amplitude effect in square-wave voltammetry

Dariusz Guziejewski

of
ro
Department of Inorganic and Analytical Chemistry, Division of Instrumental Analysis,
-p
Faculty of Chemistry, University of Lodz, Pomorska 163, 92-236 Lodz, Poland
re
lP
na
ur
Jo

Corresponding author (dguziejewski@uni.lodz.pl)

1
 Journal Pre-proof

Abstract

This article presents the theoretical prediction of square-wave amplitude effect

on electrode reaction mechanisms coupled with chemical reaction under conditions
of square-wave voltammetry. A systematic change in simulated voltammograms
occurs following a change in the applied square-wave amplitude parameter. The
obtained results help to assess the generated impact on the peak potential
separation of square-wave forward and backward components from conventional and

of
potential corrected voltammograms as well as on the so-called ‘amplitude-based
quasireversible maximum’ acquired during the analysis of the net response peak

ro
height. In most cases, these features are independent of the parameters of coupled
-p
chemical reaction, and electrode kinetics can be estimated without their prior
knowledge. Some characteristic criteria can be deduced from the observed trends,
re
which can serve as a means to elucidate electron transfer kinetics. Under these
conditions, even nonexperts in the square-wave voltammetry technique can
lP

characterise the studied experimental systems.

na
ur
Jo

Keywords: EC mechanism; CE mechanism; peak potential separation of square-

wave components; amplitude-based quasireversible maximum; square-wave

voltammetry

2
 Journal Pre-proof

Introduction

Square-wave voltammetry (SWV) is one of the many electrochemical

techniques [1, 2] introduced in the previous century. It is mostly applied in analytical
chemistry [3-7] (together with another technique known as differential pulse
voltammetry [8]), especially when combined with the accumulation step (so-called
‘stripping voltammetry’). Although the superior characteristics of the pulse techniques
enable us to analyse many aspects of the studied experimental systems, their use for
such purpose has not yet been fully explored. Characterization of electroactive
compounds or determination of electrode reaction mechanism is mainly performed by

of
cyclic voltammetry (CV), especially when electrochemical methods are occasionally

ro
used. The well-known theory of CV formulated by Nicholson [9] and further
elaborated by later scientists [10-12] stabilised the use of CV. Nevertheless, during
-p
the last 20–30 years, there has been an increasing application of the pulse technique
to characterise electrode reactions [8, 13-16]. Cyclic staircase [17, 18], differential
re
pulse [19, 20], square-wave (SW) [21-24], and cyclic square-wave (CSW) [25-27]
lP

voltammetry are some of the well-established electrochemical techniques that can

also evaluate electrode kinetics. It is also worth mentioning several attempts in the
development of alternative electrochemical techniques, for example, electrochemical
na

faradaic spectroscopy, which may find broader application in the forthcoming years
[16, 28-30].
ur

Complex responses due to the coupled chemical reactions could be

Jo

encountered while studying electrochemical signals. These responses occur either as

preceding (CE) or following (EC) chemical transformation of electroactive species.
Additionally, the overall process is often affected by the adsorption phenomena of
reactant/product or both. To help better understand these complex, coupled
electrode reaction mechanisms, several electrochemical techniques have been used
to date, including CV, coulometry, pulse polarography, and SWV [31]. SWV is mostly
used to analyse the response within a certain range of SW frequencies, as an
analogy to the scan rate effect in CV. If the so-called quasireversible maximum [32] is
observed alone in the frequency-normalized peak current vs. SW frequency function,
it is possible to obtain information on the reversibility and electron transfer rate of the
studied electrode system [33]. The applicability of SWV to understand EC

3
 Journal Pre-proof

mechanisms has been recently critically assessed in a broad range of electron

transfer and chemical reaction kinetics [34].
Recently, the kinetic evaluation of electrode reaction is reported with the SW
amplitude effect [35]. Useful information can be obtained by observing the
interposition of SW forward and backward responses that are affected by alteration of
the pulse height in SWV (i.e. square-wave amplitude) [36]. The amplitude effect is
reported for simple diffusion-controlled and surface-confined electrode systems (the
latter one includes systems coupled with interactions in the adsorbed layer), an EE
mechanism, and an anodic and cathodic stripping electrode mechanism for a range
of electroactive species [37-39].

of
The electrochemical behaviour of uric acid has been intensively studied [40-
42]. The resolution of detection in the presence of ascorbic acid has stimulated many

ro
experiments [43]. This biomolecule is quite valuable as it can serve as an indicator of
-p
critical diseases such as gout, hyperuricaemia, and Lesch-Nyhan syndrome. The
electrochemical response of uric acid can serve as an example of an EC electrode
re
reaction, at least under SW voltammetric conditions. Therefore, a careful study of this
useful biomolecule can enable the development of new experimental methodology
lP

and increase the possibility of gaining information on kinetic parameters of a

particular redox mechanism from simple voltammetric dataset.
na

This report critically evaluates whether electrode reaction mechanisms

coupled with chemical reaction can be studied with SWV and amplitude effect. The
ur

kinetic characterisation employs either amplitude-based quasireversible maximum or

relative position of peak potential of SW components inferred from conventional and
Jo

potential-corrected voltammograms. The theoretical analysis is performed for three

general and most popular EC and CE mechanisms. The influence of the coupled
chemical reaction parameters is described, and it is assessed whether electrode
kinetics can be estimated without their prior knowledge. The applicability of the
reported methodology is confirmed experimentally with the uric acid electrode system
studied at the boron-doped diamond electrode surface.

Theory

CE solution-based mechanism

4
 Journal Pre-proof

In the simplest form of CE mechanism, first, the preceding homogenous

chemical reaction creates an electroactive reactant. Here, it is assumed that the
chemical reaction is chemically reversible and characterised by first-order forward kf
(s−1) and backward kb (s−1) rate constants. When the electron(s) is(are) released in
the electrochemical step, the following reaction scheme can be depicted (hereafter
charges are omitted for better understanding):
𝑘𝑓
𝐼𝑠𝑜𝑙 →← 𝑅𝑠𝑜𝑙 (1)
𝑘𝑏

𝑅𝑠𝑜𝑙 →
← 𝑂𝑥𝑠𝑜𝑙 + 𝑛𝑒 − (2)

In this case, all species have been attributed with common diffusion coefficient D. It is

of
assumed that the studied chemical reaction is at equilibrium at the beginning of the
experiment, represented by the equilibrium constant, K, which can be defined as

ro
follows: K = kf/kb. The overall kinetics of the chemical step in the time window during
-p
voltammetric measurement can be represented by the critical dimensionless
chemical kinetic parameter defined as ε = (kf + kb)/f, where f is the frequency of SW
re
potential pulses. The thermodynamic parameter K and the dimensionless kinetic
parameter ε show the outcome of the preceding chemical reaction on the resulting
lP

voltammetric signal of electron transfer reaction. While K controls mainly the initial
amount of electroactive substrate R (and also its creation during measurement, if
na

only the chemical reaction rate is fast enough to reach the equilibrium), the
dimensionless chemical kinetic parameter provides information on the rate of
ur

regaining the chemical equilibrium distorted by successive electrode reactions. The

influence of the electrode reaction kinetics on the resulting final response can be
Jo

determined using the electrode kinetic parameter, which is defined as ω = ks (D f)−1/2,

where ks (cm s−1) is a heterogeneous standard rate constant [1].

EC solution-based mechanism
Similar to the above description, the scheme can be written as follows:

𝑅𝑠𝑜𝑙 →
← 𝑂𝑥𝑠𝑜𝑙 + 𝑛𝑒 − (3)
𝑘𝑓
→
𝑂𝑥𝑠𝑜𝑙 ← 𝐼𝑠𝑜𝑙 (4)
𝑘𝑏

The electron transfer at the solution–electrode surface interface is influenced by the

first-order homogenous chemical reaction. In the latter equation, the product of the

5
 Journal Pre-proof

electrode reaction is transformed into an electroinactive product Isol. The definition

and meaning of all the parameters are analogous to those for the previously
described CE mechanism. The recorded response again depends on the chemical
reaction parameters such as the equilibrium constant K, the dimensionless chemical
kinetic parameter ε, and the electrode kinetic parameter ω [1].

EsurfCirr surface-confined electrode reaction coupled with irreversible chemical

reaction
This special case of EC electrode mechanism can be better understood
through the following scheme:

of
𝑅𝑎𝑑𝑠 →
← 𝑂𝑥𝑎𝑑𝑠 + 𝑛𝑒 − (5)

ro
kf
𝑂𝑥𝑎𝑑𝑠  𝐼𝑎𝑑𝑠 -p (6)
In this particular surface EC mechanism, it is assumed that the electroactive
substrate is adsorbed on the electrode surface. The electron transfer occurs only
re
within a monolayer or submonolayer, and there is no diffusion control of the electrode
lP

reaction from species in the bulk solution. Therefore, the diffusion mass transport
does not need to be considered during modelling of this mechanism. The overall
outcome depends only on the surface concentration variation of the redox species.
na

During the chemical reaction, the product of electrode reaction is chemically

irreversibly transformed into an electroinactive species. The influence of this step can
ur

be defined through the chemical kinetic parameter εirr = kf/f. The effect of the
Jo

electrode reaction on the overall response can also be identified using the
dimensionless electrode kinetic parameter ωs = ksur/f where ksur (s−1) implies the
heterogeneous rate constant of electron transfer [1].
The Butler-Volmer kinetic model was applied for all the aforementioned
electrode mechanisms. The final integral equation obtained from mathematical
modelling for SW potential waveform applied in SWV can be found elsewhere [1].
The theoretical data discussed in this manuscript are given as dimensionless current,
which is related to the real current recorded during voltammetric experiment with the
   
relationship either   I / nFAc* ( Df )1 / 2 or   I / nFA* f for diffusion-controlled or

surface-confined mechanism, respectively. The symbols given in the aforementioned

equations have their usual physical meaning. The simulation can be performed using

6
 Journal Pre-proof

the Mathcad software. The exemplary voltammograms of each of the studied

electrode mechanisms are given in Supporting Information as Fig. S1–S3 for CE, EC,
and EsurfCirr surface-confined electrode reaction coupled with irreversible chemical
reaction mechanism, respectively.

Experimental

Apparatus
Multideviced electrochemical potentiostat mAutolab (Metrohm Autolab, The
Netherlands) equipped with PGSTAT101 and controlled by Nova software (v. 1.10.3)

of
was used for the experiments. A classic three-electrode configuration was used. It
consisted of a platinum wire, a boron-doped diamond immersed in a Teflon body

ro
(Windsor Sci., Ø = 3 mm), and silver/silver chloride (3 M KCl) that served as auxiliary,
-p
working, and reference electrodes, respectively. A 10-mL single-compartment
voltammetric cell at an ambient room temperature (22 ± 1 °C) was used for the
re
electrochemical experiments.
lP

Reagents
Uric acid was purchased from Sigma-Aldrich and diluted as required to obtain
na

a standard stock solution of 0.5 mmol L−1 concentration. A standard phosphate

buffered saline (PBS, with physiological pH 7.4) served as the supporting electrolyte
ur

in the experiments. All reported solutions were prepared with water deionized using
the Polwater DL-3 purification system.
Jo

Procedure
Typically, kinetic measurements were performed using a boron-doped
diamond electrode. Alumina slurry with an average particle size of 0.05 μm, on a
cleaning pad, was used to polish the working electrode surface before each set of
experiments. Following this procedure, the freshly cleaned electrode was transferred
to the supporting electrolyte solution containing PBS with the total ionic strength 0.16
mol L-1. The SW voltammogram was recorded by applying a positive-going scan with
SW potential modulation and a 1 mV potential step usually in the potential interval
from −0.2 to 1 V.

7
 Journal Pre-proof

Results and Discussion

The SW potential modulation is constructed using a pulse train and combined

with an incrementally increasing potential. In this technique, the final form of the
potential alteration during the experiment is defined with SW amplitude (Esw, pulse
height), step potential (ΔE, potential increment), and frequency (f, number of pulses
per specific time period). Because a single potential cycle is achieved with two
neighbouring but oppositely directed pulses, the frequency can be calculated from
the duration of the pulse cycle, τ, as f = 1/τ. Further, as the current is sampled
independently twice during the entire potential cycle, the resulting net component is a

of
simple difference between the currents measured at the first and second pulse in
each cycle. In terms of analytical usage, SWV is based on linear dependence

ro
between the increasing analyte concentration and the resulting net peak current [44-
-p
46]. Analogous to the scan rate effect in CV, the spectrum of the net peak current in
the frequency domain may provide useful information on the kinetics of electron
re
exchange. In particular, the so-called quasireversible maximum provides substantial
information on the standard electrode rate constant of a studied electrode system
lP

[32]. In the present paper, another strategy is developed by studying the SW

amplitude effect. Thus, an amplitude-derived quasireversible maximum is created,
na

and it constitutes another useful tool in kinetics estimation. In addition to the net
component peak current (ΔIp) analysis, the evaluation of SW forward (from the first
ur

pulse in the cycle) and backward (the second one) component relative position is of
particular importance as it may under specific circumstances directly correlate with
Jo

the rate of electron transfer [36]. The magnitude of component peak potential
separation (ΔEp) is analysed under conventional and potential-corrected
voltammogram conditions. The latter one (ΔE′p) is artificially constructed in a domain
of the actual applied potential to the electrode, i.e. the potential of staircase ramp
given in conventional measurement is adjusted with a value of the applied pulse
potential (i.e. SW amplitude). It is worth noting that the peak potential separation of
this SW component in both analyses relies on the relative magnitude, and thus is
completely insensitive to the type of the reference electrode used in the studies [37-
39].

Theoretical data

8
 Journal Pre-proof

CE mechanism
The voltammetric response of the CE mechanism is controlled by three main
parameters, namely the equilibrium constant K; the dimensionless kinetic parameter
ε, which describes the chemical reaction; and the dimensionless electrode kinetic
parameter ω. The synergistic effect of the chemical and electrode reactions is quite
apparent. The preceding chemical reaction produces more electroactive substrate
with an increase in both K and ε, leading to an increase in the overall electrochemical
response. If the kinetics of the chemical reaction are fast, the thermodynamic
parameter controls the peak current. The voltammetric signal again depends on K if

of
the value of ε is high. The response is quasireversible and depends on the kinetics of
electrode reaction ω when ε is in the range −1 ≤ log (ε) ≤ 2, regardless of the value of

ro
K [1]. -p
In this regard, the studied SW voltammetric response must be carefully
assessed to ensure the proper evaluation of electrode reaction kinetics. The present
re
paper focuses on the SW amplitude-normalized net peak current (Ψp/Esw) as well as
on the SW components peak potential separation of classic (Ep) and potential-
lP

corrected (E′p) voltammograms. Figure 1 shows the analysis of the function of SW

amplitude. In this analysis, it is assumed that the number of electrons exchanged
na

during the electrochemical process is equal to 1 and the electron transfer coefficient
is 0.5.
ur

Panel A shows the effect of thermodynamic parameter K on the amplitude-

Jo

normalized peak current assuming a fast chemical step, i.e. log (ε) = 2, and a
medium-range rate of electron transfer, i.e. log (ω) = 0.5. If the equilibrium of the
chemical reaction is not shifted towards the left side, the function ΔΨp/Esw = f(Esw) is
kept constant (for log(K) ≥ 0). Moreover, the shape of dependence remains the same
even when the equilibrium of the chemical reaction is shifted towards higher content
of Isol as the one obtained with log(K) = −1. The same effect is observed when
analysing the peak potential separation of SW components (data not shown). On the
other hand, the rate of chemical reaction more significantly affects the height of the
SW net component, while keeping its shape constant (data not shown). The effect of
the chemical reaction rate on the relative position of SW components is shown in
panels B and C of Fig. 1 for conventional and potential-corrected voltammograms,

9
 Journal Pre-proof

respectively. In this analysis, the other two parameters are assumed as log (K) = 0
and log (ω) = 0.5. Within a reasonable range of dimensionless kinetic parameter
values (i.e. −1 ≤ log (ε) ≤ 1), the analysed function shows the same dependence and
is not significantly affected by large SW amplitude values. In Fig. 1B, the crossing of
the ordinate corresponds to the situation of no peak potential separation (i.e. ΔEp =
0). This implies that for small SW amplitude values (below 40 mV), the SW forward
component is located at less positive potential than the backward one, while the case
is opposite for large values of Esw (here, it is discussed for potential scan from
negative to positive and oxidation occurring during forward pulse potential).
Kinetic analysis based on the SW amplitude effect can be performed using the

of
function ΔΨp/Esw = f(Esw) as depicted in Fig. 2A for a range of electrode kinetic
parameters. The amplitude-normalized net peak current shows a profound maximum

ro
with a change in the applied Esw. The position of the maximum is linear for a range of
-p
electrode kinetic parameters with relatively slow electron transfer (inset of Fig. 2A).
The slowdown of electron exchange decreases the electrode kinetic parameter ω,
re
affects the reversibility of the system, and induces a shift in the maximum position.
Hence, the heterogeneous standard rate constant is estimated by evaluating the
lP

electrode kinetic parameter. It is worth noting that the experimental observation of

amplitude-based quasireversible maximum is difficult due to other effects that can
na

simultaneously influence the recorded signals. Hence, a careful analysis of the

position with varying experimental time (i.e. range of frequencies) will ensure the
ur

correctness of the estimation. One must also note that this phenomenon is true for a
range of chemical reaction parameters, but not for all of them. The above discussion
Jo

refers to the case of two electrons exchanged during the electrode process. The
same linear dependence of the position of amplitude-normalized maximum net peak
current on the applied SW amplitude for the number of electrons, n = 1 holds the
following equation: Esw(max)/mV = −172.00·log(ω) + 34.50 with a correlation
coefficient, R² = 0.978 in the range −1.25 ≤ log(ω) ≤ −0.5. These relationships are
useful for slightly narrow range of ω as noted in the comparison of peak potential
separation magnitude of SW components described in the next paragraph.
The peak-to-peak separation of SW components in conventional SWV
depends significantly but nonlinearly on SW amplitude as shown in panel B of Fig. 2.
This parameter is defined as a difference between the position of forward and
backward peaks, i.e. E = Ep,f − Ep,b, where Ep,f and Ep,b are the peak potentials of the

10
 Journal Pre-proof

forward and backward components, respectively, of an SW response on the potential

axis. Clearly, it is also a function of the electron transfer rate, which is characterized
by the dimensionless electrode reaction parameter ω. By increasing the height of the
applied potential pulse, the separation between peak potential of the components
becomes increasingly pronounced. Moreover, when the electrode reaction
decelerates (i.e. at lower ω values), the same interposition of peak potential
separation of SW components is achieved with smaller values of Esw. The
dependencies are characterized by inflection points close to the position of no
separation, i.e. (ΔEp) = 0, which can be used to estimate electrode kinetics. As
shown in the inset of Fig. 2B, a linear dependence is observed between the value of

of
a particular SW amplitude at which the relationship crosses the ordinate axis and the
value of ω. Thus, the standard rate constant can be evaluated by recalling that ks =

ro
ω/(D f)−1/2. To confirm the precision of this method, the same experiment can be
-p
repeated for other reasonable value(s) of frequency. This theoretical prediction was
performed for a set of other parameters such as log (ε) = 0, log (K) = 0, and n = 2.
re
The same relationship for the transfer of only one electron holds the equation: Esw (V)
= −105.27 log(ω) + 44.75, R² = 0.9952, which is true for −1.75 ≤ log(ω) ≤ 0.
lP

A recently introduced potential-corrected voltammogram [36] is thought to be

another possible means for elucidating electrode kinetics. The basis of this new
na

voltammogram is simple and similar to the method described above. The only
difference lies in the foundation of voltammograms being analysed. Here, the position
ur

of SW components is displayed and measured vs. the actual potential at which the
current is sampled. Nevertheless, it is also a useful and valuable method of electrode
Jo

kinetic parameter estimation as it is not always easy to measure the position of SW

components of sluggish and poorly resolved electron transfer. For the CE mechanism
analysed here, the behaviour of peak potential separation of potential-corrected SW
components with the amplitude effect is shown in panel C of Fig. 2. A nonlinear
behaviour is observed for any rate of electron transfer regardless of the value of the
applied SW amplitude. Nevertheless, one can observe that these dependencies
cross the so-called blank (see dashed line in Fig. 2C) at a specific value of SW
amplitude, Esw(x), thus showing sensitivity to the electrode kinetic parameter. This
specific line is created on the assumption that the peak potential separation of implicit
SW components results from potential correction with Esw alone, and no deviation is
expected from the kinetics of electron transfer. In other words, this line is created as

11
 Journal Pre-proof

ΔE′p = 2 Esw. It should also be noted that the crossing point with the blank can be
characterized with the size of peak potential separation of SW components, ΔE′p(x).
By plotting the dependence of ΔE′p(x) on the dimensionless electrode kinetic
parameter, as depicted in the inset of Fig. 2C, one finds a perfect tool for evaluating
electrode kinetics in a broad range of ω. This method is introduced for the first time in
the electrode kinetics analysis despite many previous attempts to determine the best
application of potential-corrected voltammograms [36, 37, 39]. Most probably, it
would be worth recalling the previously discussed electrode mechanisms to
determine whether these could also be used for such cases. Note that the data given
in Fig. 2C are obtained for the same set of parameters as shown in Fig. 2B. The

of
same dependence is observed for one electron transfer for ΔE′p(x) (V) = −0.2176
log(ω) + 0.0020, R² = 0.997, which is true in the range −2.25 ≤ log(ω) ≤ −0.5. It is

ro
also possible to analyse this simulation data in another way, for example, by plotting
-p
the value of ΔE′p in a function of the rate of electron transfer at a given, constant
value of SW amplitude (data not shown). This other method relies on plotting the
re
function of intercepts of linear parts of the curves as a function of dimensionless
electrode kinetic parameter (data not shown). The usefulness and applicability of
lP

such functions depend only on the shape of the obtained experimental dataset.
na

EC mechanism
As noted for CE mechanism, three main parameters control the overall
ur

voltammetric response of a redox system, namely the equilibrium constant K, the

dimensionless chemical kinetic parameter ε, and the electrode kinetic parameter ω.
Jo

The general effect of ε on the voltammetric signal can be presented using three
separate cases. In the first part, when the chemical reaction is slow, the recorded
peak current does not depend on K. The second part corresponds to a medium rate
of chemical kinetics where the response gains parabolic function with the position of
minimum being dependent on the value of the equilibrium constant. The third case,
because of high values of ε, resupplies the electroactive material during the
backward pulses. The response becomes quasireversible in terms of electrode
reaction, when ε is in the range −2 ≤ log (ε) ≤ 1 [1].
Theoretically, the situation is just an analogue (only reversed) of the CE
mechanism as discussed in the above section. Unexpectedly, the analysis of the
amplitude-normalized SW net peak current on the effect of the equilibrium constant

12
 Journal Pre-proof

and the dimensionless chemical kinetic parameter concludes that their influence
cannot be ignored (data not shown). Only when the chemical reaction is sufficiently
fast (i.e. log(ε) ≥ 2), the amplitude-based quasireversible maximum is observed and
found to be unaffected by the overall rate of chemical transformation. The same
finding is obtained for log(K) ≤ 0. Fortunately, in the analysis of the influence of the
chemical reaction on the peak potential separation of SW components, as shown in
Fig. 3, it is possible to determine the effect of SW amplitude without prior estimation
of ε and K. The observed change can be discarded in terms of method precision. The
deviation mentioned here actually results from the influence of chemical reaction
factors that cover most of the typical values; hence, such deviations are highly

of
unlikely to be observed in real experiments [1].
Despite the slight influence of the chemical reaction parameters on the SW net

ro
response, it is still possible to evaluate the kinetics of the electrode reaction as shown
-p
in Fig. 4A. If prior estimation of ε and K is performed using some other methods, the
observed amplitude-based quasireversible maximum can serve as a means to
re
elucidate ω. The illustration is made with log(ε) = 2 and log(K) = 1, which implies
rather fast takeover of the electrode reaction product and transformation towards the
lP

product of chemical reaction. The observed position of the maximum shifts towards
higher values of SW amplitude with a decrease in the electrode kinetic parameter.
na

This effect can be observed under the same conditions for the case of one-electron
electrode reaction; it holds the equation Esw(max)/mV = −172.00·ω + 34.50, R2 = 0.980
ur

and is obeyed within a narrower range of ω (−1.25 ≤ log (ω) ≤ −0.5, data not shown).
The best method of electrokinetic estimation for EC mechanism out of the
Jo

three methods considered in this paper seems to be the one based on the peak
potential separation of SW components in conventional voltammograms. The effect
of SW amplitude on this parameter is depicted in Fig. 4B for log(ε) = 2 and log(K) = 1.
If a quasireversible response is obtained for the given electrode kinetic parameter,
then most of the signals are derived from the forward and backward components
which are at less and more positive potential, respectively. Assuming that the position
of ΔEp = 0 (i.e. the position of forward and backward components is the same on the
potential axis) is the most characteristic point in the above-mentioned plot, it is
possible to define a linear dependence of its associated Esw(ΔE=0) value on a particular
electrode kinetic parameter as shown in the inset of Fig. 4B. If n = 1, the expression

13
 Journal Pre-proof

is as follows: Esw(ΔE=0) (V) = −105.27·log(ω) + 44.75, R2 = 0,995, and it holds within

the range −1.75 ≤ log (ω) ≤ 0 (data not shown).
The electrode reaction kinetics for EC mechanism can also be evaluated with
potential-corrected voltammogram [36]. As indicated in the discussion from the
previous section on CE mechanism, a careful analysis of the actual position of SW
component interposition can enable estimation of the electrode kinetic parameter.
Although the discussed mechanism seems to be an inverse situation to the electrode
mechanism with preceding chemical reaction, the analysis of the SW amplitude effect
on ΔE′p is not completely the same as shown in Fig. 4C. Again, the relative position
of peak components seems to be nonlinear and difficult to investigate. Nevertheless,

of
this method could be applied to find the proportionality between the analysed
parameter and ω, assuming that the crossing point with the artificial blank line can

ro
serve as a solution. Here, it is possible to use the critical value of SW amplitude
-p
(ESW(x)) at which ΔE′p(x) crosses the blank line as it can be analysed as a function of
ω, as shown in the inset of Fig. 4C. By plotting the same dependence for one-
re
electron reaction, the equation can be written as follows: ESW(x) (V) = −0.1052 log(ω)
+ 0.0455, R² = 0.999, which is true for the range −2 ≤ log(ω) ≤ 0.
lP

EsurfCirr surface-confined electrode reaction coupled with irreversible chemical

na

reaction
The influence of chemical reaction on surface EC mechanism is the same as
ur

that on a dissolved redox couple. As observed for every electrode reaction

associated with adsorption phenomena, the quasireversible maximum can also be
Jo

easily observed here. The splitting of the net response is also apparent. In the latter
case, the position of the separated net signal is unaffected by the value of the kinetic
parameter of the chemical reaction. Hence, εirr has almost negligible influence on the
peak potential separation of SW components as shown in Fig. 5A. Only slight
changes can be observed for the lowest values of SW amplitude. Moreover, the
effect of the dimensionless chemical reaction kinetic parameter is even less
pronounced in potential-corrected voltammograms, as depicted in Fig. 5B. Although
the literature suggests possible evaluation of εirr based on the ratio between forward
and backward peak current [1], it does not influence the relative position of the initial
components of the SW response. The analysis of the amplitude-normalized SW net
peak current vs. Esw for different values of εirr suggests that the dimensionless

14
 Journal Pre-proof

chemical reaction kinetic parameter can affect the height of the signal but does not
influence the position of the amplitude-based quasireversible maximum (confirmed in
the range −4 ≤ log(εirr) ≤ 0, data not shown).
By analysing the amplitude effect for EsurfCirr mechanism, we can start
observing the amplitude-based quasireversible maximum. For one-electron electrode
reaction, the position of the quasireversible maximum shifts together with the
electrode kinetic parameter (Fig. 6A). With the decrease in ωs values, the position of
ΔΨp/Esw shifts towards higher values of SW amplitude. The corresponding calibration
line is given in the inset of Fig. 6A. However, when the electrode reaction is
significantly fast, the amplitude-based quasireversible maximum cannot be observed.

of
As the number of electrons increases to two, the discussed relationship gains the
following formulae: Esw(max)/mV = −63.495·log (ωs) − 2.626, R2 = 0.997 and is obeyed

ro
within a broader range of ωs (−3.5 ≤ log (ωs) ≤ −0.5, data not shown).
-p
A nonlinear function is observed when analysing the dependence of peak
potential separation of SW components as a function of SW amplitude (Fig. 6B).
re
Nevertheless, this behaviour can be used for elucidating electrode reaction kinetics
when considering the crossing of a particular relationship with a given standard rate
lP

constant with the Esw axis. In such cases, the outcome corresponds to the absence of
separation between the peaks of SW components, and hence, ΔEp = 0. The variation
na

of this specific SW amplitude with a logarithmic change in the electrode kinetic

parameter is given in the left inset of Fig. 6B. The corresponding function for n = 2
ur

reads: Esw(ΔEp=0)/mV = 57.838 log (ωs) − 22.757, R2 = 0.999 for −4.5 ≤ log (ωs) ≤ −0.5.
The dependencies shown in Fig. 6B can also be analysed based on the size of peak
Jo

potential separation of SW components for given Esw. Here, for SW amplitude of 100
mV, a linear relationship with the electrode kinetic parameter is observed as shown in
the right inset of Fig. 6B. The same analysis for n = 2 shows ΔEp(Esw=100)/V = −0.0217
log (ωs) − 0.0466, R2 = 0.988 for −2.75 ≤ log (ωs) ≤ −1.25. It is worth noting that these
analyses could be performed using any value of Esw, whenever ωs affects the
proportionality of the interposition of SW components.
Finally, potential-corrected SW voltammograms can serve as a means to
elucidate electrode reaction kinetics for EsurfCirr mechanism. Figure 6C presents the
typical behaviour of peak potential separation of SW components on the SW
amplitude for a range of the electrode kinetic parameter. The analysis of only linear
portions of the curves and creation of a plot of the corresponding intercepts vs. ωs is

15
 Journal Pre-proof

possible as indicated in a previous study [36]. However, the resulting dependence

shows poor sensitivity and hence produces a rather high estimation error. Therefore,
as shown in Fig. 4C, it is worth to analyse the crossing point of ΔE′p with the artificial
blank line. The obtained critical value of SW amplitude, Esw(x), is a function of the
studied electron transfer rate as shown in the inset of Fig. 6C. The same dependence
but in the case of two-electron transfer reaction generates the following dependence:
Esw(x)/V = −0.0587 log(ωs) − 0.0257, R² = 0.999, which is true for −4.5 ≤ log(ωs) ≤
−0.75. This method is definitely much more accurate than the previously reported
one [36] for the analysis of potential-corrected voltammograms.

of
Experimental results
The usefulness of the different methodologies described in this paper for

ro
elucidating electrode kinetics was verified with the uric acid electrode system. Studies
-p
were performed in a PBS solution at pH 7.4 by using a boron-doped diamond
electrode.
re
Experimental assays were performed in the potential range from −0.2 to 1 V with a
uric acid solution as a redox probe. The cyclic voltammetric measurements revealed
lP

quasireversible behaviour with easily defined anodic Ep,a = 0.646 V and cathodic Ep,c
= 0.49 V peaks (measured at scan rate ν = 100 mV s−1). The effect of the scan rate
na

on the electrochemical oxidation of uric acid at the boron-doped diamond electrode

was investigated by position and height analysis of the anodic and cathodic branch
ur

from the recorded voltammetric curves. Both the anodic and cathodic peak currents
increased linearly with the square root of the scan rate (analysed in the range from
Jo

20 to 500 mV s−1). This suggested a diffusion-controlled characteristic of electrode

processes. The peak current ratios (Ip,a/Ip,c) decreased with the increase in the scan
rate and suggested that electrochemical processes were followed by the chemical
reaction, which is consistent with the well-known electrode mechanism of uric acid
[40, 42, 47]. The uric acid oxidation signal shifted towards more positive potentials
with the increasing scan rate as predicted for kinetic limitation from the electron
transfer reaction. The dependence of Ep,a as a function of ln(ν) yielded a straight line
with slope equal to 0.026 V. Assuming a two-electron electrode reaction and other
standard conditions, the electron transfer coefficient was found to be 0.50 [48].
Further, in the analysis of frequency-normalized dependence of the peak current in

16
 Journal Pre-proof

SWV as a function of log(f), the quasireversible maximum is not observed as it

continuously decreases.
The SW amplitude effect was analysed for uric acid electrode systems. The
experiments were conducted within a range of SW amplitude from 20 to 250 mV at a
constant frequency. The frequency is then changed several times in the range of 8–
150 Hz to mimic the change in the electrode kinetic parameter. The obtained peak
potential separation of SW components resembled qualitatively the theoretical
predictions (cf. Supporting Information Fig. S4). Additionally, it allowed to use the
working curves shown in Fig. 4 (experimental data are given in Fig. S5). The
calculated average value of the standard rate constant of uric acid at the boron-

of
doped diamond electrode was found to be (7.8 ± 0.2) x 10−4 cm s−1, assuming that
the diffusion coefficient is 6.97 x 10-6 cm2 s-1 [49]. The results given herein confirm

ro
the possibility of kinetic characterization with amplitude change alone. The evaluated
-p
rate of electron transfer at the boron-doped diamond electrode surface is more slow
than that reported in the literature studies performed at glassy carbon electrode
re
surface modified with multiwalled carbon nanotubes and chitosan [50], where the
estimated value was 2.3 x 10−2 cm s−1.
lP

Conclusion
na

This is the first report that presents a detailed analysis of the SW amplitude
ur

effect on the response of the electrode mechanism coupled with chemical reaction.
The assay performed under the conditions of conventional and potential-corrected
Jo

square-wave voltammetry sheds light on the possible electrode reaction kinetics

evaluation using Esw. In most of the discussed cases, no prior knowledge on
chemical reaction parameters is required. This theoretical model addresses diffusion-
controlled EC and CE mechanisms as well as surface-confined EC mechanism with
irreversible, chemical transformation of the product of the electrode reaction. This
numerical solution serves as a means for studying Esw that affects not only the SW
net response but also SW forward and backward components. The constant
timescale of the analysis reported here at the particular SW frequency is one of the
main advantages of the proposed methodology. Although the Butler-Volmer kinetic
model could also be applied to analyse the electrode mechanism response [19], the
method described in the present paper correlates with and resembles perfectly

17