Journal of Electroanalytical Chemistry 880 (2021) 114891

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Determination of standard electrochemical rate constants from semi-circular

sweep voltammetry: A combined theoretical and experimental study
Hatem M.A. Amin a,b, Yuki Uchida a, Enno Kätelhön a,1, Richard G. Compton a,
⁎
a
Department of Chemistry, Physical & Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, United Kingdom
b
Chemistry Department, Faculty of Science, Cairo University, 12613, Giza, Egypt

A R T I C L E I N F O A B S T R A C T

Article history: Semi-circular potential sweep voltammetry has recently been proposed as a sensitive method to estimate electrochem-
Received 19 October 2020 ical rate constants [J. Electroanal. Chem., 835 (2019) 60–66]. Herein, this approach is experimentally verified using
Received in revised form 24 November 2020 microdisc electrode voltammetry. The reduction of hexaamineruthenium (III) chloride and the oxidation of
Accepted 25 November 2020
ferrocenemethanol, both in aqueous solution, at carbon electrodes were studied. The rate constants obtained from
Available online 28 November 2020
semi-circular voltammetry for both investigated redox systems are in agreement with independent values obtained
Keywords:
from the conventional Nicholson method at macroelectrodes. The method compares favourably in terms of simplicity
Standard electrochemical rate constant and speed as it requires recording only a single voltammogram. This approach provides a novel, fast complementary
Semi-circular sweep voltammetry method for the evaluation of the standard electrochemical rate constant.
[Ru(NH3)6]Cl3 reduction
FcCH2OH oxidation
Kinetics

1. Introduction or nanoelectrodes [8,9]. In their method, ko is determined directly from

Measuring the rate of electron transfer is crucial in understanding di-
verse electrochemical reactions including systems of fundamental, biologi-
cal and medical relevance [1–3]. The standard electrochemical rate
constant (ko) is the important parameter which quantifies the reversibility
of the electron transfer and the kinetics of the reaction [2,4,5]. Linear
sweep- and cyclic voltammetry at macroelectrodes are commonly used to
measure ko values [2,4,6]. Specifically, from cyclic voltammetry data at a
macroelectrode, the standard rate constant of electron transfer is routinely
determined using the method of Nicholson [7]. In the Nicholson procedure,
ko is calculated based on the peak-to-peak potential separation (ΔE) at var-
ious scan rates (υ) according to the following Eq. [7]:
½πDox υðnF=RT Þ1=2
ko ¼ Ѱ
ðDox =Dred Þα=2
where Ѱ is the “kinetic parameter”, Dox and Dred are the diffusion co-
efficients of the oxidized and reduced species, respectively, υ is the scan
rate, F is the Faraday constant, R is the ideal gas constant, T is the temper-
ature, n is the number of electrons transferred, and α is the transfer coeffi-
cient. Another approach has been introduced by Mirkin and Bard for
calculating the parameter ko based on steady-state voltammetry at micro-
two easily accessible experimental parameters, (E1/4 − E1/2) and (E1/2 −
E3/4), where E1/2 is the half-wave potential and E1/2 and E3/4 are quartile
wave potentials [8]. The use of microelectrodes is advantageous for mea-
suring fast electron transfer kinetics as they increase the mass transport
rate (so accessing faster rate constants) and minimize the effects of ohmic
(IR) drop in solution, the double layer charging and the reactant adsorption
[10–12]. Linear cyclic voltammetry (CVs) at microelectrodes but at larger
scan rates together with simulations could also be used to determine ko,
however the attraction of using lower scan rates and accounting for the con-
vergent diffusion allows measurements at scan rates essentially free from
capacitive currents [13]. Transient methods at microelectrodes have also
been reported [14–17].
In our previous work, we have presented the theoretical treatment of an
alternative method of voltammetry that employs a semi-circular potential
ð1Þ waveform rather than the typical and conventional linear waveform
[18,19]. Recently, we have experimentally implemented the semi-circular
sweep voltammetry (SCV) to determine the formal potential of a redox sys-
tem [20]. This theory was further developed via simulation to give a basis
for measuring electrode kinetics [21]. In this paper we present an experi-
mental verification of the semi-circular sweep voltammetry at a microelec-
trode and its application to evaluate the ko values of the aqueous redox
couples Ru(NH3)2+/3+ and FcCH2OH0/1+. These redox systems were
6

⁎ Corresponding author.
E-mail address: richard.compton@chem.ox.ac.uk. (R.G. Compton).
1
Current address: MHP Management- und IT-Beratung GmbH, Office Frankfurt, Edmund-Rumpler-Strasse 3, Alpha Rotex, 60,549 Frankfurt am Main, Germany.

http://dx.doi.org/10.1016/j.jelechem.2020.114891
1572-6657/© 2020 Elsevier B.V. All rights reserved.
H.M.A. Amin et al.
selected for study at carbon electrodes as they have relatively fast electron
transfer kinetics and likely involve outer-sphere electron transfer [9,11].
Satisfactory agreement between the results obtained from this new method
at microelectrodes and the traditional Nicholson method at macro-
electrodes was seen. In addition, the voltammograms obtained experimen-
tally show good agreement with the simulated ones, further validating the
theory given in [21].
2. Semi-circular potential wave sweep voltammetry (SCV)
In this section, we describe briefly the method and the waveform
employed in our work. Details of the theoretical model can be found in
our previous reports [19,21]. In linear sweep voltammetry, the potential
waveform is expressed as:
EðtÞ ¼ Eðt ¼ 0Þ  υt ð2Þ
where the potential of the working electrode E(t) is swept linearly from an
initial potential E (t = 0) with a constant scan rate (υ). Recently, Uchida
et al. have proposed the semi-circular potential waveform as an alternative
wave and can be described as follows [19–21]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  2
t
EðtÞ ¼ Ao j 1− 2 −c j þ Ecentre ð3Þ
t max
where Ao is the amplitude of the potential wave, t is the time and tmax is the
duration of a single potential sweep between the initial potential Ei and the
final potential Ef. Experimentally, the duration of the potential scan tmax de-
fines the applied average scan rate. c = 0 for t ≤ tmax/2 and c = 1 for tmax/
2 < t < tmax. Ecentre is the average of the minimum and maximum values of
the applied potential (i.e. the mid-point potential of the applied potential
window in this context) with respect to the reference electrode and it can
be expressed as follows:
Ei þ E f
Ecentre ¼ ð4Þ
2 rent signal. For data acquisition, a USB-6003 DAQs device (National Instru-
Fig. 1a displays the linear and semi-circular potential waveforms inves-
tigated. So as to compare linear sweep voltammetry (LSV) and semi-circular
sweep voltammetry (SCV) whilst ensuring that the average scan rate over a
single semi-circular wave is the same as the constant scan rate of the linear
wave, the duration and limits of the sweep are kept the same for both
waves. The semi-circular wave shows specific features that are obviously
Fig. 1. (a) Linear and semi-circular waveforms. The semi-circular wave shown has an amplitude of 0.514 V and a scan duration of 67 s which corresponds to 15 mV s−1 in the
linear wave. (b) Recorded experimental voltammograms corresponding to the two waves shown on (a) obtained at a carbon microdisc electrode (23.5 μm diameter) in
1.0 mM [Ru(NH3)6]Cl3/0.1 M KCl solution with an average scan rate of 15 mV s−1. The arrow shows the direction of potential sweep.
2
Journal of Electroanalytical Chemistry 880 (2021) 114891
different from the conventional linear wave. As shown in Fig. 1a, the linear
potential wave exhibits a constant scan rate over the entire potential sweep,
whilst the semi-circular wave shows significant changes in the scan rate
throughout the potential sweep. At the mid-point of the wave (Ecentre), in-
stantaneously, an infinite scan rate is reached (in principle) while slower
scan rates are seen towards the limits of the potential window, see
Fig. S1. The characteristics of the semi-circular potential wave result in se-
lective amplification of the peak current if Ecentre, corresponding to the max-
imum scan rate, is set within the close vicinity of the formal potential of the
redox couple of interest, see Fig. 1b. Comparing the two voltammograms in
Fig. 1b, the LSV shows a near steady-state response whilst the SCV shows a
peak feature corresponding to the region of faster than average scan rates.
3. Experimental
3.1. Materials
Ferrocenemethanol (C11H12FeO, “FcCH2OH”, 97%, ChemCruz®, Santa
Cruz Biotechnology, Inc., USA), Hexaammineruthenium(III) chloride ([Ru
(NH3)6]Cl3, Ru 32.1% min, Alfa Aesar, UK), potassium hexacyanoferrate
(K3[Fe(CN)6], 98 + %, Lancaster Synthesis, UK) and potassium chloride
(KCl, >99%, Aldrich) were used without further purification. All solutions
were prepared using Milli-Q water with a resistivity of 18.2 MΩ cm−1 at
298 K (Millipore Water Systems, UK).
3.2. Electrochemical measurements
All electrochemical measurements were carried out with an in-house
made potentiostat. Details of the potentiostat can be found elsewhere
[22,23]. This is a low-noise potentiostat with a nominal 60 μV interval of
applied potential on the working electrode. A variable gain sub-femto Am-
pere current amplifier DDPCA-300 (FEMTO® Messtechnik GmbH, Berlin,
Germany) was used to measure the current. Two cascaded 2 kHz passive
RC-filters were used to remove high frequency components from the cur-
ments, TX, USA) with 32-bit resolution was used. The resulting analogue
signal was digitized at a sampling rate of 100 kHz. Control of the
potentiostat was run through a software written in Python. The data were
collected with Python and then were plotted using OriginPro 2017. To
record a semi-circular voltammogram, we set the following parameters
in the software: Ecentre, amplitude of 0.514 V, duration of the scan that
is equivalent to the desired average scan rate. Before recording each
H.M.A. Amin et al.
voltammogram, the potential of the working electrode was kept at the
starting potential for 3 s to attain equilibrium.
A single-compartment, three-electrode glass cell with a carbon elec-
trode as the working electrode, Pt wire (GoodFellow, Cambridge, UK) as
the counter electrode and a saturated calomel electrode (SCE, ALS Co.
Ltd., Japan) as the reference electrode was used. Two types of carbon
working electrodes from ALS Co. Ltd., Japan, were used: a glassy
carbon (GC) macrodisc electrode with 3.0 mm diameter and a carbon
fibre microdisc electrode with a nominal 33 μm diameter. An accurate
radius of the microdisc electrode was determined from the diffusion-
limited current in a steady-state voltammogram recorded in 1.0 mM
[Ru(NH 3 ) 6 ]Cl3 /0.1 M KCl solution, see Fig. S2 in the SI. The radius
was found to be 23.5 ± 0.2 μm, using the known diffusion coefficient
[23], which is larger than the nominal value given by the manufacturer.
Before running each experiment, the microelectrode was polished with
MicroPolish alumina slurries with successively smaller sizes of alumina
powder (1, 0.3 and 0.05 μm from Buehler, IL, USA) applied on three sep-
arate soft lapping pads (Buehler, USA). After each polishing step, the
electrode was rinsed with Milli-Q water and finally was dried under a
nitrogen flow.
The electrochemical cell was kept at 25 °C throughout the entire ex-
periment by using a water bath with a temperature controller (SCT1,
Stuart, UK). The whole setup was placed in a Faraday cage. All solutions
were purged with nitrogen (99.998%, BOC, UK) for at least 30 min prior
to each experiment and were surrounded by nitrogen during the
measurement.
The simulations in this work were carried out using C++ with OpenMP
by applying the Alternating Direction Implicit method as previously described
[13,24,25].
4. Results and discussion
In this section, we first determine the standard electrochemical rate con-
stant for both the [Ru(NH3)6]2+/3+ and FcCH2OH0/1+ redox couples from
cyclic voltammetry data at GC macroelectodes using the Nicholson ap-
proach. We also determine the formal potential of these systems from the
corresponding cyclic voltammograms. Next, we discuss the voltammetric
features arising from the application of the semi-circular potential wave-
form at a microelectrode and finally deduce the rate constants for both
redox systems based on these experimental data and the theoretical
model for semi-circular potential sweep voltammetry. Comparisons are
then made.
4.1. Evaluationof thestandardelectrochemical rateconstant for [Ru(NH3)6]2+/3+
at a GC electrode from macroelectrode cyclic voltammetry data
In this section, we investigate the one-electron reduction of [Ru(NH3)6]3+
to [Ru(NH3)6]2+ at a planar macrodisc GC electrode:
3þ − 2þ
RuðNH 3 Þ6 þ e ⇌ RuðNH 3 Þ6 ð5Þ
We first focus on the estimation of the rate constant using the Nich-
olson procedure which is based on the peak-to-peak potential separa-
tion in cyclic voltammograms at various scan rates as discussed in the
Introduction section [7].
Fig. 2a shows cyclic voltammograms obtained at the GC (3.0 mm)
electrode in 1.0 mM [Ru(NH3)6]Cl3/0.1 M KCl at scan rates from 25 to
500 mV s−1. Faradaic-only currents are obtained by subtraction of the
capacitive currents measured in 0.1 M KCl solution. Fig. S3 shows exam-
ples of the voltammograms obtained at 25 and 500 mV s−1 before and
after subtraction of the capacitive currents. The potential was swept
from +0.332 V to −0.696 V and reduction and oxidation peaks are ob-
served. The oxidation and reduction peak potentials slightly shift, but in
opposite directions, as the scan rate increases. Accordingly, the peak-to-
peak separation (ΔE) increases with the scan rate increase as shown in
the plot of ΔE vs. log υ in Fig. 2b. The peak separation is larger than
3
Journal of Electroanalytical Chemistry 880 (2021) 114891
the value of 59 mV expected at 25 °C for a fully reversible system. The
formal potential can be estimated from the midpoint potential between
the oxidation and reduction peak potentials assuming that the species in
the redox couple have identical diffusion coefficients. A value of Eof =
−0.182 ± 0.002 V was obtained. The error bar represents the uncer-
tainty in determining the peak potentials. This formal potential is used
below for analysing the semi-circular sweep voltammograms. The ob-
tained Eof is very close to the reported value of −0.178 V for the same
redox system [26].
The kinetic parameter Ѱ was then calculated from the peak-to-peak sep-
aration (ΔE is in mV) according to the following empirical Eq. [27]:
ð−0:6288 þ 0:0021 nðΔEÞÞ
Ѱ¼ ð6Þ
ð1−0:017 nðΔEÞÞ
In our calculations, we assumed α = 0.5 and Dox = Dred. A diffusion co-
efficient D = 8.43 × 10−10 m2 s−1 for [Ru(NH3)6]3+ was used. This is
close to but not exactly the same as that of [Ru(NH3)6]2+ (D =
11.9 × 10−10 m2 s−1) in 0.1 M KCl [23]. Fig. 2c displays the plot of Ѱ
versus ΔE for the various scan rates. It is clearly seen that Ѱ decreases as
ΔE decreases. The heterogeneous rate constant ko is calculated according
to Nicholson equation (Eq. 1) where the slope of the plot of Ѱ versus
[πDnF/(RT)]−1/2v−1/2 gives the value of ko. As shown in Fig. 2d, the
slope of the straight line for [Ru(NH3)6]2+/3+ system gives ko =
0.046 ± 0.001 cm s−1. The error bar represents the standard error in the
value of the slope.
The [Ru(NH3)6]2+/3+ system was also investigated in a higher
supporting electrolyte concentration, namely 1.0 M KCl, as shown in
Fig. S4. The potential was swept from +0.302 V to −0.726 at scan rates
from 25 to 300 mV s−1. Eof was found to be −0.212 ± 0.002 V in 1.0 M
KCl which is more negative than in 0.1 M KCl reflecting the change of for-
mal potential with the concentration. After analysis of the voltammograms
according to the Nicholson method, a value of ko = 0.099 ± 0.006 cm s−1
was obtained using a literature value of D = 5.5 × 10−10 m2 s−1 [23].
The lower D value in 1.0 M KCl than in 0.1 M KCl is probably in part due
to the increased viscosity of the solution with the higher ionic strength
[23]. The ko value in 1.0 M KCl is higher than the value obtained for the
lower supporting electrolyte concentration; The influence of the electrolyte
on the kinetics reflects the nature of the redox couple, as has previously
been reported [11,28,29].
4.2. Evaluation of the standard electrochemical rate constant at a GC electrode
for ferrocenemethanol from cyclic voltammetry data
Next, we studied the oxidation of ferrocenemethanol in aqueous solu-
tion, again at a GC (3.0 mm) macroelectrode. In this reaction, FcCH2OH
is oxidized to FcCH2OH+:
FcCH 2 OH⇌FcCH 2 OH þ þ e− ð7Þ
Fig. 3a shows the voltammetric behaviour obtained at a GC
macroelectrode in 1.04 mM FcCH2OH/ 0.10 M KCl solution over the scan
rate of 10 to 300 mV s−1. For recording these voltammograms, the poten-
tial was swept from 0.330 V to +0.698 V. The formal potential was esti-
mated from the mid-point potential of the CVs in Fig. 3a and was found
to be Eof = +0.185 V, which is close to the literature value of ~0.200 V
at GC in 0.1 M phosphate buffer solution (PBS) [1]. The voltammograms,
after correction for the capacitive background, were analysed and the
plots of ΔE vs. log υ and Ѱ vs. ΔE are depicted in Fig. 3b and c, respectively.
Again, as the scan rate increases, ΔE increases and accordingly Ѱ decreases.
The Nicholson method is then applied to estimate ko for ferrocenemethanol
redox reaction. As shown in Fig. 3d, a plot of Ѱ vs. [πDnF/(RT)]−1/2υ−1/2
gave a linear regression with r = 0.999, indicating that the response of this
redox system is governed by the Nicholson eq. A diffusion coefficient D =
7.8 × 10−10 m2 s−1 for FcCH2OH0/1+ was used [9]. The resulting slope
yields ko = 0.057 ± 0.001 cm s−1 for the FcCH2OH0/1+ redox couple.
H.M.A. Amin et al.
Fig. 2. (a) Cyclic voltammograms recorded at GC (3.0 mm) macroelectrode in 1.0 mM [Ru(NH3)6]Cl3/0.1 M KCl at scan rates from 25 to 500 mV s−1 at 298 K. The plotted
currents are corrected for capacitive current contributions by subtraction of the currents obtained in blank 0.1 M KCl solution. (b) Plot of ΔE vs. log υ for the corresponding
data. (c) Plot of Ѱ versus ΔE. (d) Plot of Ѱ versus [πDnF/(RT)] −1/2v−1/2 for the same data.
4.3. Voltammetric behaviour of linear vs. semi-circular potential waveforms
We next report the voltammetric behaviour generated from semi-
circular potential waveforms and compare it with linear sweep voltamme-
try. Fig. 4 displays the voltammetric response obtained from the application
of the linear and semi-circular waveforms in 1.0 mM [Ru(NH3)6]Cl3/ 0.1 M
KCl at carbon microdisc (23.5 μm radius) electrode.
In the linear sweep voltammogram (dark yellow line), the potential was
swept from +0.332 to 0.696 V at a constant scan rate of 15 mV s−1. To run
the equivalent experiment using the semi-circle potential wave (red line)
within the same potential window, the amplitude was set at 0.514 V and
the duration of the potential scan was set at 67 s such that the average
scan rate over the entire sweep equals 15 mV s−1. Semi-circular sweep volt-
ammetry gives the largest peak current signal when Ecentre = Eof for revers-
ible systems. Therefore, this voltammogram was recorded at Ecentre = Eof =
0.182 V (obtained from the midpoint of the CVs in Fig. 2a). The scan rate of
15 mV s−1 corresponds to the dimensionless scan rate of σ = 0.389 used to
generate theoretical simulations as described elsewhere: [13].
 2  
r F
σ¼ υ ð8Þ
D RT
The Faradaic-only currents (green line) were obtained by subtracting
the capacitive currents recorded in blank 0.1 M KCl solution (blue line)
from the measured currents in [Ru(NH3)6]Cl3/0.1 M KCl solution (red
line), as shown in Fig. 4. From Fig. 4, it is clear that the voltammetric
4
Journal of Electroanalytical Chemistry 880 (2021) 114891
response obtained using linear potential wave is different from that ob-
tained from using the semi-circular wave: The linear sweep voltammetry
shows almost no peak but a typical plateau corresponding to the near
steady-state, diffusion limited, behaviour at potentials more negative to
ca. 0.25 V, whilst the semi-circular sweep voltammogram reveals a sharp
peak. The highest currents measured are significantly larger for the semi-
circular wave than the traditional linear sweep. Near Ecentre = Eof, the cur-
rent reaches a maximum and rapidly fall off at all other potentials. This is
caused by the singularity of the scan rate at the midpoint of the semi-
circular wave as shown in Fig. 1 and Fig. S1 and as expected theoretically
[18–21]. Simulated currents using the semi-circular potential wave are
displayed in the black dashed line and are used to calculate ko value
below. Fig. 5 shows the response of [Ru(NH3)6]Cl3/1.0 M KCl containing
a higher concentration of supporting electrolyte; a similar response as
seen in Fig. 4 is observed.
4.4. Determination of the standard rate constants for the [Ru(NH3)6]Cl2+/3+
3
and ferrocenemethanol0/1+ redox couples using semi-circular sweep
voltammetry
The data of the semi-circular potential sweep voltammetry was
analysed using our previously reported theoretical model [21]. Provided
that the parameters D, C, r, Eof are known for the redox system, only a single
voltammogram recorded using SCV (red line shown in Fig. 4) with Ecentre =
Eof is needed to determine the ko value if a value of the transfer coefficient is
assumed. Herein we take for the transfer coefficients α = β = 0.5. The
H.M.A. Amin et al.
Fig. 3. (a) Cyclic voltammograms recorded at GC (3.0 mm) macroelectrode in 1.04 mM FcCH2OH/0.1 M KCl at scan rates from 10 to 300 mV s−1 at 298 K. The Faradaic
currents are corrected for capacitive current contribution by subtraction of the currents obtained in blank 0.1 M KCl solution. (b) plot of ΔE vs. log υ for the
corresponding data. (c) plot of Ѱ vs. ΔE. (d) plot of Ѱ vs. [πDnF/(RT)]−1/2v−1/2 for the same data.
semi-circular potential sweep voltammograms were analysed to obtain ko.
Simulations using the semi-circular potential wave were carried out to
find the ko value that generates the best fit of theory to the part of the volt-
ammogram where electrode kinetics dominate (i.e. at potentials more pos-
itive to 0.18 V for the 1.0 mM [Ru(NH3)6]Cl3/0.1 M KCl). All simulated
data were obtained using σ = 0.389, α = 0.5 and Ecentre = Eof. The simu-
lated currents (dashed black line in Fig. 4) for 1.0 mM [Ru(NH3)6]Cl3/
0.1 M KCl solution best fit the experimental results (green line) in the
kinetic-dominated range of +0.22 to 0.18 V when ko = 0.037 ± 0.01 V.
The error bar reflects the range of ko values that still give a degree of fit
to the experimental curve. Fig. S5 shows the simulated voltammograms ob-
tained when a ko = 0.02 cm s−1 was used in the simulation. This
0.02 cm s−1 value very clearly does not show a high quality of fitting con-
sistent with the estimated error. At potentials beyond the maximum of the
semi-circular voltammograms an incomplete match between experimental
and simulated data is observed. The discrepancy between theory and exper-
iment necessarily increases as the potential is swept as the modelling is pro-
gressive, moving step by step through the voltammogram. Thus, tiny
differences between theory and experiment progressively accumulate. Nev-
ertheless, fitting of theory to the experimental data in the electrode kinetics
dominated part of the voltammograms provides an effective alternative
method to determine ko values for redox systems.
For the solution 1.01 mM [Ru(NH3)6]Cl3/1.0 M KCl, the simulated cur-
rents (dashed black line in Fig. 5) fit very well with the experimental data
(green line) in the range of +0.2 to 0.2 V, when ko = 0.11 ±
0.01 cm s−1. The ko values obtained for the [Ru(NH3)6]2+/3+ redox system
5
Journal of Electroanalytical Chemistry 880 (2021) 114891
using the semi-circular potential sweep voltammetry and the Nicholson
method are summarized and compared to the literature values as shown
in Table 1. As can be seen in Table 1, the rate constant obtained for [Ru
(NH3)6]2+/3+/ 0.1 M KCl is smaller (23 times) than the value obtained
for [Ru(NH3)6]2+/3+/ 1.0 M KCl solution where the effect of the
supporting electrolyte has been previously noted [11,28].
The ko values obtained using semi-circular sweep voltammetry are in
satisfactory agreement with the values obtained independently from the cy-
clic voltammetric data using the Nicholson method under the same experi-
mental conditions, see Table 1. As the semi-circular potential sweep
voltammetry method needs (in principle) the recording of only one voltam-
mogram (as well as knowing the formal potential of the redox system), it of-
fers speed and simplicity over the traditional Nicholson method and can
usefully complement the latter measurement.
The second studied redox system is the oxidation of FcCH2OH to
FcCH2OH+. Fig. 6 shows the voltammograms obtained using both linear
and semi-circular waves at a microdisc electrode in 1.04 mM FcCH2OH/
0.10 M KCl solution. In this case the potential was swept from 0.330 to
+0.698 V at an average scan rate of 14 mV s−1 (i.e. sweep duration =
73 s). This average scan rate was selected in order to have the same dimen-
sionless scan rate of σ = 0.389 as in the case of the [Ru(NH3)6]2+/3+ sys-
tem. The general voltammetric features arising from the semi-circular
sweep voltammetry in FcCH2OH0/1+ redox couple are similar to that ob-
served in the [Ru(NH3)6]2+/3+ system. Again, a significant amplification
of the current is observed at the close vicinity of Ecentre which is set at
Eof = +0.185 V. In the linear sweep voltammogram, a near steady-state
H.M.A. Amin et al.
Fig. 4. Voltammograms obtained using a semi-circular potential waveform at a
carbon microdisc electrode in 0.1 M KCl (blue line) and in 1.0 mM [Ru(NH3)6]
Cl3/0.1 M KCl solution (red line, Faradaic+ capacitive currents) at Ecentre =
0.182 V, amplitude = 0.514 V, duration of scan 67 s and an average scan rate of
15 mV s−1. The capacitive current corrected voltammogram for [Ru(NH3)6]Cl3/
KCl is shown in the green line. The linear sweep voltammogram in the same
solution at 15 mV s−1 is displayed as a dark yellow line. The simulated Faradaic
currents obtained using a dimensionless scan rate σ = 0.389 are shown in the
dashed black line. The definition of the dimensionless parameters can be found in
our previous paper [21]. The arrow shows the direction of potential sweep.
Fig. 5. Voltammograms obtained using a semi-circular potential waveform at a
carbon microdisc electrode in 1.0 M KCl (blue line) and in 1.01 mM [Ru(NH3)6]
Cl3/1.0 M KCl solution (red line, Faradaic+ capacitive currents) at Ecentre =
0.212 V, amplitude = 0.514 V, duration of scan 103 s and an average scan rate of
10 mV s−1. The capacitive current corrected voltammogram for [Ru(NH3)6]Cl3/
KCl is shown in the green line. The linear sweep voltammogram in the same
solution at 15 mV s−1 is displayed as a dark yellow line. The simulated Faradaic
currents obtained using a dimensionless scan rate σ = 0.389 are shown in the
dashed black line. The definition of the dimensionless parameters can be found in
our previous paper [21]. The arrow shows the direction of potential sweep.
Table 1
Summary of the standard heterogeneous rate constants for [Ru(NH3)6]2+/3+ and FcCH2OH0/+1 redox systems obtained at carbon electrode and compared to literature
values. The experiments were done such that σ = 0.389 for both systems.
Redox system Avg. scan rate (mV s−1) ko (cm s−1)
From semi-circular voltammetry
1.00 mM Ru(NH3)6]Cl3/0.1 M KCl 15 0.037 ± 0.01
1.01 mM Ru(NH3)6]Cl3/1.0 M KCl 10 0.11 ± 0.01
1.04 mM FcCH2OH/0.1MKCl 14 0.055 ± 0.01
6
Journal of Electroanalytical Chemistry 880 (2021) 114891
Fig. 6. Voltammograms obtained using a semi-circular potential waveform at a
carbon microdisc electrode in 0.10 M KCl (blue line) and in 1.04 mM FcCH2OH/
0.10 M KCl solution (red line, Faradaic+ capacitive currents) at Ecentre =
+0.185 V, amplitude = 0.514 V, duration of scan 73 s and an average scan rate
of 14 mV s−1. The capacitive current corrected voltammogram for FcCH2OH/KCl
is shown in the green line. The linear sweep voltammogram in the same solution
at 14 mV s−1 is displayed as a dark yellow line. The simulated Faradaic currents
which are obtained using a dimensionless scan rate σ = 0.389 are shown in the
dashed black line. The definition of the dimensionless parameters can be found in
our previous paper [21]. The arrow shows the direction of potential sweep.
behaviour with no peaks is observed. For the FcCH2OH0/1+ redox system,
in the potential range of 0.22 to +0.18 V, the simulated currents for the
semi-circular sweep voltammetry (dashed black line) are in good agree-
ment with the measured Faradaic-only currents (green line) when ko =
0.055 ± 0.01 cm s−1 is used, see Fig. 6. Table 1 summarises the ko values
for both studied systems, [Ru(NH3)6]2+/3+ and FcCH2OH0/1+, determined
using both the Nicholson method and the semi-circular sweep voltammetry
as well as Ko values reported in literature.
Overall Table 1, for all the studied redox systems, the rate constants ob-
tained using the semi-circular sweep voltammetry agree with that obtained
using the Nicholson method and with literature where literature data exist
for the same electrolyte.
5. Conclusions
In this work we experimentally investigated the voltammetric behaviour
of redox systems at microelectrodes while applying the semi-circular poten-
tial wave and compared this response with the response from linear sweep
voltammetry. The peak current obtained using semi-circular sweep wave
is much larger than that obtained from linear sweep wave when the poten-
tial window is centred within the close vicinity of the formal potential of the
redox system. Semi-circular potential voltammetry was exploited to quanti-
tatively study the kinetics of electron transfer. The [Ru(NH3)6]2+/3+ and
FcCH2OH0/1+ redox couples were selected as examples and the electro-
chemical rate constants were determined via SCV and independently from
cyclic voltammetry data using Nicholson method. The results showed satis-
factory agreement between the two methods. A practical advantage of the
new method is the need (in principle) of the recording of only a single
Ref.
From Nicholson equation From literature @GC
0.046 ± 0.001 – –
0.099 ± 0.006 0.13 ± 0.15 (in 1 M KCl) [28]
0.057 ± 0.011 0.19 ± 0.05 (in 0.1 M PBS) [1]
H.M.A. Amin et al.
voltammogram to determine the rate constant. This renders the method a
fast and complementary route to the classical procedures.
Declaration of Competing Interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
H. M. Amin gratefully acknowledges DFG for funding (No. AB 702/1-1).
The authors thank Dr. Christopher Batchelor-McAuley for writing the soft-
ware to run the semi-circular potential wave.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jelechem.2020.114891.
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