Journal of Electroanalytical Chemistry 895 (2021) 115449

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Journal of Electroanalytical Chemistry

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

Determination of cyanide concentration by chronoamperometry, cyclic

voltammetry and fast Fourier transform electrochemical impedance
spectroscopy
Povilas Virbickas a, Aušra Valiūnienė a,⇑, Diana Baryševa a, Georgi Popkirov c, Arūnas Ramanavičius a,b,⇑
a
Faculty of Chemistry and Geosciences, Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania
b
Laboratory of Nanotechnology, State Research Institute Center for Physical Sciences and Technology, Sauletekio Ave. 3, LT-10257 Vilnius, Lithuania
c
Central Laboratory of Solar Energy and New Energy Sources, Bulgarian Academy of Sciences, Sofia, Bulgaria

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

Keywords: In this research electroanalytical methods based on chronoamperometry, cyclic voltammetry and fast Fourier
Cyanide detection transform electrochemical impedance spectroscopy (FFT-EIS) were adapted for the determination of cyanide
Cyanide electrochemical oxidation ion concentration in the range between 2 mmol l−1 and 1 mol l−1. The widest range of linearly detectable con-
Fast Fourier transform electrochemical centration of cyanide ions was obtained by cyclic voltammetry-based method that allowed to quantify concen-
impedance spectroscopy (FFT-EIS)
tration of cyanide ions in the range from 10 mmol l−1 to 1 mol l−1 (R2 = 0.993). Chronoamperometry-based
Cyclic voltammetry
Chronoamperometry
method showed the highest sensitivity to the low concentrations of cyanide enabling to detect cyanide ion in
Platinum electrode the linear range from 2 mmol l−1 to 50 mmol l−1 (R2 = 0.995). The FFT-EIS-based method exhibited linear
range from 100 mmol l−1 to 700 mmol l−1 (R2 = 0.975) showing suitability of this method for the quantifi-
cation of cyanide ion concentration in highly concentrated cyanide solutions. Moreover, the FFT-EIS-based
method allows to carry out quantification of cyanide very fast, by registering the impedance spectrum within
0.5 s. Therefore, all three cyanide quantification methods presented in this research are convenient for the esti-
mation of cyanide concentration in the relevant concentration ranges.

1. Introduction few of these techniques are suitable for the determination of high cya-
nide concentration, e.g.: a potentiometric biosensor capable to detect
Cyanide ion is a highly toxic material, especially when it forms cyanide ion concentration in the range up to 100 mmol l−1 was con-
hydrogen containing HCN form [1–3]. The main sources of environ- structed by combining a whole cell cyanide dihydratase (from
mental contamination with cyanides are related to human industrial Flavobacterium indicum) with an ammonium ion selective electrode
activities, mostly to metal finishing and mining industries [1]. In the [15] and the sensor constructed by immobilizing cyanide ion-selective
case of these activities cyanides concentration in wastewaters can ionophores on the screen-printed electrode was able to detect cyanide
reach over 3 mol l−1 [4,5], while predicted no effect concentration ion concentrations up to 10 mmol l−1 [18]. Other techniques
of cyanide for freshwater organisms under European chemicals man- [7,10–14,17] are dedicated for the determination of very low cyanide
agement directive “Registration, Evaluation, Authorisation and concentrations – their linear range of detectable cyanide concentration
Restriction of Chemicals” (REACh) is lower than 1 μmol l−1 [6]. In do not exceed 1 mmol l−1 [7,10–14,17]. Therefore, taking into
order to control the concentration of cyanide in effluence and to main- account that cyanide concentration in wastewater can be significantly
tain appropriate conditions of surface water, different analytical meth- greater than 1 mmol l−1 [4,5], the development of methods for direct
ods allowing to detect a wide range of cyanides concentration should determination of high cyanide concentration still remains important.
be evaluated. Electrochemical determination of various analytes is one of the
Recently various optical [3,7–9], electrochemical [10–12], bio- most convenient analytical techniques [14,19]. In addition, electro-
electrochemical [13–15] and other [1,2,16–18] techniques have been chemical methods (e.g. potentiometry and cyclic voltammetry) can
developed in order to decrease the detection limit of cyanide concen- be used to quantify concentration of cyanide ions by monitoring cya-
tration and to make its determination more accurate. However, only nide ion complexation reaction [10–12,16,18,20], oxygen consump-

⇑ Corresponding authors at: Faculty of Chemistry and Geosciences, Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania.
E-mail addresses: [email protected] (A. Valiūnienė), [email protected] (A. Ramanavičius).

https://doi.org/10.1016/j.jelechem.2021.115449
Received 9 April 2021; Received in revised form 3 June 2021; Accepted 4 June 2021
Available online 7 June 2021
1572-6657/© 2021 Elsevier B.V. All rights reserved.
P. Virbickas et al. Journal of Electroanalytical Chemistry 895 (2021) 115449

tion [13,14] and cyanide-caused changes in ammonium ion concentra- 2.2. Experimental design and equipment used for electrochemical
tion [15]. Among many electrochemical methods used for cyanide measurements
determination [10–18,20] the monitoring of electrochemical cyanide
oxidation may turn out to be easy-to-perform and inexpensive way All electrochemical measurements were performed at room tem-
of cyanide sensing. Lately electrochemical oxidation of cyanide ions perature (25 ± 1 °C) and standard pressure (760 ± 25 mmHg). All
on a platinum surface has been investigated as an ecologically friendly experiments were conducted in a three-electrode system, consisting
way to remove cyanide from contaminated waters [21,22]. During of platinum working electrode (geometric surface area 0.0437 cm2),
these investigations the rate of cyanide’s oxidation on platinum surface Ag/AgCl/KClsat electrode as reference electrode, placed as close as pos-
at galvanostatic conditions proved to be linearly proportional to the sible to the working electrode by using a ‘Luggin capillary’ based con-
concentration of cyanide ions (CN−) in the range from 10 mmol l−1 nector and platinum wire as an auxiliary electrode. Before performing
to 80 mmol l−1 [22]. Therefore, electrochemical cyanide oxidation each experiment, working electrode was degreased and gently pol-
on platinum surface may be suitable for the quantification of cyanide ished to a clean surface.
concentration in water samples. Cyclic voltammetry and chronoamperometry-based measurements
Even though the detailed mechanism of electrochemical cyanide were performed by using μAUTOLAB potentiostat/galvanostat from
oxidation is still under discuss [21,22], it is claimed that during the ECO-Chemie (Utrecht, The Netherlands). The potential of the working
first stage of reaction (Eq. (1)) cyanide ion (CN−) is oxidized into cya- electrode was scanned from 0.1 V to 0.9 V vs Ag/AgCl/KClsat at a scan
nate ion (CNO−), which is further decomposed into N2 and CO2 (Eq. rate of 50 mVs−1 during cyclic voltammetry measurements. Mean-
(2)) [23,24,25,26,27]. while, during chronoamperometry-based measurements the potential
of the working electrode was set to 0.7 V vs Ag/AgCl/KClsat.
CN
þ 2OH
! CNO
þ H 2 O þ 2e
ð1Þ FFT-EIS measurements were performed with FFT impedance spec-
trometer EIS-128/16 constructed by prof. G. Popkirov (University of
Kiel, Germany) [31]. In FFT impedance spectrometry a frequency rich
2CNO
þ 4OH
! 2CO2 þ N 2 þ 2H 2 O þ 6e
ð2Þ perturbation signal composed as sum of up to 80 pre-selected frequen-
In addition to the reaction (2), decomposition of cyanate ion pro- cies is applied to the sample under test using a 16-bit digital-to-analog
ducing ammonium may occur as well (Eq. (3)) [28,29]: converter. Both, the perturbation voltage and sample response current
are measured in the time domain by means of respective amplifiers
CNO
þ 2H 2 O ! CO2
þ and two simultaneous 16-bit analog-to-digital converters. The
3 þ NH 4 ð3Þ
obtained time-domain data are transferred to the frequency domain
The way at which cyanate ion is decomposed depends on pH: at by means of FFT and the impedance is calculated as a complex value
strongly alkaline conditions (pH 13) cyanate ion predominantly for every single frequency of the perturbation. The impedance spectra
decomposes into N2 and CO2 (Eq. (2)), and in less alkaline conditions measurement time is equal to 2/fmin seconds, where fmin is the lowest
(pH 10) – into CO2−
3 and NH+ 4 (Eq. (3)). Moreover, decomposition of frequency harmonic of the perturbation signal. As an example, a full
cyanate ion into N2 and CO2 (Eq. (2)) causes decrease in pH of solu- impedance spectrum from 10 Hz to 50 kHz can be obtained in 0.2 s.
tion, while decomposition into CO2− +
3 and NH4 (Eq. (3)) does not cause In this research FFT- electrochemical impedance spectra were
any significant change in pH. recorded in potentiostatic mode (0.7 V vs Ag/AgCl/KClsat) and the
In this work chronoamperometry, cyclic voltammetry and fast range of alternating current frequencies varied from 5 Hz to 43 kHz.
Fourier transform electrochemical impedance spectroscopy (FFT- Data analysis software “Zview” was used to create the model repre-
EIS)-based methods were used for direct determination of concentra- senting the elements of selected equivalent circuit.
tion of cyanide ions in ammonium buffer solution (ABS). All three During the all electrochemical investigations, after the addition of
methods appeared to be suitable for the quantification of cyanide KCN stock solution (5 mol l−1) into ABS, cyanide-containing ABS
ion concentration in ABS in the concentration ranges varying from was further stirred for 2 min and then left to settle down for 1 min,
2 mmol l−1 to 1 mmol l−1. to eliminate any unwanted underwater stream that may interfere with
measurement performance.

2. Experimental
3. Results and discussion
2.1. Materials
3.1. Cyclic voltammetry and chronoamperometry-based investigations of Pt
NH4Cl (purity ≥ 99.7%, CAS No. 12125–02-9) and KOH (pu- electrode in cyanide ion-containing ABS
rity ≥ 85%, CAS No. 1310–58-3) were acquired from ROTH (Karl-
sruhe, Germany). KCN (purity ≥ 98%, CAS No. 151–50-8) was Cyclic voltammetry-based investigation of Pt electrode in cyanide
purchased from SIGMA-ALDRICH (Munich, Germany). All salts were ion-containing ABS indicated that oxidation current increases with
stored at room temperature (25 ± 1 °C). Ultrapure deionized water an increase in CN− concentration (Fig. 1A). From the data of cyclic
(R ≥ 18 MΩ cm) provided by a Milli Q-plius-Millipore system (USA) voltammograms the linear dependencies between cyanide electrooxi-
was used to prepare all solutions. Potassium cyanide stock solution dation current and concentration of cyanide ions in ABS were observed
(5 mol l−1) was used performing all electrochemical investigations (Fig. 1B) at the potentials of 0.7 V, 0.8 V and 0.9 V (Fig. 1B), and the
in KCN-containing buffer solutions. Ammonium buffer solution linearly detectable range of cyanide concentration appears to be in the
(1 mol l−1 NH4Cl; pH 10) was used for cyclic voltammetry, chronoam- range from 10 mmol l−1 to 1 mol l−1. Moreover, the relation between
perometry and FFT-EIS based measurements. Considering that cya- cyanide electrooxidation current and concentration of cyanide ions
nide-containing solution generates poisonous hydrogen cyanide gas was found to be well linear (R2 = 0.993) at the potential of 0.7 V vs
at neutral or acidic pH, in this work buffer solution was adjusted to Ag/AgCl/KClsat (Fig. 1B, curve 1). At higher potentials (0.8 V and
pH 10 with potassium hydroxide (1 mol l−1 KOH). Moreover, at pH 0.9 V) of the working electrode, a lower correlation between CN− con-
10 electrochemical oxidation of cyanide is followed by only trace con- centration and oxidation current density was observed (Fig. 1B, curves
sumption of OH− ions [24] and it helps to maintain a stable value of 2 and 3). Particularly, the coefficient of determination (R2) decreases
pH. In addition, stable value of pH is necessary to maintain the con- to 0.977 and 0.970 at 0.8 V and 0.9 V, respectively. This effect may
stant rate of electrochemical oxidation of cyanide [30]. be related to potential-dependent changes in kinetics of cyanide elec-

2
P. Virbickas et al. Journal of Electroanalytical Chemistry 895 (2021) 115449

A 6
1.00
5
4
0.75 3 An Increase in
-
2 CN concentration
-2
j, mA cm

0.50 1

0.25

0.00

0.2 0.4 0.6 0.8

E, V
3
y = 0.395x + 0.7190
B 0.9 V
2
R = 0.970
1.0

0.8 2
-2

y = 0.2483x + 0.4633
j, mA cm

2
0.8 V R = 0.977
0.6
1
y = 0.1438x + 0.3090
2
0.4 0.7 V R = 0.993

0.00 0.25 0.50 0.75 1.00

- -1
[ CN ] , mol l
Fig. 1. A – cyclic voltammograms registered: (1) – in ABS pH 10 and in ABS pH 10 containing (2) – 0.01 mol l−1 [CN−]; (3) – 0.05 mol l−1 [CN−]; (4) –
0.1 mol l−1 [CN−]; (5) – 0.5 mol l−1 [CN−] and (6) – 1 mol l−1 [CN−]. B – linear relation between oxidation current and concentration of cyanide ions in ABS pH
10 at various values of the electrode potential vs Ag/AgCl/KClsat: (1) – 0.7 V; (2) – 0.8 V and (3) – 0.9 V.

trooxidation caused by higher overpotentials of the working Pt elec- 1 mol l−1, chronoamperometry-based detection of cyanide ion
trode because the impact of water electrolysis on net current density appeared to be more suitable for the determination of low (lower than
increases as higher potentials are applied to the Pt electrode during 50 mmol l−1) concentrations of cyanide ions.
the oxidation of cyanide [22]. Therefore, we conclude that potential
of 0.7 V vs Ag/AgCl/KClsat is suitable for further investigations devel- 3.2. FFT-EIS-based investigation of Pt electrode in cyanide ion-containing
oping methods for quantification of cyanide ion concentration using ABS
chronoamperometry- and FFT-EIS-based methods.
During the chronoamperometry-based investigation of Pt electrode In this research we applied the FFT-EIS technique that enables reg-
in cyanide ion-containing ABS (Fig. 2A) an increment of anodic cur- istering EIS spectra much faster than conventional EIS equipment [32].
rent was observed after each addition of cyanide stock solution The possibility to reduce the time needed for determination of electro-
(5 mol l−1 KCN) into ABS (Fig. 2A). It was observed that anodic cur- chemical impedance spectrum is very important for investigating elec-
rent of cyanide oxidation linearly depends on the concentration of cya- trochemical oxidation of cyanide ions because together with direct
nide ions in the range from 2 mmol l−1 to 50 mmol l−1 (Fig. 2B). In cyanide oxidation reaction (Eq.1), the competing anodic reaction of
comparison to cyclic volammetry-based method, which enables linear water electrolysis occurs on the Pt electrode [21] (Eq. (4)):
detection of cyanide ion in concentration range from 10 mmol l−1 to
4OH
! O2 þ H 2 O þ 4e
ð4Þ

3
P. Virbickas et al. Journal of Electroanalytical Chemistry 895 (2021) 115449

Fig. 2. A – chronoamperometric investigation of the Pt electrode in cyanide-ion containing ABS at the potential of 0.7 V vs Ag/AgCl/KClsat. B – linear relation
between oxidation current and concentration of cyanide ions in ABS.

Reaction of water electrolysis may influence the quality of EIS mea- Accuracy of values of the equivalent circuit elements was verified
surements due to possible formation of oxygen bubbles as a blocking by using Chi Square Goodness of Fit Test (Eq. (7)), which is used to
layer on the electrode. In order to avoid this undesirable effect, the evaluate the closeness of the observed values (Eq. (7), symbol “Oi ”)
EIS measurement should be carried out under appropriate conditions: to those obtained by the fitted model (Eq. (7), symbol “E i ”) [35]:
(i) bias potential of the electrode should be selected very carefully con-
sidering that the rate of water electrolysis should be minimal while the ðOi
E i Þ2
χ2 ¼ ∑ ð7Þ
rate of cyanide electrooxidation should be detectable; (ii) registration Ei
of EIS spectrum should be fast as much as possible. Both (i) and (ii) The subscript “i” in Eq. (7) represents each element of the equiva-
were taken into account when the FFT-EIS equipment was applied lent circuit; the function “χ 2 ” is known as “Chi Square Goodness of Fit
for the measurements: (i) bias potential of 0.7 V vs Ag/AgCl/KClsat Coefficient”. When the value of χ2 approaches zero, the best fit is
was selected after evaluating cyclic voltammetry-based investigations observed (Eq. (7)).
(Fig. 1); (ii) the influence of possible formation of oxygen bubbles After processing the data of the FFT-EIS investigation of Pt elec-
on the Pt electrode was avoided registering all FFT-EIS spectra very trode in cyanide-containing ABS it was found that values of the equiv-
quickly, within 0.5 s, i.e. before the formation of any bubbles on the alent circuit elements (Table 1) fitted appropriately to the
electrode surface. experimental data (χ 2 = 6 × 10−5 ± 3 × 10−5). The addition of
In order to determine the cause of the cyanide-related decrease in CN− ions into ABS changed the electrochemical parameters of the
electrochemical impedance, the FFT-EIS data (Fig. 3 A) were analyzed investigated system (Table 1), and by increasing CN− concentration
by applying electrochemical equivalent circuit (Fig. 3 C) consisting of from 0.1 mol l−1 to 0.7 mol l−1, these changes became tendentious,
uncompensated solution resistance RO; capacitor CD representing the indicating that kinetics of electrochemical reaction on the Pt electrode
capacitance of the electric double layer (EDL); adsorption resistance strongly depends on the concentration of CN− ions in ABS. It is seen
RA; constant phase element CPE, which represents capacitance of from the data in Table 1 that the values of CD and CPE increase with
adsorption; and parallel resistance Rct, which represents the charge increasing CN− concentration, whereas the values of RA and Rct
transfer at the interface Pt electrode – ABS. The component of the decrease. The increase in CD and CPE can be related to increasing
EDL capacitance, CD, may be used only for systems that represent heterogeneity of Pt electrode due to simultaneous adsorption of vari-
homogeneous electrode surface. If the surface of solid electrode is
ous byproducts that are produced during CN− electrooxidation reac-
not equipotential enough, CPE should be introduced into the equiva- tion [21,36]. Adsorption resistance RA with increasing CN−
lent circuit instead of the component of electrical double layer capac-
concentration just slightly decreases from 2.88 to 1.71, showing only
itance CD. The impedance of CPE can be defined according equation: marginal influence of RA on cyanide electrooxidation reaction. How-
Z CPE ¼ C
1
n ever, the values of Rct decreased significantly from 3527 Ω cm2 to
D ðjwÞ ð5Þ
789.1 Ω cm2, suggesting that Rct dependence on CN− concentration
where j is an imaginary unit; w is the frequency; n is the exponen- can be represented as a calibration curve for cyanide ion quantification
tial number which shows the impedance phase shift describing the in ABS. Fig. 3B shows that charge transfer resistance depends linearly
non-ideality of the EDL [33]. When the electrode surface is homoge- (R2 = 0.937) on the concentration of cyanide ion in ABS in range from
nous, i.e. n = 1, Eq. (5) transforms into the simple double layer capac- 0.1 mol l−1 to 0.7 mol l−1. We suggest that complex data analysis for
itor impedance equation: quantification of electrochemical parameters can be easily avoided by
plotting the obtained values of imaginary part of the FFT-EIS against
Z CPE ¼ ðCD jwÞ
1 ð6Þ
concentration of CN− at fixed value of frequency. For example, at
While analyzing the impedance spectra of Pt electrode that were the frequency of 5 Hz, the calibration curve exhibits good linearity
determined in ABS with various CN− concentrations, it was found that (R2 = 0.975) (Fig. 3D), thus, it is suitable for quantification of cyanide
the exponential number n is very close to 1 (0.998 ≤ n ≤ 1.00) [34]. concentration. Therefore, this finding suggests that the FFT-EIS tech-
Thus, according to Eqs. (5) and (6), CPE in the equivalent circuit rep- nique can be used for the construction of impedimetric sensor for
resenting capacitance of the EDL at the Pt electrode - electrolyte inter- quantification of cyanide ion concentration.
face turns into conventional component of double layer capacitance CD All in all, detection of high (⩾ 2 mmol l−1) concentrations of cya-
(Fig. 3C). nide ions in ammonium ion containing buffer solution can be achieved

4
P. Virbickas et al. Journal of Electroanalytical Chemistry 895 (2021) 115449

-600
A 0.1 M
2500 B
-500 y = -2711.0 x + 2715.4
2
2000 R = 0.937

2
0M

Rct, : cm
0.3 M
-400
1500
2

0.5 M
Z'', : cm

-300
1000

-200 0.7 M
0.1 0.2 0.3 0.4 0.5 0.6 0.7
- -1
[CN ], mol l
-100 -600
y = 496.9 x -642.6
2
0 R = 0.975
0 100 200 2 -500
2
Z'', : cm
Z', : cm
-400

C -300
D
0.1 0.2 0.3 0.4 0.5 0.6 0.7
- -1
[CN ], mol l
Fig. 3. A – the FFT-EIS investigation of Pt electrode in ABS before the addition of CN− (curve 0 M) and after the addition of each concentration of CN−, which
varied from 0.1 mol l−1 to 0.7 mol l−1. Bias potential 0.7 V vs Ag/AgCl/KClsat electrode. B – linear relation between concentration of CN− and the charge transfer
resistance (Rct). C – the equivalent circuit and suggested model of fitting the FFT-EIS data, representing adsorption and charge transfer on the surface of Pt
electrode. RO is uncompensated solution resistance; Rct is charge transfer resistance; RA is the resistance of adsorption; CD is the capacitance of EDL and CPE is the
capacitance of adsorption. D – linear relation between the concentration of CN− and the imaginary part of FFT-EIS (Z’’) at 5 Hz.

Table 1
Values of the elements of the equivalent circuit presented in Fig. 3C.

[CN−], mol l−1 RO, Ω cm2 CD, μF cm−2 RA, Ω cm2 CPE, μF cm−2 n Rct, Ω cm2

0 0.71 23.87 2.43 51.74 0.87 3527

0.1 0.62 22.1 2.88 42.73 0.86 2648
0.2 0.5 26.12 2.72 45.61 0.85 1993
0.3 0.44 28.75 2.54 47.19 0.85 1866
0.4 0.44 28.21 2.31 50.04 0.85 1531
0.5 0.33 34.36 2.07 55.53 0.84 1337
0.6 0.26 42.47 1.93 66.84 0.84 1252
0.7 0.25 43.98 1.71 65.68 0.84 789.1

by using electrochemical methods described in this research. However, chemical oxidation of ammonium ion is negligible or did not occur
it should be considered whether there may be some organic or inor- at the applied potential value of 0.7 V. Moreover, cyclic voltammetry
ganic substances in real samples that could eventually be co-oxidized curves (Fig. 1A) showed that addition of millimolar concentration of
together with cyanide anions. For example, ammonia, ionized ammo- cyanide ions into buffer solution significantly increases current density
nia [37] and sulfide ions [38] can potentially be present in water. It is in the potential range from 0.7 V to 0.9 V vs Ag/AgCl/KClsat, indicating
known that ammonium ion can be electrochemically oxidized at gal- that oxidation of cyanide ions occurs on the Pt electrode rather than
vanostatic conditions when high current density (>10 mA cm−2) is oxidation of ammonium ions. If sulfide ions are present in the sample,
applied to the anode [37], however, in this research only small anodic the process of water electrolysis should be avoided, because oxygen
current (ca. 20 μA cm−2) has been observed when 0.7 V vs Ag/AgCl/ released during water electrolysis is involved in sulfide oxidation
KClsat potential was applied to the Pt electrode in buffer solution con- [38]. In our research electrolysis of water was minimized by choosing
taining 1 M of NH+ 4 (Fig. 2A). Therefore, we consider that electro- relatively low potential (0.7 V vs Ag/AgCl/KClsat) of the Pt electrode,

5
P. Virbickas et al. Journal of Electroanalytical Chemistry 895 (2021) 115449

thus, the presence of sulfide ions in the sample would not have a sig- Acknowledgements
nificant impact on the accuracy of cyanide determination. Moreover,
FFT-EIS electrochemical technique is very suitable for such measure- This project has received funding from European Regional Devel-
ments because it enables us to significantly reduce the duration of opment Fund (project No 01.2.2-LMT-K-718-01-0063) under grant
EIS spectra registration and to avoid electrolysis of water and possible agreement with the Research Council of Lithuania (LMTLT).
formation of oxygen bubbles on the anode.

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