A comprehensive heterogeneous electron transfer rate constant evaluation of

dissolved oxygen in DMSO at glassy carbon electrode measured by different
electrochemical methods

Haji Muhammad, Iftikhar Ahmad Tahiri, Mehboob Muhammad, Zaheer

Masood, Muhammad Ali Versiani, Obaid Khaliq, Muhammad Latif, Muddasir
Hanif

PII: S1572-6657(16)30280-6
DOI: doi: 10.1016/j.jelechem.2016.05.049
Reference: JEAC 2681

To appear in: Journal of Electroanalytical Chemistry

Received date: 9 March 2016

Revised date: 27 May 2016
Accepted date: 31 May 2016

Please cite this article as: Haji Muhammad, Iftikhar Ahmad Tahiri, Mehboob Muham-
mad, Zaheer Masood, Muhammad Ali Versiani, Obaid Khaliq, Muhammad Latif,
Muddasir Hanif, A comprehensive heterogeneous electron transfer rate constant eval-
uation of dissolved oxygen in DMSO at glassy carbon electrode measured by dif-
ferent electrochemical methods, Journal of Electroanalytical Chemistry (2016), doi:
10.1016/j.jelechem.2016.05.049

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 ACCEPTED MANUSCRIPT

A comprehensive heterogeneous electron transfer rate constant evaluation of

dissolved oxygen in DMSO at glassy carbon electrode measured by different

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electrochemical methods

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Haji Muhammada, Iftikhar Ahmad Tahiria*, Mehboob Muhammadb, Zaheer Masooda, Muhammad
Ali Versiania*, Obaid Khaliqa, Muhammad Latifa, Muddasir Hanifc*

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a
Department of Chemistry, Federal Urdu University of Arts, Sciences and Technology, Gulshan-e-Iqbal, Science

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Campus, Karachi-75300, Pakistan
b
HEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of
Karachi, Karachi-75270, Pakistan
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c
Department of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022,
People’s Republic of China
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Correspondence: E-mail: [email protected] (I.A. Tahiri), [email protected] (M.A. Versiani) & [email protected] (M. Hanif)
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Abstract

Molecular oxygen radicals are responsible for many problems like aging, cancer, lipid
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peroxidation, protein denaturation, oxidative stress etc., We present a comprehensive

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electrochemical investigation of the dissolved oxygen in DMSO containing 0.1 M TBAP as the
supporting electrolyte. Different electrochemical techniques such as cyclic voltammetry,
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chronoamperometry and chronopotentiometry were used to extract heterogeneous kinetics and

chemically coupled reaction kinetics related to the O2 radicals. The experimentally determined
parameters obtained through different methods were further confirmed through digital simulation
(DIGISIM). Heterogeneous electron transfer rate constant (k⁰) was determined by three different
methods, Nicholson & Shain, Gileadi, and the Kochi methods. The calculated k⁰ values are
different from the previously cited values.

Keywords: Heterogeneous electron transfer rate constant (k⁰), transfer coefficient, diffusion

coefficient, Tafel Plot.

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Introduction
.-
Superoxide (O2 ) is one of the important free radicals responsible for many diseases like aging,

cancer, lipid peroxidation and protein denaturation [1]. This radical is a product of single electron

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reduction of molecular oxygen (O2). Various electrochemical studies have been conducted to

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.-
elucidate reaction mechanism of O2/O2 [2-4]. Reaction of molecular oxygen at an electrode has

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been described by M. E. Ortiz et al. (2003), by the following equations [4].

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The eq. 2 shows an exergonic (negative free energy, spontaneous), dismutation reaction in which

a species is simultaneously reduced and oxidized to form two products. Previously (1987) J. M.
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Saveant et al., explained this reaction differently due to presence of protons in the reaction

medium [7] by the following reactions.

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By using equations 2a & 2b Saveant et al., explained that proton transfer is the reason for the

partial irreversibility observed in the cyclic voltammograms. The quantity of protons is very low

in dry DMSO, so it does not affect the mechanism very significantly but it explains why the

return peak current is smaller.

The reaction shown in equation 1 has central importance because it involves free radical

generation, capable to initiate side reactions in a living cell and damages the living cells.

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Electrochemical characterization of (eq.1) has been carried out [4-6] with some differences in the

values of heterogeneous electron transfer rate constant (k⁰). The first process has been reported

by several researchers [4, 5 and 6]. Ortiz and co-workers [4] have carried out elaborative work

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about kinetics and electrodics of the first reaction. They described the determination of

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heterogeneous charge transfer rate constant by single method (Nicholson and Shain) [8] and

drawn their conclusions. The present study is unique because we have applied different methods

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to determine electrode kinetic parameters. We have studied parameters such as the transfer

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coefficient, diffusion coefficient, number of electrons involved and heterogeneous electron

transfer rate constant associated with the reaction (eq. 1) while values of kf and kb were also
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determined for the reaction (eq. 2a & 2b). In the previous literature the value of transfer

coefficient was assumed to be 0.5 but we are the first to report its value determined by two
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different experimental methods. Previously heterogeneous electron transfer rate constant was

determined only by the Nicholson method, but in the present investigation Kochi [9] and
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Gileadi’s methods [10] were used to get more reliable values of heterogeneous electron transfer
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rate constant. Gileadi method is one of the reliable methods to determine heterogeneous electron
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transfer rate constant because uncompensated IR drop slightly affect the result [11]. In addition,

this study also reports the values of kf and kb determined through Digital Simulation (DIGISIM)

according to the mechanism given by the Saveant et al.

Materials and Methods

Reagents

A 0.1 M tetrabutylammonium perchlorate (TBAP, TCI, and Japan) was used as the supporting

electrolyte in dimethylsulfoxide (DMSO 99%, Merck, Darmstadt, Germany).

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Procedures

Cyclic voltammetry, chronoamperomety and chronopotentiometry were carried out in unstirred

solutions using a three electrode configuration, connected to CH Instruments electrochemical

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workstation equipped with an electrochemical analyzer (CHI760D). A platinum wire was used as

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counter electrode and saturated calomel electrode (SCE) (supplied by CH instruments) as

reference electrode. Glassy carbon (supplied by CH instruments) with an area of 0.07 cm2 was

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used as working electrode. Between each electrochemical reading the working electrode was

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polished with 0.2 µm alumina powder provided by CHI Instruments. All cyclic voltammograms

were recorded at a constant temperature of 25 oC.

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Nicholson [8], Kochi [9] and Gileadi [10] methods were used for heterogeneous electron transfer

rate constant. Randless-Sevcik equation was used to determine diffusion coefficient. For more
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accurate measurement chronoamperometry was used to determine diffusion coefficient.

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Chronopotentiometry was used to determine number of electrons involved in the electrode

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process. Tafel plot and cyclic voltammetry were used to determine the transfer coefficient.
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Digital simulation was carried out with CHI Software installed in CHI 760D software. Switching
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potential was selected at least 90/n, mV beyond the cathodic peak, where n is the number of

electrons involved in the reaction.

Results and discussion

Cyclic voltammograms of a saturated O2 in DMSO with 0.1 M TBAP solution as the supporting

electrolyte, at a glassy carbon electrode were recorded at different scan rates (0.025 V/s to 0.600

V/s). For all the CV scans negative sweep started at -0.200 V and stopped at -1.100 V versus

SCE. Cathodic peak at -0.804 V at a scan rate of 25 mV/s shifted towards more negative

potential as scan rate increased and reached -0.836 V at 0.6 V/s scan rate.
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20 100 mV/s
200 mV/s
300 mV/s
10
400 mV/s
600 mV/s

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Peak Current (A)
0

-10

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-20

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-30

-40
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0

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Potential (V)

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Figure 1: Overlay of dissolved O2 voltammograms at different scan rates at glassy carbon electrode with SCE as the reference electrode in 0.1 M

TBAP as supporting electrolyte.

Anodic peak at reverse scan appeared at -0.730 V and shifted toward more positive potential
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with increasing scan rate up to 0.6 V/s. The ∆Ep increased from 74 mV to 141 mV with
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increasing scan rate from 0.025 V/s to 0.600 V/s. Peak separation is greater than one electron
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transfer for reversible system and some typical cyclic voltammograms are shown in Fig. 1 at
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different scan rates. The reverse-to-forward peak current ratio, Ipr/Ipf values are less than 1, which
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shows chemically coupled nature of reaction or slow heterogeneous electron transfer processes

[12].

0.110 2
R = 0.941
0.105 y = 0.075x + 0.0634

0.100
Peak Separation (V)

0.095

0.090

0.085

0.080

0.075

0.070
0.1 0.2 0.3 0.4 0.5 0.6
1/2
Sq. root of scan rate (V/s)

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Figure 2. Plot between peak separation (O2 voltammetric peaks) and square root of scan rate; at glassy carbon electrode with SCE as reference
electrode in 0.1 M TBAP as supporting electrolyte

Here we have tried to evaluate whether the quasi-reversible reaction with peaks separation

beyond 59/n (mV) is due to slow kinetics or solution uncompensated resistance. Therefore, we

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plotted a graph between the values of peak separation and square root of the scan rate at different

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scan rates (Fig. 2) [4]. A good linear relation agrees well with the theory for quasi-reversible

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system [8]. These results ensure that possible uncompensated resistance is sufficiently small so

that the resulting voltage drops are negligible compared to the ∆Ep attributed to the kinetic effect

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[12].

The quasi-reversibility for this process was also confirmed from the Ip versus v1/2 plot, which
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exhibits a linear trend (Fig. 3). This plot also shows that the oxygen transport to and away from

the electrode is diffusion controlled. Another test was carried out to confirm that reduction of
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oxygen is diffusion controlled reaction at the electrode: a plot between log(scan rate) and log

(peak potential) was found to be linear as shown in (Fig. 4)[13][14].

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-5
2.2x10
-5
2.0x10 Peak Current (A)
-5
1.8x10 2
R = 0.998
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-5 -5 -7
1.6x10 y = 3.73x10 x - 4.523x10
Peak Current (A)

-5
1.4x10
-5
1.2x10
-5
1.0x10
-6
8.0x10
-6
6.0x10
-6
4.0x10

-6
2.0x10

0.0
0.1 0.2 0.3 0.4 0.5 0.6
1/2
sq. root of scan rate (V/s)

Figure 3: Graph between peak current and square root of scan rate of O2 reduction; at glassy carbon electrode with SCE as reference electrode in
0.1 M TBAP as supporting electrolyte

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-4.7 Log of Peak Potential

Linear fit of Log of Peak Potential
2
-4.8 R = 0.997
y = 0.515x -4.431

log of Peak Potential (V)

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-4.9

-5.0

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-5.1

-5.2

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-5.3
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4
-1
log of Scan Rate (Vs )

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Figure 4: Plot of log of peak potential (V) of O2 reduction versus log of scan rate (Vs-1); at glassy carbon electrode with SCE as reference
electrode in 0.1 M TBAP as supporting electrolyte MA
This logarithmic plot gave the slope = 0.51 with R2 value of 0.998. This slope value is very close

to 0.5, which is the theoretical value for the diffusion controlled reaction [13]. Therefore, these
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observations further confirm that the reaction under investigation is diffusion controlled-charge
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transfer reaction.
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Transfer coefficient
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2 CV scan @25 mV
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0
Current ()

-2

-4

-6

-8

-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0

Potential (V)

Figure 5: CV of O2 reduction at 25 mV/s scan rate; at glassy carbon electrode with SCE as reference electrode in 0.1 M TBAP as supporting
electrolyte

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-5.0

-5.1

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Log (i) (A)
-5.2 Log of Current
Linear fit of Log of Current

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-5.3 y = -7.99x - 11.068
2
R = 0.996
-5.4

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-5.5
-0.77 -0.76 -0.75 -0.74 -0.73 -0.72 -0.71 -0.70
Potential (V)

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Figure 6: Tafel plot of O2 at 25 mV/s scan rate; at glassy carbon electrode with SCE as reference electrode in 0.1 M TBAP as supporting
electrolyte
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In a previous study [4] value of transfer coefficient (α) was assumed to be 0.5, but in the present

study, we report experimentally observed value of α, determined from the Tafel plot [15][16].
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This Tafel plot was drawn from the first descending part of the cathodic peak of cyclic
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voltammogram [13] at 0.025 V/s scan rate as shown in Fig. 5 and Fig. 6.
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This method uses a plot of log(i) versus potential. The values of current and potential were taken
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from the descending part of the cathodic peak [16]. Slope of this plot is taken and eq. (3) is used
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to determine the transfer coefficient [15]. According to this procedure value of slope = -8 which

corresponds to the value of 0.48 for transfer coefficient [16] [17].

(3)

We have also investigated the transfer coefficient (α) value by using the following equation (4)

[12][18].

Ep-Ep/2 = 48 mV/αn (Ep and Ep/2 measured in mV) (4)

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The value of transfer coefficient was found to be 0.66 with a standard deviation of 0.052 while

averaging its value, for the range of scan rates (0.025-0.600 V/s). The digital simulation for this

experiment gives the transfer coefficient value equal to 0.6. The values of transfer coefficient

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determined from the equation (4) and digital simulation are comparable but slightly different from

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the one obtained from the Tafel plot. This difference is not very significant because both the

values lie in the quasi-reversible zone.

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Diffusion coefficient

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Next, we have determined the diffusion coefficient through Randles-Sevcik equation [19]. The
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Randles-Sevcik equation (5) is given by the following expression [20][21]

Ip = (2.69×105)n3/2ACD1/2ν1/2 (5)
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For equation (5), the Ip is peak current (A), constant (2.69 x 105) expressed in C mol–1 V–1/2, n is
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the number of electron exchanged during the electrochemical process (electron stoichiometry), A
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is the active surface area of the working electrode (cm2), D is the diffusion coefficient (cm2·s−1),
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C is the bulk concentration of the diffusing species (mol·cm−3), ν is the voltage scan rate (V·s−1).
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From this equation average value of diffusion coefficient was found to be 4.4 x 10-6 cm2s-1.

Another equation commonly used for the quasi-reversible systems, and the determination of

diffusion coefficient follows the equation (6) [15].

Ip = 2.99 x 105nAC(αnDv)1/2 (6)

We have obtained an average value of D₀ = 4.4 x 10-6 cm2s-1 from the above equations (5 or 6).

This diffusion coefficient value was also determined from the digital simulation, which provided

D₀ = 5 x 10-6 cm2s-1 (Table 1).

Table 1. Summary of investigated parameters

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(k⁰)
E1/2 Transfer Coefficient Diffusion Coefficient kf kb
Technique N cms-1
(V) (α) (D x 10-6)/cm2s-1 M-1s-1 M-1s-1
N & Shain Kochi Gileadi
CV -0.765 0.6 1 4.4 0.0051 0.0014 0.005
Tafel Plot 0.48
CP - - 1.03 - - - -
CA - - - 7.7 - - -

Digital Simulation 0.85a 3.6a

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-0.762 0.6 1 5 0.005
(scan-rate=0.15 V/s) 2.6b 0.01b

a
For equation 2a; bFor equation 2b

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Chronoamperometry

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For the chronoamperometric technique, Cottrell equation is best known to determine diffusion

coefficient [15][22]. The equation predicts the current measured at any time after a potential step

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is applied (to large over potentials) and correlates the observed current at any time following a

large forward potential step in a reversible redox reaction as a function of t-1/2.

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In a recent work (Fig. 7) a single potential step to E1/2 was used [15][22] for the evaluation of
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diffusion coefficient. Therefore, we have explored this method for the determination of diffusion
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coefficient. The following equation, eq. (7), was used to evaluate the diffusion coefficient.
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(7)
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-4
6.0x10

-4
4.0x10
Current i (Ampere)

-4
2.0x10

0.0
Init E(V) = 0, High E(V) = 0

Low E(V) =-0.77, Init P/N = N, Step = 2

-4
-2.0x10 Pulse Width(s) = 4, Smpl Intvl (s) = 0.001

Quiet Time (s) = 2, Sensitivity (A/V) = 1x10-4

-4
-4.0x10 Forward: Reverse:
-5 -6
Slp = -1.077x10 Slp = 4.068x10
-4
-6.0x10 Int = -1.781x10
-6 -7
Int = -5.35x10

Cor = -0.99982 Cor = 0.99252

-4
-8.0x10
-1 0 1 2 3 4 5 6 7 8 9
Time, t (s)

Figure 7: Chronoamperometrogram of O2 at glassy carbon electrode with potential step E1/2; at glassy carbon electrode with SCE as reference
electrode in 0.1M TBAP as supporting electrolyte

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The diffusion coefficient was calculated from a plot of i(t) vs. t-1/2. The slope of this line is

provided directly by the instrument CHI 760D (inset Fig. 7). The slope (slope = nFAD1/2C/π1/2,

where n = number of electrons; F = Faraday’s constant (96,485 C/mol), A = electrode area (cm2),

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C = concentration (mol/cm3), and D = diffusion coefficient (cm2/s)) was used to determine the

diffusion coefficient. Diffusion coefficient evaluated from the Cottrell equation = 7.7 x 10-6

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cm2/s which is close to the value obtained from the cyclic voltammetry experiment.

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Number of electrons

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Chronopotentiometry MA
In chronopotentiometry (Fig. 8) polarization current was kept at 0.1 µA and only single

transition time was found (2.9 second) which shows one charge transfer. Then we have used
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Sand equation (8) [23] to calculate the number of electrons in the reduction process (equation 1)
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which is 1.03, very close to unity, and the same as previously reported [4].
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τ1/2 = π1/2 nFAD1/2C/2ί₀ (8)

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The equation (8) predicts the transition time of a chronopotentiometry experiment and shows τ as
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the transition time (the time between cell turn on and the rapid change in potential) and ί₀ as the

polarization current.

-0.6
Chronopotentiometrogram of O2
-5
-0.7 Cathodic i (A) = 1x10
-5
Anodic i (A) = 1x10
InitP/N = N
-0.8
Data Interval (s) = 0.1
Potential (V)

High E Limit (V) = 0

-0.9 Low E Limit (V) = -1.2
Segment = 1

-1.0

-1.1

-1.2

0 1 2 3 4 5 6 7 8
Time (s)

Figure 8: Chronopotentiometrogram of O2; at glassy carbon electrode with SCE as reference electrode in 0.1 M TBAP as supporting electrolyte

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Heterogeneous Electron Transfer Rate Constant

Linear scan / Cyclic voltammetric methods
Table 2. Values of k⁰ determined from Nicholson and Shain Method

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Scan Rate (V/s) ∆Ep(mV) Ψ (k⁰) cms-1 Average (k⁰) cms-1
0.025 74 1.83 0.0060
0.05 84 1 0.0047

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0.075 84 0.58 0.0033
0.1 88 0.88 0.0058

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0.125 88 0.88 0.0065
0.00516
0.15 91 0.71 0.0058
0.175 94 0.335 0.0029 Standard deviation

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= 0.0012
0.2 97 0.65 0.0061
0.225 96
MA 0.67 0.0066
0.25 101 0.58 0.0060
0.275 102 0.56 0.0061
0.3 109 0.46 0.0052
D
P TE
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Table 3. Values of (k⁰) determined from Kochi Method

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∆Ep (k⁰) Average

Scan Rate (V/s) Transfer Coefficient α
(V) (cms-1) (k⁰) cms-1
0.025 0.68 0.074 0.000689
0.05 0.70 0.084 0.000975
0.075 0.68 0.084 0.001147
0.1 0.72 0.088 0.00133
0.125 0.67 0.088 0.001487
0.00142
0.15 0.66 0.091 0.001541
0.175 0.66 0.094 0.00144 Standard deviation
= 0.00034
0.2 0.62 0.097 0.001592
0.225 0.59 0.096 0.001494
0.25 0.58 0.101 0.001729
0.275 0.58 0.102 0.001861
0.3 0.59 0.109 0.001799

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We have used following three methods for the evaluation of standard heterogeneous electron

transfer rate constant (k⁰). The two methods, that of Nicholson as well as of Kochi, are based on

the peak separation and the third method is Gileadi. Nicholson [8] method is used frequently to

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determine standard heterogeneous electron transfer rate constant k0 by relating it with a

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dimensionless kinetic parameter Ψ (eq. 9).

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₀
⁰ (9)

The dimensionless parameter can be obtained from literature in which values of Ψ has been

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tabulated against peak separation [8]. The Ψ values along with calculated k0 values for various
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scan rates are reported in the Table 2.

Second method was devised by Kochi and Klinger [10]. This method also depends on peak
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separation (eq. 10). The method first requires value of transfer coefficient to be determined.
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⁰ (10)
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Heterogeneous electron transfer rate constant (k⁰) calculated from this method is reported in the
AC

Table 3. The third method is known as the Gileadi method [11] which is comparatively simple to

evaluate the heterogeneous electron transfer rate constant (k⁰) and does not require peak

separation.

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0.836 Peak Potential at High Scan Rate

0.832 Peak Potential at Low Scan Rate
Linear fit on both scan rate
0.828

Peak Potential (V)

0.824

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0.820

0.816

0.812

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0.808

0.804 logVc

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-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2
-1
log of Scan rate (Vs )

Figure 9: Plot between log of peak potential verses log of scan rate for critical scan rate (Vc); at glassy carbon electrode with SCE as reference

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electrode in 0.1 M TBAP as supporting electrolyte

This method is based upon the determination of critical scan rate at which the electrode reaction
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changes from reversible to irreversible. We have determined critical scan rate graphically by Ep

plotted against the log of scan rate at low and high scan rates. Two lines can be fitted for the low
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and high scan rates with two different slopes. Critical scan rate can be found from the
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intersection of the two lines (Fig. 9). Both curves are extrapolated and critical scan rate is
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determined from the intersection of curves (Fig. 9); then following equation (11) is used to
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calculate the value of k⁰.

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₀
⁰ (11)

By this method the value of heterogeneous electron transfer rate constant (k⁰) was calculated to

be 0.0051 cms-1.

We have also determined the value of k⁰ from the digital simulation (Table 1). Digital simulation

(Fig. 10) was carried out, as reaction scheme shown below.

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PT
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-5 Experimental at 150 mV/s
1.5x10
Digitally Simulated (DIGISIM)
-5
1.0x10

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-6
5.0x10
Current (A)

0.0

-6
-5.0x10

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-5
-1.0x10
-5
-1.5x10
-5
-2.0x10

-1.0
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-0.8 -0.6 -0.4 -0.2
Potential (V) vs SCE

Figure 10: Digitally simulated voltammograms of O2 at 0.150 V/s (150 mV/s) scan rate. Experimental CV recorded at glassy carbon electrode
with SCE as reference electrode in 0.1 M TBAP as supporting electrolyte.
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Peak current ratio of forward to backward (Ipf/Ipb ) remained less than unity at all scan rates
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(0.025 to 0.600 V/s) indicating some coupled chemical reaction(s). This ratio started increasing
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from 0.68 to 0.85 (as scan rate increased) which shows chemically coupled reaction. It is due to
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proton transfer reaction (equations 2a, 2b) as explained by the J. M. Saveant et al. [7]. The
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transfer coefficient (α) calculated from the Tafel plot is 0.48, which is close to the previously

assumed value of 0.5. [4] But transfer coefficient determined from equation (4) through cyclic

voltammetry is 0.7 for the low scan rate and 0.6 for the scan rate greater than 0.3 V/s.

Diffusion coefficient determined from the Randles-Sevcik equation (eq. 5) and from quasi

reversible situation (eq. 6) is consistent with the value determined from the chronoamperometry.

The number of electron involved was determined from Sand equation (eq. 8) and gave the value

1.03 which is close to 1 and consistent with previous reports. [4]

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The parameters determined from experiments were confirmed by the digital simulation. The kf

and kb (functions of potential) are the rate constants for the forward and reverse electron transfer

respectively. Digital simulation provided the charging capacitance = 4 µF at the scan rate of

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0.150 V/s. The kinetic parameters kf and kb (for eq. 2a) are 0.85 M-1s-1 and 3.6 M-1s-1,

respectively. The value of kf = 2.6 M-1s-1 and kb = 0.01 M-1s-1 for eq. 2b, respectively. These

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values differ from previous reports [4] because of different reaction mechanism. To achieve

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better understanding of results we conducted digital simulation at different scan rates and data of

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different digital simulations (Fig.S1a, Fig.S1b & Table S1 in the Supporting Information) were

comparable to the values reported in Table 1.

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Conclusions
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Heterogeneous electron transfer rate constant (k⁰) for the conversion of molecular oxygen (O2) to
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superoxide (O2.-) at the surface of glassy carbon electrode in DMSO solution (0.1M
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tetrabutylammonium perchlorate (TBAP) as the supporting electrolyte) shows quasi-reversible

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reaction by the cyclic voltammetry. In previous studies, value of k⁰ was determined only by the

Nicholson method [4]. In addition, we have measured k⁰ with other two methods (Gileadi and
AC

Kochi). Heterogeneous electron transfer rate constant (k⁰) determined from the Nicholson,

Gileadi method and digital simulation was 0.005 cm.s-1, while the Kochi method gave k⁰ =

0.0014 cm.s-1. This small difference has been observed by other researchers when different

methods (Kochi method gives some different values than Nicholson and Shain or Gileadi

method) were applied [20] while working on Viologen cations. We have determined the values

of kf and kb (kinetic parameters) = 0.85 M-1s-1 and 3.6 M-1s-1, respectively, for eq. 2a. The kf and

kb are 2.6 M-1s-1 and 0.01 M-1s-1, respectively, for the eq. 2b. We performed digital simulation by

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using previously reported mechanism (eq. 1, 2a & 2b). [7] Different methodologies show that the

reaction is quasi-reversible with k⁰ = 0.005 cm.s-1. In summary, first we used electroanalytical

techniques such as cyclic voltammetry, Tafel plot, chronoamperometry and chronopotentiometry

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to study the electrode kinetics. Finally we used DIGISIM voltammogram fitting over the

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experimental cyclic voltammogram to verify the experimentally calculated parameters.

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Acknowledgments; We gratefully acknowledge the Higher Education Commission (HEC)

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Govt. of Pakistan for the research work financial support through the HEC Project (Project #
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P&D/12(156)/46/2008).
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References

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[2] V. Lvovich, A. Scheeline, Anal. Chem. 69 (1997) 454-462.

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[6] J. F. Wu, Y. Che, T. Okajima, F. Matsumoto, K. Tokuda, T. Ohsaka, Electrochim. Acta.
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[7] C. P. Andrieux, P. Hapiot, and J. M. Saveant, J. Am. Chem. Soc 109 (1987) 3768-3775.
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[9] R.J. Klinger and J. K. Kochi, J. Phys. Chem. 85 (1981) 1731-1741.
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[12] A. J. Bard, L. R. Faulkner, Electrochemical methods Fundamentals and Applications,

second ed., John Wiley & Sons, Inc. NewYork, 2001.
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[14] M. Srivastava, A. K. Das, P. Khanra, M. E. Uddin, N. H. Kim, J. H. Lee J. Mater. Chem.

A, 1 (2013) 9792-9801.
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[21] D. D. Perrin, W. L. F. Armarego, D. R. Perrin, “Purification of Laboratory Chemicals",

Paragon, London, 1966.
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Highlights
 Generation of superoxide is the key step to study antioxidant activity through cyclic
voltammetery.
 Heterogeneous electron transfer rate constant ko value validates the generation of

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superoxide free radical and its capability towards antioxidant activity.
 Evaluation of ko through different methods,limitation and validation of each method.
 Electrochemical reaction mechanism of dissolved oxygen has been confirmed through

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digital simulation.

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