1

The electrochemical redox behaviour of Pyro catechol violet and its quantitative
measurement at carbon paste electrode: A voltammetric study
G. V. Raghunatha Reddy, T. Madhusudana Reddy*, P. Gopal and P. V. Narayana
Electrochemical Research Laboratory, Department of Chemistry, S.V.U. College of Sciences, Sri
Venkateswara University, Tirupati-517502, Andhra Pradesh, India.
Abstract
The electrochemical oxidation and reduction behavior of pyrocatechol violet (PCV) at glassy
carbon electrode (GCE) was investigated by employing cyclic voltammetry (CV) and differential pulse
voltammetry (DPV) techniques. PCV was exhibited that a oxidation peak at 0.16 V and a reversible
reduction peak was observed at 0.14 V. The effect of pH on the PCV was observed by using the
phosphate buffer solution and pH-5.0 was chosen as optimum pH for all the remaining experiments. The
effect of scan rate on the PCV was observed and it was determined as the system was controlled by
diffusion process. We have studied the effect of PCV concentration on the peak current response, from
the linear plot of the calibration curve, we have evaluated the limit of detection (LOD) and limit of
quantification (LOQ) as ----. Finally the surface nature of the electrode was characterized by using the
electrochemical impedance spectroscopy (EIS).

Key words: pyrocatechol violet, cyclic voltammetry, Differential pulse voltammetry, Electrochemical
impedance spectroscopy, glassy carbon electrode.
Corresponding author E-mail address: *tmsreddysvu@gmail.com, Tel.: +91-877-2289303

Introduction
Pyrocatechol violet (PCV) is a sulphone dye which was made from condensing
pyrocatechol with O-sulfobenzoic acid anhydride. PCV is also having indicator properties and
forms complexes with metal ions. It is photometric reagent and indicator for heavy metals and
rare earth metals. This was used as pH indicator with a transition interval from 0-8 (red to violet).
In general the dyes are chemically bonded to the substance and become a part of the material on
which it was applied.. In our daily life the usage of dyes was increased more rapidly because of its
wide range of applications. The dyes are toxic in nature, and makes contamination with effluents
eluted from the industries. The water contamination with dyes causes severe health diseases
hence the selective determination, separation and quantification of dyes are of great importance.
CV was the technique which was widely used in many fields of chemistry. This technique is
based on current response against applied potential. By using this technique we can predict the
redox mechanism of analyte. DPV is a sensitive technique in comparison with CV, because it
minimizes the migration current. Glassy carbon electrodes (GCE) has been used by many number
of electrochemists, in our present study, we have used GCE modified with Graphene as a working
electrode.
At present, very few reports were established about the quantitative determination of PCV
Among the all analytical techniques, due to its simple rapid cost free applications electroanalytical
techniques such as CV and DPV were widely used for the quantification of the various analytes.
These techniques were mainly based on the surface modification of working electrodes with
different conductive materials. In this study due to its condutive and catalytic properties of
graphene, GCE was modified with graphene and used as working electrode.

In our present work, we have studied the redox behavior of PCV at GCE/graphene working
electrode and proposed a redox mechanism (SCHEME-II). We have studied the redox nature of
PCV in different pH values, scan rate and concentration. Electrochemical impedance spectroscopy
was employed for the determination of surface nature of the working electrode.
Position for Scheme-I

Materials and Methods:

Experimental
1.1 Apparatus
CHI-660D (CH-Instruments) electrochemical work station was used for CV, DPV and
EIS experiments. The experiments were done with a conventional three electrode electrochemical
cell. In the three electrode system glassy carbon electrode (GCE) was used as a working
electrode, Pt - wire and silver-silver chloride Electrodes were used as counter and reference
electrode respectively. A model LI 120 (ELICO) pH meter was used for the preparation of various
pH buffer solutions.
1.2 Chemicals
Graphene (Graphene-oxide Clarify from NYS sir) was received from Dropsens (Address
from N.Y. Sreedhar Sir), Pyrocatechol violet (PCV) was obtained from Sigma Aldrich and
dissolved in double distilled water to prepare 0.1 mM/L standard stock solution.
NaH2PO4.2H2O and Na2HPO4 were received from Fisher scientific, India and Merck India.
0.1 M phosphate buffer solution was prepared from NaH 2PO4.2H2O and Na2HPO4. All other
chemicals used were of analytical grade quality.
1.3 Modification of glassy carbon electrode

Prior to the modification of GCE, GCE was first polished with alumina slurry having
different sizes. After getting mirror like shine 5 L of graphene solution which was dissolved
in ethanol (1:2 W/v) was immobilized on the surface of the GCE and allowed to dry and
formed electrode was used as working electrode and denoted as graphene/GCE.

Results and Discussions:

1. Electrochemistry of pyrocatechol violet (PCV):
The electrochemical redox behavior of 1mM PCV in PBS having pH-5.0 at graphene/GCE
was studied by employing CV technique. The CV responce of 1 m M solution of PCV was
exhibited that, in a forward scan i.e. -0.2 V to 0.8 V an oxidation peak was observed at the
potential of 0.16V, which is corresponds to the oxidation of catechol group present in the PCV
was forms a carbonyl compound. An another oxidation peak was observed at potential 0.48 V,
which is responsible for the oxidation of phenolic group of PCV. In reverse scan i.e. from 0.8
to -0.2 V, we hav observed that two reduction peaks were observed for corresponding to the
reduction of carbonyl compound into catechol group. Scheme-II depicted that redox
mechanism of PCV at Graphene/GCE.
Position for Fig. 1a and Fig.1b
Position for Scheme-II
2. Voltammetric study of different electrodes at K3[Fe(CN)6]:In order to elevate the surface morphology of bare GCE and GO modified GCE,
we have carried out impedance spectroscopy which gives the clear information about the
surface nature of the different materials. EIS was recorded for 1mM K3[Fe(CN)6] in 1M
KCl solution at two different electrodes.
The CV responses of bare GCE and GO modified GCE was observed for the 1mM
K3[Fe(CN)6] in 1M KCl solution. From the fig. a it clearly exhibiting that the GO

modified GCE was having high peak response than that of the bare GCE, which clearly
indicating the catalytic and conductivity properties of the graphene oxide immobilized
onthe surface of the GCE electrode. Base on the CV results of the bare GCE and GO/GCE
we have elevated the diffution coefficient (D) values for bare GCE and GO/GCE as
Position for Fig. 2a and Fig. 2b
3. Effect of pH:The effect of different pHs on the electrochemical responces of the 1mM PCV
was studied with phosphate buffer solutions. The pH of the supporting electrolyte was
varied with the ranges from pH-5.0 to 8.5 and recorded the DPV responses between the
potential window of -0.2 to 0.6 V. Fig. A shown that the pH of the supporting electrolyte
was influencing on the peak currents and peak potentials of the PCV indicating the
involvement of protons in the electrochemical redox reaction system of PCV. From fig. a
the DPV responses for pH-5.0 was having more peak currents than other pH values
therefore pH 5.0 was selected as optimum pH for all further experiments. At higher pH
values an another peak appeared at potential of 0.4 V corresponds to the oxidation of
phenolic group present in the PCV. From fig. B linearity was achieved for the pH verses
potential plot and the linear regration equation was found to be as E p(V) = 0.544 (V)
0.077pH with the correlation coefficient as 0.995. The slope value of the linear regration
equation was close to the theoretical value of 0.060 V and which confirms the involvement
of equal number of protons and electrons.
Position for Fig. 3a and Fig. 3b
4. Effect of scan rate:-

To evaluate the kinetic parameters for the electrochemical oxidation and reduction of PCV,
we have studied the scan rate effect by changing scan rate ranges from 10 mV s -1 to 100 mV s-1.
From Fig. a exhibiting the LSVs of 1mM PCV in PBS solution having pH-5.0 at different scan
rates. From Fig. a we have observed that the LSV responses of 1mM PCV in PBS pH-5.0 were
gradually increase with increase in the scan rate. From fig. b a typical linearity was observed for
the peak current responces of PCV and square root of scan rate and the linear regration equation
was obtained as ip(A) = 3.779 (A) + 0.139 1/2 (mV/s)1/2 with the correlation coefficient R2 =
0.986.
Position for Fig. 5a and Fig. 5b
5. Effect of concentration:Differential pulse voltammetry was most widely used sensitive analytical technique for the
quantification of various analytes. To analytical quantification of PCV in buffer solution,
we have performed the DPV measurements for different concentrations of PCV. From fig.
a Based on following equations we have found the limit of detection (LOD) and limit of
quantification (LOQ) as 3.248 10-8 M and 10.22 10-8 M respectively. Where Sb was the
standard deviation and m was the slope of calibration curve [39, 40].
LOD = 3Sb/m
LOQ = 10 Sb/m
Position for Fig. 6a Fig. 6b
6. Repeatability, reprodusibility and stability:
The practical utilization of graphene/GCE was examined with 1mM PCV by using CV. We
have recorded several CVs and all the CVs were exhibited the same results with low relative
standard deviation values, conforms the good repeatability of the modified electrode. We have
scanned the CV responses for few newly prepared graphene/GCEs and the results produced
were almost same and conforms the good reproducibility of the fabricated electrode. We have

also observed the stability of the graphene/GCE by storing the electrode for nearly one month
and the results were in satisfactory range.
Conclusions:
In our present work, we have elevated that the electrochemical redox behavior of PCV at
graphene/GCE. It was found that the redox mechanism of PCV was dependent on the pH of the
solution. To elevate kinetic parameters for the PCV we have observed the scan rate effect and the
results shows that the redox process was controlled by diffusion process. The limit of detection
(LOD) and limit of quantification (LOQ) values were achieved from effect of concentration.
Finally the surface nature, repeatability, reprodusibility and stability of graphene/GCE was
examined and the results were in satisfactory range.
Acknowledgements
One of the co-author expresses his grateful acknowledge to Basic Scientific Research
(BSR) Fellowship, UGC, New Delhi, India for providing financial assistance.

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Figure captions and Schemes:

Fig. 1a: The Cyclic voltamogram of 1 10 -4 M AB 25 in pH-7.0 phosphate buffer solution with
scan rate of 100 mVs-1 at carbon paste electrode verses saturated calomel electrode.
Fig. 1b: The Differential pulse voltammograme of 1 10-4 M AB 25 in pH-7.0 phosphate buffer
solution at carbon paste electrode verses saturated calomel electrode.

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Fig. 2a: The nyquest plot of EIS representing three different electrodes, red colored (CPE), blue
colored (GCE) and grey colored (Pt electrode).
Fig. 2b: The bode plot of three different electrodes, black squares represents CPE, red circles
represents GCE and blue stars represents Pt electrode.
Fig. 3: The Cyclic voltamogram of 1 10 -4 M AB 25 solutions in pH-5.0, pH-6.0, pH-7.0, pH-8.0
phosphate buffer solution with scan rate 100 mVs -1 at carbon paste electrode verses
saturated calomel electrode.
Fig. 4: A plot drawn between accumulation time (in sec) and their respective peak currents black
square boxes represents first redox system and red circles represents second redox system.
Fig. 5a: The Cyclic voltammograms of 1 10-4 M AB 25 in phosphate buffer solution of pH-7.0
with scan rates 10 mVs-1 (a), 20 mVs-1 (b), 30 mVs-1 (c), 40 mVs-1 (d), 50 mVs-1 (e), 60
mVs-1 (f), 70 mVs-1 (g), 80 mVs-1 (h), 90 mVs-1 (i), 100 mVs-1 (j), 110 mVs-1 (k), 120
mVs-1 (l), 130 mVs-1 (m), 140 mVs-1 (n) and 150 mVs-1 (o) at carbon paste electrode
verses saturated calomel electrode with an initial pre concentration time of 20 minutes.
Fig. 5b: A plot between square root of scan rate and peak currents of first redox system at 0.2 V.
Fig. 5c: The plot between scan rate and their peak currents of second redox system at 0.56 V.
Fig. 6a: The Differential pulse voltammograms of AB 25 with different concentrations 1.6 10 -8
M (a), 2.5 10-8 M (b), 4 10-8 M (c), 4.5 10-8 M (d), 5 10-8 M (e), 6 10-8 M (f), 7
10-8 M (g), 8 10-8 M (h), 10 10-8 M (i), 12 10-8 M (j), 14 10-8 M (k), 16 10-8 M
(l), 20 10-8 M (m), 25 10-8 M (n), 30 10-8 M (o), 40 10-8 M (p), 50 10-8 M (q),

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70 10-8 M (r), 100 10-8 M (s), 150 10-8 M (t) at carbon paste electrode verses
saturated calomel electrode.
Fig. 6b: The plot between the peak currents to the against different concentrations.
Scheme-1: Molecular structure of PCV.
Scheme-2: Proposed electrochemical redox mechanism for PCV at graphene/GCE.

Figures:

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