Experiment ELECTROCHEMICAL ANALYSIS OF FERRICYANIDE USING CYCLIC

VOLTAMMETRY
2013-19846; 2013-67188
November 17, 2016
I. Abstract
Cyclic voltammetry is classified as a type of potentiodynamic electroanalytical
technique used for the study of electroactive species and is extensively utilized in
industrial applications and academic research laboratories. In this experiment,
the formal reduction potential of ferricyanide was determined to be 0.2165 V
while in contrast, the theoretical formal reduction potential is 0.36 V. The effect of
scan rate and concentration on peak current was observed. Peak current was
determined to be directly proportional to both the square root of scan rate (v 1/2)
and concentration. Using two standard curves of Ip ox and Ip red against
concentration, the concentration of the unknown was obtained using the linear
equations. The concentration of the unknown was determined to be 7.55 mM .

II. Keywords: Formal Reduction Potential, Scan Rate, Anodic Peak Current, Cathodic Peak

III. Introduction
Cyclic voltammetry is a widely used
technique in order to acquire qualitative
information about the electrochemical
reactions occurring (Bard & Faulkner, 2008).
It gives a quick location of redox potentials
of the species found to be electroactive
(Bard & Faulkner, 2008).
A Cyclic voltammeter consist of
three main parts namely a working
electrode, a reference electrode and a
counter electrode (Bard & Faulkner, 2008).
A reversible electrochemical reaction the
cyclic voltammetry produces have well
defined characteristics such as the ratio of
the peak currents is equal to one, The peak
currents are proportional to the square root
of the scan rate, and The positions of peak
voltage do not alter as a function of voltage
scan rate (University of Cambridge, 2015).
The study aims to create a cyclic
voltammetry in order to the formal reduction
potential (E0) of the [FeIII(CN)6] 3- /
[FeII(CN)6] 4- coupling, to define the
consequences of scan rate and
concentration variant of K3[Fe(CN)6] on
peak current, and to quantify the
concentration of unknown K3[Fe(CN)6]
solution
Electrochemistry - Cyclic Voltammetry
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[Fe(CN)5]3- + e- [Fe(CN)6]4-
IV. Experimental
A. Stock Preparation
Stock Solution
A 1.6462 g of K3[Fe(CN)6] was
diluted with 0.1M HNO3 in a 100 ml
volumetric flask in order to prepare 50 mM
K3[Fe(CN)6] stock solution.
Determining the Formal Reduction Potential
and the effect of Scan Rate
An aliquot of 4 ml of the stock
solution was diluted in a 50 ml volumetric
flask in order to prepare a 4 mM K3[Fe(CN)6]
solution
Determining the Effect of Varying Scan Rate
and Concentration
A varying concentration of
K3[Fe(CN)6] was prepared in 50 ml
volumetric flask at concentrations of 2,4,6,
8, 10 mM of K3[Fe(CN)6] solution diluted
with 0.1M HNO3

B. Determining the Formal Reduction
Potential
The Ecorder and Potentiostat were
set up with the working electrode polished
using Buehler cloth with alumina. The
ionizers were rinsed and dry before setup. A
2ml of 4mM K3[Fe(CN)6] solution was used
as the standard. The green clip was
attached to the working electrode, the red to
the counter electrode and the yellow to the
reference electrode.
The parameters were set up with the
initial and the final both -800mv, the rate
was set to100mV/s, upper limit was set to
800mV, and the lower limit was set to
-800mV. The scans were obtained and the
Epa and Epc was determined in order to
calculate formal reduction potential.
C. Determining the Effect of Scan Rate
The steps for formal reduction
Potential was repeated at varying scan rate
of 50, 100, 160, and 200 mV/s. The peak
oxidation and peak reduction was
determined by switching the graph to IE vs
time. The peak oxidation and reduction was
plotted against v1/2 and the effect of scan
rate was then evaluated.
D. Determination of the concentration of the
unknown K3[Fe(CN)6] solution
A standard curve was made by
repeating the steps in determining the
formal reduction potential upon varying the
concentration of K3[Fe(CN)6] using
2,4,6,8,10 mM K3[Fe(CN)6] solutions. The
peak oxidation and reduction was plotted
against concentration and evaluated the
effect of concentration on the peak current.
The standard curve was used to calculate
the concentration of the unknown sample.
V. Results and Discussion
Cyclic voltammetry has the ability
rapidly observing redox behaviour over
wide potential range. It involves cycling
the potential of an electrode, which
Electrochemistry - Cyclic Voltammetry
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immersed in an unstirred solution and
measuring the resulting current. (Anderson,
1991)
In cyclic voltammetry the
potentiostat applies the desired potential
between a working electrode (glassy
carbon) and a reference electrode
(Ag/AgCl). In addition, the working
electrode is the location where the reaction
being studied takes place. The auxiliary
electrode, typically platinum wire, generates
the current (polarized) needed to maintain
electrolysis at the working electrode. The
potential of the working electrode is
controlled versus a reference electrode
such as a Ag/AgCl electrode which
maintains constant potential (polarized).
(Anderson, 1991)
The current response from an
excitation potential is measured and a cyclic
voltammogram (current-potential plot)
results. A scan performed towards a more
positive potential is called an The anodic
scan is performed towards a more positive
potential whereas a cathodic scan is
towards the direction of a more negative
potential. The reduction potential (Eo) can
then be calculated using the formula below
and the following parameters.
E pa+ E pc
Eo =
2
Initial= -800 mV
Final= -800 mV
Rate= 100 mV/s
Upper limit= 800 mV
Lower limit= -800 mV
The anodic potential and cathodic
potential for the redox reaction of
ferricyanide was recorded to be 0.2650V
and 0.1680V respectively. Subsequently,
the reduction potential (Eo) was calculated
of to be 0.2165 V. The theoretical reduction
a potential of ferricyanide however is 0.36 V
of (Standard Reduction Potentials (E0), 25oC,
is n.d.)
 Table 1. Data for Ip ox and Ip red at varying
scan rates
Table 2. Data for Ip ox and Ip red at varying
Scan Scan concentrations of ferricyanide
rate rate1/2 Ip ox Ip red
7.07106 Concentratio
50 8 3.8162 -4.5793 n Ip ox Ip red
100 10 5.8536 -8.4031 2 2.957 -4.5793
12.6491 4 5.8536 -8.4031
160 1 7.8097 -9.417 6 9.17204 -11.8457
14.1421 - 8 12.0441 -14.8457
200 4 9.1048 10.1927
10 14.3699 -17.4692
Unknown 11.5199 -13.4851
15
10 20
5 f(x) = 0.74x - 1.5 15
R = 1 f(x) = 1.45x + 0.17
Current 0 10
R = 1
5
-5 6 7 8 9 10 11 12 13 14 15
f(x) = - 0.77x + 0.27 Current 0
-10 -5 1 2 3 4 5 6 7 8 9 10 11
R = 0.92
-10 f(x) = - 1.61x - 1.76
-15
R = 0.99
-15
Scan rate1/2
-20
Concentration
Figure 1. Plot of Ip ox and Ip red against scan
rate1/2, showing the effect of scan rate.
Figure 2. Plot of Ip ox and Ip red against
The effect of scan rate (v) on cyclic
concentracion, showing the effect of
voltammograms of 4 mM K3Fe(CN)6 in 0.1M concentration.
KNO3 was observed at 50, 100, 160, 200
mV/s. It was determined that peak current is It was determined that concentration
directly proportional to (v1/2). It is important affects the magnitude of the peak current.
to note that as scan rate is decreased the Figure 2. shows the peak currents at
cyclic sweep of the voltammogram will take varying concentrations of (2, 4, 6, 8, and 10
longer to record. This data agrees with mM) of K3Fe(CN)6 in 0.1 M KNO3 at 100
Randles-Sevcik equation at 25C, wherein, mV/s. The data shows that peak current is
n is the number of electrons, A is the directly proportional to concentration. This
electrode area (m2), C is the concentration standard curve can then be utilized to
(mol/L), D is the diffusion coefficient (m 2/s) evaluate the concentration of the unknown
and v is the potential scan rate (V/s); as since the Ip ox and Ip red of the unknown
scan rate increases peak current increases. was obtained to be 11.5199 mA and
-13.4851 mA respectively.

Electrochemistry - Cyclic Voltammetry

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 observed and visualized on the
voltammograms. Finally, the concentration
of the unknown was extrapolated using the
standard curve.

It is recommended that before each

Sample computations for unknown part of the methodology, the working
Using Ip ox = 11.5199 electrode be polished using a Buehler cloth
with alumina at sufficiently in order to obtain
y=1.4508 x+ 0.1744 better results in the voltammograms.

( 11.5199 =1.4508 x +0.1744

11.51990.1744
x=
1.4508 VII Reference
Anderson, A. J. (1991).
ELECTROCHEMISTRY. Retrieved
x=7.82 mM
from PHATTIMES:
http://www.phattimes.com/myoglobin
Using Ip red = -13.4851 /chapter3.htm

y=1.6111 x1.7619 Bott, A. W., & Jackson, B. P. (1996). Study

of Ferricyanide by Cyclic
Voltammetry Using the CV-50W.
(13.4851 ) =1.6111 x1.7619 Current Separations.4

Bard, A. J., & Faulkner, L. R. (2008).

13.4851+1.7619 Electrochemical Methods:
x=
1.6111 Fundamentals and Applications.

Nicholson, R. S. (1965). Theory and

x=7.28 mM Application of Cyclic Voltammetry for
Measurement of Electrode Reaction
7.82+7.28 Kinetics. Anal. Chem.
Concentration of unknown

2 Pandurangachar, M., Swamy, B. E.,
Chandrashekar, B. N., Gilbert, O.,
7.55 mM Reddy, S., & S.Sherigara, B. (2010).
Electrochemical Investigations of
Potassium Ferricyanide
andDopamine by 1-butyl-4-
methylpyridinium tetrafluoro borate
VI Conclusion Modified Carbon Paste Electrode: A
Cyclic Voltammetric Study .
The electrochemical analysis of
International Journal of Electrochem
ferricyanide, K3Fe(CN)6, using cyclic
Science.
voltammetry was successfully performed in
determining the formal reduction potential of University of Cambridge. (2015). Linear
ferricyanide. The effects of scan rate and Sweep and Cyclic Voltametry: The
concentration on the peak currents were Principles. Retrieved from
Electrochemistry - Cyclic Voltammetry
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 Department of Chemical sweep-and-cyclic-voltametry-the-
Engineering and Biotechnology: principles
http://www.ceb.cam.ac.uk/research/g
roups/rg-eme/teaching-notes/linear-

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