CV: Cyclic Voltammetry for the Determination of the Concentration of

Ferrocyanide/Ferricyanide Redox Couple.

Maha Zerkan
02/03/2022
Abstract:
Cyclic voltammetry is the experiment performed on an electroactive analyte because of its
ability to provide the redox potential of that analyte. This technique also allows fast evaluation of
a particular matrix’s effect on a redox process. During a typical cyclic voltammetry experiment,
a component of ferricyanide/ferrocyanide complex solution is electrolyzed (oxidized and
reduced) by placing the solution in contact with an electrode and then applying a potential to that
electrode. The electrode’s voltage is adjusted higher or lower linearly, and finally, the voltage is
returned to the original value at the same linear rate. When the electrode becomes sufficiently
negative or positive, a species in solution may gain electrons from the electrode’s surface or
transfer electrons to that surface. The purpose of this experiment is to determine the
concentration of unknown using cyclic voltammetry; thus, the concentration of the unknown was
found at 6.5mM.

Introduction:
Cyclic voltammetry is the most commonly used electroanalytical technique for obtaining
rapid quantitative data about an electrochemical reaction. The importance of cyclic voltammetry
is that it provides a quick result concerning the kinetics of a heterogeneous electron transfer,
diffusion coefficients, and thermodynamic information for a process. Cyclic voltammetry also
can give data on subsequent chemical reactions or adsorption processes. Cyclic voltammetry
(CV) is a widely used electrochemical technique that involves the cyclical scanning of the
potential (i.e., scanning from a starting to an ending potential and back again at a constant rate)
and measuring the resultant current. The resulting "cyclic voltammogram" relays information
about the redox potential of the analyte, the number of electrons transferred in the reduction or
oxidation, the reversibility and speed of the electrochemical process, the stability of the analyte's
oxidized or reduced form, and the analyte's concentration. A three-electrode cell (working,
reference, and counter) is used in a typical setup, with the measured current passing between the
working and counter electrodes. The analyte solution must be made to contain a supporting
electrolyte. Thus, care should be taken to choose an electrolyte that will not react with the
analyte or be electroactive within the scan range. Cyclic voltammetry (CV) is used to study
reaction mechanisms involving electrons' transferring. The method involves linearly varying an
electrode potential between two limits at a specific rate while monitoring the current that
develops in an electrochemical cell. This experiment is performed under conditions where
voltage is more than predicted by the Nernst equation (Eq. 1). Although CV provides qualitative
information about reaction mechanisms, several quantitative properties of the charge transfer
reaction can also be determined.

E=E°+(0.0591/n) log(C0x/Cred) (1)

As an essential tool for studying mechanisms and rates of oxidation and reduction processes, CV
provides the capability for generating a species during the forward scan and then probing its fate
with the reverse scan or subsequent cycles. This process can occur within a few seconds. There is
a unique aspect of cyclic voltammetry: three electrodes are used. The electrodes are a working
electrode, a reference electrode, and a counter electrode. The working electrode can be seen as a
medium whose magnitude of the applied potential can externally adjust reductive or oxidative
power. As the potential is increased or decreased linearly versus time, the working electrode
becomes a more potent oxidant or reductant, respectively. Therefore, the working electrode,
which typically consists of a chemically inert conductive material such as platinum, acts as a
donor or acceptor. Electrode’s voltage is adjusted higher or lower linearly, and finally, the
voltage is returned to the original value at the same linear rate. When the electrode becomes
sufficiently negative or positive, a species in solution may gain electrons from the electrode’s
surface or transfer electrons to that surface. As the potential is swept back and forth past the
formal potential, E°, of an analyte, a current flows through the electrode that either oxidizes or
reduces the analyte. Electron transfer is a measurable current in the electrode’s circuitry. The
magnitude of this current is proportional to the concentration of the analyte in solution, which
allows cyclic voltammetry to be used in an analytical determination of concentration. The result
is a cyclic voltammogram (or CV), in the form of a cycle between current and potential, where
potential is plotted on the x-axis, and current is plotted on the y-axis, as in figure 1. In this
experiment, the couple [Fe(CN)6]3-/[Fe(CN)6]4- was used as an example of an electrochemically
reversible redox system to determine the concentration of the unknown solution.

[Fe(CN)6]3-+ e- [Fe(CN)6]4- (2)

Figure1 A) schematic of the three-electrode electrochemical cells. B) CV plot of redox reaction.

Procedure:

0.1M of KCl was prepared in a 250mL volumetric flask, by weighted 1.8604g of KCl and
dissolved with deionized water. A stock solution was prepared from dissolving 0.4160g of
ferrocyanide and 0.3230g of ferricyanide in 100mL of the volumetric flask with the KCl solution
and diluted to the mark. Four standards solutions were prepared in a 25mL volumetric flask by
measuring 2.5mL, 6.25mL. 12.5mL, and 18.75mL of the matrix solution into 25mL volumetric
flask and had been diluted to the mark with KCl solution. VMP2 multichannel potential state
instrument by Princeton research was used to measure the redox potentials for the different
concentrations of the standard solutions and the unknowns.

Results:

 To the mass of KCl solution:

Mass=concentration* volume* molecular weight
=0.1M* 0.25L * 74.5g/mol
= 1.8625g
 To prepare matrix solution:
Mass=concentration* volume* molecular weight
=0.01M* 0.1L * 423.39g/mol
=0.42239g of ferrocyanide
Mass=0.01M* 0.1L* 329.24g/mol
=0.32924g of ferricyanide
 To prepare 1.0M, 2.5M, 5.0M, and 7.5M of standard solutions
C1V1=C2V2
10mM*V=1.0mM *25mL
V=2.5, 6.25, 12.5, and 18.75mL of matrix solution diluted with KCl solution.

<I> vs. Ew e
1_1 mM FFC_GCE_100 mV_-0.8 V to 0.9 V_15.mpr, cycle 2 5_unknow n.mM FFC_GCE_100 mV_-0.8 V to 0.9 V_15.mpr, cycle 2 2_2.5 mM FFC_GCE_100 mV_-0.8 V to 0.9 V_15.mpr, cycle 2 #
3_5.0 mM FFC_GCE_100 mV_-0.8 V to 0.9 V_15.mpr, cycle 2 4_7.5 mM FFC_GCE_100 mV_-0.8 V to 0.9 V_15.mpr, cycle 2

0.2

0.15

0.1

0.05

-0.05
<I>/mA

-0.1

-0.15

-0.2

-0.25

-0.3

-0.35

-0.4

-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8

Ew e /V vs . SCE

Figure2, redox peaks using VMP2 multichannel potential instrument (run on channel 15).

I peak (ox.)/mA I peak (red.)/ mA concentration/ mM

0.0322 -0.03193 1.0
0.06576 -0.06344 2.5
0.1087 -0.1033 5.0
0.1777 -0.1671 7.5
0.1506 -0.1444 unknown
Table1, potential measurements for the standard solutions……..
 0.2
0.15 f(x) = 0.0218534693877551 x + 0.00867612244897961
0.1
0.05
I peak/mA
0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
-0.05 f(x) = − 0.0202938775510204 x − 0.0102669897959184
-0.1
-0.15
-0.2
concentration/mM

I peak (ox.)/mA Linear (I peak (ox.)/mA)

I peak (red.)/ mA Linear (I peak (red.)/ mA)

Figure3, plot diagram of peak height vs. the concentration.

 From ox. Peak we can use the equation to find the concentration of the unknown:
y = 0.0219x + 0.0087
0.1506=0.0219x +0.0087
X=6.5mM concentration of the unknown.

Discussion:

Basically, in this voltammetric technique, three types of electrodes are connected to the
potential, as shown in figure1. The current flowing between the working electrode and the
counter electrode is detected while controlling the electrode potential of the working electrode
concerning the potential of the reference electrode. This is done by detecting the current flowing
between the two electrodes. When an oxidation reaction occurs at the working electrode
interface, electrons flow from the working electrode to the counter electrode from the external
circuit connected to the potential, so current flows from the counter electrode to the working
electrode. The purpose of this experiment was to determine the concentration of an unknown
solution of the complex ferricyanide/ ferrocyanide, using cyclic voltammetry to measure redox
reactions. A calibration curve is constructed based on the anodic/cathodic current peak height
and the anodic/cathodic potential versus standard concentration in the solutions. The
concentration of the unknown solution was determined as 6.5 mM with a percent of error due to
the inaccurate measurement of using a 100mL volumetric flask as 25mL volumetric flask for 5.0
mM concentration standard solution.

 The purpose of using a mediator in the electrochemical experiment is that the mediator
helps to shuttle electrons from the redox site within the solution to the surface of the
electrode at the anode. In contrast, it helps to shuttle electrons from the electrode surface
to the solution at the cathode.
 Other redox mediators that can be used instead of ferrocyanide/ferricyanide are
Hexaammineruthenium, 1,4Naphthaquinone, Benzoquinone, 1,1’-dimethylferrocen.

References:

Cyclic voltammetry - zimmerandpeacock (zimmerpeacocktech.com)

Harris, D. C. Voltammetry. In Quantitative Chemical Analysis, 9th ed; W. H. Freeman &

Company, New York, N. Y. 2015; 412-422.

Wang, J., Analytical Electrochemistry, Chapter 2, John Wiley & Sons (2000)