Date : 05/02/2018

Experiment Number : 14

Experiment Title : A Cyclic Voltametric Study of the Electrochemistry Behavior of

K3[Fe(CN)6]/K4[Fe(CN)6] System

Aims and objectives :

 To use cyclic voltammetry for determination the E° and n values of the [Fe(CN)6]3-
/[Fe(CN)6]4- couple.
 To study the effect of changing in the sweep rate, concentration of electroactive
species, supporting electrolyte, electrode material and irreversibility are evaluated.

Theory :

Cyclic voltammetry(CV) is perhaps the most versatile electro analytical technique

used for the study of electroactive species. It’s versatility combined with ease of
measurements has resulted in extensive use of CV in the fields of electrochemistry,
inorganic chemistry, organic chemistry and biochemistry.CV is often the first experiment
performed in an electrochemical study of an inorganic or organic compound, a biological
material or an electrode surface.

CV consists of cycling the potential of an electrode, which is immersed in an unstirred

solution, and measuring the resulting current. The potential of the working electrode is
controlled vs. a reference electrode such as an SCE or Ag/AgCl electrode. The controlling
potential that is applied across these two electrodes can be considered as an excitation
signal. The excitation signal for CV is a linear potential scan with a triangular waveform as
shown below.

This triangular potential excitation signal sweeps the potential of the electrode between
two values. The excitation signal in above figure causes the potential to first scan negatively
from 0.8V- 0.2V vs SCE at which point the scan direction is reversed, causing a positive scan
back to the original potential of 0.8V. The scan rate, as reflected by the slope, is 50mV/s. A
second cycle is indicated by the dashed line. Modern instrumentation enables switching
potentials and scan rates to be easily varied.

A cyclic voltammogram is obtained by measuring the current at the working electrode

during the potential scan. The current can be considered as the response signal to the
potential excitation signal. The voltammogram is a display of current (vertical axis) versus
potential (horizontal axis).

The important parameters of a cyclic voltammogram are the magnitudes of the anodic peak
current (ipa), cathodic peak current (ipc) , anodic peak potential (Epa) and cathodic peak
potential (Epc). These parameters are labelled in above figure. One method for measuring ip
involves extrapolation of a base-linecurrent as shown in the figure. The establishment of a
correct base line is essential for the accurate measurement of peak currents. This is not
always easy, particularly for more complicated systems.

A redox couple in which both species rapidly exchange electrons with the working electrode
is termed an electrochemically reversible couple. The formal reduction potential for a
reversible couple is centered between Epa and Epc :
Epa +Epc
𝐸° =
2
The number (n) of electrons transferred in the electrode reaction for a reversible couple can
be determined from the separation between the peak potentials:

∆E=Epa-Epc=0.059/n

Thus, a one-electron process such as the reduction of [Fe(CN)6]3-to [Fe(CN)6]4- exhibits a Ep of

approximately 0.059V. Slow electron transfer at the electode surface ‘irreversibility’ causes
this peak separation to increase.

The peak current for a reversible system is described by the equation for the forward
sweep of the first cycle

ip = 2.69 x 105 n3/2 A D1/2 C Ʋ1/2

Where ;

ip = peak current (A)

n = electron stoichiometry
A = electron area(cm2)
D = diffusion coefficient(cm2/s)
C = concentration(mol/cm3)
Ʋ = scan rate(V/s)

Accordingly, ip increases with Ʋ1/2and is directly proportion concentration. The relationship

to concentration is particularly important in analytical application and in studies of
electrode mechanisms. The vales of ipa and ipc should be close for a simple reversible (fast)
couple.
This is:

ipa
=1
ipc

However, the ratio can be significantly influenced by chemical reaction coupled to the
electrode process.
Pre Lab Questions :

1) Diffusion – Transportation of ions in a concentration gradient defined as diffusion.

Migration – Occurs when a charged particle in solution is attracted to or repelled from an

electrode that carries a surface charge.

Convection – Occurs when we technically mix the solution. The most common form of
convection is stirring the solution.

2) Diffusion

3) To avoid migration we can use a supporting electrolyte ant by avoiding stirring we can
get rid of convection.

4) If the electrolytes reduction potential is much closer to that of oxygen’s reduction

potential, purging with nitrogen should be done. From this we can deoxygenate the
solution. O2(g) + 2H+(aq) + 2e → H2O2(aq)

O2 + e → O2-

1 2-
O + e → O2-
2

5) Concentration polarization is the polarization of an electrolytic cell resulting from

changes in the electrolyte concentration due to the passage of current through the
electrode/solution interface.

Ideally polarisable electrode is an electrode characterized by an absence of net current

between the two sides of the electric double layer.
Procedure :

Solution of 100 mmol dm-3 of potassium ferricyanide was prepared in 0.1 mol dm-3
potassium nitrate stock solution. Similarly, a solution of 4 mmol dm-3K3[Fe (CN)6] was
prepared in 0.1 mol dm-3Na2SO4. From the prepared K3[Fe(CN)6] solution which was diluted
by KNO3, series of solutions was prepared in to 100 mL volumetric flasks and making up to
the mark by adding KNO3.

The cell was filled with the respective solutions and the electrodes were fixed in such a way
that their tips were immersed. Before fixing the electrodes, they were washed with
deionized water. The glassy carbon was first polished using alumina on a micro cloth pad
and then rinsed with deionized water.

The parameters were set and the CVs were obtained for each of the solution of the series.

A study of the effect of scan rate CV measurements was done by varying the scan rate for
the 4 mM solution of K3[Fe(CN)6] In KNO3. Next a study of the effect of the supporting
electrolyte on CV measurements was done by recording the voltammogram of the 4
mmoldm-3 K3[Fe (CN)6] prepared in 0.1 moldm-3 Na2SO4.

Results:
Cyclic voltammograms for concentration series of K3[Fe(CN)6] with KNO3 as a supportive
electrolyte.
Cyclic voltammograms for different scan rates of 4 mM of Fe3+
Calculation :

Preparation of solutions.

 0.1 moldm-3 KNO3 solution (Stock solution)

Mass of KNO3 = 0.1 moldm-3×103×10-3dm3×101.10gmol-1
= 10.11 g

10.11g of KNO3 was dissolved in a 1 L volumetric flask and top up with deionized water.

 100 mmoldm-3 K3[Fe(CN)6].

Mass of K3[Fe(CN)6] = 100 × 10−3mol dm−3×100×10−3dm3 ×329.24 gmol−1
= 3.29 g

3.29 g of K3[Fe(CN)6] was dissolved in a 100 ml volumetric flask and top up with
prepared KNO3 solution.

 0.1 moldm-3 Na2SO4 solution.

Mass of Na2SO4 = 0.1 mol dm−3×100×10−3dm3 ×142.04 g mol−1

= 1.42 g
1.42 g of Na2SO4 was dissolved in a 100 ml volumetric flask and top up with deionized
water.

 4 mmoldm-3 K3[Fe(CN)6] solution.

Mass of Na2SO4= 4 × 10−3mol dm−3×100×10−3dm3 ×329.24 g mol−1

= 0.13 g

0.13 g of K3[Fe(CN)6] was dissolved in a 100 ml volumetric flask and top up with
prepared Na2SO4 solution.
2.0, 4.0, 6.0, 8.0 and 10.0 mM K3[Fe(CN)6] solution series were prepared by taking 2.0, 4.0,
6.0, 8.0 and 10.0 mL of K3[Fe(CN)6] and top up the 100 mL volumetric flask by KNO3.

Determination of E° and n value

Epc = 0.1700 V
Epa = 0.2546 V
Epa +Epc
E0 = 2

0.2546 V +0.1700 V
= 2

= 0.2123V
0.059
∆E = Epa - Epc = = 0.2546V −0.1700V = 0.0846V
n
0.059
0.0846 V = n

n =0.7
Calculation of ipc and ipa for the various scan rates

ipc/µA ipa/µA υ/V υ1/2

-27.1155 19.3608 0.020 0.141421

-38.6982 23.9841 0.050 0.223607
-57.2348 41.4138 0.100 0.316228
-60.9491 35.1166 0.150 0.387298

ipc and ipa vs Ʋ1/2

60
y = 80.309x + 8.5151
R² = 0.7286
40

20

0 Ʋ1/2
ipc /ipa

0 0.1 0.2 0.3 0.4 0.5

-20

-40

-60
y = -145.88x - 7.03
R² = 0.9678
-80
Determination of unknown concentration

[Fe(CN)6]-3/mM ipc/µA ipa/µA

2.0 8.8890 -13.7380
4.0 19.3608 -27.1155
6.0 26.5467 -40.0618
8.0 39.4470 -53.4141
10.0 44.2296 -60.9484

ipc vs [Fe(CN)6]-3
50

40

30
ipc/µA

20 y = 4.5384x + 0.4644
R² = 0.9856
10

0
0 2 4 6 8 10 12
[Fe(CN)6]-3/moldm-3

ipa vs [Fe(CN)6]-3
0
0 2 4 6 8 10 12
-10

-20

-30
ipa/µA

y = -6.036x - 2.8397
-40 R² = 0.9914

-50

-60

-70
[Fe(CN)6]-3/moldm-3

Concentration of the unknown sample = 6.0 moldm-3

Post Laboratory Questions :

1. The working electrode should not easily polarized.

The working electrode should not react.
Eg: Pt, Au and graphite electrodes.
2. Must have a known constant potential and should be stable for a long period of time.
3. Deviation of the measured potential due to IR drop caused by the resistance of the
solution and cannot measure the current produced simultaneously while scanning the
potential.
4.

Working electrode - adjust potential for analyte which to be oxidize or reduce.

Reference electrode - to measure the potential of the working electrode.
Counter electrode - which is complete electric current path way.

5. There is no current flow through working electrode and reference electrode. So there
won’t be an IR drop. Using the auxiliary electrode enable to measure the current.

Discussion :

In electrochemical experiments, the reactions of interest occur at the surface of the working
electrode. Therefore we are interested in controlling the potential drop across the interface
between the surface of the working electrode and the solution.

Voltammetry measurements are carried out using an electrochemical cell made up of

three electrodes immersed in a solution containing the analyte and an excess of a
nonreactive electrolyte called the supporting electrolyte. One of the three electrodes is the
working electrode, which is typically made of platinum, gold, silver or palladium etc. The
redox process occurs at this electrode. The second electrode is the reference electrode,
which provides calibration for the applied potential. Examples of commonly used references
are the normal hydrogen electrode, Ag/AgCl electrode, and calomel electrode. The third
electrode is the counter electrode, which is often a platinum wire that simply serves to
conduct electricity from the signal source through the solution to the other electrodes.

The function of the supporting electrode is,

 Provide counter ions for the analyte to protect it

 Carry out the electrons from analyte to the electrode surface
 Carry out the electrons across the electrode surface

In this experiment first we should deoxygenate the cell before doing the experiment. But if
the reduction potential of the compound is away from the oxygen reduction no need of
deoxygenate the cell.

Solution series Electrodes

Electrode polishing

Three electrode system