The goal of this experiment is to use a voltammetric technique to ascertain the iron concentration

of an unknown solution. This experiment teaches us more about this approach and how it
functions.

THEORY:

Voltammetry focuses on the analysis of the voltage-current-time relationship that occurs during
electrolysis in a cell. A voltammogram, which charts the current generated by the analyte against
the potential of the working electrode, serves as the analytical data for a voltametric experiment.
Typically, a cell with three electrodes is used in the technique,

• A working electrode where electrolysis takes place

• A reference electrode used to measure the potential of the working electrode

• An auxiliary electrode that, along with the working electrode, carries the electrolysis current

• Techniques classified as up voltammetry include: • Polarography • Anodic stripping

voltammetry • Cronopotentiometry

This voltametric method is used to determine the quantitative composition of specific ionic
species. In the deposition step of the experiment, the analyte of interest is electroplated on the
working electrode and then oxidized from the electrode in the stripping step. Depending on the
type of electrochemical stripping analysis in progress, current is measured during deposition or
stripping. The data from the analysis can be used to create a voltammogram.

Cyclic Voltammogram
In Figure 1, the scan starts at -0.4V and sweeps forward to more positive, oxidative potentials. At
first, the potential is insufficient to oxidize the analyte (a). As the onset (Eonset) of oxidation is
reached, the current (b) increases exponentially as the analyte is oxidized at the working
electrode surface. The process is under electrochemical control here, with the current increasing
linearly with increasing voltage and the analyte concentration gradient near the electrode surface
within the diffuse double layer remaining constant. As the analyte depletes and the diffuse
double layer expands in size, the current response deviates from linearity. At point c, the current
reaches its maximum (anodic peak current (ipa) for oxidation at the anodic peak potential) (Epa).
More positive potentials cause an increase in current, which is offset by a decreasing flux of
analyte from a greater and greater distance from the electrode surface. The mass transport of
analyte from the bulk to the DDL interface is slow on the electrochemical timescale and thus
does not satisfy the Nernst equation from this point. As the potentials are scanned more
positively, the current (d) decreases until a steady-state is reached where further increases in
potential have no effect. Scan reversal to negative potentials (reductive scan) continues to
oxidize the analyte until the applied potential reaches the value where the oxidized analyte that
has accumulated at the end of the scan is at the electrode surface can be re-reduced (e). The
reduction process is similar to the oxidation process, but with an opposite scan direction and a
cathodic peak (ipc) at the cathodic peak potential (Epc) (f). If the process is reversible, the anodic
and cathodic peak currents should be of equal magnitude but opposite sign.

Randles-Sevcik Equation

The peak current, ip, of the reversible redox process is described by the Randles-Sevcik equation

At 298 K, the Randles-Sevcik equation is:

3 1 1
i p=( 2.69 ×10 5 ) n 2 AC D 2 v 2

where n is the number of electrons, A the electrode area (cm 2), C the concentration (mol·cm-3), D
the diffusion coefficient (cm2·s-1), and v the potential scan rate (V·s-1).

Chemical Reactions

The following reaction takes place inside the instrument for this experiment,
Fe3+ + e- ⇌ Fe2+

APPARATUS AND CHEMICALS:

• Potassium ferricyanide solution (K3[Fe(CN)6)

• Potassium nitrate solution (KNO3)

• Distilled water

• Pipette

• Beaker

• Round bottom flask

• Three electrode setup (voltameter)

PROCEDURE:

The procedure mentioned below is followed while performing this experiment.

1. Six 100 mL volumetric flasks were filled with prepared solutions. 1, 2, 5, 8, 10 mM

Were prepared.

2. solution with unknown concentration of potassium ferricyanide was prepared.

3. 10 mL of 0.1 M potassium nitrate was added to each of the solutions.

4. Rest of 100 mL was filled with distilled water.

5. The solutions were stirred nicely.

6. The solutions were then poured into the three-electrode setup.

Data Collection and Calculation:

 Current vs Potential
8.00E-05

6.00E-05

4.00E-05

1 mM
2.00E-05 2 mM
Current, A

5 mM
8 mM
0.00E+00 10 mM
Unknown

-2.00E-05

-4.00E-05

-6.00E-05
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Potential, V

Figure 1: The cyclic voltammogram found for different concentrations.

Table 1: Observed Data for Analytes.

Voltage at Voltage at
Concentration Anodic Peak Cathodic
Anodic Peak Cathodic
Sample of Analyte Current Peak Current
Current Peak Current
(mM) (µA) (µA)
(V) (V)

1 1 0.267 8.06 0.186 -6.63

2 2 0.266 8.14 0.190 -7.40

3 5 0.273 37.00 0.193 -27.40

4 8 0.276 43.30 0.192 -32.80

 5 10 0.280 62.50 0.191 -46.40

7 Unknown 0.268 21.20 0.192 -16.20

Graphical Representation:

Anodic Peak Current vs Concentration

70.00
60.00
f(x) = 6.01938775510204 x + 0.499183673469386
50.00
Peak Current, µA

40.00
30.00
20.00
10.00
0.00
0 2 4 6 8 10 12
Concentration, mM

Figure 1: Calibration Curve for Anodic Peak Current

Cathodic Peak Current vs Concentration

0 2 4 6 8 10 12
0.00
-5.00
Peak Current, µA

-10.00 f(x) = − 4.38017006802721 x − 1.3491156462585

-15.00
-20.00
-25.00
-30.00
-35.00
-40.00
-45.00
-50.00

Concentration, mM

Figure 2: Calibration Curve for Cathodic Peak Current.

Sample Calculation:

From calibration curve for anodic peak current,

Equation of the straight line, 𝑦 = 6.0881 𝑥 + 0.1506

Where, y = anodic peak current (µA) and x = concentration (mM)
For the unknown sample, anodic peak current, y = 21.20 µA
y−0.1506
From above equation, x= =3.46 mM
6.0881

From calibration curve for cathodic peak current,

Equation of the straight line, 𝑦 = - 4.1147 𝑥 - 2.6967

Where, y = cathodic peak current (µA) and x = concentration (mM)
For the unknown sample, cathodic peak current, y = -16.20 µA
y +2.6967
From above equation, x= =3.28 mM
−4.1147

RESULT:

Anodic peak current 21.20 µA and concentration 3.46 mM and cathodic peak current, y = -16.20
µA and concentration 3.28 mM

Discussion

Except for a few minor differences, the voltammograms for various solutions were very close to
expectations. Minor discrepancies were caused by impurities in iron or a variety of technical
issues. It could also be because each solution was made by hand, so the concentration may not
have been exactly as calculated and some error may have been introduced. The experiment was
carried out using cyclic voltammetry. The term "cyclic" refers to the fact that it returns to where
it began. Voltammetric means using voltage to produce something, which is current. Voltages
were applied to the solution, and as a result of oxidation and reduction, free charges were
produced, and the current was displayed on the monitor as a duck shape in the I vs V graph.

The electrochemical cell first demonstrated moving electrons, followed by diffusion. A non-
faradaic current was discovered for these two segments of the graph. The sudden increase in
current in the I vs V graph was caused by the decomposition of the redox active element. When a
negative charge was close to the surface of an anode, it donated an electron to the anode, which
became a free charge and produced current. It is called forward reaction for an anode and a
similarly reversed voltage reversing current was discovered. Following this, we discovered some
errors for which we did not obtain the actual peak current. The following are the reasons:

Three electrodes were used in the electrochemical cell, and the reference electrode was used to
maintain the electrode potential, but it is possible that the electrode potential was not maintained,
which is why the results were inaccurate. In addition, we used a supporting electrolyte in the
solvent as a redox neutral species to avoid reacting with redox elements. However, there could
be anode reaction. Because of impurities, accurate peak current could not be determined.