Group #

Name: Professor:
Date:

Activity 4
Polarography - Determination of Unknown Concentration of Cadmium

I. Introduction:

Jaroslav Heyrovsky received Nobel Prize in chemistry in 1959 for his discovery and development of the
polarographic methods of analysis. He is known as the father of electroanalytical method. Polarographic method
directly contributed to the development of innovative ideas in electrochemical techniques, instrumentation and
applications.

Jaroslav Heyrovský

Theory:

Voltammetry comprises a group of electroanalytical methods widely employed in analytical chemistry and other
industrial processes. In voltammetry the information about the analyte is obtained from the measurement of
current as a function of applied potential, under the conditions of complete concentration polarization.
Voltammetry is widely used by inorganic, physical and biological chemists for nonanalytical purposes, such as
the studies of the oxidation and reduction process, adsorption process in various media, and electron transfer
processes at chemically modified electron surfaces.

Polarography, is a branch of voltammetry, is the study of the electrolysis of solutions of electrooxidizable and
or electroreducible substances between a dropping mercury electrode (DME) and some reference electrode (RE)
which is saturated calomel electrode (SCE). This falls into the general category of linear-sweep voltammetry. In
this the electrode potential is usually altered in a linear fashion from the initial potential to the final potential.
The only difference in polarography is, the working electrode takes the form of a dropping mercury
electrode(DME). It consists of about 10 cm of a fine capillary tubing through which mercury is forced by a
mercury head of about 50cm. The diameter of the capillary tube is adjusted in such a way that a new drop will
form and breaks at specific timings; usually 2 to 6s. The drop time can be controlled by a mechanical knocker
that will help to dislodge the drop at a fixed time after the drop begins to form. The potential between the
reference electrode and DME is varied and the resulting change in the current flow is measured. Since the linear
sweep method is controlled by combined diffusion or connection mass transport method, the resulting the
current versus potential response i-E curve is known as Polarogram and it is sigmoid in shape(S-Shape). The
position of a wave in a polarogram along the potential axis provides an identity of the substance while the
magnitude of the limiting current provides the concentration variation of this material.

Fig 1.

Since there is an increased flow of current at the starting region of the polarographic wave there is a marked
decrease in the concentration of electro-active substance at the surface of the electrode. With the increase in
voltage and current the concentration of the reactive species reaches to a minimal value near to the electrode
surface. The current is then limited which depends on the diffusion rate of the reacting species from the solution
to the electrode surface. The rapid increase of current at the final stage is due to the supporting electrolyte in
the reaction. Since the concentration of the electrolyte is too large within the applied potential range, it
will prevent the reactive species to reach the electrode by the electrical migration process, and hence the limiting
current is assured as diffusion controlled.

Residual current is the slowly increasing current at the foot of the wave which is non faradaic in nature. The
distance between the limiting diffusion plateau and the residual current is known as diffusion current (id). The
potential at the midpoint of the wave is represented as half-wave potential E1/2, in this region the current is
exactly half its limiting value. The limiting current is found to be the sum of the diffusion residual current. The
wave height can be calculated by subtracting residual current from the limiting current.

Fig 2.

The limiting current (the plateau on the sigmoid), called the diffusion current since diffusion is the most
important contribution to the flux of electroactive material at that point of the Hg drop life, is linked to analyte
concentration by the Ilkovic equation:

Where,

id = average diffusion current during the life of the drop(µA).

D= Diffusion coefficient of the analyte in the medium (cm2/s).
n = Number of electrons transferred per mole of analyte.
m = mass flow rate of Hg through the capillary (mg/sec).
t = drop lifetime(s).
c = analyte concentration (mol/cm3).

Where,
E= applied voltage.
i= current.

II. Objectives
 To discuss the elements or compounds determined with the help of polarography in
different types of samples like food stuff, sea water, fuels, etc.
 To discuss other industrial important determinations for traces or minor constituents.

III. Materials and Reagents

A. Polarographic Instrument.
B. Beaker.
C. 10 mL Pipette.
D. Wash bottle.
E. 100 mL volumetric flask.
F. 1, 2, 3, 4 and 5 mM Cadmium standards.
G. 2 M KCl solution.
H. 0.2% gelatin solution.
I. Distilled water.
IV. Procedure

1. Select the concentration from the list.

2. Click “Load Cadmium Sample” button.
3. Select “Scan Analysis”.
4. Click “Plot Graph”.
5. Select the unknown concentration from the concentration list.
6. Repeat the steps 2, 3 and 4.
7. Enter the concentration values on the worksheet.
8. Plot calibration curve by clicking the “plot” button on the worksheet.

IV. Data and Results

Trial 1

Concentration Drop time Scan Rate Average Diffusion

(mM)
1
2
3
4
5

Trial 2
Concentration Drop time Scan Rate Average Diffusion
(mM)
1
2
3
4
5

V. Interpretation of Results

VI. Documentations:

VII. Conclusion:
VIII. Reference/s: