POLAROGRAPHY

Polarography is a electroanalytical technique in which current voltage relationships are

studied with an electrolysis cell where one of the electrodes is a microelectrode, usually a
Dropping Mercury Electrode (DME).
It was first discovered by J. Heyrovsky in the 1923.
In polarography, the electric potential ( i.e. voltage) of a growing mercury drop (which is
the microelectrode) dipped in an electrolyte containing an electroactive species is varied as
a function of time and the resulting current due to the electrochemical reaction is measured.
One of the virtues of polarography is that solutions as dilute as 10 -8 M can be analyzed and
sample volumes as small as 0.05 ml = 50 microliter can be handled easily.

PRINCIPLE:
As the electrode size becomes much smaller compared to the concentration of the electrolyte
solution, concentration gradient is developed, if electrolysis is carried out without stirring the
electrolyte.

If more than one ions are present in the electrolyte then, ions with lower discharge potentials
will discharge first, in preference to those having higher discharge potential.
 Cd2+

X2+

Voltage Current
(V) (i) mA
Anode + - Cathode Limiting
0.5 ~0 Cd2+2+2+
CdCd Current
0.45 ~0 Current
S2+
S2+
0.4 ~0 S2+ X2+ S2+ (i) mA
S2+
S2+ S2+
0.35 ~0 S2+

0.34 1 Diffusion
id
Current
0.335 1.5 CdCl2
0.33 2
Residual
Current

Voltage (V)
 POLAROGRAPHY
The technique of polarography does not involve complete electrolysis of species (ions)
present in the solution, but the main aim is to study the current-voltage relationships
which are characteristics of the ions present in the electrolyte.

Thus, by studying the current-voltage relationships, we can find out the nature and
concentration of the analyte ions (test ions) present in the electrolyte.

If a steady increasing voltage is applied to cell containing dropping mercury electrode as

cathode, and a pool of mercury as anode, it is possible to get a reproducible current voltage
curve.

The electrolyte is an electroactive dilute solution of the material under examination in a

suitable medium containing an excess of indifferent (inert) electrolyte which is called as
supporting electrolyte.

This supporting electrolyte is useful in carrying the bulk of the current by raising the
conductivity of the solution. However, the discharge potential of the supporting electrolyte
must be very high compared to the electroactive dilute solution of the material under
examination which is known as test ion or test electrolyte.
 POLAROGRAPHY
The plot of current flowing through the cell for varying amount of applied voltage is known as
POLAROGRAM. The instrument used for studying this technique is known as POLAROGRAPH.
APPARATUS:
The dropping mercury electrode (DME) consists
of mercury reservoir from which mercury trickles
down as small drops through a capillary. It acts as
cathode. It is also known as indicator electrode or
microelectrode.
The anode is the reference electrode which
consists of a pool of mercury. Hence its surface
area is very large and hence it cannot be
polarized.- internal electrode
Thus, the potential of the anode remains constant
in medium containing ions capable of forming
insoluble salts such as chloride, sulphate, etc.
In certain cases, saturated Calomel electrode is
used as external electrode. But it is convenient to
use internal electrode.
Inlet and outlet tubes are provided for passing
nitrogen or hydrogen in order to remove dissolved
oxygen from the electrolyte. Since oxygen is also
capable of undergoing reduction, it is necessary to
remove oxygen.
POLAROGRAM
 POLAROGRAPHY
A typical polarographic reduction can be given as:

Oxn+ + ne = Red

Let us consider the chemical changes taking place in the film of the liquid immediately
surrounding the surface of microelectrode. This layer is so thin that its constituents may be
regarded instantaneous equilibrium with the surface of electrode.

The potential of the electrode can then be used in calculating the concentration of reactants in
this layer. The potential is given by:

Ecathode = E0 + (0.059/n) log [Ox]0 / [Red] 0

Ecell = Ecathode – Eanode = E0 + (0.059/n) log [Ox]0 / [Red] 0 - ESCE

log [Ox]0 / [Red] 0 = n (Ecell + - ESCE - E0 )/ 0.059

This equation can be used to calculate the ratio of oxidized species and reduced species at any
instant
 POLAROGRAPHY
A typical polarographic reduction can be given as:

Oxn+ + ne = Red

Ecell = Ecathode – Eanode = E0 + (0.059/n) log [Ox]0 / [Red] 0 - ESCE

Now if the electrochemical reaction is instantaneous, the current will directly depend upon the
rate at which “Ox” particles are transported into the surface.

Thus, we can say i = k’ × rate at “Ox” particles are transported to the electrode surface
i = k’ × k × ([Ox] - [Ox]0)
i = k” ([Ox] - [Ox]0)

If at any time t, the concentration of “Ox” at the surface be [Ox]’0 ,

i = k” ([Ox] - [Ox]’0)

then at time t + dt, i' = k” ([Ox] - [Ox]”0)

When drops falls [Ox]0 = 0, i = k” [Ox] = constant

That is the current reaches limiting value and becomes constant. This current in known as limiting current.
If the value of residual current is very very small then,
(limiting current – residual current) ~ Limiting current = i
 POLAROGRAPHY
Ecell = Ecathode – Eanode = E0 + (0.059/n) log [Ox]0 / [Red] 0 - ESCE
id = k” [Ox]
id = k D 1/2 ox [Ox]
i = k” ([Ox] - [Ox]0)

i = id - k” [Ox]0

[Ox]0 = (id - i )/ k”

i = kr [Red]0

[Red]0 = i / kr
Ecell = E0 + (0.059/n) log [(id - i )/ k”]/ [i / kr] - ESCE
Ecell = E0 + (0.059/n) log [(id - i )/ i] + (0.059/n) log [ kr/ k”] - ESCE

When Ecell = E1/2 , i = id /2

E1/2 = E0 + (0.059/n) log [ kr/ k”] - ESCE
Ecell = E1/2 + (0.059/n) log [(id - i )/ i]
 POLAROGRAPHY
Ecell = E0 + (0.059/n) log [(id - i )/ i] + (0.059/n) log [ kr / k”] - ESCE

E1/2 = E0 + (0.059/n) log [ kr/ k”] - ESCE

Ecell = E1/2 + (0.059/n) log [(id - i )/ i]

k” = k D 1/2 ox and kr = k D 1/2 red

where, k depends on capillary characteristics of the DME and Dox is the diffusion constant of the
particular ionic species and Dred is the diffusion constant of the respective reduced species.

Ecell = E0 + (0.059/n) log [(id - i )/ i] + (0.059/n) log [ D red / Dox ]1/2 - ESCE

E1/2 = E0 + (0.059/n) log [ D red / Dox ]1/2 - ESCE

Ecell = Eobs = Eapplied = E1/2 + (0.059/n) log [(id - i )/ i]

This E1/2 is called as Half-wave potential and is the property of the given redox system and can be used
for its identification.
Types of Current in Polarography

The total current that flow in consists of the

following components:
a) Residual Current,
b) Migration Current and
c) Diffusion Current.

a) Residual Current
The current that flows even when there is no discharge of the test ions is called residual
current.
This current flows due to the supporting electrolyte or impurities. This has to be taken into
consideration while interpreting the polarogram.
This current flows when the applied voltage is not sufficient to cause either /reduction of
analyte.
Residual Current is denoted by ir and it is composed of two types of current: charging
current (ic) and faradaic current (if) .
ir = i c + i f
Charging current (ic) is due to the charging double layer at the surface of mercury drop
Faradaic current (if) is due to the presence of impurities and supporting electrolyte.
Types of Current in Polarography
b) Migration Current
If the concentration of supporting electrolyte is very less, then the migration current is
observed.
When the concentration of supporting electrolyte is less than 25 to 30 times than that of test
ion, migration of these electrolytes under electrostatic attraction influence current observed
is known as Migration Current.
It is the current due to migration of ions caused by the electrostatic field between the two
polarographic electrodes.
The contribution of this component is minimized under experimental conditions by taking
large concentrations of the supporting electrolyte.

c) Diffusion Current
When the applied potential is more negative than the Discharge Potential of the analyte ion,
in presence of excess supporting electrolyte, diffusion current flows through the system and
it is due to analyte ions.
The analyte ion are reduced as soon as they reach the electrode surface. As a result they are
consumed and their concentration in a thin layer of solution in contact with the electrode
becomes zero.
Now, there is a concentration gradient of the analyte ion in the solution and these ions or
molecules diffuse towards the drop from electrical double layers. The current observed due
to flow of this ions is known as Diffusion current.
 DME

Length of the capillary = 5-12 cm

Bore of the capillary = 0.02 -0.05 mm

Some of the advantages of dropping mercury electrode(DME) are as follows:

Mercury form amalgam with most metals.
Mercury has a high hydrogen overpotential.
It provides a identical, smooth, fresh surface for the reaction.
There is no poisoning effect. Each drop remains unaffected and does not become
contaminated by the deposited metal.
Diffusion equilibrium is readily established at mercury-solution interface.
Mercury forms amalgam, with many metals and hence makes ions more reducible.
 DME
Some of the disadvantages of dropping mercury electrode(DME) are as follows:

It is poisonous so care should be taken in its handling.

Surface area of a drop of mercury is never constant.
Applied voltage produces changes in surface tension and hence change in drop size.
Mercury has limited applications in analysis of more positive potential range.

Following care must be taken while using dropping mercury electrode:

Pure and triple distilled mercury should be used in DME.

Tip of DME should be always immersed in water when not in use.
Tip of DME should be cleaned by dipping in nitric acid.
The DME assembly should be mounted vertical on a heavy stand to be free from
vibrations.
It is essential to use clean and dust free tubing while setting the DME.
There should be sufficient mercury in reservoir so that the pressure changes are
negligible.