‫‪POLAROGRAPHic‬‬

‫‪Advances‬‬
‫استاد ‪:‬آقاى حكيم فرجى‬
‫نامه دانشجو ‪ :‬حنان ناصر حسين‬
‫‪ ‬‬
‫تاريخ ‪: may- 2021-29‬‬

‫‪1‬‬
 INTRODUCTION
Polarographic wave*
Quantitative analysis and the covic*
equation
FACTORS AFFECTING THE DIFFUSION*
CURRENT
THE DROPPING MERCURY*
ELECTRODE (DME)
The dropping mercury electrode has*
several advantages
DISADVANTAGES OF DME*
INSTRUMENTATION*
Polarographic mapping methods*
POLAROGRAPHIC EQUATION*
APPLICATIONS OF POLAROGRAPH*
References*

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 Summary of the presentation

The presentation contained an introduction and the importance of the

POLAROGRAPHY technique and for the purpose of identifying this
technique by revealing the strengths and weaknesses and the reason
for the use of micro-electrodes in all voltmeters and what the subject of
polarography and the scientific basis for it and identifying some of the
terms and here lies the importance of the presentation through the
identification of the DMC device, which is one of The most important
methods used in voltmetryIt is considered one of the most important
simple, sensitive and reliable analytical methods used in
electrochemistry to measure voltage and some books and articles have
. ,been used to identify this technique

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INTRODUCTION
POLAROGRAPHY; The polarographic method of analysis was
developed by Jaroslav Heyrovsky in 1922
which is the earliest voltammetric technique introduced. He received
Nobel Prize in
for developing this technique using dropping mercury electrode 1952
as the working
electrode. He called the recorded current-potential curves as
polarograms and
.introduced the term polarography
is one of the widely used voltmetric methods and is characterized
by its use of Dropping mercury electrodo as a guide

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The basic idea was to pass the current between two 
,electrodes
.Polarographic Analysis
Is a method of analysis based on the measurement of current
electrolysis of an electroactive species at a given electrode
.potential under controlled conditions
 
It is the branch of voltammetry where the working electrode is a
dropping mercury electrode (DME) or a static mercury drop
electrode (SMDE), which useful for their wide cathodic ranges
and renewable surfaces

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 POLAROGRAPH
The apparatus which measures the value of
current flowing through the cell at any given
applied voltage is called Polarography. The
basic apparatus with the essential parts required
to obtain current-voltage data are shown in
.above figure
Polarographic measurements require the means
for varying the voltage continuously
.over the range from 0 to 3 volts
The resulting current flowing through the cell
is measured with the help of galvanometer. The
current grows with the size of the drop due to
increase in reduction at the surface and
becomes zero when the drop falls down in the
cell. This is indicated by the movement of the
.spot of galvanometer on the scale

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 POLAROGRAM
This figure represents a typical or an
ideal polarogram which is obtained
upon reducing a substance
electrolytically at the dropping
mercury cathode. The usual method of
plotting the current-voltage curve
(polarogram) is to plot the applied
potential (emf) as abscissa reading in
increasing negative values on the right
and the current in microamperes as the
ordinates. The step shaped or ᶘ shaped
curve is obtained. It is also called a
polarographic wave or polarogram.
This type of curves is obtained only if
a large excess of supporting electrolyte
is used in the solution to be
analysed. :The polarographic wave
may be considered to consist of three
parts
A-B portion (ii)B-C portion and)i(
.(iii) C-D portion

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In the portion A-B, the current is small)i(
and varies linearly with the applied
voltage. The applied potential is
insufficient to reduce the metal ions in the
solution. This is residual current. It is
carried out by the supporting electrolyte
and the impurities present (ii)Near the
point B, the decomposition potential of the
metal ion is reached.The reduction of the
metal ion begins and the current begins to
increase sharply with the increasing
applied voltage. This forms of a
polarographic curve or wave. This portion
.B-C represents the diffusion current
Along C-D no increase in current is)iii(
observed at higher potential. At point “c’
the rates of reduction and transport of the
reducing cation at the surface of the
electrode is nearly same. The current is
limited by the rate of transport of reducible
cation to the electrode. Hence, this portion
.C-D is of limiting current
.in the sample

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 polarogram
The polarogram is characterized by the following
parameters
Residual current-
Limiting current-
Diffusion current-
Half wave potential (E1/2)-
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 Polarographic wave
 

 
We have shown that the
polarographic data can be obtained
from current measurements as a
function of the applied voltage in an
electrolyte cell consisting of a
polarizable electrode (micro-
electrode) with another non-polarized
electrode, and the two current-
voltage curves are called a
polarogram, which gives descriptive
information about the solution.
Submerged in it the electrodes. That
this curvature corresponds to a wave
in shape and is also known as a
polaroscopic wave Polarogram A is
0.5mM Cd(II) in 1M HCI Polarogram
B is IM HCl, supporting
electrolyte

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 FACTORS AFFECTING
POLAROGRAPHIC WAVE
:Residual current.1
.Residual current = condenser current +Faradic current
In polarographic wave, the small current flows in the
beginning, this is known as residual current and is
carried by the supporting electrolyte and impurities
present in the sample. This increases linearly with
applied voltage even in presence of oxygen free
solution. It cannot be only due to the reduction of
impurities. It is considered to be due to (i)Condenser
:Migration current.2
The electroactive substance can reach the DME
electrode surface by electrostatic forces of attraction and
.by the influence of concentration gradient
When the electric field is applied, the positively charged
ion will move to words the cathode under the influence
of these forces. This causes increase in cathodic
diffusion. It is expected that the cation under study
should migrate to words the cathode under
concentration gradient and not by electrostatic forces of
attraction. This effect of migration current is limited by
adding relatively large quantities of inert electrolyte like
.KCl into the solution
.current (ii)Faradic current

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:Diffusion current.3
When an excess of supporting electrolyte is present
in the solution, the electrical force on the reducible
ions is nullified. This is because the ions of the added
salt carry practically all the current and potential
gradient is shortened to a region close to the surface
of the electrode and cannot affect the reducible ions.
Under these conditions, the current is almost all due
to diffusion process governed by the concentration
gradient of the test cation and called as the diffusion
.current
A- Negatively charged drop of mercury
B- Region of almost zero concentration of test
cations due to reduction process and
.dissolution in mercury
C-Region of large concentration of test cation
.in the bulk of the solution
Representation of migration of cation – )+(
towords the drop of mercury under the
.influence of concentration gradient

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 Quantitative analysis and the covic
equation
The analytical significance of Polarographic wave in quantitative analysis can be described
by an equation
. In 1934, ILKOVIC was able to arrive at a mathematical relationship that showed that the
magnitude of the diffusion current is directly proportional to the reduced class concentration
at the dme pole under favorable conditions. The general Kovitch equation at the degree of
25 is written
As follows:
Taif= 607 neDé m2/3 + 1/6 ... (1-11)
Where :
lair = rate of diffusion current in microamps over the life of the mercury drop.
607 = A constant originating from 77 and a constant, individual and density of mercury n =
the number of electrons involved in the microelectrode reaction.
D = diffusion coefficient of the material under examination cm 2 / s.
c = concentration of the electrically active substance mmol / L.
m = the mass of mercury flowing through the capillary mg / s,
t = time between two successive drops of mercury (seconds).

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FACTORS AFFECTING THE DIFFUSION CURRENT

CONCENTRATION of Electroactive Substance : Diffusion current is *
directly proportional to concentration of the electroreducible ions. This
forms the basis quantitative analysis. i.e, if concentration is less, then
diffusion current is less . If concentration is more then diffusion current
also more
The Capillary Characteristics and the Factors Affecting Them*
TEMPERATURE*
Diffusion of ions is being affected by temperature hence diffusion current
also varies with respect is temperature (directly proportional)

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 In polarography,
the microelectrolysis is carried out with the help of two electrodes,
- These two electrodes are
-Reference electrode-1
This electrode has a comparatively large
surface area. This is the non polarisable
(constant potential) electrode. This is
generally acts as an anode and may be pool
.of mercury or saturated calomel electrode
—Indicator electrode.2
This electrode has a comparatively small
surface area. This is the polarisable
electrode. An electrode is considered to be
polarized when it adopts a potential
impressed upon it with little or no change
of current. This is generally functioning as
a cathode and is dropping mercury
electrode (DME). This is also called as
.microelectrode or working electrode

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 Polarographic Cell

Polarographic Cell

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 Polarographic Cell
A polarographic cell consist of a small easily polarisable microelectrode or indicator electrode, a
large non-polarisable reference electrode and the solution (electrolyte) to be analysed

The Electrolyte Solution

The Cathode
The dropping mercury electrode acts as a
cathode. It acts as an indicator electrode. In this
electrode, mercury is forced by a gravity
through a fine capillary
so that continuous stream of identical drops are
given out. The life time of a drop is 3 to 6
.second and its diameter is about 0.5 mm
The Anode
Large amount of mercury is placed at the bottom
of the cell and the electrolyte solution is placed
above it. This pool of mercury acts as an anode
and its area is comparatively large. It is non-
polarisable electrode. Its potential remains almost
constant. It acts as a suitable non-standardised
reference electrode. Its exact potential will depend
the nature and the concentration of the supporting
electrolyte. Saturated calomel electrode can also
.be employed as a reference electrode
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The polarographic cell contains the solution of the
substance to be analysed (electrolyssed) and the
large amount of potassium chloride. Here KCl acts
as a supporting electrolyte whose concentration is
at least 1000 times larger than that of analyte.In this
solution, solution of maximum suppressor
.(e.g.gelatin ) is added
Removal of Oxygen from the
Solution
The inert nitrogen gas is bubbled through the
sample solution in a polarorgaphic cell. Inlet and
outlet tubes are provided to the cell, for passing N2
gas and expelling dissolved oxygen from the
solution respectively.N2 gas is bubbled through the
solution before but not during an actual
measurement. A nitrogen atmosphere is maintained
.above the solution during the measurement
 THE DROPPING MERCURY
ELECTRODE (DME)
This small polarizable electrode is
produced by passing a stream of
mercury through a
resistance glass capillary having a
very fine bore of 0.05–0.08 mm
internal diameter
and 5−9 cm long. The drops fall at a
steady rate of 3−5 sec per drop and is
adjusted
under a head of 40−60 cm of mercury.
The current oscillates between a
near-zero
value as drop falls from the capillary
to a maximum value as the surface
area of a new
drop increases

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WORKING
*Electrolyte is a dilute solution of electro active material to be analyzed in
a suitable medium containing excess of supporting electrolyte.
*Consider a Polarographic cell, containing a solution of cadmium
chloride, to which an external E.M.F is applied.
* Mercury drops form at the end of a capillary delivery tube, grow with
time to a certain size, and then fall off. Typical drop lifetime is on the
order of 5 seconds

* Electrochemistry is done on the mercury drop (e.g. amalgam

formation) and the electrode is regenerated following the loss of the
each droplet
*The positively charged ions present in the solution will be attracted
towards the mercury drop of the dropping mercury electrode (DME).
*The total current flowing through the cell may be regarded as being the
“ sum of the electrical and diffusive forces.”
*When the applied voltage is increased and the current is recorded a
graph will obtained

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 The dropping mercury electrode
The dropping mercury electrode has several advantages:
DISADVANTAGES OF DME
1- Its surface area is reproducible with a given capillary
2- The constant renewal of the electrode surface eliminates passivity or
poisoning effects. 1- The area of the microelectrode is constantly changing as the
3- The large hydrogen overpotential on mercury renders possible the
deposition of substances difficult to reduce such as aluminium ion and size of the drop changes
manganese (II) ion. (The current-potential curves of these ions are not 2- Mercury may be easily oxidized and thus limits the feasible
accessible with platinum .
4- Mercury forms amalgams with many metals. range of electrode
5- The diffusion current assumes a steady value immediately and is 3- The capillary may be easily plugged and thus care must be
reproducible.
6- The surface area of the electrode can be calculated from the weight of taken to avoid touching the tip of the capillary with any foreign
the drops.
material
The dropping mercury electrode therefore is useful over the range + 0.3
to − 2.0 V vs. SCE. Above + 0.4 V mercury dissolves and gives an
anodic wave due to oxidation to mercury (I) ion. At potentials more
negative than − 1.8 V vs SCE visible hydrogen evolution occurs in acid
solutions and at − 2.0 V the supporting electrolytes of alkali salts begin
to discharge

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 INSTRUMENTATION
The basic apparatus for polarographic analysis
is given in fig. The commonly
used polarographic cell has an external
reference electrode and is the H-cell. It consists
Oxygen present in sample solution is removed
by passing nitrogen or using alkaline pyrogallol
solution. Maximum suppressors are added in the
.req conc
of two compartments, one containing the
solution to be studied and the other
containing reference electrode. These
compartments are separated by a cross-
member
filled with 4% agar-saturated potassium
chloride gel, which held in place by a
medium–porosity sintered disc. The second
compartment is the solution compartment
into which DME is inserted and this has N2
.inlet and outlet provision
This simple recording polarogram unit has a
potentiometer, ‘P’ by which any emf upto 3
Volts may be gradually applied to the cell. ‘R’
.is a pen recorder and ‘V’ is voltmeter
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Polarographic mapping methods
Direct comparison_1
 
It includes two separate tow polychram records, one for the unknown substance group and
the other for measuring solutions of the same ions of the unknown substance under the same
conditions. Using the kovitch equation, the ratio C / Taif - can be calculated from the
measured solution polarocram. Then the concentration of the unknown is calculated by
.multiplying this ratio by the velocity of the unknown solution diffusion current

Calibration curve_2
 
In it, the values Taif of ar are measured for two or more solutions with a known concentration
of the same type of substance under examination (the unknown). calibration curve is drawn
between the Taif values and the concentrations, and the concentration of the unknown
substance solution can be extracted from knowing its Taif value under the same experimental
.conditions for the calibration curve

Standard addition_3
This method involves recording polarocram for a specific volume (V1) of the solution under
examination of unknown concentration (C1) to find out its diffusion current (I1). In a second
process, a known volume of (V2) is added to (V1) a solution of a known concentration (C2) of
.the same type under examination
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 POLAROGRAPHIC
EQUATION
There is an analytical importance of the Polarographic
wave in the descriptive analysis
The voltage at which the sudden rise in polarocram has
a special value for the varieties present in the solution,
and it is an independent value from the concentration of
the variety under analysis. The voltage at which this
point of inflection is obtained is called the half-wave
potential because the value of the current at this point
is half the magnitude of the propagation current, and
.this voltage is symbolized by (E)
 
The half-wave voltage (E) is a characteristic of a
material that suffers oxidation or reduction on the micro-
electrode and this amount can be used for a qualitative
diagnosis of materials. Its value for a specific substance
depends on the nature of the electrolyte solution
.dissolved in it and the electrolyte dissolved in it
It represents the potential as a function of
.current at any point on the polarographic wave

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24
 Applications of Polarography
Q u a l i t a t i v e A n a l y s i s. 1
—a)Detection of metal ions
The metal ions in a mixture can be detected if their half wave potentials differ by an
appreciable magnitude. Ex-unknown solutions 1,2 and 3 are
polarographically analysed in 1M KCl solution and against SCE and their
polarograms are obtained

—b)Detection of Organic compounds

A very large number of electrode reactions of organic compounds and their
half wave potentials are known. The values of half wave potentials are used
for their detection. The functional groups like ketone, aldehyde, alkene,
nitrite, azo,azoxy, nitro, hydroxylamine etc.are reducible in polarographic
technique. Ex- When benzaldehyde is reduced in basic solutions, a wave is
obtained giving half wave potential equal to -1.4 volts. During the reaction,
.benzaldehyde converts into benzyl alcohol
—c)Detection of trace amounts of electroactive substances
Polarography has special importance in environmental studies, forensic
analysis and medico legal cases, for the detection of toxic elements in
.trace amounts in ppm to ppb level

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 Quantitative Analysis.2

A-Quantitative analysis and the covic equation

B-UNKNOWN CONCENTRATION (CUNKN) OF
—CATION

The polarograms of different solutions of

known concentration (say solution 1 to 6) and
that of given sample of unknown concentration
are obtained experimently under identical
.conditions

Calibration curve (Id vs concentration) is

plotted after knowing the diffusion current
values of standard solution and their
concentrations. The diffusion current value of
unknown [Id (unkn)] is found out with the help
.of calibration curve

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:C-SIMULTANEOUS DETERMINATION OF CATIONS FROM THEIR MIXTURE

It is possible to determine concentration of two or more

cations in their mixture simultaneously. Ex-consider a
mixture of Pb2+ and Zn2+ as a sample. A polarogram of the
.sample is obtained

Using suitable supporting electrolyte and reference electrode

and diffusion current values of two cations are found out.
The standard solutions of each of Pb2+ and Zn2+ are treated
in similar way. Two separate calibration curves are plotted
for Pb2+ and Zn2+.. Knowing the Id (Pb2+) and Id (Zn2+)of
the test solution experimently and referring to their
calibration curves, the individual concentration of Pb2+ and
.Zn2+ can be determined simultaneously
:D e t e r m i n a t i o n o f d i s s o l v e d o x y g e n . 3

Dissolved oxygen in water or aqueous solution is readily reduced at DME. Such solutions containing
dissolved oxygen show two distinct ways.This type of polarographic estimation of oxygen has been
.widely used in biochemistry for the study of respiration of green algae, photosynthesis etc

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References
 
Gurdeep.R. chatwal,sham k.anand, instrumental method of chemical -1
.analysis,himalaya publishing house, 2008,p.no.2.482-2.497
 
Hovert H.willard, lynne L.merritt,john A.dean,frank A.settle,jr.,instrumental -2
.method of analysis CBS publishers 1986,p.no.732-750
 
Kenneth A. connors,e textbook of pharmaceutical analysis, third-3
.edition,wiley india,p.no. 334
 
Danniel christein, analytical chemistry, 2nd edition, wiley -4
 
.india,p.no. 274
In book: Progress on Drinking Water Research (pp.171-198); Publisher: ... -5
 .In polarography and voltammetry, different working mercury
 

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