POLAROGRAPHY

Electro - analytical technique

M. Sc. Paper 4103 – A

 DEFINATION

!  Polarography is a method of analysis in which the solution to be

analyzed is electrolyzed under diffusion controlled condition.

!  The graph of current (generated) as a function of voltage

(applied) is known as POLAROGRAM.
The technique is known as POLAROGRAPHY.

!  It can be used for qualitative as well as quantitative analysis

(inorganic, organic and biological samples) without the
requirement of prior separation step (in most of the cases).
 HISTORY AND BACKGROUND
Polarography was created by Jaroslav Heyrovsky in Feb. 10th 1922

1922 1959

On December 10th 1959 he was awarded the Nobel Prize.

 INTRODUCTION
•  The basic idea was to pass the current between two electrodes,
one having large surface area and other having very small
surface area. Both electrodes can be of mercury metal.

•  The large electrode can be a pool of mercury at the bottom of

the cell.

•  Small electrode is a drop of mercury coming out of a very fine

capillary tube, DME.

•  Thus, if a steady voltage is applied to such a cell, it is possible

to construct a reproducible current voltage curve.
DROPPING MERCURY ELECTRODE

DME
Polarography uses regularly renewed mercury drop electrode for analysis
 INSTRUMENTATION

Polarography uses regularly renewed mercury drop electrode for analysis.

 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.

!  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.
CURRENT VOLTAGE CURVE
 ADVANTAGES OF DME
!  Its surface area is reproducible with single capillary.

!  The surface area can be calculated from the weight of

the drops.

!  Mercury possesses the property of forming amalgams

with many metals and therefore lowers their
reduction potential.

!  High over voltage of hydrogen on mercury makes

possible the deposition of ions which are difficult to be
reduced on many other metal electrodes.
 DISADVANTAGES OF DME

•  The area of the microelectrode is constantly

changing as the size of the drop changes

•  Mercury may be easily oxidized and thus limits

the feasible range of electrode

•  The capillary may be easily plugged and thus

care must be taken to avoid touching the tip of
the capillary with any foreign material.
 TYPES OF POLAROGRAPHY

!  Differential Pulse Polarography

!  Pulse Polarography

!  AC Polarography
 JAROSLAV HEYROVSKÝ
“The trends of polarography”, *Nobel Lecture, December 11, 1959

Polarographic spectrum showing seven cations in the solution

R. E. Cu Pb Cd Zn Mn Al Ba

1959, E1/2 0.00 -0.37 -0.62 -1.00 -1.40 -1.64 -1.94

2009, E1/2 4.44 4.07 3.82 3.44 3.04 2.80 2.50

SCE = 4.44
 TYPICAL POLAROGRAM

A – 5x10-4 M Cd+2 in 1 M HCl, B – 1 M HCl

•  Residual current, ir, (charging, condenser)
•  Diffusion current, id or iL, (limiting)
•  Half-wave potential, E½
INSTRUMENTATION
 DIFFERENTIAL PULSE POLAROGRAPHY

•  Differential pulse polarography is a polarographic

technique that use a series of discrete potential
steps rather than a linear potential ramp to
obtained the experimental polarogram

•  The differential current is plotted vs. the average

potential to obtain the differential pulse
polarogram,
NORMAL PULSE POLAROGRAPHY

•  In normal pulse polarography (NPP) each step

begins at the same value and the amplitude of each
step increases in small increments.

•  When Hg drop is dislodged from the capillary the

potential is returned to initial value in preparation
for a new step
RECORDING POLAROGRAPHS
!  This type of Polarography records current-
voltage curve automatically.

PROCEDURE
!  The applied voltage is increased at a steady
controlled rate by means of a constant speed
motor
!  Simultaneously the chart paper is moved at
steady rate.
!  The recording pen move in accordance with the
current passing through the cell
FACTORS AFFECTING LIMITING CURRENT

!  Kinetic current

!  Residual current

!  Diffusion current

!  Migration current
!  RESIDUAL CURRENT:
RESIDUAL CURRENT = Faradic Current + Condenser current

!  MIGRATION CURRENT:
The electro active material reaches the surface of electrode by
two processes

"  The first involves the migration of charge particles in the

electrical fields caused by the potential difference existing
between the electrode surface and the solution.

"  The second involves the diffusion of particles.

!  DIFFUSION CURRENT:
Diffusion current is directly proportional to
the concentration of the electro active
material.
!  KINETIC CURRENT:
The limited current may be affected by the
rate of non electrode reaction called kinetic
current.
Steps in an electron transfer event
!  O must be successfully transported from
bulk solution (mass transport)
!  O must adsorb transiently onto electrode
surface (non-faradaic)
!  CT must occur between electrode and O
(faradaic)
!  R must desorb from electrode surface
(non-faradaic)
!  R must be transported away from
electrode surface back into bulk solution
(mass transport)
APPLICATIONS OF POLAROGRAPHY

INORGANIC COMPOUNDS:
Polarography can be used for estimation
of cation and anions.

DETERMINATION OF TRACE
ELEMENTS:
Polarography can be used for
determination of trace elements
e.g CO, Al, Cu, Ni, etc
APPLICATION TO ORGANIC COMPOUND:
For quantitative identification of compounds and
for quantitative analysis of mixtures.

DETERMINATION OF DISSOLVED OXYGEN:

The determination of dissolved oxygen in aqueous
solution or organic solvents can be carried out
successfully with the help of polarography.
DETERMINATION OF PLANT CONTENTS:
A polarographic analysis of content of essential oils.
STUDIES OF COMPLEXES:
Polarography is powerful tool for study of
composition of complexes
if the sample metal ion and
complex of that metal ion in the
same oxidation state.
APPLICATION TO PARMACEUTICALS:
! Oxidation process of medicines like
epinephrine and nor-epinephrine.
! The use of A.C. polarography has proved
advantageous in the analysis of tetracycline.
ANALYSIS OF BIOLOGICAL SYSTEMS:

The possibility of being able to determine vitamins,

alkaloids, hormones, terpenoid substances, and
natural coloring substances has made polarography
useful in analysis of biological systems
 DETERMINTION OF PESTICIDE AND
HERBICIDE:

Polarography is also used for the determination of

pesticides or herbicides residues in foods.
 VOLTAMMETRY
•  The measurement of variations in current produced by
variations of the potential applied to a working
electrode.

Polarography

•  Heyrovsky (1922): first Voltammetry experiments using

a dropping mercury working electrode

•  In Voltammetry, once the applied potential is sufficiently

negative, electron transfer occurs between the electrode
and the electroactive species:
Cu2+ + 2e → Cu(Hg)
 WHY ELECTRONS TRANSFER

Reduction Oxidation

EF Eredox
E E
Eredox E
F

"  Net flow of electrons from "  Net flow of electrons from
M to solute solute to M
"  Ef more negative than Eredox "  Ef more positive than Eredox
"  more cathodic "  more anodic
"  more reducing "  more oxidizing
 MASS TRANSFER
•  Migration – movement of a charged particle in a potential field.

•  Diffusion – movement due to a concentration gradient.

If electrochemical reaction depletes (or produces) some species at the
electrode surface, then a concentration gradient develops and the
electroactive species will tend to diffuse from the bulk solution to the
electrode (or from the electrode out into the bulk solution).

•  Convection – mass transfer due to stirring.

Achieved by some form of mechanical movement of the solution or the
electrode i.e., stir solution, rotate or vibrate electrode.
Difficult to get perfect reproducibility with stirring, better to move
the electrode.
Convection is considerably more efficient than diffusion or migration
higher currents for a given concentration therefore, greater analytical
sensitivity
 NERNST-PLANCK EQUATION

Ji(x) = flux of species i at distance x from electrode (mole/cm2 s)

Di = diffusion coefficient (cm2/s)
∂Ci(x)/∂x = concentration gradient at distance x from electrode
∂φ(x)/∂x = potential gradient at distance x from electrode
ν(x) = velocity at which species i moves (cm/s)
 DIFFUSION
Fick’s 1st Law

I = nFAJ

Solving Fick’s Law for particular

applications
like electrochemistry involves
establishing Initial Conditions and
Boundary Conditions
CHRONOAMPEROMETRY
DOUBLE LAYER
 Nernst-Planck Equation

Diffusion Migration Convection

Ji(x) = flux of species i at distance x from electrode (mole/cm2 s)

Di = diffusion coefficient (cm2/s)
∂Ci(x)/∂x = concentration gradient at distance x from electrode
∂φ(x)/∂x = potential gradient at distance x from electrode
ν(x) = velocity at which species i moves (cm/s)
 Diffusion
Fick’s 1st Law

I = nFAJ

Solving Fick’s Laws

for particular
applications like
electrochemistry
involves establishing
Initial Conditions and
Boundary Conditions
Simplest Experiment
Chronoamperometry
Recall-Double layer
 Working electrode choice
! Depends upon potenBal window desired
# OverpotenBal
# Stability of material
# ConducBvity
# contaminaBon
 The polarogram
points a to b
I = E/R
points b to c
electron transfer to the
electroacBve species.
I(reducBon) depends on the
no. of molecules reduced/s:
this rises as a funcBon of E
points c to d
when E is sufficiently
negaBve, every molecule that
reaches the electrode surface
is reduced.
 Dropping Mercury Electrode
! Renewable surface
! PotenBal window expanded for reducBon
(high overpotenBal for proton reducBon at
mercury)
 Polarography
A=4 (3mt/4 d)2/3 = 0.85(mt)2/3
Density of Mass flow rate of drop
drop

We can substitute this into Cottrell Equation

i(t) = nFACD1/2/ π1/2t1/2
We also replace D by 7/3D to account for the compression of the diffusion
layer by the expanding drop
Giving the Ilkovich Equation:
id = 708nD1/2m2/3t1/6C
I has units of Amps when D is in cm2s-1,m is in g/s and t is in
seconds. C is in mol/cm3

This expression gives the current at the end of the drop life. The average
current is obtained by integrating the current over this time period

iav = 607nD1/2m2/3t1/6C
Polarograms

E1/2 = E0 + RT/nF log (DR/Do)1/2

(reversible couple)

Usually D’s are similar so half

wave potential is similar to formal
potential. Also potential is
independent of concentration and
can therefore be used as a
diagnostic of identity of analytes.
DifferenBal pulse voltammetry
 DPP
!  current measured twice during the lifeBme of each drop
difference in current is ploQed.
!  Results in a peak-shaped feature, where the top of the peak
corresponds to E1/2, and the height gives concentraBon
!  This shape is the deriva/ve of the regular DC data.
!  DPP has the advantage of sensiBve detecBon limits and
discriminaBon against background currents. TradiBonally,
metals in the ppm range can be determined with DPP.
!  DerivaBve improves contrast (resoluBon) between
overlapping waves
 DPP vs DCP
Ep ~ E1/2 (Ep= E1/2±ΔE/2)

where ΔE=pulse amplitude

σ = exp[(nF/RT)(ΔE/2)]

ResoluBon depends on ΔE
W1/2 = 3.52RT/nF when ΔE$0

Improved response
because charging current
is subtracted and adsorpBve
effects are discriminated against.
l.o.d. 10-8M
ResoluBon
Square wave voltammetry
SWV
SWV Response
 SWV

•  advantage of square wave voltammetry is that the entire

scan can be performed on a single mercury drop in about 10
seconds, as opposed to about 5 minutes for the techniques
described previously. SWV saves time, reduces the amount of
mercury used per scan by a factor of 100. If used with a pre-
reduction step, detection limits of 1-10 ppb can be achieved,
which rivals graphite furnace AA in sensitivity.

• data for SWV similar to DPP

• height and width of the wave depends on the exact
combination of experimental parameters (i.e. scan rate
and pulse height
 Stripping Voltammetry
•  Preconcentration technique.

1. Preconcentration or accumulation step. Here the analyte species

is collected onto/into the working electrode
2. Measurement step : here a potential waveform is applied to the
electrode to remove (strip) the accumulated analyte.
DeposiBon potenBal
ASV
ASV or CSV
 Adsorptive Stripping
Voltammetry

•  Use a chelating
ligand that
adsorbs to the
WE.
•  Can detect by
redox process of
metal or ligand.
MulB-Element
Standard AddiBon