Voltammetry

z
and
Polarography
1. NORMAL PULSE VOLTAMMETRY

2. DIFFERENTIAL PULSE VOLTAMMETRY

Voltammetry
• It is an Electro- analytical technique.

• It gives information about the analyte.

• We can even measure the amount of current by

varying the voltage.

• The change in current with the varying voltage gives

the plot and is known as voltammogram

• There is a minimum potential required to initiate an

oxidation or reduction reaction at an electrode.
Instrumentation
• It is a three electrode system.
• 1. Working electrode
2. Reference electrode and
3. Auxiliary electrode.

(1) working electrode;

(2) auxiliary electrode;
(3) reference electrode
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Working Electrode

• Ranges from small

mercury drop to flat
platinum disc.

• Other commonly used

electrode materials
gold, platinum and
glassy carbon.
Depending on the choice of working electrode, the type of
voltammetry is decided.

Example :
• We use Dropping Mercury Electrode (DME) in
Polarography technique
• We use Platinum electrode in Cyclic
Voltammetry
• We use Glassy Carbon as electrode in Linear
Sweep Voltammetry
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Reference Electrode
• Usually Standard
electrode is used as
Reference electrode.
• Its potential is constant.
• It provides potential to
the Working electrode.
• Common reference
electrode are
Calomel electrode and
Ag/AgCl electrode
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Auxiliary Electrode

• It is usually a thin platinum

wire.

• It serves merely to carry the

current flowing through the
cell.

• Usually redox reaction occur

simultaneously at the auxiliary
electrode.
Type of Voltammetry
• LINEAR SWEEP VOLTAMMETRY
• STAIRCASE VOLTAMMETRY
• CYCLIC VOLTAMMETRY
• SQUAREWAVE VOLTAMMETRY
• ANODIC STRIPPING VOLTAMMETRY
• CATHODIC STRIPPING VOLTAMMETRY
• ABSORPTIVE STRIPPING VOLTAMMETRY
• ALTERNATING CURRENT VOLTAMMETRY
• POLAROGRAPHY
• ROTATED ELECTRODE VOLTAMMETRY
• NORMAL PULSE VOLTAMMETRY
• DIFFERENTIAL PULSE VOLTAMMETRY
• CHRONOAMPEROMETRY.
Linear Sweep Voltammetry

• In linear sweep voltammetry (LSV) a fixed potential range.

• the voltage is scanned from a lower limit to an upper limit
• In LSV measurements the current response is plotted as a function
of voltage rather than time.

• The scan begins from the left hand side of the current/voltage plot
where no current flows.

• As the voltage is swept further to the right (to more reductive

values) a current begins to flow and eventually reaches a peak
before dropping
 Normal Pulse Voltammetry

• Normal polarography has been replaced by various forms of pulse

polarography.

• It uses a series of potential pulses.

• Here the pulse time (tp) is 50ms.

• Each potential has different amplitude

Differential Pulse Voltammetry
• If potential pulse is applied periodically to the Linear
Sweep Voltammetry, then it is known as Differential
Pulse Polarography.
• Hence it is denoted as the differential of linear sweep
voltammetry.
• The current is measured twice per cycle.

• Here the pulse time (tp) is 17ms.

• The difference in the two currents gives rise to the peak-

shaped voltammogram.

• consistent enhancement of the signal is achieved

• Detection limit is as low as 10-8 M

• Each potential step has the same amplitude

z
ANODIC STRIPPING VOLTAMMETRY

 Anodic Stripping Voltammetry is a voltammetric

method for quantitative determination of specific ionic
species

 It allows researchers to detect multiple types of

dissolved metal in one experiment.

 The metal film formed during the reduction step

concentrates the metal particles at the electrode, so
the detection of very low concentrations (ppb range)
of metal ions is possible.
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 It detect μg/L concentrations of analyte. This method

has an excellent detection limit (typically 10-9 - 10−10
M)

 The stripping step can be either linear, staircase,

squarewave, or pulse.
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Polarography
• Polarography is the branch of
voltammetry in which a dropping
mercury electrode (DME) is used
as the working electrode.
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• Conventional DC

• Wide cathodic potential range and a renewable surface

• Hence widely used for the determination of many

reducible species

• Reduction begins at sufficiently negative potential

• voltage applied to the polarisable electrode is increased

over the range of 0-2V

• It is known as incomplete electrolysis.

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Jaroslav Heyrovsky

• He was the inventor of

Polarographic technique.

• He received Nobel Prize in

1959

• He is known as father of
electro analytical method.
• z Polarography has a special characteristic;

1. Use of polarized electrode.

2. Use of depolarized electrode.

• POLARIZED ELECTRODE : DME

• DEPOLARIZED ELECTRODE : SCE

Dropping Mercury Electrode

• It is the working electrode in one

of the voltammetry technique
known as polarography
Advantages of DME

• Clean Surface generated

• Rapid constant current achievement
• Even metal with high negative standard voltage systems can be
studied without hydrogen.
• Amalgam formation more favourable.