Voltammetry

and
Polarography
 parameter to Constant Variable(contr Electrochemic
be Measured olled) al Analytical
parameter Method

Potential or Current = 0 Concentration Potentiometric

Voltage Titration

Diffusion Concentration Potential or Polarography

current Voltage
Diffusion Potential Concentration Amperometric
current (vs) ml (Voltage) at titration
of titrant or limiting
time voltage
• Voltammetry techniques measure current as a function of
applied potential under conditions that promote
polarization of a working electrode
• Polarography: Invented by J. Heyrovsky (Nobel Prize 1959).
Differs from voltammetry in that it employs a dropping
mercury electrode (DME) to continuously renew the
electrode surface.
• Amperometry: current proportional to analyte
concentration is monitored at a fixed potential
BASIC APPARATUS -Voltammetry
• Indicator electrode The electrode whose potential is a function of the
analyte’s concentration (also known as the working electrode).
• Counter electrode or Reference electrode The second electrode in a two-
electrode cell that completes the circuit. An electrode whose potential
remains constant and against which other potentials can be measured.
• Auxiliary electrode The third electrode in a three-electrode cell that
completes the circuit.
• Anode The electrode where oxidation occurs.
• Cathode The electrode where reduction occurs.
• Voltammetry An electrochemical method in which we measure current as a
function of the applied potential.
• Voltammogram A plot of current as a function of applied potential.
• Amalgam A metallic solution of mercury with another metal.
 Polarography
• A MICRO SCALE “ELECTROLYSIS” OF ANALYTE SOLUTION
• Analyte, be AN OXIDIZABLE / REDUCIBLE SPECIES (Directly or indirectly) in
organic or aqueous solution
• l E“WE”l > l Eeqbm l
• For “Oxidation” : E “WE”more (+)ve than E eqbm
• For “Reduction” : E “WE”more (-)ve than E eqbm

• WE: Dropping Mercury Electrode: “Polarography”

• WE: Other electrodes, mostly solids: “Voltammetry”
• CELL CURRENT ---------Quantification
• POTENTIAL OF “WE” ---------Identification
The earliest voltammetric techniques, including polarography, used mercury
for the working electrode. Since mercury is a liquid, the working electrode
often consists of a drop suspended from the end of a capillary tube.
• In the hanging mercury drop electrode, or HMDE, a drop of the desired size
is formed by the action of a micrometer screw that pushes the mercury
through a narrow capillary tube.
• In the dropping mercury electrode, or DME, mercury drops form at the end
of the capillary tube as a result of gravity. Unlike the HMDE, the mercury
drop of a DME grows continuously and has a finite lifetime of several
seconds. At the end of its lifetime the mercury drop is dislodged, either
manually or by gravity, and replaced by a new drop.
• The static mercury drop electrode, or SMDE, uses a solenoid-driven plunger
to control the flow of mercury. The SMDE can be used as either a hanging
mercury drop electrode or as a dropping mercury electrode.
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.
• 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.
Polarographic Curve
 ION TRANSPORT DURING ELECTROLYSIS
MIGRATION DIFFUSION CONVECTION
Movement of Movement of ions Transport of ions
oppositely charged from region of towards electrode
ions towards higher concentration due to agitation,
electrode due to (bulk) to region of vibration and
electrostatic lower concentration temperature
attractions. (near the electrode gradients
surface)

Voltammetry under diffusion controlled mass (ion) transfer

Ex. Polarography
Voltammetry under convection controlled mass (ion) transfer
 Voltammetry under diffusion controlled mass (ion) transfer
Ex. Polarography

NO MIGRATION ONLY DIFFUSION NO CONVECTION

METHODS OF STOPPING OR MINIMIZING MIGRATION

• Add an excess (100 fold or more) an

inert electrolyte (Supporting
electrolyte) to the analyte solution

• This screens the electric field

produced by the electrode

• Therefore no attraction of ions from

the bulk to the electrode
NO MIGRATION
• The migration current is due to the migration of reducible or oxidizable
ions which is proportional to the electrical potential gradient at the
electrode due to attraction.
• This migration current is usually eliminated by adding 50 or 100 fold
excess of an inert supporting electrolyte. Commonly used supporting
electrolytes are potassium or sodium salts. The potassium ions cannot be
discharged at cathode until the impressed voltage becomes large. The
• large number of potassium ions therefore remain as a crowd around
cathode and restrict the potential gradient to a region so very close to
the electrode surface. So there is no longer an electrostatic attraction
operative to attract other reducible ions from the bulk of the solution.
• Under these circumstances the limiting current is solely controlled by the
diffusion of the electroactive species through the concentration gradient
adjacent to the electrode.
 HOW TO STOP CONVECTION?

• In the solution
No Vibration

No Agitation

No Shaking

No Temperature gradient

NO CONVECTION
ONLY DIFFUSION
 Main event
Residual Current

Diffusion Current

Limiting Current

Polarographic Curve
Half Wave potential
Residual Current
• Even in the absence of electroactive substance in the solution having only
supporting electrolytes a small current is always present which is referred
as residual current which consists of two components.
• The first is reduction of trace impurities (faradaic current) present in the
large concentration of supporting electrolyte used. These include dissolved
oxygen, traces of metal ions such as ferric iron, lead and arsenic. Out of
these, dissolved oxygen can be removed by passing pure nitrogen for 10 to
15 minutes before taking C-V curve.
• The second source is charging current or capacitive current which is non-
faradaic and is present whenever the working electrode potential changes.
• The small current that is observed as the mercury is covered with an
electrical double layer of positively and negatively charged ions of the
electrolyte.
Diffusion Current
• In the presence of excess supporting electrolyte the electrical force on the
reducible/oxidizable ions is nullified and therefore, the limiting current is
solely a diffusion current. Ilkovic (1934) examined the various factors which
govern the diffusion current and deduced a theoretical equation as
Limiting Current
• The limiting current obtained by the extreme state of concentration
polarization which results from the depletion of the concentration of the
electro-reducible or electro-oxidizable substance at the electrode surface by
the electrode reaction.
1. A diffusive force, proportional to the concentration gradient at the electrode surface.
2. An electrical force, proportional to the electrical potential difference between the
surface and the solution.
• So the limiting current is regarded as the sum of ‘diffusion current’ and a
‘migration current’.
Half Wave potential
• The electro-active material in
polarography is characterized by its half-
wave potential, E1/2. Under any defined
set of experimental conditions, each
substance has its own characteristic E1/2
and this is the basis of qualitative
polarographic analysis.
• The halfwave potential is defined as the
potential at which the current due to the
reduction or oxidation of the substance
responsible for the wave is half as large
as on the plateau
Advantages of DME
• Its surface area is reproducible with a given capillary
• The constant renewal of the electrode surface eliminates non reactivity
• The large hydrogen over potential on mercury renders possible the
deposition of substances difficult to reduce such as aluminum ion and
manganese (II) ion (The current-potential curves of these ions are not
accessible with platinum micro electrode).
• Mercury forms amalgams with many metals. (mercury with another metal)
• The diffusion current assumes a steady value immediately and is
reproducible.
• The surface area of the electrode can be calculated from the weight of the
drops.
Limitation of DME
• 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.
Applications
• Handles high salt concentrations better than chromatographic
instrumentation
• Can differentiate between ionic species
– Example: Cr6+ Cr3+
• Ultra Trace range metals (sub-ppb)
• Wastewater Analysis
• Industrial Water/Liquor Analysis
• Pharmaceutics
• Environmental Studies
• Biological/Biochemical Analysis
• Plating Analysis