Linear Potential Polarography

Lovelle Mae P. Galia

MS Chemistry
 Electrochemistry

analytical techniques that use a

measurement of potential, charge,
or current to determine an analytes
concentration or to characterize
an analytes chemical reactivity
 Electrochemistry Concepts

(1) the electrodes potential determines the analytes form at the electrodes surface

(2) the concentration of analyte at the electrodes surface may not be the same as its
concentration in bulk solution

(3) in addition to an oxidationreduction reaction, the analyte may participate in other

reactions

(4) current is a measure of the rate of the analytes oxidation or reduction

(5) we cannot simultaneously control current and potential

 (1) the electrodes potential determines
the analytes form at the electrodes surface

Figure on the left. Redox ladder diagram for

Fe3+/Fe2+ and for Sn4+/ Sn2+ redox couples. The
areas in blue show the potential range where the
oxidized forms are the predominate species; the
reduced forms are the predominate species in the
areas shown in pink. Note that a more positive
potential favors the oxidized forms. At a potential
of +0.500 V (green arrow) Fe3+ reduces to Fe2+, but
Sn4+ remains unchanged.
(2) the concentration of analyte at the electrodes surface
may not be the same as its concentration in bulk solution

Figure on the left. Concentration of Fe3+ as

a function of distance from the electrodes
surface at (a) E = +1.00 V and (b) E = +0.500
V. The electrode is shown in gray and the
solution in blue.
 (3) in addition to an oxidationreduction reaction,
the analyte may participate in other reactions

The reduction of Fe3+ to Fe2+, which is governed

by equation on the right, may not be the only
reaction affecting the concentration of Fe3+ in
bulk solution or at the electrodes surface.

The adsorption of Fe3+ at the electrodes surface or the formation of a metalligand

complex in bulk solution, such as Fe(OH)2+, also affects the concentration of Fe3+
Controlling and Measuring Current and Potential

(1) we can measure the potential when

the current is zero
(2) we can measure the potential while
controlling the current
(3) we can measure the current while
controlling the potential.
 Electrolysis
Methods
* Potentiometry
* Coulometry
* Voltammetry and Amperometry

The specific techniques are shown in red, the experimental conditions are shown
in blue, and the analytical signals are shown in green
Voltammetry

The earliest voltammetric technique

is polarography, developed by
Jaroslav Heyrovsky in the early
1920san achievement for which
he was awarded the Nobel Prize in
Chemistry in 1959
Current in Voltammetry

Faradaic current- the current from redox

reactions at the working electrode and
the auxiliary electrodes
Charging Current- flows every time we
change the electrodes potential
Residual Current- a small, measurable
current that flows through an
electrochemical cell even in the absence
of analyte.
What affects current reading?

Applied Potential influences Faradaic current- the electrodes potential

determines the analytes form at the electrodes surface.

The magnitude of the current is determined by the rate of the resulting

redox reaction
Rate of mass transport (the reactants and products are
transported to and from the electrode)
Rate at which electrons pass between the electrode and the
reactants and products in solution
 What affects current reading?

Applied Potential influences Faradaic current- the

electrodes potential determines the analytes form
at the electrodes surface.

The magnitude of the current is determined by the

rate of the resulting redox reaction
Rate of mass transport (the reactants and
products are transported to and from the
electrode)
Rate at which electrons pass between the
electrode and the reactants and products in
solution
 What affects current reading?

Applied Potential influences Faradaic current- the

electrodes potential determines the analytes form
at the electrodes surface.

The magnitude of the current is determined by the

rate of the resulting redox reaction
Rate of mass transport (the reactants and
products are transported to and from the
electrode)
Rate at which electrons pass between the
electrode and the reactants and products in
solution
What affects current reading?

Modes of Mass Transport that affect rate at which reactant or product

move away or towards the electrode surface

Diffusion-occurs whenever the concentration of an ion or molecule at

the surface of the electrode is different from that in bulk solution

Convection-occurs when we mechanically mix the solution, carrying

reactants toward the electrode and removing products from the
electrode

Migration-occurs when a charged particle in solution is attracted to or

repelled from an electrode that carries a surface charge
 What affects current reading?

Concentration gradients (in red) for Fe(CN)63 following the

application of a potential that completely reduces it to Fe(CN)64-.
Before applying the potential (t = 0) the concentration of
Fe(CN)63- is the same at all distances from the electrodes surface.
After applying the potential, its concentration at the electrodes
surface decreases to zero and Fe(CN)63- diffuses to the electrode
from bulk solution. The longer we apply the potential, the greater
the distance over which diffusion occurs. The dashed red line
shows the extent of the diffusion layer at time t3. These profiles
assume that convection and migration do not significantly
contribute to the mass transport of Fe(CN)63-.
 Shapes of Voltammogram

Limiting Current Peak Current

Polarography

The first important

voltammetric technique to be
developedpolarography
uses the dropping mercury
electrode as working
electrode.
 Polarography

Details of normal polarography: (a) the linear

potential-excitation signal, and (b) the resulting
voltammogram.
 Ilkovic Equation

where n is the number of electrons in the redox reaction, D is the analytes

diffusion coefficient, m is the flow rate of the Hg, t is the drops lifetime and
Kmax and Kavg are constants. The half-wave potential, E1/2, provides
qualitative information about the redox reaction.
Polarography
Instrumentation
 Polarography

Advantages Limitations
High overvoltage for the reductio n The ease with mercury is oxidized
of H+ The nonfaradic residual or charging
A renewable metal surface with current, which limits the sensitivity of
each droplet the classical method to concentrations
Reproducible currents are obtained of about 10-5 M. At low concentrations,
very rapidly the residual current can be greater than
the diffusion current, which prohibits
accurate diffusion current measurement
Eslam Khodier
**https://www.academia.edu/9500630/polarography
 Polarography

Advantages Limitations
High overvoltage for the reductio n Is also cumbersome to use and tends to
of H+ malfunction as a result of clogging
A renewable metal surface with Convection around the expanding
each droplet mercury drop causes the rises of peaks
Reproducible currents are obtained on the current- voltage curves, termed
very rapidly polarographic maxima.
Toxicity if nercury
Eslam Khodier
**https://www.academia.edu/9500630/polarography
Linear Sweep Voltammetry

is a voltammetric method where the current at a working electrode is

measured while the potential between the working electrode and
a reference electrode is swept linearly in time. Oxidation or reduction of
species is registered as a peak or trough in the current signal at the
potential at which the species begins to be oxidized or reduced.
Linear Sweep Voltammetry

The experimental setup for linear sweep voltammetry utilizes a

potentiostat and a three-electrode setup to deliver a potential to a
solution and monitor its change in current. The three-electrode setup
consists of a working electrode, an auxiliary electrode, and a reference
electrode. The potentiostat delivers the potentials through the three-
electrode setup.
-end-
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