Voltammetry and Polarography

Lecture 5

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 Differential Pulse Polarography
In direct current polarography, the voltage applied to the
working electrode increases linearly with time. The
current is recorded continuously, and a polarogram such
as that shown previously results. The shape of the plot
is called a linear voltage ramp.
In differential pulse polarography, small voltage pulses are
superimposed on the linear voltage ramp, as in the
figure below.
The height of the pulse is called its modulation amplitude.
Each pulse of magnitude 5‑100 mV is applied during the
last 60 ms of the life of each mercury drop.

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• The drop is then mechanically dislodged.
• The current is not measured continuously. Rather, it
is measured once before the pulse and again for the
last 17 ms of the pulse.
• The polarograph subtracts the first current from the
second and plots this difference versus the applied
potential (measured just before the voltage pulse).
• The resulting differential pulse polarogram is nearly
the derivative of a direct current polarogram.

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 Pulse Superimposed on a Linear Scan Potential

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• The current is sampled twice, just before the pulse
application (at 1) and again late in the pulse life
(after ~40ms, at 2, when the charging current has
decayed). The first current is instrumentally
subtracted from the second, and this current
difference [Δi = i(t2) − i(t1)] is plotted against the
applied potential.
• The resulting differential-pulse polarogram consists
of current peaks, the height of which is directly
proportional to the concentration of the
corresponding analytes

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 Pulse Superimposed on a Staircase potential

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In a reduction, at potentials well positive of the
redox potential, there is no faradaic reaction
in repsonse to the pulse, so the difference
current is zero. At potential around the redox
potential, the difference current reaches a
maximum, and decreases to zero as the
current becomes diffusion-controlled. The
current response is therefore a symmetric
peak.

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Differential-pulse (left) and DC (right) polarograms for a 1.3 *10−5
M chloramphenicol solution.

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Normal-pulse (curve A) and
differential-pulse (curve B)
polarograms for
a mixture of 1 mg/L
cadmium and lead ions.

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 Square-Wave Voltammetry (SWV)
Square-wave voltammetry is a large-amplitude differential
technique in which a waveform composed of a symmetric
square wave, superimposed on a base staircase potential, is
applied to the working electrode.The current is sampled
twice during each square-wave cycle, once at the end of the
forward pulse (at t1) and once at the end of the reverse pulse
(at t2).
Since the square-wave modulation amplitude is very large, the
reverse pulses cause the reverse reaction of the product (of
the forward pulse). The current difference between the two
measurements is plotted versus the base staircase potential.

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There are two advantages to measuring the
difference current. First, it increases the
discrimination against the charging current,
since any residual charging current is
subtracted out. Second, the shape of the
current response is a symmetric peak, rather
than the sigmoidal curve typically found for
normal pulse voltammetry.

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If we consider a reduction, then at potential well
positive of the redox potential, both the forward
and reverse currents are zero, so the difference
current is also zero. At potentials well negative of
the redox potential, the current is diffusion-
controlled, and the potential pulse has no effect;
hence, the forward and reverse currents are equal,
and the difference current is again zero. The largest
difference between the forward and reverse
currents (and hence the largest current response) is
at the redox potential.

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 Comments on Performance of SWV
1. The sensitivity of this technique can be increased by
enhancing the amplitude of the square wave or the
frequency. The limits of the enhancing is strictly related to
the kinetics aspects of the redox system.
2. The interference due to capacitive current are lowered to
minimum because the current is sampled just at the end of
the half waves, when the current of the electrical double
layer is least.
3. Detection limits range from 5 – 50 µg/l.
4. The procedure is fast (few seconds) and can be done using
one mercury drop (on a DME) or using a HMDE.

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 Cyclic Voltammetry
Cyclic voltammetry is a very important electrochemical
technique it can be used to study the redox behaviour of
compounds and to determine mechanisms and rates of
oxidation/reduction reactions.
Cyclic voltammetry is a simple extension of the linear sweep
technique. Conventional cyclic voltammetry is especially
informative about the qualitative aspects of an electrode
process.
The use of a triangular waveform at stationary electrodes,
allows both the oxidation and reduction pathways to be
studied conveniently from the experiment.

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Cyclic voltammetry has been established as the electrochemical
method of choice for the evaluation of the mechanism of
charge transfer for more than five decades. During these
years a number of methods have been developed for the
measurement of electrode reaction kinetics.
Furthermore, the presence of homogeneous reactions in the
mechanism is readily detected, and interpretation of results
usually is simple. A direct estimate of electrode reversibility
is provided, because the potentials at which oxidation and
reduction occur are observed directly within range.

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 Conventions
The potential is graphed along the x-axis with more positive (or
oxidizing) potentials plotted to the left, and more negative
(or reducing) potentials to the right. The current is plotted
on the y-axis of the voltammogram, with cathodic (i.e.,
reducing) currents plotted up along the positive direction,
and anodic (i.e., oxidizing) currents plotted down in the
negative direction. (A voltammogram is almost always
plotted in this fashion by North American electrochemists,
but in Europe, the axes are typically reversed.)

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 Cyclic Voltammetry at Planar Electrodes
Cyclic voltammetry experiments are conducted in unstirred solutions
using large (millimetric dimension) electrodes such that diffusion
normal to the electrode is the major form of mass transport.
The observed faradaic current depends on the kinetics and transport
by diffusion of the electroactive species.
The system is described as “reversible” when the electrode kinetics
are much faster than the rate of diffusion.
The Nernst equation is obeyed for a reversible system.

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Randles-Sevcik equation for the peak current in linear
sweep voltammetry (at 298 K) is:

where, A is the area in cm2, D0 is the diffusion coefficient

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 Comparison between Reversible and Irreversible
Voltammograms
For systems (reversible and irreversible), the peak current ip,
increases when the scan rate and the concentration of the
reactant species increase. This increase of ip with increasing
scan rate is due to fact that the diffusion layer becomes
thinner and the concentration gradient steeper.
The separation of the peak potentials, Epa - Epc, is an important
parameter in cyclic voltammetry which can be used to
calculate the reversibility of the reaction. The peak potential
separation for a reaction with reversible electron transfer is
given by: Epa-Epc = {~59/n} mV

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The value of the peak potential separation at 298 K is
approximately 56.5 mV and is independent of scan rate.
A ratio of the peak currents, ipa/ipc which is one for reversible
systems, is another important parameter in these systems.
It is independent of the scan rate.

On the other hand in irreversible systems, the ratio of the peak

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 Judging Reversibility from CV
1. n DEpeak ~ 59 mV
2. ipa / ipc = 1
3. Eo = (Epa + Epc) / 2
4. ipa and ipc a (scan rate)1/2
5. Epeak independent on scan rate
0.028
6. Half wave potential: E p/2  E 1/2  V
n
Sign +ve for reduction and –ve for oxidation.
Quantitative information regarding analyte concentration can be
obtained from the voltammogram using the Randles-Sevcik equation
seen before (v is the sweep rate):

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Just look at location of peak potential as a function of scan rate:

reversible irreversible

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 Cyclic voltammetry

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