Voltammetric Techniques

VOLTAMMETRIC TECHNIQUES
AND ELECTRODES
PRESENTED BY RUTESH V. SAVALIA
GUIDE: Dr. SANGHAMITRA CHATTERJEE
1
CONTENT
• Types of Voltammetry
• Linear Sweep Voltammetry
• Cyclic Voltammetry
• Differential Pulse Voltammetry
• Square Wave Voltammetry
• Glassy Carbon Electrodes
• Screen Printed Electrodes
2
Polarography
Linear
Sweep
Voltammetry
Cyclic
Differential
Pulse
Square wave
Voltammetric
Techniques Pulse
Voltammetry Staircase
Normal Pulse
Hydrodynamic
Voltammetry Reverse Pulse
Anodic
Stripping
Cathodic 3
Voltammetry
Adsorptive
LINEAR SWEEP VOLTAMMETRY
• In LSV, the potential of the working

electrode is varied linearly with time
between two values i.e. the initial (Ei) and
final (Ef) potentials and current is
measured.
• The voltage scan rate (v) is calculated
from the slope of the line.
4
VOLTAMMOGRAM
Scan
Begins
No current
flows
Current
increases
Reaches
at peak
Starts
dropping
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PEAK CURRENT
• The equilibrium at electrode surface means reversible electrochemical, thus the
Nernst equation is followed.
where,
DR = diffusion coefficient of reduced species
DO = diffusion coefficient of oxidized species
• The Randles-Sevcik equation for reversible systems
ip = 0.4463 n F A C (n F v D / R T)1/2
• At 25°C (298.15 K), the Randles-Sevcik equation can be written in a more concise
form,
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ip = (2.687x105) n3/2 v1/2 D1/2 A C
FACTORS
• The rate of the electron transfer in reaction(s)
• The chemical reactivity of the electroactive species
• The voltage scan rate
• Slow scan rate lower

magnitude of current
• Higher scan rate higher
magnitude of current
• For rapid process, peak potential is

same
• For slow process, Quasi reversible or
7
irreversible reactions current takes more
time to respond, hence shift in potential.
APPLICATION
• Identify unknown species and determine the concentration of solutions.

• E1/2 can be used to identify the unknown species while the height of the diffusion
current can determine the concentration.
• The sensitivity of current changes vs. voltage can be increased by increasing the
scan rate.
8
CYCLIC VOLTAMMETRY
• Varying the applied potential at a working

electrode in both forward and reverse
direction while monitoring the current.
9
VOLTAMMOGRAM
• Forward scan is identical to LSV and
reverse scan moves back through the
equilibrium positions gradually
converting electrolysis product.
• The current flow is now from the solution
species back to the electrode and so
occurs in the opposite sense to the
forward sweep.
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FACTORS
•For a reversible electrochemical:
• The voltage separation between the
current peaks is
• The positions of peak voltage do not alter

as a function of voltage scan rate
• The peak currents are proportional to the
square root of the scan rate
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APPLICATION
• Variety of redox processes,
• Determining the stability of reaction products, presence of intermediates in
redox reactions.
• Reduction potential of an analyte, which can be used as an identification tool.
• The concentration of an unknown solution by calibration curve of current vs.
concentration.
12
DIFFERENTIAL PULSE
VOLTAMMETRY
• The potential form consists of small pulses of constant amplitude (10–100 mV)
superimposed on a staircase-wave form.
• The current in this technique is measured twice in each pulse period, first at
potential at the beginning of the applied pulse, and second at the ending of the
same pulse.
13
VOLTAMMOGRAM
• The measured current is referred to as differential pulse

voltammogram, is actually the difference between the
currents measured for each single pulse.
• Just before the pulse application (i1) and late in the
pulse life when the charging current has decayed (i2)
• ∆i (= i2 – i1) is plotted against the applied potential and
displayed.
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FACTORS
• The charging current contribution to the
differential current is negligible
• The pulse height is a parameter that can
be varied in differential pulse
polarography to improve the sensitivity.
• As the pulse height increases the peak
potential increases in an almost linear
manner.
15
APPLICATION
• Trace levels of organic and inorganic species

• Only faradaic current is extracted, so electrode reactions can be analyzed
more precisely.
16
SQUARE WAVE VOLTAMMETRY
• A symmetrical square wave is superimposed on a staircase waveform where

the forward pulse of the square wave (pulse direction same as the scan
direction) is coincident with the staircase step.
• The reverse pulse of the square wave occurs half way through the staircase
step.
17
VOLTAMMOGRAM
• The current is sampled twice during
each square wave cycle, one at the
end of the forward pulse, and again at
the end of the reverse pulse.
• The difference in current between the
two measurements is plotted vs. the
potential staircase.
• SWV yields peaks for faradaic
processes, where the peak height is
directly proportional to the
concentration of the species in
solution.
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FACTORS
• Frequencies used for square wave voltammetry typically range from

approximately 8 Hz to 120 Hz.
• This frequency range allows square wave experiments to be up to 100
times faster than other pulse techniques.
• Low detection limits ~10-9 M
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APPLICATION
• High sensitivity screening

• SWV suppressed background currents much more effectively than cyclic
voltammetry - for this reason, analyte concentrations on the nano molar
scale can be registered utilizing SWV over CV
20
THANK YOU

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VOLTAMMETRIC TECHNIQUES

• In LSV, the potential of the working

• Slow scan rate lower

• For rapid process, peak potential is

• Identify unknown species and determine the concentration of solutions.

• Varying the applied potential at a working

• The positions of peak voltage do not alter

• The measured current is referred to as differential pulse

• Trace levels of organic and inorganic species

• A symmetrical square wave is superimposed on a staircase waveform where

• Frequencies used for square wave voltammetry typically range from

• High sensitivity screening

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