Presentation Of Analytical Chemistry
Cyclic Voltammetry
Supervisor
Dr. Munawar Saeed
Presented by
MCH-172061
MCH-172070
MCH-172071
MCH-172072
MSc Chemistry-iii Analytical
KFUEIT
Cyclic Voltammetry
Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical
measurement which is used to study the electrochemical properties of an
analyte in solution or of a molecule.
This is a complex technique, which provides a wealth of information of
both kinetic and thermodynamic details of many chemical systems.
It consist of scanning linearly the potential of stationary W.E (in an
unstirred solution), using a triangular potential waveform (potential vs.
time).
This plot is termed as cyclic
voltammogram.
The cyclic votammogram is a
complicated, time dependent
function of a large number of
physical and chemical
parameters.
Cyclic voltammetry offers a rapid location of a redox potentials of the
electro-active species, and convenient evaluation of the effects of many
factors on redox process.
In short CV is used to study qualitative information about electrochemical
processes under various conditions, such as the presence of intermediates in
oxidation and reduction reactions and the reversibility of a reaction.
CV is performed by cycling the potential of a W.E and measure the resulting
current.
Experimental setup
CV experiments are conducted on a solution in a cell fitted with electrodes.
The solution consist of solvent in which the electrolyte and the sample is
dissolved.
The cell
A CV cell consist of 3 electrodes W.E, R.E and a counter electrode ( three-
electrode setup).
The solution consist of solvent in which the electrolyte and the sample is
dissolved.
The electrodes are immobile and sit in an unstirred solution which give rise
to the diffusion controlled peaks.
The analyte is diffused on the electrode surface for the oxidation or
reduction.
Interpretation
The potential of the W.E is measured against a reference electrode which
maintains a constant potential, and the resulting applied potential produce an
excitation signal such as that in figure;
In the forward scan, the
potential first scans negatively,
starting from greater potential (a)
and ending at the lower potential
(d) and a typical reduction occur.
The potential extrema (d) is the
switching potential and is the point
where voltage is sufficient enough
to have caused an oxidation or
reduction of an analyte.
The reverse scan occur from (d) to (g) where potential is positive and
oxidation occur.
It is important to note that some analytes
undergo oxidation first. So, in this
case the potential first scan
positively.
This cycle can be repeated and the
scan rate can be varied. The slope
of the excitational signal gives the
scan rate used.
Example 2
A cyclic voltammogram is obtained by measuring the current at W.E during
the potential scans which shows a voltammogram resulting from a single
electron reduction and oxidation.
Consider the following reversible
reaction;
M
oxidation occur from initial
potential (a) to switching potential
(d) and potential is positive.
The resulting current is anodic
current ().
The peak potential occur at (c) and
is anodic peak potential (.
After switching potential (d), the potential scan negatively from (d) to (g).
This results in cathodic current ( and reduction occur.
The peak potential is at (f) and is called cathodic peak potential ( and is
reached when all the analyte at the
surface of electrode has been reduced.
Application
CV has become an important and widely used in many areas of chemistry.
1. To study a variety of redox processes.
2. To determine the stability of reaction products.
3. The presence of intermediates in redox reactions.
4. Electron transfer kinetics.
5. Reversibility of a reaction.
6. Determine the electron stoichiometry of a system.
7. The diffusion co-efficient of an analyte.
8. The formal reduction potential of an analyte.
9. To determine the concentration of the unknown analyte by current-
concentration curve.
10. In cellular biology, it is used to measure the conc. in living ones.
11. In organometallic chemistry, it is used to evaluate redox mechanisms.
