Paper No: 2Analytical Chemistry

Module: 29 Cyclic Voltammetry

Development Team
Principal Investigator
&
Co- Principal Investigator
Paper Coordinator
Content Writer
Content Reviewer
Prof. R.K. Kohli
Prof. V.K. Garg&Prof.AshokDhawan
Central University of Punjab, Bathinda
Dr. J. N. Babu,
Central University of Punjab, Bathinda
Dr. HeenaRekhi and Neha Sharma
Department of Chemistry,
Punjabi University, Patiala
Prof. Ashok Kumar
Punjabi University, Patiala

Anchor Institute Central University of Punjab

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 Description of Module

Subject Name Environmental Sciences

Paper Name Analytical Chemistry

Module
Cyclic Voltammetry
Name/Title
Module Id EVS/AC-II/29

Pre-requisites
1. What is cyclic voltammetry?
2. Where and how they are used?
3. What is there working and principle?
4. What are the factors effecting the measurements?
Objectives
5. What is the use of cyclic voltammetry?
6. What is its working and Principle of cyclic voltammetry?.
7.What are the applications of cyclic voltammetry?

Keywords

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
Module 29: Cyclic voltammetry
Objectives: To study the basics of cyclic voltammetry and know the followingabout self
generated questions.
1. What is cyclic voltammetry?
2. Where and how they are used?
3. What is there working and principle?
4. What are the factors effecting the measurements?
5. What is the use of cyclic voltammetry?
6. What is its working and Principle of cyclic voltammetry?.
7.What are the applications of cyclic voltammetry?

Key points

 Cyclic voltammetry is a very popular technique for electrochemical studies, useful

for obtaining information about fairly complicated electrode reactions.
 Cyclic voltammetry is used to investigate electrode mechanism.
 It is a technique to control electrode’s potential and measure resultant current.
 Offers a rapid location of redox potentials of the electroactive species.
 Can be used to get valuable kinetic information of electrode reaction.
 Electrode reaction usually involve e-transfer reaction which is influenced by
electrode potential.
 Mass transfer (diffusion) in some cases can control over-all electrode reaction
 Electrode reaction may be reversible or irreversible.

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 MODULE 29: Cyclic Voltammetry
1. Description
Cyclic voltammetry is an analytical technique which is highly efficient for obtaining qualitative
information of electrochemical reactions. Cyclic voltammetry is a very popular technique for
electrochemical studies, for obtaining information about fairly complicated electrode reactions. CV is
infrequently used for quantitative analysis, it find wide applicability in study of oxidation/reduction
reactions, the detection of reaction intermediates, and the observation of follow-up reactions of
products formed at electrodes. In CV the applied potential is swept in first one direction and then the
other while the current is measured. A CV experiment may use one full cycle, a partial cycle, or
several cycles.

• CV provide information on the thermodynamics of redox processes, coupled

Step 1
chemical reactions and adsorption processes.

• CV offers rapid location of redox potentials of the electroactive species.

Step 2

• CV is used to study kinetics of heterogeneous electron-transfer reactions.

Step 3

• CV offers convenient evaluation of the effect of media upon the redox process.
Step 4

Graphical representation of functions of Cyclic Voltammetry

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 2. Principle of Cyclic Voltammetry
A cyclic voltammogram is obtained by applying a linear potential sweep (that is, a potential that
increases or decreases linearly with time) to the working electrode. As potential is applied below and
above the formal potential, E°, of an analyte, current flows through the electrode as a result of either
oxidation or reduction of analyte. The magnitude of this current is proportional to the concentration of
the analyte in solution, which allows cyclic voltammetry to be used in an analytical determination of
concentration. The instrumentation pertaining to process cyclic voltammetry comprises three-electrode
assembly constituting working, reference and auxiliary electrode immersed in a test solution. The
potentiostat applies and maintains the potential between the working and reference electrode while at
the same time measuring the current at the working electrode due toflow of charge between auxillary
electrode and working electrode. A plotter or a computer serves as a recording device for resulting
cyclic voltammogram which is a plot of current versus potential.
3. Fundamentals of Cyclic Voltammetry
Cyclic Voltammetry constitutes an electroanalytical techniques where measuring current as a function
ofapplied potential gives information about in the analyte. Moreover cyclic voltammetry is used for
various non-analytical techniques such as surface adsorption, fundamental studies on redox processes
and electrode kinetics, electron transfer mechanism as well. CV is useful to obtain information
concerning its physical and chemical properties. However, electroanalytical methods serve as a
quantitative tool for the determination of diffusion coefficients, transfer numbers and oxidation
potential. Moreover, CV can be combined with spectroscopy in situ to provide information concerning
molecular structures and reaction mechanisms of transient electroactive species. Measurement of
current while cycling the potential of an electrode, which is immersed in an unstirred solution is
involved in cyclic voltammetry. The potential of this working electrode is controlled versus a
reference electrode.

CV is a potential sweep technique. It involves sweeping the electrode potential between

potential limits Ei and E2 at a known sweep rate (also called scan rate). On reaching limit E2 the
sweep is reversed to Ei to obtain a cyclic scan. The CV scan is a plot of current versus potential 5
and indicates the potential at which redox process occur.

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 The potential axis is also a time axis that is related to scan rate. The excitation signal for CV is a linear
potential scan with triangular waveform. On sweeping the potential of an electrode between two
values often called switching potential is observed on triangular potential excitation signal. The
current density is referred to as normalisation of measured current to the electrode surface. Plot of
applied potential versus current density is referred to as cyclic voltammogram. Corresponding to every
electrode reaction there exist unique value of potential for which a peak in the measure current can be
observed.The electrode material, sweep rate and concentration of electrolyte affects the peak width
and height of a particular electrochemical process.
To bring out an oxidation process, a positive potential is applied giving rise to an anodic peak
current (ipa) which frequently gives an oxidation peak at known potential (Epa). To bring out a
reduction process, a negative potential is applied giving rise to an cathodic peak current (ipc) which
frequently gives a reduction peak at known potential (Epc).
Instrumentation
The most common planning to deal with electrochemical cell mainly consists of three different
electrodes:

• Working electrode (WE)

• Reference electrode (RE)

• Counter electrode (CE)

4.1.1. Working Electrode.

The ideal working electrode is very clean metal surface with a well defined geometry that is in direct
contact with an electrochemical test solution. Working electrodes commonly employed are made from
electrochemically inert metal. The most widely used metals are mercury, platinum, gold, and various
forms of carbon. Solid metals are typically fashioned into disks surrounded by a chemically inert layer
made up of teflon, glass, or epoxy. Mercury, being a liquid, tends to be used as a spherical droplet in
contact with the solution. Voltammetric response of the electrode is affected by shape and size of the
6

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 electrode. Surface area is directly proportional to the overall current observed at an electrode so disk
shaped electrodes with diameters greater than 100 mm, or macro electrodes, generally produce easily
measured currents in the microampere to milliampere range. Microelectrodes with dimensions less
than 100 mm are typically produce currents in the pico to nanoampere range. However there are no
specific electrochemical equipment are required to observe overall currents at microelectrodes.
Following electrodes are used as working electrodes:
a) Mercury Electrode
b) Platinum Electrode
c) Gold Electrodes
d) Carbon Electrodes
e) Rotated Electrodes
4.1.2. Reference Electrode
In the experiment concerning voltammetry the measurement of potential of a working electrode is
always done with respect to standard electrode that is reference electrode. To build an electrochemical
cell the reference electrode is the simplest cell used as a half cell. Half cell allows the potential of the
to be determined alternate to standard hydrogen electrode. For this reason, a number of other reference
electrodes have been developed. However in dealing with aqueous solution saturated calomel
electrode (SCE) is used as a reference electrodes.

4.1.3. The Counter Electrode

Whenever the measurement is made the current is necessarily forced to flow through the reference
electrode. Internal composition of a reference electrode is greatly affected on the flow of large amount
of current through it resulting in potential drift from expected standard value. For this reasons, it is
enviable to make electrochemical measurements without current flowing through the reference
electrode. Modem three and four electrode potentiostat use a feedback circuit to prevent this from
happening, but this feedback circuit requires that an additional auxiliary electrode be introduced into
the electrochemical cell. The function of the auxillary electrode is to make sure that large amount of
current flows through it so that only a small current flows through reference electrode. The auxiliary
electrode can be prepared from any material using the desired geometry of an electrode.

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 Material constituting electrode should be chemically inert to the test solution and auxillary
electrode should have large surface area because large amount of current can then flow through it.
Mostly platinum wire is used, but stainless steel, aluminium or copper wire may work in non-corrosive
solutions where metal cation interference is not a concern. However electrochemical cell can itself
serve the purpose of auxillary electrode if it is made of metal. Because current flows at the auxiliary
electrode, electrochemical processes willalso occur there. The auxiliary electrode must oxidize if the
working electrode is reducing. Diffusion of products generated at auxillary electrode to the working
electrodemay cause interference with the experimental measurement. When this trouble arises, the
auxiliary electrode is positioned in a separate section containing an electrolyte solution that is in ionic
contact with the main test solution via a glass frit.

Sweep voltammetry depends on diffusion of electroactive

species to electrode surface

The mass transport of (O) as function of time and distance

can predicted by Fick’s 2nd law of diffusion

Potential of WE is swept from E1 where no reaction

undergo to E2 where electron transfer is rapid (linear
sweep) and back to E1

Theory
In theory, any atom or molecule can be oxidized or reduced if enough energy canbe provided.
However, the range of energies that can be applied is limited by theexperimental conditions. So we
need only consider molecules that are said to beelectrochemically active. Application of reverse scan
results in reoxidation of a species that underwent reduction during cathodicpolarization of working
electrode in unstirred solution. Voltage scan rates has been correlated to cathodic and anodic peak
currents and differences incathodic and anodic peak potentials rates has been donemathematically for

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
 various electrochemical reactions. However, no much differences in sweep rates are observed in cyclic
and single sweep voltammetry.
The important parameters of a cyclic voltammogram are the magnitudes of anodic peak
current, the cathodic peak current, the anodic peak potential andcathodic peak potential. Initially, the
bulk solution contains only the reduced form (R) so that at potentials lower than the redox potential,
i.e. the initial potential, there is no net conversion of R into O, the oxidised form (point A).
Exponential increase in anodic current is observed on varying potential.As R is converted into O,
concentration gradients are set up for both R and O, anddiffusion occurs down these concentration
gradients. Instantaneous oxidation of R to O is observed at anodic peak. Therefore, the current now
depends upon the rate of masstransfer to the electrode surface and so the time dependence is resulting
in anasymmetric peak shape.
Applications of CV

 Cyclic voltammogram is widely employed in organic and inorganic chemistry. CV has become a
very popular technique for electrochemical studies and has proved as a sensitive tool for obtaining
information about fairlycomplicated electrode reactions.
 For the assessment of various kinetic and thermodynamic parameters such as entropy (S), change
in number of electrons (n), heterogeneous rate constant (ko), Gibb's free energy (G) and diffusion
coefficient (Do) of a number of redox reactions and associated chemical reactions cyclic
voltammetry has found an extensive applications. These methods are chiefly valuable in redox
process and to study the multiple electron transfer in an electrochemical reaction.
 CV techniques can be used for the estimation of a number of inorganic, organic andorganometallic
compounds.
 CV studies in rat brain, in vivo studies in animals, bacteriaand even plants are picking up.
 With the introduction of newer electrode material of very small size, these methods of chemical
analysis in living systems might grow even faster.
 CV studies of solid and molten electrolyte might prove useful for trace analysis.
 Background-subtracted cyclic voltammetry can be employed for measuring lowerconcentration.

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry
  Cyclic voltammetry finds applications in in-vivo monitoring in neurotransmitters. Rapid
voltammetric measurements makes it suitable technique forthe detection of dynamic concentration
changes in the micromolar range that occurs in the extracellular environment of the brain.
 The good temporal and chemical resolution of such in-vivo cyclic voltammetric experiment offers
improved understanding of the chemistry of the brain.
 Cyclic Voltammetric detectors have large applications in chromatography.
 Industrial corrosion processes are being monitored using CV technique.
 Voltammetric amazingly low detection limits are being used to monitor lead levels in
thebloodstreams.
 Electrodes coated with special polymers find use as glucose detectors fordiabetics.

Bibilography

1. R.L.McCreery, K.K.Kline "Laboratory Techniques in Electroanalytical Chemistry" 2nd

Edition (P.T.Kissinger, and W.R.Heineman, New York Eds), 1995.
2. R.L.McCreery, "Electroanalytical Chemistry" Vol.17 (Dekker, New York Eds),1991.
3. Journal of Chemical Education, 702-706 (1983)
4. Journal of Chemical Education, 697-702 (1983)
5. M. Gomez, F. J. Gonzalez, and I. Gonzalez, Electroanalysis 15, 635 (2003).

10

Analytical Chemistry
Environmental
Sciences Cyclic Voltammetry