ASSIGNMENT.

02

“CYCLIC VOLTAMETRY, ITS PRINCIPLE AND ITS

ASUS
APPLICATIONS”
SUBMITTED TO
DR. SHAISTA IBRAHIM

SUBMITTED BY
AQSA AROOJ
ATEEQA BATOOL
AYESHA ZAKIR
HIRRA MANZOOR
JAWERIA KHALID
 CYCLIC VOLTAMETRY

Table of Contents
1.ABSTRACT 4
2.INTRODUCTION 5
2.1 ELECTROCHEMISTRY 5
2.1.1 ELECTROCHEMICAL SYSTEM: .................................................................................................... 5
2.1.2 ELECTROCHEMICAL CELL:.......................................................................................................... 6
2.2INTRODUCTION TO VOLTAMETRY 6
2.2.1 GENERAL PRIINCIPLE ................................................................................................................. 6
2.3TYPES OF VOLTAMMETRY 7
2.3.1 LINEAR SWEEP VOLTAMMETRY ................................................................................................ 7
2.4 CYCLIC VOLTAMETRY .................................................................................................................... 8
2.4.1 BASIC PRINCIPLE........................................................................................................................ 9
3.INSTRUMENTATION 10
3.1 ELECTROCHEMICAL CELL ............................................................................................................. 10
3.2 PREPARATION OF ELECTROLYTE SOLUTION ............................................................................... 11
3.3 ELECTRODES ................................................................................................................................ 12
3.3.1 WORKING ELECTRODE (WE) ............................................................................................... 13
3.3.2 REFERENCE ELECTRODE (RE) ........................................................................................................ 13
3.3.3 COUNTER ELECTRODE (CE) ................................................................................................. 14
4.CURRENT IN VOLTAMMETRY 14
4.1 FARADAIC CURRENT.................................................................................................................... 14
4.2 NON-FARADAIC CURRENT........................................................................................................... 15
4.3 RESIDUAL CURRENT .................................................................................................................... 15
5.STEPS TOWARD DATA RECORDING 15
5.1 RECORDING A BACKGROUND SCAN ........................................................................................... 15
5.2 MEASURING THE OPEN CIRCUIT POTENTIAL .............................................................................. 17
5.3 MINIMIZING OHMIC DROP ......................................................................................................... 17
5.4 MITIGATION OF OHMIC DROP .................................................................................................... 18
5.5 RECORDING THE CYCLIC VOLTAMMOGRAM .............................................................................. 18

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6. VOLTAMMOGRAM 18
6.1 CYCLIC VOLTAMMOGRAM: ......................................................................................................... 19
6.2 THE RANDLES-SEVCIK EQUATION ............................................................................................... 21
6.3 CYCLIC VOLTAMMETRY OF FERROCENE ..................................................................................... 22
6.4 TYPES OF CV VOLTAMMOGRAM................................................................................................. 23
6.4.1. REVERSIBLE VOLTAMMOGRAM .................................................................................................... 23
6.4.2. IRREVERSIBLE VOLTAMMOGRAM................................................................................................. 24
6.4.3. QUASI-REVERSIBLE VOLTAMMOGRAM ........................................................................................ 24
7.APPLICATION: 25
Characterization and synthesis ............................................................................................................... 26
7.1 Metals, metal complexes, and inorganic compounds ...................................................................... 27
7.2 Mechanism........................................................................................................................................ 28
7.3 Analysis ............................................................................................................................................. 29
7.3.1 Organic compounds ................................................................................................................... 29
7.3.2 Inorganic compounds................................................................................................................. 30
7.3.3 Other aspects of analysis ........................................................................................................... 31
7.4 Areas of applications ......................................................................................................................... 31
7.5 Other areas ....................................................................................................................................... 32
8.CONCLUSION 33

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1. ABSTRACT
Cyclic voltammetry or CV is a type of potentiodynamic electrochemical measurement. It is
an electrochemical method which measures the current that develops in an electrochemical
cell under conditions where voltage is in excess of that predicted by the Nernst equation. CV
is performed by cycling the potential of a working electrode, and measuring the resulting
current.
In a cyclic voltammetry experiment, the working electrode potential is ramped linearly
versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV
experiment, the working electrode’s potential is ramped in the opposite direction to return to
the initial potential. These cycles of ramps in potential may be repeated as many times as
desired. The current at the electrode is plotted versus the applied voltage (i.e., the working
electrode’s potential) to give the cyclic voltammogram trace. Cyclic voltammetry is generally
used to study the electrochemical properties of an analyte in solution, and also used to
examine the reversibility of the adsorption process and its effect on oxygen reduction current.
It can also be used to determine the electron stoichiometry of a system, the diffusion
coefficient of an analyte.

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2. INTRODUCTION

2.1 ELECTROCHEMISTRY
Electrochemistry is the study of chemical processes to facilitate the electrons to move from their
places. This movement of electrons is called electricity and it can be generated by movements of
electrons from one element to another in a reaction known as an oxidation-reduction reaction.
Electrochemistry shows emphasis on chemical reactions which involves the transfer of electric
charge from corner to corner of the electrified interface in-between electronic and ionic
conductors. Electrochemical reactions are intrinsically associated with currents and voltages.

2.1.1 ELECTROCHEMICAL SYSTEM:

Electrochemist’s study chemical reactions which involve electron exchange processes for a
variety of purposes like chemical and biochemical sensing, technological applications (e.g.,
electroplating, electro-chromic displays), energy storage, imaging, synthesis, which highlight
much of modern biology and nanotechnology.

Electron Transfer: For understanding cyclic voltammetry one must understand electron transfer
before. There are two types of electron transfer

➢ Homogeneous: The electron transfer involves specie in the same phase. It is usually a
chemical process that utilizes chemical reductants.
➢ Heterogeneous: The electron can transfer through an interface and is usually
electrochemical electron transfer wherein the electron transfer occurs to/from electrode. It
occurs between molecules. eg, electron transfers at liquid-liquid interfaces or between an
electronic conductor (the electrode) and a molecule

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2.1.2 ELECTROCHEMICAL CELL:

An electrochemical cell is a gadget in which a chemical reaction induces an electrical signal or,
an electrical current is applied to activate a chemical reaction. The simplest electrochemical cell
consists of 2 connected electrodes in an electrolyte solution. In cyclic voltammetry, 3
electrodes are used.

2.2 INTRODUCTION TO VOLTAMETRY

Voltammetry is an analytical method that provides information about analyte through electrical
currents that is obtained from a potential variation. The potential is changed frequently while the
current is monitored in voltammetry.

2.1.2 GENERAL PRIINCIPLE:

In voltammetry current is measured as a function of changing potential which is denoted as E.

As potential is applied the electrolysis of analyte begins and current rises until it reaches the
current limit that is present.

For example:

Cd2+ + 2e =======→ Cd

The magnitude of the electric current is directly proportional to the concentration of the analyte
that is written as, I =k C

Were,

I= Current

C= Concentration of analyte

k= Constant

In voltamogram graph is plotted between

current and potential, the plot is I/E.

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 CYCLIC VOLTAMETRY

2.3 TYPES OF VOLTAMMETRY

Voltammetry represents an electrochemical method in which an exact voltage profile is applied
to a working electrode. The working electrode is present as a function of time and the current
which is produced by the system and it is measured accordingly. Voltammetric methods include
the following types.

➢ Linear sweep voltammetry

➢ Cyclic voltammetry

There are also other types of voltammetry that include anodic stripping voltammetry and
cathodic stripping voltammetry.

2.3.1 LINEAR SWEEP VOLTAMMETRY

In linear sweep voltammetry (LSV) may be a fixed potential range. it's in use the maximum
amount like potential step measurements. But in LSV the voltage is scanned from lower to upper
limit. Reduction/ oxidation of species are shown as a peak or trough inside the current signal at
the potential in which the species start to be oxidized or reduced. The characteristics of the linear
sweep voltamogram that are recorded
depend on a number of factors which
include:

➢ The rate of the electron transfer

reactions
➢ The chemical reactivity of the electro
active species
➢ The voltage scan rate

THE EXPERIMENTAL SETUP

A linear sweep voltammetry uses a potentiostat and a 3-electrode setup to deliver a potential to a
solution and it observe its change in current.

➢ Working Electrode
➢ Auxiliary Electrode
➢ Reference Electrode

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The potentiostat send the potentials through the three-electrode setup. A possible, E, is delivered
through the working electrode. The slope of the potential drop vs. time graph is named the scan
rate and it can range from mV/s to 1,000,000 V/s.

2.4 CYCLIC VOLTAMETRY

Cyclic Voltammetry is an electrochemical technique which determines the current that is
produced in an electrochemical cell in conditions where voltage is in excess amount than that
predicted by the Nernst equation. CV is carried out by cycling the potential difference of a
working electrode, and then determining the consequential current. It contains 3 working
electrodes.

Working Electrode
Counter Electrode Reference Electrode

In a cyclic voltammetry experiment, the working electrode potential is plotted linearly versus
time. Contrasting to linear sweep voltammetry, when the set potential is achieved in a CV
experiment, then the working electrode's potential is increased in the opposite direction to come
back to the initial potential.

2.3. CYCLIC VOLTAMETRY

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 CYCLIC VOLTAMETRY

Cyclic voltammetry is an electrochemical technique for determining and calculating the current
response of a redox active solution to a linearly cycled potential sweep in between two or more
set values. It’s a useful method for quickly finding information about the thermodynamics of
redox processes, also the energy levels of the analyte and consequently the kinetics of electronic-
transfer reactions.

To carryout cyclic voltammetry, the

electrolyte solution is first added to an
electro-chemical cell along with a
reference solution and the 3
electrodes. A potentiostat is then
accustomed linearly sweep the
potential between the working and
reference electrodes until it reaches a
fixed limit, at which point it's swept back within the opposite direction. This process is repeated
multiple times during a scan and also the changing current between the working and counter
probes is determined by the device in real time. The result's a characteristic duck-shaped plot
called a cyclic voltammogram.

2.4 BASIC PRINCIPLE

Potentiometry is a way of determining and calculating the electrical potential of an

electrochemical cell under no current flow (i.e., static conditions).

For a common redox reaction, the standard potential is associated to the concentration of the
reactants A and products B at the electrode containing solution interface that are according to the
Nernst equation:

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 CYCLIC VOLTAMETRY

Here in the above equation

E = electrode potential

E0′ = formal potential

R= gas constant (8.3145 J·K-1·mol-1)

T = temperature

n= number of moles of electrons involved

F = Faraday constant (96,485 C·mol-1).

The term [B]b/ [A]a represents the ratio of products to reactants and is raised to their particular
stoichiometric powers. This is replaceable for activity term when the concentration of reactants is
sufficiently low (< 0.1 mol·dm˗3).

STANDARD CONDITIONS:

The Nernst equation for standard conditions of temperature and pressure can be written as
follow:

An electrochemical reaction is reversible in characteristics. When the kinetics of electron transfer

is adequately fast as the concentration of oxidized species and the concentration of reduced
species is present in equilibrium.

3. INSTRUMENTATION

3.1ELECTROCHEMICAL CELL
The vessel used for a cyclic voltammetry experiment is called an electrochemical cell. It consists
of the sample dissolved in a solvent, an ionic electrolyte, and three (or sometimes two)
electrodes. Cells (that is, sample holders) come in a variety of sizes, shapes, and materials. The

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type used depends on the amount and type of sample, the technique, and the analytical data to be
obtained. The material of the cell (glass, Teflon, polyethylene) is selected to minimize reaction
with the sample. In most cases the reference electrode should be as close as possible to the
working electrode; in some cases, to avoid contamination, it may be necessary to place the
reference electrode in a separate compartment.

Schematic representation of an electrochemical cell for CV experiments

3.2 PREPARATION OF ELECTROLYTE SOLUTION

As electron transfer occurs during a CV experiment, electrical neutrality is maintained via
migration of ions in solution. As electrons transfer from the electrode to the analyte, ions move
in solution to compensate the charge and close the electrical circuit. A salt, called a supporting
electrolyte, is dissolved in the solvent to help decrease the solution resistance. The mixture of the
solvent and supporting electrolyte is commonly termed the “electrolyte solution.”

➢ SOLVENT

A good solvent has these characteristics:

• It is liquid at experimental temperatures.

• It dissolves the analyte and high concentrations of the supporting electrolyte completely.

• It is stable toward oxidation and reduction in the potential range of the experiment.

• It does not lead to deleterious reactions with the analyte or supporting electrolyte.

• It can be purified.

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➢ SUPPORTING ELECTROLYTE
A good supporting electrolyte has these characteristics:

• It is highly soluble in the solvent chosen.

• It is chemically and electrochemically inert in the conditions of the experiment.

• It can be purified.

Large supporting electrolyte concentrations are necessary to increase solution conductivity. As

electron transfers occur at the electrodes, the supporting electrolyte will migrate to balance the
charge and complete the electrical circuit. The conductivity of the solution is dependent on the
concentrations of the dissolved salt. Without the electrolyte available to achieve charge balance,
the solution will be resistive to charge transfer. High absolute electrolyte concentrations are thus
necessary.

Large supporting electrolyte concentrations are also necessary to limit analyte migration.
Movement of the analyte to the electrode surface is controlled by three modes of mass transport:
convection, migration, and diffusion. High electrolyte concentration relative to the analyte
concentration ensures that it is statistically more probable that the electrolyte will migrate to the
electrode surface for charge balance.

For aqueous solutions, many electrolytes are available, but typical ones are alkali metal salts of
perchlorate and nitrate. In nonaqueous solvents, the range of electrolytes is more limited, and a
popular choice is tetrabutylammonium hexafluorophosphate.

3.3ELECTRODES
A three-electrode setup used, including a glassy carbon working electrode, glass carbon counter
electrode, and Ag+/Ag pseudo reference electrode. This setup is typical for common
electrochemical experiments, including cyclic voltammetry, and the three electrodes represent a
working electrode, counter electrode, and reference electrode, respectively. While the current
flows between the working and counter electrodes, the reference electrode is used to accurately
measure the applied potential relative to a stable reference reaction.

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3.3.1 WORKING ELECTRODE (WE)

The working electrode carries out the electrochemical event of interest. A potentiostat is used to
control the applied potential of the working electrode as a function of the reference electrode
potential. The most important aspect of the working electrode is that it is composed of redox-
inert material in the potential range of interest. These electrodes are of various geometries and
materials, ranging from small Hg drops to flat Pt disks. Mercury is useful because it displays a
wide negative potential range (because it is difficult to reduce hydrogen ion or water at the
mercury surface), its surface is readily regenerated by producing a new drop or film, and many
metal ions can be reversibly reduced into it. Other commonly used electrode materials are gold,
platinum, and glassy carbon.

It is necessary to polish the electrode prior to measurements, and often, electrodes need to be
repolished between measurements over the course of an experiment because some analytes are
prone to electrode surface adsorption. To determine if an analyte is adsorbed to the electrode
surface, a simple rinse test can be performed: after recording a voltammogram, the working
electrode is rinsed and then transferred to an electrolyte-only solution. If no electrochemical
features are observed by CV, this rules out strong adsorption (although not weak adsorption).
Since electrodes are capable of adsorbing species during an experiment, it is good practice to
polish them after every experiment. Ideally, separate polishing pads are used before and after
experiments to avoid contamination.

3.3.2 REFERENCE ELECTRODE (RE)

A reference electrode has a well-defined and stable equilibrium potential. It is used as a reference
point against which the potential of other electrodes can be measured in an electrochemical cell.
The applied potential is thus typically reported as “vs” a specific reference. There are a few
commonly used (and usually commercially available) electrode assemblies that have an electrode
potential independent of the electrolyte used in the cell. Some common reference electrodes used
in aqueous media include the saturated calomel electrode (SCE), standard hydrogen electrode
(SHE), and the AgCl/Ag electrode. These reference electrodes are generally separated from the
solution by a porous frit.

In nonaqueous solvents, reference electrodes based on the Ag+/Ag couple are commonly
employed. These consist of a silver wire in a solution containing an Ag+ salt, typically AgNO3.

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Conversion tables exist which enable referencing of data obtained with an Ag+/Ag electrode to
other types of reference electrodes for several silver salt, solvent, and concentration
combinations. The potential of Ag+/Ag reference electrodes can vary between experiments due to
variations in [Ag+], electrolyte, or solvent used, so it is important to note the specific details of a
nonaqueous reference electrode. To circumvent these problems, reduction potentials should be
referenced to an internal reference compound with a known E0′. Ferrocene is commonly included
in all measurements as an internal standard, and researchers are encouraged to reference reported
potentials vs the Ferrocene couple at 0 V vs Fc+/Fc.

3.3.3 COUNTER ELECTRODE (CE)

When a potential is applied to the working electrode such that reduction (or oxidation) of the
analyte can occur, current begins to flow. The purpose of the counter electrode is to complete the
electrical circuit. Current is recorded as electrons flow between the working electrode and
counter electrode. To ensure that the kinetics of the reaction occurring at the counter electrode do
not inhibit those occurring at the working electrode, the surface area of the counter electrode is
greater than the surface area of the working electrode. A platinum wire or disk is typically used
as a counter electrode, though carbon-based counter electrodes are also available.

When studying a reduction at the working electrode, an oxidation occurs at the CE. As such, the
CE should be chosen to be as inert as possible. Counter electrodes can generate byproducts
depending on the experiment; therefore, these electrodes may sometimes be isolated from the
rest of the system by a fritted compartment. One example is the oxidative polymerization of THF
that can occur at the CE when studying a reductive process in THF at the working electrode.

4. CURRENT IN VOLTAMMETRY

4.1FARADAIC CURRENT
When we oxidize an analyte at the working electrode, the resulting electrons pass through the
potentiostat to the auxiliary electrode, reducing the solvent or some other component of the
solution matrix. If we reduce the analyte at the working electrode, the current flows from the
auxiliary electrode to the cathode. In either case, the current from redox reactions at the working
electrode and the auxiliary electrodes is called a faradaic current.

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4.2NON-FARADAIC CURRENT
In addition to current resulting from redox reactions—what we call faradaic current—the current
in an electrochemical cell includes other, non-faradaic sources. Suppose the charge on an
electrode is zero and that we suddenly change its potential so that the electrode’s surface
acquires a positive charge. Cations near the electrode’s surface respond to this positive charge by
migrating away from the electrode; anions, on the other hand, migrate toward the electrode. This
migration of ions occurs until the electrode’s positive surface charge and the negative charge of
the solution near the electrode are equal. Because the movement of ions and the movement of
electrons are indistinguishable, the result is a small, short-lived non-faradaic current that we
call the charging current. Every time we change the electrode’s potential, a transient charging
current flow.

4.3RESIDUAL CURRENT
Even in the absence of analyte, a small, measurable current flows through an electrochemical
cell. This residual current has two components: a faradaic current due to the oxidation or
reduction of trace impurities and the charging current.

5. STEPS TOWARD DATA RECORDING

5.1RECORDING A BACKGROUND SCAN

Now that the components are ready, the cell can be assembled, and voltammograms can be
recorded. When no electro active species have been added to the electrolyte solution,
voltammograms should exhibit the profile of the blue trace. A small current is still flowing
between the electrodes, but no distinct features are observed. This background current is
sometimes called capacitive current, double-layer current, or non-Faradaic current. The
intensity of the current varies linearly with the scan rate used. The background scan is essential
to test if all the components of the cells are in good condition before adding the analyte as well
as to quantify the capacitive current.

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➢ IMPORTANCE OF AN INERT ATMOSPHERE

Once the electrolyte solution is prepared, and the cell is assembled, one may begin experiments.
Consider a 0.25 M [NBu4] [PF6] solution in acetonitrile prepared in a fume hood. The potential
window for this acetonitrile solution is wide. If the potential is scanned within this window, no
redox events should be observed (i.e., the current
response should be relatively flat). However, if this
experiment is performed with the solution prepared as
described above, one would instead see an unexpected
peak as the potential is scanned cathodically. In the
reverse scan, another peak emerges that seems related to
the first peak. Peaks appear in the absence of analyte
because solution prepared in open atmosphere. While
nitrogen is electrochemically inert within this window,
oxygen is not. Oxygen undergoes a reversible one-
electron reduction to form the oxygen radical anion
(superoxide, O2•–). The peaks in the red trace are attributed to the reduction of oxygen and then
the subsequent reoxidation. Note that in solvents besides acetonitrile, the reduction of oxygen
may not be cleanly reversible.

In electrochemical experiments, the presence of

oxygen can also alter the electrochemical response of
analytes. For example, under inert atmosphere,
[CoCp(dppe)(CH3CN)] [PF6]2 undergoes two
reversible, one-electron reductions (green trace).
However, if oxygen is introduced, reversibility is lost
as the reduced analyte can transfer an electron to
dissolved O2, becoming oxidized through this chemical
step (orange trace). To avoid interference from dissolved O2, all electrolyte solutions should be
sparged with an inert gas before measurements are taken. Once all the O2 is removed from the
cell, the Teflon tubing used for sparging is placed above the surface of the solution to continue
flushing the headspace while not perturbing the solution in the cell. Another option is to feed

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electrode cables into an inert atmosphere glovebox and run electrochemical experiments using
previously deoxygenated solvents.

5.2MEASURING THE OPEN CIRCUIT POTENTIAL

When the cell is assembled, and the analyte has been added, a potential develops at the
electrodes. For example, when Fc+ is added to a cell, the potential of the electrode equilibrates
with the solution (so that no current flows). The potential observed when no current is flowing is
called the open circuit potential (OCP). The OCP can give information about the redox state of
species in the bulk solution as well as the concentration of different species when the solution
contains a mixture.

5.3MINIMIZING OHMIC DROP

The electrochemical cell considered so far was assumed to be ideal. However, electrolytic
solutions have an intrinsic resistance Rsol in the electrochemical cell. While some potentiostats
can compensate for most of this solution resistance (Rc), there remains a portion of
uncompensated resistance (Ru) between the WE and the RE (technically between the WE and the
entire equipotential surface that traverses the tip of the RE. During electrochemical
measurements, the potential that the instrument records may not be the potential experienced by
the analyte in solution due to Ru. This phenomenon is called ohmic drop. A telltale sign of ohmic
drop in CV is increased peak-to-peak separation in the voltammogram for a redox event that is
known to be electrochemically reversible.

The potential difference due to ohmic drop, per Ohm’s Law, equals the current passed (I) times
the resistance, Ru. For large values of Ru or I, the resulting ohmic drop may be unacceptably large
and affect the accuracy of the data.

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5.4MITIGATION OF OHMIC DROP

Ohmic drop can be mitigated by three methods:

1. Diminish i, by reducing the size of the working electrode or restricting the experiment to
slow scan rates
2. Decrease Rsol, and therefore decrease Ru, by increasing the conductivity of the solution with
higher electrolyte concentrations.
3. Decrease Ru directly (and increase Rc) by diminishing the distance separating the reference
and working electrodes.

For most experiments, these approaches will reduce ohmic drop enough that its overall effect
will be negligible. There are times, however, when experimental conditions restrict the
employment of these methods. To account for this, many potentiostats have software to
experimentally determine Ru and compensate for it in real time.

5.5RECORDING THE CYCLIC VOLTAMMOGRAM

Once the cell has been assembled and sparged of oxygen and precautions have been taken to
minimize ohmic drop, experiments can be run. The electrodes are connected to the potentiostat,
and the experimental parameters are selected through the potentiostat software. While different
software will require different parameters, fundamental ones are the potential window that will
be scanned (defined by the initial, switching, and final potentials), the scan rate, and the number
of segments/scans. Some potentiostats allow one to start the scan at the OCP, where the solution
is at equilibrium, and no net current is passed. Advanced parameters include an automatic or
manual compensation of Ru and are generally specific to each manufacturer’s instrument.

6. VOLTAMMOGRAM

DEFINITION:
A Voltammogram is a graph of electrochemical experiment in which current (i) is measured in
volt against the potential (E).

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The x-axis represents the applied potential (E) and y-axis represents current (i). The arrow
indicates the direction of forward scan. The scan rate shows that the potential was changed at the
speed (scan rate) per second.

6.1 CYCLIC VOLTAMMOGRAM:

The Cyclic Voltammogram is generated in duck shape.

The curve sweeps forward at point ‘a’ towards more positive oxidative potentials. At this point
potential is not enough to oxidize the analyte.

As the onset oxidation potential (Eonset) is attained, the current increases exponentially at point
‘b’. Here the analyte is oxidized at working electrode. We see that the current is increasing in a
linear pattern with increasing voltage and there is a constant gradient of concentration of analyte
near the electrode surface within the diffuse double layer.

The current reaches at maximum peak at point ‘c’ for oxidation at the potential which is called as
anodic peak potential (Epa) and current at this potential as anodic peak current (ipa). The
current decreases from linearity as the analyte concentration is decreased and diffuse double
layer increases in size. So, the more positive potentials cause an increase in current that is offset
by decreasing flux of analyte from distance from the electrode surface.

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O + e- → R

After the point ‘c’ the current is decreased little due to analyte transportation which is slow on
electrochemical scale and thus do not satisfy Nernst equation. This causes the decrease in current
and is reached at point d and the potential are scanned more positive until a steady-state is
reached where further increases in potential no longer has an effect.

The Nernst equation gives the relation of cell potential (E) to standard potential (Eo) of analyte. It
also related the activities of oxidized and reduced specie in system at equilibrium condition. The
Nernst equation is given as;

Where;

F is Faraday’s constant,

R is the universal gas constant,

n is the number of electrons, and

T is the temperature

In cyclic voltammetry during the scan of potential, concentration of analyte in solution changes
with time according to Nernst equation.

Now the reversal of scan occurs to negative potential which is called as reductive scan. But until
point ‘e’ it continues to oxidize the analyte until the potential value at which the oxidized analyte
gets accumulated at electrode surface and now can be reduced at point ‘e’.

The process for reduction is same as for oxidation in opposite direction like the mirror images.
The scan rate for reduction sweeps with opposite sign to the scan rate of oxidation. At point ‘f’
the reduction of analyte reaches at maximum point where the reductive peak current is called as
cathodic peak current(ipc) a potential at this current is called as cathodic peak potential (Epc).
The anodic and cathodic peak currents should have equal magnitude but opposite direction for
the reversibility of process.

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R → O + e-

6.2THE RANDLES-SEVCIK EQUATION

The peak current of oxidation and reduction (ip) of a reversible cyclic voltammetry is explained
by RANDLES-SEVCIK equation. It gives the relation of peak current with the scan rate for the
determination of diffusing coefficient. Faster is the scan the larger is the current.

At 298 K, the equation is given as:

Where;

n is the number of electrons,

The electrode area (cm2),

C the concentration (mol·cm-3),

D the diffusion coefficient (cm2·s-1),

v the potential scan rate (V·s-1).

According to IUPAC convention the CV plot is given as;

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In US convention CV plot is 180o rotated to that of IUPAC convention.

6.3 CYCLIC VOLTAMMETRY OF FERROCENE

Ferrocene (Fc) is generally used as the internal standard for CV. The application of Nernst
equation is observed for one electron reduction of ferrocene as Fc+ to Fc.

Here n = 1 and Eo = Eo' (formal potential)

The formal potential is estimated according to experimentally measured half potential E1/2 value.
When the potential E = E°′ ≈ E1/2 is applied, the Nernst equation shows that Fc+ would be
reduced to Fc only if [Fc+] = [Fc] and so equilibrium is gained.

The positive onset potential is applied between working and reference electrodes. As the
potential is increased ferrocene close to working electrode is oxidized to Fc+. The oxidation
continues, the electric current is increased and Fc+ is accumulated at the electrode. This buildup
of Fc+ is called as the diffusion layer. It affects the rate of arriving un-oxidized analyte at the
electrode.

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As the diffusion layer grows to certain size, the oxidation slows down and electric current is
decreased along with oxidation rate. The process then reverses and reduction takes place. Fc
reduces to Fc. The electric current creates a negative current value.

6.4TYPES OF CV VOLTAMMOGRAM

6.4.1. REVERSIBLE VOLTAMMOGRAM:

The reversible system follows the rendles-sevcik equation. The current increases with the square
root of scan rate. The criteria for reversible system include;

The ratio of anodic current and cathodic current is 1.

Ia/Ic=1

The formal potential for a reversible couple is given between Epa and Epc.

E° = (Epa + Epc)/2

Potential of cathodic and anodic current gives reversibility if the separation between peak
potential is;

Ep = Epa - Epc = 59mV/n

n= no. of electrons transfer

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6.4.2. IRREVERSIBLE VOLTAMMOGRAM

In reversible process, the size of peaks is reduced and separation is wide. The scan rate and
potential relation in irreversible system is given as;

Ep = E° - (RT/anaF)[0.78 - ln(ko/(D)1/2) + ln (anaFn/RT)1/2]

Where;

a is the transfer coefficient; na is the number of electrons involved in the charge-transfer step.

Ep occurs at potentials higher than E°, with the over potential related to k° and a. Independent of
the value k°, such peak displacement can be compensated by an appropriate change of the scan
rate.

The irreversibility criteria include;

The difference of peak potential and half peak potential (298 K) is;

E= Ep-Ep1/2= 48/an mV

Thus, the Voltammogram appears to be more withdrawn as a decrease.

The rendles-sevcik equation is still followed but with lower height of peaks.

6.4.3. QUASI-REVERSIBLE VOLTAMMOGRAM

The shape of Voltammogram is a function of the ratio k°/(pnnFD/RT)1/2. As this ratio is

increased the process becomes reversible and with the decrease process becomes irreversible.
Hence quasi-reversible is between the reversible and irreversible system.

The Voltammogram are more drawn out with the larger separation of peak potentials than for
reversible systems. The peak current in quasi-reversible Voltammogram is given by:

ip = (2.99x105)n(ana)1/2ACD1/2n1/2

Where;

n is equal to the number of electrons gained in the reduction,

A is the surface area of the working electrode in cm2,

D is the diffusion coefficient in cm2/s,

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 CYCLIC VOLTAMETRY

n is the sweep rate in V/s, and

C is the bulk molar concentration in mole/cm3.

7. APPLICATION:
Cyclic voltammetry is a multipurpose method for scientific investigation and innovation due to
the fact that most procedures involve electron transfer, which makes them be able to be observed
by this technique. Its uses contain characterization, synthesis, mechanisms, and analysis. In all
applications, the technique can work well with a great variety of compounds including organic,
inorganic, polymer, films, and semiconductors, among others. Additionally, the method operates
acceptably whether in a direct or an indirect approach. It can be considered to be a vital part at
the very start that leads further to the grand project. As an analytical tool, it plays a significant
role in not only chemistry but also other relating areas.

Cyclic voltammetry has long been well known for its adaptable applications in a number of areas
involving electron transfer process, both directly and indirectly. It should be familiar at first that
the techniques are generally not the main or the most significant one in the research. Rather, their
data are really useful in satisfying the work as an indispensable complementary technique. It has
been well applied in monitoring electrochemical behavior of an inordinate variability of
substances due to the fact that it can provide the insights into the relationship of structure,

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 CYCLIC VOLTAMETRY

potential, and characteristic activities. The technique is protuberant with its advantages of
simplicity, sensitivity, speed, and low costs, among others, which results in an extensive range of
applications so far. Brief information for examples of recent applications is focused here along
with corresponding references for further studies in specific area of interest. Additionally, due to
the fact that there have been a large variety of applications, it is not easy to categorize.
Consequently, the content has been arranged to suit its further use, vision extension, and
initiation of new research.

We are going to discuss three main uses of cyclic voltammetry first for different types of
compounds, then continue with concerning areas that cyclic voltammetry is considered useful.

Characterization and synthesis

All-purpose concepts on using Cyclic Voltammetry for the characterization of polymers as well
as inorganic materials. Organic compounds and polymers Cyclic Voltammetry have been proved
to be accommodating in characterizing xanthone, a bioactive compound, revealing that catechol
is the key moiety to make it an operative scavenger for reactive species.

CV in methanol of antibiotic named amoxicillin revealed quasi reversible behavior and

the change of redox potential upon the interactions with both metal ions and amino acids,
which helps guiding in suggesting the medicine that they should not to be used together
with the antibiotic.
Electrochemical behavior of ibuprofen and its degradation could be observed closely by
CV and found to be different for various types of electrodes: for example, adsorption was
observed on silver composite electrode, providing the insights into selecting the
appropriate electrode for removing this pollutant.
Together with EIS, CV is also found to be very useful in characterizing redox designing
biosensors their behaviors depend on diffusion and capacitance, which might well shed
the light on designing biosensors. N-dodecylacrylamide (DDA) can form copolymer well
with ferrocene derivatives on ITO to be appropriate in the catalytic and sensor devices.
Its electron transfer characteristic is determined by the formation of monolayer or
multilayer on the surface. A polymer-modified electrode namely poly(vinylferrocenium)

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 CYCLIC VOLTAMETRY

on Pt was investigated and developed effectively by Cyclic Voltammetry technique to

make it applicable in analyzing organic compounds such as adenine. The film of
ruthenium complex can be synthesized via electropolymerization and then modified onto
Pt electrode as a sensor for hydrazine with the characterization by CV. Due to the fact
that pyrrole is electroactive, the behavior of various types of polypyrrole can be
conveniently followed by electrochemical methods, especially CV, and they were
extensively examined in past.
• CV could also be applied well in characterizing polyaniline to get suggestion in film
preparations that its kinetic behaviors have the effect from the dopant acid. Cyclic
Voltammetry can be used in electrografting born-doped diamond (BDD) surface via CV
cycling without the use of reducing agent to prepare ex-situ working electrode for Cd
purpose.
• With its lead of speed, fast scan Cyclic Voltammetry has been used to commend the use
of paraffin wax as a sealant instead of epoxy in making electrode for both in vivo and
in vitro applications. For natural polymers, CV has paved its way in examining specific
electroactive compounds such as quinones in natural rubbers, which is very helpful in
considerate their properties.

7.1 Metals, metal complexes, and inorganic compounds

Due to the fact that complex formation includes electron transfer, considerate the behavior of
metal-ligand interaction can be studied well by Cyclic Voltammetry and proven reasonably for
simulations for both higher and lower ligand concentrations as well as for obtaining general
formation constants.

The use of Cyclic Voltammetry to support the results from X-ray crystallography to describe the
behavior of copper thiourea-halide complexes. Redox potential and reversibility obtained by CV
have been proved to be useful in studying metalloenzymes with cofactor of molybdenum
complexes as a model to define its physiological role.

The characterizations of metal complexes have also been showed to help investigate the catalytic
activities of complexes for the removal of toxic phenolic substances, especially dyes.

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 CYCLIC VOLTAMETRY

At quantum level, redox potentials from Cyclic Voltammetry can be used in calculating LUMO
and HOMO as well as the gaps of novel organic semiconductors, which are relevant in everyday
life. CV has been proved to be beneficial in characterizing quantum dots (QDs), mainly in terms
of their stabilities in vivo.

Cyclic Voltammetry has been shown to be effective in subsequent molecular imprinting of

copper complexes. CV can also be used in tracing activated iridium oxide film (AIROF)
microelectrode via the dissimilarity of scan rate during the steps of fabrications and animal
implantation.

In particular, Cyclic Voltammetry from gold rotating disk electrode (Au RDE) has also been
proved to be beneficial in determining surface coverage of silica microparticle monolayer and
revealing that the adsorption is stronger with increasing diameter and surface coverage, which
sheds the light on the deposition of a diversity of particles onto the surface.

In terms of fuel cells, CV has been used to describe the synthesized Pt-Ru catalysts and their
catalytic activities. Application of Cyclic Voltammetry has been seen in characterization of metal
hydride. Using NaOH instead of KOH decreases hydrogen adsorption/desorption, resulting in
improved performance of nickel-metal hydride batteries.

7.2 Mechanism

Generally, Cyclic Voltammetry has been extensively recognized to be able to recognize the
mechanism of coupled chemical reaction. For recent applications, cyclic voltammetry was
applied together with voltabsorptometry in considerate the reaction of lumazine. Special
technique of fast Fourier transform continuous cyclic voltammetry was developed to be used
well in investigation of the mechanism of 4-nitrocatechol and its electrochemical synthesis.

This technique is also used in investigating proteolysis of milk protein by the research group.
The nontriangular waveform of CV has also been approved with the benefit of suitable
determination of transfer coefficient and electron transfer rate constant. Moreover, staircase was
compared with linear scan to support in investigating adsorbed species. Amazingly, CV can also
be used in perusal of the mechanism of surface coating. Cyclic voltammetry was used composed
with potentiometry in understanding interactions between nicotine and metal ions. The

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 CYCLIC VOLTAMETRY

mechanism of electropolymerization and catalytic reaction of phenol red can be described well
by CV in order to examine acetaminophen and dopamine. The technique is also helpful in
interpretation of Ni electrodeposition for encompassing methanol oxidation. Furthermore, it can
be used in understanding the mechanism of synthesizing graphene-coated electro grafting
electrode suitably and fast in only one step. The technique has been showed to be a helpful tool
for mechanistic modeling for biosensors.

7.3 Analysis

CV can be used widely for a wide range of both inorganic and organic compounds. In
accumulation, it can be applied indirectly to investigate other types of characteristics, for
example, microorganisms or antioxidant properties.

7.3.1 Organic compounds

For the analysis of organic compounds, cyclic voltammetry can be measured versatile in terms of
a great variety of compounds.

• glucose with graphene modified electrode

The technique has been used in the recognition of glucose with graphene modified electrode.
Due to the overlapping of redox peaks in cyclic voltammetry, mathematical operation such as
deconvolution has been practical in analyzing electroactive species including explosives,
particularly nitro Voltammetry 4 compounds. With modern technology in data analysis, the
techniques can be used in the resolve and identification of pesticides. Separation technology, for
example, electro membrane is also cooperative in eliminating interferences in diclofenac
analysis. Carbon black-modified also known as GCE was used in estradiol by voltammetry in
collaboration with FIA and amperometry.

• curcumin
Another important natural compound that has been extensively used is curcumin, and its
characteristics from CV can shed the light for its analysis in numerous corresponding
products.CV was also proved to be hypersensitive for hydrazine sensing.

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 CYCLIC VOLTAMETRY

• Boron-doped diamond

Boron-doped diamond also exhibits its performance as an electrode with superb sensitivity for
metronidazole in the examination by CV whereas bismuth electrode proved its specific
characteristic in monitoring thiol content in fossil fuel.

• 2,4,6-trichloroanisole

The determination of 2,4,6-trichloroanisole in cork stoppers to reduce the wine defect can be
accomplished acceptably with cyclic voltammetry.

• analysis of juice and wine

CV has played very significant role in the analysis of juice and wine with certain analytes such
as phenolic compounds.

• ionic liquids (ILs)

The analysis by CV helps in investigating standpoint ionic liquids (ILs) to be used as solvents
and electrolytes with their specific properties of cation and anion dependence.

• indicator compounds

It is also significant to state here that CV can be used in analysis with the increase or decrease of
the current signals of indicator compounds such as quinones or ferricyanide. Examines of
organic compounds by CV are sure to appear lengthily in the near future in the analytical
literature.

7.3.2 Inorganic compounds

Cyclic voltammetry can be used well with abundant inorganic compounds. It is normally applied
to simple inorganic compounds perhaps because their electrochemical behavior is less complex.
It is worth mentioning here that metal ions are normally monitored by stripping voltammetry, so
it is not going to delve into minutiae here. Surely, voltammetry is sensitive to metal ions, but its
specificity can be enhanced by electrode modifications and stripping potential.

An example of application of cyclic voltammetry to complex inorganic compounds is the case of

nanostructured iron oxides. Moreover, corrosive impurities can be monitored closely in molten

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 CYCLIC VOLTAMETRY

chloride by cyclic voltammetry, which is very useful for energy storage. With the use of chitosan
and silver nanocomposite modified electrode, hydrogen peroxide can be detected, and this can be
additional extended to the determination of other compounds involving hydrogen peroxide such
as glucose.

7.3.3 Other aspects of analysis

With electrochemical characteristics of CV, numerous analytical aspects of applications in
analysis can be realized as well. It was used in the estimation of antioxidant potential, which is
very significant in making wine. The technique, along with EIS, CV can be used in assessing
emulsion stability. Additionally, CV can be used in determining HOMO and LUMO levels with
an acceptable correctness.

With its understanding for antioxidant, CV can be used in classifying black tea. It is clear that
indirect uses of CV can be used in the future in a diversity of applications.

7.4 Areas of applications

➢ Chemistry

Electron transfer definitely plays a significant role in all reactions; consequently,

electrochemistry and CV in specific have an important part in all aspects of chemistry as
summarized in Table below.

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 CYCLIC VOLTAMETRY

7.5 Other areas

Due to the fact that CV offers vital information for better understanding and the instrument is
quite cost-effective now, thanks to modern technology, not to mention the way that it is easy to
access, cyclic voltammograph in the form of potentiostat and specific programs is a must in
maximum research and development labs.

Table below summarizes the use of CV in other areas besides chemistry.

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 CYCLIC VOLTAMETRY

8. CONCLUSION
Cyclic voltammetry is simple, sensitive, speedy and low cost among other techniques. It has
many diverse applications in analytical chemistry. The cyclic voltammetry works on the
principle of potential versus current. It consists of three electrode system. The plot of current
versus potential is called cyclic voltammograph. The cyclic voltammetry gives the oxidation and
reduction peaks giving three types of voltammograph reversible, irreversible or quasi reversible.

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9. REFERENCES

➢ https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Ana
lytical_Chemistry)/Instrumental_Analysis/Cyclic_Voltammetry
➢ googleusercontent.com/attachment/u/0/?ui=2&ik=4bba3c8c68&attid=0.2&permmsgid=msg-
f:1701120296126985138&th=179b97e57adb33b2&view=att&disp=inline&realattid=f_kpa4
➢ https://www.ossila.com/pages/cyclic-voltammetry#voltammetry
➢ https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Ana
lytical_Chemistry)/Analytical_Sciences_Digital_Library/Active_Learning/In_Class_Activiti
es/Electrochemical_Methods_of_Analysis/02_Text/7%3A_Electrochemical_Analytical_Met
hods/7.5%3A_Voltammetric_Methods
➢ https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Supplemental_Modules_(Ana
lytical_Chemistry)/Instrumental_Analysis/Cyclic_Voltammetry#:~:text=Cyclic%20Voltamm
etry%20(CV)%20is%20an,and%20measuring%20the%20resulting%20current.
➢ https://www.slideshare.net/AnuRadha66/cyclic-voltammetry-principle-instrumentation-
applications
➢ https://www.ossila.com/pages/cyclic-voltammetry
➢ https://www.intechopen.com/books/voltammetry/cyclic-voltammetry-and-its-applications
➢ https://pineresearch.com/shop/kb/software/methods-and-techniques/voltammetric-
methods/cyclic-voltammetry-cv/
➢ https://www.researchgate.net/publication/329014747_A_Brief_Study_of_Cyclic_Voltammet
ry_and_Electrochemical_Analysis
➢ https://link.springer.com/article/10.1007/s40828-015-0016-y

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