Lecture Cyclic Voltammetry 25-8-22

Chapter
Electrochemical Cell
Introduction And Application

Cyclic voltammetry
Cyclic Voltammetry (CV) is an electrochemical technique which

measures the current that develops in an electrochemical cell
under conditions where voltage is applied. CV is performed by
cycling the potential of a working electrode, and measuring the
resulting current.
It is a useful method for quickly determining information about

the thermodynamics of redox processes, the energy levels of the
analyte and the kinetics of electronic-transfer reactions.
Cyclic Voltammetry: Basic Principles & Introduction
Cyclic voltammetry is an electrochemical technique for

measuring the current response of a redox active solution
to a linearly cycled potential sweep between two or more
set values. It is a useful method for quickly determining
information about the thermodynamics of redox processes,
the energy levels of the analyte and the kinetics of
electronic-transfer reactions.
Like other voltammetric methods methods, cyclic
voltammetry uses a three electrode system consisting of a
working electrode, reference electrode, and counter
electrode.
To perform cyclic voltammetry, the electrolyte solution
is first added to an electrochemical cell along with a
reference solution and the three electrodes. To measure Duck-shaped cyclic voltammogram
and control the potential difference applied, as required for
cyclic voltammetry, the potential of the working electrode
is varied while the potential of reference electrode remains
fixed by a electrochemical redox reaction with a well-
defined value.
To keep the potential fixed, the reference electrode must
contain constant concentrations of each component of the
Cyclic Voltammetry: Basic Principles & Introduction
A potentiostat is then used to linearly sweep the potential

between the working and reference electrodes until it
reaches a preset limit, at which point it is swept back in the
opposite direction.
This process is repeated multiple times during a scan
and the changing current between the working and
counter probes is measured by the device in real time. The
result is a characteristic duck-shaped plot known as a
cyclic voltammogram.
Duck-shaped cyclic voltammogram

Introduction
A cyclic voltammogram is obtained by measuring the current at the working electrode
during the potential scans. Figure 2 shows a cyclic voltammogram resulting from a
single electron reduction and oxidation. Consider the following reversible reaction:
In Figure , the oxidation process occurs from (a)

the initial potential to (d) the switching potential.
In this region the potential is scanned positively
to cause a oxidation. The resulting current is
called aniodic current (ipa). The corresponding
peak potential occurs at (c), and is called the
aniodic peak potential (Epa). The Epa is reached
when all of the substrate at the surface of the
electrode has been oxidized. After the switching
potential has been reached (d), the potential
scans negatively from (d) to (g). This results in
cathodic current (Ipc) and reduction to occur. The
peak potential at (f) is called the catodic peak
potential (Epc), and is reached when all of the
substrate at the surface of the electrode has
The Potentiometry Principle
Potentiometry is a way of measuring the electrical potential of an electrochemical cell under
static conditions (i.e. no current flow).
For a general reduction or oxidation (redox) reaction the standard potential is related to the
concentration of the reactants (A) and products (B) at the electrode/solution interface
according to the Nernst equation:
Introduction to Voltammetry
In the general sense, voltammetry is any technique where the current is measured while the
potential between two electrodes is varied. Voltammetric methods include cyclic voltammetry,
linear sweep voltammetry, and a number of variations such as staircase voltammetry,
squarewave voltammetry and fast-scan cyclic voltammetry.
In voltammetry experiments, the current generated is the result of electron transfer between the
redox species and the electrodes. This is carried through the solution by the migration of ions.
Although in principle voltammetry only requires
two electrodes, in practice it is very difficult to
maintain a constant potential while also passing
current to counteract the redox events at the
working electrode.
As a result, a three-electrode (working electrode,
counter electrode, and reference electrode) cell is
often used to separate the role of referencing the
potential applied and balancing the current
To measure and control the potential difference
produced.
applied, as required for cyclic voltammetry, the
potential of the working electrode is varied while
the potential of reference electrode remains fixed
by a electrochemical redox reaction with a well-
defined value.
To keep the potential fixed, the reference electrode must contain constant concentrations of each
component of the reaction, such as a silver wire and a saturated solution of silver ions.
Introduction to Voltammetry
Importantly, no current passes between the reference and working electrodes. The current
observed at the working electrode is completely balanced by the current passing at the
counter electrode, which has a much larger surface area.
The electron transfer between the redox species at the working electrode and counter
electrode generates current that is carried through the solution by the migration of ions.
This forms a capacitive electrical double layer at the surface of the electrode called the
diffuse double layer (DDL). The DDL is composed of ions and orientated electric dipoles that
serve to counteract the charge on the electrode.
Cyclic Voltammograms Explained
The ‘duck-shaped’ plot generated by cyclic voltammetry is called a cyclic voltammogram.
An example is displayed in Figure 1.
In Figure 1, the scan starts at -0.4V and sweeps

forward to more positive, oxidative potentials.
Initially the potential is not sufficient to oxidise the
analyte (Figure 1, a).
As the onset (Eonset) of oxidation is reached the
current exponentially increases (b) as the analyte is
being oxidised at the working electrode surface.
Here the process is under electrochemical control
with the current linearly increasing with increasing
voltage with a constant concentration gradient of
the analyte near the electrode surface within
the diffuse double layer.
The current response decreases from linearity as
the analyte is depleted and the diffuse double
layer grows in size. The current reaches peak
maximum at point c (anodic peak current (ipa) for
oxidation at the anodic peak potential (Epa). The Figure 1. Cyclic voltammogram
process is now under mixed control: more positive for an electrochemically-
potentials cause an increase in current that is offset reversible one-electron redox
Cyclic voltammograms
From this point the current is limited by the mass
transport of analyte from the bulk to the DDL
interface, which is slow on the electrochemical
timescale and therefore does not satisfy the Nernst
equation. This results in a decrease in current (d)
as the potentials are scanned more positive until a
steady-state is reached where further increases in
potential no longer has an effect.
Scan reversal to negative potentials (reductive
scan) continues to oxidise the analyte until the
applied potential reaches the value where the
oxidised analyte which has accumulated at the
electrode surface can be re-reduced (e).
The process for reduction mirrors that for the
oxidation, only with an opposite scan direction and
a cathodic peak (ipc) at the cathodic peak potential
Figure 1. Cyclic voltammogram for an
(Epc) (f). The anodic and cathodic peak currents electrochemically-reversible one-
should be of equal magnitude but with opposite electron redox process
sign, provided that the process is reversible.

Lecture Cyclic Voltammetry 25-8-22

Uploaded by

Copyright:

Available Formats

Lecture Cyclic Voltammetry 25-8-22

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lecture Cyclic Voltammetry 25-8-22

Uploaded by

Copyright:

Available Formats

Chapter

Introduction And Application

Cyclic Voltammetry (CV) is an electrochemical technique which

It is a useful method for quickly determining information about

Cyclic voltammetry is an electrochemical technique for

A potentiostat is then used to linearly sweep the potential

Duck-shaped cyclic voltammogram

In Figure , the oxidation process occurs from (a)

In Figure 1, the scan starts at -0.4V and sweeps

You might also like