Chemistry

Department

CHM 4283
Assignment topic
0
“Voltammogram” Voltammogram

Instructor: Mam Fatima Jabbar

Submitted by:
Usman Ghani Section: CF3-17
Reg. id: R217BSCH0062 Submission Date: 1st Feb
Semester: 7th Due Date: 1st Feb
 Voltammogram

A voltammogram is a plot of the current as a function of the applied potential. The shape of a
voltammogram depends on the type of indicator electrode and the potential ramp that is used. 

The typical shape of the voltammogram is due to the way in which an electrochemical
experiment is usually set up. There are roughly two groups of measurements that are plotted as
voltammograms: pulsed techniques and linear sweeps.

A cyclic voltammogram is obtained by measuring the current at the working electrode during
the potential scans. Following shows a cyclic voltammogram resulting from a single electron
reduction and oxidation. Consider the following reversible reaction:

M++e− ⇌ M

1 Voltammogram

A Typical cyclic voltammogram

 Voltammogram Depiction:

Plot of current versus applied potential a voltammogram, and it is the electrochemical

equivalent of a spectrum in spectroscopy, providing quantitative and qualitative information
about the species involved in the oxidation or reduction reaction. Quantitative and qualitative
information may be extracted from a voltammogram. Quantitative information is obtained by
relating current to the concentration of analyte in the bulk solution. Qualitative information is
obtained from the voltammogram by extracting the standard-state potential for the redox
reaction. Voltammogram also facilitate about

 Determining Concentration 

 Determining the Standard-State Potential 

Phases in a voltammogram

1. In order to investigate the presence of a particular substance in a liquid, a potential is applied

2 to an electrode in the liquid by means of a potentiostat. This potential is increased linearly by

Voltammogram
a fixed increase per period of time. The potential of the electrode will cause the substance to
react. The initial cathodic (negative), where no reaction took place, turns into a more anodic
(positive) potential. The electrode starts to draw electrons from the substance in the liquid
towards itself. The curve now shows an exponentially upward trend, i.e., with increasing
potential the current increases.

2. After reaching the so-called redox potential, the initial exponential rise of the curve levels
off. The cause being the decreasing amount of substance in front of the electrode, which also
results in a lack of electrons, until eventually no electrons are left to draw close. The curve is
at its highest point.

3. The potential is still being increased towards anodic (positive) potentials. Still the current is
decreasing, because there is less and less substance left to collect. Due to diffusion substance
is transported towards the electrode. All substance that reaches the electrode is immediately
converted. A further increase of potential doesn’t lead to an increase of current. The current
is limited by the diffusion of new substance towards the electrode.
 4. There is no reason to increase the potential any further. In case of Cyclic Voltammetry, the
potential descends linearly again. This drop in potential causes the lower curve, that shows
exactly the same gradient as the upper curve of the voltammogram, but then reversed. The
substance, which was converted during the anodic increase will now be reduced (receiving
electrons) again.

Shape and Types of Voltammograms

In voltammetry we measure current as a function of the

applied potential. The shape of a voltammogram is
determined by several experimental factors, the most
important of which are how we measure the current and
whether convection is included as a means of mass transport.
As suggested here, there are three common shapes for
voltammograms.

3 For the voltammogram in (a), the current increases from a Voltammogram

background residual current to a limiting current, il. Because
the faradaic current is inversely proportional to the thickness
of the diffusion layer, δ, a limiting current occurs only if the
thickness of the diffusion layer remains constant because we
are stirring the solution. In the absence of convection the
diffusion layer increases with time, and the resulting
voltammogram has a peak current instead of a limiting
current (b).For the voltammograms in (a) and (b), we
measure current as a function of the applied potential. We
also can monitor the change in current, Δi, following a
change in potential. As shown in (c), the resulting
voltammogram also exhibits a peak current.
 Different Tupes of Voltammogram:

4 Voltammogram

Voltammogram: Potential and current response and the concentration profile in the
vicinity of the electrode surface
5 Voltammogram

voltammograms for (a) normal pulse polarography, (b) differential pulse polarography, (c)
staircase polarography, and (d) square-wave polarography