SUBJECT FORENSIC SCIENCE

Paper No. and Title PAPER No.4: Instrumental Methods and Analysis

Module No. and Title MODULE No.30: Voltammetric Techniques

Module Tag FSC_P14_M30

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Principle of Voltammetric Techniques

4. Instrumentation in Voltammetric experiments

5. Types of Voltammetric Techniques

6. Applications and Limitations

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 7. Summary

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 1. Learning Outcomes

After studying this module, you shall be able to know about-

 The basic introduction to voltammetry

 The principle and instrumentation of voltammetry
 Various types of voltammetry
 Applications of voltammetry

2. Introduction

Earlier the voltammetry was known as electrochemistry, in 1922 voltammetry was established
from the invention of Polarography by Jaroslav Heyrovsky, a Czech chemist. For his work he
also got Nobel Prize in chemistry in 1959. In the years of 1960s and 1970s many advancements
were made in voltammetry, these advancements improved the sensitivity and range of analytical
techniques. All the voltammetric techniques apply potential (E) to an electrode and the resultant
current (i) is observed, this current flows through the electrochemical cell. In other cases, the
applied potential varies and the current is observed over a time period (t). All the types of
voltammetric methods can be termed as function of i, E and t. Voltammetric techniques are
active methods, the amount of electroactive species changes when forced by applied potential at
the surface of electrode by reducing and oxidizing. There are various analytical advantages of
voltammetric methods like, high sensitivity range for both organic and inorganic species,
solvents, electrolytes, fast analysis, concurrent analysis of several analytes, estimating the values
of unknown factors, etc. Voltammetric techniques are used routinely by chemists for
quantitatively determining mixture of dissolved inorganic and organic compounds. Analysis of
pharmaceutical compounds are also done using voltammetric techniques coupled with High
performance Liquid Chromatography.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 3. Principle of Voltammetric Techniques

All the voltammetric experimentations are carried out in an electrochemical cells. An

electrochemical cell composed of three types of electrode- working electrode, counter (auxiliary)
electrode and reference electrode. At working electrode all the reactions and transfer takes place
and it is an electron conductor. In every voltammetric experiments, it is compulsory that one of
the electrode is kept at constant potential. The reference electrode is designed in such a way that
it has constant potential. For harmonizing the total charge in the electrode cell, counter reaction
takes place at auxiliary electrode. Electroactive species are present in the electrochemical cell,
there concentration changes on the surface of the electrode by electrochemically oxidizing and
reducing these species. At working electrode the concentration of electroactive species changes,
this results in flow of mass in the direction of electrode and the current flowing across the
electrode is directly proportional to the concentration of the analyte. The voltammetric
techniques are used on daily basis for quantifying various organic and inorganic compounds
because of this reliance between concentrations of analyte and measured current.

R - Reference electrode
W - Working electrode
C - Counter electrode
A - Ampere meter
V - Voltmeter

Figure 1- representing simple electrochemical cell

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 4. Instrumentation in Voltammetric experiments

Modern instrumentation for voltammetric experiments consist of three parts-

i. Potentiostat
ii. Personal computer
iii. An electrochemical cell

Figure- 2 flow diagram for instrumentation for voltammetric experiments

In some instruments potentiostat and personal computer comes into one part.

4.1 Potentiostat
It is the “heart” of instrumentation for voltammetric experiments. The main work of potentiostat
is to execute an accurate potential and to monitor the changes in current in the system. In modern
electrochemical instruments, potentiostat comprises of converters, electrometer circuits,
microprocessor with internal memory and amplifier.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 4.2 Electrochemical cells and electrodes
Electrochemical cell is a sample holder, where desolvation of analyte in a specific solvent takes
place and this dissolved sample is placed into an ionic electrolyte. Ionic electrolyte comprises of
three electrodes – working electrode, reference electrode and counter electrode. These
electrochemical cells comes in different designs and made from glass, polyethylene and Teflon
material. All the electrodes in the electrochemical cells are fully submerged, but in some designs
the reference electrode is separately placed to prevent contamination and via electrolyte bridge
the reference electrode is connected to the system.

An electrode is said to be a reference electrode when it gives reversible half reaction with
Nernstian behavior, the electrode having constant potential over a time period and maintenance
is easy. Most commonly used reference electrodes for experiments executed in aqueous mediums
are the calomel electrodes. The calomel electrode’s potential is estimated by the following
reaction-

Hg2Cl2 (s) + 2e ⇌ 2Hg (l) + 2Cl-

Silver/Silver Chloride electrodes are also used and its potential is determined by the following
reaction-

AgCl (s) + e ⇌ Ag (s) + Cl-

Commonly used counter electrodes are platinum wire, gold wire and graphite wire. The function
of the counter electrode is to maintain the electroneturality in the system. In case of working
electrodes, metallic electrodes like mercury drops, platinum or gold disk. Mercury is widely used
as the working electrode because it has high negative potential for hydrogen ions.

The only limitation of mercury electrode is that it has low potential of oxidation and that is why
various compounds cannot be studied in this mode. For lipophilic organic compounds carbon
electrodes are used, because they are highly lipophilic in nature.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 Carbon electrodes are also present in many forms like glassy carbon electrodes, screen printed
electrodes, carbon paste electrodes, diamond electrodes, etc. Biosensors, gold-bismuth films and
immunosensors are various types of materials used in an electrode.

5. Types of Voltammetric Techniques

5.1Cyclic Voltammetry

Cyclic voltammetry is one of the most commonly used techniques. Its primary benefit is that it
gives vision of both the half reactions going on the working electrode and delivering the same
information about the phenomena for studying the electrochemical reaction. Therefore, it is also
called as Electrochemical Spectroscopy. In cyclic voltammetry, to the working electrode a stair
case potential sweep is employed. Then the sweep is reversed back to its initial value after
reaching the switching potential (Ef). Scan rate is a very important parameter of cyclic
voltammetry, as it controls the time scale of the experiment. The functional range of scan rate is
1 to 1000 mV/s. a cyclic voltammogram is produced, which is a current- potential curve.

Following are the characteristic of a cyclic voltammogram – half-peak potential, anodic and
cathodic peak currents and the cathodic and anodic peak potential. Half peak potential means a
median between anodic and cathodic potential. Half-peak potential gives information about
thermodynamics, whereas the magnitude of the peak currents provides kinetics included in
electrochemical reaction. The shape of voltammogram reveals data about the type of electrode
reaction and the number of electrons involved in this electrochemical transformation

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 Figure 3- (a) Staircase potential ramp; (b) Cyclic voltammogram

5.2 Pulse Voltammetry techniques

This type of technique was prompted by this fact that from potential changing and in the pulse
fashion the current should be measured, by this a significant distinction of the charging current
can be attained. Maintaining the potential difference between the reference electrode and
working electrode is an essential condition for commencing exchange of electrons between the
electroactive analyte and the working electrode in the cell. This modification in potential
difference results in discharging and charging of the double electrical layer present at the
interface of electrolyte and electrode, which also starts the flow of capacitive current. The main
principle of pulse voltammetry is difference in rate of decay of faradaic and capacitive current
supporting potential steps. The decay rate for diffusion controlled reactions of faradaic current is
t-1/2 and with time the capacitive current decays at exponential rate.

Following are the important criteria’s of all pulse voltammetric techniques-

i. Pulse amplitude
ii. Pulse width
iii. Sampling period

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 Time
Figure 5- Potential Form of Differential Pulse Voltammetry

dE- Potential Step

ESW- Potential amplitude

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 Figure 6- Potential Form of square wave voltammetry

Pulse voltammetry is of three types-

i. Normal pulse voltammetry: In this type of technique a series of potential pulses are applied
which have same width and increased amplitude, and the potential keep coming back to its
initial value after every pulse (Fig-4). The measurement of current is done after the end of
every pulse. The range of the duration of pulses are 1 -200 m/s and the interval is of several
seconds. Normal pulse voltammogram is of sigmoidal shape.

ii. Differential pulse voltammetry: In this type of technique the potential form comprises of
small pulses of same amplitude of 10-100 mV and these pulses are superimposed on each
other in a stair-case wave fashion (Fig-5). The measurement of current is done twice after
every pulse period, firstly it is measured at the starting of the applied pulse and then at the
ending of the same pulse. The differential pulse voltammogram shows the differentiation
between the measured current for every pulse.

iii. Square wave voltammetry (SWV): It is one of the most advanced, fast and sophisticated
technique. The potential form of SWV comprises of symmetrical square wave pulses having
same amplitude (ESW), and these pluses are superimposed in a stair-case wave fashion. In
SWV, the potential changes for a same potential step i.e. dE.

In this technique the current is measured for two times in the end of every half cycle.
Oxidative current i.e. forward current is produced when the measurement of current is done
at end of half cycle of oxidation, similarly the reduction current i.e. backward current is
produced when the measurement of current is done at the end of half cycle of reduction.
From subtraction between the backward and the forward current the net current in square
wave voltammetry is achieved.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 6. Applications and Limitations

Applications:

 Quantitative analysis of pharmaceutical compounds

 Estimation of concentration of metal-ions present in water in levels of part-per-billion
(ppb).
 Determination of redox potential
 Estimation of analytes eluted in High performance Liquid Chromatography.
 Estimation of number of electrons present in a redox reaction.
 Estimation of thermodynamic properties of species.
 To study the process of adsorption on the surface.
 Quantitative analysis of inorganic and organic compounds in non-aqueous and aqueous
medium.

Limitations:

 The level of accuracy varies from technique to technique

 Level of sensitivity and level of detection also varies from techniques to techniques like
parts-per-thousand to parts-per-trillion
 Sample should be in dissolved state.
 On species identification it provides very little information.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques
 7. Summary

 In 1922 voltammetry was established from the invention of Polarography by Jaroslav

Heyrovsky, he was a Czech chemist.
 An electrochemical cell composed of three types of electrode- working electrode, counter
(auxiliary) electrode and reference electrode.
 The voltammetric techniques are used on daily basis for quantifying various organic and
inorganic compounds because of this reliance between concentrations of analyte and
measured current.
 The main work of potentiostat is to execute an accurate potential and to monitor the changes
in current in the system. In modern electrochemical instruments, potentiostat comprises of
converters, electrometer circuits, microprocessor with internal memory and amplifier.
 Electrochemical cell is a sample holder, where desolvation of analyte in a specific solvent
takes place and this dissolved sample is placed into an ionic electrolyte. Ionic electrolyte
comprises of three electrodes – working electrode, reference electrode and counter electrode.
 Cyclic voltammetry is one of the most commonly used techniques. Its primary benefit is that
it gives vision of both the half reactions going on the working electrode and delivering the
same information about the phenomena for studying the electrochemical reaction
 Pulse voltammetric technique was prompted by this fact that from potential changing and in
the pulse fashion the current should be measured, by this a significant distinction of the
charging current can be attained.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.30: Voltammetric Techniques