Unit 1

Introduction to Electroanalytical techniques

Conventional analytical techniques or laboratory-based procedures, such as gas

chromatography (GC), high-performance liquid chromatography (HPLC), atomic absorption
spectroscopy (AAS), atomic fluorescence spectrometry (AFS), and inductively coupled plasma
mass spectrometry (ICP-MS), are sensitive, precise, and consistent. They are regularly used to
measure analyte parameters with the help of trained operators. However, they are involved with
bulky and costly instrumentation, take much time for sample preparation, and are unsuitable for
in situ measurements, especially requiring trained operators’ help and transporting the samples to
laboratories for assessment. These characteristics encourage developing new technologies that
are more low-cost, portable, sensitive, and efficient in the on-site real-time detection of multi-
contaminants containing a wide variety of materials.

1.1 Electroanalytical techniques

Electroanalytical techniques are a sub discipline of analytical chemistry which determines

the characteristics of an analyte present in an electrochemical cell. The analyte is dissolved in the
electrolyte of the cell, and one can perform either qualitative analysis (determination of the type
of constituents present) or quantitative analysis (determination of the amount of a given
constituent).

Electroanalytical techniques involve the application of an electrical potential or current to

a sample and the measurement of resulting electrical quantities, such as current, voltage, or
charge, to obtain information about the analyte of interest. It is a qualitative and quantitative
methods of analysis based on electrochemical phenomena occurring within a medium or at the
phase boundary.

The key principle behind electroanalytical methods is the relationship between the
electrical quantities and the chemical processes occurring at an electrode/solution interface. By
controlling the applied potential or current and monitoring the resulting electrical signals,
valuable information about the analyte can be obtained.

There are various electroanalytical techniques available, each with its own specific
advantages and applications. Some commonly used techniques include voltammetry,
potentiometry, coulometry, amperometry, electrogravimetry, and conductometry.

1.2 Why Electroanalytical Techniques?

Electroanalytical methods have certain advantages over other analytical methods:

1) Electrochemical analysis allows for the determination of different oxidation states of an

element in a solution, not just the total concentration of the element.
2) Electroanalytical techniques are capable of producing exceptionally low detection limits and
an abundance of characterization information including chemical kinetics information.
3) Selective for particular redox state of a species e.g. Ce3+ vs Ce4+
4) low cost.
5) Fastness
6) portable
7) efficient in the on-site real-time detection of multi-contaminants containing a wide variety of
materials.
8) No or little sample preparation

1.3 Classification of electroanalytical techniques

Two common approaches in electroanalytical techniques are bulk methods and interfacial
methods.

1.3.1 Bulk Techniques:

Bulk electroanalytical techniques involve the measurement of electrical properties in a
bulk solution. The electrode is typically immersed in the solution, and the electrical properties of
the solution as a whole are analyzed.e.g. Conductometry
 1.3.2 Interfacial Techniques:
Interfacial electroanalytical techniques involve the measurement of electrical properties
at the interface between an electrode and the solution. interfacial techniques can be broadly
classified into static and dynamic methods.

i) Static Methods: No current passes in the electrochemical cell. e.g. potentiometry.

ii) Dynamic Methods: Current flows in the electrochemical cell. There are two types of
dynamics methods;
a) Controlled potential techniques:
Controlled potential techniques refer to a group of electroanalytical methods
where the potential applied to the working electrode is controlled (constant or vary under
controlled conditions) throughout the measurement. E.g amperometry, voltammetry,
controlled potential coulometry, controlled potential electrogravimetry.
b) Constant current techniques:
A constant current is applied to the working electrode during the measurement
e.g. Constant current coulometry, constant current electrogravimetry.

Electroanalytical
techniques

Interfacial techniques Bulk technique

і=0 і≠0
Conductometry
Static techniqus Dynamic techniques

Potentiometry
Controlled-potential Constant-current
techniques techniques

Amperometry Voltammetry Coulometry Electrogravimetry

Fig 1.1: Classification of Electrochemical Techniques

1.4 Applications of electroanalytical techniques
The electroanalytical techniques have large range of applications including analytical,
environmental monitoring, industrial quality control & biomedical analysis. Here are some
examples:

a. Blood Glucose Monitoring: Electrochemical sensors based on amperometry are

commonly used in glucose meters for monitoring blood glucose levels in individuals with
diabetes. The sensor measures the electrical current produced by the enzymatic reaction
between glucose and glucose oxidase, providing a quantitative measurement of glucose
concentration.
b. Water Quality Analysis: Electroanalytical techniques, such as voltammetry and
conductometry, are employed to assess water quality parameters. These techniques can
detect and quantify various contaminants, such as heavy metals, organic pollutants, and
disinfection by-products, ensuring safe drinking water.
c. Environmental Monitoring: Electroanalytical methods are valuable in environmental
monitoring and pollution control. They can detect and quantify pollutants in soil, air, and
water samples, aiding in environmental assessment and remediation efforts.
d. Pharmaceutical Analysis: Electroanalytical techniques play a significant role in
pharmaceutical research and development. They are used for quality control,
determination of drug concentrations, and assessment of drug stability. Voltammetry and
coulometry are employed in drug release studies from controlled-release formulations.
e. Electroplating and Surface Coating: Electroanalytical techniques are crucial in
electroplating processes for depositing metal coatings onto various substrates. They help
control the deposition rate, thickness, and quality of the coatings, ensuring desired
surface properties and enhancing durability.

These are just a few examples of how electroanalytical techniques are applied in everyday life.
The versatility and precision of these methods make them valuable tools in various industries and
scientific research fields, contributing to quality control, safety, and technological advancements.
1.5 Electrochemical Cells
The devices used for converting chemical energy to electrical energy & electrical energy into
chemical energy are known as electrochemical cells they contain two electrodes in contact with
an electrolyte, they are mainly of two types.

1) Galvanic cells

2) Electrolytic cell

1.5.1 Galvanic Cell

The electrochemical cell in which a spontaneous chemical reaction takes place and
generates electric current is called galvanic or voltaic cell. The initial experiments on the
conversion of chemical energy into electrical energy were carried out by Luigi Galvanic and
Alessandro Volta. Examples of this type of cell are Daniel cell, Nickel–Cadmium (NiCad)
Battery. Lead–Acid (Lead Storage) Battery, Fuel Cells etc.

The construction of a galvanic cell involves the following components:

1. Two half-cells: A galvanic cell consists of two half-cells, each with a different electrode
and electrolyte solution. The two half-cells are separated by a salt bridge or porous
membrane.

2. Electrodes: The two electrodes used in a galvanic cell are typically made of different
materials, such as copper and zinc. The choice of electrode materials depends on the
specific redox reaction to be used and the desired voltage and current output.

3. Electrolyte solution: The electrolyte solution in each half-cell is typically an aqueous

solution of an ionic compound, such as copper sulfate or zinc sulfate. The electrolyte
solution can be an acid, base, or salt solution, depending on the specific reaction. For
example, zinc can be immersed in a solution of zinc sulfate, while copper can be
immersed in a solution of copper sulfate.

4. Salt bridge or porous membrane: The salt bridge or porous membrane is used to
separate the two half-cells while still allowing the flow of ions between them. The salt
bridge is typically a U-shaped tube filled with a gel-like substance, such as agar, that is
saturated with an electrolyte solution. Salt bridge maintain electrical neutrality. As
 electrons flow from one electrode to the other in a galvanic cell, each half-cell's charge
can become unbalanced. The salt bridge allows ions to flow between the two half-cells,
maintaining electrical neutrality and preventing a buildup of charge that could interfere
with the redox reactions at the electrodes.

5. Voltmeter: The galvanic cell will generate a voltage difference between the two
electrodes, which can be measured using a voltmeter. The direction of the current flow
and the polarity of the electrodes depend on the specific half-cell reactions.

The construction of a galvanic cell involves connecting the two half-cells with a wire or other
conductive material to complete the circuit. When the two electrodes are immersed in their
respective electrolyte solutions, a redox reaction occurs at each electrode, generating an electric
current that flows through the wire or other external circuit.

1.5.1.1 Daniel Cell

The Daniel cell is an example of galvanic cell that was invented by a British chemist
named John Frederic Daniel in 1836. It was an important early device for generating electricity,
and it was widely used in the 19th century for telegraphy and other applications.

The Daniel cell consists of two half-cells, each with a different electrode and electrolyte
solution. The anode is made of zinc, and it is immersed in a solution of zinc sulfate (ZnSO 4). The
cathode is made of copper, and it is immersed in a solution of copper sulfate (CuSO 4). The two
half-cells are connected by a salt bridge or porous membrane, which allows the flow of ions
between the two electrolyte solutions to maintain charge neutrality.
 Figure 1.2: Daniel cell.
Working of Daniel cell

The Zn metal has tendency to lose electrons more readily than copper. As a result,
oxidation takes place at Zn-electrode. The electrons flow from Zn-electrode through the external
wire in a circuit to copper electrode. These electrons are gained by the copper ions of the solution
and copper atoms deposit at the electrode. The respective oxidation and reduction processes
going on at two electrodes are as follows:

Half-cell reaction at anode (oxidation)

Zn(s) → Zn2+(aq) + 2e-

Half-cell reaction at cathode (reduction)

Cu2+(aq) + 2e- → Cu(s)

Overall galvanic reaction is the sum of these two half-cell reactions.

Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s) E0= 1.1 V

The overall result is the transfer of electrons from the zinc electrode to the copper electrode,
producing an electric current that can be used to power a device or be measured for other
purposes.
1.5.1.2 Representation of Galvanic Cell:

a. The anode (negative electrode) is written on the left hand side and cathode (positive
electrode) on the right hand side.
b. The anode of the cell is represented by writing metal or solid phase and then the metal
ion (or compound) present in the cell.
c. The cathode of the cell is represented by writing the cation (or compound) and then the
metal.

Here's an example of a cell notation for a galvanic cell based on the Daniel cell:

Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s)

Or

Zn(s) | Zn2+ || Cu2+ | Cu(s)

In this notation, the single vertical line ( | ) represents the boundary between the two
phases, and the double vertical line ( || ) represents the salt bridge or porous membrane that
separates the two electrolyte solutions. The left-hand side of the notation represents the anode
(the negative electrode), and the right-hand side represents the cathode (the positive electrode).

1.5.2 Electrolytic Cell

An electrolytic cell is an electrochemical cell in which electrical energy is used to drive a
non-spontaneous chemical reaction. Unlike a galvanic cell, which generates electrical energy
from a spontaneous chemical reaction, an electrolytic cell requires an external energy source,
such as a battery or power supply, to drive the reaction. Examples of these cells are Downs cell,
Nelson's cell.

In an electrolytic cell, a voltage is applied across two electrodes that are immersed in an
electrolyte solution. The voltage causes an electric current to flow through the solution, which
drives a non-spontaneous redox reaction. The electrode connected to the positive terminal of the
power source is called the anode, and the electrode connected to the negative terminal is called
the cathode.
Here are the main components of a typical electrolytic cell:

1. Anode: The anode is the positive electrode in an electrolytic cell, and it is the site of the
oxidation reaction. The anode attracts negatively charged ions from the electrolyte
solution, which give up electrons to the anode and become neutral atoms or molecules.

2. Cathode: The cathode is the negative electrode in an electrolytic cell, and it is the site of
the reduction reaction. The cathode attracts positively charged ions from the electrolyte
solution, which gain electrons from the cathode and become neutral atoms or molecules.

3. Electrolyte: The electrolyte is the substance that conducts ions between the anode and
cathode. It is typically a liquid or a molten salt that contains the ions that participate in
the electrochemical reaction.

4. External Circuit: The external circuit connects the anode and cathode to an external
power source, such as a battery or power supply, which provides the energy needed to
drive the reaction.

5. Power Source: The power source is the external device that provides the voltage needed
to drive the electrochemical reaction. The voltage determines the rate of the reaction and
the amount of product that is produced.

Electrolytic cells are used in a variety of applications, including metal plating, electrorefining,
and the production of industrial chemicals such as chlorine and sodium hydroxide. The principles
of electrolysis are also used in the electrolytic production of hydrogen and other gases from
water and other sources.

Working

When electric current is applied from battery, the ions in the electrolyte migrate to their
respective electrodes. The anions, which are negatively charged, move towards the anode and
discharge there by losing their electrons. Thus oxidation takes place at anode. While cations,
which are positively charged ions, move towards cathode. Cations gain electrons from the
electrode and as a result reduction takes place at cathode.
 Figure 1.3: Electrolytic Cell.
For example, when fused salt of sodium chloride is electrolysed, Na + ions start moving
towards the cathode and Cl- ions towards the anode. Then

At cathode:

2Na+ + 2e- → 2Na (reduction)

At anode:

2Cl- → Cl2 + 2e- (oxidation).

Electrolytic cells, like galvanic cells, are composed of two half-cells--one is a reduction
half-cell, the other is an oxidation half-cell. Though the direction of electron flow in electrolytic
cells is in reverse direction from that of spontaneous electron flow in galvanic cells, the
definition of both cathode and anode remains the same as reduction takes place at the cathode
and oxidation occurs at the anode.
 Table 1.1 Differences between Galvanic Cell and Electrolytic Cell

Galvanic Cell Electrolytic Cell

It converts chemical energy into electrical It converts electrical energy into chemical
energy. energy.
It is based upon the redox reactions which are The redox reactions are non-spontaneous and
spontaneous. take place only when energy is supplied.
The chemical changes occurring in the two Only one chemical compound undergoes
beakers are different. decomposition.
Anode (-ve) - Oxidation takes place. Anode (+ve) - Oxidation takes place.
Cathode (+ve) - Reduction takes place. Cathode (-ve) - Reduction