Najam A.

Qureshi Potentiometery

CELL
In chemistry, there are two main types of cells- galvanic cells and electrolytic cells.
Both these cells come under electrochemical cells. Galvanic cells are those in
which redox reactions occur spontaneously due to the composition of chemicals
inside the cell, causing the creation of chemical energy which is then converted
into electrical energy. Contradictory to this, electrolytic cells convert electrical
energy into chemical energy. However, this electrical energy is supplied externally
through the application of a voltage.

Galvanic Cells
A galvanic cell, also known as a voltaic cell, is an electrochemical cell that
converts chemical energy into electrical energy through a spontaneous redox
reaction. In galvanic cells, oxidation occurs at the anode while reduction occurs at
the cathode. This causes the electrons to flow from the anode to the cathode,
creating a flow of current.

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The galvanic cell basically contains two half-cells that are connected by a salt
bridge. The electrode in the anode half-cell undergoes oxidation and loses
electrons to the solution. These electrons travel through an external wire to the
cathode half-cell. At the cathode half-cell, the electrode gains electrons and
undergoes reduction.

The main purpose of the salt bridge is to complete the circuit as well as maintain
the electrical neutrality of the half-cells. It allows the flow of the ions between the
half cells to balance the charge and maintain electrochemical equilibrium.

Daniell cell: This type of cell consists of a copper electrode in a copper (II)
sulphate solution and a zinc electrode in a zinc sulphate solution. The two half-
cells are connected by a salt bridge and the reaction between the copper and zinc
electrodes generates a voltage difference in the cell.

Dry cell: This is the commonly used AA or AAA battery cell you must have seen
being used in daily life. It consists of a zinc anode, a carbon cathode, and a paste of
manganese dioxide and ammonium chloride electrolyte. The reaction between the
zinc anode and the manganese dioxide cathode generates a voltage.

Lead-acid battery: This is not a cell in itself but a battery which uses a galvanic
cell. It consists of a lead dioxide cathode, a lead anode and a sulphuric acid
electrolyte. This reaction between the lead and lead dioxide electrodes generates a
voltage difference.

Fuel cell: This type of galvanic cell generates electricity from the reaction between
a fuel and an oxidant. For example, a hydrogen fuel cell consists of a hydrogen
anode and an oxygen cathode, with a proton-conducting electrolyte in between.
The reaction between hydrogen and oxygen generates a voltage.

Galvanic cells, are used in a variety of pharmaceutical applications due to their

ability to convert chemical energy into electrical energy through spontaneous
redox reactions. Here are some key pharmaceutical applications of galvanic cells:

1. Biosensors
Application: Detection and monitoring of glucose levels in diabetic patients.
Description: Glucose biosensors often use a galvanic cell configuration
where the enzyme glucose oxidase catalyzes the oxidation of glucose. This

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reaction generates an electrical current proportional to the glucose

concentration, which can be measured and displayed.
Example: Continuous glucose monitors (CGMs) and glucose meters.
2. Drug Delivery Systems
Application: Controlled drug release.
Description: Galvanic cells can be integrated into drug delivery systems to
control the release rate of a drug. For example, electric fields generated by
the cell can facilitate the iontophoretic delivery of drugs through the skin.
Example: Iontophoretic drug delivery patches for pain management or
localized drug administration.
3. Implantable Medical Devices
Application: Powering implantable devices.
Description: Galvanic cells can provide a reliable and consistent power
source for implantable medical devices such as pacemakers,
neurostimulators, and drug infusion pumps.
Example: Zinc-air batteries are commonly used in hearing aids and other
implantable medical devices.
4. Electrochemical Synthesis
Application: Synthesis of pharmaceutical compounds.
Description: Galvanic cells can be used in electrochemical synthesis
processes to produce pharmaceutical intermediates or active pharmaceutical
ingredients (APIs) through controlled redox reactions.
Example: Electrochemical synthesis of complex organic molecules used in
drug manufacturing.
5. Pharmaceutical Analysis
Application: Electrochemical analysis of drug compounds.
Description: Galvanic cells are used in various electroanalytical techniques,
such as cyclic voltammetry and amperometry, to analyze the redox
properties and concentrations of pharmaceutical compounds.
Example: Detection and quantification of drug metabolites in biological
samples.
6. Energy Storage for Portable Medical Devices
Application: Portable diagnostic and therapeutic devices.

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Description: Galvanic cells provide the necessary energy storage for

portable medical devices, ensuring they are lightweight and have a long
operational life.
Example: Portable ECG monitors and portable infusion pumps.

Electrolytic Cells
Electrolytic cells are basically defined as electrochemical cells that use an external
electric current to initiate a non-spontaneous redox reaction. An electrical current
is required to drive this reaction.

An electrolytic cell consists of a power supply, electrodes, electrolyte, ion-

conducting medium, container, and an external circuit. These components work
together to convert electrical energy into chemical energy, driving non-
spontaneous reactions. The specific materials and configuration depend on the type
of electrolytic process being carried out.

PRINCIPLE
The basic working principle of an electrolytic cell is that an external power supply
is used to provide electrons to the anode which is the positive electrode and

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remove electrons from the cathode, which is the negative electrode. This causes a
non-spontaneous redox reaction to take place, the products of which are in the
form of dissolved ions or gases.

A DC power supply or battery is connected to the anode and cathode of the

electrolytic cell as an external power source.

The anode is the site of oxidation whereas the cathode is the site of reduction.
Hence, electrons are removed from the anode and enter the external circuit,
generating positively charged ions in the solution.

The cathode is the site of reduction and hence, the electrons from the external
circuit are transferred to the cathode, causing the reduction of positively charged
ions in the electrolyte solution. This is how the circuit is completed.

Electroplating:

Electroplating is basically the process of coating the surface of a metal with

a thin sheet of another metal with the use of an electrolytic cell. In this case,
the object to be coated is the cathode while the metal used for coating is the
anode. The electrolyte solution contains ions of the metal to be deposited,
and when an electric current is passed through the solution, the metal ions
are reduced and deposited onto the object.

Chlor-alkali production:

The chlor-alkali process is a method of production of chlorine gas, hydrogen

gas, and sodium hydroxide using an electrolytic cell. Here, a brine solution
(sodium chloride dissolved in water) is used as an electrolyte. Chlorine gas
is produced at the anode and hydrogen gas at the cathode. Sodium hydroxide
is formed in the solution.

Electrolysis of water:

Electrolysis of water is the process of breaking up water into its constituents,

namely hydrogen and oxygen, using electrolytic cells. Here, the electrodes
are made of inert material such as platinum or carbon and the electrolyte
solution is water. When an electric current is passed through the solution,
water molecules are split into hydrogen ions and hydroxide ions. The
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hydrogen ions are reduced at the cathode to form hydrogen gas, while the
hydroxide ions are oxidized at the anode to form oxygen gas.

PARAMETER GALVANIC CELLS ELECTROLYTIC CELLS

Working Spontaneous Non-spontaneous
Reaction Chemical energy is converted Electrical energy is converted into
into electrical energy chemical energy
Electrodes Anode (negative electrode) Anode (positive electrode) and cathode
and cathode (positive (negative electrode)
electrode)
Electrical flow Electrons flow from the Electrons flow from the external source to
anode to the cathode the cathode
Electrolyte Salt bridge or porous Conductive solution or molten electrolyte
separator
Sign of potential Positive (+) Negative (-)
Examples Daniell cell, dry cell, fuel cell Electroplating, electrolysis of water,
chlor-alkali process

It consists of several key components that work together to achieve this process.

1. Power Supply

It provides the necessary electrical energy to drive the non-spontaneous reaction. A

DC power source, such as a battery or a regulated power supply unit, is used. It
creates a potential difference (voltage) between the two electrodes, which forces
the reaction to occur. The voltage applied needs to be sufficient to overcome the
activation energy of the electrochemical reactions.

2. Electrodes

Anode (Positive Electrode):

It is the Site where oxidation occurs (loss of electrons). The anode is connected to
the positive terminal of the power supply. It attracts anions (negative ions) from
the electrolyte. Common materials include inert substances like platinum, graphite,
or other non-reactive metals that can withstand the oxidizing environment. In the
electrolysis of water, oxygen gas (O₂) is produced at the anode.

Cathode (Negative Electrode):

It is the Site where reduction occurs (gain of electrons). The cathode is connected
to the negative terminal of the power supply. It attracts cations (positive ions) from
the electrolyte. Like the anode, it is typically made of inert materials such as
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platinum or graphite. In the electrolysis of water, hydrogen gas (H₂) is produced at

the cathode.

3. Electrolyte

It provides a medium that allows the flow of ions, facilitating the redox reactions at
the electrodes. The electrolyte is a substance that contains free ions, which are the
charge carriers. It can be in the form of a liquid solution (e.g., sulfuric acid, sodium
chloride solution), molten salt, or even a solid-state conductor. The electrolyte
must be chosen based on its ability to dissociate into ions and its chemical stability
during the electrolysis process.

4. Ion-Conducting Medium

It ensures the movement of ions within the cell. This medium is typically the
electrolyte itself. It allows the ions to move towards their respective electrodes
(cations to the cathode, anions to the anode). The movement of ions completes the
electrical circuit and maintains charge balance.

5. Container

It Holds the electrolyte and electrodes in place and maintains the integrity of the
cell. The container is made of materials that are chemically inert and do not react
with the electrolyte or the products of electrolysis. Common materials include
glass, plastic, or specialized chemical-resistant containers. The design must ensure
safety and stability during the electrolysis process.

6. External Circuit

It completes the electrical circuit, allowing the flow of electrons from the power
supply through the cell. The external circuit includes connecting wires, clips, and
any necessary measuring instruments (e.g., ammeters, voltmeters) to control and
monitor the current and voltage. The wires are typically made of conductive
materials like copper, insulated to prevent short circuits.

Example of an Electrolytic Cell: Electrolysis of Water

Power Supply:

A 12V DC power source (e.g., a battery).

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Electrodes:

Anode: Platinum electrode connected to the positive terminal.

Cathode: Platinum electrode connected to the negative terminal.

Electrolyte:

Dilute sulfuric acid (H₂SO₄) or sodium hydroxide (NaOH) to increase water

conductivity.

Ion-Conducting Medium:

The water solution contains the electrolyte.

Container:

A glass beaker or specialized electrolysis cell that can hold the electrolyte and
electrodes securely.

External Circuit:

Copper wires connecting the power supply to the electrodes, with an ammeter to
measure the current. Electrolytic Cell Reactions

In this example:

a. Oxygen gas is produced at the anode.

b. Hydrogen gas is produced at the cathode.

Electrolytic cells play a significant role in pharmaceutical applications, primarily in

the synthesis and analysis of drugs. Here are some key applications:

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Applications of Electrolytic Cells in Pharmaceuticals

1. Electrochemical Synthesis of Drugs:

Electroorganic Synthesis. Electrolytic cells are used to perform organic synthesis

reactions that are environmentally friendly and selective. For instance, the
synthesis of certain active pharmaceutical ingredients (APIs) and intermediates can
be achieved through electrochemical methods.

Oxidation and Reduction Reactions: Electrolytic cells facilitate specific oxidation

and reduction reactions essential in drug synthesis, which may be difficult to
achieve using traditional chemical methods.

2. Purification of Pharmaceuticals:

Electrolytic Refining: Electrolytic processes can purify pharmaceutical compounds,

removing impurities and enhancing the quality of the final product.

Electrochemical Degradation: Used for the degradation of impurities or unwanted

by-products in pharmaceutical formulations.

3. Analytical Applications:

Electrochemical Detection: Electrolytic cells are used in electrochemical detectors

coupled with chromatographic techniques like HPLC to analyze pharmaceuticals.
These detectors are highly sensitive and can detect trace amounts of drugs and their
metabolites.

Potentiometric and Voltammetric Analysis: Electrolytic cells help in potentiometric

titrations and voltammetric analysis to determine the concentration of specific ions
or molecules in pharmaceutical samples.

4. Drug Delivery Systems:

Controlled Drug Release: Electrolytic cells can be part of drug delivery systems
where electric stimuli control the release rate of drugs from certain delivery
devices, providing a controlled and sustained release.

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Iontophoresis: A technique that uses a small electric charge to deliver drugs

through the skin. Electrolytic cells generate the required electric field, enhancing
the transdermal delivery of drugs.

5. Waste Treatment and Environmental Protection:

Electrochemical Treatment of Pharmaceutical Waste: Electrolytic cells are used to

treat wastewater from pharmaceutical manufacturing, reducing the environmental
impact of pharmaceutical contaminants.

Examples in Pharmaceuticals

1. Electrochemical Reduction of Nitro Compounds:

Electrolytic cells are used to reduce nitro compounds to amines, which are
important intermediates in the synthesis of various drugs, such as local anesthetics
and antibacterial agents.

Electrochemical reduction of nitro compounds in pharmaceuticals is a significant

process due to its applications in synthesizing important drugs and intermediates.
This process is used in the pharmaceutical industry:

1. Synthesis of Aniline Derivatives

For example in the Synthesis of Aniline from Nitrobenzene.

Process: Nitrobenzene is reduced electrochemically to aniline.

Application: Aniline is a precursor for various pharmaceuticals, including

paracetamol (acetaminophen) and sulfa drugs.

2. Synthesis of Nitroimidazoles

For Example the Reduction of Nitroimidazole Derivatives

Process: Nitroimidazoles are reduced to their corresponding amines or

hydroxylamines.

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Application: Nitroimidazole derivatives are used as antimicrobial agents.

Metronidazole, a nitroimidazole, is reduced to an active form in anaerobic bacteria
and protozoa, making it effective against infections.

3. Reduction of Nitrofurans

For Example the Synthesis of Aminofurazans from Nitrofurans

Process: Nitrofurans are reduced to their corresponding amino derivatives.

Application: Nitrofurazone and nitrofurantoin are examples of nitrofuran

antibiotics used to treat bacterial infections. The reduction process activates these
compounds in the body.

4. Synthesis of Antiparasitic Drugs

For Example the Reduction of Nitroquinoline Derivatives

Process: Electrochemical reduction of nitroquinoline derivatives to

aminoquinolines.

Application: Aminoquinolines, such as chloroquine and primaquine, are used as

antimalarial agents.

5. Synthesis of Aromatic Amines

For example the Reduction of Nitrobenzene Derivatives.

Process: Nitrobenzene derivatives are electrochemically reduced to aromatic

amines.

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Application: Aromatic amines are intermediates in the synthesis of dyes, drugs, and
agrochemicals. For instance, p-phenylenediamine is used in the manufacture of
dyes and hair colorants.

Mechanism and Process

The reduction of nitro compounds involves several steps and can proceed through
the formation of nitroso, hydroxylamine, and finally to the amine. The steps
typically involved are:

1. Nitro Compound (RNO2)

2. Nitroso Intermediate (RNO)
3. Hydroxylamine (R-NHOH)
4. Amine (R-NH2)

2.Electrochemical Oxidation of Alcohols:

- The oxidation of alcohols to aldehydes or ketones using electrolytic cells is

crucial in the synthesis of various drugs, including corticosteroids and other
hormone-related pharmaceuticals. The Synthesis of Ketones from Secondary
Alcohols. For Example the Synthesis of Ibuprofen Intermediate

Process: Electrochemical oxidation of 1-(4-isobutylphenyl) ethanol to 4-

isobutylacetophenone.

Application: 4-isobutylacetophenone is an intermediate in the synthesis of

ibuprofen, a widely used non-steroidal anti-inflammatory drug (NSAID).

3. Potentiometric Determination of Drug Compounds:

Electrolytic cells equipped with ion-selective electrodes are used to determine the
concentration of specific drug compounds in formulations, ensuring accurate
dosage and quality control.

1. Determination of Paracetamol (Acetaminophen)

Method: Potentiometric titration using a pH electrode.

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Procedure: Paracetamol can be titrated potentiometrically with a strong acid

or base to determine its content in pharmaceutical formulations. The
endpoint is detected by a sudden change in pH.
Application: Ensuring the correct dosage of paracetamol in tablets, syrups,
and other dosage forms.
2. Determination of Aspirin (Acetylsalicylic Acid)
Method: Potentiometric titration using a pH electrode or a redox electrode.
Procedure: Aspirin can be hydrolyzed to salicylic acid and acetic acid. The
resulting mixture can be titrated with a strong base, and the endpoint is
determined potentiometrically.
Application: Quality control of aspirin tablets and other formulations.
3. Determination of Chloride Ions in Saline Solutions
Method: Potentiometric titration using a silver-silver chloride electrode.
Procedure: Chloride ions in saline solutions can be titrated with silver
nitrate. The endpoint is detected by a change in the potential of the silver-
silver chloride electrode.
Application: Ensuring the correct chloride ion concentration in intravenous
saline solutions.
4. Determination of Caffeine
Method: Potentiometric titration using a pH electrode.
Procedure: Caffeine can be titrated with a standard acid or base solution. The
potentiometric method is used to determine the endpoint accurately.
Application: Quality control of caffeine in beverages and pharmaceutical
products.
5. Determination of Antihistamines (e.g., Diphenhydramine)
Method: Potentiometric titration using an ion-selective electrode.
Procedure: Diphenhydramine can be titrated with a suitable titrant, and the
endpoint is determined using an ion-selective electrode specific for
diphenhydramine.
Application: Assuring the correct dosage in antihistamine tablets and syrups.
6. Determination of Sulfates in Pharmaceuticals
Method: Potentiometric titration using a lead ion-selective electrode.
Procedure: Sulfate ions can be titrated with a lead nitrate solution. The
endpoint is detected potentiometrically using a lead ion-selective electrode.

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Application: Ensuring the correct sulfate content in various pharmaceutical

formulations.
7. Determination of pH-Sensitive Drugs (e.g., Ibuprofen)
Method: Potentiometric pH measurement.
Procedure: The pH of solutions of pH-sensitive drugs can be measured to
determine their solubility and stability in different pH environments.
Application: Ensuring the stability and proper formulation of ibuprofen in
different dosage forms.
8. Determination of Vitamin C (Ascorbic Acid)
Method: Potentiometric redox titration.
Procedure: Vitamin C can be titrated with a suitable oxidizing agent, such as
iodine. The endpoint is determined using a redox electrode.
Application: Quality control of vitamin C tablets, syrups, and other
formulations.
9. Determination of Antibiotics (e.g., Penicillin)
Method: Potentiometric titration using a specific ion-selective electrode.
Procedure: Penicillin can be titrated with a titrant that reacts specifically
with the antibiotic. The endpoint is determined using an ion-selective
electrode.
Application: Ensuring the correct dosage and potency of antibiotic
formulations.

Advantages of Using Electrolytic Cells

a. High Selectivity: Electrolytic cells can provide high selectivity in oxidation

or reduction reactions, leading to fewer side products.
b. Environmentally Friendly: Electrochemical methods are often more
environmentally friendly compared to traditional chemical synthesis, as they
can reduce the need for hazardous reagents and solvents.
c. Cost-Effective: Electrolytic processes can be cost-effective due to the use of
electricity as a clean reagent and the potential for lower material costs.

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