UNIT IV CHEMICAL SENSOR 9

Sensors, sensor science and technology, types of sensors. Chemical Sensors - characteristics of a chemical
sensor, elements of chemical sensors. Electro chemical sensors – voltammetry, potentiometric sensors,
amperometric sensors, polarization techniques.

1. Sensors, sensor science and technology

2. Sensor Characteristics & Types of Sensors

3. Chemical sensors

4. Breathalyzer: Chemistry of breathalyzer Breathalyzer sensors Characteristics of a Chemical Sensor

5. Electrochemical sensors, Principles, Characteristics of electrochemical sensors & Application of

electrochemical sensors

6. Voltammetry, Current In Voltammetry, Sign Conventions The types of voltammetry

7. Cyclic voltammetry, The Three Electrode System & Instrumentation

8. Differential pulse voltammetry – Polarography & Definition of Electric Polarization

9. Potentiometric sensor, Classification & Application. Amperometry and its Application.

A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon.

Sensor Science

Sensor science is the study of the underlying principles of sensor operation. This includes the study of
the physical and chemical properties of sensor materials, the mechanisms of signal transduction, and
the development of new sensor technologies.

Sensor Technology

Sensor technology is the development of practical sensors that can be used in real-world applications.
This includes the design and fabrication of sensor devices, the development of signal processing and
data analysis algorithms, and the integration of sensors into larger systems.

A bubble and block diagram illustrating the contributing fields of sensor science

The human senses are a remarkable gift that allow us to experience and interact with the world around
us. They provide us with information about our environment, help us to avoid danger, and enable us
to connect with others. The five basic senses are sight, hearing, touch, taste, and smell. Each of these
senses has a specialized organ that detects and transmits information to the brain.

• Sight is the ability to perceive light and images. The eyes are the organs of sight, and they
contain specialized cells called photoreceptors that convert light into electrical signals. These
signals are then sent to the brain, where they are interpreted as visual information.
• Hearing is the ability to perceive sound waves. The ears are the organs of hearing, and they
contain specialized cells called hair cells that convert sound waves into electrical signals.
These signals are then sent to the brain, where they are interpreted as auditory information.
 • Touch is the ability to perceive pressure, temperature, and pain. The skin is the organ of
touch, and it contains specialized cells called mechanoreceptors that detect these stimuli.
These signals are then sent to the brain, where they are interpreted as tactile information.
• Taste is the ability to perceive the five basic tastes: sweet, sour, salty, bitter, and umami. The
tongue is the organ of taste, and it contains specialized cells called taste buds that detect these
stimuli. These signals are then sent to the brain, where they are interpreted as gustatory
information.
• Smell is the ability to perceive odor molecules. The nose is the organ of smell, and it contains
specialized cells called olfactory receptors that detect these stimuli. These signals are then
sent to the brain, where they are interpreted as olfactory information.

The human senses in their COMETMAN environment

Sensor Characteristics:

Sensors are devices that convert one type of physical quantity into another. They are used in a wide
variety of applications, including measuring temperature, pressure, light, and sound. The characteristics
of a sensor can be divided into two main categories: static and dynamic.

Static characteristics are those that describe the sensor's performance under steady-state conditions.
These characteristics include:
 • Sensitivity: This is a measure of how much the sensor's output changes in response to a
change in the input.
• Resolution: This is the smallest change in the input that the sensor can detect.
• Linearity: This is a measure of how closely the sensor's output is proportional to the input.
• Zero drift: This is the tendency of the sensor's output to change over time, even when the
input is constant.
• Full-scale drift: This is the change in the sensor's output over its entire range.
• Range: This is the range of inputs that the sensor can measure.
• Repeatability: This is the ability of the sensor to produce the same output for the same input,
under the same conditions.
• Reproducibility: This is the ability of the sensor to produce the same output for the same
input, under different conditions.

Dynamic characteristics are those that describe the sensor's performance under transient conditions.
These characteristics include:

• Rise time: This is the time it takes for the sensor's output to reach 90% of its final value, after
a step change in the input.
• Fall time: This is the time it takes for the sensor's output to fall to 10% of its initial value,
after a step change in the input.
• Time constant: This is the time it takes for the sensor's output to reach 63.2% of its final
value, after a step change in the input.
• Bandwidth: This is the range of frequencies that the sensor can respond to.
• Damping factor: This is a measure of how quickly the sensor's output decays after a transient
input.

The specific characteristics that are important for a particular sensor will depend on the application.
For example, a sensor that is used to measure temperature in a furnace may need to have a high
sensitivity and a wide range, while a sensor that is used to measure pressure in a tire may need to have
a high accuracy and a low drift rate.

In addition to the static and dynamic characteristics listed above, there are a number of other factors
that can affect the performance of a sensor. These factors include:

• Noise: This is unwanted electrical or optical interference that can affect the sensor's output.
• Temperature: The output of many sensors is affected by temperature.
• Humidity: The output of some sensors is affected by humidity.
• Vibration: The output of some sensors is affected by vibration.
 • Chemical exposure: Some sensors are sensitive to certain chemicals.

The choice of sensor for a particular application will depend on a number of factors, including the
required performance, the operating environment, and the cost.

Future of sensor technology

Sensors can improve the world through diagnostics in medical applications; improved performance of
energy sources like fuel cells and batteries and solar power; improved health and safety and security for
people; sensors for exploring space and the known university; and improved environmental monitoring.

Types of Sensors

There are many different types of sensors, but some of the most common include:

• Position sensors measure the position of an object. Examples include linear potentiometers,
rotary encoders, and optical encoders.

Position sensors

• Pressure sensors measure the pressure of a fluid or gas. Examples include strain gauges,
diaphragms, and piezoelectric sensors.
 Pressure sensors

• Temperature sensors measure the temperature of an object or environment. Examples

include thermocouples, thermistors, and RTDs.

Temperature sensors

• Force sensors measure the force applied to an object. Examples include load cells, strain
gauges, and piezoelectric sensors.

Force sensors
• Vibration sensors measure the vibration of an object or surface. Examples include
accelerometers, geophones, and piezoelectric sensors.

Vibration sensors

• Piezo sensors generate an electrical signal when subjected to mechanical stress. Examples
include piezoelectric accelerometers, piezoelectric pressure sensors, and piezoelectric
microphones.

Piezo sensors

• Fluid property sensors measure the properties of a fluid, such as its viscosity, density, and
flow rate. Examples include flowmeters, level sensors, and viscosity meters.
 Fluid property sensors

• Humidity sensors measure the humidity of an environment. Examples include capacitive

humidity sensors, resistive humidity sensors, and gravimetric humidity sensors.

Humidity sensors

• Strain gauges measure the strain in a material. Examples include foil strain gauges, wire
strain gauges, and semiconductor strain gauges.

Strain gauges
 • Photo optic sensors detect the presence or absence of light. Examples include photodiodes,
phototransistors, and photoresistors.

Photo optic sensors

• Flow and level switches detect the flow of a fluid or the level of a liquid or solid. Examples
include flow switches, level switches, and pressure switches.

Flow and level switches

Applications of Sensors

Sensors are used in a wide variety of applications, including:

• Medical diagnostics: Sensors are used in a variety of medical devices, such as blood pressure
monitors, heart rate monitors, and glucose monitors.
• Environmental monitoring: Sensors are used to monitor air quality, water quality, and soil
quality. They are also used to monitor for hazardous substances, such as pollutants and toxins.
• Industrial automation: Sensors are used in a variety of industrial applications, such as
robotics, manufacturing, and process control.
 • Consumer electronics: Sensors are used in a variety of consumer electronics devices, such as
smartphones, tablets, and wearable devices.

The Future of Sensor Technology

The future of sensor technology is bright. Sensors are becoming increasingly sophisticated, smaller, and
cheaper. This is leading to a wide range of new applications for sensors. Some of the key trends in
sensor technology include:

• Miniaturization: Sensors are becoming increasingly smaller, which is making them more
versatile and easier to integrate into new applications.
• Wireless technology: Sensors are increasingly being equipped with wireless capabilities,
which is making them easier to deploy and use in a wider range of applications.
• Artificial intelligence: Sensors are increasingly being integrated with artificial intelligence
(AI), which is making them more intelligent and capable of making more informed decisions.

Sensors are playing an increasingly important role in our lives. They are making our lives safer,
healthier, and more efficient. The future of sensor technology is bright, and we can expect to see even
more innovative and sophisticated sensors in the years to come.
Chemical sensors

What is a chemical sensor?

Chemical sensors are devices that detect and convert chemical information into a measurable signal.
They are used in a wide variety of applications, including environmental monitoring, industrial process
control, and medical diagnostics.

Essential components of a chemical sensor:

• Recognition element: This is the part of the sensor that interacts with the target analyte and
generates a signal.
• Transducer: This is the part of the sensor that converts the signal from the recognition
element into a measurable output.

Types of chemical sensors:

• Electrochemical sensors: These sensors measure changes in electrical properties, such as

conductivity or potential, in response to the presence of an analyte.
• Optical sensors: These sensors measure changes in optical properties, such as absorption or
emission of light, in response to the presence of an analyte.
• Mass sensors: These sensors measure changes in mass in response to the presence of an
analyte.

Applications of chemical sensors:

• Environmental monitoring: Chemical sensors are used to monitor air and water quality for
pollutants such as carbon monoxide, nitrogen dioxide, and sulfur dioxide.
• Industrial process control: Chemical sensors are used to monitor and control industrial
processes, such as chemical production and refining.
• Medical diagnostics: Chemical sensors are used to diagnose diseases, such as diabetes and
kidney disease.

Examples of chemical sensors:

• Carbon monoxide detectors: These sensors are used to detect the presence of carbon
monoxide, a colorless, odorless gas that can be fatal in high concentrations.
• Breathalyzers: These sensors are used to measure blood alcohol content (BAC) by detecting
the presence of alcohol in breath.
 • pH meters: These sensors are used to measure the pH of a solution, which is a measure of its
acidity or alkalinity.

Chemical sensors are a versatile and powerful tool that is used in a wide variety of applications. As
technology advances, chemical sensors are becoming increasingly sensitive, selective, and affordable.
This is making them even more valuable in the effort to monitor and control our environment, improve
industrial processes, and diagnose and treat diseases.

Schematic diagram of a sensor that produces an electrical output in response to the presence of an input
quantity.

Chemical Sensor Diagram

Breathalyzer:

A breathalyzer is a device that measures blood alcohol content (BAC) by detecting the presence of
ethanol in a person's breath. It works by using a chemical reaction to change the color of a solution, and
the amount of color change is proportional to the amount of ethanol present. The most common type of
breathalyzer uses a solution of potassium dichromate, which turns green when it reacts with ethanol.
The amount of green color is measured by a photocell, and this information is used to calculate the
BAC.

Breathalyzers are used by law enforcement to determine whether or not a person is safe to drive, and
they are also used in some workplaces to test employees for alcohol consumption.

Overview of the breathalyzer process:

1. The person blows into the breathalyzer.

2. The ethanol in the person's breath reacts with the potassium dichromate solution, turning it
green.
3. The amount of green color is measured by a photocell.
4. This information is used to calculate the BAC.

The BAC is a measure of the amount of alcohol in a person's blood. The legal limit for BAC in most
countries is 0.08%. A person with a BAC of 0.08% is considered to be legally intoxicated.

When the user exhales into a breath analyzer, any ethanol present in their breath is oxidized to acetic
acid at the anode:

C2H5OH(g) + H2O(l) → CH3COOH(l) + 4H+(aq) + 4e−

At the cathode, atmospheric oxygen is reduced:

O2(g) + 4H+(aq) + 4e− → 2H2O(l)

The overall reaction is the oxidation of ethanol to acetic acid and water.

C2H5OH(l) + O2(g) → CH3COOH(aq) + H2O(l)

The provided text describes the preparation and procedure for a breathalyzer test using acidified
potassium dichromate. It also explains the chemical reactions involved in the test and the safety
precautions to be taken. Here's a summary of the key points:

Preparation

1. Wear protective gloves and eye protection.

2. Weigh out potassium dichromate crystals and dilute sulfuric acid in a beaker.
3. Mix the crystals and acid to produce moistened crystals of potassium dichromate.
4. Half-fill a U-tube with the crystals.
5. Fill a conical flask with ethanol.
6. Attach a sterile mouthpiece to the longer glass tube of the flask.
7. Insert the shorter glass tube into the ethanol and attach a plastic bag to the rubber bung.

Procedure

1. Deflate the plastic bag.

2. Blow air through the ethanol to saturate it with ethanol vapor.
3. Connect the flask, U-tube, and plastic bag.
4. Gently blow into the flask to pass ethanol vapor over the acidified potassium dichromate.
5. Observe the color change of the crystals from orange to brown and eventually to green.
6. For a complete color change, connect a filter pump to draw ethanol vapor over the crystals for
several minutes.
7. Disconnect the U-tube and remove the stoppers.
8. Smell the products of the reaction and compare them to ethanal and ethanoic acid.

Model an early ‘breathalyser’ test using acidified potassium dichromate in this demonstration
featuring the same reaction with ethanol
Electrochemical sensors

Electrochemical sensors are a versatile and widely used analytical tool that relies on the principles of
electrochemistry to measure the concentration of various substances. They are based on the interaction
between an analyte, or target substance, and an electrode, which generates an electrical signal that is
proportional to the analyte concentration. This signal can then be converted into a measurable value,
such as a voltage or current, which can be used to determine the concentration of the analyte.

Electrochemical sensors can be classified into several different types based on the type of
electrochemical measurement they perform. These include:

1. Potentiometric sensors: These sensors measure the potential difference between two
electrodes, one of which is sensitive to the analyte. The potential difference is directly
proportional to the analyte concentration.
2. Conductivity sensors: These sensors measure the conductivity of a solution, which is a
measure of its ability to conduct electricity. The conductivity of a solution is affected by the
presence of ions, and therefore can be used to measure the concentration of dissolved ions.
3. Amperometric sensors: These sensors measure the current flowing through a solution
between two electrodes. The current is proportional to the rate of electrochemical reaction
occurring at the electrodes, which is in turn proportional to the analyte concentration.
4. Voltammetric sensors: These sensors measure the current flowing through a solution as the
potential between two electrodes is varied. The resulting current-voltage curve, or
voltammogram, can be used to identify and quantify the analyte.
5. Impedimetric sensors: These sensors measure the impedance of a solution, which is a
measure of its resistance to the flow of alternating current. The impedance of a solution is
affected by the presence of ions, and therefore can be used to measure the concentration of
dissolved ions.

Principles of Electrochemical Sensors

Electrochemical sensors are a type of sensor that detects and measures the concentration of a target gas
or substance by converting the chemical reaction between the target gas and the sensor's electrodes into
an electrical signal. The electrical signal is typically a current or voltage that is proportional to the
concentration of the target gas.
 Electrochemical sensor structure diagram

Components of an Electrochemical Sensor

An electrochemical sensor typically consists of three main components:

1. Working electrode: The working electrode is the electrode where the chemical reaction
between the target gas and the sensor occurs. The material of the working electrode is chosen
based on its ability to catalyze the desired reaction.
2. Reference electrode: The reference electrode provides a stable potential that is used to
measure the potential of the working electrode. The reference electrode is typically made of a
material that has a stable and well-known potential, such as silver/silver chloride (Ag/AgCl).
3. Counter electrode: The counter electrode is used to complete the electrical circuit and allow
current to flow between the working electrode and the reference electrode. The counter
electrode is typically made of a conductive material, such as platinum or gold.

Operation of an Electrochemical Sensor

When the target gas enters the sensor, it reacts with the working electrode, causing a change in the
potential of the working electrode. This change in potential is measured by comparing it to the potential
of the reference electrode. The resulting electrical signal is proportional to the concentration of the
target gas.

Advantages of Electrochemical Sensors

Electrochemical sensors have several advantages over other types of sensors, including:
 • High sensitivity
• Fast response time
• Low cost
• Portability
• Versatility

Disadvantages of Electrochemical Sensors

Electrochemical sensors also have some disadvantages, including:

• Limited selectivity
• Short lifespan
• Susceptibility to interference from other gases

Applications of Electrochemical Sensors

Electrochemical sensors are used in a wide variety of applications, including:

• Environmental monitoring
• Industrial safety
• Medical diagnostics
• Automotive sensors
• Food safety
Voltammetry

Voltammetry is an electroanalytical technique that measures the current as a function of applied

potential. It is a powerful tool for studying the electrochemical properties of materials, including their
reduction and oxidation potentials, electron transfer rates, and surface reactivity.

Current in Voltammetry

The current in voltammetry is a result of the transfer of electrons between the working electrode and
the analyte. When the potential of the working electrode is changed, the energy of the electrons in the
electrode is also changed. If the energy of the electrons in the electrode is high enough, they can be
transferred to the analyte, resulting in a reduction reaction. Conversely, if the energy of the electrons in
the electrode is low enough, they can be taken from the analyte, resulting in an oxidation reaction.

The current in voltammetry is proportional to the rate of electron transfer. The rate of electron transfer
is a function of the potential of the working electrode, the concentration of the analyte, the temperature,
and other factors.

Sign Conventions

In voltammetry, the sign of the current is used to indicate whether a reduction or oxidation reaction is
occurring. A positive current indicates that a reduction reaction is occurring, while a negative current
indicates that an oxidation reaction is occurring.

Types of Voltammetry

There are many different types of voltammetry, each with its own strengths and weaknesses. Some of
the most common types of voltammetry include:

• Linear sweep voltammetry (LSV): In LSV, the potential of the working electrode is scanned
linearly from a starting potential to a final potential. The current is measured as a function of
potential.
• Cyclic voltammetry (CV): In CV, the potential of the working electrode is scanned from a
starting potential to a final potential, and then back to the starting potential.
• Pulsed voltammetry: In pulsed voltammetry, the potential of the working electrode is
applied in a series of pulses. The current is measured during each pulse.
• Square wave voltammetry (SWV): In SWV, the potential of the working electrode is
applied in a series of square waves. The current is measured at the end of each positive and
negative pulse.
 • Differential pulse voltammetry (DPV): In DPV, the potential of the working electrode is
applied in a series of square waves, superimposed with a small sinusoidal wave. The current
is measured at the end of each positive and negative pulse.

Applications of Voltammetry

Voltammetry has a wide range of applications in analytical chemistry, environmental science,

materials science, and bioelectrochemistry. Some of the specific applications of voltammetry include:

• Determination of the concentration of analytes: Voltammetry can be used to determine the

concentration of analytes in solution by measuring the current as a function of potential.
• Study of redox reactions: Voltammetry can be used to study the redox reactions of analytes
by measuring the potential at which the current is zero.
• Characterization of materials: Voltammetry can be used to characterize the surface
properties of materials by measuring the current as a function of potential.
• Development of sensors: Voltammetry can be used to develop sensors for the detection of
analytes in solution.

Voltammetry is a versatile and powerful technique that has a wide range of applications. It is a
valuable tool for scientists and engineers in many different fields.
Cyclic voltammetry

Cyclic voltammetry (CV) is a powerful electrochemical technique used to investigate the redox
properties of molecules in solution. It involves applying a linearly varying potential to a working
electrode while measuring the resulting current. The resulting cyclic voltammogram provides
information about the oxidation and reduction potentials, reversibility of the redox process, and the
kinetics of the electron transfer reaction.

The Three Electrode System

The three electrode system is essential for accurate cyclic voltammetry measurements. It consists of
three electrodes:

1. Working electrode (WE): The electrode at which the redox reaction of interest occurs. The
WE is typically a small, inert electrode made of a material such as gold, platinum, or glassy
carbon.
2. Counter electrode (CE): The electrode that provides the current necessary to balance the
current flowing at the WE. The CE is typically a larger electrode made of a conductive
material such as platinum or graphite.
3. Reference electrode (RE): The electrode that provides a stable and well-defined potential.
The RE is typically a non-polarizable electrode that maintains a constant potential against a
known redox couple. Common REs include the standard hydrogen electrode (SHE) and the
silver/silver chloride electrode (Ag/AgCl).

Three-electrode setup: (1) working electrode; (2) auxiliary electrode; (3) reference electrode
Instrumentation

Cyclic voltammetry is typically performed using a potentiostat, an instrument that can control the
potential of the working electrode and measure the resulting current. The potentiostat is connected to
the three electrodes in the electrochemical cell. The potential of the WE is swept linearly from an initial
potential (Ei) to a vertex potential (E1), then reversed back to Ei, and finally swept to a second vertex
potential (E2). The current flowing at the WE is measured as a function of the applied potential, and
the resulting cyclic voltammogram is plotted.

Applications of Cyclic Voltammetry

Cyclic voltammetry has a wide range of applications in chemistry, including:

• Determining redox potentials of molecules

• Investigating the reversibility of redox processes
• Studying the kinetics of electron transfer reactions
• Characterizing catalysts
• Analyzing the stability of organic and inorganic compounds
• Monitoring the progress of chemical reactions

Cyclic voltammetry is a versatile and powerful technique that is widely used in electrochemical
research. It provides valuable information about the redox properties of molecules and is an essential
tool for understanding the mechanisms of electron transfer reactions.
Differential pulse voltammetry

Differential pulse voltammetry (DPV) is a highly sensitive electrochemical technique used to measure
the current responses of electroactive species in solution. It is a derivative of linear sweep voltammetry
(LSV) and staircase voltammetry (SV), with the key difference being that a series of small, regular
voltage pulses are superimposed on the linear or staircase potential sweep. This modification provides
several advantages over LSV and SV, including:

• Improved sensitivity: DPV is significantly more sensitive than LSV and SV due to the
cancellation of non-faradaic currents, such as the charging current. This allows for the
detection of analytes at lower concentrations.
• Enhanced selectivity: The differential nature of the DPV signal makes it more selective than
LSV and SV, as it is less susceptible to interference from background currents. This is
particularly important in complex samples containing multiple electroactive species.
• Better resolution: DPV produces sharper peaks than LSV and SV, which makes it easier to
distinguish between closely spaced redox events.

Instrumentation

A typical DPV setup consists of the following components:

• Potentiostat: A potentiostat is an electronic device that is used to control the potential of the
working electrode.
• Working electrode: The working electrode is the electrode at which the electrochemical
reaction occurs. It is typically made of a noble metal, such as gold or platinum.
• Reference electrode: The reference electrode is a stable electrode that provides a fixed
potential against which the working electrode potential is measured. A common reference
electrode is the silver/silver chloride (Ag/AgCl) electrode.
• Counter electrode: The counter electrode is an electrode that provides a path for the current
to flow. It is typically made of a large, inert material, such as graphite or stainless steel.
• Solution: The solution is the sample that contains the analyte to be measured. It is typically
an aqueous solution containing a supporting electrolyte.
• Data acquisition system: A data acquisition system is used to record the current as a function
of potential.

The following is a simplified diagram of a DPV setup:

 differential pulse voltammetry setup

Procedure

In a DPV experiment, the potential of the working electrode is scanned linearly from an initial potential
to a final potential. A series of small, regular voltage pulses are superimposed on the linear potential
sweep. The current is measured immediately before each potential change, and the current difference is
plotted as a function of potential. The resulting plot is called a differential pulse voltammogram (DPV).

Applications

DPV is a versatile technique that can be used to study a wide variety of electrochemical reactions.
Some common applications of DPV include:

• Determination of trace metals: DPV is a highly sensitive technique for the determination of
trace metals in solution.
• Study of redox reactions: DPV can be used to study the kinetics and thermodynamics of
redox reactions.
• Analysis of pharmaceuticals: DPV can be used to analyze pharmaceuticals and their
metabolites in biological fluids.
• Characterization of nanomaterials: DPV can be used to characterize the electrochemical
properties of nanomaterials.

DPV is a powerful tool for the study of electrochemistry. It is a sensitive, selective, and versatile
technique that can be used to study a wide variety of electrochemical systems.
Polarography

Polarography is an electroanalytical technique that measures the current flowing between two electrodes
in a solution as a function of applied voltage. It is used to identify and quantify oxidizable or reducible
substances in a solution. The main component of a polarograph is the dropping mercury electrode
(DME), which is a continuously forming mercury droplet that serves as the working electrode. The
other electrode, the reference electrode, is a non-polarizable electrode that provides a stable potential.

Instrumentation of Polarography

A typical polarograph consists of the following components:

1. Dropping Mercury Electrode (DME): The DME is the heart of the polarograph. It is a
capillary tube that continuously forms mercury droplets at its tip. The fresh surface of the
mercury droplet provides a consistently reproducible electrode surface.
2. Reference Electrode: The reference electrode provides a stable potential against which the
DME potential is measured. Common reference electrodes include the saturated calomel
electrode (SCE) and the silver/silver chloride electrode (Ag/AgCl).
3. Polarographic Cell: The polarographic cell is the container that holds the solution to be
analyzed. It has two or three compartments, one for the solution, one for the reference
electrode, and sometimes one for an inert gas that is bubbled through the solution to remove
oxygen.
4. Power Supply: The power supply provides a voltage that is applied across the electrodes. The
voltage is gradually increased, and the current flowing between the electrodes is measured.
5. Recorder: The recorder plots the current flowing between the electrodes as a function of
applied voltage. This plot, called a polarogram, is used to identify and quantify the substances
in the solution.

Types of Polarography

There are two main types of polarography:

1. DC Polarography: This is the original form of polarography, in which a direct current (DC)
voltage is applied to the electrodes.
2. Pulse Polarography: This is a more modern technique, in which a pulsed voltage is applied
to the electrodes. Pulse polarography is more sensitive than DC polarography and is less
susceptible to interference from dissolved oxygen.

Applications of Polarography
Polarography has a wide range of applications in analytical chemistry, including:

1. Qualitative Analysis: Polarograms can be used to identify the presence of certain substances
in a solution.
2. Quantitative Analysis: Polarograms can be used to quantify the concentration of certain
substances in a solution.
3. Study of Electrode Processes: Polarography can be used to study the kinetics and
thermodynamics of electrode reactions.

Polarography is a versatile and powerful technique that has been used for many decades in analytical
chemistry. It is a relatively simple and inexpensive technique that can be used to analyze a wide range
of substances.
Potentiometric Sensor: Definition, Classification & Applications

Definition

A potentiometric sensor is a type of electrochemical sensor that measures the electrical potential of an
electrode when no current is flowing through it. This potential, known as the electrode potential, is
related to the concentration of the analyte in the solution or gas being measured. Potentiometric sensors
are widely used in a variety of applications, including environmental monitoring, industrial process
control, and clinical diagnostics.

Classification

Potentiometric sensors can be classified into two main types:

• Membrane sensors: These sensors have an ion-selective membrane that allows only specific
ions to pass through it. The potential difference between the reference electrode and the
working electrode is related to the concentration of the target ion in the solution.
• Solid-state sensors: These sensors have a solid electrolyte that allows the transport of ions.
The potential difference between the reference electrode and the working electrode is related
to the concentration of the target ion in the gas or solid being measured.

Applications

Potentiometric sensors are used in a wide variety of applications, including:

• Environmental monitoring: Potentiometric sensors are used to monitor the concentration of

pollutants in air, water, and soil.
• Industrial process control: Potentiometric sensors are used to monitor the concentration of
chemicals in industrial processes.
• Clinical diagnostics: Potentiometric sensors are used to measure the concentration of ions in
blood and other bodily fluids.

Examples of Potentiometric Sensors

• pH electrode: This sensor measures the concentration of hydrogen ions (H+) in a solution.
• Ion-selective electrode: This sensor measures the concentration of a specific ion in a
solution.
• Oxygen sensor: This sensor measures the concentration of oxygen in a gas or liquid.
Advantages of Potentiometric Sensors

Potentiometric sensors have several advantages over other types of sensors, including:

• Selectivity: Potentiometric sensors can be very selective for specific ions or gases.
• Sensitivity: Potentiometric sensors can be very sensitive to changes in analyte concentration.
• Stability: Potentiometric sensors are relatively stable over long periods of time.
• Simplicity: Potentiometric sensors are relatively simple to operate and maintain.

Disadvantages of Potentiometric Sensors

Potentiometric sensors also have some disadvantages, including:

• Limited range: Potentiometric sensors have a limited range of measurement.

• Interferences: Potentiometric sensors can be affected by interferences from other ions or
gases.
• Response time: Potentiometric sensors can have a relatively slow response time.

Overall, potentiometric sensors are a versatile and valuable tool for measuring the
concentration of ions and gases in a variety of applications.
Amperometry

Amperometry is an electroanalytical technique that measures the current produced by a chemical

reaction occurring at an electrode. The current is directly proportional to the concentration of the
analyte, making amperometry a sensitive and quantitative method for analysis.

Principles of Amperometry

Amperometry is based on the principle that when an electrochemical reaction occurs at an electrode, a
flow of electrons is generated. This flow of electrons is measured as an electric current. The
magnitude of the current is proportional to the rate of the electrochemical reaction, which in turn is
proportional to the concentration of the analyte.

Instrumentation for Amperometry

The basic instrumentation for amperometry consists of a working electrode, a reference electrode, and
a potentiometer or amperometer. The working electrode is the electrode at which the electrochemical
reaction occurs. The reference electrode is used to establish a stable potential between the working
electrode and the solution. The potentiometer or amperometer is used to measure the current produced
by the electrochemical reaction.

Applications of Amperometry

Amperometry is a versatile technique that has a wide range of applications in analytical chemistry.
Some of the most common applications of amperometry include:

• Determination of inorganic and organic compounds: Amperometry can be used to

determine a wide variety of inorganic and organic compounds, including metals, anions,
cations, and organic molecules.
• Titrations: Amperometry can be used to determine the endpoint of titrations. In an
amperometric titration, the current is monitored as a titrant is added to the solution. The
endpoint of the titration is reached when the current reaches a maximum or minimum value.
• Flow analysis: Amperometry is a common detection method in flow analysis. In flow
analysis, the sample is injected into a flowing stream of carrier solution. The sample is then
passed through a detector, such as an amperometric detector, which measures the
concentration of the analyte.
Amperometry is a powerful and versatile technique that has a wide range of applications in analytical
chemistry. It is a sensitive, quantitative, and relatively simple technique that can be used to determine
a wide variety of compounds.
The terms "current" and "potential" are often used interchangeably, but they have distinct
meanings in physics and other contexts. Here's a comparison and contrast between current
and potential:

Current

In physics, electric current is the flow of electric charge through a conductor. It is measured
in amperes (A) and represents the rate at which charge passes through a specific point or
cross-section of a conductor. Electric current is analogous to the flow of water in a pipe. The
higher the current, the faster the charge is moving through the conductor.

Potential

Electric potential, also known as voltage, is the electrical energy stored per unit charge. It is
measured in volts (V) and represents the difference in energy between two points in an
electric field. Electric potential is analogous to the elevation of water in a reservoir. The
higher the potential, the greater the potential energy stored per unit charge.

Comparison

Both current and potential are fundamental concepts in electricity. Current is the movement
of charge, while potential is the energy associated with that movement. They are related by
Ohm's law, which states that the current through a conductor is directly proportional to the
potential difference across it and inversely proportional to its resistance.

Contrast

The key difference between current and potential is that current is a flow of charge, while
potential is a measure of energy. Current exists when charges are moving, while potential can
exist even when there is no current flow. Additionally, current is measured in amperes (A),
while potential is measured in volts (V).

Feature Current Potential

Definition Flow of electric charge Electrical energy per unit charge
Units Amperes (A) Volts (V)
Analogy Flow of water in a pipe Elevation of water in a reservoir
Relationship Current is directly proportional to potential difference and inversely proportional to
resistance (Ohm's law)

Comparative explanation of each technique:

Feature Voltammetry Potentiometric Amperometric Polarization

sensors sensors techniques
Measurement Measures the Measures the Measures the current Applies a potential to
principle current flowing potential difference flowing through a an electrode and
between two between two working electrode as measures the
electrodes as the electrodes the potential is varied resulting current or
potential is varied potential
 Applications Analyzes the Measures the Measures the Studies the kinetics
concentration of a concentration of a concentration of a of electrochemical
dissolved species in dissolved species in dissolved species in a reactions
a solution a solution solution
Advantages High sensitivity Simple to use High sensitivity Can be used to study
a wide range of
electrochemical
reactions
Disadvantages Requires a Can be susceptible Requires a relatively Can be time-
relatively large to interference from large sample size consuming
sample size other dissolved
species

Voltammetry is an electrochemical technique that measures the current flowing between two
electrodes as the potential is varied. The current is a function of the concentration of the
dissolved species, so voltammetry can be used to analyze the concentration of a dissolved
species in a solution.

Potentiometric sensors are electrochemical sensors that measure the potential difference
between two electrodes. The potential difference is a function of the concentration of the
dissolved species, so potentiometric sensors can be used to measure the concentration of a
dissolved species in a solution.

Amperometric sensors are electrochemical sensors that measure the current flowing through
a working electrode as the potential is varied. The current is a function of the concentration of
the dissolved species, so amperometric sensors can be used to measure the concentration of a
dissolved species in a solution.

Polarization techniques are a group of techniques that apply a potential to an electrode and
measure the resulting current or potential. Polarization techniques can be used to study the
kinetics of electrochemical reactions.