MODULE-1

SENSORS AND ENERGY SYSTEMS

(For CSE streams)

G.K. Prashanth
Dept. of Chemistry, Sir MVIT
A sensor is a device that measures physical input from its environment and converts it into
data. Sensors are an integral part of modern living. If we are reading this on a computer, we
are most likely using a mouse, which contains an optical sensor. If we are on a smartphone, we
are using touch sensors every time we touch the screen. But what exactly is a sensor?
Definition: A sensor is a device that measures physical input (heat, light, weight, sound
etc) from its environment and converts it into data that can be interpreted by either a
human or a machine. [In the broadest definition, a sensor is a device, module, machine, or
subsystem that detects events or changes in its environment and sends the information to other
electronics, frequently a computer processor. Sensors are always used with other electronics.
Most sensors are electronic (the data is converted into electronic data), but some are more
simple, such as a glass thermometer, which presents visual data. People use sensors to measure
temperature, gauge distance, detect smoke, and regulate pressure and a myriad of other uses].
The word “sensor” comes from Latin (sensus: sense) and means feeler.
SENSORS, AND TRANSDUCERS:
Transducers can be categorized by which direction information passes through them:
Transducers: A transducer is an electronic device that converts energy from one form to
another. The process of converting energy from one form to another is known as transduction.
Actuator: is a part of a device or machine that helps it to achieve physical movements by
converting energy, often electrical, air, or hydraulic, into mechanical force. It is the component
in any machine that enables movement.
A chemical sensor is a device that is capable of giving analytical information about an
analyte. It interacts with the analyte, detects it, and produces a signal proportional to the
quantity of the analyte (A sensor is a transducer that receives and responds to a signal or
stimulus from a physical system. It produces a signal, which represents information about the
system, which is used by some type of telemetry, information or control system).
Receptor: It binds the sample. Receptor is a chemical or biological element that interacts
selectively with the analyte. Interaction of receptor with the analyte produces a signal which
can be measured. The receptors are variable and can range from activated or doped surfaces to
complex (macro) molecules that create highly specific interactions with the analyte.

ELECTROCHEMICAL SENSORS:
Electrochemical sensors convert the effect of electrochemical reaction between analyte and
electrode surface into a useful signal. There are many different applications of electrochemical
sensors, and they continue to play an important role in many industries.
Electrochemical sensor technology has been used in industry for many years. The current
requirements for small sensors with low energy consumption and ease of use have enabled the
continuous development of the technology. Electrochemical sensors can be constructed
differently depending on the application, and therefore, provide tailored solutions to new
emerging applications. In electrochemical sensors the electrode is used as transducer.
An electrochemical sensor may be:

a. Potentiometric
b. Amperometric
c. Conductometric

Principle:

In electrochemical sensors:

The electrode is used as transducer. It is called the working or sensing electrode. It is typically
made from metals such as platinum or gold. It has a chemically modified surface with a
recognition element. The recognition element interacts with the analyte and generates the signal
(The electrode will either oxidize or reduce the analyte of interest. The current that is produced
from the reaction is monitored and used to calculate important data such as concentrations from
the sample).
Electrolyte - the electrolyte facilitates the cell reaction and carries the ionic charge across the
electrodes.
Electrode (cathode) – this is the point where the current leaves the electrode.
Working of an electrochemical sensors involves:
1. Diffusion of the analyte to the electrode and electrolyte interface.
2. Adsorption of analyte onto the electrode surface.
3. Electrochemical reaction occurs with electron transfer.
4. Desorption of the products.
Electrochemical sensors are used to detect the presence of toxic gases such as H2S, Cl2, and
SO2, and variation of oxygen in the air.
Closed electrical circuit is a common requirement of all electrochemical sensors. A closed
electrochemical circuit used for selective determination of pH is shown as below:
Applications:
Electrochemical sensors are used in a variety of applications, and they continue to play an
important role in many industries. Some of the most common applications include:

1. Environmental monitoring of air quality

2. Detection of toxic vapours
3. Food quality control
4. Oxygen monitoring in the medical sector
5. Electrochemical sensors can detect and measure a variety of gases—ranging from toxic
to explosive to air quality—depending on the needs of the application, including the
following: Oxygen, Carbon Monoxide, Nitrogen Dioxide, Nitrogen Oxide, Sulphur
Dioxide, Hydrogen sulphide
6. Humidity sensor
7. Detection of pesticides
8. In soil parameter analysis.
Advantages of electrochemical sensors:
1. Straight performance, low necessities for force and great goal.
2. Remarkable repeatability and accuracy. The sensor can give an exact perusing of a
repeatable objective gas once adjusted to a known fixation.
3. Doesn't get harmed by other gases. The presence of other surrounding fumes would not
abbreviate or restrict the sensor 's life.
4. Less expensive than most different advances for gas detection.
5. It could be interesting to a particular gas or fume in the scope of parts per million. The
level of selectivity relies upon the kind of sensor, the sensor is worked to distinguish,
the objective gas, and the gas focus.
Types of electrochemical sensors:
There are three main types of electrochemical sensors: Potentiometric, Amperometric and
Conductometric. For potentiometric sensors, a local equilibrium is established at the sensor
interface, where either the electrode or membrane potential is measured, and information about
the composition of a sample is obtained from the potential difference between two electrodes.
Amperometric sensors exploit the use of a potential applied between a reference and a working
electrode, to cause the oxidation or reduction of an electroactive species; the resultant current
is measured. On the other hand, conductometric sensors are involved with the measurement of
conductivity at a series of frequencies.

CONDUCTOMETRIC SENSORS:
Sensors in this group rely on changes of electric conductivity of a material, whose conductivity
is affected by the analyte present. The conductance is defined as the current flow through the
conductor. In other words, it is defined as the reciprocal of the resistance. The unit for the
conductance is Seimens (S) which is the reciprocal of Ohm's (Ω −1). Conductometry is the
measurement of the electrical conductivity of a solution.
It is an electrochemical method of analysis used for the determination or measurement of the
electrical conductance of an electrolyte solution by means of a conductometer.
Instrumentation:
The instrument used for measurement of conductance is known as conductometer. It consists
of:
Current source: Mechanical high frequency AC generator
Conductivity cell: Made of pyrex or quartz fit with two platinum electrodes
Electrodes: Platinum sheets, each of 1 cm2 fixed at a distance of 1 cm. The surface is coated
with platinum black to avoid polarization effects and to increase the effective surface area.

Principle:
Electric conductivity of an electrolyte solution depends on:
 Type of ions (cations, anions, singly or doubly charged)
 Concentration of ions
 Temperature
 Mobility of ions
The main principle involved in this method is that the movement of the ions creates the
electrical conductivity. The movement of the ions is mainly depended on the concentration of
the ions.
The electric conductance in accordance with ohms law which states that the strength of current
(i) passing through conductor is directly proportional to potential difference & inversely to
resistance.
i =V/R
A solution may have the following conductivity:
 Specific conductivity
  Equivalent conductivity
 Molar conductivity
Specific conductivity is measured during conductometric titration.
Specific conductivity: It is the conductivity of a solution of 1 cm3 material [i.e., between 1 cm2
area and kept 1 cm apart]
Measurement of conductance can be employed to determine the equivalence point in acid base
titrations. When indicators used, the end point is detected by a change in the colour. In
conductometric titrations, there is a sudden increase in the conductance of the solution at the
equivalence point. Hence the equivalence point is determined graphically by plotting
conductance against titre values. The principle underlying conductometric titration is the
replacement of ion of a particular conductance by ions of different conductance during the
titration.
For example in the titration of an acid with a base, the acid is taken in a beaker and the base is
added from a burette. The conductance of an acid is due to the H+ ions and the anions. When a
base is added slowly from the burette, the hydrogen ions are replaced by sodium ions. Na+ ions
have lower mobility than H+ ions and hence on continued addition of NaOH, the conductance
goes on decreasing until the acid is completely neutralised. Further addition of base leads to an
increase in number of more mobile OH– ions and conductance increases. Therefore during the
titration the conductance initially decreases, reaches a minimum value and again increases. A
plot of conductance against volume of base added gives two straight lines. The point of
intersection of the two lines gives the neutralization point.
Conductometer consists of two platinum electrodes and a conductance measuring device. The
two electrodes have unit area of cross-section and are placed unit distance apart. The assembly
responds rapidly to the changes in the concentration of the analyte.
Advantages:
 Accurate in dilute as well as more concentrated solutions.
 Can also be employed with coloured solutions.
 Very weak acids which cannot be titrated potentiometrically in aqueous solutions can
be titrated conductometrically.
 Mixtures of acids can be titrated more accurate.
Applications:
 To detect the amount of ionic impurities in a water sample.
 Used in measuring alkalinity or acidity of a water sample.
 It can be used in enzyme catalysis to determine analyte concentration and enzyme
activity.
 Used to estimate acids/bases and their mixtures:
 Strong acid with a strong base (dil. HCl vs NaOH)
 Strong acid with a weak base (dil. H2SO4 vs dil NH4OH)
 Weak acid with a strong base (dil. CH3COOH vs dil. NaOH)
 Weak acid with a weak base (dil. CH3COOH vs dil. NH4OH)
  Mixture of strong acid and a weak acid with a strong base (e.g. HCl + CH 3COOH vs
NaOH)
 Mixture of a strong acid and a weak acid with a weak base (e.g. HCl + CH3COOH vs
NH4OH)
 Precipitation titrations (Sodium Sulphate vs BaCl2 solution, KCl vs AgNO3)

OPTICAL SENSORS:
An optical sensor is a device that converts light rays into electronic signals. Optical sensors
detect and measure light rays into electrical signals. Similar to a photoresistor, it measures the
physical quantity of light and translates it into a form read by the instrument.
Optical sensors are a class of devices that use various forms of light–matter (i.e., photon–atom)
interactions to detect, interrogate, and quantify molecules for multiple applications. An optical
sensor is composed of a light source that generates electromagnetic waves, a sensing platform
in which light–matter interactions occur, and a detector that identifies and quantifies spectral
shifts in electromagnetic waves upon interaction with targeted analytes.
Optical sensors have the ability to detect light, typically at a specific range of the
electromagnetic spectra (ultraviolet, visible, and infrared). The sensor detects either
wavelength, frequency, or polarization of light and converts it into electric signal due to
photoelectric effect. The presence of an analyte causes change in absorbance, luminescence, or
refractive index of the material resulting in a change in the output signal.
Optical sensors have unique advantages, such as high sensitivity, immunity to electromagnetic
interference, small size, light weight, robustness, flexibility, and the ability to provide
multiplexed or distributed sensing.
Example of optical sensor: Colorimetry
COLORIMETRY
Chemical analysis through measurement of absorption of light radiation in the visible region
of the spectrum (400-760 nm) with respect to a known concentration of the substance is known
as colorimetry. Electromagnetic radiations are divided into several regions based on their
wavelength as gamma rays, X-rays, UV, visible, IR, microwaves and radio waves. These
radiations when passed through matter get absorbed. The amount and wavelength of the
radiation absorbed are the basis of chemical analysis involving electromagnetic radiation.
Beer-Lambert’s law
When a monochromatic radiation of intensity I is passed though a solution of a sample under
investigation taken in a cell of thickness t, a portion of the radiation is absorbed (Ia) a portion
is reflected (Ir) and the remainder is transmitted (It).
I = Ia + Ir + It
For glass cells, Ir is negligible
So, I = Ia + It
Lambert’s Law
“When monochromatic light passes through a transparent medium, the rate of decrease in
intensity with thickness of the medium is proportional to the intensity of the light.”
Beer’s law
“The intensity of the transmitted light decreases exponentially as the concentration of the
medium increases arithmetically”.

Block diagram of colorimeter

Advantages of colorimetry (Any 4):
 Easily carriable and transportable.
 It is inexpensive
 It gives accurate results at very low concentration.
 The substances for which gravimetric or titrimetric procedures are not available this
technique can be used to find out their concentration.
 It is ideal for quick and routine analysis of components of a number of similar samples.
Applications of colorimetry (Any 4):
 It is used in laboratories and hospitals to estimate biochemical samples such as urine,
cerebrospinal fluid, plasma, serum, etc.
 It is used in the manufacturing of paints.
 It is used in textile and food industry.
 It is used in the quantitative analysis of proteins, glucose, and other biochemical
compounds.
 It is used to test water quality.
 It is used to determine the concentration of haemoglobin in the blood.
Applications of optical sensors (Any 4):
 Optical sensors are integral parts of many common devices, including computers, copy
machines (xerox) and light fixtures that turn on automatically in the dark. And some of
the common applications include alarm systems, synchros for photographic flashes and
systems that can detect the presence of objects.
 Common applications are smartphones where sensors are used to adjust screen
brightness, and smart watches in which sensors are used to measure the wearer's
heartbeat.
  Optical sensors can be found in the energy field to monitor structures that generate,
produce, distribute, and convert electrical power. The distributed and nonconductive
nature of optical fibres makes optical sensors perfect for oil and gas applications,
including pipeline monitoring.
 Another important application of optical sensor is to measure the concentration of
different compounds by both visible and infrared spectroscopy.
 Optical sensors have been widely used in the biomedical field, including developing an
optical heart-rate monitor that uses light.
 Contactless sanitizer dispensers
 Agricultural application: Optical sensors have enabled on-site detection of pesticides in
agricultural food products.
 Industrial and commercial applications: Optical sensors are used to detect liquid levels
in engineering facilities. For instance, optical sensors detect petroleum levels in
hydrocarbon refineries and tanks
 Environmental application: Food security and human health are significantly affected
by heavy metal pollution, such as cadmium, in soil.
 Breath analyzers

THERMOMETRIC SENSORS:
Temperature is the most often-measured environmental quantity. This might be expected since
most physical, electronic, chemical, mechanical, and biological systems are affected by
temperature. Certain chemical reactions, biological processes, and even electronic circuits
perform best within limited temperature ranges. Temperature is one of the most commonly
measured variables. They are devices to measure temperature readings through electrical
signals. The sensor is made up of two metals, which generate electrical voltage or resistance
once it notices a change in temperature.
We use temperature sensors every day for temperature control in buildings, water temperature
regulation, and to control refrigerators. Temperature sensors are also vital in many other
applications such as consumer, medical, and industrial electronics.

Example: FLAME PHOTOMETRY

Theory: Na, K, Ca, Li and other common elements impart characteristic colours with Bunsen
flame. The intensity of the coloured flame varies with the amount of element introduced. This
forms the basis of flame photometry.
When the solution containing a compound of the metal to be investigated is aspirated into a
flame, the following processes occur:
1. Solvent evaporates leaving behind a solid residue
2. Vaporisation of the solid coupled with dissolution in to its constituent atoms, which are
initially in the ground state
3. Some gaseous atoms get excited by the thermal energy of the flame to higher energy levels.
The excited atoms which are unstable quality exit photons and return to lower energy
state i.e., ground state. Flame photometry involves the measurement of emitted radiation

It is summarized as

The intensity of the emitted radiation measured as detector response is related to the
concentration by an expression similar to Beer’s relation.
E=K€C
where E is the detector response; K is a constant, € is the efficiency of atomic excitation
and C is the concentration of the solution.
Instrumentation
A flame photometry consists of the following points
• Pressure regulator: to match the flow of gas through the regulator to the demand for the gas
placed upon the system.
• Atomizer: Main function of it is breaking of liquid into tiny droplets in the form of fine spray.
• Lens/Iris diaphragm: To control intensity of the light that irradiates.
• Filter: It permits only the radiation characteristic of the element under investigation.
• Photocell: To convert emitted radiation in to electrical signal.
• Meter: To read values directly as emission intensity.
Applications:
Flame photometry is used for the determination of alkali metals because excitation of which
requires only a low energy input from 10 w tempo flame.
Estimation of Na:
Standard sodium stock solution: Dissolve 2.54 g of NaCl in distilled water and diluted to one
litre. The resulting solution contains 1000 mg of sodium per litre (1000 ppm of Na)
Procedure:
1. Transfer 2,4,6,8 and 10 ml of standard NaCl solution in to different 100 ml standard
volumetric flasks and dilute up to the mark with double distilled water.
2. Place the distilled water in the suction capillary and set the instrument to read 2,4,6,8 and
10.
3. Dilute the given test solution up to the mark and shake well and place the solution in the
suction capillary and record the reading.
4. Draw a calibration curve by plotting the reading on y-axis and volume of NaCl solution on
x-axis.
5. From the calibration curve, find out the volume of the given test solution and from which
calculate the amount of Na.

ELECTROCHEMICAL SENSOR FOR THE MEASUREMENT OF

DISSOLVED OXYGEN (DO)
It is the amount of free molecular oxygen dissolved in water. It is expressed in mg/litre of
molecular oxygen. DO is essential for the survival of aquatic animals
DO levels above 5 mg/litre of molecular oxygen are considered optimal. They can be
determined by Winkler’s method.
Modern method of dissolved oxygen (DO) measurement in the lab or field involves a DO
sensor connected to a meter that records calibration and measurement data. DO sensors can be
designed for discrete sampling, biological oxygen demand (BOD) tests, or long-term
monitoring applications.
There are two types of DO sensors—electrochemical and optical. Electrochemical DO sensors,
also known as amperometric or Clark-type sensors, measure dissolved oxygen concentration
in water based on electrical current produced. Polarographic and galvanic are types of
electrochemical DO sensors. The advantages of galvanic sensors over polarographic sensors
are that they don’t require outside voltage source and warm-up time to operate and their
electrolyte can be used for a long time.
Industrial DO probe:

Components:
Cathode, Anode, Electrolyte, Membrane

The cathode and anode are dissimilar metals (different electropotentials). In order to reduce
oxygen without an external applied potential, the difference in potential between the anode and
the cathode should be at least 0.5V. When placed in an electrolyte solution, the potential
between dissimilar metals causes them to self-polarize with the electrons travelling internally
from the anode to the cathode. For this reason, galvanic DO sensor does not require any warm-
up time.
The cathode (e.g., Ag or another noble metal) accepts electrons from the anode via an internal
circuit and passes them on to the oxygen molecules. It does not interfere in the reaction. Thus,
the anode (e.g., Zn, Pb, or another active metal) is oxidized and oxygen is reduced at the surface
of the cathode.
Both the cathode and anode are submerged in an electrolyte (e.g., NaOH, KOH, NaCl, or
another inert electrolyte) and enclosed in a cap fitted with thin hydrophobic, oxygen-
permeable membrane.
When galvanic DO sensor is immersed in water sample, oxygen that diffuses across
the oxygen-permeable membrane at a rate proportional to the pressure of oxygen in
the water is reduced and consumed at the cathode. This reaction produces an electr ical
current that is directly related to the oxygen concentration. This current is carried by
the ions in the electrolyte and runs from the cathode to the anode.

Anode (Pb) – lead oxidation reaction: 2Pb 2Pb 2+ + 4e -

Cathode (Ag) – oxygen reduction reaction: O 2 + 4e - + 2H 2 O 4OH -
Overall reaction: O 2 + 2H 2 O + 2Pb 2Pb(OH) 2
The current produced is proportional to oxygen consumed and thus to the partial
pressure of oxygen in the sample.

The white solid, Pb(OH) 2 , that is produced by these reactions is precipitated out into
the electrolyte solution. It neither coats the anode nor consumes the electrolyte, and
thus does not affect the sensor’s performance until the quantity becomes excessive. If
this happens, it may interfere with the ions’ ability to carry current.

As galvanic DO sensor is self-polarizing, the anode is continuously consumed even

when the sensor is not in use. When there is no measurement for a long period, the DO
tip should be disconnected and stored according to the manual.

ELECTROCHEMICAL SENSOR FOR PHARMACEUTICALS

Diclofenac [2-[2-(2,6-dichloroanilino)phenyl]acetic acid]

The use of pharmaceuticals in society has become vital for treating diverse illnesses. The non
steroidal anti-inflammatory drugs (NSAIDS) have analgesic, antipyretic and anti inflamatory
effects. The reason for their popularity is because they do not produce sedation or addiction
and of their unrestricted purchase.
Diclofenac (DCF) is used to treat mild to moderate pain, or signs and symptoms of
osteoarthritis or rheumatoid arthritis.
Modified electrodes have gained attention thanks to their high sensitivity and simplicity. An
electrochemical sensor consists of an electrochemical transducer coated with a chemical film
acting as conducting material. Due to the high electroactivity of DCF, it can be detected at low
concentrations using various types of modified electrodes based on advanced materials. In fact,
the use of these electrodes allows enhancement of electrical signal and improvement of
selectivity related to the oxidation of diclofenac. Many electrochemical investigations by
unmodified electrodes have also been reported for the analysis of diclofenac in pharmaceutical,
biological, and environmental samples. Due to their low cost and low chemical reactivity,
electrodes based on carbon materials still dominate in the electrochemical analysis of DCF.
Experimental part: A potentiostat is used to perform the electrochemical study aided by a
conventional three-electrode cell comprising:
Working electrode: A carbon paste electrode (CPE) with multi-walled carbon nanotubes
(MWCNTs) and graphene
OR
Graphite electrode coated with MWCNTs and gold nanoparticles.
The counter-electrode: Pt wire or A CPE with MWCNTs and graphene.
Reference electrode: Ag/AgCl electrode serves as the reference electrode.
The electrochemical quantification is carried out at pH 7.
Electrochemical mechanism proposed involved during the DCF electrochemical oxidation in
an aqueous medium at pH 7, using CPE:
Polycyclic aromatic hydrocarbons (PAHs):
1-hydroxypyrene:

Sources of PAHs: Industry, Motor vehicle exhaust, Coal, Wood burnings, and tobacco
smoking. Also formed during the incomplete combustion of coal, and oil products.
Found in: the atmosphere, soil, water, food, and so forth.
Urinary 1-hydroxypyrene (1-OHP) is a widely used biomarker as an indicator of
exposure to polycyclic aromatic hydrocarbons (PAHs).
PAHS are metabolized into hydroxyl PAHS (OH-PAHs), which are excreted with urine. The
OH-PAHs in urine can effectively reflect the recent exposure to PAHs, and the samples are
easy to collect. Therefore, OH-PAHs in urine have been widely used as biomarkers to evaluate
PAH exposure levels in the human body. Among them, 1-hydroxypyrene (1-OHP) can more
accurately indicate the total internal exposure level of PAHs.
As 1-OHP is stable and relatively easy to detect in urine, urinary 1-OHP has been used as a
biomarker of exposure to PAHs.
Many methods for 1-OHP analysis have been developed such as HPLC−MS, GC−MS, and
LC−MS/MS, but most of the equipment used is large, expensive, and difficult to operate,
laborious sample pretreatment and toxic reagents are used, and the pretreatment processes are
time consuming. Therefore, a novel, simple, effective, fast, and low-cost approach for the
determination of urinary 1-OHP is urgently needed. Studies on electrochemical sensors in 1-
OHP analysis are beginning to be reported. The OHPAH structure contains electrochemically
active hydroxyl groups, so they can be used for electrochemical detection.
Usually the:
Sensing electrode: Graphite coated with chromium metal organic frame work (Cr-MOF) and
grapheme oxide.
Counter electrode: Pt wire
Reference electrode: Ag/AgCl/Calomel electrode
The following oxidation of 1-OHP occurs:

ELECTROCHEMICAL GAS SENSORS:

Electrochemical sensors use a chemical reaction to measure the concentration of a specific gas
in an environment. There are many different applications for electrochemical sensors, and they
continue to play an important role in many industries.
Electrochemical sensor technology has been used in industry for many years. The current
requirements for small sensors with low energy consumption and ease of use have enabled the
continuous development of the technology. Electrochemical sensors can be constructed
differently depending on the application, and therefore, provide tailored solutions to new
emerging applications.
Electrochemical sensors work by reacting with the gas of interest and producing an electrical
signal proportional to the gas concentration. Consisting of two electrodes (a working electrode
and a counter electrode), the sensor operates by allowing charged molecules to pass through a
thin layer of electrolyte.
An electrochemical gas sensor consists of the following components:
Gas permeable membrane – this material covers the sensing electrode and is used to control
the amount of gas molecules reaching the electrode surface. The membrane also performs the
important role of filtering unwanted contaminants mainly particulates.
Electrodes: Two or three electrodes system is used based on the requirement. Sensing
electrode/working electrode, counter electrode and reference electrode.
Electrode (anode) – to create an effective reaction with gas molecules, the electrode is
typically made from metals such as platinum or gold and works as a transducer. The anode is
the point at which the current enters the electrode.
Electrode (cathode) – this is the point where the current leaves the electrode.
Electrolyte - the electrolyte facilitates the cell reaction and carries the ionic charge across the
electrodes. It should be a good ionic conductor and chemically stable.
Working principle:
The diffusion of gas through membrane and finally through electrolyte onto the surface of the
sensing/working electrode.
Adsorption of gas molecules on the surface of sensing electrode.
Oxidation/reduction on the surface of sensing/working electrode. This electrochemical reaction
results in an electric current that passes through the external circuit. At the counter electrode
an equal and opposite reaction occurs, such that if the working electrode is oxidation, then the
counter electrode is reduction.

EELECTROCHEMICAL SENSOR FOR SOX AND NOX

Electrochemical gas sensors are gas detectors that measure the concentration of a target gas by
oxidizing or reducing the target gas at an electrode and measuring the resulting current. Any
gaseous compound which undergoes redox reaction on the surface of the electrode can be
measured with an electrochemical sensor.
In electrochemical sensors, gas molecules diffuse through a porous membrane that is placed in
contact with a metallic electrode, known as the working electrode. This surface is where the
analyzed gas is subjected to oxidation or reduction; i.e., gas molecules lose or acquire electrons
at the working electrode. An equal and opposite reaction occurs at a second electrode, known
as the counter electrode. For example, if oxidation occurs on the working electrode, reduction
occurs on the counter electrode. The reduction of oxygen commonly occurs at the counter
electrode in electrochemical sensors.
The electrodes are separated and immersed in aqueous medium (electrolyte) that may include
soluble salts, acids, or bases dissolved in a polar solvent such as water. The medium provides
hydrogen ions (H+) that move through the aqueous solution.

Detection of SO2 with the help of an electrochemical sensor with Au/Nafion sensing electrode
is based on the following oxidation reaction on the surface of the working electrode. H2SO4 is
the electrolyte.
SO2 + H2O SO3 + 2 H+ + 2 e-
Reaction at the counter electrode: ½ O2 + 2 H+ + 2 e- H2O
Detection of NO2 with the help on an electrochemical sensor with Au/Nafion sensing electrode
is based on the following reduction reaction on the surface of the working electrode. H2SO4 is
the electrolyte.
NO2 + 2 H+ + 2 e- NO + H2O
Reaction at the counter electrode: H2O ½ O2 + 2 H+ + 2 e-
Detection of NO with the help on an electrochemical sensor with Au as the sensing electrode
is based on the following oxidation reaction on the surface of the working electrode. Yttrium
stabilized zirconia (YSZ), a solid material is the electrolyte.
NO + 2 H2O NO32- + 4 H+ + 2 e-
Reaction at the counter electrode: O2 + 4 H+ + 4 e- 2H2O

DISPOSABLE SENSORS:
Disposable sensors:
Disposable sensors are low-cost and easy-to-use sensing devices intended for short-term
or rapid single-point measurements. Disposable strip of a bio sensor is a special type of
paper over which receptor, and electrodes are coated. They are coated in the form of thin
film strip using screen printing technology. The growing demand for fast, accessible, and
reliable information in a vastly connected world makes disposable sensors increasingly
important.
Applications: The areas of application for such devices are numerous, ranging from
pharmaceutical, agricultural, environmental, forensic, and food sciences to wearables and
clinical diagnostics, especially in resource-limited settings. The capabilities of disposable
sensors can extend beyond measuring traditional physical quantities (for example, temperature
or pressure); they can provide critical chemical and biological information (chemo- and
biosensors). They transduce physical, chemical, or biological changes in their environment to
an analytical signal.

Disposable and portable screen printed electrode (with reference, working and auxiliary electrodes
on the same substrate).

Advantages:

 They are biodegradable.

 Fast response times.
 Prevents the contamination of samples.
 Affordable and easy-to-use devices for short-term or single-shot measurements.

DETECTION OF ASCORBIC ACID:

Ascorbic acid, namely vitamin C, is a dietary supplement naturally found in various fruits and
vegetables and plays a vital role with anti-oxidant properties in the metabolism of organisms,
cosmetics and pharmaceuticals. However, human body cannot spontaneously synthesize
ascorbic acid, and insufficient or excess ascorbic acid intake is either injurious to health,
causing rheumatoid arthritis, stomach convulsions, cardiovascular disease or diarrhea, etc. Due
to its increasing clinical and industrial applications, the development of accurate and
quantitative method for ascorbic acid determination is highly desirable. Compared to the
traditional mass spectrometry and chromatography methods for ascorbic acid detection, the
electrochemical method has attracted more attentions due to its high sensitivity, simple
operation and high selectivity.
Electrochemical biosensor has a modified carbon electrode [surface of the sensing electrode is
coated with active materials such as Nafion/Ionic Liquids/Graphene Composite, CdO,
electrografted O-aminophenol film, poly(ethylene glycol) and diglycidyl ether, etc.] that acts
as the reaction site. Ascorbic acid gets oxidized on this surface into dehydroascorbic acid.

Depending on what electrochemical method is used, the current measured by the electrode or
the change in potential caused by the redox reaction occurring on the electrode, is directly
proportional to the concentration of a given sample.

DETECTION OF GLYPHOSATE:
Pesticides are substances that are meant to control pests. This includes herbicide, insecticide,
bactericide, insect repellent, animal repellent, microbicide, fungicide, etc. The most common
of these are herbicides which account for approximately 80% of all pesticide use. Most
pesticides are intended to serve as plant protection products (also known as crop protection
products), which in general, protect plants from weeds, fungi, or insects.

As an example, the Glyphosate [IUPAC name: N-(phosphonomethyl)glycine] is a broad-

spectrum systemic herbicide and crop desiccant. It is an organophosphorus compound,
specifically a phosphonate, which acts by inhibiting the plant enzyme. It is used to kill weeds,
especially annual broadleaf weeds and grasses that compete with crops.

Glyphosate is an organophosphorous pesticide that controls broadleaf weeds and grasses.

Glyphosate is effective in killing a wide variety of plants, including grasses and broadleaf and
woody plants. It is commonly used for agriculture, horticulture, as well as garden maintenance
(including home use).
Enzyme glycine oxidase can catalyze the oxidative estimation of Glyphosate. It involves the
cleavage of C-N bond in glyphosate to amidomethylphosphonic acid (AMPA) and glyoxylate.
From the change in potential, the concentration of glyphosate is estimated.
 ENERGY STORAGE SYSTEMS

Definition: Battery is a device that consists of two or more galvanic cells connected in series
or parallel or both, which converts chemical energy into electrical energy through redox
reactions.

Example: Zn – Air battery, Lead-acid battery, Lithium batteries, etc.

With the increased human activities and comforts a number of battery dependent appliances
have come into existence. Batteries are used in flash lights, hearing aids, radio sets, watches,
electric clocks, rescue electric calling bells, calculators, alarm signal devices, portable
computers, toys, cordless appliances, motor ignitions and a host of other applications. Besides
these applications batteries are used in car engines, electroplating industrial, military, missile
firing units and space applications.

What is a commercial cell?

All voltaic cells do not find commercial applications. A useful commercial cell should possess
the following requirements.
 Should be compact and light weight
 Should be portable
 Wide range of operating temperature
 Low cell resistance
 Good shelf life
 High cell voltage
 Low initial cost and should be maintenance free
 Good cycle life
 Sealed and leak proof

Batteries are used for many different purposes, each with different requirements. For example,
batteries used in hearing aids must be very tiny, batteries used in pacemakers (A pacemaker is
a small device that is placed in chest or abdomen to control abnormal heart rhythm. The primary
purpose of a pacemaker is to maintain an adequate heart rate either because there is a block in
the hearts electrical conduction system or hearts natural pacemaker is not fast enough) must be
very reliable and batteries for driving submarines while submerged must be very large and
rechargeable.
Basic components of a battery:
A battery consists of four major components. They are anode, cathode, electrolyte and
separator as shown in the figure.

1. Anode: An electrode at the surface of which oxidation takes place. It releases

electrons into the external circuit by undergoing oxidation. It is a negative
electrode.
M Mn+ + ne-
It contains active materials which spontaneously take part in the oxidation reaction. To
become effective anode, anodic material should possess the following properties.
(i) Low reduction potential (should easily undergo oxidation).
(ii) Good conductivity.
(iii) High stability.
(iv) Fabrication must be easy and of low cost.
(v) Good capacity to deliver high Coulombic output.
Zn has these properties and hence commonly used as anode. Li in spite of its
high cost is used in many batteries.

2. Cathode: An electrode at the surface of which reduction takes place. It accepts

electrons from anode through an external circuit. Reduction of active species
occurs at cathode. It is a positive electrode.
Mn+ + ne– M
It contains active materials which spontaneously take part in the reduction reaction. To
become effective cathode, cathodic material should possess the following properties:
(i) High reduction potential.
(ii) Good resistance to electrolyte.
(iii) Good conductivity and stability.
(iv) Fabrication must be easy and of low cost.
3. Electrolyte: It provides medium for migration of ions inside the battery between
anode and cathode leading to the generation of electricity. It is the active mass in
 the anodic and cathodic compartments in the form of a solution or a slurry of
an acid, alkali. The electrolyte should have
(i) Good ionic conductivity.
(ii) Resistance to the electrode materials.

4. Separator: It is used to isolate anode and cathode in a battery to prevent internal short
circuiting. It is permeable to ions but does not conduct electrons. It transports ions from
anode to cathode and vice versa. Fibrous forms of regenerated cellulose, vinyl
polymers, polyolefins, Nafion are commonly used as separators.

CLASSIFICATION OF BATTERIES:
Batteries are broadly classified into three categories:
1. Primary Batteries: In primary batteries, the chemical energy is converted into
electrical energy as long as the chemical components are active. In these batteries,
the reaction occurs only once and after that they have to be discarded. These batteries
cannot be recharged as the chemical reactions which occur within the primary
batteries are irreversible. Examples: Zn – air battery, Dry cell, Li – MnO2 battery,
etc.
2. Secondary Batteries/Storage Batteries: Secondary batteries are those which after
discharging can be recharged. In these batteries chemical reactions taking place are
reversible. The redox reaction which converts chemical energy into electrical energy
can be reversed by passage of current. The discharged cell can be recharged by
passing current through it in the opposite direction to that of discharge. These
batteries behave like a galvanic cell during discharge, whereas they behave as an
electrolytic cell while recharging. As electrical energy is stored in the form of
chemical energy these batteries are also known as storage cells.
Examples: Lead storage battery, Ni-Cd battery, Ni-MH battery, Lithium ion battery,
etc.
3. Reserve Batteries: In these batteries one of the components is isolated and
incorporated into the battery when required. Usually, electrolyte is the component
that is isolated, but some water activated batteries contain the electrolyte solute and
only water is added for activation.
The advantages of reserve batteries are long shelf life, high performance reliability
and variety of design options. These batteries use highly active component materials
for low temperature performance. They are designed to meet long and
environmentally severe storage requirements. They are used to deliver high power for
relatively short periods of time in applications such as radiosonodes (air borne
instruments to send meterological information back to earth by radio), missiles,
grenades, mid ocean disasters and crisis in space.
Examples: Mg batteries activated by water (Mg – AgCl and Mg – CuCl), Zn – Ag2O
batteries, etc.)
Lithium batteries:

Lithium “lithion/lithina” was discovered in 1817 by Arfwedson and Berzelius by analyzing

petalite ore (LiAlSi4O10), but the element was isolated through the electrolysis of a lithium
oxide by Brande and Davy in 1821. It was only a century later that Lewis began exploring its
electrochemical properties. Considering lithium’s excellent physical properties, such as its low
density (0.534 g cm−3), high specific capacity (3860 mAh g−1), and low redox potential (−3.04
V Vs. SHE), it was quickly realized that lithium could serve well as a battery anode.

In early 1958, Harris examined the solubility of lithium in various non-aqueous (aprotic)
electrolytes—including cyclic esters (carbonates, γ-butyrolactone, and γ-valerolactone),
molten salts, and inorganic lithium salt (LiClO4)—dissolved in propylene carbonate. He
observed the formation of a passivation layer that was capable of preventing a direct chemical
reaction between lithium and the electrolyte while still allowing for ionic transport across it,
which led to studies on the stability of lithium-ion batteries. These studies also increased
interest in the commercialization of primary lithium-ion batteries.

Advantages:
 Li batteries are smaller and more powerful than other batteries.
 Li batteries stand up well to repeated charging and discharging.
 Li batteries can be fast-charging.
 Li batteries support wireless charging.
 Low self-discharge.
 Safety. Inherently safe chemistry.
 Drop-in Replacement. Available in standard industry sizes.
 Lightweight. 50-60% less weight than lead-acid equivalent.
 Longest Life.
 More Usable Capacity.
 Constant Power.
 Temperature Tolerant.
 Charging - Fast & Safe.
 High energy density.

Applications:

Lithium-ion batteries' most common applications are:

Energy Storage Systems. Electric Mobility. Laptops, mobiles, and others usually utilized
consumer electronic goods. UPS/Power backups.
Lithium-ion battery:

The use of lithium-ion batteries has grown significantly in recent years. Rechargeable lithium
batteries are found in many cell phones, laptops and digital cameras. They do not contain
metallic lithium. They make use of lithium ions and are called lithium ion cells.
Lithium ion battery uses lithium intercalated metal oxide as cathode and lithium intercalatable
graphite as anode. Anode and cathode are able to insert lithium ions into their layered
structures reversible.

Construction:

1. Anode: Graphite or carbon with Cu current collector.

2. Cathode: Lithium metal oxide [LiMO (LixCoO2 | LixNiO2 | Lix MnO2)] having
aluminium foil as current collector.
3. Electrolyte: A lithium salt such as LiPF6, LiAsF6, LiC1O4, LiBF4 dissolved in an
organic solvent such as ethylene carbonate, dimethyl carbonate or dimethoxy ethane.
4. Separator: Microporous polyethylene or polypropylene.
Current collector (Cu) Current collector (Al)
Cell potential: 3.7 V
The cell can be represented as: LiC | LiX in ethylene carbonate | Li-MO2

Working: The operation of this cell does not actually involve true oxidation and reduction.
The cell reaction involves the migration of lithium ions between positive and negative
electrodes. Graphite being layered can be accommodated or intercalated with lithium between
the layers to form Li-C6 on lithium atom is present for every six carbon atoms.
During discharge, lithium atoms present in graphite layer are oxidised liberating electrons
and lithium ions. Electrons flow through external circuit to cathode to balance the charge and
lithium ions move towards cathode through the organic solvent. At cathode, lithium ions are
reduced to lithium atoms and are inserted into the layered structure of metal oxide. Reactions
are reversed during charging of the battery.
Cell reactions:
At th e anode: Lix–C6 xLi+ + 6C + xe–
At th e cathode: xLi+ + xe– + Li1-xCoO2 LiCoO2
Overall reaction: LixC6 + Li1–xCoO2 Discharging LiCoO2 + 6C
Charging
Reverse reaction occurs during charging. Thus lithium ions move back and forth between
anode and cathode during charge and discharge.
Advantages of Lithium Ion Battery:
• High energy density.
• Relatively low self-discharge.
• Low maintenance.
• High cell voltage.
• Wide range of operating temperature.
Applications: They are used in cell phones, laptops, LCD TV, and portable CD player.
Sodium-ion battery (SIB):
Sodium-ion batteries (SIBs) are energy conversion and storage devices that use sodium-ions
to shuttle positive charge between the anode & cathode in order to convert electrical energy
to chemical energy and vice versa. They are analogous to the Li-ion battery (LIB) but use
sodium ion as the charge carriers.
SIB is a type of rechargeable battery that uses sodium ions (Na+) as its charge carriers. Its
working principle and cell construction are almost identical with those of LIB types, but replace
lithium with sodium.
SIBs are a potential alternative to lithium-based battery technologies, largely due to sodium's
lower cost and greater availability. Since SIBs use abundant and cheap materials, they are
expected to be less expensive than LIBs. The environmental impacts of SIBs are also lower.
Although SIBs are heavier and larger than LIBs, they are feasible for stationary energy storage
systems where the weight and volume are less crucial.
Construction:

Cell Potential: 1.85 to 3.45 V

Cell representation: Na-C/Na+, C/NaF6P in ethylene carbonate/NaMnO2

1. Anode: Hard carbon is used as the “standard” anode material in SIB that stores
sodium-ions at a low potential coated on Al current collector.
2. Cathode: Cathode material is sodium incorporated metal layered such as NaMnO2
coated on Al current collector.
3. Electrolyte: Electrolytes can be solids or liquids. The solid electrolytes are either
polymeric or ceramic. Solvents primarily consist of mixtures of carbonate solvents
such as ethylene carbonate (EC), diethyl carbonate (DEC) or ethers such as
dimethoxyethane (DME), or tetraethylene glycol dimethyl ether (TEGDME) [The
current most widely used non-aqueous electrolyte uses sodium hexafluorophophate
(NaF6P) as the salt dissolved in a mixture of these solvents],
4. Separator: Usually polypropylene microporous separators are used.
Working: SIBs generally contain two electrodes, one anode and one cathode, both consisting
of the respective active materials coated on an aluminium foil current collector. A thin liquid-
permeable sheet called the separator is placed between the two electrodes to keep them
electrically insulated from each other, while allowing sodium ions to move freely between the
electrodes. The anode or negative electrode, is where the sodium is stored when the cell is in
the charged state, while the cathode or positive electrode, hosts the sodium-ions in the
discharged state. The transport of positively charged sodium ions between the electrodes is
enabled by a solvent salt solution called the electrolyte, while electrons move between the
current collectors through an external circuit.
Reactions are reversed during charging of the battery
Cell reactions:
At the anode: Na-C Na+ + C + e-
At the cathode: Na+ + e- + Na1-xMnO2 NaMnO2
Overall reaction: Na-C + Na1-xMnO2 Discharging NaMnO2 + C
Charging
Advantages:
 High stability and high efficiency
 Low-cost and environmental-friendly
 Better safety characteristics
 These are high-rate batteries and operate at lower temperature.
 Fast charging

Disadvantages:
 Batteries are less powerful.
 Anode graphite absorbs too little sodium.

Applications:
 Used in cellular phones and laptops.
 In electric vehicles and power tools.
 SOLAR ENERGY
Photovoltaic (PV) cells or solar cells are semiconductor devices that convert sunlight into direct
current. As long as light is shining on the solar cell, it generates electrical power. When the
light stops, electricity stops.

Quantum Dot Sensitized Solar Cells (QDSSC’s):

A quantum dot solar cell is a solar cell design that uses quantum dots as the absorbing PV
material. It tries to replace bulk materials such as silicon, copper indium gallium arsenide.
Quantum dots have band gaps that are tunable across a wide range of energy levels by changing
the dot’s size. Quantum-dot-sensitized solar cells are a promising low-cost alternative to
existing photovoltaic technologies such as crystalline silicon and thin inorganic films.

Construction:
A typical structure of QDSSCs includes the photoanode, counter electrode, and polysulfide
electrolyte.

Photoanode is the working electrode. It is basically a conducting glass coated with a

semiconductor with long band gaps such as ZnS, SiO2, MgO, ZnO, TiO2, ZrO2, SnO2, Al2O3.
The outer layer of photoanode is coated with quantum dots (such as PbS, PbSe, CdS, CdSe,
doped with Mn/Cu/Zn along with ZnS passivation layer).
Cathode such as CuS, carbon fibre, MoO3, CuS, CuSe, Pt, carbon black, etc is used to
regenerate electricity and to complete the circuit.
Electrolyte: Polysulphide electrolyte, Cobalt complex
Working:

Upon the illumination of light, the QDs generate the exciton (electron-hole pairs).
Consequently, electron is injected into the photoanode to generate photocurrent, the hole is
transported to the counter through redox couple toward electrode (Cathode). The overall power
conversion efficiency (PCE) of a QDSSC is governed by the light harvesting efficiency,
quantum yield for charge injection, and charge collection efficiency.

When the light is incident on the solar cell through the photoanode, photons are absorbed by
the QDs to generate excitons.
Electrons move from valence to conduction band. The ejected electrons move to the
photoanode, leaving behind the holes on the surface of the quantum dots.
The electrolyte reduces the reductant species, i.e., hole created in the QD (The hole is
transported to the cathode, where they are taken up by the electrolyte to get reduced) and gets
itself oxidised.
Electrons move through the external circuit from photoanode to cathode generating electricity.
Electrons at the cathode regenerate the electrolyte.

Advantages:
 Favourable power to weight ratio
 High efficiency
 Mass and area savings as well as flexibility leads to miniaturisation.
 Lower power consumption
 Versatility
 Increased electrical performance at low production costs.
 It can be used in complete buildings including windows and not just rooftops.

Disadvantages:
 CdSe based quantum dot solar cells are highly toxic in nature and require very stable
polymer shell.
 In aqueous and UV conditions its degradation increases.
  The shells can alter optical properties and it is hard to control the size of the particles.
Applications:
 Used as photovoltaics
 Used as LEDs
 Used in catalysis
 Used as photoconductors and photodetectors
 In biological labeling.
 In Biomedicine
 QUESTION BANK
MODULE-1: SENSORS AND ENERGY SYSTEMS

1. What is a sensor? Briefly discuss the functions of the main components of a sensor.
2. Explain the working principle and applications of an electrochemical sensor.
3. Define the terms: Transducers, Receptor, and Actuator.
4. Discuss the principle, working and applications of conductometric sensors.
5. Discuss the principle, working and applications of thermometric sensors.
6. Discuss the principle, working and applications of optical sensors.
7. Discuss the determination of DO using electrochemical sensor.
8. Discuss the application of electrochemical sensor for the detection of pharmaceuticals
taking diclofenac as example with electro oxidation reaction.
9. Discuss the application of electrochemical sensor for the detection of PAHs taking 1-
hydroxypyreneas example with electro oxidation reaction.
10. What is an electrochemical gas sensor? Discuss the working principle of
electrochemical gas sensors for the detection of SOx and NOx.
11. What is a disposable sensor? Give its advantages.
12. Describe the application of disposable sensor in the detection of biomolecule,
Ascorbic acid.
13. Discuss the detection of pesticide/herbicide-Glyphosate using disposable sensor with
the reaction involved.
14. What are batteries? Explain the classification of batteries with examples.
15. Discuss the construction and working principle of Li-ion battery. Mention its
applications.
16. Briefly discuss the construction and working principle of Na-ion battery. Mention its
applications.
17. What is a Quantum Dot Sensitized Solar Cell (QDSSC)? Explain its construction and
working principle. Mention its advantages and applications.