MODULE- 1

SENSORS AND ENERGY SYSTEMS

Sensors:
“A device that responds to a physical stimulus (such as heat, light, sound, pressure, magnetism, or a
particular motion) and transmits a corresponding signal is known as sensor”.
A chemical sensor is a device that is capable of giving real time analytical information about a test
sample or analyte. A chemical sensor is a device that interacts with a analyte, detects it and produces
measurable signal that is proportional to the analyte concentration or quantity.
Basic components of Sensors:
Receptor: The receptor is the component of the chemical sensor which is capable of interacting with
analyte specifically and selectively and produces a signal proportional to its quantity.
Actuator: Actuator would receive inputs from any system in the form of electrical signals and then
generate an output for its environment. Here electrical signal is converted into mechanical work. It is
used for generating movement or a change in environment. For example, a fan is used to reduce
temperature.
Transducer: Transducers is used to convert the signal created by the receptor-analyte interaction into
a readable value. Usual converts a non-electrical signal into an electrical signal. The electronic system
analyses the signal given by the transducer, helps in signal amplification and converts the signal from
analog to digital form. These amplified signals are then displayed. Signal can be displayed in various
forms such as numeric value, graph, image etc
Electrochemical sensors
Electrochemical sensors convert the information associated with electrochemical reactions (the
reaction between an electrode and analyte) into an applicable quantitative signal.
Electrochemical sensors are made up of three essential components: a receptor that binds the sample,
the sample or analyte, and a transducer to convert the chemical interactions into a measurable
electrical signal.
In electrochemical sensors, the surface of the electrode which is in contact with analyte acts as receptor
because on this site of the electrode, electrochemical reactions take place and produces non-electrical
signal. The electrode will either oxidize or reduce the analyte producing non -electrical signals, then it
will convert into electrical signals by transducer.

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The following steps are involved in the working of an electrochemical sensor.
1) Diffusion of the analyte to the electrode /electrolyte interface.
2) Adsorption onto the electrode surface
3) Oxidation or reduction of the analyte by electrode to produce non-electrical signal which is
proportional to the concentration of the analyte. Electrochemical reaction with electron
transfer.
4) Desorption of products
5) Diffusion of the products away from the reaction zone to the bulk of electrolyte or gas phase.
Application
 The oxygen sensor is used in detecting dissolved oxygen in water boilers.
 They are used in security and defence applications like detection of toxic gas like CO, H2S etc
 Used in water analysis and environmental monitoring.
 They are used in diagnostic and health care application.
 Used in soil parameter analysis and in agricultural applications.
Conductometric sensor
It involves the determination of the concentration of analyte based on the measurement of changes
occur in electrolyte solution. Here electrodes are used to measure the conductance of the electrolyte.
Conductance is depending on number of ions and mobility of ions.
Working:
Electrode used is conductivity cell. It is made up of two platinum foils
with unit cross sectional area and unit distance between them. Volume
between the electrode is 1cm3. Conductance of unit volume of the
solution is called specific conductance and it is given by

Here l/a is known as cell constant, R is resistance.

The conductivity is result of dissociation an electrolyte, into ions. The migration of the ions is induced
by an electrical field. When a potential difference is applied to the electrode, there is an electrical field
within the electrolyte, so the positively charged ions move towards cathode and negatively charged
ions are move towards anode. Thus, the current in the electrolyte is caused by the ion movement
towards the electrodes where the ions are neutralized and isolated as neutral atoms (or molecules). This
chemical change is recognized by working electrode and transducers converts this chemical change
into electrical signal.
Application
 It is used to estimate acids, bases and their mixtures in a sample.
 Used to check the amount of ionic impurities in waste samples.
 Measure the acidity or alkalinity of sea water and fresh water.
 In environment monitoring, bio technology and agriculture related applications.
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Optical Sensors
 These sensors based on the interaction of electromagnetic radiation with the chemical species.
Commonly UV-Visible-Infrared electromagnetic radiations are used. In an optical sensor, the
optical signal arises from the interaction of the analyte with an incident radiation. This interaction
could results in absorption, emission, scattering and reflection of light. The intensity of the radiation
produced by the analyte gives the information on the concentration of the analyte.
 Optical sensors are used to determine the concentration of coloured solution. It is based on the
measurement of absorbance of the coloured solution at particular wavelength and is governed by
Beer-Lambertz law.
 The optical sensors components are light source, filters, photocell and display system.
Working:

A monochromatic light is pass through analyte at particular wavelength. A part of light is absorbed by
the analyte. The absorbance depends on the concentration of the solution and the path length of the
light through the solution. The photocell converts emitted light into electrical signal These signals are
recorded and displayed.
Applications of Optical Sensors
 Optical Fibre based biosensors are used in detection of explosive.
 These are used in smartwatches to measure the heartbeat of the person.
 Water and Liquid levels in industries.
 Adjusting screen brightness in smart phones.
 Can be used in environmental, pharmaceuticals, food related applications
Sensors for the measurement of dissolved oxygen (DO):
The oxygen present in the water in dissolved form is called as dissolved oxygen.
Two types of Sensors are used for measurement of dissolved oxygen (DO)
1. Optical Sensors 2. Electrochemical Sensors
Optical Sensors:
The main component of optical sensors is semi permeable membrane, sensing element, lightemitting
diode (LED) and photo detector. The sensing element contains a luminescent dye.
Working: When the dye is exposed to light, it moves to excited state and return to ground state by
emitting light with known intensity. When the DO crosses the semi permeable membrane and interacts
with the dye, it reduces the intensity of the light emitted by dye. The intensity of the emitted light
inversely proportional to the DO concentration. This intensity of light is measured using photo
detector.

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Electrochemical Sensor for measurement of Dissolved oxygen (DO)
In an electrochemical DO sensor, dissolved oxygen diffuses from the sample across an oxygen
permeable membrane and into the sensor. Once inside the sensor, the oxygen undergoes a chemical
reduction reaction, which produces an electrical signal. This signal can be read by a dissolved oxygen
instrument.
In electrochemical sensors, two electrodes are used.
Anode: Zn, Pb or any other active metal
Cathode: silver metal as inert anode
Electrolyte: KOH, NaOH or any other inert electrolyte
Membrane: Teflon
When the electrode assembly is dipped in water to measure its dissolved oxygen, at anode undergoes
oxidation liberating electrons
2Zn → 2Zn 2+ + 4 e -
At cathode dissolved oxygen undergoes reduction. Ag Cathode is inert, it only passes electrons to
oxygen for reduction.
O2 + 2H2O + 4 e- → 4OH-
Overall reaction is,
Zn + O2 + 2H2O → 2Zn (OH)2
The current produced by the reduction of oxygen at Cathode is proportional to the partial pressure of
oxygen in the water sample. The Zinc hydroxide that is produced by this reaction is precipitated out
will gradually affect the sensor performance. That has to be removed regularly. Zinc anodes must be
replaced during the course of the reaction.
Electrochemical Gas Sensors for NOX and SOX :
An electrochemical gas sensor generally consists of a sensing electrode, counter and reference electrode
along with a gas-permeable membrane used to regulate the gas flow into the sensor. A filter is used to
prevent unwanted contaminants.
During sensing operations, sensor is submerged in an
electrolytic liquid(electrolyte) which is a good ionic
conductor and chemically physically stable during
operation. The gas-permeable membrane allows allows
only analyte gas to pass and prevent the leakage of the
electrolyte.
An electrochemical reaction is either oxidation or reduction occurs depending on the type of gas interact
with sensing electrode. During oxidation reaction electrons moves from the working electrode to the
counter electrode, while a reduction reaction causes electrons to move from the counter electrode to the
working electrode. The electrical current generated is proportional to the concentration of the target gas.
The current is then amplified and processed to give the user a reading in either parts per million (PPM) or
percentage volume.

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Detection of NO2:- in an amperometric gas sensor in aqueous electrolyte is based electrochemical
reduction reaction on the surface of the sensing electrode.
Sensing electrode: Au, Pt /Nafion sensing electrode
Reference electrode: Ag/AgCl electrode
Electrolyte:-10 M H2SO4
NO2 + 2H+ + 2e- → NO + H2O
Detection of NO:- in an amperometric gas sensor in aqueous electrolyte is based electrochemical
Oxidation reaction on the surface of the sensing electrode.
Sensing electrode:-Au/NASICON
Reference electrode: Ag/AgCl electrode
Electrolyte:- NaNO2
NO + 2H2O → NO32- + 4H+ + 3e-
Detection of SO2:- in an amperometric gas sensor in aqueous electrolyte is based electrochemical
Oxidation reaction on the surface of sensing electrode.
Sensing electrode:- Au/nafion
Reference electrode: Ag/AgCl electrode
Electrolyte:- 0.5 M H2SO4
SO2 + 2H2O → SO42- + 4H+ + 2e-

Electrochemical Sensor used for the Detection of pharmaceuticals : example Diclofenac

It is necessary to use sensors for the detection of pharmaceuticals to monitor their concentration and to
know their toxic effects on ecosystem.
Electrochemical detection occurs at the interface between an analyte (diclofenac) of interest and the
working electrode to which a potential is applied with respect to the reference electrode, while the
corresponding current is measured.
Working electrode: Carbon coated with MWCNT or Graphene and gold nano particles.
Counter Electrode: Carbon coated with MWCNT or Graphene and gold nano particles.
Reference Electrode: Ag/AgCl.
When the sample containing diclofenac is put in the sensor, oxidation of diclofenac occurs on the
surface of the sensing electrode. The change in potential of the reaction gives the concentration of
diclofenac.

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Electrochemical Sensors for Hydrocarbons
Hydrocarbon pollutant, polycyclic aromatic Hydrocarbons (PAHs) are widely found in the in the air,
water, soil and food. PAHs are known to be carcinogenic and mutagenic compounds. Detection of
PAHs is essential to monitor their toxicity and carcinogenic risk. After entering the body some PAHs
are metabolised into hydroxyl PAHs which are excreted with urine. 1-hydroxypyrene is commonly
found hydroxy PAHs in urine sample. Therefore, concentration of 1-hydroxypyrene is used to evaluate
PAHs exposure level in the human body.
Electrochemical sensors are being developed for detection of 1-hydroxypyrene in urine sample. These
sensors are fast, low cost and sensitive and use disposable strips. The sensors can be used for on spot
analysis.
Working electrode: Carbon coated with chromium containing metal organic frame work) Cr- MOF)
and Graphene Oxide (Composite)
Counter Electrode: Carbon coated with chromium containing metal organic frame work) Cr- MOF)
and Graphene Oxide (Composite)
Reference Electrode: Ag/AgCl
When the sample containing 1- Hydroxypyrene is put in the sensor, oxidation of 1- Hydroxypyrene
into Quinone occurs on the surface of the sensing electrode. The change in potential of the reaction
gives the concentration of 1- Hydroxypyrene.

Biosensors:
Biosensors are devices that are used to detect and measure bioanalyte. Main component of a biosensor
is a receptor which can selectively interact with the bioanalyte and produce a signal corresponding to
the interaction. Receptor contains immobilized biomaterials like enzymes or nucleic acids on its
surface. Signal produced is detected and converted to appropriate electrical signal by a transducer.
Then amplifies and processes the signals before displaying it using an electronic display system.
Disposable sensors
Portable sensors used for on-spot analysis using disposable strip with receptor and electrode printed on
it is called disposable sensor. They are low-cost and easy-to-use sensing devices designed for short-
term or rapid single-point measurements.
Advantages of disposable sensors:
 They transduce physical, chemical, or biological changes in their environment to an analytical
signal.

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 Disposable sensors are biodegradable and sustainable
 They have a short duration of analysis and fast response times.
 It provides digitized chemical and biological information.
 Prevents the contamination of samples
The disposable sensors are a type of paper over which receptor and
electrodes are printed. Electrodes reference, working and counter
electrode and bio receptor (enzymes) is printed on a single platform as
shown in the fig. These electrodes are called screen-printed electrode and
are main components of disposable sensors. These strips can be inserted
into the portable system for on spot sample analysis.

Detection of Ascorbic acid.

Ascorbic acid is a chemical name of Vitamin-C, it is water soluble. It is an antioxidant essential for life
and helps in protecting the body against oxidative stress. In the disposable strip, the sensing electrode,
counter and reference electrode are printed using screen printing technology.
Sensing electrode and counter electrode:The active material ascorbate oxidase enzyme was
immobilized on a screen-printed carbon electrode with poly(ethylene glycol) and diglycidyl ether as a
crosslinking agent.
Reference electrode: Ag/AgCl
The sensor is immersed in the analyte. The analyte diffuses and adsorbed on the sensing electrode. The
sensing electrode oxidizes ascorbic acid into dehydroascorbic acid and produces electric current or
voltage and it is proportional to the concentration of the ascorbic acid.

Disposable Sensors in the Detection of Pesticides- Glyphosate

Glyphosate is an organophosphorus pesticide, used as herbicide in agriculture. Its residues are present
in large amount in agriculture products and enters the ecosystem in large quantity. It is carcinogenic.
Therefore, there is a need to develop a rapid, reliable and sensitive method to detect Glyphosate in
environmental samples.
The analytical method based on electrochemical biosensor has been designed and used for glyphosate
determination. It consists of three electrode system.

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Sensing (working) electrode: The glycine oxidase
enzyme immobilized on a screen-printed carbon
electrode
Reference electrode: Ag/AgCl
Potential applied: 0.78V When the glyphosate molecule
come in contact with electrode, it oxidizes glyphosate
into amidomethyl phosphoric acid and glyoxylate.
Concentration of glyphosate is determined from the
change in potential of the oxidation process.

Thermometric Sensors:-
Thermometric sensor is based on the measurement of thermal changes during the interaction between
analyte and receptor. Thermal changes are converted to measurable change in the temperature or
potential. Thermometric transduction is feasible only in those processes which generate sufficient heat
to produce a measurable change of temperature. Chemical or biological species which undergo
catalytic chemical reactions and enzyme-catalyzed reactions liberating heat (exothermic reactions) can
be determined by thermometric sensors.
Working:-Main component of a thermometric sensor is a small tubular catalytic reactor fitted with a
temperature transducer. Analyte (reactant) is fed in to the reactor. The wall of the reactor is coated
with a catalyst or enzyme capable of catalysing the reaction, liberating heat energy. Heat liberated is
quantified by means of a temperature transducer. The change in temperature is converted to the output
voltage by transducer which is amplified and fed to the data storage and processing unit. In order to
convert change in temperature into an electric signal, two main kinds of transducers which exhibit
thermoelectric effect are used:
1. Resistive transducer: Most commonly used resistive transducer is the thermistor. It is a ceramic
semiconductor device made of oxides of transition metals. Most thermistors have a negative
temperature coefficient. That is, their resistance decreases with increasing temperature. The decrease in
resistance is converted to output voltage.
2. Thermocouple: A thermocouple a device that converts the temperature difference directly into an
electrical voltage. It consists of a loop formed by two different materials (metals or semiconductors).
The output voltage is proportional to the temperature difference between the two junctions.
Applications:
Used in determination of metabolites, bioprocess monitoring and environmental control and
determination of combustible gases

Energy storage systems:

Battery is a device consisting of two or more galvanic cells connected in series or parallel or both,
that can store chemical energy in the form of active materials and on demand convert it into electrical
energy through electrochemical redox reaction.

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Primary battery or primary cells: The batteries in which the cell reaction is not completely
reversible are called primary batteries. They are also referred to as irreversible batteries. They are not
rechargeable and once discharged have no further electrical use. They have no cycle life. Produces
electrical energy only if active materials are present. Eg; dry cell or Zn-MnO2 Cell, Li-MnO2 battery.
Secondary battery: The batteries in which the cell reaction is reversible and are rechargeable are
referred to as secondary batteries. Secondary batteries after discharge can be recharged electrically to
their original condition by passing electric current through them in the direction opposite to that of
discharge current. They are also referred to as storage batteries or accumulators. They have cycle life.
Eg: Lead – acid battery, Ni – Cd battery, Li-ion battery
Reserve Batteries: The batteries, which may be stored in an inactive state and made ready for use by
activating them (by adding an electrolyte, another cell component) prior to application are referred to
as reserve batteries. In these batteries, a key component is separated from the rest prior to activation.
Usually electrolyte component is isolated and hence the batteries are capable of long – term storage
and has a good shelf life. They are designed to meet extremely long and environmentally serve
storage requirements.
Water or heat may be the activators. In water activated batteries electrolyte solute is contained in the
cell and only water is added for activation, Heating results melting of the electrolyte, causes
conduction and reactions. Eg: Magnesium water activated batteries, zinc–silver oxide
batteries etc.

Construction, working and applications of Li-ion batteries:-

Rechargeable, Lithium ion batteries include high voltage, high energy density (240 W hr/Kg), high
cyclic life and very low self-discharge when not in use.
Anode: Lithium intercalated (reversibly included between the layer) graphite with thin Copper foil is
used as current collector (LixC6).
Cathode: Lithium cobalt oxide (Li1-x CoO2) with Aluminium foil as current collector.
Separator: Porous polymer film like polythene or polypropylene
Electrolyte: A lithium salt in an organic solvent like LiPF6 dissolved in propylene carbonate/ethylene
carbonate/ dimethoxy ethane.
Cell representation: Li│Li+, C│ LiPF6 in ethylene carbonate│Li+- MO2 │ Li+- MO2

Reactions:
During discharging of battery, Lithium atoms present in
graphite layer gets oxidized, liberating electrons and lithium
ions. Electrons flow through external circuit to cathode and
lithium ions flow through the electrolyte towards cathode.
At cathode, lithium ions are reduced to lithium atoms and
are inserted in to the layered structure of metal oxide.

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At anode LixC6 xLi+ + Xe- + 6C
At Cathode Li1-xCoO2 + xLi+ + Xe- LiCoO2
Cell reaction LixC6 + Li1-xCoO2 6 C + LiCoO2
When the cell is charging the reaction gets reversed.
This electrolyte effectively transport Li+ ion to cathode during discharge of battery. The voltage of
LIB is about 3.6-3.7 V

Applications of lithium-ion battery:

1. Used in portable devices like cell phones, laptops, digital cameras, flashlights
2. Used in tools such as cordless drills, sanders etc
3. Used in cardian pacemakers and other implantable devices
4. Used in telecommunication equipment’s, portable radios and TV’s
5. Because of their light weight and high energy density, they are used in electric vehicles.

Sodium ion battery:-

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.
Anode: Hard carbon is used as the “standard”
anode material in SIB, that stores sodium- ions at
a low potential with aluminum as a current
collector.
Cathode: cathode material is sodium inserted
layered transition metal oxides, dioxides NaMO2
wher M = Fe, Ni, Mn, Co with Aluminum
current collector.
Electrolyte: Sodium salts like NaPF6 dissolved in an organic solvents such as ethylene carbonate
(EC), diethyl carbonate (DEC) etc.
Separator: polymer separators like polypropylene or glass fiber.
Cell Potential: 1.85 to 3.45 V.
Reaction:
At anode NaxC xNa+ + Xe- + C
At Cathode Na1-xMnO2 + xNa+ + Xe- NaMnO2
Cell reaction NaxC + Na1-xMnO2 C + NaMnO2
At anode oxidation takes place and electrons flows from anode to cathode through external circuit.
Sodium ions migrate towards cathode through the electrolyte. At cathode, sodium ions reduced to
sodium atom and inserted into the layered structure of metal oxide.
During charging, the cell reactions get reversed.

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 Advantages: Disadvantages:
1) Low-cost and environmentally-friendly. 1) Batteries are less powerful.
2) Slightly lower energy density and high 2. Anode graphite absorbs too little sodium
efficiency.
3) Better safety characteristics.
4) These are high rate batteries and operation at
lower temperature

Applications:
1) Used in cellular phones and laptops.
2) In electric vehicles and power tools.

Quantum Dot Sensitized Solar Cells (QDSSC’)

A quantum dot solar cell (QDSC) is a solar cell that uses quantum dots as the absorbing photovoltaic
material. Quantum dots are nanoparticles made from semiconducting materials. The dimensions range
of quantum dots lies between 1nm to 10 nm. These are zero-dimensional nanostructure with discrete
quantized energy levels. It is used to replace bulky materials such as silicon or gallium selenide. The
energy band gap increases with a decrease in size of the quantum dot. The efficiency of conversion of
solar energy into electrical energy is very high compared to conventional solar cell.
Construction
A QDSSCs consist of three components
a) Photo anode: It is the working electrode in the cell. It is a conducting glass, over which a large band
gap semiconductor like TiO2, Nb2O5, ZnO or SnO2 is coated. This is further coated with Quantum
dots(QD’s) such as PbS, PbSe, CdSe or CdS which acts as photosensitizer.
b) Electrolyte: Polysulphide is the redox electrolyte which is placed between anode and cathode which
also acts as separator.
c) Cathode (CE): Cathode is inert metal which helps to complete the circuit and helps to catalyses the
reduction of oxidized electrolyte.

Working
1. QD’s present on photo anode is exposed to sunlight.
2. QD’s absorb solar energy and get excited, generate charge carriers (electron), i.e electrons jump
from valence band to conduction band producing electron hole pairs.

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 QDs + hγ QDs*
QDs* e- + h+
3. The electrons from QDs are transferred to the conduction band of wide band gap TiO2
semiconductor, leaving holes on the surface of QD’s.
4. Electrons from conduction band of semiconductor are transferred to Photo anode and driven
through external circuit to reach cathode. This produces electric current.
5. At the surface of cathode, polysulphide anion of electrolyte dissociates producing sulphur atom
which takes up electrons and gets converted to sulphide anion.
S2−n → S + S2−(n-1) (n= 2 to 5)
S + 2e- S2-
6. Sulphide anion, then moves to the surface of QDs and takes up two holes from valence band of QDs
and re-injects electrons into it.
S2− + 2h+ → S + 2e−
7. Sulphur atom then recombines with polysulphide anion to regenerate electrolyte.
S + S2-n−1 → S2−n
8. Therefore, at the end of one cycle, electrons are re-injected to valence band of QDs and ready for
ejection again. Similarly, electrolyte is regenerated again and ready to take up electrons from
cathode.
9. In this way, QDSSCs can generate electric current continuously as long as they are exposed to
sunlight without undergoing any change.
Advantages of QDSSC:
 They have a favourable power to weight ratio with high efficiency.
 Their power consumption is low.
 There is an increase of electrical performance at low production costs.
 Their use is versatile and can be used in windows, not just rooftops.
Disadvantages of QDSSC:
 Cadmium selenide-based quantum dot solar cells are highly toxic in nature and require a very stable
polymer shell.
 Cadmium and selenium ions which are used in the core of quantum dots are known to be cytotoxic.
Applications
 It is used as light-emitting Diodes
 Used for biological labelling
 It is used as Photoconductors and photodetectors
 It is used in biomedicine and environment.
 Biosensors

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