Module - 1 Solutions

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Applied Chemistry for Computer Science & Engineering stream Dr . S.K.

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Solutions :Module -1 Sensors and Energy systems

1.Define the following: Sensor, transducer and actuator.

Sensors: "Sensors are electronic devices that detect and measure physical/
chemical phenomenon or information into an electrical signal".
Physical/Chemical phenomena such as temperature, pressure, motion, light,
or sound / composition, concentration, chemical activity, partial pressure.
Sensor interacts with a specific chemical or biological analyte, detects it and
produces the signal proportional to its quantity.

Transducer: " Transducer is a device that converts a physical quantity or non-


electrical signal into an electrical signal".
Transducer convert the signal created by the receptor–analyte interaction(non-
electric quantity) into a readable electric quantity like voltage, current or
resistance

Actuator: An actuator is a device that receives a signal or input and produces a


physical output.

2. What are sensors? Explain the components of sensors with schematic


diagram.

Sensors: "Sensors are electronic devices that detect and measure physical/
chemical phenomenon or information into an electrical signal".
Physical/Chemical phenomena such as temperature, pressure, motion, light,
or sound / composition, concentration, chemical activity, partial pressure.
Components of Sensor:
Main basic components of a sensor are:
 Receptor or Chemical (molecular) recognition system
 Physicochemical transducer
 Electronic system
 Display system

Receptor: "Receptor is a chemical or biological recognition element and is able to


interact specifically and selectively with the analyte molecules, catalyze a reaction,
or participate in a chemical equilibrium together with analyte".

Transducer: " Transducer is a device that converts a physical quantity or non-


electrical signal into an electrical signal".

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 Transducer convert the signal created by the receptor–analyte


interaction(non-electric quantity) into a readable electric quantity like voltage,
current or resistance.
Electronic system (Signal conditioner): Electronic system is a
microprocessor analyzes the signal given by the transducer and it is transmitted
and conditioned if needed(amplify, converts analog to digital form, filters etc.)

Display system: Display system is a output device which displays amplified


signal in various forms such as numeric value, graph or image etc.

3.What are electrochemical sensors? Explain the principle and working of


electrochemical sensors and mention the applications of electrochemical
sensors.
Electrochemical sensors: "Electrochemical sensors are devices that detect
and measure the concentration of a target analyte by converting a electro
chemical reaction into an electrical signal in the form of potential, current or
conductance".

In electrochemical sensors the electrode or a set of electrodes is used as


transducer element. Hence these sensors are also called as Electrochemical cells.
Construction of Electrochemical sensor:
 Electrochemical sensor consists of a sensing electrode ( or working
electrode) and a counter electrode and is separated by a thin layer of electrolyte
and reference electrode.
 The sensing electrode has a chemically modified surface. Hence it is
selectively facilitate the reduction or oxidation of the analyte.
 Electrolyte transports charge within the sensor and, contact all
electrodes and it is stable physically and chemically under sensor's operation.
Working Principle of electrochemical sensor:
 Electrochemical sensor consists of a transducer element covered by a
recognition element.
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 The recognition element interacts with target analyte and signal is


generated.
 Electrochemical transducers transform the chemical changes into
electrical signals.
 The electric signals are related to the concentration of analyte.
 Electrochemical sensing always requires a closed circuit. Current must
flow to make a measurement.

Fig - electrochemical sensor

Applications of electrochemical sensor( any 4)


 They are used to detect dissolved oxygen in boiler water and to monitor dissolved
oxygen concentration in metal melts, glasses and in hydrogen fuel.
 They are used in security and defense applications like detection of toxic gases,
warfare agents.
 They are used in water analysis and environmental monitoring like measurements
of toxic metal concentration in water, pH of water and detection of oxides of
nitrogen, sulphur and carbon.
 They are used in soil parameter analysis and in agriculture applications.
 They are use in Clinical chemistry, namely, the determination of physiologically
relevant electrolytes in physiological fluids.
 They are used for detection of enzymes and hormones to monitor cancer diseases.
 They are used for the detection of blood glucose.

 They are used to detect pesticides

4.Discuss the principle, working and applications of conductometric


sensors.
Conductometric Sensors: "Conductometric sensors are electrochemical sensors
that measure changes in electrical conductivity when a specific analyte interacts
between the electrodes".
Principle: A reaction that can change the concentration of ionic species. The
ions or electrons produced during an electrochemical reaction changes
the electrical conductivity or resistivity of the solution. The change in
conductivity is measured and correlated with the concentration of the analyte in

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the sample. The final output is a quantitative measure of the concentration of the
analyte.

Working: Conductometric sensors consists of two inert metal


electrodes. 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.
Applications:

 Conductometric sensors can be used to monitor any chemical which can


change the electrolytic conductance of solution on chemical reaction.
 They are used to estimate acids , bases and their mixtures in the sample.
 They are used to check the amount of ionic impurities in water samples.
 They are used in measuring acidity or alkalinity of sea water and fresh
water.
 Conductometic biosensors are used in biomedicine, environment monitoring,
biotechnology and agriculture related applications.

5.Discuss the principle, working and applications of optical sensors.


Optical sensors:"Optical sensors are electronic devices in which
electromagnetic radiation is used to generate the analytical signal in a
transduction element. The interaction of this radiation with the sample is
evaluated from the change of a particular optical parameter and is related
to the concentration of the analyte".

The receptor identifies a parameter, e.g., the concentration of a given compound,

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pH, etc., and provides an optical signal proportional to the magnitude of this
parameter
Absorption based optical sensors- Colorimeter

Absorption-based optical sensors are colorimetric or spectroscopic in nature.


Colorimetric sensors are type of optical sensors used to analyze coloured analyte
by using incident light in visible range (400-800nm).

Principle of colorimeter: When a sample solution is interacted with a light of


suitable wavelength, certain quantity of light is absorbed by the analyte solution
achemical or physical change occur. This change in the sensing material's
properties observed by a sensor and transducer converts intensity of absorbed
light into electrical signal. The change in intensity at certain wavelength within
visible (400–800mm) range can be determined ..

Components of Colorimeter: The basic components includes

1. Light source is Tungsten lamp 2. Converging lens 3. Optical filter

4. Narrow slit 5. Sample holder contains analyte solution 5. Photo detector

5. Display meter or read-out device

The light source generates an intense and stable radiation signal needed to probe
an optical property of the molecular recognition element in the sensor.

A block diagram of Colorimeter is shown in Fig.

Working : A monochromatic light is made to pass through analyte solution where


certain quantity of light is absorbed and it is a function of concentration of
analyte. The change in the intensity of light is detected by photo detector . The
amount of absorbance is governed by Beer- lamberts law.

Applications of optical sensors:


1.They are used to monitor chemical species in chemical industry,
biotechnology, medicine, environmental sciences, personal protection, etc.
2. They are used detect different types of chemicals, biomolecules and ions.

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3. They are used in health monitoring of structures such as bridges, buildings,


monuments, tunnels, dams, dykes, pipelines, landslides etc. and employed to
measure the depth of a submerged body (such as a diver or submarine).

4. They are used in imaging, remote sensing satellite, metrology, and quality
process control-based applications.
5. Optical fiber based (bio) sensors are used in screening of drugs, detection of
food borne pathogens, detection of explosives .

6.They are used in biomedical and healthcare applications- Flow monitoring by


laser Dopplerimetry, Heart rate monitoring, Contactless sanitizer dispensers and
Breath analyzers.

7. They are used in industrial applications: A variety of in-process inspection and


control functions can be performed through non-contact optical sensors.-.
Temperature measurement by infrared sensors, Surface and subsurface defects,
Surface inspection for gauging roughness and thickness, In-situ monitoring of
coatings and lubricant films. These are used as water and liquid level indicators.

8. They are used in agricultural application: On-site detection of pesticides in


agricultural food products.
9. Thet are used in environmental application: To detect heavy metals like
cadmium present in soil.
10. They are used in smart phones for adjusting the brightness of the screen, smart
watches to measure the heartbeat of the person and Biometrics applications.

6.What are Electrochemical Sensors? Explain its application in the


measurement of Dissolved Oxygen (DO)
Electrochemical DO sensors, also known as Amperometric or Clark-type
sensors, measures dissolved oxygen concentration in water based on
electrical current produced.

Galvanic electrochemical DO sensor: It is a type electrochemical DO sensor and it


comprises of electrodes of different metals . The difference in potential between
two electrodes should be at least 0.5V to reduce dissolved oxygen without an
external applied potential. The potential difference 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.

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Components:
Anode : Zinc or Lead Cathode(working
electrode): Silver metal
Electrolyte solution : Potassium
hydroxide or Sodium hydroxide
Hydrophobic membrane : Teflon, allows the oxygen from analyte solution to
sensor.

Working:
 When galvanic DO sensor is immersed in water sample and the
difference in potential between the anode and the cathode should
be at least 0.5V.
 Oxygen molecules diffuses in to sensor across the thin hydrophobic
Teflon membrane at a rate proportional to the pressure of oxygen in the
water.
 At cathode molecular oxygen is reduced to OH-. This reaction
produces an electrical 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. The current produced is proportional to the partial
pressure of oxygen in the water sample.
 At anode metal undergoes oxidation and produces electrons.
 Following reactions are taking place during the operation of sensor

The white solid, Pb(OH)2, produced by these reactions is precipitated out into the
electrolyte solution does not affect the sensor’s performance until the quantity
becomes excessive.

7.Discuss the working principle of electrochemical gas sensors for the


detection of SOx and NOx

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"Electrochemical gas sensors are devices interacts with analyte gas to measure
its concentration by converting the gas molecules into an electrical signal through
electrochemical reactions".

Sensors for NO2 detection:


Principle: Electrochemical gas sensors for NO 2 detection are based on the principle
of electrochemical reduction of NO2 to NO on specifically modified sensing
electrode generates an electrical current proportional to the concentration of NO2.
Components :
Sensing electrode: Gold, Platinum coated Nafion electrode (facilitates the
reduction of NO2 to NO)
Counter electrode: Platinum wire (used to complete the circuit)

Reference electrode: Ag/AgCl (provides a stable potential)

Electrolyte :10 M H2SO4 (It is used to facilitate ion transport between the
electrodes).

Working: NO2 gas of air sample comes in contact with sensor initially pass
through a small opening and diffuses through a hydrophobic membrane, at last
reaches the working electrodes surface.
When NO2 gas comes into contact with the working electrode, it undergoes
reduction to produce NO, which generates an electrical current proportional to the
concentration of NO2 in the environment.
Reaction at sensing electrode: NO2 + 2H+ + 2e → NO + H2O (NO2 + e- → NO)
Sensors for NO detection :
Principle: Electrochemical gas sensors for NO detection are based on the principle
of electrochemical oxidation of NO on specifically modified sensing electrode
generates an electrical current proportional to the concentration of NO.

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Components:
Electrochemical sensor used to detect NO consists of following components.
Sensing electrode: Platinum coated Nafion electrode
Counter electrode: Platinum wire

Reference electrode: Ag/AgCl

Electrolyte : 0.5 M H2SO4

Working: NO gas that comes in contact with sensor initially goes through a small
opening of narrow structure and diffuses through a hydrophobic membrane, at
last reaches the working electrodes surface.

The NO gas at working or sensing electrode undergoes oxidation reaction.


Reactions are catalyzed by Platinum/ Nafion electrode specially developed for the
NO gas. The direct electro oxidation of NO in solution changes number of
electrons and current flowing from cathode to anode and is related to
concentration of NO.

Reaction at sensing electrode is NO(g) + 2H2O → HNO3 + 3H+ +3e-

Sensors for SO2 detection:


Principle: Electrochemical gas sensors for SO2 detection are based on the principle
of electrochemical oxidation of SO2 on specifically modified sensing electrode
generates an electrical current proportional to the concentration of SO2.

Construction: Electrochemical sensor used to detect SO2 consists of


Sensing electrode: Gold coated Nafion electrode
Counter electrode: Platinum wire

Reference electrode: Ag/AgCl

Electrolyte : 0.5 M H2SO4

Working: When SO2 gas enters the sensor, it undergoes oxidation. During this
process, electrons are released from the sensing electrode and the number of
electrons on the electrode surface increases. This change in the number of electrons
creates an electrical signal that can be measured and used to determine the
concentration of SO2 gas in the environment.

Reactions: SO 2 + 2H2O → SO 42- + 4H+ +2e-

8.Explain the detection of pharmaceutical pollutant diclofenac using

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Electrochemical sensor with electro-oxidation reactions.


Screen printed disposable electrochemical sensor
Components :
Working electrode: Carbon Paste electrode coated with MWCNT or
Graphene. Surface of carbon electrode is chemically modified to increase its selectivity
and sensitivity to DCF by coating with a polymer or nanopartiles that can specifically
bind to DCF.
Counter Electrode: Carbon Paste electrode coated with MWCNT or
Graphene
Reference Electrode: Ag/AgCl
MWCNT- Multi walled carbon nano tube
Principle: Concentration of DCF is detected on the basis of current flowing between
the electrodes through electro oxidation of DCF on sensing or working electrode at
specific applied potential.
Working: When the sample containing diclofanec is taken in the sensor, it undergoes
oxidation reaction on the surface of the sensing electrode. The following changes occurs
during the operation of sensor.
• DCF undergoes reversible electrochemical oxidation on chemically
modified sensing electrode at of pH 7.0.

• At sensing electrode surface electrons are released due to the oxidation of


DCF and to form radical intermediates and followed by hydrolysis of radical
intermediate species to stable products.

• The products formed are 2,6-dichloro aniline and 2-2(- hydroxy


phenyl) acetic acid.

• Reactions on the electrode cause the current to flow.

• The intensity of this current is a function of the number of oxidized


/ reduced molecules.

9.Explain the detection of hydrocarbon pollutant 1-hydroxy pyrene using


Electrochemical sensor with electro-oxidation reactions
 The 1-hydroxypyrene contains electrochemically active hydroxyl
group, the active hydroxyl group can be effectively oxidized.

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 An Electrochemical cell with modified working electrode , counter


and reference electrodes system was used.
Working electrode: PAMAM/Cr-MOF/ERGO/GCE (Composite)
Counter Electrode:Platinum wire
Reference Electrode: Calomel electrode
Operating Voltage: +0.7 to −0.5 V
PAMAM: Dendrimer polyamidoamine, Cr-MOF: Chromium-centred metal–
organic framework GO: Graphene Oxide, GCE: Glassy carbon electrode
Principle: The electrochemical oxidation of 1-hydroxypyrene is the basis for its
detection using an electrochemical sensor with modified electrodes.
Working:
 A sample containing 1-hydroxy pyrene is put in the sensor and voltage is
applied the following changes takes place .
 At the surface of working electrode electro-oxidation of 1-HP takes place
to yield hydroxylated species and then hydroquinone by losing
2e−and 2H+.
 Reactions on the electrode cause the current to flow.
 The quantity of this current is a function of the number of
oxidized / reduced molecules.
 Current produced is directly proportional to the concentration 1-
Hydroxypyrene.

10.What are disposable sensors? Mention the advantages of disposable


sensors.
Disposable sensors: Disposable sensors are low-cost and easy-to-use
sensing devices designed for short-term or rapid single-point
measurements.
Screen printed electrode is a single device comprises a chemically inert substrate
on which three electrodes, including working electrode, reference electrode and
counter electrode, are printed through screen printing methodology. The working
electrode is the principal electrode on which electrochemical reactions are

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performed, while the reference electrode and counter electrode are used to
complete the electronic circuit.

1.The three electrodes could be printed on different types of substrates like plastic
or ceramic and could be manufactured with a great variety of inks.

2. The composition of the different inks carbon, silver, gold, platinum ,palladium
or copper used in the manufacture of the electrode determines its selectivity and
sensitivity.
3 In addition, the electrodes can be modified with enzymes,
metallic nanoparticles, carbon nanotubes, polymers or complexing agents.
4.The electrode ink composition is chosen according to the final application and
the selectivity and sensitivity required for the analysis.
The electrode manufacturing process involves the sequential deposition of
different layers of conductive and/or insulating inks on the substrates of interest.
Advantages of disposable sensors:

1. They are low cost, flexibility of their design, great reproducibility of the
process
2.They are biodegradable and sustainable.

3. They provide digitized chemical and biological information.

4. They are typically cheaper than classical sensors. (Cost-effective)


5. They do not require calibration or maintenance.(Convenient)

6. They can help to reduce the risk of cross contamination in medical and food
safety applications. (Hygienic)

8. They are typically smaller and lighter than classical sensors.(Portable)

9. They can provide results quickly, allowing for faster decision-making.(Rapid

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testing)

10. They are designed to be used once and then discarded. (Reduced waste)

11.Discuss the detection of a bio-molecule ascorbic acid using disposable


sensor also write the electro oxidation reaction.
Disposable screen-printed carbon electrodes sensor (CNT with gold
nanoparticles) for biomolecule detection- Ascorbic acid(AA)

 SPE sensor consists of three electrodes, working electrode, auxiliary


or counter electrode, and reference electrode.
 All electrodes have been manufactured by silk screen
printing technology with conductive material ink on a
plastic polyester (PET) sheet.

 The active surfaces of the counter electrode and working


electrode have been printed with a conductive ink of C
(MWCNT) and modified with gold nanoparticles.

 Active surface of the reference electrode has been


printed with an Ag/AgCl ink .
Working : The electrochemical sensor catalyze electro oxidation of AA to L- dehydro
ascorbic acid and electrons are released to the electrode surface. The number of electrons
released is proportional to the concentration of AA in the sample. The electric current
or voltage produced is proportional to the concentration of the ascorbic acid.

12.Explain the detection of Herbicide-Glyphosate with reactions.


Electrochemical Sensor for Glyphosate Detection
The sensor is a silicon- based chip comprising of three-electrode system. It
is fabricated by electro deposition technique.

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Working Electrode: G old electrode of 4 mm diameter coated with 200nm


thickness gold nanoparticles
Counter electrode: G old electrode of 4 mm diameter coated with 20nm
thickness gold nanoparticles
Reference Electrode: Ag/AgCl/Cl-
Electrolytes: They are added to increase the conductivity of the solution
and minimizes the resistance between the working and counter electrode.

Working:
 The electrochemical detection is based on the oxidation of
Glyphosate on gold working electrode.
 Potential of 0.78V is applied on working electrode, there is a
interaction between analyte and electrode surface.
 Glyphosate oxidizes on the working electrode brings a
change in current in the electrolyte medium.
 The change in the current is a measure of concentration of
Glyphosate.
Reactions:

At the anode
(working electrode): Glyphosate (Gly) + H2O → GlyO4P + H+ + 2e-
At the cathode:
(counter electrode): 2H+ + 2e- → H2
13.Define a battery. Give the classification of batteries with examples.

Battery : Battery is a union of two or more cells connected in series or parallel


that can convert chemical energy into electrical energy.
A cell represents a single unit of two electrodes (an anode and a cathode) in
contact with the electrolyte. The driving force behind the working of any cell or
battery is spontaneous redox reaction.

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Classification of Batteries: Batteries are classified as primary battery, secondary


battery and reserve battery. Following are the differences between the primary
and secondary batteries.
1. Primary batteries (irreversible): Primary battery is one in which chemical
energy of the active material is converted into electrical energy and all the cell
reactions are irreversible. Hence Once the cell or battery is completely discharged,
it is not rechargeable & is discarded. These cells function as galvanic cells during
discharge.
Examples: Zn-MnO2 battery & Zn-Ag2O battery
2. Secondary batteries (reversible): These are the batteries in which the cell
reactions are completely reversible and hence are rechargeable. All the cell
reactions are reversible. These cells function as galvanic cells during discharge and
as electrolytic cells during recharge.
Example: Lead-acid battery, nickel-cadmium battery
3. Reserve batteries: These are the batteries which are kept in inactive state by
isolating the battery from one of the key components. The battery is activated by
addition of the key component prior to use.
Example: Mg-AgCl battery, Li-V2O5 battery
14.What is a secondary battery? Explain the construction and working of
Li-Ion battery. Mention its applications
Secondary batteries (reversible): These are the batteries in which the cell reactions
are completely reversible and hence are rechargeable. All the cell reactions are
reversible. These cells function as galvanic cells during discharge and as
electrolytic cells during recharge.
Construction:
Anode (negative electrode) is layered structure intercalated graphite and binder
coated on a copper foil.
Cathode (positive electrode) is a layered structure lithium cobalt oxide( LiCoO2) or
lithium manganese oxide (LiMnO2) mixed with conductor and binder are coated
on Aluminium foil.
Electrolyte is a lithium hexafluoro phosphate (or lithium perchlorite or lithium
tetrafluoro borate or lithium halide) dissolved in an organic solvent such as
propylene carbonate and ethylene carbonate or diethyl carbonate with gelling
agent.
Separator is micro porous Polypropylene membrane which separates the cathode
& anode and which allows the movement of ions from anode to cathode and
cathode to anode .
Binder: poly vinylidene fluoride
Container: Stainless steel or aluminium alloy

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Cell representation:
Lithiated 𝐺𝑟𝑎𝑝ℎi𝑡𝑒 𝑙𝑎𝑦𝑒𝑟 /𝐿i𝑃𝐹 6 dissolved i𝑛 𝑜𝑟𝑔𝑎𝑛i𝑐 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 & 𝑔𝑒𝑙𝑙i𝑛𝑔 𝑎𝑔𝑒𝑛𝑡/𝐿i𝐶𝑜𝑂 2

Working Principle:

Both electrodes allow lithium ions to move in and out of their interiors. During
intercalation ions move into the electrode. During the reverse process,
deintercalation, ions move back out. The electrolyte conducts Lithium-ions to move
between theelectrodes.

1. During charging of battery, lithium atoms present in layers of metal oxide are
oxidized, liberating electrons and lithium ions. Electrons flow through external
circuit and lithium ions into graphite (anode) through electrolyte. At graphite
electrode lithium ions are reduced to lithium atoms and are inserted back into
layers of graphite.

2. When all the lithium ions moved from cathode to anode and all are stored in
thelayers of graphite, then the battery is fully charged and ready to use.

3. During discharging of battery, at anode lithium atoms present in graphite layer


are oxidized, liberating electrons and lithium ions. Electrons flows 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 layers of lithium metal oxide.

4. When all the ions have moved back (from anode to cathode), the battery is
fullydischarged and needs charging up again.

Discharging reactions:

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Applications of LIBs:

1. These are high energy density secondary batteries used in electronic devices
such as mobile phones, laptops, note PC, portable CD player, semiconductor driven
audio electric devices.
2. Used for emergency power backup or an uninterruptable power supply
3. Used in Electric vehicles
4. Energy storage systems.
5. Defense and Aerospace applications

15.What is a secondary battery? Explain the construction and working of Na-Ion


battery. List important applications of NIBs
Secondary batteries (reversible): These are the batteries in which the cell reactions
are completely reversible and hence are rechargeable. All the cell reactions are
reversible. These cells function as galvanic cells during discharge and as
electrolytic cells during recharge.
Construction of Sodium-ion battery

 Anode (Negative electrode): Hard-carbon layer in which the Na atoms


are intercalated. Hard carbon is most preferable due to its high capacity,
good cycling stability which can accommodate the larger sized sodium
ions compared to lithium ions.

 Cathode (Positive electrode): Sodium metal oxide (NaCoO2),


Chalcogenides, fluorides, polyanion compounds such as sodium
vanadium phosphates and fluorophosphates, 𝑁𝑎2𝐹𝑒𝑃𝑂4𝐹 and
chromium used as cathode material.

 Electrolyte is Sodium salts like sodium hexa fluorophosphate (NaPF6) or


NaCl or NaBr dissolved in an organic solvent like propylene carbonate and
ethylene carbonate or diethyl carbonate with gelling agent.

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 Separator is Polypropylene membrane which separates the cathode & anode and
which allows the movement of ions from anode to cathode and cathode to
anode.

Cell representation :
𝐺𝑟𝑎𝑝ℎi𝑡𝑒 𝑙𝑎𝑦𝑒𝑟 (𝐶)𝑁𝑎/𝑁𝑎𝑃𝐹 6i𝑛 𝑜𝑟𝑔𝑎𝑛i𝑐 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 & 𝑔𝑒𝑙𝑙i𝑛𝑔 𝑎𝑔𝑒𝑛𝑡/𝑁𝑎𝐶𝑜𝑂 2

Working principle:
SIBs consist of a cathode based on a sodium containing material, an anode
intercalated carbon and a liquid electrolyte containing dissociated sodium salts in
polar protic or aprotic solvents. During charging, sodium ions de-intercalate and
move from the cathode to the anode while electrons travel through the external
circuit. During discharge, the reverse process occurs. Once the circuit is completed
electrons pass back from anode to cathode through external circuit and sodium ions
move back from anode to the cathode through electrolyte medium.

NIBs have the same general operating principles as LIBs but use sodium ions in
placeof lithium ions. Both batteries shuttle ions between electrodes, storing them
in the negative electrode when charged, and the positive electrode when
discharged. This is not a trivial change; sodium ions are larger than lithium and
have different reactivity.

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Applied Chemistry for Computer Science & Engineering stream Dr . S.K.Revathi

Applications
• NIB technology is becoming attractive where high power is
advantageous (e.g., power tools) and uninterruptible power supply (UPS)
applications inthe telecommunications sector.
• NIBs have low cost, used in numerous stationary energy storage
applications.
• Large scale grid storage applications and used in large -scale storage of
renewable energy.
• SLI batteries are inexpensive and operate across a broad temperature
range. NIBs are an excellent fit with the SLI application, outperforming
lead-acid batteries by providing the specified power across the same
temperature rangebut with lighter batteries.

16.What is Quantum Dot Sensitized Solar Cell (QDSSC? Explain the construction
and working of QDSSC.
Quantum dots-sensitized solar cells (QDSCs): Quantum dot solar cell (QDSC) is a
solar cell design that uses quantum dots as the absorbing photovoltaic material.

The structure and operation principle of QD sensitized solar cell is almost


identical to dye sensitized cells with the exception that now the QDs are the
source of current injection.

Construction and Working of QDSSC

Construction of a QDSSC involves several layers of materials, each with a


specific purpose.
Transparent Conductive Oxide (TCO or FTO) substrate: This layer is
Fluorinated Tin Oxide serves as the bottom electrode and allows
light to pass through.

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Photo anode layer: This layer is made up of a semiconductor material,


such as titanium dioxide (TiO2), which is coated with quantum dots
(QDs).

Sensitizer: CdS is a sensitizer, it is a Quantum dot


nanocrystal made of semiconductor materials. The QDs are typically
made of semiconductor materials such as cadmium sulfide (CdS),
cadmium selenide (CdSe), or lead sulfide (PbS).

Working Electrode (Anode): FTO substrate is coated with


mesoporous wide band gap semiconducting TiO . Quantum
dots are coated on TiO . TiO2 act as electron conductors (or
acceptors) and transport layers. It also provide the necessary
large surface area to adsorb sensitizers.

Quantum dots are responsible for absorbing the light and converting it
into electrons. QDs facilitates the charge separation.

Electrolyte layer: This layer is sandwiched between the photo -anode


and counter electrode and is typically composed of an organic solvent
containing a redox couple, which acts as a charge transfer medium,
which transfer charges between counter electrode and photo anode
for the regeneration of oxidized quantum dots.

For example Polysulfide in organic solvent is used as


electrolyte (S2-/Sx2-). It is a redox electrolyte or hole conductor.
Redox electrolyte significantly influence both stability and
efficiency of QDSSC.

Counter electrode layer: This layer is made up of a conductive


material, such as platinum and carbon based materials are coated
on a brass substrate and serves as the top electrode. Counter electrode
is acting as cathode, and it transfers electrons from external circuit
to electrolyte and catalyze the reduction reaction of the oxidized
electrolyte at the electrolyte/counter electrode interface (completes the
circuit).
Principle: QDSSCs work based on the principle of the photovoltaic effect,
which is the generation of electrical energy from light. The QDs used
here are semiconducting materials that absorb light energy and
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Applied Chemistry for Computer Science & Engineering stream Dr . S.K.Revathi

generate electrons, which are then collected to produce an electric


current.

The operation of the cell can be described by the following steps and the
corresponding process equations:

1. Upon absorption of a photon, a quantum dot is excited from the


ground state (QDS ) to a higher energy state (QDS*)

Excitation: 𝑄𝐷𝑠 + ℎ𝜈 ⟶ 𝑄𝐷𝑠∗

QDs and QDs* is the quantum dot in its ground state and excited state
respectively.

2. The absorption process results in the creation of electron-hole pair in the


form of exciton. Dissociation of the exciton occurs if the thermal energy
exceeds its binding energy

Electron hole – pair formation: 𝑄𝐷𝑠∗ ⟶𝑄𝐷𝑠 (𝑒−∗+ ℎ+∗) (free carriers)

3. The excited electron is then injected in the conduction band of the wide
band gap semi conductor nano structured TiO2 thin film. This process will
cause the oxidation of the photo sensitizer QDs(h +*).
Injection process: 𝑄𝐷𝑠 (𝑒−∗+ ℎ+∗)+ 𝑇𝑖𝑂2 ⟶ 𝑇𝑖𝑂2 (𝑒−∗)+𝑄𝐷𝑠 (ℎ+∗)

4. The injected electron is transported between the TiO2 nano


particles, and then gets extracted to a load where the work done is delivered
as electrical energy.

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Applied Chemistry for Computer Science & Engineering stream Dr . S.K.Revathi

Energy generation: 𝑇𝑖𝑂2 (𝑒−∗)+𝐶𝐸 ⟶ 𝑇𝑖𝑂2+𝐶𝐸 (𝑒−∗)+𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦

Where CE stands for counter electrode


5. Electrolytes containing(S 2-/Sx2-) redox ions is used as an electron
mediator between the TiO 2 photo electrode and the counter electrode.
Therefore, the oxidized quantum dots {QDs(h +*)} are regenerated to the
ground state (QDS) by receiving electrons from the S2- ion of redox
mediator that get oxidized to Sx2-.

Regeneration of QDs : QDs(h+*) + S2- → QDs + Sx2-

6. The Sx2- diffuses to counter electrode and substitutes the internally


donated electron with that from the external load and reduced back to
S2- ion through electron capture reaction.

Electron capture reaction : Sx2- + e- (C.E) → S2- + (C.E)

The movement of electrons in the conduction band of the wide band gap
nanostructure semiconductor is accompanied by the diffusion of charge-
compensating cations in the electrolyte layer close to the nanoparticle surface.
Therefore, generation of electric power in QDSSC causes no permanent chemical
change or transformation .
17.Write the properties and applications of Quantum Dot Sensitized Solar Cell
(QDSSC).

Properties: Some key properties of QDSSCs:

1. High efficiency: QDSSCs can achieve high conversion efficiencies due


to their ability to absorb a broader range of the solar spectrum compared
to conventional solar cells.
2. Size tunability: The optical and electronic properties of QDs can be
tuned by adjusting their size, making them highly versatile for use in
various applications.

3. Low cost: QDSSCs are relatively low-cost to produce compared to


other types of solar cells, which makes them attractive for large-scale
commercialization.

Applications:

Potential applications of QDSSCs are:

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Applied Chemistry for Computer Science & Engineering stream Dr . S.K.Revathi

1. Portable devices: QDSSCs can be used to power portable electronic


devices. 2.Building-integrated photovoltaic's (BIPV): QDSSCs can be
integrated into the windows and walls of buildings to generate
electricity.
3.Military applications: Due to their light weight, flexibility, and
ability to operate in low-light conditions.
4.Space applications: QDSSCs could be used to power space vehicles and
satellites.

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