Chemistry Notes Vtu

MODULE 1: Sensors and Energy Systems

Sensors: Introduction, working, principle and applications of Conductometric sensors,
Electrochemical sensors, Thermometric sensors (Flame photometry) and Optical sensors
(colorimetry). Sensors for the measurement of dissolved oxygen (DO). Electrochemical sensors for
the pharmaceuticals. Electrochemical gas sensors for SO x and NOx. Disposable sensors in the detection
of biomolecules and pesticides.
Energy Systems: Introduction to batteries, construction, working and applications of Lithium ion and
Sodium ion batteries. Quantum Dot Sensitized Solar Cells (QDSSC’s)- Principle, Properties and
Applications.
Self-learning: Types of electrochemical sensor, Gas sensor - O2 sensor, Biosensor - Glucose sensors.
Sensors
Sensor is an object that detects signals from its surrounding environment and converts it to
meaningful or quantifiable information. Eyes, ears, and nose are all different types of sensors that help
you navigate your surroundings on a day-to-day basis by detecting and processing light, sound, and
smell/taste.
Conductometric sensors
Principle:
The basic principle of conductometric detection involves a reaction that can change the
concentration of ionic species. This reaction leads to changes in electrical conductivity or current flow.
Conductometric biosensors can measure the change of the specific conductance/electrical conductivity
of the analyte. In this method, two inert metal electrodes are used. The ions or electrons produces
during an electrochemical reaction may change the conductivity or resistivity of the solution.
Working of conductometric sensor
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 (Figure). 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.
Applied Chemistry for CSE Stream (BCHES102) 1

Figure 1. Construction of Conductometric sensor
Application of conductometric sensor
i.Aptamer Technology for the Detection of Foodborne Pathogens and Toxins

ii.Advanced Nanoparticle-Based Biosensors for Diagnosing Foodborne Pathogens
iii.Microfluidic electrochemical devices for pollution analysis.
iv. It is used for DNA Detection.
v. It is used in enzyme catalysis to determine analyte concentration and enzyme activity and
selectivity.
vi. Screen-printed conductometric sensor with inter digital gold electrodes on glass substrate
coated with molecularly imprinted polyurethane layers was fabricated to detect polycyclic
aromatic hydrocarbons (PAHs) in water.
vii. A conductometric sensor consisting of a silicon substance with a pair of gold inter digitized
and serpentine electrodes is used to determine urea.
viii. The conductometric biosensor based on inhibition analysis, was intended for the determination
of organophosphorus pesticides.
Electrochemical Sensors:
Principle:
Electrochemical reactions take place at electrode-electrolyte interfaces and provide a switch

for electricity to flow between two phases of different conductivity, i.e. the electrode (electrons or
holes are the charge carriers) and solid or liquid electrolyte (ions are the main charge carriers). The
reactions which occur at the interface of the surface of an electrode between the recognition element,
and the target/binding analyte generate an electrical double layer and thus this potential is measured
after transforming these chemical reactions into this measurable electrochemical signal by a
recognition element, and a transducer of the sensor.
Construction and Working
• The fundamental concept in the detection of analytes by electrochemical sensors involves the
measurement of electric current generated by chemical reactions in the electrochemical system.

• 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 reaction into a measurable
electrical signal. In the case of electrochemical sensors, the electrode acts as the transducer.
Electrochemical sensing always requires a closed circuit. Current must flow to make a
measurement In most electrochemical sensors. An electrode surface is used as the site of the
reaction. 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
• Electrochemical sensor’s working mechanism involves the interaction of the target analyte
material with the electrode surface and bringing the desired change as a consequence to a redox
reaction, which generates an electrical signal that can be transformed to explore the nature of
the analyte species.
Figure 2. Electrochemical Sensor
Application Electrochemical sensors-
• Detection of important molecules or biomarkers that are used for the diagnosis of diseases and
disorders.
• They are used for the monitoring toxic levels of different substances in food quality and
environmental control.
• The biosensor application areas of these sensors extend to medical and biomedical applications,
process control, bioreactors, quality control, agriculture, bacterial and viral diagnosis,
industrial wastewater control.
Thermometric Sensors
A temperature sensor is an electronic device that measures the temperature of its environment
and converts the input data into electronic data to record, monitor, or signal temperature changes. There
are many different types of temperature sensors. The fundamental working of this sensor is based on
the voltage in its diode. The temperature variation is directly related to the resistance of this diode. The
resistance of the diode is detected and transformed into simple and readable values of temperature such
as Fahrenheit, Kelvin, or Centigrade and demonstrated in meaningful formats instead of readout

values. These temperature sensors are employed to sense the internal temperature of various structures
like power plants.
Figure 3. Thermometric sensor setup
A thermocouple is another common example of them. Thermocouple, is constructed from two

different metals that produce an electrical output voltage in direct relation with the temperature
modification.
1. Thermostats
• A thermostat is a contact type sensor containing a bi-metallic section constructed from two
different metals such as aluminium, nickel, tungsten, or copper.
• The main principle of thermostats is based on the difference in the linear expansion coefficient
of the metals. Therefore, it forces them to generate a mechanical movement due to heat rise.
Figure 4. Thermostat sensor setup
2. Thermistors
• Thermally sensitive resistors or briefly thermistors are particular sensors because of the
modification of their physical appearance due to the change in the temperature.
• The thermistors are constructed from ceramic substances like oxides of particular metals
covered with glass. It will allow them to form simply.
• Some thermistors are NTCs and have a negative temperature coefficient but there are a lot of
thermistors that have a positive temperature coefficient. They are introduced as PTCs, and their
resistance increases by increasing the temperature.

Applications
• In hazardous locations like nuclear power plants.

• To identify the heat of hydration in concrete structures in geothermal control. They can also be
employed to control the migration of seepage or groundwater.
• Detect rock temperatures in order to identify storage tanks of liquid gasses and the ground
freezing process.
Optical sensors:
Optical sensors are electronic components designed to detect and convert incident light rays
into electrical signals. Eg: Colorimetric Sensors. Optical sensors are divided into several subclasses
such as resonance, dispersion, reflection, refraction, phosphorescence, infrared absorption, Raman
scattering, fluorescence, and chemiluminescence.
Figure 5. Optical sensor
Principle and Working-
• When a sample solution is interacted with a light of suitable wavelength, certain quantity of
light is absorbed by the analyte solution and it is observed by a sensor. The transducer converts
intensity of absorbed light into electrical signal. The change in intensity at certain wavelength
within visible (400–800mm) range can be determined using special instrumentation.
• The relationship between the incident light intensity and the transmitted radiation is given by
the Beer-Lambert law:
𝐼0
𝐴 (𝜆) = log = 𝜀 (𝜆) ∙ 𝑑 ∙ 𝑐
𝐼
𝐼0
where 𝐴 (𝜆) = log is the absorbance at a given wavelength A, (𝐼0 and I are the incident and
𝐼
transmitted light intensities); 𝜀 is the molar absorptivity; d is the optical path through the
absorbing sample and c is the molar concentration of absorbing analyte.

Figure 6. Beer-lamberts law
• What the detector monitors varies by technique (e.g., refractive index, scattering, diffraction,
absorbance, reflectance, photoluminescence, chemiluminescence, etc.), can cover different
regions of the electromagnetic spectrum, and can allow measurement of multiple properties.
Eg: Colorimetry: a quantitative measurement of absorbance or reflectance spectra, is one of the

oldest of analytical techniques. Optical sensors depends on the colour of the analyte with in the
visible range (400-800nm). Its basic components include a light source, a wavelength selector, a
photodetector and a read-out device. A block diagram of a typical instrumentation system
employed colorimetry. 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 photodetector (sensing). The light source generates an intense
and stable radiation signal needed to probe an optical property of the molecular recognition element
in the sensor. The amount of absorbance is governed by Beer- lamberts law.
Applications of Optical Sensors
• Computers
• motion detectors.
• copy machines (xerox machines)
• light fixtures that turn on automatically in the dark.
• alarm systems
• synchro for photographic flashes
• systems that can detect the presence of objects.
Sensors for the measurement of dissolved oxygen (DO)
The two methods for estimation of DO are optical method and electrochemical method.
(a) Optical method: Optical DO sensors are made of two parts, a sensor spot and a fibre optic reader.
The sensor spot is attached to the interior of a cell culture vessel and contains a fluorescent dye
suspended in a hydrogel. The external reader is connected to a computer or data hub and is responsible
for sending and receiving optical signals to the sensor spot.

(b) Electrochemical Method: Electrochemical DO sensors, also known as amperometric or Clark-
type sensors, measures dissolved oxygen concentration in water based on electrical current produced.
Galvanic Sensor is a Electrochemical sensor, which is used to measure DO The following are the
components:
• Cathode : Working electrode-Ag

• Anode : Zn, Pb or any other active metal
• Electrolyte: KOH, NaOH or any other inert electrolyte
• Membrane: Teflon
Working Principle
The difference in potential between the anode and the cathode should be at least 0.5V. DO
sensor is immersed in water sample. Oxygen molecule diffuses across the oxygen-permeable
membrane (Teflon) and the rate of diffusion is proportional to the pressure of oxygen in the water.
Molecular Oxygen reduces to OH- at cathode. 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.
Anode (Pb): Oxidation: 2Pb → 2Pb2+ + 4e-
Cathode (Ag): Reduction: O2 + 4e- + 2H2O → 4OH-
Overall: 2Pb + O2 + 2H2O → 2Pb(OH)2
Electrochemical Sensors for-
1. Pharmaceuticals
a. for the analysis of diclofenac.
Diclofenac is a nonsteroidal anti-inflammatory drug (NSAID). This medicine works by

reducing substances in the body that cause pain and inflammation. Diclofenac is used to treat mild to
moderate pain, or signs and symptoms of arthritis.
Carbon based-electrodes are the most investigated electrodes in diclofenac analysis. Carbon
nanotubes (CNTs) and graphene-based composites are the most efficient modifiers for diclofenac
detection that allowed the detection of diclofenac up to picomolar levels. CNT-based electrochemical
diclofenac sensors: Electrochemical sensors, in particular, are a class of chemical sensors in which an
electrode is used as a transducer element in the presence of an analyte. The following are the
components:

• Working electrode: Carbon Paste with

MWCNT or Graphene
• Counter Electrode: Carbon Paste with
MWCNT or Graphene
• Reference Electrode: Ag/AgCl
• Process: Screen Printing Technique on PVC
substrate. Insulating ink was printed on the
remaining PVC surface.
Figure 7. Printed sensor for Diclofenac
The electrochemical oxidation of DCF on carbon-based sensor at pH 7.0 is reversible reaction.

Oxidation of Declofenac occurs at carbon electrode to release e -, to form radical intermediates and
followed by hydrolysis of radical intermediate species. The products formed are 2,6- dichloro aniline
and 2-2-hydroxyphenyl 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.
Electro-oxidation mechanism of DCF
b. For the detection of hydrocarbons (1-hydroxypyrene):
Urinary 1-hydroxypyrene (1-OHP) is a widely used biomarker as an indicator of exposure to

polycyclic aromatic hydrocarbons (PAHs). PAHs are a class of compounds found in crude oils, mineral
oils and tars and are formed during the incomplete combustion of fossil fuels and oil products. These
are genotoxic carcinogens. Hence their detection is necessary.
The following are the components of the electrochemical sensor used for the detection of the
hydrocarbons-
Working electrode: PAMAM/Cr-MOF/GO (Composite) [PAMAM: Dendrimer polyamidoamine

Cr-MOF: Chromium-centered metal–organic framework GO: Graphene Oxide]
Counter Electrode: PAMAM/Cr-MOF/GO
Reference Electrode: Ag/AgCl
Operating Voltage: +0.7 to −0.5 V

Working: When this electrode is used to detect the sample containing 1-Hydroxypyrene (water
sample) the following changes takes place: At the electrode surface electro-oxidation takes place to
yield several 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.
Electro-oxidation scheme of 1-hydroxypyrene
2. Electrochemical Gas Sensors:

(a) Detection of SOx
Sulphur dioxide is one of the main substances that pollute the air. Sulfur oxides, SO2 released
from thermal power stations and other industrial plants, are gases harmful to the environment. It is
very important to detect and control the concentrations of SOx in industrial processes. The attempt to
detect sulphur dioxide in the air is a regular task of air inspection.
Figure 8. SOx sensor
Gas sensors detect chemicals in the gas phase. The gas sensors operate by reacting with the gas
of interest and producing an electrical signal proportional to the gas concentration. A typical
electrochemical sensor consists of: a sensing electrode (or working electrode), counter electrode
separated by a thin layer of electrolyte and a reference electrode. Gases diffuse through a membrane
to be reduced or oxidized at an electrode. Initially the gas passes through a small capillary-type opening
and then diffuses through a hydrophobic barrier, and eventually reaches the electrode surface. SOx
sensors utilizing a solid electrolyte such as K2SO4, Na2SO4, Li2SO4, Ag2SO4, Nasicon, Na-Al2O3 and

Ag-Al2O3, because this type of sensor has its own advantages like continuous quantitative
measurement; high selectivity and sensitivity; easy operation and fast response; simple construction
and low price.
Anode reaction: 2Ag → 2Ag+ + 2e-
Cathode reaction: 2Ag+ + SO3 + 𝟏⁄𝟐O2 + 2e- → Ag2SO4
Total reaction was: 2Ag + SO3 + 𝟏⁄𝟐O2 → Ag2SO4.
SO3 was produced by the reaction can be checked by sensor.
Applications:
1. It is used in thermal power plant.

2. It is used chemical industries to detect sulphur dioxide emission level
(b) Detection of NOx
Nitrogen oxide is the general term for a gas mixture composed of various oxides of nitrogen,
often referred as NOx. The normal air is nitric oxide and nitrogen dioxide. In environmental
analysis, nitrogen oxide generally refers to NO and NO 2. NO is an important vasodilator, and
monitoring its levels becomes crucial in the diagnostics of cardiovascular complications.
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 reaction into a measurable electrical
signal. In the case of electrochemical sensors, the electrode acts as the transducer.
Figure 8. NOx sensor
The electrode surface is used as the site of the reaction. 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. The NO x sensor monitors the
oxidation of NO as it occurs on the electrode surface. In many instances of electrochemical sensors,
the electrode surface can be modified with catalysts, membranes, or other metals to make the
electrode more sensitive and/or more selective toward the analyte (in the instance below, the Glassy

Carbon (GC) electrode is modified with Cobalt (IV) Oxide and Platinum). The direct electro
oxidation of NO in solutions follows the following 3 step reaction.
NO → NO+ + e-
NO+ + OH-→HNO2
HNO2 + H2O → NO3- + 2e- + 3H+
The ΔE for the overall process is +0.5V vs. a Ag/AgCl reference electrode. The reaction for the
Ag/AgCl reference electrode is the following: AgCl + e- ↔ Ag + Cl- ; Eo+0.222V
3. Disposable sensor for the detection of-
Disposable sensors: Disposable sensors are low-cost and easy-to-use sensing devices designed for
short-term or rapid single-point measurements.
Advantages of disposable sensors:
o They transduce physical, chemical, or biological changes in their environment to an

analytical signal.
o Disposable sensors are biodegradable and sustainable
o They have a short duration of analysis and fast response times.
o It provide digitized chemical and biological information.
o Prevents the contamination of samples.
a. Biomolecules: Ascorbic acid
The desired biomolecules such as enzyme, hormones, antibodies etc. are

immobilized via physisorption/chemisorption, which will cause an intimate contact with the
transducer. The analyte of interest will selectively bind with the biomaterial that produces the
measurable electronic response.
L-Ascorbic acid (AA) or adsorbate, commonly known as vitamin C, is an important water-

soluble vitamin derived from green vegetables, fruits, and other dietary supplements.
AA improves the immune system. It enables collagen synthesis, which is needed to maintain healthy
bones, teeth, skins, cartilages, enhances antibody levels and acts as an antioxidant; reduces necrosis.
However, abnormal AA levels in bodily fluids have been reported to cause cancer, cardiovascular
diseases, and Alzheimer’s and Parkinson’s diseases. Extended use of AA could cause urinary oxalate
calculus, increase infertility in a woman, and affect embryo development. Excessive AA use has been
reported to cause diarrhoea, nausea, vomiting, headache, insomnia, gastric irritation, renal problems,
loss of food taste, and vomiting.
Principle and Working of biosensor:

• It is comprising three disposable electrodes: one working electrode, one counter/auxiliary
electrode, and one reference electrode.
• Each one includes a contact or terminal, a section and an active area. All electrodes have been
manufactured by silkscreen printing 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.
• Electrochemical biosensors, for instance, have an electrode surface that acts as the reaction site
and as the transducer. In this case, electrodes, an enzyme to catalyse a reaction, and the sample
would make up the biosensor. For example, the electrode is placed in a solution containing an
enzyme (the bioreceptor) specific to the analyte—let’s say in this case, glucose—and the change
in potential is measured as the enzyme reacts with the glucose on the surface of the electrode, also
known as the transducer.
Figure 9. working of biomolecule sensor
• 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. Example electrochemical oxidation of ascorbic acid and
oxidation of glucose.
Oxidation of Ascorbic acid
Application of biosensors

1. Biomolecules/biological molecules are essential organic compounds present in all the living
systems. They are the building blocks of the body and are responsible for maintenance and
metabolic process. The major classes of biomolecules include carbohydrates, proteins, lipids,
nucleic acids, enzymes, hormones, etc. Each class are vital in the day-to-day activities of every
living organism.
2. In the medical field, patients’ glucose and oxygen levels are often measured to help doctors
diagnose and treat them. For instance, an individual might present with frequent urination, high
levels of hunger, and fatigue. Without sensors and further testing, a number of diagnoses might be
applicable to said patient (type these symptoms into WebMD and see for yourselves!). Glucose
sensors, in particular, are important for confirming whether a patient is hyperglycemic (has high
blood glucose), which may often be a result of diabetes. Today, glucose monitoring is possible
through finger-pricking, which involves using the blood from the patient’s pricked finger to
measure blood glucose via test strips and glucometers.
Figure 10. disposable Biosensor
b. Pesticides
To achieve improved cultivation in agricultural fields, farmers started to use large amount of
(more than prescribed ppm/ppb levels) harmful synthetic/chemical pesticides instead of organic
manure. These synthetic pesticides also have a direct impact on the soil as well as the agro-
products. The accumulation of pesticides into the vegetables lead to a poisoning effect. Pesticides
in the cultivated agro-products can induce a number of diseases such as asthma, diabetes, birth
defects, reproductive dysfunction, etc. They do this by suppressing the activity of many enzymes
in the human system. Therefore, monitoring the level of pesticides in soil, water and cultivated
agro-products is one of the best ways to detect the abuse of pesticides.
Working: One of the most commonly used pesticides is glyphosate. Glyphosate has the ability to
attach to the soil colloids and degraded by the soil microorganisms. As glyphosate led to the
appearance of resistant species, the pesticide was used more intensively. As a consequence of the
heavy use of glyphosate, residues of this compound are increasingly observed in food and water.
Recent studies reported a direct link between glyphosate and chronic effects such as tetrogenic,
tumorigenic. Electrochemical Sensor for Glyphosate Detection The sensor is a silicon- based chip
comprising of three-electrode system. It is fabricated by electro deposition technique. The following
are the components –

Figure 11. Working of sensor for pesticide detection
• Working Electrode: A gold electrode of 4 mm diameter coated with 200nm thickness gold
nanoparticles
• Counter electrode: A gold electrode of 4 mm diameter coated with 20nm thickness gold
nanoparticles
• Reference Electrode: Ag/AgCl/Cl-
• Electrolytes are added to increase the conductivity of the solution and minimizes the
resistance between the working and counter electrode.
The electrochemical detection is based on the oxidation of Glyphosate on gold working

electrode. A 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.
Electrochemical oxidation of glyphosate

Energy Systems
Batteries
Conversion of chemical energy into electrical energy is the function involved in cells. One of
galvanic cells that convert chemical energy into electrical energy. In general battery is a combination
of galvanic cells neither in series (or) parallel both in order to get the required amount of electrical
energy. Battery is a device which transforms chemical energy of a redox reaction into electrical energy.
Example: Zn-Air battery, lead acid battery, lithium batteries, etc. The following are the components of
batteries-
• Anode: The anode (-ve electrode) is oxidized during the electrochemical reaction and
liberates electrons of the external circuit.
M → Mn+ + e- Metal
• Cathode: The cathode (Positive electrode) is reduced during the electrochemical reaction
which accepts electrons from external circuit.
• Electrolyte: The electrolyte which provide the medium for transfer of ions inside the cell
between the anode and cathode. The electrolyte must have good ionic conductivity and
resistance to the electrode materials.
• Separator: The separator: the material that electronically isolates the anode and the cathode in
a battery to prevent internal short-circuiting.
Example: Cellulose, Vinyl polymer, Polyolefins
Classification of batteries:
Batteries are classified as (a) Primary, (b) secondary and (c) reserve batteries.
a. Primary batteries
In primary batteries, the chemical energy is converted into electrical energy as long as the chemical
components are active. These batteries the reaction occurs only once and after that they must 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, Leclanche cell (Zn-MnO2), Li-
MnO2 battery, Magnesium cell (Mg- MnO2)
b. Secondary batteries
Secondary batteries are those which after discharging can be recharged. 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 electric energy is stored in the form of chemical
energy these batteries are also known a storage cell. Examples: Lead storage battery, Nickel-cadmium
battery, Nickel-metal hydride battery and Lithium-ion battery.

c. Reserve Batteries
These batteries one of the components is isolated and incorporated into the battery when required.
The electrolyte is the component that is isolated, but some water activated batteries contain the
electrolyte solute and water is added for activation. They are used to deliver high power for relatively
short periods of time in application such as radiosondes (air borne instruments to send to
meteorological information back to earth by radio).Examples: Mg batteries activated by water (Mg-
AgCl, Mg-CuCl), Zn-Ag2O batteries etc
Li-ion Battery
Construction & Working: Li-ion cell consists of a
(a) cathode (positive electrode): e.g., LiCoO2, LiFePO 4, Lithium manganese oxide, Nickel cobalt
aluminium, Lithium nickel manganese cobalt oxide
(b) anode (negative electrode): e.g., carbon or graphite which are contacted by an electrolyte
containing lithium ions. The electrodes are isolated from each other by a separator, typically
microporous polymer membrane, which allows the exchange of Li-ions between the two
electrodes but not electrons.
(c) Electrolyte: A lithium salt such as LiPF6, LiAsF6, LiClO4, LiBF4 dissolved in an organic solvent
such as ethylene carbonate dimethyl carbonate or dimethoxy ethane.
(d) Separator: Microporous polyethylene or polypropylene
• Li-ion batteries use a process known as intercalation, in which lithium ions are incorporated into
the structure of the electrode materials.
• Inside the cell, lithium ions move from the positive to the negative electrode during charging and
from the negative to the positive electrode as the battery is discharged.
• In this way the external energy are electrochemically stored in the battery in the form of chemical
energy in the anode and cathode materials with different chemical potentials.
• Electrons move through an external circuit in the same direction as the lithium ions, driven by an
external charger (when charging) or by the stored potential chemical energy (available to drive a
load) when the battery is discharging.
The Li-ion cell is represented as: LiLi+, C  LiPF6 (in ethylene carbonate)LiCoO2
The cell reaction during discharge or charging are:
At anode: LixC6 ⇄ xLi+ + xe- + 6C
At cathode: Li1-xCoO2 + xLi+ + xe- ⇄ LiCoO2
Overall reaction: LixC + Li1-xCoO2 ⇄ LiCoO2 + C
Typical Li-ion cell provides a potential of 3.7 V.

Figure 12(a) Charging/discharging in Li-ion battery
Advantages:
• High energy density

• relatively low self-discharge
• high cell voltage (3.7 V)
Disadvantages:
• Require protection from being over-charged or over-discharged.

• Require cool storage area
• Expensive
Applications:
a. electric-powered vehicles
b. buffer the intermittent and fluctuating green energy supply from renewable resources, such as
solar and wind
c. grid application
d. cell phones
e. powering hybrid electric vehicles (HEVs)
f. plug-in hybrid electric vehicles (PHEVs)
g. electric vehicles (EVs)
Na-ion Battery
Construction and Working:
The components of Na-ion batteries are-
(a) Anode materials (negative electrode): carbon-based (hard-carbon), transition metals, and their
alloy compounds.

(b) Cathode materials (positive electrode): Metal oxides , Layered oxides, Polyanion phosphate
compounds
(c) Electrolyte: Sodium-Ion aqueous electrolyte, Sodium-ion solid polymer electrolyte, Ion
electrolyte of SIB
(d) Porous Separator
Figure 13. Na-ion Battery
It stores energy in the chemical bonds of anode. When battery is recharging sodium ions moves from
cathode to the anode. Meanwhile charge balancing electrons pass from the cathode through the external
circuit containing the charger and into the anode During discharge process electrons move from and
anode to external circuit, it can be used for various applications. Meanwhile, Na+ ions move from
anode to the cathode. Voltage obtained from every sodium ion cell is 3.6 V. The electrode reactions
are as follow,
Anode: 2Na ⇄ 2Na+ + 2e-

Cathode: nS + 2Na+ + 2e- ⇄ Na2Sn
Overall cell reaction: nS + 2Na ⇄ Na2Sn
The NaCoO2 cathode, like LiCoO2, is initially brought into the Na-ion cell in the discharged state, and
the cell is activated by charging first to form the Na intercalated anode and Na deintercalated cathode
in the fully charged cell.
Advantages
• Sodium resources are more abundant

• The cost of sodium-ion batteries is about 30% lower than that of lithium batteries
• Sodium-ion batteries are safer and are not easy to produce lithium dendrites.
Disadvantages:
• Lower energy density of sodium ion batteries

• short cycle life

• The industrial chain is still incomplete
Applications:
a. Power backup: Data and telecom sectors heavily rely on battery powered infrastructures and
operations to drive to the global economy. Na-ion batteries can provide on demand power to
ensure safe and seamless power supply.
b. Automobiles and Transportation: In electric vehicles including electric cars and buses.
c. Grid-level applications: Na-ion batteries can help optimise the solar and wind energy to meet
grid energy storage requirements.
d. Industrial mobility: Na-ion batteries can maximize asset utilization and minimize operating
cost with constant state of readiness and powerful peak power.
Quantum dots sensitized solar cells (QDSSC’s)
The concept of a ‘‘sensitized semiconductor,’’ in which a wide- band-gap semiconductor is

sensitized with a narrow band gap semiconductor to harvest sunlight and to generate charge carriers.
Principle: Upon light irradiation, the sensitizer is photoexcited. The excited electrons of QDs are
injected into the conduction band of the TiO2. The electrons penetrate through the nanocrystalline TiO2
film to the back contact of the conducting substrate, and flow through an external circuit to the CEs.
At the CEs, the oxidized component of redox couple in the electrolyte is reduced. The oxidized form
of the sensitizer is finally regenerated by the reduced component of redox couple in the electrolyte.
The external load is connected to the cell to complete the circuit through electron migration. When the
cell is irradiated with sunlight, the potential difference between the photo-electrode (due to the Fermi
level of the electrons) and electrolyte (due to the redox potential) produces a voltage across the load,
and the solar energy conversion efficiency (η) of the cells is obtained as follow.
Jm • Vm • FF
𝜂=
𝑃
where P is the power density at the operating point, and J m and Vm represent current density and
voltage, respectively, at the actual maximum power.
Figure 14. Complete setup of QDSSC

Construction and working: The following are the components of QDSSC: photoanode, sensitizer,
counter electrode and electrolyte.
(a) Photoanode: Photoanode usually consists of semiconducting metal oxide deposited on a transparent
conducting oxide substrate. Eg: Metal oxide electron-transporting/acceptor materials (TiO2, ZnO,
ZrO2, PbS-based photoanodes)
(b) QD sensitizers: To maximize the harvesting efficiency of the incident light, it should possess a high
absorption coefficient and appropriate band-gap energy. Eg: ZnS, ZnSe, Ag2S, Bi2S3, CdS, CdSe,
CdTe, InAs, In2S3, InP, PbS, PbSe, Si, Graphene, Cu-ZnS, and halides
(c) Counter electrodes (CE): transfers electrons from the external circuit into electrolyte and catalyses
the reduction reaction of the oxidized electrolytes at the electrolyte/CE interface. Eg: Noble metals
(Pt), Metal chalcogenides, Carbon materials (graphene, carbon fiber, carbon black, multiwalled
carbon nanotubes)
(d) Electrolyte: Redox electrolytes enhances the efficiency and stability of QDSSCs. It is a medium
which transfers charges between counter electrodes and photoanodes for the regeneration of
oxidized QDs. Eg: iodide/triiodide (I-/I3-) electrolyte
Advantages of QDSCCs: The following are the benefits of quantum dot solar cells.
• 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 QDSC.
• 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:
a. DSSCs as the photosensitizer instead of organic dyes to form QDSSCs

b. larger scale, flexible solar panels can be used to cover tents to power sophisticated equipment.
Lightweight wearable solar panels could power and recharge the electrical devices the military
carry, eliminating the need for extra battery packs in the field or bags full of batteries.
c. portable power systems
d. architecture, interior applications
e. electronic devices: mobile phones, e-books, cameras, and portable LED lighting systems.
f. biological labelling
g. Imaging, and detection and as efficient fluorescence resonance energy transfer donors.
h. It is used as light-emitting Diodes
i. It is used as Photoconductors and photodectors
j. It is used in Biomedicine and environment.

k. It is used in catalysis

Module 2: Materials for memory and display systems.
MODULE 2: Materials for memory and display systems (8hr)

Syllabus: Memory Devices: Introduction, Basic concepts of electronic memory, History of
organic/polymer electronic memory devices, Classification of electronic memory devices, types of
organic memory devices (organic molecules, polymeric materials, organic-inorganic hybrid materials).
Display Systems: Photoactive and electro active materials, Nanomaterials and organic materials used
in optoelectronic devices. Liquid crystals (LC’s) - Introduction, classification, properties and
application in Liquid Crystal Displays (LCD’s). Properties and application of Organic Light Emitting
Diodes (OLED’s) and Quantum Light Emitting Diodes (QLED’s), Light emitting electrochemical
cells.
Self-learning: Properties and functions of Silicon(Si), Germanium(Ge), Copper(Cu), Aluminium(Al),

and Brominated flame retardants in computers.
Memory Devices
Introduction, Basic concepts of electronic memory
The basic goal of a memory device is to provide a means for storing and accessing binary digital
data sequences of “1’s” and “0’s”, as one of the core functions (primary storage) of modern computers.
An electronic memory device is a form of semiconductor storage which is fast in response and compact
in size, and can be read and written when coupled with a central processing unit (CPU, a processor).
In conventional silicon-based electronic memory, data are stored based on the amount of charge stored
in the memory cells. Organic/polymer electronic memory stores data in an entirely different way, for
instance, based on different electrical conductivity states (ON and OFF states) in response to an applied
electric field. Organic/polymer electronic memory is likely to be an alternative or at least a
supplementary technology to conventional semiconductor electronic memory. According to the
storage type of the device, electronic memory can be divided into two primary categories: volatile and
non-volatile memory.
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1. Non-volatile memory: Non-volatile memory (NVM) or non-volatile storage is a type of
memory that can retain stored information even after power is removed. ROM (WORM,
EPROM) and Hybrid (Flash, EEPROM) memories are non-volatile memories.
2. Volatile Memory: Volatile memory is a type of memory that maintains its data only while the
device is powered. If the power is interrupted for any reason, the data is lost.
1.a. ROM: Read Only Memory
 ROM is a non-volatile memory.

 Information stored in ROM is permanent.
 Information and programs stored on it, we can only read.
 Information and programs are stored on ROM in binary format.
 It is used in the start-up process of the computer.
 WORM and EPROM are ROM based memories.
i. WORM (Write Once Read Many times)
 Describes a data storage device in which information once written, cannot be modified.
 This write protection affords the assurance that the data cannot be tampered with once
it is written to the device, excluding the possibility of data loss from human error,
computer bugs, or malware
ii. EPROM (Erasable programmable read-only memory)
 EPROM also called EROM, is a type of PROM but it can be reprogrammed.

 The data stored in EPROM can be erased and reprogrammed again by ultraviolet light.
 Reprogrammed of it is limited.
 Before the era of EEPROM and flash memory, EPROM was used in microcontrollers.
1.b. Hybrid memories
Hybrid memories can be read and written as desired, like RAM, but maintain their contents
without electrical power, just like ROM. It is a Non-Volatile memory. Flash and EEPROM are the two
types.
i. Flash
 Flash is an electronic non-volatile computer memory storage medium that can be

electrically erased and reprogrammed.
 Flash memory is a non-volatile memory chip used for storage and for transferring
data between a personal computer (PC) and digital devices.
ii. EEPROM (Electrically erasable programmable read-only memory)
 Electronically erasable programmable read only memory, is a standalone memory

storage device such as a USB drive.
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 It is a type of data memory device using an electronic device to erase or write digital
data.
2.a. RAM: Random Access Memory
It is a computer's short-term memory. It can be read and changed in any order, typically used
to store working data and machine code. RAMs consist of ferromagnetic particles embedded in a
polymer matrix having a high dielectric constant.
i. DRAM (Dynamic random access memory):
 It is a type of semiconductor memory that is typically used for the data or program
code needed by a computer processor to function.
 All DRAM chips manufactured to date use capacitors containing electrodes made of
doped silicon or polysilicon and dielectric films of silicon dioxide and/or silicon
nitride.
ii. SRAM (Static Random Access Memory)
 It is a type of RAM that holds data in a static form, that is, as long as the memory has
power.
 SRAM: It is made up of metal-oxide-semiconductor field-effect transistors
(MOSFETs)
Classification of Electrical Memory Devices
1. Transistor-Type Electronic Memory

2. Capacitor-Type Electronic Memory
3. Resistor-Type Electronic Memory
4. Charge Transfer Effects
1. Transistor-Type Electronic Memory
Transistors are made from silicon, a semiconductor. It is converted to p-type and n-type
semiconductor by doping trivalent and pentavalent impurities. Transistors are made using p-type and
n-type semiconductor. The main components are-
(a) source
(b) drain
(c) gate
(d) dielectric layer of inorganic and polymer insulator
(e) active semiconducting layer made of conjugated molecule or polymer
(f) electrodes: Au for polymer-based FETs
(g) Substrate: glass, wafer or plastic
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A transistor is a miniature electronic component that can work either as an amplifier or a switch. A
computer memory chip consists of billions of transistors, each transistor is working as a switch, which
can be switched ON or OFF. Each transistor can be in two different states and store two different
numbers, ZERO and ONE. Since chip is made of billions of such transistors and can store billions of
Zeros and Ones, and almost every number and letter can be stored.
Device Structure
2. Capacitor-Type Electronic Memory
Capacitors can store charges on two parallel plate electrodes under an applied electric field.
Based on the amount of charge stored in the cell, the bit level (either “0” or “1”) can be encoded
accordingly. A capacitor consists of two metal plates which are capable of storing an electric charge.
It is used to store data. It is like a battery that holds data based on energy.
If the capacitor is charged, it holds the binary numeral,”1” and holds “0’ when the cell is discharged.
If the parallel plates of a capacitor are separated by dielectric layer, charges dissipate slowly and
memory would be volatile. On the other hand, if the medium between the electrodes is ferroelectric
in nature, can maintain permanent electric polarization that can be repeatedly switched between two
stable states (bistable) by an external electric field. Thus, memory based on ferroelectric capacitors
(FeRAM) is non-volatile memory.
3. Resistor-type Electronic Memory
Device Structure
Memory devices containing resistive materials are generically classified as resistor-type

memory, or resistive random access memory (RRAM). Unlike transistor and capacitor memory
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devices, resistor-type memory does not require a specific cell structure (e.g. FET) or to be integrated
with the CMOS (complementary metal-oxide-semiconductor) technology. Resistor-type memory
devices store data in an entirely different form, for instance, based on different electrical conductivity
states (ON and OFF states). Memory devices containing switchable resistive materials are classified
as resistor-type memory, or resistive random access memory (RRAM). Resistor-type electronic
memory usually has a simple structure, having a metal-insulator-metal structure generally referred to
as MIM structure. Resistor-type memory is based on the change of the electrical conductivity of
materials in response to an applied voltage (electric field). The structure comprises of an insulating
layer sandwiched between the two metal electrodes and supported on a substrate (glass, silicon wafer,
plastic or metal foil). Initially, the device is under high resistance state or “OFF” and logically “0”
state, when resistance changed or under external applied field changes to low resistance state or “ON”
logical value “1”. The top and bottom electrodes can be either symmetric or asymmetric, with
aluminium, gold, copper, p- or n-doped silicon, and ITO being the most widely used electrode
materials. Various mechanisms have been proposed to explain electrical conductance switching in
organic/polymer memory devices. Among them, the most widely reported mechanisms include
filament conduction, space charges and traps, charge transfer effects, and conformational changes.
4. Charge-transfer type Electronic Memory
A charge transfer (CT) complex is defined as an electron donor–acceptor (D–A) complex,

characterized by an electronic transition to an excited state in which a partial transfer of charge occurs
from the donor moiety to the acceptor moiety. The conductivity of a CT complex is dependent on the
ionic binding between the D–A components. If the donor is characterized by small size and low
ionization potential, a strongly ionic salt forms and a complete transfer of charge (or with the CT
degree value, δ > 0.7) occurs from the donor to the acceptor, making the ionic salt insulating. When
the donor is very large and has a high ionization potential, a neutral molecular solid (δ < 0.4) forms,
which is also insulating. If the donor has intermediate size and ionization potential, it tends to form a
weakly ionic salt with the acceptor, which possesses incomplete CT (0.4 < δ < 0.7) and thus is
potentially conductive. The formation of a conductive CT complex can be employed to design
molecular electronic devices. Many organic CT systems, including organometallic complexes, carbon
allotrope (fullerene, carbon nanotubes and graphene)-based polymer complexes, gold nanoparticle–
polymer complexes, and single polymers with intra-molecular D–A structures.
Organic-Based Electrical Memory Devices/Organic semiconductors

If organic molecular material used to store the data is called organic –based memory device.
Organic semiconductors are π-conjugated polycyclic and heterocyclic systems which have a certain
degree of electrical conductivity. Organic electronic memory device stores data based on different
electrical conductivity states (ON and OFF states) in response to an applied electric field.
The advantages of organic and polymer electronic memory over traditional silicon-based memory
include-
 good processability
 molecular design through chemical synthesis
 simple device structure: use of low cost substrate like plastic and paper
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 miniaturized dimensions
 low-cost
 low-power operation
 multiple state properties
 large capacity for data storage
 lighter
 more flexible
Based on materials used Organic memory devices (OMDs) broadly classified as:
a) resistive switch and ‘write once, read many times’ (WORM) devices,
b) molecular memory devices, and
c) polymer memory devices (PMDs)
There are two major classes of organic semiconductors: -low molecular weight materials and
polymers. Organic semiconductors can be divided according to the character of charge carriers into p-
type (a positive charge or hole as the major carrier), n-type (a negative charge or electron as the major
carrier) or Ambipolar organic semiconductors (both electrons and holes are involved as charge
carriers)
a. The p-Type Organic Semiconductor Material “Pentacene (C22H14)”
An Organic molecule with π conjugated system and possess holes as major charge carrier is
called p-type semiconductor. Example: Pentacene. Pentacene is a polycyclic, linear aromatic
hydrocarbon formed by the fusion of five benzene rings. The extended π-system allows the continuous
delocalization of π-electrons and there is a lateral overlapping of pi-electrons between the molecules.
To show that Pentacene is a p-Type semiconductor
Consider OTFT (Optical Thin Film Transistor) as shown above. Source and drain was made of
gold and semiconductor was Pentacene. When a Positive voltage is applied to the gate negative charges
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are induced at the source electrode (Au). Since, Fermi level of gold is away from LUMO of Pentacene,
electron flow cannot takes place. When a negative voltage is applied to the gate holes are injected from
source to semiconductor because Fermi level energy of gold is close to energy of HOMO of Pentacene.
A conducting channel is formed at the insulator and semiconductor interface and allows the movement
of charge carriers holes from source to drain when secondary voltage is applied. Hence pentacene is a
p-type semiconductor
Note:
 Source is the terminal through which the majority charge carriers are entered in a transistor. Drain:
Drain is the terminal through which the majority charge carriers exit in a transistor
 The highest energy level that an electron can occupy at the absolute zero temperature is known as
the Fermi Level.
b. The n-type organic semiconducting material Perfluoropentacene
An Organic molecule with π conjugated system with electron withdrawing substituent groups
and possess electrons as major charge carrier is called n- type semiconductor. When a p-type
semiconductor Pentacene is modified with electronegative fluorine atoms to lower the Lowest
Unoccupied Molecular Orbital (LUMO) energy levels of materials for electron injection and transport.
The HOMO-LUMO gaps of perfluorinated pentacene are smaller than those of the corresponding
Pentacene.
To show that Perfluropentacene is a n-Type semiconductor
Consider OTFT(Optical Thin Film Transistor) as shown above. Source and drain was made of
gold and semiconductor was Perfluropentacene. The HOMO-LUMO gaps are 2.07 eV for pentacene
and 1.95eV for perfluoropentacene. When a Positive voltage is applied to the gate negative charges
are induced at the source electrode (Au). The source and drain electrodes inject electrons in its LUMO
level. This charge forms a conducting channel at the insulator and semiconductor interface and allows
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the charge carriers electron from source to drain. Hence, Perfluropentacene is considered as a n-Type
semiconductor.
Polymeric material for Organic memory device
A volatile memory is a type of memory which cannot sustain the two distinct electronic states
without an external electronic power supply, that is, the written data will disappear. A non-volatile
memory can sustain the two distinct states without the power supply, that is, the written data will not
disappear when an external electronic power supply is removed.
Understanding the relationship between the chemical structure and memory properties is a
subject of utmost importance in the development of polymer memory materials. One such polymer
used for organic memory device is Polyimide with Donor- Triphenylamine and Acceptor- phthalimide.
Donor: Triphenyl Amine group (TPA) Acceptor: Phthalimide group. Hexafluoroisopropylidene (6F):
Increases the solubility of PI.
The donors and acceptors of PIs contribute to the electronic transition based on an induced
charge transfer (CT) effect under an applied electric field. When an electric field more than threshold
energy is applied, the electrons of the HOMO (TPA unit) is excited to LUMO. The energy of LUMO
of donor and acceptor are similar and therefore, after excitation the electron transferred to
LUMO(acceptor), generating a CT state. This permits the generation of holes in the HOMO, which
produces the open channel for the charge carriers to migrate through. Therefore, Field-induced charge
transfer from triphenylamine to phthalimide exhibit the switching behaviour (bistable states ON/OFF).
This device exhibits dynamic random access memory (DRAM) behaviour with an ON/OFF current
ratio of up to 105.
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Display System
Display: Display is an output device used to present visual information.
Display System: Display system is a system through which information is conveyed to people
through visual means
Photoactive and electro active organic materials:
Organic semiconductors used in electronic and optoelectronic devices are called as electro
active and Photoactive materials. Photoactive and electro active organic materials are the
semiconductors composed of π-electron systems.
Working Principle
Photoactive and electroactive material absorb and emit light in the UV to IR region. Display
system (OLED) consisting of photoactive and electroactive material absorb light and allows an
electron to jump from HOMO of a Donor to LUMO of an Acceptor. This phenomenon generate and
transport charge carriers. In an OLED device, the light-emitting layer is excited by the recombination
energy of electrons from the cathode and holes from the anode, and then the light-emitting layer emits
light when returning to the ground state. One of the electrodes consists of transparent material in order
to extract light from the light emitting layer.
Optoelectronics
Optoelectronics is the communication between optics and electronics which includes the study,
design and manufacture of a hardware device that converts electrical energy into light and light into
energy through semiconductors. Optoelectronic devices: A hardware device that converts electrical
energy into light and light into energy through semiconductors. Optoelectronic devices are primarily
transducers i.e. they can convert one energy form to another.
They can also detect light and transform light signals to electrical signals for processing by a computer.
Working principle
Optoelectronic devices are special types of semiconductor devices that are able to convert light
energy to electrical energy or electrical energy to light energy. If the photon has an energy larger than
the energy a gap, the photon will be absorbed by the semiconductor, exciting an electron from the
9
valence band into the conduction band, where it is free to move. A free hole is left behind in the valence
band. When the excited electron is returning to valence band, extra photon energy is emitted in the
form a light. This principle is used in Optoelectronic devices.
Nanomaterials (Silicon Nanocrystals: Si NC) for Optoelectronic devices
Any substance in which at least one dimension is less than 100nm is called nanomaterials. The
properties of nanomaterials are different from bulk materials due to: Quantum Confinement effect,
Increased surface area to volume ratio. The improved electronic properties yielded for nanostructured
silicon in comparison to its bulk, which led the use of Silicon Nanocrystals in electronics and
optoelectronics fields.
Properties of Silicon Nanocrystals for optoelectronics:
 Silicon Nano crystal has wider bandgap energy due to quantum confinement.
 Si NCs shows higher light emission property (Photoluminescence)
 Si NCs exhibit quantum yield of more than 60%.
 Si-NCs exhibit tuneable electronic structure.
 Larger surface area-volume ratio
Applications:
 Si NCs are used in neuromorphic computing and down-shifting in photovoltaics
 Si NCs are used in the construction of novel solar cells, photodetectors and optoelectronic
synaptic devices.
Organic materials for Optoelectronic devices [Light absorbing materials –

Polythiophenes] (P3HT)
Polythiophenes are an important class of conjugated polymers,

environmentally and thermally stable material.Chemical structure of P3HT
Poly(3-hexylthiophene) is a polymer with chemical formula (C10H14S)n. It is a
polythiophene with a short alkyl group on each repeat unit. Highly ordered
(P3HT) are composed of closely packed, p–p stacked (p–p distance of 0.33
nm) fully extended chains which are oriented perpendicular to the substrate.
Properties:
10
 P3HT is a semiconducting polymer with high stability and exhibits conductivity due to holes
therefore considered as p-type semiconductor.
 Poly-3-hexylthiophene (P3HT) have great capability as light-absorbing materials in organic
electronic devices.
 P3HT has a crystalline structure and good charge-transport properties required for
Optoelectronics.
 P3HT has a direct-allowed optical transition with a fundamental energy gap of 2.14 eV.
 Fundamental bandgap of P3HT is 490nm visible region, corresponding to π →π* transition,
giving electron-hole pair.
 P3HT indicate that an increase in the conductivity is associated with an increase in the degree of
Crystallinity.
Applications:
 P3HT-ITO forms a p-n junction permit the charge carriers to move in opposite direction and
hence, used in Photovoltaic devices.
 It can be used as a positive electrode in Lithium batteries.
 Used in the construction of Organic Solar Cells.
 Manufacture of smart windows .
 Used in the fabrication new types of memory devices.
Light emitting material - Poly[9-vinylcarbazole] (PVK)]
Poly (N-vinyl carbazole) (PVK) is one of the

highly processable polymers as hole
conducting material and therefore used as an
efficient hole transport material to prepare
highly efficient and stable planar
heterojunction perovskite solar cells. Structure of poly(9-vinylcarbazole) (PVK)
Applications
 PVK has been commonly used in OLEDs , light harvesting applications , photorefractive
polymer composites and memory devices
 Used in the fabrication of light-emitting diodes and laser printers.
 Used in the fabrication of organic solar cells when combined with TIO on glass substrate.
 Used in the fabrication of solar cells when combined with Perovskite materials.
 PVK-Perovskite junction is used in Light-Emitting Diodes with Enhanced Efficiency and
Stability
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Liquid Crystals
The liquid crystals are a unique state of matter between solid (crystalline) and liquid (isotropic)
phases. Liquid crystal is a material which flows like a liquid and shows some properties of solid. The
molecular structure of liquid crystal is in between solid crystal and liquid isotropic. Liquid Crystal
Display (LCD) is an flat display screen used in electronic devices such as laptop, computer, TV, cell
phones and portable video games. These LCD are very thin displays and it consumes less power than
LEDs. In Liquid crystal display (LCD) nematic type of liquid crystal molecular arrangement is used
in which molecules are oriented in some degree of alignment. For example when we increase the
temperature the ice cube melts and liquid crystal is like the state in between ice cube and water.
LC are classified as follows
1. Thermotropic liquid crystals

2. Lyotropic liquid crystals
1. Thermotropic liquid crystal
A liquid crystal is said to be thermotropic if molecules orientation

is dependent on the temperature. By increasing the temperature, the
increase in energy and thereby movement of constituent molecules, will
induce phase changes. Eg:
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Thermotropic liquid crystals have been classified into the following types:
(a) Nematic liquid crystals

(b) Smectic liquid crystals
(c) Cholesteric liquid crystals
(d) Discotic liquid crystals
(a) Nematic (or thread-like liquid crystals)
The molecules move either sideways or up and down. Each molecule can also twist or rotate
around its axis giving rise to a twisted nematic. Since the molecules are oriented in one direction, they
exhibit anisotropy. In this case, the molecules are readily aligned in the same direction in the presence
of electric and magnetic fields. The alignment of molecules is temperature sensitive – as the
temperature is increased, the degree of orientation of the nematic crystals decreases and they change
into isotropic liquids. Examples: p-azoxyphenetole, anisaldazine.
(b) Smectic (or soap-like liquid crystals)
The molecules in smectic crystals are oriented parallel to each other as in the nematic phase
but in layers. These layers can slide pass each other because the force between the layers is weak. They
are denoted by alphabet letter A, B, C, etc. Some common types of smectic liquid crystals are given
below.
i. Smectic A: In smectic A, the molecules are aligned perpendicular to the layer planes.
ii. Smectic C: The arrangement of molecules is similar to smectic A except that the molecules
are slightly tilted. They have high viscosity and are not suitable for devices.
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(c) Cholesteric liquid crystals
This type of mesophase is formed by derivatives of cholesterol such as cholesteryl esters. Like
the nematic phase, the molecules in this type of crystal are also parallel to each other but arranged in
layers. The molecules in successive layers are slightly twisted or rotated with respect to the layers
above and below so as to form a continuous helical or spiral pattern. Cholesteryl benzoate, the first
known liquid crystal, is of cholesteric type. Its transition temperature is 146 °C and melting point is
178.5 °C.
(d) Discotic liquid crystals
Molecules are arranged in a column arrangement with disc like structure. These are referred to
as columnar phases. Applications are: in photovoltaic devices, organic light emitting diodes (OLED),
and molecular wires.
2. Lyotropic liquid crystals
The orientational behaviour of lyotropic crystals is a function of concentration and solvent.

These molecules are amphiphilic – they have both hydrophilic and hydrophobic ends in their
molecules. The hydrophilic end is attracted towards water, whereas the hydrophobic end is water
repellent and attracted towards non-polar solvents. At low concentrations, these molecules are
randomly oriented but as the concentration increases, the molecules start arranging themselves. Cell
membranes and cell walls are examples of lyotropic liquid crystals. Soaps and detergents form
lyotropic crystals when they combine with water.
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Properties of liquid crystals
 They exhibit optical anisotropy which is defined as the difference between refractive index
parallel to the director and refractive index perpendicular to the director. These two properties
are important for the electro-optic effects in liquid crystals.
 The intermolecular forces are rather weak and can be perturbed by an applied electric field.
 Because the molecules are polar, they interact with an electric field, which causes them to
change their orientation slightly.
 Liquid Crystal can flow like a liquid, due to loss of positional order.
 Liquid crystal is optically birefringent, due to its orientation order.
 Liquid crystals, like all other kinds of matter, exhibits thermal expansion (Thermal Imaging).
Applications of liquid crystals
Liquid crystals have a wide range of applications in various fields, including electronics, optics,
displays, sensors, and medicine. Some of the major applications of liquid crystals are:
 Liquid Crystal Displays (LCDs): The liquid crystal layer in LCDs allows for the display of images
and text through the use of electrical currents that control the orientation of the crystals.
 Sensors: Liquid crystal sensors are used in various applications such as temperature sensing,
humidity sensing, and chemical sensing.
 Optical Devices: Liquid crystals are used in various optical devices such as variable optical
attenuators, phase shifters, and tuneable filters. These devices are used in optical communication
systems, spectroscopy, and imaging.
 Medicine: Liquid crystals have been used in drug delivery systems, where the drug is encapsulated
in the liquid crystal matrix and delivered to specific target cells.
Application in Liquid Crystal Displays (LCD’s)
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A liquid crystal display (LCD) is a flat panel display technology that uses liquid crystals to
produce images. LCDs are commonly used in electronic devices such as televisions, computer
monitors, and mobile phones. LCD consists of two polarized glass pieces. Two electrodes, one is
positive and the other one is negative. External potential is applied to LCD through this electrodes and
it is made up of indium-tin-oxide. Liquid crystal layer of about 10μm- 20μm is placed between two
glass sheets. The light is passed or blocked by changing the polarization.
Working principles of LCD
 The working principle of an LCD is based on the optical properties of liquid crystals.
 An LCD consists of a layer of liquid crystal material sandwiched between two transparent
electrodes.
 When an electric field is applied to the liquid crystal, it twists the orientation of the liquid crystal
molecules, which changes the polarization of the light passing through the liquid crystal.
 Polarizing filter is placed in front of and behind the liquid crystal layer to control the orientation
of the light passing through it.
 The LCD also has a backlight, which shines light through the liquid crystal layer to produce an
image.
 The LCD can display images in colour by using filters that absorb different colours of light.
Each pixel of an LCD contains three sub-pixels that can produce red, green, and blue colours. By
adjusting the voltage applied to each sub-pixel, the LCD can create millions of different colours.
 Overall, the working principle of an LCD is based on the manipulation of light using liquid crystals
and polarizing filters to create images.
 When the external bias is applied the molecular arrangement is
disturbed and that area looks dark and the other area looks clear.
 In the segment arrangement the conducting segment looks dark
and the other segment looks clear. To display number 2 the
segments A, B, G, E, D are energized.
Organic Light Emitting Diodes (OLED’s)
“OLEDs are thin film devices consisting of a stack of organic layers sandwiched between two
electrodes. OLEDs operate by converting electrical current into light via an organic emitter”. The basic
OLED cell structure consists of a stack of thin organic layers sandwiched between a conducting anode
and a conducting cathode.
Working principle of OLED: The components of OLED are-
 Substrate (can be plastic, glass, or metal foil) – Foundation of the OLED

 Anode (may or may not be transparent depending on the type of OLED) – Positively charged
to injects holes (absence of electrons) into the organic layers that make up the OLED device
 Hole Injection Layer (HIL) – Deposited on top of the anode this layer receives holes from the
anode and injects them deeper into the device
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 Hole Transport Layer (HTL) – This layer supports the transport of holes across it so they can
reach the emissive layer
 Emissive Layer – The heart of the device and where light is made, the emissive layer consists
of a colour defining emitter doped into a host. This is the layer where the electrical energy is
directly converted into light.
 Blocking layer (BL) – Commonly used to improve OLED technology by confining electrons
(charge carriers) to the emissive layer
 Electron Transport Layer (ETL) – Supports the transport of electrons across it so they can reach
the emissive layer.
 Cathode (may or may not be transparent depending on the type of OLED) – Negatively charged
to inject electrons into the organic layers that make up the OLED device.
When a voltage is applied across the OLED, a current flows through the device and into the
emissive layer. As the current passes through the emissive layer, the organic molecules become excited
and move to a higher energy state. When they return to their original energy state, they release energy
in the form of photons, which create the visible light that we see.
Properties of OLED
 Thinness and flexibility: OLEDs are very thin and flexible, which makes them suitable for use in
curved or flexible displays.
 High contrast: OLEDs have a high contrast ratio, which means that they can produce deep blacks
and bright ewhites, resulting in images with vivid and rich colours.
 Fast response time: OLEDs have a fast response time, which means that they can switch on and
off quickly, resulting in smooth and seamless motion in video content.
 Wide viewing angle: OLEDs have a wide viewing angle, which means that the image quality is
maintained even when viewed from different angles.
 Energy efficiency: OLEDs are energy efficient, as they do not require a backlight like traditional
LCD displays, resulting in lower power consumption.
 Self-emissive: OLEDs are self-emissive, which means that they do not require a separate light
source, resulting in a thinner display.
 Long lifespan: OLEDs have a long lifespan, as they do not contain a backlight that can degrade
over time, resulting in a longer-lasting display.
Applications
17
Organic Light Emitting Diodes (OLEDs) have a wide range of applications due to their unique
properties, including high contrast, energy efficiency, thinness, and flexibility. Like,
 Televisions and displays: OLED displays are used in televisions, monitors, smartphones, and other
electronic devices.
 Lighting: OLEDs can also be used as a source of lighting in various applications, including
automotive lighting, street lighting, and architectural lighting.
 Wearable devices: The thin and flexible nature of OLEDs makes them suitable for use in wearable
devices, such as smartwatches and fitness trackers.
 Automotive: OLEDs can be used in automotive applications, such as dashboard displays, interior
lighting, and taillights.
 Medical: OLEDs can be used in medical applications, such as in surgical lighting and medical
imaging. They offer bright and highly accurate lighting options that can help improve medical
procedures and diagnosis.
Quantum Light Emitting Diodes (QLED’s)
Quantum dot light emitting diodes are a form of light emitting technology and consist of nano-
scale crystals that can provide an alternative for applications such as display technology”.
Properties of QLED
 Accurate and vibrant colours: QLEDs are capable of producing highly accurate and vibrant
colours due to their use of quantum dots, which emit light of a specific colour when they are
excited by a light source or an electrical current.
 Energy-efficient: QLEDs are more energy-efficient than traditional LCD displays because they
do not require as much backlighting.
 High contrast: QLED displays have high contrast ratios, which means that the difference between
the darkest and brightest areas of the display is greater, resulting in more detailed and lifelike
images.
 Long lifespan: QLEDs have a longer lifespan than traditional LCD displays because they do not
suffer from the same issues of backlight burnout or color fading over time.
 Fast response times: QLED displays have fast response times, which means that they can display
fast-moving images without motion blur or ghosting.
 Flexibility: QLEDs can be made on flexible substrates, which allows for the creation of flexible
displays that can be bent or curved.
Applications of QLED
 Televisions and displays: QLED displays are commonly used in televisions, monitors,
smartphones, and other electronic devices. They offer superior image quality and color
accuracy compared to traditional LCD displays.
 Lighting: QLEDs can also be used as a source of lighting in various applications, including
automotive lighting, street lighting, and architectural lighting. They offer energy-efficient and
highly customizable lighting options.
18
 Medical imaging: QLEDs can be used in medical imaging applications, such as in MRI
machines, to produce high-resolution and accurate images.
 Virtual and augmented reality: QLED displays are suitable for use in virtual and augmented
reality applications due to their ability to produce vibrant and accurate colours, which can
enhance the immersive experience.
 Advertising displays: QLED displays can be used in advertising displays, such as digital
billboards and signage, to produce high-quality and eye-catching visuals.
Light emitting electrochemical cells.
Organic semiconductors offer a series of advantages over their inorganic counterparts such as
the possibility to fabricate light-weight and very thin devices, their processability on flexible and large-
area substrates and the ease of tuning their electrical and optical properties. Efficient and stable state-
of-the-art OLEDs are based on a multi-stack architecture of small molecular-weight components that
make use of injection layers or reactive metals for an efficient injection of electrons. The multi-layer
geometry is obtained by sequentially evaporating the active materials under high-vacuum conditions.
These devices require rigorous encapsulation to prevent degradation of the air-sensitive materials
supporting electron injection. As a result, production costs of OLEDs are considerable delaying their
large-scale market entry for lighting applications. OLEDs require multiple layers, some of them
processed by evaporation under high-vacuum conditions. Air-sensitive low work function metals or
electron injecting layers are needed for efficient charge carrier injection. LECs can be prepared from
just a single active layer. The movement of the ions in the layer under an applied bias allows for
efficient charge carrier injection from air-stable electrodes. Taken from The properties of OLEDs can
be drastically altered by mixing high concentrations of mobile ions with a conjugated polymer and a
solid electrolyte. They described the injection of electronic charges from the
metallic electrodes as electrochemical oxidation and reduction of the conjugated polymer, from which
the name of the new devices (light- emitting electrochemical cells or LECs) was derived. An ionic
transition-metal complex (iTMC) sandwiched in between two electrodes also leads to efficient
electroluminescence .
Operation mechanism
 Two models have been proposed, the electrodynamic model (ED) and the electrochemical
doping model (ECD) and measurement results have been interpreted in either of them.
 In the following, the current understanding of the functional principle of LECs is briefly
reviewed.
 After applying an external bias, the first step in LEC operation involves a redistribution of the
ions in the active layer.
 Driven by the electrical field, anions and cations migrate to the respective electrode interfaces
to form thin sheets of uncompensated charge referred to as electric double layers. The external
quantum efficiency (EQE) is determined by the fraction of electrons and holes that recombine
to form excitons (b), the exciton-to- photon generation efficiency (φ) and the amount of photons
that can escape the device or out coupling efficiency.
19
20
MODULE-III
CORROSION AND ELECTRODE SYSTEM
CORROSION
Introduction
Corrosion is defined as the destruction and consequent loss of metals through chemical or
electrochemical attack by the environment.
Ill effects of corrosion
 Contamination of product
 Damage of metallic equipments.
 Inability to use metallic materials
 Lose of valuable materials such as blockage of pipes, mechanical damage of underground
water pipes
 Accidents due to mechanical loss of metallic bridges, cars, aircrafts etc.
Global losses of corrosion
 Efficiency loss.
 Equipment shut down due to corrosion failure and cost of replacing the corroded
equipment
 Sudden failure of equipment due to corrosion can cause an explosion, fire, release of a
toxic product, and/or construction collapse which challenges the safety measures.
 An escaping product from corroded equipment or corrosion product itself can cause
pollution hence may result serious health problems.
Electrochemical Theory of Corrosion:

Principle: According to electrochemical theory, corrosion of the metal take place due to the
formation of anodic and cathodic regions on the same metal surface in the presence of a
conducting medium. At the anodic region oxidation reaction takes place and the metal gets
corroded into ions liberating the electrons. Consequently, metals undergo corrosion at the anodic
region. At the cathodic region reduction reaction takes place. Metal ions in the cathodic region
are unaffected by the cathodic reaction.
1
The electrons liberated at the anodic region migrate towards the cathodic region
constituting corrosion current. The metal ions liberated at the anode and some anions formed at
the cathode region diffuse towards each other through the conducting medium and form a
corrosion product somewhere between the anode and the cathode. Corrosion of metal continues
as long as both the anodic and cathodic reactions take place simultaneously.
Corrosion reactions:
At the anodic region:
At anodic region, iron is liberating Fe2+ ions and electrons,
Fe →Fe2+ +2e-
At the cathodic region:
The chemical species present in the surrounding of cathode under goes reduction by accepting
electrons coming through metal from the anodic region. Depending on the surrounding medium,
there are four possible reduction reactions at the cathodic region,
1) Hydrogen liberation takes place in the absence of oxygen.
(a) In acidic medium and in the absence of oxygen the cathodic reaction is
2H++2e-→H2↑
(b) In neutral or alkaline medium and in the absence of oxygen, hydroxide ions are
formed with simultaneous liberation of hydrogen
2H2O+2e- →2OH─+ H2
2) Absorption of oxygen takes place in the presence of oxygen.
(a) In acidic medium and in the presence of oxygen
2H+ +1/2O2 +2e- →H2O
(b) In neutral or alkaline medium and in the presence of oxygen hydroxide ions are
formed by the following reaction.
H2O+1/2O2 +2e- →2OH─
Corrosion of iron produces Fe2+ and OH─ ions at the anode and cathode sites respectively.
These ions diffuse towards each other to produce insoluble Fe (OH)2.
Fe2++2OH─→ Fe (OH) 2
. In an oxidizing environment it is oxidized to ferric oxide and the yellow rust is hydrated
ferric oxide.
4 Fe (OH) 2+ O2+2H2O →2 [Fe2O3. 3H2O] (rust)
2
In the presence of limited oxygen ferrous oxide is converted into magnetic oxide of iron
(Fe3O4) and is known as black rust.
3 Fe (OH) 2+1/2 O2→ [Fe3O4. 3H2O] (black rust)
Types of Corrosion:
(1) Differential metal corrosion (Galvanic corrosion)
(2) Differential Aeration corrosion
1. Differential metal Corrosion
Definition: When two dissimilar metals are in contact with each other a potential difference is
set up resulting in a galvanic current.
Principle: The two metals differ in their tendencies to undergo oxidation, the one with lower
electrode potential or the more active metal acts as anode and the one with higher electrode
potential acts as cathode. The anodic metal undergoes corrosion and the cathodic metal is
generally unattacked.
At the anode), Fe→ Fe2+ + ne-
At the cathode H2O + ½ O2 + 2e- → 2OH-
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)
Process: When two metals having different electrode potentials are in contact with each other in
the presence of an electrolyte, one metal acts as a cathode whereas the other acts as an anode.
This leads to an electrochemical reaction as a result of which, the anode is dissolved into the
electrolyte. Galvanic corrosion can only occur when there exists an electric conducting path
3
connecting the metals and when an electrolyte which can offer a channel for the migration of
ions is present.
Differential Metal Corrosion

Examples:
(1) Steel pipes joined to Copper plumbing, undergo galvanic corrosion, since Steel acts as the
anode.
E0Fe+2/Fe = - 0.44 V E0Cu+2/Cu = +0.34 V
(2) Steel screws or rivets used on Copper sheet, or screws and washers of unlike metals.
(3) Steel propeller shaft in Bronze bearing.
2. Differential Aeration Corrosion

Differential aeration corrosion occurs when a metal surface is exposed to differential air
concentrations of Oxygen concentrations. The part of the metal exposed to higher oxygen
concentration acts as a cathodic region and the part of the metal exposed to lower oxygen
concentration acts as anodic region.
Corrosion of metal arising as a result of the formation of an oxygen concentration cell
due to uneven supply of air on the metal surface is known as differential aeration corrosion.
At the anode (less O2 concentration), Fe → Fe2+ + ne-
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)
Eg.:- 1. Part of the nail inside the wall, being exposed to lower oxygen concentration than the
exposed part, under goes corrosion.
2. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.
4
3. Metal under dirt, dust, scale or water undergoes corrosion.
Water line Corrosion:
Principle: Water line corrosion is a case of differential aeration corrosion. The water line
corrosion takes place due to the formation of differential oxygen concentration cells. The part of
the metal below the water line is exposed only to dissolved oxygen (acts as anode) while the part
above the water is exposed to higher oxygen concentration (acts as cathode) of the atmosphere.
A distinct brown line is formed below the water line due to deposition of rust.
At the anode (less O2 concentration), Fe → Fen+ + ne
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
2Fe (OH) 2+1/2O2+H2O →[Fe2O3. 3H2O] (rust)
Water - line Oxygen

Cathode
Corroded part (anode)
Examples:
(1) Ships that are left in the water for extended periods of time can be at risk of waterline
corrosion.
(2) Steel water tanks in which water is stored for a long period.
Corrosion Control
(a) Galvanisation
Galvanisation is a process of coating a base metal surface with Zinc metal. It is an anodic
coating which is produced by coating a base metal with more active metals which are anodic to
the base metal. Eg.: Iron is coated with anodic and active metals like Zn, Mg, and Al.
Galvanisation is carried out by hot dipping method.
5
The galvanization process involves the following steps.
(1) The metal surface is washed with organic solvents to remove organic matter on the
surface
(2) Rust and other deposits are removed by washing with dilute sulphuric acid.
(3) Finally the article is well washed with water and air-dried.
(4) The article is then dipped in a bath of molten zinc, maintained at 425 – 430C and
covered with a flux of ammonium chloride to prevent the oxidation of molten Zinc.
(5) The excess Zinc on the surface is removed by passing through a pair of hot rollers, which
wipes out excess of Zinc coating and produces a thin coating.
One advantage of gavanisation is that, even if the coating is ruptured, the base metal does not
undergo corrosion. The exposed surface of the metal is cathodic with respect to zinc. Therefore,
galvanisation is also known as sacrificial coating.
(b) Anodization
Anodization is generally produced on nonferrous metals like Al, Zn, Mg and their alloys
by anodic oxidation process. It is a type of inorganic coating where surface layer of the metal is
converted into a compound, by chemical or electrochemical reactions, which forms a barrier
between the underlying metal surface and the corrosion environment
In anodization of aluminium, clean, polished aluminium is taken as anode and immersed
in an electrolytic cell containing chromic acid. Inert electrodes like lead is generally used as
cathode. The anodic oxide film formed on Al in bath as aluminium oxide, which is porous. The
pores are finally sealed by dipping in hot water to produce Al2O3 .H2O, which acts as a non-
porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2
6
(c) Sacrificial anode method:
In this method, the protected metal structure is converted into a cathode by connecting it
to a more active metal. This active metal acts as an auxillary anode Zn, Mg and Al are the
common auxillary anodes and are more reactive undergo corrosion, protecting the metal
structure. Since the anodic metals are sacrificed to protect the metal structure, the method is
known as sacrificial anode method. Exhausted sacrificial anodes are replaced by new ones as and
when required.
Eg.;1. A magnesium block connected to a burried oil storage tank
1. Mg bars are fixed to the sides of ocean going ships to act as sacrificial anodes.
2. Mg blocks are connected to buried pipe lines.
Anodic Reaction : Mg → Mg2+ + 2e

Cathodic Reaction : ½ O2 + H2O + 2e →2OH-
Mg
Under
ground Mg Mg
steel Pipe line
tank
(a) (b) (c)
7
Corrosion Penetration Rate (CPR)
The Corrosion penetration rate is the speed at which any metal or alloy deteriorates in a specific
corrosive environment through chemical or electrochemical reactions. It is also defined as the
amount of weight loss per year in the thickness of metal or alloy due to corrosion. The Corrosion
penetration rate also referred as corrosion rate.
Corrosion penetration rate depends on following factors;
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of metal.
The Corrosion penetration rate is calculated using the following formula;
CPR =
Where,
W is weight loss after exposure time.
T is exposure time in corrosive medium.
D is the density of metal or alloy.
A is surface area of exposed specimen.
K is constant.
Numerical Problem on CPR:
1. A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After one-year period it
was found to experience a weight loss 375 g due to corrosion. If the density of the brass is
7.9 g/cm2 calculate the corrosion penetrating rate in mpy and mmpy (given K= 534 in mpy
and 87.6 in mmpy).
To calculate CPR in mmpy:
Given CPR in mmpy
K 534 87.6
W (wt loss) 375 g 375 x 1000 mg
ρ 7.9 g/ cm3 7.9 g/ cm3
8
A 400 cm 2 400 cm 2
t 1 year 1 x 365 x 24 hrs
CPR =
CPR =1.186 mmpy
To calculate CPR in mpy :
Given CPR in mpy
K 534
W (wt loss) 375 g 375 x 1000 mg
Ρ 7.9 g/ cm3 7.9 g/ cm3
A 400 cm2 400 X 0.155 inch2

T 1 year 1 x 365 x 24 hrs
(1 cm2 = 0.155 inch2)
CPR =
CPR = 46.67 mpy
2) Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2 which
experiences a weight loss of 485g after one year. (Density of steel=7.9g/cm3).
9
To calculate CPR in mmpy :
Given CPR in mmpy
K 534 87.6
W (wt loss) 485 g 485 x 1000 mg
ρ 7.9 g/ cm3 7.9 g/ cm3
A 100 inch 2 100 X 6.45 cm 2

1inch2=6.45cm2
= 87.6 X 485 X 1000

7.9 x 100 x 6.45 x 365 x 24
=
= 0.9518 mmpy
To calculate CPR in mpy :
Given CPR in mpy
K 534 534
W (wt loss) 485 g 485 x 1000 mg
ρ 7.9 g/ cm3 7.9 g/ cm3
A 100 inch 2 100 inch 2

10
534 X 485 X 1000
7.9 x 100 x 365 x 24
= 37.424 mpy
ELECTRODE SYSTEM
Introduction
An Electrode can be defined as the point where current either enters or leaves the electrolyte or
circuit. When the current leaves the Electrode it is known as the cathode while when the current
enters the Electrode it is known as an anode.
Electrodes are the main component of electrochemical cells. An Electrode must be a good
conductor of electricity.
Types of electrodes:
1. Metal-metal ion electrode:

An electrode of this type consists of a metal dipped in a solution containing its own ions
eg:Zn/Zn2+, Cu/Cu2+
2. Metal-metal salt ion electrode: (Metal-insoluble salt electrode):
These electrodes consist of a metal in contact with a sparingly soluble salt of the same
metal dipped in a solution containing anoin of the salt.
Eg: Calomel Electrode (Hg/Hg2Cl2/Cl-)
Silver-silver chloride electrode (Ag/AgCl/Cl-)
Lead-lead sulphate electrode (Pb/PbSO4/SO42-)
3. Gas electrode:
Gas electrodes consist of a gas bubbling about an inert metal wire or foil, immersed in a
solution containing ions to which the gas is reversible.
Eg: H2 electrode (Pt/H2/H+)
Chlorine electrode (Pt/Cl2/Cl-)
4. Amalgum electrode:
Amalgum electrode is similar to metal-metal ion electrode except for the fact that in an
amalgam electrode, metal-amalgum is in contact with a solution containing its own metal
ions.
Eg: Lead amalgam electrode (Pb-Hg/Pb2+)
5. Oxidation- Reduction electrode:
11
An oxidation-Reduction electrode is the one in which the electrode potential arises from
the presence of oxidized and reduced forms of the same substance in solution. The
potential arises from the tendency of one form to change onto the other more stable form.
The potential developed is picked up by inert electrode like platinum.
Eg: Pt/Fe2+,Fe3+
6. Ion selective electrode: (Membrane electrode):
IN an ion selective electrode, a membrane is in contact with a solution, with which it can
exchange ions.
Eg: Glass electrode: (exchanges H+ ions with the solution)
Ion Selective Electrode
Definition: Ion-selective electrode is one, which selectively responds to a specific ion in a

mixture of ions in solutions ignoring all other ions and develops a potential. The potential
developed is a function of the concentration of that particular ion.
The electrode generally consists of a membrane which is capable of exchanging the specific ions
with the solution with which it is in contact. Therefore, these electrodes are also referred to as
membrane electrodes.
Glass Electrode:
Principle:
12
When two solutions of different hydrogen ion concentrations, ie different pH values are
separated by a thin glass membrane, there develops a potential difference between the two
surfaces of the glass membrane.
The potential developed is proportional to the difference in the pH values of the two solutions. If
the pH of the one solution is kept constant, the potential becomes proportional only to the pH of
the other solution. This is the basis of the glass electrode.
Construction:
The glass electrode consists of a glass bulb made up of a special type of glass with high electrical
conductivity. The composition of the glass membrane is approximately 22% Na2O, 6% CaO, and
72% SiO2. The glass bulb is filled with a solution of known pH (0.1M HCl) and is inserted with
an Ag-AgCl electrode, which is the internal reference electrode and also serves for the external
electrical contact. The electrode is dipped in a solution whose pH is to be determined (containing
H+ ions).
The glass electrode system can be represented as follows:
Ag/AgCl(s)/0.1MHCl/glass
When dipped in a solution of unknown pH, it can be represented as,
The glass membrane exchanges ions with the solution

H+(solution) + Na+Gl (glass) Na+(solution) + H+Gl(glass)
The exchange of ions by the inner and outer membrane gives rise to a boundary potential. This
boundary potential consists of two potential E1 and E2, which are associated with the outer and
inner membrane respectively.
Therefore,
From thermodynamic consideration it has been shown that E1 and E2 are related to the hydrogen
ion activities at each face, by Nernst like equation,
13
Where j1 and j2 are constants and a1 and a2 are activities of H+ in the outer and inner solution
respectively, a11 and a21 are the activities of H+ ions at the external and internal surface of the
glass membrane.
Since the glass at the inner solution and outer membrane are identical, j1 = j2 and also a11 = a21
Then (n = 1 for H+ ions)
Thus the boundary potential Eb depends only upon the hydrogen ion activities of the solutions.
Since the concentration of the inner solution is constant, a2 is constant. The above equation
simplifies to,
Where L1 = −0.0591, loga2 = −0.0591logC2

The total potential of the glass electrode EG has three components
(i) The boundary potential
(ii) The potential of the internal Ag/AgCl reference electrode and
(iii) A small asymmetry potential
14
Where is a combination of three constant terms.
Asymmetric potential arises due to the difference in response of the inner and outer surface of
the glass bulb to changes in H+ ion activity. This may originate as a result of differing conditions
of strain in the two glass surfaces (due to difference in curvature). This asymmetric potential
varies with time and therefore, glass electrode must be standardized frequently by placing a
solution of known H+ activity (pH).
Applications
 Glass electrodes have been utilized in a wide range of applications including pure
research, control of industrial processes.
 Analysis of foods and cosmetics.
 measurement of environmental indicators, and microelectrode measurements such as cell
membrane electrical potential.
Determination of pH using Glass Electrode:
 The given glass electrode is dipped in the unknown solution containing hydrogen ions,
constitutes a half cell.
 It is coupled with reference electrode (ex: saturated calomel electrode) through a salt bridge,
where calomel electrode forms an outer reference electrode.
 The above cell may be represented as:

15
Hg  Hg2Cl2 (paste) Sat. KCl  experimental solution  glass membrane 0.1M HCl AgCl Ag
 In the above cell, the glass electrode behaves as cathode and calomel electrode as anode.
 The cell potential may be determined using electronic potentiometer.
 The EG0 is obtained by repeating the experiment using the solution of known pH.
 The pH value of the experimental solution can be calculated by substituting the values of
Ecell, Ecalomel and EG0 in the following relation:
0.0591pH = E0G – ESCE - Ecell
Reference electrode:
The absolute value of single electrode potential cannot be measured since the metal and its
ions are in equilibrium. We can only measure the potential difference between two electrodes.
This can be done by choosing a reference electrode whose electrode potential is arbitrarily fixed
or known. This reference electrode can be combined with other electrodes to form a galvanic
cell. From the measured cell potential we can calculate the electrode potential of any particular
electrode, with reference to the reference electrode.
Definition: Reference electrode is an electrode whose electrode potential is arbitrarily fixed or
known and is reliable.
This can be used to measure the electrode potentials of other electrodes by constructing a
galvanic cell using the electrode tend the reference electrode.
Two types of reference electrodes:
1. Primary reference electrode, Example: Hydrogen gas electrode
2. Secondary reference electrode, Example: Calomel electrode and silver-silver electrode
Limitations of Primary Reference Electrode (Standard hydrogen electrode):
1.The equilibrium between the two processes is not reached quickly.
2.It is difficult to control the pressure of hydrogen gas at 1 atm.
16
3.The electrode cannot be easily setup.
4. The electrode gets poisoned by impurities
Secondary Reference Electrodes:
For the sake simplicity and to overcome the above difficulties, there was a need for the
development of secondary reference electrodes. The potentials of these electrodes are known on
the hydrogen scale and are used in place of hydrogen electrode. These electrodes can be easily
set up.
Calomel electrode:
Construction and working:

It is a metal-insoluble salt electrode, where metal in contact with its insoluble salt and the
solution contains the anion of the salt.
Electrode representation: Hg(s)Hg2Cl2 (paste);Cl-
Mercury is placed at the bottom of the glass tube above which a
paste of mercury and mercurous chloride are present. It is filled
on the top with the saturated solution of KCl. A platinum wire
sealed into a glass tube is dipped into mercury and used to
provide the external electrical contact. Depending on the nature
of the other electrode it can either acts as anode or cathode.
If the electrode behaves as anode, the electrode reaction is:
2Hg (l)  Hg2+2 +2e-
Hg2+2 +2Cl- Hg2Cl2(s)
2Hg (l) +2Cl- Hg2Cl2(s)+2e-
If the electrode behaves as cathode, the electrode reaction is:

Hg2+2 +2e-2Hg (l)
Hg2Cl2(s)Hg2+2+2Cl-
Hg2Cl2(s) +2e- 2Hg(l)+2Cl-
The electrode potential may be represented by the Nernst equation as
17
at 298K
E = E 0  0.0591 logCl   at 298K

The electrode potential decreases with increase in the concentration of chloride ions.
The potential values depend on the concentration of the solution used in the construction of the
For saturated KCl E=0.2422V (called Saturated calomel electrode)
Uses: It is used as a secondary reference electrode in the measurement of single electrode
potential. It is the most commonly used reference electrode in all potentiometric determination.
Applications
 Calomel electrode is used in cyclic voltammetry to study the electrochemical properties
of an analyte in solution or of a molecule that is adsorbed onto the electrode.
 General aqueous electrochemistry.
 For pH measurement in all practical and research fields.
Concentration cells:
Definition: Concentration cells are those in which both the anode and the cathode are made up
of the same element (metal or nonmetal) in contact with the solutions of the same electrolyte, but
of different concentrations.
Eg: A cell in which the electrodes are made up of zinc metal dipped in ZnSO 4 solutions of
different concentrations C1 and C2. The cell is represented as:
Zn / Zn2+ (C1) // Zn2+ (C2) / Zn
18
At the anode zinc gets converted into Zn2+ ions and goes into the solution liberating two
electrons.
At the anode: Zn(s) → Zn2+ (C1) + 2e-
At the cathode Zn2+ ions are deposited as zinc metal.
At the cathode: Zn2+ (C2) + 2e- → Zn(s)
There is no net cell reaction. At one electrode zinc atoms go into the solution and at the equal
number of zinc atoms are deposited. The emf of the cell is given by,
Ecell = Ecathode - Eanode
logC 2cathode  E 0  logC1anode

2.303RT 2.303RT
Ecell  E 0 
nF nF
2.303 RT 2.303 RT
E cell  log(C 2 )  log(C 1 )
nF nF
2.303 RT C  0.0591  C 2 
E cell  log 2  (or) E cell  log  ; at 298 K
nF  C1  n  C1 
It is evident from the above expression that Ecell can be positive only if C2>C1.
Thus in a concentration cell, the electrode with lower electrolyte concentration acts as the anode
and the one with higher electrolyte concentration acts as the cathode. The concentration of ions
increases at the anode and decreases at the cathode when cell is in operation. The emf of the cell
is dependent on the ratio of electrolyte concentrations at two electrodes. Higher the ratio (C2/C1),
higher is the emf. Therefore, the cell can operate only as long as the concentration terms are
different. When the current is drawn from the cell, C1 increases and C2 decreases and as a result
the emf of the cell goes on decreasing and becomes zero when the two becomes equal.
Numerical Problems
1) The cell potential of Cu concentration cell Cu I Cu 2+(0.0093 M) II CuSO4 (X) I Cu is 0.086 V

at 25o C. Write cell reactions and calculate the value of X.
Equation to be used is E = 0.0591 𝑛 log
19
0.086 = 0.0591 x 2 x log
x =0.0093M
2) The cell potential of Cd concentration cell Cd I Cd2+(XM) II CdSO4(0.025 M) I Cd is 0.035

V at 28o C. Calculate the value of X.
Equation to be used is E= 0.0591𝑛 log 𝐶2/𝐶1
0.035= 0.05912 log 0.025/𝑥
x =0.0016M
Analytical Techniques
Analytical techniques are the techniques involved in the study of separation, identification and
quantification of chemical components of materials. Qualitative analysis and quantitative
analysis are the analytical techniques used to determine the identity of chemical species and
amount or concentration of species present in the sample respectively.
Instrumental methods use simple or advanced instrument to measure physical quantities of

analyte by relating concentration with light absorption, fluorescence, conductivity or potential.
Some of the important instrumental methods of analysis are discussed below.
1. Conductometric titrations
Principle:
According to Ohm’s law, current (i) flowing in a conductor is directly proportional to emf (E)
and inversely proportional to resistance (R).
E
Therefore, i =
R
The reciprocal of resistance is conductance. It is expressed in ohm-1,mho
20
Or Siemen. The resistance of a homogeneous material of uniform cross section with an area of
‘a’sq.cm and length ‘l’ cm is given by,
x l is specific resistance

R =
a
The reciprocal of specific resistance is specific conductance
Specific conductance:
Specific conductance is the conductance of a solution present between 2 parallel electrodes of
area 1cm2 which are kept 1cm apart.
1 l l
K= X a = cell constant
R a
The specific conductance of an electrolytic solution at any temperature depends on ions present
and hence varies with ionic concentration. On dilution, specific conductance decreases as no of
ions per ml also decrease.
Equivalent conductance is defined as the conductance of a solution containing one gram
equivalent weight of the electrolyte. It is denoted as γ. Molar conductance is defined as the
conductance of a solution containing one mole of an electrolyte. It is denoted as μ.
Instrumentation:
It consists of two platinum electrodes of unit area of cross-section placed unit distance apart. The
electrodes are dipped in electrolyte solution taken in a beaker. It is connected to a conductance
measuring device. The titrant is added from the burette and the solution is stirred. The
conductance is measured after the addition of the titrant at intervals of 0.5ml.
21
To, conductometer
Stirrer
1cm2 Platinum electrode

1cm
Application
Titration of Weak acid v/s Strong base (Ex: CH3COOH Vs NaOH)
The conductance of the acid will be initially less since
conductance(mhocm-1)
acetic aided acid is a weak electrolyte. When NaOH is
added to the acid, the salt formed is highly ionized
because of this conductance increases.
CH3COOH + NaOH  CH3COONa + H2O equivalence point
After the neutralization point, further addition of base
volume of strong base
(NaOH) increases the fast moving OH- ions. Hence the
conductance increases sharply. A plot of conductance against the volume of base added is shown
in the figure. The point of intersection of two curves gives the neutralization point.
2. Potentiometry
Principle:
Redox titrations can be carried out potentiometrically using platinum calomel electrode
combination in a manner similar to acid-base neutralizations. For the reaction,
Reduced form  Oxidised form + n e-
The potential is given by;
o 0.0591 Oxidizedform 
E  E 
n
log
Re ducedform
o 0.0591 
Fe3 
E  E 
n
log

Fe2 
22
Where Eo is the standard potential of the system. The potential of the system is controlled by the
ratio of concentration of the oxidized and reduced form of the species present. As the reactions
proceed the ratio increases and reaches to a highest value at the end point.
Instrumentation:
To, potentiometer
Potentiometer consists of a reference
electrode (Saturated Calomel Electrode), Indicator electrode
an indicator electrode, and a potential Reference electrode
measuring device. The indicator Stirrer
electrode responds to the changes in

concentration of analyte. An emf is
measured at each time when titrant is added in the increments of 0.5 ml to a known volume of
analyte taken in the beaker. At equivalence point, emf increases rapidly and a few readings are
taken beyond the end point.
Application of potentiometry in the estimation of iron
Mohr’s salt is treated with 2 test of dil H2SO4. The calomel and platinum electrodes are dipped
and connected to a potentiometer.and the initial potential is measured. The burette is filled with
standard potassium dichromate solution. Added 0.5 ml of potassium dichromate solution to the
beaker, stirred well and the potential is measured. Potential is continuously measured by adding
0.5 ml increments of dichromate solution at a time. Initially the emf increases slowly and at the
equivalence point there will be a sudden jump in the emf. At least 5-6 readings are recorded
after equivalence point.
The end point is determined by plotting ∆E/∆V versus volume of potassium dichromate. The
volume of potassium dichromate corresponding to the peak of the curve indicates the end point.
From this the concentration and finally the amount of FAS, in turn amount of iron per litre is
determined.
Observations and Calculation:
Volume of Mohr’s salt pipetted out VFAS = 25 ml
Normality of K2Cr2O7, NK2Cr2O7 = 0.5 N
Vol. of
K2Cr2O7 in Emf (mv) ∆E ∆V ∆E/∆V
ml
0.0
23
0.5 0.5
1.0 0.5
1.5 0.5
2.0 0.5
2.5 0.5
3.0 0.5
3.5 0.5
4.0 0.5
4.5 0.5
5.0 0.5
5.5 0.5
6.0 0.5
6.5 0.5
7.0 0.5
7.5 0.5
8.0 0.5
8.5 0.5
9.0 0.5
9.5 0.5
10.0 0.5
E
V
Volume of K2Cr2O7 required for the reaction = ……………… (V eq) ml (determined from
graph)
Normality of FAS solution, NFAS = NK2Cr2O7 x VK2Cr2O7
-----------------------------------
VFAS
=--------------------------N
24
Amount of FAS (iron) per litre = NFAS x Eq. wt. of FAS
= x 392
= -------------------- g
25
Module-4
Polymers and Green Fuels
A polymer is a giant or macro molecule formed by the repeated union of several simple
molecules called monomers. The repeating units (monomers) are linked through strong covalent
bonds.
Monomers
A monomer is a simple molecule having two or more bonding sites through which each can link
to the other monomers to form a polymer chain.
Types of polymerization
Addition polymerization (Chain polymerization)
The reaction in which a rapid self addition of several bifunctional monomers to each other takes
place by chain reaction without elimination of any by products.
addition
Eg: n H2C CH2
H2 C CH2
polymerization n
Ethene Polythene
addition
n H2C CH H2C CH
polymerization n
Cl Cl
Vinyl Chloride Poly vinyl chloride
addition
n F 2C CF 2
F2C CF2
polymerization n
Tetra fluoro ethene Teflon
Condensation polymerization (Step growth polymerization)

Condensation polymerization takes place by linking together different monomer molecules and
is accompanied by the elimination of small molecules like H2O, NH3 and HCl. The polymer
obtained is called copolymer.
Example:
Eg: Synthesis of nylon 6,6
n HOOC CH2 COOH + n H2N CH2 NH2

4 6
Adipic acid Hexamethylene diamine
OC CH2 CONH CH2 NH + 2n H2O

4 6 n
Nylon 6,6
Eg: Synthesis of Terylene
n HOOC C6H4 COOH + n OH C2H4 OH

Terephthalic acid Ethylene glycol
OC C6H4 CO O C2H4 O + 2n H2O

n
As the polymers are made up of mixture of molecules having different properties, its molecular
weight can be determined in two different ways:
Number average molecular mass: (Mn) It is determined by measuring the colligative properties
such as freezing point depression, boiling point elevation, osmotic pressure and lowering of
vapour pressure. It is defined as total mass of all the molecules in a polymer sample divided by
total number of molecules present.
M n  W  N   Ni

NiMi 𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
Mn = =
 ∑𝑁 𝑁1+𝑁2+𝑁3+⋯
where Ni is the number of molecules of mass Mi..

No. average molecular weight assumes that each molecule makes an equal contribution to
polymer properties regardless of size or weight.

Weight average molecular mass ( M W ): It gives representation to various molecular species in
proportion to their weight in the given material. It is obtained from light scattering and ultra
centrifugation technique which measures molecular size.I n the averaging process molecular
weight of each individual species is multiplied by weight and not by number.
MW  
 WiMi
Wi
Where Wi is the weight fraction of the molecules whose mass is Mi.
We have Wi = NiMi

MW 
N M Mi i i

N Mi i
2
N M i i N Mi i
∑𝑤𝑖𝑀𝑖 𝑁1 𝑀12 +𝑁2𝑀22 +𝑁3𝑀32 ……

Mw = =
∑𝑊𝑖 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3……
Problems:
1. A polymer sample contain 100 molecules of molecular mass 1000g/mol 200 molecules of
molecular mass 2000g/mol, 500 molecules of molecular mass 5000 g/mol. Calculate number
average and weight average molecular weight.
𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
Number average molecular weight= Mn = =
∑𝑁 𝑁1+𝑁2+𝑁3+⋯
100𝑋 1000+200𝑋2000+500𝑋5000
= 100+200+500
1𝑋105 +4𝑋 105 +25𝑋105
= 800
= 3.75 x 103 g/mol

∑𝑤𝑖𝑀𝑖 𝑁1 (𝑀1)2 +𝑁2(𝑀2)2 +𝑁3(𝑀3)2 ……
Weight average molecular weight = Mw = =
100𝑋 (1000)2 + 200𝑋(2000)2 + 500𝑋(5000)2

100𝑋1000 + 200𝑥2000 + 500𝑥5000
1𝑋108 +8𝑋108 +125𝑋108

= 30𝑋(10)5
= 4.46 x 103 g/mol
2. A polymer sample contains 5 molecules having molecular weight 2000, 4 molecules having
molecular weight 3000, 3 molecules having molecular weight 4000. Calculate number average
and weight average molecular weight.
𝑤 𝑁1𝑀1+𝑁2𝑀2+𝑁3𝑀3+⋯.
No. average molecular weight = Mn = =
∑𝑁 𝑁1+𝑁2+𝑁3+⋯
5𝑋 2000+4𝑋3000+3𝑋4000
= 5+4+3
10000+12000+12000
= 3+4+5
= 2833.3 g/mol
∑𝑤𝑖𝑀𝑖 𝑁1 (𝑀1)2 +𝑁2(𝑀2)2 +𝑁3(𝑀3)2 ……

Weight average molecular weight = Mw = =
5𝑋 (2000)2 +4𝑋(3000)2 +3𝑋(4000)2

= 5𝑋2000+4𝑥3000+3𝑥4000
20𝑋106 +36𝑋106 +48𝑋106

= 10𝑋(10)3 + 12𝑋(10)3 +12𝑋(10)3
106 (20+36+48)
= = 3058.8 g/mol
103 (10+ 12+12
Conducting polymers:
An organic polymer with highly delocalized pi- electron system, having electrical conductance
of the order of a conductor is called a conducting polymer.
Synthesis:
The conducting polymers are synthesized by doping in which charged species are introduced in
organic polymers having pi- back bone. The important doping reactions are
1. Oxidative doping ( p-doping )
2. Reductive doping( n- doping )
3. Protonic acid doping ( p- doping )
Oxidative doping (p- doping): In this process pi- back bone of a polymer is partially oxidized
using a suitable oxidizing agent. This creates positively charged site on polymer backbone,
which are current carriers for conduction.
The oxidising agents used in p- doping are iodine vapour, iodine in CCl4, HBF4,
perchloric acid and benzoquine.
Mechanism of conduction in polyacetylene by Oxidative doping
CH2 Polyacetylene
H2C
I oxidation
I2 in CCl4
CH2 Radical ion

H2C (polaron)
+ I3 -
II oxidation
I2 in CCl4
+ I3 - CH2 Biradical ion

H2C (bipolaron)
+ I3 -
Recombination of radicals
-
+ I3 CH2 Conducting
H2C
+I - Polyacetylene
3
The removal of an electron from the polymer pi- back bone using a suitable oxidising agent leads
to the formation of delocalized radical ion called polaron. The second oxidation of the chain
containing polaron followed by radical recombination yields two charge carriers on each chain.
The positively charged sites on the polymer chains are compensated by anions I-3 formed by the
oxidising agent during doping.
The delocalized positive charges on the polymer chain are mobile, not the dopant
anions. Thus these delocalized positive charges are current carriers for conduction. These
charges must move from chain to chain as well as along the chain for bulk conduction.
Reductive doping (n- doping): In n- doping, pi back bone of a polymer is partially reduced by a
suitable reducing agent. This creates negatively charged sites on polymer backbone. These
negatively charged sites are responsible for the conduction. Reducing agent is solution of sodium
naphthalide in tetrahydrofuran
Mechanism of conduction in polyacetylene by Reductive doping
CH2 Polyacetylene
H2C
I reduction
Sodium naphthalide in THF
CH2 Radical ion

H2C (polaron)
Na+
II reduction
Sodium naphthalide in THF
Na+ CH2 Biradical ion
H2C (bipolaron)
Na+
Recombination of radicals
Na+
CH2 Conducting
H2C Polyacetylene
Na+
The addition of an electron to the polymer backbone by using a reducing agent generates a
radical ion or polaron. A second reduction of chain containing polaron followed by the
recombination of radicals yields two charge carriers on each chain. These charged sites on the
polymer chains are compensated by cations (Na+ ions) formed by the reducing agent.
The negative charges on the polymer chains are mobile and are responsible for
conduction.
Applications
 As electrode material for commercial rechargeable batteries(coin type batteries).
 As conductive tracks on printed circuit boards.
 As sensors-humidity sensor, gas sensor, radiation sensor, biosensor for glucose,galactose
etc.
 In electrochromic display windows.
 In information storage devices.
 As film membranes for gas separations.
 In light emitting diodes.
 In fuel cells as the electro catalytic materials.
Graphene oxide:
Carbon can able to form different allotropes such as Diamond, graphite,

buckminsterfullerene, nanotubes, nano buds, and nanoribbons because of its valency.
Graphene is a single atomic layer of carbon in which a layer of sp2 bonded carbon atom
arranged in a hexagonal or honeycomb lattice.
Graphene oxide is two-dimensional materials stack together to form graphite oxide is a
compound of carbon, oxygen, and hydrogen arranged in variable ratio. It contains a
hydroxyl (-OH), alkoxy (C-O-C), carbonyl (C=O), the carboxylic acid (-COOH), and
other oxygen-based functional groups. The oxygen-containing functional group
introduces both sides of a single graphite sheet and overcome the inter -sheet in van der
Waals force and enlarges the interlayer spacing and disturbs the sp2 bond of graphene so
reduces the conductivity of graphene oxide.
Structure of Graphene Oxide
Preparation of Graphene Oxide:

Hummer’s method of synthesis Graphene oxide was synthesized by Hummers method
through oxidation of graphite. The stepwise preparation is given as follows:
1. Graphite flakes (2 g) and NaNO3 (2 g) were mixed in 50 mL of H2SO4 (98%) in 1000
mL volumetric flask kept under at ice bath (0-5°C) with continuous stirring.
2. The mixture was stirred for 2 hrs at this temperature and potassium permanganate (6 g)
was added to the suspension very slowly. The rate of addition was carefully controlled to
keep the reaction temperature lower than 15°C.
3. The ice bath was then removed, and the mixture was stirred at 35°C until it became
pasty brownish and kept under stirring for 2 days.
4. It is then diluted with slow addition of 100 ml water. The reaction temperature was
rapidly increased to 98°C with effervescence, and the color changed to brown color.
5. Further this solution was diluted by adding additional 200 ml of water stirred
continuously.
6. The solution is finally treated with 10 ml H2O2 to terminate the reaction by appearance
of yellow color.
7. For purification, the mixture was washed by rinsing and centrifugation with 10% HCl
and then deionized (DI) water several times.
8. After filtration and drying under vacuum at room temperature, the graphene oxide
(GO) was obtained as a powder.
Green Fuels:
Energy can neither be created nor be destroyed; it can only be changed from one form to another.
Thus, we cannot produce energy to do certain work. Therefore, we use certain substances which
help us to transform one form of energy into another form. Hence a fuel is defined as a
combustible substance, which on burning produces significant amount of heat which can be used
economically for industrial and domestic purposes.
Types of Fuels:
Fuels can be generally classified on the basis of two factors:
1. On the basis of their fuels state:

 Solid Fuels
 Liquid Fuels
 Gaseous Fuels
2. On the basis of their occurrence:
 Natural Fuels
 Artificial Fuels
Green fuels are carbon-neutral or even carbon-free alternatives to fossil fuels. Produced
from hydrogen and electricity from renewable sources, they are seen as crucial to
decarbonize heavy industries, shipping or head generation in the future. In sectors, where
direct electrification is not feasible, green fuels allow a smooth transition from fossil to
sustainable energy sources – as they can be used in existing storage and propulsion
systems.
Past and future perspective of green fuels:
Due to their high energy density, green fuels are well suited for both transport and power
generation. However, their production is energy-intensive and not yet economically viable. Even
though they are being tried and tested extensively, there is still a lack of infrastructure for mass
production. Therefore, facilities have to be scaled-up to reduce costs, and renewable power
generation must be expanded.
Today, most hydrogen is not produced from carbon-neutral energy sources, but with natural gas
(gray hydrogen), coal (brown or black hydrogen), nuclear power (pink or red hydrogen) or from
fossil fuels combined with carbon capture (blue hydrogen). But in order to reduce the carbon
footprint, green hydrogen is paramount. Hydrogen requires storage and transportation at either
high-pressure or very low temperatures; conversion to other green fuels with higher energy
density can mitigate that issue.
SOLAR ENERGY
Introduction:
A wide range of power technologies exist which can make use of the solar energy
reaching earth and converting them into different useful forms of energy. Solar energy utilization
can be of two types, direct solar power and indirect solar power.
Direct solar power: It involves only one step transformation into a usable.
Ex: 1) Sun light hits photovoltaic cell (also called photoelectric cell) generating electricity.
2) Sun light hits the dark absorbing surface of a solar thermal collector and the surface warms.
The heat energy may be carried away by a fluid circuit.
Indirect Solar Power: It involves more than one transformation to reach a usable form.
Ex: 1) Vegetation uses photosynthesis to convert solar energy to chemical energy, which can
later be burnt as fuel to generate electricity (biofuel). Methane (natural gas) may be derived from
the biofuel.
Photovoltaic cells:
Introduction: Photovoltaic cells or solar cells are semiconductor devices that convert
sunlight into direct current electricity. As long as light is shining on the solar cell, it generates
electrical power. When the light stops, electricity stops.
Groups of photovoltaic cells are electrically configured into modules and arrays, which
can be used to charge batteries, operate motors and to power any number of electrical loads.
With the appropriate power conversion equipment, photovoltaic systems can produce alternating
current (AC) compatible with any conventional appliances.
Working principle of photovoltaic cells:
All electromagnetic radiations including sunlight consist of particles called photons. The
photons carry a certain amount of energy given by E = hc/λ
Where h is Planck’s constant, c is the velocity of light, λ is the wave length of radiation.
When electromagnetic radiation (sunlight) is incident normal to the plane of the solar cell, the
photons which possess energy sufficient to overcome the barrier potential are absorbed &
electron-hole pairs are formed. Electrons are driven out into the external circuit & could be
stored & used for various applications.
Construction of a photovoltaic cell & its working:-

A typical silicon photovoltaic cell is composed of a thin wafer consisting of an ultra thin
layer of Phosphorous doped (n-type) silicon on top and Boron doped (p-type) silicon at the
bottom. Hence a p-n junction is formed between the two. A metallic grid forms one of the
electrical contacts of the diode and allows light to fall on the semiconductor between the grid
lines. An antireflective layer between the grid lines increases the amount of light transmitted to
the semiconductor. The cells other electrical contact is formed by a metallic layer on the back of
the solar cell.
When light radiation falls on the p-n junction diode, electron-hole pairs are generated by
the absorption of the radiation. The electrons are drifted to and collected at the n-type end
and the holes are drifted to and collected at the p-type end. When these two ends are
electrically connected through a conductor, there is a flow of current between the two ends
through the external circuit. Thus photoelectric current is produced and available for use.
Solar energy is the energy which has a greatest potential of acting as alternate source of energy
because of the reason that the reserves of fossil fuels are very limited and are depleted very fast.
Advantages:
1) Fuel source is vast and essentially infinite.
2) No emission, no combustion or radioactive residues for disposal. Does not contribute to global
climate change or pollution.
3) Low operating costs (no fuel).
4) No moving parts and no wear or tear.
5) Quick installation
6) High public acceptance and excellent safety record.
Disadvantages:
1) Sunlight is a diffuse source; i.e. it is relatively low density energy.
2) High installation costs.
3) Energy can be produced only during the day time.
Green hydrogen:
Hydrogen is a colorless, odorless, tasteless, and nonpoisonous gas under normal conditions on
Earth. It typically exists as a diatomic molecule, meaning each molecule has two atoms of
hydrogen; this is why pure hydrogen is commonly expressed as “H2”. Hydrogen is the most
abundant element in the universe, accounting for 90 percent of the universe by weight. However,
it is not commonly found in its pure form, since it readily combines with other elements. It is
also the lightest element, having a density of 0.08988 grams per liter at standard pressure.
Hydrogen has several important chemical properties that affect its use as a fuel:
 It combines with oxygen to form water, which is absolutely necessary for life on this
planet.
 It has a high energy content per weight (nearly 3 times as much as gasoline), but the energy
density per volume is quite low at standard temperature and pressure. Volumetric energy
density can be increased by storing the hydrogen under increased pressure or storing it at
extremely low temperatures as a liquid. Hydrogen can also be adsorbed into metal
hydrides.
 Hydrogen is highly flammable; it only takes a small amount of energy to ignite it and make
it burn. It also has a wide flammability range, meaning it can burn when it makes up 4 to 74
percent of the air by volume.
 Hydrogen burns with a pale-blue, almost-invisible flame, making hydrogen fires difficult to
see.
 The combustion of hydrogen does not produce carbon dioxide (CO2), particulate, or sulfur
emissions. It can produce nitrous oxide (NOX) emissions under some conditions.
 Hydrogen can be produced from renewable resources, such as by reforming ethanol (this
process emits some carbon dioxide) and by the electrolysis of water (electrolysis is very
expensive).
Green hydrogen is the most basic electrofuels (e-fuels). It is created by splitting water (H2O) into
oxygen (O) and hydrogen (H2) in a process called electrolysis, using power from renewables.
Hydrogen can then be used either directly as fuel e.g. for internal combustion engines – or as
core component for the synthesis of other green fuels such as ammonia (with nitrogen) or
methanol, SNG (with carbon, captured from the air, biomass or industrial plants' exhaust gases).
Generation of hydrogen by electrolysis of water: Alkaline water electrolysis

Water electrolysis is one of the simplest methods used for hydrogen production. Water
electrolysis is mainly carried out to yield pure hydrogen and oxygen gases. It involves passing an
electric current through the water which results in the decomposition of water into hydrogen and
oxygen.
Alkaline Water Electrolysis
Two electrodes or plates that are made from an inert metal such as platinum or iridium are placed
in the water. A DC electrical power source is connected to these plates. At the cathode (where
electrons enter the water) part Hydrogen will appear. On the anode side, oxygen will appear. If
we consider the ideal faradaic efficiency, hydrogen will be produced twice the amount of
oxygen. On the other hand, both will be proportional to the total electrical charge conducted by
the solution. However, in some cells side reactions can occur and different products are formed
with less than ideal faradaic efficiency.
The cell potential of electrolysis of pure water is negative and hence is thermodynamically
unfavourable. Because of the low concentration of ions and the interfaces to be crossed electrons
an extra voltage (Overvoltage) at each electrode is needed to about 0.6V. In practice, continuous
electrolysis of pure water is possible only at an external voltage of 2.4V. Since the electrolysis of
pure water is thermodynamically non-feasible, methods to make it kinetically feasible are being
investigated. One of the methods is to increase the conductivity by increasing the number of ions
available by adding acid, base, or non-reacting salts.
Additional hydroxyl ions, release their electrons to anode, while electrons at the cathode oxidize
water molecules near it.
Half reactions of electrolysis in the presence of a base are-
Like electrolysis in an acid medium, electrolysis in the basic medium also needs much lower
potential.
Advantages of Alkaline water electrolysis:

1. It has the advantage of being able to produce hydrogen using only renewable
energy.
2. The main advantage of alkaline water electrolysis over other water electrolysis
technology lies in the fact that alkaline electrolysers can be made of abundant and
inexpensive materials.
3. Simple iron or nickel steel electrodes are used to produce hydrogen and nickel
used for oxygen production.
4. Higher gas purity due to lower gas diffusivity in alkaline electrolyte.
Electrolysis of water – Proton Exchange Membrane Electrolysis

Hydrogen can be obtained from different sources of raw materials including water.
Among many hydrogen production methods, eco-friendly and high purity of hydrogen
can be obtained by water electrolysis. However, In terms of sustainability and
environmental impact, PEM water electrolysis was considered as most promising
techniques for high pure efficient hydrogen production from renewable energy sources
and emits only oxygen as byproduct without any carbon emissions.
In PEM water electrolysis, water is electrochemically split into hydrogen and oxygen at
their respective electrodes such as hydrogen at the cathode and oxygen at the anode. PEM
water electrolysis is accrued by pumping of water to the anode where it is spilt into
oxygen (O2), protons (H+ ) and electrons (e). These protons are traveled via proton
conducting membrane to the cathode side. The electrons exit from the anode through the
external power circuit, which provides the driving force (cell voltage) for the reaction. At
the cathode side the protons and electrons re-combine to produce the hydrogen, the
following mechanism as shown in Figure. Typically, in PEM water electrolysis noble
metal based electrocatalysts are used such as Pt/Pd-based catalysts as cathode towards the
hydrogen evolution reaction (HER) and RuO2/IrO2 catalysts as anode for oxygen
evolution reaction (OER).
Advantages of PEM water electrolysis:
1. PEM water electrolysis has great advantages such as compact design.
2. High current density (above 2 A cm-2)
3. High efficiency, fast response, small footprint.
4. Operates under lower temperatures (20–80oC) and produced ultrapure hydrogen
and also produced oxygen as a byproduct.
MODULE V
E-WASTE MANAGEMENT
E-Waste: Introduction, sources of e-waste, Composition, Characteristics, and Need of e waste

management. Toxic materials used in manufacturing electronic and electrical products, health
hazards due to exposure to e-waste. Recycling and Recovery: Different approaches of recycling
(separation, thermal treatments, hydrometallurgical extraction, pyrometallurgical methods, direct
recycling). Extraction of gold from E-waste. Role of stake holders in environmental management
of e-waste (producers, consumers, recyclers, and statutory bodies).
Self-learning: Impact of heavy metals on environment and human health.
E waste:
All electronics and electrical items which is discarded on completion of their useful life together
is called as E-waste
Sources of E-Waste:
1. Computer peripherals: monitor, keyboard, mouse, motherboard, laptops, CDs etc

2. Telecommunication device: phones, cell phones, routers, pagers, fax machine etc.
3. Household appliances: washing machines, vacuum cleaners, toasters, drying machines,
refrigerators, irons, air conditioners etc.
4. Industrial electronics: sensors, medical device, automobile device etc.

5. Electrical devices: switches, wires, bulbs etc
Composition
1. E-waste contains about 65% of iron, steel, and other metallic materials including costly
metals like platinum, gold, silver, and toxic metals like lead mercury, cadmium,
chromium etc.
2. E-waste contains about 21% of polymeric non biodegrable materials including PVC (poly
vinyl chlorides), polychlorinated biphenyl and brominated flame retardant plastics.
3. E-waste also contains about 11.8 % of CRT (Cathode Ray Tube) and LCD screen and
other materials like glass and ceramics.
Applied Chemistry for CSEStream(22CHES12) 1

MODULE V
Characteristics of e Waste
 E waste contains hazardous substances such as lead, polychlorinated biphenyls (PCBs),
polybrominated biphenyls (PBBs), mercury, polybrominated diphenyl ethers (PBDEs),
brominated flame retardants (BFRs), and toxic metal like mercury, lead, cadmium,
chromium as well as valuable substances such as iron, steel, copper, aluminum, gold,
silver, platinum, palladium, and plastics.
 Hazardous substances like plastic, lead, mercury, cadmium, arsenic etc. pose health
hazards on the human being to the most when treated in uncontrolled condition via air,
water and soil. The people engaged in the recycling and recovery from the e waste are
severely affected with chronic and acute diseases like cancer etc.
Need for E- waste management

 E waste is a complex mixture of metals, nonmetals, organics, and ceramics. Disposing of
this mixture in land fill can cause environmental issues. This results in serious
environmental problems due to passing of dangerous chemicals into soils, water, air and
human beings.
 Also it results loss of metals whose quantities are limited in the earth’s crust. Due to these
facts, proper efficient E-waste management is required for the recovery and reuse of
components of E- wastes
 E- waste contains hazardous and non-hazardous substances. Hazardous substances are

toxic and affect the quality of ecosystem and also the human health. Hazardous
substances include lead, mercury, cadmium, zinc, yttrium, chromium, beryllium and
nickel.
 Organic compounds like chlorofluorocarbon, polycyclic aromatic hydrocarbons,

polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), brominated
flame retardants (BFRs) etc.
TOXIC MATERIALS USED IN MANUFACTURING ELECTRONIC AND

ELECTRICAL PRODUCTS // HEALTH HAZARDS DUE TO EXPOSURE TO E-
WASTE
Toxic materials used in manufacturing electronic and electrical products are hazardous. Hazardous
substances are toxic and can affect the quality of ecosystem and have harmful effects on human health.
These include
1. Heavy metals like Cd, Cr, Pb and Hg
MODULE V
2. Organic compounds like CFC (chlorofluorocarbons), ployacyclic aromatic hydrocarbons,

(PAHs), Poly chlorinated biphenyls(PCBs) etc.
Constituents sources Health effect

Lead Solder in Damage to central and peripheral nervous system,
printed circuit blood system, kidney damage, effect the brain
development of children
board, glass,
gaskets in
computer
monitor panel
Cadmium Chip resistors Accumulate in kidney and liver, causes nerval damage
and
semiconductors
Mercury Relays and Chronic damage to brain and respiratory system.

switches,
printed circuit
board
Plastic Circuit board, Burning produces dioxin. It causes reproductive and
including cabinets and development problem. Immune system damage
cables
PVC
Beryllium fond in carcinogenic and causes lungs cancer, skin
motherboard diseases
RECYCLING AND RECOVERY OF E-WASTE

In e-waste, among various components metals contribute to the significant economic value and
efforts are focused on extracting the metals during recycling operation.
DIFFERENT APPROACHES OF RECYCLING
SEPARATION &THERMAL TREATMENTS
The recycling of e-waste is initiated with physical or mechanical pre-process.
 The first step involves physical removal of toxic materials and unwanted components

MODULE V
 Manual dismantling and separation of components such as PCBs, monitors, batteries etc into
various fractions like metals, ceramics, plastics, wood and paper using hammer, screwdrivers
and conveyer beds for disassembling.
 In second step shredding of materials mechanically through crushers or grinders to collect

fragments of metal bearing components. Metals such as aluminium and copper can be
separated from non-metallic components from eddy current method.
 Next the waste is passed through electrical separators to separate metallic and nonmetallic
components.
 Magnetic separator is used to ferrous metals.
 Gravity separation is used to separate Al metal.

 Finally, after physical separation, various chemical treatments are employed to recover
metals.
HYDROMETALLURGY METHOD
There are 3 stages in metal recovery by hydrometallurgy method
1. Pretreatment stage
2. Chemical treatment stage
3. Metal recovery stage
In the pretreatment step, E- waste is manually dismantled to separate various fractions like
metals, ceramics, plastics, papers and wood. The technique such as gravity separation,
electrostatic separation, magnetic separation and eddy current separation are used to separate
metals from other fractions.
In this method metals are leached into solutions by treating with different leaching reagents.
The techniques are given below
a. Cyanide leaching
Even though cyanide solutions are toxic, they are mainly used to leach gold metals. Sodium salts of 3-
nitrobenzene sulphonic acid with KCN in the presence of oxygen are used to extract gold.
b. Acid and alkaline leaching;

MODULE V
Nitric acids, sulphuric acid, hydrochloric acids are used for leaching of targeted metals. Organic acids
such ascorbic acid acetic acids and citric acids are used to leach light metals from batteries and mobile
devices.
c. Thiosulphate leaching
Thiosulphate is used as alternative leaching agent for the recovery of precious metals like gold and silver.
Ammonium thiosulphate solution is used to solubilize gold, silver, platinum and other precious metals in
form of anionic stable complex. This reagent is safe nontoxic, non-corrosive and metal can be recovered
from the complex.
d. Thiourea leaching
Thiourea forms a cationic soluble complex with target metal.Thiourea gives quick rates of leaching less
interference of ions, is environmentally friendly, and has low cost. In printed circuit boards, the gold and
silver selectively forms a metal-thiourea cationic complex.
e. Halide leaching
Chloride, bromide and iodide ions can be used to leach gold from the PCB waste. They are cheaper,
selective to the target and ideal leaching agent

In the last step metal is recovered from leach solution. Varieties of methods like electro
deposition, solvent extraction, ion exchange, adsorption, precipitation and cementation are used
to recover metals from leached solution.
a) Solvent extraction
In this method leaching solution is treated with an organic solvent in a separating funnel. it
results in two phase system. Metal is extracted from leached solution phase to organic phase.
Different extractants such as anionic, cationic, or solvating type are employed.

Example: Diamine extractants is used for platinum and palladium.
Anionic type amide extractants is used for gold, iridium and tungsten.
b) Electrodeposition:
In this method pure metal is obtained from leached solution by electro deposition. Pure metal is
used as cathode and inert metal is used as anode is dipped leached solution. When current is
applied pure metal is electrodeposited on cathode.
Example: lead, tin and copper from PCBs can be recovered by electrodeposition.
c) Adsorption
MODULE V
Metal can be leached from the leached solution by adsorption on appropriate adsorbemt.
Activated carbon is founf to be effective adsorbent.Example: Adsorption of gold complex on
activated carbon is effective, cost effective process.
d) Ion exchange
This is improved version of solvent extraction method. Solvent extracting reagents are
impregnated on polymer beads. The functional groups of reagents act as chelating groups and
selectively bind to the metals. This method is used for selective recovery of the desired metal
ions. Ion exchange resins have found effective in recovering gold from cyanide and thisulphate
leach solutions
PYROMETALLURGICAL PROCESS
Pyrometallurgy process is used to extract pure nonferrous and precious metals from e-waste. The
methods require high temperature to reduce /extract metals. Smelting, incineration, combustion,
pyrolysis, and molten salt process are the main pyrometallurgical methods employed for
recovery of metals of e-waste .
1. Smelting
Copper smelting is commonly used for recovery of nonferrous metal fractions from e-waste.
The processed scrap after preliminary stage contains mainly Iron, Aluminium, Copper, Lead,
Tin, antimony, Zinc and precious metals as metallic constituents. The mixture is fed to high
temperature furnace of copper smelters. The copper metal is converted to liquid copper. The
impure copper undergoes electro refining process to get pure copper (99.99 %). The precious and
valuable metals like Au, Pt, Lead, Tin and antimony are recovered from sludge with high
recovery rates of 90% using hydrometallurgical process. Here iron, silicon and aluminium are
not recovered but are collected as slag.
2. Combustion
It is a low technology, low-cost method which focuses on recovery of precious metals. The
ewaste is subjected to open burning in uncontrolled manner which releases all sorts of pollutants
into atmosphere. The method is highly dangerous for the environment and also increases the
health risk of all the workers involved in it.
3. Incineration
It is a controlled combustion of waste with suitable emission units. The incinerator has two
connected furnaces. In first furnace e-waste is burnt at temperature 800oC and in second furnace
MODULE V
for gaseous products of the first incinerator are further oxidised at 1110oC. Heavy metals and fly
ash are collected at the bottom. Hydrometallurgical process is used for further recovery of
metals. These methods are not advisable due to pollutant gas emission and low metal recycling
performance.
4. Pyrolysis
Pyrolysis is a thermal decomposition of e-waste at higher temperature in an oxygen free
environment. During pyrolysis irreversible thermal decomposition reactions takes place leading
to the formation of low molecular weight products (gases and Liquids) at temperature between
450oC and 1100oC. The gases, chars and oils produced have an economic value and can be used
as fuel. The metallic components can be separated by separation. The process also involves
release of toxic halogens along with flue gases into atmosphere.
5. Molten salt Process

In this method inorganic salts such as potassium hydroxide (KOH)-sodium Hydroxide (NaOH)
are used at different temperature between 3000C and 1100oC in a furnace depending upon the
requirement. E-waste is fed with the salt and salt is melted at desired temperature in an inert
atmosphere. The organic part decomposes in salt forming carbonate and silicates and gets
trapped in salt. Halogens are converted to alkali metal halides which remain in molten salt.
Molten salts dissolve glasses, oxides and to destruct plastics present in wastes without oxidizing
the most valuable metals. This method is efficient for recovering a copper-rich metallic fraction.
A large quantity of hydrogen is produced and might be used as fuel gas. The metallic component
is collected at the bottom of the furnace after removing the molten salt by washing with hot
water. The metal is further processed to get pure metal.
DIRECT RECYCLING OF E-WASTE

In this process the electronic components are harvested directly from e-waste without breaking
them further into small components. The harvested materials are further processed with healing
methods to regenerate recycled materials. The regenerated materials have performance
equivalent to originally manufactured materials. Thus, in this method the complicated chemical
and metallurgical steps involved in conversion of e-waste components into chemicals are
avoided. The process requires less energy and is eco-friendly. There are certain problems related
with this method. Direct regeneration of components depends upon state of health of used
electronic materials. Defects and impurities accumulated during usage could affect the quality of

MODULE V
refurbished active material. Presently direct recycling of lithiumion batteries is studied. Here
battery is discharged first to ovoid short circuiting and selfignition of battery and dismantled to
separate anode, cathode, electrolyte and separated.
These components are not dismantled further. Here each component is regenerated using
appropriate process to recover its function. These components are reassembled for reuse.
EXTRACTION OF GOLD FROM E-WASTE:
Gold metal has good electric conductivity and chemical stability and hence it is used for making
integrated circuits of electronic devices, coating for contacts and connectors. E-wase contains 10
times more excessive concentration of gold compared to gold ores. Among the E waste PCBs are
rich in metals. It contains around 35% of Cu, 0.16% Ag, and 0.13% gold by weight. Several
methods are pyrometallurgy, hydrometallurgy, biometallurgy, microwave treatment etc are
employed to recover precious, metals from E-waste. Among these, recovery of metals
hydrometallurgy is more economical.
Hydrometallurgy method of Extraction of gold from E waste

There are 3 stages in metal recovery by hydrometallurgy method\
Pretreatment stage
In the pretreatment step, e waste is manually dismantled to separate various fractions like metals,
ceramics, plastics, papers and wood. The technique such as gravity separation, electrostatic
separation, magnetic separation and eddy current separation are used to separate metals from
other fractions.
Chemical treatment stage

In this method metals are leached into solutions by treating with appropriate chemical reagents.
Several leaching agents such as thiosulfate, alkaline cyanide, and many acids such as
hydrochloric acid, sulphuric acid and nitric acids can be used to leach gold into solution. Cyanide
leaching is the most common method used to extract gold metals. Sodium salt of 3- nitrobenzene
sulphonic acid with KCN in the presence of oxygen used as leaching agent. A water soluble
dicyanoaurate gold complex is obtained in the process
4 Au + 8CN- + O2 + 2H2O 4 Au (CN)2 - + 4 (OH) -

MODULE V
Metal recovery stage

In the last step metal is recovered from leach solution. Varieties of methods like electro
deposition, solvent extraction, ion exchange, adsorption, precipitation and cementation are used
to recover metals from leached solution. In electro deposition method, gold is extracted by
electro deposition of gold from dicyanoaurate gold complex. Pure gold metal is taken as cathode
and inert metal is used as anode is dipped leached solution. When current is applied gold is
electrodeposited on cathode.
ROLE OF STAKE HOLDERS IN ENVIRONMENT MANAGEMENT OF E-WASTE

(PRODUCERS, CONSUMERS, RECYCLERS AND STATUTORY BODIES)
The e-waste management program is designed by statutory government regulatory bodies. The
members of the body frame the policies and execute it for protection of the environment. To
achieve the plan of management of e-waste a green tax is collected from consumer through
manufacturer. Penalties are implied on manufacturer and consumers when green tax is not paid.
Manufacturing units must support the agenda of e-waste management by doing dismantling
processing of e-waste, management of scarp materials and reselling of recycled materials.
Consumer must pay green and must be aware of importance of e-waste management. All
stakeholders must effectively work in tandem form for effective e-waste management.
There are four stakeholders in environmental management of e-waste. They are as follows.
1. Statutory Government Regulatory bodies.
2. Producers (Manufacturing units).
3. Recyclers (Recycling units and collection units)
4. Consumers.
1. Statutory government Regulatory bodies
The statutory bodies play a Vitol role in management of e-waste. Main roles are:
a) To collect the green tax from consumer through producer.
b) Apply extra charges on producers (manufacturing units) in form of penalty when no

proper recycling is assured from manufacturing units.
c) Provide incentives in form of subsidy to recyclers and collectors when recycling of e-

waste is done properly.

MODULE V
d) To conduct programs of awareness in the society about importance of e-waste

recycling in reduction of hazardous substances.
2. Producers (Manufacturing units)

a) The accountability to collect green tax.
b) Charging an additional amount on consumer during sell of e-products and returning it
with interest at the time of exchange of e-product.
c) Forming the group of manufactures who monitor and encourage the recycling of e-
waste.
d) Bearing the transportation cost and collection fees to ease collection process.
e) Purchase the recycling material at fixed value and using of recycled e-waste during
manufacturing.
f) Giving discount to consumer on the basis of e-waste generated from gadget.

3. Recyclers (Recycling units &Collection Units)
a) The accountability of recycling units is dismantling, recycling processing of e-waste
materials, management of scarp materials and reselling of recycling materials
b) Establish collection units and group of people who can ensure return back of eproducts
by consumer in exchange offer or directly approach consumer for door-todoor collection.
c) Collect the e-waste from the collection units, dealer or retailer.

d) Providing incentives when proper collection of e-waste assured by collection units.
4. Consumer
a) The accountability to pay green taxes.
b) Develop self-awareness on e-waste management and involve in awareness programs.
c) Returning back of e-waste to collection units .

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MODULE 1: Sensors and Energy Systems

MODULE 1: Sensors and Energy Systems

Working of conductometric sensor

Applied Chemistry for CSE Stream (BCHES102) 1

Figure 1. Construction of Conductometric sensor

Application of conductometric sensor

i.Aptamer Technology for the Detection of Foodborne Pathogens and Toxins

Electrochemical reactions take place at electrode-electrolyte interfaces and provide a switch

Construction and Working

Applied Chemistry for CSE Stream (BCHES102) 2

Figure 2. Electrochemical Sensor

Application Electrochemical sensors-

Applied Chemistry for CSE Stream (BCHES102) 3

Figure 3. Thermometric sensor setup

A thermocouple is another common example of them. Thermocouple, is constructed from two

Figure 4. Thermostat sensor setup

Applied Chemistry for CSE Stream (BCHES102) 4

• In hazardous locations like nuclear power plants.

Figure 5. Optical sensor

Principle and Working-

Applied Chemistry for CSE Stream (BCHES102) 5

Figure 6. Beer-lamberts law

Eg: Colorimetry: a quantitative measurement of absorbance or reflectance spectra, is one of the

Applications of Optical Sensors

Sensors for the measurement of dissolved oxygen (DO)

Applied Chemistry for CSE Stream (BCHES102) 6

• Cathode : Working electrode-Ag

Anode (Pb): Oxidation: 2Pb → 2Pb2+ + 4e-

Cathode (Ag): Reduction: O2 + 4e- + 2H2O → 4OH-

Overall: 2Pb + O2 + 2H2O → 2Pb(OH)2

Electrochemical Sensors for-

Diclofenac is a nonsteroidal anti-inflammatory drug (NSAID). This medicine works by

Applied Chemistry for CSE Stream (BCHES102) 7

• Working electrode: Carbon Paste with

The electrochemical oxidation of DCF on carbon-based sensor at pH 7.0 is reversible reaction.

Electro-oxidation mechanism of DCF

b. For the detection of hydrocarbons (1-hydroxypyrene):

Urinary 1-hydroxypyrene (1-OHP) is a widely used biomarker as an indicator of exposure to

Working electrode: PAMAM/Cr-MOF/GO (Composite) [PAMAM: Dendrimer polyamidoamine

Applied Chemistry for CSE Stream (BCHES102) 8

Electro-oxidation scheme of 1-hydroxypyrene

2. Electrochemical Gas Sensors:

Figure 8. SOx sensor

Applied Chemistry for CSE Stream (BCHES102) 9

Anode reaction: 2Ag → 2Ag+ + 2e-

Cathode reaction: 2Ag+ + SO3 + 𝟏⁄𝟐O2 + 2e- → Ag2SO4

Total reaction was: 2Ag + SO3 + 𝟏⁄𝟐O2 → Ag2SO4.

SO3 was produced by the reaction can be checked by sensor.

1. It is used in thermal power plant.

(b) Detection of NOx

Figure 8. NOx sensor

Applied Chemistry for CSE Stream (BCHES102) 10

HNO2 + H2O → NO3- + 2e- + 3H+

3. Disposable sensor for the detection of-

Advantages of disposable sensors:

o They transduce physical, chemical, or biological changes in their environment to an

a. Biomolecules: Ascorbic acid

The desired biomolecules such as enzyme, hormones, antibodies etc. are

L-Ascorbic acid (AA) or adsorbate, commonly known as vitamin C, is an important water-