Module 2 Chem
Module 2 Chem
DEPARTMENT OF CHEMISTRY
SHAVIGE MALLESWARA HILLS, KUMARASWAMY LAYOUT
BENGALURU-560111
2022-23
Dayananda Sagar College of Engineering
Department of Chemistry
Module 2:
Monomers: Small molecules of low molecular weight, which combine to give a polymer, are
called monomers.
Degree of polymerization: The number of monomers used in the process is called degree of
polymerization.
Functionality: The total number of functional groups or bonding sites present in a monomer
molecule is called the functionality of the monomer.
Polymerization: Is the process of conversion of low molecular weight substances into high
molecular weight substances with or without the elimination of by products such as HCl,
H2O, NH3 etc.
Number Average and Weight Average:
Number Average: The number average molecular weight is defined as the total weight of
polymer divided by the total number of molecules.
Mn¯ =∑niMi
∑ni
(Where n1, n2 etc are number of particles having mass M1, M2 etc.)
That means
Mn¯=n1 M1 + n2 M2 + ------
n1 + n2+ ----
Weight average molecular weight (Mw¯): Molecular weight of each particle is
multiplied by totalweight of this species. These factors are added for allthe size species and
divided by the sum of weights ofall individual sizes.
Mw¯ = ∑niMi2
∑niMi
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That means
Mw¯ = n1 M12 + n2 M22 +
n1 M1 + n2 M2 +-----
NUMERICAL PROBLEMS ON POLYMER
1. A polymer sample contains 2, 3 and 4 molecules having molecular weights 2 x 103, 3
x 103 and 4 x 103 respectively. Solve for the number average and weight average molecular
weights of the polymer.
Answer: Mn¯= n1 M1 + n2 M2 + n3 M3
n1 + n2+ n3
150+200+350
=50307
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CONDUCTING POLYMERS
Conducting polymers or, more precisely, intrinsically conducting polymers (ICPs) are
organic polymers that conduct electricity. Such compounds may have metallic conductivity
or can be semiconductors. The biggest advantage of conductive polymers is their process
ability, mainly by dispersion. But, like insulating polymers, they are organic materials.
They can offer high electrical conductivity but do not show similar mechanical properties to
other commercially available polymers. The electrical properties can be fine-tuned using the
methods of organic synthesis and by advanced dispersion techniques. Organic polymers
with a highly delocalized pi electron system having electrical conductance of the orderof a
conductor is called conducting polymers.
Requirements for the polymer to be conducting:
1. Presence of delocalized pi electron (conjugation) in the main chain
2. Linearity/Planarity of the molecule
3. Presence of atoms having lone pair of electrons
Synthesis of Polyacetylene
Polyacetylene is the simplest linear synthetic polymer. Fundamental unit consists from one
carbon and one hydrogen atoms, as has been called simply (CH). Each carbon is ϭ bonded by
sp2 hybrid orbital to one hydrogen and two adjacent carbon atoms to form a planar chain
molecule. Polyacetylene is synthesized by catalytic polymerization of acetylene using
Ziegler-Natta catalyst (Et)3Al and titanium(IV) propoxide at 75°C, with a catalyst molar ratio
(Al/Ti) of 2.5.
Synthesis of polyacetylene.
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Graphene Oxide
Graphene oxide (GO), is a compound of carbon, oxygen, and hydrogen in variable ratios,
obtained by treating graphite with strong oxidizers. Graphene oxide by analogy to graphene is
a single-layer form of graphite having epoxide groups, carbonyl (C=O) and hydroxyl (-OH)
functional groups.
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2. Then 24g KMnO4 was gradually added into the flask with ice bath for 2 hours.
3. The mixture was diluted by 800ml de-ionized water (DI water). After that, 5% H2O2
was added into the solution until the color of the mixture changed to brown,
indicating fully oxidized graphite was obtained.
4. The resulting mixture is washed repeatedly by centrifugation with 10% HCl. The as-
obtained graphite oxide slurry was re-dispersed in DI water. Then, the mixture
washed with DI water to remove the residual acid until the pH was reached to ~7.
5. The resulting mixture is centrifuged and is vacuum dried at 60°C for more than 6 hrs
to GO powder.
Properties:
1. In contrast to graphene having high electrical conductivity (6500 Sm-1 ) GO is an
electrically insulating or semiconducting material having electrical resistivity around 1.64
× 10-4 because of disruption of sp2 bonding orbital of graphene due to presence of oxygen
functionality
2. Low thermal conductivity of 0.5–1 W m−1 K−1 making it not an ideal option for most
applications requiring good thermal properties
3. It is hydrophilic and easily dispersed in water and organic solvents.
4. Functionalization of graphene oxide can change graphene oxide’s properties.
5. High surface area
Applications:
1. Graphene Oxide is used is in the production of transparent conductive films after
being deposited on any substrate. Such coatings could be used in flexible electronics,
liquid crystal devices, chemical sensors, touch screen devices, LEDs
2. GO is used as electrode materials in batteries and double-layered capacitors, as well
as fuel cells and solar cells due to its extremely high surface area.
3. Drug-delivery systems: GO is used as drug delivery systems for anticancer drugs
because it does not target healthy cells, only tumors, and has a low toxicity.
4. As GO is a fluorescent material it is used for bio sensing applications.
5. Although GO shows poor performance in anode materials of Li-ion batteries, they
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have been used in the cathode materials successfully and also in dye-sensitized solar
cells.
6. GO shows good sensing abilities due to active surface and high surface area.
7. Chemically active nature and porous structure of graphene oxide have been utilized
for the enhancement of membrane properties and separation performance.
8. The fluorescent behavior of GO material is used for the optical biosensing
applications to detect different biological molecules, such as cancer biomarkers
glucose, H2O2, dopamine, food toxins, and metal ions.
Green energy: Introduction
Solar energy is an essential source of renewable energy. Utilization and conversion solar
energy utilization can be of two types
1. Direct solar power.
2. Indirect solar power.
Direct Solar Power: Direct solar power involves only one step transformation into a usable
form.
Example 1. Photovoltaic cells: It convert solar energy to electrical energy.
Example 2. Solar Thermal collector. Sunlight hits the dark absorber surfaces of a solar
thermal collector and surface warms the heat energy may be carried away by a fluid circuit.
Indirect solar power: Indirect solar power involves more than one transformation to reach
usable form.
Example, (i) plants convert solar energy to chemical energy when they are burnt.
(ii) Fossils fuels are obtained from plants which produce heat energy that can later be
burned as fuel to generate electricity.
(iii) Ocean thermal energy production uses the thermal gradient that is present across ocean
depths to generate power. This temperature difference is ultimately due to the energy of the
sun.
Photovoltaic cells
Photo-voltaic cells: Photovoltaic cells or solar cells are semiconductor devices that convert
sunlight into direct current. As long as light is shining on the solar cell it generates electrical
power. When the light stops electricity stops. Solar cells are generally classified into three
generations depending on time and categories of materials which are used for their
fabrication.
1. The most common solar cells available in the market are the first-generation solar
cells which comprise single and polycrystalline silicon.
2. Second-generation solar cells were introduced as a response to high material usage
and cost of silicon solar cell. To reduce the material usage the maximum film
thickness for this generation was brought down to a few nanometers to tens of
micrometers.
3. Third generation solar cell- dye-sensitized solar cells (DSSCs), perovskite, organic
solar cells, photo chemical cells, QDs,
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Working
The solar cell works on the principle of photoelectric effect which is phenomenon in which
electrically charged particles are released from or within a material when it absorbs
electromagnetic radiation. The effect is often defined as the ejection of electrons from a
metal plate when light falls on it.
Electromagnetic radiation consists of photon. The photon carries a certain amount of
energy. It is given by the Planck Constant equation is E=hc/λ, where h is called Planck
constant C is the velocity of light and λ is wavelength of the radiation.
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 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.
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Zone refining
Photovoltaic's deal with the conversion of sunlight into electrical energy. Classic photovoltaic
solar cells based on inorganic semiconductors i.e., silicon and today silicon is still the leading
technology on the world market of photovoltaic solar cells, with power conversion
efficiencies approaching 15 – 20% for mono-crystalline devices. An approach for lowering
the manufacturing costs of solar cells is to use organic materials that can be processed under
less demanding conditions. Their solution processability makes them a promising technology
for delivering cheap solar power. They are very strong light absorbers, with a 100 nm or so
thick film capable of absorbing most of the incident light.
Definition: An OSC is a type of photovoltaic that uses conductive organic polymers or small
organic molecules, for light absorption and charge transport to produce electricity from
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sunlight by the photovoltaic effect. Most organic photovoltaic cells are polymer solar cells.
Construction: These cells are made by sandwiching a layer of organic electronic materials
between two conductive layer of indium tin oxide (ITO) coated glass and and a layer of low
work function metal such as Aluminum, Magnesium or Calcium.
Working: Unlike classical p-n junction cells with spatially separated p- and n-type regions of
doped semiconductors, bulk hetero junction cells consist of an intimate mixture of two un-
doped (intrinsic) semiconductors that are mixed and that generate a randomly oriented
interface. Absorbed photons generate a bound, neutral excited state, an exciton. In order to
generate a current from these the exciton must be separated into its constituent electron and
hole and the charges extracted from the device. This is achieved by blending the organic
semiconductor with an electron acceptor.
1. Incident light creates and exciton in the donor material (P3HT) of the active layer.
2. Upon applied voltage, the exciton diffuses between the donor (P3HT) and the
acceptor (PCBM) material as hole and electron, respectively.
3. Hole diffuses from HOMO of polymer towards PEDOT:PSS and then to ITO.
4. Electron diffuses from LUMO of acceptor material (PCBM) towards the Al electrode.
5. Finally, electron from Al travels in the external circuit towards ITO generating
electricity.
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Department of Chemistry
A quantum dot solar cell is mainly the type of cell design which makes use of quantum
dots as the key absorbing photovoltaic material. These solar cells are designed so that they
can increase the maximum thermodynamic conversion efficiency which can be attained by
as much as 66%.
• Quantum dots are a special class of semiconductors, which are nanocrystals, composed of
materials from II-VI, III-V, or IV-VI groups
• The energy band gap increases with a decrease in size of the quantum dot
• The adjustable bandgap of quantum dots allow the construction of nanostructured solar cell
that is able to harvest more of the solar spectrum
• The structure and operation principle of QD sensitized photovoltaic cell is almost identical
to dye sensitized cells
Fig: (a) Quantum Dots Solar Cells, (b) Energy band diagram.
Construction: These cells are made by sandwiching a layer of photosensitive materials
between two conductive layer of Fluorine-doped Tin Oxide (FTO) coated glass/ flexible
transparent substrate. The subsequent layers are as follows
Working Principle
Upon absorption of a photon, a quantum dot is excited from the ground state (QD S) to a
higher energy state (QDS*).
Excitation process: QDS + hν→ QDS*
The absorption process results in the creation of electron-hole pair in the form of exciton.
Dissociation of the exciton occurs if the thermal energy exceeds its binding energy
Exciton dissociation: QDS*→ e-* + h+* (free carriers)
The excited electron is then injected in the conduction band of the wide bandgap
semiconductor nanostructured TiO2 thin film. This process will cause the oxidation of the
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Applications
Compared to conventional solar cells QDSSC development have shown that higher-power
conversion efficiency and hence can be used for solar to electrical energy conversion.
Hydrogen energy
Hydrogen is considered an alternative fuel under the Energy Policy Act of 1992. The interest
in hydrogen as an alternative transportation fuel stems from its ability to power fuel cells in
zero-emission vehicles, its potential for domestic production, and the fuel cell's fast filling
time and high efficiency. Hydrogen fuel is a zero carbon fuel burned with oxygen; provided it
is created in a zero carbon way. It can be used in fuel cells or internal combustion engines.
Regarding hydrogen vehicles, hydrogen has begun to be used in commercial fuel cell
vehicles, such as passenger cars, and has been used in fuel cell buses for many years. It is
also used as a fuel for spacecraft propulsion. In the early 2020s, most hydrogen is produced
by steam methane reforming of fossil gas. Only a small quantity is made by alternative routes
such as biomass gasification or electrolysis of water or solar thermochemistry.
Types of hydrogen fuel: It takes energy to produce molecular hydrogen. The source of
energy and the production method used to make molecular hydrogen determines whether
it’s classified as grey hydrogen, blue hydrogen or green hydrogen.
Grey hydrogen
Grey hydrogen is hydrogen produced using fossil fuels such as natural gas or coal. Grey
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hydrogen accounts for roughly 95% of the hydrogen produced in the world today. The two
main production methods are steam methane reforming and coal gasification. Both of these
processes release CO2. If the carbon dioxide is released into the atmosphere, then the
hydrogen produced is referred to as grey hydrogen. Grey hydrogen is not considered a low-
carbon fuel.
Blue hydrogen
Blue hydrogen is similar to grey hydrogen, except that most of the CO 2 emissions are
sequestered (stored in the ground) using carbon capture and storage (CCS). Capturing and
storing the carbon dioxide instead of releasing it into the atmosphere allows blue hydrogen
to be a low-carbon fuel. The two main production methods are steam methane reforming
and coal gasification, both with carbon capture and storage. Blue hydrogen is a cleaner
alternative to grey hydrogen, but is expensive since carbon capture technology is used.
Green hydrogen
Green hydrogen is hydrogen produced using electricity from clean energy sources. Green
hydrogen is considered low or zero-emission hydrogen because it uses energy sources such
as wind and solar which don’t release greenhouse gases when generating electricity. Green
hydrogen is made when water (H2O) is split into hydrogen (H2) and oxygen (O2). Water
splitting is also known as electrolysis, and requires an energy input. The method of
supplying electricity to split water is an expensive process, but much more
environmentally-friendly compared to the production of grey hydrogen.
Advantage:
1. Renewable and Readily Available
2. Hydrogen fuel cells do not produce any CO2 emissions
3. The refuelling process for hydrogen fuel cells is easy and takes about three
minutes
4. The energy density of hydrogen fuel cells is very high
Disadvantage:
1. It is expensive
2. Highly Flammable
3. Storage and transportation of hydrogen is more complex
4. This hydrogen production process is costly and emits carbon dioxide
Application: Hydrogen fuel cells can be used in a wide range of applications, including
transportation, material handling and stationary, portable, and emergency backup power.
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Dayananda Sagar College of Engineering
Department of Chemistry
Advantage
1. Renewable and Readily Available
2. Hydrogen fuel cells do not produce any CO2 emissions
3. The refuelling process for hydrogen fuel cells is easy and takes about three
minutes
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Department of Chemistry
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