Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT.

Bengaluru

Chemistry of Electronic Materials

Conductors, Semiconductors and Insulators:
Conductivity of materials can be explained on the basis of band theory. According to this theory,
there are three types of bands namely i) Conduction band ii) Valence band and iii) Forbidden gap

The band formed by a series of energy levels containing the valence electrons is called the
Valence Band (VB).
 It is highest occupied energy band.
 It may be completely filled or partially filled with electrons.

The next higher permitted energy band is called the Conduction Band (CB).
 It is lowest unoccupied energy band.
 It may be empty or partially filled with electrons.
 The electrons can move freely in the conduction band and hence the electrons in
conduction band are called conduction electrons.

The energy gap between the VB and CB is called the Forbidden Energy Gap or Forbidden Band.
 It is formed by a series of non-permitted energy levels above the top of valence band and
below the bottom of the conduction band.
 It is the amount of energy to be supplied to the electron in VB to get excited into the CB.
 When an electron gains sufficient energy, it ejects from the valence band creating hole,
which is supposed to behave as a positive charge.

Conductivity of a material depends on the available charge carriers (ionic) and their mobility,
valency of ions and the temperature. It is based on Ohm`s law, which states that the current (I)
flowing through a conductor is directly proportional to the applied potential (E) and
inversely proportional to the resistance (R).
Conductors: A conductor or electrical conductor is a substance or material that allows electricity
to flow through it. In conductors, electrical charge carriers (electrons or ions), move easily from
atom to atom when voltage is applied and also, conduction band and valence band are

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

overlapped. Therefore there is easy flow of electrons and thus they are good conductors of heat
and electricity. Typically, metals, metal alloys, electrolytes and even some nonmetals, like
graphite and liquids, including water, are good electrical conductors. Pure elemental silver is one
of the best electrical conductors. Other examples include copper, steel, gold, silver, platinum,
aluminium, brass, etc. Copper has the second-highest electrical conductivity of all metals
(5.9×107 Siemens/m).

Insulators: Materials that don't allow electrical current or heat to pass through them are known
as insulators. In insulators, due to a large forbidden gap between conduction and valence band,
there is no easy flow of charge carriers. Therefore, they are bad conductors of heat and
electricity. Most insulators are solids in nature. Ex:- wood, glass, quartz, plastic, etc. The
electrical conductivity of polymer is in the range of 10-10 to 10-8 S/m.

Semiconductor: Any of a class of solids (such as germanium or silicon) whose electrical

conductivity is between that of a conductor and an insulator. In semiconductors, because of small
gap (forbidden gap) in between conduction band and valence band, there conductivity lies
between that of conductors and insulators. However, their conductivity can be increased by
increasing temperature or by adding dopants. The conductivity of Silicon is 16.7 S/m.

1. Intrinsic semiconductor: Conductivity of a pure semiconductor increases with increase

in temperature.
2. Extrinsic semiconductor: Conductivity of a semiconductor increases with the addition
of dopants.
i) n-type Semiconductor: In n-type semiconductor, negatively charged (electrons)
species are responsible for conduction.
Ex-When pentavalent dopant like phosphorus (P) is added to tetravalent silicon (Si), four
of five electrons of P form four covalent bonds with four Si atoms and one electron
remain free in the lattice of Si.
p-type Semiconductor: In p-type semiconductor, positively charged species (holes) are
responsible for conduction.
Ex-When a trivalent dopant like aluminum (Al) is added to tetravalent silicon (Si), three
electrons of Al form three covalent bonds with three Si atoms and fourth covalent bond
contains only one electron from Si. So hole is created in the lattice of Si.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Organic Semiconductor Inorganic Semiconductor

Composition: Made of carbon-based Composition: Consist of non-carbon-
molecules, polymers, or pi-bonded based materials such as silicon,
structures, often including heteroatoms like germanium, and gallium arsenide.
hydrogen, nitrogen, and oxygen.
Structure & Bonding: Molecules are held Structure & Bonding: Typically have
together by weak van der Waals forces, crystalline structures with strong covalent
forming amorphous or polycrystalline thin bonds, forming well-defined energy bands.
films rather than highly ordered crystals.
Processing & Cost: Can be processed using Processing & Cost: Require more
low-cost, solution-based wet chemistry complex manufacturing processes, often
methods and offer high yields. involving single-crystal forms.
Flexibility: Inherently flexible and can Flexibility: Generally rigid and brittle.
conform to various shapes.
Mobility: Lower electron mobility Mobility: Exhibit high electron mobility
compared to inorganic semiconductors. due to their optimal crystalline structure.
Stability: More sensitive to humidity, Stability: More stable and durable in
oxygen, and high temperatures. various environmental conditions.
Applications: Used in flexible Applications: Widely used in transistors,
displays (OLEDs), solar cells, and diodes, and integrated circuits for
sensors. traditional electronics.

Pentacene (p-type):
Pentacene (C22H14) is a polycyclic aromatic hydrocarbon consisting of five linearly-fused benzene
rings. It is one of the most commonly studied conjugated organic molecules since its hole mobility
i.e., p-type semiconductor nature in which holes are the majority carriers.
When an electric field is applied, it generates excitons and exhibits high field-effect mobility. The
planar shape of pentacene facilitates easy crystal packing and the π-system extends over pentacene
molecules, enabling the intermolecular overlapping.

Properties:
 It has monoclinic crystal structure with strong π-π stacking, enhancing charge transfer ability.
 It is primarily a p-type (hole transport) material due to its low ionization energy (~5.0–5.3 eV).
 It has a charge carrier mobility of 1 cm²/V·s in high-quality films, making it suitable for organic
field-effect transistors (OFETs).
 It has strong absorption in the visible range (~600-700 nm), making it useful in organic
photovoltaics (OPVs).

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 Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Applications:
 It is used in Organic Field-Effect Transistors (OFETs) due to its high mobility (~1-3 cm²/V·s)
and low operating voltage.
 It is used in Organic Photo Voltaics (OPVs) due to its strong visible absorption (~600-700 nm) and
power conversion efficiency typically around 2-5%.
 It is used in light weight, flexible solar cells for wearable, and space applications.
 It is used in gas and chemical sensors due to surface sensitivity.
 It finds limited usage in Organic Light-Emitting Diodes (OLEDs) due to weak
fluorescence.

Perfluoropentacene (n-type):

Perfluoropentacene is a well-known n-type organic semiconductor in which electrons are the majority
carriers. It can be obtained by the fluorination of pentacene. Introduction of fluorine atoms enhances
electron density on the structure and possess high electron field-effect mobility.

Properties:
 It has a band gap of 1.7–1.9 eV (narrower than pentacene)
 It is a n-type (electron transport) material due to strong electron affinity (5.6 eV).
 It has electron mobility up to 0.1–1 cm²/V/s in thin films, making it suitable for logic circuits
when paired with p-type semiconductors like pentacene.
 It has strong absorption in the visible range (550–700 nm), suitable for organic
photovoltaics (OPVs).
 It forms charge-transfer complex type memory device when paired with pentacene.
 It is more stable than pentacene in air due to fluorination, which reduces oxidation and
degradation.
Applications: PFP has several important applications, including:

 Organic Field-Effect Transistors: PFP exhibits high charge carrier mobility and stability, making
it suitable for use in organic electronics, including flexible and printed circuits.
 Organic Photovoltaics: Its strong electron affinity and stability under ambient conditions make
PFP a potential n-type semiconductor in organic solar cells.
 Organic Light-Emitting Diodes: PFP can be used in OLEDs as a charge transport or emissive
material.
 Thin-Film Transistors: The stability and strong π-π stacking interactions in PFP make it suitable
for thin-film transistors.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Nano materials and quantum dots:

Nanotechnology is an interdisciplinary science involving chemistry, physics, material science, biology
and medicine. In broad sense, nanotechnology is the study of all the phenomena and processes
involved in the synthesis, properties and applications of nanostructures and nanomaterials. Now days,
everyone uses the term ‘nano’ for anything which is small. But in chemistry, a nanomaterial refers to a
material with at least one of its dimension is in nanoscale.
Nanomaterials are of interest because at this scale they show unique optical, magnetic, electrical, and
other properties. These emergent properties have the potential for great impacts in electronics,
medicine and other fields showing new applications.

Quantum dots (QDs) are zero dimensional nanomaterials, typically ranging from 2 to 10 nanometers
in diameter. They are often referred to as "artificial atoms" because of their unique electronic and
optical properties, which are governed by the laws of quantum mechanics.

Quantum confinement effect:

The quantum confinement effect is a phenomenon in quantum mechanics where the properties of a
material change dramatically when its dimensions are reduced to the nanoscale, typically less than 10
nanometers. Bulk materials electrons can move freely due to larger than the natural wavelength of
electron that is de Broglie wavelength. Electrons in the valence band are bound to atoms and restricts
the movement, whereas electrons in the conduction band are free to move.

When the materials cut down into smaller particles in the range of 2-10 nm. The electrons get
compressed/ squeezed into a very small space, now the materials size is comparable with the wave
length of free electron that is de Broglie wavelength. Instead of having continuous energy levels like
in bulk materials, due to less size of particles electrons can occupy only specific, discrete energy
levels. This spatial restriction electron to bind in particular energy levels is called quantum
confinement effect. This effect alters the material's electronic structure in a way that is not seen in
larger, "bulk" materials.

Size dependent properties of Quantum dots: Due to quantum confinement effect several properties
changed, those are catalytic property, electrical property, optical property, band gap (semi conducting
property), surface area to volume ratio.

Surface area to volume ratio: The SA: V ratio increases as the radius decreases. For a smaller
quantum dot, a larger proportion of atoms are at the surface. This means more surface area exposed to
the surrounding, improves the catalytic property, optical behaviour. For example, for spherical
quantum dot written as below.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

𝟒𝝅𝒓𝟐 𝟑
𝐴𝑟𝑒𝑎 𝑜𝑓 𝑠𝑝ℎ𝑒𝑟𝑒 = 𝟒 =
𝝅𝒓𝟑 𝒓
𝟑
Radius (nm) SA:V (1/nm)
10 nm 0.3
5 nm 0.6
2 nm 1.5
1 nm 3.0

As we can see, shrinking the dot to 1 nm increases the SA:V by 10x compared to a 10 nm dot.

Quantum dots are much more chemically reactive than the bulk material, because more atoms are
exposed at the surface, and are easily accessible to reactant molecules, to catalyse, sensing or
adsorption applications.

Band gap engineering: Band gap is one of the fundamental property of semiconductors, to determine
electrical and optical properties of materials.
The band gap energy of a quantum dot is inversely proportional to its size. Smaller QDs have a larger
band gap, requiring more energy to excite an electron. When the electron returns to its ground state, it
releases a higher-energy photon.
Color emission: The size of a quantum dot dictates the color of light it emits.
Smaller QDs: With a larger band gap, they emit higher-energy, shorter-wavelength light, appearing
bluer.
Larger QDs: With a smaller band gap, they emit lower-energy, longer-wavelength light, appearing red.
Broad absorption and narrow emission: Quantum dots can be excited by a broad range of wavelengths
but emit a narrow, symmetric, and specific color determined by their size. This allows different sized
QDs to be excited by a single light source for applications like multiplexed imaging.

Example (for CdSe QDs):

Dot Diameter Band Gap (approx.) Emission Color

2 nm ~2.7 eV Blue
4 nm ~2.3 eV Green
6 nm ~2.0 eV Red

Optical property:
The optical efficiency of quantum dots is also affected by their size.
High quantum yield: QDs are highly efficient at converting absorbed light into emitted light, a
property measured by their quantum yield. The efficiency can be improved by adding a protective
shell of a wider band gap material, which reduces access to surface defects that can quench
fluorescence.
Photostability: Compared to traditional organic dyes, quantum dots are very resistant to photo
bleaching, meaning their brightness lasts much longer with continuous excitation.
Enhanced absorption: The molar extinction coefficient, which indicates how strongly a substance
absorbs light, also varies with size. For some QDs like PbS, the absorption around the band gap
increases with the dot size.
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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Fluorescence lifetime: The lifetime of a QD's fluorescence the time it takes for an excited electron
to return to its ground state and emit a photon is also size-dependent. Larger QDs generally have a
longer fluorescence lifetime. This occurs because larger dots have more closely spaced energy
levels, which can temporarily trap the electron-hole pair for a longer period.
Visualization Example (CdSe Quantum Dots)
Diameter (nm) Band Gap (eV) Emission Color Emission Wavelength (nm)
~2.0 ~2.7 Blue ~460 nm
~3.0 ~2.4 Green ~520 nm
~4.0 ~2.2 Yellow ~560 nm
~5.0 ~2.0 Red ~620 nm

Electronic property:
As the size of these semiconductor QDs decreases, their electronic bandgap widens, causing
significant changes in their conductivity, exciton behaviour, and overall electrical characteristics.
Hopping conduction: In a quantum dots, electrons move by "hopping" from one QD to another. The
efficiency and nature of this hopping depend on the variations in size and spacing between QDs,
quantum confinement effects, and the energy barrier presented by the QD's.
Coulomb blockade: Since QDs are so small, the addition of a single electron significantly increases
their charging energy. This increased energy creates a large electrostatic repulsion, effectively
blocking subsequent electrons from entering the QD. This phenomenon, known as the Coulomb
blockade effect, makes individual QDs behave like a single-electron transistor.

Inorganic Quantum dots:

Synthesis of CdSe quantum dots by hot Injection method:

Prepare the selenium precursor: In a fume hood, Prepare NaHSe by reacting Se powder with NaBH₄
in water under inert gas.
Prepare the cadmium solution: In a three-neck round-bottom flask, Dissolve CdCl₂ in water, add
TGA- thioglycolic acid (molar ratio TGA: Cd ~ 2:1 to 4:1). Adjust pH to ~11 with NaOH to form
cadmium-thiolate complex.
Degas and heat: The cadmium solution is degassed under vacuum to remove all air and moisture. The
flask is then filled with an inert gas like argon or nitrogen and heated to a 60-90 °C temperature,
depending on the desired particle size.
Hot injection: Once the cadmium solution reaches the target temperature, the prepared selenium
precursor solution is rapidly injected into the flask using a syringe. The sudden, high concentration of
monomers triggers a burst of nucleation, forming seed crystals. A rapid color change is often observed.
Growth phase: After the injection, the temperature is typically lowered and held constant. The
remaining monomers deposit onto the initial seed crystals, causing them to grow uniformly. The size
of the resulting quantum dots can be controlled by varying the growth temperature and reaction time.
Quenching and purification: The reaction is quenched by removing the heat and adding a non-
solvent, such as methanol, which causes the nanocrystals to precipitate. The particles are then isolated
by centrifugation, washed to remove excess ligands and precursors, and dried.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Applications:
This emerging technology uses QDs that emit light directly when an electric current is applied,
CdSe QDs are used as color converters in LEDs and are a key component in emerging
electroluminescent QD-LED displays.
CdSe QDs are excellent light absorbers and have been investigated for their use in photovoltaic
devices, including quantum dot-sensitized solar cells (QDSSCs).
CdSe QDs are sensitive to light in the visible spectrum, making them useful in photodetectors and
sensors.
In addition to opto-electronics, the luminescent properties of CdSe QDs are valuable for biomedical
uses, especially in vitro. Bio-imaging and Diagnostics.
The strong light emission properties of CdSe QDs also allow them to be used in laser technology.

Synthesis of TiO₂ nanoparticles by Sol-Gel method for sensor applications:

A titanium precursor like titanium isopropoxide (TTIP) is hydrolyzed and then polymerized with a
solvent and catalyst, forming a gel. This gel is subsequently dried and calcined at elevated
temperatures to form crystalline TiO₂ nanoparticles.
1. Precursor Solution Preparation: It involves mixing a titanium alkoxide precursor (such as titanium
isopropoxide) with an alcohol solvent (like ethanol), with small amount of an acid (e.g., acetic acid or
nitric acid) or water as catalyst for the hydrolysis reaction.
2. Hydrolysis: The addition of water causes the titanium precursor to react, forming Ti(OH)₄.
3. Polymerization: The Ti(OH)₄ then undergoes condensation reactions, linking through ≡Ti-O-Ti≡
bonds to form a three-dimensional network of titanium oxide.
4. Sol Formation: This process results in a "sol," which is a stable colloidal solution.
5. Gelation: As the hydrolysis and condensation reactions continue, the sol's viscosity increases,
leading to the formation of a gel. This gel is a continuous, three-dimensional polymer network
containing trapped solvent molecules.
6. Drying and Calcination: The gel is dried, often in a hot-air oven, to evaporate the solvent and
further consolidate the material and calcined at a high-temperature (e.g., 400-600 °C) to form
nanoparticles.

Applications of TiO2 in sensors:

TiO₂ QDs are widely used in chemiresistive gas sensors, where their electrical resistance changes
when gas (H₂, NO₂, NH₃, CO, CH₄, H₂S) molecules adsorb on their surface.
These can be functionalized with biomolecules (enzymes) to detect biological targets such as
glucose, DNA and Protein/antibodies.
Due to strong light absorption and charge separation efficiency make them ideal for Photo
Electrochemical sensors to detect heavy metals such as Hg²⁺, Pb²⁺, Cd²⁺ and Organic pollutants
(phenol, pesticides) as well Biomolecules (dopamine, ascorbic acid, uric acid).
TiO₂ QDs’ has large surface area and hydrophilicity make them sensitive to water vapor and
volatile organic compounds (VOCs).

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Copper conductive ink by wet chemical reduction method:

Prepare precursor solution: Dissolve CuSO₄·5H₂O in deionized water or ethylene glycol.

Add stabilizer: Add PVP or citrate under stirring to control particle growth.
Reduction: Add ascorbic acid solution slowly under stirring at 60–90 °C.
The solution changes color (from blue → reddish brown), indicating Cu nanoparticle formation.

Reaction:
ethylene glycol, H 2O
2Cu2+ + C6H8O6 60-90°C
+
2Cu + C6H6O6 + 2H
Washing: Centrifuge and wash the Cu NPs with ethanol/water to remove by-products, dry the solid
particulates under vaccum at 80 °C for 16 hours.
Dispersion (Ink formation): Re-disperse Cu NPs in solvent (e.g., ethylene glycol, water,
isopropanol) with surfactants to achieve proper viscosity and surface tension for printing.
Sintering: After printing, Cu inks must be sintered to remove organic layers and connect particles. Sintering
should be rapid in inert/reducing atmosphere to avoid oxidation of Cu species.

Properties of Copper conductive ink.

Electrical Properties: After sintering: typically 10⁵–10⁶ S/m. The conductivity depends on
particle size and shape, the type and loading of quantum dots : sintering conditions and
film thickness and density Quantum dot incorporation.
Optical properties: Fresh copper ink looks reddish-brown and metallic. If copper oxidizes to
CuO it turns a green-blue Quantum dot protection helps maintain a metallic appearance.
Mechanical properties: Nano-Cu inks on flexible polymers can survive bending radii of <5 mm
with minimal conductivity loss. Quantum dots incorporation improve adhesion to various
substrates.
Flexibility: Important for flexible electronics is improved. Quantum dots may act as
stress-relief points. hence, crack resistance during bending is improved
Thermal properties: Good up to ~200°C after sintering; above this, oxidation and conductivity
loss can occur unless protected.
Chemical property: Copper easily oxidizes to Cu₂O/CuO, which severely increases resistance.
Many inks include antioxidants, protective coatings, or are formulated for photonic sintering or
plasma reduction to minimize oxidation.

Applications of Copper conductive ink.

Printed circuits and antennas (RFID tags, sensors).
Flexible electronics (on PET, PI, paper substrates).
Heaters and electrodes (touch panels, batteries).
Electromagnetic shielding coatings.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Synthesis of Graphene Quantum Dots using citric acid method:

To synthesize Graphene Quantum Dots (GQDs) using citric acid, the acid is first heated to its melting
point until it turns orange-red, indicating the start of carbonization. This intermediate product is then
mixed with a NaOH solution, and sometimes other agents like urea, followed by sonication or
microwave treatment to break down larger particles into GQDs. Finally, the GQDs are purified
through filtration to obtain a fluorescent suspension.

General Synthesis Steps:

1. Precursor Preparation: Citric acid is heated to a high temperature (~150-200 °C) in a beaker or
flask. As it melts and undergoes pyrolysis, its color changes from colorless to pale yellow and then
to an orange or red liquid. This process forms the basis for the GQDs.
2. Carbonization: after dehydration of citric acid (C₆H₈O₇) to form nanometer-scale sp²-carbon
domains with oxygen-containing functional groups.
3. Functionalization/Stabilization: A solution of NaOH is added dropwise to the melted citric acid to
control the pH and aid in the formation of GQDs.
4. Particle Dispersion: The orange-red intermediate liquid is then added to a more dilute NaOH
solution.
5. Disaggregation and Suspension: Ultrasonication for several minutes is used to break down the
larger particles and suspend the smaller GQDs in the solution. A microwave oven can also be used
for a few minutes to agitate the mixture and break up particles.
6. Purification: The mixture is filtered using a syringe and a 22-micron filter to remove any particles
larger than 220 nanometers, though the GQDs themselves are much smaller. A 22-micron filter is
too large for nanoscale particles.
7. Storage: The resulting yellow-green GQD solution is adjusted to a pH of 7.0 and diluted to a final
volume, then stored in a cool place, like 4 °C, for later use.

Applications:

Super capacitors: GQDs serve as pseudo capacitive materials or conductive additives in carbon
electrodes, enhancing charge storage via high surface area and abundant redox sites.
Batteries: Used to improve electrode/electrolyte interfaces and reduce ion diffusion resistance.
Energy harvesting: GQD-based triboelectric nanogenerators (TENGs) and piezoelectric devices
convert motion into electrical signals for self-powered wearables.
Flexible LEDs & OLEDs: GQDs act as emissive layers or charge transport layers due to their stable,
tunable luminescence.
Photodetectors: Incorporating GQDs improves light absorption and response time while maintaining
flexibility.
Solar cells: GQDs can serve as electron acceptors or transport materials in perovskite or organic
photovoltaics.
Biocompatibility and surface functional groups allow non-toxic integration with skin-contact devices.
GQD-based electrodes detect biomarkers (glucose, lactate, cortisol) and physiological signals (sweat,
pulse, ECG).
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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Photoluminescence changes upon analyte binding enable optical biosensors.

GQD–Ag nanocomposite flexible electrodes have been used for noninvasive sweat glucose monitoring
with high sensitivity and selectivity.
GQDs contribute to charge dissipation through polymer matrix formation.
Useful for optically clear antistatic coatings on touchscreens, lenses, or display panels.
Hybrid GQD shows enhanced charge dissipation with improved mechanical strength and
environmental stability.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Polymers:
Polymers are macromolecules, formed by the combination of many smaller repeating molecules.
These smaller molecules are termed as monomers. The word “polymer” is derived from Greek
language poly means many, meros means molecules. ”Deoxyribonucleic acid (DNA),
ribonucleic acid (RNA) and proteins are macromolecules and are essential forms of life and
hence polymers are linked to life. Cellulose, lignin, starch and natural rubber are other examples
of natural polymers. Polypropylene, Polyester, PTFE, Polyethylene are the well-known synthetic
polymers. They find applications in every possible field of human activity from personal care
products like clothing, shoes to electrical and electronic appliances, packaging, utensils,
automobile parts, coatings, paints, adhesives, tires and so on. Hence the synthetic polymers are
more important to modern society in terms of their utility and the economic value that they
signify.
The process of linking the repeating molecules is called polymerisation. It can be shown as,
Catalyst
nM [M]n

where, M is monomer

If a polymer is made of one type of monomer, it is called homopolymer. Ex- Polyethylene. If the
polymer is made of different types of monomers, it is called copolymer, Ex- Phenol-
formaldehyde resin. Number of times the monomer unit is repeated in a polymer is called degree
of polymerisation. Higher the degree of polymerisation, higher will be the molecular mass.

Molecular Mass of Polymer:

The substances like water, ammonia, benzene, etc., are monodispersed in nature i.e., their
molecules have same size whereas polymers contain molecules of different size depending on
their chain length. Therefore polymers supposed to have average molecular mass. The average
molecular mass can be calculated in two ways viz.

i) Number-average molecular mass (Mn)

ii) Weight-average molecular mass (Mw)

Number-average molecular mass (Mn): It is the ratio of total mass of all the molecules of a
sample to the total number of molecules.

Ex;- in a polymer sample, Suppose

N1 molecules have molecular mass M1 each.

N2 molecules have molecular mass M2 each.
In general, Ni molecules have molecular mass Mi each.
Then,

Total mass of all the N1 molecules = N1M1

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Total mass of all the N2 molecules = N2M2

In general, Total mass of all the Ni molecules = NiMi
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
So, ̅̅̅̅
𝑀𝑛 = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠

𝑁 𝑀 +𝑁 𝑀 +𝑁 𝑀 +⋯⋯+𝑁𝑖 𝑀𝑖
i.e. ̅̅̅̅
𝑀𝑛 = 1 1 2 2 3 3
𝑁1 +𝑁2 +𝑁3 +⋯⋯+𝑁𝑖

∑ 𝑁𝑖 𝑀𝑖
̅̅̅̅
𝑀𝑛 =
∑ 𝑁𝑖

Weight-average molecular mass (Mw): It is the ratio of products of total mass of groups of
molecules to the total mass of all molecules.

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑔𝑟𝑜𝑢𝑝𝑠 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠

̅̅̅̅
𝑀 𝑤 = 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑤1 𝑀1 + 𝑤2 𝑀2 + 𝑤3 𝑀3 + ⋯ ⋯ + 𝑤𝑖 𝑀𝑖
̅̅̅̅
𝑀 𝑤 =
𝑤 1 + 𝑤2 + 𝑤3 + ⋯ ⋯ + 𝑤𝑖
Since, w = NxM
𝑁1 𝑀21 + 𝑁2 𝑀22 + 𝑁3 𝑀23 + ⋯ ⋯ + 𝑁𝑖 𝑀2𝑖
̅̅̅̅
𝑀 𝑤 =
𝑁1 𝑀1 + 𝑁2 𝑀2 + 𝑁3 𝑀3 + ⋯ ⋯ + 𝑁𝑖 𝑀𝑖

∑ 𝑁𝑖 𝑀2𝑖
̅̅̅̅
𝑀 𝑤 =
∑ 𝑁𝑖 𝑀𝑖
In general Polydispersity Index: It is the measure of number of molecular species having different
sizes, equal to the ratio of weight average molecular mass to number average molecular mass.
𝑛̅̅̅̅̅
𝑀
𝑃𝐷𝐼 = ̅̅̅̅̅ ≥1 higher the value, greater is the polydispersity.
𝑀 𝑤

Numerical Problems:
1. In a sample of a polymer, 100 molecules have molecular mass 103 g/mol, 200 molecules have
molecular mass 104 g/mol and 250 molecules have molecular mass 105 g/mol. Calculate the
number average, weight average molecular mass of the polymer and PDI.

Solution, Given
N1 = 100, M1 = 103 g/mol,
N2 = 200, M2 = 104 g/mol,
N3 = 250, M3 = 105 g/mol

𝑁 𝑀1 +𝑁2 𝑀2 +𝑁3 𝑀3
We have ̅̅̅̅
𝑀𝑛 = 1 𝑁 +𝑁 +𝑁
1 2 3
(100×103)  (200×104 )  (250×105)

Mn  

100  200  250

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

𝑀𝑛  49272g / mol
̅̅̅̅̅
𝑁1 𝑀21 + 𝑁2 𝑀22 + 𝑁3 𝑀23
̅̅̅̅
𝑀 𝑤 =
𝑁1 𝑀1 + 𝑁2 𝑀2 + 𝑁3 𝑀3

100×(103)2  200×(104 )2  250×(105)2

Mw 
(100×103)  (200×104 )  (250×105)
Mw  92992g / mol

Mw 92992
PDI    1.89
Mn 49272

2. In a polymer sample, 20 % of molecules have molecular mass 12000 g/mol 30% molecules
have molecular mass 20000 g/mol, remaining molecules have molecular mass 22000 g/mol.
Calculate the number average, weight average molecular mass of the polymer and PDI.

Solution, Given
N1 = 20, M1 = 12000 g/mol,
N2 = 30, M2 = 20000 g/mol,
N3 = 50, M3 = 22000 g/mol
𝑁 𝑀1 +𝑁2 𝑀2 +𝑁3 𝑀3
̅̅̅̅
𝑀𝑛 = 1 𝑁 +𝑁 +𝑁
1 2 3

(20×12000)  (30×20000)  (50×22000)

Mn 
20  30  50
Mn  19400g / mol
𝑁1 𝑀21 +𝑁2 𝑀22 +𝑁3 𝑀23
̅̅̅̅
𝑀 𝑤 = 𝑁1 𝑀1 +𝑁2 𝑀2 +𝑁3 𝑀3

20×(12000)2  30×(20000)2  50×(22000)2

Mw 
(20×12000)  (30×20000)  (50×22000)
Mw  20144g / mol

Mw 20144
PDI    1.04
Mn 19400

3. A polymer sample contains

100 molecules with the formula -(CH3- CHCI)1000
200 molecules with the formula -(CH3- CHCI)2000
300 molecules with the form ula -(CH3- CHCI)4000
Calculate the number average, weight average molecular mass of the polymer and PDI.
Solution,
Molecular mass of -(CH3- CHCI)- = 62.5 g/mol

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Therefore

N1 = 100, M1 = 62.5 x 1000 = 62500 g/mol,

N2 = 200, M2 = 62.5 x 2000 = 125000 g/mol,
N3 = 300, M3 = 62.5 x 4000 = 250000 g/mol
𝑁 𝑀1 +𝑁2 𝑀2 +𝑁3 𝑀3
We have ̅̅̅̅
𝑀𝑛 = 1 𝑁 +𝑁 +𝑁 1 2 3

(100×62500)  (200×125000)  (300×250000)

Mn 
100  200  300
Mn  177083g / mol

𝑁1 𝑀21 +𝑁2 𝑀22 +𝑁3 𝑀23

̅̅̅̅
𝑀 𝑤 = 𝑁1 𝑀1 +𝑁2 𝑀2 +𝑁3 𝑀3

100×(62500)2  200×(125000)2  300×(250000)2


Mw  

(100×62500)  (200×125000)  (300×250000)

Mw  209558g / mol

Mw 209558
PDI    1.18
Mn 177083

4. Calculate the weight average molecular weight of polypropylene, if the degree of

polymerisation is 15000.

Solution,

The structure of polypropylene monomer is

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Molecular mass of polypropylene monomer is = 43 g/mol

Degree of polymerisation (n) is = 15000

We know that,
Molecular mass of polymer = Degree of polymerisation x Molecular weight of monomer unit
= 15000 x 43
Mw = 645000 g/mol

Conducting Polymers:
Polymers possess properties which are comparable with those of metals are strength, elasticity,
plasticity, toughness and frictional resistance. The most important advantages over the metals
are lighter weight, greater workability, resistance to corrosion and lower cost. As a result, these
materials have not only replaced metals but have also intervened in our day-to-day life from
most common consumer goods to highly specialized applications in space and aeronautics.
However, one important fundamental property which distinguishes metals from polymers is
electrical conductivity. Metals generally have very high conductivity of the order 106 to 108 S/m
(e.g. copper and silver), while for polymers, it is of the order 10-12 S/m (e.g., Teflon and
Polystyrene). This low electrical conductivity makes polymers to use them extensively in
making insulators and dielectric substances.

Conducting polymers have been intensively investigated due to their fundamental physical
properties, chemical properties and their applications in various fields such as electronic devices,
optoelectronic devices, chemical and biological sensors and secondary batteries. The electronic
properties of conducting polymers are of great interest due to their applications such as Diodes,
Transistors, Light Emitting Diodes, Solar cells, Sensors, Photo-detector etc.

In polymer, electrons are localized and do not take part in conduction and also there a wide
energy gap between valence band and conduction band. This makes polymer exhibit poor
conductivity. But doping can delocalize the electrons responsible for conduction. The insulating
polymer with conjugated backbone consisting of alternative double and single carbon-carbon
bonds, can be converted into a conductor by doping it with either an electron acceptor or an
electron donor or a protonating agent like HCl.

i) Oxidative dopant takes away electrons from the ᴨ-backbone of polymer and creates
holes in the chain, resulting in the increase of conductivity of polymer. Ex-
Polyacetylene
ii) Reductive dopant donates electrons to ᴨ-backbone of the polymer. These electrons
are free to move along c-chain, resulting in the increase of conductivity of polymer.
Ex- Polyacetylene.

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

iii) Protonating agent creates positive and negative charges in the polymer chain,
resulting in the increase of conductivity. Ex- Polyaniline.

Polyaniline Synthesis:

Several methods have been developed to synthesize polyaniline from pure aniline monomers.
One of the most common methods uses ammonium persulfate catalyst.

Dil HCl
n NH2 5-8°C, Ammonium persulfate NH NH NH
n

Mechanism of conduction in Polyaniline

The conductivity of polyacetylene is 1.1×10-6 S/m. But the doped polyaniline shows the
conductivity of 1.1×102 S/m. When polyaniline is partially oxidized with an oxidative dopant
like H2O2, it produces quinonoid ring formation, which on further treatment with HCl generates a
bipolaron is formed. The polarons condense pair-wise to form solitons which merge with the
edges of conduction bond (CB) and valence bond (VB) exhibiting more conductivity.

N N N N
H H H H n

Partial Oxidation (H2O2)

N N N N
H H n
Quinonoid
HCl

+ +
N N N N

H H H H n

Reaarangement

+ +
N N N N

H H H H n
Bipolaron
Reaarangement

+ +
N N N N
H H H H n
Bipolaron

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Applied Chemistry for EEE stream-Module-1: Dr. Venkatesha, Asst. Prof. BIT. Bengaluru

Antistatic Applications of Polyaniline

Electrostatic charge build-up on plastics or surfaces can cause dust attraction, spark discharge, or
damage to electronics.
Adding PANI provides a permanent, stable, and non-metallic way to dissipate static electricity.
Used in Antistatic coatings for packaging in electronics. In Clean-room flooring / mats,
Electronic component housings, Electronic component housings, Optical / photographic films to
prevent dust attraction.

Flexible Electronics Applications of Polyaniline

Polyaniline is one of the few conducting polymers that combines mechanical flexibility,
environmental stability, and tunable conductivity - all of which make it ideal for flexible and
wearable electronics.
Used in bendable batteries, supercapacitors, sensors as flexible electrodes.
It is used in wearable sensors to detect strain, pressure, temperature, pH, or gas.
Used in displays due to highly transparent or semi-transparent conducting in OLED.
Used in energy storage devices as active electrode material due to its high pseudo-capacitance and
redox activity.
Used in making of Smart textiles, conductive fibers or coatings for motion tracking, heating, or
signal transmission.

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