“ज्ञान,विज्ञान आणि सस

ु स्
ं कार यांसाठी शिक्षिप्रसार”
- शिक्षिमहर्षी डॉ. बापूजी साळंु खे

श्री स्वामी वववेकानंद शिक्षण संस्था , कोल्हापूर.

ववद्या सशमति
E- Content Development
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
 Chapter No.- 16

GREEN CHEMISTRY &

NANOCHEMISTRY
Marks without option - 3
Marks with option - 4

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
Introduction

• To minimize the problems of energy crisis and pollution all nations

are adopting to green chemistry.
• GREEN CHEMISTRY is an approach to chemistry that aims to
maximize efficiency and minimize hazardous effect on human health
& environment.
• Paul T. Anastas – father of green chemistry

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
 Definition of Green Chemistry

“Green chemistry is the use of chemistry for pollution prevention by

environmentally conscious design of chemical products and processes
that reduce the use or generation of hazardous substances.”

• Sustainable development-
It is development that meets the needs of the present, without
compromising the ability of future generations to meet their own needs.
• This can be achieved by adapting the 12 principles of Green chemistry.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
 Principles of Green chemistry

1. Prevention of waste or by products -

“To give priority for the prevention of waste rather than cleaning up &
treating waste after it has been created.”
Illustration -
• To develop Zero Waste Technology (ZWT).
• It also aims to use the waste product of one system as a raw material of
other system.
Example –
1) Bottom ash of thermal power station can be used as raw material
for cement & brick industries.
2) Effluent coming out from cleansing of machinery parts may be
used as coolant water in thermal power station.
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
2. Atom economy -
“Atom economy is the measure of the amount of atoms from the starting
materials that are present in the useful products at the end of chemical
process.”
Illustration -
Atom economy gives the measure of unwanted product produced in the
reaction.
Formula weight of desired product
% atom economy = 9 × 100
Sum of formula weight of all reactants used in
reaction

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
3. Less hazardous chemical synthesis–

“Designed chemical reactions and synthesis routes should be as safe as

possible. So that we can avoid formation of hazardous waste from chemical
processes.”
Illustration -
• Earlier DDT was used as insecticides & which was effective in controlling
diseases like typhoid& malaria. but it was harmful to living things.
• Now days it is replaced with Benzene hexachloride(BHC).
• One of the γ-isomer (gamma) of BHC is called gammexane or lindane.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
4. Designing safer chemicals–
“ To develop products that are less toxic or which require less toxic raw
materials.”
Illustration –
• In chemical industries workers are exposed to toxic environment. In order to
prevent workers from exposure to toxicity, we should think of designing
safer chemicals.
• Example- Adipic acid is widely used in polymer industry. To synthesize
adipic acid earlier raw material is benzene but it is carcinogenic & volatile
organic compound (VOC) pollutes air.
• In green technology developed by Drath & Frost, adipic acid is enzymatically
synthesized from glucose.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
5. Use safer solvents & auxilaries –
“Choose the safer solvent available for any given step of reaction. Minimize
the total amount of solvents & auxiliary substances used, as these make up
a large percentage of the total waste created”
Illustration – The main aim behind this principle is to use green solvents.
• For example – water, supercritical CO2 in place of volatile halogenated
organic solvents, for example CH2Cl2 , CHCl3 , CCl4 for chemical synthesis
& other purposes. Solvents as chemicals that dissolve solutes & form
solutions, facilitate many reactions.
• Their use creates large amount of waste,air pollution & other health impacts.
• Finding safer, more efficient alternatives is one of the best way to improve
the process or product.
Earlier used solvents- CH2Cl2 , CHCl3 , CCl4
Problem with it- Toxic for environment & workers
Shri Swami Vivekanand Shikshan Sanstha,
Now replaced with- Water, super critical CO2
Kolhapur
6. Design for energy efficiency –
“Chemical synthesis should be designed to minimize the use of energy. It is
better to minimize the energy by carrying out reactions at room
temperature & pressure.”
This can be achieved by -
use of proper catalyst,
use micro-organism for organic synthesis,
use of renewable materials & renewable material.
Illustration -
• The biocatalyst can work at the ambient condition. Similarly, in chemical
synthesis, refluxing conditions require less energy, improving the
technology of heating system, use microwave heating etc.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
7. Use of renewable feedstocks –
“The perspective of this principle is largely towards petrochemicals. Use
chemicals which are made from renewable (plant based) sources rather
than other (for example-crude oil).”
Illustration –
• Overexploitation of nonrenewable feed stocks will deplete the resources and
future generation will deprived. Moreover use of these nonrenewable
sources puts burden on environment.
• On the other hand, use of renewable sources for example agricultural or
biological product ensures the sharing of resources by future generation.
• This practice generally does not put much burden on environment. The
products and waste are generally biodegradable.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
8. Reduce derivatives –(Minimization of steps)
“ A commonly used technique in organic synthesis is use of protecting or
blocking group. Unnecessary derivatization should be minimized or avoided if
possible, because such steps require additional reagents& can generate waste.”
Illustration –
• In organic synthesis we need often protection of some functional groups.
Finally we again need their deprotection.
• It is explained in the following example of synthesis of m-hydroxybenzoic
acid from m-hydroxy benzaldehyde.
• Green chemistry principle aims to develop the methodology where
unnecessary step should be avoided, if practicable biocatalytic reactions very
often need no protection of selective group.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
9. Use of catalysis –
• Use of catalyst in chemical reaction speeds up its rate, it helps to increase
selectivity, minimize waste and reduces reaction time & energy demands.

Reaction Name of catalyst used

Hydrogenation (Hardening) of oil Ni

Haber’s process of manufacture of ammonia Fe

Manufacture of HDPE polymer Ziglar-Natta

Manufacture of H₂SO₄ by contact process V₂O₅

Fischer- Tropsch process(synthesis of gasoline) Co, Fe

Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
10. Design for degradation –
“Design chemicals that degrade and can be discarded easily.”
Illustration -
• The aim behind this principle is that waste product should degrade
automatically to clean the environment.
• Thus the biodegradable polymers & pesticides are always preferred.
• To make separation easier for the consumer an international plastic recycle
mark is printed on larger items.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
11. Real-time analysis pollution prevention -
“Analytical methods need to be further developed to allow real-time, in
process monitoring and control prior to the formation of hazardous
substances.”
• Develop & modify analytical methods for continuous production.
• This is very much important for chemical industries & nuclear reactors.

12. Safer chemistry for accident prevention -

“We need to develop chemical processes that are safer and minimize the
risk of accidents.”
• By selecting proper substances chemical accidents, explosion, fire &
emission are minimized.
• Example- If the chemical processes works with gaseous substances then
possibility of accidents isShrihigher than the non volatile liquid or solid
Swami Vivekanand Shikshan Sanstha,
substances. Kolhapur
The role of Green chemistry

• To promote innovative chemical technologies that reduce the use or

generation of hazardous substances in design & use of chemical
products.
• It helps - to reduce capital expenditure, to prevent pollution.
to minimize negative environmental effects.
to protect the ozone layer.
to control green house effect (global warming).
• It helps pollution prevention practices in manufacture of chemicals
and promotes pollution promotion and industrial ecology.
• It helps to minimize manufacturing process and negative
environmental effects.
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
 Introduction to Nano chemistry

➢ Nanoscience – The study of phenomena & manipulation of

materials at atomic, molecular & macromolecule scales where
properties differ significantly from those at larger scale.
➢ Nanotechnology – The design, characterization, production &
application of structures, device & system by controlling shape & size
at nanometer scale.(1 nm is one billionth of a meter.)
➢ Nanomaterial – It is the material having structural components
with at least one dimension in the nanometer scale that is 1-100nm.
➢ Nanochemistry – It is the combination of chemistry and
nanoscience.
It deals with designing and synthesis of materials of nanoscale with
different size & shape, structure & composition & their organization
into functional architectures.
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Zero, one and two dimensional nanoscale system :-

i. Zero-Dimensional nanostructures-
A zero dimensional structure is one in
which all three dimensions are in
nanoscale.
Example- Nanoparticles
ii. One-Dimensional nanostructures-
A one dimensional structure is one in
which two dimensions are in nanoscale.
Example- Nanowires & Nano rods
iii. Two-Dimensional nanostructures-
A two dimensional structure is one in
which one dimensions are in nanoscale.
Shri Swami Vivekanand Shikshan Sanstha,
Example- Thin films Kolhapur
 Characteristic features of
Nanoparticles

Surface Catalytic Thermal Mechanical Electrical

Color
area Activity properties properties conductivity

Increase
in surface They Mechanical
It is area with shows Melting Strength of It
optical decrease increase point nanopartic changes
Property in d depends al is harder at
particle catalytic on size than bulk nanoscale
size activity metal

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
Characteristic features of nanoparticles

1) Colour –
• It is an optical property that is different at nanoscale.
• Elemental gold has yellow colour. However if we had only 100 gold
atoms arranged in cube, its colour would be much more red.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
2) Surface area –
• High surface-to-volume ratio is a very important characteristic of
nanoparticles.
• If a bulk material is sub divided into group of
individual nanoparticles, the total volume
remains the same, but collective surface area
is largely increased.
• Figure shows surface area when a cube
of 1 m³ were progressively cut into
smaller cube until 1 nm³ formed.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
3) Catalytic activity –
• Due to increase in surface area with decrease in particle size, nanomaterial
based catalysts show increased catalytic activity.
• Usually they are heterogeneous catalysts that means catalysts are in solid
form and the reactions occur on surface of catalyst.
• Nanoparticle catalysts can be easily separated and can be recycled.
• Examples- Pd , Pt metal nanoparticles used in hydrogenation reactions.
TiO₂, ZnO are used in photocatalysis.
Gold in bulk form is unreactive, but gold nanoparticles are found
to be very good catalyst for various organic reactions.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
4) Thermal properties :- melting point
• The melting point of nanomaterial changes drastically and depends on size.
• xample – sodium clusters of 1000 atoms appeared to melt at 288 K while
cluster of 10,000 atoms melted at 303 K & bulk sodium melts at 371 K.
5) Mechanical properties –
• Mechanical strength : Nanosized copper & palladium clusters with
diameter in the size range of 5-7 nm can have hardness upto 500% greater
than bulk metal.
6) Electrical conductivity –
• Electrical conductivity is observed to change at nanoscale.
• Example – carbon nanotube can act as a conductor or semiconductor in
behaviour.

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
 Synthesis of
nanomaterials

By Bottom-up
By Top-down method
method

Molecular components are

arranged themselves into Nanomaterials are
more complex assemblies synthesized from bulk
atom by atom, molecule by material by breaking
molecule & cluster by the material.
cluster from Bottom
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Wet chemical synthesis of nanomaterials :-
• Sol-Gel process-
Sols- are dispersion of colloidal particles in a liquid.
Gel- are interconnected rigid network with pores of sub micrometer
dimensions of polymeric chains whose average length is greater than
micrometer.
This process is based on inorganic polymerization reaction by 4 steps-
step1- Hydrolysis
step2- Polycondensation
step3- Drying
step4- Thermal decomposition
• Use- to prepare oxide materials
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
The reaction involved in the sol gel process can be described as follows
MOR + H₂O MOH + ROH (hydrolysis)
metal alkoxide
MOH + ROM M-O-M + ROH (condensation)

1. Formation of different stable solution of alkoxide or solvated metal

precursor.
2. Gelation resulting from the formation of an oxide or alcohol-bridged
network(gel). By a polycondensation reaction.
3. Aging of the gel means during that period gel transforms into solid mass.
4. Drying of the gel- water & other volatile liquids are removed from gel
network.
5. Dehydration- the material is heated at temperature up to 800⁰C
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
 Analysis or characterization of nanomaterials

The synthesized material is analyzed by various analytical tools or techniques.

The name of technique and its use is described in following table-

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
History of nanotechnology

• Nanomaterials have been produced and used for hundred of years due to
development of advanced tool it has been possible to revel the information at
nanoscale.
Nanomaterials Use
Gold & silver nanoparticles trapped in Beautiful ruby red color for some ancient glass
glass matrix paintings.
Certain metallic nanoparticles Decorative glaze or metallic film known as
luster found on some medieval pottery.

Carbon black tyres

Carbon nanotubes Food industries
Fumed sillica Component of silicon rubber, coatings, sealant
andShikshan
Shri Swami Vivekanand adhesives.
Sanstha,
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
 Applications of nanomaterials
1. Used in manufacturing of scratchproof eyeglasses, transport, sunscreen,
crack resistance paint.
2. Used in electronic devices like Magnetoresistive Random Access
Memory(MRAM).
3. Used in water purification techniques. Water contains water borne
pathogens like viruses, bacteria. The provision of safe drinking water is
currently high priority. Recently cost effective filter materials coated with
silver Nanoparticles (AgNps) is an alternative technology.(For example-:
water purifier) AgNps act as highly effective bacterial disinfectant, remove
E.Coli from water.
4. Can be used as self cleaning materials (lotus effect). Lotus plant grows in
muddy water, its leaves always appears clean because leaves are
superhydrophobic. Nanostructures on lotus leaves repel water which
carries dirt as it rolls off.Shri
Lotus effect is the basis of self cleaning windows.
Swami Vivekanand Shikshan Sanstha,
Kolhapur
 Nanopartical & Nanotechnology

➢ Advantages –
1. Revolution in electronics & computing.
2. Energy sector- nanotechnology will make solar power more
economical. Energy storage devices will become more efficient.
3. Medical field- Manufacture of smart drugs, helps cure faster &
without side effects
➢ Disadvantages –
1. Nanotechnology has raised standard of living but at the same time
it has increased pollution. The pollution caused by nanotechnology
is called as nano pollution.
2. Nanoparticles can cause lung damage. Inhaled particulated matter
can deposite in human respiratory
Kolhapur track & deposite lungs.
Shri Swami Vivekanand Shikshan Sanstha,
 QUESTIONS

1. Choose the correct options.

i. Which of the following instrument is used for information of
particle size?
a) SEM b) TEM c) FTIR d) XRD
ii. Lindane is γ-isomer of --------?
a) Benzene b)DDT c) Chloroform d) BHC

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
2. Answer the following.
i. What is the name of γ-isomer of benzene?
ii. Write the name of nanomaterials used in tyres.
iii. Give full form of MRAM.
iv. Which instrument is used for detection of particle size?

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
3. Answer the following.
i. What is the role of green chemistry ?
ii. Give applications of nanomaterials.
iii. Define- a) nanochemistry b) nanomaterials
iv. Define catalyst with examples.

4. Answer the following.

i. Explain characteristic features of nano chemistry.
ii. Give advantages & disadvantages of Nanoparticles & nanotechnology.
iii. Explain any three principles of green chemistry.
iv. What is nanotechnology? How it plays an important role in water
purification techniques?

Shri Swami Vivekanand Shikshan Sanstha,

Kolhapur
Deleted or non-evaluative Portion due to Covid-19 for H.S.C Board exam 2021

Sr.no. Page no. Deleted & non-evaluative portion

1. 345 Fig.16.1 Macro-materials to atoms

Fig.16.2 Scale of Nanomaterials

16.6.4 Thermal properties

2. 347 16.6.5 Mechanical property
16.6.6 Electrical conductivity
16.7 Synthesis of Nanomaterial

3. 348 16.7.4 photographs of Instruments

Shri Swami Vivekanand Shikshan Sanstha,
Kolhapur
 श्री स्िामी वििेकानंद शिक्षि संस्था , कोल्हापर
ू .
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