Chapter 16

Green Chemistry and

Nano Chemistry
STD XII : Chemistry

STD XII Chemistry Slide 1 Green Chemistry and Nano Chemistry

 CONTENTS
Sr. No. Topic Slide no.
16.1 Green Chemistry and Nano Chemistry 3-4
16.2 Chapter 1
Principles of Green Chemistry 5-21
16.3 The role of Green Chemistry 22
16.4
16.5
Nanoscience
Solid State
Characteristic Features of Nanoparticles
23-29
30-34
16.6 Synthesis of Nanomaterials 35-41
16.7 Analysis or Characterization of Nanomaterials 42-43
16.8 Applications of Nanomaterials 44
Advantages and Disadvantages
16.9 45-46
Nanoparticles and Nanotechnology
16.10 Some Interesting Facts 47

STD XII Chemistry Slide 2 Green Chemistry and Nano Chemistry

16.1 Green Chemistry and Nano Chemistry
Definition

Green Chemistry
Green Chemistry is the use of Chemistry for pollution prevention by environmentally
conscious design of chemical products and processes that reduce or eliminate the use
or generation of hazardous substances.

STD XII Chemistry Slide 3 Green Chemistry and Nano Chemistry

16.1 Green Chemistry and Nano Chemistry
Sustainable development

 Green Chemistry plays an important role in sustainable development.

 We can achieve sustainable development by adapting the twelve principles of green

Chemistry.

 Sustainable development is development that meets the needs of the present, without
compromising the ability of future generations to meet their own need.

 Sustainable development has been continued to evolve as that protecting the world’s re-
sources.

STD XII Chemistry Slide 4 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.1 Prevention of waste or by products

To give priority for the prevention of waste rather than cleaning up and treating waste after it
has been created.
Illustration
To develop the zero waste technology (ZWT).
In terms of ZWT, in a chemical synthesis, waste product should be zero or minimum.
It also aims to use the waste product of one system as the raw material for other system.

E.g.,: 1. bottom ash of thermal power station can be used as a raw material for cement
and brick industry.
2. Effluent coming out from cleansing of machinery parts may be used as coolant water
in thermal power station.
STD XII Chemistry Slide 5 Green Chemistry and Nano Chemistry
16.2 Principles of Green Chemistry
16.2.2 Atom economy

Atom economy is a measure of the amount of atoms from the starting materials that are
present in the useful products at the end of chemical process.

Good atom economy means most of the atoms of the reactants are incorporated in the desired
products and only small amounts of unwanted byproducts are formed and hence lesser prob-
lems of waste disposal .

STD XII Chemistry Slide 6 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.2 Atom economy

Illustration
The concept of atom economy gives the measure of the unwanted product produced in a particu-
lar reaction.
% atom economy =

E.g.,: Conversion of Butan-1-ol to 1-bromobutane

CH3CH2CH2CH2OH + NaBr + H2SO4 CH3CH2CH2CH2-Br + NaHSO4 + H2O

% atom economy =

137 u
¿
275 u
¿
×49.81
100 %
STD XII Chemistry Slide 7 Green Chemistry and Nano Chemistry
16.2 Principles of Green Chemistry
16.2.3 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 (Dichlorodiphenyl trichloroethane) was used as insecticide and which was effective
in controlling diseases like typhoid and malaria carrying mosquitos.
It was realized that DDT is harmful to living things.

Nowadays benzene hexachloride (BHC) is used as insecticide.

One of the ϒ-isomer (gamma) of BHC is called gammexane or lindane.

STD XII Chemistry Slide 8 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.4 Desigining 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 the workers from exposure to toxicity, we should think of designing safer
chemicals.
E.g .,: Adipic acid is widely used in polymer industry.
Benzene is the starting material for the synthesis of adipic acid.
Benzene is carcinogenic and benzene being volatile organic compound (VOC) pollutes
air.
In green technology developed by Drath and Frost, adipic acid is enzymatically synthe-
sized from glucose.
STD XII Chemistry Slide 9 Green Chemistry and Nano Chemistry
16.2 Principles of Green Chemistry
16.2.5 Use Safer Solvents and Auxilaries

Choose the safer solvent available for any given step of reaction.
Minimize the total amount of solvents and 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.

E.g.,: water, supercritical CO2 in place of volatile halogenated organic solvents.
CH2Cl2, CHCl3, CCl4 for chemical synthesis and other purposes.

Solvents as chemicals that dissolve solutes and form solutions, facilitate many reactions.

Water is a safe benign solvent while dichloromethane is hazardous.

STD XII Chemistry Slide 10 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.5 Safer Solvents and Auxiliaries-Uses

Use of toxic solvent affects millions of workers every year and has implications for consumers
and the environment as well.

Many solvents are used in high volumes and many are volatile organic compounds.

Their use creates large amounts of waste, air pollution and other health impacts.

Finding safer, more efficient alternatives or removing solvents altogether is one of the best
ways to improve a process or product.

STD XII Chemistry Slide 11 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.6 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 and pressure.

This can be achieved by use of proper catalyst, use of micro organisms for organic synthesis, use
of renewable materials, etc.
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.

STD XII Chemistry Slide 12 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.7 Use of renewable feed stocks

The perspective of this principle is largely toward petrochemicals.

Use chemicals which are made from renewable (plant based) sources rather than others.
(for example : Crude Oil).
Illustration
 Overexploitation of nonrenewable feed stocks will deplete the resources and future genera-
tion will be deprived of it.
 Moreover, use of these nonrenewable resources puts burden on the environment.
 Use of renewable resources for example agricultural or biological product ensures the shar-
ing of resources by future generations.
 This practice generally does not put much burden on the environment.
 The products and wastes are generally biodegradable.
STD XII Chemistry Slide 13 Green Chemistry and Nano Chemistry
16.2 Principles of Green Chemistry
16.2.8 Reduce derivatives : [Minimization of steps]

A commonly used technique in organic synthesis is the use of protecting or blocking group
Unnecessary derivatization (for example installation/removal of use of protecting groups)
should be minimized or avoided if possible, because such steps require additional reagents and
can generate waste.

STD XII Chemistry Slide 14 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.8 Reduce derivatives : [Minimization of steps]

Illustration
In organic synthesis, we need very often protection of some functional groups.
Finally, we again need their deportation.

It is explained in the following example of synthesis of m-hydroxybenzoic acid from

m-hydroxy benzaldehyde.
In such cases, atom economy is also less.
The Green Chemistry principle aims to develop the methodology where unnecessary steps
should be avoided.
If practicable biocatalytic reactions very often need no protection of selective group.

STD XII Chemistry Slide 15 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.8 Reduce derivatives : [Minimization of steps]

Illustration

STD XII Chemistry Slide 16 Green Chemistry and Nano Chemistry

16.2 Principles of Green Chemistry
16.2.9 Use of catalysis

Use of catalyst in the chemical reaction speeds up its rate.

Catalyst Helps, to
 Incease selectivity
 Minimize waste
 Reduce reaction time
 Reduce energy demands

STD XII Chemistry Slide 17 Green Chemistry and Nano Chemistry

Complete the Chart

Reaction Name of Catalyst used

1. Hydrogenation of oil (Hardening) Ni

2. Haber’s process to manufacture of ammonia Fe

3. Manufacture of HDPE polymer Zieglar Natta

4. Manufacture of H2SO4 by contact process V 2 O5

5. Fischer-Tropsch process (synthesis of gasoline) Fe, Co, Ni & Ru

STD XII Chemistry Slide 18 Green Chemistry and Nano Chemistry

 16.2 Principles of Green Chemistry
16.2.10 Design for degradation

Design chemicals that degrade and can be discarded easily.

Ensure that both chemicals and their degradation products are :

 Not toxic
 Bioaccumulative
 Environmentally persistent

Illustration
Waste products should degrade automatically to clean the environment.
Biodegradable polymers and pesticides are always preferred.

STD XII Chemistry Slide 19 Green Chemistry and Nano Chemistry

 16.2 Principles of Green Chemistry
16.2.11 Real-time Analysis Pollution Prevention

Analytical methods need to be developed to allow for real-time, in process monitoring and
control prior to the formation of hazardous substances.

Illustration

Analytical methodologies should be developed or modified, so that continuous monitoring of

the manufacturing and processing units is possible. This is very much important for the chemi-
cal industries and nuclear reactors.

STD XII Chemistry Slide 20 Green Chemistry and Nano Chemistry

 16.2 Principles of Green Chemistry
16.2.12 Safer Chemistry for Accident prevention

We need to develop chemical processes that are safer and minimize the risk of accidents.

Illustration
The substances to be used in a chemical reaction should be selected in such a way that they
can minimize the occurrence of chemical accidents, explosions, fire and emissions.

E.g., if the chemical process works with the gaseous substances, then the possibility of acci-
dents including explosion is relatively higher compared to the system working with non
volatile liquid and solid substances.

STD XII Chemistry Slide 21 Green Chemistry and Nano Chemistry

16.3 The Role of Green Chemistry

Green Chemistry approach recognizes that the Earth does have a natural capacity for dealing with
much of the waste and pollution that society generates.

It is only when that capacity is exceeded that we become unsustainable.

 To promote innovative chemical technologies that reduce or eliminate the use or generation of
hazardous substances in the design, manufacture and use of chemical products.
 Green Chemistry helps to reduce capital expenditure, to prevent pollution.
 Green Chemistry incorporates pollution prevention practices in the manufacture of chemicals and
promotes pollution prevention and industrial ecology.

 Green Chemistry is a new way of looking at chemicals and their manufacturing process to mini-
mize any negative environmental effects.
 Green Chemistry helps to protect the presence of ozone in the stratosphere essential for the sur-
vival of life on the earth.
 Green Chemistry is useful to control Green house effect (Global warming).
STD XII Chemistry Slide 22 Green Chemistry and Nano Chemistry
16.4 Nanoscience
Definition

Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular

and macromolecular scales where properties differ significantly from those at a larger scale.

STD XII Chemistry Slide 23 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.1 Nanotechnology

We need to develop chemical processes that are safer and minimize the risk of accidents.

• The design
• Characterization
• Production
• Application of structures, device and system by controlling shape and size at nanometer
scale.

STD XII Chemistry Slide 24 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.2 Nano

The nanometer scale is defined as 1-100 nm.

One nanometer is one billionth of a metre.

−9
1 nm=10 m
Material synthesized at nanoscale (1nm - 100nm) possesses unique optical, structural, ther-
mal, catalytic, magnetic and electrical properties.

These properties change as a function of size and are very different from their bulk materials.

STD XII Chemistry Slide 25 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.4 Nanomaterial

The nanomaterial is a material having structural components with at least one dimension in
the nanometer scale that is 1-100 nm.

𝐙𝐞𝐫𝐨 − 𝐃𝐢𝐦𝐞𝐧𝐬𝐢𝐨𝐧𝐚𝐥𝐍𝐚𝐧𝐨𝐬𝐭𝐫𝐮𝐜𝐭𝐮𝐫𝐞𝐬
 A zero dimensional structure is one in which all three dimensions are in the nanoscale.

𝐎𝐧𝐞 − 𝐃𝐢𝐦𝐞𝐧𝐬𝐢𝐨𝐧𝐚𝐥 𝐍𝐚𝐧𝐨𝐬𝐭𝐫𝐮𝐜𝐭𝐮𝐫𝐞𝐬

 A one dimensional nanostructure is one in which two dimensions are in the nanoscale.

𝐓𝐰𝐨 − 𝐃𝐢𝐦𝐞𝐧𝐬𝐢𝐨𝐧𝐚𝐥𝐍𝐚𝐧𝐨𝐬𝐭𝐫𝐮𝐜𝐭𝐮𝐫𝐞𝐬
 A two-dimensional nanostructure is one in which one dimension is in the nanoscale.

STD XII Chemistry Slide 26 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.4 Illustration of zero, one, two dimensions

Example
Nanomaterial Nanomaterial
Example
Dimension Type

All three Nanoparticles, Quantum

dimensions < 100 nm dots,
nanoshells, nanorings,
microcapsules
Two dimensions < 100 nm Nanotubes, fibres,
nanowires

One dimension < 100 nm Thin films, layers and

coatings

STD XII Chemistry Slide 27 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.5 Classification of nanomaterials

(a) 0D spheres and clusters (b) 1D nanofibers, wires and rods

(c) 2D films, plates and networks, (d) 3D nanomaterials

STD XII Chemistry Slide 28 Green Chemistry and Nano Chemistry

16.4 Nanoscience
16.4.6 Nano Chemistry

It is the combination of Chemistry and nanoscience.

Definition
It deals with designing and synthesis of materials of nanoscale with different size and shape,
structure and composition and their organization into functional architectures.

Application
Nano Chemistry is used in chemical, physical, materials science as well as engineering,
biological and medical applications.

STD XII Chemistry Slide 29 Green Chemistry and Nano Chemistry

16.5 Characteristic Features of Nanoparticles
16.5.1 Colour

It is an optical property that is different at nanoscale.

Elemental gold as we know, has nice shining yellow colour.

However, if you had only 100 gold atoms arranged in a cube,

its colour would be much more red.

Formation of gold nanoparticles solution

STD XII Chemistry Slide 30 Green Chemistry and Nano Chemistry

16.5 Characteristic Features of Nanoparticles
16.5.2 Surface area

High surface-to-volume ratio is a very important charac-

teristic of nanoparticles.

If a bulk material is sub divided into a group of individual

nanoparticles, the total volume remains the same. 𝐀𝐫𝐞𝐚 =𝟔×𝟏 𝐦 𝟐=𝟔 𝐦 𝟐

But the collective surface area is largely increased.

𝐀𝐫𝐞𝐚 =𝟔×(𝟏/𝟐 𝐦 )𝟐×𝟖=𝟏𝟐 𝐦
With large surface area for the same volume, these small
particles react much faster because more surface area
provides more number of reaction sites, leading to more
chemical reactivity.

𝐀𝐫𝐞𝐚 =𝟔×(𝟏/𝟑 𝐦 )𝟐×𝟐𝟕=𝟏𝟖 𝐦 𝟐

STD XII Chemistry Slide 31 Green Chemistry and Nano Chemistry
16.5 Characteristic Features of Nanoparticles
16.5.3 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.

Catalysts are in solid form and the reactions occur on the surface of the catalyst.

Nanoparticle catalysts can be easily separated and can be recycled.

Eg.,: 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.

STD XII Chemistry Slide 32 Green Chemistry and Nano Chemistry

16.5 Characteristic Features of Nanoparticles
16.5.4 Thermal properties : melting point

The melting point of nanomaterial changes drastically and depends on size.

For example
 Sodium clusters (Nan) of 1000 atoms appeared to melt at 288 K while Cluster of
10,000 atoms melted at 303 K.
 Bulk sodium melts at 371K.

STD XII Chemistry Slide 33 Green Chemistry and Nano Chemistry

16.5 Characteristic Features of Nanoparticles
16.5.5 Mechanical properties

Mechanical strength
Nanosized copper and palladium clusters with diameter in the size range of 5-7 nm can
have hardness up to 500% greater than bulk metal.

Electrical conductivity
Electrical conductivity is observed to change at nanoscale.
Eg.., Carbon nanotube can act as a conductor or semiconductor in behaviour.

STD XII Chemistry Slide 34 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials

There are two approaches to the synthesis of nanomaterials

Bottom up and Top Down.

Schematic illustration of the preparation of nanoparticles

STD XII Chemistry Slide 35 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials
16.6.1 Bottom up approach

Molecular components arrange themselves into more complex assemblies atom by atom,
molecule by molecule and cluster by cluster from the bottom.

Eg.,: Synthesis of nanoparticles by colloidal dispersion.

STD XII Chemistry Slide 36 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials
16.6.2 Top-down approach

Nanomaterials are synthesized from bulk material by breaking the material.

The bulk solids are dis-assembled into finer pieces until they are constituted of only few
atoms.

STD XII Chemistry Slide 37 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials
16.6.3 Wet chemical synthesis of Nanomaterials : Sol-gel process

Sols are dispersions of colloidal particles in a liquid.

Colloids are solid particles with diameters of 1-100nm.
A gel is interconnected rigid network with pores of submicrometer dimensions and polymeric chains
whose average length is greater than a micrometer.
A sol-gel process is based on inorganic polymerization reactions.
It is generally carried out at room temperature and includes four steps.
 Hydrolysis
 Polycondensation
 Drying
 Thermal decomposition
This method is widely employed to prepare oxide materials.
STD XII Chemistry Slide 38 Green Chemistry and Nano Chemistry
16.6 Synthesis of Nanomaterials
16.6.3 Wet chemical synthesis of Nanomaterials : Sol-gel process

Schematic representation of sol-gel process of synthesis of nanoparticles

STD XII Chemistry Slide 39 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials
16.6.3 Wet chemical synthesis of Nanomaterials: Sol-gel process

Reactions involved in the sol-gel process

MOR + H2O MOH + ROH (hydrolysis)

metal alkoxide

MOH + ROM M-O-M + ROH (condensation)

STD XII Chemistry Slide 40 Green Chemistry and Nano Chemistry

16.6 Synthesis of Nanomaterials
16.6.3 Wet chemical synthesis of Nanomaterials : Sol-gel process

Steps in sol-gel process

Formation of different stable solution of the alkoxide or solvated metal precursor.

Gelation resulting from the formation of an oxide or alcohol-bridged network. (gel) by a

polycondensation reaction.
Aging of the gel means during that period gel transforms into a solid mass.

Drying of the gel: In this step, water and other volatile liquids are removed from the gel net-
work.
Dehydration: The material is heated at temperatures up to 800 C.

STD XII Chemistry Slide 41 Green Chemistry and Nano Chemistry

16.7 Analysis or Characterization of Nanomaterials

Name of Technique Instrument used Information

1. UV-visible spectroscopy UV-visible spectrophotometer Preliminary confirmation of

formation of nanoparticles

2. X-ray Diffraction (XRD) X-ray diffractometer particle size, crystal structure,

geometry

3. Scanning electron mi- Scanning electron microscope Structure of surface of

croscopy (SEM) material that is morphology

4. Transmission electron Transmission electron micro- particle size

microscopy scope (TEM)

5. FTIR Fourier transform Fourier transform infrared Absorption of functional

infrared spectroscopy spectrophotometer groups, binding nature.

STD XII Chemistry Slide 42 Green Chemistry and Nano Chemistry

16.7 Analysis or Characterization of Nanomaterials
16.7.1 History of nanotechnology

Beautiful ruby red colour of some ancient glass paintings is

due to gold and silver nanoparticles trapped in the glass matrix.

The decorative glaze or metallic film known as lustre found

on some medieval pottery is due to certain spherical metallic
nanoparticles.
Ruby red colour
Carbon black is a nanostructured material that is used in
tyres of car to increase the life of tyre.
Carbon nanotubes are made up of graphite sheets with nanosized diameter.
They have highest strength
Fumed silica, a component of silicon rubber, coatings, sealants and adhesives is also a
nanostructured material.

STD XII Chemistry Slide 43 Green Chemistry and Nano Chemistry

16.8 Applications of Nanomaterials

Nanoparticles can contribute to stronger, lighter, cleaner and smarter surfaces and systems.
They are used in the manufacturing of scratchproof eyeglasses, transport, sunscreen, crack
resistant paints and so on.

Used in electronic devices. For example, Magnetoresistive Random Acess memory (MRAM)
Nanotechnology plays an important role in water purification techniques.

Cost effective filter materials coated with silver nanoparticles (AgNps) is an alternative tech-
nology. for safe drinking water (For example : water purifier)
Silver nanoparticles act as highly effective bacterial disinfectant, remove E.Coli from water.

Self cleaning materials : Lotus is an example of self cleaning

Nanostructures on lotus leaves repel water which carries dirt as it rolls off.
Lotus effect is the basis of self cleaning windows.
STD XII Chemistry Slide 44 Green Chemistry and Nano Chemistry
16.9 Advantages and Disadvantages
16.9.1 Advantages Nanoparticles and Nanotechnology

Revolution

In electronics and computing.

Energy sector

Nanotechnology will make solar power more economical.

Energy storage devices will become more efficient.

Medical field

Manufacturing of smart drugs, helps cure faster and without side effects. Curing of life threat-
ening diseases like cancer and diabetes.

STD XII Chemistry Slide 45 Green Chemistry and Nano Chemistry

16.9 Advantages and Disadvantages
16.9.2 Disadvantages of Nanoparticles and Nanotechnology

It has increased the pollution which includes air pollution.

The pollution caused by nanotechnology is known as nano pollution

This kind of pollution is very dangerous for living organisms.

Nanoparticles can cause lung damage.

Inhaled particulated matter can be deposited throughout the human respiratory tract
and then deposit in lungs.

STD XII Chemistry Slide 46 Green Chemistry and Nano Chemistry

16.10 Some Interesting Facts

The term ‘nanotechnology’ was defined by Tokyo science University Professor, Nario
Taniguchi in 1974.
Invention of Scanning Tunneling Microscope (STM) in 1980, led to the discovery of
fullerenes in 1986 and carbon nanotubes a few years later.

STD XII Chemistry Slide 47 Green Chemistry and Nano Chemistry