XII-16-Green Chemistry and Nanochemistry (1)

16 GREEN CHEMISTRY AND NANOCHEMISTRY

*Q.1. Define : (i) Green chemistry (ii) Sustainable development.

Ans: (i) Green chemistry : The concept of green chemistry was coined by Poul T. Anastas
Definition : 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.
(ii) Sustainable development : We can achieve sustainable development by adopting
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
resources.

*Q.2. Explain principles of green chemistry.

Ans: (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. For example :
(i) Bottom ash of thermal power station can be used as a row material for
cement and brick industry.
(ii) Effluent coming out from cleansing of machinery parts may be used as
coolant water in thermal power station.
*(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 by-products are formed
and hence lesser problems of waste disposal.
Illustration : The concept of atom economy gives the measure of the unwanted
product produced in a particular reaction.
Formula weight of the desired product
% atom economy = — — — — — — — — — — — — — — — — — — — — — — x 100
sum of formula weight of all the reactants used in
the reaction
For example : Conversion of Butan-1-ol to 1-bromobutane
CH3CH2CH2CH2OH + NaBr + H2SO4 CH3CH2CH2CH2Br + NaHSO4 + H2O
mass of (4C + 9H + 1Br) atoms
% atom economy = — — — — — — — — — — — — — — — — — — — — — — — x 100
mass of (4C + 12H + 5O + 1Br + 1Na + 1S) atoms

137 u
= — — — — x 100 = 49.81 %
275 u
*(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 -isomer
(gamma) of BHC is called gammexene or lindane.
XII-16-Green Chemistry and Nanochemistry (2)
(4) Desigining Safer Chemicals : This principle is quite similar to the previous one.
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.
For example : Adipic acid is widely used in polymer industry. Benzene is the
starting material for the synthesis of adipic acid but benzene is carcinogenic and
benzene being volatile organic compound (VOC) pollutes air. In green technology
developed by Drath and Frost, adipic acid is enzymatically synthesized from
glucose.

*(5) Use Safer solvent 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.
For example, water, supercritical CO2 (fluid state of CO2) in place of volatile
halogenated organic solvents like CH2Cl2, CHCl3, CCl4 for chemical synthesis and
other purposes.
Water is a safe solvent while dichloromethane is hazardous. Use of toxic solvent
affects millions of workers every year and the environment. 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.
(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.
(7) Use of renewable feedstocks : The perspective of this principle is largely toward
petrochemicals. Use chemicals which are made from renewable (plant based)
sources rather than other (for example : Crude Oil).
Illustration : Over exploitation of nonrenewable feed stocks will deplete the
resources and future generation will be deprived. Moreover, use of these
nonrenewable resources puts burden on the environment.
On the other hand use of renewable resources 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.
*(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.
Illustration : In organic synthesis, we need very 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.
Obviously, 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.
XII-16-Green Chemistry and Nanochemistry (3)
CHO CHO
| |
C6H5CH2Cl (O)
Protection oh -OH group
OH OCH2C6H5
(m-hydroxybenzaldehyde)
COOH COOH
| |
Deprotection of -OH group

OCH2C6H5 OH
(m-hydroxybenzoic acid)

*(9) Use of catalysis : Use of catalyst in the chemical reaction speeds up its rate.
Catalyst helps to increase selectivity minimize waste and reduce reaction times and
energy demands.

Reaction Name of Catalyst used

1. Hydrogenation of oil (Hardening) Ni or Pt or Pd
2. Haber's process of manufacture of ammonia Fe and V2 O5
3. Manufacture of HDPE Polymer Ziegler-Natta catalyst
[ TiCl4 -(C2 H5 )3 Al ]
4. Manufacture of H2 SO4 by contact process V2 O 5
5. Fischer-Tropsch process Co and Fe
(synthesis of gasoline)

(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 or environmentally persistent.
Illustration : The aim behind this principle is that the waste product should degrade
automatically to clean the environment. Thus, the biodegradable polymers and
pesticides are always preferred. To make separation easier for the consumer an
international plastic recycle mark is printed on larger items.
(11) Real-time Analysis Pollution Prevention: Analytical methods need to be further
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 chemical industries and nuclear reactors.
(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 emission. For example, if the chemical process works with the
gaseous substances, then the possibility of accidents including explosion is
relatively higher compared to the system working with non volatile liquid and solid
substances.
 XII-16-Green Chemistry and Nanochemistry (4)
Q.3. Explain the role of green chemistry.
Ans: (i) The green chemistry helps to reduce capital expenditure, to prevent pollution.
(ii) Green chemistry incorporates pollution prevention practices in the manufacture of
chemicals and promotes pollution prevention and industrial ecology.
(iii) Green chemistry is a new way of looking at chemicals and their manufacturing,
process to minimize any negative environmental effects.
(iv) The green chemistry revolution is beginning and it is an exciting time with new
challenges for chemists involved with the discovery manufacture and use of
chemicals.
(v) Green chemistry helps to protect the presence of ozone in the stratosphere
essential for the survival of life on the earth.
(vi) Green chemistry is useful to control green house effect (Global worming). So we
should think about save environment and save earth.
Introduction to nano chemistry.
(i) From clothes, sunglasses you wear to computer hard drives and even cleaning
products, nanotechnology plays a big part in the manufacture of many materials.
(ii) We have been using Lasers in DVD, CD players for a long time which contain
nanosize components.
(iii) Bacteria, virus, red blood cell, we can not observe with naked eye. These are known
as nanomaterials.

Q.4. What is nanoscience ?

Ans: Nanoscience is the study of phenomena and manipulation of materials of atomic, molecular
and macromolecular scales where properties differ significantly from those at a larger scale.

Q.5. Define nanotechnology.

Ans: Nanotechnology is the design, characterization, production and application of structures,
device and system by controlling shape and size of nanometer scale.

Q.6. What is nano scale ?

Ans: ‘Nano’in Greek means dwarf but in actual case 'nano' is even smaller than dwarf.
Conventionally the nanometer scale is defined as 1 -100 nm. 1 nm = 10–9 m.
The material synthesized at nanoscale (1 nm -100 nm) possesses unique optical,
structural, thermal, catalytic, magnetic and electrical properties. These properties change
as a function of size and are very different from their bulk materials.

Q.7. What is nanomaterial ?

Ans: (i) The nanomaterial is a material having structural components with at least one
dimension in the nanometer scale that is 1 -100 nm.
(ii) Nanomaterials are larger than single atoms but smaller than bacteria and cells.
These may be nanoparticles, nanowires and nanotubes according to dimensions.
(iii) Nanostructured materials may be large organic molecules, inorganic cluster
compounds and metallic or semiconductor particles.

Q.8. What are zero, one and two dimensional nanoscale system ?
Ans: (i) Zero-Dimensional Nanostructures : For example, Nanoparticles.
A zero dimensional structure is one in which all three dimensions are in the
nanoscale.
 XII-16-Green Chemistry and Nanochemistry (5)
(ii) One-Dimensional Nanostructures : For example, Nanowires and Nano rods.
A one dimensional nanostructure is one in which two dimensions are in the
nanoscale.
(iii) Two-Dimensional Nanostructures : For example, Thin films.
A two-dimensional nanostructure is one in which one dimension is in the nanoscale.

Nanomaterial Dimension Nanomaterial Type Example

All three dimensions < Nanoparticles, Quantum dots,

100 nm nanoshells, nanorings, microcapsules

Two dimensions < 100 nm Nanotubes, fibres, nanowires

One dimension < 100 nm Thin films, layers and coatings

Q.9. Define Nanochemistry :

Ans : It is the combination of chemistry and nanoscience. It deals with designing and synthesis of
materials of nanoscale with different size and shape, structure and composition and their
organization into functional architectures.
Nanochemistry is used in chemical, physical, materials science as well as engineering,
biological and medical applications.

*[Link] nanomaterial is used in sunscreen lotion ? Write its use.

Ans : Sunscreen lotion contains nanoparticles of Zinc oxide, (ZnO) and Titanium dioxide, (TiO2).
These chemicals protect the skin against harmful UV (ultraviolet) rays by absorbing or
reflecting the light and prevent the skin from damage.

Q.11. Give characteristic features of Nanoparticles.

Ans : (i) Colour : It is an optical property that is different at nanoscale. Elemental gold has
nice shining yellow colour. However, if you had only 100 gold atoms arranged in
cube, its colour would be much more red.
(ii) Surface area : High surface to volume ratio is a very important characteristic of
nanoparticles. If a bulk material is sub divided into a group of individual
nanoparticles, the total volume remains the same, but the collective surface area is
largely increased.
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 x 1 m2 = 6 m3 Area = 6 x (½ m2) x 8 = 12 m3 Area = 6 x (1/3 m3) x 27 = 18 m3

 XII-16-Green Chemistry and Nanochemistry (6)
(iii) Catalytic activity : Due to increase in surface area with decrease in particle size,
nanomaterial-based catalysts show increased catalytic activity. They are
heterogeneous catalysts that means 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. e.g.
1. Pd, Pt metal nanoparticles used in hydrogenation reactions.
2. TiO2, ZnO are used in photocatalysis.
3. Gold in bulk form is unreactive, but gold nanoparticles are found to be very
good catalyst for various organic reactions.
(iv) Thermal property (m.p.): The melting point of nanomaterial changes drastically
and depends on size. e.g. Sodium clusters (Nan) of 1000 atoms melt at 288 K while
cluster of 10,000 atoms melted at 303 K and bulk sodium melts at 371 K.
(v) Mechanical strength : Nanosized copper and palladium clusters with diameter in
the size range of 5-7 nm can have hardness upto 500 % greater than bulk metal.
(vi) Electrical conductivity : Electrical conductivity is observed to change at
nanoscale. e.g. carbon nanotube can act as a conductor or semiconductor.

Q.12. Give synthesis of Nanomaterials.

Ans : There are two approaches to the synthesis of
nanomaterials. Bottom up and Top down.
In the bottom approach, molecular components
arrange themselves into more complex assemblies
atom by atom, molecule by molecule and cluster by
cluster from the bottom. Example : Synthesis of
nanoparticles by colloidal dispersion.
In the 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.

*Q.13. What do you mean by sol and gel? Describe the sol-gel method of preparation for
nanoparticles.
Ans : Sol are dispersions of colloidal particles in a liquid. Colloids are solid particles with
diameters of 1-100 nm. 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 and
thermal decomposition. This method is widely employed to prepare oxide materials.
The reactions involved in the sol-gel process are
MOR + H2 O MOH + ROH (hydrolysis)
metal alkoxide
MOH + ROM M–O–M + ROH (condensation)
1. Formation of different stable solution of the 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 a solid mass.
4. Drying of the gel:In this step, water and other volatile liquids are removed from the
gel network.
5. Dehydration: The material is heated at temperatures upto 800 oC.
 XII-16-Green Chemistry and Nanochemistry (7)

Q.14. Give different analytical techniques used for analysis of Nanomaterials.

Ans : The synthesized material is analyzed by various analytical tools or techniques. The name of
the technique and its use is described as follows:

Name of Technique Instrument used Information

1. UV-visible spectroscopy U V-visible spectrophotometer Preliminary confirmation
of formation of
nanoparticles
2. X-ray Diffraction (XRD) X-ray diffractometer particle size, crystal
structure, geometry.
3. Scanning electron Scanning electron microscope Structure of surface of
microscopy (SEM) material that is morphology
4. Transmission electron Transmission electron particle size
microscopy microscope (TEM)
5. FTIR Fourier transform Fourier transform infrared Absorption of functional
infrared spectroscopy spectrophotometer groups. Binding nature.

*Q.15. Ridhima wants to detect structure of surface of materials. Name the technique she
has to use.
Ans: Scanning electron microscopy.

*Q.16. Give the full form (long form) of the names for following instruments.
a. XRD b. TEM. c. STM d. FTIR e. SEM
Ans: a. XRD X-ray diffractometer
b. TEM Transmission Electron Microscope
c. SMT Scanning Tunneling Microscope
d. FTIR Fourier transform infrared spectrophotometer
e. SEM Scanning Electron Microscope.

Q.17. Give history of Nanotechnology.

Ans : The term 'nanotechnology' was defined by Tokyo science University Professor, Nario
Taniguchi in 1974.
Nanomaterials have been produced and used by humans for hundreds of years. However,
understanding of certain materials as nanostructured materials is relatively recent.
 XII-16-Green Chemistry and Nanochemistry (8)
Due to the development of advanced tools that is sophisticated instruments, it has been
possible to reveal the information at nanoscale.
(a) Beautiful ruby red colour of some ancient glass paintings is due to gold and silver
nanoparticles trapped in the glass matrix.
(b) The decorative glaze or metallic film known as lustre found on some medieval
pottery is due to certain spherical metallic nanoparticles.
(c) Carbon black is a nanostructured material that is used in tyres of car to increase the
life of tyre. (Discovery in 1900). Carbon nanotubes are made up of graphite sheets
with nanosized diameter. They have highest strength.
(d) Fumed silica, a component of silicon rubber, coatings, sealants and adhesives is
also a nanostructured material.
Invention of Scanning Tunneling Microscope (STM) in 1980, led to the discovery of
fullerenes in 1986 and carbon nanotubes a few years later.

*Q.18. Which nanomaterial is used for tyres of car to increase the life of tyres ?
Ans: Carbon black.

Q.19. Give applications of Nanomaterials.

Ans : Nanochemistry has already contributed to number of innovative products in various fields
because of their unique physical, chemical, optical, structural, catalatic properties and so
on.
Applications:
(a) 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.
(b) Used in electronic devices. For example, Magnetoresistive Random Access
memory (MRAM)
(c) Nanotechnology plays an important role in water purification techniques.
Water contains waterborne pathogens like viruses, bacteria. 1.1 billion people are
without access to an improved water supply. 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)
Silver nanoparticles act as highly effective bacterial disinfectant, remove [Link] from
water.
(d) Self cleaning materials : Lotus is an example of self cleaning. The lotus plant
(Nelumbo nucifera) although grows in muddy water, its leaves always appear clean.
The plants leaves are superhydrophobic. Nanostructures on lotus leaves repel
water which carries dirt as it rolls off. Lotus effect is the basis of self cleaning
windows.

Q.20. Give advantages and disadvantages of Nanomaterials and Nanotechnology.

Ans: Advantages :
(1) Revolution in electronics and computing.
(2) Energy sector -nanotechnology will make solar power more economical. Energy
storage devices will become more efficient.
(3) Medical field : Manufacturing of smart drugs, helps cure faster and without side
effects. Curing of life threatening diseases like cancer and diabetes.
Disadvantages : Despite the possibilities and the advancements that the nanotechnology
offers to the world, there also exist certain potential risks involved with the disadvantages of
it.
(1) Nanotechnology has raised the standard of living but at the same time, it has
 XII-16-Green Chemistry and Nanochemistry (9)
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.
(2) Nanoparticles can cause lung damage. Inhaled particulated matter can be deposited
throughout the human respiratory tract and then deposit in lungs.
(3) The characteristics of nanoparticles that are relevant for health effects are size,
chemical composition and shape.



Exercises
1. Choose the most correct option.
i. The development that meets the needs of present without compromising the ability of
future generations to meet their own need is known as
a. Continuous development b. Sustainable development
c. True development d. Irrational development
ii. Which of the following is -isomer of BHC?
a. DDT b. lindane c. Chloroform d. Chlorobenzene
iii. The prefix 'nano' comes from
a. French word meaning billion b. Greek word meaning dwarf
c. Spanish word meaning particle d. Latin word meaning invisible
iv. Which of the following information is given by FTIR technique ?
a. Absorption of functional groups b. Particle size
c. Confirmation of formation of nanoparticles d. Crystal structure
v. The concept of green chemistry was coined by
a. Born Haber b. Nario Taniguchi
c. Richard Feynman d. Paul T. Anastas