Module-5: Green Technology

Microwave synthesis
Microwave irradiation provides an alternative to the conventional methods, for heating or
introducing energy into the system. It utilizes the ability of mobile electric charges present in
liquid or conducting ions in solid to transform electromagnetic energy into heat. Microwave-
assisted reactions are fast, clean, economic and eco-friendly and this technique has been
proposed as the “technology of tomorrow. Microwave radiation is electromagnetic radiation
spanning the frequency range 30 GHz-300 MHz (i.e., from a wavelength of 1 m to 1 cm).
Within this region of electromagnetic energy only molecular rotation is affected not the
molecular structure.
Working Principle
Microwave dielectric heating
Microwave chemistry is based on the efficient heating of materials by dielectric heating
effects.The definition of dielectric heating can be stated as – the process of heating up
material by causing dielectric motion in its molecules using alternating electric fields.
Dielectric heating works by two major mechanisms:
1) Dipolar polarization
2) Ionic conduction
1) Dipolar polarization
Polar molecules contains electric dipole moments. For a
substance to be able to generate heat when irradiated with
microwaves it must be a dipole, i.e. its molecular structure must
be partly negatively and partly positively charged. Since the
microwave field is oscillating, the dipoles in the field align to the
oscillating field. This alignment causes rotation, which results in
friction and ultimately heat is produced.
Here, the temperature of the molecules is related to the kinetic
energy of the molecules. As dielectric rotation of the molecules
occurs then the kinetic energy of the molecules increases and thus
the temperature of the molecules also increases. When the
molecules collide or come in contact with each other, this energy
gets transferred to all parts of the material thus heating up of
material takes place.

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2) Ionic conduction
During ionic conduction, dissolved (completely)
charged particles (usually ions) oscillate back and
forth under the influence of microwave irradiation.
This oscillation causes collisions of the charged
particles with neighbouring molecules or atoms, which
are ultimately responsible for creating heat energy. As
an example: if equal amounts of distilled water and tap
water are heated by microwave irradiation, then more
rapid heating will occur for the tap water because of its
ionic content.

Advantages of MW-assisted synthesis

1. Higher temperatures
2. Faster reactions, lesser by-products, pure compounds
3. Absolute control over reaction parameters
4. Selective heating/activation of catalysts
5. Energy efficient, rapid energy transfer
6. Easy access to high pressure performance
Difference between microwave heating and conventional heating
Microwave heating Conventional heating
The energy or heat transferred directly into The energy or heat is transferred through the
the molecules which is present in the reaction walls of the reaction vessel and then it transfers
mixture into the reaction mixture
Heat is transferred to the surface of the Heat is transferred to the surface of the material
material by Electromagnetic radiation by conduction or convection
The heat transfer does not require physical The heat transfer requires physical contact
contact between materials surface and vessel between materials surface and vessel
Heating takes place by Microwaves produced Heating takes place by electric or thermal
by Magnetron source
Heating of material involves Dielectric Heating of material involves Thermal
polarization of material Conduction mechanism
Heating is dependent on the properties of the Heating is less dependent on the properties of
materials. i.e., Selective in nature the materials. i.e., non selective in nature
Higher heating rate Lower heating rate

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Microwave assisted reactions
a) Hydrolysis:Benzyl chloride can be converted to benzyl alcoholusing water as the
nucleophile under microwave conditions in short time (3 min, 97% yield) than classical
method (about 35-40 min, 90% yield)

b) Hydrolysis of benzamide:A microwave assisted reaction is faster (approx. 10 min

with99% yield) than the classical method (approx. 1hour with 90% yield).

c) Oxidation: oxidation of toluene under microwave conditions in short time than

conventional method (~10-12 hours with low yield)

d) Reduction:Reduction of ketones to secondary alcohols and aldehydes toprimary

alcohols can be synthesised by using sodium borohydride(NaBH4) and aluminawithin 2
min with higher yield under MW condition.

e) Esterification: Conversion of p-methoxy benzoic acid to methyl benzoate with catalytic

amount of conc H2SO4 in methanol and irradiated under microwave radiation at 62 °C
for 3 min (Yield 95%)

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Bio-catalyzed reactions
Enzymes are catalysts evolved in nature to achieve the speedand coordination of a multitude
of chemical reaction necessaryto develop and maintain life.Enzymes are globular proteins
which range from 62to over 2500 amino acidresidues, but only a small portion(~3-4 amino
acids) are directly involved in catalysis. Enzymes do speed up the rates at which the
equilibrium positions of reversible reactions are attained. In terms of thermodynamics,
enzymes reduce the activation energies of reactions, enabling them to occur much more
readily at low temperatures - essential for biological systems.
The basic characteristics of enzymes includes
(i) All the enzymes are proteins and they follow the physical and chemical reactions of
proteins
(ii) Enzymes are sensitive and labile to heat
(iii) Enzymes are water soluble
(iv) Enzymes could be precipitated by protein precipitating agents such asammonium
sulfate and trichloroacetic acid.
Classification of enzymes
Enzymes are classified into six categories according to the type of reaction catalyzed
1) Oxidoreductases:The enzyme Oxidoreductase catalyzes oxidation/reduction
Example: Alcohol Dehydrogenases (ADH)

2) Transferases: The Transferases enzymes help in the transportation of the functional

group such as amine, carboxyl, carbonyl, methyl, acyl, etc., from a donor substrate to an
acceptor compound
Example: Transaminases

3) Hydrolases: Hydrolases are hydrolytic enzymes, which catalyze the hydrolysis reaction by
adding water to cleave covalent bond.
Example: Esterases, Proteases

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4) Lyases: Enzyme that catalyzes the breaking of various chemical bonds by means other
than hydrolysis and oxidation. Lyases that cleave carbon-carbon bonds, carbon-oxygen
bonds or carbon-nitrogen bonds
Example: Decarboxylases

5) Isomerases: Enzymes that catalyze reactions involving a structural rearrangement of a

molecule that can change a molecule from one isomer to another isomer.
Example: Alanine Racemases, Lactate Racemases

6) Ligases: Enzymes that are involved in bond formation reactions that joining (ligation) of
two molecules by forming a new chemical bond
Example: Carboxylase

Advantages of bio-catalysed reaction

1) Energy saving-active in mild condition. It can work at Low temperatures and moderate
pH.
2) Cost saving: Reduction in the amount of chemicals used, like solvents
3) Time saving – Reactions need less time.
4) Eco friendly – Fully bio degradable
5) Easy handling-less toxic in nature

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 6) Enzymes are highly selective for substrate
7) Less formation of by products
8) Recovery and reuse of catalyst at the end of the reaction
Synthesis of typical organic compounds by conventional and green route
1) Adipic acid:
Adipic acid or hexanedioic acid is the organic compound with the formula
(CH2)4(COOH)2. From an industrial perspective, it is the most important dicarboxylic
acid, mainly as a precursor for the production of nylon. Adipic acid otherwise rarely
occurs in nature, but it is known as manufactured E number food additive.
Conventional method:
Adipic acid is synthesized from a mixture of cyclohexanone and cyclohexanol called
KA oil (which stands for ketone-alcohol oil). The KA oil is oxidized with nitric acid to
give adipic acid as the final product of the reaction.

Green method: Adipic acid is synthesized by using Protocatechuic acid (PCA).

Protocatechuic acid is a simple phenolic acid which is found in a large variety of edible
plants. In this method Protocatechuic acid undergo decarboxylation by using an enzyme
Decarboxylase to form Catechol and further it undergoes oxidation to form Muconic
acid which is catalysed by an enzyme called Dioxygenase. Finally, Muconic acid
undergoes reduction in presence of enzyme Reductase to form Adipic acid

2) Paracetamol
Paracetamol also known as acetaminophen, is a medication used to treat fever and mild
to moderate pain. At a standard dose, paracetamol only slightly decreases body

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 temperature. Paracetamol may relieve pain in acute mild migraine but only slightly in
episodic tension headache. It is on the World Health Organization's List of Essential
Medicines. Paracetamol is available as a generic medication, with brand names
including Tylenol and Panadol among others.
Conventional method: Paracetamol is synthesized from Phenols. Phenols upon
treatment with dilute nitric acid and H2SO4 undergo nitration to give a mixture of ortho
and para nitrophenols. Then the mixture formed is further separated into ortho and para
nitrophenols by steam distillation. Separating the desired p-nitro phenol from the ortho-
byproduct, and reducing the nitro group with sodium borohydride. The resultant p-
aminophenol is then acetylated with acetic anhydride in presence of Sulphuric acid as
catalyst to form Paracetomol or Acetaminophen.

Green method: A biosynthetic pathway for direct biosynthesis of paracetamol from

glucose is as follows: first glucose is converted to p-aminobenzoic acid via the
upstream enzymes, then p-aminobenzoic acid is converted to p-aminophenol via
monooxygenase (MNX1), and finally p-aminophenol is converted to paracetamol via P.
aeruginosa arylamine N-acetyltransferase (PANAT).

3) Ethylene oxide
Ethylene oxide is a surface disinfectant that is widely used in hospitals and the medical
equipment industry to replace steam in the sterilization of heat-sensitive tools and

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 equipment, such as disposable plastic syringes. It is so flammable and extremely
explosive that it is used as a main component of thermobaric weapons;therefore, it is
commonly handled and shipped as a refrigerated liquid to control its hazardous nature.
Conventional method: The synthesis of ethylene oxide is as follows, first ethylene is
reacting with chlorine leads to the formation of ethylene chlorohydrin. Finally
dehydrochlorination of ethylene chlorohydrin leads to the formation of ethylene oxide.

Green method: Ethylene oxide can be synthesised by the oxidation of ethylene by

using enzyme Alkene Monooxygenases in presence of oxygen.

4) Methyl methacrylate
It is a colourless liquid and it is a monomer produced on a large scale for the production
of polymethyl methacrylate. Methyl methacrylate is also used for the production of the
co-polymer methyl methacrylate-butadiene-styrene, used as a modifier for PVC.
Another application is as cement used in total hip replacements as well as total knee
replacements.
Conventional method: Acetone and hydrogen cyanide are first reacted to produce
acetone cyanohydrin. Sulphuric acid converts the cyanohydrin to methylmethacrylate
with a methanol/water mixture under heating conditions.

Green method: In this method, the direct chemical conversion of a widely available
carbohydrate-derived itaconic acid/methanol into the methyl methacrylate via
decarboxylation/esterification reactions has been accomplished over solid barium
hexaaluminate (BHA) catalyst.
O O
OH BHA catalyst
HO O
CH3OH
O
Synthesis of nanoparticles by using plant extract and their applications

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Figure 1: Plant extract mediated nanoparticle synthesis

Silver nanoparticles (AgNPs)

The three main concepts for the preparation of nanoparticles in a green synthesis approach
are the choice of the solvent medium (preferably water), an environmentally friendly
reducing agent, and a nontoxic material for the stabilization of the nanoparticles.The
literature reports reveals thatdifferent plants such as Azadirachta indica (neem),
Ocimumtenuiforum (black Tulsi), Ficus benghalensis (Banyantree), Ocimum Sanctum
(Tulsi), Solanum nigrum (blackberry), Clitoriaternatea, etc. have been used for the
synthesis of AgNPs.
Synthesis of AgNPs using leaf extracts of Ocimum Sanctum
Preparation of plant extract
Plant extract was prepared from leaves of Ocimum Sanctum that were first rinsed with tap
water and then distilled water to remove all the dust and unwanted visible particles. Then
the leaves were dried at room temperature to remove the water from the surface of the
leaves. Tulsi leaves were boiled in 50 ml distilled water at 60 °C for about 10 min. The
supernatant was filtered using Whatman filter paper to remove the particulate matter. The
resultant pale-yellow colour solution should be stored at 4-8 °C.

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Preparation of AgNPs
1 mL of Tulsi leaf extract was slowly added to 5 mL of 2mM AgNO3 solution. On
addition, the colour change from pale yellow to colloidal brown indicated the formation of
silver nanoparticles.
Applications
1. Ag-NPs are widely known for its antimicrobial properties against microbes such as
bacteria, fungi, and virus.
2. Due to their proven antimicrobial properties, Ag-NPs are widely used in the daily
used commercial products.
3. Its importance can be judged from the fact that Ag-NPs can be used in various
form, such as colloidal (enamel, coating, and in paints), in liquid form (shampoo),
or in solid form (blending Ag-NPs with a solid material such as polymer scaffolds)
and even can be found suspended in materials like soap and nonwoven fabrics.
4. Ag-NPs are used in the water filtration membranes. The idea behind the use of Ag-
NPs in the water filtration membrane is based on the utilization of their proven
antimicrobial properties and slow-release rate of Ag-NPs from the membrane. The
slow-release rate prolongs capability of the membrane to be used as a protective
barrier against various bacterial and other pathogenic microbes present in the
water.
5. Silver nanoparticles have been demonstrated to present catalytic redox properties
for biological agents such as dyes, as well as chemical agents such as benzene.
Gold nanoparticles (AuNPs)
Greener synthesis of AuNPs for different industrial applications has been recognized
globally for their non-hazardous effects on the environment and human health. The plant-
based methods of AuNPs synthesis have been instrumental in defining new outlets for
generating nanoparticles of varied sizes, shapes and morphologies including gold nano
triangles, prismatic, tetrahedral, hexagonal platelet, icosahedral multiple twinned,
decahedral multiple twinned, and irregularly shaped particles. This has been achieved
through the application of extracts from different plants such as Coriander, Pea nut,
Solanum nigrum, Hibiscus cannabinus, Olive, Mango, etc.
Synthesis of AuNPs using Fruit peel extract of G. mangostana
Preparation of plant extract
The peels were washed thoroughly with tap water to remove dirt and washed again with
distilled water before being dried in ovenat 40°C. All the peels were ground into fine
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powder and stored at room temperature for further use. The extract was prepared by taking
the fine powder of fruit peel with 20 mL distilled water and boiled at 60°C for 30 mins.
The crude extract was filtered with filter paper.
Synthesis of AuNPs
In a conical flask, 20 mL of the peel extract was reacted with 10 mM of tetrachloroaurate
at room temperature under static conditions. While adding the solution colour changes
immediately from pale brownish to purple colour indicating the formation of Au
nanoparticles. The Au-NPs nanoparticles emulsion obtained was kept at 4°C.
Applications
1. Electronics - Gold nanoparticles are designed for use as conductors from printable
inks to electronic chips.As the world of electronics become smaller, nanoparticles
are important components in chip design. Nanoscale gold nanoparticles are being
used to connect resistors, conductors, and other elements of an electronic chip.
2. Photodynamic Therapy - Near-IR absorbing gold nanoparticles (including gold
nanoshells and nanorods) produce heat when excited by light at wavelengths from
700 to 800 nm. This enables these nanoparticles to eradicate targeted
tumours.When light is applied to a tumour containing gold nanoparticles, the
particles rapidly heat up, killing tumour cells in a treatment also known as
hyperthermia therapy.
3. Therapeutic Agent Delivery - Therapeutic agents can also be coated onto the
surface of gold nanoparticles.The large surface area-to-volume ratio of gold
nanoparticles enables their surface to be coated with hundreds of molecules
(including therapeutics, targeting agents, and anti-fouling polymers).
4. Sensors - Gold nanoparticles are used in a variety of sensors. For example, a
colorimetric sensor based on gold nanoparticles can identify if foods are suitable
for consumption.Other methods, such as surface enhanced Raman spectroscopy,
exploit gold nanoparticles as substrates to enable the measurement of vibrational
energies of chemical bonds. This strategy could also be used for the detection of
proteins, pollutants, and other molecules label-free.
5. Probes - Gold nanoparticles also scatter light and can produce an array of
interesting colours under dark-field microscopy. The scattered colours of gold
nanoparticles are currently used for biological imaging applications.Also, gold
nanoparticles are relatively dense, making them useful as probes for transmission
electron microscopy.
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6. Diagnostics - Gold nanoparticles are also used to detect biomarkers in the
diagnosis of heart diseases, cancers, and infectious agents. They are also common
in lateral flow immunoassays, a common household example being the home
pregnancy test.
7. Catalysis - Gold nanoparticles are used as catalysts in a number of chemical
reactions.The surface of a gold nanoparticle can be used for selective oxidation or
in certain cases the surface can reduce a reaction (nitrogen oxides). Gold
nanoparticles are being developed for fuel cell applications. These technologies
would be useful in the automotive and display industry.

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Self-study component: Major Environmental Pollutants
Air Pollutants
Primary air pollutants
Primary air pollutants are emitted directly into the air from sources. They can have effects
both directly and as precursors of secondary air pollutants (chemicals formed through
reactions in the atmosphere), which are discussed in the following section.
Sources, effects and control of primary air pollutants
i) Oxides of Carbon
Carbon monoxide (CO) and carbon dioxide (CO2) are the two oxides of carbon
Carbon monoxide
Carbon monoxide is one of the most serious air pollutants. It is a colourless and odourless
gas, highly poisonous to living beings because of its ability to block the delivery of
oxygen to the organs and tissues.
Sources
It is produced as a result of incomplete combustion of carbon.
Carbon monoxide is mainly released into the air by automobile exhaust.
Other sources, which produce CO, involve incomplete combustion of coal, firewood,
petrol, etc.
It is also formed during the decay of vegetables and animal matter
It is produced during the reaction of CO2 with carbonaceous materials at a higher temperature:
2CO2 + C → 2CO
CO is also formed by the dissociation of CO2 at a higher temperature:
2CO2 → 2CO + O2
In addition, vaious natural disasters such as volcanic eruption, natural gas emission, electrical
discharge during storms, seed germination etc., also liberates carbon monoxide.
Effects
CO is highly poisonous to humans being.CO binds to haemoglobin to form
carboxyhaemoglobin, which is higlystable than the oxygen-haemoglobin complex. In
blood, when the concentration of carboxyhaemoglobin reaches about 3-4 %, the oxygen
carrying capacity of blood is greatly reduced. This oxygen deficiency, results into
headache, weak eyesight, nervousness and cardiovascular disorder.
Hb + O2 → HbO2 (Oxygenated haemoglobin)
HbO2 + CO →HbCO (Carboxyhaemoglobin) + O2

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Control
Modification of internal combustion of engines to reduce the amounts of pollutants.
Carbon monoxide emissions from vehicles can be reduced bymaintaining properly tuned
engines and regularly checking for defects in the exhaust system.
The typical catalytic converter is used to combine oxygen and carbon monoxide and form
non-poisonous carbon dioxide.
The three-way catalytic converter for taking care of NOx, hydrocarbons and carbon
monoxide simultaneously.
Indoor carbon monoxide pollution due to use of charcoal grills, stoves,heating systems etc.
can be controlled by keeping the home or workplace well-ventilated.
Development of substituent fuels such as alcohol Development of pollution free power
sources to replace the internal engine.
Carbon dioxide (CO2)
Sources
Carbon dioxide is released into the atmosphere by respiration, deforestation, burning of
fossil fuels for energy, and by decomposition of limestone during the manufacture of
cement.Volcanic eruption and hot springs are natural sources of carbon dioxide.
Effects
It is a major greenhousegas, this, in turn melt glaciers, polar ice caps and result in flooding
of many coastal cities.
The increased amount of CO2 in the air is mainly responsible for global warming
It causes respiratory dissorders and suffocation.
ii) Oxides of Nitrogen
Nitrogen forms a series of oxides on combining with oxygen: nitrous oxide (N2O), nitric
oxide (NO),nitrogen dioxide (NO2), dinitrogen trioxide (N2O3), dinitrogen tetroxide
(N2O4) and dinitrogenpentoxide (N2O5).However, only the NO and NO2 are important
from the pointof view of environmental pollution. They are collectively referred to as
NOx. These oxides act asprimary pollutants by producing toxic reactions themselves and
they also act as secondarypollutants by combining with other constituents of the
atmosphere to give rise to photochemicalsmog, acid rain and aerosols.
N2 + O2 →2NO 2NO + O2 → 2NO2
Sources:
Automobile exhaust and large power plant
Supersonic jets and rockets.

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Industries manufacturing explosives and nitrogenous fertilizers.
Bacterial action releases 3x108 tons of NO.
Effects:
They affect the color of textiles
They affect lungs, heart, eyes etc.
They reduce oxygen carrying ability of blood
Responsible for chronic asthma and bronchitis
Causes yellowing of green leaf.
Higher concentrations of NO2 damage the leaves of plants and retard the rate of
photosynthesis.
Control:
The fuel is fired at a relatively high temperature with a stoichiometric supply of 90-95% of
air.
Two stages combustion process must be used in power plant,
A three-way catalytic converter removes hydrocarbon, carbon monoxide and
nitrogenoxides from auto-exhaust. Hydrocarbons and carbon monoxide are oxidised
whilenitrogen oxides are reduced.NO reacts with CO in the exhaust system as shown
below
2NO + 2CO → N2 + CO2
Nitric oxide and nitrogen dioxide interact with hydrocarbons
nNOx + Hydrocarbons → n N2 + CO2 + H2O
A three-way catalyst consists of a mixture of platinum, palladium and rhodium deposited
on a high surface area honeycomb made of ceramic and metal, or alumina pellets.
iii) Oxides of Sulphur
SOxis a general term used to refer all oxides of sulphur, out of these, sulphur dioxide
(SO2) andsulphur trioxide (SO3) are major ones. Sulphur dioxide is a colourless gas having
a pungent,irritating odour and taste. It is water soluble, forming sulphurous acid, which is
a weak acid.Sulphur dioxide slowly combines with oxygen in the air to form sulphur
trioxide. This thenrapidly reacts with water to give sulphuric acid.
Sources
Sulphur dioxide is produced naturally from volcanoes and hot springs.
Sulphur dioxide is alsoobtained by oxidation in air of hydrogen sulphide released from
marshes and swamps on land andfrom biological decay in oceans.
2H2S + 3O2 → 2H2O + 2SO2
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2SO2 + O2 → 2SO3
Combustion of fossil fuels at power plants, other industries and vehicles is the largest
anthropogenicsource of SO2.
Other sources of SO2 emissions include smelting of sulphide ores, refining ofpetroleum,
manufacture of sulphuric acid, paper making and burning of domestic refuse.
Coalcombustion is the largest source of sulphur dioxide, contributing approximately 60%
of itglobally.
It is formed during the roasting of sulphide ores
Effects
Higher levels of exposure to sulphur oxides lead to asthama, bronchitis and lung cancer.
Sulphur oxides destroy plant cells and interfere with chlorophyll synthesis.
Crop yields are reduced in the presence of sulphur dioxide pollution
H2SO4 mist with soot particles and SO2 forms a smog called London Smog or Industrial
Smog.
SO2 and H2SO4 mist attacks marble or limestone causes Stone leprosy.
Paper becomes yellow and loses its strength, corrodes metals and textiles
Control
Removal of Sulphur from fuel before burning
Use of low Sulphur content fuel
Substitution of other energy sources
SO2 formed during the burning of coal is controlled by using limestone-dolomite process.
Limestone decomposes into CO2 and CaO. CaO combines with SO2 to form CaCO3 and
CaSO4

iv) Mercury
Sources:
Mining and metallurgical operation.
Industries manufacturing Batteries, amalgam, thermometer and mercury vapor lamp.
Chloro-alkali & pesticide industries
Discarded amalgams and tooth filling

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Combustion of lignite coal.
Effects:
It can cause neurological damage including paralysis.
causes irritability and depression.
Responsible for blindness, insanity, birth defects etc.,
Control:
Reducing mercury mining and consumption of raw materials and products that generate
mercury.
Substitution of non-mercury alternatives.
Mercury waste management.

v) Lead
Sources:
Mining and metallurgical operation.
Industries manufacturing Batteries.
Red lead (Pb3O4), lead chromate (PbCrO4)and white lead (PbCO3, Pb (OH)2) are used as
pigments in paints.
Tetraethyl lead used as anti-knocking agents
Effects:
It affects renal system.
It retards the growth of mental ability of a child.
Affects the intelligent quotient of a child.
Affects the reproductive and gastrointestinal functions of human beings.
It adversely affects central and peripheral nervous systems and inhibits the synthesis of
haemoglobin.
Control:
Reducing lead mining and consumption of raw materials and products that generate lead.
Substitution of non-lead alternatives.
High-octane content petrol.
Lead waste management.

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