Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Module-4
Green Chemistry
Green Chemistry is the utilization of a set of principles that reduces or eliminates the use or
generation of hazardous substances in the design, manufacture, and applications of chemical
products. Green chemistry is also known as sustainable chemistry. Green chemistry is the
practice of chemical science and manufacturing in a manner that is sustainable, safe, and non-
polluting and that consumes minimum amounts of materials and energy while producing little
or no waste material.

Basic Principles of Green Chemistry

According to the work carried out by Paul T Anastas, the following basic principles of green
chemistry have been formulated.
1. Design chemical syntheses to prevent waste.
2. Avoid hazardous products.
3. Design syntheses so that the final product contains the maximum proportion of the
starting materials.
4. Design safer chemicals.
5. Design syntheses with less energy requirement.
6. Appropriate solvent must be selected.
7. Use renewable starting materials rather than depletable.
8. Avoid using blocking or protecting groups or any temporary modifications.
9. Use catalyst wherever possible.
10. Design chemical products that are biodegradable.
11. Design chemicals to eliminate chemical accidents during preparations.
12. Use proper analytical techniques to control hazardous compounds.

Major environmental pollutants

The waste matter that contaminates the environment is called pollutants. Major environmental
pollutants and their effect on our planet earth are
1. Carbon monoxide: partial combustion of fuel in automobiles, industries, and oil-
refineries, cigarette smoke, and domestic-heat appliances are the sources of carbon
monoxide. It causes a headache, visual difficulty, paralysis, death in human beings, effect
on the cardiovascular system and reduces the oxygen-carrying capacity of the blood.
2. Nitrogen oxides: Combustion of coal, oil, natural gas, and gasoline are man-made
sources. It is naturally produced by lightning. Other sources are acid manufacture,
explosive industry, and acid-pickling plants. Excess concentration of oxides of nitrogen
limits the visibility of roads causes eye irritation and difficulty in breathing thereby
leading to asthma and bronchitis.
3. Oxides of Sulfur: Thermal power plants, petroleum industries, oil refineries, sulfuric acid
plants, and sulfide ore-roasting plants are the main sources of oxides of sulfur. It is the
cause of cardiac, respiratory, and pulmonary diseases, eye irritation, and throat troubles.

Mrs. BHAGYA N P/ Mr. RAVEENDRA R S/ Mr. ANIL KUMARA K V/ Mr. MUTTURAJU M Page 1
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

It also leads to metal corrosion, damage to plant cells, membranes, and chlorophyll.
Green chemical approach
Microwave synthesis
A microwave is a form of electromagnetic energy, which lies between infrared radiation and
radio waves. Microwave passes through the material and causes the oscillation of molecules,
which produces heat.
Microwave-assisted organic synthesis is a promising green chemical approach and is defined
as the preparation of desired organic compounds from starting materials by involving
microwave irradiation. Microwave radiation is a nonionizing form of energy which do not alter
the molecular structure of the compounds and provides only thermal activation. This
phenomenon is based on the ability of a specific material to absorb microwave energy and
convert it into heat. The principle of microwave heating is that the energy can be applied
directly to the sample rather than via the vessel. Teflon and polystyrene containers are used as
reaction containers but not metallic containers.
In microwave-induced organic reactions, the reactions can be carried out in a solvent medium
or on a solid support i.e., without using the solvent. Some solvents used are N, N-
dimethylformamide, formamide, methanol, ethanol and chlorobenzene.
Some important microwave-assisted organic synthesis are
1. Hydrolysis of benzyl chloride.
Hydrolysis of benzyl chloride with water under microwave conditions yields 97% in 3
minutes.While the normal way takes about 35 minutes.
C6H5CH2Cl + H2O C6H5CH2OH
2. Hydrolysis of benzamide.
Hydrolysis of benzamide yields 99% in 7 minutes under microwave conditions. While under
normal conditions, it takes 1 hour.
C6H5CONH2 C6H5COOH
3. Oxidation of toluene
Oxidation of toluene with potassium permanganate under normal conditions of refluxing takes
10-12 hr. While under microwave conditions, it takes only 5 minutes with 40% yield.
4. Saponification of methyl benzoate.
Saponification of methyl benzoate to benzoic acid under microwave conditions yields 84% in
2.5minutes.

C6H5COOCH3 C6H5COOH

5. Esterification of carboxylic acid and alcohol.

Benzoic acid and n-propanol under microwave conditions yield 70% propyl benzoate in
6minutes in the presence of a sulfuric acid catalyst.
C6H5COOH + nC3H7OH C6H5COOC3H7
Advantages
1. Time-saving.
2. Can be carried out in solid-state.
3. Can be carried out in the water or organic solvent.
4. Organic solvent required is a small quantity.
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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Bio-catalyzed reactions
A catalyst is a substance that promotes the reaction. The substances like enzyme, that initiates
or modify the rate of chemical reaction in a living body is called biocatalyst. Enzymes are
proteins that catalyze all aspects of cell metabolism. Using enzymes as catalysts can improve
the purity and reduce the amount of organic solvent needed, resulting in a greener
manufacturing process.
The biocatalytic reaction has many advantages in relevance to green chemistry. Some of them
are

1. Most of the reactions are performed in an aqueous medium in the surrounding

temperature and pressure.
2. Biocatalytic conversions involve only one step and are stereospecific.
3. Reactions are fast.
4. Protection and deprotection of functional groups are not necessary.
Biochemical reactions are chemoselective, regioselective, stereoselective in comparison with
conventional chemical reactions. The major six classes of enzymes that catalyze biochemical
reactions are

1. Oxidoreductases: These enzymes catalyze oxidation-reduction reactions.

E.g., Oxidases directly oxidize molecular oxygen. Dehydrogenases catalyze the
removal of hydrogen from one substance and transfer it to another substance.
2. Transferases: These enzymes catalyze the transfer of various functional groups.
e.g.,transaminase.
3. Hydrolases: These enzymes catalyze hydrolytic reactions. e.g., penteases (proteins)
and esterase (esters).
4. Lyases: These types of enzymes are of two types, one that catalyzes addition to
the double bonds, functional group and the other which catalyzes the removal of
groups and leaves a double bond.

5. Isomerases: These enzymes catalyze isomerization. e.g., racemases and epimerases.

6. Ligases: These enzymes catalyze the formation or cleavage of sp3-hybridized carbon.

Solvent-free reactions
There was a belief that no reaction is possible without the use of a solvent. It has been found
that many reactions occur in solid state without the solvent. Such reactions occur more
efficiently and with more selectivity compared to reactions carried out in solvents. They are
simple to handle, reduce pollution, comparatively cheaper to operate and are especially
important in industry. It is believed that solvent free organic synthesis and transformations are
industrially useful and largely green.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Advantages of Solvent-free Reactions

1. Economic.
2. As solvent is not required, it is environmentally friendly.
3. Solvent removal after reaction completion is not required i.e. purification step not
required.
4. Reaction rate is high due to more availability of reactants.
5. Bring down handling costs.
6. Lower energy usage.

Issues with organic solvents: they are expensive, highly regulated, volatile, flammable, toxic,
and carcinogenic.

Disadvantages of Solvent-free Reactions

1. Require homogenous reactants.
2. Viscosity is high in the reaction system.
3. Unsuitable for solvent-assisted chemical reactions.

Conditions of Solvent-free Reactions/Supercritical fluid (SCF)

Beyond a specific temperature and pressure, some liquid becomes a supercritical fluid. At this
state, it is neither a gas nor a liquid but has properties of both of these, known as critical point.
Commonly used supercritical fluid are carbon di oxides and water.

Properties of Supercritical fluid

1. Penetrate solids like gas.
2. Dissolves materials like liquid.
3. There is no surface tension.
4. In supercritical environment only one phase exists and hence no liquid-gas phase
boundary.
5. All supercritical fluids are completely miscible with each other.
6. Solubility in a SCF tends to increase with density of the fluid at constant temp.
7. Easily recoverable by changing pressure and temp.

Synthesis of adipic acid

Adipic acid is required in large quantity, about 1 billion kg per year for the synthesis of nylon,
plastic, and lubricants. Conventionally, adipic acid is prepared using benzene as starting
material. Disadvantage of preparing adipic acid by conventional method are 1. Benzene is
produced from non-renewable source. 2. Nitrous oxide is produced as a by-product, which
contributes to the greenhouse effect and destruction of the ozone layer.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Conventional synthesis of adipic acid

Traditional pathway: Using Benzene (Carcinogenic solvent)

Benzene is hydrogenated using Ni-Al2O3 catalyst at 370–800 psi to cyclohexane. This is oxidized
using Co catalyst to a mixture of cyclohexanone and cyclohexanol. This is then converted to adipic
acid using ammonium vanadate and nitric acid, with the help of a catalyst

Green synthesis of adipic acid Method 1: Using glucose (safe)

Adipic acid is synthesized using glucose as starting material and E. coli bacteria as a
biocatalyst. Synthesis involves nontoxic and renewable resource D-glucose as staring material
and is conducted in water instead of organic solvent.

Synthesis of Paracetamol
Paracetamol (or acetaminophen) is a common analgesic, a drug that is used to relieve pain,
reduce fever and headache. Conventionally, it is prepared from p-nitro phenol by reduction
using tin and hydrochloric acid followed by reaction with acetic anhydride-acetic acid mixture.

Conventional synthesis of Paracetamol from Phenol

The starting material of Paracetamol is phenol, which is nitrated to give a mixture of the ortho
and para-nitro phenol. The o-isomer is removed by steam distillation, and the p-nitro group
reduced to a p-amino group. This is then acetylated to give paracetamol.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Green synthesis of Paracetamol

In green synthesis of paracetamol, p-hydroxyacetophenone is treated with ammonia and
hydrogen peroxide in presence of titanium (IV)-silicate catalyst to give the oxime of p-
hydroxyacetophenone. This oxime of p-hydroxyacetophenone on Beckmann rearrangement (A
rearrangement of an oxime functional group to substituted amides) gives paracetamol.

Industrial applications of green chemistry

1. Pharmaceutical industry was among the first to recognize the value of green chemistry.
By using green chemistry procedures, we can minimize the waste of materials, maintain
the atom economy, and prevent the use of hazardous chemicals and pollution in drug
discovery.
2. Food & Flavour Industry: Green chemistry can provide new opportunities to produce
a wider range of natural flavouring substances using clean technologies.
3. Polymer Industry.
4. Textile and Tannery Industry.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Green fuel
Introduction
A fuel derived from biomass is called as green fuel. They are considered as renewable, eco-
friendly, relatively less flammable compared to fossil fuel, has better lubricating properties and
reduce greenhouse gases up to 65 percent. It can be manufactured from wide range of materials.
Most common forms of green fuels are
1. Solar Power.
2. Wind Power.
3. Hydropower.
4. Geothermal Energy.
5. Biomass.
6. Biofuels.

Hydrogen fuel
Hydrogen fuel that is created using renewable energy instead of fossil fuels. It is a universal,
light, and highly reactive fuel. Hydrogen has the highest energy content per unit of mass of any
chemical fuel and can be substituted hydrocarbon in a broad range of applications. It can be
easily produced from water found in abundance. The flame speed of hydrogen burning in air
is greater than for natural gas and the energy required to initiate the combustion is very less.
Hydrogen production
Pure hydrogen does not occur naturally in the earth in large quantities, it is extracted from other
compounds by a chemical process. Based on the source of energy they are a different way to
the production of hydrogen. Most of the industrial hydrogen is produced from natural gas
through a process known as steam methane reforming. However, this method has the
disadvantage of releasing large quantities of CO2 into the atmosphere. The abandoned supply
of water and sunlight offers us an alternative source to produce hydrogen apart from fossil fuels
and biomass.
Photo electrocatalytic (PEC)
PEC water splitting involves the photo-generated carriers on the surface and reactants
adsorbed on surface or in electrolytes. The reaction takes place at the electrode-electrolyte
interface
Principle: Photo electro catalytic water splitting is based on the conversion of the light energy
into electricity within a cell containing two electrodes (or three), immersed in an aqueous
electrolyte. Out of two electrodes at least one electrode or both electrode is made up of a
semiconductor and able to absorb the light. This electricity is then used for water electrolysis.
TiO2 based photo catalysts is used for these processes.

Reaction mechanism
Light-induced intrinsic ionization of the semiconducting material resulting in theformation of
electronic charge carriers.

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

2h ᶹ 2𝑒- + 2h+

Where, h is the Planck’s constant, ᶹ is the frequency, 𝑒- is the electron, h+ is the hole.
Oxidation of the water at the photo anode by the holes.
2h + + H2O ½ O2 + 2H+
Transport of 𝐻+ ions from the photoanode to the cathode through the electrolyte and
transport of electrons from photoanode to the cathode through the external circuit.
Reduction of hydrogen ions at the cathode by electrons.
2H+ + 2𝑒- H2

Fuel Cells
Introduction:
Fuel cell is a device, which converts chemical energy of the fuel and oxidant into electrical
energy. Electrical energy is obtained by the combustion of fuels in these galvanic cells.
“Fuel cells are galvanic cells which converts chemical energy of the fuels into electrical energy through
catalyzed redox reactions with elimination of minimum harmful byproducts”.
Fuel is represented as
Fuel / electrode / electrolyte / electrode / oxidant
At anode, fuel undergoes oxidation, when battery discharge potential, the following reactions takes
place at respective electrodes.
Fuel Oxidized product + ne-
At cathode, oxidant is reduced.
Oxidant + ne- reduced product

S. No Conventional battery Fuel cells

1 Battery makes electricity from the Fuel cell makes its electricity from
energy it has stored inside the battery fuel in an external fuel tank
2 Battery may run dead Fuel cell will make electricity as
long as fuel is supplied
3 Store chemical energy Do not store chemical energy

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

4 Reactants are not supplied and the Reactants are supplied

products are not removed continuously and the products are
removed simultaneously
5 Construction cost is high Construction cost is low
6 Life time is less Life time is higher than battery
Limitation of Fuel cell:

1. Power output is moderate.

2. Fuels are to be stored in tanks under very high pressure in tanks.
3. It generates only DC and should be converted to AC.

Advantages of fuel cells:

1. Do not pollute the atmosphere.

2. Electrical energy can be obtained continuously.
3. Fuel cell provides high quality of DC power.
4. Fuel cells have a higher efficiency than diesel or gas engines.

Methanol – Oxygen fuel cell (CH3OH - O2)

Composition:
Fuel : CH3OH
Oxidant : Oxygen
Electrolyte : H2SO4
Voltage : 1.2V

Construction:

1. It consists of anodic and cathodic compartments.

2. Both the compartments contain platinum electrodes.
3. Methanol containing H2SO4 is passed through anodic compartment and oxygen is passed through

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

cathodic compartment.
4. Sulphuric acid is used as electrolyte
5. A membrane made of cellulose is provided which prevents the diffusion of methanol into the
cathode.
6. The output voltage is 1.2V
Working:

Application:
1. Used in military applications
2. Large-scale power productions.

Solar Energy
Photovoltaic cells (Solar cells):
The device, which converts solar energy into electrical energy, is called photovoltaic cell and the
phenomenon is called photovoltaic effect.

Construction, working and applications of PV Cell:

Principle: The principle involved is the ejection of electrons from metal surface by striking with
photons of solar radiation.

Construction:

1. The device consists of p-n junction diode coated with anti reflective la yer (TiO2).
2. Two electrical contacts are provided, one in the form of metallic grid at the top of the junction and
the other is a layer silver on the bottom of the cell.
3. The antireflective layer coated in between the metallic grids allows light to fall on the
semiconductor.
Working:
The photons of solar radiations enters n-type semiconductor breaks barrier potential and moves to p-
type semiconductor where photons knocks the electrons in p type to form electron hole pair. The free

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 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

electrons so formed will travels through the circuit from n-type and recombines with holes again in p-
region. The movement of electrons from n type to p type generates electric current. The electrical
energy produced from the solar cell is used for various applications.

Advantages of PV cells:
1. Eco friendly energy conversion device.
2. Do not undergo corrode
3. No moving parts in PV cell, hence no wear and tear.

Disadvantages of PV cells:
1. Installation cost is high.
2. Produced only during the day time.
3. It generates only DC current.

Applications:
1. Used in toys, watches, remote lighting systems
2. Used in water pumping, water treatment.
3. Used in emergency power, satellites etc.

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