GREEN CHEMISTRY AND

ALTERNATIVE ENERGY
RESOURCES
Keerthana V
Niveditha Shekhar
Misba Khanum S
Anantha Lakhsmi LG
WHAT IS GREEN CHEMISTRY?
1. Green chemistry is the invention, design,
development and application of chemical products
and processes that reduce or eliminates the use and
generation of hazardous substances.

2. It aims to provide:
• Eco-friendly chemical technology.
• Replacement of organic solvent and to minimize
waste product.
• Use of renewable feed stocks.

3. Environmental pollutants are basically oxides of

nitrogen, sulphur and carbon.
 OXIDES OF NITROGEN:
1. NO, NO2, NO-3 & N2O are the common oxides of nitrogen.

2. Sources:
* N2 & O2 are the main constituents of air.
* When fossil fuel is burnt, di nitrogen & di oxygen
combine to yield NO & NO2.
N2 (g) + O2 (g) → 2NO(g)
2NO(g) + O2(g) → 2NO2(g)
* Bacterial decomposition of nitrogenous compounds releases
NOx in atmosphere.

3. Impacts:
* Higher levels of NO2 promotes the formation of
photochemical smog.
* Decreases immunity, limits in visibility of roads and dries out eye irritation.
* Exposure of high level NO2 causes:
(i). Chronic lung disease.
(ii). Damages respiratory tract.
(iii). Causes Asthma &lung cancer.

* Causes acid rain – NO2 and N2O5 reacts with H2O and O2 to
form HNO3.
 OXIDES OF SULPHUR :
1. SO2 is a primary pollutant & SO3 is a secondary pollutant.
2. Sources of SOx:

* Natural sources of release of sulphur dioxide into atmosphere

is volcanic eruptions.

*Oxides of sulphur are produced when sulphur containing fossil

fuel is burnt.
* Petroleum industries, oil refineries, sulphuric acid plants and
nuclear power plants leads to sulphur dioxide and these
further reacts with oxygen to give sulphur trioxide & sulphuric
acid.

SO2(g) + O2(g) -----> SO3(g) + O2(g)

SO2(g) +H2O -----> H2SO4(aq)

3. Impacts of SOx :

* 1ppm of SO3 in air causes breathing discomfort and irritation to the respiratory tract.

* Eye irritation, throat troubles

* Cause acid rain that causes damage to aquatic life.

* Affects plant life on land by causing an imbalance in plant nutrients.

 OXIDES OF CARBON :
1. CO and CO2 are the oxides of carbon found in nature. It is
estimated that about 290 million tonnes of carbon monoxide are
discharged into the atmosphere annually. It is colourless,
odourless, non-corrosive and toxic in nature.

2. Sources of CO:
* Carbon monoxide is released by the partial combustion of
fuel in automobiles, industries & oil-refineries.
2C + O2 →2CO

* Cigarette, beedi and domestic heat-appliances are the other

sources of CO.

* Dissociation of CO2 at very high temperature gives CO.

CO2→CO + O

3. Impact:
* When air contaminated with CO is inhaled:
(i). CO binds to haemoglobin-forms carboxy hemoglobin.
HbO2 + CO→ HbCO + O2
(ii). Causes headache
(iii). Weak eyesight
(iv). Heart disease, paralysis & even death of person.

* Affects leaf drop, leaf curling, reduction of leaf size &

chlorophyll with premature aging.

* Increases Global warming.

12 PRINCIPLES OF GREEN CHEMISTRY
1. Prevent waste.

2. Maximize atom economy.

3. Design less hazardous chemical synthesis.

4. Design safer chemicals and products.

5. Use safer solvents and reaction conditions.

6. Increase energy efficiency.

7. Use renewable feedstocks.

8. Avoid chemical derivatives.

9. Use catalysts, not stoichiometric reagents.

10. Design chemicals that degrades after use.

11. Analyse in real time to prevent pollution.

12. Minimize the potential for accidents.

 VARIOUS GREEN CHEMICAL APPROACHES
1. Green chemistry aims to design and
produce cost-competitive chemical
products and processes that attain the
highest level of the pollution-prevention
hierarchy by reducing pollution at its
source.

2. There are three main approaches of

green chemistry. They are: Bio�catalysed�reactions

* Microwave synthesis.
* Bio catalysed reactions.
* Solvent free reactions.

Solvent free reactions

MICROWAVE SYNTHESIS
MICROWAVE SYNTHESIS
Definition: Heating chemicals for their reaction by microwave
radiation is generally referred as microwave synthesis.

Example:
• Synthesis of methyl benzoate – Classical synthesis
require 1 hour but microwave synthesis require 5 min
for esterification of benzoic acid to methyl benzoate.

Principle: When substance is exposed to MW radiation, 3 process

may occur. MW may be absorbed, reflected or just pass through it.

There are 2 mechanisms of interaction between material & MWR.

* Dipole interaction.
* Ionic interaction.
Both involves coupling between MWR and target material.
• When a dipolar molecule is subjected to MWR, it tries to oscillate
in the direction of electric field.
• This makes the molecules to rotate back and forth constantly,
trying to align its dipole with the oscillating electric field.
• Now when all molecules start orienting, there will be friction
generated between them.
• The friction between each rotating molecule results in heat
generation.

Advantages:
* Most reactions are completed within few minutes. So, reactions
are rapid.
* Small volume of solvent is sufficient.
* Low operating cost and reduction in unwanted waste.
 BIO CATALYSED REACTIONS
Biocatalysts is defined as the use of natural substances that include enzymes
from biological sources to speed up chemical reactions and the phenomenon is
called biochemical catalysis or enzyme catalysis.

Characteristics:
• Enzymes can be derived from plants, animal tissue or
micro-organisms (bacteria, fungi, yeast).
• They have 3D structure that fits the reactants and catalyse
nearly all biochemical reactions.
• Enzymes are highly sensitive to temperature. For any enzyme
temperature and pH will be in the range of 15-350C and pH
range 5-7.

Example: Biofuels-
The enzyme invertase catalyses the hydrolysis of sucrose to
glucose and fructose. The zymase enzyme catalyses the
fermentation of glucose or fructose to ethanol.
C12H22O11 + H2O → C6H12O6 + C6H12O6
(Enzyme - Invertase)
C6H12O6→ 2C2H5OH + 2CO2
(Enzyme- Zymase)

Applications:
• Enzymes can be used in the textile industries.
• Enzymes have the importance in the paper manufacturing.
• Enzymes can be used as surface disinfectants. Example: Trypsin

Advantages:
• Bio-catalysed reactions are performed at mild conditions and use water as solvents.
• They are economically and environmentally more efficient.
• Bio-catalysed reactions generate less waste and higher purity than conventional method.
 SOLVENT FREE REACTIONS
Definition: Solvent free reaction is a chemical reaction carried out
in the absence of solvent.
• Solvent free reactions are more efficient and more selective
compared to reactions carried out in solvents.
• These reactions are simple to handle, reduces pollution and
comparatively cheaper to operate.
• A solvent-free reaction may be carried out using the reactants
alone or incorporating them in clays, zeolites, silica, alumina or
other matrices to achieve high degree of stereoselectivity in the
products and to reduce by-products.
• These solid-state reactions can be easily monitored by IR and
UV spectra in the solid state.

Example: Grignard reaction

When ketone is treated with Grignard reagent in the
absence of solvent it forms an adduct and an alcohol.
Ph2CO + R-MgX → Ph2RCOH + Ph2CHOH

Advantages:
• Less expensive.
• Simple to handle.
• Reaction rate is high.
• Less energy is required.
 SYNTHESIS OF ADIPIC ACID
Adipic acid is an organic compound that is used in the production
of various products such as Nylon, Polyurethane, Polyvinyl chloride etc.

The molecular structure of Adipic acid is:

It is mainly used in pharmaceuticals, as food additives, cosmetic

products, as lubricant.

It is also used in some calcium carbonate antacids to make them tart.

Adipic acid can be prepared by two methods:

*Conventional synthesis. Applications of Adipic Acid
*Green synthesis ( route).

In conventional synthesis method starting material is

benzene whereas in green route method starting
material is glucose.

Also, conventional method requires high pressure and

temperature whereas greener route requires less temperature and pressure.
CONVENTIONAL�SYNTHESIS�OF�ADIPIC�ACID
When benzene is hydrogenated using nickel in presence of
Aluminium oxide at very high pressure gives cyclohexane
which on oxidation yields two products in presence of Cobalt
that is cyclohexanone and cyclohexanol. When both
cyclohexanone and cyclohexanol is treated with ammonium
vanadate at 80°C, along with Cu in 60% HNO3. Adipic acid is
obtained.

GREEN�SYNTHESIS�OF�ADIPIC�ACID
Adipic acid is obtained from glucose via green route as it is a
renewable and non- carcinogenic. In this method glucose is
treated with bacteria E coli, which brings about
degradation and ring opening to form cis muconic acid.
 SYNTHESIS OF PARACETAMOL
* Paracetamol is an analgesic and antipyretic drug that is used
to temporarily relieve mild-to-moderate pain and fever. It is
commonly included as an ingredient in cold and flu medications.

* It is used to get relief of headache, toothache, sore throat,

migraine etc.

* It's IUPAC name is N-(4-hydroxyphenyl)acetamide.

* Molecular structure of Paracetamol is :

* It can be prepared by following two methods :

Conventional synthesis.
Green synthesis.

* In both these methods phenol is used as a starting

product.
 CONVENTIONAL SYNTHESIS OF
PARACETAMOL
In this method, paracetamol is prepared by acetylation of aminophenol.
Phenol is nitrated by treating it with dilute H2SO4 and HNO3 mixture which
yields o-nitro phenol and p-nitro phenol. p-nitro phenol is separated through
Conventional synthesis steam distillation from o-nitro phenol. Later p-nitro phenol is reduced using
sodium borohydride to form p–amino phenol, which yields paracetamol on
N-acetylation using acetic anhydride.

GREEN SYNTHESIS OF PARACETAMOL

Here phenol is treated with acetic anhydride directly in presence of HF
to form 4-hydroxy acetophenone, which yields 4-hydroxy acetophenoxime
on treating with hydroxyl amine, causing Beckmann rearrangement to
form Paracetamol.

Green synthesis
INDUSTRIAL APPLICATIONS OF GREEN CHEMISTRY
* Waste minimization in drug discovery.
* Green Technologies in the Pharmaceutical Industry.
* Environmental and Regulatory Aspects.
* Food & Flavour Industry.
* Paper & Pulp Industry.
* Polymer Industry.
* Sugar & Distillery Industries.
* Textile and Tannery Industry.
1. Green fuels also called green hydrocarbons,
biofuels, are fuel produced from biomass
sources through a variety of biological and
thermochemical processes.

2. Hydrogen production: Sunlight and water are

the most abundant, clean, renewable and
natural energy resources on earth. Their
conversion to hydrogen has been described as an
ideal solution to counter the environmental
issues associated with fossil fuels. Hydrogen is
regarded as the clean, efficient, and viable
alternative source of energy, provided it is
sourced via sustainable processes.

3. Hydrogen production is done in two ways:

(a). Hydrogen production by photo-

electrocatalytic water splitting.
(b). Hydrogen production by
photo-catalytic water splitting.
 Hydrogen production by
photo-electrocatalytic water splitting

Step 1: Formation of electron–hole pairs from sun light irradiation on the photo-anode.

Photo-anode + 2hv -----> 2e- + 2h+

(Excitation of TiO2 by sun light)

Step 2: The oxidation of water molecule by holes on the surface of anode to produce O2 and H+
ion.

H2O + 2h+ ------> 2H+ + ½O2

(At the surface of photo-anode)

Step 3: The transfer of electrons through an external circuit to the cathode and the reduction
of H+ion by electrons on the cathode surface to produce H2.

2H+ + 2e- -----> H2

❖ The overall reaction is

H2O + 2hv -----> H2 + ½O2

❖ The produced hydrogen can be used as fuel in hydrogen fuel cell.

 HYDROGEN PRODUCTION BY
PHOTO-CATALYTIC WATER SPLITTING

Splitting of water to get hydrogen by using a photocatalyst and by

using solar energy is called
photocatalytic water splitting.

• In this process, semiconducting photocatalyst (TiO2) is directly

suspended in water. When sunlight falls on the photocatalyst,
sunlight energy excites an electron from photocatalyst. Hence it
forms electron–hole pairs.

• The oxidation of water by holes on the surface of photocatalyst

to produce O2 and H+ ion.
H2O + hv + 2h+ -----> 2H+ + ½O2

• The H+ ions undergo reduction on the surface of the

co-catalyst (Pt, NiO, RuO2, etc.) to produce H2.
2H+ + 2e- -----> H2

❖ The overall reaction is H2O + 2hv -----> H2 + ½O2

❖ The produced hydrogen can be used as fuel in hydrogen fuel cel

 FUEL CELLS
Fuel cell can be defined as a galvanic cell in which the electrical
energy is directly derived by the combustion of chemical fuels and oxidant supplied continuously.
Ex: Hydrogen fuel cell, Methanol Oxygen Fuel cell etc.

Construction and working of Methanol – Oxygen fuel cell:

Working:
At anode: CH3OH + H2O -----> CO2 + 6H++ 6e-

At cathode: 3/2 O2 + 6H+ + 6e- -----> 3H2O

Net reaction: CH3OH + 3 /2O2 -----> CO2 + 2H2O

1. A membrane is inserted adjacent to the cathode on the electrolyte side to minimize the
diffusion of methanol into the cathode and thereby prevents the oxidation of methanol at
cathode.

2. Methanol – H2SO4 mixture is circulated through the anode chamber. Pure oxygen is passed
through the cathode chamber.

3. The advantage of acid electrolyte is that the CO2, a product of the reaction, can be easily
removed.
APPLICATIONS OF HYDROGEN FUEL CELL: Methanol-Oxygen fuel cell
1. Transportation – Passenger cars, buses, trucks, airport ground
support equipment, planes, trains, boats etc.

2. Stationary – Primary power and heat for homes and buildings;

emergency power for critical lighting, generator, uninterrupted power
supply (UPS) to provide instant protection from power outages.

3. Portable – Consumer electronics; remote construction site

equipment.

4. Other applications- Petroleum refining, Glass purification,

Semiconductor manufacturing, Aerospace applications, Fertilizer
production, Welding and heat-treating metals, Pharmaceuticals, As a
coolant in power plant generators, For hydrogenation of unsaturated
fatty acids in vegetable oil.

Hydrogen fuel cell

APPLICATIONS OF METHANOL-OXYGEN FUEL
CELL:
1. Used in Military applications.
2. Used in large scale power- production.
3. Ideal for small vehicles like forklifts, tuggers etc.