GREEN CHEMISTRY

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 What is Green Chemistry?
Green chemistry is the design of chemical products and
processes that reduce or eliminate the use or generation of
hazardous substances. Green chemistry applies across the
life cycle of a chemical product, including its design,
manufacture, use, and ultimate disposal.
The concept of Green Chemistry was given by
“Paul T. Anastas.

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 Sustainable Development

"Sustainable development is development that

meets the needs of the present without
compromising the ability of future generations to
meet their own needs."
 Green Chemicals

Green chemicals which minimize the formation of side

product and create low pollution and toxicity.

EXAMPLES
(i) Green reagent: Dimethyl carbonate is used for
methylation reaction and it is non toxic.
It reduce side product formation.
 Green Chemicals
(ii) Supercritical Carbon dioxide: Highly compressed
gases possess properties of both gases and liquid. It is non-
flammable, non-toxic and does not contribute to global
warming.
(iii) Methanol, Acetone, 1-butanol, 1-propanol etc. are the
green solvent.
(iv) CO2 is used as blowing agent.s
(v) Ionic liquid are green chemicals.
 WHY DO WE NEED GREEN
CHEMISTRY?
•Chemistry is undeniably a very prominent
part of our daily lives.
•Chemical developments bring new
environmental problems and harmful
unexpected side effects, which result in the
need for ‘greener’ chemical products. Eg.
DDT.
•Green chemistry looks at pollution
prevention on the molecular scale 6
 WHY DO WE NEED GREEN CHEMISTRY?

It is an extremely important area of Chemistry

due to the importance of Chemistry in our
world today and the implications it can show
on our environment.
•The Green Chemistry program supports the
invention of more environmentally friendly
chemical processes which reduce or even
eliminate the generation of hazardous
substances.
This program works very closely with the 7

twelve principles of Green Chemistry.

 12 Principles of Green Chemistry
1. Prevention.
2. Atom Economy
3. Less Hazardous Chemical Synthesis
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feedstocks
8. Reduce Derivatives
9. Catalysis
10.Design for Degradation
11.Real-time Analysis for Pollution Prevention
12.Inherently Safer Chemistry for Accident Prevention
 1 . Prevention of Waste/By-Products
• It is better to prevent waste/By-
Products than to treat or clean up
waste after it is formed
• carry out a synthesis in such a way so
that formation of waste (by-roducts)
is minimumor absent
• cost involved in the treatment and
disposal of waste adds to the
overall production cost.
• the unreacted starting materials
also form part of the waste.
• if discharged causes pollution and
requires expenditure for cleaning-
up
Example: Production of hydrazine

NaOCl + 2NH3 NH2.NH2 + NaCl +H2O (i)

Side product
H2O2 + 2NH3 NH2.NH2 + H2O (ii)

In reaction (i) efficiency of the reaction is 50% and

waste product are formed in same amount.
In reaction(ii) Efficiency of reaction increases as waste
product is prevented.
 Case study: Phenols
Alternative production of phenols from biomass
waste using depolymerization:
• This method uses abundant product (waste) as a
starting material.

Biomass Phenols
Image: Pixaay
 2. Atom Economy

Evaluation of efficiency of chemical transformation and

calculated as ratio of total mass of atoms in desired product
to total mass of atoms in reactant.

No. of atom present in product

% Atomic economy = X 100
No. of atom present in reactant
 Example
e.g.
CaCO3 CaO + CO2
100 56 44

A.E.= 56/100 x 100 = 56%

(%) Atom Economy clears that how many reactants

atoms are converting into products.
Benzene can be oxidised to make maleic anhydride, an important intermediate
chemical.

The Atom Economy of this reaction is 43%, calculated using the relative formula masses.
This means that 43% of the mass of the reactants ends up in the desired product.

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dienophile diene cyclohexene
 • Green synthesis
maximum
100% yield synthesis incorporation of the
-perfectly efficient starting
and materials
reagents in the
But, it generate significant final product
amount of waste (or
byproducts) - not green
synthesis.
 3. Less Hazardous Chemical Synthesis

Whenever practicable, synthetic methodologies should be

designed to use and generate substances that possess little or no
toxicity to human health and the environment.
Risk=f(HAZARD, Exposure)

Eliminate the hazard, no need to worry about the exposure!

In green chemistry we replace toxic substance with safer chemicals.

Example
Avoid the synthesis of chemicals like organic mercury which caused
minamata disaster.

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 Case study: Paper Bleaching

Conventional paper bleaching with

Chlorine dioxide (ClO2):
• Produces unacceptable
quantities of chlorinated
pollutants.
• Many of these pollutants are
exceptionally toxic.

Alternative technology for paper

bleaching with H2O2:
• Alternative catalytic
breakdown of H2O2 provides
the oxidative equivalent.
• Lower temperature and time
requirements.
 4. Designing safer chemicals

Minimize toxicity directly by molecular design .

Predict and evaluate aspects such as physical
properties, toxicity and environmental fate through out
the design process.
 DESIGNING
SAFER
CHEMICALS

Case study: Pesticides

Conventional use of agricultural pesticide and a malarial control
agent Dichlorodiphenyltrichloroethane (DDT):
• Carcinogenic.
• The threat to wildlife - especially birds – has almost
led to the extinction of a bald eagle population.

DDT
 DESIGNING
SAFER Case study: Pesticides
CHEMICALS

Alternative (and natural) use of Spinosad for

insect control:
• Produced by bacteria Saccharopolyspora spinosa.
• Isolated from Caribbean soil samples (sugar mill). Toxicity scorecard
• It selectively targets nervous system of insects.
Rat: LD50>5000 mg/kg
• Demonstrates high selectivity, low mammalian toxicity, Duck: LD50>5000 mg/kg
Fish: LC50-96h=30.0 mg/L
and a good environmental profile. Bee:
LD50=0.0025 mg/bee

Saccharopolyspora spinosa
 5. Safer Solvents and Auxiliaries.

The use of auxiliary substances (solvents, separation agents,

etc.) should be made unnecessary whenever possible and,
when used, innocuous.
Minimize the total amount of solvent auxillary substances as
these make up a large percentage of total waste created.
Solvents like benzene, chloroform, carbon tetrachloride are
toxic. These solvent can be replace by green solvent like water,
Methanol, Acetone, 1-butanol, 1-propanol etc.

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 6. Design for Energy Efficiency
Energy requirements should be recognized for their
environmental and economic impacts and should be minimized.
Avoid heating and cooling as well as pressurized and vacuum
conditions.

Green Chemistry- Ramesh - GEC Kozhikode 23

 DESIGN FOR
ENERGY
EFFICIENCY
Most energy is used for heating, cooling, separations and pumping.

Ideally, all reactions are performed at ‘ambient’ conditions – room temperature and
atmospheric pressure – in order to minimize energy usage.
 DESIGN FOR
ENERGY
EFFICIENCY

Sono-, microwave-, and photo-assisted chemistry are known to save energy,

improve reaction time, and catalytic activity.

Sonochemistry Microwave Photo-assisted

• Uses of high • Uses a high-frequency • Naturally occurring, such
frequency (20- 100 electric field to heat as using the sun as a
kHz) sound waves to or cool the local catalyst.
promote chemical environment with • Used in photo-driven
reaction. electrical charges. acylation for the
• The collapse of • Avoids unnecessarily production of valuable
bubbles formed in a prolonged residence synthetic intermediates
solution generates a time at a given and commercial
very high temperature temperature. fragrances in bulk.
and a higher pressure
than conventional
heating.
 7. Use of Renewable Feedstocks.
A raw material or feedstock should be renewable rather
than depleting whenever technically and economically
practical. Use of chemical which are made by plant based
sources.

In the manufacturing of Adipic acid benzene is used

which is toxic and carcinogenic. So in place of
benzene glucose is used as green chemical.

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 USE OF
RENEWABLE
FEEDSTOCKS

Case study: Development and commercialization of toners

Alternative process:
• The development of a novel, bioderived
printer toner that is easier to deink from
paper.
• This technology incorporates functional
groups in their toners that are susceptible
to chemical degradation for recycling.
• These toners are biobased, derived from
soybean oil and corn.
• At 25% market penetration, this
technology could reduce CO2 emissions
by 360,000 tons/year.
8. Reduce Derivatives

Minimize the use of temporary derivatives such

as protecting groups. Avoid derivative to reduce
reaction steps, resources required and waste
created.
 REDUCE
DERIVATIVES
Case study: 6-aminopenicillanic acid

Synthesis of 6-aminopenicillanic acid – core

moiety of penicillin
Conventional synthesis of 6-aminopenicillanic acid using 3 steps and intermediate
products:

Alternative synthesis using enzyme and fewer derivatives:

 CATALYSIS

Catalysts can facilitate complex reactions by:

• Lowering the activation energy of the

reaction.
• Reducing temperature necessary to achieve a
reaction.
• Controlling the site of the reaction (selectivity
enhancement).

Image source: Adobe stock

Catalysts performs transformation without
consumed in the reaction and without
being incorporated in the final product
hence is preferred whenever possible.

ADVATAGES
 Better yield
 Reaction becomes feasible
 Selectivity
 Advantage in energy requirement
better utilisation of starting materials
and minimum waste product formation.
 10. Design for Degradation
Chemical products should be designed so that at
the end of their function they do not persist in
the environment and instead break down into
innocuous degradation products.

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 Products Designed Should be Biodegradable
Eg. insecticides and polymers are non biodegradable
Insecticides

(DDT) bioaccumulate in many plant and animal species

and. Incorporate into the food chain.
Some of the insecticides are also responsible for
population decline" of beneficial insects

 insecticides must be biodegradable

. during degradation the products themselves should not
possess any toxic effects or be harmful to human
health.
It is possible to have a molecule which may possess
functional groups that facilitate it.for biodegradation.
The functional groups should be susceptible to hydrolysis, 33

photolysis or other cleavage.

.

11. Real-time Analysis for Pollution Prevention.

Analytical methodologies need to be further
developed to allow for real-time in-process
monitoring and control prior to the formation
of hazardous substances.
 REAL-TIME ANALYSIS
FOR POLLUTION
PREVENTION
Analytical methodologies need to be further developed to allow for real-time in-
process monitoring and control prior to the formation of hazardous substances.

Image: Wikimedia Commons,

Author: Hindustanilanguage
 SAFER CHEMISTRY FOR
ACCIDENT PREVENTION

Substance and the form of a substance used in a chemical process should be chosen
so as to minimize the potential for chemical accidents, including releases,
explosions, and fires.

Image: Flickr, Author: sea turtle

 Importance of Green synthesis
 Decrease in environmental issues like global warming,
ozone layer depletion, photo chemical smog and
pollution.
 Less release of hazardous chemicals to air leading to
less damage to lungs.
 Protection of animals and plants suffer from toxic
chemicals in the environment.
 Less chemical disruption of ecosystem.
 less release of hazardous chemical wastes to water
leading to cleaner drinking and recreational water.
In the end we can say that Green
chemistry is a solution to
Not all But the most
environmental problems
fundamental approach to preventing
pollution
 Synthesis of Adipic acid HOOC(CH2)4COOH
(a) Conventional method
 Synthesis of Adipic acid HOOC(CH2)4COOH

(b) Green synthesis

 Synthesis of Paracetamol N(4-hydroxyphenyl)ethanamide)

(a) Conventional method

 Synthesis of Paracetamol N(4-hydroxyphenyl)ethanamide)

(b) Green synthesis