Chapter

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Green Chemistry ***wwRE

1.1 INTRODUCTION
In the last two hundred fifty
years, starting after first chemical revolution,
chemistry has
improved and changed modern life with excellent amenities and
services. Unfortunately this achievement
has come at a price: our collective human
health global environment and
non-renewable natural resources are threatened.
Our bodies are contaminated with
large number of synthetic chemicals, many of
which are known to be toxic and
carcinogenic while others remain untested for their
health effects. They come to us from
food, air, water and dust. We now know that
many such chemicals enter the environment, not
only from smoke-stacks,
drainpipes, leaky storage tanks and waste sites but also as they migrate irom
furniture, textiles building materials, electronics, toys, personal care products,
packaging and many more manufactured goods we encounter every day. As a result
many of these chemicals are present in indoor air and dust. Many are in the food
web and in our bodies.
Disease Pollution
Waste disposal

Chemistry- A dirty word- Depletion of natural resources

Toxic emissions
Accident Land fill
Fig. 1,1 (a): The dirty form of chemistry.

Environment is a sphere around us which comprises of some physical and

chemical components with which we are interacting and also are a part of it. Due to
development in chemical science, the use of chemicals has become a quantity; same
is the case with our environment. The chemical components in our environment are
increasing day by day of which some can be degraded but most of them are
undegradable. The addition of undegradable products that causes instability,
disorder, harm and discomfort to the ecosystem, is termed as pollution. Pollution is
order to reduce the risk of pollution.
creating a risk to the environment. Thus in a

(1)
 ****www aree
2 een Cnemis
introduced that must reduce the risk by not chanoi
system should be ng the ell
but by changing the
cause.
Can the chemistry be dirty

Atmospheric Pollution Aqueous Pollution

Green house effect Fertilizers, pesticides, insecticides
and energy consumption
Industrial waste water
Ozone layer depletion
Solvents
Photochemical smog
Detergents and urban waste water
Smoke (NO, & SO)

Solid Pollution
Industrial soil.
Nuclear and radioactive waste.
Chemical residues.

Fig. 1.1 (b). The dirty form of chemistry.

This led to a concept named "Green

Chemistry". Green chemistry is an
inventive science based on fundamental research towards the
sustainable chemical processes. lt is a new development of ne
approach to an old science. There is a
great need to create new production system in order to
prepare the younger
generation to get a greener future. Thus green chemistry is cutting
chemical industry today and can edge of the
fundamentally change our lives for the better i
the future assessing environmental concern
today.
What is green chemistry

Environmentally friendly processes. Benign

Sustainability. disposal
Recycle/reuse
Reduce- Chemical usage
Energy usage
Replace- InHazardous materials, processes
efficient processes.

Non substainable components

Cost Materials

Risks&Reducing
Hazards Energy
Waste Non-renewables
Fig. 1.2. The heart of green
chemistry.
 3
Green Chemistry

In 1990's "Green Chemistry" waas The Clean Technological Pool

defined as the utillisation of set of principles
that reduces or eliminates the use of Safer reactions and
hazardous substances or eliminates the use reagents
of hazardous substances in the design, New Chemistry
manufacture and application of chemical Renewable
products. The term Green Chemistry" was
Catalysis Feedstocks
coined by Prof. Paul T. Anastas in 1991
Green Chemistry is the largest and Chemical Alternative
multifaceted field in chemistry. Green recycling solvents

chemistry is also called as sustainable

chemistry. Now the term "Green chemistry" Membrane Innovative
reactions
is defined as "The invention, design and Engineering
application of chemical1 products and
Fig. 1.3. The clean technological pool.
processes to reduce or eliminate the use and
the generation of hazardous substances for workers and consumers". This definition
of green chemistry starts with the concept of "invention and design." This means
that the scientists and technologists must take into account from the start that what
they are looking for, what kind of product, how they are going to design its
manufacture and its use. The impact of chemical products and chemical processes
must be included as design criteria. Hazard considerations for initial materials and
final products must also be concluded in the performance criteria.
Another aspect of the definition is in the phrase "use and generation of
hazardous substances". Green chemistry also recognises that there are significant
consequences to the use of hazardous substances, ranging from regulatory, handling
and transport, production of waste and liability issues. Therefore, green chemistry is
a tool not only for minimising negative impacts but also has legitimate and
complementary objectives of impact minimisation and process optimisation. Green
chemistry applies to industrial prospects, organic chemistry, inorganic chemistry
biochemistry, analytical chemistry and even physical chemistry.
Green chemistry is a branch of chemistry which involves pulling together tools,
techniques and technologies. It is helpful to chemists and chemical engineers in
research development and production of more eco-friendly and efficient methods
which may also have significant financial benefits. It is now going to become an
essential tool in the field of synthetic chemistry.
This new approach is also known as
environmentally benign chemistry.
clean chemistry.
>atom economy.
benign-by-design chemistry.
One obvious but important point-nothing is benign. All substances and all
activities have some aspects just by their being. What is being diseussed, when the
 4
GreenChemistry
term "benign by design" or "environmentally benign
ideal chemistry' is used, is simply an
striving to make chemistry more benign whereever
benign chemistry is merely a statement of possible, 1s merely a goal;
aiming for perfection.
1.2 THE TWELVE PRINCIPLES OF GREEN CHEMISTRY
Paul Anastas and John Warner moved
to produce a set of
since been adopted as "mantra" for the guidelines that have
"The Twelve Principles of Green design of environmentally
benign process as
for professional chemists to chemistry. These principles comprise instructions
implement new chemical
compounds, new syntheses and
new
technological processes. The first principle describes the basic idea of green
chemistry i.e., protecting the environment from pollution. The
are focused on such issues as
atom economy,
remaining principles
toxicity, solvent and other media,
consumption of energy, application of raw materials from renewable
degradation of chemical products to simple nontoxic substances that sources and
environment. are friendly for

The twelve principles are

1. Prevention: It is better to prevent waste than to treat
or, clean-up waste
after it has been created.
2. Atom Economy :
Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final
3. Less Hazardous Chemical
product.
Syntheses Wherever practicable, synthetic
methods should be designated to use and
little or no toxicity to human health and the
generate substances that possess
environment.
4. Design Safer Chemicals: Chemical products should be
preserve efficacy of function while minimizing designed to
toxicity.
5. Safer Solvents and
Auxillaries: The use of auxillary substances (solvents,
separation agents etc.,) should be made unnecessary wherever
when used, innocuous. possible and,
6. Design for Energy Efficiency: Energy requirements of chemical
should be recognised for their environmental and processes
economic impacts and
should be minimised. Synthetic methods should
be conducted at ambient
temperature and pressure.
7. Use of Renewable Feedstocks A
: material or feedstock should be
raw
renewable rather than
depleting whenever technically and economically
practicable.
8. Reduce Derivatives:
Unnecessary derivatisation (use of blocking groups,
protection/deprotection, temporary modification of physicallchemical
process) should be minimised or avoided if
possible, because
require additional regents and can generate waste.
such steps
Green Chemistry 5

9. Catalysis: Catalytic reagents (as selective as possible) are superior to

stoichiometric reagents.
10. Design for Degradation: Chemical products should be designed so that at
the end of their function
they break down into innocuous degradation
products and do not persist in the environment.
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.
12. Inherently Safer Chemistry for Accident Prevention: Substances and
the form of a substance used in a chemical process should be chosen to
minimise the potential for chemical
accidents, releases, including explosions,
and fire.
Atom
Safety Economy, Waste
control Reduction/
Quality
control Benign by
Green design
Chemistryy
Catalyst Reduced
Efficiency Toxicity
Renewable Fewer
Feed
Stocks
Auxillaries
Energy
Efficiency
Fig. 1.4.

EXPLANATION OF THE TWELVE PRINCIPLES OF GREEN CHEMISTRY

1. Principle No. 1 Prevention
This principle is fundamental, most obvious and over-arches the other
principles. It goes back to the old adage "an ounce of prevention is worth, a pound of
cure. Most of the chemical processes and synthetic routes produce waste and tOxic
secondary substances. Hence, synthesis should be designed and carried out in such a
way so that the waste or byproduct formation is minimum. However, it is best if the
by-products and waste are not generated at all. Waste generation increases the cost
of production as overall cost of production depends on the cost of disposal of waste
and at the same time clearing-up processes also require expenditure. The discharge
of by products or waste into atmosphere, land or sea causes pollution also.
Sometimes the unreacted starting material (which may or may not be hazardous)
forms part of the waste.
Human being are depleting resources and making wastes much faster than
nature can take the wastes and convert then back into resources.
6
R Green Chemistry
Nature versus Industrial Society
Nature Industrial Society
(The natural cycle disrupted)

Resources Consumption
Resources Consumption

Waste
Waste
This principle
has also led to "grinding
chemistry" i.e., the reactants are
grinded mixed without solvent thus reducing the possibility of waste. Onesimply
or
of the
best example is three
component Friedel Crafts-reaction.
NH2 NH Ph
+HCOOEt r.t. COOEt
Solvent
NH free NH
indole aniline indole derivative
Use of microwaves is an expansion of
grinding chemistry or solvent less
chemistry. Using this technique triphenyl methane derivative is synthesised as below
R1
R3 R3
R3 R N R

O Ph NH2. HCI
R 2 N

NR?
NR?
NR

*uH R5 MW
R1-RÒ are
alkyls or Solvent free alkyls
substituted alkyls
R

R4

2. Principle No. 2 Maximise Synthetic Methods, Atom Economyy

This principle gets into the actual chemistry of how products are made. As
chemists, atoms are assembled to make molecules. The molecules are assembled
together to make materials. This principle states that it is best to use all the atoms
in a process as those atoms that are not used end-up as waste.

Originally the concept of "yield" was used to account the success of a reaction.
This concept is perspective, it is not the full picture. It is because the yield is
calculated by considering only one reactant and one product. However, such a
synthesis may generate by products or waste which is not taken into consideration.
ror example Grignard reaction proceeds with 100% yield but in calculations the
byproducts Mg (OH) I is not taken into account.
OH
1. CH 3Mgl
CH CHO CH-C-CH3 + Mg (OH)I
2. H30 (byproduct)
H
(product)
Green Chemistry 7

The yield of above synthesis may be 100% but it is no considered to be green

synthesis .e., synthetic methods can be designed in advance to be green synthesis
that is synthetie methods can be designed in advance to maximise the incorporation
of all reagents used in the chemical processes into the final products. The concept of
"Atom Economy" was developed by Barry Trost for which he received
"Presidential Green" chemistry Challenge Award" in 1988. It is a method or
the
expressing how efficiently a particular reaction makes use of the reactant atoms.

3. Principle No. 3 Less Hazardous Chemical

Synthesis
This principle is focused on how we make molecules and materials. The methods
used to make chemical materials, called synthetic methods, have often employed
toxic chemicals such as cyanide, chlorine etc. In addition, these methods at times
generate large quantitative of hazardous wastes. The goal of this principle is to
reduce the hazard of the chemicals that are used to make the products. Chemists
must strive, wherever practical, to design safer synthetic methods by using less toxic
substances as well as the products of the syntheses. Less toxic materials means
lower hazards to workers in industry and research laboratories and less pollution to
the environment.

Example-Production of styrene
Traditional route: It is two step method starting with benzene, which is
carcinogenic, and ethylene to form ethyl benzene.
CH2 CH3
Catalyst
+CH2 CH2
benzene ethyl benzene
(carcinogenic)
In the second step ethyl benzene is catalytically dehydrogenated to obtain
styrene.
CH CH3 CH = CH2
Catalyst
- H2

Styrene
Greener route -

In this route instead of benzene, xylene, which is cheapest

Source of aromatics and
environmentally safer than benzene, is used as starting
material.
Synthesis of polycarbonate-In the synthesis of polymer poly carbonate
phosgene gas was used which is highly toxic and corrosive.

OH OH+COCl2 NaOH, o- -0
phosgene
polymer polycarbonate
 wwwww

ww

The above method requires large amount of dichloro methane the product and
the product poly-carbonate contaminated with chlorine impurities is obtained.
In a greener method poly carbonate is synthesised by solid state process.

OH- - OH +

The advantages of this method are

Phosgene gas is not used.
> Use of dichloro methane is eliminated.
Higher quality poly-carbonate is obtained.
Green chemistry principle gives great emphasis to the scientific term

"hazardous', for processes and life cycle of chemical substances. Greenchemistry 1s

the way of dealing with risk reduction and pollution prevention by addressing the
intrinsic hazards of the substances rather than dealing with condition of their use,
they might increase their risk.
Risk, in its most fundamental terms, is the product of hazard and exposure.
Risk =f (Hazardx Exposure)
To calculate the risk associated with certain substances we have to quantify its
hazard (how toxic or dangerous to human and environment it is) and multiply it
with a quantitable exposure (dose, time ete.)
In the past, all common approaches to risk reduction was focused on reducing
exposure to hazardous substances. Green chemistry goes to the heart of risk
prevention or adequate reduction, in advance before the substance is made or used.
Green chemistry demands to design products and use raw materials with lower
hazardous properties as practical as possible.
Now-a-days green chemistry research is developing to make these synthetic
methods more efficient and to minimise waste while also ensuring that the
chemicals used and generated by these methods are as non-hazardous as possible.
For example a number of industries such as pulp and paper industry use chlorine
compounds in processes that generate toxic chlorinated organic waste. Green
chemists have developed a new technology that converts wood pulp into paper using
Oxygen, water and polyoxomatalato salts while producing only water and
carbon-di-oxide as by product.
Green chemistry illustrates another important point about the use of the term
"hazards. This term is not restricted to physical hazards such as explosiveness,
flammability and corrosibility but includes acute and chronic toxicity, carcinogenity
environmental pollution to water, air and soil and ecological toxicity.
4. Principle No. 4 Designing Safer Chemicals
Principle 3 is focused on the process while principle 4 is focused on the product
that is made. This principle is aimed at designing products that are safe, non-tox1c
Green Chemistry
9
and efficacious.
Thus,
green chemistry aims to eliminate hazards
designing stage. Designing must become the fundamental aim of
right at thee
effect the desired function and properties of the green chemist to
their toXIcity to human
and the environment. chemical product while minimising
regulations From 1980s there are more
and new chemicals are monitored more effectively. In 1963 stringent
drug was used to reduce the Thalidomide
effect of morning sickness
Subsequently it was found that this during pregnaney.
born to woman taking this drug causes serious birth defects in children
drug. The drug was banned and
The more we know
about a chemical's structure that withdrawn.
more options are causes a toxic effect, the
available to design a safer chemical.
many sources of information to Chemists now have access to
they design and the ingredients determine the potential toxicity of the molecules
information into the design of thethey choose. Green chemists are trained to use this
molecules to avoid or reduce toxic
example. they might design a molecule large enough properties. For
deep into so that it is unable to
lungs, where toxic effects can
Similarly they might change the
occur. penetrate
properties of a molecule to
prevent its
breakdown in the environment. absorption by the skin or ensure its safe
Now polymers have been
known polymers and also able to
developed which are much less flammable than the
absorb severe impacts without
breaking. One such polymer is poly phenylsulphone which cracking and
is now wiueiy used in the
interior panels of aircrafts and
underground trains.

to O
Detergents used are sodium salt of alkyl benzene sulphonic acids with branched
alkyl groups. These were not degraded naturally in sewage works and caused
foaming which made the sewage difficult to manage. Now these compounds have
been replaced by sodium salts of linear alkyl benzene
sulphonic acid which are
readily degraded.
The designing of
highly selective, environmentally friendly insecticide spinosad
1s an example of a technological development that demonstrates how a safer
chemical can be created and produced. It has a favorable environmental profile. It
does not leach, bio- accumulative, volatilize or persists in the environment.
It
degrades photochemically.
5. Principle No. 5 Safer Solvents and Auxillaries
Traditionally in organic synthesis a number of solvents with excellent solvent
PTODerties are employed. These solvents are mostly volatile organic compounds
a n d include methylene chloride, chloroform, perchloro ethylene, carbon
tetrachloride, benzene and other aromatic hydrocarbons. Out of these solvents
halogenated
nalogenated compounds
compounds and benzene are carcinogenic while some other solvents
and Denzei
caluents
have hazardous effect on environment. are not only
Solvents are only an
an important liquid
important liqula
medium for synthesis but also for extraction, separation, purification and drying.
Solvents are also very important in chemical analytical methodologies,
spectrophotometery and measurements of physio-chemical properties.
T0 a r e e n Cnemistry

This principle of green chemistry is to promote the idea of "greener" solvents

be substituted
(non-toxic, benign to environment), replacement in cases that can
with safer alternatives, or changes in the methodologies of organic synthesis, when
solvents are not needed i.e., solvent less synthesis. Some green solvents are water,
and its solutions and
Super-critical carbon dioxide, ionic liquids, polyethylene glycolknown
Thuorous solvents. ln this respect we can quote one of the well example of nail
saloons. The solvents traditionally used in nail saloons have potential toxicity. A
water-based alternative polish would avoid the exposure that goes along with nail
products and reduce the hazards associated with traditional products.
6. Principle No. 6 Design for Energy Efficiency
According to this principle energy requirements should be recognised for their
environmental and economic impacts and should be minimised. Chemists use lots of
energy in heating, drying and cooling. Energy is not only expensive, most of the time
the power plant that creats the energy contributes to pollution.
Today, there is a focus on renewable energy and energy conservation.
Traditional methods for generating energy have been found to contribute to global
environmental problems such as global warming and the energy used can also be of
significant cost. This principle focuses on creating products and materials ina
highly efficient manner and reducing the energy associated with creating products,
therefore reducing associated pollution and cost.

Heating
Cooling
Stirring
Distillation
Compression
Pumpingg Global
Separation Warming

Carbon dioxide
Energy requirement Burn fossil
(Electricity) fuels to
atmosphere
One of the alternate energy source is photo chemical reaction, for example
conversion of cyclohexane to caprolactam can be done photochemically.

+ NOCI 535 nm

Other methods include microwave, ultra sound etc.

CgHNONHC,H5 -
MW 12 min
CH,C0OH
RCOOH+ ROHeste
esterification
RCOODR
HSO4
Ultra sound
 11
Green Chemistry

processes are being overhauled and substituted by more energy

raaltional
etficient methods. Catalysts are being developed so that a process can be run a

lower temperatures and pressure as high temperature and pressure are very energy
consuming. Similarly the development of molecular seive means those processes
such as purification of ethanol can be carried out at ambient temperature instead or
by distillation.
Waste often has energy content and it may be possible to convert this to a useful
tue. Waste solvents from the manufacture of paints, varnishes, adhesives, inks,
cleaning fhuids etc. are made into a liquid fuel for use by the cement industry. A
solid fuel is also made from the shredded carpets, packing, furniture, plastics and
papers. Most of them otherwise would be destined for landfill.
A boom is currently occurring in the use of these green energy sources and this
is also associated with a marked decrease in
reaction time, to higher yields and very
often, to higher product purity.
7. Principle No. 7
Use of Renewable Feedstock
Our society not only
depends on petroleum for transportation and energy, but
also for making products. This
principle seeks to shift our dependence on petroleum
and to make products from renewable materials
that can be gathered or harvested
locally. For example
Biodiesel obtained from biomass is used alternative fuel.
as an

Poly lactic acid (PLA), a biodiesel plastic is being made from renewable
feedstock such as corn and potato waste.
D-glucose is converted into lactic acid using certain enzymes which helps to
prepare certain aliphatic compounds from lactic acid.
Isomaltulose which is widely available in biomass can be
converted into
glucosyl methyl furfural which can be used for production of
compounds. many heterocyclic
Besides biomass, cash crop is a new hope as ethanol from sugarcane has been
derived successfully and now scientists are trying to use this
source of energy for vehicle in future. big alcohol as a
8. Principle No. 8 Reduce Derivatives
This principle is
methods that chemists
perhaps the most abstract principle for a non-chemist.
use to make The
many of the methods chemists products are sometimes
highly sophisticated. In
molecules into what manipulate the molecules in order to
shape the
they want them to look. This
process and to look at natural principle aims to simplify the
manner. system in order to design products in a
simplified
Unnecessary derivatization such as
blocking of groups, protection and
deprotection of groups, temporary modification and
be avoided as these of physical chemical
processes increase synthetic process should
steps which lead to decrease
in
12 Green Chemistry

yield and atom economy. Bromination at the para or ortho position of aniline
without protection of amino group is a process in which protection/deprotection steps
have been removed.
Br
NaBO3. 4H20, KBr
NH2
NH.
ACOH NH2
X =0, S
Brom nation of amine compound without protection/deprotection

9. Principle
No. 9 Catalysts
In a chemical process catalysts are used in order to reduce energy requirements
and to make reactions happen more efficiently. Another benefit of using a catalyst is
that general small amounts of catalyst i.e., catalytic amount not stoichiometric
amounts are required to have an effect. Catalytic reagents (as selective as possible)
are superior to stiochionmetric reagents.
Now the chemists prefer the use of "green" catalyst, a catalyst that will have
little to no toxicity and is recyclable i.e., can be used over and over again in the
process. Enzymes are wonderful green catalysts. Green chemists are investigating
using enzymes to perform chemistry in the laboratory in order to obtain the desired
product. These biocatalysts have following benefits
F a s t reactions due to correct orientation.
Orientation of site gives high sterospecificity.
Substrate specificity.
Naturally occuring.
Moderate conditions.
Possibility oftandom reaction (one pot).
For many years aluminium chloride was used as an active surfactant in the
production of alkyl benzene sulphonates, and in any other detergents. The
aluminium chloride can not be recycled and became waste as aluminium hydroxide
and oxide. Now the solid zeolite catalyst with acid groups is used and can be reused
many times without yielding any waste.
10. Principle No. 10. Design for Degradation
Not only we want materials and products to come from renewable resources, but
we would also like them not to persist in the environment. Hence chemical products
should be designed in such a way, so that at the end of their function they do not
persist in the environment and breakdown into innocuous degradation products.
Design for degradation means when green chemists design a new chemical such as a
pharmaceutical drug or medicine or new material such as plastic, they should design
it in such a way that at the end of its useful ifetime it breaks down. Early examples
of chemicals persistent in the environment are sulfonated detergents,
chlorofluorocarbons, DDT, plastics, antibiotics etc. Plastics do not degrade in our
 Green Chemistry 13

landills and pharmaceutical drugs such as antibiotics accumulate and built-up

our water stream. Recently developed poly lactic acid polymers can be recyclea and
composted.

This approach is best

exemplified by the creation of biodegradable green
polymers. Conventional polymers such as
polyethylene and polypropylene persist
many years afterdisposal. On the contrary the biodegradable polymers are
ror
by enzymatic action of micro-organisms such as bacteria, fungi and algae degraaea
aiter
disposal.
11. Principle
No. 11. Real-time
Analysis for Pollution Prevention
In making products, if there was a
way to see inside the reaction and to know
exactly when it would be done, then this would reduce waste in the process and
ensure that your product is "done" and is the
right product you intended to make.
Thus, real-time analysis for a chemist is the
process of "checking the progres of a
chemical reaction as it happens". Knowing when
your product be "doe", can save
not only lots of waste but also time and
energy. Hence analytical methodologies need
to be further developed to allow for real-time in
process monitoring and control prior
to the formation of hazardous substance.
The sensor in analytical chemistry will
have particularly important role to
play.
In recent time micro fabricated micro fluidic
devices are referred to as
analytical devices are used. These
lab-on-a-chip" device. In these devices sample
pretreatment such as
pre-concentration extraction,
chemical/biochemical
derivatisation reactions electrophoretic separations and detections
have been
carried out on single microchip platform.
12. Principle No. 12. Inherently Safer Chemicals for Accident Prevention
This principle focuses on
safety of workers and the surrounding community
where industry resides. It is better to
use, in chemical process, substances and
materials which would minimise the
potential for chemical accidents such as
explosions, catch fire or ignition in air. There are many
chemicals were not used and the result was examples where safe
disaster. The most widely known and
perhaps one of the most devasting disaster was that of
a chemical Bhopal, India in
plant had an accidental release that resulted in thousands 1984 where
and of lives lost
many more injuries. The chemical reaction that
reaction occurred was an exothermic
that went astray and
toxic fumes were released to the
while
creating products it is best to avoid highly reactive surroundings so

potential to result in accidents. chemicals that have

In the synthesis of most widely used
2-imino diethanoic acid is herbicide, glyphosate, sodium salt of 2,
of the
reactions form ammonia, intermediates.
one This intermediate is made
series of
methanol and hydrogen cyanide. by
hydrogen cyanide is very
has been the useful reagent, it is extremely toxic. A recent Although
introduction of a new route to the sodium salt. The innovation
are ammonia
and
epoxyethane which on starting materials
reaction from 2, 2-iminodiethanol
often
 ARDGreen Chemistry

named as diethanol amine. This is then converted to the sodium salt of 2,

2-imminodiethanoic acid.

HO OH
2 HC-CH2 +NH3 N
diethanolamine

glycophosphate
herbicide
0=c
Na e0
ONa"

Thus, in the event of an accident, the consequences would not be as serious, and
clean-up would be simpler.
Tang et.al. (2008) very cleverly and beautifully condensed the twelve principles
of green chemistry to a single word "Productively".
Principles of Green Chemistry.
P -Prevent waste
R Renewable materials
O Omit derivitization steps
D Degradable chemical products
Catalytic reagents.
T Temperature and pressure ambient.
I - In-process monitoring.

V Very few auxillary substances.

E E-factor, maximise feed in products.
L Low toxicity of chemical products.
Y Yes, it is safe-
Although in conducting a chemical process, efforts are always being made to
fulfill the twelve principles but practically it is not feasible to satisfy all the
conditions. Hence the word "Green" is used in comparative degree by comparing
With "gray chemical" process. In this way a chemical process is greener than other
chemical process (for the same chemical reaction) as it fulfills more conditions o
twelve principles.

1.3 HAZARDS AND GREEN CHEMISTRY

Green Chemistry is an approach that aims to eliminate the usage ana
generation of hazardous substances by designing better manufacturing processes
chemical products. Specifically, the goal of making the finished product an
Green Chemistry

by-products less toxic

directs the decisions made chemical production. Tne
manufacturing process includes the aspect of during
initial selection of chemicals, the
mechanism of chemical synthesis, the end
management of toOxic product of the process and the
products generated
chemistry principles should be applied toduring
the production. It means that
green
all aspects of the product life cycle, from
its invention to the disposal,
including the environmental fate after the use.
Potential Risks
Raw Material
Chemical Synthesis End Products End of Life

To workers. Management
To workers. To workers. To workers.
To suppliers. To community
To shippers To suppliers To communities
near manufacturing
To communities nearf To shippers near manu-
site. To waste handlers
manufacturing site facturing site
To local
To local To communities near| To local
environment manufacturing site environment
environment
To global To consumers To global
To global environment To local environment
environment
environment
To global
environment

Fig. 1.5. Potential risks in the life cycle of chemical.

At the heart of green chemistry is the

another property of a chemical substance.
recognition that "hazard" is simply
Properties of chemicals are caused by
their molecular structure; they can be modified
the greatest strengths of
by changing that structure. One of
green chemistry is its focus on the molecular basis of
Alternative
Feed stocks
Waste
minimisation Pre-Manufacturing
Safe & Responsible
Extraction
Greater use of « Non VOCs
Catalyst
Manufacturing
More Atom Safe& Intensive
efficiency routes Processing
Close to Market
Product Delivery Minimal Packaging
Manufacturing L
Benign Chemicals
in Formulation Product Use Safe Products
Recyclable or Quickly Biodegradable
Reversable End of Life
on Disposal
Fig. 1.6. Green Chemistry in the life cycle of a product.
 Green Chemistry

toxicity. Through an understanding of the mechanism of action of toxicity both in

the body and within ecosystems, green chemistry engages to design molecular
structure that are inherently either incapable of manifesting a particular toxio
endpoint, or at a maximum, greatly disfavouring these toxic mechanisms. These
principles and techniques are applied to substances ranging from dyes to pesticides.
Regarding toxicity, according to Paracelsus "Everything' is toxic, it is simply a
matter of the dose. This citation is taken as a reminder one can never say that
something possesses no toxicity.
The types of hazards that can be addressed by green chemistry vary. They
include physical hazards (being explosive or flammable), toxicity (being carcinogenic
cancer causing or lethal) or global hazards (climate change or stratospheric ozone
depletion). By limiting the hazards intrinsic to the chemical products, the risk
introduced by the product is consequently reduced. There are two major aspects of
risk- hazards presented by a product or process and exposure of humans and other
potential targets to those hazards.
Spirit of Green Chemistry
Risk = F (hazards x exposure)

Now Before
A hazard can be defined as a situation which may lead to harm whilst risk is the
probability that harm will occur. This relationship simply states that risk is a
function of hazards times exposure. It shows that risk can be reduced by a reduetion
of hazards, a reduction of exposure and various combinations of both.
One way to reduce risk is to limit the exposure by some physical means, or by
introduction of systems and working practices. Here the hazards remains, but the
exposure to it is reduced. Such efforts have used various kinds of controls and
protective measures to limit exposure. The most common example of such a measure
is wearing safety goggles around eyes. Goggles will not by themselves prevent acid
from splashing into the face, but they protect eyes from any damage. Explosion
shields will not prevent explosions but they do protect chemist or others in vicinity
from any harm. Thus reduction of exposure is effective in preventing injury and
harm.
The alternative way to minimise risk is the green chemistry approach accordingB
at its
to which is to reduce the hazard. The hazard is diminished or eliminated
hazard. This
source, measures still may be taken to reduce exposure to remaining
of "what
approach gets to the root cause of the problem and is based on the principle
you don't" have can't harm you.
Protective measures are most effective against acute effects but less so against

long term chronic exposures that may toxic responses over many years periou
cause

of time. Where feasible, hazard reduction is a much more

certain way of reducing8
risk than is exposure reduction. For example, the use
of volatile, flamnable
somewhat toxic organic solvent used for cleaning and degreasing of machined me
 Green Chemistry
used
of nontoxic cleaning agent
parts. The same can be done with water solution a
to avoid
for the same purpose. The use of organic solvent requires constant vigilance
sources
of ignition
such hazards as formation of explosive mixture with air, presence
inhalation or absorption
that could result in a fire, and excessive exposure by in workers.
nerve disorder)
through skin that might cause peripheral neuropathy (a
accident or serious harm to
of protective measures can result in a bad
Faiure would not present any
worker's health. The water based cleaning solution, however,
create a problem.
of these hazards so that failure of protective m e a s u r e s would not
Minimization|

Recycling at source
Reduction at source

Product Process
modification modification

Good Substitution of Technological|

practices materials changes
Fig. 1.7. Minimisation of hazardous products.

1.4 GREEN CHEMISTRY AND CHALLENGES

Sustainability : It is just one word but still there are over 300 definitions of it.
The word sustainability is derived from the Latin word sustinere
(tinere-to hold,
susus-up). According to Dictionary, there are more than one meaning for sustain
but mainly it is taken as to "maintain",
"upport" or "endure". The most quoted
definition of sustainability and sustainable
development, that of Brandtland
Commission of United Nations: "substainable development that meets the
needs of
the present without
compromising the ability of Equitable
future generatiions to meet Social
their own needs." Bearable .

The three
Sustainable
pillars of
sustainability are the
environmental, social and Environmental
economic demands. These Economie
three pillars are expressed
by three overlapping ellipses V1able
Fig. 1.8(a). The pillars of sustainability.
18 Green Chemistry

(Fig. 1.8a) which point out that these three pillar are not mutually exclusive and can

be mutually reinforcing.
Another representation of substainability shows that how both economic and
society are constrained by environmental limits. Green chemistry is sustainable
chemistry. There are several important respects in which green chemistry is
sustainable.
Economic: At a high level of sophistication,
green chemistry normally costs less in strictly
economic terms than chemistry as it is
normally practiced.
Materials : By efficiently using materials, Economy
maximum recycling and minimum use of virgin
raw materials, green chemistry is sustainable
Society
with respect to materials.
Environment
Waste: By reducing insofar as possible, or even
totally eliminating their production, green
chemistry is sustainable with respect to wastes.
Fig. 1.8 (b). The three pillars of
sustainability.
Green Chemistry and Challenges
In the glorious day of 1950's and 1960's chemists envisioned chemistry as the
solution to a host of society's need. Indeed they created many things such as dyes,
paints, plastics, cosmetics and other materials which improved the quality of life on
the earth, At the same time chemistry brought a medical revolution
through
antibiotics. All these things prove Dupont Slogan. "Better things for better living
through chemistry." But this achievement has come at a price for global
environment and non-renewable natural sources. Sustainability is at stake and
continuation of quality of life is under threat. Many chemicals work their way up the
food chain and circulate round the globe, pesticide residues were found in the
tropics
and in the Arctic, flame retardants from electronics are now commonly found in
aquatic organisms, especially in marine mammals.
How sustainability is defined ? According to Brundtland commission
sustainability is defined as "The ability to meet the needs of current generation
while preserving the ability of future
generations to meet their needs". A simpler
way of expressing this idea may be "Preserving the things you cannot live without
and preserving them forever."
What role does green
chemistry has to play to these challenges and the ultimate
goal of sustainability. Green chemistry fulfills a fundamental and crosscutting
that is essential to the critical role
its ten principles want to
pathway towards sustainability. Green chemistry ana
change all these negative impacts and through design,
innovation and green
processes to restore the plant's sustainable
Simply stated, it is difficult to imagine a way to address the developmen
sustainability without engaging in green chemistry. The green chemistry challenges.
revolutlo
 19
Green Chemistry

itself is providing an enormous number of challenges to those who practice them in

industry, education and research. With these challenges, however, there are equal
number of opportunities to discover and apply new chemistry, to improve the
economies of manufacturing and to enhance the much tarnished image of chemistry.
The term sustainable chemistry" proposed in the beginning was changed to "green"
because it can the meaning of radical change, innovation, rejection of old attitudes
and practices.
Although many chemists and some large and smaller companies are actively
pursuing "green chemistry", there are still many barriers to green chemistry. The
most pressing pressing issues that the planet is facing are as

(a) Solutions that enable the of low environmental impact

use
renewable feed-stocks-Drop-in chemicals or materials from biological input
versus constrained resources such as petroleum.
With the increasing population, the raw materials extracted from earth are
depleting in that there is finite supply that cannot be replenished after they are
used. Renewable resource utilisation is central tenet of
green chemistry and a very
active area of engagement. Use of biomass
(plants and animal waste, products from
fermentation of plant waste etc.) as feed stock is being
developed in everything from
polyester, materials and fuels. The use of nano-science is beginning to be pursued to
achieve material efficiency through green
chemistry that will have
applications from computing sustainability. Non-conventional biomass potential such as
seafood by-products e.g., chitin continue to be
developed into materials like chitosan.
However, an overarching theme may be that green chemistry strives to turn
materials and energy sources that may have once been viewed
as waste into value
added renewable materials.
(b) Solutions that increase energy, water and raw material
minimising the use of constrained resources. efficiency
Energy consumption poses economic and environmental costs in
synthetic and manufacturing
all virtually
processes. Therefore
minimised. Currently the energy supply of world is energy requirement should be
of carbon. The extraction and largely based on the combustion
collection of carbon through mining,
processing etc. has well documented environmental consequences. The drilling,
carbon dioxide and other gases has been cited production of
as
contributing global
to
the production of fossil fuels andwarming.
The generation of associated toxics
at which this finite resource is
during the rate
Concern.
being depleted are also areas of environmental

Green chemistry, however, is engaged in addressing energy needs

development of more sustainable energy technologies. The through the
chemistry are being employed in the development of the principles of green
cells. The sustainable sources of hydrogen economy and fuel
manner are
hydrogen generation in an economically
sustainable
an areaof active research both in
green chemistry and green
engineering. The design and
development of photovoltaic and solar energy devices
20 owRDGreen Chemistry

that are both economically viable and also ensure a positive energy balance through
their manufacture and use is being perused. Material that are needed to make wind
and geothermal energy systems possible are being developed through green
chemistry research. The energy future will need to be shifted to a more sustainable
balance and green chemistry is essential in making that shift happen.
Water, the molecule most associated with life on the earth, is also one of the
greatest challenges to sustainability in the 21st century. In many countries, water
shortages stem from inefficient use, degradation of available water by pollution and
the unsustainable use of underground water. Green chemistry is improving water
supply and water quality through the prevention of contamination and more
environmentally benign treatment methodologies. Green chemistry is also being
engaged to find more sustainable ways to purify drinking water. With the use of
chlorine free disinfection agent water can be both pure and also not contribute to the
generation of toxic and bio-accumulating substances.
(c) Solutions to reduce the use of hazardous chemicals in materials and
processes.
There are now enough data for the toxicological and for the long term
ecotoxicological properties of most of the high volume chemicals, reagents, solvents,
catalyst etc. are used for industry.
and recycling etc.
Synthesis, separation of product, cleaning, drying, analysis
are some of the processes where solvents are used. Solvent in the chemical industry
is one of the major problems concerning worker's health and safety and
environmental pollution because most of the solvents used are volatile organic
solvents, out of them banned and some others are restricted due to toxic
some are
nature. Changing solvents and processes is not an easy task. There are many
alternatives but can be more expensive, time consuming or difficult to implement
under
under the established order of chemical methodologies. In the recent years,
have been used
the influence of green chemistry principles, some green solvents
solvent must ideally
such as ionic liquids, super critical carbon dioxide etc. A green
dissolve a
have high boiling point a low vapour pressure, non-toxic inexpensive,
be recyclable. All these things put
great range of organic compounds and of course class o
a compound or a
together tend to narrow the possibilities of finding
solvent. However, many etforts
compounds that can effectively be called as green
of some gooa
from research all over the world have enabled the appearance
groups
alternatives of organic solvents as stated above.
chemical
been used for many synthetic
Similarly biocatalysts, enzymes, have industries.
routes with great advantages specially
in the food and pharmaceutical
use less energy,
lower temperatures,
These biosynthetic methods are more selective,
materials which are less toxic.
higher yields and demand raw
techniques
more alternative and greener
In recent years there are many
yield, saving energy and
minimise was
improving sustainability, the product
Green Chemistry
21

Photochemical reactions microwave and

catalytic reactions are some of the new ultrasound assisted organic synthesis,
(d) Solutions for waste techniques in synthesising chemicals.
prevention:
Waste prevention is better than having to treat or clean up wastes.
In the
earher years the waste
treatment cost was very low as wastes were
into water
ways, into the grounds or in the air as simply discarded
and enforcement of stack emissions. With the passage
environmental laws after 1970, cost of waste treatment
inereased steadily. The clean
up of pollutants including asbestos, dioxins,
manufacture residues,
perchlorate and mercury pesticide
concerns. Hence
chemical industries will
are costing high to various
very
technology with an increasing emphasisrequire level of innovation and new
a
on the reduction of waste. Thus
"Enviro-economics" will become the driving force for new
(e) To develop chemistry that enables
product and processes.
the potential for closed end-of-life recycling or maximise
loop system:
A major source of waste in the fine chemicals industry is derived
mineral acids and Lewis acid which end by the use of
up via a
hydrolytic work up, as waste
stream. They cannot easily be
recycled.
solid acids such as zeolites, acidic
Their widespread replacement by recyclable
waste (Fig. 1.9).
clay etc. could afford a dramatic reduction in

recycling or solvent and catalysts

reagents and
renewal of solvent wateer
and catalysts
Substrate (s)
Product (s)
Fig. 1.9. Close loop system for solvents and catalyst.
(f) Population and Education:
Population is such type of challenge to sustainability that it drives many other
challenges as well
"Teaching must be in harmony with practice" i.e., education is specially
important in the popularisation of green chemistry. Despite the progress made in
recent years, however, there are still barriers which
prevent a further diffusion and
acceptance green chemistry. "Like for any new technology, innovation, there are
of
always barriers and resistance to full acceptance." In the case of green
is sometimes difficult to find chemistry it
economically variable "safer" alternatives to a certain
product or process. In many cases, there is lack of of what is
agreement considered
"safer". On the business supply chain side, it takes
always time to switch from
something old to something new; issues such as new product re-design, for instance,
can be difficult and long.
 Surely education is key to the future it is essential to have chemists and
chemical engineers who understand how to incorporate Green Sustainable
Chemistry into their work. The success of green chemistry depends on the trainine
and education of a new generation of chemists. Students at all levels have to be
introduced to the philosophy and practice of green chemistry.
Thus, one can say that it is still early days for "Green and Sustainable
Chemistry" and there is much more to go ahead. Significant progress is being made
in several key research areas, such as catalysis, the design of safer chemicals and
environmentally benign solvents and the development of renewable feedstock
Current and future chemists are being trained to design products and processes
with an increased awareness for environmental impact. Outreach activities
within
the green chemistry community highlight the potential for chemistry to solve many
of theglobal environmental challenges we now face. For every challenge offered by
the green chemistry revolution there is also an exciting
opportunity.
2020 Sustainability Goals
> Zero waste eliminate the concept of waste in
products, process, materials and
energy.
Zero Toxic Substances eliminate substances known or
suspected to be
harmful to human health or the health of biological system.
100% closed loop Processes : Take 100%
responsibility for our products at all
stages of our product and process life cycle.
Sustainable Growth and Profitability : Create an
economy the planet
is
capable of sustaining indefinitely.
1.5 GREEN CHEMISTRY AWARENESS INITIATIVEs
Some developed nations have done quite well to realise the importance of
concept of green chemistry and initiated some programmes and incentives for
effective implementation.
The Presidential Green
of green
Chemistry Challenge Awards In the promotion
chemistry awareness USA has been a forerunner. These awards are
presented annually at the National Academy of Sciences in
these are the only awards for Washington DC. In fact
awards are distributed each
chemistry that are given at presidential level. Five
year with the categories being academic, sma
:
business, alternate synthesis, alternative solvents or reaction conditions an
designing safer chemicals.
Some other countries, namely, UK, Australia, Italy have instituted
awards to render green several
chemistry practice more popular and lucrative. The Koya
Australian Chemical Institute (RACI)
presents Australia's Green Chemistry
Challenge Awards. This award program is similar to that of the United States
Environmental Protection Agency (EPA)
although the RACI has included a category
 MMMMMM 23
Green Chemistry

academic or
for green chemistry education as well as small business and
government.
The Canadian Green Chemistry Medal is an annual award given to an
or group for promotion and development of green chemistry in Canada
individual
and internationally. The winner is presented with a citation recognising the

achievements together with a sculpture.

Green Chemistry activities in Italy center around an inter-university
consortium known as INCA. Begining in 1999, the INCA has given three awards
annualy industry for applications for green chemistry. The winners
to receive a

plaque at the annual INCA meeting.

ln Japan, the Green and sustainable chemistry Network (GSCN) formed in
1999, is an organisation consisting of representatives from chemical manufacturers
and researchers. In 2001, the organisation began an awards program GSC awards
are to be granted to individuals, groups or companies who greatly
contr1buted to

green chemistry through their research, development

and their industrialisation.
The achievements are awarded by Ministers of related government agencies.
In the United kingdom the Crystal Faraday Part, a non-profit group founded in
Green
2001, awards business annually for incorporation of green chemistry. The
Chemical Technology Awards have been given by Crystal Farady since 2004. The
awards were presented by the Royal Society of Chemistry prior to that time. The
award is to a
given only researcher or business, while other notable entries
single
are given recognition as well.

The Nobel Prize Committee recognised the importance of green chemistry in

the
2005 by awarding Yves Chauvin Robert H. Grubbs and Richard R. Schrock,
Nobel Prize for Chemistry "the development of the metathesis method in organic

synthesis".The Nobel Prize Committee states this represents a great step forward
waste through smarter
for green chemistry, reducing potentially hazardous
production."

1.6| PRESIDENTIAL GREEN CHEMISTRY CHALLENGE AWARDS

as a n effort
presidential Green Chemistry challenge Awards began in 1995
The
to recognise individuals and businesses for innovations in green chemistry. Typically
five awards are given each year one in each of five categories. AcademiC, Small
Greener Synthefic Pathways, Greener ReactionConditions and Designing
Business Chemicals.
Greener Some cases of Green Chemistry/Technologythat have won the
Presidential Green Chemistry challenge Awards may be cited as ideal examples

B a r y Trost's concept of atom economy, which looks at utilized and wasted

atoms in a reaction.
dioxide to be
Development of surfactants for carbon dioxide, enabling carbon
used as solvent (for example in dry cleaning).
Development of oxygen activators for hydrogen peroxide. It has application in
paper manufacture where hydrogen peroxide replaces chlorine
bleaches (Ozone depleting).
containin
aining
A synthesis
new
ofibuprofen
The conventional method uses a toxic materal
aluminium chloride in stoichiometric amount. It results in enormous amount ot
waste by product : aluminium trichloride hydrate that is land filled. New
synthesis has much hetter record of atom economy and pollution prevention
4-1sobutylacetophenone is key intermediate in this synthesis.
In the polystyrene foam product the
of waste carbon dioxide as a blowing
use
agents. Traditional method used CFCs as blowing agent which are ozone
depleter. Flammable, explosive and in some cases toxic hydrocarbons have also
been used as CFC replacement.
The development of new insecticides that are specific to target organisms.
more

Greener gasoline alkylation. The conventional method of synthesis of a isooctane,

an integral part of gasoline, requires large amounts of highly toxic and corrosive
acids. The greener alternative is the use of suitable solid acids such as alumina,
zeouile etc.
Improved polylactic acid polymerisation process-lactic acid is produced by
fermenting corn and converted to lactide, the cyclic dimer ester of lactic acid
using an efficient tin-catalysed cyclisation.
In 2002, Cargill Dow won the Greener Reaction Conditions Award for this
In 2003, show Industries was recognised with the Designing Greener
Chemicals Award for developing Eco Wrox Carpet Tiles. Eco work met all of the
design criteria necessary to satisfy the needs of the market place from a
performanee, health and environmental standpoint.
> In 2005 Midland and Novozymes won the Greener Synthetic Pathways Award
for their enzyme inter-esterfication process.
In 2006, professor Galen J. Suppes was awarded the Academic Award for his
system of converting waste glycerine from bio-diesel production to propylene
glycol through the use of copper-chromite catalyst.