Introduction to Green Chemistry

By
Dr. Ajay Taneja
Head, Department of Chemistry, IBS
Dr. B.R. Ambedkar University, Agra

Green chemistry is defined as environmentally benign chemical synthesis. It focuses on a process

(whether carried out in industry or a chemical laboratory) that reduces the use and generation of
hazardous substances or by-products. The term “Green Chemistry” was coined by Prof. Paul T
Anastas of the US Environment Protection Agency (EPA), according to him “Green chemistry”
or “Sustainable Technology” necessitates a paradigm shift from traditional concepts of process
efficiency, that focus largely on chemical yield, to one that assigns economic value to
eliminating waste at source and avoiding the use of toxic and/ or hazardous substances.

The Noble prize for green chemistry has been awarded for 2005 to Yves Chauvin (France),
Robert Grubb (USA) and Richard Schrock (USA). These chemists shared this prize for their
contribution to the development of metathesis (meaning change places), an energetically favored
and less hazardous method in organic synthesis. This has immense industrial applications.
Besides its applications in the polymer chemistry (for making stronger plastics), metathesis has
also found an important role in biotechnology in recent times. It represents a great step forward
for “Green Chemistry” reducing potentially hazardous waste through smart chemistry.
Metathesis is an example of how important is basic science for the benefit of man, society and
environment.

.Dr. Paul Anastas was born on May 16, 1962 in Quincy, Massachusetts. He obtained a
B.S in chemistry from Brandies University. He joined the U.S. Environmental
Protection Agency in 1989, serving as the chief of the industrial chemistry branch and
the Director of the US green chemistry Program. In 1999 Dr. Anastas become a senior
Policy analyst at the White house office of Science and Technology Policy,
coordinating environmental and international issues for the office.

The Need for Green Chemistry.

Chemistry has played a vital role in improving our life but all these development are responsible
for various environmental problems. Some examples can be mentioned here for chemical which
were synthesized for the benefit of human beings has other detrimental effects like pesticides,
chlorofluorocarbons (CFC as refrigerants), Dioxins, Thalidomide drug. Some diseases which
became famous by the discharge of poisonous pollutants from the industries were Minamata
disease (mercury poisoning), Itai-Itai Disease (cadmium poisoning), Methaemoglobinaemia
(excessive amount of nitrogen fertilizers) etc. On the basis of what has been stated, it is clear that
most of the environmental and health problems would not have been there, had the various
industries followed the basic norms. It is in this context that green chemistry plays a vital role in
keeping the environment clean. The concept of green chemist addresses environmental issues in
an economic profitable manner. Green chemistry must permeate not only to the chemical
industries, but it is necessary to bring about changes at the grass root level. This can be achieved
by bringing about necessary changes in the chemistry curriculum not only in the college and
university but also in the secondary school. The next generation of scientists needs to be trained
in the methodologies, techniques and principles that are central to green chemistry.

Principles of Green Chemistry

It was only in 1991 (after the pollution preservation act of 1990) that Environmental Protection
Agency (EPA) of USA introduced Green Chemistry as a formal area of work with a view to
eliminate the use of hazardous substances during the design, manufacture and use of chemical
products and processes. Prof. Anastas and Prof. John C Warner have postulated twelve principles
of green Chemistry. These are (See Fig.1).

Figure 1.
1. It is better to prevent waste than to treat or clean up waste after it is formed:

It is most appropriate to carry out a synthesis by following a pathway so that formation of waste
is minimum or absent. One type of waste product common and often avoidable is the starting
material or reagent that remains unreacted. The well known saying “Prevention is better than
cure should be followed”. In universities and colleges, the cost of disposal of waste from
chemical laboratory can be reduced by carrying out experiments on a much smaller scale (micro
scale).

Students should be encouraged to use waste generated in the labs. Designing of

experiments in various disciplines is very important in this context. Qualitative
analysis of organic compounds and preparation of their derivatives is an important
exercise done at various levels of undergraduate teaching. Various derivatives can
be used as ligands for the preparation of complexes

2. Synthetic methods should be designed to maximize the incorporation of all the materials
used in the process into the final product.

If one mole of the starting material produces one mole of the product, the yield is 100 %.
However, such a synthesis may generate significant amount of waste or by product which is not
visible in the above calculation. Such a synthesis, even though gives 100% yield is not
considered to be green synthesis.

In order to find, if a particular reaction is green, the concept of atom economy was developed by
Berry Trost of Stanford University. This considers the amount of stating materials incorporated
into the desired final product. Thus by incorporation of greater amounts of the atoms contained
in the starting materials (reactants) in to the formed products, fewer waste by products are
obtained. In this way, using the concept of atom economy along with ideas of selectivity and
yield, “greener” more efficient synthesis can be developed. For examples

(a) Claisen rearrangement of allyl phenyl ether on heating at 200 C to give o-allyl phenol.
The above rearrangement reaction is 100% atom economical reaction, such all the reactant is
incorporated into final product.

The concept of selectivity (chemo selectivity, regioselectivity, enantioselectivity

and diastereoselectivity) is concerned with controlling reactions in such a way
that the desired product is obtained over competing side products.

3. Whenever practicable synthetic methodologies should be designed to use and generate a

substance that poses little or no toxicity to human health and the environment.

(3) TNT is also a product of chemistry lab so

it is better see what you are mixing

Wherever practicable, synthetic methodologies should be designed to use and generate

substances that posses little or no toxicity to human health and the environment. Redesigning
existing transformations to incorporate less hazardous materials is at the heart of Green
Chemistry.

4. Chemical products should be designed to preserve efficiency of function while reducing

toxicity

(4) All that Glitters is not Gold……………………

It may be Mercury which is poisonous

The designing of safer chemical is now possible since there have been great advances in the
understanding of chemical toxicity. It is now fairly understood that a correlation exist between
chemical structure e.g. presence of functional groups and the existence of toxic effects. The idea
is to avoid the functionality related to the toxic effect. Chemical properties of a molecule, such as
water solubility, polarity etc. so that they can manipulate molecules to the desired effects.

5. The use auxiliary substances (e.g. solvents, separating agents) should be made
unnecessary wherever possible and innocuous when used.

(5) Too much of anything is Harmful……………………

Even heating, it can cause Explosion

An auxiliary substance is one that helps in manufacture of a substance, but does not become an
integral part of the chemical. Such substances are used in the manufacture, processing at every
step. Major problem with many solvents is their volatility that may damage human health and the
environment. Even processes like recrystalisation require energy and substances to change the
solubility. The problem of solvents has been overcome by using such solvents which do not
pollute the environment. Such solvents are known as green solvents. Examples include liquid
carbon dioxide (supercritical CO2), ionic liquid water. Even reactions have been conducted in
solid state. For example the condensation reaction of orthoesters with o-phenylenediamines in
presence of KSF clay under solvent free conditions using microwave.
6. Energy requirements should be recognized for their environmental and economic
impacts and should be minimized.

(6) Conservation is the wise use of the Earth and its resources

For the lasting good of man

Energy generation, as we know has a major environmental effect. The requirement of energy can
be kept to a base minimum in certain cases by the use of a catalyst. For example in conversion of
benzyl chloride into benzyl cyanide if we use phase transfer catalyst, the conversion goes to
completion in a very short time.

C6H5CH2Cl + aq KCN C6H5CH2CN + KCl

Benzyl chloride Benzyl cyanide

Conventionally, we have been carrying reaction by heating on wire gauze, in oil bath or heating
mantels. It is now possible that the energy to a reaction can be supplied by using microwaves, by
sonication or photo chemically. Simple examples are

(a) C6H5CONHC6H5 C6H5COOH

20% 12
MW, H2SO
MINS
4

Esterification
(b) RCOOH + ROH RCOOR
H2SO4, Ultrasound

7. A raw material or feedstock should be renewable rather than depleting, whenever

technically and economically practicable

(8) The chemical industry reliance on petroleum-based

Feedstocks must be addressed

Non reversible or depleting sources can exhausted by their continual use. So these are not
regarded as sustainable from environmental point of view. The starting materials which are
obtained agricultural or biological processes are referred to as renewable starting materials.
Substances like carbon di oxide (generated from natural sources or synthetic routes like
fermentation etc) and methane gas (obtained from natural sources such as marsh gas, natural gas
etc) are available in reasonable amounts and so are considered as renewable starting material.
Methane, a constituent of biogas and natural gas can easily be converted into acetylene by partial
combustion. Acetylene is a potential source of number of chemicals such as ethyl alcohol,
acetaldehyde, vinyl acetate etc.

(8) Unnecessary derivatization (blocking group, protection, deportation, temporary

modification of physical/chemical processes) should be avoided whenever possible.

Fundamentally green chemistry is change in perspective and thinking in the way that
chemical design is approached, an important element to achieve that change in the
effective communication of green chemistry

A commonly used technique in organic synthesis is the use of protecting or blocking group.
These groups are used to protect a sensitive moiety from the conditions of the reaction, which
may make the reaction to go in an unwanted way if it is left unprotected. This procedure adds to
the problem of waste disposal.

(7) Success is a journey, not a destination.

The doing is often more important than the outcome.

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

2001 Noble Prize winning work of Sharpless, Noyori and Knowles met many green
chemistry goals. Their research on catalytic asymmetric synthesis has been crucial in
producing single enantiomer compounds, particularly for the pharmaceutical industry. The
area of catalysis is sometimes referred to as a “foundation pillar” of green chemistry.

The catalyst as we know facilitates transformation without being consumed or without being
incorporated into the final product. Catalysts are selective in their action in that the degree of
reaction that takes place is controlled, e.g. mono addition v/s multiple addition. A typical
example is that reduction of triple bond to a double bond or single bond
 5%Pd-C or 5%Pd-BaSo4
-CH=CH-
Alkenes
-CH≡CH-
Alkynes
- CH2-CH2-
PtO2 or Raney Ni Alkanes

In addition to the benefits of yield and atom economy, the catalysts are helpful in reducing
consumption of energy. Catalyst carriers out thousands of transformation before being
exhausted.

(10) Chemical products should be designed so that at the end of their function they do not
persist in the environment and break down into innocuous degradation products:

Green chemistry represents the pillars that hold up our sustainable future. It is
imperative to teach the value of green chemistry to tomorrow’s chemists.

It is extremely important that the products designed to be synthesized should be biodegradable.

They should not be persistent chemicals or persistent bio accumulators. It is now possible to
place functional groups in a molecule that will facilitate its biodegradation. Functional groups
which are susceptible to hydrolysis, photolysis or other cleavage have been used to ensure that
products will be biodegradable. It is also important that degradation products do not possess any
toxicity and detrimental effects to the environment. Plastic, Pesticides (organic halogen based)
are examples which pose to environment.

(11) Analytical methodologies need to be further developed to allow for real time, in
process monitoring and control prior to the formation of hazardous substances.

Problems cannot be solved at the same level

Of awareness that created them.

Methods and technologies should be developed so that the prevention or minimization of
generation of hazardous waste is achieved. It is necessary to have accurate and reliable reasons,
monitors and other analytical methodologies to assess the hazardous that may be present in the
process stream. These can prevent any accidents which may occur in chemical plants.

(12) Substances 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.

One factor that can greatly facilitate the research, development and implementation
of green chemicals technologies in academe, industry and government is the
incorporation of green chemistry concepts, principals and examples at all the levels
of chemical education.

The occurrence of accidents in chemical industry must be avoided. It is well known that the
incidents in Bhopal (India) and Seveso (Italy) and many others have resulted in the loss of
thousands of life. It is possible sometimes to increase accidents potential inadvertently with a
view to minimize the generation of waste in order to prevent pollution. It has been found that in
an attempt to recycle solvents from a process (for economic reasons) increases the potential for a
chemical accident or fire.

Future Challenges:
The future challenges facing green chemistry are as diverse as the scientific imagination and
address the broadest issues of sustainability. Because of this breadth, it should be no surprise that
a number of these challenges are being pursued for reasons ranging from economic to scientific.
1. Transformations utilizing energy rather than material.
2. Efficient spitting of water by visible light.
3. Solvent systems that effect efficient heat and mass transfer while catalyzing reactions and
intrinsically adding in product separation.
4. Development of a synthetic methodologies “toolbox” that is both atom economical and
benign to human health and the environment.
5. Plastic and polymers designed for innocuous degradation through the use of additives-
free design.
6. Materials design for recycle/reuse decisions based on embedded entropy.
7. Development of “preventative toxicology” where increasing knowledge of biological and
environmental mechanism of action are continuously incorporated into design of
chemical products.
8. Less energy-intensive manufacture of photovoltaic cells that are more efficient.
9. Development of non combustion, non-material-intensive energy sources.
 10. Value-added consumptive/fixation use of CO2 and other greenhouse gases at high
volume.
11. Transformation preserving sensitive functionally without the use of protecting groups.
12. Development of surfaces and materials that are durable and do not require coating and
cleaners.

Conclusion
The growth of green chemistry over the course of the past decades needs to increase at an
accelerated pace if molecular science is to meet the challenges of sustainability. It has been said
that the revolution of one day becomes the new orthodoxy of the next. When the 12 Principals of
Green Chemistry are simple incorporated as an integral part of everyday chemistry, there will no
longer be need for the focusing, highlighting, and moniker of green chemistry. And when that
day comes, the challenges that chemistry will meet cannot be imagined.

Books Suggested for further Reading

1 Green chemistry theory and practice by Anastas Paul T; Warner John C. Oxford
University Press, New York.
2 Green chemistry, Environmentally Benign reaction by V K Ahluwalia, Ane books
India.
3 Green chemistry and catalysis by Roger A Sheldon, Isable Arends, Ulf Hanefeld,
Wiley-VCH, Weinheim.