Green chemistry its applications and benefits:

Green Chemistry NOT just a definite solution… BUT an ultimate necessity…

2. Some light upon the term-Green Chemistry: Definition- “The design of chemical products and
processes that are more environmentally friendly and reduce negative impacts to human health and the
environment.” Green chemistry looks at pollution prevention on the molecular scale and 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. Property of Amit Amola. To be used only as a reference and by consent.

3. Father of Green Chemistry The concept of green chemistry was formally established at the
ENVIRONMENTAL PROTECTION AGENCY 15 years ago in response to the Pollution Prevention Act of
1990. Paul T. Anastas for the first time in 1991 coined the term Green Chemistry. Though it is said that
the concept was originated by Trevor Kletz in his 1978 paper where he proposed that chemists should
seek alternative processes to those involving more dangerous substances and conditions. Property of
Amit Amola. To be used only as a reference and by consent.

4. Principles of Green Chemistry Paul T. Anastas and John C. Warner developed 12 principles of green
chemistry, which help to explain what the definition means in practice. a. Prevention b. Atom Economy
c. Less Hazardous Chemical Synthesis d. Designing Safer Chemicals e. Safer Solvents and Auxiliaries f.
Design for Energy Efficiency g. Use of Renewable Feedstocks h. Reduce Derivatives i. Catalysis j. Design
for Degradation k. Real-time Analysis for Pollution Prevention. l. Inherently Safer Chemistry for Accident
Prevention.Property of Amit Amola. To be used only as a reference and by consent.

5. 1.Prevention: “It is better to prevent waste than to treat or clean up waste after it is formed.” It is
advantageous to carry out a synthesis in such a way that the formation of waste products is minimum or
absent. The waste if discharged in the atmosphere, sea and land causes not only pollution but also
requires expenditure for cleaning up. Chemical Process Property of Amit Amola. To be used only as a
reference and by consent.

6. Some dreadful examples of ill effects from untreated waste disposal: 1.Love Canal: In Niagara Falls, NY
a chemical and plastics company had used an old canal bed as a chemical dump from 1930s to 1950s.
The land was then used for a new school and housing track. The chemicals leaked through a clay cap
that sealed the dump. It was contaminated with at least 82 chemicals (benzene, chlorinated
hydrocarbons, dioxin). Health effects of the people living there included: high birth defect incidence and
seizure-inducing nervous disease among the children. Property of Amit Amola. To be used only as a
reference and by consent.

7. continued… 2.Cuyahoga River – Cleveland, Ohio • There were many things being dumped in the river
such as: gasoline, oil, paint, and metals. The river was called "a rainbow of many different colors". • Fires
erupted on the river several times before June 22, 1969, when a river fire captured national attention
when Time Magazine reported it. Some river! Chocolate-brown, oily, bubbling with subsurface gases, it
oozes rather than flows. "Anyone who falls into the Cuyahoga does not drown," Cleveland's citizens joke
grimly, “he decays.“ Property of Amit Amola. To be used only as a reference and by consent.

8. 2.Atom Economy: “Synthetic methods should be designed to maximize the incorporation of all
materials used in the process into the final product.” A synthesis is Perfectly Efficient or Atom
Economical if it generates significant amount of waste which is not visible in percentage yield
calculation. Percent yield: % Yield= actual yield) theoretical yield × 𝟏𝟎𝟎 Atom Economy: % AE = 𝑭𝑾 𝒐𝒇
𝒂𝒕𝒐𝒎𝒔 𝒖𝒕𝒊𝒍𝒊𝒔𝒆𝒅) (𝑭𝑾 𝒐𝒇 𝒂𝒍𝒍 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 × 𝟏𝟎𝟎 Property of Amit Amola. To be used only as a
reference and by consent.

9. Rearrangement and Addition reactions are 100% atom economical reactions since all the reactants
are incorporated into products. While Substitution and Elimination reactions are less atom economical.
1. H3C-CH=CH2 + H2 H3C-CH2-CH3 propene propane the reaction takes place in presence of Nickel.
Here 64.8% reactants are incorporated into product. Hence this is an atom economical reaction. 2.
CH3(CH2)4CH2OH +SOCl2 SO2 + CH3(CH2)4CH2Cl this reaction is less atom economical as the % atom
economy is 36.5%. Property of Amit Amola. To be used only as a reference and by consent.

10. 3.Less Hazardous Chemical Synthesis “Wherever practicable, synthetic methodologies should be
designed to use and generate substances that possess little or no toxicity to human health and the
environment.” Example of an unsafe drug is THALIDOMIDE for lessening the effect of nausea and
vomiting during pregnancy. The child born to women taking the drug suffers from birth defects like
deformed-limbs. Property of Amit Amola. To be used only as a reference and by consent.

11. Another example but with a remedial substitute: Polycarbonate Synthesis: 1.Phosgene Process
Disadvantages:- 1.phosgene is highly toxic, corrosive 2.requires large amount of CH2Cl2 3.polycarbonate
contaminated with Cl impurities OH OH Cl Cl O + NaOH O O * O * n Property of Amit Amola. To be used
only as a reference and by consent.

12. 2. Solid-State Process Advantages: 1.diphenylcarbonate synthesized without phosgene 2.eliminates

use of CH2Cl2 3.higher-quality polycarbonates OH OH + O O * O * n O O O Property of Amit Amola. To
be used only as a reference and by consent.

13. 4.Designing Safer Chemicals “Chemical products should be designed to preserve efficacy of function
while reducing toxicity.” • Synthetic methodologies should be designed to generate substances that
generate substances that possess less harmful or toxic products. • This principle focuses on choosing
reagents that pose the least risk and generate only safe by-products. • For example: in the manufacture
of Polystyrene, CFC’s which contribute to ozone depletion and global warming are replaced by CO2.
Property of Amit Amola. To be used only as a reference and by consent.

14. 5.Safer Solvents and Auxiliaries “The use of auxiliary substances (e.g. solvents, separation agents,
etc.) should be made unnecessary wherever possible and innocuous when used.” • The solvent selected
for a particular reaction shouldn't cause any environmental pollution or hazard (e.g. benzene, alcohol). •
One major problem with many solvents is their volatility that may damage environment and human
health. • To avoid this many reactions are carried out in safer green solvents like ionic liquids,
supercritical CO2 fluid etc. which maintain the solvency of the material and are also non-volatile.
Property of Amit Amola. To be used only as a reference and by consent.

15. Solvent selection Property of Amit Amola. To be used only as a reference and by consent.

16. Solvent replacement table Property of Amit Amola. To be used only as a reference and by consent.

17. 6.Design for Energy Efficiency “Energy requirements should be recognized for their environmental
and economic impacts and should be minimized. Synthetic methods should be conducted at ambient
temperature and pressure.” In any chemical synthesis the energy requirement should be kept low ,for
example: 1) If the starting material is soluble in the particular solvent, the reaction mixture has to be
heated till the reaction is complete. 2) If the final product is impure it has to be purified by distillation or
recrystallization . All these steps involve the use of high amount of energy which is uneconomical.
Property of Amit Amola. To be used only as a reference and by consent.

18. 7.Use of Renewable Feedstocks “A raw material or feedstock should be renewable rather than
depleting wherever technically and economically practicable.” Renewable feedstock are often made
from agricultural products or are the wastes of other processes; depleting feedstock are made from
fossil fuels (petroleum, natural gas or coal) or are mined. For example :- Substances like CO2(generated
from natural sources) and methane gas (marsh gas) are considered as renewable starting materials.
Property of Amit Amola. To be used only as a reference and by consent.

19. Polymers from Renewable Resources: Poly(lactic acid) Property of Amit Amola. To be used only as a
reference and by consent.

20. Raw Materials from Renewable Resources: The BioFine Process Paper mill sludge Agricultural
residues, Waste wood Municipal solid waste and waste paper O HO O Levulinic acid Green Chemistry
Challenge Award 1999 Small Business Award Property of Amit Amola. To be used only as a reference
and by consent.

21. Levulinic acid as a platform chemical Property of Amit Amola. To be used only as a reference and by
consent.

22. 8.Reduce Derivatives “Reduce derivatives - Unnecessary derivatization (blocking group,

protection/deprotection, temporary modification) should be avoided whenever possible.” Avoid using
blocking or protecting groups or any temporary modifications if possible. Derivatives use additional
reagents and generate more waste. Two synthetic steps are added each time when one is used. Overall
yield and atom economy decrease. Instead, more selective and better alternative synthetic sequences
that eliminate the need for functional group protection should be adopted. Property of Amit Amola. To
be used only as a reference and by consent.

23. 9. Catalysis “Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.” Use
of a catalyst facilitates transformation without the catalyst being consumed in the reaction and without
being incorporated in the final product. Some advantages of catalyst are: 1)Better yields H3C-CH=CH2 +
H2 H3C-CH2-CH3 Propene Propane the hydrogenation of olefins is carried out in presence of nickel.
2)The reaction becomes feasible in those cases where no reaction is normally possible. 3)Better
utilization of starting material and minimum waste product formation. Property of Amit Amola. To be
used only as a reference and by consent.

24. 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 break down into innocuous degradation products.”
For example- • Sulfonated detergents Alkylbenzene sulfonates – 1950’s & 60’s Foam in sewage
plants, rivers and streams Persistence was due to long alkyl chain Introduction of alkene group into
the chain increased degradation • Chlorofluorocarbons (CFCs) Do not break down, persist in
atmosphere and contribute to destruction of ozone layer • DDT Insecticides like DDT tend to bio-
accumulate in many plant and animal species and incorporate into the food chain resulting in population
decline of beneficial insects and animals.Property of Amit Amola. To be used only as a reference and by
consent.

25. 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 a chemist is the process of “checking the progress of chemical
reactions as it happens.” Knowing when your product is “done” can save a lot of waste, time and
energy! Property of Amit Amola. To be used only as a reference and by consent.

26. 12. Inherently Safer Chemistry for Accident Prevention “Substances and the form of a substance
used in a chemical process should be chosen to minimize potential for chemical accidents, including
releases, explosions, and fires.” Design chemicals and their forms (solid, liquid, or gas) to minimize the
potential for chemical accidents including explosions, fires and releases to the environment. Example of
such incident due to lack of such measures:- December 3, 1984 – poison gas leaked from a Union
Carbide factory, killing thousands instantly and injuring many more (many of who died later of
exposure). Up to 20,000 people have died as a result of exposure (3-8,000 instantly). More than 120,000
still suffer from ailments caused by exposure. Property of Amit Amola. To be used only as a reference
and by consent.

27. Synthesis Of Some Industrial Compounds Involving Basic Principles Of Green Chemistry Ibuprofen
Property of Amit Amola. To be used only as a reference and by consent.

28. Synthesis Of Acetaldehyde Commercially • Acetaldehyde was obtained by catalytic oxidation of ethyl
alcohol or by hydration of acetylene. • CH3CH2OH oxidation CH3CHO • The above reaction occurs at a
very high temperature (675K). Green Synthesis Of Acetaldehyde • It is most conveniently obtained by
oxidation of ethylene in presence of catalyst solution. • CH2=CH2 +O2 oxidation CH3CHO • The reaction
takes place in the presence of Pd/Cu and in aqueous medium.Property of Amit Amola. To be used only
as a reference and by consent.

29. Free Radical Bromination • The usual Bromination of toluene with N-bbomosuccinimide (NBS) gives
benzyl bromide. This process requires a solvent (CCl4). • It has been found that free radical bromination
of toluene with NBS in supercritical carbon dioxide gave 100% yield of benzyl bromide. • Toluene
(hv,NBS,CO2,139 bar) Benzyl bromide(100%) Property of Amit Amola. To be used only as a reference
and by consent.

30. Synthesis Of Adipic Acid • Adipic acid is required in large quantities for synthesis of nylon and
lubricants. • But Adipic acid is obtained from benzene which causes environmental and health problems.
Also, nitrous oxide is generated as by-product which causes greenhouse effect. • Green synthesis of
adipic acid uses D-glucose (renewable source) as starting material. Also the synthesis is conducted in
water instead of organic solvents. Property of Amit Amola. To be used only as a reference and by
consent.

31. Disinfection of water • Disinfection of water by chlorination. Chlorine oxidizes the pathogens there
by killing them, but at the same time forms harmful chlorinated compounds. • A remedy is to use
another oxidant, such as O3 or supercritical water oxidation. Property of Amit Amola. To be used only as
a reference and by consent.

32. Production of allyl alcohol CH2=CHCH2OH • Traditional route: Alkaline hydrolysis of allyl chloride,
which generates the product and hydrochloric acid as a by-product • Greener route, to avoid chlorine:
Two-step; using propylene (CH2=CHCH3), acetic acid (CH3COOH) and oxygen (O2) • Added benefit: The
acetic acid produced in the 2nd reaction can be recovered and used again for the 1st reaction, leaving
no unwanted by-product. CH2=CHCH2Cl + H2O CH2=CHCH2OH + HCl problem product CH2=CHCH3 +
CH3COOH + 1/2 O2 CH2=CHCH2OCOCH3 + H2O CH2=CHCH2OCOCH3 + H2O CH2=CHCH2OH + CH3COOH
Property of Amit Amola. To be used only as a reference and by consent.

33. Production of styrene (benzene ring with CH=CH2 tail) • Traditional route: Two-step method starting
with benzene, which is carcinogenic) and ethylene to form ethylbenzene, followed by dehydrogenation
to obtain styrene • Greener route: To avoid benzene, start with xylene (cheapest source of aromatics
and environmentally safer than benzene). • Another option, still under development, is to start with
toluene (benzene ring with CH3 tail). + H2C=CH2 catayst CH2CH3 ethylbenzene catayst CH=CH2CH2-CH3
ethylbenzene styrene Property of Amit Amola. To be used only as a reference and by consent.

34. Synthesis Of Ibuprofen • Ibuprofen is one of the products used in large quantities for making
pharmaceutical drugs, in particular various kinds analgesics (pain killers). • The traditional commercial
synthesis of ibuprofen was developed by the Boots Company of England in 1960s. It is a 6 step process
and results in large quantities of by-products. There is 40% atom economy in this synthesis. Property of
Amit Amola. To be used only as a reference and by consent.

35. conti…Classic Route to Ibuprofen… Ac2O AlCl3 COCH3 HCl, AcOH, Al Waste ClCH2CO2Et NaOEt O
EtO2C HCl H2O / H+ OHC AcOH NH2OH OHNN H2O / H+ HO2C NH3Property of Amit Amola. To be used
only as a reference and by consent.

36. conti…Green Synthesis Of Ibuprofen The BHC Company developed a new greener synthesis of
Ibuprofen that consists only of 3 steps. It results in small amount of unwanted products and has very
good atom economy(77%). O HF AcOH Ac2O H2 / Ni OH CO, Pd HO2C Property of Amit Amola. To be
used only as a reference and by consent.
37. Conclusion As Paul T. Anastas said that his dream is not that Green Chemistry is practiced by every
person but rather whole Chemistry is Green. Remember:- Green chemistry is NOT a solution to all
environmental problems BUT the most fundamental approach to preventing pollution. Property of Amit
Amola. To be used only as a reference and by consent.

38. Acknowledgement I am really thankful to my teacher Dr. Shuchi Dhingra who gave me this topic as
my project and had faith in my work. Her sincere help and devotion has led me to fulfillment of this
presentation. I would also like to thank my family, my parents, my friends and above all my brother
Summit Amola whose utmost help led me to finalize my presentation. Property of Amit Amola. To be
used only as a reference and by consent.