UNIT 3: GREEN CHEMISTRY

Definition: Green chemistry, also called sustainable chemistry, is an area of chemistry

and chemical engineering focused on the design of products and processes that minimize or
eliminate the use and generation of hazardous substances.
While environmental chemistry focuses on the effects of polluting chemicals on nature,
green chemistry focuses on the environmental impact of chemistry, including reducing
consumption of nonrenewable resources and technological approaches for
preventing pollution.

Significance of Green Chemistry: The significance of Green chemistry in different

areas is as given below.
Human health:
(1) Cleaner air: Less release of hazardous chemicals to air.
(2) Cleaner water: Less release of hazardous chemical wastes to water leading to cleaner
drinking and recreational water.
(3) Increased safety for workers in the chemical industry: Less use of toxic materials;
less personal protective equipment required; less potential for accidents (e.g., fires or
explosions).
(4) Safer consumer products of all types: New, safer products will become available for
purchase; some products (e.g., drugs) will be made with less waste; some products (i.e.,
pesticides, cleaning products) will be replacements for less safe products.

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 (5) Safer food: Elimination of persistent toxic chemicals that can enter the food chain.
Safer pesticides that are toxic only to specific pests and degrade rapidly after use can be
syntheiszed.
(6) Less exposure to such toxic chemicals which may cause endocrine disruption.

Environment:
(1) Many chemicals end up in the environment by intentional release during use (e.g.,
pesticides), by unintended releases (including emissions during manufacturing), or by disposal.
Green chemicals either degrade to innocuous products or are recovered for further use.
(2) Plants and animals suffer less harm from toxic chemicals in the environment.
(3) Lower potential for global warming, ozone depletion and smog formation.
(4) Less chemical disruption of ecosystems.

Economy and business:

(1) Higher yields for chemical reactions, consuming smaller amounts of feedstock to
obtain the same amount of product.
(2) Fewer synthetic steps, often allowing faster manufacturing of products, increasing
plant capacity and saving energy and water.
(3) Reduced waste, eliminating costly remediation, hazardous waste disposal.
(4) Allow replacement of a purchased feedstock by a waste product.
(5) Reduced use of petroleum products, slowing their depletion and avoiding their
hazards and price fluctuations.

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Twelve principles of Green Chemistry:

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 Conventional and Green synthesis of few important compounds:
(i) Carbaryl: Carbaryl is used as a pesticide. The traditional and greener routes for the
synthesis of Carbaryl are shown in Figure 1.
(A) Traditional method:

(B) Greener method:

Figure 1 : Synthesis of Carbaryl

Traditional method for carbaryl involves use of 1-naphthol and methyl isocyanate,
which is highly hazardous. Previously suggested greener method involves use of 1-naphthol
and phosgene similar to traditional method to form 1-naphthalenyl chloroformate, which reacts
with methyl amine to form carbaryl, but it eliminates the formation of methyl isocyanate.
Hence, it is less hazardous that traditional method.
Principle involved: Less hazardous chemical synthesis.

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 (ii) Indigo: Indigo is basically used as dye, it is also being used as a nematicide and
treatment for a range of ills including scorpion bites and ovarian and stomach cancer. The
traditional and greener routes for the synthesis of Indigo are shown in Figure 2.
(A) Traditional Method:

(B) Greener Method:

Figure 2 : Synthesis of Indigo

Traditional method for indigo involves aniline, chloroacetic acid and soda amide.
Therefore, waste is generated at the end of the process. Also, aniline is hazardous in nature
whereas greener method brings about enzymatic transformation.
Principles involved: (i) Prevention of waste. (ii) Less hazardous chemical synthesis.

(iii) Adipic acid: Adipic acid is used in the production of nylon 66, plasticizers and
lubricant components. The traditional and greener routes for the synthesis of Adipic acid are
shown in Figure 1.
(A) Traditional Method:

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 (B) Greener Method:

Figure 3 : Synthesis of Adipic acid

Traditional method for adipic acid uses benzene which is carcinogenic in nature
whereas greener pathway uses glucose which is a renewable feedstock, hence safe.
Additionally, reaction conditions used in greener pathway are mild as conversion is carried out
using E.coli bacteria.
Principles involved: (i) Use of renewable feedstock. (ii) Design for energy efficiency.

(iv) Disodium iminodiacetate: Disodium iminodiacetate is a salt of iminodiacetic acid

(IDA). The iminodiacetate anion can act as a tridentate ligand to form a metal complex with
two, fused, five-membered chelate rings. Iminodiacetic acid is used to diagnose problems of
the liver, gallbladder and bile ducts in an imaging procedure, called as hepatobiliary
iminodiacetic acid (HIDA) scan. The traditional and greener routes for the synthesis of
Disodium iminodiacetate are shown in Figure 4.
(A) Traditional method:

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 (B) Greener Method:

Figure 4 : Synthesis of Disodium iminodiacetate

Traditional method for Disodium iminodiacetate involves use of hazardous chemicals,
viz., hydrogen cyanide whereas greener method uses diethanolamine with copper catalyst.
Principles involved: Less hazardous chemical synthesis.

(v) Acrylamide: Acrylamide is a chemical used primarily to make substances called

polyacrylamide and acrylamide copolymers. The traditional and greener routes for the
synthesis of Acrylamide are shown in Figure 5.
(A) Traditional method:

(B) Greener Method:

Figure 5 : Synthesis of Disodium iminodiacetate

Traditional method for Acrylamide involves use of acid and formation of ammonium
sulphate whereas greener method uses enzyame as a catalyst, which is selective in nature.
Principles involved: Use of catalyst.

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Percentage Atom economy:

Molecular weight of desired product

% Atom Economy = _________________________________ x 100
Molecular weight of all reactants

Atomic weights:
H = 1, C =12, N = 14, O = 16, Na = 23, Mg = 24, Al = 27, Si = 28, S = 32, Cl = 35.5, K = 39,
Ca = 40, Fe = 56, Ti = 48

Solved Numericals:
Example 1: Calculate the % Atom economy for the following reaction w.r.t. methyl
isocyanate.
CH3NH2 + COCl2 CH3-N=C=O + 2HCl
Methyl isocyanate
Solution: CH3NH2 + COCl2 CH3-N=C=O + 2HCl
31 99 57

Molecular weight of desired product

% Atom Economy = _________________________________ x 100
Molecular weight of all reactants

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% Atom Economy = _________ x 100
31 + 99
57
% Atom Economy = ______ x 100
130

∴ % Atom economy = 43.85%

Example 2: Calculate the % Atom economy for the fermentation of sugar (glucose) to make
ethanol w.r.t. ethanol.
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
Solution: C6H12O6(aq) 2C2H5OH(aq) + 2CO2 (g)
180 2 x 46

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 Molecular weight of desired product
% Atom Economy = _________________________________ x 100
Molecular weight of all reactants
92
% Atom Economy = ______ x 100
180

∴ % Atom economy = 51.1%

Example 3: Calculate the % Atom economy for the below reaction w.r.t. (a) biodiesel and (b)
glycerin. Comment: Which product is favourable in terms of % Atom economy?
CH2OCOC16H33 CH2OH
CHOCOC16H33 + 3CH3OH 3CH3OCOC16H33 + CHOH
CH2OCOC16H33 CH2OH
Triglyceride Methanol Biodiesel Glycerin
Solution:
CH2OCOC16H33 CH2OH
CHOCOC16H33 + 3CH3OH 3CH3OCOC16H33 + CHOH
CH2OCOC16H33 CH2OH
(C54H104O6) 3(CH4O) 3(C18H36O2) C3H8O3
848 3 x 32 3 x 284 92

Molecular weight of desired product

% Atom Economy = _________________________________ x 100
Molecular weight of all reactants
(a) % Atom Economy w.r.t. biodiesel:
852
% Atom Economy = _________ x 100
848 + 96

∴ % Atom economy = 90.25%

(b) % Atom Economy w.r.t. glycerine:

92
% Atom Economy = _________ x 100
848 + 96

∴ % Atom economy = 9.75%

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 As % Atom economy of biodiesel (90.25 %) is more than that of glycerin (9.75 %),
biodiesel is the favourable product in terms of % Atom economy.

Example 4: Titanium can be extracted from its ore by two methods-

(1) TiO2 + 2Mg Ti + 2MgO ……. (displacement with a more reactive metal)
(2) TiO2 Ti + O2 ………………... (electrolysis of ore)
Which of the method is better in terms of % Atom economy?
Solution:
(1) TiO2 + 2Mg Ti + 2MgO
80 2 x 24 48 2 x 40

Molecular weight of desired product

% Atom Economy = _________________________________ x 100
Molecular weight of all reactants

48
= _______ x 100
80 + 48

∴ % Atom economy = 37.5%

(2) TiO2 Ti + O2
80 48 32
Molecular weight of desired product
% Atom Economy = _________________________________ x 100
Molecular weight of all reactants

48
= _______ x 100
48 + 32

∴ % Atom economy = 60%

Hence, method 2 is better in terms of % Atom economy.

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 Supercritical fluids: Any substance is characterized by a critical point which is
obtained at specific conditions of pressure and temperature. The critical point is the highest
temperature and pressure at which the substance exists as a vapour and liquid in equilibrium.
When a compound is subjected to a pressure and a temperature higher than its critical point,
the fluid is said to be ‘supercritical’. In other words, the fluid is said to be ‘supercritical’ when
it is heated above its critical temperature and compressed above its critical pressure. In the
supercritical region, only one phase exists.
In the supercritical region, the fluid exhibits particular properties and has an
intermediate behaviour between that of a liquid and a gas. In particular, supercritical fluids
(SCFs) possess liquid-like densities, gas-like viscosities and diffusities intermediate to that of
a liquid and a gas. It can effuse through porous solids like a gas and it can dissolve solids as
well as liquids. As shown in the phase diagram (Figure 6), the gas-liquid equilibrium curve is
interrupted at the critical point, providing a continuum of physicochemical properties.

Figure 6 : Representation of supercritical fluid

The most widely used supercritical fluids are CO2 and water.

Supercritical CO2: CO2 is cheap, chemically inert, non-toxic, non-flammable and

readily available at high purity and at low cost. Besides, the critical point of CO2 is easily
accessible (critical temperature 31°C or 304 K and critical pressure 74 bar) allowing the fluid
to be used at mild conditions of temperatures (40-60°C) without leaving harmful organic

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residues. Hence, CO2 is the widely used supercritical fluid. The pressure-temperature phase
diagram of CO2 is shown in Figure 7.

Figure 7 : Carbon dioxide pressure-temperature phase diagram

Applications:
(1) Supercritical carbon dioxide is useful for the decaffeination of coffee. The process
is economic and environmentally sustainable.
(2) Supercritical carbon dioxide is used as the extraction solvent for creation of essential
oils and other herbal distillates. As an extracting solvent, supercritical carbon dioxide find its
applications in the food industry.
(3) By using supercritical carbon dioxide, separation of the reaction components from
the starting material is much simpler than with traditional organic solvents.
(4) Supercritical carbon dioxide is used to remove organochloride pesticides and metals
from agricultural crops without adulterating the desired constituents from the plant matter in
the herbal supplement industry.
(5) Supercritical carbon dioxide can be used as a more environmentally friendly solvent
for dry cleaning over traditional solvents such as hydrocarbons.
(6) An electrochemical carboxylation of a para-isobutylbenzyl chloride to ibuprofen is
promoted using supercritical carbon dioxide.

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 (7) Supercritical CO2 is a good plasticizing agent because it reduces the glass transition
temperature.
(8) Supercritical CO2 is an alternative for thermal sterilization of biological materials
and medical devices with combination of the additive peracetic acid (PAA).
(Supercritical CO2 does not sterilize the media because it does not kill the spores of
microorganisms. Moreover, this process is gentle, as the morphology, ultrastructure and protein
profiles of inactivated microbes are preserved.)
(9) Supercritical CO2 is used in certain industrial cleaning processes.
(10) Supercritical CO2 is used as a catalyst in chemical reactions. It is used in the
continuous catalytic hydrogenation of aromatic compounds.
(11) Supercritical CO2 is used as a solvent in dying textile.
(12) Supercritical CO2 is used in tanning of skin into leather.

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