Engg.

Chemistry

Module – 4

Green Chemistry and Alternative energy

resources
Green Chemistry:
Green Chemistry: Introduction, definition, Major environmental pollutants – oxides of Nitrogen,
Sulphur and Carbon, Basic principles of green chemistry. Various green chemical approaches –
Microwave synthesis, Bio catalyzed reactions, Solvent free reactions – advantages and conditions.
Synthesis of typical organic compounds by conventional and green route; i) Adipic acid
ii) Paracetamol, Industrial applications of green chemistry.

Green fuel:
:
Hydrogen-production (Photo electro catalytic and photo catalytic water splitting) and applications
in hydrogen fuel cells. Construction, working and applications of Methanol-Oxygen fuel cell
(H2SO4 as electrolyte).

Solar Energy:

Introduction, construction, working and applications of photovoltaic cell.

Green Chemistry:
Introduction: -
Green chemistry is the design of chemical products and processes that reduce or eliminate
the use or generation of hazardous substances.

The term was first used by Paul T. Anastas in the last decade of the 20th century.

Green Chemistry implies

 To develop products that are less toxic.

 To develop products that are less toxic.
 Reduces the negative impacts of chemical products and processes on human health and
the environment
 To develop products that degrade more rapidly in the environment than the current
products
 To develop processes based on renewable rather than non- renewable raw materials.

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Major environmental pollutants:-

1. Carbon monoxide:

Sources:-

 Natural source such as forest fire, natural gas emission, volcanic actions.
 Produced by burning of organic material (coal, gas, wood, trash, etc.)
 Incomplete combustion of fuel [or] carbonaceous compounds.
2C + O2 2CO
 Reaction b/w CO2 & carbonaceous material at high temperature gives CO.
CO2 + C 2CO
 Dissociation of CO2 at very high temperature gives CO

CO2 CO + C
 CO formed during the decomposition of Chlorophyll.
 Cigarette & Beedi smoke & domestic heat appliances are the other sources of CO.

Effects:-

 Causes headache, visual difficulty, paralysis & even death.

 Causes Chromic effects include weakness, fatigue, increased red blood cells
[polycythemia] in blood.
 It reacts with hemoglobin to from carboxy-haemoglobin.
HbO2 + CO COHb + O2
 In the presence of CO reduces the oxygen carrying of blood.
 Causes serious effects on the cardio vascular system, thereby causing heart diseases.
 High concentration of CO [100-1000PPM] can affect leaf drop, leaf curling, and
reduction in the leaf size in plants.

2. Oxides of Nitrogen:

Sources:-

 Produced naturally by lighting, volcano & bacterial decay process.

 Produced by automobile exhaust, combustion of coal, oil, natural gas & gasoline.
 Other sources like acid manufacture, power plants, fertilizer industry, explosive
industries, etc…

Effects:-
 High concentration of NO2 causes inflammation of lung tissue, respiratory illness.
 NO2 reacts with H2O & O3 to form, HNO3, & N2O5, which cause acid rain.

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 A use chromic effects like, cell membrane damage, stress on the heart.
 In sunlight nitrogen oxides combines with hydrocarbons from photochemical smog.
Which cause
i) Limits the visibility of roads,
ii) Cause eye irritation
iii) Cause difficulty in breathing
iv) Cause lung cancer, asthma & bronchitts.

3. Oxides of Sulphur:-

Sources:-
 Natural process like Volcanic activity releases SO2, SO3, H2S, S & Particulate matter
in to atmosphere.
 Combustion of fossil fuels
 Combustion of sulphur containing fuels [coal] in thermal power plants, automobiles.
S + O2 SO2
 Oxygen formed by thermal decomposition of ozone oxidizes H2S in the atmosphere
to SO2.
H2S + 3[O] SO2 + H2O

Effects:-
 Cause the cardiac, respiratory & pulmonary diseases.
 Cause eye irritation, throat troubles.
 Cause the corrosion of metals.
 Damages of plant cells & membrane, chlorophyll, reduce crop yield.
 SO3 in air causes breathing discomfort & irritation to the respiratory track.
 SO2 & SO3 formed in the atmosphere can combine with water vapour forming H 2SO3
& H2SO4 mist. It causes the acid rain.
SO2 + H2O + H2SO3 SO3 + H2O H2SO4
 H2SO4 mist can damage natural & synthetic fibers.
 Cause the yellowing of paper & the loss of its mechanical strength.

Principles of Green Chemistry:-

There are 12 main principles of green chemistry, which widely followed by industries and
chemists.
1. Prevention of waste/by-products: It is always best to carry out a synthesis in such a way
that formation of waste is minimum or absent.
2. Maximize Atom Economy: Design synthesis so that the final product contains the
maximum proportion of starting materials.

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3. Prevention or minimization of hazardous products: The most important principle of
green chemistry is to try to minimize utilization and formation of hazardous chemicals.
4. Designing of safer chemicals: Design chemical products that are fully effective yet have
little or no toxicity.
5. Use safer solvents and reaction conditions: Avoid using solvents, separation agents or
other auxiliary chemicals.
6. Increase energy efficiency: Run chemical reactions at room temperature and pressure
whenever possible.
7. Use of renewable feed stocks: Starting materials are those obtained from a renewable or
renewable material.
8. Reduce chemical derivatives: Avoid using blocking or protecting groups if possible.
9. Use of catalysts: Minimize waste by using catalytic reactions. Catalysts are effective in
small amounts and can out a single reaction many times.
10. Products obtained should be biodegradable: Design chemical products to break down
to innocuous substances after use so that they do not accumulate in the environment.
11. Analyze in real time to prevent pollution: Include in-process, real-time monitoring and
control during syntheses to minimize or eliminate the formation of byproducts.
12. Minimize the potential for accidents: Design chemicals and their physical forms (solid,
liquid, or gas) to minimize the potential for chemical accidents including explosions, fires,
and releases to the environment.

Various green chemical approaches:

Microwave Synthesis:-
In microwave induced organic reactions, the reactions can be carried out in a solvent
medium or on a solid support in which no solvent is used. For reactions in a solvent medium, the
choice of the solvent is very important. The solvent to be used must have a dipole moment so as to
absorb microwaves and a boilingpoint at least 20-30°C higher than the normal desired reaction
temperature.

Ex: - 1. Hydrolysis of Benzyl Chloride with water in Microwave oven gives 97% yield of Benzyl
alcohol in 3 min.

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2. Hydrolysis of methyl benzoate to benzoic acid

2. Bio Catalyzed Reactions:

 Bio catalyzed reactions are the chemical reactions which use biomolecules, especially
enzymes.
 Enzymes act as catalysts for the synthesis of new materials.
 Many organic synthesis are difficult to synthesize, requiring multiple steps, large amounts
of solvents and extensive purifications.
 Using enzymes as catalysts can improve the purity, enhance the speed of reaction highly
efficient, mild operating conditions
 Protection and deprotection of the functional group not needed.
Ex:- Synthesis of ethyl alcohol from molasses using Zymase enzyme.

Solvent free reactions:-

It is a dry media reaction or solid-state reaction where the chemical system does not have
any solvent.

Solid-state reaction follows fifth principle of green chemistry, which avoid using toxic
solvents in the chemical reaction.

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Conditions:-
A solvent-free or solid-state reaction may be carried out using the reactants alone or
incorporating them in clays, zeolites, silica, alumina or other matrices to achieve high degree of
stereo-selectivity in the products, to reduce byproducts, to maximize rate of reaction.

Advantages:-
 More efficient with more selective compared to reactions with solvents
 Reactions are simple to handle and reduce pollution comparatively
 Synthesis free from solvents are more economical
 Not required to remove a solvent after reaction
 Purification step is avoided
 Reaction rate is high due to more availability of reactants
 Environmentally friendly as no solvent is used.

Synthesis of typical organic compounds by conventional and green route:-

1. Adipic acid:-
Adipic acid is a very important starting material in preparation of resins, nylons,
cosmetics, adhesives, lubricants and used in the pharmaceutical and pesticide industries.

Conventional Route:-

Benzene is hydrogenated over a Ni/Alumina catalyst to form cyclohexane, which is then

oxidized in presence of Cobalt catalyst that produces both cyclohexanone and cyclohexanol. These
molecules are catalytically oxidized in the presence ammonium vanadate at 800C, along with Cu in
60% of nitric acid to form adipic acid.

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Green Route:-
In this method glucose is treated with bacteria E coli, which brings about degradation and
ring opening to form cis mucanoic acid. The corresponding mucanoic acid undergoes
hydrogenation in presence of platinum catalyst to give adipic acid.

2. Paracetamol:-
Paracetamol is a pain reliever and a fever reducer. It is an Analgesic and Anti-pyretic drug

Conventional Route:-
 Phenol is nitrated by treating it with dilute sulphuric acid and sodium nitrate which yields
ortho and para nitro phenol.
 Where para nitro phenol is separated through steam distillation from ortho nitro phenol.
 Later para nitro phenol is reduced using sodium boro hydride to form para–amino phenol,
which yields paracetamol on N-acetylation using acetic anhydride.

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Green Route:-

 Phenol is treated with acetic anhydride directly in presence of HF to form 4-hydroxy

acetophenone.
 Which yields 4-hydroxy aceto phenoxime on treating with hydroxyl amine, causing
Beckmann rearrangement to form Paracetamol.

Industrial Applications of Green Chemistry:-

 The development of less hazardous processes and commercial products.
 The shift from inefficient chemical routes towards bio-based synthesis.
 The replacement of oil-based feed stocks by renewable starting materials.
 Replacement of oil-based feed stocks by renewable starting materials.

Green fuel:
Hydrogen Production:-

Photo Catalytic Water Splitting:-

Spliting of water to get hydrogen by using photocatalyst and solar energy is called
photocatalytic water spilitting.
 When solar energy interacts the photocatalyst, produces charge carriers holes and electrons
due to absorption of energy.
 Thus produced hole will react with the neighbouring water molecule liberates the hydogen
ions and oxygen.
 Later electrons recduces the H + ions in to hydrogen gas.

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Reactions:-
1
H2 O(l) + [hν] + 2h+ 2H + (aq) + O
2 2 (g)
2H + + 2e− H2 (g)

Cocatalyst
H2 2H+
(Nanoparticles) 2H+ + 1/2O2

H2O
Sun 𝟐𝐞 −
𝟐𝐡 +

Light

Photo catalyst
Photo electro Catalytic Water Splitting:-
 In which two electrodes are dipped in aqueous electrolyte and one of the electrode is
semiconductor photocatalyst.
 The system is irradiated with the sunlight and charge carriers are produced.
 Thus produced hole will react with the neighbouring water molecule liberates the hydogen
ions and oxygen.
 Later H + ions formed will then bond with one other proton and combine with two electrons
to form hydrogen gas.
Reactions:-
1
At Photo anode:- H2 O(l) + [hν] + 2h+ + 𝑒 − 2H + (aq) + O2 (g) + 𝑒 −
2

At Cathode :- 2H + + 2e− H2 (g)

1 𝐇𝟐 𝟐𝐞−
O
Solar Energy 2 2

Cathode
𝟐𝐇+ 𝟐𝐇+
Electrolyte
Photoanode

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Methanol – oxygen Fuel Cell:-

Methanol is preferred as a fuel in fuel cells because of the following reasons.
 It has low carbon content.
 It possesses a readily oxidizable alcoholic group.
 It has high solubility in aqueous electrolytes.
Construction:-
 It consists of anodic and cathodic compartments and both the compartments contain
platinum electrodes.
 Methanol containing H2SO4 is passed through anodic compartments.
 Oxygen is passed through cathodic compartments.
 Electrolyte consists of sulphuric acid [3.7M]
 A membrane is provided which prevents the diffusion of methanol into the cathode.
CO2

CH3OH O2

Cathode
Anode
Membrane

H2SO4 (electrolyte)

Excess Oxygen
and water
CO2

Working: -
 At anode, CH3OH undergoes oxidation to CO2 and liberates electrons, proton H+ released
are transported across the proton conducting memberane to the cathode where they react
with oxygen to produce water.
 During this process electrons are flowing through an external circuit from anode to cathode,
providing power to connected device

Reactions:-
At Anode: - CH3OH + H2O CO2 +6H+ + 6e-
3
At Cathode: - 2 O2 + 6H+ + 6e- 3H2O
3
Net reaction: - CH3OH + 2 O2 CO2 + 2H2O

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°
The cell potential is 1.21V at 25 C.
Uses: -
It is used in Military applications.
USED as electric power source in space vehicles.
Used in large scale power production.

Solar Energy:
Introduction:-
Solar energy is one of the solutions for sustainable energy conversion processes. Solar
radiation coming from sun is highly useful in photosynthesis and is the major energy source for
ecosystem. Solar energy is non-depleting, non-polluting and available freely & can be utilized for
various applications.

Radiations from the sun called as Solar energy.

It is a clean and renewable source of energy available in abundance.

Photovoltaic Cells:-

Photovoltaic cells are semiconductor device which convert solar energy into electrical
energy.

Photovoltaic cells can generate electricity as long as Sun light is available.

Construction and working of Photovoltaic cells:-

 Photovoltaic cell is composed of a thin mater consisting of an ultra-thin layer of

phosphorous doped [n-type] silicon on the top of boron doped [p-type] silicon. Hence P-n
junction is formed b/w the two.
Sunlight
 A metallic grid forms one of the electrical
Antireflective layer
contacts of the diode and allows light to fall on
Metal grid
the semiconductor b/w grid lines.
N-type layer
 An antirefractive layer b/w the grid lines increase
the amount of light transmitted to the h+ P- Type layer

semiconductor. e
-

 The cells other electrical contact is formed by a e-

metallic layer on the back of the solar cell. Metallic layer

Working:-
 When light radiation falls on the P-n junction diode, electrons-hole pairs are generated by the
absorption of the radiation.
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 The electrons are drifted and collected at n-type end and the holes are drifted and collected at
the P-type end.
 When these two ends are electrically connected through a conductor, there is a flow of current
b/w the two ends through the external circuit. Thus Photoelectric current is produced and
available for use.

Applications of Photovoltaic Cell:-

The Photovoltaic cell can be used to supply electricity for

 Parking meters
 Temporary traffic signs
 Emergency phones
 Radio transmitters
 Water irrigation pumps
 Stream-flow gauges
 Remote guard posts
 Lighting for roadways

Important Questions on Module-5:-

Green Chemistry:
1. Explain principles of green chemistry.
2. Describe Microwave synthesis and Bio catalyzed reactions with examples.
3. Explain synthesis of Adipic acid by conventional route and Green route.
4. Explain synthesis of Paracetamol by conventional route and Green route.
Green Fuel:
1. Explain production of hydrogen by Photocatalytic and Photoelectro catalytic splitting
methods.
2. Describe construction and working of Methanol-oxygen fuel cell.
Solar Energy:-
1. Explain the construction and working of Photovoltaic cell.

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