MODULE: 4

Green Chemistry and alternative energy resources

Green Chemistry
The design of processes that reduce or eliminate the use and production of toxic products is known
as green chemistry. The term was first used by Paul T. Anastas in the last decade of the 20th
century. Green Chemistry implies
 Prevention of pollution rather than treatment of pollution,
 Environmentally Benign Chemistry
 Sustainable Chemistry
 Ecofriendly Chemistry
 Clean Chemistry
Green chemistry is a method of preventing pollution and environmental chemistry is pollution
treatment approach.
Major environmental pollutants- Oxides of Nitrogen, Sulphur and Carbon monoxide
Carbon monoxide is one of the most serious air pollutants. It is a colorless and odorless gas, highly
poisonous to living beings.
CO2 + C   2CO

Sources
1. Incomplete combustion of carbonaceous matter, automobile engines & also in defective
furnaces,
2. Produced by burning of organic material (coal, gas, wood, trash, etc.)
3. Cigarette smoke another major source
4. Forest fires, marsh gas production
Volcanic eruption and partial combustion of fuel releases CO
2C + O2   2CO
CO is formed during the decomposition of chlorophyll
Dissociation of CO2
CO2 + C   2CO

Ill effects
1. Carbon monoxide is poisonous as it combines with hemoglobin of red blood cells about 300
times faster than O2, thus forming carboxyl hemoglobin.
2. This decreases the transport of oxygen to the body organs & cells.
3. This results in headache, weak eyesight, nervousness and cardiovascular disorder.
4. Decreases size of leaves in plants and reduction of chlorophyll with premature aging.
Oxides of Sulphur
Sulphur dioxide, is a gas that is poisonous to both animals and plants.
2SO2 (g) + O2(g)   SO3(g)
SO2 (g) + O3(g) 
 SO3(g) + O2(g)
SO2(g) + H2O2(l) 
 H2SO4
Sources
1. Volcanic eruptions (natural activity).
2. Combustion of Sulphur bearing fuels such as coal & oil (human activity).
S + O2 SO2
Oxygen formed by thermal decomposition of ozone oxidizes H2S in the atmosphere to SO2.
H2S + 3[O] SO2 + H2O

3. Roasting & smelting of Sulphide ores (human activity)

4. SO3 is formed by the oxidation of SO2 in the atmosphere by atomic oxygen [or] molecular O2
[or] ozone.
SO2 + [O] SO3
1
SO2 +2O2 SO3
SO2 + O3 SO3 + O2

Ill effects of SO2

1. It causes cough, shortness of breath & spasm of larynx, acute irritation to the membrane of gas
resulting tears & reduces hearing ability.
2. SO2 irritates the respiratory system of animals & human, produces leaf injuries (called necrotic
bloating) to board leaved plants & gases. It also causes deterioration of fabric (cotton, rayon)
paper & leather.
3. The oxidation of Sulphur dioxide to Sulphur trioxide occurs which reacts with water to form
Sulphuric acid( Acid Rain)

Oxides of Nitrogen
Dinitrogen and dioxygen are the main constituents of air.
N2(g) + O2(g)   2NO(g) [at 1483 K]
2NO(g) + O2(g) 
 2NO2(g)
NO(g) + O3(g) 
 NO2(g) + O2(g)
Sources
1. Vehicular emissions or automobile emissions
2. Burning of coal in thermal power station
3. When fossil fuel is burnt, di-nitrogen and di-oxygen combine to yield significant quantities of
nitric oxide (NO) and nitrogen dioxide (NO2).
4. Produced by automobile exhaust, combustion of fuel (petrol), coal, oil & natural gas. Other
sources like acid manufacture, power plants, fertilizer industry, explosive industries, etc

Ill effects
1. High concentration of NO2 causes inflammation of lung tissue, respiratory problems.
2. NO2 and other NOx interact with water, oxygen and other chemicals in the atmosphere to form
acid rain.
3. The nitrate particles that result from NOx make the air hazy and difficult to see though (
Visibility)
4. Accounts for global warming.
5. Accounts for photochemical smog formation.
6. In sunlight nitrogen oxides combines with hydrocarbons to from photochemical smog. Which
i) Limits the visibility of roads,
ii) Cause eye irritation
iii) Cause difficulty in breathing
iv) Cause lung cancer, asthma & bronchitis.

Basic principles of green chemistry -Brief discussion on 12 principles of green chemistry

1. Prevention: Design chemical syntheses to prevent waste. Leave no waste to treat or clean
up.
(a) If a process produces waste, it invokes the need for its treatment/disposal, whichin turn
amounts to additional expenditure.
(b) Secondly if the waste is toxic or hazardous, the release of waste in to the environment
leads to its pollution, which further invokes the need of treatment,causing additional expenses.
Amount of waste generated is given by E-Factor, also known as Environmental (mass) efficiency
factor is calculated as:
𝑻𝒐𝒕𝒂𝒍 𝒘𝒂𝒔𝒕𝒆(𝒌𝒈)
E-Factor = 𝑷𝒓𝒐𝒅𝒖𝒄𝒕(𝒌𝒈)
If you’re generating 1 kilogram of waste for every 5 kilograms of final product, your E-Factor is
1/5 or 0.2. The lower the E-factor, the better performing the product is.

2. Maximize Atom Economy: Design syntheses so that the final product contains the
maximum proportion of the starting materials. Waste few or no atoms.
Atom economy is defined as the measure of the amount of reactants that end up directly into the
desired product.
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
% 𝐴𝑡𝑜𝑚 𝐸𝑐𝑜𝑛𝑜𝑚𝑦 = x 100
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
 e.g the percent atom economy of the reaction given below is as:

138
% Atom economy= 𝑋100= 100
136+2

3. Less Hazardous Chemical Synthesis: Design syntheses to use and generate substances
with little or no toxicity to either humans or the environment.
This principle aims at use of less hazard raw material and formation of less hazard product during
synthesis. An important example concerning the use of safe chemicals is the manufacture of
polystyrene foam sheet packaging material, wherein chemists have replaced the use of hazardous
chloro-fluorocarbons (which cause ozone depletion, global warming) by CO2 as the blooming
agent.

4. Designing safer chemicals:- Design chemical products that are fully effective yet have little
or no toxicity. Products should be designed to preserve their efficacy of function while reducing
toxicity. Chemical products to be synthesized should be safe to use.
A well-known example of retro-metabolic design is that of ethylene glycol, which is used as an
antifreeze and has been replaced by propylene glycol which is less hazardous.

5. Use safer solvents and reaction conditions: Avoid using solvents, separation agents, or other
auxiliary chemicals. Solvents used are VOCs, they are able to form Ozone and smog through free
radical-air reactions and halogenated solvents are carcinogenic. One should avoid use of these solvents
or green alternatives like water, ionic liquids and liquid CO2 must be used.

6. Design for energy efficiency: Run chemical reactions at room temperature and pressure whenever
possible.
Most commonly used energy is thermal energy, which is not targeted direct at a bond or ongoing
reaction instead most of the thermal energy is wasted in heating up the reactors, solvents and
surrounding environment. This problem can be avoided by using alternative sources such as
photochemical, microwave and ultrasonic energy.
7. Use of renewable feed stocks (Raw-materials): Use starting materials (also known as
feedstocks) that are renewable rather than depletable. The source of renewable feedstocks is often
agricultural products or the wastes of other processes; the source of depletable feedstocks is often fossil
fuels (petroleum, natural gas, or coal) or mining operations.
Eg: Europe has successfully utilized rapeseed oil as raw material for the production of bio-diesel

8. Reduce derivatives: Avoid using blocking or protecting groups or any temporary modifications if
possible. Derivatives use additional reagents and generate waste.
Protecting groups in organic synthesis are important and used to protect a sensitive functionality from
reaction reagents/conditions., which make the reaction go away in an unwanted direction, if unprotected.
9. Use catalysts, not stoichiometric reagents: Minimize waste by using catalytic reactions. Catalysts are
effective in small amounts and can carry out a single reaction many times. They are preferable to
stoichiometric reagents, which are used in excess and carry out a reaction only once.
10. Design chemicals and products to degrade after use: Design chemical products to break down to
innocuous substances after use so that they do not accumulate in the environment. This principle demands
the synthesis of such products, which after performing their function properly must be able to convert into
non-toxic end-products.
e.g DDT is non- biodegradable and causes severe problem. Therefore a product to be designed such that
it degrades to innocuous products 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. One need to have accurate and
reliable sensors, monitors, and techniques to assess the hazards that are present in the process stream.
Using various techniques a process can be monitored for generation of hazardous byproducts and side
reactions.
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:
Microwave chemistry is based on the efficient heating of materials (in most cases solvents) by dielectric
heating effects. Dielectric heating works by two major mechanisms:

i) Dipolar polarization

For a substance to be able to generate heat when irradiated with microwaves it must be a dipole, since, the
microwave field is oscillating, the dipoles in the field align to the oscillating field. This alignment causes
rotation, which results in friction and ultimately in heat energy.

ii) Ionic Conduction:

During ionic conduction, dissolved (completely) charged particles (usually ions) oscillate back and
forth under the influence of microwave irradiation. This oscillation causes collisions of the charged
particles with neighboring molecules or atoms, which are ultimately responsible for creating heat
energy

Microwave dielectric heating uses the ability of some liquids and solids to transform
electromagnetic radiation into heat to drive chemical reactions.
General applications of Microwave Chemistry are,
1. Microwave assisted synthesis using Water.
2. Microwave assisted synthesis using Organic Solvents.
3. Solvent free Reactions.

Hydrolysis of Benzyl Chloride:

Hydrolysis of Benzyl Chloride with water in Microwave oven gives 97% yield of Benzyl alcohol in 3 min.
Whereas conventional method takes about 35 min.
 Cl OH

mw
+ H2O
[Link]
(chloromethyl)benzene phenylmethanol

Oxidation
Oxidation of toluene by conventional method takes 10 – 12 hr. but by Microwave irradiation the
reaction completed in 7 min. with 40% yield.

CH3
COOH
[O]

[Link] 4 + [Link]
methylbenzene mw. 5min
benzoic acid

Biocatalyst for green chemistry

Bio-Catalyst is an enzyme which alters the rate of chemical or bio-chemical reaction.

Bio-Catalyzed reaction:
Enzymes are biocatalyst. These biocatalysts (enzymes) are used in the industrial preparation of
ethanol.
Ethanol is prepared by the fermentation of molasses -a dark brown coloured syrup left after
crystallization of sugar which still contains about 60% of sugar.
The process of fermentation actually involves breaking down of large molecules into simple ones
in the presence of enzymes. The source of these enzymes is yeast.
The various reaction taking place during fermentation of carbohydrates are

INVERTASE
C12H22O11 C6H12O6 + C6H12O6
Sucrose glucose fructose

ZYMASE
C6H12O6 2 C2H5OH + 2 CO2

Solvent free reactions

Dry media reaction or solid state reaction or solvent less reaction is a chemical reaction system in
the absence of a solvent. Solid state reaction follows fifth principle of green chemistry which avoid
using toxic solvents in the chemical reaction.

Condition for solvent free reactions

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;

i) Synthesis of adipic acid

ii) Synthesis of Paracetamol from p-amino phenol
Green Synthesis of Paracetamol using Phenol
Green method is direct acetylation of phenol with acetic anhydride and HF catalyst.

This is considered as greener method because:

1. Chemicals used are less harsh in nature
2. Percentage atom economy is good
 3. Simple steps are involved.
4. Cost effective.

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.

Green fuel:
Hydrogen is the future green fuel and does not cause environmental pollution.

Production of hydrogen by splitting of water

a) Photocatalytic reaction

Input: Photocatalyst particles, sunlight and water

Output: Oxygen and hydrogen

Photocatalyst in the form of particles is immersed in water based electrolyte and it produces
charge carriers holes and electrons after absorbing sunlight. Charges are moved to surface of the
photocatalyst to start the chemical reaction. Holes are oxidizing the water and electrons reduces
hydrogen ions to Hydrogen gas.

a) Photo electro catalytic water splitting:

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. The
charges oxidises and reduces the water to produce oxygen at anode and hydrogen at cathode.

Input: Semiconductor photocatalyst (anode), Sunlight and water

Output: Hydrogen and Oxygen

At Photoanode 2H2O + 4h O2 + 4H+

Cathode 4H+ + 4e- 2H2

Photo electro catalytic water splitting is more useful because it permits separation of gases and
prevents reverse reaction.

Fuel Cell:

Fuel cells are galvanic cells which converts chemical energy of the fuels into electrical energy through
catalyzed redox reaction with elimination of minimum harmful byproducts.

Representation of fuel cell is Fuel/Electrode, Electrolyte, Electrode / Oxidant

Methanol Oxygen Fuel cell

It consists of two porous carbon electrodes. Anode is coated with platinum catalyst and cathode
with silver catalyst. The electrolyte is an aqueous solution of H2SO4. The Methane gas is
continuously supplied at the anode and oxygen is supplied at the cathode. Methanol diffuses
through the anode is adsorbed on the electrode surface. At the cathode Oxygen diffusing through
the electrode is adsorbed and gets reduced. A membrane is placed adjacent to cathode to prevent
the diffusion of methanol to cathode.
 Working
Anode CH3OH + H2O  CO2 + 6H+ + 6e
Cathode 3/2O2 + 6H+ + 6e  3H2O
Overall CH3OH + 3/2O2  CO2 + 2H2O

Advantages
 Methanol has low carbon content
 The fuel is easily oxidizes
 Methanol is highly soluble in water.

Applications

1. Used in trains, ships and vehicles as a source of electrical energy.

2. Supplying electrical power for residential or industrial utility.

3. Used in military applications.

Solar Energy:

Photovoltaic cells
Photovoltaic cells or Solar cells are the semiconductor devices which converts sunlight into direct current
electricity.

Construction and working of photovoltaic cells

The Solar cells or Photovoltaic cells are made out of semiconductors which have the capacity to absorb
light. When n-type and p-type semiconductor are bought together a semiconductor diode is formed. The
semiconductor diode separates and collects the carriers and conducts the generated electrical current
preferentially in a specific direction.
e

e
Sunlight Sunlight

Metal grid
Anti reflective layer e

n-type layer

Electron hole
pair +e h

+e Electron hole Application

p-type layer
pair
Metal contact
Photovoltaic cell

A typical silicon photovoltaic cell is composed of a thin poly crystalline silicon wafer consisting of
an ultra-thin layer of phosphorus doped. (n-type) silicon on top of boron doped (p-type) silicon.
Hence a p-n junction is formed. A metallic grid forms one of the electrical current contacts of the
diode and allows light to fall on the semiconductor between the grid lines as shown in Fig. An
antireflective layer between the grid lines increases the amount of light transmitted to the
semiconductor. The cell’s other electrical contacts is formed by a metallic layer on the back of the
solar cell.
PV cell works on the principle of photoelectric effect E=hγ, When light radiation falls on the p-n
junction diode, electron – hole pairs are generated by the absorption of the radiation. The
electrons are drifted to and collected at the n-type end and the holes are drifted to p-type end.
When these two ends are electrically connected through a conductor, there is a flow of current
between the two ends through the external circuit. Thus photoelectric current is produced.

Applications:
PV can meet the need for electricity for parking meters, temporary traffic signs, emergency phones,
radio transmitters, water irrigation pumps, stream-flow gauges, remote guard posts, lighting for
roadways, and more.