UGSemsterSyllabus Chemistry 5Sem6AChemistry English

BS514CHEDSE(A)-E
B.Sc.
THIRD YEAR SEMESTER – 5
CHEMISTRY
Green Chemistry, Organic Chemistry,
Environmental Chemistry- DSE (A)
“We may forgo material benefits of civilization, but we cannot forgo

our right and opportunity to reap the benefitsof the highest education
to the fullest extent as the education is the greatest material benefit”
-Dr. B. R. Ambedkar
Dr. B. R. AMBEDKAR OPEN UNIVERSITY

HYDERABAD
2020
C O U R S E T EAM
Course Development Team Course Development Team
(CBCS)
Editor Editor
Prof. K. Rajmohan. Dr. J. Mohan Babu
Prof. G. Ramachandraiah.
Associate Editor
Writers Dr. K. Prameela
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Prof. G. Ramachandraiah. Writers
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Dr. K. Prameela
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Cover Design
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First Edition : 2020
© 2020, Dr. B. R. Ambedkar Open University, Hyderabad, T.S.
All rights reserved. No part of this book may be reproduced in any form without the
permission in writing from the University.
The text forms part of Dr. B. R. Ambedkar Open University Programme.
Further information on Dr. B. R. Ambedkar Open University courses may be obtained

from the Director (Academic), Dr. B. R. Ambedkar Open University, Road No. 46,
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Printed on behalf of Dr. B. R. Ambedkar Open University, Hyderabad by the Registrar.
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PREFACE
This course deals with topics included in B.Sc 3 year chemistry, fifth semester
discipline specific elective course -A by the department of chemistry, Dr. B. R. Ambedkar
Open University - Hyderbad.
The course material is covered in four blocks, each block comprising of three
units. Each unit contains statement of objectives, brief introduction, subject matter, summary,
check your progress - answers, model examination questions, and refferences for futher
reading.
The first block, Green chemistry, in this we explained need, goals, limitations, and
principles of green chemistry. Included green synthesis of some importent reactions by
microwave and ultrasound methods. Described applications of Green chemistry.
The second block is Organic Chemistry, it deals with the classification of pericyclic
rections, its features and stereochemistry. Explained molecular orbitals of C-C single
bond, double bond, 1,3-butadiene and allylic radical, cation and anion. Also included
principles, terminology in Assymetric synthesis and discussed about the classification of
stereoselectivity.
The third and forth blocks are Environmental chemistry-1&2, included atmosphere
and its components, environmental pollution, airpollution, green house effect, acid rains,
water polution, soil and sound pollution. Also discussed chemical toxicology of various
organic and inorganic substances and described the state of the global environment and
related issues. .
Keeping in view the diversity of learners in the Open University with regards to
their age, learning abilities and the minimum academic pre-requirements, the course material
is prepared in Self Instruction Mode with all the inputs to help the learner to learn by
himself/herself.
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CONTENTS
BLOCK-1: GREEN CHEMISTRY 1
Unit - 1 : Introduction to Green Chemistry 3
Unit - 2 : Principles of Green Chemistry. 7
Unit - 3 : Green synthesis - Some Reactions. 22
BLOCK-2 : ORGANIC CHEMISTRY 31
Unit - 4 : Introduction to Pericyclic Reactions 33
Unit - 5 : Introduction to Assymetric Synthesis 54
Unit - 6 : Structural Elucidation of Organic Compounds
by Chemical Methods 70
BLOCK-3: ENVIRONMENTAL CHEMISTRY-1 83
Unit – 7: Atmosphere and its components 85
Unit – 8: Air Pollution 97
Unit – 9: Water Pollution 116
BLOCK-4 : ENVIRONMENTAL CHEMISTRY-2 127
Unit – 10: Soil and Sound Pollution. 129
Unit – 11: Chemical toxicology 138
Unit – 12: The state of global environment 149
Model question papers 159
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BLOCK-1
GREEN CHEMISTRY
This block deals with Green chemistry. Explained need, goals of green chem-
istry, described principles of green chemistry and given some importent synthesis of
organic compounds by Microwave assisted and Ultrasound assisted. Discussed
applications of green chemistry.
Block-1 includes the following three units.

Unit - 1 : Introduction to Green Chemistry
Unit - 2 : Principles of Green Chemistry.
Unit - 3 : Green synthesis - Some Reactions.
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UNIT – 1: INTRODUCTION TO GREEN CHEMISTRY
Contents:
1.0. Objectives
1.1 Introduction
1.2 What is Green Chemistry
1.3 Need for Green Chemistry
1.4 Goals of Green Chemistry
1.5 Limitations/Obstacles in the persuit of the goals of Green Chemistry
1.6 Summary
1.7 Check your progress- Answers
1.8 Model Examination Questions
1.9 Further Reading
1.0. OBJECTIVES
After a study of this unit you should be able to
• Account for the definition of Green Chemistry
• Explain the need for Green Chemistry
• Appreciate the goals of Green Chemistry
• Account the obstacles in the persuit of the goals of Green Chemistry.
1.1. INTRODUCTION
Green Chemistry is the branch of chemistry which deals with the study of design of
products and processes that reduce or eliminate the use and generation of hazardous substances.
Green Chemistry deals with chemical synthesis which are benign. It involves reducing cost,
energy, impact on environment, toxicity, materilas including plants, waste, risks and hazards.
1.2. WHAT IS GREEN CHEMISTRY
Green Chemistry is the design of chemical products and processes that reduce or elimi-
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nate the use or generation of hazardous substances. Green Chemistry applies across the life
cycle of a chemical product, including its design, manufacture use, and ultimate disposal. Green
Chemistry is also known as sustainable chemistry.
1.3. NEED FOR GREEN CHEMISTRY
Chemistry has improved our quality of life and made thousands of products possible. The
20 century has been highly successful in this regard. However with the advent of the 21st century
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the public is equally aware of the hazardous substances used and generated by the chemical pro-
cesses. Our environment which is encloved by nature, needs to be protected from ever increasing
chemical pollution associated with contemporary life styles and emerging technologies.
1.4. GOALS OF GREEN CHEMISTRY
• Prevents pollution at the molecular level.
• Is a philosophy that applies to all areas of chemistry, not a single discipline of chemistry.
• Applies innovative scientific solutions to real-world environmental problems.
• Results in source reduction because it prevents the generation of pollution.
• Reduces the negative impacts of chemical products and processes on human health
and the environment.
• Lessens and sometimes eliminates hazards from existing products and processes.
• Designs chemical products and processes to reduce their intrinsic hazards.
1.5. LIMITATIONS/OBSTACLES IN THE PURSUIT OF THE

GOALS OF GREEN CHEMISTRY
Most stakeholders of chemical institutions including industry, academic, research and
development organisations, government associated regulatory bodies, teachers, students and
investors etc are aware of sound knowledge about green Chemistry and all should agree that
green chemistry is a powerful tool that can lead us to a sustainable future with eco friendly
procedures and operations.
Limitations:
1. Availability of green technologies:
We still do not have viable green chemistry based solution for many chemistries/processes
like nitration, sulphonation Friedal-Craft alkylation or acylation etc. In the absence of such
solutions, the industry does these chemistries with conventional ways, using huge quantities of
acids, alkalies and other hazardous regents.
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2. Scale-up and Commercialisation:
These are many inventions that have already been developed by various academic and
research institutes and these are potential solutions for some of the environmental challenges
faced by the industry.
3. Connecting Green Chemistry solution provides to industry:
These are many green Chemistry solutions that are ready and are proven. One of the
key limitation is the communication gap between the industry and such solution providers. This
could also be due to industry not putting enough effort to search and look around for solutions.
4. Understanding of basic principles:
One of the limitation in implimentation of green chemistry is that our team of chemists
and chemical engineers working on designing new products and processes have limited knowledge
about the basic principles of green chemistry & engineering.
5. Green Chemistry is costly, complex and not viable for SME’s:
Myths like green chemistry is good theory but practically not feasible, green Chemistry
is difficult & complex, it is not viable for small & medium size organisations, it requires huge
resources etc.
6. Regulatory hurdles:
This is a big obstacle for pharmaceutical and other industries where any change in
process(when a green chemistry process is replacing a conventional process) has to go through
validation trails, change in documentations and filings as well as series of approvals from internal
regulatory affairs team, customers. Finally from external regulatory affairs like FDA.
Check your progress
Note: a) Space provided below for writing your answer.
b) Compare your answer with one given at end of the unit.
1.Define the term Green Chemistry.
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2. What is the important need of Green Chemistry?
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1.6. SUMMARY
This unit deal with

• Definition of Green Chemistry
• Need of Green Chemistry to reduce the environmental pollution.
• Goals of Green Chemistry
• Limitations in the persuit of the goals of Green Chemistry.
1.7. CHECK YOUR PROGRESS - ANSWERS
1. Green Chemistry is the design of chemical products and processes that reduce or
eliminate hazardous substances.
2.The need of Green Chemistry is to reduce environmental pollution.
1.8. MODEL EXAMINATION QUESTIONS
I. Answer each of the following in 10 lines
1. Define Green Chemistry.
2. What is the need of Green Chemistry?
1. What are the important goals of Green Chemistry?
2. Explain about obstacles in the persuit of the goals of Green Chemistry.
1.9. FURTHER READING

1. New trends in Green Chemistry by V.K.Ahluwalia and M.Kidwai.
2. Green Chemistry by Rashmi Singi and M.M.Shrivaslava.
3. Green organic synthesis by V.K. Ahluwalia.
4. P.T.Anastas and J.C Warnes Green Chemistry Theory and Practice.
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UNIT - 2: PRINCIPLES OF GREEN CHEMISTRY
Contents:
2.0. Objectives
2.1. Introduction
2.2. Twelve principles of Green Chemistry
2.3. Designing a Green Synthesis. Prevention of waste or by-products.
2.4. Prevention or minimization of Hazardous or toxic products.
2.5. Green Solvents
2.6. Sources of energy for green reactions
2.7. Selection of starting materials
2.8. Use of catalysis
2.9. Chemical accidents and Prevention
2.9.1 Development of Analytical techniques
2.10. Summary
2.11. Check your progress-Answers
2.12. Model Examination Questions
2.13. Further Reading
2.0. OBJECTIVES
After complete reading and understanding of this unit you must be able to
• Explain the twelve principles of Green Chemistry

• Know the atom economy and calculation of atom economy.
• Account prevention of pollution or waste.
• Present preventions of chemical accidents and principle of ISD.
• Describe about green solvents, catalytic reagents and selection of starting materials.
• Account development of analytical techniques to prevent hazardous substances in
chemical processes.
2.1. INTRODUCTION
Green chemistry also called ‘sustainable chemistry’ is a chemical philosophy encouraging

the design of products and processes that reduce or eliminate the use and generation of hazardous
substances.
It deals with
• Twelve principles of green chemistry.
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• The principles cover such concepts as the design of processes to maximize
the amount of raw material that ends up in the product.
• The use of safe, environment benign substances including solvents,

whenever possible.
• The best form of waste disposal etc.
• Atom economy, calculation of atom economy of various reactions.
• Green solvents, alternative energy sources, starting materials.
2.2. PRINCIPLES OF GREEN CHEMISTRY
Following are the twelve principles of Green chemistry developed by Paul. T Anastas
and John. C.Warner.
1) Prevention of waste or by products.
2) Maximum incorporation of the reactions (starting materials and reagents) into the
final product.
3) Prevention or minimization of hazardous products.
4) Designing of safer chemicals.
5) Energy requirements for any synthesis should be minimum.
6) Selecting the most appropriate solvent.
7) Selecting the appropriate starting materials.
8) Use of catalysts should be preffered whenever possible.
9) Products obtained should be biodegradable.
10) Use of protecting groups should be avoided whenever possible.
11) The manufacturing plants should be so designed as to eliminate the possibility of

accidents during operations.
12) Strengthening of analytical techniques to control hazardous compounds.
2.3. DESIGNING A GREEN SYNTHESIS AND PREVENTION

OF WASTE OR BY-PRODUCTS:
It is most advantageous to carry out a synthesis in such a way so that formation of
waste (by-product) is minimum or absent. It is especially important because in most of the
cases the cost involved in the treatment and disposal of waste adds to the unreacted starting
materials (which may or may not be hazardous) form part of the waste. The formation of the
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waste (or by products) should be avoided as far as possible. The waste if discharged in the
atmosphere, sea or land not only causes pollution but also requires expenditure for cleaning up.
Maximum Incorporation of the Reactants (Starting materials and Reagents) into the
Final Product:
Chemists globally consider that if the yield of a reaction is about 90%, the reaction is
good. The percentage yield is calculated by
Actual yield of the product

% Yield= ×100
Theoretical yield of the product
The reaction or the synthesis is considered to be screen if there is maximum incorporation of

the starting materials and reagents in the final product. We should take into account the
percentage atom utilization, which is determined by the equation.
Molecular weight of desired products

% atom utilisation= ×100
Molecular weight of desired products+ waste(by)products
The concept of atom economy developed by B.M.Trost is a consideration of ‘how much of the
reactants end up in the final product’.
The same concept determined by R.A.Sheldon is given as
Formula weight of atoms utilized

% atom economy = ×100
Formula weight of reactants used in the reaction
Calculation of atom economy of the rearrangement, addition, substraction and

elimination reactions:
Rearrangement Reactions: (Claisen rearrangement)
These reactions involve rearrangement of the atoms that makeup a molecule. For example,
allyl phenyl ether on heating at 2000C gives o-allyl phenol.
O OH
0
200 C
(allyloxy)benzene 2-(prop-1-en-1-yl)phenol
or
o-allyl phenol
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This is a 100% atom economical reaction, since all the reactions are incorporated into the
product.
Addition Reactions:
Consider the addition of hydrogen to an olefin.
Ni H2
H3C C CH2 + H 2 H3C C CH 3
H
propene propane
Here also all elements of the reactants (propene and hydrogen) are incorporated in the
final product (propane). The reaction is a 100% atom economical reaction.
Similarly, cycloaddition reactions and bromination of olefins are 100% atom economical
reactions.
CH2
HC CH2 MW
+
HC CH2
CH2
H H2
H3C C CH2 + Br2 H 3C C C Br
H
propene
Br
1,2-dibromopropane
Substitution Reactions:
In substitution reactions, one atom or group of atoms, is replaced by another atom (or)
group of atoms. The atom or group that is replaced is not utilised in the final product. So the
substitution reaction is less atom-economical than rearrangement or addition reactions. Consider
the substitution reaction of ethyl propionate with methyl amine.
O O
H2 H2 H
H3C C C OC2H 5 H3C C C N CH3
Ethyl propionate N -methylpropionamide
+ +
H3C NH2 H2
H3C C OH
methanamine
ethanol
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In this reaction, the leaving group (OC2H5) is not utilised in the formed amide. Also,
one hydrogen atom of the amine is not utilised. The remaining atoms of the reactants are
incorporated into the final product.
The total atomic weights of the atoms in reactions that are utilised is 87.106g/mole,
while the total molecular weight including the reagent used is 133.189 g/mole. Thus, a molecular
weight of 46.069 g/mole remains unutilised in the reaction.
87.106
Therefore, the % of atom economy =  100  65.40%
133.189
Elimination Reactions:
In an elimination reaction, two atoms or group of atoms are lost from the reactant to
form a -bond. Consider the following Hofmann elimination.
H3C C CH2
H
CH3 +
H2 H2 OH H3C
H3C C C N CH3
N CH3

CH3
H3C +
H2O
The elimination reaction is not very atom economical. The percentage atom economy
is 35.30%. This is the least atom economical of all the above reactions.
2.4. PRESERVATION OR MINIMIZATION OF HAZARDOUS

OR TOXIC PRODUCTS
The most important principle of green chemistry is to prevent or atleast minimize the
formation of hazardous products, which may be toxic or environmentally harmful.
Risk associated with a toxic chemical is a function of hazard and exposure.
Risk = f (Hazard, exposure)
The “end of the pipe” laws attempt to control risk by dealing with the prevention of the
exposure to toxic hazardous chemicals.
2.5. GREEN SOLVENTS
The solvent selected for a particular reaction should not cause any environmental pollution
and health hazard. The use of liquid or super critical liquid CO2 should be explored. If possible,
the reaction should be carried out in aqueous phase or without the use of a solvent (solvent less
reactions). A better method is to carryout reactions in the solid phase.
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One major problem with many solvents is their volatility that may damage human health
and the environment. To avoid this, a lot of work has been carried out on the use of immobilized
solvents. The immobilised solvent maintains the solvency (solvation) of the material, but it is
non-volatile and does not expose humans or the environment to the hazards of the substances.
Ionic liquids: The ionic liquids, comprising entirely of ions. Ionic liquids are of two types
simple salts made up of a single anion and cation and binary ionic liquids are salts where an
equilibrium is involved.
Example of simple ionic salts
-
Et 3NH NO3 BF 4
+
N
C6H13
CH3
N AlCl4
N
H3C C
H2
Binary ionic liquid  Mixture of Al(III) chloride and 1,3-dialkyl immidazolium chloride.
The reactions in ionic liquids are easy to perform and no need of special apparatus or
methodologies. Also, the ionic liquids can be recycled and this leads to reduction of the costs of
the processes.
Fluorous biphatic solvent:
Ex:- Chloro benzene and perfluorooctane
It is used in oxidation of alcohols into aldehydes and ketones by TEMPO (2,2,6,6-

Tetramethylpiperidinyloxy).
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PEG:-Polyethylene glycol (PEG) is a polyether compound with many applications from industrial
manufacturing to medicine. PEG is also known as polyethylene oxide (POE). structure of PEG
is H-(O-CH2-CH2)n-OH. It is used as a green solvent for carbon-carbon bond formation
reactions. It is an inexpensive solvent.
Solvent-less processes: In a dry media reaction or solid state reaction system in the absence
of a solvent. Dry media reactions in chemistry is environmentally friendly because solvent is
not required.
Immobilized Solvents: The immobilized solvent maintains the solvency of the material but it
is non-volatile and does not expose humans or the environment to the hazards of the substances.
2.6. E N E R G Y R E Q U I R E M E N T S F O R G R E E N R E A C T I O N S:
Alternative Sources of energy:
Use of microwaves and ultrasonic energy
In any c-fect of ultrasound waves on chemical reactivity.
In any chemical synthesis, the energy requirements should be kept to a minimum. Use
of a catalyst has the great advantages of lowering the energy requirement of a reaction. If the
final product is impure it has to be purified by distillation, recrystallization or ultra filtration. All
these steps involve the use of energy. By designing the process such that there is no need for
separation or purification the final energy requirements can be kept at the minimum. Energy to
reaction can be supplied by photochemical, microwave or sonication methods.
Use of microwave energy:-
Microwave may be considered as a more efficient source of heating than conventional steam
(or oil heated vessels), since the energy is directly imparted to the reaction medium rather than
through the walls of a reaction vessel. Infact, the rapid heating capability of the microwave
leads to considerable saving in the reaction time.
Use of Ultrasonic energy:-
The ultrasound frequencies used for chemical reactions are much lower than used for medical
applications, but the power used is higher. The ultrasound is generated with the help of an
instrument having an ultrasonic transducer, a device by which electrical or mechanical energy
can be converted into sound energy. The term sonochemistry is used to describe the effect of
ultrasound waves on chemical reactivity.
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2.7. SELECTION OF STARTING MATERIALS
As far as possible, the starting materials selected should be obtainable from renewable
sources. The starting materials should not cause any harm to the person handling these.
The starting materials which can be obtained from agricultural or biological products
are referred to as renewable starting materials. Substances like carbon dioxide (generated
from natural sources or synthetic routes) and methane gas (obtained from natural sources such
as marsh gas) are available in abundance. These are considered as renewable starting materials.
Use of protecting group should be avoided as far as possible, since these generate wastes.
In case an organic molecule contains two reactive groups and you want to use only one
of these groups, the other group has to be protected, the desired reaction completed and the
protecting group removed.
For example
HO CHO Ph O CHO
H2
Ph C Cl
[O]
Ph O CHO
HO COOH
HCl
+
H2
Ph C Cl
In the above reaction/protection benzyl chloride (a known hazard) and the waste
generated after deprotection should be handled carefully.
2.8. USE OF CATALYST
We know that catalysts facilitate transformation and the conversions can be affected in short
duration of time and consume less energy. Such reactions should be preferred with advances in
the selectively of catalysts, certain reactions in green synthesis have become very convenient.
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Better yields hydrogenation or reduction of olefins in presence of nickel catalyst.
Ni H2
H3C C CH2 + H 2 H3C C CH 3
H
propene propane
Comparison of heterogeneous and homogenous catalysis.
Homogenous catalysis Heterogeneous catalysis
1. Liquid phase. Liquid / gas / Solid phase.

2. Low temperature. High temperature.
3. High selectivity. Low selectivity.
4. Easy heat transfer. Heat transfer can be an issue.
5. Difficult to catalyst separation. Easy catalyst transfer.
6. Expensive recycling. Simple recycling.
7. Well defined active site. Poorly defined active site.
8. Easy catalyst modification. Difficult catalyst modification.
9. Reaction mechanism well understood. Poorly understood.
Biocatalysis:- The reactions which are obtained by the influence of bacteria, fungi and
other microorganisms called bio-catalytic reactions. The substances which obtained from
the microorganisms are called biocatalysts. Various organic reactions such as oxidations,
reductions, hydrolysis etc are influenced by the microorganisms in nature.
The biocatalytic conversions have many advantages in relevance to green chemistry. Some of
these are given below
• Most of the reactions are performed in aqueous medium.

• The biocatalytic conversions involve only one step.
• Protection and deprotection of functional groups is not necessary.
• The reactions are fast reactions.
Ex: biochemical oxidation
Bacterium
H2
H3 C C OH + O2 H3 C COOH + H2O
acetic
Invertase
C12H22O 11 + H2 O 2 C6H12O6
Yeast Glucose & Fructose
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Zymase
C6H12O6 2C2H5OH + 2CO2
Asymmetric catalysis:-
Asymmetric catalysis is a type of catalysis in which a chiral compound such that formation
of one particular stereoisomer is favoured.
Ex:
Ex:
O OH
Baker's
COOEt COOEt
Yeast
Photo catalysis:-
A large number of conversions/synthesis have been carried out photolytically.
Titanium oxide (TiO2)-based photo catalytic systems are important for the purification of polluted
water, the decomposition of offensive atmospheric odours as well as toxic, the fixation of CO2
and the decomposition of chlorofluoro carbons on a huge global scale.
2.9. CHEMICAL ACCIDENTS AND PREVENSIONS

Greener alternative to Bhopal gas tragedy (safer route to carbaryl).
Bhopal gas Tragedy:-
In 1984 in the city of Bhopal, central India, a poisonous vapour burst from the tall tanks
of the union carbide pesticide plant. This vapour was highly toxic cloud of methyl isocyanate.
Among the 500,000. People exposed to the gas 20,000 have died till date and 1,20,000 continue
to suffer.
The UCIL factory was built to produce the pesticide sevin (carbaryl) using methyl
isocyanate.
Methylamine reacts with phosgene producing methyl isocyanate, which reacts with 1-
naphthol to yield carbaryl.
Safer route to carbaryl:- 1 - naphthol on carbonyl group addition followed by reaction

with methyl amine would gives carbaryl.
This process does not require handling phosgene and storage of MIC. Inherently safe
process. Prevention of chemical accidents designing greener processes.
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Inherent-safer design (ISD):
Inherent safer design is a philosophy for addressing safety issues in the design and
operation of facilities that use or process hazardous chemicals.
Principle of ISD:
Inherently safer design (ISD) is a holistic approach to safer chemical manufacture.

ISD provides more robust and reliable risk management and has the potential to make the
chemical processing technology simpler and more economical by eliminating the need for
expensive safely systems and procedures.
ISD also addresses the immediate impart of single events (chemical accidents) on
people, the environment, property and business.
Carbaryl (sevin) synthesis without using of toxic reagents.
OH O CH3
O NH
H 3C CH 3
NH NH
1,3-dimethylurea
naphthalen-1-ol naphthalen-1-yl methylcarbamate
Flixiborough accident:
Flixiborough accident was an explosion occured in chemical plant located at the village
of Flixiborough in England.
In the plant reactors, compressed air was passed through hot cyclohexane, causing a
small percentage (6%) of the cyclohexane to oxidise and produced cyclohexanone, some
cyclohexanol also being produced. It is manufactured in 6 reactors loop.
In 1974, there was a massive release of hot cyclohexane in the area of the missing
reactor 5, followed shortly by ignition of the resulting cloud of flammable vapour and massive
explosion in the plant.
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Safer route to cyclohexanol:
OH
Br
Br
Subdivision of ISD:
Chemical process safety strategies can be grouped into five categories.
1) Minimization:
Use small quantities of hazardous materials or reduce the size of equipment operating
under hazardous condition (eg. High temperature, pressure).
2) Simplification:
Eliminate unnecessary, complexity and design user friendly plants.
3) Substitution:
Use less hazardous materials and chemical processes.
Water based latex paints eliminate fire, toxicity and environmental hazards associated
with solvent based paints.
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4) Moderation:
Reduce hazards by dilution, refrigeration or process alternatives that operate at less

hazardous conditions.
Combustible solid was handled as a pellet instead of fine powder, reducing the dust
explosion.
5) Limitation:
Limit effects by design, location or transportation of equipment so that the worst possible
condition less danger.
Eg:- Gravity will take a level to a safe place, the use of bunds (storage place of polluting
substances).
2.10. DEVELOPMENT OF ANALYTICAL TECHNIQUES
Strengthening/development of analytical techniques to prevent and minimize the

generation of hazardous substances in chemical processes.
Analytical techniques should be so designed that they require minimum usage of
chemicals, like recycling of some unreacted reagent (chemical) for the completion of a particular
reaction. Further, placement of accurate sensors to monitor the generation of hazardous by
products during chemical reaction is also advantageous.
Check your progress
1) What is atom economy?
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2) What are green solvents?
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3) What is Inherent safer design?
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2.10. SUMMARY
This unit deals with
• Twelve principles of Green chemistry with their explanations.
• Prevention of waste/by-products, atom economy, calculation of atom economy.
• Minimization of toxic products, use of green solvents, alternative sources of energy,
selection of starting materials, prevention of chemical accidents-ISD principle and
development of analytical techniques to prevent generation of hazardous substances.
1) Atom economy is a consideration of how much of the reactants end up in the final
product. Percentage of atom economy can be calculated from the formula
Formula weight of atoms utilized

% atom economy = ×100
Formula weight of reactants used in the reaction
2) The solvents selected for particular reaction should not cause any environmental
pollution and health hazard are called Green solvents.
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3) Inherent safer design (ISD)
Inherent safer design is a philosophy for addressing safety issues in the design and
operation of facilities that use or process hazardous chemicals.
1. write the basic principles of green chemistry.
2. Give a brief account of atom economy.
3. Under atom economic reactions, briefly explain rearrangement reactions.
4. Write an explanatory note on addition reactions atom economy.
1. Briefly explain the following giving examples.
(i) Aqueous phase reactions
(ii) Reactions in ionic liquids
2. What do you mean by solvent free reactions?
3. Explain about use of microwaves and ultrasonic energy.
3. Explain the following
(i) Biocatalysis
(ii) Asymmetric catalysis
(iii) photo catalysis
4. Write a note on Green solvents.
5. What is the principle of inherent safer design (ISD).
6. Write a note on Bhopal gas Tragedy and Flixiborough accidents.

1. Green chemistry theory and practice P.T.Anastas and J.C Warner.
2. New Trends in Green chemistry by V.K.Ahluwalia and M.Kidwai.
3. Green chemistry by Rashmi Singi & M.M.Shrivastava.
4. Green organic synthesis by V.K.Ahluwalia.
21
UNIT – 3 : GREEN SYNTHESIS-SOME REACTIONS
Contents
3.0. Objectives
3.1. Introduction
3.2. Green Synthesis of the Compounds
3.3. Microwave assisted reactions
3.4. Ultrasound assisted reactions
3.5. Applications of Green chemistry
3.6. Summary
3.7. Check your progress-Answers
3.0. OBJECTIVES
After a study of this unit, the student will able to
• Explain the Green synthesis of the compounds by microwave assisted and ultrasound
assisted reactions.
• Account the applications of Green chemistry like marine antifoulant, right-Fit-
pigments, polyl aceticacid and healthier fats and oils by Green chemistry.
3.1 INTRODUCTION
The objective of green chemistry is not only to design new green synthesis but also to
design green methods for the synthesis of already existing molecules whose known synthesis
are responsible for environmental pollution. It is most advantageous to carry out reactions in
aqueous media. Water is the cheapest available solvent. Also when water is used as a solvent,
the final product can be separated and there is least waste generation. Under applications of
green chemistry, environmentally safe marine antifoulant, Rightfil pigments and production of
trans-fats and oils are discussed.
Green synthesis of the following compounds.
Synthesis of Adipic acid:-
An environmental green synthesis of adipic acid has been developed by John W.Frost
and M.Draths starting with glucose and using a biocatalyst.
22
OH
COOH
OH
O E.Coli
OH
O OH
OH OH
OH
D-Glucose 3-dehydroshikimicacid
COOH
HO
HO
OH
OH
Catechol Protocatechuic acid (PCA)
H 2/Cat
COOH COOH
HOOC HOOC
cis, cis muconic acid Adipic acid
Synthesis of catechol:
OH
COOH
OH
O E.Coli
OH
O OH
OH OH
OH
D-Glucose 3-dehydroshikimicacid
COOH
HO
HO
OH
OH
Catechol
Protocatechuic acid (PCA)
23
Green synthesis of disodium iminodiacetate (DSIDA) (Alternative to strecker’s
synthesis)
Green synthesis of DSIDA was developed by Monsanto.
2NaOH NaOOC N COONa

HO OH H
N
H Cu-Catalyst DSIDA
diethanol amine +
4H2
3.3. MICROWAVE ASSISTED REACTIONS IN ORGANIC

SOLVENTS
I. Microwave assisted reactions in water:
(1)Hoffmann Elimination:-
Use of microwave is radiation has led to high-yielding synthesis of a thermally unstable
Hoffmann elimination product.
O
I O
NH2R3
Water/CHCl 3
M.W - 1 min
OEt
OEt
(2)Methyl benzoate to benzoic acid (Saponification):-
Saponification of methyl benzoate in aqsodium hydroxide under microwave conditions
gives 84% yield of the benzoic acid.
O OCH3 O OH
aq NaOH
M.W, 2.5 min
methyl benzoate benzoic acid

(3)Oxidation of Toluene:-
24
Oxidation of Toluene with KMnO4 under microwave conditions takes only 5min and
the yield is 40%.
O OH
CH3
[O]
aq KMnO4
aq KOH
MW, 5 min
toluene benzoic acid
(4) Oxidation of alcohols:-

A number of primary alcohols can be oxidized to the corresponding carboxylic acid using sodium
tungstate as catalyst in 30% aq.hydrogen peroxide.
O
30% H2O 2
R OH R OH
Na2WO4
Primary alcohol MW Carboxylic acid
II. Microwave assisted reactions in carbon solvents:

1. Diels-Alder Reaction:
The reaction involves 1,4 addition of an alkene (Maleic anhydride) to a conjugated
diene (anthracene) to form an adduct of six membered ring.
Under microwave conditions diglyme is used as a solvent and 80% yield of the adduct
is obtained in 90sec.
+ O
O
Adduct (80%)
anthracene O
O
Maleic anhydride (furan-2,5-dione)
25
2. Decarboxylation:- In the presence of microwaves decarboxylation takes place in much
shorter time.
MW
12 min
COOH
N N
H3CO H H3CO H
6-methoxy-1H -indole-2-carboxylic acid 6-methoxy-1H-indole
99%
3.4. ULTRASOUND ASSISTED REACTIONS

Simmons-Smith Reaction:-
In this reaction, sonochemically activated zinc and methylene iodide are used. The
generated carbene adds on to an olefin bond to give 91% of yield of cyclopropane derivative.
Zn, CH2I2
H3C (CH2) 7 (H2C)7 COOCH3 ))))), 50KHz H3C (CH2 )7 (H2 C) 7 COOCH3
3.5. APPLICATIONS OF GREEN CHEMISTRY

Designing of Environmentally safe marine antifoulant:
The antifouling agents are used on boat hulls to reduce the build up of marine organisms.
(such as algeve & plants)
A build up of these organisms causes additional costs involved in increased fuel

consumption and cleaning time.
Rohm and Haas has developed the use of 4,5-dichloro-2-n-octyl-4-isothiacolin-3-one

(DCOI) as an antifouling agent.
O
CH3
Cl (CH2)7
N
S
Cl
4,5-dichloro-2-octylisothiazol-3(2H )-one
26
An efficient green synthesis of a compostable and widely applicable plastic (polylactic
acid) made from corn
Polylactic acid (PLA) is one of the most versatile environment friendly biodegreadable
thermoplastic polyster. It is linear aliphatic thermoplastic polyester derived from 100% green
and renewable sources such as corn. PLA has wide range of properties such as bio-compatibility,
bio-degradability, less toxicity, vast-range of mechanical properties and the ability to be molded
into different shapes. These properties make it a very suitable material for applications similar
to plastics and more widely in biomedical fields.
PLA will be formed into containers and packaging for food and consumer goods. PLA is in
principle compostable, meaning that it will break down under certain conditions into harmless
natural compounds.
Right-fit pigment: Synthesis azopigments to replace toxic organic and inorganic pigments.
Engelhard has developed a wide range of environmentally friendly Right-fitted organic

pigments with the objective of replacing heavy metal pigments in some niche masleets at
significant cost savings compared to currently available high performance pigments.
Eliminate exposure to heavy metals such as cadmium, chromium(VI) and lead used in
the manufacture of cadmium and chrome yellow pigments. Aqueous manufacturing processes
are usefull.
Examples of synthesis Azopigments
Cl HO COO Cl HO
H 3C N N H 3C N N
+2
SO3 Ca SO3 Sr+2
Pigment red
Right f it scarlet
SO3
Healthier fats and oil by Green chemistry: Enzymatic interesterification for production
of no trans-fats and oils chemistry
Enzymatic interesterification is the catalytic reaction that occurs when an enzyme is introduced
into oil and rearranges the fatty acids on the glycerol backbone of a triglyceride. Triglycerides
are either liquids or solids at room temperature. The rearrangement of the fatty acids that
27
occurs with enzymatic interesterification provides structure and functionality to triglycerides at
room temperature. This process adjusts the melting properties, increasing functionality and
plasting in food production applications. Enzymatic interesterification produces no trans fatty
acids and lowers saturated fat content.
Fats and oils created by enzymatic interesterification provide several benefits to food
manufacturers. These oils provide better health profiles than either palm oil or partially
hydrogenated oil because they are trans fat and lower in saturated fat.
Check your progress

1) What is Green Synthesis?
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2) What is Microwave assisted reaction.
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3) What is Ultrasound assisted reactions.
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4) Write a note on applications of Green chemistry.
28
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3.6. SUMMARY
This unit deals with
· Green synthesis of the compounds like adipic acid, catechol etc.
· Microwave assisted reactions like Hoffmann elimination, methyl benzoate synthesis
and oxidation of toluene etc.
· Ultrasound assisted reactions like Simmons-Smith reaction.
· Applications of Green chemistry.
3.7. CHECK YOUR PROGRESS-ANSWERS

1) Green Synthesis:
Design and synthesis of molecules without environmental pollution is called green synthesis.
2) Microwave assisted reactions:
In these reactions, substances are subjected to microwave radiations. In these reactions time
taken is less and its a solvent free reaction.
3) Ultrasound assisted reactions:
In these reactions, ultrasound waves are used. It is also called as sonochemistry which
describes the effect of ultrasound waves on chemical reactivity.
4) Applications of Green chemistry
Synthesis of environmentally safe marine antifoulant, synthesis of Right-fit pigments and
production of no-trans-fats and oils are the important applications.

1) Write the Green synthesis of the following compounds.

(i) Adipic acid (ii) catechol (iii) disodium iminodiacetate
2) Explain Microwave assisted green synthesis of the following
a) Hofmann reaction
29
b) Benzoic acid synthesis
c) Oxidation of Toluene
d) Oxidation of alcohols
3) Write the microwave assisted reactions in organic solvents
a) Diels-Alder reactions
b) Decarboxylation reaction
II. Answer each of the following in 10 lines
1) Explain about sonochemical simmons-smith reaction.

2) Write a note on important applications of green chemistry.

1) New trends in Green chemistry by V.K.Ahluwalia andM.Kidwai.
2) Green chemistry by Rashmi Singi and M.M.Shrivastava.
3) Green organic synthesis by V.K.Ahluwalia.
30
BLOCK-2
ORGANIC CHEMISTRY
This block deals with introductory concepts of pericyclic reactions and assymetric
synthesis pertaining to organic chemistry. Classification, features and stereochemistry of
pericyclic reactions are explained. Terminology and classifed various stereo selectivity of
assymetric synthesis are included. In addition to pericycli reactions and assymetric syn-
thesis, we also discussed various chemical methods required for structure determination
of organic compounds under the heading of structure elucidation of organic compounds
by chemical methods.

Unit - 4 : Introduction to Pericyclic Reactions
Unit - 5 : Introduction to Assymetric Synthesis
Unit - 6 : Structural Elucidation of Organic Compounds by Chemical Methods
31
32
UNIT – 4: INTRODUCTION TO PERICYCLIC REACTIONS
Contents:
4.0. Objectives.
4.1. Introduction.
4.2. Definition of pericyclic reactions and features.
4.3. Classification of Pericyclic reactions.
4.4. Stereochemistry of Pericyclic reactions
4.5. Molecular Orbitals and Symmetry Properties.
4.6. Summary.
4.7. Check your progress – Answers.
4.8. Model examination questions.
4.9. Further reading.
4.0. OBJECTIVES
After completion of this unit you should be able to
 define pericyclic reactions,
 classify pericyclic reactions,
 explain the stereochemistry of pericyclic reactions,
 describe molecular orbitals and symmetry of some π - systems.
4.1. INTRODUCTION
In organic chemistry we have seen various reactions such as additions, eliminations
and substitution reactions in various compounds. All these reactions moving through ionic or
free radical intermediates. However, there are many reactions which do not follow ionic as
well as free radical mechanism such reactions are called pericyclic reactions.
4.2. DEFINITION OF PERICYCLIC REACTIONS AND FEATURES

What are pericyclic reactions?
Reactions which are concerted reactions, taking place through a cyclic transition state
i.e. cyclic rearrangement of electrons. it involves in the transforming of one molecule to another
new molecules without involving ionic or radical intermediates are called Pericyclic reactions.
Features of Pericyclic reactions:
These reactions are reversible, induced by heat or light and highly stereospecific (under
thermal and photo chemical conditions a substrate gives products of different stereochemistry).
These reactions do not involve a reactive intermediate like a carbocation, carbanion or
a free radical.
33
However a reactive intermediate may undergo pericyclic reaction. Pericyclic reactions
are largely unaffected by catalysts or solvent polarity.
Check your progress
1.What are the features of pericyclic reactions?
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4.3. CLASSIFICATION OF PERICYCLIC REACTIONS

Pericyclic reactions are classified into 3 types. They are
1. Electrocyclic reactions.
2. Cycloaddition reactions.
3. Sigmatropic rearrangement reactions (Sigmatropic shift).
4.3.1. Electrocyclic reactions.
An electrocyclic reaction may be defined as formation of a σ bond between the
termini of a conjugated π-system or the reverse process.
Ex:1
Δ / h‫ט‬
A 1, 3 diene (4πē) A cyclobutene (2πē and 2σē)

Electrocyclic reaction of a 4ē or 4nē system (n=1).
The forward reaction, in which 4πē participate, is called electrocyclic ring
closure of 4nπē system(where n=1).The reverse reaction in which 2πē and 2σē participate is
called electrocyclic ring opening of 4nē system(n=1).The observance of electrocyclic ring closure
and the electrocyclic ring opening depends on the thermodynamic stability of the corresponding
products.
Other examples of electrocyclic reactions are:
Ex:2 Δ / h‫ט‬
A hexa-1,3,5-triene, (6πē) A cyclohexa-1,3-diene

(4πē and 2σē)
Electrocyclic reaction of a 6ē or 4n+2 ē system(n=1).
34
An ion may also undergo electrocyclic reaction:
Ex :
Δ / h‫ט‬
+
+
An allyl carbocation (2πē) A cyclopropyl carbocation (2σē)
Electrocyclic reaction of a 2ē or 4n+2ē system (n=0).
4.3.2. Cycloaddition reactions .
A cycloaddition reaction may be defined as an addition reaction between two or

more π-systems to form a cyclic adduct, or the reverse process.
Δ / h‫ט‬
+
[2+2] cycloaddition
Two alkene molecules A cyclobutane derivative

(each with 2πē)
In the forward reaction, two σ bonds are formed at the expense of two π bonds. This
reaction is known as cycloaddition. In the reverse reaction in which two π bonds develop at the
expense of two σ bonds, is called cycloreversion reaction.
The cycloaddition reactions are generally classified as [m+n] cycloaddition reactions.
In a [m+n] cycloaddition, two components with m and n πē react to give a cyclic adduct. In the
above example, two components each with 2πē undergo addition. The reaction is called [2+2]
cycloaddition. Other examples of cycloaddition are:
Ex:1 A diene (4πē)
Δ / h‫ט‬
+
An alkene (2πē) [4+2] cycloaddition
A cyclohexene
EX:2
Δ / h‫ט‬
+
[2+2+2] cycloaddition.
Norbornadiene (two An alkene
isolated double bonds)
35
In norbornadiene, the two isolated double bonds function as two separate π- components,
each with two πē. Thus the reaction is considered as [2+2+2] cycloaddition.
4.3.3. Sigmatropic reactions.
These are also known as sigmatropic rearrangements. In these reactions an atom (H
or D) or a group migrates with its σ-bond, from the α-position of a double bond to a new position
in the π-system. The sigmatropic reactions are classified as [i,j] shifts or shifts of order
[i,j].Following is an example of [1,5] sigmatropic shift of a H:
While determining the order of a sigmatropic shift, the system is numbered by taking
the migrating σ-bond as the reference. The atoms in the system are numbered on either side of
the σ-bond. If in the product, the new sigma bond appears between i and j atoms, the reaction
is called [i, j] shift. In other words, in an [i, j] sigmatropic shift, the σ- bond migrates from 1, 1-
position to i, j position.
4.4. STEREOCHEMISTRY OF PERICYCLIC REACTIONS
4.4.1. Electrocyclic reactions:
CONROTATORY and DISROTATORY electrocyclic reactions.
Two distinct stereochemical modes of electrocyclic reactions are possible. They have
been designated by Woodward and Hoffmann as conrotatory and disrotatory electrocyclic
reactions. In the electrocyclic ring closure of butadiene to cyclobutane, a σ-bond is formed
between the two termini of diene system by the linear overlap of P orbitals present on the
terminal olefinic carbon atoms.
36
The linear overlap requires rotation of the P-orbitals, on the end carbons, about the C-C bond
axis. If the rotation of the two P-orbitals is in the same direction (both clockwise or both
anticlockwise), the cyclisation is called conrotatory or con electrocyclisation. On the other
hand the rotation of two P orbitals in opposite directions (one clockwise and the other
anticlockwise or vice versa) is called disrotatory or dis electrocyclisation.
Similarly, in the electrocyclic ring opening of Cyclobutane, the orbitals constituting the
σ-bond should be pulled apart to generate P orbitals at the terminal olefinic carbons in the
product. This process could, again, be conrotatory or disrotatory ring opening .The stereochemical
significance of these two modes of ring closure (or ring opening) becomes clear when substituted
reactants are considered.
37
In fact two dis electrocyclic ring opening processes are possible in the case of
cis-3, 4-dimethylcyclobutane.
Following are the products resulting by con and dis electrocyclic ring closure of trans, cis, trans-
2, 4, 6-octatriene.
Check your progress

2.What are the sterochemical modes shown by electrocyclic reactions?.
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4.4.2. Cycloaddition reactions: suprafacial and antarafacial additions.
Addition to a π system can take place in two ways. Addition may be on the same face
(side)of the π-system or on the opposite faces. These are known as suprafacial and antarafacial
additions respectively.
38
In cycloadditions two or more components participate. Therefore stereochemical mode
of cycloaddition has to be specified with respect to each component. Thus in the [π2+π2 ]
cycloaddition involving two molecules of cis-2-butene, four stereochemically different
cycloadditions viz. supra-supra, supra-antara, antara-supra and antara-antara cyclo additions
are possible. In supra-supra cycloadditions, the π-components approach one over the other in
parallel planes.
On the other hand, supra-antara or antara-supra and antara-antara cycloadditions

actually proceed through an orthogonal approach of the π-components:
39
Check your progress
3.Define cyclo addition reactions?.
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Even in these orientations, the overlap is poor due to steric reasons. Therefore, supra-antara
or antara-supra and antara-antara cycloadditions are rare with common π-components. However,
such additions are feasible when the π-component contains large number of conjugated double
bonds or when some structural features are present in the π-component that favour orthogonal
approach (as in [π2s+π2a] cycloaddition between an olefin and a ketene or a vinyl cation).
Supra-Supra cycloaddition: [π2s+π2s] cycloaddition
40
Supra-Antara cycloaddition: [π2s +
π2a] cycloaddition
Antara-Supra cycloaddition: [π2a+π2s] cycloaddition
Antara - Antara cycloaddition: [π2a+π2a] cycloaddition
It can be seen from the above examples that:

a) In a supra-supra cycloadditions , the stereochemistry of both the components is retained
in the product ,
b) In a supra-antara or antara-supra cycloaddition, the stereochemistry of supra component
is retained in the adduct, while that of the antara component changes at one centre in
the adduct, and
41
c) In an antara-antara cycloaddition, the stereochemistry of each component changes at
one centre in the adduct.
Following general scheme is helpful in writing the stereochemistry of the adduct formed
4 + 2
in [π s π s] cycloaddition (Diels-Alder reaction).
Example:

+
The diene (4πē component) and dienophile (2πē component) approach one over the
other, during supra-supra cycloaddition.
Sigmatropic reactions: suprafacial and antarafacial shifts.
In a sigmatropic reaction, an atom or group migrates with its σ-bond across the π-
electron system. This may take place by two different stereochemical pathways. When the
migrating σ-bond moves across the same face or side of the π-system, it is called a suprafacial
shift. On the other hand, in the antarafacial shifts the migrating σ-bond moves to the opposite
face of the π-system. In general terms, suprafacial and antarafacial shifts can be described as
follows:
42
In a suprafacial shift the migrating group remains on the same side of the π molecular
frame work throughout the course of reaction. In an antarafacial shift the group is transferred
from the top face of the migration source to the bottom face of the migration terminus and vice
versa. Following are the examples of [1,3]-suprafacial and [1,3]-antarafacial shifts of a H:
4.4.3. [i, j] Sigmatropic shifts of a H involving 4nē:
1,3-Sigmatropic shift of a H may be taken as an example:
For writing the transition state, the double bond in the substrate is shown as a pair of P
orbitals and the migrating C—H bond as a P orbital of C and a s orbital of H. Four electrons
participate in the reaction.
a) [1, 3] Suprafacial shift of a H:
a) [1, 3] Antarafacial shift of a H:
43
4.5. MOLECULAR ORBITALS AND SYMMETRY PROPERTIES
Broadly, the stereoselectivity of pericyclic reactions can be analysed by three methods

viz. a) Perturbation molecular orbital method. b) Frontier molecular orbital method and c) orbital
symmetry correlation diagram method.
All these methods require knowledge of the molecular orbitals of a σ-bond, π-bond and
conjugated π-systems, and their symmetry properties.
Overlap of two atomic orbitals or Linear Combination of Atomic Orbitals (LCAO)

produces two molecular orbital. One of these is bonding molecular orbitals (BMO) and the
other is anti bonding molecular orbital (ABMO). BMO is more stable (with lower energy) and
the ABMO is less stable (with higher energy) compared to the atomic orbitals.
4.5.1. Molecular orbitals of C-C single bond

LCAO of two SP3 hybridised atomic orbitals, each with one electron, gives two molecular
orbitals viz σ molecular orbital (bonding molecular orbital) and σ* molecular orbital (antibonding
molecular orbital).
The energy of a molecular orbital increases with increasing number of nodes. In σ*

molecular orbital there is one node (the region where the sign of wave function changes). On
the other hand there is no node in σ molecular orbital. Thus, σ molecular orbital is more stable
than σ* molecular orbital.
The two electrons are accommodated in σ, and σ* is vacant. Thus the ground state
electronic configuration of a C—C σ bond is σ2σ*.The absorption of light of suitable wave
length (about 154 nm) promotes an electron from σ molecular orbital to σ* molecular orbital.
This results in the formation of σ1σ*1, the first excited state of C—C σ bond.
σ* σ*
E h‫ט‬ E
Nonbonding Nonbonding
σ-σ* transition
level level
σ σ
Ground state configuration (σ2σ*) First excited state configuration (σ1σ*1)
44
Molecular orbitals can be classified as symmetric (S) and antisymmetric (A) with
respect to two symmetry elements, m (mirror plane symmetry or plane of symmetry) and C2
(two-fold simple axis symmetry). Mirror plane symmetry is present, when a plane, perpendicular
to the plane of atoms, bisects the molecular orbital into two halves which are mirror images of
each other. C2 symmetry is present when rotation of the molecular orbital about the axis (passing
at right angles through the center of carbon framework and in the plane of atoms forming the
molecular orbital) by 1800 results in an identical molecular orbital with the original.
T he σ molecular orbital has mirror plane symmetry (m) and it is also symmetric
with respect to C2:
m
C2
The σ* molecular orbital is antisymmetric (A) with respect to both m and C2:
m
C2
Molecular orbital m-symmetry C2-symmetry
σ* A A
σ S S
4.5.2. Molecular orbitals of C-C double bond or π bond
Molecular orbitals of a π bond (multiple bond) are also known as π molecular orbitals.
LCAO of two P atomic orbitals in ethylene produces π and π* molecular orbitals. π is bonding
molecular orbital, and π* is antibonding molecular orbital with one node:
π* (ABMO)
LCAO node
E
Two P atomic orbitals π (BMO)
45
The two P electrons are accommodated in π MO and π* MO is vacant (π2π*). This is
the ground state configuration of a carbon-carbon double bond. Upon absorption of light (~180
nm) an electron from π MO is promoted to π* MO (π-π* transition), producing first excited
state of carbon-carbon double bond(π1π*1).
π* (LUMO) π* (HOMO)
E h‫ט‬ E
(nonbonding level) π-π* transition (nonbonding level)
π (HOMO) π
Ground state πē configuration First excited state πē configuration

of C=C(π2π*) of C=C (π1π*1)
In the ground state the highest occupied molecular orbital (HOMO) is π, and the lowest
unoccupied molecular orbital (LUMO) is π*. On the other hand, in the first excited state,
HOMO is π* and there is no LUMO in the first excited state.
The π MO is symmetric (S) with respect to m symmetry and antisymmetric (A) with
respect to C2 symmetry:
m C2 axis m C2 axis
Molecular orbital m-symmetry C2-symmetry
π* A S
π S A
4.5.3. -molecular orbitals of conjugated -systems

The number, symmetry, stability and electron distribution in the molecular orbitals of an
acyclic conjugated -system are summarised below:
1. LCAO of n p-atomic orbitals produces n molecular orbitals.
2. When n=even number, n/2 are bonding molecular orbitals (BMO) and n/2 are antibonding
molecular orbitals (ABMO).
3. When n=odd number, (n-1)/2 will be BMO, (n-1)/2 ABMO, and one nonbonding
molecular orbital (NBMO). NBMO is of same energy as that of P atomic orbitals.
4. MO are designated as 1,2…………..n in order of increasing energy.
5. In n molecular orbital, there will be (n-1) nodes.
46
6. n, with n=odd number, will be symmetric with respect to m and antisymmertric with
respect to C2.
7. When n=even number, n will be antisymmertric with respect to m and symmetric with
respect to C2.
8. Available electrons are accommodated in the MO, following aufbau principle, Hund’s
rule and Pauli exclusion principle.
9. The ground state(GS) is converted to first excited state (FES) by promotion of an
electron from the BMO of highest energy to ABMO of least energy.
10. Occupied MO of highest energy is called highest occupied molecular orbital (HOMO)
and the unoccupied (vacant) MO of lowest energy is called lowest unoccupied
molecular orbital (LUMO).
4.5.4. -MOLECULAR ORBITALS OF 1,3-BUTADIENE.
The simplest polyene is 1,3-butadiene (CH2 =CH-CH=CH2).The conjugated diene

system consists of four P orbitals and four p electrons. Linear combination of four P atomic
orbital gives four  MO, 1, 2, 3 and 4 in order of increasing energy:
π MO Designation. No of m-symmetry. C2 symmetry.

Nodes.
Ψ4 3 A S
ABMO
Ψ3 2 S A
Nonbonding level
E BMO
Ψ2 1 A S
Ψ1 zero S A
Ψ1 and Ψ2 are BMO and Ψ3 and Ψ4 are ABMO:
In the ground state the four πē are accommodated in Ψ1 and Ψ2, and Ψ3 and Ψ4 are
empty (unoccupied). The πē configuration in the ground state is . Therefore the
HOMO and LUMO in the ground state of butadiene are Ψ2 and Ψ3 respectively. First excited
state is obtained from the ground state by promotion of an ē from Ψ2 to Ψ3. The πē configuration
47
in the first excited state (FES) is . The HOMO and LUMO in the FES of butadiene
are Ψ3 and Ψ4 respectively. Conjugated carbocations, free radicals and carbanions belong to
this group of π-systems.
Ψ4 Ψ4 (LUMO)
Ψ3 (LUMO) Ψ3 (HOMO)
hʋ
E Nonbonding level E
Nonbonding level
Ψ2 (HOMO) Ψ2
Ψ1 Ψ1
Ground state πē configuration of First excited state πē configuration of

2 1 1
butadiene(Ψ21,Ψ2,2 Ψ3,Ψ4) butadiene(Ψ1,Ψ2,Ψ3,Ψ4)
4.5.5. π-MOLECULAR ORBITALS OF ALLYLIC SYSTEMS. (CH2=CH-CH2—)

These systems contain three p orbitals. Allyl carbocation, allyl free radical and allyl
carbanion serve as examples:
H
H
+
H + H
Ξ H H
H
H
H H
Allyl carbocation
(three p atomic orbitals and two p ē)
H
H
H H
Ξ H H
H H
H H
Allyl free radical
(three p atomic orbitals and three p ē)
H
H
-
H —
H
Ξ H H
H H
H H
Allyl carbanion
(three p atomic orbitals and four p ē)
48
Linear combination of three p atomic orbitals of an allyl system gives three molecular
orbitals, Ψ1,Ψ2 and Ψ3. Ψ1 is BMO (with no nodes) Ψ2 is NBMO (with one node) and Ψ3 is
ABMO (with two nodes);
Ψ1(BMO) Ψ3(ABMO)
The node in Ψ2 (NBMO) can be shown between C2 and C3 or C1 and C2 i.e. on either
side of the C2. In other words the sign of wave function changes on either side of C2.
2 2
1 3 o 1 3
r
Therefore Ψ2 is depicted with a node located at C2 :
2 2
1 3 or 1 3
nodes
The stability and symmetry properties of the π MO of an allyl system are as following.
πMO Designation Number of m-symmetry C2-symmetry
nodes
Ψ3 2 S A
E
Ψ2 1 A S
Ψ1 0 S A
49
a) Allyl carbocation: CH2 =CH-H2 C+,
In allyl carbocation there are three π MO and two p electrons. The πē configuration of
allyl carbocation in GS is . In the FES it is . Therefore HOMO and LUMO in
the GS are Ψ1 and Ψ2, whereas in the FES, HOMO and LUMO are Ψ2 and Ψ3 respectively:
Ψ3 Ψ3 (LUMO)
Nonbonding level
hʋ Nonbonding level
E Ψ2 E Ψ2
(LUMO) (HOMO)
Ψ1 (HOMO) Ψ1
1 1
πē configuration in the GS πē configuration in the FES ( 1 2 3)
( 12 2 3 )
b. Allyl radical: (CH2=CH-H2C )
In allyl freeradical there are three π MO and three P electrons. The πē configuration,
HOMO and LUMO in the GS. And FES of an allyl free radical as following:
Nonbonding level h‫ט‬

E Ψ2 (HOMO) E Ψ2 (LUMO)Nonbonding level
Ψ1 Ψ1
2 1 2 1
πē configuration in the GS ( 1 2 3) πē configuration in the FES ( 1 2 3)
c. Allyl carbanion: (CH2=CH-H2C– )

The carbanion has three π MO and four p electrons.
Nonbonding level
h‫ט‬ Nonbonding level
E Ψ2 E Ψ2
(HOMO)
Ψ1 Ψ1
πē configuration in the GS πē configuration in the FES ( 12 1

2 3
( 12 22 3 ) (There is no LUMO in FES)
50
4.6. SUMMARY
1. Pericyclic reactions are concerted reactions and involve cyclic rearrangement of

electrons. They are reversible and induced by heat or light.
2. Pericyclic reactions are classified as electrocyclic reactions, cycloadditions and

sigmatropic rearrangements.
3. Formation of a σ-bond between the two termini of a conjugated π-system is called

electrocyclic ring closure. The reverse process is called electrocyclic ring opening.
Electrocyclic reactions may involve 4nē or 4n+2ē.
4. Formation of a cyclic adduct by the addition between two or more π-components is

called cycloaddition. The reverse process is called cycloreversion. Cycloadditions are
classified as [m+n] cycloadditions.
5. In sigmatropic rearrangements an atom or a group migrates from an α- position of a

double bond to a new position in the π-system. Sigmatropic shifts are classified as [i, j]
shifts.
6. Electrocyclic reactions are stereochemically classified as con and dis reactions.
7. Stereochemically cycloadditions may be supra-supra, supra-antara, antara-supra and

antara-antara cycloadditions.
8. Sigmatropic rearrangements may involve suprafacial or antarafacial shift of an atom

or a group.
9. Linear combination of atomic orbitals (LACO) generates molecular orbitals (MO).
10. The MO may be bonding molecular orbitals (BMO), antibonding molecular orbitals
(ABMO) or nonbonding molecular orbitals (NBMO).
11. The MO are classified as symmetric (S) and anti-symmetric (A) with respect to mirror
plane (m) symmetry and two-fold rotation (C2) symmetry.
12. The π MO of conjugated π system are designated as Ψ1,Ψ2…… ………Ψn. in order of

increasing energy.
13. When n = odd number, Ψn will be symmetric with respect to m-symmetry and anti-
symmetric with respect to C2 symmetry.
14. When n = even number, Ψn will be antisymmetric with respect to m-symmetry and
symmetric with respect to C2 symmetry.
15. Available π ē are accommodated in the π MO following aufbau principle, Hund’s rule
and Pauli exclusion principle.
51
16. First excited state (FES) of a π system is obtained from the ground state (GS) by
promotion of an electron from the BMO of highest energy to the ABMO or NBMO of
lowest energy.
17. The occupied molecular orbital of highest energy is called highest occupied molecular
orbital (HOMO), and the unoccupied or vacant molecular orbital of lowest energy is
called lowest unoccupied molecular orbital (LUMO).
4.7. CHECK YOUR PROGRESS – ANSWERS
1. Pericyclic reactions are concerted reactions, proceeds through cyclic transition state,
initiated by heat or light source, highly stereospecific and no intermediates formed in
the reaction but intermediate can participate and no solvents effect..
2. Electro cyclic reactions takes place through two stereochemical modes. They are CON
electro cyclisations and DIS electro cyclisation.
3. A conjugate addition of two are more π-systems to produce a cyclic product is called
cyclo additions or the cleavage of cyclic compound to two or more π-systems called
cyclo cycloreversion.
1. What are pericyclic reactions? Explain their salient features.
2. Define electrocyclic reactions. Explain 4nē and 4n+2ē electrocyclic reactions with
examples.
3. What are con and dis electrocyclic reactions? Explain with two examples.
4. What are sigmatropic shifts?
5. What are [i, j] shifts? Explain with two examples.
6. Draw the π MO of carbon –carbon double bond. Explain their symmetry properties.
7. What is π-π* transition? Draw the HOMO and LUMO in the GS of ethylene.
II. Answer each of the following in 30 lines
1. Write the structure and stereochemistry of products in the following reactions:
Con electrocyclic ring closure

a) Cis,trans-2,4-hexadiene
Dis electrocyclic ring opening
b) Cis-3,4- dimethyl cyclobutene
52
2. Define cycloaddition reactions, what are [m+n] cycloadditions? Explain with two
examples.
3. Explain the stereochemistry of products obtained in the supra-supra and antara-antara

cycloaddition between two molecules of cis-2-butene.
4. Explain [1, 3] - suprafacial and [1, 3]-antarafacial shifts of a H, with suitable examples.
5. Draw the π MO of 1, 3-butadiene. Indicate their stability and symmetry properties.
6. Draw the π MO of allylic carbocation. What are the HOMO and LUMO in its ground
state and first excited state?
1. Organic Reactions Stereochemistry And Mechanism (Through Solved Problems)- P.

S. Kalsi (New Age International Publisher), 2006.
2. Reaction and Reagents-O. P. Agrawal (Goel Publishing House, Meerut), 2004.
3. Organic Chemistry- Robert Thornton Morrison and Robert Neilson Boyd (Pearson
Education) 2007.
4. Advanced Organic Chemistry, Part A: Structure and Mechanisms, Springer

Sciencepublication, F. Carey and R. Sundberg, 5th edition 2007 .
5. Organic Chemistry, J. Clayden, N. Geeves, S. Warren, Oxford Publication, 2000
6. Pericyclic Reactions, Ian Flaming, Oxford Science Publication, 1998
7. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, J. March, John

Wiley & Sons publication, 1992.
53
UNIT – 5: INTRODUCTION TO ASYMMETRIC
SYNTHESIS
Contents:
5.0. Objective.
5.1. Introduction.
5.2. Terminology.
5.3. Classification of stereoselective reactions.
5.4. Substrate stereoselective reactions
5.5. Product stereoselective reactions
5.6. Enantiomeric excess and diastereomeric excess.

5.7. Summary.
5.8. Check your progress - Answers.
5.9. Model examination question.
5.10. Further Reading.
5.0. OBJECTIVES
After completion of this unit you should be able to

 define Asyymetric synthesis and associated terms,
 classification of stereoselective reactions,
 explain Substrate and product stereoselective reactions,
 describe cram’s rule.
5.1. INTRODUCTION
Asymmetric synthesis may be defined as the formation of unequal amounts of

stereoisomers by creation of asymmetric centre(s) selectively in a substrate.
COOH
H H
H H H OH + HO H
CH3
CH3 CH3
Propionic acid
D-lactic acid L-lactic acid
Unequal amounts
54
Conversion of propionic acid into unequal amounts of D-and L-lactic acids may be
considered as a hypothetical example of asymmetric synthesis. D-and L-lactic acids are chiral
molecules and propionic acid is called prochiral molecule. Although the two hydrogens at -
carbon of propionic acid are apparently identical, they are called heterotopic. In the following
sections we shall define the terms involved in the discussion of asymmetric synthesis.
5.2. TERMINOLOGY
To understand concepts of assymetric synthesis we must familier about the terms

involved in it. Here are some terms are given as follows.
Homomorpic ligands:
Two or more structurally and configurationally indistinguishable ligands (atoms or groups
in a molecule), when considered in isolation are called homomorphic ligands.
Ex: Two hydrogens, two chlorines, two methyl group or two phenyl groups are called
homomorphic ligands.
For examples, in propionic acid , the H in COOH group, the two hydrogens at  
carbon and the three hydrogens in methyl group are distinguishable (different). But when detached
from the molecule (considered in isolation), all the six hydrogens are indistinguishable (identical)
and therefore called homomorphic ligands.
Homomorphic faces:
Two planes of a Sp2 carbon (carbonyl C or olefinic C) and two lone pairs of electrons
on a disubstituted hetero atom are called homomorphic faces.
O
the top and bottom faces (sides) of the carbonyl groups are
homomorphic faces
A carbonyl compound
the top and bottom faces of an olefin are homomorphic

C C
An olefin
:
S
Two lone pairs of elections on S are homomorphic
:
A sulphide
55
TOPICITY:
Homomorphic units (ligands and faces) may be indistinguishable in an intact molecule.
The formation of unequal amounts of stereoisomers by creation of asymmetric centre(s)
selectively in a substrate
Homotopic units:
Homomorphic units in a molecule having same structural and spatial relationship with
the rest of the molecule are called homotopic units.
Homotopic ligands:
Homotopic ligands bear completely identical relationship with the rest of the molecule.
Hypothetical replacement of homotopic ligands one at time by another ligand (not already
present on the ligating centre) results in the formation of homomers (completely identical
products).
For example, the four hydrogens in ethylene are homotopic ligands. Replacement of
any hydrogen by chlorine gives identical products.
H H H H H Cl
C C C C C C
H Cl H H H H
Cl H H
H
C C C C
H H Cl H
Replacement of homotopic hydrogens in ethylene by Cl
Homotopic faces:
Homotopic faces bear completely identical relationship with the rest of the molecule.
Addition on either homotopic face, one at a time, results in the formation of homomers. For
example, the two faces of acetone are homotopic. Addition of Grignard reagent or LiAlH4
reduction on each face gives homomers:
Top face
H3C
Ph
H3C H3C OH
PhMgX
C O homomers
Attack by Ph
H3C H3C
OH
Bottom face
H3C Ph
56
Heterotopic units:
Heterotopic units are the homomorphic units in a molecule having different structural
or spatial relationship with the rest of molecule.
structurally heterotopic units:
Heterotopic units having different structural relationship with the rest of the molecule
are called structurally or constitutionally heterotopic units. Upon hypothetical replacement of
constitutionally heterotopic ligands one at a time, structural isomers are obtained. For example
in propane, the hydrogen atoms on C-1 and those on C-2 are structurally heterotopic ligands.
On C-1 H2C Cl
H C H
H
n-propylchloride
H C H
H C H
Replacement H
H C H of H by Cl H (structural isomers)
H C H H C H
H OnC-2 H C Cl
H C H isopropyl chloride
H
Structural heterotopicity has no stereochemical relevance and therefore will not be

discussed any further.
Stereoheterotopic units:
Heterotopic units having different spatial relationship with the rest of the molecule are
called stereoheterotopic units. Stereoheterotopic units are further classified into enantiotopic
and diastereotopic units. The units can be lignads or faces.
Enatiotopic ligands:
Stereoheterotopic ligands bearing enantiomeric relationship with the rest of the molecule
are called enantiotopic ligands. Substitution of enantiotopic lignds one at a time by another
ligand (not already present on the ligating centre) results in the formation of enantiomers. For
example the hydrogens at C-2 of propionic acid are enantiotopic ligands.
COOH
HA by Cl
Cl
COOH H3C
HA H
CH3 Substitution R-2-Chloropropionic acid
by Cl Enantiomers
HB
COOH
HB by Cl
H
H3C
Cl
S-2-Chloropropionic acid
57
Enantiotopic faces:
Stereoheterotopic faces bearing enantiotopic relationship with the rest of molecule are
called enantiotopic faces. Addition on either faces, one at a time, gives enantiomers. For example,
the two faces of acetaldehyde are enantiotopic faces and addition of a PhMgX on either face
of acetaldehyde (one at a time) gives enantiomers:
Top face
H3C
Ph
H3C R
H OH
PhMgX
C O R-2-phenylethanol
Attack by Ph
H (enantiomers)
H3C
OH
Bottom face
H S Ph
S-2-phenylethanol
Enantiotopic faces are present in all aldehydes, unsymmetrical ketones, trans olefins,
monosubstituted ethylenes, unsymmetrical disulphides.
Diastereotopic ligands:
Two or more homomorphic ligands bearing diastereomeric relationship with the rest of
molecule are called diastereotopic ligands. Hypothetical substitution of diastereotopic ligands
one at a time by another ligand (not already present on the ligating centre) forms diasteromeric
products.
For example the hydrogens at C-1 of propene are diastereotopic. Hypothetical chemical
substitution of these hydrogens gives diastereomers:
H3C Cl
C C
H3C H H
H
Substitution cis-1-Chloropropene
C C Cis trans-isomers
H by Cl diastereomers
H H3C
H H
C C
H Cl
trans-1-Chloropropene
Diastereotopic faces:
Two homomorphic faces bearing diastereomeric relationship with the rest of molecule
are called diastereotopic faces. Hypothetical addition on either face one at a time leads to the
formation of diastereomers.
58
In 4-t-butylcyclohexanone the two faces of carbonyl carbon are diastereotopic. Addition
–
of H on these faces one at a time for instance, gives two diastereomers.
H
Top face
OH
O
LiAlH4 trans-4-t-Butyl
cyclohexanol cis-trans isomers
–
H attack (diastereomers)
OH
4-t-Butyl Bottom face

cyclohexanone H
cis-4-t-Butyl
cyclohexanol
The two faces of α-hydroxyethyl phenyl ketone and the two lone pairs of electrons on S of α-
hydroxyethyl methyl sulphide are diastereotopic.
The classification of homomorphic units is summarized below.
Homomorphic units
Homotopic units Heterotopic units
Homomorphic ligands Homomorphic faces
Stereoheterotopic units Structurally or constitutionally

heterotopic ligands
Diastereotopic units
Enantiotopic units
Enantiotopic ligands Enantiotopic faces Diastereotopic Diastereotopic

ligands faces
Prochirality:
Prochiral molecules are converted into stereoisomeric products (chiral products) by

appropriate chemical and biochemical reactions. The phenomenon is called prochirality or
prostereoiomerism. In other words prochirality is the property by virtue of which certain molecules
can be converted into enantiomeric or diastereomeric products.
59
COOH
Ex: H OH
CH3
COOH
Chemical or D-lactic acid
HB HA
biochemical
CH3 reaction COOH
HO H
Propionic acid
CH3
L-lactic acid
Propioric acid = prochiral or prostereogenic molecule

HA and HB = stereoheterotopic (enantiotopic) ligands
C-2 in propionic acid= prochiral or prostereogenic centre
D-and L-latic acids=stereoisomeric products (enantiomers)
Prochiral symbols:
To describe stereoheterotopic ligands and faces in molecules, configurational symbols

or descriptors like R,S or E, Z or cis-trans and symbols Re and Si with prefix ‘pro’ are used.
For example in ethanol, CH3-CH2-OH, the two hydrogens on -C are paired ligands,
while the CH3 and OH groups are unpaired ligands. α-Carbon is the prochiral centre and is
projected as cross formula and the paired ligands are labelled as HA and HB. For assigning
prochiral symbol to HA and HB are replaced by D. If the priority order OH>CH3>D>HB. Their
arrangement gives R configurational symbol. Therefore HA is given Pro-R symbol. If the
priority order is HO>CH3>D>HA. Their arrangement in the formula gives S configurational
symbol. Therefore HB is assigned pro-S descreptor.
OH OH OH
HB HA or HS HR HB CH3
CH3 CH3 HA
Pro S Pro R Pro R Pro S
Each enantiotopic face of a carbonyl compound has a trigonal carbon attached to three
different ligands. If their arrangement, according to ClP sequence rules is clolckwise, the face
is assigned Re symbol. Si descriptor is assigned in case the arrangement of the three groups is
anticlockwise. For example acetaldehyde has two faces. On the top face O  CH3  H
arrangement is anti clockwise. Therefore it is Si face. On the other hand the bottom face with
clockwise OCH3H arrangement is assingned Re symbol.
60
H3C H3C H3C H H3C H
O O C C C C
H H CH3 Cl H
H
Top face Top face Top face Top face
(Si face) Bottom face Bottom face
Bottom face trans-2-Butene 2-Chloropropene
5.3. CLASSIFYCATION OF STEREOSELECTIVE REACTIONS
Two broad types of stereoselectivity viz. stereoselectivity and stereospecificity are

widely encountered in organic reactions. The terms stereoselectivity and stereospecificity are
often used synonymously and the difference is seldom maintained. To avoid the confusion, the
two types of selectivity are brought under common terminology i.e stereoselectivity preceded
by substrate or product. Stereoselectivity without a qualifying term denotes product stereo-
selectivity.
Stereoselectivity may be defined as discrimination between stereoisomers or two

stereoheterotopic units. Accordingly stereoselectivity is of two main types viz. substrate
stereoselectivity and product stereoselectivity. Product stereoselectivity is sometimes referred
to as stereoselectivity.
The following diagram clarifies the classification of Stereoselectivity:
61
5.4. SUBSTRATE STEREOSELECTIVE REACTIONS
Substrate stereoselectivity is a reagent which transforms two different substrates A
and B (enantiomers or diastereomers) under same conditions at different rates to different or
same product. In substrate stereoselectivity two stereoisomers are differentiated. The
stereoisomers may be enantiomers or diastereomers. Therefore substrate stereoselectivity
may be substrate enantioselectivity or substrate diastereoselectivity.
Substrate enantioselectivity:
Substrate enantioselectivity is a reagent which differentiates two enantiomers. Only
chiral reagents can differentiate enantiomers. For example, when (±)-ammonium tartarate is
treated with pencillium glaucum, (+)-isomer is consumed by the microorganism and (-)-isomer
is recovered.
Similarly the enzyme oxidase oxides L--amino acid 1000 times faster than the
corresponding D-amino acid.
(-)-menthol esterifies (+)-mandelic acid faster than the (-)-mandelic acid. Substrate
diatereoselectivity involves enantiomer differentiation reaction.
Substrate diastereoselectivity:
Substrate diastereoselectivity is a reagent which differentiates two diastereomers. Even
an achiral reagent can differentiate two diastereomers. For example, iodide ion induced
debromination of meso-2,3-dibromobutane gives trans-2-butene whereas under identical
conditions (+) or (-)-2,3-dibromobutane forms cis-2-butene.
Few other examples of substrate diastereoselectivity are:
Ph OH O
+
C N H
Ph C NH CH3
H3C
N-methyl benzamide
Z-acetophenone oxime
Ph + O
H
C N H3C C NH Ph
H3C OH Acetanilide
E-acetophenone oxime
Ex: Diastereomeric 4-t-butylcyclohexanols are oxidised by chromic acid at different rates to
give same product. kax/keq=3.2.
H
OH O
Slow e
a Fast
oxidation OH
oxidation
H H2CrO4
H2CrO4
H H
H 4-t-Butyl trans-4-t-Butyl
cis-4-t-Butyl
cyclohexanone cyclohexanol
cyclohexanol
62
The reactions by which diastereomers are differentiated are called diastereomers differentiation
reactions.
5.5. PRODUCT STEREOSELECTIVE REACTIONS
Product stereoselectivity is a reaction in which a single substrate capable of forming

two or more different stereoisomeric products, forms predominantly one product. The products
may be enantiomers or diastereomers. Accordingly product stereoselectivity can be product
enantioselectivity or product diastereoselectivity.
Product enantioselectivity or enantioselectivity:
In these reactions a chiral reagent or catalyst differentiates enantiotopic units in a

substrate and selectivity transform into an enantiomer. The enantiotopic units may be enantiotopic
ligands or faces. Thus product enantioselectivity may involve either enantiotopos differentiation
or enantioface differentiation reaction.
Enantiotopos differentiation reactions:
A chiral reagent or catalyst differentiates enantitopic ligands in a substrate. For example,

ATP phosphorylates glycerol to give exclusively R-glycerol-1-phosphate.
CH2OH CH2OH
HO H ATP HO R H O
CH2OH H2C O P OH
Glycerol
OH
R-glycerol-1-phosphate
In this reaction, pro-R enatiotopic ligand undergoes phosphorylation.
COOH
H
H3C C2H5 (-) Brucine
H3C C2H5
COOH Δ
-CO2 COOH
Ethyl methyl malonic acid S-2-methyl-butanoicacid
(major)
On decarboxylation of ethyl methyl malonic acid in the presence of (-) brucine, S-2-
methyl butanoic acid is obtained as the major product. In this reaction pro-S enatiotopic ligand
undergoes decarboxylation.
Enantioface differentiation reactions:

A chiral reagent or catalyst differentiates two enantiotopic faces in a molecule. For
example, in the reaction of S-2-methylbutyl magnesium chloride with phenyl isopropyl ketone,
addition of hydride ion occurs predominantly on the Re face (bottom faces) of the ketone.
63
Ph O Cl
Ph Cl Mg Mg
O +
i
CH3 i
Pr H
Pr H
C2H5 CH3
Phenyl isopropyl ketone C2H5
S-2-methyl butyl Sterically less hindered
magnesium chloride Transition state
Ph OH Ph OMgCl
HOH CH2
C C H5C2
i
C
Pr H i
Pr H +
CH3
S-1-phenyl-2-methyl propanol
(Major product)
Product diastereoselectivity or diastereoselectivity:

In these reactions even an achiral reagent differentiates diastereotopic units in a substrate,
and a diastereomer is the predominant product. The diastereotopic units may be diastereotopic
ligands or faces. Therefore diastereoselectivity involves either diastereotopos differentiation
reaction or diastereoface differentiation reaction.
Diastereotopos differentiation reactions:
In these reactions, diastereotopic ligands of the substrate are differentiated. Even an
achiral catalyst can differentiate diastereotopic ligands. For example, R-2-bromo-1,2-
diphenylethane undergoes base catalysed dehydrobromination by E2 mechanism to give trans-
stilbene as the major product:
Br
H Br
Ph H
R HSR – Ph
H Br OH
Ξ Ph Ph
HRR HSR
HSR HRR
Ph Ph HRR
– -H2O
OH –
-Br
H
Ph
Ph
H
trans stilbene
The two diastereotopic hydrogens in the substrate are labeled as HRR and HSR. It can
be seen that in the formation of trans-stilbene, HRR is preferentially eliminated.
64
17.3.2.6. Diastreoface differentiation reactions:
In these reactions even an achiral reagent differentiates two diastereotopic faces of a

substrate. For example, in the lithium aluminium hydride reduction of 4-t-butylcylcohexanone,
trans-4-t-butylcyclohexanol is the major product. In other words, hydride ion adds on the pro-
cis face of the ketone giving more stable equatorial alcohol.
H
O –
H e
OH
4-t-Butyl trans-4-t-Butyl
cyclohexanone cyclohexanol
Another example of diastereoface differentiation is addition of PhMgI to R-3-phenyl-

2-butanone to give predominantly erythro , 2S, 3R-2,3-diphenyl-2-butanol. The stereochemistry
of the reaction can be explained through Cram’s open-chain model. In the transition state
phenyl carbanion adds to the Re face of the carbonyl group.
5.6. ENANTIOMERIC EXCESS & DIASTEREOMERIC EXCESS
The success of stereoselectivity in an asymmetric synthesis is expressed in several

ways. In an enantioselective synthesis the enantiomers composition can be expressed in terms
of percentage of the major enantiomer.
65
The enantiomer composition is usually expressed in terms of enantiomeric excess (ee).
Enantiomeric excess is defined as the percentage excess of major enantiomer over the racemate
in the mixture. For example if in a reaction a mixture containing 80%R-and 20%S-isomers is
formed, the ee of R will be (80%-20%) or 60%.
no of moles of major enantiomer - no of moles of minor enantiomer

% ee =
no of moles of major enantiomer + no of moles of minor enantiomer
In a diastereoselective synthesis, similarly diastereomeric excess (de) can be defined
as the proportion of the major diastereomer produced, less that of the minor.
De=%of major diastereomer-%of minor diastereomer.
Another method of expressing enantiomer composition is by optical purity (O.P). Optical

purity is the absolute ratio of observed specific rotation of product sample (made up of only two
enantiomers) to the corresponding specific rotation of one pure enantiomer expressed as
percentage.
For example, [ ]D25 of pure S-2-butanol is + 13.52 A0 (nm) and observed specific
rotation of a mixture of 2-butanols under identical conditions is +6.76 A0 (nm). the optical purity
=6.76/13.52x100=50% i.e., 50% S isomer and 50% R isomer or racemic mixture. Thus optical
purity is equal to ee or 75%S+25%R. Optical purity is an older expression. Use of this term is
becoming obsolute since now a days enantiomer composition is determined by non-polarimetric
methods.
Check your progress
1.Define the term Assymetric synthesis.
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2..What is topicity? how many types it is?
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66
3.Define prochirality?
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4.How Stereoselectivity classified?
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5.7. SUMMARY
1) Homomorphic ligands and faces are classified into homotopic and heterotopic.
2) Homomorphic ligands and faces on hypothetical chemical transformation yield
homomers.
3) Stereoheterotopic ligands and faces are further subdivided into enantiotopic and
diastereotopic
4) Enantiotopic ligands or faces bear enantiomeric relationship with the rest of molecule.
Upon hypothetical chemical transformation (substitution or addition) give enantiomers.
5) Diasteretopic ligand or faces reside in diastereomeric environments and on substitution
or addition give diastereomers.
6) Prochirality is a property of certain molecules by virtue of which certain molecules can
be converted into enantiomeric or diastereomeric products
7) Prochiral symbols like R, S or E,Z or cis, trans with prefix ‘Pro’ and Re and Si are
assigned to stereoheterotopic units.
8) Pro-R and pro-S symbols are assigned to enantiotopic ligands
9) Re and Si descriptors are assigned to enantiotopic faces.
10) Stereoselectivity is broadly classified into substrate stereoselectivity and product
stereoselectivity
11 Substrate selectivity is simply differentiation of stereoisomers but not asymmetric
synthesis.
12) Product stereoselectivity deals with enantioselectivity and diastereoselectivity
13) Enantioselectivity comprises of enantiotopos differentiation reactions and enantioface
differentiation reactions.
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14) Diastereoselectivity consists of diastereotopos differentiation and diastereoface
differentiation reactions
15) Product composition in an asymmetric synthesis is expressed as enantiomeric excess
or diastereomeric excess

1. The formation of unequal amounts of stereoisomers by creation of asymmetric centre(s)
selectively in a reaction of substrate called Asymmetric synthesis.
2. The formation of unequal amounts of stereoisomers by creation of asymmetric centre(s)
selectively in a substrate called topocity. It is of 1> Homotopic and 2. Heterotopic.
3. Conversion of a centre or centers in a substrate into stereoisomeric products (chiral
products) by appropriate chemical and biochemical reactions called prochilrality.
4. Stereoselectivity classified into substrate stereoselectivity and product stereoselectivity.
substrate stereoselectivity devided into substrate enantiostereo selectivity and substrate
diastereo selectivity. Product stereoselectivity is again devided into product
enantioselectivity and product diastereoselectivity.

1. Define Assymetric synthesis and give one example.
2. Define the following terms
a) Homomorphic ligands
b) Homomorphic faces
3. Define prochirality and assign the prochiral symbol for acetophenone and benzaldehyde.
4. Explain Enantiotopos differentiation reactions with example.
5. Explain Enantioface differentiation reactions with example
6. Explain Diastereotopos differentiation reactions with example
7. Explain Diastereoface differentiation reactions with example
1. Define the following terms with suitable examples
a) Prochirality
b) Enatiotopic faces
c) Diastereotopic ligands
d) Homotopic faces
2. Explain substrate selectivity with examples
3. Write notes on:
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a) Enantiotopos differentiation reactions b) Enantioface differentiation reactions.
4. How is product composition in an asymmetric synthesis expressed? explained
1. Fundamentals of Asymmetric Synthesis by G. L. David Krupadanam, 2014.

2. Principles of Asymmetric Synthesis by J. Aubé and Robert E. Gawley, 1996.
3. Principles and applications of asymmetric synthesis by Guo-Qiang Lin
4. March’s Advanced Organic Chemistry: Reactions, Mechanisms and Structure by
Michael B. Smith
5. Stereochemistry of organic compounds by by Ernest L. Eliel, Samuel H. Wilen 2009.
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UNIT-6: STRUCTURAL ELUCIDATION OF ORGANIC
COMPOUNDS BY CHEMICAL ANALYSIS
Contents
6.0. Objectives
6.1. Introduction
6.2. Evaluation of purity
6.3. Detection of elements
6.4. Estimation of elements
6.5. Calculation of empirical formula
6.6. Functional group analysis
6.7. Summary
6.8. Examination model questions
6.0. OBJECTIVES
After a thorough study and understanding of the contents of this unit, you must be able to:
 know the evaluation methods of purity of organic compounds.
 describe the detection of elements in organic compounds- Lassaigne test.
 realise the importance of the estimation of carbon, hydrogen, nitrogen, halogens and
sulphur in organic compounds.
 determine and understand the relation between empirical formulae and molecular
formulae.
 give the detection methods of functional group in organic compounds.
6.1. INTRODUCTION
The methods of structure determination of organic compounds have undergone revolutionary
changes in the last few decades. Now a days physical methods are preferred over chemical
methods due to a number of advantages in the former. It is necessary to find whether an
organic compound is pure or not before its analysis. M.P; mixed M.P; B.P. and T.L.C. are the
methods of judging the purity. If necessary they can be purified by
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a) recrystallisation
b) distillation
c) sublimation
d) steam distillation and
e) column chromatography
The steps involved in the analysis of an organic compound are elemental detection,
their estimation, molecular formula and finally molecular structure determination. Now a days
spectroscopic methods of structure determination are in wide application. These are IR, UV,
NMR, and mass spectroscopic methods.
One of the aims of an organic chemist’ is to purify and establish the structure of
unknown organic compounds. The structure determination of an organic compound involves
several stages such as evaluation of its purity, detection and estimation of elements, molecular
weight determination and functional group analysis.
6.2. EVALUATION OF PURITY

The most important criterion of the purity of an organic compound is its sharp melting
or boiling point. For pure organic compounds, the gap between the temperatures at which they
begin to melt or boil and at which the boiling or melting is complete is less than two degrees. In
the case of impure compounds this gap is more.
Solid organic compounds are generally purified by recrystallisation. Solids that sublime
can be purified by sublimation. In special cases chromatographic methods may be employed
for purification. Pure organic solids have well defined crystalline shape. Liquid samples are
purified by fractional distillation. Steam volatile compounds are purified by steam distillation.
6.3. DETECTION OF ELEMENTS

Carbon is essentially present in all organic compounds. Most of the organic compounds
contain” hydrogen, and in some oxygen, sulphur, nitrogen and halogens. Usually, the presence
of carbon, hydrogen and oxygen in organic compounds is not tested. The presence of oxygen
may be inferred by the functional group tests.
i)Lassaigne test:
is performed to detect the presence of nitrogen, sulphur and halogens in organic

compounds. On heating an organic compound with sodium metal, the nitrogen along with the
carbon, present in the compound, is converted into sodium cyanide (Na CN), whereas sulphur
and halogens are converted into sodium sulphide (Na2S) and sodium halide (NaX) respectively.
In Lassaigne test, an organic compound is fused with sufficient quantity of sodium metal in an
ignition tube, plunged into water, taken in a mortor, finely ground and filtered. The filtrate should
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be clear and colourless. This filtrate is called sodium fusion extract. The fusion extract is then
tested for the presence of sodium cyanide, sodium sulphide and sodium halides.
Na + C+N  NaCN
2Na+ S  Na2S
Na+X  NaX(Sodium halide)
ii) Test for nitrogen:
The fusion extract is boiled for a few minutes with excess of ferrous sulphate and then
acidified with dilute sulphuric acid. After the addition of ferrous sulphate if a bluish green
precipitate is not obtained, a few drops of sodium hydroxide are added. During heating, oxidation
of some of Fe2+ ions to Fe3+ ions occurs. Formation of a prussian blue precipitate or colour, due
to ferricferrocyanide, indicates the presence of nitrogen in the given compound. Following
equations explain the test.
FeSO4 + 2 NaOH  Fe (OH)2 + Na2SO4
Fe (OH)2 + 6 NaCN  Na4 [Fe(CN)6]+ 2 NaOH
(Sodium ferrocyanide)
3Na4 [Fe(CN)6]+2 Fe2 (SO4)3  Fe4 [ Fe (CN)6]3+ 6Na2SO4
Ferricferrocyanide
iii) Tests for sulphur:
(a) A black precipitate of lead sulphide (PbS) is formed by the addition of acetic acid
and a solution of lead acetate to the sodium fusion extract.
Na2S + (CH3COO2 )Pb  PbS  +2CH3COONa
b) Another test for sulphur is to add one or two drops of freshly prepared dilute solution
of sodium nitropursside. Appearance of a violet or pink colour is a positive test for
sulphide ion in the extract, and therefore the presence of sulphur in the organic
compound.
Na2S + Na2 [Fe (NO) (CN)5 ]  Na3 [Fe CONSNa (CN)5]
iv) Test for halogens:
The fusion extract is strongly heated with conc.nitric acid to destroy sodium cyanide
which interferes with the test for sodium halides. Then the presence of halides in the fusion
solution i.e, halogens in the given compound, is tested by the addition of silver nitrate solution.
Formation of a white, pale yellow or yellow precipitate indicates the presence of chlorine,
bromine or iodine respectively in the compound.
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Na X+Ag NO3  Ag X+Na NO3
6.4. ESTIMATION OF ELEMENTS

Carbon, hydrogen, nitrogen, sulphur and halogens in organic compounds are estimated
by different methods.
i) Estimation of carbon and hydrogen:
When an organic compound is strongly heated with dry cupric oxide, the carbon and
hydrogen are converted into carbon dioxide and water respectively. This is the principle underlying
Liebig and Gay-Lussac methods for the estimation of carbon and hydrogen respectively. A
known weight of the compound (W/ gm) is subjected to combustion at about 700-8000 in the
presence of copper oxide. The products of combustion (CO2 and H2O) are swept, by a stream
of dry nitrogen gas, into weighed absorption tubes containing dry KOH and CaCl2 respectively.
The increase in the weights of absorption tubes containing potassium hydroxide and calcium
chloride corresponds to the amounts of carbon dioxide (X gm ) and water (Y gm ) respectively
formed in the combustion of the compound.
C+2CuO  CO2+2Cu
2H +CuO  H2O+ Cu
From the weights of carbondioxide and water formed in the combustion, the percentage
of carbon and hydrogen in the given compound are calculated as follows.
12 X
% Carbon =   100
44 W
2 Y
% Hydrogen =   100
18 W
When X = Weight of carbondioxide formed
Y = Weight of water formed
ii) Estimation of nitrogen:
There are two methods for the estimation of nitrogen
(a) Dumas method: In this method, a weighed amount of the organic compound containing
nitrogen is mixed with dry copper oxide and heated in an atmosphere of carbon dioxide. The
nitrogen gas thus produced is collected and measured in a nitrometer. From the volume of
nitrogen evolved at STP, the percentage of nitrogen is calculated.
Weight of the compound = W gm
Volume of nitrogen collected in nitrometer at T0(Absolute) and pmm (pressure) = Vml
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P V 273
Volume of nitrogen at STP (V0 ml)  
T 760
28
wt of nitrogen   V0 gm
22400
28 V
 %Nitrogen   0  100
22400 W
b) Kjeldahl’s Method: The estimation of nitrogen, is generally carried out in the laboratory by
this method. A known weight of the sample (x gm) is digested with excess of concentrated
sulphuric acid in the presence of a catalyst (a mixture of copper sulphate, selenium and potassium
sulphate). During digestion, the nitrogen present in the compound is converted into ammonium
sulphate. To this excess of sodium hydroxide is added and steam distilled. The liberated ammonia
is absorbed in known excess of standard sulphuric acid solution. The remaining sulphuric acid
is back titrated against a standard sodium hydroxide solution. The percentage of nitrogen is
calculated as follows.
Weight of the Nitrogen containing compound = W gm
Volume of 0.1 N H2SO4 in which ammonia is absorbede = ’x’ml
Volume of 0.1 N NaOH required to titrate = ’ V’ml
sulphuric acid remaining
Volume of 0.1 N H2SO4 used for neutralisation of liberated ammonia = (x-V) ml
 Ammonia liberated is equivalent to (x-V) ml of 0.1N NH3 solution 1000ml of 0.1N NH3
solution= 17 gm of NH3= 14 gm of nitrogen
X  V 14
 (x-v)ml of o.IN NH3 solution   g of nitrogen
1000 10
( X  V ) 14 100 ( X  V ) 14
 %Nitrogen     
1000 10 W 100 W
iii) Estimation of halogens: Halogens are estimated by Carius method. A known weight
of the organic substance is heated with fuming nitric acid and silver nitrate solution in a sealed
tube. The halogen is converted into silver halide. The precipitate of silver halide is filtered,
washed while on filter, dried and weighed. The percentage of chlorine, for instance, is calculated
as follows:
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Weight of the sample =W gm.
Weight of silver chloride =W1 gm.
Molecular weight of AgCI=108+35.5=143.5
143.5 gm of AgCl contains 35.5 g of chlorine
w gm of AgCl conaning 
35.5
 W1 gm of chlorine
143.5
35.5 100
 % chlorine  
143.5 W
iv) Estimation of sulphur: Sulphur present in a compound is converted into a soluble

sulphate by oxidation with a mixture of sodium peroxide and sodium carbonate. The soluble
sulphate is then converted into barium sulphate by adding a solution of barium chloride. The
precipitate of barium sulphate is filtered, washed, dried and weighed. From the weight of BaSO4
obtained (x gm) from a known weight (w gm)of the organic compound the percentage of
sulphur is calculated.
32 X
% of S=   100
233.4 W
The oxygen in an organic compound is not experimentally determinated directly. The percentage
of oxygen in a compound is obtained indirectly. If the total of the percentages of C,H, N, S, and
halogens in a compound is less than 100, the difference is generally taken as the percentage of
oxygen. For instance, in a compound containing C, H and O only with 76.6% C, 6.27% H, -%
oxygen would be 100-(76.6+6.27)=17.13.
Check your progress

1. How do you determine the percentage amount of oxygen of an organic compound ?
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6.5. CALCULATION OF EMPIRICAL FORMULA
Empirical formula of a compound is the simplest ratio of atoms of different elements

present in the compound, obtained experimentally. Molecular formula, on the other hand,
represents the number of atoms of different elements present in a molecule of a compound.
The molecular formula of acetic acid (CH3COOH) for example, is C2H4O2. But its empirical
formula is CH2O. In some cases molecular formula and empirical formula are one and the
same. For instance, CH3Cl represents empirical formula and as well as molecular formula of
methyl chloride. From composition of the compound, its empirical formula may be deduced.
Following are the steps in the determination of empirical formula.
(a) Divide the percentage of different elements in the organic compound by the atomic
weights of the respective elements. This gives relative number of atoms of the elements
in the compound.
(b) Divide the relative number of atoms of different elements with the smallest relative
number. The values so obtained are rounded off to nearest whole numbers. These
numbers represent the simplest ratio of the atoms of the elements in the compound or
the empirical formula of the compound.
Following example illustrates the steps:
Example -1
An organic compound contains 76.6% C, 6.27% H, and 17.13% oxygen. Calculate the
empirical formula of the compound.
Element % Composition Relative number of atoms Simplest ratio of atoms
C 76.6 76.6 6.38

 6.38  5.96  6
12 1.07
H 6.27 6.27
6.27  6.27  5.86  6
1 1.07
17.13 1.07
O 17.13  1.07 1
16 1.07
The empirical formula is C6H6O
Molecular formula
Molecular formula of a compound is a simple multiple of empirical formula
Molecular formula = n(Empirical formula)
or
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Molecular formula weight or Molecular weight = n (Empirical formula weight)
Where n is an integer
The value of ‘n’ may be obtained by dividing the molecular weight of the compound with
empirical formula weight.
Molecular weight
n
Empirical formula weight
With the knowledge of empirical formula (and therefore empirical formula weight) and the
value of ‘n’ the molecular formula can be determined. Following example illustrates the point.
The empirical formula of a compound is C2H6O.Its molecular weight is 91.8 Calculate its
molecular formula.
Example- 2
Empirical formula C2H6O
Empirical formula weight =(12 x2+1x6+16x1)=24+6+16 =46
Molecular weight 91.8

n   1.99  2
Empirical formula weight 46
Molecular formula= n (Empirical formula) =2(C2H6O)=C4H12O2
Various methods are available for the determination of molecular weights of compounds.
Depending upon the nature of the compound. Victor Meyer’s method, Cryoscopic (depression
of freezing point) or ebullioscopic method (elevation of boiling point) may be employed. In the
case of acids and bases, the equivalent weight may be determined, and multiplied with basicity
or acidity to give the molecular weight. The molecular weight of acids and bases may also be
determined by silver salt method and chloroplatinic salt metiod respectively.
6.6. FUNCTIONAL GROUP ANALYSIS

Functional groups in organic compounds are detected by chemical reactions. In all these
reactions formation of a precipitate, appearance of a colour or discharge of colour is observed.
Following are some characteristic chemical tests for different functional groups.
(i) Tests for Carbonyl compound (Aldehyde/Ketone)
2.4-Dinitre phenyl hydrazone formation: All aldehydes and ketones respond positively to
this reaction. To 2.4-dinitrophenyl hydrazine reagent (2 ml) add 1 or 2 drops of the substance.
If a yellowish (or) orange red precipitate is formed within 5 minutes, the test is positive. For a
solid compound 50mg, of its solution in ethanol or dioxane is used. If it is a liquid, it can be
added directly.
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(a) Tollens test: To a solution of silver nitrate (2ml), ammonical aq. sodium hydroxide solution
is added drop by drop with shaking, in a clean test tube, until the precipitate of silver oxide
formed just dissolves. This is called Tollens’ reagent. To this add 50 mg or 2 to 3 drops of the
compound and if necessary heat on steam bath for 5 minutes. If a black precipitate or silver
mirror is formed the test is positive. This test differentiates aldehydes from ketones. With the
former test is positive. Hydroxy ketones, such as fructose, also give positive test.
(b) Fehling’s test: To a solution of 0.2 gm of the compound in water or dioxane, 5ml of
freshly prepared fehling’s reagent is added and the mixture heated on steam bath. If a red ppt.
is formed the test is positive. This test differentiates aliphatic aldehydes from aromatic aldehydes
the former gives positive test.
(ii) Test for phenols
To 0.1 gm. of the compound in methyl alcohol (4ml) (or) water, 2 drops of freshly
prepared neutral ferric chloride, are added. Phenols exhibit a vivid colour change, viz, violet,
blue or green.
Phenols are soluble in strong alkali (NaOH) but insoluble in NaHCO3 solution. Phenols
react readily with bromine- water and thus discharge the colour of bromine, with evolution of
HBr.
(iii) Test for carboxylic acids
Carboxylic acids are strong enough to react with a solution of sodium bicarbonate and
evolve carbon dioxide i.e, effervescence is observed.
(iv) Test for alcohols
Alcohols change the colour of Ceric nitrate reagent from yellow to red. To a small
quantity- of compound (about 50 mg) in water or dioxan add 0.5 ml. of the reagent, shake and
note the colour.
Alcohols react with sodium metal and evolve hydrogen Primary, secondary and tertiary
alcohols may be differentiated by Lucas test.
(v)Test for amines
(a) Primary amines:
Both aliphatic and aromatic primary amines give positive carbylamine test. To a small
quantity of the substance add a few drops of chloroform and alcoholic KOH solution and warm
gently. If an offensive odour due to formation of isocyanide is observed, the test is positive.
(b) Secondary amines: Both aliphatic and aromatic secondary amines undergo Liebermanns
nitroso reaction. To the amine (0. 1 gm) a solution of sodium nitrite in water is added dropwise
with cooling. Separate the resulting yellow oily substance(N-Nitroso derivative). The yellow oil
78
is mixed with a drop of phenol and conc. sulphuric acid, when a red colour is obtained. The
colour changes to green on making the solution alkaline.
(c)Aromatic tertiary amines on diazotisation give C-nitroso derivatives as green solids. Primary,
secondary and tertiary amines can be separated and differentiated by Hinsberg’s test.
(vi) Test for nitro compounds
All nitro compounds give positive Barker-Mullikan test. To 0.1 gm.of the compound, ammonium
chloride (0.5 gm) zinc dust (0.5 gm) and water (5 ml), are added. Boil the mixture for few
minutes and filter into a test tube containing Tollens’ reagent. If a black ppt or silver mirror is
formed the test is positive.
(vii) Test for amides
Primary amides on strong heating with sodium hydroxide, evolve ammonia. To 0.1 gm of the
compound 5 ml of 10% NaOH are added and heated strongly. If ammonia is evolved, the test
positive.
(viii) Tests for carbohydrates
(a) Molisch test: To 0.1 gm. of the compound add 5ml. of water and 2 drops of a strong
solution of -naphthol in alcohol, are added first and then 5 ml. of conc. H2SO4 are added
down the sides of the test tube. A red ring is formed at the junction of the two layers. This is a
general test for carbohydrates.
(b) Carbohydrates (mono and disaccharides) are soluble in water, but insoluble in ether.
(c) All reducing sugars give positive test with tollens and Fehlings reagents
(ix) Test for unsaturation
Unsaturated compounds discharge the colour of bromine solutions or the pink colour of
Baeyer’s reagent.
(a) Bromine in carbon tetrachloride: 50mg (or) 2 to 3 drops of the compound are dissolved
in 2 ml. of carbon tetrachloride. To this a 5% of bromine in carbon tetrachloride is added drop
by drop. If the colour of bromine solution is discharged without evolution of HBr the test is
positive.
(b) Baeyer’s test: 50mg of the solution (or) 2 to 3 drops of the compound are dissolved in
water or alcohol (2 ml) and add a 2% aq. solution of KMnO4 drop by drop. If the pink color of
the reagent is discharged the test is positive.
The structure determination of a complex organic compound, isolated from plant or

animal source also requires chemical degradation of the molecule into smaller molecules.
79
Identification of these smaller molecules considerably helps in understanding the structure of
the complex molecule. The structure assigned to the compound is finally confirmed by its
synthesis by unambiguous methods starting from simple molecules of known structure, and
establishing the identity of synthetic sample with the compound isolated from the natural source.
Check your progress

2. What is the tollen’s reagent?
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6.7. SUMMARY
In this unit the methods of evaluation of purity of organic compounds, detection and
estimation of different elements of organic compounds are presented. There are no direct
methods of detection and estimation of oxygen. Extra elements are detected by Lassaigne’s
method. Nitrogen can be estimated by either Dumas method or kjeldahl’s method. Sulphur and
halogens are estimated by Carius method. Empirical formula and molecular formula are related.
E. form, x n =Mol. Form.
Functional groups of organic compounds are identified by different chemical and physical
tests. In addition to the above the synthesis of the organic compound isolated in the laboratory
finally proves the structure proposed.

1. The oxygen in an organic compound is not experimentally determinated directly. The
percentage of oxygen in a compound is obtained indirectly. If the total of the percentages
of C,H, N, S, and halogens in a compound is less than 100, the difference is generally
taken as the percentage of oxygen.
2. silver nitrate (2ml), ammonical aq. sodium hydroxide solution is added drop by drop
with shaking, in a clean test tube, until the precipitate of silver oxide formed just
dissolves. This is called Tollens’ reagent. Its active ingredient is Di- ammine-
silver(I) complex ( [Ag(NH3)2] +)
80
6.9. EXAMINATION MODEL QUESTIONS
I Answer each of the following in 10 lines.
1. How are the presence of nitrogen and halogens in an organic compound
tested, using its sodium fusion extract?
2. Outline the Dumas method for the estimation of nitrogen.
3. How are halogens and sulphur in an organic compound estimated?
4. How is empirical formula of a compound determined?
II Answer the following in 30 lines?
1. Analysis of an organic substance (A) containing C, H and O only, gave the following
results: 0.2115 gm of the substance gave 0.4655 gm CO2 and 0.2533 gm H2O. Its
vapour density was found to have 29.7. The compound reacted with sodium metal
liberating hydrogen. The compound on oxidation gave compound (B) which gives
positive lodofrom test. What are A and B?
2. An organic compound contains 78.6% C, 8.42% H and 13.06% N. Its molecular
weight was found to be 106.8. The compound gives positive carbylamine test.
What possible structural formulae may be assigned to the organic compound?

1. Svehla, G. Vogel’s Qualitative Inorganic Analysis, Pearson Education, 2012.
2. Mendham, J. Vogel’s Quantitative Chemical Analysis, Pearson, 2009.
3. Vogel, A.I., Tatchell, A.R., Furnis, B.S., Hannaford, A.J. & Smith, P.W.G.,
4. Textbook of Practical Organic Chemistry, Prentice-Hall, 5th edition, 1996.
Mann, F.G.& Saunders, B.C.
5. Practical Organic Chemistry Orient-Longman, 1960.
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BLOCK - 3
ENVIRONMENTAL CHEMISTRY-1
This block deals with the environment segments, environment pollution, primary
pollutants and their sources, acid rains, Ozone depletion, Green house effect, aquatic eco
system, aquatic environment and water pollution.

Unit – 7: Atmosphere and its components
Unit – 8: Air Pollution
Unit – 9: Water Pollution
83
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UNIT-7: ATMOSPHERE AND ITS COMPONENTS
Contents:
7.0. Objectives
7.1. Introduction
7.2. Environmental segments
7.3. Environmental pollution
7.4. Summary
7.5. Check your progress - Answers
7.7. Further reading.
7.0. OBJECTIVES
After you completed the reading of the unit you must be able to understand the following .
 The importance of the different segments of the atmosphere for the life on the
planet earth.
 How these segments are getting polluted?
 The dangers associated with environmental pollution.
7.1. INTRODUCTION
The concern for the protection of the environment spread over the developed countries
in the sixties and reached its climax in 1970 with the celebration of “Earth Day” under the
auspcies of the United Nations. From 1972 onwards, this concern started sweeping across
India and other developing countries as a result of United Nations conference on Human
Environment at Stockholm. Therefore a need for environmental education at formal and non-
formal levels was realised.
Presently many environmental issues of great size and complexity are threatening the
survival of the mankind itself on the earth. These issues are linked with ecological, social and
economical problems. Before we take up these issues it is essential that we should know
1) What is environment?
2) What are its main segments?
3) What is the composition and physical nature of each of the segments?
These aspects you will learn in this unit.
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7.2. ENVIRONMENTAL SEGMENTS
Environment basically consists of four segments. These are
Atmosphere, Hydrosphere, Lithosphere and Biosphere You learn about the details concerning
the composition and other physical aspects of each of these segments in the following paragraphs.
Atmosphere:
This is the protective blanket of gases surrounding the planet “earth”. This sustains life on
earth and also protects the life from the adverse effects of environment of outer space.
It absorbs most of the cosmic rays reaching the earth from outer space and the sun. It filters
out tissue damaging ultra violet radiation of wave length below 300 nm. It also plays a significant
role in maintaing the heat balance of the earth. For this it absorbs infrared radiation emitted by
the sun and re-emits it from the earth. Atmosphere contains in major proportions nitrogen and
oxygen. The minor components are argon, carbon-di-oxide, and traces of few other gases. It is
these the major source for O2 and N2 required for the sustenance of life on the earth.
Structure of Atmosphere
Atmosphere is broadly divided in to four regions. It starts from the surface of the earth and
ends up to 500 km with temperature varying from -20C to 12000C.
Table 7.1 Major regions of the atmosphere
Temperature Important Chemical

Region Athride (KM)
range 0C componentss
Troposphere 0 – 11 -15 to -56 N2, O2, CO2, H2O(vap)
Stratosphere 11 – 50 -56 to -2 O3
Mesosphere 50 – 55 -2 to -92 O2+, NO+
Thermosphere 85 - 500 -92 to 1200 O2+, O+, NO+
Troposphere:
This layer extends from 0-11 Km. N2, O2, CO2, H2O are present in this. This contains
70% of the mass of the atmosphere. The density and temperature of the air are not uniform
throughout. Density decreases exponentially with the altitude. As far as composition is concerned,
troposphere is homogeneous in the absence of air pollution. The water content varies due to the
hydrological cycle. This is also a turblent region due to the global energy flows.
The temperature falls uniformly with increasing altitude. The cold layer (-560 C) at the
top of the troposphere is called tropopause.
Stratosphere:
The layer extends from 11 to 50km. The temperature increases from -560 C with
increase in altitude upto a maximum of -20C. Ozone (O3) is present in this layer and it absorbs
U.V radiations and raises the temperature causing a positive lapse (Fig.7.1).
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Ozone acts as a protective shield for life on earth from the injurious effects of sun’s
ultra-violet rays. The residence times of molecules or particles are large due to slow mixing.
It is for this region, the pollutants, if any, present in this sphere cause more threat to the
life on the earth.
Mesosphere:
This extends from 50 to 85 km. It contains mainly O2+, NO+. The temperature falls
from -20 to -920 C with a rise in the altitude. It shows thus negative lapse rate. This decrease in
temperature is due to the presence of low levels of ozone in this layer.
Thermosphere:
This extends from 85 to 500 km. It contains mainly O2+, NO+ etc. The temperature
increases with the increasing altitude an ranges from-92°C to 12000C. Here the gases split into
atoms, which eventually lose electrons to form ions. These reactions occur due to absorption of
solar radiation in the far ultra violet region.
Earths Heat Radiation Balance
Earth receives large quantity of heat daily from the sun. But it maintains a steady state
of heat by giving off the bulk of heat energy back at the same rate. But the earth absorbs
radiation mainly in the visible region (483 nm) but emits the radiation at the same rate in the
infrared region (2.40 ). The surface temperature of the sun is about 6000 K and the surface
temperature of the earth is 290 K. Earth abrobs about 66% of the solar flux incident on it and
reflects or scatters back about 94% of the solar flux. Energy transport plays a crucial role in the
radiation balance. The transport mechanisms can be considered as
(i) Radiation of energy by the earth in the infrared region.
(ii) Conduction of energy through the interaction of atoms or molecules
(iii) Convection of energy through vast air circulation. The average surface temperature of
170 C is maintained by the earth by reabsorption of most of outgoing infrared radiation by
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water vapour and carbon di oxide. This combined effect of water vapour & carbondioxide is
known as green house effect. You will learn about this in detail later.
Particles, Ions and radicals in the atmosphere:
Atmosphere contains different particles, ions and radicals and these result out of
chemical, photochemical and other reactions taking place in the atmosphere.
Particles:
These are present in troposphere. The number varies form 10 2 to 105 per cubic
centimeter depending on the quality of the air. The mass varies from 10 g/gm3 to 2000g /m3
as per the quality of the air. The particles originate from vegetation mainly but there are also
particles of natural origin. These are bacteria, pollen grains and volcanic ash.
Inorganic particulate matter that originates from the combustion of fuels and the metal
oxides form a major group.
Organic particulate matter originates from a wide variety of sources e.g. emissions
from vegetation and automobiles, combustion of fuels. Ions dominate above the stratosphere in
the region known as ionosphere. O2+, O+, NO+ are not the major ions. Free radicals are formed
in the photochemical reactions occurring in the atmosphere. O2 and O3 undergo photochemical
decomposition.
hv
O + O
O2
hv O + O2
O3
hv
2O O+ + e
hv O 2+ + e
O2
Check your progress

1. What are the segments of the environment?
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2. What are the different parts of the atmosphere?
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3. Give the altitudes and temperature ranges of different parts of the atmosphere.
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Hydrosphere:
Water supply and civilization are almost synonymous. About 97% of water supply is in
the ocean. But this is unfit for human consumption 2% of the remaining 3% is trapped in the ice
caps. Thus water useful for mankind is only 1%. The hydrosphere includes all types of water
resources namely oceans, seas, rivers, lakes, streams, reservoirs, glaciers, polar ice caps and
ground water.
About 97% of the earth’s water supply is in the Ocean and 2% is locked ice caps. Thus
only 1% is available as fresh water (surface water-rivers, lakes streams and ground water).
The major uses of water are for irrigation (30%), and thermal power plants (80%) other uses
are domestic (8%) and industrial (12%).
The water balance is maintained by the hydrological cycle. It is a continuous natural
process in which exchange of water occurs between the atmosphere, land, sea, living plants
and animals.
Water as rain, hail or snow is s precipilated on land and water surfaces. Water on land
surfaces seeps into the soil as ground water. Below the ground water. Below the ground there
is water table. Water moves up above the water table by capillary action and thereby supply
water to the surface layer. Thus the hydrological cycle consists of a balanced continuous process
of evaporation, transpiration, precipiration, surface run-off and ground water movements. Sea
water contains about 2000 times more dissolved salts than fresh water.
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Check Your Progress
4. What is hydrosphere?
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5. What is water - table?
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The average composition of sea water is as follows.
T able 7.2: Elemental composition of sea water
Element Abundance mg/L Principal Species Residence time (Years)
Na 10.5 x 103 Na+ 6 x 103

Mg 1.4 x 103 Mg2+ 6 x 103
K 380 K+ 1.1 x 107
Sr 8 Sr2+ 1.1 x 107
Ba 0.03 Ba2+ 8.4 x 107
Fe 0.01 Fe(OH)3(s) 1.4 x 102
Zn 0.01 Zn2+ 1.8 x 105
Al 0.01 Al(OH)3 1.0 x 102
Cu 0.002 Cu2+ 5 x 104
Ni 0.002 Ni2+ 1.4 x 104
Mn 0.002 Mn2+ 1.0 x 104
(Besides these, there will be Cs, Rb, Mo, U, V, Ti, K)
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Lithosphere:
This is the outermost mantle of the hardered rigid layer of earth. This consists of minerals
occurring in earth crust and the soil. Soil contains a complex mixture of minerals and organic
matter, air and water. Soil is the most important part of the lithosphere. Good soil and a congenial
climate are important assets for any nation. Soil contains different layers called horizons. The
top horizon or A horizon is the layer of biological activity and contains most of the organic
matter. ‘B’ horizon subsoil receives all minerals, salts, organic matter and clay practices. ‘C’
horizon is composed of weathered rock from which soil is originated.
The soil is essentially silicate mineral 74.3% of it consists of silicon and Oxygen. The elemental
composition is,
O2-46.6%, Si-27.7%, Al-8.1%, Fe-5.0%, Ca-3.6%, Na-2.8%, K-2.6%, Mg-2.1%.
One of the important functions of soils is the exchange of cations. Trace metals are made
available to plants. Clay & minerals perform this exchange. Humres shows very high cation
exchange capacity.
Check your progress

6. What is soil?
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7. What are the functions of the soil?
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Biosphere
This is the realm of living organisms. This is the region where the living organisms interact
with the other environmental segments namely atmosphere, hydrosphere and Lithosphere. But
both biosphere and the environment are influenced mutually by each other. The Oxygen and
carbon dioxide levels of the atmosphere depend on the plants. The biological world is intimately
related with energy flows and water flows in the environment. Biosphere consists of earths
crust, the atmosphere and the various species of life. These species exist in the zone two
meters above land and 10,000 meters below sea level. The biosphere is very vast and hence is
generally divided into different smaller systems. These are called ecosystems. An ecosystem in
general can be considered to consist of plants, animals micro organisms which live in a definite
zone along with the physical factors such as soil, water and air. In any ecosystem, there will be
dynamic inter relationships between the living forms and their physical environment. These
relationships are manifested in the form of different natural cycles. These cycles provide a
continuous circulation of essential constituents necessary for life. The natural cycles and the
ecosystems operate in a balanced manner. Thus balance stabilizes the biosphere and sustains
the life process on earth. Hence it is very essential that the biodiversity is kept intact without
destroying it by human activities. Some of the natural cycles are
1. The hydrological cycle
2. The Oxygen Cycle
3. The nitrogen Cycle
4. The phosphate Cycle
5. The sulphur Cycle
Check Your Progress

8. What is biosphere?
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7.3. ENVIRONMENTAL POLLUTION
As mentioned in the earlier sections, a dynamic equilibrium is maintained between the living
and the non-living things on the planet, earth. This is referred to as “ecological balance”. But it
is very unfortunate that this equilibrium is disturbed in the recent decades beyond an alarming
and unwarranted level.
The important reasons for such an undesirable happening are probably population explosion,
industrial growth, increased agricultural activities and indescriminate use of natural resources
and deforestation activities.
As a result of all the human activities mentioned above, the quality of the environment has
decreased to an alarming level and most probably to irrepairable levels. All the segments of the
environment are being packed with undesirable and harmful chemical as well as microorganisms.
This phenomenon is referred to as “environmental pollution”. Probably the better word will be
“environmental degradation”. In this context there is a need to mention two terms which are
used to describe the level of environmental degradation. These are Contaminant and pollutant.
Contaminant is not originally present and may not be harmful. Pollutant may be originally present
but highly harmful.
7.4. SUMMARY
1. Environment comprises of the segments atmosphere. Hydrosphere, Lithosphere and

biosphere.
2. Atmosphere is the blanket of gases surrounding the earth and protecting life on the
earth from the harmful radiations coming from the outer space and the sun.
3. The atmosphere is divided into different regions or spheres as per the altitude and
the physical and chemical nature of them. These are troposphere. Stratosphere,
Mesosphere and Thermosphere.
4. The altitude, temperature profile and the important chemical species are as follows
Contaminant: A material which does not occur in nature but is introduced by human activities
into the environment, affecting its composition. A contaminant is called as pollutant when it
effects the surroundings and consequently the life on the earth. For example ClI2 released into
the atmosphere is a contaminant but since it affects human health, it is also called pollutant.
Pollutant: A substance present in nature is greater than normal abundance due to human
activity or natural happenings or a harmful substance released into the atmosphere.
Receptor: The medium which is effected by the pollutant. For example all living things including
human beings and some inanimate things come under this classification.
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Sink: The medium which retains and interacts with a long lived pollutant Oceans are sinks
CO 2 .
Hydrosphere
5. All the forms of water resources existing on the planet earth together constitute thus
hydrosphere for example oceans, seas, rivers, lakes, streams, reservoirs. glaciers, polar
caps and ground water. About 97% of the water supply is in the oceans, about 2%
locked in polar ice caps and glaciers and only 1 % is available as fresh water. The
major uses of water are irrigation (30%), thermal power plants (50%), domestic (7%),
and industries (72%).
6. Lithosphere is the outer mantle of solid earth. It consists of minerals and the soil. Soil
is a complex mixture of minerals, organic matter, air and water. Soil is the most important
component of the lithosphere. A good soil and plenty of water are the important
requirements for any agricultural country.
Biosphere:
7. The realm of all living organisms are their interactions with the environment is denoted
by biosphere. Biosphere and environment are influenced mutually.. . by each other. For
example O2, CO2 levels are dependent on plant Kingdom. Biodiversity is the most
important aspect and it shall be always presented for a clean environment. There are
many natural cycles which operate in a balanced way together with the eco systems of
the biosphere. These cycles are : hydrological cycle, oxygen cycle, nitrogen cycle,
phosphorus cycle, sulphur cycle.
8. There exists always a balance between the living things and the non-living things on
the earth. This is known as ecological balance.
9. The disturbance of the ecological balance leads to environmental degradation or
environmental pollution.
10. A material which does not occur in nature but is introduced into the environment due
to human activity is known as contaminant. A harmful contaminant is known as
pollutant.
11. A substance present in nature is greater than natural abundance due to human
activity which adversely effects life on the earth is called pollutant.
12. The medium which is effected by a pollutant is called receptor. The medium which
requires and interacts with a long lived pollutant is called sink.
7.5.CHECK YOUR PROGRESS - ANSWERS
1. Environment basically consists of four segments. These are Atmosphere, Hydrosphere,

Lithosphere and Biosphere.
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2. Troposphere, Stratosphere, Mesosphere, Thermosphere
3. Troposphere (0-11 KM) (-15 to -5.60C), Stratosphere (11-50 KM) (-5.6 to -20C) ,,
Mesosphere (50-55 KM) (-2 to 920C),, Thermosphere (855001 KM) (92 to -
12000C),
4. The hydrosphere includes all types of water resources namely oceans, seas, rivers
lakes, streams, reservoirs, glaciers, polar ice caps and ground water.
5. The water table is the surface where the water pressure head is equal to the
atmospheric pressure.
6. The soil is essentially silicate mineral 74.3% of it consists of silicon and Oxygen. The
elemental composition is, O2-46.6%, Si-27.7%, Al-8.1%, Fe-5.0%, Ca-3.6%, Na-2.8%,
K-2.6%, Mg-2.1%..
7. One of the important functions of soils is the exchange of cations.

8. The region where the living organisms interact with the other environmental segments
namely atmosphere, hydrosphere and Lithosphere. But both biosphere and the
environment are influenced mutually by each other.
7.6 MODEL EXAMINATION QUESTIONS
I. Answer the following in 10 lines each.
1. Explain the terms atmosphere, lithosphere
2. Explain the terms hydrosphere, biosphere
3. Define the terms, contaminant, pollutant medium and sink.
4. What are natural cycles? and what is their importance?
5. What is an ecosystem? What is its importance?
II. Answer the following in 30 lines each.
1. What is the “environment”? and what are its segments? Discuss each at length?
2. Describe the following terms? atmosphere, hydrosphere, lithosphere, and

biosphere
3. What are the different layers of the atmosphere? Describe each in detail.
1. K. De, Environmental Chemistry: New Age International Pvt., Ltd, New Delhi. S.
M. Khopkar,
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2. Environmental Pollution Analysis: Wiley Eastern Ltd, New Delhi. S.E. Manahan,
3. Environmental Chemistry, CRC Press (2005), G.T. Miller,
4. Environmental Science 11th edition. Brooks/ Cole (2006). A. Mishra,
5. Environmental Studies. Selective and Scientific Books, New Delhi (2005).
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UNIT - 8: AIR POLLUTION
Contents
8.0. Objectives
8.1. Introduction
8.2. Primary Pollutants and their sources
8.3. Particulates
8.4. Acid rain
8.5. Ozone depletion
8.6. Green house effect
8.7. Summary
8.0. OBJECTIVES
After you completed the reading of the unit, your must be able to understand the following .
• The main causes for air pollution
• The pollutants and their harmful effects.
• The methods in which air pollution can be controlled.
8.1. INTRODUCTION
Air is never found clean in nature these days. This may be due to natural happenings or due
to human activities. Many gases and solid particles are continuously released into the atmosphere
through human activities as a consequence of industrialization. Vegetation decay and forest
fires may also cause deterioration in the quality of the air. These harmful gases and solid
particles entering into the atmosphere are called air pollutants. These are present in the atmosphere
in concentrations that disturb the ecological balance. This in turn effects man and his
environment.
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8.2. PRIMARY POLLUTANTS AND THEIR SOURCES
There are five primary pollutants which together contribute more than 90% of global
air pollution. These are:
1. Carbon monoxide (CO)
2. Nitrogen Oxides (NOx)
3. Sulphur Oxides (SOx)
4. Hydro Carbons (CH)x
5. Particulates
1. Carbon Monoxide (CO):
This is the major individual pollutant entering into the atmosphere. It is a colourless,
odourless and Poisonous gas. It is as heavy as air and not soluble in water.
Carbon monoxide occurs in nature due to the following important reactions.
a) Incomplete combustion of fuels or carbon containing compournds
2C + O2  2CO
b) Reactions between CO2 and Carbon containing materials at elevated

temperatures.
CO2 + C  2CO
c) Dissociation of CO2 at high temperatures CO2  CO+O.
Sources:
Natural Processes: Volcanic erruptions, natural gas emissions, electrical discharges during
storms, marsh gas production and seed germinations.
Human activity: Transportation (motor vehicles, air crafts and rail roads) Forest fires,
agricultural burnings (debris, crop residues, bush weeds etc.) Industrial processes (iron & steel,
petroleum and paper).
Sink: Soil microorganisms.
Hazards: CO attacks haemoglobin and replaces O2 to form carboxy haemoglobin.
O2 Hb + CO  CO Hb+O2
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Initial effect of CO poisoning is loss of awareness and judgement.
Biochemical effects of CO
CO level (ppm) Effects
10 loss of judgement and partial loss of vision
100 Headache, dizziness
250 loss of consciousness
750 Death after several hours
1000 Rapid death
Remedial measures: 1.CO tests for automobiles and prevent bad vehicles to run on the roads
2. Use of masks
3. Exposure of effected persons to fresh O2.
Check your progress
1.What are the sources for CO?
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2. What hazards do CO create?
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Nitrogen Oxides (NOx)
NOx is used as symbol for NO and NO2 together. These are primarily involved for air
pollution.
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Sources:
Natural bacterial action discharges about 5x 103 tonnes of NOx (mainly as NO) in the world
every year. Human activities release about 5 x 107 tonnes. But the amount varies depending on
urban and rural areas. In urban areas NOx released is about 100 times greater than that released
in rural areas.
Human activity mainly relates to combustion of Coal, oil, natural gas and gasoline.
Power Plants : 4 million tonnes/year
Industries : 4.8 millions tonnes/ year
Domestic and commercial heating plants: 1.2 million tonnes/ year
The average residence time in the atmosphere is 4 days for NO and 3 days for NO2.
In urban areas, before day light NOx level remain stable, but between 6-8 A.M. The
level of NO increases and reaches maximum. At mid-morning with increased UV. level, NO2
level increases due to conversion of NO to NO2. In the evening NO level goes up again.
Hazards caused by NOx.
NO is less toxic than NO2. Like CO it also forms bonds with haemoglobin and reduces
O2 transport efficiency of it. NO2 is more harmful to human health than NO. The biochemical
mechanisms of NO2 toxicity is not clear. Probably some cellular enzyme systems are disrupted.
A possible antidote is Vitamin E.
Bio-chemical effects of NO X
Level of NOx((PPm)) Effects on human health
50-100 Inflammation of lung tissues.

150-200 Bronchiolitis fibrosa obligerars Fatal if exposure is
for 3-5 weeks
500 or more Death
NOx removal from stable gases is possible only through chemical treatment. H2SO4 or
alkaline solutions containing Ca2(OH)2, Mg(OH)2 can absorb NOx gases.
Check your progress

3.What are the sources for NOx pollutants?
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4. How earn NOx be removed from stable gases?
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Sulphur Oxides SOx
SO2, SO3 mixture is generally referred to as SOx.
Sources
Natural processes: Volcanoes are responsible for 70% of the SOx pollution. This is spread all
over the globe.
Man made sources: These sources constitute about 30%. This is localized in some urban
areas. Annual production of SOx is 1.5 x 106 tonnes. Fuel combustion (coal) accounts for 74%,
Industries (H2SO4 etc) contribute 22%, Transportation 2%.
Much of NOx and SOx entering the atmosphere is converted into HNO3 and H2SO4 in photo
chemical reactions. There are responsible for acid rain.
NO+O3  NO2+ O2
NO2+O3  NO3 + O2
NO2 +NO3  N2 O 5
N2O5+H2O  2HNO3
SO2+1/2 O2+H2O  H2SO4
Biochemical effects of SO x:
Sulphur dioxide is mainly responsible for air pollution hazards.
The primary effect is on the respiratory tract. Above 5 ppm, this irritation is experienced by
many. The most wide spread disaster occurs when SO2 is accompanied by smoke. This is
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known as smog. In london 4000 deaths occured in December 1952 on account of this smog.
The cause of death were bronchitis. Pneumonia and allied respiratory problems.
SO2 is injurious to plants also. It causes destruction of leaf tissue. Chronic exposure to
SO2 causes chlorosis (bleaching of green plants) SO2 causes acid rain, which damages plants
besides aquatic lives in rivers and lakes.
Control of SOx
There are four approaches for this. These are:
1. Removal of SOx from fuel gases
2. Removal of Sulphur from the fuel
3. Use of low sulphur fuels
4. Use of non-conventional energy sources in places of fuels.
Check your progress
5. What are bio chemical effects of SOx
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6. How can SO2 pollution be controlled?
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Hydro Carbons pollution
Organic compounds containing only carbon and hydrogen are known as hydrocarbons. Trees
emit large amounts of hydrocarbons in the atmosphere. CH4 (methane) is the major naturally
occurring hydrocarbon emitted into the atmosphere. In the anaerobic decomposition of biomass
in water and soil by bacteria large quantities of CH4 are released.
Bacteria
2(CH2O)  CO2+CH4
Domesticated animals contribute large quantities of CH4. The residence tune of methane
is as large as 3.7 years in the atmosphere. Human activities also the contribute large quantities
of hydrocarbons. Automobiles are the major source. Hydrocarbons from human activities are
generally found in high population density areas.
For example about 20 difficient hydrocarbons are identified in this context.
These are ethane, ethylene, acetylene, propane. n-butane, isopentane, toluene, n-pentane, m-
xylene and isobutene.
The sources for hydro carbons:
Petroleum 55%
Coal 4%
Wood 3%
Refuse homing 29%
Solvent evaporation 2%
Hazards caused by hydro carbons:
The harmful effects are not directly caused by the hydrocarbons. These are from the products
of photochemical reactions in which hydrocarbons participate. Hydrocarbons do not react with
light directly. Photo chemical oxidants in the atmosphere are responsible for this. These are the
sources for photo chemical smog. Smog is an odd combination of smoke and fog.
Photo chemical smog is oxidising smog having high concentration of oxidants. Brown fumes
which irritate the eyes and the lungs characterise this smog. This causes extensive damage to
plant life.
The probable mechanism of smog formation can be illustrated as follows:
1. Hydrocarbons containing C C released from auto exhaust interact with O3
to form Hydro Carbon free radical R CH2•.
2. This combines with O3• to form R CH2O2 another free radical.
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3. RCH2O2 reacts with NO to form NOx and RCH2O•.
4. R CH2O• reacts with O2 to yield RCHO and HO2•.
5. HO2• reacts with NO to give NO2 and HO•.

•
6. OH is highly reactive and reacts with RCH33 to yield H2O and RCH2•. This completes
the cycle.
But the aldehyde may initiate another route by interaction with. OH and forms R-C= O.
This reacts with O2 gives RCO(free radical). Finally peroxy acyl nitrate (PAN) is formed by
reaction with NO2. PAN is the most harmful pollutant.
R CHO formation:
Hydrocarbons
O3
O2
RCH2 RCO2
NO
RCH3
RCH 2O + NO2
NO2 + HO
O3
NO HO2
+
RCHO
PAN formation:
HO
RCHO RC=O
acyl radical
O O
NO2
R O R O
ONO2 O
(PAN) Peroxy Acyl Nitrate peroxyacylradical
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Bio chemical effects of PAN
This is the product of photo chemical smog. This causes irritation of the eyes respiratory
tratcts of human beings. Enzymes are most effected by PAN. Cysteine is badly effected. The
enzymes involved in citric acid cycle are also effected most. The enzymes which synthesise
cellulose and lipids in plants are also effected most
Control of Hydro Carbons and Photo chemical Smog:
PAN formation is controlled by preventing formation of hydro carbons and NOx. Hence
control of these is important to prevent smog formation.
Check your progress
7. What type of pollution is caused by hydrocarbons?
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8. How are hydrocarbons released into the atmosphere?
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9. What are the adverse effects caused by PAN?
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Sinks for gaseous pollutants:
1. Oceans: SO2 is transferred to the ocean via the formates of H2SO4.
2. Plants : Some plants even metabolyze the maize, grassland, bean and alfa alfa show
uptake of O3, SO2, CO, NO2.
8.3. PARTICULATES
Small solid particles and liquid droplets are collectively termed as particulates.
The size plays on important role. The size varies from 0.0001 to 250  [1=10-6 m].
The life time of the particulates varies from few seconds to several months. The number of
particulates varies from several hundreds/cm3 in clean air to more than 100,000/cm3 in highly
polluted air. The particulates possess large surface areas in general and hence exhibit adsorption
properties. They scatter light and reduce visibility also.
Sources:
Natural: Volcanic eruptions, blowing of dust and soil by the winds, spraying of salts and other
particles by the seas and oceans.
Man-made: The ash from power plants, mining operations smoke from incomplete combustion
processes (coal, fuel oil, natural gas wood etc.)
Metal oxides halides comprise a major class of inorganic particles. Some of the examples
are Fe3O4, CaO, PbCl2, PbBrCl, PbBr2.
Organic particulate matter consists of polycyclic aromatic hydro carbons (PAH) & Soot.
Effects on Homan beings:
Metals cause more harm than other particulates. This is because metals are carcinogenic
(cancer coursing). Fine particles are more dangerous than coarse particles. Particles lodged in
the lungs cause severe breathing troubles. For example coal minors back-lung disease, asbestos
workers pulmonary fibrosis and emphysema of urban people are all due to accumulation of
small particles.
Effect on materials:
Soot, dust, fumes, and mist are harmful for many materials. They are more harmful if
they carry with them toxic substances. Particles accelerate corrosion of metals.
Effects on climate:
Particles in the air reduce visibility. They act as nuclei for cloud formations.
Control of particulate ejections:
The removal of particulate matter from gas streams is important. This is done by four ways.
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1. Cyclone collector: The gas is forced into a tight circular spiral. The centrifugal force
produced forces the particles to move outward. 95% of the particulate matter is collected
in this way.
2. Electrostatic scrubbers: The gas stream is led through a high voltage tubes. The
particles acquire charge and are attracted to a granulated surface. They are then
removed.
3. Water scrubbers: Spray chambers are used in which water is sprayed. Towers where
the liquid is introduced into the gas stream as spray are also used. These remove the
particles.
4. Gravity settling chambers: Effluent gases are led into chambers which are tall. The
chamber is of horizontal rectangular tank shape. Particles of size greater than 25 are
removed by these.
Check your progress

10.What are particulates?
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11. What harmful effects are caused by these particles?
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8.4. ACID RAIN

Much of NOx and SOx entering the atmosphere are converted into HNO3 and H2SO4
HNO3 & H2SO4 combine with HCl emission to generate acid rain. Acid rain causes extensive
damage to building and sculptured materials of marble, limestones, slate and mortar. These are
pitted and weakened. They are converted into soluble sulphates.
CaCO3 + H2SO4  CaSO4 + CO2 + H2O
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Tajmahal in India is effected badly by acid rain. The pH of acid rain is about 5-4.5. Flora and
fauna were lost. The fish mortality is in the increase. H2SO4 is the major contributor for acid
rain, HNO3 is the third contributor.
8.5. OZONE DEPLETION

You learnt in unit 7 that stratosphere of the atmosphere contained Ozone (O3). This
absorbs ultraviolet rays reaching the earth from outer space and protects living organisms from
the harmful effects of these radiations. The maximum concentration of O3 in the stratosphere
at an altitude of 20-30km is about 10ppm. Ozone is formed by the photo chemical reactions.
hv
O2 O + O
(242 nm)
O + O 2 + M (N2 or O2) O3 + M
In the early eighties scientists reported a large hole in the ozone layer over Antarcitica.
The O3 level dropped by 30%. Subsequently a similar hole was discovered over the northern
hemirphere. A study by NASA (National Aeronautics and Space Administration, USA) scientists
revealed that the O3 level decreased by 3% between 1969 and 1986.
In June 1992, Japanese scientists announced that the Ozone hole is 13 times wider in
1991 than it was in 1981.
In view of the rapid depletion of O3 layer occurring year by year, an international
agreement was reached in 1987 at a conference in Montreal. This was signed by 34 ( till now
197) countries. This is popularly known as Montreal Protocol. It was agreed upon in this
conference, to take steps to reduce the use of chlorofluro carbons (CFC) responsible for ozone
depletion by 50% by the end of the centuary. In June 1990, the developed countries agreed to
100% ban on the use of CFC by 2000 A.D. at the conference held in London. They allowed a
10-year time lag for developing countries. This agreement was ratified in May 1992 and the
implementation came into effect on August 10, 1992.
Three decades later, we're now reaping the benefits, the ozone layer above Antarc-
tica seems to be healing. A 2018 report from the United Nations says that the hole in the
ozone layer could be totally healed by the 2060. In some areas of the world, it could be as
soon as 2030.
Check your progress
12. What is acid rain?
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13. What is meant by Ozone hole?
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14. What International agreements were reached to reduce this hole?
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Chemistry responsible for Ozone depletion

O3 chemistry in the atmosphere is complex. NO is known to react with O3 giving an
intermediate NO3 and O2.
NO + O3  NO3 + O
NO3 reacts with NO2 and gives N2O5
NO3 + NO2  N2O5
Nuclear explosions produce large amounts of NO x. These are injected into the
atmosphere directly. Tests conducted by USA and USSR in the early sixties showed that reduced
O3 concentrated by 4%.
Apart from NOx. Chlorine is found to play a major role in removing O3 in the stratosphere.
This chlorine enters into it through the use of CFC. Chlorofluro Carbons (CFC) are used
extensively as refrigerants. These are met in the atmosphere, but slowly diffuse into the
stratosphere. There they are subjected to UV radiations (200nm). In the photo chemical reaction
between CFC and UV, Cl. is produced. This reacts immediately with O3.
109
hv
CFCl3 CFCl2 + Cl
Cl + O3 ClO + O 2
ClO + O Cl + O2
In a cyclic reaction each ClO active initiate a serious of chemical reactions which
lead to the destruction of 100,000 molecules of O3.
Many other gases are found to be achieve in reducing the O 3 concentration in the
stratosphere.
Adverse effects of O 3 depletion
O3 functions as a protective layer for uv rarations. Therefore depletion of O3 in the

atmosphere leads to exposure of living things on the earth to the uv radiations. This exposure
may lead to several skin deseases including the skin cancer.
Check your progress
15. What chemicals are known to deplete O3 in the atmosphere primarily?
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8.6. GREEN HOUSE EFFECT

Among the chemical constituents present naturally in the atmosphere, Carbon dioxide
and water vapour absorb strongly the infrared radiations (14000-25000 nm) reaching the earth
from the sun. Not only this but they (IR radiations) block effectively a large part of the radiation
emitted by the earth. Therefore the radiation is partly reemitted to the earth’s surface.
Consequently earth’s surface is heated up. This phenomenon is called green house effect.
Thus CO2 an insignificant non-pollutant species present in the atmosphere is of serious
environmental concern. Increase in the carbondioxide content of the atmosphere is ascribed
mainly to the following two causes.
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1)Deforestation (2) Combustion of fossil fuels. But the real increase in CO2 percentage
from the above two causes is only 60% of the expected increase. This is attributed to the
removal of a part of CO2 by plants and a part by other sinks of CO2. The major sink for CO2 is
the ocean carbondioxide is taken up by sea water and is converted into bicarbonate ion. The
other major sink is bio-mass. This converts CO2 into carbohydrate by the process known as
photo synthesis.
Other green house gases
Relative contributions are shown in the figure 8.3.
6% N2O 2% O3
15% CFC'S
17% METHANE Carbon dioxide

60%
Fig. 8.3. Relative contributio of gases for the green house effected.
Carbondioxide alone is not the culprit. Of course it is the major gas that is responsible
for the green house effect. Other gases such as methane chloroflurocarbons, nitrous oxide and
water vapour also contribute significantly for the green house effect.
Adverse results of Greenhouse effect:
The temperature effect will have a significant long range impact on the global climate.
The earth’s temperature increases as a result of accumulation of CO2. Consequently the rate
of evaporation of surface water decreases. This results in the further increase of the
temperature. The combined effect is expected to bring a rise of 30C in surface temperature
(for doubling of CO2).
1. A rise in temperature by even 10C is expected to effect adversely food production.
2. The biological productivity of the ocean also decreases by temperature rise. This is
because the transport of nutrients form deeper layers to surface layers by vertical
movement.
3. The sea levels rise as a result of this transport rise. This may be as much as 2 metres.
This rise is attributed to expansion of sea water and partial melting of ice caps.
4. This rise in sea water levels may lead to submerging of few island nations. For example
Maldives, Bangladesh and coastal cities like Chennai and Goa.
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5. Some of the fertile belts of Mediteranean and North America mery turn arid.
6. More violent cyclones and floods are likely to occur.
But without CO2 in the atmosphere the earth would be as cold as the moon. By trapping
the heat radiating from the earth’s surface, CO2 regulates global temperature to life
sustaining 150C. But if CO2 amount increases greatly, the earth may record a surface
temperature of 4500C as that of Venus, the neighbouring planet.
Check your progress
16. What is green house effect?
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17. What would happen if there is no CO2 in the atmosphere? or if there is too much of
CO2 in the atmosphere.
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8.7. SUMMARY
This unit describes the chemicals that enter into the atmosphere and pollute it. These
chemicals are led into the atmosphere by either natural phenomenon or by human activities.
i. The primary pollutants are CO, oxides of nitrogen (NOx), oxides of sulphur
(SOx) hydrocarbons, and particulates.
ii. CO enters into the atmosphere mainly through the incomplete combustion of
fossil fuels.
iii. Lung exposures to CO, causes instantaneous death. This combines with
haemoglobin and reduces the O2 transport efficiency of haemoglobin.
iv. Oxides of nitrogen, sulphur are released into the atmosphere in the form of
effluent gases from the industries. Many industries include iron, steel, paper,
fertilizers etc., are responsible for the release of these pollutants.
v. These gases cause lung diseases and respiratory tract diseases.
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vi. Hydrocarbons are the compounds of carbon and hydrogen and these are forced
into the atmosphere though petroleum refinery operations and through natural
gas excavations.
vii. These are carsinogenic and may cause cancer.
viii. Particulate matter is released into the atmosphere through human activity as
well as from volcanic eruptions, biomass degradations etc.
ix. These cause bronchitis and respiratory tract diseases.
x. The other three important factors caused by the air pollutants are acid rain,
ozone depletion and green house effect. Acid rain causes damage to human
beings, crop as wells as to buildings. Ozone depletion causes skin diseases
including cancer.
xi. Green house effect is caused by chloro fluoros carbons (CFC), methane, N2O
and H2O vapour besides CO2. Carbon dioxide is the major compound responsible
for the green house effect. The effect, causes global warming and consequently
rise of sea levels.
xii. Many international agreements were signed by developed as well as developing
countries to reduce drastically the use of CFC’s to prevent ozone depletion.
xiii. A great care is needed in using fossil fuels as they cause major pollutions.
xiv. The water pollution is caused by pesticides, insecticides, agriculture wastes,
domestic wastes etc.
xv. Sound pollution is caused by transport vehicles, heavy machines, loud speakers
etc.

1. Natural Processes: Volcanic erruptions, natural gas emissions, electrical discharges
during storms marsh gas production and seed germinations. Human activity:
Transportation (motor vehicles, air crafts and rail roads) Forest fires, agricultural burnings
(debris, rop residues, bush weeds etc.) Industrial processes (iron & steel, petroleum...
and paper). Sink: Soil microorganisms.
2. CO attacks haemoglobin and displaces O2 from carboxy haemoglobin. Initial effect of

CO poisoning is loss of awareness and judgement.
3. Human activity mainly relates to combustionn of Coal, oil, natural gas and gasoline.
4. NOx removal from stable gases is possible only through chemical treatment. H2SO4
or alkaline solutions containing Ca2(OH)2, Mg(OH)2 can absorb NOx gases.
5. Sulphur dioxide is mainly responsible for air pollution hazards, SO2 is injurious to plants
also. It causes destruction of leaf tissue. Chronic exposure to SO2 causes chlorosis
(bleachug of green plants) SO2 causes acid rain,
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6. Methods of Control of SOx are Removal of SOx from fuel gases, Removal of S
from the fuel, Use of low sulphur fuels, Use of non-conventional energy sources in
places of fuels.
7. This is caused mainly by accidents on oil platforms and ships used for hydrocarbon
transportation but also by discharging water into the sea which is used to wash tanks
of tanker vessels.
8. Trees emit large amounts of hydrocarbons in the atmosphere. CH4 (methane) is the
major naturally occurring hydrocarbon emitted into the atmosphere.
9. This causes irritation of the eyes respiratory tratcts of human beings. Enzymes are
most effected by PAN.
10. Small solid particles and liquid droplets are collectively termed as particulates.
11. Metals cause more harm than other particulates. This is because metals are
carcinogenic (cancer coursing). Fine particles are more dangerous than coarse
particles. Particles lodged in the lungs cause severe breathing troubles.
12. NOx and SOx entering the atmosphere are converted into HNO3 and H2SO4
HNO3&H2SO4 combine with HCl emission to generate acid rain.
13. a region of marked thinning of the ozone layer in high latitudes, attributed to the
chemical action of CFCs and other atmospheric pollutants.
14. an international agreement was reached in 1987 at a conference in Montreal, known

as Montreal Protocol. It was agreed upon in this conference, to take steps to reduce
the use of chlorofluro carbons (CFC) responsible for ozone depletion by 50% by the
end of the centuary.
15. The chemical action of CFCs and other atmospheric pollutants.
16. Burning fossil fuels such as natural gas, coal, oil and gasoline raises the level of
carbon dioxide in the atmosphere, and carbon dioxide is a major contributor to the
greenhouse effect.
17. The earth’s temperature increases as a result of accumulation of CO2. But without
CO2 in the atmosphere the earth would be as cold as the moon

1. What are the primary air pollutants? How are these formed?
2. What is Ozone depletion? How is it cause?
3. Explain the term “acid rain” and hazards caused by it.
114
4. What is green house effect? What gases are likely to cause this.
5. What harmful effects are likely to occur due to the “Green House Effect”?
1. What is air pollution? Name the primary pollutants and the sources for these
pollutants.
2. Name the hazards caused by the primary air pollutants CO, NOx,
SOx, hydrocarbons and particulates. Suggest the remedial measures.
3. Write about the green house effect in detail what are the hazards
likely to be caused by this?
4. Explain the phenomena “Ozone depletion” and “acid rain” with the
possible hazards caused by these?
5. What international agreements were reached to prevent Ozone
depletion?

M. Khopkar,
115
UNIT 9: WATER POLLUTION
Contents
9.0. Objectives
9.1. Introduction
9.2. Aquatic Ecosystem
9.3. Aquatic Environment
9.4. Water Pollution
9.5. Summary
9.8. Further reading
9.0. OBJECTIVES
After you complete reading of the unit you must be able to understand the following
• Is water pollution controllable or not?
• If controllable what steps are necessary?
• The health hazards caused by water pollution
• The sources for water pollution.
9.1. INTRODUCTION
The quality and purity of water is of great importance for all mankind. “Generally
faecal pollution of drinking water causes water borne diseases. Some times these diseases
wipe out the entire populations of towns and villages. But present water is being polluted heavily
due to industrialization, enlarged agricultural activities and use of agro-chemicals indiscriminately.
As a result of water pollution, the normal functions of water are drastically effected. The signs
of water pollution are obvious for all. For example bad odour, taste and growth of water bodies
and floating of oils are well known to all of us.
9.2. AQUATIC ECOSYSTEM

Continuous circulation, transformation and accumulation of energy and matter through
the medium of living things and their activities characterize any ecosystem. Rivers, lakes and
estuaries are continuously subjected to a dynamic state of change with geological and geochemical
characteristics. This can be broadly classified as ecological balance. But the dynamic balance
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in the aquatic ecosystem is very much disturbed these days due to human activities. This results
in water pollution.
9.3. AQUATIC ENVIROMENT

The major elements in aquatic ecosystems are P, N, C, O. Of these elements the P, N,
C levels depend on the synthesis or the decomposition of organic matter by the aquatic biota.
The types and distribution of this biota depend largely on the physico-chemical characteristics of
the aqueous phase.
Similarly the physic chemical characteristics are also influenced by the activity of these
biota. In many stagnant waters, the dissolved O2 is consumed for the biological decomposition
of organic matter and this deficiency can not be made up because the waters are stagnant and
cut off from the atmosphere as a consequence of O2 depletion, the anaerobic bacteria dominate
and the following reduction reactions are likely to occur.
NO3- NO2- NH3 N2
SO4-2 H2S
On account of the above reduction reactions heavy metal ions are likely to be precipated
as metal sulphides. At surface waters (O meters depth) 200 C temperature will be there and
the aerobic conditions and photosynthesis occur.
At a depth of 21 meters, the temperature will be 70 C and anaerobic conditions occur.

The reduction reactions take place. At a depth of 36 meters, the temperature will be 40 C,
sediments consisting of organic matter, metal sulphides exist.
Check your progress

1. What is aquatic environment?
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2. What type of reactions are likely to take place at different depths of sea?
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9.4. WATER POLLUTION

All types of water sources are polluted these days due to enhanced agricultural activities
and high industrialization. The water pollutants can be broadly grouped into
1. Organic pollutants
2. Inorganic pollutants
3. Sediments
4. Radioactive materials
5. Thermal pollutants
Organic Pollutants:
The Oxygen demanding wastes. Sewage, oil, synthetic carbon components. Plant nutrients,
agrochemicals and disease causing agents are all grouped as organic pollutants. All these materials
undergo degradation by bacterial activity in presence of dissolved oxygen in the water sources.
As a result of this the disolved oxygen content of waters decreases.
Dissolved Oxygen:
This is an essential requirement for life in natural waters. The life in natural waters includes
plants and animal population. The optimum amount of dissolved Oxygen (D.O.) in pure natural
waters is 4-6 ppm. Therefore decrease in this value of any water source is an indication that
the water source is polluted.
Biochemical Oxygen Demand (BOD): This is empirical in nature. It is measured by the

quantity of O2 used by suitable aquatic micro organisms for a 5 day period.
Chemical Oxygen Demand (COD) : The Oxygen required for chemical oxidation of material
by K2Cr2O7 in 50% H2SO4 is the chemical oxygen Demand.
Sources of Organic Pollutants. The organic matter as mentioned above includes.
Sewage (domestic & industrial) : Industrial wastes (paper mills, tanneries, dye industries
etc) run-off from agricultural lands (agro-chemicals) synthetic organic chemicals (fuels, plastics,
fibres, detergents, paints insecticides, food additives, pharmaceuticals etc. In reality this list is
unendig and it is not possible to list out all types in the limited space. There is no human activity,
where the synthetic organic wastes are unavoidable.
Oils: Oil spills from cargo oil tankers on the seas, off-shore oil explorations leakages from oil
pipelines.
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The most threatening organic pollution is from pesticides. Due to very large increase in the
activity in agricultural sector, the organic pollution due to pesticides has also increased greatly
pesticides is the general name or term for insecticides, acaricides, rodenticides, herbicides ,
fungicides and other similarly active compounds. There are more than 10,000 pesticides now in
the agricultural sector.
These can be broadly considered under 3 categories chemically
Insecticides:
Organphosphorus compounds: Malathion etc.
Organic chlorine compounds : DDT etc
Herbicides:
Chloro phenoxy acid compounds: 2,4 di chloro phenoxy acetic acid.
Fungicides:
Di thio carbamátes : Thiram
Organo metallics : Phenyl mercuric acetate
Marine Pollution:
The oceans are now-a-days considered as large dustbins. All types of industrial waste and
waste liquids are dumped into the seas. Industrial wastes, farm and forest –offs are all allowed
into the oceans. It is estimated that more than 400 million tonnes of toxic wastes are thrown into
the oceans. These wastes include bio-degradable and non bio-degradable, radioactive and non
radioactive materials.
Irrigation Water:
The water used for irrigation purposes must be free from salinity and dissolved solids.
Check your progress

3. What parameters are important for establishing the quality of water?
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4. Water used for irrigation purposes shall be free from ————— and ——————
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Quality of surface water:
The surface water used for different purposes recreation, aesthetic, aquatic life, fish culture
and wild life and irrigation are required to satisfy the following.
Recreation and Aesthetics :
The surface water used for these purposes shall be free from
(i) All materials which impart colour or bad taste or turbidity
(ii) debris, oil and scram which form objectional deposits
(iii) toxic substances harmful for human beings, aquatic animals and plants.
(iv) Substances which promote the growth of undesirable aquatic life.
Aquatic life:
The surface water shall be free from
(i) Substances which are likely to be settled and inhibits the growth of flora
(ii) floating substances like oil, greeze etc which carry toxicity to human and aquatic animals
Oil Pollutants:
It is estimated that the total animal influx of petroleum wastes (hydro carbons) into the
ocean is about 10 million tonnes per year. This is mainly due to transportation taken petrolium
products and drilling activities. Besides these, the oil pollution due to spills are through out a
region by wind, currents, waves and tides. The oil is also subjected to different natural processes
such as evaporation, dissolution, emulsification, oxidation, uptake by marine organisms and
sedimentation. As a result of all these processes, the composition of oil changes continually The
overall effects of oil on marine organisms are
(i) direct lethal toxicity
(ii) disruption of physiological activity
(iii) direct entry into the organisms
(iv) Changes in biological habitates.
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Check your progress
5. What are the different types of water pollution?
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6. What is dissolved oxygen (D.O.)? and what is the significance of its value in natural waters?
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Oxidation of organic Pollutants:
All organic compounds are likely to be oxidised on exposure to sunlight and air .The photo-
oxidation is the major route for the decomposition of organic compounds. The other ways are
simple oxidation and hydrolysis. Soil micro organisms assist biological oxidation. There processes
may convert toxic organic chemicals into non-toxic ones.
Inorganic Pollutants:
The following types of inorganic substances are found to pollute water. Hence these are
considered as inorganic pollutants. These are
Inorganic salts, mineral acids, metal compounds, finely divided metals, trace elements, metal
complexes, organo metallics, radio acute wastes.
Sources:
1. Industrial wastes
2. Agricultural wastes
3. Domestic wastes
4. Acid mine drainage wastes
5. Soil erosions
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Bio-chemical effects of inorganic pollutants:
The toxic chemicals discharged by industries into water sources get into human food chain.
When these enter into our body, they disturb the biological processes. This leads to ill health and
in some cases even to death. The list of toxic inorganic chemicals, marine metals and metal
organics is very long some of the toxic elements and the toxicity caused are given the table
(9.1).
Table 9.1 some toxic elements in natural & waste waters
element source Bad effect
As Mines Carcinogenic
Cd metal plating & other industries high blood pressure, kidneys, blood
cells are effected
B detergent factories toxic to plants
Cr metal platting carcisnogenic
Cu metal plating and anemia, kidney&Nerve disorders
Mn Mines, industries Toxic to plants
Hg Mines, Industries highly toxic
Sc Mines, Coal operations Toxic
Zn Mines, metal plating Toxic to plants
Sediments:
Soil erosion leads to sediment in water. It is extensive pollution of surface waters. Soil
erosion is enhanced by agricultural activities. Bottom sediments are rich sources of inorganic
and organic matter. Bottom sediments undergo anaerobic reductions. The level of organic
matter sediments is higher than in soils Cr, Cu, Mo, Ni, CO, Mn are the metals associated with
sediments.
Radio achieve materials:
Four human activities are mainly responsible These are:
1. Mining operation of radioactive minerals
2. Preparation of radioactive materials used in nuclear weapons.
3. Preparative Use of radioactive materials employed in nuclear power plants.
4. Use of radio active isotopes in medicine, agriculture, Industry and research.
Some radioactive elements are
122
U238, Sr90, Ra226, I131, Cs137, Bc140, Kr85, Co60, Mn54, Fe55, Pu239
Nuclear power plants generate low level radioactive liquid wastes, liquid & gaseous
wastes obtained from fusion processes are radioactive.
Thermal Pollution:
Coal-fired and nuclear fuel fired, power stations are the major sources for thermal
pollution. The condenser coils are cooled with water from nearly river or lake and the heated
water is discharged back into the same river or lake. The temperature of the waters therefore
rises by 100C. This will have harmful effects on aquatic life. In addition to thermal pollution
there may be radioactive pollution due to the water containing radioactive materials discharged
into river & lakes.
Eutrophication:
Sewage & agricultural run offs contain phosphates and other nutrients. Therefore
when these are discharged into rivers or lakes, the nutrients get accumulated in these waters.
These waters will therefore suffer from over nutrition. This causes eutrophication. As a result
of over nutrition, there will be algal bloom. This makes the lake become marshy or debris. The
lake will be filled with sediments and aquatic animal life will perish. Finally the lake may turn
into a dry land. But there will be two processes, (1) production of aquatic life and (2) the
decomposition of it by bacteria. In normal fresh waters these two balance each other. But in
lakes with large amounts of nutrients the former dominates the decomposition process and thus
leads to eutrophication.
Check your progress
7. What are sediments? How are these formed?
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8. What is eutrophication? What are its bad effects?
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Water Quality Standards:

The parameters generally considered for establishing the standard of water are:
1. Colour, Odour, taste
2. PH
3. Dissolved Oxygen (BOD & COD)
4. Total dissolved salts
5. Suspended solids
6. Inorganic Chemicals
7. Organic Chemicals
8. Radio Activity
9. Bacteriological parameters
The permissible limits of these parameters are laid down for drinking water by Indian standard
Institute (ISI). These are listed in the table 9.3
Table 9.3 ISI standards for drinking water.
Colour, odour, taste --
pH 6.0-9.0
Dissolved oxygen (DO) 30ppm
Total dissolved salts 500 ppm
Suspended solids 5.0
9.5 SUMMARY
i. Industrialization, population growth large scale agricultural activities are the main
causes for pollution.
ii. Pollution causes not only ill health in human beings, plants and inanimate things are
124
also effected by pollution.
iii. The major threating effects of pollution are O3 depletion, acid rain, green house effect
and eutrophication.
iv. Any kind of pollution causes damage to bio chemical path ways of human beings by
interfering with enzyme activity.
v. Hence International and National laws are promulgated from time to time to prevent
environmental degradation.

1. Aquatic environments include inland surface water, seas, and ground water.
2. At surface waters (O meters depth) 200 C temperature will be there and the aerobic
conditions and photosynthesis occur. At a depth of 21 meters, the temperature will be 70 C
and anaerobic conditions occur. The reduction reactions take place. At a depth of 36 meters,
the temperature will be 40 C, sediments consisting of organic matter, metal sulphides exist.
3. Dissolved oxygen, Biochemical oxygen demmand and chemical oxygen demand.
4. Salinity and dissolved solids.
5. Organic pollutants, Inorganic pollutants, Sediments, Radio active materials and Thermal
pollutants..
6. The quantity of oxygen is an essenntial requirement for life in natural water.
7. Settiling of solid particles are called sedimentation. soil erosion leads to sedmentation in
water.
8. Sewage&agricultural run offs contain phosphates and other nutrients. Therefore when these
are discharged into rivers or lakes, the nutrients get accumulated in these waters. These waters
will therefore suffer from over nutrition.

1. What are the different segments of environment? Explain
2. What are the different regions of atmosphere? Give the physicochemical
details
3. What is environmental degradation? Explain the terms, contaminant, pollutant,

sink, medium.
125
II Answer the following in 30 lines each.
1. Write the different segments of environment in detail?
2. What are the different regions of the atmosphere and give their characteristics.
3. Explain the terms. Biosphere, Lithosphere, Hydrosphere and Ecosystems.

M. Khopkar,
126
BLOCK - 4
ENVIRONMENTAL CHEMISTRY-2
This block deals with classification of water and its disposal, human acoustics,
sound measurements, noise and it’s classification and sound pollution Hazards, toxic ele-
ments in air and water, also discussed state of global environment.
Unit – 10: Soil and Sound Pollution.
Unit – 11: Chemical toxicology
Unit – 12: The state of global environment
127
128
UNIT - 10: SOIL AND SOUND POLILUTIONS
Contents :
10.0. Objectives
10.1. Introduction
10.2. Waste classification & disposal
10.3. Human acoustics
10.4. Sound measurements
10.5. Noise and its classification
10.6. Sound pollution hazards
10.7. Summary
10.0. OBJECTIVES
After you completed reading of the unit you must be able to realise
• the need for the waste disposal

• the bad effects caused by high sounds
• · the sources for high sounds in any society
10.1. INTRODUCTION
Soil:
Soil is the receptor of large quantities of waste products - domestic, human, animal, industrial
and agricultural.
Combustion of sulphur containing fuels emit SO2 and thus leaves finally sulphates on the soil.
Similarly nitrates are also deposited from emissions of NOx.
Fertilizers and pesticides are largely retained by agricultural lands and the nearby soils.
The quality of soil has an impact on public health standards through the human food chain.
Thus the environmental health aspects of soil deserve serious attention.
129
Sound:
Sound can be a pleasure or sometimes can be an hazard. The proverb says “silence is
golden but speed is silver”.
Thus both silence and speech are essential in some circumstances and hazardous in other
situations. Hence only civilized person shall decide for himself when and at what level sound is
a pleasure or a hazard.
10.2. WASTE CLASSIFICATION AND DISPOAL

Wastes are classified into 3 categories, these are
1. Domestic
2. Trade and
3.Industrial wastes
Domestic wastes:
These include refuges and garbage, arising from houses and other residential premises.
Trade wastes:
These, involve refuse arising from retail, commercial and business premises.
Industrial Wastes:
These originate from mineral manufacturing and processing establishments.
Some of these wastes are toxic and others are non-toxic. The toxic wastes are tarry liquids,
Solid tarry materials, acid tars, waste oils, lubricants waste paints, Pesticide residues, photo
graphic wastes, aromatic hydrocarbons, chloro - carbon compounds noxious organic solvents.
Depending on the nature of the waste there are difficult methods of waste disposal.
The modes of waste disposal are schematically illustrated below
Water source Method Disposal site

Nuclear Storage Land, Sea
Industrial Recovery & recycling

or
Treatment Land
Agriculture Run of f land
Domestic Garbage Land or waterbodies
collection treatment land, sea

& Transport
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Recycling technology of plastic wastes is being followed now in many developed countries.
Some wastes are now being used for power generation.
Advanced countries are adopting modern technology and treating the wastes at the
plant itself.
In some cases the wastes are pulverized and incinerated. The heat evolved in such
processes is also put to better uses.
10.3. HUMAN ACCOUSTICS
Human ear receives sound waves in the audio frequency range between 20HZ - 20,000 Hz
(1Hz = 1 cycle /sec). But the audio sense is very sharp in the range 2000 - 5500 Hz. But the
sensitivity of the ear varies from person to person. With ageing people lose hearing power
progressively. Further ear is susceptible for damage if it receives high sounds or high intensity
noise. But ear is provided with natural protective devices through reflex actions (auralreflexes).
The reflex actions are valued only for short durations. Longer exposures to high sounds
may cause permanent damage to the ears. Therefore one should be careful about exposing
himself for high sounds for longer periods.
Check Your Progress

1. What is the audio range of human ear?
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2. What are the consequences of exposing one’s ear to high sounds for long periods.
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10.4. SOUND MEASUREMENT
Two important parameters of sound are sound pressure and sound intensity. These two are
measured in two different units. The common scientific acoustic unit is the Decibel (dB). It is
a relative unit but not an absolute unit.
int ensity measured

1 decibel (dB)  10 log10
reference int erests
The reference unit is the threshold of hearing i.e. the sound which is heard first at a
sound pressure of 2x 10-5 Newton m-2 or sound intensity of 10-12 m-2. The relation between
intensity, pressure and db is shown in the table
Inlimit Persue dB
(wm-2) (n/m-2)
100 200000 200

1.0 20 120
10-2 20 100
10-4 0.2 80
10-6 0.02 60
10-8 0.002 40
10-2 2×10-5 0(threshold of hearing)
Sound intensity is the quantum of sound energy that flows through unit area of the
medium in unit time. It is expressed in watts/m². Sounds not suiting to the ear can be broadly
called as “noise”. But in environmental science studies sound and noise are used synonymously.
Thus noise has become part of our environment. With industrialization, the noise level is in-
creasing gradually.
Check your progress

3. How is sound level expressed?
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4. What are the different parameters of sound that play significant role ?
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10.5. NOISE AND ITS CLASSIFICATION
Noise is classified as
(1) Transport noise

(2) Occupational noise
(3) Neighbourhood noise
1. The transport noise includes noises produced in road traffic, air craft and rail traffic.
2. Occupational noise is produced by industrial machines domestic gadjects.
Neighbourhood noise implies variety of sources of noise which disturb and annoy the general
public. For example loud TV & radio sets, loud speakers in public functions disco music and
dance in late evenings
Some typical occupational noise levels are given in the false
Source dB
Steel plate riveting 130

Textile loom 112
Farm tractor 103
News paper press (conventional) 100
Bench lathe 95
High speed dril 85
Super market 10(dB)
10.6. SOUND POLLUTION HAZARDS
Sound or noise is air-brone mechanical energy striking the human ear drum.
65 dB ( A) is thc sound level for conversation heard at a distance of one metre.
125 dB (A) produces pain in the car
150 dB (A) might kill a human being
133
[dB(A) is the arithmetic average hourly values of noise level exceeded for 10% of the time
over 18 hours between 06 to 24.00 hours an any normal working day]
Sound pollution hazards include

1. Impaired hearing and ear damage and
2. Pathological or psychological disorders.
Permissible sound levels are given in the table
Area Day Night
Industrial 75 dB(A) 65 dB(A)
Commercial 65 dB(A) 55 dB(A)
Residential 50 dB(A) 45 dB(A)
Sensitive areas 50 dB(A) 45 dB(A)
(Hospitals, Schools)
Ear damage
The most commonly occuring ear damage is brought aboutBy continuous periods of high
intensity noise. If the sound level exceeds 90 dB, in the mid-frequency range for more than few
minutes the sensitivity of the ear is reduced.
There may also be an instantaneous damage or aquatic trauma. These arise from very high
intensity impulse type noise., Some looms or over pressure from supersonic and explosions are
some examples.
Pathological effects:
These are caused by particular noise frequencies causing vibration or resonance in materials
or human bodies. Some of the pathological effects are nausia, dizziness, reduced heart beat,
variations in blood pressure and breathing problems.
Mild and the band frequencies can generate resonance in skull and effect the brain and
nervous system. These will have ill effects in thinking and co-ordination of the limbs.
Moderate vibrations can lead lo pain numbness and cyanonis (blue colouration) of fingers
Severe vibrations may damage bones and joints in the hands with swelling and stiff-ness.
Children exposed to excessive noise show signs of behavioural disorders.
The maximum permissable noise levels are presented in the table
Situation Permissible level dB(A)
Read traffic near residential areas 70
Factory work for 8 hr day for 6 days a week 105
Maximum of impulse noise 150
Ear drum rupture 180
Lung damage 195
134
Check your progress
5. What are the ill effects caused by high noises?
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6. Name the permissible noise levels for different areas & situations
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10.7. SUMMARY
i. Land is polluted with solid wastes. Hence solid disposal methods are important
ii. Human ear receives sound waves in the audio range 20HZ - 20000 Hz (1Hz =1 cycle/
sec).
iii. The audiosense is very sharp in the frequency range 2000 - 5500 Hz.
iv. Sound parameters are
a) Frequency (b) pressure and (c) intensity
v. Frequency is measured in Hz, pressure in Newtons/Cm2 and intensities in walts/Cm2
vi. The common scientific acoustic unit is decibel (dB). It is a relative unit
vii. 1 dB =10 log 10
viii. Sound intents, pressure and decibels are related to each other.
ix. Noise is classified as
a) Transport noise b) occupational noise and c) Neighbourhood noise
x. Transport noise includes
a) Road traffic b) Aircraft c) Rail traffic
135
xi.Occupational noise includes sounds from industries domestic gadgets etc.
Xii. Neighbourhood noise comprises of loud TV and radio sets
Loud speakers in public functions.
Disco music & dance
xiii. Sound pollution hazards are
1. Ear damages and
2. Physiological disorders.
xiv. Physiological damages include
a) Reduced heart rate
b) Blood pressure variations
c) Brain & Nervous effects
d) Numbness and cyanosis
e) Damage to Bones & Joints
xv. The perminant noise levels are
Road path 70 dB(A)
Factory work 105 dB(A)
Impulse noise 150 dB(A)
Lung damage 195 dB(A)
1. Human ear receives sound waves in the audio frequency range between 20HZ and
20,000 Hz (1Hz = I cycle /sec).
2. Ear is susceptible for damage if it receives high sounds or high intensity noise.
3. The common scientific acoustic unit is the Decibel (dB). It is a relative unit but not an
absolute unit.
4. Two important parameters of sound are sound pressure and sound intensity. These two
are measured in two different units.
136
5. There may also be an instantaneous damage or aquatic trauma. These arise from very
high intensity impulse type noise, these will have ill effects in thinking and co-ordination
of the limbs.
Source dB
Steel plate riveting 130

Textile loom 112
Farm tractor 103
News paper press (conventional) 100
6. Bench lathe 95
High speed dril 85
Super market 10(dBA)
1. What is the audible range of sound in human ear?

2. How is sound level measured?
3. How is noise classified? Give examples
4. Write are the ill effects of sound pollution? Give examples
5. What is land pollution? How is it avoided?
1. Write about the different types of noise, their measurement and the permissable
levels.
2. What are the ill effects caused by sound pollution?
M. Khopkar,
137
UNIT- 11: CHEMICAL TOXICOLOGY
Contents:
11.0. Objectives
11.1. Introduction
11.2. Toxic elements in air
11.3. Toxic elements in water
11.4. Biochemical. Ill effects of some metals and other substances
11.5. Summary
11.7. Model examination questions
11.0. OBJECTIVES
After you completed the unit you must be able to
• appreciate the importance of the topic

• to think of remedial measures to avoid metal pollution in general and
• toxic metal pollution in particular.
11.1. INTRODUCTION
The study of toxic chemicals and their modes of action on the human body is called
chemical toxicology.
There are a large number of chemicals present in the polluted atmosphere. But all these are
not harmful to human health. Such chemicals which lead to ill health of human beings are called
toxic chemicals. Those chemicals are released into air, water, and soil through industrial and
domestic activities. Eventually these enter into the food chain and cause damage.
It is also not known definitely whether a particular chemical is toxic or not since the
toxicity depends on several factors including the (1) general health of the individual (2) economic
status of the individual (3) the food habits and (4) the concentration of the toxic substance.
Beside all these conditions, the chemical nature of the species plays a significant role in
causing toxicity or not. For example metallic Hg is not as toxic as alkylated mercury Hg(CH3)4.
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11.2. TOXIC ELEMENTS IN AIR
Toxic elements enter into air through industrial, domestic and nature’s activities most of the
toxicity of air is caused by the fuel gases of the industries. These toxic chemicals may be metals,
non-metals, inorganic compounds or carbons compounds. These days the air is heavily polluted
with organic toxic substances in view the large growth of organic chemical industry.
Some chemicals which are listed under “toxic chemicals” by many international organizations
are as follows. The list is only illustrative but not exhaustic.
Organic:
Acrylo nitrile, benzene, chlorinated solvents, chlorofloro carbons (CFC) ethylene dibromide
ethylene oxide, nitroso amines, polybrominated biphenyls, Vinyl chloride.
Inorganic:
As, asbestos, Be, Cd, Chromates, Coke oven emissions. Pb, Hg, O3, SO2 and Oxides of
nitrogen.
In addition to the above there are many trace elements in the atmosphere.
These are many chemicals named under the category “carcinogens”. These cause cancer
in human beings and animals. Carcinogens effect DNA and prevent it to synthesise the required
chemicals in the body. In general toxic elements attack the active sites of the enzymes and
inhibit the enzyme activity. Heavy metal ions are in particular cause the inhilition of enzyme
activity because they show ability to form bond’s with sulphur containing groups.
Check your progress

1. What is a toxic element?
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2. Are all elements toxic?
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3. Name few organic and inorganic toxic chemicals present in polluted air ?
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4. What are the sources for the inorganic and organic toxic substances ?
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11.3. TOXIC ELEMENTS IN WATER

Toxic substances are present in natural waters as well as in industrial waste waters. But
some of there are essential at low level for animals and plants. They serve as nutrients. But
these substance in large amounts cause lot of damage.
Organic toxic substances:
These go into the natural, water resources through industrial agricultural and domestic
waste waters.
Industrial waste waters contain many organic chemicals pertaining to plastic industry, dye
industry and pharmaceutical industry. Even oil refineries also contribute to these organic toxic
substances.
The water bodies contain a large number of pesticides (from the damage of agricultural-
land). The pesticides are mainly chlorinated hydro carbons and organic phosphates. Many
140
organic compounds present in polluted waters are carcinogenic. Some of the carcinogens are
Vinyl chloride, ethylene dichloride, benzidine, 3,3-dichloro benzidine, 2-chloro amline. This list is
only illustrative but not exhaustive. Poly cyclic aeronatic hydro carbons too are found highly
carcinogenic. These are benzo -pyrene, chrysene, benzofluoranthrene.
The organic chemical industries responsible for the release of the toxic organic substances
(as mentioned earlier) shall take necessary precautions to treat their efftuents before release)
into the rivers.
Inorganic toxic chemicals:
The sources for inorganic toxic substances are
Mining operations, industrial discharges, coal, nuclear power stress and space research
stations.., metal plating industries and natural geological sources. Metals and non-metallic
elements constitute the major class of toxic substances some of these are
As, Cd, Be, B, Cr, Cu, Pb, Mn, Hg, Mo, Se and Zn. Amongs the non-metallic fluoride ion
is the most toxic substance. But it is to be noted that it is the chemical form that is more
significant than the amount of the toxic element since chemical forms are more harmful than
the other forms. Besides this the lipid solubility of the substance plays an important role.
The hazards caused and the remedial measures required are presented in the next section.
Check your progress

5. What are the major organic and inorganic toxic substances in polluted waters?
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6. Name some important sources which release the toxic substances into natural waters.
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11.4. BIOCHEMICAL ILL EFFECTS OF SOME TOXIC

METALS AND OTHER SUBSTANCES
The biochemical ill-effects of some select metals, non-metals, inorganic and organic
substances are presented in the foregoing pages. The list is illustrative but not exhaustive.
Similarly the effects given or the mechanism of adverse action propored are not unequivocal
but are only representative.
Bio-Chemical effect of lead:
The major source of air-borne pb is the combustion of leaded petrol. Lead is added as
Pb(C2H5)4 to petrol to prevent knocking. But these days this addition is banned. Pb intake by
human beings is from diet, air and water Out of the total intake major part of Pb is excreted
while a minor part (aburt 25 g) is stored in the bones each day.
The major effect is its interference in the synthesis of haeme. It inhibits the action of
enzymes responsible for the synthesis.
Thus the overall effect is the disruption of haemoglobin synthesis as well as cytochromes.
Thus Pb impairs utilization of O2 and glucose for life sustaining energy production.
Lead poisoning is cured by feeding the patient with calcium chelate (with EDTA)
solution. Pb replaces calcium and forms the lead chelate. This is excreted through urine.
Check your progress

7. How is lead poisoned patient treated?
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Bio chemical Effects of Hg
Toxic nature of mercury is known since the incidence of Minamata disease in 1953-60 in
Japan. In Minamata Bay in Japan more than 100 people lost their lives and many thousands
were permanantly paralysed by eating Hg contaminated fish. The Minamata incident was
142
followed by a more tragic report of Hg poisoning from Iraq in 1972. Many people died after
eating wheat which was dusted with a mercury containing pesticide. Chemical industries are
the main sources for Hg contamination beside agricultural waste waters.
The toxicity of Hg depends on the chemical species.
Hg generally non-toxic
Hg2+2 low toxicity
2+
Hg Toxic but easily transported across biological
membrances
R Hg+ highly toxic (CH3 Hg+) causes nerve and brain
damage
R2 Hg low toxicity
Attachment of Hg to cell membrane is likely to inhibit active transport of sugars across the
membranes and allow the passage of K to the membrane. In the case of brain cells, it causes
disorders in the transmission of nerve impulses. Methyl mercury poisoning leads to segregation
of chromosomes, breakage of chromosomes in cells and also inhibit cell division.
Mechanism of propagation is willten as follows.
Hg2+
Anaerobic bacteria
CH3Hg+
Plankton
Insects Small f ish
Birds
Large fish Man
Hg concentration builds up at each level of the food chain.
Remedial measures:
1. All chemical industries must stop using Hg – electrodes
2. Alkyl Hg pesticides must be banned
143
Check your progress
8. What is the species of Hg, more harmful for human life?
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Bio-chemical ill effects of Cd
The outbreak of Cd poisoning occurred in Japan in the form of “itai” disease. In this
disease, the bones become fragile. High levels of Cd cause kidney problems anaenna and bone
disorders. Cd exchanges with Zn2+ in the enzymes containing Zn. This alters metabolic activity
and causes anaemia, hypertension, cancer and bone disorders. Most of the Cd is eliminated
through kidneys. But a part of it is bound to present in the kidneys excessive amounts if Cd
however exchanges with Zn and causes metabolic disorders.
Biochemical effects of pesticides:
Amongst the pesticides, DDT is most widely studied in respect of its hazards on human
life. Central nervous system is the target of DDT. DDT dissolves in lipid tissue and accumulates
in the fatly membrane surrounding nerve cells.
DDT is fairly stable in the environment but organic phosphates and carbamates degrade
biologically rapidly.
It is believed that the pesticides dissolve in the fatty membrane surrounding nerve tubes and
interfere with the transport of ions in and out of the fibre. These inhibit a vital enzyme acetyl -
cholinsterase
DDT gets concentrated from about 0.04 ppm to 75 ppm from planktono
Plankton  Clans  fish  fish eating birds
(0.04) (0.4) (2.7) (7.5)
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Biochemical ill-effect of O3 and PAN
O3 and PAN are the products of photo chemical smog
PAN – peroxy acetyl nitrate – C O

H3C O NO2
These are harmful to plants, animals and human beings too. These cause irritation of the
eyes and the respiratory tracts of human beings. Exposure to 50 ppm of O3 causes death due to
pulmonary edema (accumulation of fluids in the lungs). The biochemical effects are caused by
the free radicals produced by O3 & PAÑ. The -SH 9 mps of enzymes are oxidised O3 or PAN.
The enzymes affected are isocitric dehydrogenase, malic dehydrogenase and glucose-6-phosphate
dehydrogenase.
Bio Chemical ill-effects of CO, SOx and NOx are already described in the unit on air
pollution.
Check your progress
9. Which chemical amongest pesticides is move dangerous?
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10. What is the effect caused by DDT
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11. What is PAN? What are its harmful effects ?
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11.5. SUMMARY
i. The metals, non-metals and inorganic and organic compounds that accumulate in air or water
due to human activity or the natural phenomena interfere with the proper functioning of the
enzymes in the body
ii. This in turn causes several diseases and in many occasions causes even death
iii. The harmful effects caused by these chemical substances are generally referred to as “toxic
effects”
iv. The toxic effect of the individual substances varies in magnitude as well as nature depending
on the nature of the chemical species.
v. For example metals in particular oxidation states are only toxic. Similarly inorganic substances
which are non-bio degradable and lipid soluble are generally more toxic than the other.
vi.These toxic chemicals get accumulated in the human body through food chain
vii.Hence the persistence time of the chemical is very important for its toxicity
viii. Reduction of the concentration of the toxic chemical and prevention of exposure to the
toxic chemical are the main remedial measures.
1. The substance which is harmfull to any leaving being especially hymans are called
toxic elements.
2. There are a large number of chemicals present in the polluted atmosphere. But all
these are not harmful to human health. Such chemicals which lead to ill health of
human beings are called toxic chemicals.
3. Organic: Acrylo nitrile, benzene, chlorinated solvents, chlorofloro carbons (CFC)

ethylene dibromide ethylene oxide, nitroso amines, polybrominated biphenyls, Vinyl
146
chloride. Inorganic: As, asbestos, Be, Cd, Chromates, Coke oven emissions. Pb, Hg,
O3, SO2 and Oxides of nitrogen.
4. These days the air is heavily polluted with organic toxic substances in view the large
growth of organic chemical industry.
5. Vinyl chloride, ethylene dichloride, benzilidine, 3,3-dichloro benzilidine, 2-chloro amline.

This list is only illustrative but not exhaustive. Poly cyclic aeronatic hydro carbons too
are found highly carcinogenic. These are benzo -pyrene, chrysene, benzofluoranthrene,
As, Cd, Be, B, Cr, Cu, Pb, Mn, Hg, Mo, Se and Zn.
6. Oil refineries also contribute to these organic toxic substances, Mining operations,
industrial discharges, coal, nuclear power stress and space research stations.
7. Lead poisoning is cured by feeding the patient with calcium chelate (with EDTA)
solution. Pb replaces calcium and forms the lead chelate. This is excreted through
urine.
8. R Hg+ is highly toxic (CH3 Hg+) causes nerve and brain damage.
9. Amongst the pesticides, DDT is most widely studied in respect of its hazards on human
life.
10. Central nervous system is the target of DDT. DDT dissolves in lipid tissue and
accumulates in the fatly membrane surrounding nerve cells.
11. PAN – peroxy acetyl nitrate – C O

H3C O NO2
These are harmful to plants, animals and human beings too. These cause irritation of the
eyes and the respiratory tracts of human beings.
11.7. EXAMINATION MODEL QUESTIONS
1. What are toxic elements? Name them
2.Describe the toxic effects of Hg, Pb
3. How are pesticides harmful to human life?
1. What are toxic substances? Name six of them and give their toxic effects.
2. Describe the toxic effects of Pb, Cd, Hg, O3, PAN, DDT.
147
M. Khopkar,
148
UNIT - 12: THE STATE OF THE GLOBAL ENVIRONMENT
Contents:
12.0. Objectives
12.1. Introduction
12.2. State of global environment
12.3. The Earth Summit
12.4. Some action plans to reduce environmental pollution
12.5. Summary
12.6. Check your progress – Answers
12.6. Model examination questions
12.0. OBJECTIVES
After you completed the unit you must be in a position
 to realise the mis deeds done by the entire human community and
 to think for yourself about, the remedial measures one shall take to keep the
environment clean enough for the human race to survive for long.
12.1. INTRODUCTION
Man is getting civilized and in turn self centred day by day perhaps to lead a comfortable
and luxurious life. In this process, it is rather unfortunate to say, that man is cutting himself the
branch of the tree on which he is standing. His attention is directed only towards comfortable
living, and quick transport and communication facilities but not on the quality of the environment.
It is not untrue that industrialization, green revolution, white revolution and related activities are
quite essential for a developed human being. But at the same time one shall not forget that
these human activities directly or indirectly are linked with the quality of the environment.
Therefore prevention of environmental degradation is also important as the progress of the
human civilization. Hence a meaningful balance has to be struck between “growth of human
civilization” and “prevention of environmental degradation” so what is to be done? and how is
it to be done? are the million dollar questions before all the human beings and all the civilistions.
149
12.2. STATE OF GLOBAL ENVIRONMENT
State of global environment at my point of time shall be studied and examined in respect of
1. Human population and Health
2. Water resources and quality of water
3 Air Quality
4. Land and trees
5. Bio diversity
6. Industry, energy and wastes and
7. Transport
Finally the laws and resolutions adopted by the world organisations to keep the
environment fit for human survival.
Human Population and growth:
World population is increasing rapidly day by day. Even with all remedial measures scientific
as well as social, the world is unable to control the population explosion. Word Population has
doubled in 40 years from 1950 to 1990 to cross five billion. It is unfortunate that this increase in
population is more in developing countries as compared to the developed countries. It is expected
that by 2010, the world population may reach even 7 billion since world population is growing by
92 million people each year. Population growth in the developed countries is less than 1% and
in the developing Countries it is about 2%. The survey shows that one in every seven is an
indian some countries such as central America, Carribean and some parts of Asia surprisingly
could reduce the growth dramatically.
One of the chief adverse impact of population growth on human race is ill-health of human
beings. In developing countries, this is very much reflected in infant mortality and malnutrition
of children. It is estimated that about 3 million children die annually from diseases that could be
avoided by proper immunization and proper nutrition. The ignorance, illiteracy and poverty of
parents in villages are also the main causes for the ill-health of children in the developing and
under developed countries. More than 100 million children of primary school age are not in the
school. About 1 billion adults cannot read or write. These also add to the alarming situation that
is existing in respect of human health.
Thus the major problem before army human society is how to control unwarranted Population
growth? and consequential poverty, illiteracy and ill health. For sustained human development
therefore adequate measures are to be taken to control the population growth and increase the
health care.
150
Water Resources and Quality of water:
Water is very essential for existence of life on earth At the same time the quality of water is of
vital concern for mankind since it is directly related to good health. The natural water resources,
rivers, lakes and esuaries are continuously subjected to a dynamic equilibrium state of change
with respect to the geological age and geochemical characteristics. But this dynamic balance in
the aquatic ecosystem is upset by human activities.
About 97% of the earth’s water supply is in the oceans. About 1% is locked in ice caps
and glaciers. Thus only 1% is available as fresh water (rivers, lakes, streams and ground
water) for human consumption. The major uses of water are for irrigation, thermal power
plants, domestic and industrial sectors.
Therefore it is the duty of every responsible citizen to preserve and protect this 1% water
available for human consumption. Rain water seeps into the soil as ground water. Below the
ground there is water table. Hydrological cycle in nature consists of a balanced continuous
process of evaporation, transpiration precipitation, surface run offs and ground water movements.
Therefore it is the responsibility of every human being to preserve water and not to waste a
drop of it.
Another issue of global importance is to prevent the widespread degradation of aquatic

habitats. Coastal marine pollution shows symptoms of decline in the quality and quantity of
marine food due to pollution. 30% of the protein is obtained from marine fish. Sewage and
agricultural nitrate fertilizers are causing algal blooms. These deplete the dissolved oxygen and
produce dead ones in the seas. So all effluent nations shall realise that the seas are not their
“dustbins and take necessary steps not to dump their industrial wastes into the seas”.
Air Quality:
Air quality is deteriorating day by day due to the pollution caused by SOx, NOx, CO and
CO2. The developed continues started cleaning up air by developing suitable technology. These
efforts seemed to give encouraging results. But unfortunately the pollution of air in the developing
countries is increasing day by day.
The emission of the main green house gas CO2 by the different countries is in the order.
USA> Brazil>China>India > Japan. In a similar way the emission of CFC is in the order.
USA> Japan>China>Brazil>India. The quantity of acid rain is also in the rise in the last few
decades. Several developed countries had agreed to reduce the SOx, NOx, CO2 CFC emissions
into the atmosphere by 2000. India also shall adopt such policy. One of the ways of reducing air
pollution is the strict treatment of flue gases.
151
Land and Trees:
Every year more than 25 billion tons of top soil are lost from farm land by erosion. The worst
victim of soil erosion is the dry land and covers 47% of worlds land area.The man reasons for
the sad state of affairs is mismanagement and indescriminate cutting of trees in the forests and
wood lands. Forests are vanishing very rapidly roughly at the rate of 17 million hectares a year.
The bad victims are Amazonion forests of Brazil, tumber ranges of Malaysia, bush jungle of
Ghana and the thick forests of Uttar Pradesh in India. Forests prevent soil erosion and provide
means for water management. Deforestation is also adding about 30% CO2 to the atmosphere.
Therefore it is but essential that all countries shall take up the turn programmes of
1. Reduction of deforestation and
2. Increase of aforestation.
Bio diversily:
Forests are important bio-reserves. Tropical forests occupy special place in this direction
and these forests are mostly in poor countries. Even though these forests constitute about 7%,
of the land surface, in the nature 50% of the worlds is flora and fauna.
It appears there are about 30 million species on Earth. But only 1.5 million are on record.
Of this the majority are insects (7.5 lakhs) and vertebrates and plants are 0.4 and 2.5 lakhs
respectively. The rest are invertebrates, fungi and micro organisms. Most species are available
near the equator. Biodiversity is maximum in tropical forests.
Deforestation, especially of tropical forests are therefore causing a great reduction in the
biodiversity. It is estimated that by 2020, 20% of the species will be probably eliminated due to
deforestation of tropical forests.
Rural people use many different species for their food, fuel and raw materials for their
daily uses. Therefore of these species are lost, it is the rural folk that suffers great, world wide
madicinal plants are worth about 40 billion US dollars.
It is therefore obious that protecting of existing forests and creating new ones is most
essential for the survival of mankind deforestation leads to many damages as mentioned earlier
of which the most important are
1. Increase of CO2 in the atmosphere
2. Erosion of top soil
3. Loss of bio-diversity
Strict laws must be enforced by every country especially the poor to prevent deforestation.
152
Industry, Energy and Wastes:
Industries are major criminals in the developed and developing countries for the
environmental degradation. Every year the industries produce about 25000 million tons of Solid
waste and 350 million tons of hazardous waste. The most threatening thing is “the disposal of
radio active wastes from nuclear reactors”. Many industries in the developing and under
developed countries are not at all treating, the wastes before they are dumped into rivers and
seas. In some cases, the industrialists report that the waste treatment plants cost more than the
products producing plants in the industry. Linked with waste disposal problems every industry
needs lot of electrical or other forms of energy. These in turn add to the pollution problems. So
industrialization appears to a common man as a vicious cycle. But proper management, strict
enforcement of pollution laws and great vigilance by pollution control boards can ease the
situation to a large extent. Besides this new technological processes with least production of
wastes must be worked out. Bio technology and Electrochemical industry seem to occupy a
special place in this direction.
Transport:
Transport consumes land and energy. It is estimated that 30% world’s energy is consumed
by transport. About 80% of this is consumed by road transport. The road transport releases
most of the CO2, CO, and NOx into the atmosphere. Attempts are being made all over the
world to reduce petrol consumption in order to reduce air pollution.
In developing countries, thinking of alternatives to petrol is of two fold necessity. These

alternatives not only save lot of foreign exchange but also reduces air pollution to a great
extent. In recent times, India is encouraging road vehicles run by LPG rather than petrol and is
replacing diesel run rail engines by electrical engines. A time has therefore cone for every
country to three alternative modes of transport which save not only conventional fuel but also
reduce to a large extent air pollution.
Check your progress

1. What is meant by state of global environment?
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2. How can green house effect be reduced?
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12.3. THE EARTIH SUMMIT
The first prominent earth summit of Heads of 150 Nations took place at Rio de Janeiro from
June, 3-14, 1992. This is the second United Nations Conference on Environment and
Development (UNCED). This was attended by 40,000 delegates, 150 heads of states, 7,000
media persons and many others.
The impact of science and technology on the environment in the post-industrial revolution
period was assessed by many nations over the last 3 decades. In fact “environment” has
become a major foreign policy for many countries.
Environment and its protection has been added to the list of issues such as foreign debt,
trade, poverty, irrigation, unemployment and inequality.
The different regions of the world alligned themselves into North and South Block as far as
environmental pollution problems are concerned China, India and third world Nations come
under the South Block. This block emphatically says that “the developed countries are the main
polluters and that they must accept the responsibilities and pay for it. North block may have
only 16% of world population but they consume 60% of worlds food, 70% of global energy
resources and 80%, industrial wood. North Block however feels that poverty and population
explonion in the South Block are the major causes for the environmental degradation. Two
main proposals were made at the summit. But unfortunately these did not have the unanimous
acceptance.
The resolutions are
(i) curtailment of green house gas by 20% by 2002 and
(ii) conservation and management of bio diversity
154
Thus though earth summit could not achieve the expected results, it generated worldwide
Interest and provided a frame work for the nations to negotiate in future. The bio diversity
treaty was finally signed with source ammendments in December 1993.
But each nation made its own land laws to prevent environmental degradation and preserve
natural resources and bio diversity.
In 2012, the United Nations Conference on Sustainable Development was also held
in Rio, and is also commonly called Rio+20 or Rio Earth Summit 2012.
The issues addressed included:
 systematic scrutiny of patterns of production — particularly the production of toxic

components, such as lead in gasoline, or poisonous waste including radioactive
chemicals
 alternative sources of energy to replace the use of fossil fuels which delegates linked
to global climate change
 new reliance on public transportation systems in order to reduce vehicle emissions,
congestion in cities and the health problems caused by polluted air and smoke
 the growing usage and limited supply of water
An important achievement of the summit was an agreement on the Climate Change

Convention which in turn led to the Kyoto Protocol and the Paris Agreement.
In order to ensure compliance to the agreements at Rio (particularly the Rio Declaration
on Environment and Development and Agenda 21), delegates to the Earth Summit established
the Commission on Sustainable Development (CSD). In 2013, the CSD was replaced by
the High-level Political Forum on Sustainable Development that meets every year as part
of the ECOSOC meetings, and every fourth year as part of the General Assembly meetings.
12.4. A SOME ACTION PLANS TO REDUCE

ENVIRONMENTAL DEGRADATION
1. All steps must be taken to arrest population explosion and reduce the rate of population
growth.
2. Shift from coal fired thermal stations to gas-fuel ones.
3. Alternate or non-conventional energy sources such as wind, solar, bio-gas should be

used in place of conventional hydro-electric and thermo-electric forms of electrical
energy.
4. Impose heavy penalties for motor vehicles exceeding emission levels or cancel licences
for such vehicles.
155
5. The usage of CFC must be banned and their substitutes must be developed.
6. Pollution control boards must be given more powers to take action against erring
industries.
7. Environmental science education must be made compulsory at all levels of education.
8. Media should co-operate and help government bodies voluntary organizations and even
individuals to exposing the industries, institutions and individuals responsible for
environmental degradation.
12.5. SUMMARY
i. As far as quality of environment is concerned every body shall think of global situation
and act locally
ii. All nations shall need once in few years, review the situation and pass the necessary
resolutions to prevent pollution, In 1992. Earth summit held at Rio de Jeniro on June 3-
14 was attended by 40000 delegates, 150 heads of nations and 7000 media persons
besides others.
iii. The world nations got divided into two blocks, North and South Blocks and each claimed
the other for the global environmental degradation.
iv. State of global environment must be discussed and reserved periodically in respect of
population & health, water resources, quality of air & water, land & trees, and bio-
diverts.
v. Action plans such as
(a) eradication of poverty, illiteracy and arresting of population growth
(b) shifting from coal based energy to gas-based energy
(c) substituting conventional reserves energy by non-conventional ones
(d) enforcing strict rules on industries and defectives vehicles.
(e) educating all sections of people about environmental science is very essential.
1. State of global environment at my point of time shall be studied and exammed in

respect of
1. Human population and Health
2. Water resources and quality of water
156
3 Air Quality
4. Land and trees
5. Bio diversity
6. Industry, energy and wastes and
7. Transport
Finally the laws and resolutions adopted by the world organisations to keep the
environment fit for human survival.
2. The following is a list of 10 steps to reduce green house effect
a. Reduce, Reuse, Recycle
b. Use Less Heat and Air Conditioning
c. Replace Your Light Bulbs
d. Drive Less and Drive Smart
e. Buy Energy-Efficient Products
f. Use Less Hot Water
g. Use the “Off” Switch
h. Plant a Tree
i. Get a Report Card from Your Utility Company
j. Encourage Others to Conserve
1. What aspects are important to stop environmental degradation?
2. What is 1992 Earth Summit?
3. What are the action plans to environmental pollution?
1. Give a critical account of the present global situation as far as environmental
degradation is concurred?
2. Discuss the action plans to prevent further deterioaration of global environment.
157
1. K. De, Environmental Chemistry: New Age International Pvt., Ltd, New

Delhi. S. M. Khopkar,
2. Environmental Pollution Analysis: Wiley Eastern Ltd, New Delhi. S.E.

Manahan,
158
DR. B. R. AMBEDKAR OPEN UNIVERSITY
FACULTY OF SCIENCE
3rd YEAR (3 YEARS DEGEREE COURSE)
MODEL QUESTION PAPER
CHEMISTRY SEMESTER - 5
Chemistry – 5B: Green Chemistry, Catalysis, Environmental Chemistry (DSE)
[Time : 3 hours] [Max Marks : 60]
Section - A
[Short Answer questions]
[Marks : 4 x 5 = 20]
Note : a) Answer any four of the following in about 10 lines each.
b) Each question carries 5 Marks.
1. [Block - 1] Define Green Chemistry.?
2. [Block - 1] Explain about use of microwaves and ultrasonic energy.
3. [Block - 2] What are pericyclic reactions? Explain their salient features.
4. [Block - 2] Outline the Dumas method for the estimation of nitrogen..
5. [Block - 3] Define the terms, contaminant, pollutant medium and sink.
6. [Block - 3] What is Ozone depletion? How is it cause?
7. [Block - 4] How is sound level measured?.
8. [Block - 4] Describe the toxic effects of Hg, Pb.
Section - B
[Short Answer questions]
[Marks : 4 x 10 = 40]
Note : a) Answer any four of the following in about 30 lines each.
b) Each question carries 10 Marks.

9. [Block - 1] write the basic principles of green chemistry.
(or)
10. [Block - 1] Write the Green synthesis of the following compounds.
159
(i) Adipic acid (ii) catechol (iii) disodium iminodiacetate
11. [Block - 2] Define cycloaddition reactions, what are [m+n] cycloadditions? Explain
with two examples.
(or)
12. [Block - 2] Explain substrate selectivity with examples
13. [Block - 3] What are the different regions of the atmosphere and give their
characteristics.
(or)
14. [Block - 3] What is air pollution? Name the primary pollutants and the sources for
these pollutants..
15. [Block - 4] What are toxic substances? Name six of them and give their toxic
effects..
(or)
16. [Block - 4] Discuss the action plans to prevent further deterioration of global
environment..
SECTION - C
Total Number of Questions 20
I. Multiple Choice Questions.
1. Green chemistry relates _______________
a) Prevent pollution [ ]
b) Atom economy
c) reduce their intrinsic hazards d). All
2. —————— is the one of the principle of green chemistry
a. obtain by products along with desired product [ ]
b. Best Form of Waste Disposal
c. usage of any chemical d. All
3. Which one of the following is good agreement with atom economy ——— [ ]
a. Diel’s Alder reaction
b. addition of H2 to propane
160
c. conversion of allyloxybenezene to o-allyl phenol d. All
4. Electro cyclic reaction shows ______________ no of stereo chemical modes
a. 2 b. 3 c. 1 d. 4 [ ]
5. Cyclo addition reaction shows ______________ no of stereo chemical modes
a. 2 b. 3 c. 1 d. 4 [ ]
6. Sift of H in 2- deutero-2-pentane shows ______________ no of stereo chemical modes
a. 2 b. 3 c. 1 d. 4 [ ]
7. Sound Measured in __________ [ ]
a. decibel b. mm
c. cm d. m
8. Extra element in organic compound detected by_____________ [ ]
a. Mod’s test b. 2,4-DNP test c. Lassaigne test d. Tollen’s
9. Basically environment consists of ____________ segments [ ]
a. 3 b. 4 c. 2 d. 1
10. Most abundant ion in sea water ____________
a. Na+ [ ]
b. K+
c. Mg+2
d. Ni+2
II. Match the follwing
1. Acid rain [ ] a. CO2, Methane, Water, CFC

2. Green house effect [ ] b. NOx, SOx
3. Hydrocarbons [ ] c. Sedimentation
4. PAN [ ] d. Petrol, Coal, Wood
5. Water pollution [ ] e. Photochemical smog
f. CO2, NO2
g Water, CFC
161
III. Fill in the blanks.
1. Polyl aceticacid (PLA) is used as _________________.
2. Domestic Waste is _____________________.
3. In ground state what is the HOMO of ethene _________
4. One example for Homotopic ligand ______________
5. One example for Heterotopic face ————————————-
******
162
163

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BS514CHEDSE(A)-E

“We may forgo material benefits of civilization, but we cannot forgo

Dr. B. R. AMBEDKAR OPEN UNIVERSITY

First Edition : 2020

© 2020, Dr. B. R. Ambedkar Open University, Hyderabad, T.S.

The text forms part of Dr. B. R. Ambedkar Open University Programme.

Further information on Dr. B. R. Ambedkar Open University courses may be obtained

Printed on behalf of Dr. B. R. Ambedkar Open University, Hyderabad by the Registrar.

BLOCK-1: GREEN CHEMISTRY 1

Unit - 1 : Introduction to Green Chemistry 3

Unit - 2 : Principles of Green Chemistry. 7

Unit - 3 : Green synthesis - Some Reactions. 22

BLOCK-2 : ORGANIC CHEMISTRY 31

Unit - 4 : Introduction to Pericyclic Reactions 33

Unit - 5 : Introduction to Assymetric Synthesis 54

Unit - 6 : Structural Elucidation of Organic Compounds

BLOCK-3: ENVIRONMENTAL CHEMISTRY-1 83

Unit – 7: Atmosphere and its components 85

Unit – 8: Air Pollution 97

Unit – 9: Water Pollution 116

BLOCK-4 : ENVIRONMENTAL CHEMISTRY-2 127

Unit – 10: Soil and Sound Pollution. 129

Unit – 11: Chemical toxicology 138

Unit – 12: The state of global environment 149

Model question papers 159

Block-1 includes the following three units.

1.2 What is Green Chemistry

1.3 Need for Green Chemistry

1.4 Goals of Green Chemistry

1.5 Limitations/Obstacles in the persuit of the goals of Green Chemistry

1.7 Check your progress- Answers

1.8 Model Examination Questions

1.9 Further Reading

After a study of this unit you should be able to

• Account for the definition of Green Chemistry

• Explain the need for Green Chemistry

• Appreciate the goals of Green Chemistry

• Account the obstacles in the persuit of the goals of Green Chemistry.

1.2. WHAT IS GREEN CHEMISTRY

1.3. NEED FOR GREEN CHEMISTRY

1.4. GOALS OF GREEN CHEMISTRY

• Prevents pollution at the molecular level.

• Applies innovative scientific solutions to real-world environmental problems.

• Results in source reduction because it prevents the generation of pollution.

• Designs chemical products and processes to reduce their intrinsic hazards.

1.5. LIMITATIONS/OBSTACLES IN THE PURSUIT OF THE

3. Connecting Green Chemistry solution provides to industry:

4. Understanding of basic principles:

5. Green Chemistry is costly, complex and not viable for SME’s:

Check your progress

Note: a) Space provided below for writing your answer.

b) Compare your answer with one given at end of the unit.

1.Define the term Green Chemistry.

This unit deal with

1.7. CHECK YOUR PROGRESS - ANSWERS

2.The need of Green Chemistry is to reduce environmental pollution.

1.8. MODEL EXAMINATION QUESTIONS

I. Answer each of the following in 10 lines

1. Define Green Chemistry.

2. What is the need of Green Chemistry?

I. Answer each of the following in 30 lines

1. What are the important goals of Green Chemistry?

2. Explain about obstacles in the persuit of the goals of Green Chemistry.