MEV-13

ENVIRONMENTAL
CHEMISTRY

SCHOOL OF INTER-DISCIPLINARY AND TRANS-DISCIPLINARY

STUDIES (SOITS)
INDIRA GANDHI NATIONAL OPEN UNIVERSITY
MAIDAN GARHI, NEW DELHI-110068
PROGRAMME DESIGN AND EXPERT COMMITTEE
Dr. Himanshu Pathak Prof. Nandini Sinha Kapoor
Director, ICAR-National Rice Research SOITS, IGNOU
Institute Cuttack, Odisha
Prof. Shachi Shah
Prof. P.A. Azeez Director, SOITS, IGNOU
Director, SACON, Coimbatore
Prof. B. Rupini
Prof I.S. Thakur SOITS, IGNOU
School of Environmental Sciences, JNU,
Dr. Surendra Singh Suthar
New Delhi
School of Environment & Natural
Prof Uma Melkania Resources, Doon University, Dehradun
Dean, College of Basic Sciences and
Dr. Vijay Kumar Baraik
Humanities, GBPUAT, Pantnagar
SOS, IGNOU
Prof. Nidhi Rai
Dr. Tanushree Bhattacharya
University College of Science, M.L.
Department of Civil and Environmental
Sukhadia University, Udaipur
Engineering, Birla Institute of Technology,
Prof. Jitendra Pandey Mesra, Ranchi
Centre of Advanced Study in Botany,
Dr. Pulak Das
BHU
School of Human Ecology,
Prof. R. Baskar Ambedkar University, Delhi
Department of Environmental Science &
Dr. Shubhangi Vaidya
Engineering, Guru Jambheshwar
SOITS, IGNOU
University of Science & Technology,
Hisar, Haryana Dr. Sadananda Sahoo
SOITS, IGNOU
Prof. Jaswant Sokhi
SOS, IGNOU Dr. Sushmitha Baskar
SOITS, IGNOU
Prof Neera Kapoor
SOS, IGNOU Dr. V. Venkat Ramanan
SOITS, IGNOU
Prof. P.K. Biswas
STRIDE, IGNOU Dr. Deeksha Dave
SOITS, IGNOU
Prof. [Link]
SOA, IGNOU Dr. Y.S.C. Khuman
SOITS, IGNOU

PROGRAMME COORDINATORS
Prof. Shachi Shah, Director, SOITS, IGNOU, Dr. V. Venkat Ramanan, SOITS, IGNOU,
Dr. Deeksha Dave, SOITS, IGNOU

BLOCK PREPARATION TEAM

BLOCK 1 BLOCK 2 BLOCK 3 BLOCK 4
Unit 1 Unit-5 Unit-8 Unit-12
Dr. Vivek Mishra, Dr. Anju Srivastava Dr. Anju Srivastava Prof. Lalita S.
Department of and Dr. Reena Jain, and Dr. Reena Jain, Kumar,
Chemistry, Amity Department of Department of School of Science,
University, Noida Chemistry, Hindu Chemistry, Hindu IGNOU, New Delhi
College, University College, University
of Delhi of Delhi
Unit-2 Unit-6 Unit-9 Unit-13
Dr. Kanika Solanki, Dr. Anju Srivastava Dr. Anju Srivastava Prof Sanjeev
Green Chemistry and Dr. Reena Jain, and Dr. Reena Jain, Kumar,
Network Centre, Department of Department of School of Science,
University of Delhi Chemistry, Hindu Chemistry, Hindu IGNOU, New Delhi
College, University College, University
of Delhi of Delhi
Unit-3 Unit-7 Unit-10 Unit-14
Dr. Deepti Rawat Dr. Anju Srivastava Dr. Reena Jain & Prof. Lalita S.
& Dr. Rahul and Dr. Devanshi Dr. Devanshi Kumar,
Singhal, Magoo, Magoo, School of Science,
Green Chemistry Department of Department of IGNOU, New Delhi
Network Centre, Chemistry Hindu Chemistry, Hindu
University of Delhi College, University College, University
of Delhi of Delhi
Unit-4 Unit-11 Unit-15
Dr. Sriparna Dutta, Dr. Anju Srivastava Dr. M. Abdul
Green Chemistry and Dr. Reena Jain, Kareem,
Network Centre, Department of School of Science,
University of Delhi Chemistry, Hindu IGNOU, New Delhi
College, University
of Delhi

COURSE COORDINATOR
Prof. B. Rupini, Environmental Studies, School of Interdisciplinary and
Transdisciplinary Studies, Indira Gandhi National Open University, New Delhi

CONTENT EDITORS
Prof. R. K. Sharma, Department of Chemistry, University of Delhi, New Delhi &
Prof. B. Rupini, School of Interdisciplinary and Transdisciplinary Studies, Indira
Gandhi National Open University, New Delhi

FORMAT EDITOR
Prof.B. Rupini, Environmental Studies, School of Interdisciplinary and
Transdisciplinary Studies, Indira Gandhi National Open University, New Delhi

PRINT PRODUCTION
Mr. Y. N. Sharma Mr. Sudhir Kumar
Assistant Registrar (Publication) Section Officer (Publication)
MPDD, IGNOU MPDD, IGNOU
March, 2021
© Indira Gandhi National Open University, 2021
ISBN: 978-93-90773-59-6
All rights reserved. No part of this work may be reproduced in any form, by mimeograph
or any other means, without permission in writing from the Copyright holder.
Further information on the Indira Gandhi National Open University courses may
be obtained from the University’s office at Maidan Garhi, New Delhi-110 068 or
the official website of IGNOU at [Link].
Printed and published on behalf of Indira Gandhi National Open University, New Delhi
by the Registrar, MPDD, IGNOU
Composed & Printed at: Hi-Tech Graphics, D-4/3, Okhla [Link], Ph.-II, N. D.-20
COURSE INTRODUCTION
Welcome to the MSc (Environmental Science) programme of IGNOU. The
curriculum prepared for this programme is relevant and significant in the present-
day scenario.

This core course is entitled “Environmental Chemistry (MEV-013)”. This course

consists of 4 blocks comprising of 15 Units.

Block 1 deals with Fundamentals of Environmental Chemistry. In this block

we tried to explain the fundamentals of environmental chemistry. The block also
deals with the state of atmosphere in the Earth’s geological reservoirs. It provides
a modern and concise introduction to environmental chemistry principles and the
dynamic nature of environmental systems. It is this limited size that makes the
atmosphere potentially so vulnerable to contamination. It explains how even the
addition of a small amount of material can lead to significant changes in the way
the atmosphere, and how the chemical species exist in equilibrium.

Block 2 deals with Chemistry of Air, Water and Soil. This block explains
chemistry of air, water and soil, their composition. Distribution of chemical species
in air and water, their properties, – Cation exchange capacity, pH, NPK in soils, soil
organic matter, water soluble organic carbon and its significance, soil fertility have
also been explained.

Block 3 deals with Pollution Chemistry. The block explains air, water, soil pollution
and pollution parameters. The emphasis has been made on various organic and
inorganic air pollutants, photochemical smog and their reactions, consequent health
effects are addressed. It also elaborated parameters of water pollution, chemistry of
hazardous substance and wastes.

Block 4 deals with Analytical Techniques in Environmental Chemistry. The block

details on the classical methods of analysis required in environmental chemistry
such as basic analytical techniques like titrimetry, gravimetry, spectrometry,
chromatographic techniques and radio techniques. Finally, the block describes the
application of these techniques in the environmental monitoring.

All these Blocks will provide you with sufficient knowledge about the pollutants,
management, hazards, risk assessment, standards and laws pertaining to the
industrial sector.

INTRODUCTION TO BLOCK 1
This block focuses on the fundamental principles of environmental chemistry. The
block mainly deals with the state of atmosphere in the earth’s geological reservoirs.
It provides a modern and concise introduction to environmental chemistry principles
and the dynamic nature of environmental systems.

Unit 1 deals with the Environmental Chemistry Part 1. In this we discussed

the concept and scope of environmental chemistry, Fundamentals of Elemental
Stoichiometry, Chemical equilibrium, Chemical potential, Chemical Kinetics
- Simple reaction mechanisms, Order and molecularity of chemical reactions;
Chemical reactions, Catalysis, Adsorption. The study of the chemical balance in
natural systems and how the disturbance in this chemical balance happens by the
anthropogenic activities by releasing of chemicals into the environment which
change the natural ecosystem levels.

Unit 2 deals with the Environmental Chemistry Part 2. This unit deals with the
chemical reactions that occur between an acid and base and result into formation of
salt and water are generally called acid- base reactions. These reactions play a critical
role in maintaining balance in our body as well as our environment. It explained how
highly purified water also behaves like a weak electrolyte and shows conductivity
and how it ionizes in hydrogen and hydroxyl ions but hydrogen ions do not exist
in free form. It introduced to modern concept of oxidation and reduction reactions,
by defining them as removal of electrons from a species is termed as oxidation
whereas addition of electrons is called reduction. Almost all the elements and their
compounds have tendency to undergo oxidation-reduction reactions. The unit also
explained other redox chemical reactions of the environment like photosynthesis,
respiration, corrosion that we experience in our day to day life.

Unit 3 deals with the Environmental Chemistry Part 3. This unit discussed about
the concept of solubility, solubility product and solubility of gases governed by
Henry’s law. How carbonate cycle dominates pH control in most of aquatic system
and regulation of various biogeochemical processes in environment. The role of
Chemical speciation in assessing the toxicity associated with different forms of
chemical element and their oxidation state illustrating it with arsenic Sources and
toxicity of heavy metals such as Pb, Cd, As, Hg in the environment Different types of
radionuclides and its effects. Impact of hydrocarbon (saturated and unsaturated) on
environment. Mechanism, functions and classification of lubricants into lubricating
oil, greases and solid lubricants. It concluded by explaining about degradation of
biological waste into biogas.

Unit 4 deals with the Developments in Environmental Chemistry. The unit

describes about the scientific methodologies/solutions showing phenomenal
capability to protect human health and environment and these innovative solutions
have been possible through green chemistry. We have had fantastic accomplishments
as the solutions were at the molecular level since green chemistry preached the
prevention of waste at source rather than treating it up after generation. So, quite
a few of the existing processes were redesigned using the basic tenets of green
chemistry. Progressively, industries also started adopting the path of green synthesis.

INTRODUCTION TO BLOCK 2
This block focuses on the sources and types of pollutants in air, water and soil. This
block explains chemistry of air, water and soil, their composition. Distribution of
chemical species in air and water, their properties, – Cation exchange capacity, pH,
NPK in soils, soil organic matter, water soluble organic carbon and its significance.
This block contains three units.
Unit 1 deals with Atmospheric Chemistry. It focusses on atmosphere, the
gaseous envelope of the earth, nurtures life on earth and protects it from the harsh
environment of the outer space. It serves as a source of oxygen for the sustenance
of life on earth and carbon dioxide for plant’s photosynthesis, provides nitrogen
which is consumed by nitrogen fixing bacteria in producing nitrogen-based
molecules, an essential component of life molecules. The emphasis was given on
various chemical species, including oxides of nitrogen, carbon and sulphur as well
as their particulate matter, present naturally and due to man’s activities undergo
photochemical reactions, and are responsible for several environmental episodes.

Unit 2 deals with the Water Chemistry. This chapter, highlighted the importance of
water, distribution and unique properties of water. Apart from various other factors,
the properties of water also depend on the salt content in it. Thus, the physical
and chemical properties of fresh water differ from those of sea water of. It also
discussed the presence / addition of chemical species, gases, and organic matter in
the water not only alters its physical properties such as colour, odour etc., but also
changes its chemical and biological characteristics.

Unit 3 deals with the Soil Chemistry. In this unit we have elaborated upon the
importance of soil, its nature, chemical properties and composition along with
various processes that are involved in the formation of soil. The study of soil is based
on two approaches, pedology that deals with studying soil as a natural body while
edaphology deals with the study of soil properties with respect to plant production

INTRODUCTION TO BLOCK 3
This block focuses on the Pollution Chemistry. The block explains air, water, soil
pollution and pollution parameters. The emphasis has been made on various organic
and inorganic air pollutants, photochemical smog and their reactions, consequent
health effects are addressed. This block contains four units.

Unit 1 deals with Chemistry of Air Pollution – I. It explained about gaseous

inorganic air pollutants, Carbon monoxide, carbon dioxide, sulphur dioxide,
nitrogen oxides, ozone. You will be interested to know about detailed account of
various effects of air pollution and the chemistry of acid rain.

Unit 2 deals with the Chemistry of Air Pollution Part II. It focusses on the
classification of organic air pollutants and their sources. It described in detail
about the ozone layer depletion and its impact on biosphere. This unit make you to
understand the organic reactions that causing photochemical smog and it concluded
by explaining the effects of photochemical smog in humans

Unit 3 deals with the Parameters of Water Pollution. It explained basic concept
of physico chemical and biological parameters of that are responsible for the
constituents found in water systems. This unit also elaborated about the significance
of chelating agents in aqueous system, describe the properties of colloidal substance
present in water bodies, and the ion exchange method of water management.

Unit 4 deals with the Chemistry of Hazardous Substances and Wastes. It

explained about various physical and chemical hazards and the effects of physical
and chemical hazards. It provided the knowledge of identifying various types
of combustible chemicals and make you to understand the effects of hazardous
substance

INTRODUCTION TO BLOCK 4
This block focuses on the Analytical Techniques in Environmental Chemistry.
In block 3you have studied about chemistry of air, water and soil pollution. This
block deals with the classical method of analysis. This block contains four units.

Unit 1 deals with Basic Analytical Techniques. The unit gives a detailed account
of the various types of analytical techniques available and used by the analysts.
The basic principles involved in the process of analysis will be explained. The unit
also deals with the criteria for evaluating that includes sampling and measurement.
A brief about evaluation of the analytical data would be given along with an
introduction to the concepts of errors, accuracy, precision and significant figures.
The unit ends with the ways of reporting the results of analysis. Optical methods
based on absorption and emission are discussed in this unit.

Unit 2 deals with Spectrophotometry. In this introductory unit on spectrometry

we have discussed about the principle and applications of three important analytical
tools. Two of these, viz., UV-VIS spectrophotometry and IR spectrometry being
techniques based on spectroscopy. We started the unit by defining spectroscopy as
an important domain that concerns study of interaction of electromagnetic radiation
with matter. It is also discussed the difference between spectroscopy, spectrometry
and spectrophotometry before taking up UV-VIS spectrophotometry.

Unit 3 deals with Chromatographic Techniques. This unit mainly focused on

chromatographic techniques which are used for the quantitative and qualitative analysis
in various pharmaceuticals, food and dyes industries. Column chromatography has
various disadvantages including manual setup, time consuming and accuracy. It
explained various advanced techniques like gas liquid chromatography, HPLC Super
critical liquid chromatography and their application which are being employed not
only in industries but also for monitoring the environment, GLC is an advanced
technique compared to conventional chromatography.

Unit 4 deals with Radiochemical Techniques. In this unit we have studied about
the basics of radiochemical techniques like isotopes radioactive decay and various
units used to measure the radioactivity. Apart from that we have discussed about the
terminology that is frequently used while studying radioisotopes and the techniques
associated with it. The concept of carbon dating is highlighted that is widely used by
anthropologist and paleontologist to estimate the age of dead or decaying material
obtained from fossils. At the end of this unit we have discussed about techniques
that are popularly used to measure the radiation, principles and brief working
mechanisms along with their applications with special reference to environment.
 CONTENTS
BLOCK 1 : FUNDAMENTALS OF
ENVIRONMENTAL CHEMISTRY
UNIT 1 : Environmental Chemistry-I 13
UNIT 2 : Environment Chemistry-II 39
UNIT 3 : Environmental Chemistry-III 61
UNIT 4 : Developments In Environmental Chemistry 89

BLOCK 2 : CHEMISTRY OF AIR, WATER AND SOIL

UNIT 5 : Atmospheric Chemistry 121
UNIT 6 : Water Chemistry 157
UNIT 7 : Soil Chemistry 201

BLOCK 3 : POLLUTION CHEMISTRY

UNIT 8 : Chemistry of Air Pollution-I 227
UNIT 9 : Chemistry of Air Pollution-II 259
UNIT 10 : Parameters of Water Pollution 287
UNIT 11 : Chemistry of Hazardous Substances and Wastes 319

BLOCK 4 : ANALYTICAL TECHNIQUES IN

ENVIRONMENTAL CHEMISTRY
UNIT 12 : Basic Analytical Techniques 347
UNIT 13 : Spectrometry 373
UNIT 14 : Chromatography Techniques 397
UNIT 15 : Radiochemical Techniques 423
 BLOCK 1
Fundamentals of
Environmental
Chemistry
UNIT 1 : ENVIRONMENTAL CHEMISTRY-I
Structure
1.1 Introduction
1.2 Objectives
1.3 Concept and Scope of Environmental Chemistry
1.4 Fundamentals of Elemental Stoichiometry
1.5 Chemical Equilibrium
1.5.1 Open and Closed System
1.5.2 Reversible Reactions

1.6 Chemical Potential

1.7 Chemical Kinetics
1.7.1 Kinetics of Reactions of Different Orders

1.8 Simple Reaction Mechanisms

1.9 Order and Molecularity of chemical reactions
1.9.1 Reaction Order
1.9.2 Molecularity of the Reaction

1.10 Chemical Reactions

1.10.1 Hydrolysis
1.10.2 Reduction
[Link] Reductive Dehalogenation
[Link] Nitroaromatic Reduction
[Link] Aromatic Azo Reduction
[Link] N-Nitrosamine Reduction
[Link] Sulfoxide Reduction
[Link] Quinone Reduction
[Link] Reductive Dealkylation
1.10.3 Oxidation

1.11. Catalysis
1.12. Adsorption in Catalysis
1.13 Let Us Sum Up
1.14 Key Words
1.15 References and Suggested Further Readings
1.16 Terminal Questions

1.1 INTRODUCTION
Environmental Chemistry is traditionally outlined as “The study of the origin roots,
reactions, impacts, transport, and fortunes of chemical species, in water, soil, and
air environments, and the human activity influence on these”. So according to this
definition, the environmental chemistry is generally focusing on the pollutants in
the various environments.

However, an updated definition would be “The study of the chemical balance in

natural systems and how the disturbance in this chemical balance happens by the
anthropogenic activities by releasing of chemicals into the environment which change
the natural ecosystem levels”. Environmental chemistry encompasses all branches

13
Fundamentals of of chemistry that are influenced on a regional basis by the loss of stratospheric
Environmental ozone or global warming by urban air pollution or hazardous compounds that
Chemistry
emerge from a chemical waste site, or on a global scale. Our courses concentrate on
gaining a basic understanding of the nature of these chemical processes, so that the
actions of humanity can be measured accurately.

1.2 OBJECTIVES
After studying this unit, you will be able to:

z Understand the concept and scope of environmental chemistry

z Explain chemical equilibrium

z Understand the concept of rate of reaction

z Explain chemical reactions involved in environments

1.3 CONCEPT AND SCOPE OF

ENVIRONMENTAL CHEMISTRY
Environmental chemistry should never be synonymous with “green chemistry.”
The green chemistry aim is to implement chemical processes that use smaller
amounts of harmless chemicals as well as less energy use to reduce their impact on
the environment. While, the goal of environmental chemistry is to understand the
chemical reactions and processes that regulate the environmental systems and how
the introduction of anthropogenic chemicals affects them. This approach allows
environmental chemistry to be constructive instead of reactive.

Formerly, environmental chemistry has had a more reactive approach, to precure

and recognizing problems after the occurrence of a tragedy or a clearly obvious
impact on the environment with loss of life, damage to plants and animals, or
radical changes in environmental conditions – such as the loss of visibility in air
and water systems or the depletion of the stratospheric ozone layer. So, “Almost
everything that happens in world around us could come under the general heading
Environmental Chemistry”. Such as-
• Chemical reactions of all kind occur continuously in the atmosphere, in
oceans, lakes and rivers, in all living things and even underneath the earth’s
crust.
• These reactions take place quite independently of human activities. In order
to understand environmental concerns, we need to have awareness not only
about what products are intentionally released into the atmosphere, but also
of the process under way.
• The normal concepts must be understood so that accurate assumptions can be
made about the potential effects of new but related substances.

14
 Indeed, although convenient to segment topics for study purposes, Barry Environmental
Commoner’s first law of the environment should always keep in mind: Chemistry-I
“Everything is related everything else.”

Some topics that are rather distant from equations and reactions should be discussed.
That is-
• Knowledge in biological, meteorological, oceanographic, and other fields is
equally important to the overall understanding of the environment.
• Conservation of environmental resources along with biological diversity.
• Pollution prevention.
• The social problems associated to growth and environment.
• Design of a renewable energy network that is not polluting.
• Everybody, whatever profession, is impacted by environmental problems
such as global warming, ozone depletion, declining forests, energy resources,
global biodiversity loss, etc.
• It authorizes us to create a secure, balanced and clean natural environment.
• Large-scale heavy metal land pollution by factories. So this can be passed to
waterways and taken up by living beings.
• It also discusses important issues such as safe and fresh clean water,
hygienic living standards, fresh and clean air, soil quality, nutritious food and
development.
• Nutrients draining from farmland into waterways can contribute to algae
blooms and topsoil erosion
• Organometallic compounds
• As new career prospects for environmental protection and sustainability,
sustainable environmental law, business administration, environmental
health, sustainability and environmental engineering are emerging.
• During rainstorms metropolitan drainage of pollutants rinsing off resistant
surfaces (streets, rooftops and parking lots). Typical contaminants include
gasoline, motor oil, and other hydrocarbon, metals, chemicals, and soil.

1.4 FUNDAMENTALS OF ELEMENTAL

STOICHIOMETRY
A chemical reaction written in form of equation provides the idea of both qualitative
and quantitative features. Where qualitative is more a theoretical approach but
quantitative is explicitly a practical approach summarizing basic principle of
chemistry viz. principle of mass conversion to produce the resultant drawn in
product side.

15
Fundamentals of + HO (i)
CH4(g) + O2(g) CO2(g) 2
Environmental
Chemistry
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) (ii)

In equation (i) the reaction describes the formation of CO2 and water from methane
via the combustion process, but the quantity of elements in the reactant side and the
product side are not equal, hence requires to poise the element proportion on the
either side to determine the amount of each compound involved, which is defined
as Stoichiometry.

Stoichiometrically balanced equation can be achieved via trial-and-error approach.

As in the eqn. (i) 1 C-atom approaches on the both side of the equation, but on
the left side, there are 4H atoms and only 2H on the right, and to equalise the
stoichiometry as in eqn. (ii), we have to double the number of water molecules
so that we can get 4H atoms in either sides. Now, while adjusting the elemental
stoichiometry of hydrogen we by-chance changed the atom count for oxygen on
left-hand side (LHS) and right-hand side (RHS) of the arrow. To normalize this
issue, we can multiply the amount of molecular oxygen with 2 to get equal amount
of oxygen atom on both the sides.

The quantitative idea of a balance equation is measured in either moles= Weighed

Mass/ Molecular Weight (unit less quantity); Molarity = moles/volume (mol/L) and
Weight by Volume (W/V): unit mg/L = Molarity (mol/L) × Molecular weight (g/
mol) × 10-3 (mg/g).

1.5 ­­­­­­C HEMICAL EQUILIBRIUM

Chemical equilibrium defined as “A reaction is in chemical equilibrium if
the forward reaction rate step equivalent to the reverse reaction rate step.
a reaction exists in equilibrium, when the concentration of reactants and
products are constant.”

There are several examples of chemical equilibrium

across us. One example is a fizzy cooldrink tin can or
bottle. In the tin-can there is CO2 thawed in the liquid.
There is also CO2 gas in the state between the liquid and
the cap. There is a continual switch of CO2 from liquid to
gas phase, and from gas phase to liquid form. Though, if
we glance at the tin can there does not seem to be any
difference. The system is in equilibrium.

CO2(g) + H2O(l) ⇌ H2CO3(aq)

Without the chemical equilibrium it would not be possible to exist as we know

it. Another sign of equilibrium in our daily lives occurs within our own bodies.
Hemoglobin is a macromolecule which carries oxygen all over our bodies. We

16
wouldn’t survive without it. The hemoglobin must be Environmental
capable of consuming oxygen, while also releasing it, Chemistry-I
and this is managed by adjustments in the steadiness of
this reaction in distinct locations within our bodies.

hemoglobin(aq)+ 4O2(g) ⇌ hemoglobin(O2)4(aq)

Hemoglobin binds with oxygen within the red blood cells

of the lungs. This oxyhemoglobin flows through the blood
stream to cells in the body along with the red blood cells.

1.5.1 Open and Closed System

An open system allows the energy and matter to move within and outside of the
system.

A closed system is one where only energy can travel inside and outside the system.
Matter can’t be obtained from the system or removed from it.

Liquid-gas phase equilibrium

Apparatus

2 beakers, glass sheet, water

Method
Fill two beakers with water in half, and in each case mark the water level.

One beaker covered with a glass sheet.

Leave the beakers for 2 -3 days, watch how the water levels in both beakers change.

Note: You could accelerate this experiment by putting the two beakers over a
Bunsen burner, or by heating the water in direct sunlight.

Discussion
In the open beaker, due to evaporation, liquid water become vapors after heat, and
the water level decreases. A small proportion of gas molecules may condense again,
but condensation is far lower than evaporation, so, the vapors will escape to the
atmosphere. The first beaker was an example of an open device in the liquid-gas
demonstration, as the beaker could be heated or cooled (a variation in energy), and
water vapor (the matter) would evaporate from the beaker.

17
Fundamentals of Evaporation happens in the second beaker too. But at covered condition, the vapour
Environmental reaches the glass cover sheet, where it cools where condenses again to become
Chemistry
liquid water. It returns the water to the beaker. After start of condensation, the rate
at which the water volume falls may begin to decrease. There will be no change in
the water level at any stage, because the rate of evaporation will be equivalent to the
rate of condensation. This represents the closed System. This can be indicated as-

Liquid ⇌ vapour

Observations
Evaporation is the phenomena when a liquified constituent goes from the liquid stage to the
gaseous stage. Condensation is the phenomena when transition of gaseous substance occurs from
gas to liquid phase

You will find that; the water level falls faster because of evaporation in the open
beaker than in the covered beaker. There is an initial drop in the water volume in
the closed beaker, but evaporation tends to stop after a while and the water level in
this covered beaker is higher than that in the open one. The reaction in this example
will go on in both directions. There is a transition of liquid to water vapor in the
forward direction. There may also be a reverse transition, as vapor condenses again
to form liquid.

So, conclusion from above discussion is that, in a closed system it is apparent for
reactions to be reversible and to reach at equilibrium.

1.5.2 Reversible Reactions

There are certain reactions which can occur in two directions. First direction is
forward reaction in which reactants come together to shape the products, while
other direction is reversible direction and vice versa in which the products again
form the reactants. To display this form of reversible reaction, a special double-
headed arrow (⇋) is used.

XY+Z ⇋ X+YZ

So, in reversible reaction-

H2(g)+I2(g) ⇋ 2HI(g) is the forward reaction.

The forward reaction always written left to right from the reaction.

2HI(g)→H2(g)+I2(g) is the reverse reaction.

The reverse reaction always written right to left of the given equation.

18
 Environmental
Chemistry-I

Figure 1.1 The change in rate of forward and reverse reactions in a closed system

In any reaction, the product is formed more slowly as reactant amount decreased.
In a reversible reaction, the reactant is formed rapidly as the product quantity
increases. Ultimately, forward reaction rate (reactants → products) equals to
reverse reaction rate (products → reactants). at this moment, there are still reactants
present, but no more progresses seem to be happening. The reaction is said to be
in chemical equilibrium.

Although no macroscopic changes can always be detected, this doesn’t mean the
reaction has ended. The forward and reverse reactions tend to occur and so there are
still microscopic changes in the system. This state is called dynamic equilibrium.

Reactions which are going to be completed are irreversible. However, in some

reactions the reactants form products (in a forward reaction), and the products can
change back into reactants (in a reverse reaction).

SAQ 1

What is the traditional definition of environmental chemistry?

1.6 CHEMICAL POTENTIAL

In the year 1875 J. Gibbs coined the word “chemical potential”. Chemical potential
is a concept of thermodynamics, common to all, not only in the study of materials
but also in physical, chemical engineering and biology background. It is a key
concept because it is possible to achieve all the thermodynamically impressions of
a substance at a given temperature and pressure from knowledge of its chemical
potential. Chemical potential establishes the stability of materials under the constant
pres­sure and temperature, such as chemical products, and solutions, and their
capacity to react chemically to form new materials, to turn into another physical
states, or to move from one space position to another.

19
Fundamentals of There are few important points related to Chemical Potential. Such as-
Environmental
• Chemical potential energy mainly depends on the strength of the bonds.
Chemistry
Strong bonds have low energy and weak ones have high energy. Large
quantities of heat and/or light energy can be released during strong bonds are
forming. In other terms, chemical potential is correlated with the system’s
electronegativity.
Relation between chemical potential and electronegativity:

μ = -χ - (1)

where, μ = Chemical potential

χ = Electronegativity

• The stored energy in food molecules are preserved in form of

chemical potential energy, that can-do work in the future. When our body
breaks molecules for catabolism, the released energy can be used as work.
But potential energy can’t preserve only in food molecules.
• The value of the chemical potential of a substance depends upon both
temperature and pressure. Additionally, the potential will increase when the
pressure increase.
• Intensive properties are substance independent and depend entirely on
material. Some intensive properties are like chemical potential temperature,
density, refractive index, etc.
• Chemical energy is the capability of a chemicals to undergo
a chemical reaction to turn it into other substances. Examples include food,
batteries, fuel, etc. Breaking or creating of chemical bonds requires energy,
which may be either evolved or absorbed from a chemical system.
• Chemical energy is a type of potential energy; however, kinetic energy is
the energy in motion. Chemical energy deals with the energy stored in the
bonds between atoms.
• Chemical potential increases with the density “n” of particles. Particles flow
from high ‘n’ systems to low ‘n’ systems. The chemical potential of an ideal
gas is always negative.

1.7 CHEMICAL KINETICS

Chemical kinetics is the evaluation of the rates and the mechanisms of chemical
processes. This is of great practical importance. It is also important to know under
what conditions a slow but valuable reaction can be made to proceed rapidly to
produce a desired high yield product. For environmental chemistry, it has great
predictive value.

By observing the kinetics and environmental reaction mechanisms, we can at least

estimate approximately the residence times of both polluting and non-polluting

20
organisms. Our knowledge of various pollutants and atmospheric phenomena such Environmental
as depletion of ozone, acid rain, photochemical smog etc. is focused primarily on Chemistry-I
the study of the kinetics of individual rate constants of thermal and photochemical
reactions.

1.7.1 Kinetics of Reactions of Different Orders

Zero order reactions occur at a constant rate, and the magnitude of the rate does
not change with time. The concentration plot against time is linear, and the slope
of this line is equal to the zero-order rate constant. The differential of rate equation
and its integrated forms is in Eq1.

-d[A]/dt = k = xt -(2)

where k is the zero-order rate constant, and x is the amount reacted in time, t.

For a first order reaction, the rate depends on the first power reactant concentration.
Consider the rate of a first order reaction, defined by Eq-3.

- d[A]/dt = k[A] -(3)

On integrating Eq. 3, we obtain the following forms of rate law for a first order
reaction.
(i) log {[A]o/[A]t}= 2.303kt
(ii) [A]t = [A]o e-kt
(iii) log {a/(a-x)}= 2.303kt -(4)

where [A]o = initial concentration of the reactant, A = a and [A]t = concentration at

time t = (a-x), and concentration of the reactant reacted in t time = x.

The unit of the first order rate constant is s-1. It is independent of the unit of
concentration used.

A second order reaction is one in which the rate depends on (i) the concentration
of one reactant raised to power two or (ii) on the concentrations of two reactants
each raised to the first power as shown in the rate laws (5) and (6).
Rate = k [A]2 -(5)
Rate = k[A][B] -(6)

The Eq.6 changes into Eq. 5, if the initial concentrations of both A and B are taken
equal. So when [A] = [B], Eq. 6 becomes same as Eq. 5: rate = k[A][A] = k[A]2.

On integrating Eq. 5, we get

k = (1/[A]t – 1/[A]o)
k = (1/t)( x/{a(a-x)} -(7)

In Eq. 7, the symbols have same meaning as in case of first order reaction. The unit
of a second order rate constant is [Link]-1.s-1.

21
Fundamentals of In third order reactions, the rate expressions are of the type:
Environmental
Chemistry
Rate = k [A]3
Rate = k[A][B]2 and
Rate = k [A] [B] [C].

Under the condition, [A] = [B] = [C], rate laws (ii) and (iii) will also reduce to rate
law (i). The integrated form of the rate law: rate = k [A]3 is Eq. 8.
k = (1/2t) (1/[A]t2 – 1/[A]o2) -(8)

The atmospheric oxidation of nitrous acid by O2 (2HNO2 + O2 →2HNO3) obeys the

third order rate law: - d[O2]/dt = k [HNO2][O2]2. The unit of third order rate constant
is L2mol-2 s-1.

For Pseudo-order reactions, because of the experimental conditions used, the

order of the chemical reaction tends to be less than the true order. Pseudo-orders
arise when there is a significant excess of one or more reactants relative to others.
For example, the atmospheric reaction: NO + O3→NO2 + O2, obeyed the rate law:
-d[O2]/dt = k [NO] [O3]. -(9)

Under the condition [O3] in large excess (≥10 times) over [NO], up to the end of
reaction there would hardly be any significant change in [O3] and so [O3] would
remain virtually constant. The kinetics will then obey the rate law:
-d[O2]/dt = k1[NO] -(10)
where k1 = k[NO]. So, the apparent order in O3 during the reaction will be zero. The
reaction will, therefore, will follow a first order kinetics in [NO].

1.8 SIMPLE REACTION MECHANISMS

The transformation of organic chemicals most often occurs in several molecular
events referred to as elementary reactions. An elementary reaction is described as a
process in which reacting chemical species pass via a single transition state without
the intervention of an intermediate. A sequence of individual elementary reaction
steps constitutes a reaction mechanism. For example, the overall reaction for the
hydrolysis of a Schiff base is written:

The reaction mechanism for this seemingly simple reaction is in fact quite complex
and is composed of four elementary reactions (Cordes and Jencks, 1963).

22
 Environmental
Chemistry-I

A reaction mechanism is a hypothesis or model that has been conceived from

experimental evidence. As new experimental evidence is obtained, changes in the
proposed reaction mechanism may be required. Chemical kinetics is probably the
most powerful tool for the investigation and development of reaction mechanisms.
The consistency of a reaction mechanism can be verified in the laboratory by
determining the dependence of reaction rates on concentration.

It is useful to classify elementary reactions as per their molecularity and described

as the sum of the exponents that appear for one single elementary reaction in a rate
equation.

1.9 ORDER AND MOLECULARITY OF

CHEMICAL REACTIONS

1.9.1 Reaction Order

The reaction order relating to a chemical species is defined as the order of the
concentration in the differential form of that reactant species of the rate law, and
the order of a reaction is defined as sum of the powers of all the concentration
terms that occur in such a rate law. The experimental kinetics rate law for the
important atmospheric reaction (11) is Eq. 8.
2NO + O2 =2NO2 -(11)
- 𝑑[𝑂2]𝑑𝑡 = k[NO]2[O2] -(12)

The Eq. 12 shows the order with respect to NO is two and with respect to O2 is one,
and the order of reaction to be three (i.e., the aggregate of the orders of NO and O2).

23
Fundamentals of Consider the aqueous phase atmospheric Fe3+-catalyzed oxidation of dissolved
Environmental sulfur dioxide, generally written as sulfur (IV), by O2. It obeys the rate law:
Chemistry
𝑑𝑆(𝐼𝑉)𝑑𝑡 = k[Fe(III)][S(IV)] / [H+]. -(13)

the reaction is first order in each of Fe(III) and S(IV) and of negative first order in
[H+]. So, order can be negative, and fractional also zero.

1.9.2 Molecularity of the Reaction

Reactions typically occur in more than one step, so each reaction is comprised
of a series of elementary reactions. The molecularity is the number of reactant
molecules, ions, radicals or any other chemical species in an elementary step. A
reaction may have two or more steps and then the molecularity of each step would
depend on the number of reactant molecules involved in that step.

Unimolecular Reactions require only one molecule of reactants in the reaction.

Example-The photodissociation of ozone in troposphere.
O3 + hν (290 nm < λ <350 nm) → O + O2 -(14)

Bimolecular Reactions involve two reactant species. These are two-body reactions.
Examples-The formation of the hydroxyl radical, (OH-radical is most import in
atmospheric chemistry).
O(1D) + H2O→ 2OH. -(15)

Termolecular (or Trimolecular) Reactions involve three reactants. The formation

of carbon dioxide, formation of ozone in troposphere are classical examples of this
type.

2CO + O2 → 2CO2 -(16)

SAQ 2
What is the source of electrons in natural reducing environments?

What is the kinetic of chemical reaction in different orders?

24
1.10 CHEMICAL REACTIONS Environmental
Chemistry-I
There are several chemical reactions involved in environments. Among them,
highly involved reactions are given below-

1.10.1 Hydrolysis
Hydrolysis is an example of nucleophilic displacement reactions in which a
nucleophile (an electron-rich species containing an unshared pair of electrons)
attacks an electrophilic atom (an electron-deficient reaction center).

Hydrolytic processes are not limited to the bodies of water such as rivers, streams,
lakes, and oceans usually associated with the term aquatic ecosystems. Hydrolysis
of organic chemicals also can occur in fog water, biological systems, groundwater
systems, and the aqueous microenvironment associated with soils and sediments.

Figure 1.2 Hydrolysis reactions involved in our ecosystems

Hydrolysis is described as a chemical transition in which an organic molecule,

RX, reacts with water, resulting in the forming of a new covalent bond with OH
and a cleavage in the original molecule of the covalent bond with X (the leaving
group). The resulting reaction is that X is substituted by OH~ (Harris, 1981; Mill
and Mabey, 1988)

RX + H2O→ ROH + X-+H+ -(17)

Hydrolysis Kinetics depends on-

1. Specific Acid and Base Catalysis
2. pH Dependence

1.10.2 Reduction
Reducing environments abound in nature (soils and waters, aquatic system, sewage
sludge, hypolimnia of stratified lakes, and oxygen-free areas of eutrophic rivers);

25
Fundamentals of until recently, however, very few investigations of organic reactions characteristic
Environmental of these systems have been undertaken.
Chemistry
The realization that pollutants, which are normally considered persistent in aerobic
environments, may not be nearly as persistent in a reducing environment has
generated a great deal of interest in the behaviour of organic chemicals in anaerobic
environments. The elucidation of reductive transformation pathways may lead to
the development of remediation technologies for the removal of organic pollutants
from contaminated ecosystems.

Reduction, defined as a gain of electrons, occurs when there is a transfer of electrons

from an electron donor “or reductant” to an electron acceptor “or oxidant”. The
oxidant in this case is the organic chemical or pollutant of interest. Reductive
(and oxidative) transformations can be distinguished from other processes (e.g.,
hydrolysis) by determining if a change in the oxidation state of the atoms involved
in the reaction process has occurred.

For example, the transformation of 1,1,2,2-tetrachloroethane can result in the

formation of two reaction products, 1,1,2-trichloroethylene and 1, 2-dichloroethylene.
Although our understanding of reductive transformations in the environment has
progressed to the point that we can identify the types of functional groups that will
be susceptible to reduction in the environmental systems, our limited considerate
of reaction mechanisms for such transformations currently is a barrier to the
prediction of absolute reduction rates, and how reaction rates will vary from one
environmental system to the next.

The noticeable question arises here is, “What is the source of electrons in natural
reducing environments?” The cumulative knowledge in this area suggests that
naturally occurring reductants are not limited to two or three reactive species, as
is the case for hydrolysis, but that a complex array of species is involved, ranging
from chemical or “abiotic” reagents such as sulfide minerals, reduced metals, and
natural organic matter, through extracellular biochemical reductants such as iron
porphyrins, corrinoids, and bacterial transition-metal coenzymes, to biological
systems such as microbial populations. Furthermore, the relationship between these
various reductants in natural systems is most likely quite complex. For example,
chemical species such as reduced metals and sulfide ion may be the direct result of
microbial metabolism.

Reductive transformations are most suitably classified according to the type

of functional group that is reduced. General schemes explaining the reductive
transformations that are known to occur in natural reducing environments are
summarized-

[Link] Reductive Dehalogenation

The reduction of halogenated aliphatic and aromatic compounds chemicals has been
observed in a variety of environmental and laboratory systems, including anaerobic
sediments, soils, anaerobic sewage sludge, groundwaters, aquifer materials,
reduced iron porphyrin systems, bacterial transition-metal coenzymes, and mineral
sulphides, and various chemical reducing agents. Reductive dehalogenation is a

26
detoxification process. The motivation to understand the reaction pathways of Environmental
halogenated chemicals in these types of systems results from their widespread Chemistry-I
contamination of sediments, soils and groundwaters due to their frequent use as
agrochemicals, solvents, and synthetic intermediates.

[Link] Nitroaromatic Reduction

The reduction of nitroaromatics in anaerobic systems has received considerable
attention because of their importance as agrochemicals, munitions, textile dyes,
and dye intermediates. The reaction products resulting from the reduction of
nitroaromatic compounds are aromatic amines. The formation of aromatic amines
occurs through a series of electron transfer reactions with nitroso compounds and
hydroxylamines as even-electron intermediates. Pentachloronitrobenzene (PCNB)
is another example of a nitroaromatic agrochemical that is known to undergo facile
reduction in anaerobic systems. PCNB has been identified as a pollutant in river
water and groundwater. The reduction of trifluralin has been observed in sediments
and flooded soils. Reduction of nitroaromatics can occur through abiotic pathways.
The reduction of TNT and DNT, as well as other polynitroaromatics, has been
studied in some detail in anaerobic microbial enzyme systems. The reduction of
2-bromo-4,6-dinitroaniline, an important intermediate in the preparation of textile
dyes that has been detected in river waters, in anaerobic sediment-water systems.

Figure 1.3 Reduction reactions involved in environment systems

[Link] Aromatic Azo Reduction

Concern over the environmental status of aromatic azo compounds derives largely
from their significance in the textile dye industry. Around 50 % of the dyes
available on the market today are azo compounds. About 12 % of the synthetic fibre
dyes produced each year are expected to be lost in waste streams by production
and recycling processes, and 20 % of such loses would reach the atmosphere by
wastewater treatment system effluents. The reductive cleavage of the azo linkage of
the dyestuffs in aquatic ecosystems represents a possible pathway for the entry of
aromatic amines into these systems. The aromatic amines are considered a hazardous
class of compounds because of their mutagenic and carcinogenic properties.

27
Fundamentals of [Link] N-Nitrosamine Reduction
Environmental The N-nitrosoamines are also a highly studied and important class of chemicals due
Chemistry
to their mutagenic and carcinogenic properties. Much of this work has suggested
that the formation of N-nitrosoamines may occur in crop soils and in foodstuffs that
have been treated with agrochemicals containing secondary nitrogens (e.g, atrazine)
and heavy applications of nitrogen fertilizers. Several N-nitrosoamines also have
important uses in industrial processes. For example, N-nitrosodiphenylamine is
extensively applied in the rubber industry to delay vulcanization.

[Link] Sulfoxide Reduction

The environmental significance of organic sulfoxides results primarily from their
importance as agrochemicals; specifically, the organophosphorus and carbamate
insecticides containing sulfoxide moieties. The reduction of sulfoxides is a two-
electron transfer process that results in the formation of thioethers. Because the
reduction of sulfoxides to thioethers is reversible, reoxidation of the thioether to
the sulfoxide may occur in aerobic environments. Although oxidation of sulfoxides
to sulfones (RSO2R) has been observed in aerobic systems, no evidence exists that
suggests reduction of the sulfone functional group to the sulfoxide moiety will
occur in anaerobic systems. The chemical reduction of sulfones in the laboratory
also is known to be quite difficult.

[Link] Quinone Reduction

Quinones are reduced by a one-electron transfer reaction to the radical. Transfer of
the second electron results in formation of the hydroquinone. Because this reaction
is readily reversible, the equilibrium between the quinone, semiquinone, and
hydroquinone will be dependent on the reduction potential of the system of interest.

[Link] Reductive Dealkylation

Reductive dealkylation is the replacement of an alkyl group on a heteroatom with
hydrogen. Although dealkylation may be considered a relatively minor structural
change for many organic chemicals, the “unmasking” of a reactive functional group,
such as an amino or hydroxyl group, can significantly alter a chemical’s behaviour
in environmental systems. Dealkylation appears to be a common transformation
pathway for agrochemicals with the requisite functionality.

1.10.3 OXIDATION
Oxidation is defined as a loss of electrons. Oxidizing agents gain electrons and
are electrophiles. In organic chemistry, oxidation can either be associated with the
introduction of oxygen into a molecule or the conversion of a molecule to a higher
oxidation state. For example, in Equation 18.

RCH.--> R-CH.-OH ->R-CHO -(18)

The first step in the sequence is the incorporation of oxygen by a formal “oxygen
atom donor,” whereas the second is formally a dehydrogenation, or oxidation of the
carbon atom to a higher formal oxidation state. Almost all oxidations are kinetically
second-order reactions rate is proportionate to the concentrations of both the
oxidizing agent. Ox, and the substrate, A (Equation 19).

28
 -dA/dt = k [Ox] [A] -(19) Environmental
Chemistry-I
For reactions in water, there are few values for the rate constant, k, and few data on
the concentrations of potential oxidants.

In environmental chemistry, there are many sources of oxidants whose importance

is highly variable due to changes in concentration or reactivity as one moves
from one region of the environment to another. A potent oxidant such as the
hydroxyl radical, *OH, that is of critical importance for organic transformations
in the gaseous stage or during combustion, may not be important at all in another
environmental compartment such as the soil. This could either be due to inadequate
production rates for the species or to rapid side reactions that diminish its steady-
state concentration. For the oxidation reaction, Oxygen is present as molecular
oxygen (like autooxidation, superoxides, singlet oxygen, or in the form of ozone),
Hydrogen peroxides decay products (like hydroxyl radical, peroxy radical, alkoxy
and phenoxy radicals), clay and metal oxides, and thermal oxidation in the
environments. These considerations will be addressed as each oxidizing species is
discussed in turn for the remainder of the chapter.

A. Molecular Oxygen
a. Autooxidation
b. Superoxide
c. Singlet oxygen
d. Ozone and Related Compounds: Photochemical Smog

B. Hydrogen peroxide and its decay products

a. H2O2
b. Hydroxyl radical
c. Peroxy radical
d. Alkoxy and Phenoxy radical

C. Surface Reactions
a. Clay
b. Silicon oxides
c. Aluminium oxides
d. Iron oxides
e. Manganese oxides

D. Thermal Oxidations
a. Combustion
b. Incineration

REACTIONS WITH DISINFECTANTS

Water disinfection has been quite successful in practically eliminating many acute
waterborne diseases from the countries where it has been widely practiced, but
its possible roles in the development of chronic health disorders, such as cancer,
have not been fully scrutinized. Potential biohazards arise during drinking water
treatment and disinfecting agents are used for the treatment of industrial wastewaters
to remove undesirable colors, odors, and toxic organic compounds as well as to

29
Fundamentals of reduce the number of potentially harmful microorganisms in the effluent. Because
Environmental of the higher concentrations of organic matter typically found in these waters,
Chemistry
the likelihood of organic-disinfectant reactions occurring at significant rates is
enhanced.

A. Free aqueous chlorine (HOCI)

1. Chlorine in Water
2. Oxidation Reactions
3. Substitution and Addition Reactions
4. Enolizable Carbonyl Compounds: the Haloform Reaction

B. Combined aqueous chlorine (chloramines)

C. Ozone
D. Chlorine dioxide

ENVIRONMENTAL PHOTOCHEMISTRY
The uptake of light energy (quanta) by organic compounds may cause subsequent
photophysical or photochemical events to occur. Photophysical processes include
emission of radiant energy (light or heat), whereas photochemical changes
produce new compounds by transformations that include isomerization, bond
cleavage, rearrangement, or intermolecular chemical reactions. In the environment,
photochemical reactions have been reported to occur in the gas phase (troposphere,
stratosphere), aqueous phase (atmospheric aerosols or droplets, surface waters,
land-water interfaces) and in the solid phase (plant tissue exteriors, soil and mineral
surfaces). All these possibilities need to be considered when fates of organic
compounds in nature are considered. Although in many cases the contribution of
photochemical processes is negligible, in others photolysis is by far the dominant
pathway for loss of a chemical. There are several definitions to understand about
photochemistry. Such as-

Internal conversion, thermal reversion of the excited singlet to the ground state
with the release of heat to surrounding molecules such as the solvent. Because these
two states are of like multiplicity, the transformation is allowed in terms of quantum
theory and is often a very favourable process with a rate constant close to diffusion
control.

Fluorescence, emission of visible or ultraviolet radiation. The emitted photon is

always of a longer wavelength than the absorbed photon. This is also a quantum
mechanically allowed process and usually occurs rapidly.

Intersystem crossing, a quantum-forbidden transition that produces a new excited

state with unpaired electrons, a triplet. These transitions are usually 100 or more
times slower than diffusion control. Triplet states have some degree of diradical
character.

Quantum Yield: The quantum yield, of any photochemically induced process is

defined as that fraction of the species converted to an excited state that undergoes
a fate. Conversion of a triplet to the corresponding ground-state singlet (without
the intervention of a quencher) is another quantum-mechanically forbidden and
usually inefficient ISC process, called phosphorescence when it is accompanied

30
by emission of radiation. Phosphorescence and fluorescence are examples of Environmental
luminescence phenomena. Chemistry-I

Chemical reaction involved. Because of the low instantaneous concentrations of

most excited singlets, bimolecular chemical transformations involving them (such
as reaction with a solvent) are not usually important unless they are kinetically very
fast. Normally, one of the above processes predominates.

The Diels-Alder Reaction

The Diels-Alder reaction, a classic of synthetic organic chemistry, is theoretically a
4 + 2 cycloaddition in which a diene and a “dienophile” with very different electron
abundances combine to form a new six-membered ring. The reaction has great
synthetic usefulness and has attracted many researchers interested in its practical
applications and mechanistic aspects.

O *
* O
*
+ O O
*
O
O
"Diene" "Dienophile"

It is not at all certain whether any Diels-Alder reaction occurs under environmental
conditions, although it has been suggested as a mechanism for the formation of dl-
limonene from polyisoprene in the pyrolysis of waste rubber tire material (Equation
7.2; Pakdel et al., 1991).

CH3 H3C
2 CH3

Berzelius coined the term “catalysis” as early as 1836 to describe different reactions
to decomposition and transformation that involve the catalyst and its environmental
aspects.

1.11 CATALYSIS
Catalysis is the process where
a very little quantity of foreign
material, called a catalyst, raises
a chemical reaction rate without
being absorbed by itself.
Catalysis is environmentally
beneficial and plays a essential
role in the production of new
and existing chemicals. In the
catalysed reactions, less energy
is needed for production, and
higher efficiency is observed in

31
Fundamentals of generating less by-products, co-products and other waste substances. Catalysts can
Environmental be configured to be safe to the environment. Currently, a variety of catalysts are
Chemistry
used in industrial manufacturing, and several have advantageous impacts. The green
synthesis uses catalysts that can be recycled and reused to drive the reaction rather
than the additional reagents used for the original process, which affected waste to
accumulate at each stage. Any catalytic reaction that generates no waste will sustain
the atoms. A catalyst allows the reaction rate to increase, and we can suggest that
the catalyst speed up the chemical reaction. The catalysts are the substances that
expedite a reaction process without being absorbed and undergoing any chemical
changes. The catalysts though participate in the reaction and act by providing a
route of lower activation energy. The catalysts are regenerated at the end of the
reaction. For example, the stratospheric ozone depletion is due to catalytic action
of species such as Cl, NO etc., as in the reactions:

Cl + O3 → ClO + O2
ClO + O → Cl+ O2

In the above cycle, a single Cl can destroy thousands of O3 molecules. Another

important example is the iron-catalyzed oxidation of dissolved SO2 in rainwater.

Another Example: When KClO3 is heated at very high temperatures, the emitted
oxygen gas will escape very gradually, but if MnO2 is mixed up in tiny quantities
then oxygen gas will be produced rapidly even at normal temperatures. In the first
case Cl is serving as a catalyst and in another case MnO2 is serving as a catalyst.

Types of catalysis
There are two types of catalysis:
(i) Homogeneous catalysis: catalyst and reactants are in the same physical
state
(ii) Heterogeneous catalysis: catalyst and reactants both are in different
physical states

Types of catalyst
There are various types of catalyst but usually, there are four types which are
considerable and important-
(i) Positive catalyst: The catalyst which stimulates the rate of reaction
(ii) Negative catalyst: The catalyst which turn off the rate of reaction
(iii) Auto catalyst: If any substance is produced during any chemical reaction,
will work as catalyst for the same chemical reaction.
(iv) Induced catalyst: If any substance is produced during any chemical reaction,
will work as catalyst for some other chemical reaction.

Surface and Aqueous Catalysis

Clay Catalyzed Reactions or rearrangements:
Chemicals play an important role in contributing pollution; hence retrievable and
reusable catalysts are prime demand where clays and zeolites are noteworthy. Clay
were reintroduced in multiple reaction strategies like hydroalkoxylation in ether
formation, esterification etc. Modified clays have also been used in oxidation and

32
formylation reactions. The divergence of clay catalyst was identified when they Environmental
acted superbly with rearrangement reactions starting from pinacole -pinacolone, to Chemistry-I
isomerization, to Claisen rearrangement.

1.12 ADSORPTION IN CATALYSIS

A global environmental issue raises due to the toxic effects of chemicals, and heavy
metal contamination. At varying concentrations these contaminants are found
dissolved in water and wastewater. Because of the large quantities of coloring
required in clothing, paper product, dyes are identified as one of the heavy pollutants
of water bodies. paints and plastics. Potential risks in drinking water caused by
heavy metals and other anions have raised public concern. Generally, the intake of
metal ions and anions causes chronic effects, and humans can experience long-term
exposure to such pollutants without knowing it.

Various physical and chemical approaches have been used to remove contaminants
from polluted water. Adsorption was proposed as cheaper and more effective
than chemical or physical techniques between all these approaches. Due to their
reasonably easy design, activity, cost efficiency and energy savings these are
favoured over other methods. Many components were effectively used in means
of staining of water contaminants, such as microspheres, clays, composites
clay-alginate, activated carbon chitosan, metal oxides, etc. The main classes of
adsorbents include mesoporous silica, activated charcoal, bagasse, zeolite, metal
oxides, alumina, carbon nanotubes, clay, activated carbon, and polymeric resin, etc.

These catalysts demonstrate the value of adsorption as catalytic properties. This

type of catalysis is ecofriendly as it escalates the reaction rate without being utilized
by itself and therefore the chemical and energy industries depend heavily on
catalysis as a result. The popular Haber-Bosch method for ammonia generation uses
metal-based catalyst for adsorption of Nitrogen and hydrogen gas and synthesis of
ammonia industrially.

Figure 1.4 Different types of adsorbents

Classification of Adsorbent
Adsorbent can be categorized into three groups:

33
Fundamentals of (a) Nonpolar solids:
Environmental Most of the molecular solids are non-polar. Such non-polar molecular solids do not
Chemistry
dissolve in water. Where the adsorption is mainly physical e.g., activated charcoal.

(b) Polar solids:

These materials adsorb both polar and nonpolar molecules. However, they show
preference with polar molecules. When the adsorption is chemical e.g. silica and
aluminium oxides.

(c) Chemical Adsorbing surfaces which adsorb the molecules and subsequently
release them after reaction, which may be either show catalytic approach by leaving
the surface unchanged, or non-catalytic by replacing the surface atoms.

Adsorbent can also be classified as conventional or non-conventional adsorbents.

Activated carbon, polymeric carbon, aluminous, silica gel, bauxite etc categorized as
Convention adsorbents, while Non-conventional adsorbents include, hardwood,
lignite, fly-ash, sawdust etc.

Mechanism of Adsorption
Adsorption is a simplistic process in which adsorptive molecules (gas or liquid)
bind to a solid surface. In fact, adsorption is implemented as an operation in a
column filled with porous sorbents, whether in batch or continuous mode. In these
cases, the consequences of mass transfer are inevitable. The three common steps
include: Film diffusion (external diffusion), Pore diffusion [intraparticle diffusion
(IPD)] and Surface reaction.

Factors affecting adsorption

Some of the significant variable affecting adsorption are nature of the adsorbate
and adsorbent, diffusion through the passage with in the catalyst particles (either
macropores or micropores), surface area of adsorbent, Activation of adsorbent, rate
of air flow, vapour concentration, humidity, temperature, degree of regeneration,
contact time, processing method adopted etc. The slowest of these steps will
determine the rate for the whole process and is called rate determining step.

Equilibrium Adsorption Isotherms

The equilibrium properties of a gas-solid system are defined by a curve of the
concentration of adsorbed gas on the solid at constant temperature as a function
of the equilibrium partial pressure of the gas. Such a curve is considered as an
adsorption isotherm. Table shows the most well-known Isotherms which indicate
the adsorption heat dependence on surface coverage implied by increasing isotherm.
There are several more isotherms available according to individual requirements.

Isotherm Isotherm equation Uses

Henry’s One-Parameter Isotherm

Simplest adsorption isotherm

34
 Langmuir Homogeneous binding sites (same Environmental
Chemistry-I
affinities), alike sorption energies, and no
interactions between adsorbed species.
RL is separation aspect which decides
whether the adsorption is un-favorable
when its value is >1, linear (=1),
favourable (0 < RL < 1), and irreversible
(RL = 0)
Freundlich Heterogonous surfaces (varied affinities),
1/n (adsorption intensity) that specifies
the energy and the heterogeneity of the
adsorbent sites (1/n < 1= Langmuir, 1/n >
1 cooperative adsorption
Temkin Effective only for an intermediate range
of adsorbate concentrations and gives
information for adsorbate/adsorbate
interactions, where b (J/mol) is Temkin
isotherm constant kT (L/g)—Temkin
isotherm equilibrium binding constant
F l o r y - Account for the characteristic surface
Huggins coverage of the adsorbed adsorbate on
the adsorbent and the spontaneity of the
process using ΔGo value obtained from
KFH, where, n is number of adsorbates
occupying adsorption sites, and KFH is
Flory-Huggins equilibrium constant
([Link]−1)
Elovich Define the kinetics of chemisorption
and Multilayer adsorption, where KE is
equilibrium constant ([Link]−1) and qm is
maximum adsorption capacity (mg.g−1)

SAQ- 3
What is the difference between adsorption and absorption? Explain with example?

Explain the Catalytic cycle with figure.

35
Fundamentals of 1.13 LET US SUM UP
Environmental
Chemistry
Environmental chemistry focuses on the nature and effect of chemicals in
groundwater, surface water and soil. We will learn in the Environmental Chemistry
how chemicals-generally pollutants-pass through the environment. We are
also studying the impacts of these pollutants on habitats, animals and human
health. Environmental chemistry advises on the movement and effect of soil
and groundwater pollutants, evaluate long-term threats to ecological and human
health, apply for environmental permits to carry out corrective strategies, identify
polluted soils as hazardous waste and control their disposal, and monitor on-site
remediation. What type of reactions are happening during chemical processes and
its effect on environment? After reading contents of this unit, we will observe how
chemical reactions are involved in our surroundings. What type of reaction order
and molecularity, chemical kinetics and potential are involved? Reactions are going
on one direction or reversible.

1.14 KEY WORDS

Anthropogenic Pollution

It is defined as the introduction of harmful substances or the creation of harmful

impacts in the environment that are directly tied to man’s activities, including:
agriculture, industry, and energy production and use.

Acid rain
Acid rain, or acid deposition, is a specific term that encompasses any type of
precipitation of acidic elements, including rain, snow, fog, hail or even acidic
particles, such as sulphuric or nitric acid dropping from the atmosphere onto the
earth in wet or dry forms.

Ozone layer depletion

Ozone shield, carries high concentration of trioxygen, in Earth’s stratosphere is
a special region that absorbs most of the UV radiation coming from Sun. Ozone
depletion, steady diminishing of Earth’s ozone layer in the stratosphere caused by
the release of chemical gaseous chlorine or bromine from industry and other human
activities.

Global warming
Global warming is a human caused phenomenon, in which average temperature of
Earth climate increases. Carbon dioxide plays a vital role in elevating greenhouse
gas concentration promoting severe illness to climate in form of global warming.

Nuclear explosion
Anything excess is a poison, the intense and rapid release of energy from a high-
speed nuclear reaction or explosion more precisely cause a huge damage to the life.
Apart from heat energy nuclear explosions can introduce radioactive particles in
the stratosphere causing global fallout.

36
1.15 REFERENCES AND SUGGESTED Environmental
Chemistry-I
FURTHER READINGS
1. Environmental chemistry Tenth edition. / Manahan, Stanley E | New York: CRC
Press, [2017]; ISBN 9781498776936. (785 pages)

2. Reaction mechanisms in environmental organic chemistry, Richard A. Larson

and Eric J. Weber [1994]; ISBN 0-87371-258-7, (448 pages)

1.16 TERMINAL QUESTIONS

1. Define the following
a. Chemical equilibrium
b. Dynamic equilibrium
c. Chemical potential
d. Order of reaction

2. What is the difference between Green chemistry and Environmental

Chemistry?
3. Explain open and closed systems in equilibrium with suitable examples?
4. Explain the following in detail.
a. First order reaction b. pseudo order reaction
5. Explain the mechanism of adsorption?
6. Explain the catalytic cycle in detail?

37
UNIT 2 : ENVIRONMENT CHEMISTRY-II
Structure
2.0 Introduction
2.1 Objectives
2.2 Acid-base Reactions
2.3 Ionic product of Water
2.4 pH and pOH
2.5 Hydrolysis
2.6 Buffer solutions
2.7 Common ion Effect
2.8 Oxidation and Reduction
2.9 Let Us Sum Up
2.10 Glossary
2.11 Suggested Readings
2.12 Terminal Questions

2.0 INTRODUCTION
Most of the chemical reactions take place in solutions, thus the study of such solutions
forms an important branch of chemical sciences especially physical chemistry. If
the solubility of solutes is analyzed in different solvents, we observe that the solutes
follow the common principle of solubility which is ‘like dissolves like’ means polar
solvents dissolve polar solutes rapidly and to a great extent, while non-polar solutes
are more soluble in non-polar solvents such as NaCl quickly dissolves in water
while it remains insoluble in CCl4 as water possesses high dielectric constant and
polar properties that makes it suitable for most of ionic substances like sodium
chloride. Depending upon the relative values of conductivities in aqueous solutions,
the solutes may be categorized in following classes: (i) Strong electrolyte: highly
conducting, (ii) Weak electrolyte: mildly conducting and (iii) Non electrolyte:
non conducting but this classification also has a serious limitation i.e. a particular
electrolyte might behave differently when it is dissolved in some other solvents. For
instance:- if we dissolve acetic acid and sodium chloride in ammonia, both exhibit
strong electrolytic behavior, whereas acetic acid ionizes slightly in water therefore,
another classification is given which majorly focuses on the characteristics of solute
rather than solvent. According to it, solutes can be classified as true and potential
electrolytes. True electrolyte shows conductivity even in the pure liquid state while
potential electrolyte does not display conductive behavior in pure liquid state but
on dissolution in an ionic solvent it may provide conducting solution. When a weak
electrolyte is dissolved in a polar solvent, equilibrium is established between its
ions and unionized molecules and this phenomenon is known as ionic equilibrium.
In order to get more information regarding this, we are going to discuss some
important concepts in detail.

39
Fundamentals of 2.1 OBJECTIVES
Environmental
Chemistry
After studing this unit you will be able to
• Understand the concepts of acid-base and their reactions,
• Understand the ionization of water,
• Describe the theory of hydrolysis with examples of salt hydrolysis
• Discuss the origin of pH scale and pOH
• Define buffer solutions
• Define common ion effect and
• Explain fundamentals of oxidation- reduction with examples of redox reactions.

2.2 ACID-BASE REACTIONS

Acid
Acids are the substances that undergo dissociation when dissolved in water and
form hydrogen ions as the only positive ion species but in aqueous solutions the
hydrogen ions (H+) or protons do not exist in free state. Every hydrogen ion readily
combines with one water molecule to form hydronium ion (H3O+).

HCl + H2O H3O+ + Cl

HNO3 + H2O H3O+ + NO3-

The driving force for this ionization is the great affinity of free hydrogen ions
to combine with water molecules to form hydronium ions. The above two acids
dissociate completely in aqueous solutions. Hydrochloric and nitric acids are the
examples of monoprotic acids i.e. they liberate only one proton or hydrogen ion in
water whereas sulphuric and phosphoric acids have two and three hydrogen atoms
therefore they are called as diprotic and triprotic acids respectively.

H2SO4 + H2O H3O+ + HSO4-

HSO4- + H2O ⇌ H3O+ + SO42-

Ionization of phosphoric acid

H3PO4 + H2O ⇌ H3O+ + H2PO4- Primary ionization

H2PO4- + H2O ⇌ H3O+ + HPO42- Secondary ionization

HPO42- + H2O ⇌ H3O+ + PO43- Tertiary ionization

These ionization do not always occur to same extent. They follow the order of
primary ionization > secondary > > tertiary.

40
Some acids like carbonic acid, boric acid nitrous acid, ethanoic acid etc. do not Environment
ionize completely. Their extent of dissociation is comparatively less hence, known Chemistry - II
as weak acids while those which dissociate almost completely are called strong
acids such as hydrochloric, hydrobromic, hydroiodic, nitric and perchloric acid.

Base
Originally, base is a substance which undergoes dissociation when dissolved in
water and forms hydroxide ions (OH-) as only negative ion species. Some bases
like hydroxides of sodium potassium and certain bivalent metals dissociate almost
completely in aqueous solution therefore, they are called strong bases, whereas
those which produce small concentration of hydroxide in aqueous solution are
termed as weak bases such as ammonia NH3.

NaOH + H2O Na+ + OH-

Ba(OH)2 + H2O Ba2+ + 2 OH- Strong Base

NH3 + H2O ⇌ NH4+ + OH- Weak Base

The Bronsted-Lowry theory of acid and bases

A general theory of acids and bases was proposed in 1923 independently by J. N.
Bronsted and T. M. Lowry that defines the concept of acid and base in all solvents.
As described by these two scientists, a species that has the tendency to lose proton
is called acid while bases possess characteristic feature to accept proton.

Acid = proton + conjugate base

A ⇌ H+ + B

According to this theory, a conjugate base is formed after donation of proton from
a Bronsted-Lowry acid. Similarly, a conjugate acid is produced when a Bronsted
–Lowry base receives a proton.

Figure 2.1: Representation of conjugate acid-base pair

41
Fundamentals of It is also mentioned that strength of a conjugate base varies inversely as the strength
Environmental of its respective acid. Further, the properties of an acid or base are significantly
Chemistry
influenced by the solvent used.

Lewis Concept
In 1938, another definition of acids and bases was introduced by G.N. Lewis. Based
on his investigations, he revealed that both acids and bases are capable of forming
a covalent bond. During this phenomenon, an acid accepts a pair of electrons,
whereas a base donates it. For example: BF3, AlCl3, SO2 etc. have ability to attract
an electron pair therefore termed as Lewis acids or electron acceptors. On the other
hand, NH3, pyridine etc. possess a lone pair of electrons that can be donated easily
hence called as Lewis base or electron donor.

Acid Base Reactions

Acid and base reaction is a type of chemical reaction wherein acid and base reacts
together in stoichiometric ratio to neutralize each other as acid counteracts the base
and vice versa. Therefore, this type of reactions is generally called as neutralization
reaction.

In the above reaction, a proton is transferred to a water molecule to form hydronium

ion H3O+ that further reacts with hydroxide ion OH- to produce water and the
positive portion of base combines with negative part of acid to yield salt.
H3O+ (aq) + OH- (aq) 2H2O (l)

These reactions can also be classified in the category of double displacement

reactions. In the case of polyprotic acid, all the acidic hydrogen atoms of acid are
replaced by the base if it is added in sufficient amount.

H2SO4(aq) + NaOH(aq) Na2SO4(aq) + 2H2O(l)

H3PO4(aq) + NaOH(aq) Na3PO4(aq) + 3H2O(l)

Similarly, reaction of a diacidic base with monobasic acid

Ba(OH)2(aq) + HCl(aq) BaCl2(aq) + 2H2O(l)

As we know when an acid reacts with a base they neutralize each other and during
this process some amount of heat is liberated that depends on the nature of acid,
base and their number of gram equivalents. The energy released when one gram

42
equivalent of acid reacts with one gram equivalent of base is known as enthalpy or Environment
heat of neutralization. Chemistry - II

In the cases of weak acid- strong base, weak acid- weak base and strong acid-weak
base, heat of neutralization will be lesser than 13.7 Kcal/mole as weak acids and
bases do not dissociate completely. Some examples of weak acid-base reactions are
given below:

Acid-Base equilibria in water

To understand acid-base equilibrium in water, dissociation of a weak electrolyte i.e.
ethanoic acid in dilute aqueous solution is given below:
CH3COOH + H2O ⇌ H3O+ + CH3COO-

In conventional manner the above can be written as:

CH3COOH ⇌ H+ + CH3COO-

Here, H+ represents the hydrated hydrogen ion. On applying law of mass action:

Here, K denotes equilibrium constant at a given temperature. It is also called

ionization constant or dissociation constant of acid that can also be symbolized by
Ka in aqueous solutions.

If V liters of a solution contain 1 mole of weak electrolyte (V= 1/c, where c indicates
the concentration in mol L-1) and suppose α represents degree of ionization at
equilibrium, then α will be the amount of each ions and (1- α) will be the amount
of unionized electrolyte. In terms of concentration, (1- α)/V and α/V show the
concentration of unionized ethanoic acid and each of ions respectively. On putting
these values in equilibrium equation:

This expression represents Ostwald’s dilution law.

43
Fundamentals of Similarly, for polyprotic acids dissociation constant can be given for each ionization
Environmental as follows:
Chemistry
H2A ⇌ H+ + HA-
HA- ⇌ H+ + A2-

If acid is weak electrolyte then applying law of mass action on the above equations:
K1 = [H+] [HA-]/[ H2A]
K2 = [H+] [A2-]/[ HA-]
Likewise, consider the dissociation of a weak base in aqueous media
NH3 + H2O ⇌ NH4+ + OH-
On applying law of mass action

Here, Kb is dissociation constant of a particular base that depends on temperature,

nature of solvent.

Relative strength of weak acids and weak bases

According to Ostwald dilution law, dissociation constant of a weak acid

If degree of dissociation (α) is very less then we can neglect α in comparison to

unity so finally we get
Ka = α2 c or Ka = α2/V

If dissociation constants of two different weak acids are Ka1 and Ka2 at a same
concentration c then

Here, α1 and α2 represent the respective degree of dissociation of two acids

Similar expression can be used for weak bases with the substitution of dissociation
constant of acid with ionization constant of base i.e.

In words it can be stated as, for any two slightly ionized electrolytes (weak acid or
base) at equal dilution, the degrees of dissociation are directly proportional to the
square roots of their dissociation constants.

Significance of Acid-Base reactions

Neutralization or acid-base reactions play a critical role in maintaining the necessary
balance in our ecosystem as well as in our body. These reactions are especially very

44
useful in pharmaceutical, food and fertilizers manufacturing industries. Our day to Environment
day life is governed by these reactions such as digestion of food in our stomach. Chemistry - II
Similarly, use of an antacid to cure heartburn is also an example of neutralization
reaction wherein stomach acid is neutralized either by Mg(OH)2 or by Al(OH)3 that
are present in antacid. Besides, to resolve the problem of acidic water and soil in
mining land some basic oxides or carbonates such as CaO, CaCO3 or MgCO3 are
added to reduce their acidity.

SAQ 1

What are the fundamental theories to explain acidity and alkalinity of the substances
and how they are different from one another?

2.3 IONIC PRODUCT OF WATER

Dissociation of water
In 1894, Kohlraush and Heyweiller observed that even highly purified water
behaves like a very weak electrolyte and possesses definite conductivity. It ionizes
in the following manner:
H2O + H2O ⇌ H3O+ + OH-
To simplify, it can be written as:
H2O ⇌ H+ + OH-
Applying law of mass action to the above equation on a particular temperature

Here, Ki represents the ionization constant of water. As we know that degree

of dissociation of water is very less, so the concentration of undissociated
water molecules remain almost constant during this ionization process and this
concentration can be combined with Ki (ionization constant of water) to give a new
constant (Kw) that is known as ionic product of water.
Kw = Ki [H2O] = [H+][ OH-]

In pure water, concentration of hydrogen ion [H+] will be equal to the concentration
hydroxyl ion [OH-] i.e. 1 x 10-7 M at 25 ºC.
Kw = (1.0 x 10-7) (1.0 x 10-7) [H+] = [OH-] = 1.0 x 10-7 M
Kw = 1.0 x 10-14

45
Fundamentals of The ionic product of water primarily depends upon temperature; it increases with
Environmental increase in temperature.
Chemistry
[H+] = Kw/[OH-] and [OH-] = Kw/[H+]

Acidic or alkaline nature of a solution relies upon the relative concentration of

hydrogen ions to that of hydroxyl ions. When the concentration of hydrogen ions
is exactly equal to the concentration of hydroxyl ions, the solution is called neutral
solution. At ordinary temperatures, if the concentration of hydrogen ions [H+] is
greater than 10-7 mol L-1, solution will show acidic behavior and if less than 10-7 mol
L-1, alkaline nature will be exhibited. Similarly, if concentration of hydroxyl ions
is greater than 10-7 mol L-1, solution will be basic and if less than 10-7 mol L-1 acidic
properties will be displayed.
Neutral solution: [H+] = [OH-] = 10-7
Acidic solution: [H+] > [OH-] or [H+] >10-7
Alkaline Solution: [H+] < [OH-] or [OH-] >10-7

SAQ 2

What do you understand by ionic product of water and explain its significance?

2.4 pH and pOH

While dealing with dilute solutions, it is very difficult to represent the concentrations
of hydrogen and hydroxide ions in terms of moles per liter (mol L-1). Therefore; a
very convenient method was introduced by S. P. L. Sorensen in 1909. He proposed
a logarithmic scale to express hydrogen ion concentration as given below:
pH = log10 1/[H+] = - log10 [H+] or [H+] = 10-pH

Thus pH is the logarithm of hydrogen ions with negative sign. In this method,
numbers between 0 to 14 are used to denote all the possible states of acidity and
alkalinity from 1 mol L-1 hydrogen ions to 1 mol L-1 hydroxide ions.

As we know in neutral solution

[H+] = [OH-] = 10-7 therefore, pH = 7
For acidic solution pH < 7 and [H+] > 10-7 mol L-1
For alkaline solution pH > 7 and [H+] < 10-7 mol L-1

The concentration of hydroxyl ions can be expressed in similar manner:

pOH = 1/ log10 [OH-] = - log10 [OH-] or [OH-] = 10-pOH

46
As we know Environment
Chemistry - II
[H+][OH-] = Kw = 10-14

Taking logs of both sides

log [H+] + log [OH-] = log Kw = -14
then pH + pOH = pKw = 14

Figure 2.2 The pH scale

In quantitative analysis, small quantities are usually expressed in logarithmic or

exponential form. Dissociation constants, ionic concentrations and solubility
products may also be represented in this form for convenience.

SAQ 3

How pH and pOH are related to each other?

2.5 HYDROLYSIS
The term hydrolysis is derived from ancient Greek words (Hydro-water+ Lysis-
break down) and it means dissolution or destruction by water. Hydrolysis is a type
of chemical reaction in which chemical bonds of a substance are decomposed by
addition of water molecules. This phenomenon plays a quite significant role in
biological systems as well as in chemical sciences. The process of hydrolysis is
used to break down a variety of polymers such as carbohydrates, proteins, fats,
nucleic acids etc. These decomposition reactions are usually catalyzed by acid, base
or enzymes (hydrolases). Hydrolysis of salts is one of the most common examples
of such reactions wherein the interaction between cations or anions of a salt and
water takes place. During this process, a salt breaks down into its ions completely
or partially depending upon its solubility factor and dissolution of salt into water
may alter pH of solution that primarily relies upon its constituent ions. According

47
Fundamentals of to the nature of their fragmentary ions, these salts are generally classified into four
Environmental major categories:
Chemistry
(i) Salts of strong acids and strong bases, e.g. NaCl
(ii) Salts of weak acids and strong bases, e.g. CH3COONa
(iii) Salts of strong acids and weak bases, e.g. NH4Cl
(iv)Salts of weak acids and weak bases, e.g. CH3COONH4

Dissolution of salts of strong acids and strong bases in water results in neutral
solution as their cations and anions have no tendency to combine with hydrogen
and hydroxyl ions of water therefore, the equilibrium hydrogen ions and hydroxyl
ions remains undisturbed that maintains the neutrality of the solution whereas the
salts of other three groups may interact with the ions of water and change their
equilibrium and ultimately the pH of solution.

Degree of hydrolysis
Case 1: Salts of a weak acid and a strong base

The salts of this class give alkaline solutions on hydrolysis as the anionic part
of a weak acid interacts with hydrogen ions of water to form weak acid which
dissociates feebly. In order to maintain the constant value of ionic product (Kw),
water further ionizes but hydrogen ions are again taken up by the negative charge
bearing species of salt. Thus, the decrement in concentration of hydrogen ions with
respect to hydroxyl ions is observed and due to high concentration of hydroxyl
ions, solution becomes alkaline. Consider the hydrolysis of CH3COONa:
CH3COO- + Na+ + H2O ⇌ CH3COOH + Na++ OH-
As Na ions are present on the both side of equation therefore, they may be left out
+

and the equation can be written in following manner:

On applying law of mass action and considering the concentration of water as

constant because it is present in excess, we obtain

Here, Kh is called hydrolysis constant. Since generated acid is weak in nature

hence, it ionizes slightly while free strong base and unhydrolysed salt dissociate
completely.

‘The fraction of each mole of anion (CH3COO-) that is hydrolysed at equilibrium is

known as degree of hydrolysis.”

Assume 1 mole of salt is dissolved V litre of solution and x represents the degree of
hydrolysis then the concentrations in mol L-1 are
[CH3COOH] = [OH-] = x/V and [CH3COO-] = (1 - x)/V

Putting these values in the above equation

48
 Environment
Chemistry - II

It is evident from the above expression on increasing the dilution, the degree of
hydrolysis x is also increased.

With hydrolytic equilibrium (CH3COO- + H2O ⇌ CH3COOH + OH-),

two equilibria must be coexist i.e.
H2O ⇌ H+ + OH- and CH3COOH ⇌ H+ + CH3COO-
We know that

But

Thus, Kh = Kw / Ka or pKh = pKw / pKa

The above expression shows the relationship between hydrolysis constant, ionic
product of water and dissociation constant of water. As we know variation in
temperature affects Ka slightly but Kw is significantly dependent on temperature
therefore, the degree of hydrolysis will be majorly governed by temperature
changes.

As a result of hydrolysis, the equal amounts of acid (CH3COOH) and base (OH-)
will be produced. If the concentration of salt dissolved in water is c mol L-1 then

The above equation gives hydrogen ion concentration of hydrolyzed salt (weak
acid and strong base) solution.

Case 2: Salts of a strong acid and a weak base

The salts of this category produce acidic solution on hydrolysis as cationic part of
salt participates actively in hydrolysis and forms weak base which ionizes poorly
therefore, concentration of hydrogen ions increases and solution exhibits acidic
nature. Consider the dissociation of ammonium chloride:
NH4+ + Cl- + H2O ⇌ NH4OH + Cl- + H+
Neglecting Cl- ions as they are conjugate base of strong acid thus will not take part
actively in hydrolysis

49
Fundamentals of Applying law of mass action (Similar to case 1)
Environmental
Chemistry

Here, Kb represents dissociation constant of base and as we know the concentrations

of formed base and acid are equal therefore, substituting values in the above equation

The above expression gives pH of hydrolysed salt of strong acid and weak base.

Case 3: Salts of a weak acid and weak base

The salts of this class may give acidic or alkaline or neutral solution on hydrolysis
depending upon the strengths of their constituent acid and base e.g. ammonium
acetate

In this case both cation and anion of salt interact with hydrogen and hydroxyl ions
of water i.e. hydrolysed.

Applying law of mass action

We know that

The individual concentrations can be represented as given below if 1 mol salt is

dissolved in V L of solution and x denotes degree of hydrolysis

[CH3COOH] = [NH4OH] = x / V and [CH3COO-] = [NH4+] = (1 – x /V )

Substituting the values

50
 Environment
Chemistry - II

It is evident from the above expression that degree of hydrolysis does not depend
on the concentration of solution thus the pH of solution.

The concentration of hydrogen ions of hydrolysed salt solution can be calculated

as given below

It is clear from the above equation if Ka = Kb then solution will be neutral and if Ka
> Kb and Ka < Kb then the solution will be acidic and alkaline respectively.

SAQ 4

What is degree of hydrolysis? Derive the expression for salts of weak acid and
strong base.

2.6 BUFFER SOLUTIONS

A particular pH is required for the proper functioning of various chemical,
pharmaceutical, biological and biotechnological processes; therefore we need
to have such solutions whose pH does not change appreciably even when small
amounts of strong acid or strong base are added to them. These solutions are called
buffer solutions. “Buffers are the chemical substances that resist changes in the
concentration of hydrogen or hydroxyl ions and their resistance to change in pH
upon introduction of small quantities of acid or alkali is known as buffer action.”

Generally buffer solutions are comprised of a mixture of weak acid and its salt
with strong base (usually sodium or potassium) or they can be a combination of
weak base and its salt. In other words, buffers are the mixture of a weak acid and
its conjugate base or weak base and its conjugate acid. The buffers have ability to
reverse both acidity and alkalinity to some extent.

51
Fundamentals of Case 1: A mixture of weak acid and its salt
Environmental A very common example of this class is a mixture acetic acid and its sodium salt.
Chemistry
This buffer solution contains CH3COOH molecules, CH3COO- and Na+ ions as
acetic acid dissociates feebly whereas sodium acetate ionizes almost completely.
The buffer action of acetic acid- sodium acetate is given below:

On the addition of strong acid to this buffer solution, the introduced hydrogen ions
will be immediately consumed by acetate ions to form acetic acid that dissociates
in very slight amount.
H+ + CH3COO- →CH3COOH

Thus the neutralization of added hydrogen ions takes place. Contrary to this when a
strong base is introduced in to the solution, the hydroxyl ions are taken up by acetic
acid to maintain the neutrality.
OH- + CH3COOH →CH3COO- + H2O

Case 2: A mixture of weak base and its salt

The most common example of this category is an equimolar mixture of aqueous

solutions ammonium hydroxide and ammonium chloride. The buffer solution
contains unionized NH4OH, NH4+ and Cl- ions. Let us consider the buffer action of
this mixture:

When acid is added to this solution, the increased concentration of hydrogen ions
are neutralized by ammonium hydroxide
NH4OH + H+ →NH4+ + H2O

On addition of strong base, the neutralization of excess amount of hydroxyl ions is

attained by ammonium ions

Calculation for pH of buffer

The hydrogen ion concentration of weak acid and its salt can be expressed by
following equation:

According to law of mass action [H+] = Ka [acid]/[salt]

The above equation is called as Henderson-Hasselbalch equation that gives pH of

buffer solution which is a mixture of weak acid and it’s conjugate.

Similar expression can be given for weak base and its salt

52
and pH can be calculated by following relationship Environment
Chemistry - II
pH = pKw - pOH or pH = 14 - pOH

Buffer Capacity: The capacity of a buffer to withstand the change in pH is known

as buffer capacity. A buffer solution that contains equimolar concentrations of acid
or base and its salt exhibits the maximum buffer capacity.

SAQ 5:

What are buffers and how can we calculate the pH of buffer solution containing a
weak base and its conjugate acid?

2.7 COMMON ION EFFECT

If a strong electrolyte is introduced to a solution of feebly dissociated electrolyte
that has at least an ion common with strong electrolyte, suppression in the ionization
of weak electrolyte is observed and this phenomenon is known as common ion
effect. E.g. reduction in dissociation of acetic acid (weak electrolyte) on addition of
sodium acetate (strong electrolyte) in its solution
CH3COOH ⇌ CH3COO- + H+
slightly dissociated
CH3COONa →CH3COO- + Na+
completely dissociated

Introduction of sodium acetate to the solution of acetic acid increases concentration

of CH3COO- in the medium and to overcome the addition of salt equilibrium shifts
to backward direction hence, the degree of dissociation of CH3COOH decreases.

In the same manner, ionization of weak base (NH4OH) is suppressed in the presence
of NH4Cl (salt) or NaOH (strong base) as ammonium chloride supplies NH4+ ions,
while NaOH furnishes OH- ions and both ions cause reduction in the dissociation
of ammonium hydroxide.

Common ion effect has prime importance in qualitative analysis wherein it has
been used in salt as well as gravimetric analysis. The other applications of this
effect include softening of water, purification of common salt and salting out of
soap.

53
Fundamentals of SAQ 6
Environmental
Chemistry Explain common ion effect with example and its applications.

2.8 OXIDATION AND REDUCTION

Oxidation and reduction, these two fundamental terms have been used in chemistry
since beginning. Oxidation includes gain of oxygen, loss of hydrogen or electron
and increase in oxidation number or positive charge, whereas reduction deals with
loss of oxygen, gain of electron or hydrogen and decrease in oxidation number or
positive charge or increase in negative charge of any atom or molecule or species.
The phenomena of oxidation and reduction are just opposite to each other and they
must occur simultaneously. These processes are integral parts of chemical, physical,
biological and biotechnological sciences.

Oxidation

Reduction

A substance (atom, ion or molecule) that has ability to oxidize other substances
is called oxidizing agent and while oxidizing other species the substance itself
gets reduced whereas reducing agent are those substances which have tendency to
reduce other molecules or atom or element or species and during this process they

54
themselves get oxidized. In other words, oxidizing agents are known as electron Environment
acceptor while reducing agents are termed as electron donor. Chemistry - II

As we mentioned earlier that oxidation and reduction take place concurrently

therefore, these processes cannot be separated from each other and studied together.

Redox reactions
The chemical reactions in which the oxidation numbers of participating species
(atoms, molecule or ions) are changed by the transfer of electrons from one species
to another species are termed as redox reactions (reduction/oxidation).

Here, oxidation state of iron changes from 0 to +2 while copper is converted from
+2 to 0.

Redox reactions are prevalent in nature and almost one third reactions that have
been taking place in our surrounding are oxidation reduction reactions. These
reactions can occur abruptly, slowly or rapidly depending upon their environmental
conditions. Few examples of redox reactions are given below:

1. Respiration: As we know that respiration is the ultimate energy yielding process

in living organisms wherein consumed or stored food is transformed into energy
through a series of redox reactions. During this process, oxidation of glucose
and reduction of oxygen take place simultaneously.
C6H12O6 + 6O2 6CO2 + 6H2O + Energy

2. Photosynthesis: In this process green plant and certain micro-organisms

convert light energy to chemical energy wherein carbon dioxide and water
are transformed into energy rich organic compounds such as glucose or other
sugars and oxygen in the presence of sunlight and some specific pigments like
chlorophyll.

3. Photography: In classical approach, photographic films containing light

sensitive silver halides are treated with solution of a reducing agent such as

55
Fundamentals of hydroquinone, N-methyl-p- aminophenol, ascorbic acid etc. which reduces
Environmental silver halides to metallic sliver. Besides, fixation of image is carried out by
Chemistry
using the solution of sodium thiosulphate.

4. Corrosion: It is a natural galvanic process wherein deterioration of refined

metals takes place through oxidation.

5. Breath analyzer: In a chamber of breath analyzer, an aqueous solution containing

potassium dichromate, sulfuric acid and silver nitrate is filled. When an alcoholic
breath sample is bubbled into this solution, sulfuric acid helps in transferring of
ethanol from air to liquid where it reacts with potassium dichromate in presence
of sliver nitrate to yield acetic acid and chromium sulfate (green colour). This
process is accelerated by AgNO3 which acts as a catalyst for the above redox
reaction.

6. Cells and batteries: Generally, in cell and batteries either chemical energy
is converted into electric energy or electric energy is transformed into
electrochemical energy through redox reactions.
Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s) (galvanic cell)

Another type of redox reaction is disproportionation reaction that sometimes also

called as dismutation in which a compound or molecule is converted into two or
more dissimilar products through simultaneous oxidation and reduction of same
species.

SAQ 7

56
What are oxidizing and reducing agents? Explain with suitable examples. Environment
Chemistry - II

2.9 LET US SUM UP

The brief description of some fundamental points of this unit is given below:

The chemical reactions that occur between an acid and base and result into formation
of salt and water are generally called acid- base reactions. These reactions play a
critical role in maintaining balance in our body as well as our environment.

Highly purified water also behaves like a weak electrolyte and shows conductivity.
It ionizes in hydrogen and hydroxyl ions but hydrogen ions do not exist in free
form. They are found in the form of hydronium ions [H3O+]. The product of active
concentrations of hydronium ion and hydroxyl ions at a particular temperature is
known as ionic product of water and its value at 25ºC is Kw = 1 x 10-14.

Basically, pH scale is used to express the acidity or alkalinity of a solution.

Mathematically, it is defined as negative logarithm of hydrogen ion concentration at
a given temperature. pH > 7 represents alkaline nature of solution whereas solutions
having pH < 7 show acidic behavior and pH = 7 indicates neutrality of the solution.

The term hydrolysis is used to describe dissolution by water molecules. In simple

words we say it includes chemical breakdown of a compound because of its
reaction with water. In salt hydrolysis, reaction between salt and water takes place
that results in to formation acidic, alkaline or neutral solution depending upon the
salt used.

A buffer solution is an aqueous mixture of either weak acid and its conjugate base
or weak base and its conjugate acid that resists in alteration of pH when small
amounts of strong acid or base are added to it.

The common ion effect refers to decrease in dissociation of weak electrolyte when
a strong electrolyte having a common ion is introduced to the solution of feebly
ionized electrolyte. This effect has fundamental importance in quantitative analysis.

According to modern concept, removal of electrons from a species is termed as

oxidation whereas addition of electrons is called reduction. Almost all the elements
and their compounds have tendency to undergo oxidation-reduction reactions.

57
Fundamentals of Photosynthesis, respiration, corrosion etc are some common examples of redox
Environmental reactions that we experience in our day to day life.
Chemistry

2.10 GLOSSARY
Conductivity: A capacity of a substance to conduct electricity.

Electrolyte: A substance that conducts electricity in molten state or when dissolved

in polar solvent.

Equilibrium: It is a state of a system when the rate of forward and backward reaction
becomes equal and concentration of reactants and products remains constant.

Polyprotic acid: An acid which is capable of donating more than one hydrogen ion
per molecule to aqueous solutions.

Solute: A substance (solid, liquid or gas) which is dissolved in solvent to form

solution.

Solubility: It is the maximum amount of a solute that can be dissolved in a solvent

at particular temperature.

2.11 SUGGESTED READINGS

1. J. Mendham, R. C. Denney, J.D. Barnes, JD and M.J.K. Thomas, 2006. Vogel’s
Textbook of Quantitative Chemical Analysis, 6th.
2. K. J. Laidler and J. H. Meiser, 2006, Physical Chemistry, 2nd.
3. B.R. Puri, L.R. Sharma and M.S. Pathania, 2008. Principles of Physical
Chemistry, 7th.
4. K. L. Kapoor, 2009, A Text Book of Physical Chemistry, 3rd.
5. P. Atkins, T. Overton, J. Rourke, M. Weller, F. Armstrong, 2010, Shriver and
Atkins’ Inorganic Chemistry, 5th.

2.12 TERMINAL QUESTIONS

1. Describe general theories of acids and bases.
2. What do you mean by hydrolysis? Explain salt hydrolysis by giving an
example with equations.
3. What are buffers? Derive the formula for pH of mixture of weak acid and its
salt type buffer.
4. Give detailed description of oxidation-reduction with suitable examples.

58
5. What are neutralization reactions? Illustrate the process of neutralization with Environment
examples. Chemistry - II

ANSWERS

Self-Assessment Questions
1. Fundamental theories of acids and bases are given in section 2.2 Acid-Base
reactions that include general principle (Arrhenius theory), Bronsted-Lowry and
Lewis concept. These theories are different from each other at the basic level as
they define the concept of acidity and alkalinity on libration of hydrogen and
hydroxyl ions, conjugate acid-base pair and donation as well as acceptance of
electrons respectively.

2. The product of concentration of hydrogen ions and hydroxyl ions at a particular

temperature is known as ionic product of water. As it remains constant at a given
temperature and represents the neutrality of water therefore, it plays critical role
in gathering information about reaction medium and conditions.

3. pH and pOH are inversely proportional to each other. Moreover, pH + pOH =

pKw = 14.

4. The fraction of each mole of anion or cation that hydrolysed at equilibrium is

known as degree of hydrolysis. For the derivation of expression of salts of weak
acid and strong base refer section 2.5 Hydrolysis (case 1: salts of weak acid and
strong base).

5. Buffers are the chemical substances that resist changes in the concentration of
hydrogen or hydroxyl ions when small quantities of acid or alkali are added to
it. For calculation of pH of weak base and its conjugate acid visit section 2.6
Buffer solutions (Case 2: A mixture of weak base and its salt).

6. If a strong electrolyte is introduced to a solution of feebly dissociated electrolyte

that has at least an ion common with strong electrolyte, suppression in the
ionization of weak electrolyte is observed and this phenomenon is known
as common ion effect. E.g. reduction in dissociation of acetic acid (weak
electrolyte) on addition of sodium acetate (strong electrolyte) in its solution.

7. Common ion effect has prime importance in qualitative analysis wherein it has
been used in salt as well as gravimetric analysis. The other applications of this
effect include softening of water, purification of common salt and salting out
of soap.

8. A substance (atom, ion or molecule) that has ability to oxidize other substances
is called oxidizing agent and while oxidizing other species the substance
itself gets reduced whereas reducing agent are those substances which have
tendency to reduce other molecules or atom or element or species and during
this process they themselves get oxidized. In other words, oxidizing agents are
known as electron acceptor while reducing agents are termed as electron donor.

59
Fundamentals of For the examples of oxidizing and reducing agents refer section 2.8 Oxidation
Environmental and Reduction (Redox reactions).
Chemistry

Terminal Questions
1. General theories of acids and bases are described in section 2.2 Acid-Base
reactions. Please refer this section for more information.

2. Hydrolysis is a type of chemical reaction in which chemical bonds of a substance

are decomposed by addition of water molecules. This phenomenon plays a
quite significant role in biological systems as well as in chemical sciences. For
example of salt hydrolysis refer section 2.5 Hydrolysis.

3. The detailed description of buffers is provided in section 2.6 Buffer Solutions.

Please refer that section for answer.

4. Oxidation and reduction is explained thoroughly in section 2.8 Oxidation and

Reduction. Please visit that section for details.

5. Acid and base reaction is a type of chemical reaction wherein acid and
base reacts together in stoichiometric ratio to neutralize each other as acid
counteracts the base and vice versa. Therefore, this type of reactions generally
called neutralization reaction. For example refer subsection Acid-base reactions
in sectional heading 2.2 Acid-Base reactions.

60
UNIT 3 : ENVIRONMENTAL CHEMISTRY III
Structure
3.0 Introduction
3.1 Objective
3.2 Solubility and Solubility Product
3.3 Solubility of Gases
3.4 Carbonate System
3.5 Chemical Speciation
3.6 Chemistry of Heavy Metals
3.7 Radionuclides
3.8 Saturated and Unsaturated Hydrocarbons
3.9 Chemistry of Fuels
3.9.1 Gasoline
3.9.2 Chemistry of Gasoline Fuel additives
3.9.3 Antiknock Agents

3.10 Lubricants
3.10.1 Classification of Lubricants
3.10.2 Properties of Lubricants

3.11 Biogas
3.12 Let Us Sum Up
3.13 Glossary
3.14 Suggested Readings
3.15 Terminal Questions

3.0 INTRODUCTION
Environment chemistry is an interdisciplinary field which encompasses the
fundamental principles of chemistry, biochemistry, soil, toxicology and ecology. It
deals with chemical composition, properties, reaction rate, transport , effects and
ultimate fate of chemical species encountered in the environment. It is pertinent
to identify and understand the problems associated in the environment and to find
the mechanism by which it can be minimized or completely eliminated  from the
environment. The main objective behind environmental chemistry is to create
awareness about its importance and need to restrain human activities which leads
to indiscriminate release of pollutant into the environment.

3.1 OBJECTIVES
After studing this unit you will be able to
• describe concept of solubility and solubility product
• understand the aquatic chemistry of carbonate system

61
Fundamentals of • explain about distribution, mobility and biological availability of chemical
Environmental elements in natural system
Chemistry
• Classify atmospheric pollutants pertaining to heavy metals, radionuclides and
saturated and unsaturated hydrocarbons encountered in the atmosphere
• Understand the chemistry of gasoline and additives used
• Explain the strategies to prevent knocking in gasoline
• Describe the mechanism, classification and properties of lubricants

3.2 SOLUBILITY AND SOLUBILITY PRODUCT

Solubility product of the saturated solution of a sparingly soluble salt in water can be
defined as the product of concentrations of ions raised to a power equal to number
of times ions occur in the equation representing the dissociation of electrolyte.

When a saturated solution of an electrolyte is formed, a dynamic equilibrium is

maintained between the excess of the solute and ions furnished by the already
dissolved electrolyte.

Consider a sparingly soluble salt say, AxBy when added to water, a very small
amount of it dissolves and rest of it remains in the water in the solid form. Here, the
undissolved AxBy is in equilibrium with A and B ions formed in the solution.

This can be represented as:

AxBy (s, saturated solution) ⇌ xAy+ (aq) + yBx- (aq)

According to the law of chemical equilibrium, equilibrium constant can be

represented as:

where a Ay+ , a Bx- and a AxBy denote the activities of the furnished ions A+, B- and the
undissolved electrolyte AxBy respectively. Now, the activity of solid is taken as 1 by
convention. Therefore, the equation can be represented as:

Ksp = a xAy+ ⨯ a yBx-

Where, Ksp is known as the solubility product of electrolyte AxBy.

In common practice, concentration terms are more preferred as compared to the

activities. In such a case, solubility product Ksp becomes concentration solubility
product Kʹsp and can be written as:
Kʹsp = [Ay+]x [Bx-]y

62
In case of sparingly soluble salts, ionic concentration of the dissolved salts is very Environmental
low so that the concentrations and activities can be taken as almost same indicating Chemistry - III
that solubility product is equal to the concentration solubility product. Therefore,
Ksp = Kʹsp

Consequently,

Solubility product of a sparingly soluble salt AxBy can be represented in the equation
form as:
Ksp = [Ay+]x [Bx-]y

Interestingly, one can find the solubility of a sparingly soluble salt if its solubility
product is known and vice-versa. Solubility and solubility product are corelated
as follows. When a saturated solution of sparingly soluble salt AB is prepared, its
solubility equilibrium can be represented as:
AB (s, saturated solution) ⇌ A+ (aq) + B- (aq)
Let s denote the solubility of the salt. Then,
[A+] = s mol L-1 and similarly,
[B-] = s mol L-1
Ksp = [A+] [B-] = (s mol L-1) (s mol L-1) = s2 mol2 L-2
Therefore, Solubility, s = √ Ksp mol L-1

Thus, molar solubility is defined as the number of moles of solute that can be
dissolved in 1 litre of the solution.

The concept can be smartly employed to find out if a solution is saturated or not.
If the ionic product [Ay+]x [Bx-]y is found to be less than the solubility product, Ksp
the solution is termed as unsaturated and it has the capacity to dissolve more of the
electrolyte, whereas if the ionic product and the solubility product are found to be
the same then the solution is perfectly saturated at that particular temperature.

3.3 SOLUBILITY OF GASES

Solubility of gases in water is governed by Henry’s law. This law states that
solubility of gas at constant temperature is directly proportional to partial pressure
of gas in contact with the liquid. Consider

A (g) ⇄ A (aq)

Where A(aq) is aqueous concentration of gases in molL-1 ; px is partial pressure of

gas in atm; K is henry’s constant

Units of k = molL-1atm-1

Table illustrates the Henry’s law constants for common dissolved gases in water at
25ºC.

63
Fundamentals of
Environmental
Gas K(molL-1atm-1)
Chemistry O2 1.3 x10-3
CO2 3.4 x10-2
H2 7.8 x10-4
N2 6.5 x10-4
CH4 1.4 x10-3

In order to calculate gas solubility considering an example where concentration of

O2 in water is in equilibrium with air at 1 atmospheric pressure and temperature, a
correction must be made for partial pressure of water by subtracting it from total
pressure of gas (0.0313 atm) at 25 oC. Henry’s constant for O2=1.3 x10-3 molL-
1
atm-1 and considering that dry air is 20.95% by volume of O2 yields the following
equation”
PO2 = (1.0000 atm − 0.0313 atm) x 0.2095 = 0.2029 atm
[O (aq)]=k PO2 =1.3 x 10-3 molL-1atm-1 x 0.2029atm
[O2(aq)]= 2.6 x10-4 molL-1

Molar mass of oxygen is 32, so concentration of dissolved oxygen in water at 25oC

is 8.3mgL-1 or ppm.

The solubility of gases decrease with increasing temperature given by Clausius-

Clapeyron equation:

c1 and c2 denotes gas concentration at absolute temperatures of T1 and T2.

∆H = heat of solution and its units are in cal mol-1

R = gas constant where R = 1.987 cal degree-1 mol-1

At high temperatures, decreased solubility of O2 combined with increased respiration

rates by aquatic organisms results in depletion of oxygen making survival difficult
for aquatic species.

3.4 CARBONATE SYSTEM

The major portion of carbon is present in the oceans in form of carbonate. The
carbonate system is primarily responsible for controlling the pH and regulates
various biogeochemical processes occurring in ocean. Carbon dioxide emitted
through natural and anthropogenic sources are taken up by the oceans. This results in
limiting the increase in CO2 concentration and greenhouse warming but increasing
acidification of sea water. Rapid exchange of CO2 occurs between the atmosphere
and aquatic system through equilibrium of CO2(g) and dissolved CO2

64
CO2(g) ↔ CO2(aq) Environmental
Chemistry - III
CO2 rapidly reacts with water owing to its high solubility resulting in formation of
carbonic acid.
CO2 (aq) + H2O ↔ H2CO3 …………………….. (1)
H2CO3 ↔ HCO3- + H+ …………………….. …. (2)
HCO3- ↔ CO32- + H+ …………………………. (3)

Series of proton transfer reaction takes place resulting in bicarbonate and carbonate
ion. Reactions 2 and 3 produces H+ and lowers the pH of sea water. Dissolved CO2
occurs in three inorganic forms: free aqueous CO2, HCO3-, and CO32-which becomes
an integral part of carbonate system. When CO2 dissolves in sea water, it is not fully
dissociated to CO32- and number of H+ are smaller due to natural buffering capacity
of sea water as shown below

CO2 (aq) + H2O + CO32- ↔ 2 HCO3-

The sum of three aqueous carbonate species [CO2 (aq)]+ [HCO3-] + [CO32-] is
defined as total CO2. Most of the surface water of ocean is approx. pH 8 where
HCO3- is the dominant species and this represent 90% of DIC. A very small portion
of H2CO3 is present hence concentration of CO2 (aq) + H2CO3 is combined and
represented as [CO2 (aq)]

Ocean acidification limits the coral life all marine organisms to properly synthesize
their carbonate skeletal via the formation of biogenic calcium carbonate, CaCO3.

Due to increase in rate of anthropogenic emissions of CO2, calcification rate have

declined and reduced the alkalinity of the oceans.

SAQ 1

Explain the role of carbonate system in oceans.

3.5 CHEMICAL SPECIATION

The term chemical speciation refers to specific chemical forms of elements which
may be inorganic, organic or organometallic species in the environment. It also
refers to the oxidation state in which a particular element exists in the environment.

Metals are non-biodegradable in nature. When they enter in the environment they
get partitioned into various physico-chemical forms such as colloidal, chelated, free

65
Fundamentals of ionic combined with other chemical forms. The physical properties and chemical
Environmental behaviour vary amongst different species in the environment. The phenomena
Chemistry
such as chemical and biological transformation, metal mobility, bioavailability,
toxicity and persistence in the environment depends on chemical form or speciation
of a given metal ion. Example: Arsenic is extremely toxic in its inorganic form
but arsenobetaine is non-toxic Similarly elemental mercury is non-toxic but
alkylmercurials are highly toxic.
The toxicity and mobility of metal ions depends upon:
• Concentration of metal ions which decreases on complexation.
• Redox environment. eg. toxicity associated with As(V) is low in oxidising
environment while reduced form As(III) is highly poisonous.
• Oxidation number Cr(III) is essential element as glucose tolerance factor
while Cr(VI) is highly toxic.
Because of the above reasons, the determination of the total concentration of a metal
provides inadequate information. That is why speciation has gained considerable
importance.

Speciation studies involves estimating individual physico-chemical forms of

elements that make up the total concentration of a particular element in order to
assess its impact on organism/environment.

But at times, the determination of specific concentration of species becomes quite a

difficult task than determination of total element because of the following reasons:
1. Isolating the compound of particular interest from complex matrix is difficult.
2. Speciation techniques available disturb the equilibria existing between the
various chemical species present in the system under study.
3. Determination of species at ultra-trace level requires analytical procedures of
high degree of sensitivity.
4. Suitable standard reference materials are often unavailable.

The speciation analysis of metal ions can be performed by sequential extraction,

whereby each of the fractions obtained shows a different form of association of the
metal in the soil. The accepted modern procedure is:

Step I. Extraction of the acid soluble fraction (i.e., carbonates) with CH3COOH

Step 2. Extraction of the reducible fraction (i.e., iron/manganese oxides) with

hydroxylamine hydrochloride

Step 3. Extraction of the oxidizable fraction (i.e., organic matter and sulfides) by
H2O2 oxidation followed by extraction with NH4(CH3COO)

Chemistry of Cr(III) , Cr (VI) speciation

In natural water, chromium exhibits two common oxidation states +3 and +6
exhibiting different chemical behaviour, toxicity and bioavailability. Cr(III) is

66
associated with lesser toxicity because of limited solubility and strong complex Environmental
formation. On the contrary, Cr(VI) is highly toxic and much more bioavailable Chemistry - III
to aquatic living organisms since it is easily transported into cells as sulphate
analogues. It is also recognised as human carcinogen and mutagen.

Cr(III) speciation in sea water is dominated by Cr(III) hydrolysis products-

Cr(OH)2+; Cr(OH)3, Cr(OH)2+ and Cr(OH)4- . Cr(OH)3 is dominant species in the
pH range 7-11, while Cr(OH)4- becomes dominant above pH 11.3. Chromium is
present as Cr(VI) under oxidizing conditions as anionic species- CrO42-, HCrO4-,
and dimer Cr2O72-

In natural systems, Cr(III) does not migrate since its minerals precipitate in alkaline
or neutral range . It remains as dissolved Cr(III) in low concentration. In slightly
acidic conditions, it can be is removed by adsorption. Phenomenon of precipitation
and adsorption can be inhibited by complexation of Cr(III) with dissolved ligands.
Dissolved Cr(III) concentration becomes higher and migrates when pH reaches
around 5. Oxidants such as MnO2 can solubilise Cr(III) in form of Cr(VI) compounds.

Cr(VI) enters in to aquatic system in two ways:

(a) reduction of Cr(VI) to Cr(III). Reduction is facilitated by Fe(II) which may
be synthesized by photo-oxidation of organic matter in sea water surface.
(b) Removal of Cr(VI) by sorption process where there is high content of Mn
or Fe oxide under oxidizing conditions. But sorption is not strong enough to
keep moving Cr(VI) through soil or sediments under alkaline medium.

SAQ 2

What is meant by the term metal “speciation” and why is it important in aqueous
systems?

3.6 CHEMISTRY OF HEAVY METALS

The term heavy metal refers to those elements which have density greater than 6
gcm-3.

Heavy metals occur naturally in soils, sedimentary deposits and water bodies.
They find their way into the environment through soil, and sediments in form of
dust, smoke and aerosol by anthropogenic sources. They are also added to the
agricultural land by extensive uses of fertilizer and water bodies through industrial

67
Fundamentals of wastes, sewage sludges. Mainly, four heavy metals such as lead, mercury, cadmium
Environmental and arsenic are of greatest concern because of their extensive use, their toxicities
Chemistry
and pervasiveness in the to the environment.

Heavy metals exert their toxic action by binding to the active site of the enzyme
thereby inhibiting the enzymatic action. They have strong affinity for the sulfhydryl
group (-SH) of the enzyme. Certain enzyme contains metal ions in their structures
called metalloenzyme. Their action is inhibited when the essential metal ion of the
enzyme is replaced by the toxic meatal ion having same size or charge. Example:
substitution of Zn by Cd in Zn2+containing metalloenzyme like carbonic anhydrase,
carboxypeptidase, alcohol dehydrogenase.

Schematic representation of toxicity mechanism of heavy metals

Cadmium
Cadmium occurs in a very low concentration in the earth’s crust. It is not an essential
element and no biological function till date is reported in humans. It is used in
industries to manufacture nickel cadmium batteries, control rods in nuclear power
industry, pigments, semiconductor devices, stabilizers for PVC and other plastics.
Other applications include electroplating metals for protection against corrosion
and in non-ferrous alloys. A small amount of Cd occurs in form of impurity in zinc
containing ores.

Cadmium in water arises mainly from industrial discharge and from waste mining. It
is extremely dangerous to plants and animals because it absorbs efficiently and gets
accumulated in the tissues. Rate of Cd absorption in humans increases particularly
if they are on low Calcium diet. Majority of the cadmium ingested gets trapped in
kidneys and is eliminated. A small portion gets bound to protein metallothionein
present in kidneys. Effects of Cd poisoning in humans results in anemia, high blood
pressure, damage to testicular tissues.

Cadmium poisoning caused itai -itai or ouch -ouch disease that was first recognized
in in Jintzu river basin of Japan. Water in the Jintzu basin became contaminated
with cadmium from mining activities. This contaminated water was used to irrigate
rice fields, a staple food in that area. The bones of the victims become fragile and
broke easily from loss of Ca. Many people suffered from abdominal pain, diarrhea,
vomiting, liver damage and kidney failure.

Chemically, cadmium is similar to zinc since it occurs in association with zinc

mineral and found in similar oxidation states (+2). It is proposed that Cd poisoning
involves substitution of Zn by Cd in many metalloenzymes thereby altering the
stereostructure of the enzyme and impairing the catalytic activity.

68
Arsenic Environmental
Arsenic is commonly used in pesticides (fungicide, insecticide, herbicide), alloys Chemistry - III
and in wood preservatives. Arsenic is a by-product used in the manufacture of
some chemicals and mining operations. Many subsoils naturally contain arsenic
compounds and seep into the groundwater and contaminate the source. In some
parts of India and Bangladesh wells were dug up used for irrigation purpose have
been epidemics of acute arsenic poisoning. Presence of arsenic in drinking water
cause keratoses, skin discolouring which subsequently leads to cancer and damages
liver and kidneys.

Arsenic exerts its toxic action by binding it strongly to the sulphudryl groups on
protein. The enzyme pyruvate dehydrogenase which generates cellular energy in
citric acid cycle , is deactivated on complexation with As3+ thus preventing the
formation of ATP. Arsenic is similar to phosphorus, so it is reduced from +5 to + 3
oxidation state, so arsenic inhibits all biochemical reactions of phosphorus. Arsenic
interferes in synthesis of ATP producing 1-arseno-3-phosphoglycerate instead of
1,3-diphosphoglycerate which on hydrolysis gives arsenate and 3-phosphoglycerate
as shown in below diagram.
CH2OPO32-

Po443-3
PO H OH
Enzymatic
ATP Formation
Hydrolysis
O
CH2OPO32-
OPO3 2
H OH 1,3- Diphosphoglycerate

O
CH2OPO32-

H
Glyceraldehyde 3- Phosphate H OH
Non Enzymatic ATP Formation
3 Hydrolysis Prevention
AsO4 O
O
0 As
O
1-Arseno-3-phosphoglycerate

The three major biochemical effects of arsenic are :

1. Protein coagulation
2. Complexation with co-enzyme
3. Uncoupling of phosphorylation

As(III) [AsO33-] is more toxic than As(V) [AsO43-) because it it undergoes

methylation by bacteria that produces species that are highly reactive and damages
DNA. Antidotes for As poisoning includes chelating agents like British anti Lewsite
(BAL)which possess -SH capable of binding strongly with As(III)

Lead
The sources of inorganic lead include industries, mining and from leaded gasoline.
Lead is most abundant heavy metal in the atmosphere. The major source of
atmospheric lead comes from Et4Pb which is added to gasoline to inhibit knocking
and improve fuel efficiency. Lead enters the human system by inhaling lead and
swallowing lead salts. When it enters the blood stream as Pb2+ and it becomes
biologically active highly and potentially more toxic.

69
Fundamentals of Lead when present interferes in the heme synthesis which leads to hematological
Environmental damage. Presence of lead disrupts heme synthesis by inhibiting the conversion
Chemistry
of δ-aminolevulinic acid to prophobilinogen catalyzed by δ-aminolevulinic acid
dehydrogenase. It does not permit utilization of oxygen and glucose for energy
production. High levels of lead in blood results in anemia due to deficiency of
hemoglobin. Chronic effects include causes kidney malfunction, increased blood
pressure and interference in vitamin D metabolism. Lead exposure is highly
dangerous to unborn and young children. It crosses the placenta barrier and causes
premature births and mental impairements. Chemically, lead resemble calcium, so
it accumulates in the body replacing calcium.

Lead poisoning can be treated by administering chelating agents which bind strongly
to Pb2+.Ca-EDTA complex is given to patients poisoned by lead, it displaces Ca2+
from chelated complex and resulting complex can be excreted in urine. Other
chelating agents used to treat lead poisoning includes BAL, d-penicillamine.
O
H 2C CHCH2OH C
O O
CH2

S S
C CH2

O N CH2

Pb

Pb O N CH2

S S C CH2

O
O CH2

C
H 2C CHCH2OH O

BAL= 2,3-dimercaptopropanol Pb-BAL Chelate

Mercury
The main source of mercury is the principal ore cinnabar i.e. HgS. It is used
industrially in three different forms: elemental mercury, organic mercury compounds
and inorganic mercury. The greatest use of mercury is production of electrical
apparatus. It forms amalgams with various metals like zinc, lead, tin, cadmium and
widely used as fungicide. Mercury(II) chloride is used to make organo-metallic
compounds, as a wood preservative, and as an antiseptic for sterilising surgical
instruments. Mercury(II) sulphide is used in the red pigment, vermilion.

A s result, mercury and its compounds enters the natural bodies from manufacturing
or sources where mercury is mined. The major sources of mercury emissions into
the atmosphere is through burning of fossil fuels, electric power plants, waste
incineration or weathering of rocks

All forms of mercury are highly toxic but toxicities vary considerably. Elemental
mercury is non-toxic but its vapours when inhaled are highly toxic because it can
diffuse through lungs into the blood and then brain. Hg2+ is fairly toxic but does
not cross the biological membrane though it has strong affinity for the sulphur
containing amino acids and forms bonds with haemolglobin through sulphydryl
groups. Hg1+ is non-toxic when ingested because it forms insoluble Hg2Cl2 in the
stomach in acidic medium. Alkyl mercurial RHg+ are highly toxic forms of mercury
compounds, because they are highly soluble in fat and brain tissues. Hg-C bond is
not easily disrupted stable and remains in tissue cell for prolonged period. They
have the ability to easily cross the blood-brain and placental barrier.
70
Chemical species of mercury and their chemical and biochemical properties Environmental
Chemistry - III
Species Chemical and biochemical properties
Hg Non-toxic, but vapours when inhaled highly toxic
Hg22+ Not very soluble, low toxicity
Hg2+ Toxic but not transported across biological tissues
CH3Hg Highly toxic, highly liophilic i.e easily transported
across biological membrane
(CH3)2Hg Low toxicity but easily transformed to CH3Hg

Biological methylation
The transformation of inorganic form of mercury( Hg0, Hg1+, Hg2+) to methyl and
dimethyl derivatives by the action of anerobic bacteria in sediments and lakes is
referred to as methylation. This transformation is mediated by methylcobalamin,
Co(III) containing vitamin B12 co-enzyme. -CH3 group bonded to co-enzyme is
enzymatically transferred by methylcobalamin to Hg2+ giving CH3Hg+ or (CH3)2Hg.

Under acidic conditions, conversion of dimethylmercury to methylmercury occurs

which is soluble in water. It is the methyl mercury form which enters into the food
chain through phytoplankton. In this way concentration of mercury is build up
at every level. In alkaline medium, methyl mercury can be converted to volatile
dimethylmercury, (CH3)2Hg, may be formed which evaporates relatively quickly
both from soils and water bodies.

The deleterious effects of the mercury came into limelight after the incidence of
Minamata Bay in Japan during the period 1953-1960. The non-toxic inorganic
mercury was discharged as effluent into the Bay by Minamata chemical plant
manufacturing acetaldehyde using mercuric sulphate as catalyst . In the sediments,
inorganic mercury was converted into methyl mercury which got accumulated into
the fish which was eaten up by local inhabitants. This resulted in death of hundred
people and thousands were permanently paralysed . Congenital defects were in new
born babies whose mothers fed themselves with sea food contaminated by methyl
mercury. Other effects includes impairment of vision, hearing and neurological
damage. This was the first natural case of bioaccumulation (in fish) of a toxic species
(methylmercury) which killed hundreds of people and caused genetical damage.

Chronic effects caused by mercury poisoning mercury includes neurological

damage including increased excitability, irritability, chromosomal damage and
birth defects and kidney problems.

SAQ 3

Explain the toxic effects of heavy metals on enzymes?

71
Fundamentals of SAQ 4
Environmental
Chemistry Explain the biochemical effects of Heavy Metals

a) Arsenic b) Lead c) Mercury with reference to their source , species, pathways in

environment and impact on humans.

3.7 RADIONUCLIDES
Radionuclides are species of atoms that emit radiation when they undergo
radioactive decay through emission of alpha particles, beta particles and gamma
rays. Table provides the characteristics of defined decay processes:

Radiation Symbol Charge Transformation

Alpha (α) +2 Mass number decrease by 4, atomic
number decreases by 2
Beta (β) -1 Atomic number increases by 1, mass
remains unchanged
Gamma (γ) 0
γ0 0 No change in atomic number or mass
When α or β particles are emitted , the identity of elements is changed

e.g. decay of U-238 to Th-234,

In contrast to a emission, β decay results in increase in atomic number by 1, while

mass number remains the same.

Gamma rays are highly energetic electromagnetic radiations similar to X-rays

having no charge or mass.

U undergoes radioactive decay by forming chain of products through - variety of

238

alpha and beta emissions ultimately leading to stable Lead-206 . The transformation
of Ra-226 to Rn-222 is of particular environmental significance. Radon is a colorless,
odorless, tasteless gas that naturally occurs in rocks, soil, water, and air. Radon in
the ground, groundwater, or building materials invades working and living spaces
and disintegrates into its decay products. It is second leading cause of lung liver
cancer. Decay of radionuclides follow first order reaction

72
Radiation damages living organisms by initiating harmful chemical reactions Environmental
in tissues. In case of acute radiation poisoning, bone marrow is destroyed and Chemistry - III
concentration of RBC is decreased. Radionuclides having very short life are highly
dangerous but decay fast to affect the environment. In contrast radionuclides
having very long half-life are quite persistent but may cause very little damage.
But radionuclides having intermediate half-lives are highly dangerous and can
pose threat. Sr-90 is the waste product of nuclear testing is interchangeable with
Ra and K-40 are found in natural sources like water. Radionuclides are formed in
large quantities as waste products in nuclear power plants. Artificially produced
radionuclides find their widespread use in industrial and medical applications
particularly as tracers.

SAQ 5

What characteristic features of radionuclides make them hazardous ?

3.8 SATURATED AND UNSATURATED

HYDROCARBONS
Majority of the hydrocarbons have their widespread use in fuels and therefore
represents the most important organic pollutant of the atmosphere. The anthropogenic
source of hydrocarbon pollutant encountered in atmosphere comes from incomplete
combustion of gasoline (petroleum product). Hydrocarbons are broadly classified
as
• Saturated Hydrocarbon: comprising of alkanes ( also referred to as paraffins)
• Unsaturated Hydrocarbons: comprising of a. alkenes (olefinic compounds
with double bonds between adjacent carbon atoms) b. Alkynes (compounds
with triple bonds between adjacent carbon atoms) c. aryl compounds
(aromatic)
Alkanes have single bond between the carbon atoms and represented by the
general formula: CnH2n+2, Cyclic alkanes :CnH2n. examples include: methane,
2,2,3-trimethylbutane

The most stable hydrocarbons present in the atmosphere are alkanes. Straight chain
alkanes with carbon atoms 1-30 and branched hydrocarbons with 6 carbon atoms
are present in polluted atmosphere either as gas or as aerosol or may adsorbed to
atmospheric particles.

The hydroxyl radicals present in atmosphere react with alkanes to form alkyl radical
which then immediately picks up a molecule of oxygen leading to the formation
of alkylperoxy radical. This radicals acts as oxidant by losing an atom of oxygen

73
Fundamentals of to form alkoxy radical. These reactions of alkanes leads to the oxidized products
Environmental that are precipitated from atmosphere with particulate matter and finally undergoes
Chemistry
biodegradation in soil.
CxH2x+2 + HO• → CxH2x+1•
CxH2x+1• + O2 → CxH2x+1O2•
CxH2x+1O2• → CxH2x+1O•

Alkenes have atleast one C=C double bond per molecule. The simplest alkene is
ethylene. They are widely used to synthesize polymers for plastics (polyethylene,
polypropylene, polystyrene ), synthetic rubber (polybutadiene,) and various
applications. They are emitted into the atmosphere through internal combustion
engines, petroleum refinery, industrial applications.

Alkynes have triple bond between the carbon atoms and they are less commonly
present in the atmosphere than alkenes. acetylene which is used as fuel for cutting
and welding and butyne used in manufacture of synthetic rubber are sometimes
found in raceable amounts in atmosphere. Chemically, alkenes are more reactive
than alkanes since they possess electron available to form additional bonds with
other atoms. In the presence of NOx and sunlight, alkenes (e.g. propylene)react
readily with OH. radicals and subsequent addition of O2 leads to formation of peroxyl
radical. These reactions are quite significant in the atmosphere as they participate in
photochemical smog formation and contributes to atmospheric pollutants.

Aromatic (aryl)hydrocarbons consists of rings of six carbon atoms having alternative

single and double bond. Aryl hydrocarbons find their widespread application as
raw materials for the manufacture of monomers and plasticizers.

Simplest example is benzene. It is emitted from the exhaust engine of all petrol
and diesel vehicles as well as from chemical industries. Aromatic compounds
with multiple rings referred to as polycyclic aromatic hydrocarbons are of greatest
concern. Most important example is benzo (∝) pyrene, compound that the body can
metabolize to a carcinogenic form.

Features
• They are persistent organic pollutants because they do not break down easily.
• They are volatile making them highly mobile throughout the environment.
• These compounds are the most stable form of hydrocarbons having low
hydrogen-to- carbon ratios They are formed by the combustion of petrol and
diesel hydrocarbons under oxygen- deficient conditions.
• They are found deposited on surface of particulate matter present in smoke.
The most potent carcinogenic PAH’s include : benzo-α-anthracene, dibenzo-a-
anthracene and benzo-α-pyrene.

74
 H2 Environmental
H C C H H C C C CH3 Chemistry - III
Acetylene 1-Butyne

CH3

H3C
Benzene 2,6-Dimethylnaphthalene
Pyrene

chrysene
Bezo(a)pyrene

Figure 3.1 : Structural formulas of different types of hydrocarbon pollutants present in

environment

SAQ 5

Explain how aromatic hydrocarbons act as environmental pollutants

3.9 CHEMISTRY OF FUELS

Gasoline
The first product obtained in distillation of crude oil is gasoline. Generally, the
boiling range of gasoline is 25-150°C. Gasoline are sometimes classified as motor
gasoline for use in automobile and light trucks, aviation gasoline for use in piston
engine aircrafts. Hydrocarbons having 3-8 carbon atoms condensed from natural
gas are composed of natural gasoline. Natural gasoline does not provide good
combustion performance desirable for automobile engine. Consequently, it is now
used mainly as feedstock for petrochemical industry.

75
Fundamentals of The gasoline produced from distillation of crude oil without any chemical treatments
Environmental is straight run gasoline. It comprises primarily of straight chain hydrocarbons and is
Chemistry
of limited value as automobile fuel. A high content of straight chain hydrocarbons
causes fuel to begin burning before the spark plug ignites it. This pre-mature ignition
produces an acoustic sound called knocking. Knocking is combustion phenomenon
which takes place when air fuel mixture in the gasoline does not burn smoothly.

When the fuel in a gasoline engine is ignited by the spark plug, the flame tends to
move away from the spark plug, and the heat and pressure is generated. Chemically,
combustion is a multistage oxidation process where the organic hydroperoxides are
generated initially. These decompose to form free radicals that start branch chain
reactions. These chain reactions start local auto ignitions/detonations, ahead of the
flame front in the unburned hydrocarbon air mixture due to the high temperature
and pressure generated in the last portion of the fuel. This violent detonation creates
pressure fluctuations and noise. This noise is called knock, and damages engine
parts nd the fuel efficiency of the engine is decreased.

The tendency of gasoline to cause knocking is rated according to a scale called

octane number. It measures fuel’s ability to avoid knocking. Branched hydrocarbon
2,2,4- trimethylpentane (isooctane)was found to be superior fuel that burned
without causing knocking and is assigned an octane number of 100. Straight chain
hydrocarbon n-heptane produced severe knocking and was assigned octane rating
0.

The octane rating of gasoline is determined by burning it in a special single- cylinder

engine and comparing its anti-knocking properties with the standard mixtures of
isooctane and heptane.

Table: Octane numbers of various hydrocarbons

Hydrocarbon Formula Octane Number
n-butane C4H10 94
n-pentane C5H12 62
2-methylbutane C5H12 94
n-hexane C6H14 25
2-methylpentane C6H14 73
Heptane C7H16 0
2-methylhexane C7H16 42
2,3-dimethylpentane C7H16 90
2-methylheptane C8H18 22
2,3-dimethylhexane C8H18 71
2,2,4-trimethylpentane C8H18 100
Benzene C6H6 106
Toluene C7H8 118
o-xylene C8H10 107
p-xylene C8H10 116
From table, it is concluded that straight run gasoline has octane rating between 20-
55 which is too, low to be used in automobile engine.

76
Octane number can be increased by three ways Environmental
Chemistry - III
• Cracking
• Catalytic reforming
• Anti-knocking compounds /octane boosters
Cracking is the process in which long chain hydrocarbons are converted to short
chain hydrocarbon. The octane number of alkanes decreases as the carbon chain is
lengthened but increases as chain branching increases. (Table)

Catalytic reforming is the process in which hydrocarbon vapours of straight chain

gasoline are converted into branched or aromatic hydrocarbon in presence of
catalyst to increase octane rating .

Chemistry of Gasoline Fuel Additive

The fuel additives in very small dosage are added to enhance the performance of
the fuel which otherwise cannot be obtained through refining process.
Reasons for using additives in fuels include
• Reduction in emission from combustion of fuel
• Improvise combustion properties of fuel
• Provides cleanliness and protection to engine
• Increases stability of fuel.
There are six types of gasoline fuel additive:
1. Antioxidants: During oxidation of gasoline, free radical chain reaction
initiates which results in formation of hydroperoxides ultimately leading to the
formation of insoluble gum as the end product. Anti-oxidants minimizes the
oxidative degradation of gasoline fuel and prevents the gum forming tendency
of the fuel. Antioxidants consists of hindered phenols, and aromatic diamines.
Examples: 2,6-Di-tertiary butyl-para-cresol and 2,6-di-tertiary butyl phenol
Phenylenediamine

2. Metal deactivators/Passivators: The presence of soluble metal salts in

gasoline provides instability to fuel by catalysing oxidation reaction which
forms gum and reduces fuel stability. Most commonly used metal deactivator
is N,N-disalicylidene-1,2-propanediamine. This compounds can form chelate
with copper metal in gasoline.

3. Octane Booster: It provides cost effective improvement in gasoline octane quality

by reducing knocking. Examples : teraethyl lead (TEL), methylcyclopentadienyl
tricarbonyl (MMT)’ oxygenate additives such as ethanol, methyl tertiary butyl
ether (MTBE) considered as blending components rather than octane boosters.

4. Anti-icing additive: Anti-icing additives minimizes engine stalling and power

loss due to formation of ice crystals which may restrict the flow of fuel to
engine. It also provides protection against microbiological growth in [Link]

77
Fundamentals of comprises of freezing point depressants in particular glycol ethers example:
Environmental ethylene glycol methyl ether.
Chemistry
5. Combustion improvers: are used to heat the fuels and contains ash-less
and metal additives. Examples: tertiary butyl acetate enhances antiknock
characteristics of TEL; metal additives e.g. Compounds of boron and
Phosphorus increase the ignition point of engine. Incomplete combustion leads
to soot deposits in the combustion chambers, and impairs heat transfer and may
result in unwanted fires. Combustion improver additives minimizes misfire and
improves efficiency of the engine through reduced soot deposition,.

6. Deposit control additives/detergent dispersants: It consists of polar

hydrophilic and non polar hydrophobic group in its structure. and which is
derived from oxygen or nitrogen molecules and a which The nonpolar group
enables enables fuel to be soluble in additive. The polar group attaches to the
deposit particles and removes them from the metal surface through the detergent
action. Control Additives controls the build up of soot deposit in carburettor and
fuel injection equipment and inlet system by forming protective films. This will
provide performance benefits such as reduced exhaust Emissions, improved
fuel economy and reduced maintenance cost. Examples include amides, amines,
polybutene succinimides, polyether amines, polyolefin amines and mannich
amines.

Anti-knocking Agents
Knocking in the internal combustion engines affects the efficiency of the vehicle
and fuel economy. It can be minimized by engine design and adjusting operating
conditions or by using high octane gasoline. Most widely used additives to control
knocking includes alkyl lead compounds such as tetraethyl lead (TEL) , tetramethyl
lead (TML) and hence improves the performance of the engine. Addition of lead
additives deactivates the chain branching reactions in the pre-ignition phase . When
air-fuel mixture becomes compressed and heated, the weak bonds between the alkyl
lead breaks releasing the free lead atom. This then reacts with free O2 to form PbO
and PbO2 which tends to deposit in the combustion chamber This problem can be
solved by using scavengers such as Ethylene dibromide and ethylene dichloride
by converting non-volatile PbO2 to volatile PbX2 In this way lead is removed from
the engine and released into the atmosphere. Gradually leaded gasoline was phased
out by unleaded gasoline. The reason was that catalyst like Rh, Pt used in catalytic
convertors were poisoned by lead and rendering them inactive. Several alternative
antiknock agents were proposed and developed as substituent of lead-containing
fuels, for example: methyl-cyclo-pentadienyl-manganese- tricarbony (MMT],
ferrocene iron pentacarbonyl.

Methylcyclopentadienyl manganese tricarbonyl (MMT) an organometallic was used

as an antiknock additive. This compound releases Mn atom which is then converted
to Mn3O4 particles inside the combustion chamber which capture hydrocarbon
radicals and inhibits knocking. Toxicity associated with Mn is low once it is
released into the environment. But it was banned by USEPA because this additive
was found to be toxic when ingested or inhaled. Secondly, fouling of spark plugs

78
and of on board sensors had been reported. Recently it has been permitted in US at Environmental
level equivalent to 1/32 g of Mn gal-1of gasoline. MMT is suspected to be a strong Chemistry - III
neurotoxin and respiratory toxin. Additionally, MMT impairs the effectiveness of
automobile emission control and increases pollution of vehicles. Knocking can be
reduced by altering the composition of gasoline by reducing the fraction of low
octane components and increasing the fraction of high octane components. In
United Nations, removal of alkyl lead compounds was initially compensated by
increasing the content of aromatic compounds particularly benzene, toluene, and
xylene. Increasing the aromatic components in gasoline boosted octane rating.

Methylcyclopentadienyl manganese tricarbonyl (MMT) Ferrocene

The cause of BTX has decreased though it has high octane rating because
• Xylenes react with hydroxyl radicals and have greater potential to smog
formation than alkanes
• Benzene is a carcinogen though having low photochemical activity.
This prompted the need to develop alternative fuel additives for improving octane
rating of gasoline.

Focus has been laid on use of oxygenated compounds containing one or more oxygen
atoms. These include ethanol, methanol, methyl tertiary butyl ether (MTBE), ethyl
tertiary butyl ether (ETBE) whose octane rating >100. MTBE is made by reacting
methanol and isobutene in presence of acid catalyst.

It is synthesized in refineries in which isobutene is generated during catalytic

cracking process. However, MTBE contaminates ground water storage tanks
through gasoline leak. Its presence has unpleasant odour and is unacceptable in
water supplies. Environment Protection Agency recommended reduction its use as
gasoline oxygenate. Hence, ethanol and methanol emerged as gasoline oxygenate
Ethanol is added in amounts upto 10% of total volume to produce gasoline blends
known as gasohol. This mixture has been used as fuel without any modification of
automobile.

The advantage of using MTBE and ethanol is that they have low OH· reaction
rates and vapour pressure. It is because of this reason that oxygenates in RFG was
mandated upto level of 2% oxygen by weight according to 1990 Clean Air Act
amendments which requires reduction in ozone forming VOC. Oxygenated fuels
provide good combustion performance along with reduced emission of CO and
NOx.

79
Fundamentals of Ethanol separates out from gasoline when in contact with water because of its
Environmental extreme solubility. Vapour pressure of ethanol is twice than MTBE and requires
Chemistry
special adjustments in gasoline components to lower volatile organic compounds
.By removing lighter hydrocarbons from blend lowers gasoline volatility . In case
of MTBE, vapour pressure requirements is met by removing butane fraction but
replacing MTBE with ethanol requires removing pentane thereby increasing the
cost. With introduction of RFG smog forming precursors has been reduced.

Disadvantages of alcohols, especially methanol, produce aldehydes as by-products

during combustion. Since aldehydes are not major components of gasoline
emissions, their emission from combustion sources is not regulated. Aldehydes can
be highly irritating to the mucous membranes of the respiratory tract, and thus are
undesirable in air. This problem can be remedied by using catalytic converters in
the exhaust system to insure the complete oxidation of the aldehydes to carbon
dioxide and water.

SAQ 6

Why lead components are added to gasoline and why was it removed with the
advent of catalytic convertors ?

SAQ 7

What advantages do oxygenates offer when added to gasoline in comparison to lead

compounds.

3.10 LUBRICANTS
Lubricant is as substance which is introduced between two sliding surfaces to
reduce friction and wear rate. This process of reducing friction by application of
lubricant is referred to as lubrication.

Functions of lubricants
• Reduces friction and wear and tear of surfaces
• Acts as coolant by dissipating heat
• Prevents entry of moisture

80
• Minimizes power loss in internal combustion engine Environmental
Chemistry - III
• Reduces maintenance cost

Mechanism of Lubrication
The phenomenon of lubrication can be explained by three types of mechanism :

1. Thick Film Lubrication or hydrodynamic lubrication: In hydrodynamic

lubrication, the sliding surfaces are separated from each other by a thick
fluid film of 1000A to avoid surface to surface contact. The thick film covers
irregularities of the surfaces a so that metal surfaces do not come in contact
with each other which finally reduces the friction. The lubricant selected has
minimum viscosity to reduce internal resistance and should remain in place
and separate the surface. Hydrocarbon or mineral oils (having low molecular
carbon atoms ) are preferred lubricants for this type lubrication.

2. Thin film or boundary Lubrication: Boundary lubrication occurs when

continuous fluid film cannot persist either due to low speed , high load or low
viscosity of lubricating oil. The clearance space between the sliding surfaces
is lubricated with a material that gets adsorbed on metallic surface by physical
or chemical means which keeps the metal surfaces apart . Vegetable or animal
oils and their soaps can be used for this type of lubrication. Though vegetable
oils possess good adhesion property but they tend to break down at elevated
temperatures.

3. Extreme Pressure Lubrication: When sliding surfaces are under high pressure
and speed liquid lubricants fail to stick and decompose. To sustain such extreme
pressure conditions, additives are added to mineral oils . These additives form
strong films capable of sustaining high loads at elevated temperatures. The
additives include organic compounds such as sulphur in sulphurized oils or
phosphorus in tricresyl phosphate.

3.10.1 Classification of Lubricants:

Based on shear strength lubricants are classified into three types:
1. Lubricating oils or Liquid lubricants
2. Greases or semi-solid lubricants
3. Solid Lubricants
4. Lubricating Oils or Liquid Lubricant: They are classified into three
categories:
i. Animal and vegetable oils: Vegetable oil is extracted from castor
or rapeseed oil while animal oil extracted from animal fats such as
fish comprising of fatty acids and alcohols. They have good sticking
phenomenon and can withstand high loads at high temperatures and
pressures. But they suffer from following drawbacks :
• Expensive
• Undergo oxidation to form gummy product
• Hydrolyse easily in presence of moist air

81
Fundamentals of ii. Mineral or Petroleum oil: They are obtained by fractional distillation
Environmental of petroleum comprising of lower molecular weight hydrocarbons
Chemistry
having 12-50 carbon atoms. They are mostly used lubricants due to its
high stability, abundance, and less costly. But oiliness of mineral oil is
less, hence e higher molecular weight compounds such as oleic acid
and stearic acid are added.
iii. Blended Oils: Vegetable/animal or mineral oil suffer from drawbacks,
hence additives are added to such oil to increase their performance .
Such additives added to lubricating oils are referred to as blended oil.
Examples :stearic acid, palmitic acid, coconut or castor oil.

5. Semi-Solid Lubricants or Grease: A semi-solid lubricant obtained by

combining lubricating oil of low viscosity which is thickened by addition of
finely dispersed solids called thickeners. It consists of followings:
• Base oil: It is the principal component and can be either petroleum oil
or a synthetic hydrocarbon of low to high viscosity.
• Additives: are added to grease to increase their performance. Extreme
pressure and friction modifiers are commonly used examples include:
zinc alkyl dithiophosphate, dibenzyl sulphide
• Thickeners: It comprises of two basic types: inorganic and organic
thickeners. Organic thickeners are either soap based or non-soap based
while inorganic thickeners are non-soap based. Simple soap based
thickeners are formed by combing fatty acid or an ester with an alkali
or alkaline earth metals like Na, K, Ca, by applying heat and pressure
through process known as [Link] soap thickeners include
synthetic polymers and silica gel etc.
Advantages of grease
• Reduces noise and vibration
• Water resistant and reduces oil vapour problem
• Prolong the life of worn parts
• Support much heavier load at lower speed.
Disadvantages
• Cannot effectively dissipate heat from the bearings, so work at relatively
lower temperature
• Contaminants cannot be separated
6. Solid Lubricants: Solid lubricants are used in powder form or with binders
so that they firmly stick to the metal surface. Also available in dispersion in
non-volatile carriers such as soap, waxes, fats etc.
They are used under following conditions:
• Where high loads are required
• Operating temperatures and pressures are too high

82
 • lubricating film cannot be protected by grease Environmental
Chemistry - III
• Contamination by grease

Classification of solid lubricants

• Inorganic lubricants with lamellar structure: The crystal lattice of these
lubricants has layered structure with hexagonal rings that forms parallel layers.
Each atom is bonded to another atom by weak Vander walls thus allowing
sliding movements of plane. Examples include : Graphite is most commonly
used solid lubricant in powder or suspension form. The high thermal and
oxidation stabilities at temperature of 500-600° C makes it effective to be
used at high temperatures and high sliding speeds. It has layered structure
which enables the parallel layers to slide over one another thus making it an
efficacious lubricant Also the layer of graphite has a tendency to absorb oil
and to be wetted of it.
• Oxides: ZnO, MoO2, Re2O7, B2O3 etc.
• Soft metals: Some soft metals possess lubrication properties due to low shear
strength and high plasticity. Eg. Pb, Sn, Bi, Cd. They are used in pure form or
as alloys and applied as coatings.
• Organic lubricants with chain structure of polymeric molecules: examples:
polytetrafluoroethylene (PTFE) . The structure consists of long chain
molecules parallel to each other held by weak forces so that they may slide
past one another at low shear stress.
• Soaps: metal salts (Li, Na, K, Ca) of fatty acids.

3.10.2 Properties of Lubricants

1. Viscosity: It is defined as the resistance offered due to the motion of the
forces between the fluid molecule. It is one of the most important property
of lubricating oil. The formation of fluid film of lubricant between the metal
surfaces depends upon the viscosity. High viscosity of lubricating oil results
in excessive friction while because of low viscosity, film cannot be withstand
between the sliding surfaces. Viscosity of liquid decreases with increasing
temperature, hence as operating temperature rises, lubricating oil becomes
thinner due to low viscosity. Viscosity of lubricating oil should such that it
should not change with temperature changes.

2. Corrosion Stability: Steel or copper corrosion test are carried out to estimate the
corrosive stability of lubricant. Corrosive substances like hydrogen sulphide ,
polysulphides are present in petroleum products which are removed by refining
process. In copper corrosion test, a piece of copper strip is placed in lubricant
for stipulated period of time and defined temperature to examine for tarnishing
of strip. Steel corrosion test is carried out to determine the ability of oil to
prevent corrosion of ferrous parts in water. Inhibitors like zinc dithiophosphate
is added to prevent corrosion of lubricating oil.

3. Flash point and fire point: One of the important characteristic of good lubricant
is that it should not volatilise under operating temperatures. Flash point is

83
Fundamentals of defined as minimum temperature at which oil vapourizes to ignite momentarily
Environmental when flame is brought near to it. Fire point is the minimum temperature at
Chemistry
which lubricant oil burns continuously for atleast five seconds when flame is in
contact with oil. The temperature of fire point is 10-40 C higher than flash point.
The requirement for good lubricant is that it should have flash point above the
operating temperature thus ensuring the safety against any fire hazards.

4. Aniline Point: Aniline point is defined as minimum equilibrium solution

temperature for equal volumes of aniline and lubricant oil. It indicates
deterioration of oil when in contact with rubbing sealings. Aromatic hydrocarbons
have ability to dissolve natural and synthetic rubbers. A high value of aniline
point indicates high paraffinic hydrocarbons and low percentage of aromatic
hydrocarbons. Low content of aromatic hydrocarbon is preferred criteria for
good lubricant oil. Aniline point is determined by mixing equal proportion
of lubricating oil and aniline in a test tube and heating till a homogeneous
solution is obtained. The test tube is then cooled till two phases separates. This
temperature is recorded as aniline point.

5. Cloud point and pour point: Petroleum products are complex hydrocarbons and
do not exhibit fixed freezing point. When they are cooled, they become solid
due to congealing of hydrocarbons. Cloud point is the temperature at which
crystallization of solids occur in form of haziness, while temperature at which
oil just ceases to flow when cooled is called pour point. Cloud and pour point
determines suitability of lubricant under cold environment. Examples include
refrigerators plants and air craft engines which operates at sub-zero temperatures
requires lubricants having low pour point which otherwise cause solidification
of oil and jamming of machine parts.

SAQ 8

What are different types of mechanisms for lubrication?

SAQ 9

What are important characteristics for a good lubricant?

84
3.11 BIOGAS Environmental
Chemistry - III
Increasing production of organic waste is one of the major environmental concerns
of the present scenario. Sustainable waste management as well as waste prevention
have become major goals to reduce pollution and greenhouse gas emissions to
mitigate global climate changes. Uncontrolled waste dumping or incineration of
organic waste are now a days not recommended practices for waste disposal from
environmental point of view. This problem can be circumvented by production of
biogas by degrading biological waste (manure, sewage, sludge, solid waste) in the
presence of anaerobic bacteria.

Biochemical reaction of biomass can be represented as :

2[-CH2O] → CH4 + CO2

When micro-organisms have acted upon the biomass under anaerobic conditions,
it results in formation of digestate and biogas. Digestate refers to decomposed
substrate which is rich in nutrients and used as potent plant fertilizer.

Biogas is a combustible gas chiefly comprising of methane (50-70%) and carbon

dioxide CO2 (25-30%) as primary constituents while others include H2 (0-1%),
N2(0-10%), H2S (0-3%) O2(0-2%).

Examples of biogas include :

• Natural gas produced by decaying animal and vegetable waste buried under
the earth’s surface.
• Gobar gas produced by anaerobic fermentation of cattle dung.
• Sewage gas-produced from municipal solid waste including human and
animal faeces
The main advantage of using biogas through anaerobic digestion is that biodegradable
waste is treated thus destroying disease causing pathogens and reducing the volume
of the sludge generated. Secondly, value of the waste is conserved so that it serves
as fertilizers for the crops.

Gobar Gas
Gobar gas is produced by degrading cow dung anaerobically. The plant consist of
a digester covered with dome shaped roof made up of concrete fitted with a outlet
pipe with a gas valve. There is a sloping inlet on one side and a outlet chamber on
the other side. Manure along with wate slurry is directed to the digester through
the inlet. In the presence of anaerobic bacteria, cattle dung undergoes fermentation
resulting in the evolution of biogas. Pressure is built up on the slurry due to the
evolution of biogas which forces the spent slurry to the overflow tank via outlet
chamber. The residue (digestate) left after is withdrawn periodically and used as
biofertilizer.

The digesters used are generally located in close proximity to dwellings or sources
of the waste.

85
Fundamentals of Biogas is widely used in villages owing to its simplicity in implementation and
Environmental work up procedure and use of inexpensive raw material.
Chemistry
Advantages:
• It burns without smoke causing no pollution to the environment
• Possess high calorific value
• Cheap
• Clean and convenient
• Involves no storage problem
Disadvantages:
• Dependence on cattle dung from which it is produced through anaerobic
fermentation
• Gas stove or burner should be in vicinity of 10 m of the plant.
SAQ10
Give reasons why production of biogas should be encouraged ?

3.12 LET US SUM UP

This unit explained about
• Chemistry of the concept of solubility, solubility product and solubility of
gases
• governed by Henry’s law.
• How carbonate cycle dominates pH control in most of aquatic system and
regulation of various biogeochemical processes in environment.
• Role of Chemical speciation in assessing the toxicity associated with different
forms of chemical element and their oxidation state illustrating it with arsenic at
• Sources and toxicity of heavy metals such as Pb, Cd, As, Hg in the environment
• Different types of radionuclides and its effects.
• Impact of hydrocarbon (saturated and unsaturated) on environment.
• Chemistry of gasoline, additives added to gasoline to increase performance of
engine, and how knocking can be averted by adding antiknock compounds.
• Mechanism, functions and classification of lubricants into lubricating oil,
greases and solid lubricants.
• Degradation of biological waste into biogas.

86
3.13 GLOSSARY Environmental
Chemistry - III
Additive: The substance added to increase the performance properties
Antiknock: Resistance to pinging in sparked engines
Anti-knocking agent: Substance which is added to internal combustion engine to
reduce knocking
Aniline point: Temperature above which equal proportion of petroleum products
and aniline are miscible
Biogas: Combustible gas synthesized by decomposing biological waste under
anaerobic conditions
Cloud Point: Temperature at which solid substance crystallises from the solution
and imparts haziness
Cracking: Process to break down high molecular weight hydrocarbons to lighter
ones
Octane number: Number which denotes antiknock characteristic of gasoline
PAH: Polyaromatic hydrocarbons comprises of two or more fused aromatic rings
Gasoline: Mixture of hydrocarbons with small amount of additives added to internal
combustion engine.
Oxygenates: Oxygen containing compound used as gasoline blending agent eg.
ETBE, MTBE, TAME
Pour Point: Lowest temperature at which oil flows when it is chilled under definite
conditions
Solubility product: Equilibrium constant for a chemical reaction in which solid
ionic compounds dissolves to yield its ions in solution

3.14 SUGGESTED READINGS

• A.K. De, Environmental Chemistry: New Age International Pvt., Ltd, New
Delhi.
• S. M. Khopkar, Environmental Pollution Analysis: Wiley Eastern Ltd, New
Delhi.
• S.E. Manahan, Environmental Chemistry, CRC Press (2005).
• S. S. Dara: A Textbook of Engineering Chemistry, S. Chand & Company Ltd.
New
• James Girad, Principles of Environmental Chemistry, Third Edition, Jones
and Bartlett Publisher
• J.A. Kent: Riegel’s Handbook of Industrial Chemistry, CBS Publisher, New
Delhi

87
Fundamentals of 3.15 TERMINAL QUESTIONS
Environmental
Chemistry
1. Define solubility product.
2. Name the predominate carbonate species in natural waters of oceans.
3. Name the antidotes that can be used for heavy metal poisoning.
4. For each of the following pairs of hydrocarbons, indicate which has the higher-
octane rating.
a) Pentane or octane
b) 2-Methylpentane or 2,2-dimethylbutane
c) Octane or 2-methylheptane

5. List four compounds that are used as octane enhancers.

6. Why C2H4Br is added to antiknocking agent tetraethyl lead?
7. Give two reasons why TEL was banned as a gasoline additive?
8. Name four solid lubricants.
9. What should be the flash point of good lubricant?
10. Explain how graphite acts as a lubricant.

88
UNIT 4 : D EVELOPMENTS IN ENVIRONMENTAL
CHEMISTRY
Structure
4.0 Introduction
4.1 Objectives
4.2 Need for Emergence of Green Chemistry
4.2.1 Bhopal Gas Tragedy
4.2.2 Thalidomide Disaster
4.2.3 Times Beach
4.2.4 Love Canal Disaster

4.3 Some Important Laws for Environmental Protection

4.4 Green Chemistry and Sustainability
4.5 Concept of green chemistry
4.5.1 Twelve Principles of Green Chemistry
4.6 Greener solvents
4.6.1 Issues with the use of Traditional Solvents
4.6.2 Green Solvents
[Link] Water
[Link] Supercritical Fluids (SCFs)
[Link] Ionic Liquids
[Link] Liquid Polymers
[Link] Bio-Based Renewable Solvents

4.7 Earth friendly plastics

4.7.1 Plastics-the Biggest Source of Pollution
4.7.2 Greening of Plastics

4.8 Environmentally Benign Pesticides

4.8.1 Effect of Synthetic Pesticides on Human Health and Environment
4.8.2 Search for Environmentally Benign Pesticides
4.8.3 Examples
[Link] Microbial Pesticides
[Link] Plant-pesticides
[Link] Biochemical Pesticides
[Link] Natural Home-made Solutions for Pest-control

4.9 Let Us Sum Up

4.10 Glossary
4.11 Suggested Further Readings
4.12 Terminal Questions

4.0 INTRODUCTION
Undeniably, the past few decades have witnessed an enormous improvement in
scientific methodologies/solutions showing phenomenal capability to protect
human health and environment and these innovative solutions have been possible
through green chemistry. We have had fantastic accomplishments as the solutions

89
Fundamentals of were at the molecular level since green chemistry preached the prevention of waste
Environmental at source rather than treating it up after generation. So, quite a few of the existing
Chemistry
processes were redesigned using the basic tenets of green chemistry. Progressively,
industries also started adopting the path of green synthesis. In this unit we will learn
the concept of green chemistry and their applications to prevent the environmental
pollution.

4.1 OBJECTIVES
After studying this unit, you will be able to:
• Understand the significance of green chemistry, how it came into emergence
and how it is playing a key role in improving human health and environment.
• Understand the basic concepts and various principles of green chemistry.
• Explain about green solvents.
• Discuss the problems associated with plastics and attempts being directed
towards resolving plastic pollution through green chemistry.
• Explain about eco-friendly pesticides and their significant role in agrochemical
sector.

4.2 NEED FOR EMERGENCE OF GREEN

CHEMISTRY
If we reflect back on the past several decades, we find that chemistry has played
an indispensable role in increasing the quality of life and overall growth and
development of society besides sufficing our basic needs-right from clothes to food
to medicines (Figure 1). As per the data provided by World Health Organization
(WHO), life expectancy has increased over the years. Today, we have good
pharmaceutical drugs to combat chronic diseases, improved transportation for
energy efficiency, better nutrition, improved herbicides and pesticides for pest
control, sophisticated medical devices etc.

90
 Developments in
Environmental
Chemistry

Figure 4.1 Chemistry in everyday life.

However, the darker side of the massive production of chemicals and related goods
with the industrial revolution has been the generation of waste that has negatively
impacted both human health as well as environment. One thing is quite clear that
none of the industries or manufacturers wished to harm the environment, but due
to lack of fundamental understanding of the hazardous nature of many of the
chemical products and poor handling, ended up releasing wastes continually into
the environmental matrices. The awareness about the need to rethink chemical
processes and designing began with the story of “Silent Spring” which was published
in the form of book by Rachael Carlson way back in 1962. In this book, Carlson
had written about how the bald eagle species became extinct because of excessive
use of DDT. This was an extensively used pesticide that had entered the food chain,
resulted in thinning of egg shells that failed to produce baby birds. Some of the
other species such as ospreys and brown pelican also got affected by the use of
DDT. The book was entitled silent spring with a much heavy heart by her as she
feared that the birds who sang outside her window may become completely extinct.
Thereafter, the awareness prompted the ban on this hazardous chemical pesticide.

A number of other incidences and disasters in the past triggered the need to adopt
Green Chemistry, a few have been highlighted below:

4.2.1 Bhopal Gas Tragedy

On the night of 2nd-3rd December, 1984 the worst industrial disaster which is known
as the Bhopal Gas Tragedy occurred at Union Carbide Company of India (a pesticide
plant) due to leakage of methyl isocyanate gas. This gas spread rapidly within the
radius of eight kilometres. More than 4000 people lost their lives and 2000 were
almost injured. Studies carried out by ICMR (Indian Council of Medical Research)
revealed that people died because of suffocation and toxins that had resulted in
swelling in the brain and finally death

91
Fundamentals of SAQ 1
Environmental
Chemistry What was the major factor that lead to the Bhopal Gas Tragedy?

4.2.2 Thalidomide Disaster

Thalidomide drug was introduced in Germany in 1957 as a sedative and hypnotic
for treatment of morning sickness in pregnant women. It was one of the most sold
drugs. However, a few years later it was found that approximately 10,000 children
were born with phocomelia which resulted in limb malformation and this was a
repercussion of the consumption of thalidomide drug by the mothers of the new
born children. This is referred as the thalidomide disaster which had caused a great
deal of fear in general public about the effects of synthetic chemicals and prompted
many countries to tighten drug approval regulations.

SAQ 2

Give the structure of thalidomide drug.

4.2. 3 Times Beach

Times Beach is a small town located in the St. Louis County, Missouri, United
States, which became a permanent community of small homes and trailer parks.
In 1982, the people residing in this town were forced to leave forever as the
Environmental Protection Agency (EPA) had found high levels of a chemical called
dioxin in the soil along the roads. The source of contamination was found to be
dioxin-tainted waste oil that was sprayed on the roads almost a decade ago. The
spray of this toxic chemical had led to deaths of various animals such as horses and
birds in addition to the acute poisoning symptoms including intense stomach pain,
headache, diarrhoea, nosebleeds, skin rashes etc. experienced by people living in
and around Missouri town. The problem faced by the residents increased even more
by a flood because of which 700 families had to leave their homes. Finally, the
entire town has to be evacuated.

92
4.2.4 Love Canal Disaster Developments in
Environmental
Another incidence that caught a lot of public attention was the love canal disaster. Chemistry
Love Canal was originally built by William T. Love in the eastern edge of Niagara
Falls, New York with the vision to generate power economically to fuel the
industry as well as homes of this model city. Love believed that this could be done
by digging a short canal between the upper and lower Niagara Rivers. However,
unfortunately this project failed to sustain the economy and transmit electricity
over great distances by means of an alternating current. Even worse, the canal was
turned into a municipal and industrial chemical dumpsite from 1930’s to 1950’s,
the chemical dump continued. Years after, the chemical substances that had been
dumped began to leak and the site got contaminated by atleast 82 chemicals many
of which were suspected carcinogens including benzene, chlorinated hydrocarbons
and dioxin. As a consequence of the massive exposure to these chemicals, many
critical health issues including high birth defect, miscarriage rates, liver cancer,
seizure, nervous diseases etc. were witnessed amongst the neighbourhood children.

4.3 SOME IMPORTANT LAWS FOR

ENVIRONMENTAL PROTECTION
All these incidences are referred as unforeseen chemical consequences that resulted
in tragedy, followed by public outrage which in turn necessitated some legislations
(also called environmental laws and movements) to control the manufacture, use
and disposal of substances. Some important laws are highlighted below:
• 1970 National Environmental Policy Act (NEPA): This law promotes the
enhancement of environment by establishing the President’s Council on
Environmental Quality (CEQ).
• 1970 Clean Air Act: To prevent air pollution, protect the ozone layer and
promote public health.
• 1972 Pesticide Control Act: For controlling the sale, distribution, and application
of pesticides through an administrative registration process
• 1972 Clean Water Act: To restore and maintain the chemical, physical, and
biological integrity of the nation’s waters.
• 1976 Toxic Substances Control Act: Regulates the introduction of new or
already existing chemicals.

However, these laws primarily focussed on dealing with pollution regulation. Soon
the need was realized to prevent pollution at source rather than treating it after it
was generated and thus, Green Chemistry was introduced.

93
Fundamentals of 4.4 GREEN CHEMISTRY AND
Environmental
Chemistry SUSTAINABILITY
In the year 1990, Environmental Protection Agency (EPA) came with the first act
called as the Pollution Prevention Act that focussed on pollution prevention at
source which in turn lead to the emergence of Green Chemistry. This act states
“Pollution Prevention is reducing or eliminating waste at the source by modifying
the production process, promoting the use of non-toxic or less toxic substances,
implementing conservation technique and reusing materials rather than putting
them into the waste stream.” With the passing of this act, for the first time there
was a change in the policy from pollution control to pollution prevention and the
industries were motivated to undertake research that dealt with the production of no
waste. Soon a year after, EPA started an alternative synthetic reaction programme
that aimed at providing research grant for conducting chemical synthesis without
causing pollution. Thereafter, Paul Anastas who was working at that time at the
EPA office of Pollution Prevention and Toxics coined the term Green Chemistry.
In the year 1998, Anastas along with John C. Warner gave the twelve principles of
Green Chemistry and published the first book on Green Chemistry entitled “Green
Chemistry: Theory and Practice.” These principles are encouraging scientists,
chemists and industrialists to pursue chemistry in a greener way.

Green Chemistry is central to sustainable development or it can help in

accomplishing sustainability. As per United Nations Brundtland Commission
‘Sustainable Development” is defined as “Meeting the needs of the present without
compromising the ability of future generation to meet their own needs.”

SAQ 3

What is Green Chemistry? What is the significance of the colour green?

4.5 CONCEPT OF GREEN CHEMISTRY

The term green is often associated with the natural surroundings (for instance green
is the colour of plants). According to the founders of Green Chemistry Anastas
and Warner, “Green Chemistry is the design of chemical products and processes
that reduce or eliminate the use and/ or generation of hazardous substances.” It is
also known as “clean or sustainable chemistry” or a chemistry that is “benign by
design.” As per EPA “Green Chemistry prevents pollution at the molecular level,
is a philosophy that applies to all areas of chemistry.” We cannot define it as a new
branch of chemistry, but it is the way chemistry should be practiced i.e. dealing
with chemicals and their manufacturing processes to minimize any negative

94
environmental effects. Figure 2 highlights all the factors that green chemistry aims Developments in
at reducing. Environmental
Chemistry

Figure 4.2 Approach of Green Chemistry.

4.5.1 Twelve Principles of Green Chemistry

In this unit, we have described the twelve principles of Green Chemistry in a concise
manner which will be helpful in understanding the basic concept involved.

Principle 1: Prevent Waste

According to this principle, it is better to prevent waste rather than clean up waste
after it is formed. This is certainly one of the most effective principles which if
followed well can eliminate problems of waste generation. Also, it can significantly
reduce the costs involved in the manufacturing processes as there are huge expenses
involved in the treatment and disposal.

To understand this principle, we must know what waste is? By the name itself waste
means something undesirable or unwanted. It is a process or material that does not
add value to goods or services. We may also interpret waste as material discharged
or released into the environment in an amount of manner that may cause a disastrous
effect. If we talk about chemical waste, it is simply the unwanted product generated
during a manufacturing process or reagents which remain unutilized. For instance:
in the Leblanc process employed largely by the textile industry in Lancashire in
UK, huge amounts of waste were generated. This process dealt with the generation

95
Fundamentals of of Na2CO3 from rock salt, limestone and sulphuric acid, HCl, CaS and CO are
Environmental produced as waste as shown below:
Chemistry
2 NaCl + H2SO4 Na2SO4 + 2HCl

Na2SO4 + 4C + CaCO3 Na2CO3 + CaS + 4CO

The release of toxic HCl gas was reported to cause asthama and respiratory problems
in South Lancashire where this process was carried out. Besides, the foul smeling
CaS also lead to critical environmental issues. Roger Sheldon in 1992 gave a term
called E-factor which is also known an environmental factor to measure waste.
Larger the E-factor greater is the waste generated.

E-factor=kgs of by products (waste) produced/kg of desired product

Processes can be redesigned so that E-factor is minimized. There are successful

examples which illustrate how the use of a selective catalyst helped in reducing
E-Factor. For instance, Pzifer redesigned its Sertraline manufacturing process with
the use of TiCl4 as the catalyst that helped in minimizing the quantity of waste
generated.

SAQ 4
Give an example to illustrate Principle 1.

Principle 2: Atom Economy

Principle 2 states that “Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final product.” 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.”

To understand how atom economy is different from the yield calculation, we need
to understand what yield % is and how it is calculated.

% Yield = (Actual Quantity of desired product/Theoritical quantity of the desired

product) x 100

The biggest demerit with this calculation is that it does not consider waste or
by-products formed because a 100% yield does not ensure whether waste is not
generated. For instance: the very famous Wittig Reaction proceeds with 100%
yield, but does not take into account the large amounts of by-products obtained.
Any reaction can be considered green if there is maximum incorporation of the
starting materials and reagents in the final product.

Examples of atom economical reaction:

(i) Generation of ammonia

96
 Developments in
Environmental
Chemistry

Atom Economy = (Mass of atoms in the desired product ÷ Mass of the atoms of the
reactants) × 100
={34÷(28+6)} × 100
= 100 %

(ii) Addition Reaction

SAQ 5:
Give an example of a reaction comparing its atom economical and uneconomical
pathways.

Principle 3: Designing Less Hazardous Chemical Synthesis

As per principle 3, “Wherever practicable, synthetic methodologies should be
designed to generate substances that possess little or no toxicity to human health
and environment.” This principle motivates chemists to design products by
avoiding reagents/starting materials that could be toxic. But, if we are not able
to completely avoid the use of hazardous material, care must be taken towards
minimizing its use. There are several examples to project how this principle is
being implemented in industries due to increasing chemical consciousness with
regard to hazard and exposure. For instance: Avalon Natural Products is a company
that is based in California and has been a leader in making cosmetics has prohibited
the use of chemicals banned under EU cosmetic derivative including perfluorinated
compounds used in clothing, cookware, containers; bisphenol A-a carcinogen
found in baby bottles; phthalates used in fragrances for long lasting effect and in
nail polish to make it chip resistant, parabens employed for preventing cosmetics
from deteriorating in bathrooms, sunlight and extreme conditions.

Also, there are examples of less hazardous chemical pathway employed. For
instance: phosgene free route for the synthesis of polycarbonates using dimethyl
carbonate which is much more greener than traditional pathway as it completely
eliminates the use of HCl, CH2Cl2, does not need crystallization, generates higher
quality polycarbonates.

97
Fundamentals of Principle 4: Designing Safer Products
Environmental According to this principle “Chemical products should be designed to preserve
Chemistry
efficacy of function while reducing toxicity.” By safer chemical what we mean
to say is a chemical that would cause minimum adverse effect on human health
and environment. Examples of safer chemicals include structural analogues (i)
methacrylonitrile which is a safer replacement of acrylonitrile (the probable human
carcinogen) (ii) sodium salt of linear alkyl benzene sulphonic acid that readily
biodegrades and is a greener alternative to branched alkyl benzene sulphonic acid.

Principle 5: Safer Solvents and Auxiliaries

This principle states “The use of auxiliary substances that do not directly contribute to
the structure of the reaction product but are still necessary for the chemical reaction
or process to occur should be made unnecessary wherever possible and innocuous
when used.” The statement is self-explanatory and indicates that alternative greener
replacements should be explored for toxic organic solvents which are major
contributors to overall toxicity of a reaction. Many of the traditional solvents such
as benzene, perchloroethylene used in dry cleaning, shoe polish, white correction
fluid are known as human carcinogen and chlorinated hydrocarbons are known to
persist in the atmosphere causing depletion of ozone layer. Thus, pharmaceutical
and other industries are looking for replacements some of which include (i) Water
(ii) Supercritical Fluids (iii) ionic liquids (iv) polyethylene glycol (v) fluorinated
biphasic solvents (vi) biobased solvents (derived from renewable resources) (vi)
no solvent is the best solvent. There are solvent selection guides available which
enable scientists to use safer solvents in research.

SAQ 6:
Why do you think no solvent is the best solvent?

Principle 6: Design for Energy Efficiency

Principle 6 states “Energy requirements should be recognized for their environmental
and economic impacts and should be minimized. Synthetic methods should be
conducted at ambient temperature and pressure.”

Thermal heating processes mostly employ fossil fuels reserves of which are limited
and are soon going to exhaust. In addition, the energy supplied is not specific,
which means it is not directed to the chemical bond of the molecule of the reactants.
Besides, most of the energy is wasted in heating the container and the solvent,
while some is also lost to the environment. The energy efficient alternatives
have been lately been explored which include Microwave assisted, light induced
photochemical reaction and ultrasound assisted irradiation.

98
SAQ 7: Developments in
Environmental
How does microwave chemistry fall under the banner of green chemistry? Chemistry

Principle 7: Renewable Resources

As per this principle “A raw material or feedstock should be renewable rather than
depleting technically and economically practicable.”

All the forms of energy that we have been using with the advent of globalization
and rapid industrialization are fossil fuel based, which are not only going to
exhaust soon, but also have a serious effect on human health and environment.
Hence, attention is now being devoted towards finding out alternative renewable
resources which can work as excellent substitutes. The idea of making our future
fuels, chemicals and materials from feedstocks that never deplete is certainly quite
interesting. There are a few examples of alternative chemicals/products derived
from natural resources including adipic acid from corn starch, biofuel production
from microalgae, green plastics made from corn.

Principle 8: Reduce Derivatives

This principle states that “Unnecessary derivatization (blocking group, protection/
deprotection, and temporary modification of physical/chemical processes) should
be avoided wherever possible.

We often use protecting and deprotecting groups in organic synthesis in order to

achieve desired chemoselectivity. To put it in simple words, whenever there are
two reactive groups in a molecule and wish to use only one of the groups for the
formation of desired product, the other group needs to be protected and subsequently
deprotected. However, the incorporation of these groups require additional steps and
reagents which also lead to an increase in waste generation. This principle advocates
the reduction of using protecting groups and derivatives. The best alternative to
avoid this is to use enzymes as they work under mild conditions and lead to chemo
selectivity. They mostly react at the desired moiety and do not interfere with the
rest of the molecular structure. The antibiotic synthesis of penicillin drug is the best
example illustrating how the traditional protection deprotection method has been
replaced with an enzymatic process and the enzyme used is penacylase.

Principle 9: Use of selective catalyst

According to Principle 9 “Catalytic reagents are superior to stoichiometric reagents.”

99
Fundamentals of In comparison to the traditional stoichiometric processes that lead to enormous
Environmental amount of waste generation, use of catalysts permit higher atom economy and lesser
Chemistry
waste generation. Catalyst is a substance which expedites the rate of a reaction by
providing an alternative pathway without itself undergoing any change and also
enable a process to occur selectively. The catalytic oxidation of PHCH(OH)CH3
using CrO4/H2SO4 has an atom economy of about 42% while the same reaction
when carried out in presence of a catalyst has an atom economy of 87%. Also, when
the reduction of benzaldehyde is carried out in presence of stoichiometric reagents,
atom economy is 81% but on the other hand catalytic reduction of benzaldehyde
leads to 100% atom economy.

SAQ 8:
Give examples of catalysts that active, selective as well as reusable.

Principle 10: Design for Degradation

This principle states “Chemical products should be so designed that at the end of
their function, they do not persist in the environment and break down into innocuous
degradation products.”

In order to understand this principle, we must understand what are persistent

chemicals? These are chemicals which do not degrade easily and remain in
the environment since long, thereby exhibiting toxic effects. In environment,
degradation of the chemicals can occur via microbial activity and plants which is
called biodegradation. However persistent chemicals do not degrade owing to lack
of an appropriate enzyme or microbe. DDT is an example of organic pesticide that
persists in the environment. Thus, now greener substitutes are being developed
for DDT. Another very successful example is provided by the laundry industry.
Detergents have found a lot of use over the past decades, however there was a
problem due to its foaming which occurred because of non-biodegradability of
alkyl benzenesulphonate in detergents. This problem was however resolved by
using linear chain rather than branched chain on benzene sulphonate moiety, which
showed better biodegradability.

Principle 11: Real Time Analysis for Pollution Prevention

As per this principle Analytical methodologies need to be further developed to
allow for real-time, in-process monitoring and control prior to the formation of
hazardous substances.” In other words, what this principle underpins is that if
chemical reaction is monitored continually then, it can help prevent the release
of hazardous and polluting substances due to accidents or unexpected reactions.
Further, if effectively a reaction is monitored, then the warning signs can be
spotted, and consequently, the reaction can be stopped or managed before such

100
an event occurs. Online monitoring has been possible with the help of analytical Developments in
techniques such as GC-MS and LC-MS which help in seeing what is happening Environmental
Chemistry
inside a reaction and to know when exactly it will be completed, thereby reducing
waste, time and energy.

Principle 12: Inherently Safer Chemistry for Accident Prevention

According to this principle “substances and form of a substance used in a chemical
process should be chosen so as to minimize the potential for chemical accidents,
including releases, explosions and fires”

Often, we have also heard of chemical releases due to either routine evolution of
gases or accidental due to negligence of operator or operational malfunctioning.
These releases have a detrimental effect on human health and environment.
Therefore, there is a need to practice safer chemistry by designing chemical
processes and products with specific aim to recognize and eliminate hazards from
the manufacturing process.

4.6 GREENER SOLVENTS

Solvents have attracted a great deal of attention in the scientific community owing
to the crucial role they play in agrochemicals, pharmaceuticals, paints, household
and industrial cleaners etc. Not only do they provide a medium for the dissolution
of a wide variety of substrates, but also accelerate many of the reactions. The largest
user of solvents is the pharmaceutical sector.

4.6.1 Issues with the use of traditional solvents

Organic solvents are the major component of cleaning agents, adhesives,
pharmaceuticals and cosmetics and have been used primarily for mass and heat
transfer as well as separation of desired products from unreacted starting materials
and by-products. Unfortunately, despite being useful one cannot ignore the flip side
of the coin which has been toxicity, flammability, and environmental damage with
the usage of copious amounts of solvents. We already are aware of the carcinogenic
nature of hydrocarbon based solvents such as benzene. Also they are known to
bioaccumulate because of their poor solubility in water. Besides, there are several
other solvents (eg: carbon tetrachloride, and trichloroethylene) which may cause
adverse health effects including eye irritation, headache, allergy, skin reactions
etc. Therefore, efforts are being directed towards either reducing or completely
eliminating the use of organic solvents.

Now we all talk about greener solvents which by definition are environmentally
friendly solvents that are characterized by:
• Low toxicity
• Convenient Accessibility
• Greater Efficiency
• Enhanced reusability

101
Fundamentals of • Increased Biodegradability
Environmental
Chemistry
4.6.2 Alternative Green Solvents
In the subsequent sections, we shall be highlighting examples of alternative greener
solvents that have made a way to large scale organic synthesis.

[Link] Water
Currently, water has gained prominence as a potentially benign solvent due to
environmental benefits, safety, synthetic efficiency, low cost, high specific heat,
natural abundance etc. One might be surprized to note that water had remained a
poor solvent for organic transformations since long due to solubility reasons (poor
solubility of organic compounds in water). Also removal of water was thought
to be energy intensive; contaminated waste streams would be difficult to treat.
Fortunately, these problems have been resolved gradually. Like for instance, the
solubility issue was resolved using surfactants, phase transfer catalysts or by adding
solubilizing groups such as sulphonates, phosphonates, oxalates etc. There are
numerous examples which illustrate that reactions have been carried out “in water”
as well as “on water” successfully with very high yield.

Now, what do we mean by in water and on water should be demarcated.

In-Water Reactions: When the reactants employed are soluble in water, it is an in

water reaction. Quinoxaline synthesis is an example of in water reaction (Figure 3).
R
R

O N
+
5 mol% (NH4)2Ce(NO3)6
O 25 oC N
Tap water

R R

Isolated yield: 80-90%

Figure 4.3 Schematic of quinoxaline synthesis accomplished in water.

On-Water Reactions: When reactants are insoluble in water (hydrophobic), they

are simply suspended in water and remain in the form of aqueous emulsions or
suspensions. Reactions also occur on water with good yield the reason for which
remained unclear for long. However, in 1991 Breslow demonstrated that it could
be due to hydrophobic effect (reactants tend to be away from water and accumulate
together, which increases the probability of a reaction). Figure 4 shows Diels Alder
Reaction occurring on water. Breslow found that the rate of Diels Alder reaction
increases drastically when carried out in water (Table 1).

102
 Developments in
COCH3
Environmental
COCH3
Chemistry
+ H 2O
20 oC

Figure 4.4 Diels Alder Reaction on water.

Table 1 Comparison of rate constant values of Diels Alder reaction

Solvent Additional Component Rate Constant

k2 × 105 M−1s−1
Isooctane - 5.9
MeOH - 75.5
Water - 4,400.0
Water LiCl (4.86 M) 10,800.0
Water β-Cyclodextrin 10,900.0
Water α-Cyclodextrin 2,610.0

[Link] Supercritical Fluids (SCFs)

Although supercritical fluids (SCFs) have been known since long, yet they got
recognized as environmentally acceptable replacements for conventional solvents
after the birth of green chemistry. So, what does the word supercritical mean?
When any substance is subjected to a pressure and temperature greater than its
critical point, it is said to be supercritical. A substance is characterized by its
critical point that is obtained at specific conditions of temperature and pressure.
In the supercritical region, the particular substance exhibits properties of both
liquid as well as gas. The most commonly employed SCF includes supercritical
carbon dioxide (ScCO2) which has Tc=304 K and pc=72.8 atm. ScCO2 has
emerged as a green alternative solvent in a number of industrial reactions such as
hydrogenation, hydroformylation, polymer production, C-C bond formation owing
to myriad of advantages it offers including non-toxicity, abundance, tendency to
get easily removed from the product. In Figure 5, we have shown an example of
the hydrogenation reaction carried in scCO2 which gives the desired product with
100% yield. It is also acquiring paramount significance as a solvent for extracting
essential oils and other products from spices, aromatic herbs and medicinal plants.
It is interesting to note that the decaffeination of coffee has also been accomplished
using scCO2 as solvent.
O O

ScCO2/H2/Pd
120 bar140-200 oC

100%

Figure 4.5 Example of use of scCO2 in hydrogenation reaction.

103
Fundamentals of SAQ 9 Extraction of an important compound from orange peel has been
Environmental carried out using scCO2? Can you name the compound?
Chemistry

[Link] Ionic Liquids

Ionic liquids have emerged as a relatively new class of solvents that are primarily
composed of complex organic salts comprising of cations and anions. These are
essentially liquids at unusually lower temperature, as they have low vapour pressure.
In technical terms, any salt, even NaCl above 800 oC can be designated as ionic
liquid; however the most frequently used definition of ILs is “Salts that exist in
the liquid state below 100 oC and are liquid at room temperature.” Owing to their
complex interplay of coulumbic, hydrogen bonding and Van der Walls interactions
of their ions, ILs have emerged as greener alternatives to volatile organic compounds
(VOCs). Also, to add to their fascinating properties, ILs exihibit:
1. Non- Volatility (which allows for high temperature reactions without the
requirement of a pressure vessel to contain the vapors) and Non-Flammability
2. Work as both catalysts as well as solvents
3. Robust
4. Tailor made, task specific solvents-Allow the tailoring as per requirement.

N N
+ -
AlCl4

1-ethyl-3-methylimidazolium chloride (III) chloride ([emim]AlCl4]

N N
+ -
BF4

1-butyl-3methylimidazolium fluoride-boron trifluoride ([bmim]BF4)

Figure 4.6 Examples of room temperature ionic liquids.

Figure 6 shows examples of some of the common room temperature ionic liquids.
Some well-known reactions conducted successfully in ILs include friedel crafts
reaction, esterification, mannich reaction, regioselective alkylation, reduction of
aldehydes, Fischer Tropsch Synthesis etc.

[Link] Liquid polymers

Similar to the ILs, liquid polymers having different molecular weights have also
gained a lot of attention in organic synthesis since they possess low volatility, low

104
eco-toxicitiy, good thermal stability, non-flammability and most importantly rapid Developments in
biodegradability. Amongst several liquid polymers, polyethylene glycol (PEG) has Environmental
Chemistry
been utilized by both academic as well as industrial researchers in diverse areas
including electroplating, cosmetics, personal care, dyes, paints etc. In Figure 7, it
has been demonstrated how PEG-200 is used as a solvent in Diels Alder Reaction.
PEG can also function as an excellent aqueous biphasic system (ABS) wherein two
phases are formed when mixed with another water soluble polymer and such ABS
are good for extracting toxic dyes that would otherwise be difficult to remove from
the contaminated waste streams.
O
O

PEG-200
+ O
O
50-70 oC, 60 min
or
µW, 150W, 100 sec O
O
80-90%

Figure 4.7 Example of Diels Alder Reaction in PEG-200.

[Link] Bio-Based Renewable Solvents

Solvents which are derived from renewable feedstocks that are bio-based have
been classified as bio-based solvents. The sources generally include agricultural
crops rich in carbohydrates including corn, wheat, beetroot etc. They offer several
significant advantages including low VOC emission, low toxicity, biodegradability
and environmentally friendliness. Some typical examples of bio-based solvents
include bioethanol, glycerol and 2 Me-THF.

4.7 EARTH FRIENDLY PLASTICS

Plastics have turned out to be one of the biggest source of polluters today despite
having innumerable valuable uses in daily life. While every minute, one million
drinking plastic bottles are purchased, half or more than half of them are intended
for one time use and thrown away as such which end up in either a landfill or natural
environment, persisting for years and centuries. Not surprisingly, a staggering 8
million tonnes of plastic reaches the world’s oceans every year and it is the ocean
plastic which is known to kill millions of marine animals every year. Animals are
killed via either entanglement in plastic objects or via ingestion of these wastes,
or through the exposure to chemicals within the plastics that interfere with their
physiology.

Before moving further, it is important to understand what do the plastic wastes

comprise of and why are they so problematic?

Chemically, plastics are polymers of high molecular mass comprising of long

chains of repeating molecular subunits called as monomers. Table 2 provides data
related to the variation in plastic polymers and their uses.

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Fundamentals of Table 2 Examples of polymers used as plastics with their structures and applications.
Environmental
Chemistry Sl. Polymer Structure Use/Application
No
1. Polyethylene OH Water bottles,
terephthalate (PET) O O dispensing
containers,
H O O
biscuit trays
n

2. High—density CH2 Shampoo bottles,

polyethylene (HDPE) H2C CH2 milk bottles,
freezer bags, ice
CH2
cream containers
H2C CH2 H2C
CH2
H2C
C CH2 CH2
H2
H2C CH2
C
H2

3. Low—density Bags, trays,

polyethylene (LDPE) containers, food
packaging film

4. Polypropylene (PP) CH3 Potato chip

CH CH2 bags, microwave
n dishes, ice cream
tubs, bottle caps
5. Polystyrene (PS) Cutlery, plates,
cups

CH CH2
n

6. Expanded polystyrene CH2 CH CH2 CH Protective

(EPS) packaging, hot
drink cups

4.7.1 Primary issues with the synthetic plastics

They are produced from non-renewable sources including crude oil which are
depleting.

Most of the synthetic plastics require the use destructive thermal treatment such as
combustion or pyrolysis, which require high temperature

106
There has been increasing concerns due to the presence of toxic chemicals such as Developments in
bisphenol A (BPA) and polystyrene (PS) that might leach into water. While BPA in Environmental
Chemistry
particular is highly toxic and a known endocrine disruptor which can imitate body’s
hormones, interfering with the production, secretion, transport, action, function,
and elimination of natural hormones often at times leading to fertility problems,
male impotence, heart disease and other conditions; polystyrene has been declared
a possible human carcinogen by the U.S. Environmental Protection Agency (EPA)
and the International Agency for Research on Cancer.

Extremely small sized invisible plastics (mostly PS) called as microplastics are
released from fibres, clothings when washed ultimately reach the oceans causing
deleterious consequences to the marine species.

Considering the extreme toxicity and non-biodegradability associated with the

conventional plastics, now attention is being directed towards the design of earth
friendly or green plastics that are bio-degradable (decomposed by action of living
organism into non-toxic simple molecules including carbon dioxide, water and
biomass). These are essentially made from renewable materials such as plants,
petrochemicals or microbes. The concept behind this is utilization of principles of
green chemistry, especially principle 1 which aims at the prevention of pollution
at source rather than treating up pollution after it has been caused and principle 7:
utilization of renewable feedstocks whenever possible.

SAQ 10: Why do you think plastics have become a big issue today? What are
the underlying problems?

4.7.2 Greening of Plastics

Earth friendly plastics or bio-plastics commonly obtained from natural origins such
as plants, animals or micro-organisms may be classified into the following types:

Polyhydroxyalkanoates (PHAs): Examples of bio-based plastics include

Polyhydroxyalkanoates (PHAs) which are naturally produced by various
micro-organisms eg: Cuprividus necator. Poly-3-hydroxybutyrate (PHB),
polyhydroxyvalerate (PHV) and polyhydroxyhexanoate (PHH) are specific
examples of PHA based plastics.

Polylactic acid (PLA): PLA is a thermoplastic aliphatic polyester synthesized

from renewable biomass, typically from fermented plant starch such as from corn,
cassava, sugarcane or sugar beet pulp.

Cellulose-based Plastics: Cellulose esters such as cellulose acetate and

nitrocellulose are utilized to prepare cellulose based plastics.

107
Fundamentals of Lignin based Plastics: Lignin is commonly obtained as a by-product of
Environmental polysaccharide extraction from various plant materials during the production
Chemistry
of paper, ethanol etc. Lignin based plastics are bio-renewable natural aromatic
polymers with biodegradable properties.

Green Chemistry Challenge Award for innovation of PLA

In the year 2002, Nature Works LLC received Greener Reaction Condition Awards
for replacing petroleum based polymers with bio-based compostable and recyclable
polylactic acid (PLA). This PLA based bioplastic is one of the most promising
and popular materials as an alternative to synthetic polymer. The synthetic process
via which it is manufactured eliminates the use of organic solvents and other
hazardous materials and employed a catalyst that reduces energy usage (Figure 8).
Furthermore, the approach to synthesis biodegradable or green plastics is a much
better solution than disposing off the plastic waste to landfills or via incineration.

HOH2C HOH2C
O
H O O
H H
enzymatic hydrolysis OH
Fermentation H 3C
OH H OH
OH H H2O
OH
H O OH H
H OH OH OH

n
D- glucose Lactic Acid (99.5%)
Starch

condensation (-H2O)

H 3C O CH3 H 3C O
solvent free ring opening o
polymerization depolymerization

OH
catalyst o catalyst OH
H 3C HO
HO
n O n

Low molecular weight

High molecular weight polymer Lactide
prepolymer

Figure 4.8 Synthesis of PLA by Nature works.

Conversion of plastic wastes into valuables

The most emerging green trend now is utilization of waste materials and converting
them into valuables. This is a circular economy approach which primarily revolves
around the concept of converting resources into waste and waste back into valuable
resources which is greener and much more profitable as compared to the linear
approach that only goes a one way path and leads to extensive waste generation.
In view of pressing problems associated with plastic wastes, attempts are now
being directed towards utilizing their untapped potential by converting them into

108
either fuels such as petrol, diesel and kerosene etc using catalytic degradation or Developments in
transforming them into valuable catalytic materials. In India also, we are recycling Environmental
Chemistry
plastic wastes extensively and the current Union government’s focus is on plastic
waste management via the Swachh Bharat Abhiyan programme.

ENVIRONMENTALLY BENIGN PESTICIDES

Over the past decades, the global agricultural sector has extensively relied on
pesticides that have undoubtedly increased the crop yield and reduced post-harvest
losses, but unfortunately their expanded use has polluted the environment whilst
affecting human health considerably. As per estimates, barely 0.1% of the total
agrochemicals utilized in crop protection succumbs to reach the target pest, while
the remaining 99.9% is undeniably bound to enter the environment thus causing
hazards to non-target organisms.

4.8.1 Effect of Synthetic pesticides on human health and

environment
To understand fundamentally how the pesticides, cause massive destruction, we
need to understand the basics. These are organic chemical substances that impart
protection to plants from pests, weeds or diseases. Typically, the various forms
of pesticides employed are insecticides, fungicides, herbicides, rodenticides and
plant growth regulators. Some of the common classes of pesticides that have
negatively impacted human health and environment include organochlorines,
organophosphates, carbamates, pyrethroids, triazines, and neonicotinoids. As
already mentioned previously, DDT was the first ever pesticide that had shown
serious environmental consequences resulting in thinning of egg shells and bald
eagle species becoming extinct.

Subsequently, there have been reports mentioning how harmful the other synthetic
pesticides have proven to be. Table 3 gives examples of the various pesticides that
have exhibited toxicity. Exposure to these chemicals can occur through contact with
either the skin or via ingestion or inhalation. In fact, residues of pesticides have
often found in everyday food including cooked meals, water, wine, fruit juices,
refreshments, animal feeds etc. The fate of the pesticides within human body is
unpredictable; once inside, it may start getting metabolized, excreted, and stored or
bioaccumulated in body fat leading to dermatological gastrointestinal, neurological,
carcinogenic, respiratory, reproductive and endocrine effects.

Table 3 Rising toxicity of pesticides 1945-2003.

Pesticide Brand Name Use LD50 Toxicity
DDT Dinocide Insecticide 27,000 1
Metiocarb Mesurol Insecticide 230 117
Carbofuran Curater Insecticide 160 69
Deltamethrin Decis Insecticide 10 2700
Fipronil Regent Insecticide 4.2 6429
Clothianidin Pocncho Insecticide 4.0 6750

109
Fundamentals of
Imidacloprid gaucho Insecticide 3.7 7297
Environmental
Chemistry Source: Dr. J M Bonmatin, CNRS (France)

SAQ 11

Give examples of synthetic pesticides. In what way have they affected human
health and environment?

Search for Environmentally benign pesticides

In view of the harmful effects caused by the synthetic pesticides, the scientific
community has realized the need for implementation of sustainable practices.
Consequently, environmentally benign pesticides are being developed that are
making an important breakthrough in pest control. Most of the plant derived
materials have emerged as green pesticides as they are safer and effective against
diseases, nematodes and other organisms in addition to phytophagous insects.

4.8.3 Examples
[Link] Microbial pesticides
Naturally occurring or genetically altered bacteria, fungi, algae, protozoans
or viruses have proven to be an attractive and greener alternative to chemical
insecticides. These are called as the microbial pesticides and are pathogenic to the
targeted pest. These are applied as the conventional insecticidal sprays, dusts or
granules. The major advantages of using microbial pesticides include:
(i) They are biodegradable.
(ii) Cheaper, Renewable and can be handled safely.
(iii) Residue-Free.
(iv) Safe to natural enemies and higher organisms.
(v) Difficult for insects to develop resistance against them.

[Link] Plant-pesticides
In nature, plants guard themselves against pests by evolved defence chemicals
which alter the behaviour of selected pest. Such behaviour altering chemicals
are defined as semiochemicals well known for their static mode of action, less
persistence, and biodegradable nature. Plant pesticides are substances produced by
plants from the genetic material that has been added to the plant. Among the plant

110
products, azadirachtin, pyrethrum, sabadilla, etc. are known to have a successful Developments in
history in pest control. Environmental
Chemistry

[Link] Biochemical pesticides

These are the naturally occurring substances that successfully control the pests via
non-toxic mechanisms. They interfere with growth or mating, such as plant growth
regulators, or substances that repel or attract pests, such as pheromones.

[Link] Natural Home-made solutions for pest-control

1. Soap based insecticides
These soaps utilize the salts and fatty acids within them to target many soft-bodied
pests including aphids, whiteflies, mealy bugs, earwigs, thrips, and the early stages
of scale.

2. Neem Oil Insecticides

Insecticidal oils have also proven their efficacy in treating pests by suffocating
them. One such classic example is the oil that is extracted from the seeds of neem
tree which is biodegradable and natural fungicide. It acts as a hormone disruptor
and an antifeedant for the insects that feed on leaves and other parts of plants.
While applying to crops, 2 teaspoons neem oil and 1 teaspoon of mild liquid soap
are mixed well with 1 quart of water, and immediately sprayed on the affected part
of the plant foliage.

3. Diatomaceous earth
Diatomaceous earth made from sedimentary rocks by fossilized algae (ditoms) also
works as a natural pesticide. This substance works in quite an interesting manner
mechanistically by virtue of its abrasive qualities or tendency to absorb lipids a
waxy substance obtained from insects’ exoskeleton, which eventually dehydrates
them to death.

4. Garlic Insecticide Spray

Garlic has a typical aroma which makes it work as an insect repellent and owing
to its natural fungicidal and pesticidal properties, it has emerged as an excellent
economical, non-toxic pesticide. Examples of pests that have been controlled using
garlic include aphids, ants, termites, white flies, beetles, borers, caterpillars, slugs,
army worms etc.

5. Tomato Leaf
Tomato leaves contain alkaloids-”tomatine,” that has shown efficacy in controlling
aphids and other insects.

As most of the synthetic pesticides are not safe and many have even proven to
be cancerous to human beings, therefore these natural environmentally friendly
pesticides emerged as cleaner alternatives in pest control.

111
Fundamentals of SAQ 12
Environmental
Chemistry Environmentally friendly pesticides are making a breakthrough in pest control.
How would you justify this statement?

4.9 LET US SUM UP

Undeniably, the past few decades have witnessed an enormous improvement in
scientific methodologies/solutions showing phenomenal capability to protect
human health and environment and these innovative solutions have been possible
through green chemistry. We have had fantastic accomplishments as the solutions
were at the molecular level since green chemistry preached the prevention of waste
at source rather than treating it up after generation. So, quite a few of the existing
processes were redesigned using the basic tenets of green chemistry. Progressively,
industries also started adopting the path of green synthesis. Utilization of alternative
greener solvents, catalysts and reagents, aiming at higher atom economy, relying
on alternative renewable feedstocks have truly changed the landscape of synthesis
pursued at academic as well as industrial level. Yet, despite accomplishing a lot as
evident from the green chemistry challenge awards, a lot needs to be done as the
number of challenges that lie ahead are far many. Population growth, energy, food
supply, resource depletion, global climate change, water, toxics generation and
dispersion remain the most pressing environmental issues facing the planet even
today. Apart from this, there are research and implementation challenges in view
of stringent laws. Nonetheless, green chemists foresee that all the barriers would
be eventually resolved if there is effective preaching of green chemistry which
requires educating our future chemists. Not just chemists, but since green chemistry
is a powerful tool for safe and healthy environment for all including businessmen,
economists, environmentalists etc. To be successful, green chemistry would require
an interdisciplinary strategy in education, research and service.

4.10 GLOSSARY
Green Chemistry: Green Chemistry is the design of chemical products and
processes that reduce or eliminate the use and/ or generation of hazardous substances

Atom Economy: The atom economy of a reaction is a measure of the amount of

starting materials that end up as useful products.

E-Factor: E-factor also known as environmental impact factor measures the waste
generated in a process. Higher the E-factor greater is the waste generated.

112
Biodegradable Plastics: Plastics that can be decomposed readily by the action of Developments in
living organisms, usually microbes, into non-toxic products. Environmental
Chemistry
Polylactic acid: PLA is a thermoplastic aliphatic polyester synthesized from
renewable biomass, typically from fermented plant starch such as from corn,
cassava, sugarcane or sugar beet pulp.

In-Water Reactions: When the reactants employed are soluble in water, it is an in

water reaction.

On-Water Reactions: When reactants are insoluble in water (hydrophobic), they

are simply suspended in water and remain in the form of aqueous emulsions or
suspensions.

Supercritical Fluids: A fluid is defined as supercritical when its temperature and

pressure exceed critical values (Tc and Pc respectively).

Green Chemistry Challenge Awards: In 1995, the U.S. Environmental Protection

Agency (EPA) received support from President Bill Clinton to establish an annual
awards program highlighting scientific innovations in academia and industry that
advanced green chemistry. This created the annual Presidential Green Chemistry
Challenge Awards, which have been a major platform for promoting awareness
about green chemistry.

Ionic Liquids: These are green solvents primarily composed of complex organic
salts. These are essentially liquids at unusually lower temperature, as they have low
vapour pressure.

Pesticides: Substances that are meant to control pests, including weeds.

4.11 SUGGESTED READINGS

1. Anastas, P.T. Warner, J.C. (1998), Green Chemistry: Theory and Practice.
Oxford University Press.

2. Lancaster, M. (2010). Green Chemistry: An introductory text, RSC Publishing,

Cambridge, UK.

3. Sidhwani, I. Sharma, R. K. (2020). An introductory Text on Green Chemistry,

Wiley Publications, USA.

4.12 TERMINAL QUESTIONS

Q.1 Explain the concept of atom economy using a suitable example.

Q.2 What do you understand by earth friendly plastics?

113
Fundamentals of Q.3 How would you classify whether a solvent is green or not? What are the
Environmental problems associated with traditional solvents?
Chemistry
Q.4 What are environmentally benign pesticides? Give examples of some explaining
how they are a superior alternative to the synthetic ones.

Q.5 Fundamentally highlight the differences between green chemistry and

environmental chemistry.

Q.6 What are supercritical fluids? Give examples of reactions in which SCFs have
been employed as green solvents?

Answers

Self-Assessment Questions
1. The accident had occurred due to non-functioning refrigeration unit, bulk
storage of 42 tons methyl isocyanate (MIC) gas, non-functioning safety
system, stashing staff and switch off of the warning system.
O

N * O

NH
O O

2. Chemistry is the design of chemical products and processes that reduce or

eliminate the use and/ or generation of hazardous substances. According
to EPA “Green Chemistry prevents pollution at the molecular level, is a
philosophy that applies to all areas of chemistry.”
The colour green is associated with the natural surroundings. It is used for
environmentally friendly and sustainable manufacturing processes.

3. Principle 1 states “It is better to prevent waste rather than to treat up after it
is formed.”
Example: In the Leblanc process employed largely by the textile industry in
Lancashire in UK, huge amounts of waste were generated. This process dealt
with the generation of Na2CO3 from rock salt, limestone and sulphuric acid,
HCl, CaS and CO are produced as waste as shown below:
2 NaCl + H2SO4 Na2SO4 + 2HCl
Na2SO4 + 4C + CaCO3 Na2CO3 + CaS + 4CO

The release of toxic HCl gas was reported to cause asthama and respiratory
problems in South Lancashire where this process was carried out. Besides,
the foul smeling CaS also lead to critical environmental issues.

114
4. Oxirane synthesis has been carried out in two ways. The first approach is Developments in
two-stepped (demonstrated here as one step) requiring Ca(OH)2. The second Environmental
Chemistry
approach is single step that requires O2 as oxidant. If we compare the atom
economy of both the reactions, we find that the second approach is 100 %
atom economical while the first one has a very low atom economy of about
25.6%.

Approach 1:

Approach 2: Single Step Synthesis

5. No solvent means performing reactions without using any solvent. This is

certainly the best and greenest solution as it would not lead to any waste
generation and maximize atom economy, because the reactants are the sole
reagents utilized.
6. In conventional heating methods, oil bath or hot plate are used as a source of
heat to a chemical reaction Microwave irradiation is widely used as a source of
heating in chemical synthesis. The basic mechanisms observed in microwave
assisted synthesis are dipolar polarization and conduction. Microwave-
assisted synthesis is greener on account of the following advantages (i)
enhanced reaction rates (ii) higher yields (iii) greater selectivity (iv) more
economic for the synthesis of a large number of organic molecules.
7. Examples of catalysts that suffice the three key goals of catalysis i.e. activity,
selectivity and reusability are supported heterogeneous catalysts eg: Fe3O4
supported Cu nanocatalyst.
8. Extraction of D-Limonene from orange peels has been carried out efficiently
using scCO2. This experiment is conducted in undergraduate laboratories.
9. Plastics have become a big issue today on account of the following reasons:
• They are produced from non-renewable sources including crude oil
which are depleting.

115
Fundamentals of • Most of the synthetic plastics require the use destructive thermal
Environmental treatment such as combustion or pyrolysis, which require high
Chemistry
temperature
• There has been increasing concerns due to the presence of toxic
chemicals such as bisphenol A (BPA) and polystyrene (PS) that might
leach into water. While BPA in particular is highly toxic and a known
endocrine disruptor which can imitate body’s hormones, interfering with
the production, secretion, transport, action, function, and elimination
of natural hormones often at times leading to fertility problems, male
impotence, heart disease and other conditions; polystyrene has been
declared a possible human carcinogen by the U.S. Environmental
Protection Agency (EPA) and the International Agency for Research
on Cancer.
• Extremely small sized invisible plastics (mostly PS) called as
microplastics are released from fibres, clothings when washed
ultimately reach the oceans causing deleterious consequences to the
marine species.
10. DDT, Metiocarb, Carbofuran, Deltamethrin, Fipronil and Clothianidin are
examples of the synthetic pesticides employed. The organochlorine pesticides
like DDT are extremely persistent and accumulate in fatty tissue. Through
the process of bioaccumulation (lower amounts in the environment get
magnified sequentially up the food chain), large amounts of organochlorines
can accumulate in top species like humans; act as endocrine disruptors,
interfering with hormonal function of estrogen, testosterone and other steroid
hormones.
11. In view of the harmful effects caused by the synthetic pesticides, the scientific
community has realized the need for implementation of sustainable practices.
Consequently, environmentally benign pesticides are being developed that are
making an important breakthrough in pest control. Most of the plant derived
materials have emerged as green pesticides as they are safer and effective
against diseases, nematodes and other organisms in addition to phytophagous
insects. Examples of eco-friendly pesticides include include neem oil, garlic
spray, tomato leaves etc.

Terminal Questions
1. 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.”
Example to illustrate atom economy:

Addition Reaction

116
2. Earth friendly plastics or bio-plastics commonly obtained from natural Developments in
origins such as plants, animals or micro-organisms may be classified into Environmental
Chemistry
the following types:
(i) Polyhydroxyalkanoates (PHAs): Examples of bio-based plastics
include Polyhydroxyalkanoates (PHAs) which are naturally
produced by various micro-organisms eg: Cuprividus necator.
Poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and
polyhydroxyhexanoate (PHH) are specific examples of PHA based
plastics.
(ii) Polylactic acid (PLA): PLA is a thermoplastic aliphatic polyester
synthesized from renewable biomass, typically from fermented plant
starch such as from corn, cassava, sugarcane or sugar beet pulp.
(iii) Cellulose-based Plastics: Cellulose esters such as cellulose acetate
and nitrocellulose are utilized to prepare cellulose based plastics.
Lignin based Plastics: Lignin commonly obtained as a by-product
(iv) 
of polysaccharide extraction from various plant materials during the
production of paper, ethanol etc.

By definition, green solvents are environmentally friendly solvents that are

characterized by low toxicity, convenient accessibility, great efficiency and
reusability. Through Life Cycle Assessment (LCA) a technique that quantifies
environmental damage for each of the available solvents, one can decide which is
greener.

Problems associated with the traditional solvents include:

Many of the traditional solvents are organic based and highly toxic. Besides, they
may be volatile, flammable and also carcinogenic.

3. Environmentally benign pesticides are those which are:

• Biodegradable
• Cheaper, Renewable and can be handled safely
• Residue-Free
• Safe to natural enemies and higher organisms
• Difficult for insects to develop resistance against them.

4. The basic difference between green chemistry and environmental chemistry

is that green chemistry focusses on the design of processes and products in
an environmentally benign manner so that no waste is generate and toxicity
is minimized whereas environmental chemistry aims at the chemistry to
combat the environmental problems after they are created.

5. Supercritical fluids are those substances which when subjected to a pressure

and temperature greater than their critical point (obtained at specific
conditions of pressure and temperature), are said to be supercritical. In that
region, the SCFs exhibit properties of both liquid as well as gas. The most

117
Fundamentals of commonly employed SCF includes supercritical carbon dioxide (ScCO2)
Environmental which has Tc=304 K and pc=72.8 atm. ScCO2 has emerged as a green
Chemistry
alternative solvent in a number of industrial reactions such as hydrogenation,
hydroformylation, polymer production, C-C bond formation owing to
myriad of advantages it offers including non-toxicity, abundance, non-
renewable nature, tendency to get easily removed from the product.

118