Industrial ecology

Ecology is the study of the relationships between

living organisms, including humans, and their
physical environment; it seeks to understand the
vital connections between plants and animals and
the world around them.

Natural Ecology
Industrial ecology
Science of sustainability
The philosophy implies that a manufacturing process
needs to be examined in cooperation with its
surrounding systems rather than in isolation. It
characterizes industry as an artificial ecosystem that
functions similarly to a natural ecosystem, in which
one operation‫׳‬s waste or by-products become
another significant input. It is a systematic
perspective that optimizes the whole supply chain,
from procured resources through processed
commodities, manufactured products, and disposal. As
a growing cross-functional research issue, IE is
additionally regarded as a model for a sustainable
future.
Industrial ecology integrates the principles of science, engineering, and ecology in
industry.

Systems through which goods and services are provided in a way that minimizes
environmental impact and optimizes the utilization of resources, energy, and capital.

Every aspect of the provision of goods and services from concept, through production, and
to the final fate of products remaining after use will be considered.

An industrial ecosystem functions through groups of industrial concerns, distributors, and

other enterprises functioning to mutual advantage, using each others’ products, recycling
each others’ potential waste materials, and utilizing energy as efficiently as possible to
maximize the efficiency.
Major Components of an Industrial Ecosystem Showing Maximum Flows of
Material and Energy Within the System
Wastes and Industrial Ecology

In natural ecosystems, true wastes are virtually

nonexistent

Traditional way: Anthropospheric industrial systems have

developed in ways that generate large quantities of wastes

Industrial waste may be defined as dissipative use of natural

resources.
• Human use of materials has a tendency to dilute and dissipate
materials and disperse them to the environment
• Materials may end up in a physical or chemical form from which
reclamation becomes impractical because of the energy and effort
required
• A successful industrial ecosystem overcomes such tendencies
Minimization of Byproduct and Waste

The objective of industrial metabolism in a successful industrial ecosystem is to make desired goods with the
least amount of byproduct and waste

Consider production of Pb from Pb-ore for the production of storage batteries

Large quantities of lead-contaminated tailings left over

from mineral extraction and byproduct sulfur dioxide,
(must be reclaimed to make sulfuric acid )

The recycling pathway for lead production takes

essentially pure lead from recycled batteries and simply
melts it down to produce lead for new batteries

95% recycling efficiency

 Secondary Battery
LEAD ACID BATTERY or STORAGE CELL OR CAR BATTERY

8
Working: It shows both charging and discharging processes.
Anode : lead plate
Cathode : lead dioxide plate
Electrolyte : (25-38%) H2SO4 solution
Discharging : Voltaic cell
Anode: Pb → Pb2+ + 2 e- (oxidation)
Pb2+ + SO42- → PbSO4 
Cathode: PbO2 + 4 H+ + 2 e- → Pb2+ + 2H2O (Reduction)
Pb2+ + SO42- → PbSO4 
Net reaction: Pb + PbO2 + 4 H+ + 2 SO42- → 2 PbSO4 + 2 H2O + Energy (= 2 V)

✓ [H2SO4] decreases in course of reaction.

✓ Both electrodes covered with PbSO4.
✓ As PbSO4 is insoluble in H2SO4, it acts as a protective layer and prevents the further corrosion
of Pb.
As the PbSO4 deposited at both the electrodes is solid, the cell reactions can easily be reversed
by passing emf just above the voltage of the cell i.e., > 2 V
9
LIFE CYCLES IN INDUSTRIAL ECOSYSTEMS

In a system of industrial ecology, the entire life cycle of the product is considered as part of a life-cycle assessment.
• To determine, measure, and minimize environmental and resource impacts of products and services
Scope of the assessment
• Time period •Space
• Kinds of materials, processes, and products in the assessment
Example of the manufacture of an insecticide that releases harmful vapors and generates significant quantities of waste
material
• A narrowly focused assessment might consider control measures to capture released vapors and the best means of
disposing of the waste byproducts
• A broader scope would consider a different synthetic process that might not cause the problems mentioned
• An even broader scope might consider whether or not the insecticide even needs to be made and used; perhaps
there are more acceptable alternatives to its use.
 Life Cycle Assessment

Inventory analysis to provide information about the consumption of material and release of wastes from the point that
raw material is obtained to make a product to the time of its ultimate fate.

• Impact analysis that considers the environmental and other impacts of the product

• Improvement analysis to determine measures that can be taken to reduce impacts

Example of paper product

The environmental impact of paper products tends to be relatively low. Even when paper is discarded improperly; it does
eventually degrade without permanent effect.

Process of making paper, beginning with harvesting of wood and continuing through the chemically intensive pulping
process and final fabrication has significant environmental impact
In doing life-cycle assessments consider three major categories

• Products: Things and commodities that consumers use

• Processes: Ways in which products are made

• Facilities consisting of the infrastructural elements in which products are made and
distributed
 KINDS OF PRODUCTS

Consumable products such as laundry detergents

Recyclable commodities such as some plastics

Service products such as washing machine

➢ Consumable products are dispersed to the environment

• Nontoxic • Not bioaccumulative • Degradable
➢ Recyclable commodities should be designed with durability and recycling in mind

• Not as degradable as consumables

Service products are designed to last for relatively long times, but should be recyclable

• Channels through which such products can be recycled

• Proposed “de-shopping” centers where items such as old computers and broken small appliances can be returned for
recycling
• Designed and constructed to facilitate disassembly so that various materials can be separated for recycling.
REQUIREMENTS BY AN INDUSTRIAL ECOSYSTEM Energy

With enough energy, almost anything is possible

• Consuming abundant fossil energy resources would cause unacceptable global warming
Effects

• Solar energy and wind energy are renewable sources of energy but are intermittent
nature and require large areas of land in order to provide a significant share of energy
Needs

• Nuclear power facilities can provide abundant reliable energy, but present waste
problems
The most often cited example of a functional industrial ecosystem: is Kalundborg Eco-Industrial Park, Denmark
Environmental Chemistry

Part-5

Class-5
 GREEN CHEMISTRY
DEFINITION
Green Chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of
hazardous substances in the design, manufacture and application of chemical products.

GREEN CHEMISTRY IS ABOUT

• Waste Minimization at Source

• Use of Catalysts in place of Reagents
• Using Non-Toxic Reagents
• Use of Renewable Resources
• Improved Atom Efficiency
• Use of Solvent Free or Recyclable Environmentally Benign Solvent system

2
Principles of Green Chemistry
1. Prevention. It is better to prevent waste than to treat or clean up waste after it is formed.

2. Atom Economy. Synthetic methods should be designed to maximize the incorporation of all materials used
in the process into the final product.

3. Less Hazardous Chemical Synthesis. Whenever practicable, synthetic methodologies should be designed to
use and generate substances that possess little or no toxicity to human health and the environment.

4. Designing Safer Chemicals. Chemical products should be designed to preserve the efficacy of the function
while reducing toxicity.

5. Safer Solvents and Auxiliaries. The use of auxiliary substances (solvents, separation agents, etc.) should be
made unnecessary whenever possible and, when used, innocuous.

6. Design for Energy Efficiency. 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. 3
7. Use of Renewable Feedstocks. A raw material or feedstock should be renewable rather than depleting
whenever technically and economically practical.

8. Reduce Derivatives. Unnecessary derivatization (blocking group, protection/deprotection, temporary

modification of physical/chemical processes) should be avoided whenever possible.

9. Catalysis. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.

10. Design for Degradation. Chemical products should be designed so that at the end of their function they do
not persist in the environment and instead break down into innocuous degradation products.

11. Real-time Analysis for Pollution Prevention. Analytical methodologies need to be further developed to
allow for real-time in-process monitoring and control prior to the formation of hazardous substances.

12. Inherently Safer Chemistry for Accident Prevention. Substance and the 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.

4
1. Prevention: It is better to prevent the formation of waste than to treat the
waste after it is formed.

A chemical process/reaction must be carried out in such a manner as to reduce/minimize or completely eliminate the
production of wastes. Waste prevention is necessary because of the following reasons:-

(a) If a process produces waste, it invokes the need for its treatment/disposal, which in turn amounts to additional
expenditure.

(b) Secondly if the waste is toxic or hazardous, the release of waste into the environment leads to its pollution, which
further invokes the need for treatment, causing additional expenses. So we must try to devise processes/reactions
that minimize the production of wastes to the mass of desired products (kg) .

E-factor, also known as the Environmental (Mass) efficiency factor is calculated as:
E-factor = Total Waste (kg) / Product (kg)

5
6
 Classic Route to Ibuprofen

1. Isobutylbenzene
2. Acetic anhydride
3. Ethyl chloroacetate

7
 Hoechst Route To Ibuprofen

BHC company synthesis of Ibuprofen “an industry model of atom efficiency in chemical processing
technology

8
2. Atom Economy: Synthetic methods should be designed to maximize the
incorporation of raw materials used into the products

❖ It is one of the fundamental and most important principles of green chemistry.

❖ The concept of atom economy has been developed by B.M. Trost.
❖ Atom economy is defined as the measure of the amount of reactants that end up directly into the
desired product
❖ It is often referred to as percent atom utilization.

9
Epoxidation of an alkene using a peroxyacid

A.E. of this reaction is 23%.

77% of the products are waste
10
3. Less Hazardous Chemical Synthesis. Whenever practicable, synthetic
methodologies should be designed to use and generate substances that possess little or no
toxicity to human health and the environment.
Polycarbonate Synthesis: Phosgene Process

Bisphenol A

Disadvantages
n phosgene is highly toxic, corrosive
n requires a large amount of CH2Cl2
n polycarbonate contaminated with Cl
impurities
11
4. Designing safer chemicals
Products should be designed to preserve their efficacy of function while reducing toxicity

➢ Thalidomide tragedy:
Thalidomide was a widely used drug in the late 1950s and early 1960s for the treatment of nausea in
pregnant women. It became apparent in the 1960s that thalidomide treatment resulted in severe birth
defects in thousands of children.

R-thalidomide is used to treat nausea, but S-thalidomide can cause

birth defects.
Methyl phenidate
➢ R-R treats attention deficit hyperactive disorder (ADHD) whereas S-S is an antidepressant 12
➢ Manipulation of molecular structures has helped in lot in the design of safer chemicals. A well-known example of
retrometabolic design is that of ethylene glycol, which is used as an antifreeze and has been replaced by propylene
glycol which is less hazardous. Ethylene glycol once ingested into body gets converted into glyceraldehyde,
glyoxylic acid, and oxalic acid which are toxic to body, as against propylene glycol which gets metabolized into
normal body metabolites like lactic and pyruvic acid.

The lethal dose of ethylene glycol for man is 1.4 ml/kg while as the lethal dose of propylene glycol for man is 7 ml/kg.
Thus, in the design of safer chemicals propylene glycol is used as an antifreeze.

13
5. Safer Solvents and Auxiliaries. The use of auxiliary substances (solvents, separation agents,
etc.) should be made unnecessary whenever possible and, when used, innocuous.

Preferred Useable Undesirable

Through green chemistry initiatives, CO2 has replaced many polluting solvents.“CO2, when compressed into a
liquid state, has long been recognized as an ideal solvent.
CO2 solutions are nontoxic, nonflammable, energy-efficient, cost-effective, waste-minimizing, and reusable.

“Dry Cleaning of Clothes: perchloroethylene versus

Liquid CO2”

14
15
6. Design for Energy Efficiency
Energy requirements for the chemical reactions must be as minimal as possible

✓ The most commonly used conventional energy source in reactions is thermal energy.
✓ Thermal energy is non-specific, as it is not targeted directly at a bond or the molecules undergoing the
reaction.
✓ Much of the thermal energy is wasted in heating up the reactors, solvents, and even the general environment.
✓ To avoid these things associated with thermal energy, alternate and more specific forms of energy are used.
✓ These sources are green energy sources include photochemical, microwave, and ultrasonic sources of energy.
✓ This principle requires that energy consumption be minimized in the reactions.
✓ Various possible ways to improve the energy efficiency in processes include:

a) Good insulation and well-maintained equipment reduce heat and energy losses.

b) Generally such reactants should be chosen that require less energy/lower temperatures

c) It advocates that such catalysts be developed such that processes can be run at lower temperature and pressure
thereby reducing energy consumption.

16
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.

17
7. Use of Renewable Feedstocks
Usually, a starting material in a reaction or a process can be from a renewable or non-renewable
source.

Green chemistry however demands that a particular starting material should always be from a
renewable resource so that it is made available in abundance and does not get depleted. e.g CO2, CH4,
etc. can be obtained from natural sources and are available in abundance, and considered as renewable
resources.

This principle also implies the use of renewable energy technologies which include, solar energy,
wind energy, biomass energy, biofuels, and hydropower.

Over the past few years, the production of materials, chemicals, and fuels has been done using
renewable raw materials.. e.g Europe has successfully utilized rapeseed oil as raw material for the
production of biodiesel. Another well-defined example is furnished by the American company Nature
Works which uses bottles made from lactic acid polymers (PLA) made from lactic acid, obtained by the
fermentation of dextrose obtained from starch, most commonly corn. It is believed that to produce one
kg of PLA, 2.5 kg of corn is required.
18
Polylactic acid (PLA) for plastics production

In 2002, Nature Works, a Cargill

company, won a Green
Chemistry award for producing
a biodegradable plastic,
polylactic acid (PLA), from corn”

19
A raw material or feedstock should be renewable rather than depleting whenever
technically and economically practical.

20
Levulinic acid as a platform chemical

21
8. Reduce derivatives
Protecting groups in organic synthesis are important and used to protect a sensitive functionality from reaction
reagents/conditions., which make the reaction go away in an unwanted direction, if unprotected.

In this example, in order to reduce the ester group into an alcohol group, the ketonic group needs to be protected.
Protection is done by using ethylene glycol (II) to get the protected compound (III). The ester moiety in this protected
compound can then be reduced by using LiAlH4 to yield compound (IV). This compound (IV) can then be allowed to
undergo acid hydrolysis, i.e. deprotection which yields the desired product with the generation of protecting group,
ethylene glycol. Such type of protection and deprotection is too common in organic chemistry. In the above procedure, the
protecting group is not incorporated into the final product, which makes a reaction less atom-economical. Thus as far as
possible, the use of protecting groups should be avoided.

22
9. Catalysis. Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.

This principle advocates the use of catalytic reagents rather than stoichiometric reagents. Being unchanged the
catalytic reagent can be recovered completely as the reaction comes to an end. All catalysts including enzymes lower
the activation energy of the reaction, accelerating the reaction several million times, without being changed. Still,
biocatalysts stand out among all other catalysts because of their specificity in terms of stereochemistry, and chemical
selectivity.
Compared to non-biological catalysts, biocatalysts have a great advantage given the rate of reaction, catalytic
specificity, lower cost, etc., but lack of heat sensitivity and poor stability. Biocatalysts are biodegradable catalysts,
which imply less energy consumption.

A classical example that demonstrates the use of catalytic reagents is furnished by catechol. The classical catechol
synthesis is derived from benzene, occurs in a number of steps, and involves drastic reaction conditions giving rise to
unwanted byproducts. However, the biocatalytic route involves a synthesis of catechol from glucose in just a single
step, involves the use of Escherichia coli, and is economically viable, involving non-formation of byproduct.
23
24
10. Design for Degradation

This principle demands the synthesis of such products, which after performing their function properly must
be able to convert into non-toxic end-products. Generally, we see a number of products being synthesized
that do not degrade at the end of their usage. Thus it is required to produce a biodegradable product, otherwise,
it would remain/persist within the environment, may be taken up by plants/animals and as such get
accumulated within their biosystems, detrimental to the concerned species.

For example, the organochlorine class of pesticides, e.g. DDT is non-biodegradable and causes severe problems.
Therefore, a product be designed such that it degrades to innocuous products in the environment. It is now possible
to place groups and other features within the molecules which will facilitate its degradation. Functional groups that
are susceptible to hydrolysis, photolysis, or other possible changes have been used to ensure that products will be
biodegradable.

25
Polyhydroxyalkanoates (PHA’s)

26
11. Real-time Analysis for Pollution Prevention.

Analytical methodologies need to be further developed to allow for real-time in-process monitoring and control
prior to the formation of hazardous substances.

12. Inherently Safer Chemistry for Accident Prevention.

Substance and the 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.

Tragedy in Bhopal, India – 1984

In arguably the worst industrial accident in history, 40 tons of methyl isocyanate were accidentally released
when a holding tank overheated at a Union Carbide pesticide plant, located in the heart of the city of Bhopal.
15,000 people died and hundreds of thousands more were injured.

27
Choice of starting material
Once one intends to design a green chemical synthesis in a lab, the starting material required for that very synthesis
should of course be from a renewable source. Most of the chemical synthesis generally use petrochemicals as starting
materials. Owing to non-renewable nature, besides requiring considerable amount of energy, it is envisaged to reduce
the use of such chemicals, by replacing their use with the starting materials of biological origin. As far as possible, an
ideal feedstock (raw material) should be
a. Renewable
b. Having zero toxicity
c. Converted into products in very few steps
d. 100 % atom economy
e. 100 % yielding
e.g agricultural products like corn, potatoes, soya, and molasses are transformed through a variety of processes into
products like nylon, textiles etc. Materials like butadiene, pentane, pentene, benzene, toluene, xylene, phenolics,
aldehydes, and mannitol, have been obtained from materials of biological origin, molasses.

28
Choice of solvents (Alternative solvents):

The solvent used for a particular reaction should not cause any environmental or health hazard. e.g. All organic solvents
are said to be associated with ill effects on human health. Halogenated solvents like CH2Cl2, CHCl3, CCl4, have long been
identified as suspected human carcinogens. Owing to the concerns associated with these solvents, alternative solvents have
been proposed for use in chemical reactions. Generally, the preferred way to carry out a chemical process is to do it
without the use of solvent, if possible. One such solvent-less reaction comprises those reactions, in which the starting
material and reagents serve as solvents. Alternatively, the reaction can also be performed in molten/solid form. If the use
of solvent cannot be avoided, it is envisaged to carry out reactions in water. Other alternate solvents include, ionic liquids
have been developed. Besides these organic reactions have been carried out in supercritical carbon dioxide and water,
polyethylene glycol and its solution.

29
An ionic liquid comprises a large nitrogen-containing organic cation and a small inorganic anion.
Since one part is large and the other is small, it creates asymmetry in the compound which makes it a
low-melting solid. Simple ionic liquids when mixed with the other inorganic salts result in the
production of a multicomponent ionic liquid. Since the components of an ionic liquid are held by
strong forces of attraction, it is found that they possess no or low vapor pressure rendering them non-
volatile in nature. Further, they are non-flammable and non-explosive which is an additional feature
rendering them safe to use. They can also be used both as solvents as well as catalysts. Thus the
properties of ionic liquids that make them ideal green solvents include:

a) Lack of vapor pressure.

b) Nonflammability and non-explosiveness.

c) Stable at high temperatures which makes them better for carrying out reactions at high
temperatures.

d) The property of these ionic liquids can be changed by just changing their concentrations of
cations/anions, varying the side chain length in cations.

30
A few of the ionic liquids are mentioned below:

31
Choice of Reagents (Appropriate reagents)
Selection of an appropriate reagent for a reaction is done on the basis of efficiency, availability, and its effect on the
environment. The selection of a particular reagent versus another reagent for the same transformation can affect the nature
of byproducts, yields etc. Examples of green reagents include:
Dimethyl Carbonate: Methylation is usually carried out by using methyl halides or methyl sulfate. Being toxic they are
not desirable to be used as methylating agents. However, a green method has been reported by Tundo in literature which
employs dimethyl carbonate to carry out the methylation process at the active methylene site and does not produce any
inorganic byproduct.
Besides this a number of polymer supported reagents have been used. Such polymer-supported reagents are easy to recover
at the end of the reaction and reused and cause no inconvenience in the isolation of products. Some common examples
include:-

32
Choice of catalysts
Catalysts are versatile chemical entities that increase the rate of reaction without being changed. However, not all catalysts
are green. Certain metal catalysts are toxic in nature and cause problems both to the biotic as well as abiotic environment.
Different types of catalysts have been used and are regarded as green catalysts. These include:-

a) Acid catalysts e.g microencapsulated catalysts are replacing the traditional Lewis-acid catalysts. Similarly, fluoride
silica-alumina catalyst is used in place of the corrosive Hydrogen fluoride.

b) Basic catalyst:- Basic catalysts like γ-alumina are used in alkylating the benzene rings.

c) Oxidation catalysts:-e.g Titanium silicate is used to carry out the hydroxylation of phenol to catechol and resorcinol and
quinol.
d) Photocatalysts:- A large number of photocatalysts have been used to carry out the transformations. e.g TiO2 based
photo-catalytic systems.
e) Biocatalysts: These serve as important tools in green chemistry.

Still biocatalysts stand out among all other catalysts because of their specificity in terms of stereochemistry, and chemical
selectivity. Compared to non-biological catalysts, biocatalysts have a great advantage given the rate of reaction, catalytic
specificity, lower cost, etc., but lack of heat sensitivity and poor stability. Biocatalysts are biodegradable catalysts, which
imply less energy consumption. e.g daucous carrota enables the reduction of carbonyl groups like aldehydes, ketones, etc,
which is a biocatalytic reduction.
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Prevention of wastes

Normally a synthesis should be carried out in such a way as to prevent the formation of wastes. If waste production
cannot be ruled out, it is envisaged to carry out a process that could at least minimize the amount of waste generated.
Because once the waste is produced it needs to be disposed of. This leads to the overall cost of the process. Further, the
process should be carried out to ensure 100 percent utilization of the reactants because any amount of starting material
that remains unutilized gets mixed with the products and is regarded as waste. Finally, anything that is produced in a
laboratory ends as a waste. Once the product is formed, it is put to use and ultimately is to be discarded and thus ends up
as a waste. These wastes can pose serious problems to the biotic and abiotic environment. To prevent this, the waste
minimization, recycling, and reuse of wastes is actively employed. Most commonly it is envisaged to reduce the
minimization of waste at the source of its production. If however reduction of waste at source cannot be avoided, we
should try to reuse or recycle the waste to recover material and or energy. Disposal of waste should be the last choice
only.

34
Maximum incorporation of reactants into products (Atom economy)

It is one of the fundamental and most important principle of green chemistry. The concept of atom economy has been
developed by B.M. Trost. Atom economy is defined as the measure of the amount of reactants that end up directly into the
desired product. It is often referred to as percent atom utilization. It gives us the index of how much reactants end up as
desired products and how many end up as waste.

35
For a reaction that involves the formation of intermediates and occurs in more than one step, atom economy calculation
ignores the intermediates and considers the reactants only. Consider a two-step reaction given below.

Here in above reaction C has been ignored because it is produced in one step and consumed in the next step.
36
Reactions have been classified as atom-economic and atom uneconomic reactions. Those reactions in
which atoms of all the reactants end in desired products are highly atom-economical. In organic
chemistry mostly rearrangement reactions, addition reactions and concerted reactions like diels alder
reactions are highly atom economical reactions. While reactions like substitutions, elimination,
Grignard reaction, Wittig reactions are treated as atom-uneconomical reactions.

37
Minimization of hazardous/toxic products

This is one of the important aspects of green chemistry which advocates the minimization of toxic products in processes. A
product may be regarded as hazardous, if it is associated with toxicity, or flammability, has explosion problems, and gets
accumulated within the environment. The impact of hazardous products should be minimized on the workers by the use of
protective clothing, goggles, and respirators. The risk of hazard can be reduced on the workers working in factories producing
such chemicals, by just reducing the time of exposure. The harm being caused by the exposure is given as:

Risk = (function) Hazard x Exposure

From the above relation it is clear that to reduce the risk, we need to reduce either hazard or exposure or both. The reduction of
hazards is regarded as a green chemical approach to minimize the risk. However, if only the time limit of exposure is reduced,
it means that little harm can occur once exposed. If however no exposure is there, it completely eliminates the risk of the
hazard.

38
 Pollution Prevention Hierarchy

Green chemistry is Not a solution to all environmental problems But the most fundamental approach to
preventing pollution.

39
Environmental Chemistry

Part-4

Class-4
 Krebs Cycle
It is an eight-step process. Krebs cycle or
TCA cycle takes place in the matrix of
mitochondria under aerobic conditions.

Coenzyme A

FAD: Flavin adenine dinucleotide

NAD: nicotinamide adenine dinucleotide

GDP: Guanosine di-phosphate

Surfactants: structural diversity: difficult to formulate
Guidelines for biodegradation and the need to ``acclimate'' the bacteria population

Synthetic surfactants

1. Highly branched detergents degrade slowly in part.

2. The ease of cleavage of the surfactant increases, the further the polar sulfate or sulfonate grouping is from the alkyl
terminus of the chain.
Consequently, surfactants with branched chains that are shorter than those with linear chains containing the same
number of carbon atoms degrade more slowly. The possible reason may be the ease of binding of the surfactant to a
degradative enzyme.

3. The slower rate of degradation of surfactants in concentrated sol. than in dilute sol. suggests that minor
constituents of the surfactant mixture inhibit the microbial degradative enzymes.
These guidelines also apply to the alkyl substituent of the alkyl- and alkyl- phenol ethoxylates

1. The alkyl chain will degrade slowly if it is highly branched, and then the ethoxylate grouping will degrade.

2. The rate of degradation of the alkyl chain decreases as the number of ethoxylate groups increases.
The extent of degradation of the ethoxylate chain of an alkylphenol ethoxylate decreases as the number of ethoxylate
groupings increases from 5 to 20.

As it increase the difficulty of transport of the more hydrophilic detergent (with more ethoxylate groupings) through the
hydrophobic cell membrane of microorganisms.

3. The alkylphenol ethoxylates degrade more slowly than the alcohol ethoxylates sometimes the partially degraded
compound ppt out at waste disposal and its anaerobic degradation product (Nonlyphenol) is toxic.
Environmental degradation of polymers
Proteins: polymers of amino acids
Starch and Cellulose: polymers of sugars
Natural rubber is not easily biodegradable

➢ Globally, only 18% of plastics waste are recycled, and

24% are incinerated
➢ 58% is placed in landfills (dumping yards)
➢ Relatively little decomposition takes place in landfills, so
very little of this plastic material disappears with time
(stable for more than 500 years)
Biodegradable Polymers
water-soluble polymers : Polymers that tend to be used only once
Microorganisms use degradable polymers for their growth
• Many hydrocarbon polymers have chemical reactivity similar to that of high-boiling petroleum fractions
Nonbiodegradable Polymers
Environmental Degradation of Polymers
v Goal of the polymer chemist was to design a polymer that degrades very slowly for reusable purposes.
v Indirect photochemical processes, such as oxidation by
photochemically generated singlet oxygen can also result in polymer
degradation.

v Hydroperoxides absorb light at wavelengths greater than 290nm and

are cleaved to hydroxyl radicals and alkoxy radicals or alternatively
cleave to carbonyls

Presence of iron (III) or Titanium (IV) impurities can also trigger the same
radical processes
v Antioxidants, which react with free radicals, are added to many
polymers to slow their rate of degradation
Photochemical decomposition Triggered by Carbonyl Groups

absorb UV light at 300-325 nm and initiate reactions leading to the cleavage of the polymer backbone

Polymers have been prepared in which carbonyl groups were purposely incorporated into the chain to facilitate their
extensive photochemical degradation.
v Poly- styrene cups in which 1% of the styrene units also contained a ketone grouping broke down to a wettable
powder after standing outside in the sun for 3 weeks
 Biodegradation

Most of the biodegradable polymers contain functional groups that are subject to attack by microbial enzymes and
contain ester or amide groups that can be hydrolyzed or linear chains that can be oxidatively cleaved

Problem: inability of microorganisms to ingest high polymers through their cell walls 500 Da.

v Some microorganisms that degrade polyesters secrete esterases, enzymes that catalyze the hydrolysis of ester
groups, which break the polymer into smaller fragments that can then be ingested.
Some typical polymers that are biodegradable under aerobic conditions
 Organic Chemicals in the Environment

pharmaceutical agents
• Fibers
• building materials
• agricultural chemicals
• solvents
• cleaning agents
➢ inexpensive to manufacture
➢ used in large quantities
Stockholm Convention In 2001

POP: Persistent Organic Pollutant

➢ remain intact for exceptionally long periods of time

(many years),

➢ become widely distributed throughout the

environment as a result of natural processes
involving soil, water, and, most notably, air;

➢ accumulate in living organisms including humans,

and are found at higher concentrations at higher
levels in the food chain

➢ And are toxic to both humans and wildlife.

ENVIRONMENTAL DEGRADATION

Hydrolysis with water:

Water reacts with the functional groups; making the organic part: more soluble in water and, hence more amenable
to degradation by microorganisms

Reaction on mineral surfaces: Many organics bind to the surfaces of minerals in sediments and may catalyze the
decomposition of substituted organics
For example, sedimentary clay minerals catalyze the hydrolysis of some chloro-organics.

Photolysis: Mainly with volatile organic compounds, direct photolysis, by the radicals produced by the photolysis of
other atmospheric gases.

Oxidation by molecular oxygen: Unsaturated compounds are usually the most susceptible to oxidation by molecular
oxygen (singlet excited state
MICROBIAL DEGRADATION OF ORGANICS

Microorganisms mutate rapidly, so in some cases, there is a mutant that can live by metabolizing the xenobiotic
usually carried out by a cooperating group of microorganisms: consortium

Different steps in the degradation are carried out by different microorganisms

Degradation of 3-chlorobenzoate
Both anaerobes and aerobes degrade xenobiotics.
Anaerobes often use reductive processes to degrade organics
Aerobes use oxidative processes
Reductive Degradation
v Anaerobic dehalogenation of a pesticide was discovered.

Principal pathway for the reductive dechlorination of 2,3 dichlorobenzene

Pentachlorophenol (PCP) is rapidly converted to tetrachlorophenols, but the subsequent loss of chloride proceeds much
more slowly
Aliphatic compounds

The reductive dehalogenation of aliphatic compounds has also been observed. For example, 1,1,1-trichloroethane
(methylchloroform) can be reduced to the corresponding dichloro derivative.

Oxidative Degradation
Anaerobic microorganisms reduce the chloro groups from the highly substituted biphenyls to give lightly chlorinated
biphenyls, and the aerobic microorganisms destroy the lightly substituted biphenyls
Oxidative degradation occur mainly with lightly chlorinated chloro-organics because they require the attack of
electrophilic oxygen on an electron-rich center. Such as an aromatic ring or a double bond.
The delocalization of these electrons by electronegative chlorine atoms decreases the electron density on the aromatic
ring; hence these compounds are less readily oxidized by molecular oxygen

readily degraded to simpler compounds and

eventually to CO2, H2O, and Cl-
Dioxygenase enzyme
Hydrolytic Degradation

Hydrolytic cleavage of halogens, esters, amides, and other groupings are catalyzed by both aerobes and anaerobes

Glutathione (G-SH)

microorganisms that catalyse this reaction utilize formaldehyde

as an energy source.
TOXICITY

v Acute or immediate toxicity to humans and animals is not usually a problem for most commercial halo
organic compounds.

The toxicity associated with some halo organics is of the chronic type, where the deleterious effect appears 2-
30 years after the initial exposure

Ø For example, vinyl chloride evidently caused cancer (Liver tumors) in factory workers twenty years after
they started working with it.

➢ Most commercial halocarbons are nonpolar: removed from the bloodstream by the liver -enzyme
cytochrome P-450 (responsible for oxidative degradation of non-polar organic)

➢ Heavily chlorinated compound : high oxidation potentials :oxidized slowly, or not at all

High levels of this oxidizing enzyme: catalyze the oxidation of other nonpolar organics such as steroids. can
change the normal hormonal balance can cause endocrine, immune, and neurological effects
 v Decline in the number of eagles and hawks in the 1960s and 1970s that correlated with the buildup of
chloroorganics in the environment.
Resurgence of the birds in the 1980s following the ban of the use of DDT in 1972

The toxicity associated with some halo-organics is of the chronic type, where the deleterious effect appears 2-30 years
after the initial exposure.
 The United Nations sponsored and adopted a treaty in 2000 intended to end the production of these and other
persistent chlorinated compounds throughout the world and to destroy their stocks

The ``dirty dozen'' compounds include

• the insecticides aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, hexachlorobenzene, mirex, and toxaphene
plus
• the industrially used polychlorinated biphenyls and
• the industrial by-products, dioxins, and benzo-furans
The use of DDT for the control of malaria is the one exception to the ban since the insecticide is still used for this
purpose in Africa, Asia, and South America
 Green
Chemistry

James E. Girard. “Principles of Environmental Chemistry”

21
 Chemistry
Pros

➢ Pharmaceuticals that have improved health and extended life

➢ Fertilizers that have greatly increased food productivity
➢ Semiconductors that have made possible computers and other modern electronic devices

Cons
➢ Pollutants
➢ Toxic substances
➢ Nonbiodegradable plastic containers
These have resulted in harm to the environment.

22
The Pollution Prevention Act (PPA) states:

1. Pollution should be prevented or reduced at the source whenever

feasible

2. Pollution that cannot be prevented or reduced should be recycled

3. Pollution that cannot be prevented or reduced or recycled should be

treated

4. Disposal or other releases into the environment should be employed

only as a last resort.
23
➢ Green chemistry looks at pollution prevention on the molecular scale an extremely
important area of Chemistry due to the importance of Chemistry in our world today
and the implications it can show on our environment.

➢ The Green Chemistry program supports the invention of more environmentally

friendly chemical processes that reduce or even eliminate the generation of
hazardous substances.

➢ This program works very closely with the twelve principles of Green Chemistry.

24
 GREEN CHEMISTRY
DEFINITION
Green Chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of
hazardous substances in the design, manufacture and application of chemical products.

GREEN CHEMISTRY IS ABOUT

• Waste Minimization at Source

• Use of Catalysts in place of Reagents
• Using Non-Toxic Reagents
• Use of Renewable Resources
• Improved Atom Efficiency
• Use of Solvent Free or Recyclable Environmentally Benign Solvent system

25
Environmental Chemistry

Part-4

Class-3
Degradation of petroleum in marine environments
Alkane Degradative Pathways

The degradation of n alkanes

of medium chain length by
Pseudomonas putida
containing the OCT plasmid is
initiated by alkane
hydroxylase.

➢ Terminal oxidation of n-alkanes. α-and ω-hydroxylation is catalyzed by the same set of enzymes.

➢ With bacteria, steps 1, 2 and 3 are catalyzed by alkane hydroxylase, fatty alcohol dehydrogenase and fatty
aldehyde dehydrogenase, respectively.

➢ With yeast (Candida maltose), step 1 is catalyzed by P450 monooxygenase, while steps 2 and 3 are catalyzed
either by fatty alcohol oxidase and fatty aldehyde dehydrogenase, respectively.
 Alkane Degradation by Yeasts

Hypothetical reaction scheme for the individual monooxygenation steps in the conversion of n-alkanes to fatty acids catalyzed by
P450 . 1, n-alkane; 2, 1-alcohol; 3A, gem-diol; 3B, aldehyde; 3C, hydrated aldehyde; 4, ortho-acid intermediate; 5, fatty acid.

➢ Many yeast species, e.g. Candida maltosa, Candida tropicalis and Candida apicola, were investigated for use
with n-alkanes. The first step of alkane degradation (terminal hydroxylation) and of ,ω-hydroxylation is catalyzed
by P450 monooxygenase.

➢ The alcohols thus formed are processed by fatty alcohol oxidase and fatty aldehyde dehydrogenase. The P450
enzyme from some yeast strains can catalyze not only the terminal hydroxylation of long-chain n-alkanes and the
hydroxylation of fatty acids but also the subsequent two steps to yield fatty acids and α,ω-dioic acids.
 Yeast (Candida
maltose)

Proposed scheme of the n-alkane degradation pathway and its subcellular localization in C. maltosa including the newly found role
of P450 in the oxygenation cascade from n-alkanes to ,-dioic acids. ER, endoplasmic reticulum; FAOD, fatty alcohol oxidase;
ALDH, fatty aldehyde dehydrogenase.
Degradation of cyclohexane

➢ Cycloalkanes, including condensed cycloalkanes, are degraded by a co-oxidation mechanism. The formation
of a cyclic alcohol and a ketone has been observed. A monooxygenase introduces oxygen into the cyclic
ketone and the cyclic ring is cleaved.
Degradation of Toluene

Divergent Pathways for the Aerobic Degradation of Toluene

The pathways from the top to the bottom are found with Pseudomonas putida (TOL), Pseudomonas putida F1, Pseudomonas
mendocina KR1, Pseudomonas pickettii PKO1, and Bukholderia cepacia G4, respectively.
Degradation of fatty acid Coenzyme A
(- oxidation procedure)

➢ In this process, fatty acid molecules are

broken down in the cytosol in prokaryotes
and in the mitochondria in eukaryotes to
generate acetyl-CoA.

➢ It is referred to as beta-oxidation because FAD: Flavin adenine dinucleotide

the beta carbon of the fatty acid undergoes
oxidation to a carbonyl group. NAD: nicotinamide adenine
dinucleotide
Activation of fatty acids

1.In the cytosol of the cell, long-chain fatty acids are activated by ATP and
coenzyme A, and fatty acyl-CoA is formed.

1.The ATP is converted to AMP and pyrophosphate (PPi), which is cleaved by

pyrophosphatase to two inorganic phosphates (2 Pi). Because two high-energy
phosphate bonds are cleaved, the equivalent of two molecules of ATP is used for
fatty acid activation.
➢ FAD accepts hydrogens from a fatty acyl-CoA in the first step. A double bond is produced between
the α- and β-carbons, and an enoyl-CoA is formed. The FADH2 that is produced interacts with the
electron transport chain, generating ATP.
➢ Enzyme: Acyl-CoA dehydrogenase (Multiple variants of this enzyme)
➢ H2O adds across the double bond, and a β-hydroxyacyl-CoA is formed.
➢ Enzyme: Enoyl-CoA hydratase
➢ β -Hydroxyacyl-CoA is oxidized by NAD+ to a β-ketoacyl-CoA. The NADH that is produced
interacts with the electron transport chain, generating ATP.
➢ Enzyme: L-3-hydroxyacyl-CoA dehydrogenase (which is specific for the L-isomer of the β-
hydroxyacyl-CoA).
➢ The bond between the alpha and beta carbons of the β-ketoacyl-CoA is cleaved by a thiolase that
requires coenzyme A. Acetyl-CoA is produced from the two carbons at the carboxyl end of the
original fatty acyl-CoA, and the remaining carbons form a fatty acyl-CoA that is two carbons
shorter than the original.
➢ Enzyme: β –ketothiolase
➢ The shortened fatty acyl-CoA repeats these four steps. Repetitions continue until all the carbons of
the original fatty acyl-CoA are converted to acetyl-CoA.
Enzymes for -oxidation

•Acyl CoA dehydrogenase: Forms a double bond between the α and β

carbon atoms in the fatty acid chain. Produces one FADH2.
•Enoyl CoA hydratase: Incorporates a water molecule into the fatty
acid chain, thereby breaking the double bond between the α and β
carbon atoms.
•3-Hydroxy-acyl CoA dehydrogenase: Dehydrogenates the fatty acid
chain again, thereby forming a double bond between the β carbon
and the oxygen molecule. Produces one NADPH.
•Acyl CoA acyltransferase: Cleaves acetyl CoA off the end of the fatty
acid chain with the addition of CoA to the β carbon.
Oxidation of odd-chain fatty acids

Odd-chain fatty acids produce acetyl-CoA and propionyl-CoA.

➢ These fatty acids repeat the four steps of the β-oxidation spiral,
producing acetyl-CoA until the last cleavage when the three
remaining carbons are released as propionyl-CoA.

➢ Propionyl-CoA, can be converted to succinyl-CoA.

Oxidation of unsaturated fatty acids

β-oxidation of fatty acids with double bonds at

even- or odd-numbered positions carbons.
Degradation of fatty acids with even-numbered
double bonds results in 2,4-dienoyl-CoA esters,
which are oxidized as shown on the left. 2,5-
dienoyl-CoA esters arising from odd-numbered
double bonds can be oxidized either via an
isomerase-dependent pathway (middle) or via a
reductase-dependent pathway (right).

AD, acyl-CoA dehydrogenase,

EH, enoyl-CoA hydratase,
HD, 3-hydroxyacyl-CoA dehydrogenase,
KT, 3-ketoacyl thiolase,
ECI, Δ3,Δ2-enoyl isomerase,
DECI, Δ3,5,Δ2,4-dienoyl-CoA isomerase
DECR, 2,4-dienoyl-CoA reductase.
Environmental Chemistry

Part-4

Class-2
 Pollutants
Most organic and inorganic chemicals are subject
to enzymatic attack through the activities of living
organisms
Type of pollutants
BTEX (Benzene, Toluene, Ethylbenzene, Xylene)
PAH (Polycyclic aromatic hydrocarbon)
Nitroaromatic compounds
PCB (Polychlorinated biphenyls)
Chlorinated aliphatic compounds like, trichloroethylene (TCE), dichloroethylene (DCE), vinyl
chloride (VC)
MTBE: Methyl tert-butyl ether
Agricultural chemical wastes (Triazine, DDT)
Compounds with differential aerobic vs. anaerobic
degradation potential
Benzene, polynuclear aromatic
hydrocarbons (PAH)

Stable ring structures, aerobes

utilize oxidizing power of
oxygenases to initiate degradation

Anaerobes lack similarly powerful

oxidants
Compounds are readily degraded
aerobically, but persistent in
anaerobic environments
 Enzymes kinetics: Michaelis–Menten Equation
Enzymes are homogeneous biological catalysts. These ubiquitous compounds are special
proteins that contain an active site, which is responsible for binding the substrates, the
reactants, and processing them into products.

The Michaelis–Menten mechanism of enzyme catalysis

➢ An enzyme-substrate complex is formed in the first step.

➢ Either the substrate is released unchanged or after modification to form products

𝑘𝑎

𝑘𝑎′
𝑘𝑏

The rate of product formation according to the Michaelis–Menten mechanism is

1
The rate of change of concentration of enzyme-substrate complex and applying steady state principle

where [E] and [S] are the concentrations of free enzyme and substrate, respectively.

KM is the Michaelis constant.

It has the same units as molar concentration.
𝐸 0 = 𝐸 + 𝐸𝑆
𝑆 0 = 𝑆 + 𝐸𝑆

𝐴𝑠, 𝑆 0 » 𝐸𝑆 , 𝑆 0 ̴𝑆
 From, Equation 1,
𝒌𝒃 𝑬 𝟎 𝑺 𝟎
𝒗= 5
𝑺 𝟎 + 𝑲𝑴
When [S]0 << KM

𝒌𝒃 𝑬 𝟎 𝑺 𝟎
𝒗= 6
𝑲𝑴
When [S]0 >> KM, the rate reaches its maximum value and is independent of [S]0.

From equation 1,

Michaelis– Menten equation for the rate of product formation.

We can arrange this equation,

Lineweaver–Burk plot is a plot of 1/v against 1/[S]0

 Enzyme kinetics
Michaelis– Menten equation for the rate of product formation. 𝑘𝑎

𝑘𝑎′
Lineweaver–Burk plot is a plot of 1/v against 1/[S]0
𝑘𝑏

The catalytic efficiency of enzymes:

➢ The turnover frequency, or catalytic constant, of an enzyme, kcat, is the number of catalytic cycles (turnovers)
performed by the active site in a given interval divided by the duration of the interval.

➢ This quantity has units of a first-order rate constant and, in terms of the Michaelis–Menten mechanism, is
numerically equivalent to kb, the rate constant for the release of product from the enzyme-substrate complex.
The catalytic efficiency, ε (epsilon), of an enzyme is the ratio kcat /KM. The higher the value ofε, the more efficient the enzyme
is. We can think of the catalytic activity as the effective rate constant of the enzymatic reaction.

The efficiency reaches its maximum value of ka when kb >> k’a.

 Mechanisms of enzyme inhibition

An inhibitor, I, decreases the rate of product formation from the substrate by binding to the enzyme, to the ES complex, or to
the enzyme and ES complex simultaneously.

[𝐸𝑆]
[𝐸𝑆𝐼]

The lower the values of KI and KS the more efficient are the inhibitors.
By mass balance, the total concentration of enzyme is
1

Considering the following,

Ks
From Equation 1, we have,
2

From the definition of Michaelis Constant,

From Equation 2, we have,

There are three major modes of inhibition.
➢ In competitive inhibition the inhibitor binds only to the active site of the enzyme and
thereby inhibits the attachment of the substrate. This condition corresponds to  > 1
and 𝛼′ = 1.

The y-intercept does not change as a result of competitive inhibition.

➢ In uncompetitive inhibition the inhibitor binds to a site of the enzyme that is remote
from the active site, but only if the substrate is already present. The inhibition occurs
because ESI reduces the concentration of ES, the active type of complex. In this case =
1 (because EI does not form) and 𝛼′ > 1.

The y-intercept of the Lineweaver–Burk plot increases by a factor of ’ relative to the y-

intercept for data on the uninhibited enzyme but the slope does not change.

In non-competitive inhibition (also called mixed inhibition) the inhibitor binds to a site
other than the active site, and its presence reduces the ability of the substrate to bind to
the active site. Inhibition occurs at both the E and ES sites.
This condition corresponds to  > 1 and 𝛼′ > 1.
Both the slope and y-intercept of the Lineweaver–Burk plot increase upon addition of the
inhibitor
In all cases, the efficiency of the inhibitor may be obtained by determining KM and Vmax from a control experiment
with an uninhibited enzyme and then repeating the experiment with a known concentration of inhibitor. From the
slope and y-intercept of the Lineweaver–Burk plot for the inhibited enzyme, the mode of inhibition, the values of  or
’, and the values of KI or KS may be obtained.
 Aspects of transformations in atmosphere (microbial
degradation of organics-environmental degradation of
polymers, atmospheric lifetime, toxicity). Green
Chemistry and Industrial Ecology.

➢ Chemistry of the Environment, Second Edition by R. A. Bailey, H. M. Clark, J. P. Ferris, S. Krause, R.

L. Strong

➢ Principles of Environmental Chemistry By James E. Girard

1
 Microbial degradation of organics
Environmental degradation of polymers
Biodegradation :

1. Breakdown of organic matter by living microorganism like bacteria, fungi and other biological means.

2. It can be degraded by aerobically (in presence of oxygen) or anaerobically (in absence of oxygen).

3. Biodegradable materials provides nutrition to the microorganism.

Biotransformation:

Part of organic matter is degraded. Remaining part is converted to smaller organic molecules.

Example: Fermentation of sugar into ethanol.

Bioremediation : Use of either naturally occurring or deliberately introduced microorganisms to consume and
break down environmental pollutants.

2
 Organic Pollutants
Soil Humus: The soil organic matter consists of a whole series of products

that ranges from undecomposed plant and animal tissue to fairly Amorphous

Brown to black material bearing no trace of the anatomical structure of the

material.

Advantages:

1. It protects soil from erosion and helps in forming good soil structure.

2. It provides good aeration and better water movement by loosening the

soil.
3. For achieving maximum benefit organic matter must be decomposed and
replenished with fresh organic materials.

3
 Xenobiotics

➢ Xenobiotic chemicals are biologically active molecules that are foreign to an organism.

➢ Xenobiotic chemicals include herbicides, growth regulators, fungicides, and insecticides.

Drugs Plastic Food Additives

Originated from the greek word (Antibiotics) (Polyvinyl (Sodium nitrites))
chloride)
Xenos: Foreigner or stranger
Bios: life Pesticides Heavy Metals
Tics: suffix Cosmetics
(DDT) (As)
(Moisturizer)

Industrial
chemical
(Formalin)

4
 Man-made Xenobiotics

H2O

PET
5
Polyethylene terephthalate
 Natural product can also be a Xenobiotic like phytotoxins.

Abrin is an extremely toxic plant protein found in the seeds of

the rosary pea (or jequirity pea).

6
 Detoxification of Xenobiotics by Liver
Hepatic
enzymes Expose Conjugate
Xenobiotics polar with Excrete in
in Liver groups of sulphate, bile or in
Oxidation, these acetate or urine
reduction, chemicals glutathione
hydrolysis

Example: Benzene Phenol Phenyl sulfate

Complete removal is not possible.

7
Bioremediation

8
The breakup of the spill is slowed if it is washed up on the
shore.
• Dispersal and degradation will continue if there is a
strong wind and surf,
• but oil spills in quiet bays or lagoons may take 5-10 years
to disperse in the absence
of wave and wind action.
• The toxic effects on marine life likewise persist for 5-10
years in these environments

Due to the difficulty of achieving sufficient oil

removal by physical washing and collection,
especially for oil that had moved into the
subsurface, bioremediation became a prime
candidate for continuing treatment of the
shoreline.

9
10
Petroleum hydrocarbons occur naturally in all marine environments, there has been time for numerous diverse
microorganisms to evolve the capability of utilizing hydrocarbons as sources of carbon and energy for growth.
Oil-degrading microorganisms are ubiquitous
11
 Decomposition of various organic compounds

➢ Different organic residues contain different groups of organic compounds, so their decomposition procedure and rate
differ.

➢ Very slowly decomposed compounds are lignin, fat, wax, cellulose, and hemicellulose.

➢ Rapidly decomposed compounds are proteins, sugar, and starch.

Enzyme

Biodegradation is defined as the biologically catalyzed reduction in complexity of chemical compounds.

The enzyme is a substance, composed of proteins capable of lowering the activation energy of the reaction.

The most representative enzymes involved in bioremediation include cytochrome P450s, laccases, hydrolases,
dehalogenases, dehydrogenases, proteases, and lipases, which have shown promising potential in degradation of
polymers, aromatic hydrocarbons, halogenated compounds, dyes, detergents, agrochemical compounds, etc

12
Enzyme activity

13
 Mechanism of degradation by microorganism
The microbial organisms transform the substance through
metabolic or enzymatic processes. It is based on two processes:
growth and cometabolism.

1. In growth, an organic pollutant is used as sole source of

carbon and energy. This process results in a complete
degradation (mineralization) of organic pollutants.

2. Cometabolism is defined as the metabolism of an organic

compound in the presence of a growth substrate that is used
as the primary carbon and energy source.

3. Several microorganisms, including fungi, bacteria involved in

the biodegradation process.

14
Cometabolism
The cometabolic degradation phenomenon was first reported in 1958
observing that the methane-utilizing bacterium Pseudomonas
methanica could oxidize ethane and propane, but was unable to use
these compounds as a carbon and energy source.

Methane is a growth substrate for the methane-oxidizing bacterium,

while ethane and propane are co-metabolic substrates. Subsequent
studies have found that methanotrophs can cometabolically
transform polycyclic aromatic hydrocarbons (PAHs), dioxane,
polychlorinated biphenyls (PCBs), pesticides, and methyl tertiary-butyl
ether (MTBE).

NADPH: Nicotinamide adenine dinucleotide phosphate

15
➢ Numerous oxygenase enzymes, including methane-, ammonia-, propane-, butane-, alkane-, and toluene-oxygenases, are
known for their ability to degrade xenobiotic compounds cometabolically.

➢ Among oxygenases reported, methane monooxygenase (MMO) expressed by methane-oxidizing bacteria (i.e.,
methanotrophs) is one of the well-studied oxygenases. Methanotrophs can express two types of MMOs, particulate
(pMMO) and soluble (sMMO). Compared to pMMO, sMMO has a broader substrate range and is known for its ability to
degrade various environmental contaminants with some of the most persistent organics like pesticides, and halogenated
aliphatic and aromatic compounds.

➢ During cometabolic degradation of trichloroethylene (TCE; a chlorinated solvent), methanotrophs use MMO to oxidize
both methane (growth substrate) and TCE (co-metabolic substrate) with an expense of reducing energy, reduced
nicotinamide adenine dinucleotide (NADH), and oxygen. During methane oxidation, MMO will first convert methane to
methanol, which is further oxidized to formaldehyde, formate and then carbon dioxide, resulting in a net production of
reducing energy (NADH) and metabolites (formaldehyde and/or CO2) available for microbial cell growth.

16
There are two forms of MMO: the well-studied soluble form (sMMO) and the particulate form (pMMO). The active
site in sMMO contains a di-iron center bridged by an oxygen atom (Fe-O-Fe), whereas the active site in pMMO
utilizes copper. Structures of both proteins have been determined by X-ray crystallography; however, the location
and mechanism of the active site in pMMO is still poorly understood and is an area of active research.

17
Proposed catalytic cycle and mechanism sMMO

18
➢ As MMO is responsible for both methane and TCE oxidation, competitive inhibition of TCE degradation has
been observed in the presence of methane.

➢ Different from methane oxidation, TCE is oxidized to TCE epoxide, which is quickly hydrolyzed to chlorine
and carbon dioxide, resulting a net loss of reducing energy.

➢ Another unfavorable consequence is product toxicity- metabolites like TCE epoxide cause damage to cells
and the degradative enzymes – limiting the amount of TCE can be biotransformed per cell.

19
 TCE degradation
NADH

PQQ: Pyrroloquinoline
quinone. Peptide
derived redox cofactor

Methane and TCE oxidation pathways in methane-oxidizing bacteria. Enzymes: 1, MMO; 2, methanol dehydrogenase; 3,
formaldehyde dehydrogenase; 4, formate dehydrogenase.
20
Aerobic and Anaerobic

21
In situ Bioremediation

22
 09-Sep-24

Course Content

Lithosphere

Energy balance
Learn about our Chemistry of
environment Sustainability

Recycle

Infrared absorption, molecular vibration

Discuss Global Atmospheric window

warming issues
Residence time of greenhouse gases

Evidences and effects of global warming

Course Content
Chemistry of CO, NOx, VOCs, SO2, Industrial smog, photochemical smog
Deeper analysis of
atmospheric pollution Production
Ozone depletion
Catalytic destruction

Insecticides, Pesticides, Herbicides, and Insect Control

Organic Chemicals in Soaps, Synthetic Surfactants, Polymers, and Haloorganics.

the Environment

The fate of organic/inorganic chemicals in natural and engineered systems (the fate of
polymers after use, detergents, synthetic surfactants, insecticides, pesticides, etc., after use)

1
 09-Sep-24

Course Content

Microbial degradation of organics-environmental degradation of polymers

Aspects of transformations Atmospheric lifetime

in the atmosphere
Toxicity

Green Chemistry and Industrial Ecology.

Future challenges (CO2 sequestering, Nuclear energy).

A project on environment-related topic.

Reference books

Principles of
Environmental
Chemistry
By James E. Girard

2
 09-Sep-24

Photosynthesis

The most IMPORTANT chemical reaction for life

Photosynthesis
(uphill catalyst)
H2O + CO2 1/n (CH2O)n + O2 H = +470 KJ/mol
Respiration
(uphill catalyst)

Two Nobel Prizes:

1988: Johann Deisenhofer, Robert Huber and Hartmut Michel

“for the determination of the three-dimensional structure of a photosynthetic reaction centre”

(Bacterial Photosynthesis Process)

1992: Rudolph A. Marcus

“for contributions to the theory of electron transfer reactions in chemical systems” 6

Nitrogen Fixation
Fe/Mo catalyst
N2 + 3H2 2NH3 Urea The Haber-Bosch process
200 atm P
450 C ~15%

highly energy-intensive process consuming around 2% of global

energy output each year (steam methane reforming accounts
for over 80% of the energy required) and producing as a result
about 500 million tonnes of carbon dioxide (about 1.8% of
Nitrogen-fixing Leguminous Plant: Pisum sativum global carbon dioxide emissions)

The roots of leguminous plants have nodules

that contain N2-fixing bacteria

Nitrogenase: key enzyme for biological nitrogen fixation

The MoFe protein
7

3
 09-Sep-24

4
 09-Sep-24

In the past many environmental problems were caused by practices that now seem to be totally
unacceptable as expressed from the quote in this slide from what was regarded as a reputable book
on the American chemical industry in 1954. The result was polluted air, polluted water, dangerous
hazardous waste sites, and harm to living organisms.

10

10

Dating from around 1970, laws and regulations were implemented to control air and water pollution and
to clean up hazardous waste sites. These measures have relied largely upon “end of pipe” controls in
which pollutants were generated but were removed before release to the environment. Although costly
and requiring constant vigilance to make sure that standards have been met, these measures have been
successful in reducing pollution and preventing increases in pollutant releases.

11

11

5
 09-Sep-24

Deeper analysis of atmospheric pollution

Air quality measurement are commonly
reported in terms of:

– micrograms per cubic meter (μg/m3)

– parts per million (ppm) or parts per billion

(ppb)

• For particulate matter, sizes are expressed in

micron or micrometer.

12

12

Analysis of air and air pollutants

• Analytical measurements form the foundation on which our understanding of the

atmosphere is built

• In atmospheric chemistry, one of the most fundamental measurements is the most

difficult.

• What is the composition of air?

• Nitrogen gas represents more than 78% of the atmosphere, whereas reactive species
such as ozone are present in ppm level. The range in concentration of atmospheric
constituents is extremely wide, as large as 104

13

13

6
 09-Sep-24

Analysis of air and air pollutants

Two different measurement Techniques:

Remotely: (Remote sensing Technique): In this case by passing a beam of

In situ: It means the sample of the atmospheric gases energy that originates on a satellite, an aircraft, the space shuttle or the
must be placed inside the device (spectrometer) that is ground through a portion of the atmosphere that is to be studied.
making

Although these measurement techniques involve different instrumentation, the underlying principles are same.

14

14

Analysis of air and air pollutants

• Automobile and smoke stack emissions are major sources of anthropogenic pollutants into the atmosphere, both of
which are regulated by the Environmental Protection Agency (EPA).

• Measurements of these gases emitted from automobiles and smoke stacks are difficult to make because the exhaust
gases are hot and travel at a high velocity.
15

15

7
 09-Sep-24

In situ Absorption Measurement

• Spectroscopic Measurement: This method relies on the fact that different chemical compounds absorb
electromagnetic radiation at different wavelengths. When a molecule absorbs a photon of electromagnetic
radiation, the energy of the molecule increases.

16

16

In situ Absorption Measurement

• For example, when a molecule absorbs microwave radiation, which is EMR of relatively low energy, it only stimulates
the rotational motion of the molecule.

300 GHz – 1.24 meV –

Microwave 1 mm – 1 m
300 MHz 1.24 µeV

17

17

8
 09-Sep-24

In situ Absorption Measurement

• IR radiation which has higher energy than microwaves, stimulates vibrations of the molecules that absorb it. UV
radiation which has even higher energy than IR, causes electrons in the molecules absorbing it to be promoted into
higher energy orbitals; the molecule is said to be in the excited state. The lowest energy state of the molecule is called
the ground state.

Symmetric Stretch Asymmetric Stretch Twisting

700 nm – 300 GHz – 1.7 eV –

Infrared
1 mm 430 THz 1.24 meV
18

18

In situ Absorption Measurement

• Very high energy EMR such as X-ray and  has enough energy to break chemical bonds and ionize molecules.

• When the sample absorbs a beam of EMR radiation, the irradiance of the beam is decreased. The irradiance (P),
which is sometimes intensity or radiant power, is the energy per second per unit area of the light beam.

• EMR is passed through a monochromator (a prism) to select one wavelength of EMR. The light of a single
wavelength is called monochromatic, which means one color.

• The monochromatic light with irradiance P0 passes into a sample b. The irradiance of the beam emerging from
the other side of the sample is P. Some of the light may be absorbed by the sample, and thus P0 ≥ P.
19

19

9
 09-Sep-24

In situ Absorption Measurement

• Transmittance (T): it is defined as the fraction of the original light that has passed through the sample.

𝐏
• 𝐓= T has the range of 0 to 1. The percentage of transmittance is 100 T and has a range from 0% to
𝐏𝟎
100%. Absorbance (A) is defined as follows:

𝐏
• A = log ( 𝟎) = - log T ; When no light is absorbed P = P0 and A = 0
𝐏

20

20

In situ Absorption Measurement

• Absorbance is important because it is directly proportional to the concentration (C) of the absorbing
molecules in the sample. A is dimensionless.

• The Beer-Lambert or simply Beer’s Law:

• A = . b. C (b = path length cm or m etc., C = concentration moles/L, ppm, ppb etc.,)

•  = molar absorptivity or extinction coefficient. It is the characteristics of the molecule that indicates
how much light it will absorb at a particular wavelength.
21

21

10
 09-Sep-24

In situ Ozone measurement

• Ultraviolet absorption has been used to measure the concentration of ozone in stratospheric air. The figure
shows that ozone has a strong absorption in the UV region. Other atmospheric gases such as O2, N2, and H2O do
not absorb UV radiation and thus do not have to be removed from the air sample as they do not interfere with
the ozone measurement.

22

22

In situ Ozone measurement

• The concentration of ozone in the stratosphere is less than 100 ppm, so the spectrophotometer that is used
to make the measurement must be capable of measuring a small absorbance. This is most easily done by
making the sample cell very long. Because Beer’s law says that absorbance is proportional to the sample path
length and because we can get a lot of samples easily, a long sample path length will greatly improve our
ability to measure the ppm level of Ozone.

23

23

11
 09-Sep-24

Basic Pollutants

24

24

Biomethylation
Sea
Bacteria CH3-Hg1+ Blood Brain Barrier
Hg2+
(BBB)
Minamata
Industry
disaster (1956) Fish
Organometallic species
much more toxic than Hg2+

Karen Elizabeth Wetterhahn

(October 16, 1948 – June 8, 1997),

dimethylmercury
American professor of chemistry at Dartmouth
College, New Hampshire,

25

25

12
 09-Sep-24

Types of Pollutants
Primary pollutants are those gases or particles that are pumped into the air to make it unclean. They include
carbon monoxide from automobile (cars) exhausts and sulfur dioxide from the combustion of coal. Primarily air
pollutants can be caused by primary sources or secondary sources. The pollutants that are a direct result of the
process can be called primary pollutants.

A classic example of a primary pollutant would be the sulfur-dioxide emitted from factories.

26

26

13
 9/17/24

Types of Pollutants Chemistry of Troposphere

v Air Pollutant
Primary pollutants are those gases or particles that are pumped into the air to make it unclean. They include
Ø An air pollutant is defined as a substance that is present in the atmosphere at a concentration that is
carbon monoxide from automobile (cars) exhausts and sulfur dioxide from the combustion of coal. Primarily air
sufficient to cause harm to humans, other animals, vegetation or materials
pollutants can be caused by primary sources or secondary sources. The pollutants that are a direct result of the
Ø Approx 90% of all air pollution is caused by these primary air pollutants
process can be called primary pollutants.
ØIn addition, Secondary pollutants are also present
1. Carbon monoxide (CO)
ØHarmful substances are produced by chemical reactions
A classic example of a primary pollutant would be the sulfur-dioxide emitted from factories.
2. Sulfur dioxide (SO2)
between primary pollutants and other constituents of the
3. Nitrogen Oxides (NOx)
atmosphere. e.g., H2SO4, HNO3; SO42- and NO3- contribute to
4. Volatile Organic Compounds (VOCs)
the acid rain
5. Mostly Hydrocarbons (HCs)
6. Suspended particles

Ozone and other photochemical oxidants contribute to photochemical smog

26 27

26 27

Chemistry of Troposphere Carbon Monoxide

v Carbon Monoxide
v Effect of CO on Human Health
Ø Source of Carbon monoxide
Ø The main anthropogenic source of CO is the combustion of gasoline in automobile engines
Ø Even the CO is most abundant air pollutant, it is not very toxic at the levels usually found in the atmosphere,
1. Gasoline is a complex mixture of hydrocarbons (HCs) however if allowed a build up in a confined space, it can cause serious health problem
2. If this is ignited in an adequate supply of oxygen; the products are CO 2 and H 2O
Ø CO interferes with the oxygen carrying capacity of blood; normally hemoglobin (Hb) in red blood cells combine
2 C 8H 18 + 25 O 2 18 H 2O + 16CO 2
with oxygen in the lungs to oxyhemoglobin (HbO2). The HbO2 is carried in the blood stream to various part of
1. In the confined space of the internal combustion of the engine O 2 supply is limited, and combustion is incomplete. Thus, CO is formed

and released into the atmosphere in automobile exhaust the body, where oxygen is released to the tissues
2. 2 C 8H 18 + 17 O 2 18 H 2O + 16 CO Ø Carbon monoxide binds much more strongly to Hb than oxygen – Why?
Transportation
68.4% Ø If CO is present in the lungs, it displaces oxygen from Hb and thus reduces the amount of oxygen that can be
v However, the introduction of catalyst converter Industrial processes 11.3%
delivered to the tissues
reduce the CO emissions
Solid waste disposal 8.1% HbO2 + CO HbCO + O2
vNatural source of CO into the atmosphere is CH4 gas
Misc. 10.2% Fuel combustion stationary sources 2% v Treatment of CO poisoning:
2 CH4 + 3 O2 2 CO + 4 H2O v Symptoms of CO poisoning: headache, dizziness, impaired judgment, drowsiness, slowed reflexes, respiratory
failure and death
Methane is also produced in the stomach in the cattle and sheep and finally released into the atmosphere
28 29

28 29

1
 9/17/24

Carbon monoxide poisoning Molecular Orbital Theory

35 ppm (0.0035%)

Headache &
Dizziness

200 ppm (0.02%)

Headache & loss

of judgement

3200 ppm (0.32%)

Headache,
Dizziness, Nausea

6400 ppm (0.64%)

Respiratory arrest
& death in less
than 20 min
12800 ppm (1.28%)

Unconsciousness.
Death in less than
3 min

30 31

30 31

Molecular Orbital Theory Molecular Orbital Theory

In order to investigate the way in which CO
bonds to metals, we must appreciate the
electronic structure of the CO molecule.

Before constructing an orbital interaction

diagram for CO, we must take note of the
following:

v Zeff(O) > Zeff(C);

v the energy of the O 2s atomic orbital is lower

than that of the C 2s atomic orbital;

v the 2p level in O is at lower energy than that

in C;

v Carbon monoxide binds much more v the 2s–2p energy separation in O is greater
than that in C
strongly to Hb than oxygen – Why?
32 33

32 33

2
 9/17/24

Molecular Orbital Theory

CO = 1670-1820 cm -1
Spin multiplicity = 2S + 1

Pi-donor
Pi-acceptor

Singlet is kinetically unstable at ambient

temperature but decays slowly

MO diagram More reactive, leads to photodegradation of many organic compounds.

Bond order and bond strength Free CO = 2143 cm-1 34

34 35

36 37

36 37

3
 9/17/24

Bridging modes of CO
Carbon Monoxide

v How the wave number of CO will change in metal carbonyl complexes

38 39

38 39

Carbon Monoxide
Ø Carbon monoxide binds much more strongly to Hb than oxygen – Why?

Myoglobin is a hemoprotein, isolated from the cells

of vertebrate skeletal muscle that is both a
structural and functional relative of hemoglobin, the
oxygen-transport protein of the blood of higher
animals.

40 41

40 41

4
 9/17/24

Carbon Monoxide
Ø At the center of the heme is an Fe(II) atom. Four of the six coordination
sites around this atom are occupied by nitrogen atoms from a planar
porphyrin ring

ØThe fifth coordination site is occupied by a nitrogen atom from a histidine

side chain on one of the amino acids in the protein

ØThe last coordination site is available to bind an O2 molecule

ØThe heme is therefore the oxygen-carrying portion of the hemoglobin and

myoglobin molecules

ØThe structure of myoglobin suggests that the oxygen-carrying heme group

is buried inside the protein portion of this molecule, which keeps pairs of
hemes group from coming too close together

Ø This is important, because these proteins need to bind O2 reversibly and

the Fe(II) heme, by itself, cannot do this. When there is no globin to protect
the heme, it reacts with oxygen to form dimers.
42 43

42 43

The unsaturated molecule O2 is a pi-donor/ pi-acceptor

ligand.

dx2
dx2-y2

Filled d-orbitals of suitable symmetry

44 45

44 45

5
 9/17/24

Preferential Binding of CO and deactivation of Hb and Mb

Mb(O2) + CO Mb(CO) + O2
Carboxyhemoglobin

Binding affinity of free Heme group for

CO is about 25,000 times than O2 Fe Fe

46 47

46 47

Protein part allows easier access to

small molecules like dioxygen to bind
with Fe atoms

Steric clash Linear coordination of CO is not possible

Oxygen saturation curves of myoglobin and hemoglobin at different

pH values
Fe2+ in low spin
48 Bonding is weak when CO is bound in angular fashion 49

48 49

6
 25-Sep-24

Carbon Monoxide
Fate of Atmospheric CO
Most of the CO molecules are removed from the atmosphere by oxidation (natural) in the stratosphere.

The most important oxidizing species in the air

 Hydroxyl radical OH

'detergent of the
atmosphere'.
 Nitrate radical NO3

 Ozone molecule O3
50

50

Carbon Monoxide
Fate of Atmospheric CO
It is generally believed that CO is removed from the atmosphere by a reaction with hydroxyl radical.
Oxidized by reaction with hydroxyl radical
Systematic IUPAC name
• CO + HO• → CO2 + H (stratosphere) Dioxidanyl

• CO is oxidized to CO2 in the stratosphere, where it migrates via convection, turbulence, and mixing

• The reaction is fast and independent of temperature; thanks to it, the residence time of CO in the atmosphere
is relatively short, from 2 weeks to 3 months.

51

51

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Production of hydroperoxyl radical

Carbon Monoxide
• O2 + H → HOO•
Additional reactions
• HOO• + NO → HO• + NO2
• HOO• + HOO• → H2O2 + O2
• H2O2 + hν → HO•
O3 + hv (sun) → O + O2 (wavelength <310 nm)
O + O2 + M → O3 + M
O + H2O → 2OH 3% CO Fate in Soil
• Soil is considered one of the main sinks of atmospheric CO, responsible for 40% of total consumption

• Soil is a sink for CO

Humic acid has the average chemical formula C187H186O89N9S1
• Soil microorganisms metabolize CO

52

52

Water Content

Temperature
The most
important soil Organic matter content
parameters
pH

Soil type

The depth of CO consumption horizon, and CO concentration in the gas phase

Even small changes in this balancing between CO production and soil uptake can severely impact tropospheric chemistry

53

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 25-Sep-24

Nitrogen Oxides (NOx)

 Nitrogen dioxide (NO2) is the major pollutant in the atmosphere and is formed from nitric oxide
(NO). Collectively nitrogen oxides are designated as NOx
 Source of NOx
 Anthropogenic NOx molecules enter the atmosphere from the combustion of fossil fuels by
automobiles, aircraft, and power plants.
 At normal atmospheric temp. N2 and O2 do not react. However, at very high temp. atmospheric
N2 reacts with oxygen to give a series of complex reactions. Two gases combine to give NO
N2 + O2 2 NO 2NO + O2 2NO2

Solid waste disposal 3.2%

Transportation 49.1 Industrial processes 1.3%

Misc. 3.2%

Fuel combustion
stationary sources 43.2 54

54

Nitrogen Oxides (NOx)

 When NO is released, it combines rapidly with atmospheric oxygen to form NO2. NO has an unpaired electron
and can be written as NO●

• The bacterial decomposition of nitrogen-containing organic matter in soil is another natural source of NOx

 Fate of Atmospheric NOx

1. Regardless of its source, NO2 is ultimately removed from the atmosphere as nitric acid and nitrates in dust and rainfall.
In a series of complex reactions involving hydroxyl radicals, NO2 combines with water vapor to form nitric acid. The
simplified overall reaction is
4 NO2 + 2 H2O + O2 4 HNO3

2. Much of the nitric acid in the atmosphere is formed within aqueous aerosols. If the weather conditions are right, the

aerosols coalesce into larger droplets in clouds and the result is acid rain.
55

55

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 25-Sep-24

Fate of Atmospheric NOx

 Some of the nitric acid formed reacts with ammonia and metallic particles in the atmosphere to form
nitrates
HNO3 + NH3 NH4NO3

 Nitrates dissolve in rain and snow or settle as particles. The combined fallout contributes to acid
deposition

56

56

Effect of NOx on Human Health and Environment

 NO2 is red brown toxic gas and has unpleasant acrid odor. It
can cause irritation of the eyes, inflammation of lung
tissue, and emphysema.
 NOx is a serious health problem because of its role in the
formation of secondary pollutants associated with
photochemical smog.
 Most of the research has concentrated on reducing
automobile emission by means of the catalytic converter

Emphysema is a lung disease that damages the alveoli in

your lungs. The primary symptom of emphysema is
shortness of breath.

Atopic sensitization is defined as a positive allergen-specific serum

Melanogenesis is the production of immunoglobulin E (IgE) test or skin prick test to any food or inhalant
Erythema is redness of the skin caused by injury or allergens. It is an important risk factor for the development of asthma and
another inflammation-causing condition the melanin pigments
allergic diseases

57

4
 25-Sep-24

Catalytic Converter

Thermoelectric materials

58

Volatile Organic Compounds (VOCs)

 A great variety of VOCs, including many HCs, enter the atmosphere from both natural and anthropogenic sources
 The petroleum industry is the main anthropogenic source of HCs in the atmosphere
 Gasoline is a complex mixture of many volatile HCs, and in urban areas, gasoline vapors can escape into the
atmosphere in several ways
1. When gas is pumped at gas stations Industrial processes 12%

2. During the filling of storage tanks Transportation 60%

3. Unburned gasoline in exhaust Solid waste disposal 5.1%

from automobiles and small combustion engines

Fuel combustion stationary
sources 2.4%

Misc. 20.5%

 In the natural world, the pleasant aroma of pine, eucalyptus, and sandalwood trees are caused by the evaporation

of VOCs called terpenes from their leaves

 Natural sources account for 85% of total emission; anthropogenic source contributes 15% 59

59

5
 25-Sep-24

General formula : (C5H8)n

60

What is gasoline?

The typical composition of gasoline hydrocarbons (% volume) is as follows:

4-8% alkanes; 2-5% alkenes; 25-40% isoalkanes; 3-7% cycloalkanes; l-4% cycloalkenes; and 20-50% total aromatics
(0.5-2.5% benzene)

Tetraethyl lead acts as an anti knocking agent in gasoline and jet

fuel and is added to petrol in order to reduce the ignition of vapors
of petrol. Thus, tetraethyl lead is a petroleum additive.

Knocking occurs when fuel burns unevenly in your engine.

61

6
 25-Sep-24

Volatile Organic Compounds (VOCs)

 Automobile Four-Cycle Internal Combustion Engine
 Gasoline-powered four-cycle internal combustion engines are predominant in more developed countries
 To know how NOx, CO, and HCs are produced through this, we need to learn how this engine works
 There are four steps in one complete cycle of the gasoline engine
 In the confined space of the internal combustion engine, oxygen is in limited supply, and CO is formed and released to the
atmosphere

62

62

Volatile Organic Compounds (VOCs)

 Automobile Four Cycle Internal Combustion Engine

 In the internal combustion engine, temp and pressure are very high, and NO is formed from N2 and O2. The unburned HCs are

emitted with the burned gas as pollutant VOCs

 The air/fuel ratio has a dramatic effect on the emission of pollutants from the four-cycle engine

 During the engine tune-up, adjustment of the carburetor or the fuel injection system can greatly reduce the emission of

pollutants.

 The ideal stoichiometric air/fuel ratio is 14.7:1

 Adjustment to a more fuel-rich (lower air/fuel) ratio makes the car easier to start and decreases the emission of NOx and HCs;

unfortunately, it also decreases the fuel efficiency, and the car will get fewer Km per liter. The emission of CO is also increased

as air is less available

 Adjustment to a more air-rich (higher air/fuel) ratio will make the car harder to start; although it increases fuel efficiency, the

emission of NOx is increased

63
 The ideal ratio is a compromise between fuel efficiency and the emission of the lowest collective amount of pollutant
63

7
 25-Sep-24

Volatile Organic Compounds (VOCs)

 Gasoline Powered Two-Cycle Engine
 A two-cycle engine is used to power motor scooters, mopeds, and snowmobiles. It is less complicated than the four-cycle engine
and also less expensive.
 It takes fuel, releases exhaust in the same stroke, and emits from 25% to 30% of the fuel consumed as unburned HCs.
 The two-cycle engine has no valves, and that power is produced in one of two steps rather than one in four steps; this means the two-
cycle engine runs faster and hotter than the four-cycle engine

1. In two-cycle engine motor oil: gasoline 1: 40 ratio

2. Motor oil has C18 to C25 HCs i.e., higher molecular weight
3. In the two-cycle engine, combustion takes place at a lower temperature than
the four-cycle engine
4. Due to higher molecular weight, motor oil is not vaporized and burned
efficiently like gasoline
5. Two step cycle requires that the exhaust gases from combustion leave the
cylinder through the exhaust port while the fresh air/fuel mixture for the next
power stroke is simultaneously enters the cylinder from the side arm
64

64

Volatile Organic Compounds (VOCs)

 Comparison
1. A comparison of the emission from marine outboard two- and four-cycle engines of the same horsepower was
made. The result of those tests show that the exhaust of a two-cycle engine contained more than 12 times the
amount of HCs than a four-cycle engine of the same power

Type of Marine outboard Engine CO(g) NOx(g) HC(g)

Two cycle Engine 165 0.3 89
Four Cycle Engine 127 0.7 7
Source: Juttner F. D. et al., Water Research 1995, 29, 1976-1982

65

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 25-Sep-24

Automobile Pollutants
 Motor vehicles are a major source of CO, NOx, and volatile HCs
 Since 1975, when all new cars in the USA were required by law to be equipped with a catalytic converter,
emissions of those pollutants have been reduced significantly
 The table shows that today’s car emits 95% less pollutants than pre-1970 vehicles despite the fact that the
number of miles traveled has almost doubled in the last 20 years

Emission Standards for Light duty Vehicles

Federal Standards California Standards
Year HCs CO NOx Evaporative HCs HCs CO NOx Evaporative HCs

<1970 10.6 84 4.1 > 45 10.6 84 4.1 >45

1970 4.1 34 - - 4.1 34 - 2

1975 1.5 15 3.1 2 0.9 9 2.0 2

1980 0.41 7.0 2.0 2 0.39 9 1.0 2

1985 0.41 3.4 1.0 2 0.39 7 0.4 2

1990 0.41 3.4 1.0 2 0.39 7 0.4 2

1993 0.41 3.4 1.0 2 0.25 3.4 0.4 2

2000 0.41 3.4 0.4 2 0.25 3.4 0.4 2

66
All values reported in gms per mile except for evaporative HCs which are expressed as gms per tests

66

The Catalytic Converter

 The use of a three-way catalytic converter (used since 1981) can reduce the emission drastically

 It is called a three-way catalytic converter as it simultaneously reduces the amounts of HCs, NOx, and CO in the
exhaust stream
 The converter is a very fine honeycomb structure made of ceramic coated with precious metals like Pt, Pd, and
Rh, which act as catalysts

67

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 25-Sep-24

Top Five Automotive Catalytic Converter Market Vendors

BASF SE

CDTi Advanced Materials Inc.

Continental AG

Eberspacher Group

Faurecia SA

68

The Catalytic Converter

 The catalytic converter has two chambers in succession. As the gases enter, Rh catalyzes the reduction of NOx to
nitrogen gas by hydrogen generated at the surface of the Rh catalyst by the reaction of H2O and unburned HCs

HCs + H2O H2 + CO ; 2NO + 2H2 N2 + 2H2O

 Then air is injected into the exhaust stream to introduce oxygen and CO is oxidized to CO2 in the presence of
Pt and Pd catalyst
2 CO + O2 2 CO2 ; HC + 2O2 CO2 + 2 H2O

 Thus, overall reaction for reduction of NO and oxidation of CO can be written as

Rh, Pt, Pd Cat

2 NO + 2 CO N2 + 2 CO2

69

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10
 25-Sep-24

The Catalytic Converter

 Oxidation of a typical gasoline HC, Octane occurs as
Pt, Pd Cat
2 C8H18 + 25 O2 16 CO2 + 18 H2O

 Automobiles using catalytic converters must have their air/fuel ratio set as 14.7:1 to get optimum results.

 At room temp, the efficiency of the catalytic converter is nearly zero

Surface chemistry

Pt, Rh, and Pd (FCC)

70

70

Sulfur Dioxide
143.1 pm
 The release of SO2 into the atmosphere is the primary cause of acid rain

 Fossil fuel combustion accounts for 70% of the emission

 Industrial sources contribute approximately 23% of SO2

 Coal oil and all other fossil fuels naturally contain some sulfur (FeS).

 When sulfur containing coal is burned, the sulfur is oxidized to SO2: S + O2 2SO2 + 2H2O

 H2S (produced as an end product of anaerobic decomposition of sulfur containing organic matter by microorganism)
enter to the atmosphere to form SO2
2H2S + 3O2 2SO2 + 2H2O
71

71

11
 25-Sep-24

Sulfur Dioxide

 Volcanic eruptions are another more localized natural source of SO2; e.g., the eruption of Mt. Pinatubo in the Philippines
in June 1991 contributed 25 million tons of SO2 into the atmosphere, where it was converted into sulfuric acid aerosols

 Fate of atmospheric SO2: Acid Rain

 The residence time of SO2, controlled not only by chemical conversion to sulfate but also by dry deposition, is 10-30 days.

 SO2 in the atmosphere reacts with oxygen to form SO3, which then readily reacts with water vapor or water droplets to
form H2SO4(g). The mechanism involves hydroxyl radicals.
72

72

The fate of atmospheric SO2: Acid Rain

SO2 + OH HSO3

HSO3 + O2 SO3 + HOO

SO3 + H2O H2SO4 (g)

H2SO4 + H2O H2SO4 (aq)

 Sulfuric acid in the atmosphere becomes concentrated near the base of clouds where
the pH level is as low as 3 (pH of orange juice)
 Some of the atmospheric SO2 dissolves if there is significant water in the air to form
sulfurous acid
SO2(g) + H2O (aq) H2SO3(aq)
 The dissolved SO2 is oxidized by trace amount of H2O2 and Ozone that are also
present in the aerosol droplets to sulfate ions (SO42-)

 HSO3- + H2O2 H2O + HSO4-

HSO3- + O3 O2 + HSO4-

73

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 25-Sep-24

The fate of atmospheric SO2: Acid Rain

SO2 + OH HSO3

HSO3 + O2 SO3 + HOO

SO3 + H2O H2SO4 (g)

H2SO4 + H2O H2SO4 (aq)

 Sulfuric acid in the atmosphere becomes concentrated near the base of clouds where H2SO4 vs H2SO3
the pH level is as low as 3 (pH of orange juice)
 Some of the atmospheric SO2 dissolves if there is significant water in the air to form
sulfurous acid
SO2(g) + H2O (aq) H2SO3(aq)
 The dissolved SO2 is oxidized by trace amount of H2O2 and Ozone that are also
present in the aerosol droplets to sulfate ions (SO42-)

 HSO3- + H2O2 H2O + HSO4-

HSO3- + O3 O2 + HSO4-

74

74

The oxidation number of S

75

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 25-Sep-24

Oxoacids of Sulfur

76

Effect of Acid Rain

77

77

14
 25-Sep-24

Effect of SO2 on Human Health and Environment

 SO2 is a colorless, toxic gas with a sharp acrid odor

 Exposure to it causes irritation of eyes, respiratory passages, and aggravates symptoms of respiratory disease. Children are

susceptible to its effects

 SO2 is also harmful to plants. Crops such as barley, alfalfa, cotton, and wheat are particularly adversely affected

Barley Alfalfa Cotton Wheat

78

78

Effect of SO2 on Human Health and Environment

How to control SO2 emissions
1. Sulfur can be removed from coal before combustion
2. SO2 can be removed from the smokestack after combustion but before it reaches to atmosphere

 The second approach is cheaper and most common

 The most commonly used method is flue gas desulfurization (FGD), in which sulfur-containing compounds are washed
out by passing the Chimney (flue) gases through a slurry of water mixed with finely ground limestone (CaCO3) or
dolomite [CaMg(CO3)2] or both.

 On heating the basic CaCO3 with acidic SO2 in the presence of O2 to form CaSO4

2 SO2 + 2 CaCO3 + O2 2 CaSO4 + 2CO2

Flue Gas: a mixture of gases produced by the burning of fuel or other materials in power stations and
79
industrial plants and extracted via ducts.

79

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 25-Sep-24

a colorless liquid with an ether-like odor

Boiling point: 46.3 °C
CS2(s) + O2(g) = CO2(g) + SO2(g)

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Industrial Smog
 Particulate matter and SO2 can be a deadly combination. Released into the atmosphere together when coal is
burned, they can form industrial smog: a mixture of fly ash, soot, SO2, and some VOCs
 It is formed in winter, typically in cities where the weather is cold and wet. Visibility was often reduced to a few
yards and people in factory towns lived under a pall of black smoke

 Photochemical Smog
 The origin of photochemical smog is quite different from that of industrial smog. Typically, photochemical smog
develops as a yellow-brown haze in hot summer weather in cities like Los Angeles, where automobile traffic is
congested
 The reaction that led to its formation is initiated by sunlight and involves the HCs and NOx emitted in automobile
exhaust.
 NO2 is responsible for the brownish color of the haze

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Industrial Smog

NO2 transforms to the colorless dinitrogen tetroxide

(N2O4) at low temperatures (below −11.2 °C) and
reverts to NO2 at higher temperatures.

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Industrial Smog

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Automobile Pollutants
 Motor vehicles are a major source of CO, NOx, and volatile HCs
 Since 1975, when all new cars in the USA were required by law to be equipped with a catalytic converter,
emissions of those pollutants have been reduced significantly
 The table shows that today’s car emits 95% less pollutants than pre-1970 vehicles despite the fact that the
number of miles traveled has almost doubled in the last 20 years

Emission Standards for Light duty Vehicles

Federal Standards California Standards
Year HCs CO NOx Evaporative HCs HCs CO NOx Evaporative HCs

<1970 10.6 84 4.1 > 45 10.6 84 4.1 >45

1970 4.1 34 - - 4.1 34 - 2

1975 1.5 15 3.1 2 0.9 9 2.0 2

1980 0.41 7.0 2.0 2 0.39 9 1.0 2

1985 0.41 3.4 1.0 2 0.39 7 0.4 2

1990 0.41 3.4 1.0 2 0.39 7 0.4 2

1993 0.41 3.4 1.0 2 0.25 3.4 0.4 2

2000 0.41 3.4 0.4 2 0.25 3.4 0.4 2

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All values reported in gms per mile except for evaporative HCs which are expressed as gms per tests

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The Catalytic Converter

 The use of a three-way catalytic converter (used since 1981) can reduce the emission drastically

 It is called a three-way catalytic converter as it simultaneously reduces the amounts of HCs, NOx, and CO in the
exhaust stream
 The converter is a very fine honeycomb structure made of ceramic coated with precious metals like Pt, Pd, and
Rh, which act as catalysts

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Top Five Automotive Catalytic Converter Market Vendors

BASF SE

CDTi Advanced Materials Inc.

Continental AG

Eberspacher Group

Faurecia SA

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The Catalytic Converter

 The catalytic converter has two chambers in succession. As the gases enter, Rh catalyzes the reduction of NOx to
nitrogen gas by hydrogen generated at the surface of the Rh catalyst by the reaction of H2O and unburned HCs

HCs + H2O H2 + CO ; 2NO + 2H2 N2 + 2H2O

 Then air is injected into the exhaust stream to introduce oxygen and CO is oxidized to CO2 in the presence of
Pt and Pd catalyst
2 CO + O2 2 CO2 ; HC + 2O2 CO2 + 2 H2O

 Thus, overall reaction for reduction of NO and oxidation of CO can be written as

Rh, Pt, Pd Cat

2 NO + 2 CO N2 + 2 CO2

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The Catalytic Converter

 Oxidation of a typical gasoline HC, Octane occurs as
Pt, Pd Cat
2 C8H18 + 25 O2 16 CO2 + 18 H2O

 Automobiles using catalytic converters must have their air/fuel ratio set as 14.7:1 to get optimum results.

 At room temp, the efficiency of the catalytic converter is nearly zero

Surface chemistry

Pt, Rh, and Pd (FCC)

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Sulfur Dioxide
143.1 pm
 The release of SO2 into the atmosphere is the primary cause of acid rain

 Fossil fuel combustion accounts for 70% of the emission

 Industrial sources contribute approximately 23% of SO2

 Coal oil and all other fossil fuels naturally contain some sulfur (FeS).

 When sulfur containing coal is burned, the sulfur is oxidized to SO2: S + O2 2SO2 + 2H2O

 H2S (produced as an end product of anaerobic decomposition of sulfur containing organic matter by microorganism)
enter to the atmosphere to form SO2
2H2S + 3O2 2SO2 + 2H2O
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Sulfur Dioxide

 Volcanic eruptions are another more localized natural source of SO2; e.g., the eruption of Mt. Pinatubo in the Philippines
in June 1991 contributed 25 million tons of SO2 into the atmosphere, where it was converted into sulfuric acid aerosols

 Fate of atmospheric SO2: Acid Rain

 The residence time of SO2, controlled not only by chemical conversion to sulfate but also by dry deposition, is 10-30 days.

 SO2 in the atmosphere reacts with oxygen to form SO3, which then readily reacts with water vapor or water droplets to
form H2SO4(g). The mechanism involves hydroxyl radicals.
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The fate of atmospheric SO2: Acid Rain

SO2 + OH HSO3

HSO3 + O2 SO3 + HOO

SO3 + H2O H2SO4 (g)

H2SO4 + H2O H2SO4 (aq)

 Sulfuric acid in the atmosphere becomes concentrated near the base of clouds where
the pH level is as low as 3 (pH of orange juice)
 Some of the atmospheric SO2 dissolves if there is significant water in the air to form
sulfurous acid
SO2(g) + H2O (aq) H2SO3(aq)
 The dissolved SO2 is oxidized by trace amount of H2O2 and Ozone that are also
present in the aerosol droplets to sulfate ions (SO42-)

 HSO3- + H2O2 H2O + HSO4-

HSO3- + O3 O2 + HSO4-

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The fate of atmospheric SO2: Acid Rain

SO2 + OH HSO3

HSO3 + O2 SO3 + HOO

SO3 + H2O H2SO4 (g)

H2SO4 + H2O H2SO4 (aq)

 Sulfuric acid in the atmosphere becomes concentrated near the base of clouds where H2SO4 vs H2SO3
the pH level is as low as 3 (pH of orange juice)
 Some of the atmospheric SO2 dissolves if there is significant water in the air to form
sulfurous acid
SO2(g) + H2O (aq) H2SO3(aq)
 The dissolved SO2 is oxidized by trace amount of H2O2 and Ozone that are also
present in the aerosol droplets to sulfate ions (SO42-)

 HSO3- + H2O2 H2O + HSO4-

HSO3- + O3 O2 + HSO4-

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The oxidation number of S

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Oxoacids of Sulfur

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Effect of Acid Rain

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Effect of SO2 on Human Health and Environment

 SO2 is a colorless, toxic gas with a sharp acrid odor

 Exposure to it causes irritation of eyes, respiratory passages, and aggravates symptoms of respiratory disease. Children are

susceptible to its effects

 SO2 is also harmful to plants. Crops such as barley, alfalfa, cotton, and wheat are particularly adversely affected

Barley Alfalfa Cotton Wheat

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Effect of SO2 on Human Health and Environment

How to control SO2 emissions
1. Sulfur can be removed from coal before combustion
2. SO2 can be removed from the smokestack after combustion but before it reaches to atmosphere

 The second approach is cheaper and most common

 The most commonly used method is flue gas desulfurization (FGD), in which sulfur-containing compounds are washed
out by passing the Chimney (flue) gases through a slurry of water mixed with finely ground limestone (CaCO3) or
dolomite [CaMg(CO3)2] or both.

 On heating the basic CaCO3 with acidic SO2 in the presence of O2 to form CaSO4

2 SO2 + 2 CaCO3 + O2 2 CaSO4 + 2CO2

Flue Gas: a mixture of gases produced by the burning of fuel or other materials in power stations and 79
industrial plants and extracted via ducts.

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a colorless liquid with an ether-like odor

Boiling point: 46.3 °C
CS2(s) + O2(g) = CO2(g) + SO2(g)

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Industrial Smog
 Particulate matter and SO2 can be a deadly combination. Released into the atmosphere together when coal is
burned, they can form industrial smog: a mixture of fly ash, soot, SO2, and some VOCs
 It is formed in winter, typically in cities where the weather is cold and wet. Visibility was often reduced to a few
yards and people in factory towns lived under a pall of black smoke

 Photochemical Smog
 The origin of photochemical smog is quite different from that of industrial smog. Typically, photochemical smog
develops as a yellow-brown haze in hot summer weather in cities like Los Angeles, where automobile traffic is
congested
 The reaction that led to its formation is initiated by sunlight and involves the HCs and NOx emitted in automobile
exhaust.
 NO2 is responsible for the brownish color of the haze

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Industrial Smog

NO2 transforms to the colorless dinitrogen tetroxide

(N2O4) at low temperatures (below −11.2 °C) and
reverts to NO2 at higher temperatures.

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Industrial Smog

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Production of Hydroxyl Radicals

 By the time sunlight reaches the surface of the Earth, all of the light energy UV light has been absorbed in the
stratosphere
 NO2 is the only automobile emission that is capable of absorbing visible light that reaches the Earth’s surface
 NO2 + sunlight (< 320 nm) NO + O ; O + O2 O3
 O3 + NO NO2 + O2

 The ozone produced absorbs light in the blue region of the visible spectrum (< 320 nm) and photo dissociates:
O3 O2 + O
 The oxygen atom produced (having six electrons) reacts with water vapor in the atmosphere and abstracts a hydrogen
atom to produce hydroxyl radical (seven electrons)
 O + H2O 2OH By this way one NO2 molecule produces two hydroxyl radicals
 The concentration of hydroxyl radicals does not continue to increase out of control because there are termination
reactions that remove it from the troposphere. It can react with other radical species in the troposphere
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84

Production of Hydroxyl Radicals

OH + NO2 HNO3
 The products are very soluble in
OH + HOO H2O + O2 water and are removed from
troposphere during precipitation
2 OOH H2O2 + O2

 Unburned HCs in automobile exhausts (RCH3) react with hydroxyl radicals to form a number of
secondary pollutants, including HC radicals RCH2O2. This radical then reacts with NO to form
aldehydes and the hydroperoxide radical HO2

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Production of Hydroxyl Radicals

 Each step in this reaction produces a radical. The overall reaction can be summarized as

 This reaction produces four hydroxyl radicals for every HC reacted. This is a catalytic reaction. A very
small number of radicals can produce a large amount of product through the production of four
radicals per cycle
Reaction of Hydroxyl Radicals with HCs

 Abstraction of Hydrogen
 Hydroxyl radicals will react with certain unburned HCs from the automobile exhaust depending on
the number and type of C-H bonds in the HCs
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Reaction of Hydroxyl Radicals with HCs

Compound Bond Energy KJ/mol
Methane CH3-H 427
Ethane CH3-CH2-H 406
Propane CH3-CH2-CH2-H 393
Methanol HOCH2-H 393
Benzene H5C5C-H 427
Toluene H5C6H2C-H 326

 The dissociation reaction is R-H R + H

The bond dissociation energy depends on how the R radical is stabilized 3o>2o>1o i.e., a tertiary C-H bond
more easily dissociate than a secondary C-H bond
For benzene, the C-H has high dissociation energy as the aromatic carbon is sp2, which mean sp2 C-H bonds are
much stronger than aliphatic C-H bond due to higher s-character
 Higher reaction rates (low dissociation energy) are observed for toluene or xylene as the C6H5CH2 can be
stabilized by adjacent aromatic ring

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Reaction of Hydroxyl Radicals with HCs

 Addition to the double bond
 The reaction of hydroxyl radicals with alkenes proceeds at even a faster rate than the hydrogen abstraction for
HCs
 This reaction is not a hydrogen atom extraction but rather an addition of the hydroxyl radical to the double
bond

 The NO2 produced in this reaction can go on to make more ozone, and the products of this addition reaction i.e.,
acetaldehyde, formaldehyde, and 2-hydroxypropanol all go on to form other pollutants in secondary smog-forming
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reactions
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Secondary Smog Forming Reactions

 The products formed in the previous reactions can undergo further reactions to the troposphere. The following
reaction sequence takes place for all aldehydes formed. Acetaldehyde is used as example

PAN is the component of smog that causes major eye irritation. PANs are relatively stable molecules and have long
lifetimes in cooler air
Ozone, aldehyde, and PANs all contribute to the harmful effects of photochemical smog, but ozone the pollutant
produced in the greatest quantity causes the most serious problems in the troposphere
Ozone in the stratosphere protects us from damaging UV radiation from the Sun
Ozone is a powerful oxidizing agent and causes irritation in the eyes and nasal passages
Ozone is also very toxic to plants
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Indoor Pollution
One can expect to be safer from air pollutants indoors, but in today’s well-sealed homes and offices, this is often
not the case
In buildings where there is little or no circulation or fresh air, pollutants may accumulate to a dangerous level

Lead pipes

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Chemistry of the Stratosphere

 Today, the ozone layer is considered the Earth’s natural sun-screen because it filters harmful UV radiation before it can reach the surface
of the Earth
 A substantial reduction in the amount of ozone in the ozone layer could threaten all life on Earth
Dobson Unit
 The Dobson Unit (DU) is used to describe the amount of ozone in the stratosphere
 It is named after Gordon M. B. Dobson, who built the first instrument to measure the total abundance of ozone from the ground
 1 DU = 2.7 x 1016 ozone molecules/sq centimeter
 In the past, the average amount of ozone covering the Earth was more than 270 DU
 In 2000, the average abundance of ozone from 90o N to 90o S was 293.4 DU
 However, the amount of ozone over the Antarctic is 220 DU which is refer
to the ozone hole

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The production of Ozone in the Stratosphere

 In the absence of pollution, ozone (O3), is not present in any appreciable amount in the troposphere but occurs naturally in the
stratosphere
 Ozone’s concentration is greatest at an altitude of 20 to 30 km from the Earth’s surface
 The ozone layer is formed when an ordinary molecule of oxygen gas (O2) in the stratosphere absorbs UV radiation from the sun
wavelength less than 240 nm and this dissociates O2 to a single oxygen atom (O)
O2 + hv (< 240 nm) O + O (slow) H = 498 KJ/mol

 Single oxygen atoms are very reactive and immediately combine with O2 to form O3:
O + O2 + M O3 + M + Heat (fast)
 M can be a third molecule (N2) present in the atmosphere
 The heat generated by this reaction is carried away by the third molecule
 At the same time, the ozone formed absorbs UV radiation very strongly with wavelengths of
220-330 nm to be broken down into an oxygen molecule and oxygen atom
 Also, when O3 encounters an oxygen atom, two can combine to form two O2 molecules
 A dynamic equilibrium is established

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The production of Ozone in the Stratosphere

Common names for the UV spectrum
(nm) Name Species absorbing Location
10-240 Far UV O2, N2 Thermosphere
250-290 UV-C O3 Stratosphere
290-320 UV-B O3 Stratosphere, troposphere
320-380 UV-A NO2 Polluted troposphere
400-750 Visible Many Earth’s Surface

Catalytic destruction of Ozone

 Ozone is a very reactive molecule and is termed a meta-stable molecule i.e. it decomposes slowly in contact with a
molecule of another gas
 There are a number of species that react efficiently by abstracting an oxygen atom from the ozone molecule. Say “X”
designates the reactive species. Thus, the reaction steps are
i) X + O3 XO + O2; ii) XO + O X + O2
 These are the additional steps for ozone destruction compared to the steps discussed earlier

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The production of Ozone the Stratosphere

 So, the sum of above two reactions is O3 + O 2O2
 The overall reaction does not contain the X species, because X is not consumed in the reaction. It acts as a catalyst
for the destruction of ozone
 “X” lowers the activation energy and atomic oxygen is required to regenerate X
 The catalytic species “X” can be i) Hydroxyl radical, ii) nitric oxide, iii) Chlorine , and iv) bromine atoms

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Catalytic destruction of Ozone

Hydroxyl Radical Cycle
 Hydroxyl radical (OH) can be produced by two different photochemical processes. The first is hydrogen abstraction
with either water or methane
i) O + H2O 2 OH ; ii) O + CH4 OH + CH3
 The second is photolysis of water H2O + hv H + OH

 Hydroxyl radical is responsible for nearly one-half of the total ozone destruction in the lower stratosphere

One OH radical can have as many as 40 cycles

i.e., 40 ozone molecule can decompose

Net reaction

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Catalytic destruction of Ozone

Nitric Oxide Cycle
 Auto mobiles and truck engines release large quantities of nitric oxide (NO) into the troposphere
 Nitric oxide is converted to NO2 and eventually to HNO3 which fall down as rain fall before reaching to stratosphere
 N2O is much less reactive than NO and reaches to stratosphere
 Above 30 km, the N2O can absorb high energy photons to produce molecular nitrogen and an excited oxygen atom (O*)
N2O + hv N2 + O*
 Below 30 km in the stratosphere, the excited state oxygen reacts with the N2O to produce NO
ii) N2O + O* 2 NO
 NO can act as X in the catalytic process

1 NOx radical can catalyze the destruction of 10,000 ozone molecules

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Catalytic destruction of Ozone

The Chlorine Cycle
 The major sources of stratospheric chlorine and bromine have been the anthropogenic chlorofluoro carbons (CFCs)
and bromine-containing halons (haloalkanes)
 CFCs used as refrigerants, propellants for aerosol spray, and solvents for cleaning electric circuit
 Halons are used in commercial fire extinguisher system
 CFCs and halons are nontoxic and nonflammable, which make them superior to other gases that were used for the
same application
 CFCs are so unreactive they don't break down when released and can persist in the troposphere for more than 100
years. Over time, air currents carry them into the stratosphere
 In 1974, two chemists, F. S. Rowland and Mario Molina, predicted that when exposed to UV radiation in
stratosphere, CFCs would break down to form chlorine radical (Cl)
Each chlorine radical involved in a chain reaction has the potential to destroy 100,000 molecules of ozone before
winds carry it back to the troposphere
Bromine-containing compounds are more efficient in destroying the ozone
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Alternatives to Chloro-Fluoro Carbons

• First CIFC substitutes-------HCIFCs such as CF3CHCl2 and CHF2Cl . These have less no. of Cl atoms than other CIFCs

• HCFCs breakdown more rapidly in the atmosphere than CIFCs and thus less likely to reach the stratosphere.

• Hydrofluro carbons----much better substitutes for the CIFCs. CF3CH2F has been used as a refrigerant since 1994.

• Electronic industries-----soapy water followed by rinsed and air drying is used instead of CIFCs to clean micro circuits

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Alternatives to Chloro-Fluoro Carbons

Liquid ammonia can be used as a refrigerant, as an alternative to chlorofluorocarbons.

(i) Ammonia is environmentally compatible. It does not deplete the ozone layer and does not contribute towards

global warming.

(ii) It has superior thermodynamic qualities and as a result, ammonia refrigeration systems use less electricity.

(iii) Ammonia has a recognizable odor. So leaks are not likely to escape.

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Water Pollution

100

Types of Water Pollution

Suspended solids and sediments Dissolved solids Thermal pollution

Oil spillage Detergents

Live-stock waste Pesticides

Industrial waste Chemical Fertilizers

Leather industries

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Suspended solids and sediments

1. Oil spillage

These wastes are not completely soluble and are suspended in the water.
2. Live-stock
3. Industrial waste
4. Leather tanneries

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Oil spillage

Petroleum products
(applications)

• Fuel
• Lubricants
• Plastics
• Electrical appliances
• Synthetic rubber
• Detergents
• Manufacture of petrochemicals
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Water gets polluted by

• Accidental oil spills
• Leakage from cargo oil tankers in sea Tanker trucks
• Pipeline leakage during offshore exploration
• Leakage of underground storage tanks
1. Petroleum products are poisonous and create serious problems for the living system.

2. Polycyclic hydrocarbons are carcinogenic even at low concentrations.

3. Marine animals are seriously affected by soluble fractions of oil.

4. The spilled oil damages the feathers or fur of animals and sometimes causes their deaths.

5. When oil is spilled on the surface of the sea then the light transmission is affected.

6. The process of photosynthesis of plants does not remain very efficient moreover, the concentration of oxygen in water is

decreased.

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Live-stock waste
• Livestock waste is dumped on open land

• It is discharged into sewage and canals of rivers which pollutes the surface and groundwater

• Bacteria are present in the livestock waste. It contaminates the surface and groundwater.

• This results in many diseases like Dysentery, typhoid, Hepatitis etc

Dysentery is a gastrointestinal disease. Its causes

include bacterial or parasitic infections.

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Industrial waste
Large quantities of industrial effluents are
• leather/tanneries
• fertilizers
• oil refineries
• petrochemicals
• textiles
• food
• sugar
• paper/pulp
• ruber etc.

The waste products may be waste heat, solid or water effluent.

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Industrial waste
• The industrial pollutants are highly toxic organic compounds and heavy
metals like Pb, Cd, Cr, Hg, As, Sb, etc.

• Oil grease, mineral acids

• These pollutants make water unsuitable for irrigation and drinking purposes.

• Heavy metals accumulate in the body and create problems like anemia,
kidney diseases, nervous disorders, high blood pressure, etc.,

Leather tanneries:
• Uses Cr-salt , Cr(IV)

• Cr(VI) causes cancer

• Waste treatment can be done by reducing Cr(IV) to Cr(III)

• Cr(III) is precipitated as Cr(OH)3

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Dissolved solids
These are dissolved/soluble in water completely

These include:

• Detergents

• Pesticides

• Chemical fertilizers

• The amounts of detergents in water bodies is increasing day by day

• The detergent wastewater goes to rivers and finally reaches the ocean, which is harmful to life in seas.

• The detergents bound heavy metal ions like Pb, Cd, and Hg, and transport them from sediments into water.

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Pesticides
• These are both toxic and persistent
• Are toxic to fishes
• Endrin, even in traces, is reported to be toxic for catfish and other varieties of fish
• DDT affects the central nervous system of fish
• Toxaphene has been reported to cause bone degeneration in fish

Endrin is an organochlorine Toxaphene

compound produced in 1950
by Shell and Velsicol Chemical pesticide for cotton in the
Corporation. It was primarily used as
an insecticide, as well as
southern United
a rodenticide and piscicide. States during the late
1960s and 1970s.
Endrin Dichlorodiphenyltrichloroethane
C12H8Cl6O
colorless, tasteless, and almost
odorless crystalline developed as an insecticide,

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Chemical Fertilizers
• Nitrate/phosphate salts are generally used as fertilizers, to increase the yield of crops

• Excess fertilizers wash away and reach ponds, lakes, and rivers with rainwater and

thus pollute the water

• The wastewater coming from the fertilizer industries also contains

nitrogenous/phosphatic fertilizers

Harmful effect
• The fertilizers in the water increases the growth of algae and other aquatic plants, which later decomposes and produce bad

smelling gases

• After a long period, the lakes and slow-moving water which contain plant nutrients are converted into swamps and marshes.

• The water containing nitrate is not fit for drinking by human beings.

• This polluted water cannot be purified for drinking purposes.

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Thermal Pollution
• Many electricity-generating power plants use water to cool their generators

• The heated water is released into the river system, causing a warming trend of the surface water

• It may cause a permanent increase in temperature, which results in the decrease of solubility of dissolved oxygen.

• Metals of the pipe can react with hot water and enter in the water system. -------Cu and Ni

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Waste-water treatment

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Treatment of Industrial Wastewater

1. Solid removal
Sedimentation techniques

2. Oil and greases • Skimming devices

• Emulsified components require further treatment

• Biological materials
3. Soft organics • Conventional waste-water treatment

• Synthetic organic materials

• Specific methods
• Distillation, adsorption, nitrification, incineration, landfill disposal
4. Hard organics
• Neutralization under control conditions
• Precipitate may form
• Evaluation of gases may occur
5. Acids and alkalies

• Organic materials, metals, As, Se etc.

• Precipitation of metals by change in pH or chemical treatment
6. Toxic materials • Followed by landfilling or recycling

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Green Chemistry
• Reduces chemical hazard

• Meeting cheaper and more profitable environmental goals

• Making companies to comply with the law for environmental safety

• Can be applied to all kinds of environmental issues

Spinosad------green insecticide

• Manufactured from naturally occurring soil microbes

• Low toxicity for mammals and birds
• It does not bio-accumulate, leach, volatilize, persist in environment

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The 12 principles of Green Chemistry

Developed by Paul T. Anastas and John C. Warner

Focus on reduction in chemical use & pollution prevention

Can broadly be categorized as

---Risks reduction

---Minimizing environmental footprints

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The 12 principles of Green Chemistry

1. Use safer chemicals
2. Design less hazardous synthesis methods
3. Use safer solvents and reaction conditions
4. Accident prevention
5. Waste minimization and prevention
6. Use of catalysts instead of stoichiometric quantities
7. Reduce the use of chemical derivates
8. Synthetic efficiency (Atom economy)
9. Taking advantage of chemicals designed for degradation
10. Establishment of In-process controls for pollution prevention
11. Use of renewable feedback
12. Encourage energy efficiency

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