MODULE-IV

ENVIRONMENTAL POLLUTION AND WATER CHEMISTRY

[Environmental Pollution: Air pollutants: Sources, effects and control of primary air pollutants: Carbon
monoxide, Oxides of nitrogen and sulphur, hydrocarbons, Particulate matter, Carbon monoxide, Mercury
and Lead. Secondary air pollutant: Ozone, Ozone depletion.
Waste Management: Solid waste, e-waste & biomedical waste: Sources, characteristics & disposal
methods (Scientific land filling, composting, recycling and reuse).
Water Chemistry: Introduction, sources and impurities of water; boiler feed water, boiler troubles with
disadvantages -scale and sludge formation, boiler corrosion (due to dissolved O2, CO2 and MgCl2). Sources
of water pollution, Sewage, Definitions of Biological oxygen demand (BOD) and Chemical Oxygen
Demand (COD), determination of COD, numerical problems on COD. Chemical analysis of water:
Sulphate (gravimetry) and Fluorides (colorimetry). Sewage treatment: Primary, secondary (activated
sludge) and tertiary methods. Softening of water by ion exchange process. Desalination of sea water by
reverse osmosis.]
ENVIRONMENTAL POLLUTION
“Pollution may be defined as the excessive discharge of undesirable substances into the
environment, there by adversely affecting the natural quality of the environment and cause damage
to human, plant or animal life. The term environment includes the air, water and land.”

Primary Air pollutants: The pollutants that are directly emitted into the atmosphere through
natural or human activities are called primary air pollutants. Ex. SO2, NO, NO2, CO.

Oxides of Carbon:
Carbon monoxide: carbon monoxide is one of the most serious air pollutants. It is a colorless and
odorless gas, highly poisonous to living beings because of its ability to block the delivery of
oxygen to the organs and tissues.
Sources: CO enters atmosphere due to the-
1. Partial combustion of fuel in automobiles, industries and oil industries.
2. Smoking and domestic heat appliances.
3. Natural processes such as forest fires, volcanic actions, marsh gas production.
2C + O2 → 2CO
Effects:
i. CO binds to the hemoglobin (Hb) to form carboxy-hemoglobin complex, which is about
300 times more stable than the oxygen-hemoglobin complex and reduces the ability of Hb
to deliver oxygen to the body. This results in headache, weak eyesight, nervousness,
paralysis, vomiting and cardiovascular disorder.
CO + Hb → CO-Hb (complex)
Control: Release of CO into the atmosphere can be controlled by-
a. Developing exhaust systems which will complete the combustion process.
b. Developing pollution free power sources like fuel cell to replace internal combustion
engines.
c. Modifying internal combustion engines to minimize the emission of CO.
d. Fixing catalytic convertor in the exhaust of automobiles.

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 CO + O→ CO2

Oxides of Sulphur: SO2 and SO3 are common oxides of sulphur. According to WHO, the
permissible limits of SO2 in air is 20 μg/dm3.
Sources: oxides of sulphur release to the environment by-
1. Burning of sulphur containing fossil fuels like coal and petroleum.
2. Petroleum industries, oil refineries, sulphuric acid plants.
3. Processing and smelting of sulphide ores like PbS, HgS, etc.
S + O2 → SO2
2SO2 + O2 → 2SO3
Effects:
i. Sulphur dioxide is poisonous to both animals and plants. It has been reported that even a
low concentration (1 ppm) of sulphur dioxide causes respiratory diseases, eye irritation,
damages cells and membranes, stone leprosy, yellowing of paper, corrosion of metals etc.
ii. SO3 is highly soluble in water gives H2SO4, which is a main component of acid rain.
2SO2 + O2 → 2SO3
SO3+ H2O → H2SO4(mist)
Control: The entry of SO2 and SO3 into the atmosphere can be controlled by-
a. Adsorbing SO2 on a suitable adsorbent (Na2O.Al2O3) to form stable sulphates.
Na2O.Al2O3 + SO2 + 1/2O2 → Na2SO4 + Al2SO3
b. Using natural gas instead of high sulphur fuels like coal and petroleum, emission of SOx
can be reduced.
c. Passing SO2 through a slurry of CaCO3 to form calcium sulphite. Then inject air to the
reaction mixture to oxidize CaSO3 to CaSO4.
SO2 + CaCO3 → CaSO3 + CO2
CaSO3 + ½ O2 → CaSO4

Oxides of Nitrogen: Nitric oxide (NO) and Nitrogen dioxide (NO2) are the common oxides of
nitrogen.
Sources: the sources of NO and NO2 are-
1. Natural processes like lightening, volcano.
2. Combustion of coal, oil, natural gas and gasoline.
3. Denitrifying bacteria in soil produces N2O.
N2 + O2 → 2NO [at 1483 K]
2NO + O2 →2NO2
Effects:
i. High level of NO2 in air causes eye irritation, damages lungs.
ii. NO2 reacts with atmospheric H2O and forms acid rain.
NO2 + H2O→ HNO2 + HNO3
HNO2 + ½ O2 → HNO3
(nitrous acid)

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 iii. In presence of sun light NO2 forms ozone which damages mucous membrane and
respiratory track.
NO2 UV radiations → NO + O
O + O2 → O3
iv. Nitrogen oxides and hydrocarbons form smog, which causes asthma, bronchitis and
chlorosis.
NO + HC + O2 → NO2 + Peroxyacetyl nitrate (PAN)
O
-
C O O
PAN : H3C O N
-
Control: release of NO and NO2 can be prevented by- O

a. Treating the flue gas with ammonia in presence of vanadium catalyst. NO present in flue
gas reacts with ammonia to form N2 and H2O
4NO + 4NH3 + O2 → 4N2 + 6H2O
b. Oxides of nitrogen can be removed by treating the flue gas with sorbents like powdered
limestone or aluminum oxide.
c. Oxides of nitrogen present in automobile exhaust can be reduced to N2 and O2 by using
catalytic converters.
NOx → N2 + O2

Hydrocarbons: Hydrocarbons are composed of hydrogen and carbon.

Sources: The sources of hydrocarbons are -
1. Formed by incomplete combustion of fuels used in automobiles and industries. The
hydrocarbons found in atmosphere are methane, ethane, propane, toluene, etc.
2. Methane is major hydrocarbon formed by bacterial decomposition of organic matter in
water and sediments.
2(CH2O) → CO2 + CH4
Effects:
i. Methane is called greenhouse gas, causes global warming.
ii. Hydrocarbons inhalation causes irritation to mucous membrane and affect nervous system.
iii. Hydrocarbons at high concentration causes carcinogenic effects on lungs.
iv. Hydrocarbons in presence of sun light form photochemical smog, which causes eye
irritation and cracking of rubber.
v. Hydrocarbons harm plants by causing ageing, breakdown of tissues and shedding of leaves
and flowers.
Control:
a. Unburnt hydrocarbons present in automobile exhaust can be converted into CO2 and H2O
by installing catalytic converter in automobile exhaust.
Hydrocarbons →CO2 + H2O

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 b. The polluted air is passed through porous solid adsorbents kept in suitable containers. The
hydrocarbon pollutants are adsorbed at the surface of the porous solid and clean air passes
through.

Particulate matter:
Finally divided solid particles or liquid droplets suspended in air are called particulates.
Particulates with less than 2.5 μm in size are called fine particulates. If their size is greater than
2.5 μm are called coarse particulates. Particulates in the atmosphere may be viable or non-viable.
The viable particulates are minute living organisms that are dispersed in the atmosphere (e.g.,
bacteria, fungi, molds, algae, viruses etc.). Non-viable particulates include smoke, dust, fumes,
mist, and spray.

Non-Viable Particulates:
Sources:
1. Smoke: formed during the combustion of organic matter. Examples are cigarette smoke,
smoke from burning of fossil fuel, garbage and dry leaves, oil smoke etc.
2. Dust: Produced during crushing and grinding of solid materials. Sand from sand blasting,
saw dust from wood works, pulverized coal, cement and fly ash from factories, dust storms
etc.,
3. Mist: Formed by condensation of vapour, dispersion of liquids.
4. Spray: Formed during atomization of droplets.
5. Fumes: Condensation of vapour by sublimation, distillation calcination etc.
Effects:
i. They cause respiratory problems, reduction of visibility, sneezing, lung cancer, coughing,
nose blocking and asthma.
ii. Causes eye, nose and throat irritation.

Control: There are many techniques developed for the control of particulates.

1. Gravity settling chamber: It is oldest and

simplest means of removing suspended
particles of size greater than 50 μm from flue
gas. Gas stream enters the chamber where the
velocity of gas is reduced and the particle get
settled at the bottom under gravitational force.

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c. Wet Scrubber: Pass the flue gas containing
particulates and spray water over it. The particulates are
captured by water droplets and collected at the bottom of
chamber and clean gas moves upwards. Any mist
associated with clean gas, can be removed by mist
eliminator. Wet srubber remove partcles of size 0.1 to 200
μm efficiently.

d. Fabric filter: Blow flue gas containing

particulates into the fabric filter. It contains a
porous structured fibrous material (filter) which
retains the particulates and allows the gas to pass
through the pores. Fabric filters can provide
above 99% efficiency for particle separation.

e. Electrostatic precipitator: It has positive

(collector) electrodes and negative (discharge)
electrodes. The negative electrodes are in the
form of rod or wire mesh. Positive electrodes are
in the form of plates. Due to the high negativity of
negative electrodes, the air molecules in between
the electrodes undergo ionization releasing
electrons, and hence there will be plenty of free
electrons and ions in the space. As soon as the flue
gases enter into the electrostatic precipitator, free
electrons will be attached to the dust particles. As
a result, the dust particles become negatively
charged. Then these negatively charged particles
will be attracted by positive plates and deposited on them. Particles then fall due to gravitational
force and the flue gases become almost free from ash/dust particles and ultimately get discharged
to the atmosphere through the chimney.

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Chemical Pollutants: Heavy metals like Hg, Pb, As, etc., are dangerous to human beings
because our body can't excrete them.

Lead (Pb):
Sources:
1. Use of leaded petrol in automobiles.
2. Processing and smelting of lead ore.
3. Use of lead compounds like PbSO4, PbCl2, etc.
4. Use of lead containing materials like PVC pipes, cable sheathing, lead-acid batteries, Pb-
electrodes, cathode ray emission tubes of TV and computer monitor, etc.
Effects: If the concentration of lead exceeds permissible limit-,
i. It enters brain tissue and damages central nervous system, kidney function, immune system
and cardiovascular systems.
ii. It enters the blood stream and inhibits the production of hemoglobin causing anemia,
decreases the oxygen carrying capacity of blood.
iii. It decreases the growth and reproductive rates of plants and animals.
Control: lead contaminant in soil, water and air can be controlled by
a. Using unleaded petrol in automobiles.
b. Eliminating lead contaminant in drinking water by processes such as reverse osmosis,
distillation and filtration using carbon filters.
c. Using proper methods to dispose industrial/domestic waste containing lead.
d. Banning lead containing materials like batteries and electrodes.
e. Minimizing plant absorption of lead from soil by maintaining soil pH level at 6.5 and
adding organic matter like composted leaves and manure.

Mercury: Mercury affects human health and ecosystem and is a global pollutant.
Sources:
1. Natural sources like volcanic emissions.
2. Processing and smelting of mercury ore.
3. Use of Hg compounds like HgSO4, HgCl2, etc.
4. Use of mercury containing materials like thermometers, mercury vapour lamps, batteries,
electrodes, electric switches, dental amalgam, electrodes, etc.
Effects:
i. Elemental and mono methyl mercury once enters the body, can easily pass through the cell
membrane and brain tissue. It causes damage to central and peripheral nervous system.
ii. It affects digestive and immune systems, lungs and kidneys.
iii. It reduces the production of hemoglobin causing anemia.
iv. Inorganic salts of mercury are corrosive to skin, eyes and gastrointestinal tract.
v. It results in complex neurological problems, especially in young children and babies.
Control: Mercury contaminant in soil, water and air can be controlled by
a. Avoiding mercury mining and use of mercury in gold extraction.

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 b. Eliminating mercury contaminant in drinking water by processes such as reverse osmosis,
distillation and electrodialysis.
c. Discontinuing the usage of non-essential mercury containing products, such as batteries,
thermometers, electrodes lamps, skin lightening products etc,
d. Use fabric filters, wet scrubbers or electrostatic precipitators at the source to control the
mercury emission.
e. Using proper methods to dispose industrial/domestic waste containing mercury.

Secondary Air Pollutants: Secondary air pollutants are those they are not directly released
into the atmosphere but forms when primary pollutants react in the atmosphere. Ex. Ozone, nitric
acid, sulphuric acids.
Ozone: Ozone in the stratosphere formed by the photo dissociation of oxygen molecules by
absorbing UV radiations of 240 nm wavelength. The UV radiations split apart molecular oxygen
into free oxygen atoms. These oxygen atoms combine with the molecular oxygen to form ozone.

O + O → O2
O2 + O → O3
Ozone in the ground level is formed by the action of sun light on NO2 and volatile organic
compounds (VOCs).
NO2 + sun light → NO + O
O + O2 → O3
VOCs + sunlight → O3
Effect of ozone layer:
1. Positive effect in stratosphere: Ozone layer in the stratosphere is more beneficial
preventing the entry of harmful UV radiations reaching earth`s surface and protects the life
of plants and animals.
2. Negative effect at ground level:
a. Ozone has high oxidizing potential, can damage mucous membrane, respiratory track,
cause asthma and breathing problems.
b. Reduces the growth and yield of main crops.
c. It reacts with hydrocarbons and forms photochemical smog.
Depletion of Ozone Layer: Ozone depleting substances like Chlorofluoro carbons (CFCs)
dissociate ozone into oxygen. CFCs are used as coolants in refrigerators and air conditioners.
i. CFCs on decomposition gives Chlorine free radical
CF2Cl2 + UV radiations→ Cl • + F2CCl •
ii. The chlorine radical then reacts with stratospheric ozone to form chlorine monoxide
radicals and molecular oxygen.
Cl• + O3 → ClO• + O2
iii. Chlorine monoxide radical reacts with atomic oxygen produces more chlorine radicals.
ClO• + O → Cl• + O2
iv. The chlorine radicals are continuously regenerated and cause the breakdown of ozone.
Thus, CFCs are transporting agents for continuously generating chlorine radicals into the

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 stratosphere and damaging the ozone layer. Each Chlorine free radical can destroy one lakh
molecules of O3.

Effects of Depletion of Ozone Layer:

As ozone depletes in the stratosphere, more UV radiation enters into the troposphere. UV
radiations lead to ageing of skin, cataract, sunburn, skin cancer, damage to fish productivity etc.

Control:
a. Encourage growth of plants and discourage deforestation.
b. Ground level ozone can controlled by preventing the emission of NO2 and VOCs into the
atmosphere.
c. In stratosphere, depletion of ozone layer can be prevented by using hydro Chlorofluoro
carbons (HCFC) and hydrofluoro alkanes (HFA) instead of CFCs. HCFC and HFA
undergo degradation before reaching stratosphere.

Solid Waste Management:

Solid Waste refers to all non-liquid garbage arising from animal and human activities that are
discarded as unwanted and useless. It can be categorized based on materials such as plastic, paper,
glass, metal, demolition materials, wood, pesticides, insecticides and organic waste.

Solid Waste Management is a planned process of collection, transport and disposal of solid waste
materials in safe and economic manner.
Everyday tons of solid waste is disposing off at various landfill sites and recycling units. This
landfill sites produce foul smell if the waste is not stored and treated properly.
Based on the source, the solid waste can be classified into three types.

1. Municipal solid waste (MSW)

2. Electronic solid waste (ESW)
3. Bio-medical solid waste (BSW)

1. Municipal solid waste (MSW):

Sources: The major sources of MSW are Residential areas, Industries, Commercial
establishments, Institutions, Municipal services, Manufacturing units, and Construction and
demolition sites.
Characteristics: Information and data on characteristics of solid waste are important for selecting
a suitable disposal technique.
i) Physical characteristics:
a. Density: It is a crucial factor to design a solid waste management system, Ex. design of
sanitary landfills, storage and type of collection.
b. Moisture content: It is ratio of weight of water to the total weight of wet waste. As the
moisture content in waste increases, the cost of collection and transportation also increases.
A typical range of moisture content is 20% to 40%.

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 c. Size distribution: It is also important factor for the recovery of materials with mechanical
means like magnetic separators.
ii) Chemical characteristics: If MSW is to be used as fuel or used for any other purpose, one
must know the chemical properties.
a. Lipids: found in fats, oils, grease, they have high heating values of about 38000 kJ/kg,
suitable energy recovery.
b. Carbohydrates: found in food and yard wastes, they are readily biodegradable to CO2 and
H2O.
c. Proteins: they contain an organic acid and amine group, found in food and yard waste. The
partial decomposition of these compounds yield amines that have unpleasant odour.
d. Natural fibers: found in paper products, food and yard wastes, contain high proportion of
paper and wood products, having high heating value. They are suitable for incineration.
e. Synthetic organic material: now a days plastics become the major component of solid
waste. They are highly resistant to biodegradation. Have high heating value of about 32000
kJ/kg.

2. Electronic solid waste (ESW)

E-waste can be defined as electronic and electrical equipments/products that have become obsolete
due change in fashion, style, status and attaining the end of their useful life.
E-wastes are considered dangerous, as certain components of some electronic products contain
materials like mercury, lead, antimony, phosphorus etc., which are hazardous, poses a threat to
human health and environment.

Sources: Discarded computers, televisions. VCRs. stereos, copiers, fax machines, electric lamps,
cell phones, audio equipments, DVDs, CDs, washing machines, microwave ovens, mother boards.
PCBs, batteries, etc., if improperly disposed can penetrates into soil and groundwater.

Characteristics: E-waste is characterized by hazardous and non-hazardous materials.

i. Hazardous materials: Electronic waste consists of large number of components, some of
which contain hazardous materials that need to be removed for separate treatment. Ex.
Flame retardants used in plastics, non-biodegradable materials like PVC etc.
ii. Material composition: E-waste contains mixture of various metals like iron, copper,
aluminum with noble metals like gold, silver, platinum and toxic metals like Pb, Hg, Cd,
etc., with or without plastics and ceramics. Ex. Relays, switches etc.

4. Bio-medical solid waste (BSW)

Bio-medical waste is any kind of waste containing infectious materials, generated during
diagnosis, research, testing and treatment of biological products for humans or animals. It includes
discarded medicines, used needles, used bandages, used gloves, stools, blood, urine, syringes,
knives, toxic drugs, etc.

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Sources: The major sources of bio-medical waste are Hospitals, Clinics, Labs, research centers,
Animal research, Blood banks and Nursing homes.

Characteristics: BSW is characterized by the presence of dangerous materials-

1. Waste containing infectious material like tissues, body parts, blood, body fluids, excreta,
needles, knives etc.
2. Waste containing radioactive materials like contaminated glassware, unused liquid in
radiotherapy etc.
3. Waste containing chemicals like expired lab reagents, film developers, disinfectants, etc.
4. Waste containing pharmaceuticals like expired and contaminated medicines, etc.

Solid Waste Disposal Methods: There are various methods available for the disposal of
solid waste, to minimize pollution.
1. Landfills: It is the oldest waste disposal method where waste is directly disposed into a
large pit or trench and is covered with a thin layer of soil. In landfills, waste undergoes
anaerobic oxidation releasing methane, which is poisonous. Therefore care to be taken to
prevent accumulation of methane.
i. Ordinary landfills are associated with the problems like - i) seepage of waste into soil
and water and ii) emission of methane from waste into atmosphere. These problems
can be eliminated by scientific landfills.
ii. Scientific landfills are constructed with a base layer of 90 meters of clay to prevent
any seepage or leakage within the landfill. They also reduce the speed of methane
production. Scientific landfills generate methane slowly which can be used as
alternative fuel for electricity and heat generation purpose. Narela-Bawana in New
Delhi is the only scientific landfill in India. It has the capacity to treat 2000 tons of
waste every day, generating 24 megawatts of electricity.
2. Composting: It involves the biodegradation of organic waste. The organic waste is mixed
with water, oxygen, carbon and nitrogen, the micro-organisms are able to break down
organic matter to produce compost, which can be used as organic fertilizer. It involves the
following steps.
i. Separation of bio-degradable materials from non-biodegradable materials like plastics,
etc.
ii. Reduce the size of materials to get uniform size.
iii. Allow the waste to undergo complete biodegradation in a closed tank by providing
enough oxygen.
3. Recycling and Reuse: It is a process of taking use full things from discarded items for
next use. Before recycling, separate the materials like paper, glass, plastics, metals, rubber
etc., from waste.
i. Primary recycling involves processing of waste/scrap into materials that have
characteristics similar to those of original material. Ex.
a. Remolding of plastics.
b. Waste papers of old books and newspapers can be reused for making paper bags.

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 ii. Secondary recycling involves processing of waste/scrap into materials that have
characteristics different from those of original material. Ex.
a. The organic waste generated from household can be used for making compost,
which can be used as manure.
iii. Tertiary recycling involves the production of basic chemicals and fuels from plastic
wastes using a suitable chemical process such as pyrolysis. This method is suitable for
all types of plastic wastes including multi-layered plastics for which primary and
secondary recycling are not suitable. It allows us to recover energy from plastic waste
without burning the plastic waste.
iv. Old electrical appliances and furniture can be reused as far as possible rather than
dumping them.
4. Incineration: This process is usually selected to treat wastes that cannot be recycled,
reused or disposed of in landfills. It involves the burning of solid waste at high temperature
until the wastes are turned into ashes. It reduces the volume and weight of waste for safe
disposal in outer land fields.

WATER CHEMISTRY
Sources of water: The sources of water classified as follows
Surface water: Rain water, River water, Lake water, Sea water
1. Rain water: Purest form of water contains dissolved gases and suspended solid particles.
2. River water: Contains dissolved minerals of soil such as chlorides, sulphates, bicarbonates
of sodium, calcium, Mg, Fe etc. It also contains the organic matter, small particles of soil
and sand in suspension.
3. Lake water: It contains less dissolved minerals but high quantity of organic matters.
4. Sea water: It is the most impure form of natural water. It contains dissolved salts such as
NaCl, sulphates of Na and K, bicarbonates of Mg & Ca.
Impurities in water: The water found in nature is never pure which contains large number of
impurities in varying amount. These impurities mainly depend upon its source and are classified
into four different types.

1. Dissolved gases: these includes dissolved oxygen, CO2, SO2, NH3, (NO)x, all of which
derived from atmosphere.
2. Dissolved solids: these includes salts like bicarbonates, Chlorides and Sulphates of Ca,
Mg, & Na in addition to that small amount of nitrates, nitrites, silicates, ammonia and
ferrous salt etc.
3. Suspended impurities: Suspended impurities are the dispersed solids which can be
removed by filtration or settling. Suspended impurities are of two types.
i. Inorganic Impurities: clay, silica, oxides of Fe & Mg etc
ii. Organic Matter: organic compounds derived from the decay of vegetable and animal
matter including bacteria may be present in water. Water also gets contaminated with
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 sewage and excretal matter. Consequently, the pathogenic bacteria and microorganism
are the main causes for water borne diseases.

Boiler feed water: The water fed into the boiler for the production of steam is called boiler
feed water. If the boiler feed water is impure, it leads to boiler troubles. Boiler troubles are due to
1. Scale & sludge formation
2. Boiler corrosion
3. Priming& foaming

1. Scale & sludge formation:

Scale: The thick and hard precipitate of salts deposited on the inner wall of the boiler is called as
scale. Ex.-CaSO4, MgCl2, MgSO4, Ca(OH)2, Ca3(PO4)2 etc.,
Sludge: If the precipitate formed is loose, non-adherent and suspended in the boiler feed water, it
is called sludge. Sludge is formed due to Ca(HCO3)2, Mg(HCO3)2,

Disadvantages:
i. Sludge are poor conductors of heat and causes wastage of fuel.
ii. Danger of explosion due to excess pressure inside the boiler.
iii. Excess of sludge formation decreases the efficiency of boiler.
iv. Scales act as a thermal insulators, it decreases the efficiency of the boiler.
Prevention:
i. External treatment: This treatment is given before the feed water enters the boiler. It
involves the removal of salts responsible for scale formation by sedimentation, coagulation
and filtration techniques.
ii. Internal treatment: This involves addition of chemicals directly into the boiler to remove
the impurities, which were not removed during external treatment.
iii. Blow-down operation: It involves the periodical removal of a portion of the concentrated
boiler water and its replacement by fresh water.

Removal of Scale:
i. Scale can be removed with the help of scraper or wire brush.
ii. Brittle scale can be removed by giving thermal shocks i.e, heating the boiler and suddenly
cooling with cold water.
iii. Scale can be removed by treating them with chemicals. For Ex., Ca(CO3)2 scales are
removed by treating with 5-10% HCl. Ca(SO4)2 scale can be removed by using EDTA.

2. Boiler corrosion: Degradation of boiler due to the presence of impurities in boiler feed
water is called boiler corrosion. Corrosion of boiler due to–
1. Dissolved O2 2. Dissolved CO2 3. Dissolved MgCl2
1. Corrosion due to dissolved oxygen: Dissolved oxygen in presence of water, causes corrosion.
2Fe + 2H2O + O2 → 2Fe(OH)2
2Fe(OH)2 + O2→ 2[Fe2O3.2H2O] + 2H2O
(Rust)
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Prevention:
i. By adding Sodium Sulphite: 2Na2SO3+ O2→ 2Na2SO4
This method is less preferred as it leads to the formation of other precipitates.
ii. By adding Hydrazine: N2H4+ O2 → N2+ 2H2O
This method results in the formation of pure water, and has no side effects. So it is preferred.

2. Corrosion due to dissolved CO2

Salts like Calcium bicarbonate on heating produces CO2. CO2 dissolves in water to form
carbonic acid which corrodes the boiler metal.
Ca(HCO3)2 → CaCO3+ H2O + CO2
H2O + CO2 → H2CO3 → H+ + HCO3-
Fe2+ + HCO3- → Fe(HCO3) → Fe(OH)2 ↓ + 2CO2
2Fe(OH)2 + O2→ 2[Fe2O3.2H2O] + 2H2O
(Rust)
Prevention:
i. By treating with lime: Ca(OH)2 + CO2 → CaCO3 +H2O
ii. ii. By adding ammonium hydroxide: 2NH4OH + CO2 → (NH4)2CO3+ H2O

3. Corrosion due to MgCl2: Dissolved salt like MgCl2 causes acid formation.
MgCl2+ 2H2O → Mg(OH)2+ 2HCl (Corrosive acid)
Fe2+ +2HCl → FeCl2 + 2H+
FeCl2 + 2H2O → Fe(OH)2 + 2HCl
2Fe(OH)2 + O2→ 2[Fe2O3.2H2O] + 2H2O
(Rust)
Prevention:
This can be prevented by alkali neutralization. Excess acidic nature is neutralized by adding alkalis
and vice versa.
HCl + NaOH → NaCl + H2O

Water Pollution:
Discharge of certain foreign substances into water that affects the physical, biological and
chemical properties of water which in turn decreases the utility of water is known as water
pollution. The matter which is responsible for these unhealthy changes in water is known as water
pollutants. Eg. Pd, Hg, CN, As, Cu, acids, alkalis, pesticides, insecticides, fungicides, animal
matter, human excreta, radioactive wastes etc. The contaminated water is called sewage water or
effluent.
Depending on the sources of water pollutants, sewage water is classified into two types:
1.Domestic Sewage 2. Industrial sewage

Domestic sewage: It is the waste discharging away from residences, institutes, hospitals etc. These
include certain organic wastes, pathogenic bacteria, plant materials, pesticides, detergents and
other materials. Domestic sewage causes water borne diseases like dysentery, cholera, typhoid,
and hookworm infection.
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Industrial sewage: It is the waste released by industries. It contains Pd, Hg, CN, As, Cu, acids,
alkalis, pesticides, detergents, insecticides, fungicides, soap, phenol etc. It can be render harmless
by suitable treatments. The organic waste present in water undergoes degradation and breakdown
into simple molecules by bacteria. The bacterial degradation is of two types:

1. Aerobic degradation or oxidation: Brought about by bacteria in presence of air and dissolved
oxygen of water. Aerobic oxidation produces harmless compounds like water and CO2.

2. Anaerobic degradation or oxidation: Brought about by bacteria in absence of air and

produces harmful products such as NH3, H2S, CH4 etc.

Sewage treatment: The process of removal of contaminants present in the sewage is called
sewage treatment. It involves three stages. i). Primary, ii). Secondary and iii). Tertiary treatment.
1. Primary treatment: It is the process of removal of course, suspended and floating solids.
 Screening: It removes large suspended or floating matter in the sewage.
 Filtration: The water is passed through conventional sand filter beds to remove the last
trace of suspended matter.
 Sedimentation: Sedimentation is a process of removing suspended impurities by allowing
the water to stay undisturbed for some time in a larger tank. Due to gravitation force almost all the
suspended particles settle down.
 Coagulation: It is a process of removing colloidal particles from water by the addition of
coagulating agents. Potash alum [K2SO4. Al2(SO4)3.24H2O] and ferrous sulphate (FeSO4.7H2O)
are commonly used coagulants.

2. Secondary treatment (Activated sludge process): It involves the removal of organic matter.
The waste water after primary treatment is allowed to flow to large tanks where biological
treatment is carried out.
Activated sludge containing microorganisms is sprayed over the water and oxygen is passed
vigorously from the bottom of tank. Under these conditions, aerobic oxidation of organic matter
takes place.

14
The sludge formed is removed and the residual water (secondary effluent) is treated with chlorine
or UV radiations to remove bacteria and finally discharged into running water or reused for
watering plants.
(Sludge: The matter which settles down at the bottom after treatment is called sludge and the liquid
is called effluent).
3. Tertiary treatment: If the residual water contains high concentration of phosphates, heavy
metal ions, colloidal impurities and non-degradable organic matter, the water is taken to tertiary
treatment. It involves--
i) The removal of phosphate as insoluble calcium phosphate by treating with lime.
ii) The removal of heavy metal ions as insoluble sulphide by treating with sulphide ions.
iii) The removal of remaining organic matter by adding activated charcoal.
iv) The removal of remaining colloidal impurities by adding alum.

Biological Oxygen Demand (BOD):

The amount of oxygen required in milligrams by microorganisms to oxidize the biologically
oxidizable impurities present in 1 dm3 of waste water over a period of five days at 20oC.
Importance of BOD: BOD is most important in sewage treatment, as it indicates the amount of
decomposable organic matter in the sewage or extent of pollution or amount of dissolved oxygen.
“Greater the concentration of organic matter in the sewage, greater is the BOD”.
Example: calculate the BOD of an effluent sample containing 9 mg dm-3 of impurities denoted by
the formula CH2O.
Solution: Write the equation for the oxidation of impurities
CH2O + O2 → CO2 + H2O
30 32 44 18
According the equation, 30 mg of CH2O requires 32 mg of O2 for complete oxidation
32x9
Therefore, 9 mg of CH2O requires = mg of O2
30
= 9.6 mg of O2
⸫ BOD of effluent sample is 9.6 mg of O2

15
Chemical oxygen demand (COD):
It is the amount of oxygen in milligrams required to oxidize organic and inorganic impurities
present in one dm3 of waste water using strong oxidizing agent like acidified K2Cr2O7.
Procedure: Pipette out 25cm3 waste water into a conical flask, add 1 test tube of 1:1 sulphuric
acid containing mercuric sulphate and silver sulphate and a known amount potassium dichromate.
The above mixture is refluxed for two hours and cool to room temperature. Then the mixture is
titrated against standard FAS solution, using ferroin as indicator, till the colour changes from
greenish yellow to reddish brown. Let the volume of FAS consumed be V1 cm3.
Blank: The same procedure is repeated for 25 cm3 of distilled water. Let the volume of FAS
required be V2 cm3.

Observation and calculation

N x (V2  V1 )
Then, COD of the sample = x 8 g.dm3
V
N x (V2  V1 )
= x 8 x1000mg.dm3
V
Where, N= Normality of FAS solution
V= Volume of waste water titrated
Importance:
1) The COD test is widely used for measuring the pollution strength of domestic and industrial
wastes.
2) Management and designing of treatment plant.
3) The major advantages of COD test are that the determination is completed in three hours
as compared to the 5 days required for BOD determination.

Problem 1
In a COD test, 25 ml of sewage sample as made to react with 25 ml of K2Cr2O7 solution and the
unreacted K2Cr2O7 required 9.0 ml and 16 ml of 0.002N FAS solution for back and blank titrations
respectively. Calculate COD of the sample.

Solution:
Volume of sample taken=V= 25 ml
Volume of 0.05 N FAS required to react with unconsumed K2Cr2O7=V1= 9.0 ml
Volume of FAS consumed in blank titration =V2= 16 ml
N x (V2  V1 )
Then, COD of the sample = x 8 g.dm3
V
0.05 X (16  9)
COD of the sample= x8 x1000  112 mg / dm3
25

Problem 2: 25 ml of an effluent requires 9.5 ml of 0.001M K2Cr2O7 for oxidation. Calculate the
COD of the effluent sample. [Given molecular mass of K2Cr2O7 =294).

16
Solution:
1M K2Cr2O7 = 294g of K2Cr2O7 in 1 liter of solution ≡ 48 g of oxygen
i.e., 1000 ml of 1M K2Cr2O7 solution ≡ 48 g of oxygen
48 X 0.001X 9.5
 9.5 ml of 0.001M K2Cr2O7 solution = = 0.000456 g or 0.456 mg of oxygen
1000
It means 25 ml of effluent sample ≡ 0.456 mg of oxygen
0.456X 1000
 1000 ml of effluent sample ≡ = 18.24 mg of oxygen
25
 COD of water =18.24 mg/dm3

Problem 3: 30 ml of waste water sample required 10 ml of 0.02N K2Cr2O7 for oxidation. Calculate
the COD of the effluent sample. [Given equivalent mass of K2Cr2O7 =49).
Solution:
1N K2Cr2O7 = 49g of K2Cr2O7 in 1 liter of solution ≡ 8 g of oxygen
i.e., 1000 ml of 1N K2Cr2O7 solution ≡ 8 g of oxygen
8 X 0.02 X 10
 10 ml of 0.02N K2Cr2O7 solution = = 0.0016 g or 1.6 mg of oxygen
1000
It means, 30 ml of effluent sample ≡ 1.6 mg of oxygen
1.6 X 1000
 1000 ml of effluent sample ≡ = 53.3 mg of oxygen
30
 COD of water =53.3 mg/dm3

Determination of sulphate ions by gravimetry method

Sulphate concentration should be less than 200 mg/L. Sulphate ions in water sample reacts with
BaCl2 under acidic conditions to give BaSO4 ppt. By knowing the weight of BaSO4 ppt. formed,
the amount of sulphate in the sample can be determined.
Procedure:
i. Take 200 ml water in a beaker and heat it.
ii. Add 1 tt dil. HCl and 5% BaCl2 solution slowly with constant stirring till the precipitation
completes.
iii. Filter the BaSO4 ppt using Whatman filter paper.
iv. Transfer the filter paper containing BaSO4 into a dried, previously weighed (W1g) crucible.
v. Place the crucible in an electric burner and ignite the precipitate.
vi. Cool the crucible to lab temperature and note down its weight (W2 g).
vii. Calculate the weight of BaSO4 formed (W2 – W1 = W g).

Calculations:
233.4 g of BaSO4 contains 96.06g of sulphate
96.06 xW
W g of BaSO4 contains = g of sulphate
233.4
96.06 xW
i.e., 200ml of water sample contains = g of sulphate
233.4
17
 96.06xWx1000
⸫ 1000ml of water sample contains = = ‘a’ g of sulphate
233.4 x 200
⸫ The amount sulphate in the water sample = ‘a’ g of sulphate

Determination of fluoride by SPADNS Method

Fluoride ion severely affects the qualities of drinking water. If its concentration exceeds 1 mg/L,
causes dental fluorosis. Its concentration can be estimated colorimetrically by using Zirconyl-
SPADNS [sodium 2-(p-sulphophenylazo)-1,8-dihydroxy-3,6 naphthalene disulphonate] reagent.

Principle: Under Acidic conditions, fluoride ion reacts with Zr-SPADNS reagent and Color of
this reagent gets bleached. The extent of bleaching depends on the concentration of F- ion.

Zr-SPADNS + F- → (ZrF6)2- + SPADNS

Procedure:

i. Prepare a reference solution by adding 10 ml of SPADNS in HCl and dilute to 50 ml

and use this solution to set the colorimeter to zero at 570 nm.
ii. Prepare Zr-SPADNS reagent by dissolving ZrCl2. 8H2O and SPADNS in HCl and dilute
to 500 ml.
iii. Prepare a stock solution of NaF by dissolving 0.022 g in 1000 ml.
iv. Prepare a series of standard solutions by adding 2,4,6,8 ml of NaF Solution in 50 ml
standard flasks.
v. To each flask, 1 drop of sodium arsenite (NaAsO2) and 10ml of Zr-SPADANS reagent
are added. Dilute up to the mark using distilled water. Mix well and measure
transmittance at 570 nm.
vi. Draw a calibration curve by plotting transmittance versus concentration of fluoride ion.
vii. Take a known volume of water sample in which fluoride concentration has to be
determined, add NaAsO2 and 10ml of Zr-SPADANS and measure transmittance at 570
nm.
viii. Calculate the F- ion concentration using calibration curve.

Conc. Zr-SPADNS Conc. of F- Transmi

NaF in (mg/L) ttance
2 10 0.398 --
4 10 0.796 --
6 10 1.194 --
8 10 1.592 --
10 10 1.989 --
TS 10 ? x

18
Softening of water by Ion exchange process
The process of removing hardness causing ions such as calcium and magnesium ions from hard
water is called softening of water. Water softening process involves cation and anion exchange
resins which are made of cross linked polymers with porous structure and desirable functional
groups.
Cation exchange resin is made of Styrene-divinyl benzene copolymer with SO3H functional
groups containing replaceable H+ ions and is represented as RH+. It exchanges H+ ions with cations
like Ca2+ and Mg2+ present in hard water.
Anion exchange resin is made of Styrene-divinyl benzene copolymer with basic quaternary
ammonium functional groups containing replaceable OH- ions and is represented as ROH-. It
exchanges OH- ions with anions like SO42- and Cl- present in hard water.

Process: Cation and anion exchange resins are packed in separate columns as shown in the
diagram. Hard water is first passed through the cation exchange resin where Ca2+ and Mg2+ are
exchanged with H+ ions.

RH+ + M+ → RM+ + H+
2RH+ + M2+ → R2M2+ + 2H+
Where M+ is monovalent like Na+ and M2+ is divalent like Ca2+.

The water is then passed through anion exchange resin where anions like SO42- and Cl- are
exchanged for OH-.

ROH- + X- → RX- + OH-

2ROH- + X2- → R2X2- + 2OH-+
Where X- and X2- represents the anions like Cl- and SO42-

Regeneration: On prolonged use, resins become deactivated, they need to be regenerated.

Cation exchange resin is regenerated by HCl.
R2M2+ + 2H+→ 2RH+ + M2+
Anion exchange resin is regenerated by NaOH.
R2X2- + 2OH-→ 2ROH- + X2-
The columns finally washed with distilled water before use.
19
Advantages of Ion exchange method:
i. It can be used for high pressure boilers also.
ii. Water of 1 to 2 ppm purity can be obtained from this process.
iii. It can be regenerated and used for long period of time.
Drawbacks of Ion exchange method:
i. Expensive
ii. Fe, Mn cannot be removed as they form complexes with resins
iii. Cannot be used for turbid water as they clog the resins.

Potable water: Water which meets all the parameters of pure water and fit for drinking called
potable water. It should be clear, colorless, odorless and free from pathogenic bacteria with
agreeable taste.

Desalination or Desalting: Desalination is a process of removal of dissolved salts from saline

water (sea water) and water become potable. It can be achieved by Reverse Osmosis.

Reverse osmosis:
Semipermeable Semipermeable
Piston
membrane membrane

Salt water Pure pure

water Salt water
water

Osmosis Reverse osmosis

When pure water and salt water are separated by a semipermeable membrane, due to the difference
in chemical potential, water molecules move from pure water to salt water until the chemical
potential become equal in both the sides. This movement is called osmosis. The water molecules
can be made to move in reverse direction that is from salt water to pure water by applying pressure
on salt water, it is called reverse osmosis.
The process of movement of water through a semi permeable membrane from salt water to pure
water by the application of pressure greater than osmotic pressure on salt water is called as reverse
osmosis.
A reverse osmosis unit consists of a vessel, high pressure pump and a semi permeable membrane
made up of cellulose acetate. When pressure in the range 410-540 psi is applied on the salt water
(sea water), water molecules flow from salt water to fresh water which can be used for domestic
applications.
Advantages:
20
 1. It is economical, simple, continuous and compact.
2. The process needs extremely low energy.
3. It has long life and membrane is easily replaceable.
4. It is possible to connect number of tubes in parallel, to get more fresh water.
5. Ionic, non- ionic, colloidal and high molecular weight organic matters are easily removed.
Disadvantage:
1. Colloidal silica is not removed by this process.

..…….x………..x………x………….x………..
Question Bank
1. What is meant by primary pollutant and secondary pollutant?
2. What are viable particulates and non-viable particulates?
3. Explain the Sources, Ill effects and control of CO, NO and SO2.
4. Explain E-waste, Biomedical waste and Solid waste.
5. Explain the ozone formation, depletion and its consequences.
6. Explain the determination of concentration of fluoride ion in water by colorimetry.
7. Describe the estimation of concentration of sulphite by Gravimetry.
8. What is boiler feed water? What is sludge and scale? What are the reasons for sludge and
scale formation? Mention the disadvantages and preventive measures.
9. Explain boiler corrosion due to dissolved oxygen/CO2/MgCl2 with reactions and mention
the preventive measures for the same.
10. Define BOD and COD. Explain method of determination of COD of a waste water sample.
11. Discuss the primary, secondary and tertiary treatment steps of sewage water treatment with
neat diagram.
12. What is desalination? Discuss desalination of water by reverse osmosis process.
13. Explain purification of water by ion exchange resin method.
14. 25 cm3 of sewage sample reacted with 10cm3 of K2Cr2O7 solution and unreacted sample
requires 8.5cm3 of .025 N FAS solution. Under similar conditions in blank titration 15cm3
of same FAS is used up. Calculate the COD of the sewage sample.

21