UNIT-1

WATER AND ITS TREATMENT

Syllabus: Water and its treatment: Introduction – hardness of water – Causes of hardness -
Types of hardness: temporary and permanent – expression and units of hardness. Estimation
of hardness of water by complexometric method. Potable water and its specifications. Steps
involved in treatment of water-Disinfection of water by chlorination and ozonisation-
industrial water treatment- Boiler feed water and its treatment -internal conditioning– Calgon
and Phosphate conditioning. External treatment of water -Ion exchange process. Desalination
of water -Reverse osmosis.

Introduction

Water is nature’s most wonderful, abundant, and useful compound. Water is not only
essential for the lives of animals and plants, but also occupies a unique position in industries.
It is widely used in drinking, bathing, sanitary, washing, irrigation, firefights, air-conditioning
and also the production of industrial materials. The distribution of water on the Earth’s
surface is extremely uneven. Only 3% Of freshwater (69% resides in glaciers, 30%
underground, and less than 1% is located in lakes, rivers and swamps.) of water on the
surface is fresh; the remaining 97% resides in the ocean. Looked at another way, only one
percent of the water on the Earth’s surface is usable by humans, and 99% of the usable
quantity is situated underground.

Types of Impurities present in water:

Different types of impurities usually contaminate natural water. They are mainly three types-
Physical, Chemical and Biological impurities.

1. Physical impurities:

Colour: in water is caused by metallic substances like salts.

Turbidity: is due to the colloidal, extremely fine suspensions such as insoluble substances like
clay, slit, and micro-organisms.
Taste: presence of dissolved minerals in water produces taste. Bitter taste can be due to the
presence of Fe, Al, Mn, Sulphates and lime. Soap taste can be due to the presence of large
amount of sodium bicarbonate.
Odour: In water is undesirable for domestic as well as industrial purpose.

2. Chemical impurities:

Inorganic chemicals: Cations (Al+3, Ca+2, Mg+2, Fe+2, Zn+2, Cu+2, Na+, K+), Anions (Cl−,
SO4−2, NO3−, HCO3−, F−, NO2−)
Organic chemicals: dyes, paints, petroleum products, pesticides, detergents, drugs textile
materials, other organic related materials.

3. Biological Impurities:

Biological impurities are Algae, pathogenic bacteria, fungi, viruses, pathogens, parasite-
worms.

Hardness of Water

Hardness of water defined as which prevent the lathering of soap. This is due to presence of
certain salts like Ca+2, Mg+2 and other heavy metals dissolved in water. Soaps (Sodium or
Potassium salts of higher fatty acids) like Stearic acids (C17H35COONa).

C17H35COONa + H2O → C17H35COONa + NaOH

soap Stearic acid

Hard Water: The water which does not give lather with soap is called hard water. This is
due to presence of certain salts like Ca+2, Mg+2 and other heavy metals dissolved in water

2C17H35COONa + CaCl2/MgCl2 → (C17H35COO)2 Ca/Mg + 2NaCl

soap (soluble) salts (soluble) insoluble scum

Causes of Hardness

Hardness of water is due to the presence of Bicarbonates, Chlorides, Sulphates and Nitrates
of Calcium and Magnesium. These soluble salts get mixed with natural water due to the
following reasons:
1. When natural water containing CO2 flows over the rocks of the limestone (CaCO3) and
Dolamite (CaCO3 & MgCO3), they get converted into soluble bicarbonates. Thus, water gets
hardness.
CaCO3 + H2O + CO2 → Ca(HCO3)2
Insoluble Soluble

2. When natural water flows over the rocks containing chlorides and sulphates and Nitrates of
Calcium and magnesium, these salts dissolve in water. Thus, water gets hardness.

Disadvantages of Hardness

1. In Domestic use:
Washing: Hard water, when used for washing purposes, does not producing lather freely with
soap. As a result, cleaning quality of soap is decreased and a lot of it is wasted.
Bathing: Hard water does not lather freely with soap solution but produces sticky scum on the
bath-tub and body. Thus, the cleaning quality of soap is depressed and a lot of it is wasted.
Cooking: The boiling point of water is increased because of presence of salts. Hence more
fuel and time are required for cooking.
Drinking: Hard water causes bad effects on our digestive system. Moreover, the possibility of
forming calcium oxalate crystals in urinary tracks is increased.
2. Industrial Use:
Textile Industry: Hard water causes wastage of soap. Precipitates of calcium and magnesium
soaps adhere to the fabrics and cause problem.
Sugar Industry: The water which containing sulphates, nitrates, alkali carbonates are used in
sugar refining, cause difficulties in the crystallization of sugar.
Dyeing Industry: The dissolved salts in hard water may reacts with costly dyes forming
precipitates.
Paper Industry: Calcium, magnesium, Iron salts in water may affect the quality of paper.
Pharmaceutical Industry: Hard water may cause some undesirable products while preparation
of pharmaceutical products.
3. Steam generation in Boilers:
For steam generation, boilers are almost invariably employed. If the hard water is fed directly
to the boilers, there arise many troubles such as: Scales & sludges formation, Corrosion,
Priming & Foaming and Caustic embrittlement.

Types of Hardness

Hardness of water is mainly two types:

1. Temporary Hardness 2. Permanent Hardness
1. Temporary Hardness: Temporary Hardness mainly caused by the presence of dissolved
bicarbonates of Calcium, Magnesium [(Ca(HCO3)2, Mg(HCO3)2)]. Temporary Hardness can
be largely removed by boiling of water.
2. Permanent Hardness: It is due to the presence of dissolved Chlorides, Nitrates and
Sulphates of Calcium, Magnesium, Iron and other metals. Permanent hardness responsible
salts are CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2(SO4)3. Permanent Hardness cannot be
removed by boiling but it can be removed by the use of chemical agents.

Expression and Units of Hardness

The expression of hardness producing salts usually expressed in terms of an equivalent

amount of CaCO3. Calcium Carbonate is chosen as a standard because:

i. Its molecular weight (100) and equivalent weight (50) is a whole number, so the
calculations in water analysis can be simplified.
ii. It is the most insoluble salt that can be precipitated in water treatment.

The conversion of the hardness causing salts into CaCO3 equivalents can be achieved by
using the following formula:

Units of Hardness:
1. Parts per Million (ppm): The number of parts of calcium carbonate equivalent hardness
presents in 106 parts of water.
1ppm = 1 part of CaCO3 eq hardness in 106 parts of water

2. Milligrams per litre (mg/l): The number of milligrams of calcium carbonate equivalent
hardness presents in litre of water.
1 mg/L = 1 mg of CaCO3 eq hardness in 1 litre of water
But one litre of water weights =1 kg =1000g = 1000 x 1000 mg = 106 mg = 1 ppm

3. Clark’s degree (°Cl): The number of parts of calcium carbonate equivalent hardness
presents in 70,000 or (7×104) parts of water.
1° Clarke = 1 part of CaCO3 eq hardness per 70,000 parts of water

4. Degree French (°Fr): The number of parts of calcium carbonate equivalent hardness
presents in 105 parts of water.
1° Fr = 1 part of CaCO3 hardness eq per 105 parts of water
Determination of Hardness by Complexometric Method / EDTA Method

Hardness present in a given water sample can be determined using the complexometric
method, in which the disodium salt of EDTA is employed (soluble in water) and can be
represented as follows.

EDTA - Ethylene Diamine Tetra Acetic acid

EDTA forms complexes with calcium and magnesium ions when the pH is in the range of
around 9.5 to 10.5 and to maintain the pH, a basic buffer solution is used (NH4OH + NH4Cl).
The complexes of calcium and magnesium with EDTA are colourless; therefore, an indicator
(In) must be used to locate the endpoint. In this titration, Eriochrome black-T (EBT) is used
as an indicator, which forms an unstable wine-red coloured complex with calcium and
magnesium. Calcium ions are complexed first with EDTA, but the colour change only occurs
once all the magnesium has completely reacted. It is thus possible to determine the total
amount of these metals in the solution and the total hardness can be calculated. Calcium itself
does not give a satisfactory end point with EBT indicator unless the solution also contains
magnesium. Once EDTA completely removes all the calcium and magnesium ions, the free
indicator is left in the solution, imparting a blue colour. So, the colour change at the endpoint
is wine red to blue.

During the estimation, one can take 50.0 ml of the hard water sample into a clean conical
flask, followed by adding 2 or 3 ml of buffer solution (pH 9.5 - 10.5) and 2 or 3 drops of EBT
indicator. Then this mixture is titrated with standard EDTA (0.01 M) solution until the colour
changes from wine-red to blue, which is the reaction's endpoint. So, finally, one can find out
that 50.0 ml of hard water samples consumes 'x' ml of 0.01 M EDTA solution, which needs to
substitute in the below formula for getting the hardness of the water sample.

Total hardness of water sample per liter = X x 1000 / 50 = X x 20 mg/litre or ppm

Problems on harness of water

Calculation of CaCO3 equivalent

The concentration of hardness is usually expressed in terms of equivalent amount of CaCO3

since this mode permits the multiplication and division of concentration when required. The
selection of CaCO3 in particularly to express hardness of water is due to the following
reasons. i) CaCO3 has a molecular mass of 100 (or eq. mass of 50) a whole number, easy to
do maths and ii) It is the most insoluble salt that can be precipitated in water treatment.

Sl.No. Dissolved salt or Molecular mass Multiplication factor

constituent
1 Ca(HCO3)2 162 100/162
2 Mg(HCO3)2 146 100/146
3 CaSO4 136 100/136
4 MgSO4 120 100/120
5 FeSO4 152 100/152
6 CaCl2 111 100/111
7 MgCl2 95 100/95
8 MgCO3 84 100/84
9 CaCO3 100 100/100
10 Mg(NO3)2 148 100/148
11 Ca(NO3)2 164 100/164
12 CO2 44 100/44
13 Al2(SO4)3 114 100/114
14 FeSO4.7H2O 278 100/278
15 HCO3- 122 100/122
16 OH- 34 100/34
17 NaAlO2 164 100/164

Numerical problems on Hardness of water

1. Calculate the temporary, permanent and total hardness of a sample of water

containing the dissolved salts in mg/L. Ca(HCO3)2 = 6.8, Mg(HCO3)2 = 9.0, MgCl2 = 4.2,
Na2SO4 = 6.5, CaSO4 = 12.5, MgSO4 = 5.6
Solution:

Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L

factor
Ca(HCO3)2 6.8 100/162 6.8 x 100/162 = 4.197
Mg(HCO3)2 9.0 100/146 9.0 x 100/146 = 6.164
 MgCl2 4.2 100/95 4.2 x 100/95 = 4.421
Na2SO4 Do not contribute for hardness of water
CaSO4 12.5 100/136 12.5 x 100/136 = 9.191
MgSO4 5.6 100/120 5.6 x 100/120 = 4.666

Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (4.197 + 6.164 ) mg/L

= 10.361 ppm
Permanent hardness = MgCl2 + CaSO4 + MgSO4 = (4.421 + 9.191 + 4.666) mg/L
= 18.278 ppm
Total hardness = Temporary + Permanent = 10.361 ppm + 18.278 ppm = 28.639 ppm

2. Calculate the temporary hardness of a sample of water containing the dissolved salts
in mg/L. Ca(HCO3)2 = 7.2, Mg(HCO3)2 = 8.5, MgCl2 = 4.9, Na2SO4 = 6.5, CaSO4 = 12.1,
MgSO4 = 4.8.
Solution;

Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L

factor
Ca(HCO3)2 7.2 100/162 7.2 x 100/162 = 4.444
Mg(HCO3)2 8.5 100/146 8.5 x 100/146 = 5.821
MgCl2 4.9 100/95 4.9 x 100/95 = 4.421
Na2SO4 Do not contribute for hardness of water
CaSO4 12.1 100/136 12.1 x 100/136 = 8.897
MgSO4 4.8 100/120 4.8 x 100/120 = 4.000
Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (4.444 + 5.821 ) mg/L = 10.265 ppm

3. liters of water obtained from a bore well in Patencheru near Hyderabad gave the
following analysis for salts. FeSO4=30.4mg, CaSO4=13.6mg, MgCl2=48mg,
Ca(HCO3)2=32.4 , Mg(HCO3)2=14.6mg, NaCl=11.7mg. Find the total hardness of water
in ppm units, giving temporary &permanent hardness, assuming the At. Mass of Fe=56,
Ca=40, Mg=24, Na=22.
Solution:

Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L

factor
Ca(HCO3)2 16.2 100/162 16.2 x 100/162 = 10.00
Mg(HCO3)2 7.3 100/146 7.3 x 100/146 = 5.00
MgCl2 24 100/95 24 x 100/95 = 25.26
NaCl Do not contribute for hardness of water
CaSO4 6.8 100/136 6.8 x 100/136 = 5.00
FeSO4 15.2 100/152 15.2 x 100/152 = 10
Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (10 + 5 ) mg/L = 15 ppm

Permanent hardness = MgCl2 + CaSO4 + FeSO4 = (25.26 + 5 + 10.0) mg/L

= 40.26 ppm

Total hardness = Temporary + Permanent = 15 ppm + 40.26 ppm = 55.26 ppm

4. One liter of water from Khammam Dist. in Andhra Pradesh showed the following
analysis: Mg(HCO3)2 = 0.0256 g, Ca(HCO3)2 = 0.0156 g, NaCl = 0.0167 g, CaSO4 =
0.0065 g, and MgSO4 = 0.0054 g. Calculate temporary, permanent and total hardness.
Solution:
Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L
factor
Ca(HCO3)2 15.6 100/162 15.6 x 100/162 = 9.62
Mg(HCO3)2 25.6 100/146 25.6 x 100/146 = 17.53
NaCl Do not contribute for hardness of water
CaSO4 6.5 100/136 6.5 x 100/136 = 4.77
MgSO4 5.4 100/120 5.4 x 100/120 = 4.5
Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (9.62 + 17.53 ) mg/L = = 27.15 ppm
Permanent hardness = MgSO4 + CaSO4 = (4.5 + 4.77) mg/L = 9.27 ppm
Total hardness = Temporary + Permanent = 27.15 ppm + 9.27 ppm = 36.42 ppm

5. One liter of water from an underground reservoir in Nalgonda Town in Andhra

Pradesh the following analysis. for its contents: Mg(HCO3)2 = 0.0146 g; Ca(HCO3)2 =
0.0081 g; MgSO4 =0.0012 g; CaSO4 = 0.0136 g, NaCl = 0.0585 g; Organic impurities =
100 mg; Calculate temporary, permanent and total hardness of this sample of water in
degree French.
Solution:

6. One liter of water sample collected from a water source in Andhra Pradesh has
shown the following analysis. Mg(HCO3)2 = 14.6 mg, MgSO4 = 12 mg, Ca(HCO3)2 = 16.2
mg, CaCl2 = 22.2 mg, MgCl2 = 9.5 mg and organic impurities 100 mg. Calculate
temporary and permanent hardness in Degree French.
Solution:
7. How many mg. Of FeSO4 dissolved per litre gives 200 ppm of hardness?
Solution: 1 mole of FeSO4 + 1 mole of CaCO3 (from mole concept)
i.e FeSO4 = CaCO3
(56+16+64) = 136 g = 100 g
Therefore, 100 ppm of hardness = 136 ppm of FeSO4
Or 200 ppm of hardness = 136 x 200/100 = 272 mg/l
Hence, 272 mg of FeSO4 dissolved per litre gives 200 ppm hardness.
8. How many grams of MgCO3 dissolved per litre gives 100ppm of hardness?
Solution: 1 mole MgCO3 = 1 mole CaCO3
(24 + 12+ 16x3) = 84 g = 100 g
Therefore, 100 ppm of hardness = 84 ppm of MgCO3
Or 100 ppm of hardness = 84 x 100/100 = 84 mg/l
Hence, 84 mg of FeSO4 dissolved per litre gives 100 ppm hardness.

9. Calculate the degree of hardness of a sample of water containing 6 mg of magnesium

sulphate per kg of water
Solution:
Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L
factor
MgSO4 6 100/120 6 x 100/120 = 5
Therefore, Hardness = 5 ppm x 0.1 °Fr = 0.5°Fr

10. A sample of hardwater contains 408 mg of CaSO4 per litre. Calculate the hardness
in terms of CaCO3 equivalents.
Solution:
Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L
factor
CaSO4 408 100/136 408 x 100/136 = 300
Therefore, Hardness = 300 ppm of CaCO3
11. Calculate the temporary hardness and total hardness of a sample of water
containing
Mg(HCO3)2 = 14.6 mg/L, Ca(HCO3)2 = 32.4 mg/L , Mg Cl2 = 19.0 mg/L; CaSO4 =
27.2 mg/L.
Solution:
Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L
factor
Ca(HCO3)2 32.4 100/162 32.4 x 100/162 = 20
Mg(HCO3)2 14.6 100/146 14.6 x 100/146 = 10
CaSO4 27.2 100/136 27.2 x 100/136 = 20
MgCl2 19.0 100/95 19.0 x 100/95 = 20
Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (20 + 10 ) mg/L = 30 ppm
Permanent hardness = MgCl2 + CaSO4 = (20 + 20) mg/L = 40 ppm
Total hardness = Temporary + Permanent = 30 ppm + 40 ppm = 70 ppm

12. Calculate the temporary hardness for a sample of water contains the dissolved salts
in mg/lit, Mg(HCO3)2 : 9.0, MgSO4-5.6, Mg Cl2=4.2, CaS04 = 12.5, Na2SO4 = 6.5,
Ca(HCO3)2
= 6.8; (Mol.Units, CaCO3 = 100, Mg(HCO3)2 = 146, Ca(HCO3)2 = 162
Salt/ion Conc. In mg/L Multip. CaCO3 equivalent in mg/L
factor
Ca(HCO3)2 6.8 100/162 6.8 x 100/162 = 4.19
Mg(HCO3)2 9.0 100/146 9.0 x 100/146 = 6.16
MgSO4 5.6 100/120 5.6 x 100/120 = 4.66
Na2SO4 Do not contribute for hardness of water
CaSO4 12.5 100/136 12.5x 100/136 = 9.19
Temporary hardness = Ca(HCO3)2 + Mg(HCO3)2 = (4.19 + 6.16 ) mg/L = 10.35 ppm.

Potable water and its specifications

Municipalities have to supply drinking or potable water which is safe to drink and fit for
human consumption. The natural water from rivers, canals etc do not satisfy all the essential
requirements as given below. So, they should be treated.
Essential requirements/Specifications of potable water
➢ It should be sparking clear and odourless.
➢ It should be pleasant in taste.
➢ It should be perfectly cool.
➢ Its turbidity should be less than 10 ppm.
➢ It should be free from objectionable dissolved gases like H2S.
➢ It should be free from objectionable minerals such as Pb, As, Cr and Mn salts.
➢ Its alkalinity should be high. Its pH should be about 8.0.
➢ It should be reasonably soft, total hardness should be < 500 ppm.
➢ It should be free from microorganisms.
 ➢ Cl-, F- & SO42- contents should be less than 250 ppm, 105ppm and 250ppm.
➢ Different stages of treatment

Stages Impurity Process or method

1 Floating matter like, leaves, wood pieces etc Screening
2 Suspended matter like sand, clay etc Sedimentation
3 Fine suspended inorganic impurity Sedimentation with coagulation
4 Microorganisms and colloidal matter Filtration
5 Pathogenic bacteria Disinfection
➢

Various stages of treament of water

A. Removal of B. Disinfection
impurities

1. By boiling
1. Screening 2. Bleaching powder
2. Sedimentation 3. Chlorination
3. Sedimentation 4. Chloramine
with coagulation 5. Ozonisation
4. Filtration

A. Removal of impurities

1. Screening
Screening is the process of removing floating materials like wood pieces and leaves from
water. Raw water is allowed to pass through a screen having a large number of holes which
removes the small and large floating matter.
2. Sedimentation
Sedimentation is the process of removing suspended impurities by allowing the water to
stand undisturbed for 2-6 hours in big tanks, about 6M deep. Due to force of gravity, most of
the suspended particles settled down at the bottom and they are removed. Sedimentation
removes only 70-75% of the suspended matter.
3. Sedimentation with coagulation
Finely divided particles like silica, clay and organic matter do not settle down easily and
hence cannot be removed by mere sedimentation. Most of these particles are in colloidal form
and carry negative charge. Thus they do not coalesce due to mutual repulsions. In order to
carry out the sedimentation process successfully, some of the chemicals are added to water
before sedimentation. So sedimentation with coagulation is a process of removing fine
suspended and colloidal impurities by the addition of requisite amount of certain chemicals
called Coagulants. The coagulants when added to water form an insoluble gelatinous,
flocculent precipitates, which descends through the water and mixes-up into very fine
suspended impurities forming bigger impurities called flocs, which easily settles down. Some
of the coagulants used for sedimentation process are alum, ferrous sulphate, sodium
aluminate etc.
(a) Alum, K2SO4∙Al2SO4∙24H2O for water with pH > 7.0

(b) Sodium aluminate, NaAlO2 for water with pH < 7.0

MgSO4 + 2NaOH → Mg(OH)2 + Na2SO4

(c) Ferrous sulphate, FeSO4∙7H2O for water with pH > 8.5

4Fe(OH)2 + O2 + 2H2O → 4 Fe(OH)3, ferric hydroxide, a heavy floc.

4. Filtration
It is the process of removing colloidal matter and most of the bacteria, micro-organisms etc,
by passing water through a bed of fine sand and other proper-sized granular materials.
Filtration is carried out by using Sand-filter.
In a typical sand filter, water is passed through a tank containing different sized sand beds
like fine (thick), coarse and gravel beds. The suspended particles are unable to pass through
the gaps in the sand bed, because of their size. Water first passed through a fine sand-bed.
The suspended particles, microorganisms etc are first collected and get clogged in fine sand
and then passed through coarse sand-bed. Here colloidal matter gets collected and the water
is free from sediments. After passing the coarse sand bed the water enters through a bed of
medium sized stones called gravel or gravel-bed. This is the last bed where water is filtered
completely, and the filtered water is collected at the filter outlet. During the filtration process
the fine pores of sand bed get seized and clogged. In order to continue the filtration process,
2-3 cm of fine sand at the top is scrapped, replaced and leveled with makeup sand.
B. Removal of microorganisms or Disinfection or sterilization
1. Chlorination

Chlorination is the process of purifying the drinking water by producing a powerful

Germicide like Hypochlorous acid. When this Chlorine is mixed with water it produces
Hypochlorous acid which kills the germs present in water.
H2O + Cl2 → HOCl + HCl
Chlorine is basic (means pH value is more than 7) disinfectant and is much effective over the
germs. Hence Chlorine is widely used all over the world as a powerful disinfectant. Liquid
chlorine is the most effective reagent, 0.3-0.5 ppm chlorine is sufficient. Chlorinator is an
apparatus, which is used to purify the water by chlorination process. It is a large tower which
contains number of baffle plates. Raw water and concentrated chlorine solution are
introduced at the top. These two get thoroughly mixed during their passage through the
tower. Disinfected water is taken out from the inlet at the bottom of chlorinator.

Advantages
 • More effective and economical
• It is stable, requires small space for storage and doesn’t deteriorate on storage.
• It can be used at high as well as low temperatures.
• It doesn’t introduce any impurity in treated water.
Disadvantages
• Excess chlorine if added produces a characteristic, unpleasant taste and odour
• Its excess produces an irritation on mucus membrane
• Its concentration should not exceed 0.1-0.2 ppm
• It is more effective below pH 6.5 and less effective at higher pH values.

Break-point Chlorination
It is seen that when liquid chlorine is added or chlorine gas is passed through water, the
consumption of chlorine makes the available chlorine less and after some time the available
chlorine increases. This is due to the consumption of chlorine in oxidizing some oxidisable
organic matter present in water at first. Then available chlorine increases again due to the
formation of chloro-organic and chloroamine compounds i.e., the combined chlorine
increases in water. Then it decreases due to the consumption of this chlorine for
decomposition of chloro-organic compounds. Once all the impurities are reacted or oxidized
further addition of chlorine results in appearance of residual chlorine. This free chlorine is
responsible for the destruction of pathogenic bacteria in water. The point (c in figure) at
which the residual chlorine begins to appear is known as break point and at this point water is
devoid of bad taste and odors and is bacteria free.
Advantages of break point chlorination
• Organic matters present in water are completely oxidized leaving behind odour-free
water and sometimes color-free water.
• Pathogenic bacteria are destroyed completely.
• It prevents the growth of weeds in water in future.

2. Sterilization by Ozonation
Ozone is an unstable gas and decomposes to give nascent oxygen. This nascent oxygen
kills bacteria and oxidizes the organic matter present in the water. Ozone is an excellent
disinfectant and produced by passing silent electric discharge through cold and dry oxygen.
Electric
3O2 2 O3
Discharge
Advantages
• Sterilization, bleaching, decolorization and deodorization take place at the same
time.
• Ozone does not impart any unpleasant taste or odour to the treated water and does.
not change its pH appreciably as it simply decomposes into oxygen. So it does not
cause any irritation to the mucus membrane as is the case with chlorine or
bleaching powder treatment.
• Time of contact is only 10-15 minutes and dose strength is only 2-3 ppm.
Disadvantage
• The process is comparatively costly.
ION EXCHANGE PROCESS:

• Ion exchange process is also known as demineralization or

de- ionization process.
• Ion- Exchange resins are insoluble. Cross linked long
chain organic polymers with a micro porous structure, and
the “functional Groups” attached to the chains are
responsible for the ion-exchanging properties.
• In De-ionization process all the ions present in water are
eliminated by using ion-exchange resins.
• Basically, resins with acidic functional group are capable

of exchanging H+ ions with other cations.

• Resins with functional groups are capable of exchanging

OH- ions with other anions.

 Resins are classified as:
1. Cation Exchange Resins
2. Anion Exchange Resins

Cation Exchange Resins: These are mainly styrene divinyl

benzene co- polymers, which are on sulphonation or carboxylation.
These can exchange their hydrogen ions with cations in water.

Anion Exchange Resins: Anion exchange resins are styrene-divinyl benzene or

amine- formaldehyde copolymers, which contains amino, quaternary.

Ion-exchange process:
• Hard water is allowed to pass through cation exchange
resins, which remove Ca+2 and Mg+2 ions and exchange
equivalent amount of H+ ions.
• Anions exchange resins remove bicarbonates, chlorides, and
sulphates from water exchange equivalent amount of OH- ions.
• Thus, by passing hard water through cation hardness is
observed by the following reactions.

Cation Exchange Resins:

2R-H+ + Ca+2 R-Ca+2 + 2H+

2R-H+ + Mg+2 R-Mg+2 + 2H+ (RH+ = cation exchange resin)

Anion Exchange
2 Resins:
Regeneration:

When cation exchanger loses capacity of producing H+ ions and exchanger

loses capacity of producing OH- ions, they are said to be exhausted. The
exhausted cation exchanger is regenerated by passing it through dilute
sulphuric acid.

R2Ca+2 + 2H+ 2RH+ + Ca+2

The exhausted anion exchanger is regenerated by passing a dilute solution of

NaOH.

R2SO42- 2OH- 2ROH- + SO42-

 Advantages: 1. The process can be used to soften highly acidic or
alkaline water.
2. It produces water of very low hardness (2 ppm).

3. it is very good for treating water for use in high-pressure boilers.

Demerits of ion-exchange process:

• The equipment is costly and more expensive chemicals are needed.

• If water contains turbidity, the output of the process is reduced.

The turbidity must be below 10ppm; else it must be removed by
coagulation and filtration.

DESALINATION OF WATER -REVERSE OSMOSIS

Definition: The process of removing common salt (Sodium Chloride) from the water is
known as desalination.
The water containing dissolved salts with a salty or brackish taste is called brackish water.
Depending upon the quantity of dissolved solids, water is graded as:
i. Fresh Water: Contains less than 1000 ppm of dissolved solids.
ii. Brackish Water: Contains more than 1000 ppm to less than 35000 ppm of dissolved
solids.
iii. Sea Water: Contains more than 35000 ppm of dissolved solids.
Sea water and brackish water can be made available as drinking water through
desalination process.Desalination is carried out either by reverse osmosis or electro
dialysis.
Reverse Osmosis:
Reverse Osmosis is a process in which pressure greater than the osmotic pressure is
applied on the high concentration side of the membrane, the flow of solvent moves from
concentrated side to dilute side across the membrane.
Osmosis is the phenomenon by virtue of which flow of solvent takes place from a region
of low concentration to high concentration when two solutions of different
concentrations are separated by a semi-permeable membrane.
In this process pure water is separated from salt water. 15-40 kg/cm2 pressure is applied
for separating the water from its contaminants. The membranes used are cellulose
acetate, polymethyl acrylate and polyamide polymers. The process is also known as
super or hyperfiltration.
 Advantages:
1. It is simple and reliable process & Capital and operating expenses are low.
2. The life of the semi-permeable membrane is about two years, and it can be easily
replaced within a fewminutes, thereby nearly uninterrupted water supply can be
provided.
BOILER TROUBLES

A boiler is a closed vessel in which water under pressure is transformed into steam by the
application of heat. The steam generated is used in industries and generation of power. In
modern pressure boilers and laboratories, the water required is used pure than the distilled
water.

A boiler feed water should correspond with the following composition:

➢ Its hardness should be below 0.2ppm.
➢ Its caustic alkalinity (due to OH-) should lie between 0.15ppm to 0.45ppm.
➢ It should be free from dissolved gases like O2, CO2, to prevent boiler corrosion.
Excess of impurities in the boiler feed water generally cause the following problems:

1. Sludge’s and Scale formation 2. Caustic embrittlement

Boilers are employed for steam generation in power plants, where water is
continuously heated to produce steam. As more and more water are removed from
water in the form of steam, the boiler water gets concentrated with dissolved salts
progressively reaches the saturation point. At this point the dissolved salts are
precipitated out and slowly settle on the inner walls of the boiler plate. The precipitation
takes place in two ways.
SLUDGES:

Definition: Sludge is a soft, loose, and slimy precipitate formed within the boiler. It is
formed at comparatively colder portions of the boiler and collects in the area where the
flow rate is slow.
Ex: MgCO3, MgCl2, CaCl2, MgSO4.

Reasons for formation of sludges:

The dissolved salts whose solubility is more in hot water and less in cold water produce
sludges.

Disadvantages of sludges:
1. Sludges are bad conductors of heat and result in the wastage of heat and fuel.
2. Excessive sludge formation leads to the settling of sludge in slow circulation
areas such as pipeconnections, plug openings, gauge–glass connections leading to
the choking of the pipes.

Prevention of sludge formation:

1. Using soft water, which is free from dissolved salts like MgCO3, MgCl2, CaCl2
and MgSO4 can prevent sludge formation.
2. By blow down operation carried out frequently can prevent sludge formation.

SCALES

Definition: Scales are hard, adhering precipitates formed on the inner walls of the
boilers. Scales are stick very firmly onto the inner walls of the boiler. It is removed
with a chisel and hammer. Scales are formed by decomposition of calcium bicarbonate
in low pressure boilers.
Reasons for formation of scales:
1. Decomposition of calcium bicarbonate: The calcium bicarbonate at high
temperature decomposes to calcium carbonate, which is insoluble salt, forms scale in
low pressure boilers.
Ca(HCO3)2 → CaCO3 + H2O + CO2

2. Hydrolysis of Magnesium salts: Magnesium salts gets hydrolyzed at high

temperature forming Mg(OH)2 precipitation which forms salt type scale.
MgCl2 + H2O → Mg(OH)2↓ + 2HCl
3. Decomposition of calcium sulphate: The solubility of CaSO4 in water decreases with
the increase in temperature and forms precipitation on the surface of the boiler further
which forms hard scale. This type of scale is formed in high-pressure boilers.

4. Presence of silica: SiO2 is present even in small quantities, deposits as Calcium

silicates (CaSiO3) or Magnesium silicates (MgSiO3). The deposits form hard scale and
are very difficult to remove.

Disadvantages of Scales:
1. Wastage of heat and fuels: Scales poor thermal conductivity so that rate of
heat transformation isreduced.
2. Lowering boiler safety is due to overheating of the boiler material becoming
softer and weaker,which causes distortion of boiler.

3. Decrease in efficiency of the boiler due to scales deposited in the values and
condensers of the boilercause choking.
4. Danger of explosion which happens the formation of the scales, the boiler plate
faces highertemperature outside and lesser temperature inside due to uneven
expansion. The water comes suddenly into contact with overheated portion and
larger amount steam is formed immediately, this resultsin development of sudden
high pressure which may cause explosion of the boiler.
Prevention of scales:
a. If the scale formation is soft, it can be removed by a scraper or wire brush.
b. By giving thermal shocks, by sudden heating and sudden cooling which makes
scale brittle andremoved by scrubbing with wire brush.
c. If scale is very hard that is formed by CaCO3 can be removed by washing with
5-10% HCl andCaSO4 can be removed with EDTA solution.

INTERNAL TREATMENT OF WATER

Suitable chemicals are added to the boiler water either to precipitate or to convert the scale
into compounds. This is called internal treatment of the boiler feed water. Internal
treatment can be done with the following types.

1. Calgon conditioning: Involves adding Calgon to boiler water. It prevents the

scale and sludgeformation by forming soluble complex compound with CaSO4.
Calgon = Sodium hexa meta phosphate = Na2 [Na4 (PO3)6]
Na2 [Na4 (PO3)6] → 2Na+ + [Na4P6O18]-2

2CaSO4 + [Na4P6O18] -2 → [Ca2 P6O18]-2 + 2Na2SO4

2. Phosphate conditioning: The addition of sodium phosphate in hard water reacts

with the hardness causing agents and gives calcium and magnesium phosphates
which are soft and non-adhere and can be removed easily by blow-down
operation.
3CaCl2 + 2 Na3PO4 → Ca3(PO4)2 + 6NaCl

3MgSO4 + 2 Na3PO4 → Mg3(PO4)2 + 3Na2SO4

Generally, three types of Phosphates are employed.

i) Tri sodium Phosphate (Na3PO4): is too alkaline used for treating too acidic water.
ii) Di sodium Phosphate (Na2 HPO4): is weakly alkaline used for treating weakly
acidic water.
iii) Sodium dihydrogen Phosphate (Na H2PO4): is too acidic used for treating to too
alkaline water
3. Colloidal conditioning: The addition of organic substances such as Kerosene,
tannin, Gel. These substances get coated over the scale forming precipitates and
gives a loose and non-sticky precipitate which can be removed by using blow-
down operation.