UNIT-I

Water and its treatment

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, fire-fights, air-conditioning and also 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:
The natural water is usually contaminated by different types of impurities.
They are mainly three types. i. Physical impurities ii. Chemical impurities iii. 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).

Soft Water: The water which gives more lather with soap is called soft water.
C17H35COONa + H2O → C17H35COOH + 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
2C17 H35COONa + CaCl2/MgCl2 → (C17H35COO) 2 Ca/Mg + 2NaCl
soap (soluble) salts (soluble) insoluble scum

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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.

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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.
Ca (HCO3)2 by heating CaCO3↓ + H2O + CO2
Calcium bicarbonate
Mg (HCO3)2 by heating Mg (OH)2↓ + 2CO2
Magnesium bicarbonate

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 OF HARDNESS

The expression of hardness producing salts usually expressed in terms of an equivalent amount of CaCO 3.
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:

Degree of Hardness = The weight of hardness causing salts × 100 (Molecular weight of CaCO3)
Molecular weight of hardness causing salts

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.

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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.

Relationship between various units of hardness:

1 ppm = 1 mg/L = 0.1° Fr = 0.07° Cl
1 mg/L = 1 ppm = 0.1° Fr = 0.07° Cl
1 ° Cl = 1.433° Fr = 14.3 ppm = 14.3 mg/L
1 ° Fr = 10 ppm = 10 mg/L = 0.7° Cl

Problem-1: A sample of water is found to contains following dissolving salts in milligrams per litre
Mg(HCO3)2 = 73, CaCl2 = 111, Ca(HCO3)2 = 81, MgSO4 = 40 and MgCl2 = 95. Calculate temporary and
permanent hardness and total hardness.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 73 146 73×100/146 = 50
CaCl2 111 111 111×100/111 = 100
Ca(HCO3)2 81 162 81×100/162 = 50
MgSO4 40 120 40×100/120 = 33.3
MgCl2 95 95 95×100/95 = 100
Temporary hardness = Mg(HCO3)2 + Ca(HCO3)2
= 50 + 50 = 100mgs/Lit.
Permanent hardness = CaCl2 + MgSO4 + MgCl2
= 100 + 33.3 + 100 = 233.3mgs/Lit.
Total hardness = Temporary hardness + Permanent hardness
= 100 + 233.3 = 333.3mgs/Lit.

Problem-2: A sample of water is found to contains following dissolving salts in milligrams per litre
Mg(HCO3)2 = 16.8, MgCl2 = 12.0, MgSO4 = 29.6 and NaCl = 5.0. Calculate temporary and permanent
hardness of water.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 16.8 146 16.8×100/146 = 11.50
MgCl2 12.0 95 12.0×100/95 = 12.63
MgSO4 29.6 120 29.6×100/120 = 24.66
NaCl 5.0 NaCl does not contribute any hardness to water
hence it is ignored.

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Temporary hardness = Mg(HCO3)2

= 11.50mgs/Lit.
Permanent hardness = MgCl2 + MgSO4
= 12.63 + 24.66 = 37.29mgs/Lit.

Problem-3: A sample of water is found to contains following analytical data in milligrams per litre
Mg(HCO3)2 = 14.6, MgCl2 = 9.5, MgSO4 = 6.0 and Ca(HCO3)2 = 16.2. Calculate temporary and permanent
hardness of water in parts per million, Degree Clarke’s and Degree French.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(mg/Lit) hardness causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 14.6 146 14.6×100/146 = 10
MgCl2 9.5 95 9.5×100/95 = 10
MgSO4 6.0 120 6.0×100/120 = 5
Ca(HCO3)2 16.2 162 16.2×100/162 =10

Temporary hardness [Mg (HCO3)2 + Ca (HCO3)2] = 10 + 10 = 20mg/Lit

= 20ppm
= 20×0.07°Cl = 1.4°Cl
= 20×0.1°Fr = 2°Fr
Permanent hardness [MgCl2 + MgSO4] = 10 + 5 = 15mg/Lit
= 15ppm
= 15×0.07°Cl = 1.05°Cl
= 15×0.1°Fr = 1.5°Fr

Problem-4: Calculate the amount of temporary and permanent hardness of a water sample in Degree
Clarke’s, Degree French and Milligrams per Litre which contains following impurities.
Ca(HCO3)2 = 121.5 ppm, Mg(HCO3)2= 116.8 ppm, MgCl2 = 79.6 ppm and CaSO4 = 102 ppm.
Solution:
Name of the hardness Amount of the hardness Molecular weight of Amounts equivalent to
causing salts causing salts(ppm) hardness causing salts CaCO3 (ppm)
Ca(HCO3)2 121.5 162 121.5×100/162 = 75
Mg(HCO3)2 116.8 146 116.8×100/146 = 80
MgCl2 79.6 95 79.6×100/95 = 3.37
CaSO4 102 136 102×100/136 = 75
Temporary hardness [Mg (HCO3)2 + Ca (HCO3)2] = 75 + 80 = 155 ppm
= 155×0.07°Cl = 10.85°Cl
= 155×0.1°Fr = 15.5°Fr
= 155×1mg/Lit = 155 mg/Lit
Permanent hardness [MgCl2 + CaSO4] = 10 + 5 = 15mg/Lit
= 15ppm
= 15×0.07°Cl = 1.05°Cl
= 15×0.1°Fr = 1.5°Fr

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Determination of hardness By Complexometric Method / EDTA Method

Principle: The determination of hardness is carried out by titrating water sample with Sodium salt of
Ethylene Diamine Tetra Acetic Acid (EDTA) using
Eriochrome Black-T as an indicator and keeping
the pH of the water at 9.0 - 10.0. The
end point is the change in colour from wine - red to
blue, when the EDTA solution complexes the
calcium and magnesium salt completely.

(Ca2+ or Mg2+) + EBT → [Ca – EBT] (or) [Mg – EBT]

Hardness-salts indicator unstable complex (wine red)

[Ca – EBT] (or) [Mg – EBT] + EDTA → [Ca – EDTA] (or) [Mg – EDTA] + EBT
Unstable complex (wine red) stable complex (colourless) blue

Chemicals Required:
i. Preparation of standard hard water (0.01M): Dissolve 1g of pure, dry CaCO3 in 1 Litre solution.

ii. Preparation of EDTA solution: Dissolve 4 g of pure EDTA crystals in 1 Litre of distilled water.

iii. Preparation of Indicator (EBT): Dissolve 0.5 g of Eriochrome Black−T in 100mL alcohol.

iv. Preparation of Buffer solution: Add 67.5g of NH4Cl to 570 ml of Con. Ammonia solution and then
dilute with distilled water to 1 Litre.

Various steps involved in this method:

1. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution. Pipette out 20 ml of
standard hard water (M1) in a conical flask. Add 4ml of buffer solution and 2 drops of EBT indicator.
Titrate with EDTA solution till wine-red colour changes to clear blue. Let volume used by ‘X’ ml.
M1 V1 = M2 V2

Where, M1 = Molarity of Standard Hard water (0.01M),

V1 = Volume of Standard Hard water (20 ml),
M2 = Molarity of EDTA,
V2 = Volume of EDTA (Xml).

2. Determination of Total Hardness: Rinse and fill the burette with EDTA solution. Pipette out 20 ml of
sample water (V3) in a conical flask. Add 4 ml of buffer solution and 2 drops indicator. Titrate with
EDTA solution till wine-red colour changes to clear blue. Let volume used by ‘Y’ ml.
M2 V2 = M3 V3

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Where, M2 = Molarity of EDTA,

V2 = Volume of EDTA (Yml).
M3 = Molarity of sample water,
V3 = Volume of Sample water (20 ml).
Total Hardness = M3 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
= M3 × 105 ppm

3. Determination of Permanent Hardness: Take 100 ml of sample water in 250 ml beaker. Boil it to
remove temporary hardness to about half of its volume and cool to room temperature, filter through
filter paper to remove insoluble salts. Make up the volume to the original 100ml by adding distilled
water. Now Pipette out 20 ml of this solution (V4) in a conical flask. Add 4 ml of buffer solution and 2
drops indicator. Titrate with EDTA solution till wine-red colour changes to clear blue. Let volume used
by ‘Z’ ml.
M2 V2 = M4 V4
Where, M2 = Molarity of EDTA,
V2= Volume of EDTA (Z ml).
M4 = Molarity of Permanent hard water,
V4 = Volume of Permanent hard water (20 ml)
Permanent Hardness = M4 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
= M4 × 105 ppm

4. Determination of Temporary Hardness:

Temporary Hardness = Total Hardness - Permanent Hardness

Problem-1: 50 ml of standard hard water containing 1 gram of pure CaCO3 per liter consumed 20 ml of
EDTA. 50 ml of hard water consumed 25 ml of same EDTA solution EBT indicator. Calculate the total
hardness of water sample in ppm.
Solution:
Strength of standard hard water sample (CaCO 3 solution) M 1=
Weight of CaCO3 × 1000
Mol. wt of CaCO3 1000
= 1 gm × 1000 = 0.01 M
100 1000
Strength of EDTA solution M 2 = V1 M1 = 50 × 0.01 = 0.025 M
V2 20
V1 = Volume of standard hard water (50 ml), M1 = Strength of standard hard water (0.01M)
V2 = Volume of EDTA solution (20 ml), M2 =Strength of EDTA solution =?

Calculation of Total hardness M 3 = V2 M2 = 25 × 0.025 = 0.0125 M

V3 50
V2 = Volume of EDTA solution (25 ml), M2 =Strength of EDTA solution= 0.025M
V3 = Volume of sample hard water (50 ml), M3 = Strength of sample hard water =?

Total Hardness = 0.0125 × 105 ppm

= 0.0125 × 100 (Mol. Wt of CaCO3) × 1000 (ml)ppm
= 1250 ppm.

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Problem-2: 0.28 grams of CaCO3 were dissolved in HCl and the solution was made upto one litre with
distilled water. 100 ml of the above solution required 28 ml of EDTA solution on titration. 100 ml of hard
water sample consumed 33 ml of same EDTA solution EBT indicator. 100 ml of this water after boiling
cooling and filtering required 10 ml of EDTA solution in titration. Calculate the permanent and temporary
hardness of water sample in ppm.

Strength of standard hard water sample (CaCO3 solution) M = Weight of CaCO3 × 1000
Mol. wt of CaCO3 1000

= 0.28gm × 1000 = 0.0028 M

100 1000
Strength of EDTA solution M 2 = V1 M1 = 100 × 0.0028 = 0.01 M
V2 28
V1 = Volume of standard hard water (100 ml), M1 = Strength of standard hard water (0.0028M)
V2 = Volume of EDTA solution (28 ml), M2 = Strength of EDTA solution=?

Calculation of Total hardness M 3 = V2 M2 = 33 × 0.01 = 0.0033 M

V3 100
V2 = Volume of EDTA solution (33 ml), M2 = Strength of EDTA solution (0.01M) V3
= Volume of sample hard water (100 ml), M3 = Strength of sample hard water =?

Total Hardness = 0.0033 × 105 ppm = 0.0033 × 100 (Mol. Wt of CaCO3) × 1000 (ml)ppm
= 330 ppm

Calculation of Permanent hardness M 4 = V2 M2 = 10 × 0.01 = 0.001 M

V4 100
V2 = Volume of EDTA solution (10 ml), M2 = Strength of EDTA solution (0.01M)
V4 = Volume of sample hard water after boiling cooling and filtering (100 ml)
M4 = Strength of sample hard water after boiling cooling and filtering =?
Permanent Hardness = 0.001 × 105 ppm
= 0.001 × 100 (Mol. Wt of CaCO3) × 1000 (ml)ppm
= 100 ppm
Calculation of Temporary hardness = Total hardness - Permanent hardness
= 330 – 100 = 230 ppm

Potable water and its specifications

Water free from contaminants or water that is safe for human consumption is called potable water. The following
are the specifications of water drinking purpose.
1. The water should be clear (colorless), odorless and pleasant taste.
2. The optimum hardness of water must be 125ppm.
3. The pH of potable water should be 6.5 to 8.0.
4. The recommended maximum concentration of total dissolved solids (TDS) in potable water must not exceed
500 ppm.
5. The turbidity in drinking water should not exceed 25 ppm.
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6. The water must be free from heavy metals like Lead, Arsenic, Chromium and Manganese.
7. The water must be free from pathogenic bacteria
8. The water must be free from dissolved gases like H2S, CO2 and NH3.

Steps involved in the treatment of POTABLE WATER

Treatment of water for drinking purposes mainly includes the removal of suspended impurities, colloidal
impurities and harmful pathogenic bacteria. The following stages are involved in purification.

1. Screening: The water is passed through screens having larger number of holes; it retains floating impurities
like wood pieces, leaves, heaver objectives etc.,
2. Aeration: The water is then subjected to aeration(reacting with air) which helps in exchange of gases between
water and air, increases the oxygen content and removes the impurities like iron, manganese and dissolved gases
like H2S, CO2 and NH3.

Source of Screenin Aeration Sedimentation

water g

Coagulation

Disinfection/ sterilization Filtration

3. Sedimentation: In this process water is allowed to stand for 2-6 hours without any disturbance, 75 % of
suspended and colloidal impurities are settled down under gravitational force.

4. Coagulation: Coagulants like alum, sodium aluminates and Aluminum sulphate are added which produce
gelatinous precipitates called flock. Flock attracts and helps accumulation of the colloidal particles resulting in
setting of the colloidal particles.

5. Filtration: Filtration helps in removal of the colloidal and

suspended impurities not removed by sedimentation. Usually sand
filters are employed. In this filtration fine sand layer on the top
supported by coarse sand layer, which is supported by gravel.

6. The colloidal impurities are retained by the fine sand layer resulting
the very slow filtration of water. Periodically the top layers of the fine
sand layer is scraped off, washed, dried and introduced into the filter
bed for reuse.

7. Disinfection of water by sterilization: The process of destroying

the harmful bacteria’s is known as sterilization or disinfection.
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Disinfection includes the following methods of POTABLE WATER

1. By Chlorination: The process of adding chlorine to water is called chlorination. Chlorination can be done
by the following methods.
a. By adding Chlorine gas: Chlorine gas is a very good disinfectant, which can be bubbled in the water. In this
process calculated amount of chlorine gas is passed in order to destroy the pathogenic bacteria is called
chlorination. Chlorine is also reacts with water and generates hypochlorous acid and nascent oxygen, which acts
a powerful oxidizing agent and kills the bacteria.
Cl2 + H2O → HOCl (Hypochlorous acid) + HCl
HOCl → HCl + [O] nascent oxygen

b. By adding Chloramine: When chlorine and ammonia are mixed in the ratio 2:1 a compound chloramine is
formed.
Cl2 + NH3 → ClNH2 + HCl
Chloramine
ClNH2 + H2O → NH3 + HOCl (Hypochlorous acid)
HOCl → HCl + [O] nascent oxygen
Chloramine compounds decompose slowly to give nascent oxygen which will be act as good disinfectant than
the Chlorine. Chloramine gives good taste to the treated water.

2. By Ozonization: Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly unstable
and breaks down to give nascent oxygen.
O3 → O2 + [O] nascent oxygen
The nascent oxygen is a powerful oxidizing agent and kills the bacteria.
Disadvantages: This process is costly and cannot be used in large scale, due to unstable of ozone cannot be
stored for long time.

Break-point chlorination
Break-point chlorination: The amount of chlorine required to kill bacteria and to remove organic matter is
called break-point chlorination.
The water sample is treated with chlorine and estimated for the residual chlorine in water and ploted a
graph as shown below which gives the break-point chlorination.

From graph it is clear that:

‘a’ gms of chlorine added oxidizes reducing
impurities of water.
‘b’ gms of chlorine added forms chloramines and
other chloro compounds.
‘c’ gms of chlorine added causes distruction of
bacteria
‘d’ gms of chlorine is residual chlorine.
‘c’ gms is the break point for addition of chlorine to
water. This is called break- point chlorination.

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Advantages of break-point chlorination:

 It removes bad taste, colour, oxidizes completely organic compounds, ammonia and other

reducing impurities

 It destroys completely (100%) all disease producing bacteria.

 It prevents growth of any weeds in water.

Boiler Troubles:

A boiler is a closed vessel in which water under pressure is transformed into steam by the

application of heat. The steam so 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 caustic alkalinity (due to OH-) should lie between 0.15ppm to 0.45ppm.

 It’s should be free from dissolved gases like O2, CO2, in order 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

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1. Sludge’s and Scale formation: Boilers are employed for the steam generation in power plants, where water
as continuously heated to produce steam. As more and more water is 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.

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 flow rate is slow.
Ex: MgCO3, MgCl2, CaCl2, MgSO4.
Reasons for formation of sludges:
1. The dissolved salts whose solubility is more in hot water and less in cold water produce sludges.
Disadvantages of sludges:
2. Sludges are bad conductors of heat and results in the wastage of heat and fuel.
3. Excessive sludge formation leads to the settling of sludge in slow circulation areas such as pipe
connections, plug openings, gauge–glass connections leading to the choking of the pipes.

Prevention of sludge formation:

a. By using soft water which is free from dissolved salts like MgCO3, MgCl2, CaCl2 and MgSO4 can be
prevent sludge formation.
b. By blow down operation carried out frequently can prevent sludge formation.

Scale: Scales are hard, adhering precipitates formed on the inner walls of the boilers. They stick very
firmly on to the inner wall surface and are difficult to remove with chisel and hammer. Scales are formed by
decomposition of calcium bicarbonate in low pressure boilers.

Reasons for formation of scales:

a. 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
b. 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 scales is formed in high-pressure boilers.
c. 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

d. Presence of silica: Sio 2 present even in small quantities, deposits as Calcium silicates (CaSiO 3) or
Magnesium silicates (MgSiO3). The deposits form hard scale and are very difficult to remove.

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Disadvantages of Scales:
1. Wastage of heat and fuels: Scales poor thermal conductivity so that rate of heat transformation is
reduced.
2. Lowering of boiler safety is due to overheating of the boiler material becomes 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 boiler
cause choking.
4. Danger of explosion which happens the formation of the scales, the boiler plate faces higher
temperature outside and lesser temperature inside due to uneven expansion. The water comes suddenly
contact with overheated portion and larger amount steam is formed immediately, this results in
development of sudden high pressure which may cause explosion of the boiler.

Removal of scales:
a. If the scale formation is soft it can be removed by a scrapper, wire brush.
b. By giving thermal shocks, by sudden heating and sudden cooling which makes scale brittle and
removed 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 and CaSO4
can be removed with EDTA solution.

2. Caustic Embrittlement:
The formation of brittle and in crystalline cracks in the boiler shell is called caustic embrittlement. The
main reason for this is the presence of alkali-metal carbonates and bicarbonates in feed water and also the
presence of sodium sulphate. In lime-soda process, it is likely that, some residual Na2 CO3 is still present in
the softened water. This Na2CO3 decomposes to give NaOH and CO2, due to which the boiler water
becomes “Caustic”.
Na2CO3 + H2O → 2NaOH + CO2
The H2O evaporates, the concentration of NaOH increase progressively creating a concentration cell as
given below thus dissolving the iron of the boiler as sodium ferrate (Na 2FeO2).

(-)Anode: ‘Fe’ at bents│Conc.NaOH ║ Dil.NaOH│ ‘Fe’ at plane Surface: Cathode (+)

This causes embrittlement of boiler parts such as bends, joints, reverts etc, due to which the boiler gets fail.
The iron at plane surfaces surrounded by dilute NaOH becomes cathodic while the iron at bends and joints
surrounded by highly concentrated NaOH becomes anodic which consequently decayed or corroded.

Caustic embrittlement can be prevented:

a. By maintaining the pH value of water and neutralization of alkali.
b. By using Sodium Phosphate as softening reagents, in the external treatment of boilers.
c. Caustic embrittlement can also be prevented by adding Tannin or Lignin or Sodium sulphate which
prevents the infiltration of caustic-soda solution blocking the hair-cracks.

Internal treatment of Water

Suitable chemicals are added to the boiler water either to precipitate or to convert the scale into
compounds is called internal treatment of the boiler feed water. Internal treatment can be done following types.
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1. Calgon conditioning: Involves in adding calgon to boiler water. It prevents the scale and sludge formation 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 treat to too acidic water.
ii. Di sodium Phosphate (Na2 HPO4): is weakly alkaline used for treat to weakly acidic water.
iii. Sodium dihydrogen Phosphate (Na H2PO4): is too acidic used for treat to too alkaline water.

3. Colloidal conditioning: The addition of organic substances such as Kerosene, tannin, Gel. These substances
gets coated over the scale forming precipitates and gives a loose and non-sticky precipitates which can be
removed by using blow-down operation.

External treatment of water - ion exchange process

Ion exchange process is also known as demineralization 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. Resins with acidic functional group are capable of
exchanging H+ ions with other cations. Resins with basic functional groups are capable of exchanging OH −ions
with other anions.
Resins are classified as:
i. Cation Exchange Resins ii. Anion Exchange Resins.
i. Cation Exchange Resins: Cation exchange resins are styrene divinyl benzene co-polymers, which on
sulphonation (or) carboxylation, which contains –COOH, –SO3H functional groups which responsible for
exchanging their hydrogen ions with cations in water.
2RH + Ca(HCO)2 → R2Ca + H2CO3
2RH + Mg(HCO)2 → R2Mg + H2CO3
2RH + CaCl2 → R2Ca + 2HCl
2RH + MgCl2 → R2Mg+ 2HCl
2RH + MgSO4 → R2Mg + H2SO4
2RH + CaSO4 → R2Ca + H2SO4 (RH = Cation exchange resin)

ii. Anion Exchange Resins: Anion exchange resins are Phenol formaldehyde (or) amine formaldehyde
copolymers, which contains amino or basic functional groups which responsible for exchanging their OH −
ions with anions in water.
ROH + HCl → RCl + H2O
2ROH + H2SO4 → R2SO4 + 2H2O
ROH + H2CO3 → RHCO3 + H2O (ROH = anion exchange resin)

16
 UNIT-I
In 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. H+ and OH− ions, thus
released in water from respective cation and anion exchange columns, get combined to produce water molecules.
H+ + OH− → H2O
The water coming out from the exchanger is ion free from anions and cations. Thus water of zero hardness is
obtained.

Regeneration: When cation exchanger losses capacity of producing H+ ions and exchanger losses 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 + 2HCl → 2RH + CaCl2
R2Mg + 2H2SO4 → 2RH + MgSO4
The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.
R2SO4 + NaOH → 2ROH + Na2SO4
RCl + NaOH → ROH + NaCl
RHCO3 + NaOH → ROH + NaHCO3
Merits of Ion-exchange process:
 The process can be used to soften highly acidic or alkaline water.
 It produces water of very low hardness (2ppm)
 So 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
has to be removed by coagulation and filtration.

17
 ZEOLITE OR PERMUTIT PROCESS:

Zeolite is hydrated sodium alumino silicates capable of exchanging reversibly its sodium ions
for Ca+2 and Mg+2, having the general formula Na2O.Al2O3.xSio2.yH2O , where ‘x’ varies from
2 to 10 and ‘ y’ varies from 2 to 6 .
Zeolites are of two types:
a) Natural zeolite: These are non-porous.
Ex: Natrolite Na2O.Al2O3.3SiO2.2H2O.
b) Synthetic zeolite: Artificial zeolites are also known as permutit. These are porous and
possess gel structure. These are prepared by heating together china clay + feldspar &
soda ash.

Process:

Hard water is percolated through a bed of zeolite. The hardness causing ions (Ca2+, Mg2+ etc) are
retained by the zeolite as Ca-Ze & Mg-Ze, while the outgoing water contains sodium salts.
Reactions taking place this process are:

Zeolites are removes temporary and permanent hardness causing substances.

Na2-Ze + Ca (HCO3)2 → 2NaHCO3 + Ca-Ze

Na2-Ze + Mg (HCO3)2 → 2NaHCO3 + Mg-Ze
Na2-Ze + CaSO4 → Na2SO4 + Ca-Ze
Na2-Ze + MgSO4 → Na2SO4 + Mg-Ze

Regeneration: When the zeolite is completely converted into Ca & Mg zeolites, the bed ceases
to soften water. At this stage, the supply of hard water is stopped. And the exhausted zeolite is
reclaimed by treating the bed with conc. brine (NaCl) solution.

Ca-Ze + 2NaCl Na2Ze + CaCl2 (washings)

Mg-Ze + 2NaCl Na2Ze + MgCl2 (washings)

The washings are led to drain and the regerated bed is used again for softening purpose.

Advantages of zeolite process:

1) It removes hardness almost completely.

2) The equipment occupies less space.
3) No impurities are precipitated, so there is no danger of sludge formation.
4) It is a quite clean process.
5) It requires less time for softening.
 UNIT-I

Desalination of water (Reverse Osmosis)

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 move 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 hyper filtration.

Advantages:
 It is simple and reliable process & Capital and operating expenses are low.
 The life of the semi-permeable membrane is about two years and it can be easily replaced within a few minutes,
thereby nearly uninterrupted water supply can be provided.

18
 UNIT-I : Water and its treatment

Sl.No Question Marks CO PO BTL

a. Distinguish between Temporary hardness and Permanent
[1M] 1-4, 6-8,
1 IV
hardness. 11-12
1. b. What is Colloidal conditioning of boiler feed water? [1M] 1 1-4, 6-8,
VI
11-12
c. Explain EDTA method? [10M] 1 1-4, 6-8,
I
11-12
a. Express the reasons why CaCO3 is selected expression of the [1M] 1 1-4, 6-8,
I
hardness? 11-12
b. What is Phosphate conditioning of boiler feed water? [1M] 1 1-4, 6-8,
2. I
11-12
c. Explain the Steps involved in the treatment of potable water. [10M] 1 1-4, 6-8,
II
11-12
a. What is the chemical name of Calgon. [1M] 1 1-4, 6-8,
I
11-12
b. What is break point chlorination? [1M] 1 1-4, 6-8,
3. I
11-12
c. Explain steps involved in the treatment of Fluoride water- [10M] 1 1-4, 6-8,
II
Nalgonda Technique. 11-12
a. Describe the conversion of 10 ppm of hardness of water in [1M] 1 1-4, 6-8,
V
to degree clark. 11-12
b. What are the disadvantages of Ozonization ? [1M] 1 1-4, 6-8,
4. I
11-12
c. Discuss the Ion exchange process of softening of hard [10M] 1 1-4, 6-8,
VI
water. 11-12
a. Which chemicals are used for the regeneration of Cation and [1M] 1 1-4, 6-8,
I
Anion exchange resins? 11-12
b. Write any four specifications of Potable water. [1M] 1 1-4, 6-8,
5 I
11-12
c. Define Desalination? Explain Reverse osmosis process. [10M] 1 1-4, 6-8,
I
11-12
a. How to do the disinfection of potable water by Chlorination. [1M] 1 1-4, 6-8,
I
11-12
b. Define Hardness, write about Soft and Hard water. [1M] 1 1-4, 6-8,
6 I
11-12
c. Explain the following Boiler troubles. 1 1-4, 6-8,
[10M] I
i. Sludge’s ii. Scales iii. Caustic Embrittlement. 11-12

19
 OBJECTIVE TYPE:

1. What is the pH range maintained in EDTA method? [ ]

a. 4-5 b. 6-7 c. 9-10 d. 12-14

2. The colour of stable complex in EDTA method is [ ]

a. Blue b. Wine red
c. Colour less d. Purple

3. Which of the chemical are act as Coagulants help in the settling of [ ]

a. Alum b. Al2 (SO4)3
c. Both (a) & (b) d. Mg SO4

4. Desalination of water is. [ ]

a. Removal of NaCl b. Removal of suspended
c. Removal of gases d. Removal of metals

5. Which of the following will act as disinfectant? [ ]

a. Cl2 b. O2
c. F2 d. H2

6. EDTA method of determining hardness of water can be used to determine. [ ]

a. All types of hardness b. Temporary hardness only
c. Permanent hardness only d. alkaline hardness only

7. Coagulants help in the settling of. [ ]

a. Suspended impurities only b. Fine suspended matter only
c. Colloidal particles only d. both (b) & (c)

8. Reverse osmosis process is also called as. [ ]

a. Super filtration b. Hyper filtration
c. Both (a) & (b) d. Hypo filtration

9. Disinfection by ozone is due to liberation of [ ]

a. Oxygen b. Nascent oxygen
c. Molecular oxygen d. Oxide
10. Potable water treatment doesn’t involve [ ]
a. Demineralization b. sedimentation
c. filtration d. disinfection

20
 Fill in the blanks:

1. Convert 10 ppm of hardness of water in to Degree Clark (Cl°) ______ __.

2. Which Phosphate is used for treating of too alkaline water ______ __.

3. Temporary hardness is caused by _____ __.

4. Cation Exchange resins are regenerated by using _______ __.

5. Hardness of water is expressed in equivalents of __________ ___ __.

6. The chemical name of Calgon is _______ __.

7. Temporary hardness of water can be removed by_______ __.

8. Anion exchange resins are regenerated by using _______ __.

9. _______ __is considered to be the naturally distilled water.

10. A semi permeable membrane allows the flow of _______ _.

21