UNIT-1

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.
➢ Physical impurities
➢ Chemical impurities
➢ 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

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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.

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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.
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 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:

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.

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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.

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.

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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.

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

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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

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 minimum
quantity of dil.HCl and then evaporate the solution to dryness on a water bath. Dissolve the
residue in distilled water to make 1 Litre solution. Each ml of this solution thus contains 1mg of
CaCO3 equalent hardness.

ii. Preparation of EDTA solution: Dissolve 4 g of pure EDTA crystals + 0.lg MgCl2 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

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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
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.

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Solution:
Strength of standard hard water sample (CaCO3 solution) M1=
Weight of CaCO3 × 1000
Mol. wt of CaCO3 1000
= 1 gm × 1000 = 0.01 M
100 1000
Strength of EDTA solution M2 = 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 M3 = 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.

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 M2 = 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 M3 = 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 M4 = V2 M2 = 10 × 0.01 = 0.001 M

V4 100

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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 7.0 to 8.5.
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.
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.

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3. 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.
4. 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.

5. 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.

6. Disinfection of water by sterilization: The process of destroying the harmful bacteria’s is known as
sterilization or disinfection.

Disinfection of POTABLE WATER

1. 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.

2. 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

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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.

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.

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.

Defluoridation – Nalgonda technique

Deflouridation is the removal of excess fluoride from water. Nalgonda technique is simple and
economical. Reverse osmosis, activated alumina and distillation methods are used to remove fluorine.
In Nalgonda technique, where fluoride is precipitated using 500 mg/L of alum and 30 mg/L of lime
with small amount of bleaching powder (3 mg/L) for disinfection.

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Steps involved in Nalgonda technique:

Nalgonda Technique involves rapid mixing (with that chemical interaction is very effective),
flocculating, sedimentation, filtration and disinfection. Alum (coagulant) is used to flocculate fluoride
ions.

The process is best carried out under alkaline conditions, therefore, lime is added. For disinfecting,
bleaching powder is added. After stirring, the chemical elements coagulate into flocks and settle down in
the bottom.

Advantages: i. Nalgonda Technique is adoptable to domestic use because low price.

ii. Ease of Handling. Bleaching powder

Disadvantages: i. It is not suitable if the pH of untreated water is alkaline.

ii. It is not suitable when the fluoride concentration is very high.
Sailent features of Nalgonda Technique:
➢ Nalgonda Technique is adoptable to domestic use.
➢ Simultaneous removal of colour, odour, turbidity, bacteria and organic contaminants possible.
➢ Sludge generated is convertible to alum for reuse.
➢ No handling of caustic acids and alkalis, Local skills/capability readily employable.
➢ Needs minimum mechanical and electrical equipment and no energy except muscle power for
domestic equipment.
➢ Highly efficient removal of fluoride from 1.5 to 20 mg/L to desirable levels.

Determination of F - ion by ion- selective electrode method.

➢ An ion-selective electrode (ISE) is defined as an electro analytical sensor with a membrane whose
potential indicates the activity of the ion to be determined (fluoride) in a solution.
➢ Ion-sensitive membrane may be glass, a crystalline inorganic material, or an organic ion exchanger.
➢ The membrane interacts with the ion of choice, here fluoride, allowing electrical potential of the half
cell which is controlled by the fluorine concentration.

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➢ The potential of the ISE is measured against a suitable reference electrode using a pH meter. The
electrode potential is related to the logarithm of the concentration of the fluoride ion by the Nernst
equation.
E = E 0 + 2303 RT.log [M]
nF
n = ion charge, the equation is valid for very dilute solutions where the ionic strength is constant.
➢ In this experiment we will use fluoride-sensitive electrode, either a saturated calomel electrode or
Ag/AgCl external reference electrode to measure the fluoride ion concentration.

➢ Flouride ISEs only respond to free ionized F- in solution and can be used to measure this ion in the
presence of other fluorine compounds.

Reagents required:
➢ NaF(dried at 100°C for 1 hour)
➢ KCl
➢ Liquid NaF unknown
➢ Flouride ISE and Ag/AgCl reference electrode
➢ pH meter capable of displaying mV potentials

Procedure:
➢ Dry the NaF solid for 1 hour at 100°C
➢ NaF(10-1 ): Weigh 0.42 g of NaF, dissolve in deionized water, and dilute to 100 ml in a volumetric
flask. This solution is about 10-1 F in NaF.
➢ Transfer 10 ml of above solution to 100 ml volumetric flask and dilute with deionized water. This
solution is about 10-2 F in NaF.
➢ KCl (1 M): Weigh 7.55 g of KCl on a top loading balance and dissolve in 100 ml deionised water.
➢ Prepare four 100 ml volumetric standard flasks as follows:

NaF(10-2 M) ml KCl (1 M) ml
(a) 1.00 10
Dilute each flask with deionised water
(b) 2.00 10
(c) 5.00 10
(d)10.00 10

Analysis:
➢ Take unknown solution into a 100 ml volumetric flask and dilute upto the mark.
➢ Add 1 ml of prepared unknown solution and add 10 ml of KCl and dilute it to 100 ml with deionised
water.
➢ Measure the potential in MV of the fluoride ISE Vs reference electrode for each of the four standard
and for unknown solution.
➢ Pour about 30 ml of each standard solution (or) unknown into clean 100 ml beaker and immerse the
electrode in the solution in the depth of 2 cm and then measure the electrode potential.

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➢ After completion of the experiment rinse the electrodes with deionised water and keep the reference
electrode in the appropriate solution.
➢ The F-ISE should be stored dry and loosely capped.
Calculations:
➢ Calculate the molarity of NaF accurately.

➢ Plot a graph of the concentration of NaF Vs

potential. Find the best line passing through four
standard solution points. Calculate the slope of the
calibration curve slope = dE/dlog[NaF]
➢ By using calibration curve determine the
concentration of NaF in your prepared unknown
solution. Report this as percent fluoride (% w/v) in the prepared unknown.

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 hardness should be below 0.2ppm.
➢ 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

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.

Sludges

Sludge is a soft, loosy 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:

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

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Disadvantages of sludges:
1. Sludges are bad conductors of heat and results in the wastage of heat and fuel.
2. 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.

Scales

Scales are hard, adhering precipitates formed on the inner walls of the boilers. Scales are stick very
firmly on to the inner walls of the boiler. It is removed 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. 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

c. 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.

d. Presence of silica: Sio2 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 is
reduced.

2. Lowering of boiler safety is due to overheating of the boiler material becomes softer and weaker,
which causes distortion of boiler.

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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.
Prevention 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.

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. In
lime-soda process, it is likely that, some residual Na2CO3 is still present in the softened water. This
Na2CO3 decomposes to give NaOH and CO2, due to which the boiler water becomes “Caustic Soda”.
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 (Na2FeO2).

(-)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

Genarally 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.

Softening of Water by 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

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2ROH + H2SO4 → R2SO4 + 2H2O

ROH + H2CO3 → RHCO3 + H2O(ROH = anion exchange resin)
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.

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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.

Sewage water –steps involved in the treatment

Sewage/Waste water is the water which comes from flushing the toilet, bathing, washing clothes and
general cleaning.
Sewage treatment is the process of removing contaminants from waste water. It includes physical,
chemical, and biological processes to remove these contaminants and produce environmentally
safe treated waste water.

Steps involved in the treatment of sewage water: Waste water goes down the drain and into a pipe,
which joins a larger drainage pipe under the road; this water can be send to the treatment center. Five
steps involved in the treatment of sewage water.

I. Preliminary treatment (Screening): Screening is the first stage of the treatment of the sewage
water. Screening removes large objects like, plastics, bottles, sanitary items, papers and damaged
equipment.

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II. Primary Treatment (or) settling process: This involves the separation of organic solid matter like
human waste. This is done by putting the waste water into large settlement tanks for the solids to sink
to the bottom of the tank. The settled solids are called sludge, after removing the sludge the rest water
is then send to the secondary treatment.
Al2(SO4)3 + 6H2O → 2Al(OH)3 + 6H2SO4

III. Secondary Treatment (or) Biological treatment:

In this stage water is put into larger rectangular
tanks, which we called aeration lanes. In this
process air is pumped into the water to encourage
bacteria to break down biodegradable organic
impurities in to the small particles which are
separated through scrapping process. This is done
by Trickling filter process.

IV. Tertiary Treatment: After the secondary treatment the treated water send through settlement tank to
separate the remaining sludge. The water at this stage is almost free from harmful substances and
chemicals. The water is allowed to flow over a wall where it is filtered through a bed of sand to
remove additional particles. The filtered water is then released into the river.

V. Disposal of Sludge: This is the last stage in the sewage treatment. Sludge formed from different
steps can be disposed by dumping into low-lying areas, burning of sludge and using it as low grade
fertilizers.

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Important Questions
1. How temporary hardness differs from permanent hardness?

2. Define hardness and estimate hardness of water by using EDTA solution?

3. Explain Caustic embrittlement, Scale & Sludge.

4. Explain determination of fluoride ions (F-) by ion selective electrode method.

5. Explain softening of water using Ion exchange process.

6. What is desalination? Explain reverse osmosis process.

7. Explain Steps involved in treatment of sewage water.

8. What is Potable water and what are its specifications.

9. Explain Steps involved in the treatment of potable water.

10. 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.

11. Explain the following?

a. Calgon conditioning and Phosphate conditioning of boiler feed water.
b. What is defluoridation and explain Nalgonda technique.

12. What is Hardness and calculate 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.

Objective Questions:

1. Hard water may be softened by passing it through: [ ]

(a) Limestone (b) Ion-exchange resins (c) Calgon (d) Rock salt

2. Temporary hardness in water is removed by [ ]

(a) Filtration (b) Sedimentation (c) Boiling (d) coagulation

3. The colour of EBT indicator is [ ]

(a) Wine red (b) Blue (c) Colour less (d) Pink

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4. 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

5. One part of CaCO3 equivalent hardness per 106 parts of water is also called as [ ]
(a) Degree Clarke (b) Degree french (c) ppm (d) mg/L
6. The hardness of water is 10ppm it can be expressed in degree clark as: [ ]
(a) 0.07°Cl (b) 0. 7°Cl (c) 7.0°Cl (d) 0.007°Cl

7. The process of allowing water to stand and undisturbed in big tank for settling of the suspended
Particles due to force of gravity [ ]
(a) Coagulation (b) Sedimentation (c) Conditioning (d) Screening

8. The Soft, loose and slimy precipitate formed within the boiler is called [ ]
(a) Scale (b) sludge (c) embrittlement (d) Coagulation

9. The Hard and adherent precipitate formed on the inner walls of the boiler is called [ ]
(a) Scale (b) sludge (c) embrittlement (d) Coagulation

10. Potable water treatment does not involve [ ]

(a) Demineralization (b) sedimentation (c) filtration (d) disinfectation

11. Caustic embrittlement is due to the [ ]

(a) NaOH (b) Na2CO3 (c) Mg (OH)2 (d) H2SO4

12. Caustic embrittlement can be avoided by using [ ]

(a) Sodium phosphate (b) hydrogen (c) ammonium hydroxide (d) sodium sulphate

13. The exhausted anion exchange resin can be regenerated by the addition of [ ]

(a) dil. HCl (b) dil. NaOH (c) dil. H2SO4 (d) dil. Mg (OH)2

14. Brackish water mostly contains dissolved [ ]

(a) Calcium salts (b) Magnesium salts (c) Turbidity (d) Sodium Chloride
15. The purification of brackish water by reverse osmosis is also … called [ ]
(a) Super-Filtration (b) Supra-Filtration (c) hypo-Filtration (d) Filtration

16. Which of the fallowing methods separating both ionic and non ionic impurities from water [ ]
(a) electrodialasis (b) Demineralization (c) reverse osmosis (d) ion exchange process

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Fill in the blanks:

1. Hardness of water is expressed in terms of _______ equivalents.

2. Temporary hardness of water can be removed by _______________.
3. MgCl2 and MgSO4 present in water produces _________________ hardness.
4. In the estimation of hardness of water by EDTA method, the wine red colour is due to __________.
5. The process of killing germs in potable water is called _______.
6. ______________ is the main advantage of usage of chlorine gas than the Chloramine as a
disinfectant.
7. Chlorine, when treated with water produce _____________ acid, which act as a powerful germicide.
8. The pH of the potable water should be __________.
9. Sodium aluminate is used as _________________ during purification of water.
10. _______, __________ &___________Chemicals are required in Nalgonda de-fluoridation technique.
11. The chemical name of the calgon is __________.
12. In phosphate conditioning if boiler feed water is too alkaline _________________ is used for internal
conditioning.
13. Cation and Anion exchange resins are regenerated by using ___________& ______.
14. Best method of removing hardness of water is _______________________ process.
15. ___________ is a measure of oxidizable impurities present in the sewage.

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Two Marks and Three Marks Questions

1. Write two balanced equations to describe when hard water is heated.

2. What are the constituents that cause hardness in water? Explain the terms Carbonate hardness and
Non-Carbonate hardness.

3. What is the inter relation of units of hardness?

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4. Write the principle involved in complexometric method for the determination of hardness of
water.

5. What is the need for an alkaline buffer in the determination of hardness of water by EDTA
titration?

6. Write the specifications of potable water.

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 UNIT-1

7. Explain disinfection by chlorination.

8. What is Break-point of chlorination?

9. What is meant by deflouridation.

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10. How is Nalgonda technique carried out?

11. Write differences between scales and sludges.

12. What is Caustic embrittlement? Explain and also write its prevention.
(or)
Explain the cause of caustic embrittlement in boilers and suggest a remedy.

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 UNIT-1

13. Calgon treatment prevents scale formation in boilers. Give reasons.

14. What is Phosphate conditioning?

15. Write the principle of Ion exchange process of softening water.

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16. What are advantages of Ion exchange process?

17. What is ment by Reverse osmosis? How is it applied in the desalination of water?

18. What are advantages of Reverse osmosis?

19. What is sewage water?

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Draw the neat diagrams of the following

1. Ion – exchange process:

2. Reverse Osmosis:

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Draw the flow charts of the following:

1. Steps involved in the treatment of the “POTABLE WATER”:

2. Steps involved in the treatment of the “Defluoridation – NALGONDA

TECHNIQUE”:

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 UNIT-1

3. Steps involved in the treatment of the “SEWAGE WATER”:

32