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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 UNIT-1

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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 UNIT-1

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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 UNIT-1

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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 UNIT-1

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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 UNIT-1

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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 UNIT-1

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.

7
Water and its Treatment 1.9

Problem 4: A sample of water is found no contain the following analytical data in mgs/lit.
Mg(HCO3)3 = 14.6; MgCl2 = 9.5; MgSO4 = 6.0; Ca(HCO3)2 = 16.2. Calculate the
temporary and Permanent hardness of the sample of water.

Solution: Given: Hardness producing salt.

(i) Mg(HCO3)2 (Mol. Wt. = 146), Amount in mgs/lit. = 14.6

14.6×100 = 10 mgs/lit.
= 146
(ii) MgCl2 (Mol. Wt. = 95), Amount in mgs/lit. = 9.5
9.5×100
= = 10 mgs/lit.
95
(iii) MgSO4 (Mol. Wt. = 120), Amount in mgs/lit = 6.0

6.0×100 = 5 mgs/lit.
= 120

(iv) Ca(HCO3)2 (Mol. Wt. = 162), Amount in mgs/lit = 16.2

16.2×100 = 10 mgs/lit.
= 162

Temporary hardness = Mg(HCO3 )2 + Ca (HCO3 )2

= 10 + 10 = 20 mgs/lit.

Permanent hardness = MgCl2 + MgSO4

= 10 + 5 = 15 mgs/lit.

BOILER TROUBLES
Scale and Sludge
When hard water is used for boilers, on continuous evaporation, the salts present in the
hard water gets saturated and are finally deposited in the areas where the flow is slow. When the
precipitates formed are loose and slimy in nature, it is called sludge, whereas when the precipitates
formed are hard and adhere strongly on the inner walls of the boiler, they are called scale.
1.10 Chemistry

Sludge can be easily removed byscrapping with a brush. Sludge is formed bythe presence
of MgCO3, MgSO4, MgCl2, CaCl2 etc. These salts are more soluble in hot water.
Disadvantages of sludge formation are:

(i) poor heat conduction due to the presence of sludge on the surface;

(ii) difficulty in the operation of the boiler;

(iii) if sludge is formed along with the scale and is trapped within the scale formed and so
it is difficult to remove and
(iv) it clogs the pipe lines and other connections to the vessel near the places where water
circulation rate is slow.

Water

Boiler Hard adhering coating

Wall on inner walls of boiler
(scale)

Loose precipitate
suspended in water
(sludge)

Heat Heat

Figure 1.1: Scale and sludge formation in boilers

Removal of Sludge

Sludge formation can be prevented by:

(i) using soft water for boiler operation and

(ii) removing the concentrated salty water from time to time so that deposition of sludge
is prevented. Scales are the hard deposits on the inner surface of the boilers which are
difficult to remove.

This scale formation takes place due to the following reasons:

Water and its Treatment 1.11

(a) In low pressure boilers scale formation occurs due to the formation of CaCO3 from
Ca(HCO3)2.

Ca(HCO3 )2 ⎯⎯
→ CaCO3 ↓ + H 2 O + CO 2
scale

(b) In high pressure boilers this CaCO3 gets converted to soluble Ca(OH)2. But here
CaSO4 forms the hard scale. Since the solubility of CaSO4 decreases with increase in
temperature, and at high temperature the precipitated CaSO4 forms hard scale. Similar
hard scales are formed when SiO2 is present in the hard water. It deposits as CaSiO3
or MgSiO3. These calcium or magnesium silicate scales are very difficult to remove.
Dissolved magnesium salts also precipitate as Mg(OH)2 forming soft type of scale.

Disadvantages of scale formation are similar to sludge formation but the severity is
more, since its removal is more difficult.

Disadvantages include

(i) Poor heat transfer from boiler to water leading to increase in fuel consumption. The
increase in thickness of the scale from 1.25 mm to 12 mm leads to increase in fuel
consumption from over 50% to 150%.
(ii) Due to the overheating of the boiler, different parts of the boiler become weak and
distorted and so the operation of the boiler becomes unsafe, particularly the high
pressure boilers. The thick scales may sometimes lead to explosion due to sudden
development of high pressure.
(iii) Valves and condensers of the boilers are chocked due to scale formation and Boiler
efficiency decreases.

Removal of scales can be done by:

(i) Wooden scraper or wire brush, suitable for removing loose scales.

(ii) Blow down operations for loose scales. The operation actually involves the removal of
very hard water from a tap at the bottom of the boiler and replenishing the water with
softened water called ‘make up’ water.
 1.12 Chemistry

(iii) Giving thermal shocks, which involve alternate heating and cooling to make the scales
brittle.

(iv) Chemical treatment with 5-10% HCl for carbonates and EDTA treatment for Ca/Mg
salts forming complexes.
Differences between Sludge and Scale
S.No. Sludge Scale
1. Loose, slim , non-adherent precipitate Hard, thick , strong adherent precipitate
2. Due to salts like MgSO4, MgCl2 Due to salts like CaSO4, Ca(HCO3)2
3. Due to poor conductance, they decrease Due to poor conductance, they decrease the
the boiler efficiency to lesser extent and boiler efficiency to maximum extent, cause
causing chocking in the pipelines. reduced fuel economy, improper boiling,
boiler explosion etc.,
4. It can be prevented by periodical It can be prevented by special methods like
replacement of concentrated hard water i) External treatment of ion exchange,
by fresh water. This process is known as ii) Internal carbonate, phosphate, Calgon
“blow down” method. conditioning and iii) Mechanical hard
scrubbing methods.

2.Caustic embrittlement
Definition:Intercrystalline cracking of boiler material
It is a form of stress corrosion takes place in boilers operating at high
temperature(200-250˚ C) and pressure. Caustic embrittlement focus at stressed part of
boilers such as cracks, rivets, bents, joints etc.
The boiler fed water usually contains some residual sodium carbonate (used for
softening process). At high temperature and pressure it undergoes hydrolysis to form sodium
hydroxide.
Na2CO3 + H2O ---------2 NaOH + CO2
The alkali water sweeps through the minute cracks, crevices between the rivets and
joints by capillary action. Inside the cracks water gets evaporated leaving behind NaOH. The
concentrations of the NaOH gradually increase on these sites due to poor circulation of
water. When concentrations of the NaOH reaches a value of 10% it attacks the metal at the
stressed region dissolving it in the form of sodium ferroate ( Na2FeO2). Sodium ferroate
undergoes hydrolysis-depositing magnetite as follows
3Na2FeO2 + 4H2O -------- 6NaOH + Fe3O4 + H2
6Na2FeO2 + 6H2O + O2 -------- 12NaOH + 2Fe3O4
So NaOH is regenerated in the process and its concentration is keep on increasing
maintaining a required environment. Thus corrosion process develops cracks and making the
metal brittle by the deposition of the product.
3.Priming and foaming
Foaming:
 Water and its Treatment 1.13
Bubbles produced in the water due to heat and pass out with the steam. This is called
foaming and it is caused by high concentration of impurities in the boiler water.
Priming

It is the carry over of varying amounts of droplets of water in the steam, which
lowers the energy efficiency of the steam and leads to the deposit of water droplets of
impurities and cause the damage of boiler.

Prevention:

To prevent it, use of chemicals like anti-foaming and anti-priming agents which
prevents the formation of priming and foaming in the boiler water.

4) Boiler Corrosion
It may be due to three major reasons:
i) Dissolved Oxygen
ii) Dissolved CO2
iii) Dissolved salts like MgCl2

i)Corrosion Due to dissolved oxygen :

Dissolved oxygen in presence of water, causes corrosion.
4Fe + 6 H2O + 3O2 …………………….4 Fe (OH)3 (Rust)
Prevention from oxygen:
a) Chemical method –
i)Adding Sodium Sulphite:
2 Na2SO3 + O2 ………………………2 Na2SO4
This method results in other precipitates which can have some side effects. So this
method is less preferred.
ii)Adding Hydrazine:
N2H4 + O2 …………………..N2 + 2 H2O
This method results in inert gas and pure water, and has no side effects
b) Mechanical deaeration method:
1. This is based on the principle that at high temperature , low pressure and high exposed
area, the solubility of gases in water is decreased. So, the gases can be expelled easily.
2. Here, the water is fed into the mechanical deaerator which is provided with vacuum
pump, heaters and perforated plates.
3. The out coming water will be free from dissolved gases.
2.Corrosion due to CO2
Salts like Calcium bicarbonate on heating produces CO2 . CO2 dissolves in water to
form carbonic acid which corrodes the boiler metal. ∆
Ca(HCO3)2…………………………… CaCO3 + H2O + CO2
H2O + CO2 ………………………………….H2CO3(carbonic caid)
Prevention from CO2
1. Chemical method: By adding calculated amount of ammonium hydroxide

2NH4OH + CO2 ……………… (NH4)2CO3 + H2O 2.

2. Mechanical deaeration method ( similar to oxygen method)

Corrosion due to Dissolved salts like MgCl2 .Dissolved salts like MgCl2
 1.14 Chemistry
cause acid formation. .This will be prevented by alkali neutralisation.
MgCl2 + 2 H2O ………………………Mg(OH)2 + 2 HCl (Corrosive
acid)
Neutralisation: Excess acidic nature is neutralized by adding alkalis and vice versa.
HCl + NaOH ……………………….. NaCl + H2O

DESALINATION PROCESS
Definition: Process of removing common salt from sea water.. Seawater desalination has
the potential to reliably produce enough potable water to support large populations .

Types of process:
Reverse osmosis (RO) and Nanofiltration (NF) are the leading pressure driven
membrane processes. Contemporary membranes are primarily polymeric materials with
cellulose acetate still used to a much lesser degree. Operating pressures for RO and NF are
in the range of 50 to 1,000 psig (3.4 to 68 bar, 345 to 6896 kPa).
Electrodialysis (ED) and Electrodialysis Reversal (EDR) processes are driven by
direct current (DC) in which ions (as opposed to water in pressure driven processes) flow
through ion selective membranes to electrodes of opposite charge.
Reverse osmosis
Osmosis:
If two solutions of different concentration are separated by a semi-permeable
membrane which is permeable to the smaller solvent molecules but not to the larger solute
molecules, then the solvent will tend to diffuse across the membrane from the less
concentrated to the more concentrated solution. This process is called osmosis.
Osmosis is of great importance in biological processes where the solvent is water.
The transport of water and other molecules across biological membranes is essential to many
processes in living organisms. The energy which drives the process is usually discussed in
terms of osmotic pressure..
Reverse osmosis
If hydrostatic pressure greater than the osmotic pressure is applied then the flow of
solvent from high concentrationto low concenteration occurs. This is called reverse osmosis
.thic can also be called as Superfiltration
Water and its Treatment 1.15

TREATMENT OF BOILER FEED WATER

These are methods for the removal of the scales, when they are formed. There are also
some methods for the prevention of scale formation by internal or external treatment.

Internal Treatment

Internal Treatment involves addition of chemical to the boiler water either to (i) precipitate
the scale forming impurities in the formof sludges, which can be easily removed or (ii) convert the
impurities to soluble compounds, so that scale formation can be avoided. Important internal
treatments involve.

(a) Colloidal Conditioning: Organic substances like kerosene, tannin, agar-agar are
added to form gels and formloose non-sticky deposits with scale-forming precipitates,
which can be easily removed by blow-down operations in low pressure boilers.
1.16 Chemistry

(b) Different Sodium Phosphates like NaH2PO4, Na2HPO4 and Na3PO4 are added
to high pressure boilers to react with the hardness forming impurities to form soft
sludge of calciumand magnesium phosphates and finally this can be removed by blow
down operation.

3CaCl2 + Na3 PO 4 ⎯⎯
→ Ca3 (PO 4 ) 2 + 6NaCl

(c) Calgon Conditioning: Calgon i.e., sodium hexa meta phosphate when added to
boiler water, reacts with scale forming CaSO4 and forms soluble complex compound.

2 CaSO4 + [ Na4 P6 O8 ] → [Ca2 P6 O18 ]

2− 2−
⎯⎯ + 2Na2SO4

(d) Sodium Aluminate Conditioning: Sodium aluminate is hydrolysed yielding NaOH

and gelatinousAl(OH)3. The NaOH formed reacts with magnesium salts to precipitate
Mg(OH)2. This Mg(OH)2 and Al(OH)3 are flocculent and entraps the colloidal as
well as the finely divided impurities like silica in the boiler water and the loose precipitate
is finally removed by blow down operation.

NaAlO2 + 2H2 O ⎯⎯
→ NaOH + Al(OH)3 ↓
MgCl2 + 2 NaOH ⎯⎯
→ Mg(OH)2 ↓ + 2NaCl

External Treatment

Ion Exchange or Demineralization

Ion Exchange Resins are organic polymers which are crosslinked having microporous
structure and the functional groups are attached to the chains which are responsible for the ion
exchange properties.

(i) Cation Exchange Resins (RH+) are phenol-sulphonic acid-formaldehyde resin,

styrene- divinyl benzene copolymers which exchange their H+ ions with the cations
present in the water i.e., Ca2+ and Mg2+.
Wate
er and its Treatment
Tr 1.17

(
(ii) Anion ROH ): Thee styrene divvinyl benzenne or aminee
n Exchangee Resins (R
formald
dehyde copolyymers containn quaternary ammonium
a teertiarysulphonnium or aminoo
group in
i the resin. The
T resin on trreatment withh hard water iss capable of exxchanging thee
OH− with S 2−
w different anions of watter i.e., Cl−, SO 4 etc.

Method

The hard water is passeed first througgh cation excchange resin, the
t cations likke Ca2+, Mg2++
are reemoved from
m the hard waater and exchaanged with H+ as follows:

2 RH + + Ca 2++ / Mg 2+ ⎯⎯ H+
→ R 2 Ca 2+ / R 2 Mg 2+ + 2H
⎯
1.18 Chemistry

After this the hard water is again passed through anion exchange column, which exchanges
all the anions like SO2− − −
4 , Cl . etc. present in the water with OH .

ROH- + Cl − ⎯⎯
→ R + Cl − + OH −
These H+ from cation exchanger and OH− fromanion exchanger combine to form water
molecule. Thus the water coming out finally from the two exchangers is ion free and called
deioinized or demineralized water.

Injector Injector
Cation Anion
Exchanger Pump Exchanger
Gravel Gravel

Acid Waste Waste

regenerator Liquor Liquor Alkaline
regenerator

Figure 1.2: Demineralization of Water

Regeneration: The inactivated or exhausted cation exchange resin is regenerated by passing a

dil. H2SO4 / HCl solution.

R2 Ca2+ + 2H+ ⎯⎯
→ 2RH + + Ca 2+

Similarly, the exhausted anion exchange resin is regenerated by passing a dil. NaOH
solution.

−
R 2SO 2− → 2 ROH − + SO 2+4
4 + 2 OH ⎯⎯

The columns are finally washed with deionized water and the washings are discarded.
Water and its Treatment 1.19

Permutit or Zeolite Process

Zeolite is hydrated sodium alumino silicate capable of exchanging reversibly its sodium
ions for Ca2+ and Mg2+, having the general formula Na 2O⋅ Al 2O 3⋅ xSiO 2⋅ yH 2O. Common zeolite
is Na2O⋅ Al2O3 ⋅ 3SiO2 ⋅ 2H2O and is known as natrolith. Others gluconites, green sand etc. are
used for water softening.

Artificial Zeolite used for softening purpose is permutit. These are porous and glassy and
have greater softening capacity than green sand. They are prepared by heating together with
china clay, feldspar and soda ash.

Method of Softening: Hard water is passed through a bed of zeolite at a specific rate at ordinary
temperature; the hardness causing cations i.e., Ca2+ and Mg2+ are exchanged for Na+ and it is
converted to CaZe and MgZe.

Reactions taking place are:

Na2 Ze + Ca (HCO3 )2 = 2 NaHCO3 + CaZe

Na2 Ze + Mg (HCO3 )2 = 2 NaHCO3 + MgZe

Na2 Ze + CaSO4 = Na2SO4 + CaZe

Na2 Ze + CaCl = 2NaCl + CaZe

Regeneration of Zeolite: The process is also commercially successful since the Ca/Mg zeolites
formed by passing hard water through the bed can be easily regenerated into Na2Ze by passing
brine through the bed of inactivated zeolite.

CaZe or MgZe + NaCl = Na2 Ze+CaCl2 (or MgCl2 )

The washings containing CaCl2 or MgCl2 are wasted. The water softened by this process
can be used for laundry purposes.
1.20 Chemistry

Hard
Water in

Top Distributor

Soft
Water out

Injector Zeolite Sand

Gravel

Salt
Storage

Waste
Liquor

Figure 1.3: Softening of hard water by permutit process

Advantages:
(i) Hardness of water can be removed completely upto about 10 ppm.
(ii) The equipment used is small and easy to handle.
(iii) It requires less time for softening.
(iv) There is no sludge formation, hence the process is clean.
(v) Easy to regenerate.
(vi) Any hardness can be removed without any adjustment of the process.
Disadvantages:
(i) Coloured water or water containing suspended impurities cannot be used before
filtration.
(ii) Water containing acid cannot be used for softening since acid may destroy the zeolite.
(iii) Since on removal of Ca2+ and Mg2+ the soft water contains large amount of NaHCO3,
this on heating liberates CO2, which causes corrosion in the boilers and hence this soft
water is not suitable for boilers.