Unit – I

WATER TREATMENT
“Water is the most important element in life and useful compound, yet is also the most
misused one”
1.1 INTRODUCTION
Water is the nature’s most wonderful, abundant and useful compound. Of the many
essential elements for the existence of human beings, animals and plants, water is rated to be of
greatest importance. Without food human being can survive for a number of days, but water is
such an essential thing without it one cannot survive. Water is not only essential for the lives of
animals and plants but also occupies unique position in industries. Probably its most important
use as an engineering material is in the ‘steam generation’. Water is also used as a coolant, in
power, and chemical plants. In addition to it, water can also be used in the production of steel,
rayon, paper, textiles, chemicals, irrigation, drinking, firefighting, etc.
1.1.1 Occurrence
Water covers about three-quarters of earth’s surface
and is a necessary element for life during their constant
cycling between land, the oceans, and the atmospheric
water molecules pass repeatedly through solid, liquid and
gaseous phase (Ice, liquid water & water vapour).
Earth is a blue planet and 80% of its surface is
covered by water, the hard fact of life is that about 97.5%
of it is locked in the oceans and sea which is too saline to
drink and for direct use of agricultural or industrial
purposes. 2% is trapped in polar ice caps and giant glaciers.
>1% of water is used by man for various development,
industrial, agricultural, steam generation and domestic. Fig 1: Distribution of water
1.1.2 Sources of Water
“We won’t have a society if we destroy the environment”
“Think you can’t do anything without water. Save it”
Water is required for agricultural, municipal and industrial purposes. Natural water
broadly divided into the following categories.
(A) Surface water: It includes flowing water
1. Rain water
2. River water
3. Lake water
4. Sea water or estuarine water
(B) Underground water
Spring and well water
 From the point of view of industrial applications, it is not usually feasible to use rain
water and sea water. Rain water is irregular in supply and generally expensive to collect.
Estuarine and sea water are too saline for most industrial uses expect cooling.

1.2 CHARACTERISTICS OF WATER

“Water is the basis of life and the blue arteries of the earth”
As per the suggestion given by World Health Organisation (WHO) and by Indian Council of
Medical Research (ICMR), the following are the important characteristics of potable water.
 It should be clear, colourless, and odourless.
 It should be cool and pleasant to taste.
 It should be free from harmful bacteria and suspended impurities.
 It should be free from dissolved gases like CO 2, H2S, NH3, etc., and poisonous minerals
like lead, arsenic, manganese, etc.,
 Hardness should be less than 500 ppm.
 Chloride ion content should be less than 250 ppm.
 Fluoride ion content should be less than 1.5 ppm.
 Total Dissolved Solids (TDS) content should be less than 500 ppm.
 pH of the potable water should be 6.5 – 8.5.

Acidic Neutral Alkaline

pH=0-7 7 pH=7-14

1.2.1 Chemical Characteristics of Water

The most important chemical characteristics of water are its acidity, alkalinity, hardness,
and corrosiveness. Chemical impurities can be either natural, manmade (Industrial) or be
deployed in raw water sources by enemy forces. Some chemical impurities cause water to
behave as either an acid or a base. Since either condition has an important bearing on the water
treatment process, the pH value must be determined. Generally the pH influences the
corrosiveness of the water, chemical dosages necessary for proper disinfection and the ability to
detect contaminants.
1.2.2 Characteristics Imparted By Impurities in Water
Natural water is usually contaminated by different types of impurities. Water from a water supply
scheme may contain a number of impurities which it takes up from
 The ground or soil with which it is (comes) in contact. Eg. Soil particles, minerals.
Garbage etc.
 The sewage and industrial waste. Eg. Chemical wastes, acids, colours, heavy metals
etc.
 The decomposition of plants and animals.
 The growth of bacteria, algae, viruses etc.
 The atmosphere in the form of dissolved gases.
The characteristic and consequent effects of impurities on the quality of water are discussed
under the following three headings
 Physical Impurities
 Chemical Impurities
 Biological Impurities
Types Impurities
Physical Suspended Impurities Inorganic: Sand, Clay
Impurities Organic: Vegetable and animal matter
Colloidal Impurities Finely divided silica and clay, organic waste
pollutants, colouring matters etc.
Chemical Dissolved salts Salts like bicarbonate, carbonate, chloride, sulphate,
Impurities nitrate, phosphate of Na, K, Ca, Mg, Fe etc.
Dissolved gases Gases like O2, N2, CO2, SO2, H2S make water acidic
and they accelerate the rate of corrosion
Biological Impurities Bacteria, fungi, virus etc.,

“The process of removing all types of impurities from water and making it fit for a domestic or
industrial purpose is called water technology (or) water treatment”
1.3 HARD WATER AND SOFT WATER
i. Hard water
Water which does not produce lather with soap solution
readily, but forms a white precipitate (scum) is called hard
water. This is due to the presence of dissolved Ca and Mg
salts.
Eg. Ca(HCO3)2, Mg(HCO3)2, CaCl2, CaSO4, MgSO4, etc.
ii. Soft water
Water which produces lather readily with soap solution is
called soft water. This is due to the absence of Ca & Mg salts.
Fig 2: Hard and
soft water
Difference between hard water and soft water
S. No Hard Water Soft Water
1. Water which does not produce lather Water which lathers easily on shaking
with soap solution readily, but forms a with soap solution is called “soft
white precipitate is called “hard water”. water”.
2. Hard water contains dissolved Ca & Mg Soft water does not contain dissolved
salts in it. Ca & Mg salts in it.
3. In hard water, cleaning quality of soap is In soft water, cleansing quality of soap
depressed and a lot of it is wasted during is not depressed and so soap is not
washing and bathing. wasted during washing and bathing.
4. Due to the presence of dissolved Less fuel and time are required for
 hardness producing salts, the boiling heating soft water.
point of water is elevated. Consequently,
more fuel and time are required for
heating.

1.4 HARDNESS OF WATER

“Hardness is the property or characteristics of water, which does not produce lather with
soap”

Note: Hard water contains soluble salts of calcium and magnesium ions. When hard water is
used for washing and bathing purposes, it does not lather freely with soap, but produces sticky
precipitates of calcium and magnesium soaps. The formation of such insoluble precipitates
consumes soap, till hardness is completely precipitated.
How to detect hardness?
 When water is treated with soap solution, if it prevents lathering and forms white
scum, the water contains hardness. Hardness is rightly defined as soap consuming
capacity of water.
 Water containing hardness, gives wine red colouration with Eriochrome Black –T
(EBT) at pH 9-10.

Role of buffer solution for hardness test

Indicator Eriochrome Black –T or EBT (an alcoholic solution of blue dye), forms
unstable wine-red complex with Ca2+ and Mg2+ ions. However, this indicator is effective at a pH
of about 10. When EBT is added to hard water buffered to a pH of about 10 (NH 4OH-NH4Cl
buffer), a wine red unstable complex is formed. During the course of titration against EDTA
solution, EDTA combines with Ca2+ or Mg2+ ions form stable complex and releasing free EBT.

Hardness of water can be classified into two types.

(i) Temporary (or) Carbonate (or) Alkaline hardness
(ii) Permanent (or) Non-carbonate (or) Non-alkaline hardness.
(i) Temporary (or) Carbonate (or) Alkaline hardness
This is due to the presence of bicarbonates of calcium and magnesium. It can be
removed by boiling of water, when bicarbonates are decomposed yielding insoluble
carbonates or hydroxides, which are deposited as a crust at the bottom of vessel. This type of
hardness is also known as carbonate or alkaline hardness.
 Temporary hardness can also be removed by addition of calculated amount of lime
[Ca(OH)2].
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + 2H2O

(ii) Permanent (or) Non-carbonate (or) Non-alkaline hardness

This is due to the presence of chlorides and sulphates of Ca and Mg. It cannot be removed
by boiling because they are highly soluble in water. Hence it is called as permanent hardness. But
it can be removed by chemical methods like Lime –soda process, Zeolite and demineralisation
process
a) Lime – soda process

b) Zeolite process
CaSO4 + Na2Ze CaZe + Na2SO4
Soda
Zeolite
Total hardness
The sum of temporary hardness and permanent hardness is called the total hardness.
1.4.1 Degree of Hardness
Hardness of water is never present in the form of CaCO3 because it is insoluble in water.
The concentration of hardness is usually expressed interms of CaCO3 equivalents.
CaCO3 is used as a standard because of the following reasons.
 Its molecular weight is 100 and equivalent weight is 50 which are whole numbers.
 It is the most insoluble salt that can be precipitated in water treatment.
Thus, equivalent of CaCO3

Mass of hardness producing substance×Molecular weight of CaCO3


Molecular weight of hardness producing salt
 Mass of hardness producing substance×100
 mg / lit
Molecular weight of hardness producing salt
Note: CaCO3 equivalents mode permits easy addition and subtraction of concentrations of
hardness-causing constituents, since its mole mass is 100.

Molecular weights of hardness producing substances

S. No Hardness producing substances Molecular weight
1. Ca(HCO3)2 162

2. Mg(HCO3)2 146

3. CaCO3 100

4. MgCO3 84
1.4.2 Units of
5. CaSO4 136
Hardness
The 6. MgSO4 120 following
are the
7. CaCl2 111 common
units used
8. MgCl2 95 in hardness

9. Mg(NO3)2 148

10. CO2 22
11. HCO3- 61
12. OH- 17
13. CO32- 60
14. NaAlO2 82
15. Al2(SO4)3 342
16. FeSO4. 7 H2O 278
17. H+ 1
18. Ca2+ 40
19. Mg2+ 24
measurements.
(i) Parts per million (ppm)
It is the number of parts of CaCO3 equivalent hardness present per million (106) parts of
water.
(ii) Milligrams per litre (mg/lit)
 It is defined as the number of milligrams of CaCO3 equivalent hardness present in one
litre of water.
(iii) Clarke’s degree (ºCl)
The number of parts of CaCO3 equivalent hardness present in 70,000 parts of water is
called Clarke’s degree.
(iv) Degree French (ºFr)
The number of parts of CaCO3 equivalent hardness in 105 parts of water is called degree
French.
Relationship between various units of hardness
1 ppm = 0.1ºFr = 0.07 ºC = 1 mg/lit
1.4.3 Problem Based on Hardness
Problem 1: A sample of water contains 120 mgs of MgSO4 per liter. Calculate the hardness in
terms of CaCO3 equivalents.
Solution:
Known:
The amount of MgSO4= 120 mgs/lit
The molecular weight of CaCO3 = 100

Amount of MgSO 4 × Molecular weight of CaCO 3

¿
Molecular weight of MgSO 4
120 ×100
=
120
= 100 mgs/lit

Problem 2: If a sample of water contains 50 mgs of Ca2+ ions per liter, calculate its hardness in
terms of CaCO3 equivalents.
Known:
The amount of Ca2+ = 50 mgs/lit
The molecular weight of Ca2+= 40
The molecular weight of CaCO3 = 100

50 ×100
=
40
= 125 mgs/lit

Problem 3: A water sample contains 204 mgs of CaSO 4 and 73 mgs of Mg(HCO 3)2 per liter.
What is the total hardness in terms of CaCO3 equivalents?
Name of the hardness Amount in Molecular Amount equivalent to CaCO3
 producing salt mgs/lit weight
204 ×100
CaSO4 204 136 = 136
= 150 mgs/lit
73 ×100
Mg(HCO3)2 73 146 = 146
= 50 mgs/lit
Temporary Hardness = Mg(HCO3)2= 50 mgs/lit
Permanent Hardness = CaSO4 = 150 mgs/lit
Total Hardness = Mg(HCO3)2 + CaSO4
= 50 + 150 = 200 mgs/lit
Problem 4: Calculate the carbonate and non-carbonate hardness of a sample of water
containing the dissolved salts as given below in mgs/lit. Mg(HCO 3)2 = 7.3, Ca(HCO3)2 = 40.5,
CaSO4 = 13.6, MgCl2 = 21.75 and NaCl = 50.
Name of the hardness Amount in Molecular Amount equivalent to CaCO3
producing salt mgs/lit weight
7.3 ×100
Mg(HCO3)2 7.3 146 = 146
= 5 mgs/lit
40.5 ×100
Ca(HCO3)2 40.5 162 = 162
= 25 mgs/lit
13.6 × 100
CaSO4 13.6 136 = 136
= 10 mgs/lit
21.75 ×100
MgCl2 21.75 95 = 95
= 22.9 mgs/lit
NaCl does not contribute any hardness to water.
NaCl 50
Hence it is ignored.

Temporary Hardness = Mg(HCO3)2 + Ca(HCO3)2= 5 + 25 = 30 mgs/lit

Permanent Hardness = CaSO4 + MgCl2 = 10 + 22.9 = 32.9 mgs/lit
Total Hardness = 30 + 32.9 = 62.9 mgs/lit

1.5 WATER FOR INDUSTRIES

Specification for Industrial water
The quality of water required for industries depends upon the requirements of a particular
industry. But in general it can be stated that about 80% industrial water are used for cooling
purposes and not necessarily be of high quality. But the water required for processing industry
must be treated according to its end use. Hence each industry has its own specification for water
which is then treated accordingly.

S.No Purpose Specifications of water Disadvantages

1. Boiler feed Very soft, should contain least Hard water for scale on boiler
water amount of nitrate, organic walls, which reduce the efficiency
matter, dissolved salts and of the boiler. Hard water may cause
 alkalies priming, foaming and caustic
embrittlement.
2. Cooling Must not promote the growth of The spray nozzeles of cooling
systems slime and algae. Should have systems or circulating pumps get
least amount of dissolved gases. logged. Dissolved gases may
accelerate corrosion.
3. Alcoholic Should be very pure, free from Should confirm to the standards of
distilleries pathogenic bacteria. Should not drinking water. Alkalinity tends to
be alkaline neutralize the fruit acids and
modifies the taste.
4. Confectionary Free from pathogenic bacteria, -
dairies & colourless & odourless
Allied
industries
5. Laundries Should be as soft as possible Hard water consumes lot of soaps
and free from Mn & Fe and detergents. Mn & Fe may cause
staining on the cloth due to the
formation of iron soap.
6. Paper Mills Free from hardness and Hardness producing ions may react
alkalinity, SiO2, lime & with chemical used for paper. SiO2
magnesia. may produce cracks.
7. Textiles Free from hardness causing Hard water precipitates basic dyes
substances and Fe & Mn and decrease the solubility of acidic
dyes. These salts produce insoluble
precipitates which stain the cloth
and cause uneven dying.
8. Pharmaceutica Very pure, free from any Salts present in hard water may
l Industry pathogenic bacteria confirming react with the chemicals to form
to the standards of portable undesirable products.
water. Very soft water.

1.6 WATER QUALITY PARAMETERS

Water quality maintaining and monitoring has become an important part of sustainable
development. Many organic constituents may present in water and measurement of all of them
may be practically difficult. Organic pollution is therefore indicated by the non-parametric tests
such as Chemical Oxygen Demand (COD) or Total Organic Carbon (TOC). The parameters to be
measured are the following: total organic carbon, biochemical oxygen demand (BOD), cyanide,
pesticides, suspended solids, nitrogen, fluoride, cadmium, chromium, copper, lead, nickel, zinc,
mercury, boron, dissolved oxygen (DO), pH value, and coliform bacteria. Additional information
such as total hardness, alkalinity, calcium hardness, sulphate, phosphate, sodium, potassium etc
may be also needed if the objective is to evaluate the influence of pollution control measures on
the cost of water treatment.
 (i). Physical parameters
(ii). Chemical parameters
(iii). Biological parameters

(i). Physical parameters

(a) Colour: Colour is a shade imparted by organic or inorganic material, which change
the appearance of the water.
Sources
Organic sources: Algae, organic dyes etc.,
Inorganic sources: Fe & Mn and inorganic dyes
(b) Tastes and odour
Disagreeable odours and tastes are objectionable for various industrial process such as
food products, textiles, paper, pulb etc.,
Sources
Organic sources: Algae, decaying vegetation etc.,
Inorganic sources: Amines and sulphides etc.,
(C) Turbidity and sediments
Turbidity is the reduction of clarity of natural water due to the presence of finely divided,
insoluble impurities suspended in water.
Sources
Organic sources: finely divided vegetable and animal matters, oils, fats, micro-organisms
etc.
Inorganic sources: Clay, silica, ferric hydroxide & sulphur etc.,
(ii). Chemical parameters
(a) pH
The hydrogen ion concentration is represented by the ph value, which is defined as
PH = - log10 [H]+
The drinking water recommended pH is 6.5 to 8.5.
The rain water contaminated by SOx and NOx will have acidic pH.
(b) Acidity
Acidity of water is a measure of its base-neutralizing ability
The acidity in water is usually imparted by the dissolved CO2 (or) by the mineral acids.
Sources
(i) Mineral acids: FeS2
(ii) Carbon dioxide: Industrial smoke, smoke from vehicles
(c) Alkalinity
Alkalinity of water is a measure of its acid-neutralizing ability.
The alkalinity of water is imparted by the hydroxides, carbonates and bicarbonates.
Sources
Industrial like fertilizers, detergent, leather, and paint.
 (d) Fluorides
Fluoride is found in ground water as a result of dissolution from geologic formulations.
Sources
(i) Fluoride containing minerals
(ii) Contaminated domestic sewage, run-off from agricultural lands
(e) Nitrogen, Chlorides, Sulphates, Nitrates, Arsenic and other inorganic chemicals.
(iii). Biological impurities
Micro-Organisms
 More abundant in surface waters, where as in deep well waters. The bacterial count is
very low or even absent.
 The growth of these organisms in water used for industrial purpose, may cause
serious problems.
 Organic growths in water generally take place at temperature ranging from 10 oC-
35oC.

Specification for drinking water

1. Water should be clear, odourless, cool and pleasant to taste.
2. Turbidity of water should not be exceed 10 ppm.
3. pH of the water should be in the range of 7.0 – 8.5.
4. Chlorides and sulphates < 250 ppm
5. Total hardness of water and dissolved solids < 500 ppm
6. Fluoride content < 1.5 ppm
7. The water must be free from diseases producing bacteria & dissolved gases like H2S.
8. Water should be free from minerals like Pb, Cr, Mn and arsenic salts.

1.7 CHARACTERISTICS (OR) TESTING OF RIVER WATER (WASTE WATER)

(a) Dissolved Oxygen (DO)

The amount of oxygen dissolved in a given quantity of water at a particular pressure and
temperature.
Significance of DO
 Do is vital for the support of fish and other aquatic life in river water
 It determines whether the biological changes are brought about by aerobic or anaerobic
micro-organisms.
 DO determines serve as the means of control of river pollution
 A minimum level of DO must be maintained in river water 4mg/lit.

(b) Biological Oxygen Demand (BOD)

Biological oxygen demand (BOD), the most widely used parameter, is a measure of the
amount of oxygen used by indigenous microbial population in water in response to the
introduction of degradable organic material. This parameter depends on water characteristics:
dilution, essential nutrients (N, P, K, Fe, etc), and bacteria seed. The 5-day BOD (BOD 5) is most
widely used. The BOD5 of natural water is related to the dissolved oxygen concentration, which
is measured at zero time and after 5 days of incubation at 20 °C. The difference is the dissolved
oxygen used by the microorganisms in the biochemical oxidation of organic matter. The BOD 5
can be calculated as BOD5 = D0 - D1, in which the BOD5 is in mg/L and D0 and D1 are the
dissolved oxygen concentration in mg/L at time 0 and 5 days, respectively.
Typical concentration of BOD5 for streams and rivers throughout the world are < 2 to 15 mg/ L
and the observed range is < 2 to 65 mg/L.
Significance of BOD
 It is an important indication of the amount of organic matter present in the river water.
 Complete oxidation occurs in indefinite period.
 The rate of oxidation and demand depends on the amount and type of organic matter
present in river water.

(c) Chemical Oxygen Demand (COD)

COD is the amount of oxygen required for chemical oxidation of organic matter using some
oxidizing agent like K2Cr2O7 and KMnO4.
The chemical oxygen demand (COD) test of natural water yields the oxygen equivalent of the
organic matter that can be oxidized by strong chemical oxidizing agent in an acidic medium.
Potassium permanganate is the oxidizing chemical. Silver sulfate is added as a catalyst and to
minimize the interference of chloride on the COD test. Mercuric sulfate is also added to inhibit
interferences of metals on the oxidation of organic compounds. The reaction of the dichromate
with organic matter is presented here in general way:
Organic matter (CaHbOc) + Cr2O72- +H¯ 2Cr3+ + CO2 + H2O
The COD observed in natural streams and rivers is < 2 mg/L to 100 mg/L.
Significance of COD
 It is carried out to determine the pollutional strength of river water.
 It is rapid process and takes only 3 hours.

1.8 ESTIMATION OF HARDNESS BY EDTA METHOD/ COMPLEXOMETRIC

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 (N 1) 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.
N1 V1 = N2 V2
Where, N1 = Normality of Standard Hard water (0.01M), V 1 = Volume of Standard Hard
water (20 ml), N2 = Normality 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.
N 2 V2 = N 3 V3
Where,
N2 = Normality of EDTA,
 V2 = Volume of EDTA (Yml).
N3 = Normality of sample water,
V3 = Volume of Sample water (20 ml).
Total Hardness = N3 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
= N3 × 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 (V 4)
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.
N2 V2 = N4 V4
Where, N2 = Normality of EDTA,
V2= Volume of EDTA (Z ml).
N4 = Normality of Permanent hard water,
V4 = Volume of Permanent hard water (20 ml)
Permanent Hardness = N4 × Molecular weight of CaCO3 (100) × One Litre (1000ml)
= N4 × 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 CaCO 3 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.
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.
1.9 BOILER FEED WATER
(Water for steam production)
Water is used directly or indirectly in many industrial processes. The problem of
preparing feed water for boilers is common to many industries. Its importance and complexity is
obvious from the large number of technical investigations made in this field.
Boilers are operated under different pressures and greater the operating pressure and more
rigorous. The operating pressures for different types of boilers given below:
 Low – pressure boilers – upto 200 1b/sq.in
 Intermediate pressure boilers – 200-500 1b/sq.in
 High pressure boilers – 500-2000 1b/sq.in
 Very high pressure boilers – 2000-3200 1b/sq.in
 Supercritical boilers – Above 3209 1b/sq.in
 In industries, water is mainly required for cooling and steam generation purposes. The
water used for cooling purposes need not to be of high quality and hence requires very less
treatment. Sometimes supplies of water for cooling purposes are used without any treatment.
On the other hand water required for boiler feed purposes i.e., for steam generation should
be very high quality and they requires a lot of treatment. However in treatment of boiler feed
water, total elimination of all the impurities is generally not required. Only those impurities,
which lead to certain problems, are eliminated or kept within the prescribed range.
Untreated water, containing impurities may lead to the following problems in boilers
 Scale and sludge formation
 Priming and foaming
 Caustic embrittlement
 Boiler corrosion

1.9.1 SCALE AND SLUDGE FORMATION IN BOILERS

In boilers, water evaporates continuously and the concentration of the dissolved salts
increases progressively. When their concentrations reach saturation point, they are thrown out of
water in the form of precipitates on the inner walls of the boiler. If the precipitation takes place in
the form of loose and slimy precipitate, it is called sludge. On the other hand, if the precipitated
matter forms a hard, adhering crust/coating on the inner walls of the boiler, it is called scale.
1. Sludge
Sludge is a soft, loose and slimy precipitate formed within the comparatively colder
portions of the boiler and collects in areas of the system where the flow rate is slow or at bends.
Sludge are formed by substances which have greater solubility in hot water than in cold water,
e.g MgCO3, MgCl2, CaCl2, MgSO4, etc.
Disadvantages of sludge formation
Sludges are poor conductor of heat, so tend to waste a portion of heat generated.
 If sludges are formed along with scale, then former gets entrapped in the latter and both
get deposited as scales.
 Excessive sludge formation disturbs the working of the boiler. It settles in the regions of
poor water circulation such as pipe connection, plug opening, gauge-glass connection,
thereby causing even choking of the pipes.
Prevention of sludge formation
 By using well softened water.
 By frequent ‘blow-down operation’ i.e. drawing off a portion of the concentrated water by
fresh water.
 Fig: (a) Sludge in boiler (b) Scale in boiler
2. Scales
Scales are hard deposits, which stick very firmly to the inner surface of the boiler. Scales
are difficult to remove, even with the help of hammer and chisel. Scales are the main source of
troubles. Scales are formed by substances like Ca(HCO3)2, CaSO4 and Mg(OH)2.
(i) Decomposition of calcium bicarbonate
In low pressure boilers calcium bicarbonate decompose to give CaCO3 soft scale
low pressure boilers
Ca(HCO3)2 CaCO3 + H2O + CO2
soft scale
(insoluble)

But in high-pressure boilers, CaCO3 is soluble due to the formation of Ca(OH)2.

(ii) Deposition of Calcium Sulphate

The solubility of calcium sulphate in water decreases with rise of temperature. Thus,
solubility of CaSO4 is 3,200 ppm at 15oC and it reduces to 55 ppm at 230oC and 27 ppm at
320oC. In other words, CaSO4 is soluble in cold water, but almost completely insoluble in super-
heated water. Consequently, CaSO4 gets precipitated as hard scale on the heated portions of the
boiler. This is the main cause of scales in high-pressure boilers.

(i) Hydrolysis of magnesium salts

Dissolved magnesium salts undergo hydrolysis (at prevailing high temperature inside the
boilers) footing magnesium hydroxide precipitate, which forms a soft scale.
MgCl2 + 2 H2O Mg(OH)2 + 2HCl
(ii) Presence of silica
Silica present in small quantity get deposited as calcium silicate (CaSiO3) or magnesium
silicate (MgSiO3) hard scales, which are difficult to remove. One important source of silica in
water is the sand filter.
Disadvantages of scale formation:
(i) Wastage of fuel: Scales have a low thermal conductivity, so the rate of heat transfer from
boiler to inside water is greatly decreased. In order to provide a steady supply of heat to
water, excessive or over heating is carried out and this causes increase in fuel
consumption. The wastage depends upon the thickness and the nature of scale.
Thickness of scale (mm) 0.325 0.625 1.25 2.5 12
Wastage of fuel 10% 15% 50% 80% 150%
(ii) Lowering of boiler safety: Due to scale formation, over-heating of boiler is to be done in
order to maintain a constant supply of steam. The over-heating of the boiler tube makes
the boiler material softer and weaker and this causes distortion of boiler tube and makes
the boiler unsafe to bear the pressure of the steam, especially in high-pressure boilers.
(iii) Decrease in efficiency: Scales may sometimes deposit in the valves and condensers of
the boiler and choke them partially. This results in decrease in efficiency of boiler.
(iv) Danger of explosion: When thick scales crack, due to uneven expansion, water comes
suddenly in contact with over-heated iron plates. This develops a large amount of steam
suddenly with high pressure, which may even cause explosion of the boiler.
Removal of scales:
 Loosely adhering scale are removed by scrapping with the help of scraper or piece of wood
or wire brush,.
 Brittle scale are removed by giving thermal shocks (i.e. heating the boiler and then
suddenly cooling with cold water).
 Hard and adherent scales are removed by using proper chemicals.
(eg) a. 5-10% HCl removes CaCO3 scales.
b. EDTA removes CaSO4 scales.
 By frequent blow-down operation, if the scales are loosely adhering.
 By internal or external conditioning of boiler feed water.
Comparison of Scale and Sludge
S. No Sludge Scale
1. Loose, slim, non-adherent Hard, thick, strong adherent
precipitate. precipitate.
2. Due to salts like MgSO4 , MgCl2. Due to salts like CaSO4, Ca(HCO3)2.

3. Due to poor conductance, they Due to poor conductance, they

decrease the boiler efficiency to decrease the boiler efficiency to
lesser extent and causing chocking in maximum extent, cause reduced fuel
the pipelines. economy , improper boiling, boiler
explosion etc.
 4. It can be prevented by periodical It can be prevented by special methods
replacement of concentrated hard like
water by fresh water. This process is  External treatment of water.
known as “blow down” method.  Internal treatment of water.
 Mechanical hard scrubbing
methods.

1.9.2 PRIMING & FOAMING

Priming: When steam is produced rapidly in boilers the steam velocity suddenly increases and
some droplets of liquid water are carried along with steam. Steam containing droplets of liquid
water is called wet steam. The process of wet steam formation is called Priming.

Priming is caused by

Presence of large amount of dissolved solids.

 High steam velocity.

 Sudden boiling.
 Improper boiler design .

Priming can be prevented by

 Using treated water.

 Controlling the velocity of steam.
 Fitting mechanical steam purifiers.
 Maintaining low water level.
 Good boiler design.

Foaming: Oil or any other polymeric substance present in boiler feed water, reduces surface
tension of water forming bubbles which do not break easily in boilers giving a foam appearance.
This process is called foaming.

Foaming is caused by

 Presence of oil & grease.

 Presence of finely divided sludge particles.

Foaming can be prevented by adding coagulants like sodium aluminate, ferrous sulphate etc.

1.9.3 CAUSTIC EMBRITTLEMENT

Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler water usually
contains a small proportion of Na2CO3. In high pressure boilers this undergoes decomposition to
give NaOH. This NaOH flows into the minute hair cracks and crevices, usually present on the
boiler material, by capillary action and dissolves the surrounding area of iron as sodium ferroate.
This causes brittlement of boiler parts, particularly stressed parts like bends, joints, rivets, etc.,
causing even failure of the boiler.

Na2CO3 + H2O 2 NaOH + CO2

Fe + 2NaOH Na2FeO2 + H2

Caustic embrittlement can be prevented by i) using sodium phosphate as softening agent instead
of sodium carbonate. Ii)by adding tannin, lignin to the boiler water, which blocks the cracks.

1.9.4 BOILER CORROSION

Boiler corrosion is decay of boiler material by chemical or electrochemical attack of its

environment. Boiler corrosion is due to presence of

 Dissolved oxygen
 Dissolved carbon dioxide
 Dissolved salts like magnesium chloride

1. Dissolved oxygen : When water containing dissolved oxygen is fed into boilers the following
reaction occurs corroding the boiler material (rust formation)

2Fe + 2H2O + O2 2Fe(OH)2

4Fe(OH)2 + O2 2[Fe2O3. 2H2O]

Dissolved oxygen can be reduced

i) By adding hydrazine / sodium sulphite

N2H4 + O2 N2 + 2H2O
2Na2SO3 + O 2 2Na2SO4

ii) By mechanical deaeration method.

2. Dissolved carbon dioxide : When water containing bicarbonates is heated, carbon dioxide is
evolved which makes the water acidic. This is detrimental to the metal. It leads to corrosion
called of boiler material.

Ca(HCO3)2 CaCO3 + H2O + CO2

CO2 + H2O H2CO3

Prevention methods for removing dissolved carbon dioxide

By treatment with ammonium hydroxide

2NH4OH + CO2 (NH4)2CO3 + H2O

Can be removed by mechanical deaeration method along with oxygen.

3. Dissolved MgCl2: Acids produced from salts that are dissolved in water are mainly
responsible for the corrosion of boilers. Salts like magnesium and calcium chloride undergo
hydrolysis at high temperature to give HCl, which corrodes the boiler. Presence of HCl is more
damaging due to chain reaction.

MgCl2 can be removed by i) internal conditioning and ii) external conditioning

MgCl2 + 2H2O Mg(OH)2 + 2HCl

Fe+ 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl

Removal of acids by neutralization

Corrosion by acids can be avoided by the addition of alkali to the boiler water.

HCl + NaOH NaCl + H2O

1.10 TREATMENT OF BOILER FEED WATER (SOFTENING OR CONDITIONING

METHODS)
Water used for industrial purposes should be free from hardness producing substances,
suspended impurities and dissolved gases etc. The process of removing hardness producing
salts from water is known as softening (or) conditioning of water.
Methods of softening: (i) Internal treatment (ii) External treatment
1.10.1 INTERNAL CONDITIONING (TREATMENT or SEQUESTRATION)
It is the process of removal of scale and sludge by adding chemicals directly in to the
boiler. In this process, an ion is prohibited to exhibit its original character by ‘complexing ‘or
converting it into other more soluble salt by adding appropriate reagent. The reagents
(chemicals) added for this purpose are called Boiler compounds.
This can be done by two processes.
i. Appropriate chemicals are added to the boiler water to precipitate the scale-forming
impurities in the form of ‘sludges’ which can be removed by blow-down operation.
ii. Problem causing cations are converted into compounds that will stay in “dissolved
form” in water and thus do not cause any harm.
Important internal conditioning/treatment methods are
(i) Carbonate conditioning
(ii) Phosphate conditioning
(iii) Calgon conditioning
(iv) Colloidal conditioning
(v) Treatment with sodium aluminate
(i) Carbonate conditioning: In low-pressure boilers, scale-formation can be avoided by
adding sodium carbonate to boiler water, when CaSO4 is converted into calcium
carbonate in equilibrium.

Consequently, deposition of CaSO4 as scale does not take place and calcium is
precipitated as loose sludge of CaCO3, which can be removed by blow-down
operation.
(ii) Phosphate conditioning: In high-pressure boilers, scale formation can be avoided by
adding sodium phosphate, which reacts with hardness of water forming non-adherent
and easily removable, soft sludge of calcium and magnesium phosphates which can
be removed by blow - down operation.

Generally 3 types of phosphates are employed.

The main phosphates employed are (a) NaH 2PO4, sodium dihydrogen phosphate
(acidic) (b) Na2HPO4, disodium hydrogen phosphate (weakly alkaline) (c) Na 3PO4,
trisodium phosphate (alkaline).

S.No Types Nature Uses

1. Trisodium phosphate (Na3PO4) Too alkaline Used for too acidic
water
2. Disodium hydrogen phosphate Weakly alkaline Used for weakly
(Na2HPO4) acidic water
3. Sodium dihydrogen phosphate Acidic Used for too alkaline
(NaH2PO4) water
(iii) Calgon conditioning: Calgon is sodium hexa meta phosphate, Na2 [Na4(PO3)6].It
reacts with Ca2+ ions forming soluble complex compound and prevents the formation
of scale.

(iv) Colloidal conditioning: In low-pressure boilers, scale formation can be avoided by

adding organic substances like kerosene, tannin, agar-agar (a gel) which get coated
over the forming precipitates, thereby yielding non-sticky and loose deposits, which
can easily be removed by pre-determined blow-down operations.
(v) Treatment with sodium aluminates (NaAlO2): Sodium aluminate gets hydrolysed
yielding NaOH and a gelatinous precipitate of aluminium hydroxide.
 The sodium hydroxide, so-formed, precipitates some of the magnesium as Mg(OH)2

The flocculent precipitate of Mg(OH)2 and Al(OH)3 produced inside the boiler entraps
finely suspended and colloidal impurities, including oil drops and silica. The loose precipitate
can be removed by pre-determined blow-down operation.

1.10.2 EXTERNAL TREATMENT:

The process of removing hardness producing salts from water prior to feeding into the
boiler is known as external treatment (or) external conditioning. The external treatment of water
can be done by following methods
(i) Zeolite (or) permutit process
(ii) Ion-exchange
1. Zeolite or Pemutit Process
Zeolites are naturally occurring hydrated sodium alumino silicates (Na2O.Al2O3.xSiO2.
yH2O). They are of two types natural and synthetic zeolite. The natural zeolite that is used for
water softening is gluconites or greensand. Synthetic zeolites are porous and possess a gel
structure known as Permutit. Synthetic zeolites possess higher exchange capacity per unit
weight compared to natural zeolites. It is mostly used in water softening and capable of
exchanging reversibly its sodium ions for hardness producing ions in water. In short, it is
represented as Na2Ze.
Process
In this method, hard water is percolated at a specified rate through a zeolite bed where the
hardness causing ions (Ca2+& Mg2+) are retained by the zeolite as Ca Ze & Mg Ze. While the
outgoing water contains sodium salts.
 Fig 4: Zeolite process
The reactions taking place during the softening process

When zeolite is completely converted into calcium and magnesium zeolite, it ceases to
soften the water. It gets exhausted. At this stage, the supply of hard water is stopped and the
exhausted zeolite is regenerated by treating the bed with concentrated 10% brine (NaCl) solution.

The regenerated zeolite can be used again.

Advantages
 The hardness of water produced is nearly about 10ppm.
 The equipment used is compact and occupies less space.
 It is quite clean and rapid process that requires less time for softening.
 Less skill is needed for maintenance as well as operations.
 Impurities are not precipitated, so there is no danger of sludge
formation.
 The process automatically adjusts itself to water of different hardness.
Disadvantages
 Acidic water cannot be treated because it damages the bed due to the basic nature of
zeolite.
 Turbid water cannot be treated. Otherwise it clogs the pores of the bed and making it
inactive.
 Water containing Fe and Mn salts cannot be treated because they form stable zeolites
which is difficult to regenerate.
 The soft water contains excess sodium salts which leads to caustic embrittlement.
2. Demineralization (or) Ion – Exchange (or) De-Ionization Process
It is the process of removing mineral salts from water by using the ion exchange resins.
Mineral ions like cations of calcium, sodium, copper, iron, etc and anions such as chloride,
sulphate, nitrate, etc are commonly present in raw water. This process is generally carried out
by using ion exchange resins, which are long chain, cross linked, insoluble organic polymers
with micro porous structure. The functional groups attached to the chains are responsible for
the ion exchanging property.
The ion exchange resins are classified in to

a) Cation exchanger

b) Anion exchanger
a) Cation exchanger

These resins are mainly styrene divinyl benzene copolymers, which on sulphonation or
carboxylation, become capable to exchange their hydrogen ions with the cations in the water.
Such resins have acidic functional groups like – SO3H, - COOH, - OH (phenolic) capable of
exchanging the cationic portion of minerals by their hydrogen ions and hence they are termed as
cation exchangers.
Eg: Amberlite IR-120, Dowex – 50
Cation exchanger is represented as RH +
b) Anion exchanger
These resins are styrene-divinyl benzene or amine-formaldehyde copolymers that contain
basic functional groups like amino or quaternary ammonium (-+NR3) or quaternary phosphonium
or tertiary sulphonium groups an integral part of the resin matrix. These resins after treatment
with dilute NaOH solution, become capable of exchanging their OH- ions with anions in water.
Ex: Amberlite – 400, Dowex-3
Anion exchangers are represented as R+OH-
The hard water is first passed through a cation exchange resin, where H + ions of resin has
been replaced by the cations present in hard water.

The cation free water is then passed through the anion exchange resin, where OH - ions of
resin has been replaced by the anions (Cl-, SO42-, HCO3 – etc.) present in hard water.

The water finally coming out of the ion exchangers (cation & anion) will be completely
free from all the ions. This water is called demineralised or deionised water.

Process :
 Raw
water

Cation
exchanger Anion
exchanger

Acid for Alkali for

regeneration regeneration

Deionised
water

Fig: Demineralization of water

Regeneration

When capacities of cation and anion exchangers to exchange H+ and OH- ions are lost,
then they are said to be exhausted. The exhausted cation exchange column is regenerated by
passing a solution of dilute HCl or H2SO4.

Similarly, the exhausted anion exchange column is regenerated by passing a solution of

dilute NaOH solution.

Advantages
 It can be used to soften highly acidic and alkaline water.
 It produces water of very low hardness (2 ppm). So, the treated water is very good for use
in high pressure boilers.
 User friendly, low maintenance and easy to install.
Disadvantages
 Capital cost is high because the chemical and equipment are costly.
 If water contains turbidity then the efficiency of the process get reduced.
 Water containing Fe and Mn cannot be treated because they form stable compound with
the resin.
Note: Cation exchangers are easily attacked by alkalis; whereas all types of ion-exchangers
are not attacked by acids. When water is first passed through a cation exchanger, salts
prevent in water are converted into corresponding acids, which on passing through an anion
exchanger do not harm it and finally get converted into pure water. If reverse sequence is
used, then alkalis, produced on passing water through anion exchanger, harms the cation-
exchanger in subsequent step.
1.11. SPECIFICATIONS FOR DRINKING WATER BIS - WHO STANDARDS

 Diseases related to contamination of drinking-water constitute a major burden on human

health. Interventions to improve the quality of drinking-water provide significant benefits
to health.
 The primary purpose of the Guidelines for Drinking-water Quality is the protection of
public health
Parameters for water quality standards (Domestic water supplies)

S. Parameters BIS USPH WHO

No (Bureau of Indian (United States (World Health
Standards) Public Health) Organization)
1. pH 6.0 – 8.5 6.0 – 8.5 6.0 – 8.5
2. Total Hardness 200 mg/l - 100-200 mg/l
3. Al (Aluminium) 0.03 mg/l - <0.01mg/l
4. Arsenic (As) 0.01 mg/l 0.05 mg/l 0.01 mg/l
5. Cadmium (Cd) 0.003 mg/l 0.01 mg/l 0.01 mg/l
6. Chromium (Cr6+) 0.05 mg/l 0.05 mg/l 0.05 mg/l
7. Cu (Copper) 0.05 mg/l 1.0 mg/l 0.05 mg/l
8. Cyanide (CN) 0.05 mg/l 0.05 mg/l 0.05 mg/l
9. Fe (Iron) 0.3 mg/l <0.3 mg/l 0.3 mg/l
10. Fluoride ((F) 1.0 mg/l 1.5 mg/l 1.5 mg/l
11. Lead (Pb) 0.01 mg/l <0.05 mg/l 0.01 mg/l
12. Mercury (Hg) 0.001 mg/l 0.001 mg/l 0.01mg/l
13. Molybdenum (Mo) 0.07 mg/l - 0.07 mg/l
14. Nickel ((Ni) 0.02 mg/l - 0.07mg/l
15. Nitrate (NO3-) 45 mg/l <10 mg/l 50 mg/l
16. Se (Selenium) 0.01 mg/l 0.01 mg/l 0.01 mg/l
17. Sulphate (SO4) 200 mg/l` 0.1 ppb 200 mg/l

1.12. DOMESTIC OR MUNICIPAL WATER TREATMENT

“Pure water is the world’s first and foremost medicine”
Municipalities must supply potable water, i.e. water which is safe to drink. Water from
various sources such as rivers, lakes etc. do not meet the required characteristics of drinking
water. Drinking water should meet the following criteria for human consumption.
 It should be free from turbidity.
 It should be free from objectionable odour and heavy metal ions (lead,Arsenic, Mercury
etc.)
 It should have potable taste and must be sparking clear.
 It should be free from dissolved gases
 Its alkalinity should not be high and pH should be about 8.0
  It should be free from disease producing microorganism
 It should be reasonably soft in nature
Hence, it has to be treated before it can be used for drinking purpose. The treatment involves
(i) Removal of suspended and colloidal impurities
a. Screening b Aeration c. Sedimentation
d. Coagulation e. filtration
(ii) Removal of micro organisms
Disinfection
(i) Removal of suspended and colloidal impurities
a. Screening:
Raw water is allowed to pass through a screens, having a large number of holes which
retains floating materials (wood pieces, leaves) and allows only water.
b. Aeration :
The process of mixing water with air is called aeration. It is carried out
 To remove dissolved gases like CO2, H2S causing bad odour and taste.
 To remove Fe and Mn salts as insoluble ferric and manganic salts
 To increase the oxygen content in water
c. Sedimentation with coagulation
It is a process of removing suspended impurities by allowing the water to stand
undisturbed for 2-6 hours in big tanks. Most of the suspended matter settles at the bottom,
due to the force of gravity. The clear supernatant water is then pumped out.
However, sedimentation cannot ensure the removal of finely divided particles like clay,
silica, etc. Most of these particles are negatively charged and are in colloidal form which can
be removed by coagulation.
In this method, coagulants like alum, sodium aluminate and ferrous sulphate are added to
water and get hydrolysed to form gelatinous precipitate. This precipitate adsorbs finely
divided particles forming heavy flocs, which settle down easily.

Sodium aluminate is used for treating water having no alkalinity (i.e. pH < 7)

Ferrous sulphate gives good results above pH values of 8.5

d. Filtration:
Water is filtered by passing through filter beds containing fine sand, coarse sand and
gravel. By this, colloidal matter and micro organisms can be removed from water.
 Sand filter consists of a tank containing a thick top layer of fine sand followed by coarse
sand, fine gravel and coarse gravel. The water passes through the filtering medium.
The rate of filtration decreases gradually due to the clogging with impurities in the pores of the
sand bed. When the rate of filtration becomes very slow, the thick top layer of fine sand is
removed and replaced with fresh sand.
2. Removal of micro organisms
Disinfection
After passing through sedimentation, coagulation and filter operations, water still
contains a small percentage of pathogenic bacteria. The process of destroying or killing the
disease producing bacteria from water and making it safe for use is called disinfection.
The chemicals added for this purpose are called disinfectants. The methods available for
disinfection are given below.

Fig: Domestic water treatment process

(i) Boiling: When water is boiled for 10 – 15 min, all harmful bacterial will be killed and water
becomes safe for use.
Disadvantages:
i. Boiling affects the taste of drinking water
ii. It is impossible to employ it in municipal water works
(ii) Sterilization by UV light: Ultraviolet radiations (1000-4000 Å) emitted by mercury lamps
can be used for sterilizing water. The process is not commonly employed because it is highly
expensive. It is generally used for sterilizing swimming pool water because it does not require
any chemicals.
Disadvantages
i. Expensive
ii. Cannot be used for turbid water
(iii) Sterilization by ozone: Ozone is a powerful disinfectant. It is highly unstable. It
decomposes to give nascent oxygen. It is a powerful oxidizing agent and kills the
microorganisms effectively as well as oxidises the organic matter present in water.

Fig: Ozone sterilizer

The process of sterilization takes place in ozone sterilizer as shown in above Fig. 8 The
disinfected water is removed from the top. The contact period is about 10-15 minutes and the
dose strength is 2-3 ppm.
Advantages
Disinfection by ozone simultaneously removes colour, odour and taste without giving any
residue. It is not harmful if added in excess, since it is unstable and decomposes into oxygen.
Disadvantages
i. Expensive and not useful on the large scale
ii. Ozone cannot be stored and has to be prepared in situ

(iv) Chlorination: This is the best and most suitable method of sterilization of water. In this
process, chloride is added directly in the liquid form (or) as bleaching powder. Chlorine reacts
with water to form hypochlorous acid and nascent oxygen. Both are powerful germicides.

When chlorine is added to water, the hypochlorous acid that is formed, reacts with
bacteria and inactivates the enzymes present in the cells of bacteria. These bacteria are
responsible for the metabolic activity of the microorganisms. Since these enzymes are
inactivated, the microorganisms die and the water is sterilized. A chlorinator is a high tower
containing a number of baffle plates. Water and a known quantity of concentrated chlorine
solution are fed from the top of the tower. The chlorinated water is obtained at the bottom (Fig.
9).
 Fig: Chlorinator
(v) By adding bleaching powder: For sterilization, generally 1 kg of bleaching powder is
added to 1000 kilolitres of water and is allowed to stand undisturbed for several hours. The
chemical action produces hypochlorous acid which kills the germs.

(v) Break point chlorination: When sufficient quantity of chlorine is added to water, it first kills
the bacteria and oxidizes all organic and inorganic impurities in water. When chlorine is added
to water, initially it reacts with ammonia resulting in chloramine compounds.
 Fig: Break point chlorination curve
The amount of chloramines increases with the increasing dosage of chlorine. Continual
addition of chlorine oxidizes the chloramine compounds. At this point, the oxidation of
chloramines and other impurities starts. So, there is a sudden fall in the combined residual
chlorine. This minimum is referred to as the break point. The minimum point, or break point,
indicates completion of oxidation of chloramines. Further, chlorination increases the free residual
chlorine. The process of adding chlorine beyond the break point is called break-point
chlorination.
Advantages:
 It removes colour in water due to the presence of organic matter.
 It destroys all the disease producing bacteria,
 It oxidises completely all reducing compounds.
 The output water contains the residual chlorine to the extent of 0.2-0.3 mg/L

1.13. DESALINATION OF BRACKISH WATER - REVERSE OSMOSIS

Desalination is a process of removal of common salts from saline water. Water containing
dissolved solids and having peculiar taste is called brackish water.
Depending on the quantity of dissolved solids, water is graded as
a. Fresh water : < 1000 ppm of dissolved solids
b. Brackish water : > 1000 but < 35,000 ppm of dissolved solids
c. Sea water : > 35,000 ppm of dissolved solids.
Electro dialysis, electrocoagulation and reverse osmosis techniques are commonly used to
treat brackish water. Among them, reverse osmosis has more advantages and widely used to treat
brackish water.
1.13.1. Reverse Osmosis (RO)
When two solutions of different concentrations are separated by a semi-permeable
membrane, solvent flows from the region of lower concentration to the region of higher
concentration. This process is called osmosis.
The driving force responsible for this process is called osmotic pressure.
Method: Thin film of cellulose acetate is used as membrane. This membrane is affixed to
either side of a perforate tube. The pressure of about 15-40 kg cm -2 is applied to sea
water/impure water to force its pure water out through the semipermeable membrane.
If a hydrostatic pressure in excess of osmotic pressure is applied on the higher
concentration side, the solvent flow will be reversed, leaving the dissolved solids on the
concentrated side itself. [(i.e) from a region of higher concentration to a region of lower
concentration]. This process is called Reverse Osmosis.
 Fig: Reverse osmosis Cell
This membrane filtration is called Super-filtration or Hyper-filtration.
The membranes used in reverse osmosis are cellulose acetate, cellulose butyrate.
Advantages
 Life time of the membranes is high.
 Replacement of membranes is easy and quick.
 Removes ionic, non-ionic and colloidal impurities.
 Simple, operating and capital costs are low and hence it can be used to desalinate sea water
for drinking purposes.

1.13.2. Electrodialysis

This method involves the removal of ions from the brine solution by applying direct
current and employing pair of plastic membranes through which ions can pass. From the Fig we
can find that when direct current is passed through saline water, the Na + ions move towards and
cathode while Cl¯ ions move towards the anode through the membrane and collect in the two
side compartments while the central compartment contains pure desalinated water.

Fig. Line diagram of electrodialysis

 To make this process more effective, ions selective membranes are used that allow the
passage of either specific cations or specific anions. These membranes are selective as they are
made up of materials containing fixed functional groups.

Fig. Electrodialysis Cell

An electrodialysis cell as shown in above Fig contains a large number of pair of
membranes and saline water is passed under pressure in electric field applied perpendicular to
the direction of flowing water and concentrated salt solution.
Examples
Ion selective membranes
(i) Cation selective membrane – Poly styrene containing (-SO3H) sulphonic acid group.
(ii) Anion selective membrane – Poly styrene containing tetra ammonium chloride
Advantages
(i) It is the most compact unit, the cost of installation and operation is economical.
(ii) If efficiency is easily available, this process is best suited.

1.14 UPFLOW ANAEROBIC SLUDGE BLANKET (UASB) REACTOR

UASB process is the modified version of the contact process, based on an upward
movement of the liquid waste through a dense blanket of anaerobic sludge. No inert medium is
provided in these systems. The biomass growth takes place on the fine sludge particles, which
then develop as sludge granules of high specific gravity.
The reactor can be divided in three parts
(i) Sludge bed (ii) Sludge blanket (iii) Phase separator (gas-liquid-solid, GLS separator)
provided at the top of the reactor.
(i) Sludge bed
 It occupies about 40 to 60% of reactor volume.
 It consists of high concentration of active anaerobic bacteria (40 – 100 g/L)
 In this zone majority (> 95%) of organic matter get degraded.
  The Wastewater is pumped from the bottom into the reactor where influent
suspended solids and bacterial activity and growth lead to the formation of sludge.
 The microorganisms in the sludge layer degrade organic compounds. As a result,
gases (methane and carbon dioxide i.e. biogas) are released.
 The gases produced causes internal mixing in the reactor. Some of the gas
produced within the sludge bed gets attached to the biological granules.
 The free gas and the particles with the attached gas rise to the top of the reactor.
(ii) Sludge blanket
 It is a zone above the sludge bed and below GLS separator
 It occupies 15 to 25% of reactor volume, where a thin concentration of sludge is
maintained
 The sludge blanket is comprised of microbial granules ( small agglomerations of
microorganisms) of 1 to 3 mm in diameter, because of their weight, resist being
washed out in the upflow
 This zone is important to dilute and further treat the wastewater stream that
bypass the sludge bed portion following the rising biogas.
 Sloped walls deflect material that reaches the top of the tank downwards. The
clarified effluent is extracted from the top of the tank in an area above the sloped
walls

Fig: UASB reactor

(iii) Phase separator
 It occupies about 20 to 30% of the reactor volume.
 The particles that raise to the liquid surface strike the bottom of the degassing
baffles, which causes the attached gas bubbles to be released.
 The degassed granules typically drop back to the surface of the sludge bed.
  The free gas and gas released from the granules is captured in the gas collection
domes located at the top of the reactor.
 Liquid containing some residual solids and biological granules passes into a
settling chamber, where the residual solids are separated from the liquid.
 The separated solids fall back through the baffle system to the top of the sludge
blanket.
The reactions involved in USAB process are
a. Hydrolysis b. Acidogenesis c. Acetogenesis d. Methanogenesis
The anaerobic degradation of complex organic matter is carried out by a series of bacteria
present in the granules. There exists a coordinated interaction among these microbes. The
process may fail if certain of these organisms are inhibited.
The acidogenic bacteria are located at the outer edge of granule (200 μm) with the
syntrophs and methanogens located in the centre. The syntrophic acetogens must be located
within 1-2 μm of methanogens in order to facilitate inter species hydrogen transfer.
a. Hydrolysis: Polymeric materials such as lipids, proteins, and carbohydrates are primarily
hydrolyzed by extracellular, hydrolyses, excreted by microbes into smaller molecules (amino
acids, Fatty acids, monosaccharides, etc)
b. Acidogenesis: The products of hydrolysis are converted into acetate, propionate, butyrate,
lactate, ethanol, carbon dioxide, and hydrogen by acidogenic (Clostridium, aerobacter,
streptococcus) bacteria.
c. Acetogenesis: The acetogenic bacteria metabolizes propionate and other organic acids,
alcohols and certain aromatic compounds (i.e. benzoate) into acetate, CO2 and Hydrogen.
d. Methanogenesis: Methanogens (Ethanogenic bacteria) are physiologically united as
methane producers. They convert acetate and H2/CO2 in to CH4

Fig: UASB process

Advantages (compared to aerobic processes)
 High reduction of BOD
 No energy is required for aeration, which leads to 90% savings in operational costs.
 Significant reductions in investment costs as less treatment units are required.
  The produced CH4 is of interest for energy recovery or electricity production.
 The technologies do not make use of high-tech equipment (less dependent on imported
technologies).
 The process can with stand high hydraulic and organic loading rates.
 The system is compact with hydraulic retention times (HRTs) of 6-9 h, and is, therefore,
suitable for application in urban areas, minimising conveyance costs.
 The sludge production is low, well stabilized and easily dewatered.
 Effluent is rich in nutrients (N and P) and can be used for agricultural irrigation
Disadvantages
 Treatment may be unstable with variable hydraulic and organic loads
 Requires operation and maintenance by skilled personnel; difficult to maintain proper
hydraulic conditions (upflow and settling rates must be balanced)
 Long start-up time to work at full capacity
 A constant source of electricity is required
 Not all parts and materials may be locally available
 Requires expert design and construction
 Effluent and sludge require further treatment and/or appropriate discharge
 Not adapted for cold regions