2010chapter 1WaterTechnology

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Water Technology 1.1
CHAPTER- 1
WATER TECHNOLOGY
1.1 INTRODUCTION
Water is not only essential for human beings, plants and

animals for sustaining life but is also equally important for
agricultural, industrial and other purposes. The important sources
of water are surface water, underground water and rain water.
The increasing population in urban areas results in
concentrated discharge of large quantities of water into rivers,
lakes and estuaries. This results in the purifying capacity of the
receiving water being overtaxed, resulting in gross pollution,
severe nuisance and far reaching economic and health
consequences.
The concern is shown not only by experts and agencies
dealing with the problem of pollution but by the public at large.
Water is one of the abundant available substances in
nature. Water forms about 75% of the matter on earth’s crust. It is
an essential ingredient to both plant and animal life. Moreover it
also enjoys a unique position in industries.
1.2 SOURCES OF WATER
The chief sources of water fall in two main groups,

o Surface water
o Underground water
1.2 Engineering Chemistry-II
1.2.1 Surface Water

Surface water exists as
i) Rain water
ii) River water
iii) Sea water
iv) Lake water
i) Rain water
It is the main source of water obtained as a result of
evaporation of seawater. Rainwater may be the purest form of
water. It is made impure by polluted atmosphere. It contains a
considerable amount of industrial gases (like CO2 , SO2 , NO2
etc.) and suspended solid particles, both of organic and inorganic
origin.
ii) River water
It is the water that flows over the surface of the land.
River water starts from spring water and fed by rainwater. It
flows through different kind of terrain and dissolves the soluble
minerals of the soil. Chlorides, sulphates, bicarbonates of sodium,
calcium, magnesium and iron are some of the major mineral salts
present in river water. River water also contains organic matter,
produced by the decomposition of plants and small particles of
sand and rock suspension.
iii) Sea water
This is the most impure form of natural water. Continuous
evaporation of water makes it continuously richer in dissolved
impurities. It contains sodium chloride, sulphates of sodium,
bicarbonates of potassium, calcium, magnesium and a number of
other compounds.
iv) Lake water
It contains fewer amounts of dissolved materials.
1.2.2 Underground Water

About 9.86% of the total fresh water resources is in the
form of ground water. A part of rain water which falls on earth
surface percolates into the earth and continues it’s journey till it
meets a hard rock where it may be stored or come in the form of
spring. During its downward journey, it dissolves a number of
salts.
1.3 IMPURITIES IN WATER

The main impurities present in water are classified into
three types.
Physical impurities
Chemical impurities
Bacteriological impurities
Physical Impurities include suspended and colloidal impurities

(a) Suspended impurities
- Clay, sand, decayed vegetable and animal matter.
Causes - Make the water turbid.
(b) Colloidal impurities
- Finely divided clay and silica, colouring matter,
waste products, complex proteins, amines etc.,
Causes - Impart colour, odour and taste.
Chemical Impurities include dissolved salts and dissolved gases.

(a) Dissolved salts – Chlorides, sulphates, bicarbonates,
carbonates of Ca, Mg, Na, etc.,
Causes –
(i) CaCl2, CaSO4, Ca (HCO3)2, MgCl2, MgSO4,
Mg (HCO3) 2 make the water hard.
(ii) Mg (HCO3)2, Ca (HCO3)2, Na2CO3, NaHCO3, etc.,

make the water alkaline.
(b) Dissolved gases – Oxygen, carbon dioxide, hydrogen
sulphide etc.,
Causes -
(i) Oxygen accelerates the rate of corrosion.
(ii) CO2 and H2S makes the water acidic and
corrosive.
Bacteriological impurities – Pathogenic microorganism like
bacteria.
Causes – Spread various disease like typhoid, dysentery,
hepatitis etc.,
1.4 TYPES OF WATER

Water is classified into two types based on the property of
it with soap solution as soft water and hard water.
Soft water
Soft water is one that gives good lather readily with soap
solution.
Hard water
Water that does not produce lather with soap readily but
forms an insoluble precipitate like white scum is known as hard
water.
When water with such hardness is used for washing, large

amount of soap is consumed. Thus hardness of water can be
defined as the soap consuming capacity of water.
The reaction can be explained as follows,
2RCOONa + M2+ (RCOO) 2 M + 2Na+

Insoluble soap
Where R = long chain fatty acid like palmitic, oleic and
stearic acid.
M2+ = Ca2+, Mg2+
Common hardness producing salt present in water are

chlorides, sulphates and bicarbonates of Calcium and
Magnesium. i.e., CaCl2, CaSO4, MgCl2, MgSO4,Ca(HCO3)2 and
Mg(HCO3)2 .Their quantity only decides the extent of hardness of
water.
1.5 WATER QUALITY STANDARDS
Water used for drinking purpose should meet certain

quality criteria with respect to appearance (turbidity, colour)
potability (taste, odour), health (bacteria, nitrates, chlorides etc.,)
and toxicity (metals, organics). These criteria are established by
health or other regulating agencies to ensure that the water
quality in a resource is suitable for drinking purposes.
The following table summarises several quality criteria
and their standards for drinking water as suggested by the
following agencies.
1. Indian Council of Medical Research (ICMR)

2. World Health Organization (WHO)
Table 1.1 Standards for Drinking Water
NAME OF AGENCIES
S.NO PARAMETER ICMR WHO

A B A B
1. Colour (Units) 5 25 5 50
2. Turbidity(Units) 5 25 5 25
3. Total dissolved
- - 500 1500
solids
4. pH 7-8.5 - 7-8.5 -
5. Total hardness as
CaCO3 125 350 125 350
equivalents
6. Iron 0.3 1.0 0.3 1.0
7. Manganese 0.1 0.5 0.1 0.5
8. Nitrate 20 50 - 50-100
9. Chloride - - - 250
10. Fluoride 1.0 2.0 0.5 1.0-1.5
11. Sulphate 200 400 200 400
12. Pathogenic Micro 1 1
Organisms coliform coliform
(Coliform) - -
per 100 per 100
ml ml
A Recommended concentration (mg/lit)
B Maximum permissible concentration (mg/lit)
1.6 WATER QUALITY PARAMETERS
The water quality parameters are roughly divided into 3

categories.
1. Physical
2. Chemical
3. Biological
Table 1.2 Various Water Quality Parameters
Physical Chemical Biological

Parameters Parameters Parameters
1. Colour 1. Hardness Pathogenic

microorganisms
2. Turbidity 2. Acidity
3. Taste and 3. Alkalinity

odour
4. Dissolved
4. Total Oxygen
dissolved 5. pH
solids (TDS)
6. Biological
Oxygen demand
(BOD)
7. Chemical
Oxygen
Demand
(COD)
Some of the important Water Quality Parameters are

discussed below.
1.6.1 ALKALINITY
Definition
Alkalinity of water is a measure of its acid neutralizing
ability or it is the tendency of water to accept H+ ions in order to
neutralize it with the supply of OH - ions.
In water analysis, it is often desirable to know the kinds
and amounts of the various forms of alkalinity present in water.
Unit : ppm of CaCO3.
Sources
o Alkalinity in water is due to the presence of bicarbonates,
carbonates and hydroxides of Ca, Mg, Na and K.
o This type of alkalinity is usually introduced into the water
resource by metallurgical industries, chemical industries,
drainage from abandoned mines and from many other
industrial sewage.
Thus, the alkalinity of water may be due to
1. Hydroxide only
2. Carbonate only
3. Bicarbonate only
4. Both hydroxide and carbonates
5. Both carbonates and bicarbonates.
The possibility of hydroxide and bicarbonate existing
together in water is ruled out because they combine with each
other to form carbonate.
OH - + HCO3 - CO3 2- + H2 O
Classification
1. Bicarbonate alkalinity
2. Carbonate alkalinity
3. Hydroxide alkalinity
Sanitary Significance
1) High alkalinity in natural water favours the growth of algae
and phytoplankton’s. Usage of this alkalinity water may
cause some effects on human beings.
2) It is used in evaluating the buffering capacity of waste waters
and sludges.
3) Determines the suitability of water for irrigation.
4) Provides an idea of the nature of salts present.
5) It indicates the corrosion extent of the water.
6) Used in removal of ammonia in air striping.
7) In Water softening
Alkalinity measurements
o Alkalinity may be determined by potentiometric method
or using pH meter or titrimetry using different acid base
indicators.
o Out of these methods, determination of various types and
amounts of alkalinity is easily carried out by titration with
standard hydrochloric acid employing phenolphthalein
and methyl orange as an indicator separately or in

succession.
Estimation of Alkalinity
Titrimetric method is preferred using phenolphthalein and
methyl orange as indicators.
Principle:
Alkalinity of a given water sample can be obtained by
neutralizing the hydroxide, carbonate and bicarbonate ions with
standard acid, using phenolphthalein and methyl orange as
indicators. The phenolphthalein end point at pH 8.3 indicates the
complete neutralization of hydroxide ions and half of carbonate
ions. Further, titration upto the methyl orange endpoint indicates
the neutralization of total alkalinity due to hydroxide, carbonate
and bicarbonate ions.
OH- +H+ H2O (1) Phenolphthalein
2- + -
CO3 + H HCO3 (2) pH = 8 to 9
- +
HCO3 + H H2O + CO2 (3) Methyl orange
The end point with phenolphthalein (P) indicator indicates

the completion of reaction (1) and (2). Whereas the total volume
of the standard acid used from the beginning upto the methyl
orange end point (M) corresponds to the completion of reaction
(1), (2) (3).
From the above, following conclusions may be drawn
1. When P=0, both OH- & CO32- are absent.
2. When P=M, the sample consists of only OH - ions.

3. When P= (1/2)M, the sample consists of only CO3 2-.
CO32- + H+ HCO3-
HCO3- + H+ H2O + CO2
4. When P>(1/2)M, the sample consists of OH- and CO32-.
5. When P<(1/2)M, the sample consists of HCO3- and CO32-.
1.6.2 HARDNESS OF WATER
Hardness is the characteristic of water which does not

give good lather with soap. This property of water is due to the
presence of bicarbonates, chlorides and sulphates of calcium,
magnesium and other salts.
Classification of Hardness of Water
Hardness of water can be classified into two categories.
1. Temporary hardness (or) Carbonate hardness.
2. Permanent hardness (or) Non-Carbonate hardness.
1. Temporary (or) Carbonate hardness

This is caused by the presence of dissolved bicarbonates
of calcium and magnesium. Temporary hardness is mostly
destroyed by mere boiling of water.
During boiling, the bicarbonates are decomposed and
form insoluble precipitates. Carbonates and hydroxides can be
removed by filtration, while CO2 escapes out.
Ca(HCO3)2 CaCO3 + H2O + CO2
Insoluble
Mg(HCO3)2 Mg(OH)2 + 2CO2
Insoluble
2. Permanent (or) Non-Carbonate hardness
This is due to the presence of dissolved chlorides and

sulphates of calcium and magnesium. Unlike temporary hardness,
permanent hardness is not destroyed on boiling.
Total Hardness of Water = Carbonate Hardness +
Non-Carbonate Hardness
(or)
Temporary Hardness +
Permanent Hardness
Expression of Hardness
Hardness of water is expressed in terms of number of
parts of CaCO3 (or) its equivalent present in a particular quantity
of water because
i) CaCO3 is the most insoluble salt which can be
precipitated in water treatment.
ii) Molecular weight of CaCO3 is 100 which is easy for
calculations.
Calcium Carbonate equivalent
Hardness is expressed in terms of CaCO3 (or) its
equivalent. If water contains CaCO3 alone the hardness is a
measure of number of parts of CaCO3. Usually, water contains
some other salts. The amount of these salts is converted in to
their CaCO3 equivalent.
Weight of hardness
CaCO3 producing salt
equivalent
= x Molecular weight of
Molecular weight of CaCO3
the salt
Molecular weights of some hardness producing salts are given

in the following table.
S.No Molecular formula of the Molecular
hardness producing salt weight
2+
1. Ca 40
2. CaSO4 136
3. Ca(HCO3)2 162
4. CaCl2 111
5. CaCO3 100
6. Mg2+ 24
7. MgCO3 84
8. Mg(HCO3)2 146
9. MgCl2 95
10. MgSO4 120
Problems
1. A sample of water contains 120mgs of MgSO4 per litre.
Calculate the hardness in terms of CaCO3 equivalents.
Solution:
Given: The amount of MgSO4 = 120mgs/lit
Weight of hardness
CaCO3 producing salt
equivalent
= x Molecular weight of
Molecular weight of CaCO3
the salt
We know that , the molecular weight of MgSO4 =120.
Thus amount equivalent to CaCO3=120*100/120=100 mg/lit.
2. The analysis of three sample of water gives the following

results. Sample 1 contains 10 mg/ litre of calcium sulphate,
sample 2 contains 10 mg/ litre of magnesium bicarbonate, and
sample 3 contains 10 mg/ litre of magnesium sulphate. Find
which one of the sample is more hard.
Solution:
Sample 1:
10mg/lit calcium sulphate = 10 * 100 / 136
Amount equivalent to CaCO3 = 7.35 mg/lit
Sample 2:
10mg/lit magnesiumbicarbonate = 10*100/146
Amount equivalent to CaCO3 = 6.85mg/lit
Sample 3:
10mg/lit magnesium sulphate = 10 * 100 / 120
Amount equivalent to CaCO3 = 8.26mg/lit
Hence, the sample 3 is more hard.
3. If a sample of water contains 50mgs of Ca2+ ions per litre,
calculate its hardness in terms of CaCO3 equivalent?
Solution:
Given: The amount of Ca2+ ions = 50mg/lit.
We know that, the molecular weight of calcium = 40
Amount equivalent to CaCO3 = 50*100/40 = 125mg/lit.
4. A sample of water on analysis contains 13.6 mg/ litre of
calcium sulphate, 14.6 mg/ litre of magnesium bicarbonate,
12 mg/ litre of magnesium sulphate. Calculate the total
hardness of the sample.
Solution:
In order to calculate the total hardness of the sample,these
salts have to be converted in to their equivalents of CaCO 3.
Molecular Molecular Quantity Equivalent of

formula of the Weight Present CaCO3
salt
13.6*100 = 10
CaSO4 136 13.6
136
14.6 *100 = 10
Mg(HCO3)2 146 14.6
146
12*100 = 10
MgSO4 120 12
120
Temporary Hardness = 10 mg/ litre (Mg (HCO3) 2 alone)
Permanent Hardness = 10+10 = 20 mg/ litre (CaSO4 + MgSO4)
Total Hardness = (Temporary + Permanent) Hardness
=10 + 20 = 30 mg/litre (or) ppm
Units of Hardness
o Parts per million (ppm)
It is the number of parts of calcium carbonate
equivalent hardness per million (106) parts of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 106
parts of water.
o Milligram per Litre (Mg/L)
It is the number of milligram of CaCO3 equivalent
hardness present per litre of water.
1 mg/litre = 1 mg of CaCO3 equivalent hardness in
1 litre of water
0
Cl-degree clerk is the number of parts of calcium carbonate
equivalent hardness per 70000 parts of water. 1ppm = 0.07 0Cl
0
Fr- degree French is the number of parts of calcium carbonate
equivalent hardness per 105 parts of water. 1ppm=0.10Fr
Relationship between PPM and Mg/L

Weight of 1 litre of water = 1 kg
=1000 g
=1000 x 1000 mg
= 106 mg
Thus,
1 mg/litre = 1 mg of CaCO3 equivalent hardness in
1 litre of water
= 1 mg of CaCO3 equivalent hardness per 106 mg
of water.
Hence 1 mg / litre =1 ppm

Disadvantages of Using Hard Water
I. In domestic use
S.No Purpose Specification Disadvantages
i) Washing i) Free from Ca i) It does not lather well.

and Mg.
ii) It produces sticky

ii)Free from iron precipitate of Ca and Mg
salts soaps, which adheres on
the cloth giving spots.
iii) Wastage of soap.
iv) Presence of iron salts
cause staining of cloth.
ii) Bathing Free from It does not lather well,

hardness but produces sticky scum
producing ions on the body. Thus
cleaning quality
decreases.
iii) Cooking Free from i)Boiling point of water

hardness increases hence more
producing salts fuel and time required
for cooking.
ii)It produces unpleasant
taste and muddy-looking
extract.
(If tea is prepared in hard
water)
iv) Drinking Free from i)Bad effect on our

calcium ions digestive system
ii)Forms calcium oxalate
crystal in urinary tracks.
II. In industrial use
S.No Industry Specification Disadvantages
1. Textile & i) Free from iron They produce coloured

dyeing &manganese salts spots on fabrics.
ii) Free from They precipitate basic
calcium and dyes & decrease the
magnesium salts. solubility of acidic
dyes. So dyeing will
not be uniform.
2. Laundries i)Soft water Hard water increases

the consumption of
soaps and detergents.
ii)Free from Fe &
Impart grey or yellow
Mn salts
shades to the fabric.
3. Sugar Free from sulphates They cause difficulties

and alkali in the crystallization of
carbonates. sugar from molasses.
4. Beverages Free from alkaline They will neutralize

salts the fruit acids and
destroy the tastes.
5. Paper and i)Free from Fe & Affect colour and

pulp Mn salts brightness of the
paper.
ii)Free from It increases the ash

content of paper.
hardness
Produces cracks in the
paper.
iii)Free from SiO2.
6. Power i)Non-corrosive Produces corrosion

station ii)Non-scale Scale will act as
cooling forming insulator.
systems
7. Boiler i)Zero hardness Scale prevents

feed efficient heat transfer.
from Lead to boiler

ii)Free
dissolved gases like corrosion.
O2,CO2
III. In steam generation in boilers
S.No Purpose Specification Disadvantages
1. Steam i)Free from Ca & Mg i) Scales and

generation salts. sludge
formation
ii)Free from dissolved ii)Corrosion

gases.
iii)Free from turbidity iii)Priming and

and oil. foaming
iv)Caustic
embrittlement
DISADVANTAGES OF HARD WATER

Disadvantages in Textile industry
The hardness and impurities present in the water affects
the colour, brightness and interferes with the texture of fabric
produced and uniformity in colours dyed.
Disadvantages in Dyeing industry
Textiles need to be dyed in order to get the required
colour. The water used during this process should be soft and
free from organic matter. If hard water is used uniform dyeing
is not possible because hard water decreases the solubility of
acidic and basic dyes. Dyes even precipitate out in such water.
These precipitates form unwanted spots or shades on the fabric.
Organic matter imparts foul smell.
If the water contains Fe, Mn, colour or turbidity, it
causes uneven dyeing and leaves strain on fabrics. Hence, water
should be free from these impurities.
Disadvantages in Laundry
Laundries require soft water, free from colour, Mn and
Fe. Hardness increases the consumption of soaps. Salts of Fe
and Mn impart a grey or yellow shade to the fabric, thereby
spoiling their beauty.
Disadvantages in Washing
Textile industries needs frequent washing right from the
yarn to the fabric. So when hard water is used it does not
produce lather with soap. It produces a sticky scum of calcium
and magnesium soaps. The formation continues until all the
magnesium and calcium ions are removed from hard water. So
after complete removal of Ca and Mg only the soap will start to
lather. This thus results in wastage of soap.
Sticky scum formed adheres on to the yarn, fabric, etc.,
resulting in formation of spots. Also they do not produce the
exact required shades of colour.
Disadvantages in Starch industry:
Hard water causes precipitation of salts which accumulate in

the starch. This reduces the adherence of the starch o the fabric
thus reducing the efficiency. Also Fe & Mn salts produces
yellowish coloration to the starch.
Disadvantages in other industries
Sugar industry
Water containing sulphates, nitrates, alkali carbonates
etc., if used in sugar refining, causes difficulties in the
crystallization of sugar from molasses. It also causes the
formation of precipitate which accumulates in the refined sugar.
Moreover, the sugar so-produced may be deliquescent.
Paper industry
The hardness and impurities present interfere in the
colour, texture and uniformity in papers. So the paper industry
requires water free from
SiO2 - produces cracks in the paper;
Turbidity - Fe and Mn as they affect the brightness and
colour of the paper)
Alkalinity - consumes alum and increases the cost of
production
Calcium and magnesium salts -
increase the ash content of the paper, also
tend to react with chemicals and other
materials employed to provide a smooth and

glossy (i.e. shining) finish to paper.
Pharmaceutical industry
These require ultrapure water. Hard water, if used for
preparing pharmaceutical products, may produce certain
undesirable products in them. This will affect the efficiency of
the drug and sometimes be hazardous.
Bakeries
Organic matter such as fungi, bacteria if present in
water used in bakeries may affect the yeasts. So the quality of
the materials produced is poor.
Beverages require water which should not be alkaline. The
alkalinity destroys or modifies the taste by neutralizing the fruit
acids.
In large number of industries, water is used for the production of

steam in boilers. The water thus used is called as boiler feed
water. The boiler feed water should be free from dissolved
Calcium and magnesium salts. It should not contain any
dissolved gases such as oxygen and carbon-di-oxide.
Estimation of Hardness of Water by EDTA Method

The hardness of water can be estimated by EDTA
method. This is a reliable method because of its greater accuracy.
In this method hardness is estimated by forming complexes.
EDTA is Ethylene diamine tetra acetic acid.
Molecular structure of EDTA

HOOC-H2C CH2-COOH
N-CH2-CH2-N
HOOC-H2C CH2-COOH
In this complexometric method, disodium salt of ethylene
diamine tetra acetic acid is actually used.
Structure of disodium salt of EDTA
NaOOC-H2C CH2-COOH
N-CH2-CH2-N
HOOC-H2C CH2-COONa
Principle
o Disodium salt of EDTA forms complex with
calcium and magnesium ions present in water.
o The indicator used in this titration is Eriochrome
Black-T (EBT) which also form unstable complex
with calcium and magnesium ions present in
water, at pH value about 8-10.
o In order to maintain the pH , buffer solution
[ NH4Cl-NH4OH] mixture is added. Only at this
pH such a complexation is possible.
pH=8-10
Ca2+ / Mg2+ + EBT [Ca / Mg - EBT]

Indicator Unstable complex
(Blue colour) (Wine red)
This wine red colour solution is titrated against EDTA,
EDTA replaces EBT indicator from [Ca / Mg - EBT] complex.
The colour of the solution changes from wine red to steel blue at
the end point.
pH=8-10
[Ca / Mg - EBT] + EDTA [Ca / Mg - EDTA] + EBT
Unstable complex Stable complex (Steel blue)
(Wine red) (Colorless)
Reagents Required :
1) EDTA solution
It is prepared by dissolving 4 gms of EDTA in 1000ml of
distilled water.
ii) Standard hard water
1 gm of pure CaCO3 is dissolved in minimum quantity of
HCl and then made upto 1000ml using distilled water.
1 ml of standard hard water = 1mg of CaCO3 equivalent
hardness.
iii) EBT indicator
0.5 gms of EBT is dissolved in 100 ml of alcohol.
iv) Buffer solution:
67.5 gms of NH4Cl and 570 ml of NH3 are dissolved and the
solution is made upto 1000 ml using distilled water.
Procedure
1. Standardisation of EDTA solution
20ml of Std.hard water is taken in a conical flask. 5 ml of

buffer solution and a few drop of EBT indicator are added. The
solution is titrated against EDTA taken in burette. The endpoint
is the colour change from wine red to steel blue colour. Let the
volume of EDTA consumed be V1 ml.
Calculation
1ml of std.hard water = 1mg of CaCO3
20 ml of std. hard water = 20 mgs of CaCO3
20 ml of std. hard water consumes = V1 ml of EDTA
V1 ml of EDTA consumes = 20 ml of Std.hard water.
= 20 x 1 mg of CaCO3 eq. hardness.
20
1 ml of EDTA consumes = mg of CaCO3 eq. hardness
V1
2. Estimation of Total Hardness
20ml of sample hard water is pipetted out into a conical
flask and titrated against EDTA taken in burette by adding the
buffer and the indicator to get the end point. Let the volume of
EDTA consumed be V2 ml.
Calculation
20 ml of sample hard water = V2 ml of EDTA
20
= V2 × mg of CaCO 3 equivalent hardness
V1
In 1000 ml of water sample
.. .
20 1000
= V2 × × mg of CaCO 3 equivalent hardness
V1 20
V2
Total Hardness = 1000 × mg / litre (or) ppm.
V1
3. Estimation of Permanent Hardness

250ml of water sample is boiled off to a volume of 50 ml

in a beaker to remove temporary hardness. The temporary hard
salts settle down. Filter and wash thoroughly and make up the
solution again to 250 ml. 20 ml of this solution which is free from
carbonate hardness is titrated against the EDTA as done before.
Let the volume of EDTA consumed be V3 ml.
Calculation
20 ml of boiled sample hard water consumes = V3 ml of EDTA
20
= V3 × mg of CaCO 3 equivalent hardness
V1
In 1000 ml of water sample
20 1000
= V3 × × mg of CaCO 3 equivalent hardness
V1 20
V3
= 1000 × mg/ litre (or) ppm
V1
V3
Permanent Hardness = 1000 × mg/litre (or) ppm
V1
Estimation of Temporary Hardness

This can be calculated by using the following methods.
Temporary Hardness = Total Hardness – Permanent Hardness
(or)
V2 V3
Temporary Hardness = 1000 × mg/litre (or) ppm
V1
Advantages of EDTA method

1. This method is more accurate in the estimation of
hardness of water than other methods.
2. It is convenient and more rapid process.
Solved Problems on EDTA method :

Problem 1:
While titrating a sample of hard water, 50 ml of the sample
consumed 10 ml of 0.01 M EDTA to attain the end point.
Calculate the total hardness of the sample in terms of mg
equivalent of CaCO3 per litre.
Solution :
Number of gram moles of EDTA consumed by 50 ml of sample
Molarity × Volume 0.01 × 10
= = = 1.0 × 10 4
1000 1000
We know that
1 gram mole of EDTA = 100g of CaCO3
= 1.0 × 10 5 mg of CaCO3
Total hardness in 50ml sample = 1.0 ×10-4× 1.0 ×105
= 10 mg of CaCO3
Hence total hardness of the given sample
10
= × 1000 = 200 mg/L of CaCO 3
50
Problem 2 :
N
100 ml of water sample requires 20 ml EDTA when
100
titrated using NH4Cl – NH4OH buffer and EBT indicator.
Calculate the hardness of the sample.
Solution :
Number of gram equivalents of EDTA used by 100 ml sample
1
Normality × Volume × 20
= = 100 = 2.0 ×10 4
1000 1000
Number of gram moles of EDTA consumed
4
2.0 × 10 4
= = 1.0 × 10
2
Since, 1 gm mole of EDTA = 105 mg of CaCO3
1.0 × 10 4
gram moles of EDTA = 105 × 1.0 × 10 4
= 10 mg of CaCO3
10
Hence, total hardness of the sample = × 1000
100
= 100 mg/L of CaCO3
Problem 3 :
100 ml of a hard water sample require 25 ml of 0.01 M
EDTA with NH4Cl-NH4OH buffer and EBT indicator.
Another 100ml of the sample is boiled for about half an hour
and after filtering the precipitate, the volume of the filtrate is
made to 100 ml again by the addition of distilled water. 20ml
of this boiled sample require only 4 ml of 0.01 M EDTA
following the same procedure. Calculate the temporary and
permanent hardness of the sample.
Solution :
i)Calculation of total hardness of the sample :
100 ml of the sample requires 25 ml of 0.01 M EDTA.

0.01 × 25 4
= = 2.5 × 10
1000
 1 gram mole of EDTA = 105 mg of CaCO3
4
2.5 × 10 gram moles of EDTA = 10 5 × 2.5 × 10 4
= 25 mg of CaCO3
Hence, total hardness of the given sample
25
= × 1000 = 250 mg/L of CaCO3
100
ii) Calculation of permanent hardness :
The boiled sample will contain only permanent hardness
20 ml of the boiled sample consumes 4 ml of 0.01 M EDTA
0.01 × 4 5
= = 4 × 10
1000
 1 gram mole of EDTA = 105 mg of CaCO3
4 × 10 5 gram moles of EDTA = 10 5 × 4 × 10 5
= 4 mg of CaCO3
Hence permanent hardness of the given sample
4
= × 1000 = 200 mg/L of CaCO3
20
iii) Calculation of temporary hardness :
Temporary hardness = Total hardness – permanent hardness
= ( 250 – 200 ) mg/L of CaCO3
= 50 mg/L of CaCO3
Problem 4 :
100 ml of hard water requires 20 ml of EDTA solution for

titration. 22 ml of the same EDTA solution was required for
the titration of 100 ml of standard hardwater containing 1gm
CaCO3 per litre. Determine the hardness of water sample in
ppm.
Solution:
1 litre of standard hard water contains 1 gm of CaCO3
(or)
1000 ml of standard hard water contains 1000 mgs of CaCO3
(or)
1 ml of standard hard water = 1 mg of CaCO3
22 ml of EDTA = 100 ml of standard hard water
= 100 × 1 mg of CaCO3
100
1ml of EDTA = mgs of CaCO3
22
100 ml of sample of water = 20 ml of EDTA
100
= 20 × mgs of CaCO3
22
100 1000
For 1000 ml of sample of water = 20 × ×
22 100
= 909.1 mgs/lit (or) ppm
Problem 5 :
250 ml of hard water required 17 ml of 0.025 M EDTA
solution to attain the end point. Calculate the hardness of
water. ( Anna university May 2000)
Solution :
1 ml of 1 M EDTA = 100 mgs of CaCO3
i.e., 1 ml of 0.01 M EDTA = 1mg of CaCO3
1 ml of 0.025 M EDTA = 2.5 mgs of CaCO3 equivalent
Total hardness
250 ml of a sample of water required

= 17 ml of 0.025 M EDTA
= 17 × 2.5 mgs
= 42.5 mgs of CaCO3 equivalent
42.5 × 1000
1000 ml of hard water required = mgs
250
= 170 mgs of CaCO3 equivalent
Total hardness = 170 ppm
Problem 6:
100 ml of water sample requires 18ml of EDTA
solution for titration. 1 ml of EDTA solution is
equivalent to 1.1 mgs of CaCO 3 . Determine the
hardness in ppm.
Solution:
1 ml of EDTA solut ion = 1.1 mg of CaCO 3
18 ml of EDTA solut ion = 18 × 1.1 mg of CaCO 3
= 19.8 mg of CaCO 3
100 ml of water sample requires = 18 ml of EDT A
= 19.8 mg of CaCO 3
1000
1000 ml of water sample = 19.8 × mg of CaCO 3
100
= 198 mgs/lit or ppm
Problem 7 :
0.28 gm of CaCO 3 was dissolved in HCl and the
solution made upto one litre with distilled water.
100ml of the above solution required 28ml of EDTA
solution on titration. 100ml of hard water sample

required 27 ml of same EDTA solution on titration.
100 ml of this water, after boiling cooling and
filtering required 8ml of EDTA solution on titration.
Determine the temporary and permanent hardness of
water. (AU Dec2001)
Solution :
Given :
1000 ml of standard water contains = 0. 28 gm of CaCO 3
i.e., 1000 ml of standard water contains
= 0.28 × 1000 mgs of CaCO 3
= 280 mgs of CaCO 3
1 ml of std. hard water = 0. 28 mg of CaCO 3
28 ml of EDTA = 100 of the std. hard water
= 100 × 0.28 mgs of CaCO 3
100 × 0.28
= = 1
28
1 ml of EDTA = 1mg of CaCO 3
Total hardness
100 ml of hard water = 27 ml of EDTA
= 27 × 1 mg of CaCO 3
= 27 mgs of CaCO 3
1000
1000 ml of hard water = 27 ×
100
= 270 mgs/lit (or) ppm
Total hardness = 270 mgs/lit (or) ppm
Permanent hardness (NCH)

100 ml of the same water, after boiling, cooling and
filtering required = 8ml of EDTA
= 8× 1 mgs of CaCO 3
= 8 mgs of CaCO 3
1000
1000 ml of water = 8 × mgs of CaCO 3
100
Permanent hardness = 80 mgs/lit (or) pp m
Temporary hardness (CH)
Temporary hardness
= Total hardness – Permanent hardness
= 270 – 80
= 190 mgs/lit (or) ppm
Temporary hardness = 190 mgs/lit (or) ppm
Problem 8 :
100 ml of a sample of water required 20 ml of 0.01 M
EDTA for the titration using Eriochrome -Black-T
indicator. Calculate the total hardness
Solution :
We know that
1 ml of 0.01 M EDTA = 1mg of CaCO 3
20 ml of 0.01 M EDTA = 20 mgs of CaCO 3
100 ml sample of water = 20 ml of 0.01 M EDTA
= 20 mgs of CaCO 3 equivalent
1000 ml of water equal to
1000
= 20 × mgs of CaCO 3 equivalent
100
Total hardness = 200 mgs/lit or ppm
Problem 9 :
500 ml of a water sample is boiled for 1hr. It is then
cooled and filtered. The filtrate is made upto 500ml
again with distilled water. 50ml of this solution
requires 12 ml of N/50 EDTA with EBT-indicator and
NH 4 Cl-NH 4 OH buffer. Determine the permanent
hardness of the water sample.
Solution :
Given :
50 ml of water sample after boiling, filt ering requires
12 ml of N/50 EDTA
We know that
1ml of N/50 EDTA = 1mg of CaCO 3 equivalent
hardness
12 ml of N/50 EDTA = 12 mgs of CaCO 3
50 ml of the boiled water sample requires
= 12 ml of N/50 EDTA
= 12 mgs of CaCO 3
1000
1000 ml of the water sample = 12 ×
50
Problem 10 :
100ml of a sample of water required 1 8 ml of 0.01M
EDTA for titration using Erio-chrome Black-T
indicator. In another experiment, 100ml of the same

sample was boiled to remove the CH, the precipitate
was removed and the cold solution required 10 ml of
0.01 M EDTA using Erio-chrome Black-T indicator.
Calculate i) the total hardness, ii) permanent
hardness or NCH iii) carbonate hardness CH, in
terms of mg/lit of CaCO 3
Solution :
We know that
1 ml of 1M EDTA = 100 mgs of CaCO 3
1 ml of 0.01 M EDTA = 1 mg of CaCO 3
i) Total Hardness
100 ml of a sample of water required
= 18 ml of 0.01 M EDTA
= 18 ×1 mgs = 18 mgs of CaCO 3
1000 ml of sample of water is equivalent to
18 × 1000
= mgs of CaCO 3
100
= 180 mgs of CaCO 3
Total hardness = 180 mgs/lit or ppm
ii) Permanent Hardness (NCH)
100 ml of the same water sample after boiling, filtering
consumes = 10.0 ml of 0.01 M EDTA
= 10.0 × 1 mgs
= 10 mgs of CaCO 3
1000 ml of sample of water is equal to
10 × 1000
= mgs of CaCO 3
100
= 100 mgs of CaCO 3 equivalent

Permanent hardness of the water sample = 100 ppm
iii) Temporary Hardness (CH)
Temporary hardness
= Total hardness – Permanent hardness
= 180 – 100 = 80 ppm
Temporary hardness = 80 ppm
1.7 WATER FOR DOMESTIC USE
Water finds a variety of applications in our day to day

life. Human beings consume a considerable amount of water for
drinking and other domestic purposes. Water used for drinking
purpose i.e., municipal water must satisfy certain quality criteria.
The standards of physical and chemical qualities of water
as prescribed by the Bureau of Indian standards (BIS) are given
in the table below.
Drinking water standards as per BIS

S.No Characteristics Desirable limit
1. Colour 5 Hazan units
2. Odour Unobjectionable odour
3. Taste Agreable
4. Turbidity 5 NTU
5. Dissolved solids 500 mg/L
6. Total hardness 300 mg/L
7. pH value 6.5 to 8.5
8. Calcium 75 mg/L
9. Magnesium 30 mg/L
10. Copper 0.05 mg/L
11. Manganese 0.1 mg/L
12. Copper 0.05 mg/L
13. Lead 0.10 mg/L
14. Chloride 250 mg/L
15. Sulphate 200 mg/L
1.7.1 CHARACTERISTICS OF DRINKING WATER
The essential requisites of drinking water are as follows:

i) It should be clear, colourless and odourless.
ii) It should have an agreeable taste.
iii) It should be free from pathogenic micro-organisms.
iv) It’s turbidity should not exceed 5 pm.
v) It should be free from objectionable dissolved gases such as

H2.
vi) It’s pH should be between 6.5 to 8.
vii) The total dissolved solids in it should be less than 500 ppm.
viii) It should be neither too hard nor too soft. The recommended
hardness is about 300 mg/L as CaCO3 equivalent.
1.8 DOMESTIC WATER TREATMENT

The natural waters obtained from rivers, canals, lakes etc.,
do not confirm to the quality standards prescribed for domestic
water or municipal water and as such are not suitable for
municipal supply. They need to be treated suitably.
In order to make natural waters suitable for municipal
supply, several treatment processes are necessary to be done. The
various processes employed for this purpose are briefly described
below :
i) Screening ii) Aeration iii) Sedimentation iv) Coagulation
v) Filtration vi) Sterilisation or Disinfection.
i) Screening
The floating matters in raw water are removed by
screening. For this purpose, the raw water is passed through
screens having large number of holes, when the floating matters
are retained by them.
ii) Aeration
Aeration is the process of mixing water with air. Aeration is done
for the following purposes :
a) It removes gases like CO2 and H2S which cause bad taste
and odour to the water.
b) It also removes ferrous and manganous salts as insoluble
ferric and manganate salts.
c) It increase the O2 content in water for giving it freshness.

d) It promotes taste and odour of water.
iii)Sedimentation
It is a process of allowing water to stand undisturbed for
some time in order to facilitate the settling down of the coarse
suspended particles under the action of gravity.
The water obtained after aeration is taken into large
capacity settling tanks and is allowed to stand for a few hours or
even days. Most of the suspended particles settle down at the
bottom under the action of gravity. The clear supernatent water
is then drawn from the tanks with the help of pumps. Plain
sedimentation usually removes 70 to 75% of the suspended
water.
iv) Coagulation
When water contains finely divided silica, fine clay
particles and other impurities present in the colloidal form, do not
settle down and cannot be removed by sedimentation. In such a
case, coagulation method is adopted to remove the impurities.
Coagulants are certain chemicals which provide ions of
opposite charge. These externally added ions neutralize the
charge on colloidal particles and help them to grow in size and
finally to settle them down. This process is known as
coagulation.
Alum, Al2 (SO4)3 , Sodium aluminate and ferrous
sulphate are commonly used as the coagulants in this process.
When the alum Al2(SO4)3 is added to water , it gets
hydrolysed to form a gelatinous precipitate of Al(OH) 3 which
acts as coagulant . The gelatinous precipitate of Al(OH)3 entraps
the finely divided and colloidal impurities, and finally to settle
down to the bottom which can be removed easily.
Al2(SO4)3 + 6H2O 2Al(OH)3 + 3H2SO4
The coagulants are generally added in solution form.

Mechanical flocculators are used to ensure it’s thorough mixing .
v) Filtration
Filtration is the process of removal of coarse impurities,
colour taste and some micro organisms, by passing water through
a porous material consisting of a bed of fine sand , coarse sand
and gravels. The porous material used is called filtering medium
and equipment used for water treatment is called a filter.
The water for municipal supply is usually filtered by sand filter.
Sand Filter
The filtering medium in a sand filter consists of three
layers as shown in Fig.3.1. The top layer is thick and is made of
fine sand. The middle layer consists of coarse sand, while the
bottom layer consists of gravels. The filter is provided with an
inlet for water and an under drain channel at the bottom for the
exit of the filtered water.
Fig 1.1 Sand Filter
The sedimented water obtained from the sedimentation

tank is made to enter the filter through the inlet. It is uniformly
distributed over the fine sand bed. When the water passes through
the filtering medium, it flows through the various beds slowly.
The filtration occurs and the coarse particles are retained by the
filtering medium.
During filtration, the retained coarse particles clog the
pores of the sand and the rate of filtration becomes slow. At this
stage, 2-3 cm of the top fine sand layer is scrapped off and is
replaced with the fresh sand. Bacterias are also partly removed by
sand filters.
vi) Sterilization (or) Disinfection
The filtered water still contains small amounts of
pathogenic (disease producing) bacterias. In order to use this
water for drinking purpose, all the pathogenic bacterias and other
micro-organisms present in it must be killed.
The process of destroying /killing of pathogenic bacterias
and other micro-organisms is called disinfection and the
chemicals used for this purpose are called disinfectants.
Some of the important methods of sterilization are as follows :
a) Boiling b) By using ozone c) By using ultraviolet radiations
d) by Chlorination
a) Boiling
The harmful disease producing bacteria can be killed by
boiling water for 15-20 minutes. Boiling is a simple sterilization
method but has the following limitations:
i) The method is costly and is not much suitable for the
sterilization of water in bulk.
ii) The process kills only the micro-organisms existing at the

time of boiling. It does not protect water against any
possible future infection.
iii) The taste of water may change on boiling.
b) By using ozone
Ozone is a powerful disinfectant and is readily absorbed
by water. Ozone is highly unstable and breaks down to give
nascent oxygen.
O3 O2 + [O]
The nascent oxygen is powerful oxidizing agent and kills

the bacterias. Disadvantages of this process are
a) This process is costly and cannot be used in large scale.
b) Ozone is unstable and cannot be stored for long time.
c) By using ultra violet (UV) rays

Ultra violet ray sterilization of water can be done for
smaller quantity of water. In this process UV light from mercury
lamp enclosed by quartz globe is focused on flowing water. The
UV radiation effectively destroys the bacteria but it is found to be
a costlier process when applied to larger quantities of water.
d) By chlorination
Chlorine is the most commonly used sterilizing agent in
water treatment. It is capable of killing B.Coli and other
bacterias. The process of adding chlorine to water is known as
chlorination.
Chlorine can either be used in the gaseous form or liquid
chlorine. Chlorine reacts with water to produce nascent oxygen
which destroys the bacterias. Chlorination can be done by the
following methods :
i) By adding chlorine gas
Chlorine gas can be bubbled in the water as a very good

disinfectant
Chlorine when used directly as a gas liberates nascent
oxygen as given below :
Cl2 + H2O HCl + HOCl
Hypochlorous acid
HOCl HCl + [O]

Nascent oxygen
ii) As bleaching powder
Bleaching powder contains 30% available chlorine. It reacts with
water to produce hypochlorous acid which is a powerful
disinfectant due to it’s property of liberating nascent oxygen.
CaoCl2 + H2 O Ca(OH)2 + Cl2

(Bleaching powder)
Cl2 + H2O HCl + HOCl

Hypochlorous acid
HOCl HCl + [O]

Nascent oxygen
One kg of bleaching powder is sufficient to sterilize one million
litres of water.
The use of bleaching powder as a disinfectant has the following
limitations :
a) It is unstable during storage
b) It introduces calcium in water and thus the water becomes
more hard.
iii) As Chloramine
The use of excess chlorine gas or bleaching powder as
disinfectants often produces disagreable odour and unpleasant
taste in water.
This can be avoided by using chloramines. When chlorine
and ammonia are mixed in the ratio 2:1, a compound chloramines
is formed
Cl2 + NH3 NH2 Cl + HCl
Chloramine provide a greater lasting effect than that of chlorine.
NH2Cl + H2O HOCl + NH3
Hypochlorous acid
HOCl HCl + [O]
Nascent oxygen
Since chloramines decomposes slowly to give chlorine, it is
particularly useful when the treated water has to be stored.
Super Chlorination
The sterilization process involving a large excess of
chlorine is called superchlorination. Superchlorination not only
destroys the micro organisms but also the other organic
impurities present in water. The process is usually followed by
dechlorination by NH3 or SO2.
Break point chlorination

Break point chlorination is a carefully controlled
chlorination process in which water is treated with such an
amount of chlorine which is just sufficient to destroy bacteria,
oxidize organic matter to react with ammonia, if present and to
leave behind slight excess of free chlorine.
Chlorine may be added directly as a gas or in the form of

bleaching powder. When chlorine applied to water, the results
obtained can be depicted graphically as shown in Fig.3.2. The
graph shows the relationship between the amount of chlorine
added to water and the residual chlorine.
Destruction of
Formation of chloramines
chloramines and chloro
Residual chlorine
and chloro compounds

compounds Free residual
chlorine
Break point
chlorination
Applied chlorine dose
Fig 1.2 Break point chlorination curve

From the graph (Fig 1.2) it is clear that initially the
chlorine added is used to kill the bacterias and oxidizes all the
reducing substances present in the water and there is no free
residual chlorine.
On increasing the amount of applied chlorine, the amount
of combined residual chlorine also increases. This is due to the
formation of chloramines and other chloro compounds.
At one point, on further chlorination , the oxidation of
chloramines and other impurities starts and there is a fall in the
combined chlorine content. Thus the combined residual chlorine
decreases to a minimum point at which oxidation of chloramines
and other impurities complete and free residual chlorine begins to
appear, this minimum point is known as “break point
chlorination”.
Thus the break point chlorination eliminates bacterias,

reducing substances, organic substances responsible for the bas
taste and odour from the water.
1.9 BOILER FEED WATER

Most of the water used in industry and power houses is in
the form of steam. For steam generation, boilers are almost
invariably employed.
Classification of Boilers
Boilers are generally classified according to their
pressures into three categories.
i) Low-pressure boilers: Upto 15 kg/cm2
ii) Medium-pressure boilers: 15 to 30 kg/cm2
iii) High pressure boilers: Over 30 kg/cm 2
Boiler Feed Water

The water fed into the boiler for the production of steam
is called boiler feed water.
Requirements (or)Specification of Boiler Feed Water

Water used in boilers should be free from dissolved
calcium and magnesium salts and dissolved gases such as oxygen
(O2) and carbon dioxide (CO2).
Any natural source of water does not supply a perfectly
suitable boiler feed water. The boiler feed water must have the
following requirements.
Table 1.3 The suggested limits of tolerance for boiler feed

water
S.NO PARAMETER AMOUNT
1 Hardness
for 0-10 kg/cm2 boiler 80 ppm(max)
10-15 kg/cm2 boiler 40 ppm(max)
15-30 kg/cm2 boiler 10 ppm(max)
Above 30 kg/cm2 2 ppm(max)
2 pH 7.0
3 Colour Colourless
4 Odour Nil
5 Dissolved gases like O2 & CO2 0 ppm
1.9.1 DISADVANTAGES OF USING HARD WATER

IN BOILERS
If the boiler feed water contains impurities (or) if the hard

water obtained from natural sources is fed directly to the boilers,
the following troubles may arise
1. Scale and Sludge formation
2. Boiler corrosion
3. Caustic embrittlement
4. Priming and foaming (Carry over)
1. Scale and Sludge Formation in Boilers

In boilers, water evaporates continuously and the

concentration of the dissolved salts increases progressively.
When the salts concentration reaches their saturation point, they
are thrown out of water in the form of precipitates on the inner
walls of the boiler.
If the precipitated matter is soft and slimy, it is called
sludge. While the precipitate forms an adherent coating on the
inner walls of the boiler, it is called scale.
Boiler
Water
Heat Heat
Loose precipitate Hard, adhering coating
suspended in water on inner walls of boiler
(sludge) (scale)
(a) (b)
Fig. 1.3 (a) Sludge Formation in boilers

(b) Scale Formation in boilers
I) Sludge Formation
1. Sludge is a soft, loose and slimy precipitate forms inside the
boiler during steam generation.
2. The main sludge forming substances in water are MgCO3,
MgCl2, MgSO4,CaCl2 etc.,
3. Sludges are generally formed at cooler portions of the boiler.
4. Sludges can be easily scrapped off with a wire brush.
Disadvantages of Sludge Formation
1. Sludges are poor conductors of heat, so they waste a portion
of heat generated.
2. Excess of sludge formation decreases the efficiency of boiler.
3. If sludges are formed along with scales, then both will be

deposited on inner walls of boiler as scales, and then it
cannot be removed easily.
Prevention of Sludge Formation
Sludge formation in boilers can be prevented
1. By using well softened water.
2. By frequent blow down operation. (Blow - down operation is

a process in which a portion of concentrated water containing
large amount of dissolved salts is replaced with fresh water
frequently, during steam making).
3. It can be easily scrapped off with a wire brush.
II) Scale Formation

1. Scale is a hard, adherent coating forms on the inner walls of
the boiler during steam generation.
2. In low pressure boiler, the main scale forming substances are
Ca(HCO3)2 and MgCl2.
3. In high pressure boiler, the scale forming substances are
mainly CaSO4 and Silica.
Scale Formation Reactions

a) In Low Pressure Boilers
1. Decomposition of Ca(HCO3)2
Ca (HCO3)2 CaCO3 + H2O +CO2

Soft Scale
(Insoluble)
2. Hydrolysis of Magnesium Salts
Dissolved magnesium salts undergo hydrolysis forming

magnesium hydroxide precipitate.
MgCl2 +2H2O Mg(OH)2 +2HCl
Soft Scale
(Precipitate)
b) In High Pressure Boilers
1. Deposition of CaSO4
The solubility of calcium sulphate in water decreases with
rise of temperature. CaSO4 gets precipitated as hard scale on the
heated portion of the boiler. CaSO4 is quite adherent and difficult
to remove.
2. Presence of SiO2 (Silica)
SiO2 present in water even in small quantities deposits as
CaSiO3 and MgSiO3. These deposits stick very firmly to the inner
side of the boiler surface and are very difficult to remove.
Disadvantages of Scale Formation

1. Wastage of Fuel
Scale acts thermal insulator in boilers. Because scale has
low thermal conductivity. Scale deposit decreases the rate of heat
transfer from boiler to inside water. So, more amount of fuel is
required in order to get steady supply of heat to water. This
causes increase in fuel consumption.
2. Decrease in Efficiency
Scale may sometimes, deposit in the valves, condensers of
the boiler and choke them partially. This results in decrease in
efficiency of boiler.
3. Danger of Explosion
When a thick scale develops, any cracks due to uneven

expansion, water comes suddenly in contact with over heated
surface of the iron plate. This causes in the formation of large
amount of steam. So sudden high pressure is developed inside the
boiler which may lead to explosion in boilers.
Prevention of Scale Formation
Scale formation in boilers can be prevented by
1. External treatment
This method involves the removal of scale forming
impurities from water before feeding to the boiler.
Example
o Lime soda process
o Zeolite process
o Demineralization process
2. Internal treatment
This method involves the addition of chemicals directly to
the water in boilers to remove the scale forming substances which
were not completely removed during external treatment.
Example
o Colloidal Conditioning
o Carbonate Conditioning
o Calgon Conditioning
o Phosphate Conditioning
2. Boiler Corrosion
The decay of boiler material by its environment is termed
as boiler corrosion. Corrosion in boilers is due to the presence of
i) Dissolved oxygen
ii) Dissolved carbon dioxide
iii) Dissolved salts

i) Dissolved Oxygen
The presence of dissolved oxygen in water is the main
cause of boiler corrosion. When water containing dissolved
oxygen is heated in the boiler, the dissolved oxygen gets liberated
and corrodes the boiler material as follows
2Fe + O2+ 2H2O 2Fe(OH)2
4Fe(OH)2 +O2 2[Fe2O3.2H2O]

Ferrous hydroxide Rust
Removal of Dissolved Oxygen
Dissolved oxygen can be removed by chemical (or)
mechanical methods.
a) Chemical method
Sodium sulphite, hydrazine are some of the chemicals
used for removing oxygen.
2 Na2SO3 + O2 2 Na2SO4
Sodium sulphite Sodium sulphate
N2H4 +O2 N2 + 2 H2O
Hydrazine
Hydrazine is found to be an ideal compound for removing
dissolved oxygen in the water. It reacts with oxygen forming
nitrogen and water. Nitrogen is harmless.
b) Mechanical method
Dissolved oxygen can also be removed from water by
mechanical de-aeration.
Mechanical de-aeration
It is a mechanical method of removal of dissolved gases

such as O2 & CO2.
In this process, water is allowed to fall slowly on the
perforated plates fitted inside the tower.
Water
To vacuum
pump
Heater
Perforated
plates
Tower
Deaerated water
Fig. 4.2 Mechanical Deaerator
Fig. 1.4 Mechanical De-aerator
To reduce pressure inside the chamber, the deaerator is

connected to a vacuum pump. The sides of the tower are heated.
The water flowing down through perforated plates undergoes
deaeration at high temperature and low pressure. [(High
temperature, low pressure, and large exposed surface (provided
by perforated plates) reduces the dissolved oxygen in water].
This is because the solubility of a gas in water is directly
proportional to pressure and inversely proportional to
temperature (Dalton’s law + Henry’s law).
ii) Dissolved Carbon dioxide
Dissolved carbon dioxide in water produces carbonic
acid, which is acidic.
CO2 + H2O H2CO3
Carbonic Acid
Carbon dioxide is also released inside the boiler, if water
used for steam generation contains bicarbonates of Calcium and
Magnesium.
Ca(HCO3)2 CaCO3 +H2O +CO2
Mg(HCO3)2 MgCO3 +H2O +CO2
Removal of dissolved carbon dioxide

a) Carbon dioxide may be removed by adding calculated amount
of NH4 OH into water.
2NH4OH + CO2 (NH4)2CO3 + H2O
b) Carbon dioxide along with oxygen in water can be removed by

mechanical de-aeration.
iii) Dissolved salts

If water used for steam-generation contains dissolved
magnesium salts, they liberate acids on hydrolysis.
MgCl2 +2H2O Mg(OH)2 + 2HCl
The liberated acid reacts with iron material of the boiler in
a chain-like reaction producing HCl again and again.
Fe+2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl
Thus presence of even a small amount of MgCl2 will
cause corrosion of iron to a large extent.
Removal of acids
Corrosion by acids can be avoided by the addition of

alkali to the boiler water.
HCl + NaOH NaCl + H2O
3. Caustic Embrittlement
Caustic embrittlement is a type of boiler corrosion, caused
by using highly alkaline water in the boiler. It means the inter
crystalline cracking of boiler metal.
Boiler water usually contains a certain proportion of
sodium carbonate, added for water softening purposes. In high-
pressure boilers, Na2CO3 decomposes to give sodium hydroxide
and carbon dioxide,
Na2CO3 + H2O 2NaOH + CO2
and this makes the boiler-water “caustic”.
This NaOH flows into the minute hair cracking usually present
on the boiler material by capillary action and dissolves the
surrounding area of iron as sodium ferroate.
Fe + 2NaOH Na2FeO2 + H2
Sodium Ferroate
This causes embrittlement of boiler parts, particularly
stressed parts like bends, joints, rivets etc., causing even failure
of the boiler.
Prevention
It can be prevented by
1. adding sodium sulphate (or) sodium phosphate as softening
reagent instead of sodium carbonate.
2. adding tannin, lignin to the boiler water which blocks the hair
cracks.
3. adjusting the pH of the feed water between 8 and 9.
4. Priming and Foaming (Carry Over Process)

Steam sometimes may be associated with small droplets
of water. Such steam containing liquid water is called wet steam.
These droplets of water may carry with them some dissolved salts
and sludge materials present in water. This phenomenon is called
Carry Over Process. This occurs mainly due to Priming and
Foaming.
Priming
It refers the formation of wet steam by rapid boiling of
water at the heating surface. It may be caused by
Causes
Priming may be caused by
i) High steam velocity.
ii) Very high water level in the boiler.
iii) Improper boiler design.
iv) Sudden boiling of water.
Prevention
Priming can be controlled by
i) Controlling the velocity of steam.
ii) Keeping the water level lower.
iii) Good boiler design.
Foaming
The formation of stable bubbles above the surface of
water is called foaming. These bubbles are carried along with
steam leading to excessive priming.
Causes
Foaming may be caused by presence of oil, grease in
water and finely divided sludge particles.
Prevention
Foaming can be prevented by

i) adding coagulants like sodium aluminate,
aluminium hydroxide, ferrous sulphate etc.,
ii) adding anti-foaming chemicals such as castor oil
and synthetic polyamides.
1.10 SOFTENING METHODS
Softening of Water
Water used for industrial purposes should be pure. ie.,it
should be free from hardness, scale forming substances and
corrosive agents like dissolved O2 etc., The process of removing
hardness producing salts from water is known as softening of
water.
Softening of Water can be done by the following two ways
1. External conditioning or External treatment
2. Internal conditioning or Internal treatment.
1.10.1 EXTERNAL TREATMENT (OR)

EXTERNAL CONDITIONING
It involves the removal of hardness producing salts from
the water before feeding into the boiler. The external treatment
can be done by the following methods.
a) Lime soda process
b) Zeolite (or Permutit process
c) Demineralisation (or) Deionization.
The above said processes are the examples of ion-
exchange process of water softening.
In an ion-exchange process, a reversible exchange of ions

taking place between a stationary solid phase and an external
liquid mobile phase.
a) Lime-Soda Process
Lime-Soda process is a very important method used for
the softening of water.
[i] Principle
The lime-soda process involves the chemical conversion
of all the soluble hardness-causing salts by the addition of soda
and lime into insoluble precipitates which could easily be
removed by settling and filtration.
In this process, water to be softened is treated with
calculated amounts of lime Ca(OH)2 and soda Na2CO3. For quick
completion of reactions, the reagents may be used in 10 %
excess. The functions of lime and soda are as follows.
Functions of lime
Lime removes temporary hardness, permanent
magnesium hardness, dissolved iron and aluminium salts,
dissolved CO2 and H2S gases and free mineral acids present in
water. The reactions involved are as follows
1. Removal of temporary calcium and magnesium hardness
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O
2. Removal of permanent magnesium hardness

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

3. Removal of dissolved iron and magnesium salts

Al2(SO4)3 + 3 Ca(OH)2 2Al(OH)3 + 3CaSO4
FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4
2Fe(OH)2 + H2O +1/2 O2 2Fe(OH)3
4. Removal of dissolved CO2 and H2S

CO2+ Ca(OH)2 CaCO3 + H2O
H2S + Ca(OH)2 CaS + 2H2O
5. Removal of free mineral acid

2HCl + Ca(OH)2 CaCl2 + 2H2O
H2SO4 + Ca(OH)2 CaSO4 + 2H2O
Functions of soda
During the removal of Mg2+, Fe2+, Al3+, HCl and H2SO4
by lime, permanent calcium hardness is introduced in the water
due to formation of calcium salts. The permanent calcium
hardness thus introduced on account of the treatment of water
with lime and the permanent calcium hardness already present in
water before lime treatment are removed by soda. The reactions
involved are as follows,
CaCl2 + Na2CO3 CaCO3 + 2NaCl
CaSO4 + Na2CO3 CaCO3 + Na2SO4
The chemical reactions involved in the lime-soda process

are quite slow. Moreover, the precipitates formed [particularly of
CaCO3 and Mg(OH)2] are fine and have a tendency to form
super-saturated solutions. This results in after deposition of these
precipitates later in the pipes and boiler tubes leading to their
clogging and corrosion. These drawbacks of the process can be

overcome by
a) thorough mixing of chemicals and water.
b) allowing proper time for the completion of reactions.
c) the use of accelerators such as active charcoal and
d) the use of coagulants such as alum or NaAlO2.
[ii] Process
The lime-soda process can be carried out both at room
temperature as well as at higher temperatures. The process
carried out at room temperature is called cold lime –soda process
and that carried out at 94°-100°C is called hot lime-soda process.
1. Cold Lime-Soda Process
In this method, water to be softened is treated with
calculated quantities of lime and soda at room temperature. Small
amounts of a coagulant such as alum, aluminium sulphate,
sodium aluminate etc., are also added. The coagulant helps the
finely divided precipitate formed in the process to flocculate.
Sodium aluminate also helps in the removal of silica and oil
present in water.
Method
The mixture of water, calculated quantities of lime and
soda and a small amount of a coagulant is fed from the top into
inner chamber of a vertical circular tank (Fig.3.5). The chamber
is provided with a vertical rotating shaft carrying a number of
paddles to ensure vigorous stirring and continuous mixing of
water with the chemicals added.
Fig 1.5 Cold Lime-Soda Process

The chemical reactions take place and the hardness
producing salts get converted into insoluble precipitates which
accumulate in the form of a heavy sludge. As the softened water
reaches the outer coaxial chamber, it rises upwards and is filtered
by a wood-fibre filter and finally taken out from an outlet
provided at the top of the outer cylinder. The heavy sludge settles
down at the bottom of the outer chamber and is taken out through
an outlet. The softened water obtained from this process
contains a residual hardness of about 50-60 ppm.
2. Hot Lime-Soda Process
In this process, water is treated with the softening
chemicals at a temperature of 94°-100°C. Since the process is
carried out at a temperature close to the boiling point of the
solution, the reaction proceeds faster and the softening capacity

of the process increases several times.
Fig.1.6 Hot Lime-Soda Process

At this temperature, the viscosity of water is much less
than that at room temperature. Hence, rate of aggregation of
particles increases and there is hardly any need of adding any
coagulant. Moreover, the dissolved gases also escape to some
extent at the temperature of the process.
Method
A typical hot lime-soda water softening plant is shown in
Fig.1.6. It consists of
(i) a reaction tank
(ii) a conical sedimentation vessel and
(iii) a sand filter.
Raw water is fed from the top into the reaction tank where
it is thoroughly mixed with calculated quantities of softening
chemicals and is agitated with superheated steam. The reactions
take place and water gets softened. The softened water containing
sludge then enters into the sedimentation vessel where sludge

settles down. The softened water rises up in the vessel, while
precipitated sludge is taken out through an outlet provided at the
bottom of the vessel. The softened water is then taken to a sand
filter which ensures the complete removal of the sludge from
softened water.
The softened water obtained from this process contains a
residual hardness of 15-30 ppm.
Advantages of the process
The hot lime-soda process has the following advantages.
1. The process is much faster as compared to the cold soda-
lime process.
2. It is very economical.
3. Lesser amounts of coagulants are needed.
4. The process increases the pH value of the treated water,
thereby reducing the corrosion of distribution pipes.
5. To certain extent, iron and manganese are also removed
from water.
6. Much of dissolved gases in water are also removed.
7. Due to an increase in the pH, the amount of pathogenic
bacteria in treated water also gets reduced.
Disadvantages of the process
The hot lime-soda process has the following
disadvantages.
1. Disposal of large amounts of sludge formed in the process
poses problems.
2. The treated water obtained by this process is not
completely softened. It still contains a residual hardness
of about 15-30 ppm, which is not good for boilers.
Table 1.4 Difference between cold and hot lime soda process
S. Cold L-S Process Hot L-S Process

No
1 Done at room temperature. Done near the boiling

point of water.
2 Reactions are slow and takes Fast and takes only 15

hours to complete. minutes.
3 Precipitate is finely divided Coarse precipitate

and therefore coagulants are coagulants not needed.
needed.
4 Tank size is large. Small and compact.
5 Residual hardness 50 to 60 15 to 30 ppm

ppm.
6 Chemicals are consumed by CO2 and temporary

dissolved gas,CO2 etc., hardness are
automatically removed.
b) Zeolite (or) Permutit Process

Zeolites are naturally occuring hydrated sodium
aluminium silicate,
Na2O. Al2 O3. x SiO2 yH2O where x = 2 to 10 and y = 2 to 6.

The synthetic form of zeolite is known as permutit.
Synthetic zeolite is represented by Na2Ze. The sodium ions which
are loosely held in Na2 Ze are replaced by Ca2+ and Mg2+ ions
present in the water. Natural zeolites are non-porous.
Synthetic zeolites are porous and gelly structure. They are
prepared by heating together china clay, feldspar and soda ash.
These zeolites are higher exchange capacity per unit weight than
natural zeolites.
Process
In this process, the hard water is passed through a bed of
sodium zeolite (Na2 Ze).
The hardness causing ions (Ca2+, Mg2+ ) in hard water is
replaced by loosely held sodium ions in zeolite bed(Fig.3.7). The
outgoing soft water contains only sodium ions.
Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3
Na2Ze + CaCl2 CaZe + 2NaCl
Na2Ze + MgCl2 MgZe + 2NaCl
Na2Ze + CaSO4 CaZe + Na2SO4
Na2Ze + MgSO4 MgZe + Na2SO4

Nacl
Hard
water
Hard water
Sodium zeolite
Soft water
Fig. 2.14 Water softening (Zeolite process)

Fig. 1.7 Zeolite process
Regeneration
After the softening process, the zeolite is completely
converted into calcium and magnesium zeolites and it gets
exhausted. At this stage the hard water supply is stopped and the
exhausted bed is regenerated by treating with a concentrated 10%
brine (NaCl) solution.
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl Na2Ze + MgCl2

Exhausted Regenerated
Zeolite Zeolite
Advantages of the process
This process removes hardness upto 10ppm.
Operational cost is less

The equipment used is compact
No sludge formation.
The plant can be connected to water supply line as
it avoids double pumping.
Requires less time for softening
Maintenance and operation is easy
The process automatically adjusts itself to waters
of different hardness.
Limitations of the process

The process exchanges only Ca2+ and Mg2+ ions
with Na+ ions. It does not remove the acidic ions
like HCO3 -, CO32-. Water containing such ions is
not much suitable for boilers as it may cause
corrosion of boilers.
Turbid water, if used clogs the pores of the Zeolite
bed, making it inactive.
Highly acidic or alkaline water will destroy the
Zeolite bed.
Coloured ions (Fe2+ and Mn2+) if present in water
should be removed first and then the water is sent
to the bed, as these ions convert sodium Zeolite
into their respective Zeolites (FeZe, MnZe) which

are difficult to be regenerated.
High capital cost
c) Demineralization (or) Deionization Process

In this method ion exchange resins are used as softening
material.In this process cations like Ca2+, Mg2+ and anions like
Cl-, SO42- which are responsible for hardness are removed
respectively by cation exchange resins and anion exchange
resins.
Ion exchange resins are insoluble, cross linked, long chain
organic polymers with a micro porous structure. The functional
groups attached to the chains are responsible for the ion-
exchanging properties.
Cation exchange resins (RH+)
Resin containing acidic functional groups (-COOH, -SO3H)
are capable of exchanging their H + ions with cations of hard
water.
Example: (i) Sulphonated coals.
(ii) Sulphonated polystyrene.
R-SO3H ; R-COOH ≡ RH2
Anion exchange resins (ROH- )

Resins containing basic functional groups (-NH2, -OH)
are capable of exchanging their OH- ions with the anions of hard
water.
Example: (i) Cross-linked quaternary ammonium salts.
(ii) Urea-formaldehyde resin

R-NR3OH ; R-OH ; R-NH2 ≡ R(OH)2
Process
The hard water first passed through a cation exchange
column (Fig.1.8) which absorbs all the cations like Ca2+, Mg2+,
Na+, K+ etc., present in the hard water.
2RH+ + CaCl2 R2Ca + 2HCl
+
2RH + MgSO4 R2Mg + H2SO4
+
RH + NaCl RNa + HCl
Raw
water
Cation
Cation Anlon
Antion
exchanger
exchanger exchanger
exchanger
Acid for Alkali for

regeneration regeneration
Deionised
water
Fig. 2.15Demineralisation
Fig.1.8 Demineralizationprocess
process
The cation free water is then passed through an anion
exchange column, which absorbs all the anions like Cl-, SO42-
etc., present in the water.
2ROH- + 2HCl 2RCl + 2H2O
2ROH- + H2SO4 R2SO4 + 2H2O

Thus the water coming out from the anion exchange is

free from both cations and anions. This water is known as ion-
free water (or) deionised (or) demineralised water.
Regeneration
When the cation exchange column is exhausted, it can be
regenerated by passing a solution of dil.HCl (or) dil.H2 SO4.
R2Ca + 2HCl 2RH+ + CaCl2
R2Mg + H2SO4 2RH+ + MgSO4
RNa + HCl RH+ + NaCl
When the anion exchange column is exhausted, it can be
regenerated by passing a solution of dil. NaOH.
2RCl + 2NaOH 2ROH- + 2NaCl
R2SO4 + 2NaOH 2ROH- + Na2SO4
Advantages
1. The process can be used to soften highly acidic (or) alkaline
water.
2. It produces water of very low hardness (2ppm).
Disadvantages:
1. The equipment is costly and more expensive chemicals are
needed.
2. If the water contains turbidity, the output is low due to
clogging.
MIXED BED DEIONIZER
This comprises of a single cylinder. This contains a bed
of intimate mixture of cation exchanger resin and anion
exchanger resin. When water is passed through this bed it
comes in contact many times with both cation and anion
exchangers alternatively. The effect of mixed bed exchanger

is equivalent to passing through a series of several cation and
anion exchangers (multiple cycle). The outgoing water from
the mixed bed contains even less than 1ppm of dissolved
salts.
Regeneration
When the resins are exhausted, the mixed bed is back
washed by forcing water in the upward direction. The lighter
anion exchanger gets displaced to form an upper layer. The
heavier cation exchanger forms the lower layer. There after
the anion exchanger is regenerated by passing caustic soda
solution from the top and then rinsed and reused. The lower
cation exchanger bed is then regenerated by passing
sulphuric acid solution and rinsed and then reused. The two
beds are then mixed again by forcing compressed air. The
bed is then reused.
Table 1.5 Comparison of Zeolite & Demineralization process
S.No Zeolite (or) Permutit Demineralisation (or)

Process Deionization Process
1 This is an ion exchange This is also an ion

process. exchange process.
S.No Zeolite (or) Permutit Demineralisation (or)

Process Deionization Process
2 It exchanges only cations. Both the cation and anoin

exchanges are available.
3 Residual hardness 1-5 Residual hardness 0-2 ppm.

ppm.
4 Cost of plant and material Cost higher.

high.
5 Operating expenses are Operating expenses high.

low.
6 Acidic water cannot be Even highly acidic or

treated. highly alkaline water can
be treated.
7 Treated water contains No dissolved solids.

more dissolved solids
(sodium salts).
Characteristics of Soft, Deionised and Distilled

Water
Soft Water
1. It does not contain hardness producing ions like Ca2+,
Mg2+
2. It may contain Na+, K+, SO42-, Cl- ions and micro-
organisms.
Deionised water (mineral water)
1. It does not contain any ions including hardness producing

cations.
2. It may contain some amount of micro-organisms.
Distilled Water
It does not contain any ions and micro-organisms,
because it is prepared by condensing the vapour of boiling
water.
Hard Water
It contains all hardness producing ions.
Specification for Drinking water

The common specifications recommended by the US
Public health for Drinking water are given below.
i) Water should be clear and odourless.
ii) It should be cool.
iii) It should be pleasant to taste.
iv) Turbiditiy of water should not exceed 10 ppm.
v) pH of the water should be in the range of 7.0 –
8.5.
vi) Chloride and sulphate contents should be less than
250 ppm.
vii) Total hardness of the water should be less than
500 ppm.
viii) Total dissolved solids should be less than 500
ppm.
ix) Fluoride content of the water should be less than
1.5 ppm.
x) The water must be free from disease producing
bacteria.
xi) Water should be free from objectionable dissolved

gases like H2S.
xii) Water should be free from objectionable minerals
such as lead, chromium, manganese and arsenic
salts.
1.11.2 INTERNAL CONDITIONING (or) INTERNAL

TREATMENT (or) BOILER COMPOUNDS
This method is used to convert scale forming substances

into sludge which can be removed by blow - down operation.
i) Colloidal Conditioning
The colloidal conditioning agents are kerosene, agar-agar,
gelatin, glue etc., They are used in low pressure boilers to convert
scale forming substances like CaCO3, CaSO4 into non-adherent,
loose precipitate called sludge, which can be removed by blow
down operation.
ii) Carbonate conditioning
Scale formation due to CaSO4 in high pressure boilers can
be avoided by adding Na2 CO3 to the boiler water.
CaSO4 + Na2 CO3 ↔ CaCO3 + Na2 SO4
The forward reaction is favoured by increasing the
2-
concentration of CO3 .
iii) Calgon conditioning

Calgon is sodium hexa metaphosphate with the
composition Na2[Na4 (PO3)6 ]. During the process of softening
water, four sodium ions are replaced by double salts containing
calcium inside the complex. Since the complex is highly soluble,

there is no problem of sludge disposal.
Na2 [Na4 (PO3)6] 2Na+ + [Na4(PO3)6]2-

Calgon
2 CaSO4 + [Na4 (PO3)6]2- [Ca2 (PO3)6]2- + 2Na2SO4
Highly soluble complex
iv) Phosphate conditioning
In high pressure boilers, CaSO4 forms hard type scale.
This is because the solubility of CaSO4 decreases with increase of
temperature. It can be converted into soft sludge by adding
excess of soluble phosphates. The optimum pH for the
precipitation Ca3 (PO4)2 soft sludge is 9.5 - 10.5.
3CaSO4 + 2Na3PO4 pH =9.5 - 10.5 Ca3 (PO4)2 + 3 Na2SO4

Soft sludge
There are 3 types of phosphates employed for this purpose
1. Trisodium phosphate –Na3 PO4 (Too alkaline)
2. Disodium hydrogen phosphate –Na2 HPO4 (weakly alkaline)
3. Monosodium dihydrogen phosphate – NaH2 PO4 (acidic)
Na3 PO4 is used for too acidic water. Na2 HPO4 is used
for weakly acidic water. NaH2 PO4 is used for alkaline water in
boilers.
1.13 DESALINATION OF BRACKISH WATER

The process of removing common salt (NaCl) from the

sea water is known as desalination. The water containing
dissolved salts with peculiar salty taste is called Brackish water.
Depending upon the quantity of dissolved solids, water is
graded as
1) Fresh water - contains <1000 ppm of dissolved solids.
2) Brackish water - contains >1000 ppm but<35000 ppm of
dissolved solids.
3) Sea water -contains >35,000 ppm of dissolved solids.
Sea water and brackish water can be made available as
drinking water through desalination process.
The common method for the desalination of brackish water are
1. Electrodialysis
2. Reverse osmosis
3. Distillation
4. Freezing.
1.13.1 Electrodialysis
Electrodialysis is another efficient technique used for the
desalination of saline water.
Principle: Electrodialysis involves the separation of dissolved
salts from saline water in the form of ions under the influence of
a direct current using particular types of membranes called
ion-selective membranes.
An ion-selective membrane is permeable for only one
kind of ions having specific charge. For example, a cation-
selective membrane allows the passage of cations only. It does
not let anions to pass through it. Similarly, an anion-selective
membrane is permeable only to anions and checks the passage of
cations through it.
When a direct current is passed through saline water

enclosed between ion-selective membranes, the cations of the
dissolved salt move towards cathode through the cation-selective
membrane, whereas anions of the salts move towards anode
through the anion-selective membrane. This decreases the
concentration of ions in saline water and after some time the
saline water turns into fresh water.
Process
The process is carried out in a special type of cell called
eletrodialysis cell shown in the Fig.1.9. It consists of a large
number of paired sets of ion-selective membranes. Saline water
under a pressure of about 5-6 kg/m2 is introduced from the top of
the cell and is made to pass between membrane pairs.
Fig 1.9 Electrodialysis of saline water

An electric field is applied perpendicular to the direction

of flow of water. The ions start moving towards the oppositely
charged electrodes through the membranes. On account of this,
the concentration of ions in alternate compartments 2, 4, 6 etc.,
decreases, while the concentration of ions in alternate
compartments 1, 3, 5, 7 etc., goes on increasing.
Thus, water collected from compartments 2, 4, 6 etc., is
pure; while that collected from compartments 1, 3, 5, 7 etc., is
more concentrated saline water.
Examples for ion selective membranes
Cation selective membrane - polystyrene containing
sulphonic acid group.
Anion selective membrane - polystyrene containing tetra
ammonium chloride.
Advantages
1. It is the most compact unit, the cost of installation and
operation is economical.
2. If electricity is easily available, this process is best suited.
1.13.2 Reverse Osmosis

Process
It is a membrane process by which water is separated
from saline water. Osmosis is defined as the spontaneous flow of
‘water’ from dilute to more concentrated solution through semi
permeable membrane.
Pressure
Piston
Sea water
Semi-
permeable
membrane
Fresh water
Fresh
water
Fig. 4.6 Desalination of sea water.
Fig.1.10 Reverse Osmosis
Semi permeable membrane is one which permits only
water molecules to pass through it. Examples of semi permeable
membrane are cellulose acetate, polyamide, polymide, etc.,
This natural process can be reversed by applying pressure

higher than the osmotic pressure on the concentrated side. Thus
the solvent is forced to move from concentrated side to dilute
side across the membrane. This principle is known as Reverse
Osmosis.
In the reverse osmosis, the pure water (free from ions) is
separated from the contaminated brine water (salty water). This
membrane filtration is also called Super filtration (or) hyper
filtration.
Advantages
1. This method have greater advantages of removing ionic, non-
ionic, colloidal and high molecular weight organic matter.
2. The life time of membrane is quite high (2years).
3. The membrane can be replaced within few minutes. It
provides nearly uninterrupted water supply.
4. Due to low capital cost, low operating cost and high
reliability, this method is superior than other methods.
Applications
1. Reverse Osmosis plays a major role in providing portable
water defined by the WHO criterion of <500 ppm of total
dissolved solids. (TDS).
2. Extremely high quality water required for nuclear power
plants can be made from sea water by reverse osmosis
process.
3. Sugar concentration, waste water recovery and beverage uses
are a few of the current popular applications of reverse
osmosis process.
EFFLUENT WATER TREATMENT

Introduction
Water from a water supply scheme may contain
physical, chemical and biological impurities. Physical
impurities causes colour, turbity and odour, chemical
impurities causes hardness and water pollution, metals and
dissolved gases causes corrosion, bacteriological impurities
causes diseases like cholera, typhoid etc.
Hence Objectives of water treatment process is to make
water safe for drinking and domestic purposes, by removing
 Colour
 Odour
 Objectionable taste
 Dissolved gases
 Dissolved and suspended impurities
 Pathogenic bacteria
Different Treatment process

Removal of suspended impurities
1. Screening
2. Sedimentation
3. Aeration
4. Coagulation
5. Clariflocculation
Removal of microorganisms
1. Activated sludge process
2. Filtration
3. Disinfection
Screening
The raw water which contains larger suspended floating
impurities is passed through screens. This retains the
impurities.
Types of screens
1. Bar screen
2. Perforated screens
3. Comminutor screens
Impurities that can be removed
 Trees, logs rags etc.
Sedimentation
Certain impurities are removed by allowing the water to
stay undisturbed in a tank for a period of time. The clear
supernatant water is then drawn from tank and sent to
aerator.
Retention period – 3-4hrs (75% of impurities are settled)
Principle:
Principle of Gravity applies.
 The heavier particles settles and Removed by blow

down operation
 The lighter particles floats and Removed by skimming
 Settleable solids, soaps, detergents, suspended particles.
Types of sedimentation tanks
1. Horizontal flow tank
2. Vertical flow tank
3. Radial flow tank.
Aeration
The process of bringing water in contact air is called
aeration.
Types of Aeration
This is done either by
1. Cascading water through air (OR)
2. Passing air through water under pressure.
Construction
Fountains with spraying nozzles are used which effects
intimate contact of water and air.
Deactivating the anaerobic bacteria.
Gases like CO2 and H2S, which causes bad taste and
odour to the water.
Removing ferrous and manganous salts as insoluble

ferric and magnetic salts.
Removes colour and odour
Advantages
Gives freshness to water
Increasing the dissolved O2 content in water.
Thickens and removes of oil, grease, solid grits and
odours
Coagulation
Principle:
The suspension of particles in water is stabilized by the
mutual repulsion of like charges on the particles.
Neutralisation of these charges by coagulants (i.e. with high
valence ions) results in coalescence.
Coagulants:
These are positively charged molecules of relatively low
molecular weight. With water these form an insoluble
gelatinous precipitate. It adsorbs and entraps very fine
suspended impurities forming bigger flocs, which settles
down easily.
Example : Alum, Ferrous sulphate
 Colloids
 Finely divided silica

 Fine clay particles
Example
Aluminium sulphate
Used only in high alkaline waters. (OR) water is pretreated
with lime
The Aluminium sulphate reacts with OH - to form the
Aluminium hydroxide, which is a gelatinous precipitate.
Al2(SO4)3 + 6H2O  2Al(OH)3 + 3H2SO4
Gelatinous precipitate
The precipitate adsorbs and entraps very fine negatively
charged suspended impurities forming bigger flocs, which
settles down easily.
COAGULANTS (STUDY MATERIAL)

Sodium aluminate NaAlO2.
(Used in waters with pH range less than 7)
NaAlO2 + 2H2O  2Al(OH)3 + NaOH
The aluminium hydroxide flocs cause coagulation. The NaOH

precipitates the magnesium salts as Mg(OH)2
MgSO4 + 2NaOH Mg(OH)2 + Na2SO4

Copperas or ferrous sulphate (FeSO4. 7H2O)
(Used in waters with pH range of 8.5 or pre treated water with lime.)
FeSO4 + Mg(HCO3)2  Fe(OH)2 + MgCO3 +

CO2 + H2O
4Fe(OH)2 + O2 + 2H2O  4Fe(OH)3
Ferric salts are heavier particles which settles down easily.

Activated sludge process

Secondary or biological treatment includes processes such as
Activated sludge process. filtration etc.
The main function of secondary treatment is to convert
the remaining organic matters of the effluent into stable form
by oxidation or nitrification.
Principle
The activated sludge is obtained by settling sewage in
the presence of excess oxygen. Thus Activated sludge is that
sludge which settles down after the sewage has been freely
aerated and agitated for a certain time. The activated sludge is
biologically active and contains a large number of aerobic
bacteria and other micro-organisms.
In Activated sludge process effluent is treated biologically.
When the sludge is mixed with effluent, the bacteria in the
activated sludge multiply rapidly. These aerobic bacteria
oxidises the organic matters and promotes coagulation and
flocculation. They also convert the colloidal and suspended
solids into settleable solids.
Process
The effluent is mixed with the required quantity of
activated sludge and it is aerated for 4-10hrs. The aerated
mixture is sent to secondary clarifier.
The matters which settles down is called sludge. The liquid is

called effluent.
Settled sludge is the activated sludge and a part of it is sent
for recirculation. The rest is disposed off for drying beds,
dumping into sea etc.
Advantages
Gives clearly treated liquid
free from bad smell or odour
The degree of purity can be varied depending on the
requirements
No trickling filter flies
Disadvantages
Skilled supervision and constant check on the return
sludge is necessary.
The process is not efficient in removing all industrial
wastes.
Large volume of sludge presents difficulty in disposal.
The process gets upset when there is a change in the
quality or quantity of water.
The success depends on mainly the aeration provided.
The term sludge volume index (SVI)is used to indicate the

degree of concentration of sludge. It also indicates the
physical state of the sludge.
Desired SVI is 100ml/g. High value indicates the favourable
condition for sludge bulking.
Flocculation
Sometimes flocculators are mixed. The flocculators are
sorbed by the particles of the suspension, and forms a net
structure that helps in the formation of large particles called
flocs. These flocculant aggregations are denser and heavier
than the individual particles and settles down easily.
Example of flocculators
Polyacrylamide, BA-2 polyelectrolyte.
Flash mixing
The coagulants and flocculants are quickly and
efficiently mixed with the raw water with the help of a
rotating stirrer/ Agitator. The gelatinous precipitate thus
formed is gently mixed in rolling mix chambers to aid in the
even distribution and also assisting the formation of flocs
which settles easily.
Clariflocculation
These are the settling chambers where the floc is
allowed to settle by the principle of gravity and the sludge
thus formed is removed.

Coagulated & Dissolved solids
Colloids
Turbidity
Removal of Microorganisms
Water used for drinking and domestic purpose must be
freed from the disease producing bacteria, micro-organism
etc. This is done by Filtration and Disinfection / Sterilization
Filtration
Principle
The combination of physical straining and biological
treatment using formation of a gelatinous layer called a
schmutzdecke results in the purification of water.
Turbidity
Color
Bad odour and bad taste causing microorganism
Bacteria – eg. Giardia Cysts Cryptosporidium oocysts
Iron and sulphur gases
Sedimented
water Fine sand
Coarse sand
Gravels
Under drains
Fig 1.1 Sand Filter Filtered water outlet

Construction
In the base of each bed a series of herringbone drains are
present. These are covered with a layer of pebbles which in
turn is covered with coarse gravel. Layers of sand are placed
on top followed by a thick layer of fine sand. The whole
depth of filter material may be more than 1 metre in depth.
The majority of which is fine sand material. On top of the
sand bed sits a supernatant layer of raw, unfiltered water. The
filter materials (called media) are contained in a liner made
of concrete, plastic, or other impermeable material.
Working
Formation of a gelatinous layer (or biofilm) called the
hypogeal layer or Schmutzdecke in the fine sand layer occurs.
This layer consists of bacteria, fungi, protozoa and a range of
aquatic insect larvae. The Schmutzdecke is the layer that
provides the effective purification in potable water treatment,
the underlying sand providing the support medium for this
biological treatment layer. Water enters the filter
compartment above the media and flows down through the
sand on gravity basis. As water passes through the
Schmutzdecke, particles of foreign matter are trapped in the
mucilaginous matrix and dissolved organic material is
adsorbed and metabolised by the bacteria, fungi, protozoa
etc. The water produced from a well-managed slow sand
filter can be of exceptionally good quality with no detectable
bacterial content
Refurbishing (Cleaning) the filter

1. Scrapping the top layer and exposing a new layer of
sand
2. Backwashing the filter.
3. Wet harrowing
This involves lowering the water level to just
above the Schmutzdecke, and stirring the sand and thereby
suspending any solids held in that layer and then running the
water to waste. The filter is then filled to full depth and
brought back into service.
Advantages
Effective treatment for turbidity, bacteria, and removal
of cysts.
Cost effective and reliable
No chemicals or electricity is used
No replaceable parts
Non pressurised systems
Requires minimal operator training
Cleaning is easy
Low maintenance treatment process
No large amount of wastewater to dispose of.
No automation required.
A failure to clean the filter will result in loss of
production but no loss of quality.
Disadvantages:
Raw water turbidity must generally be low because with
raw water blinding of the filter occurs
Raw water must not have high algae counts.
Colour removal is fair to poor.
Unpredictable filter run times necessitate lengthy pilot

studies.
Need for a conservative design in the event of high
algae results in very large filters.
It produces water at a slow and constant rate.
Disinfection / Sterilization:
The process of destroying / deactivating pathogenic
bacteria and other micro-organisms
Disinfectants:
The chemicals used for deactivating or killing micro-
organisms.
Some of the important methods of disinfection are as
follows:
1. Chlorination
2. Boiling
3. By using ozone
4. By using ultraviolet radiations
Chlorination
Chlorine when treated to water produces hypochlorous acid.
Cl2 + H2O  HCl + HOCl
Hypochlorous acid
This produces nascent oxygen which is a powerful

oxidizing agent.
HOCl  HCl + [O]
Nascent oxygen
The nascent oxygen oxidizes undesirable organic and
inorganic compounds, thus removing offensive taste and
odour as well as potential toxicity.
Also hypochlorous acid is found to react with the
enzyme in the cells of micro organism and deactivate the
microorganisms. Thus hypochlorous acid is a powerful
disinfectant.
Chlorine can either be used as gas or liquid.
Review Questions
1. Define hard water and soft water
2. What are the requirements of boiler feed water?
3. What are the problems encountered in boiler feed water
4. Distinguish sludge from scale
5. What is meant by boiler corrosion ? How is it prevented ?
6. What is caustic embrittlement ? how is it prevented?
7. What is meant by priming and foaming what are their
effects in boilers ?
8. What is meant by carry over? How it is caused?
9. What is aeration ? why it is required ?
10. What are boiler compounds give examples

11. What is calgon what is its role in water treatment ?
12. What is desalination ? Explain few methods of converting
sea water into fresh water.
13. What are the requisites of water for municipal supply ?
14. What are disinfectants ? Give example s.
15. What is meant by break point chlorination
16. Explain reverse osmosis
17. What are the advantages of ion exchange method ?
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Chapter · October 2010

Syed Shabudeen P.S.

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Water is not only essential for human beings, plants and

1.2 SOURCES OF WATER

The chief sources of water fall in two main groups,

1.2.1 Surface Water

1.2.2 Underground Water

1.3 IMPURITIES IN WATER

Physical Impurities include suspended and colloidal impurities

Chemical Impurities include dissolved salts and dissolved gases.

(ii) Mg (HCO3)2, Ca (HCO3)2, Na2CO3, NaHCO3, etc.,

1.4 TYPES OF WATER

When water with such hardness is used for washing, large

2RCOONa + M2+ (RCOO) 2 M + 2Na+

M2+ = Ca2+, Mg2+

Common hardness producing salt present in water are

1.5 WATER QUALITY STANDARDS

Water used for drinking purpose should meet certain

1. Indian Council of Medical Research (ICMR)

Table 1.1 Standards for Drinking Water

S.NO PARAMETER ICMR WHO

1.6 WATER QUALITY PARAMETERS

The water quality parameters are roughly divided into 3

Physical Chemical Biological

1. Colour 1. Hardness Pathogenic

3. Taste and 3. Alkalinity

Some of the important Water Quality Parameters are

and methyl orange as an indicator separately or in

The end point with phenolphthalein (P) indicator indicates

2. When P=M, the sample consists of only OH - ions.

1.6.2 HARDNESS OF WATER

Hardness is the characteristic of water which does not

1. Temporary (or) Carbonate hardness

This is due to the presence of dissolved chlorides and

Molecular weights of some hardness producing salts are given

2. The analysis of three sample of water gives the following

Molecular Molecular Quantity Equivalent of

Relationship between PPM and Mg/L

Hence 1 mg / litre =1 ppm

S.No Purpose Specification Disadvantages

i) Washing i) Free from Ca i) It does not lather well.

ii) It produces sticky

cause staining of cloth.

ii) Bathing Free from It does not lather well,

iii) Cooking Free from i)Boiling point of water

iv) Drinking Free from i)Bad effect on our

II. In industrial use

S.No Industry Specification Disadvantages

1. Textile & i) Free from iron They produce coloured

2. Laundries i)Soft water Hard water increases

3. Sugar Free from sulphates They cause difficulties

4. Beverages Free from alkaline They will neutralize

5. Paper and i)Free from Fe & Affect colour and

ii)Free from It increases the ash

6. Power i)Non-corrosive Produces corrosion

7. Boiler i)Zero hardness Scale prevents

from Lead to boiler

III. In steam generation in boilers

S.No Purpose Specification Disadvantages