UNIT – I

WATER TECHNOLOGY

Characteristics – alkalinity – types of alkalinity and determination – hardness – types and

estimation by EDTA method (problems) – Domestic water treatment – disinfection methods
(Chlorination, Ozonation, UV treatment) – Boiler feed water – requirements – disadvantages of
using hard water in boilers – internal conditioning (Phosphate, calgon and carbonate
conditioning methods) – external conditioning – deminerlization process – desalination and
reverse osmosis.

Introduction:
Water is nature’s most wonderful, abundant and useful compound. It is most important
compound for the existence of human beings, animals and plants. Without food, human can
survive for a number of days, but water is such an essential that without it one cannot survive.
Besides these, water has great applications in industries. Water is mainly used in power
generation industry for the production of electricity through steam generation. Water is also used
as a coolant in nuclear reactor and chemical plants. In addition to it, Water is widely used in
other fields like production of steel, rayon, paper, atomic energy, textiles, chemicals, ice and for
air-conditioning, drinking, bathing, sanitary, washing, irrigation , fire-fighting , etc.

There are two main sources of water viz., surface water and underground water

Surface water:

Rain water: It is probably the purest form of natural water. However, during the journey
downwards through the atmosphere, it dissolves a considerable amount of industrial gases like
SO2, CO2, NO2 , …. and suspended solid particles.

River water: Rivers are fed by rain and spring waters. Water from these sources flow over the
surface of land dissolves the soluble minerals of the soil and finally falls in rivers. River water
thus contains dissolved minerals of the soil such as chlorides, sulphates, bicarbonates of Na,
Ca, Mg and Fe. River water also contains the organic matter obtained from the decomposition of
plants, animals, small particles of sand and rock in suspension. Thus the river water contains
considerable amount of dissolved minerals.

Lake water: It has constant chemical composition. But it contain very small amount of dissolved
minerals than well water. It contains more amount of organic matter.

Sea water: It is the most impure form of natural water. Rivers throws the impurities to the sea at
joining. Moreover, continuous evaporation of water from the surface of sea water more in
dissolved salts. It contain around 3.5 % of dissolved salts, out of this 2.6 % is NaCl. Other salts
present are Na2SO4, KHCO3, Mg(HCO3)2, Ca(HCO3)2, KBr and MgBr, etc.

Underground water: The rain water reaches the surface of the earth, percolates into the earth
and travels downward; it dissolves the number of mineral salts present in the soil. Finally it
meets a hard rock and come out in the form of ‘spring’. Generally spring and well water are very
clear in appearance due to the filtering action of the soil, but contain more amounts of dissolved
salts.
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CHARACTERISTICS:

Colour: Colour is a shade imparted by organic or inorganic material, which changes the
appearance of the water. The change in colour of water is not harmful, unless it is associated
with any chemical or toxic nature. The colour in water is caused by the inorganic sources like
salts of Fe, Mn and chemicals from dye industry, and the organic sources like algae, tannin,
peat, humus material, weeds, protozoa and industrial effluents from paper, textile, sugar
industries, etc. The range of colour varies from pale straw to dark brown. The variation in colour
of water from the same source with time often serves as indices of quality. Usually, yellowish
tinge due to the presence of Cr; and more amount of organic matter, yellowish red colour due to
the presence of Fe and reddish brown due to the presence of peaty matter. The colour and
colour producing substances are removed by coagulation, settling, adsorption and filtration, etc.

Turbidity: Turbidity is the process of reduction in clarity of water due to the presence of finely
divided, insoluble impurities suspended in water. It is caused by the inorganic sources like clay,
silt, SiO2 , Fe(OH)3 , CaCO3, etc and the organic sources like finely divided plant, animal matter ,
oils, fats, greases, micro—organisms like plankton, etc. The amount of turbidity in water decides
the grade of product being manufactured in industries and efficiency of boilers. i.e. the turbidity
creating substances in water are affects the boilers , power plants and cooling water systems.
It can be removed by sedimentation, followed by coagulation & filtration.

Taste: Usually, taste is interlinked directly with odour. The presence of dissolved mineral in
water produces taste. For example, Bitter taste is due to the presence of Fe, Al, Mn salts and
CaCO3, Soapy taste is due to the presence of more amount of NaHCO3, Brackish taste is due to
the presence of unusual amount of salts and palatable taste is due to the presence of dissolved
CO2 and nitrates. It can be removed by desalination, de-aeration & boiling followed by filtration.

Odour: The unwanted odour in water may be caused by the presence of algae, fungi, bacteria,
weeds and sulphides. The contamination of industrial effluents, containing aldehydes, phenols,
ester, ketones etc.. and sewage containing organic matters , creates unwanted odour in water
bodies. The odour can be removed by boiling or disinfection process.

Acidity: It is a measure of base neutralizing ability. It may be caused by the presence of

dissolved CO2, minerals and Mineral acids like HCl , H2SO4, etc. Mineral acids are formed by the
oxidation of S and FeS2 . CO2 is formed from the smokes from industries and automobiles.

2 S + 3 O2 + 2 H2O 2 H2SO4
2 FeS2 + O2 + 2 H2O 2 FeSO4 + 2 H2SO4

It can be removed by adding calculated quantity of NaOH or Na2CO3

Alkalinity: It is a measure of acid neutralizing ability. It is caused due to the presence of

hydroxides, carbonates and bicarbonates of alkali metals. These salts are released from the
industries like fertilizer, detergent, leather and paint, etc. As the amount of alkalinity increases in
water bodies, the aquatic organisms are greatly affected. Alkalinity in boiler feed water causes
caustic embrittlement of pipes. It can be removed by adding a small amount of HCl.

Nitrogen: It is an inert gas, and relatively unimportant as far as water treatment is concerned.
The plant matters, fertilizers are the main sources of Nitrogen. It has no corrosion action on
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metals, since it is inert, it cannot be determined practically. It can be removed by boiling the
water.

Fluoride: Fluorides are found in ground water due to the dissolution from geologic formulations.
Generally, ground water contains more concentration of fluoride than the surface water.The
main sources are Fluorapatite Ca10F2(PO4)6, Cryolite Na3AlF6, igneous rocks containing
fluosilicates and phosphate fertilizers. The optimum fluoride concentration should be 0.7 – 1.2
mg/L. If the fluoride concentration is high, it causes fluorosis. If the fluoride concentration is low,
it causes dental problems in children. Fluorides can be removed by adsorption on activated
carbon, using basic anion exchange resin and using Al salts in alkaline medium.

Water: All living things need an adequate supply of potable water. Water is necessary for the
survival of all living things – humans, animals, and plants on earth. Out of the 100% of water
sources in the world, 3% only fresh water in which 2% is in the form of ice at poles and 1% is in
lakes, rivers and reservoirs. It is the fact that proper maintenance, conservation, and use of
water resources needed to avoid scarcity of water for the future generation.

Based on the reaction with soap, the water is classified into soft and hard water. The
water which does not produce lather with soap solution readily, but forms a white precipitate is
called hard water, the water which produce lather easily on shaking with soap solution, is called
soft water. Such water does not contain dissolved Ca and Mg salts in it. Hardness is the
characteristic property of water, which prevents the lathering of soap. This is due to the
presence of bicarbonates, sulphates, chlorides of Ca and Mg and other heavy metals dissolved
in it. A sample of hard water, when treated with soap (Na or K salt of higher fatty acid) does not
produce lather, but produces a white scum or precipitate. This precipitate is formed, due to the
formation of insoluble soaps of Ca and Mg.

2 C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl

2 C17H35COONa + MgSO4 (C17H35COO) 2Mg +2 Na2SO4

Sl.No HARD WATER SOFT WATER

1 It does not give lather with soap, It gives lather with soap readily
but gives white scum or precipitate

2 It contains chlorides, sulphates and It does not contain chlorides, sulphates

bicarbonates of Ca & Mg and bicarbonates of Ca & Mg

3 It gives wine red colour with EBT It doesn’t give wine red colour with EBT

Hardness of water can be classified into temporary hardness (carbonate hardness) and
permanent hardness (non-carbonate).

Temporary hardness: Hardness of water is due to the presence of dissolved bicarbonates of

Ca and Mg, other heavy metals and carbonates of Fe is called temporary hardness. It can be
removed by either boiling the water (or) adding lime to the water. On boiling; the bicarbonates
are converted into insoluble carbonates and hydroxides.

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 Ca (HCO3)2 CaCO3 + H2O + CO2

Mg (HCO3)2 Mg (OH)2 + 2 CO2

Permanent hardness: Hardness of water due to the presence of chlorides and sulphates of Ca
and Mg, Fe and other heavy metals is called permanent hardness. It cannot be removed by
boiling, but can be removed by lime-soda process, zeolite process & de-Ionization process, etc.

Sl.No TEMPORARY HARDNESS PERMANENT HARDNESS

1 Due to the presence of dissolved Due to the presence of chlorides and

bicarbonates of Ca and Mg , other sulphates of Ca and Mg, Fe and other
heavy metals and carbonates of Fe heavy metals

2 It can be removed by either boiling It cannot be removed by boiling, but can

the water (or) adding lime to the water be removed by lime-soda process,
zeolite process and de-Ionization
process, etc .

Equivalents of CaCO3: The concentration of hardness and non-hardness expressed as

equivalents of CaCO3. The choice of CaCO3 in particular is due to its molecular weight is 100
(equivalent weight = 50) which is found to be convenient for the calculation. Moreover, it is the
most insoluble salt that can be precipitated in water treatment.

The equivalent of CaCO3

= Mass of hardness producing substance X Chemical equivalent of CaCO3

Chemical equivalent of hardness producing substance

Units of hardness:
1. Parts per million (ppm) is the parts of CaCO3 equivalent hardness per 106 parts of water.
1 ppm = i.e. 1 part of CaCO3 equivalent hardness in 106 parts of water.

2. Milligrams per litre (mg/L) is the number of milligrams of CaCO3 equivalent hardness per
litre of water.
1 mg/L = 1 mg of CaCO3 equivalent hardness of 1 litre of water
= 1 mg of CaCO3 equivalent hardness per 106 mg parts of water.
= 1 part of CaCO3 equivalent hardness per 106 parts of water
= 1 ppm

The relation between various units is given as 1 ppm = 1 mg/L.

Disadvantages of hard water:

• Hard water is unfit for various domestic purposes like washing, bathing and so on. The
hardness producing Ca2+ and Mg2+ ions convert soaps into insoluble precipitates. This
causes wastage of soaps in washing and bathing.

• When hard water is used for drinking, it affects the digestive system and it forms stones
in the kidney (as Calcium oxalate).
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 • When hard water is used for cooking, more fuel and time consumption are required.
Because of the presence of salts of Ca and Mg, this increases the boiling point of water.

• Hard water is not useful for industries like textile, sugar and paper. The dissolved salts
like Ca, Mg, Fe and Mn affect the properties like smooth and glossy finish to paper in
paper industry, lather in laundry and shades and colour to fabrics in textile industry.

• When hard water is used for steam production, the boiler affected by the problems like
scale-sludge formation, priming and foaming, corrosion and caustic embrittlement.

• Hard water should not be used for laboratory analysis, because the hardness producing
Ca2+ and Mg2+ ions interfere in reactions.

• When hard water is used for concrete making, the hydration of cement and the strength
of the concrete are affected.

ESTIMATION OF HARDNESS OF WATER: It is essential to estimate the hardness of water prior to

its use in boilers and industries.

Structure of EDTA

It can be estimated by EDTA (Ethylene Diamine Tetra Acetic acid) method. It is

a complexometric method. Since EDTA is insoluble in water, its disodium salt is used as a
complexing agent. This forms complex ions with Ca2+ and Mg2+ ions of hard water.

Structure of di-sodium salt of EDTA

Principle: Estimation of hardness by EDTA method is based on the principle that EDTA forms
metal complexes with Ca2+ and Mg2+ ions in water. These complexes are stable when pH range
is 8 – 10 and to maintain the pH, buffer solution (mixture of NH4Cl and NH4OH) is added. The
completion of the complexation reaction is indicated by EBT indicator. When this indicator is
added to the sample water, it forms metal – indicator complex of wine red or purple red colour.

[Ca2+ and Mg2+] + EBT [Ca / Mg – EBT]

Unstable complex (Wine red colour)

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 When this solution is titrated against EDTA in the burette, EDTA replaces the indicator
from metal – indicator complex. When all the Ca2+ and Mg2+ ions are complexed by EDTA, the
indicator is set free and the end point is the sharp colour change from wine red to steel blue.

[Ca, Mg – EBT] + EDTA [Ca / Mg – EDTA] + EBT

Wine red colour stable complex (colourless) (steel blue)

Thus the total hardness is determined. The temporary hardness is removed by boiling
and after the removal of precipitate by filtration; the permanent hardness in the filtrate is
determined by titration with EDTA as before. Temporary hardness can be calculated from using
the formula, Temporary hardness = Total hardness – Permanent hardness.

Procedure: Pipette out 50 ml of the hard water sample into a clean conical flask. Add 10 ml of
buffer solution and a pinch of EBT indicator. It is titrated against standard EDTA taken in the
burette. The end point is the colour change from wine red to steel blue. Repeat the titration for
concordant values. Let the volume of EDTA consumed be V1 ml.

Estimation of permanent hardness: Take 250 ml of hard water sample in a beaker and
evaporate it to 50 ml. Filter the solution into a 250 ml standard flask. Make up the filtrate again to
250 ml by adding distilled water. Pipette out 50 ml of made-up solution into a clean conical flask.
Add 10 ml of buffer solution and a pinch of EBT indicator. It is titrated against standard EDTA
taken in the burette. The end point is the colour change from wine red to steel blue. Repeat the
titration for concordant values. Let the volume of EDTA consumed be V2 ml.

Calculation:

Total hardness:
1 ml of EDTA = 1 mg of CaCO3 => V1 ml of EDTA = V1 mg of CaCO3

This hardness is present in 50 ml of hard water.

Then total hardness = V1 x 1000 / 50 ppm of CaCO3 equivalent

Permanent hardness:
1 ml of EDTA = 1 mg of CaCO3 => V2 ml of EDTA = V2 mg of CaCO3

This hardness is present in 50 ml of boiled, filtered hard water sample.

Then permanent hardness = V2 x 1000 / 50 ppm of CaCO3 equivalent

The temporary hardness can be calculated using the formula,

Temporary hardness = Total hardness – Permanent hardness

ESTIMATION OF ALKALINITY OF WATER: The acid neutralizing ability of water is called alkalinity
of water.

Principle: Alkalinity in water is due to the presence of OH-, CO32- and HCO3- ions. There are
five alkalinity conditions possible in a given water sample as follows, OH-, CO32- , HCO3- ,
combination of CO32- and OH- and combination of CO32- and HCO3-. The various alkalinities of
the given water sample can be estimated by titrating it against standard acid (H2SO4) using
phenolphthalein and methyl orange indicators successively. Hydroxide alkalinity is completely
neutralized and carbonate alkalinity is partially neutralized during phenolphthalein end point.
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 OH- + H+ H2O

CO32- + H+ HCO3-

Bicarbonate alkalinity is neutralized during methyl orange end point.

HCO3- + H+ [H2CO3] H2O + CO2

OH- + HCO3- CO32- + H2O

Eg., NaOH + NaHCO3 Na2CO3 + H2O

The possibility of OH- and HCO3- ions together is ruled out, because they combine
instantaneously to form carbonate ion. Thus, OH- and HCO3- cannot exist together in water. On
the basis of same reasoning, all the three ions (OH-, CO32- and HCO3-) cannot exist together.
From the two titre value (P and M) the different alkalinities are identified and calculated using the
following table.

Procedure: 20 cc of the given hard water sample is pipetted out into a clean conical flask. To
this, 2-3 drops of the phenolphthalein indicator is added and is titrated against H2SO4 solution
taken in the burette. The end point is the disappearance of pink colour. The volume of H2SO4
consumed is noted as P (Phenolphthalein end point). Then in the same solution, add 2 to 3
drops of methyl orange. Continue the titration, till the pink colour reappears. Now the volume of
H2SO4 is noted as M (Methyl orange end point).

Sl. No. Alkalinity OH- (ppm) CO32- (ppm) HCO3- (ppm)

1. P=0 0 0 M

2. P= M/2 0 2P 0

3. P<M/2 0 2P M-2P

4. P>M/2 2P-M 2(M-P) 0

5. P=M P=M 0 0

Calculation:
Volume of acid used to phenolphthalein end point=P cc
Volume of acid used to methyl orange end point = M cc

Thus, phenolphthalein alkalinity = P x Normality of H2SO4 x 50 x 1000 / 20 ppm

Methylorange alkalinity = M x Normality of H2SO4 x 50 x 1000 / 20 ppm

DOMESTIC WATER TREATMENT: Municipalities have to supply potable water, i.e. water which is
safe to drink.

Essential requirements of drinking water: It Should be colourles and odourless, perfectly

cool, turbidity not more than 100 ppm, free from dissolved gases like H2S, CO2 and NH3, free
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from objectionable minerals like Pb, As, Cr and Mn salts, pH around 8.0, TDS less than 500
ppm, free from pathogens and free chlorine not more than 0.1 – 0.2 ppm.

Purification of water for domestic use: Natural water from rivers, canals, etc does not satisfy
the basic requirements of drinking water. The treatment process involves various processes as
follows.

Screening: Screening is the process of removing floating materials like wood pieces and leaves
from water. Raw water is allowed to pass through a screen having a large number of holes
which removes the small and large floating matter.

Sedimentation: Sedimentation is the process of removing suspended impurities by allowing the

water to stand undisturbed for 2 to 6 hours in big tanks. Due to force of gravity, most of the
suspended particles settled down at the bottom and they are removed. Sedimentation can
remove 60 to 70 % of the suspended matter.

Coagulation: Finely divided silica, clay, colloidal particles etc do not settle down easily and
hence cannot be removed by sedimentation. Such impurities are removed by coagulation
method. Coagulation is the process of removing colloidal matter from water with the addition of
requisite amount of coagulants. Chemical substances like alum K2SO4 . Al2(SO4)3 . 24H2O,
ferrous sulphate FeSO4 . 7H2O, sodium aluminate NaAlO2, etc are used as coagulants. These
chemical substances react with carbonate and bicarbonate ions present in water and form
precipitates which settles down.

Al2(SO4)3 +3Ca(HCO3)2 2 Al(OH)3 + 3 CaSO4 + 6 CO2

FeSO4 + Mg (HCO3)2 Fe (OH)2 + MgCO3 + H2O + CO2

NaAlO2 + 2 H2O Al (OH)3 + NaOH

Filtration: Filtration is a process of removing colloidal and bacterial impurities by passing water
through sand filters. The sand filter consist of thick layer of fine sand placed over several beds of
coarse sand and gravels and water is allowed to percolate through the bed. The water flows
through the various beds slowly due to gravity. The rate of filtration slowly decreases due to the
clogging of impurities in the pores of the sand bed. When the rate of flow becomes very slow,
filtration is stopped and the fine sand bed is replaced. The sand filter method is an effective and
efficient process to treat municipal water supply. Bacteria’s are partly removed by this filtration
process.

Sand filter

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Sterilization / Disinfection: The process of killing/destroying the disease producing bacteria’s
from the water and making it safe for use is called sterilization or disinfection. The chemical
substances, which are added to the water for killing the bacteria, etc, are known as sterilizers or
disinfectants. There are various methods to sterilize the water.

Sterilization by boiling: Boiling the water for 10 to 15 minutes, all the pathogens are killed and
water become safe for use.

Chlorination: Chlorine is the most important sterilizing agent in water treatment. It can be
added in the form of bleaching powder / directly as gas / in the form of concentrated solution in
water / chloramines.

Sterilization by adding bleaching powder: When bleaching powder is added to water, the
following chemical reaction takes place. The HOCl acts as a powerful germicide, it reacts with
pathogens and all the pathogens were killed.

CaOCl2 + H2O Ca (OH)2 + Cl2

Cl2 + H2O HCl + HOCl

HOCl + Pathogens Pathogens are killed

Sterilization by adding chlorine: When chlorine gas added to the water, it produces the
powerful germicide HOCl, which kills all the pathogens.

Cl2 + H2O HCl + HOCl

HOCl + Pathogens Pathogens are killed

Sterilization by adding chloramines: When chloramine added to the water, it produces a

powerful germicide HOCl which kills the pathogens.

ClNH2 + H2O HOCl + NH3

HOCl + Pathogens Pathogens are killed

Sterilization by Ozone: Ozone (O3) is an excellent disinfectant, which is produced by passing

silent electric discharge through cold and dry oxygen.

3 O2 2 O3

O3 O2 + [O]

[O] + Pathogens Pathogens are killed

It is highly unstable and decomposes to give nascent oxygen which is a powerful oxidizing agent
and kills all the pathogens and also oxidizes the organic matter present in the water.

Advantage: It removes colour, odour and taste simultaneously without giving any residue.

Disadvantage: This process is relatively expensive.

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Sterilization by UV treatment: Sterilization of water can be done by using UV rays. In this
process, UV rays are concentrated on flowing water. The UV radiation kills bacteria. But it is
expensive process, when applied to large quantities of water.

BREAK POINT CHLORINATION: Chlorination provides the sterilization for public drinking water
systems and swimming pools, etc. Insufficient chlorination of ammoniacal water leads to the
formation of a mixture of chloramines (NH2Cl, NHCl2 & NCl3) which irritate the skin, eyes and
produces unpleasant odour to the water. At sufficiently high concentration of active chlorine
(hypochlorite, Hypochlorous acid & molecular chlorine) a phenomenon known as break point
chlorination occurs. In break point chlorination, ammonaceous & ammoniacal materials are
completely oxidizes to nitrogen and active chlorine is simultaneously reduced to chloride. “Break
point of chlorination is the application of chlorine to produce residual free available chlorine with
no combined chlorine present”. As chlorine is added to water, it reacts with NH3 and forms
chloramines.

Cl2 + NH3 ClNH2 + HCl

Cl2 + NH2Cl NHCl2 + HCl

Cl2 + NHCl2 NCl3 + HCl

Hence, chlorine in the combined form gradually increases. After a particular limit,
oxidation of chloramines & other impurities start and there is a fall in the combined chlorine
state. When all combined chlorine has been oxidized by reaction with free available chlorine, the
residual now consisting of only free available chlorine, rises again and continues to increase in
direct proportion to increased dosage. The point at which the residual again begins to increase
is the break point chlorination.

Break point of chlorination

The break point chlorination curve has four stages: Stage: 1. It shows a typical break point
of water containing a considerable amount of NH3. During the initial upward rise, chloramines
are first formed. The curve rises until sufficient free available chlorine is developed to react with
chloramines, and then it falls until a point where all NH3 compounds have been oxidized. While
less organic matter in the water, as in stage 2 and 3, free available chlorine is formed sooner,
destroying chloramines formed at the early stage. This results in lower combined chlorine

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residuals and flattened curves before break point. In stage 4, the chloramines are neutralized at
an early stage by the upswing of the curve.

Advantages:
1. It destroys all the disease producing bacteria
2. It removed colour and odour from the water
3. It completely oxidizes the organic compounds present in the water.

BOILER FEED WATER: In industry, one of the main uses of water is generation of steam by
boilers. The water fed into the boiler for the production of steam is called boiler feed water and it
should be free from dissolved salts, gases, suspended impurities, silica and oil.

BOILER FEED WATER TREATMENT: If the water containing these impurities is used in boilers,
the following problems may arise – scale & sludge formation, boiler corrosion, caustic
embrittlement and priming & foaming.

SCALE AND SLUDGE FORMATION: As water evaporates continuously in boilers for steam
production, the concentration of dissolved salts increases. When their saturation points are
reached, the salts are precipitated on the inner walls of the boilers. If the precipitate formed is
soft, loose, slimy and non-adherent; it is called sludge. Sludge’s are formed by the substances
like MgCl2, MgCO3, MgSO4 and CaCl2. Sludge’s are generally formed at comparatively colder
parts of the boiler and get collected at places where flow rate is low. They can be easily
removed by scraping off with a wire brush. These are poor conductors of heat and also cause
choking of pipes. Sludge formation can be prevented by using soft water and can be removed
by blow down operation which consists of withdrawal of portion of concentrated water from the
boiler and replacing it with fresh water. If the precipitate is hard and adherent on the inner walls,
it is called scale. These are formed by the substances like CaSO4 and Mg (OH)2 .
Scales are so hard and adherent that they are difficult to remove them even with the help of
hammer and chisel.

sludges scales

Scales are poor conductors of heat. Hence, they act as partial heat insulators and the transfer of
heat from the inner boiler surface to the water inside is greatly reduced, which causes wastage
of fuels. When the thick scales cracks due to uneven expansion may cause explosion of boiler.
Brittle scales may be removed by giving thermal shocks and loosely sticking scales that of by
scraping. Firmly sticking scales can be removed by chemical reactions.
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 Sl.No SLUDGES SCALES

1 Sludge’s are soft and non- Scales are hard and adherent deposits on the
adherent deposits. inner wall of the boiler.

2 It can be removed easily scraping It is difficult to remove even with the help of
off with a wire brush. hammer and chisel, but can be removed by
chemical reactions.

3 Sludge’s can transfer heat to some Scales are poor conductor of heat and are
extent and are less dangerous. more dangerous.

4 Sludge’s are formed by Scales are formed by the substances like

substances like MgCl2, MgCO3, CaSO4 and Mg(OH)2.
MgSO4 and CaCl2.

BOILER CORROSION: Boiler corrosion is the decay of boiler material by a chemical /

electrochemical attack by it environment. Boiler corrosion is mainly due to the presence of,
dissolved oxygen, dissolved CO2 and dissolved salts like MgCl2. Therefore the removal of these
prevents corrosion in boilers.

Removal of dissolved oxygen: Water usually contains about 8 ppm of dissolved oxygen (DO)
at room temperature. The DO in water attacks the boiler material at higher temperatures.

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

4Fe(OH)2 + O2 + 2H2O 2[Fe2O3.3H2O]
(Rust)

The DO can be removed from water by chemical / mechanical methods.

CHEMICAL METHOD: DO can be removed from water by the addition of chemicals like sodium
sulphite , hydrazine, etc

2Na2SO3 + O2 2Na2SO4

N2H4 + O2 N2 + 2H2O

Hydrazine is the best chemical for removing DO since the products are water and inert
nitrogen gas. Also it removes oxygen without increasing the concentration of dissolved salts.

MECHANICAL DE-AERATION METHOD: O2 along with CO2 can be removed by this method.
The hard water is allowed to fall slowly on the perforated plates fitted inside the tower. To reduce
the pressure inside the tower, the deaerator is connected to a vacuum pump. The sides of the
tower are heated by means of steam jacket. The water flows down through a number of
perforated plates and this arrangement exposes a large surface of water for deaeration. High
temperature, low pressure and large exposed surface, reduces the dissolved gases (O2 and
CO2) in water.

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 Mechanical de-aerator

Removal of dissolved CO2: Dissolved CO2 in water produces carbonic acid which has a slow
corrosive effect on the boiler material. CO2 is released inside the boiler, if water used for steam
generation contains bicarbonates.

Mg (HCO3)2 MgCO3 + H2O + CO2

Dissolved CO2 can be removed by the addition of NH4OH

2NH4OH + CO2 (NH4)2CO3 + H2O

Removal of dissolved salts: Water containing Mg salts liberate acids on hydrolysis.

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

The liberated acid reacts with Iron boiler in a series of reactions producing HCl again and again
which corrodes boiler severely.
Fe + 2HCl FeCl2 + H2

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

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

HCl + NaOH NaCl + H2O

CAUSTIC EMBRITTLEMENT: Caustic embrittlement means intercrystalline cracking of boiler

metal. It is a type of boiler corrosion, caused by using highly alkaline water in the boiler. Boiler
water usually contains small amounts of Na2CO3. In high pressure boilers, Na2CO3 undergoes
hydrolysis to produce NaOH.

Na2CO3 + H2O 2NaOH + CO2

This NaOH flows into the minute hair cracks and crevices usually present on the boiler material
by capillary action and dissolve the surrounding area of Fe as Sodium ferroate, Na2FeO2. This
type of electrochemical corrosion occurs when the concentration of NaOH is above 100 ppm.
This causes brittlement of boiler parts, particularly stressed parts like bends, joints, rivets etc.

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Prevention of caustic embrittlement:
1. Using Na2SO4 as softening agent instead of Na2CO3.
2. Adding chemicals like tannin, lignin to the boiler water.
3. Adjusting the pH of the boiler feed water around 8 – 9.

PRIMING & FOAMING:

Priming / Carry over process: When a boiler is producing steam rapidly, some particles of the
liquid water are carried along with the steam. This process of ‘Wet steam’ formation is called
priming.

Priming is caused by:

1. The presence of large amount of dissolved salts
2. High steam velocity
3. Sudden boiling
4. Improper boiler design
5. Sudden increase in steam production rate

Priming can be prevented by:

1. Fitting mechanical steam purifiers
2. Controlling the velocity of steam
3. Maintaining low water levels in boilers
4. Using treated water
5. Good boiler design

Foaming: The production of stable bubbles above the surface of water is called foaming.
Priming and foaming, usually, occur together.

Foaming is caused by,

1. Presence of air
2. Presence of grease
3. Presence of finely divided sludge particles

Foaming can be prevented by,

1. Adding anti—foaming agents like Castor oil
2. Adding coagulants like Sodium aluminate (NaAlO2), Ferrous sulphate (FeSO4) etc. to
remove the finely divided sludge particles and oil.

SOFTENING OF WATER: It is the process of removing hardness producing Ca/Mg salts present
in the hard water. It can be done by internal and external treatments.

INTERNAL TREATMENT: It is the process of removing scale forming salts by directly adding
suitable chemical to the boiler feed water. There are three types of internal treatment as follows,
phosphate conditioning, calgon conditioning and carbonate conditioning.

Phosphate conditioning: This process is suitable for high pressure boilers. The added sodium
phosphate reacts with Ca/Mg salts in the boiler water and forming insoluble precipitates of
Ca/Mg phosphate which can be removed by blow down operation method.

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 3 MgCl2 + 2 Na3PO4 Mg3(PO4)2 + 6 NaCl

3 CaSO4 + 2 Na3PO4 Ca3(PO4)2 + 3 Na2SO4

The chemicals Na3PO4, Na2HPO4 and NaH2PO4 are used to treat the acidic, weakly alkaline and
alkaline water respectively.

Calgon conditioning: Sodium hexametaphosphate, Na2[Na4(PO3)6] is called calgon which

react with Ca/Mg salts present in the boiler water and converting them into highly soluble
complex.
2 CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2 Na2SO4

Carbonate conditioning: This method is used in low pressure boilers. The added sodium
carbonate reacts with Ca/Mg salts in the boiler water and forming insoluble precipitates of
Ca/Mg carbonate which can be removed by blow down operation method.

CaSO4 + Na2CO3 Na2SO4 + CaCO3

EXTERNAL TREATMENT: In this method all kinds of salts including hardness producing Ca/Mg
can be removed from the hard water before fed into the boiler. In industries, ion-exchange
process and reverse osmosis are the most common methods used in softening of hard water.

ION-EXCHANGE METHOD: The boiler feed water should be free from all types’ hardness
producing salts. Water of such quality can be obtained through demineralization process. It is
also called Ion-exchange method and De-ionization method. The process, in which the cations
like Ca2+, Mg2+, K+ and Na+, etc and anions like Cl- , SO42- and HCO3- , etc are removed from
the hard water using cation and anion exchange resins respectively, is called Ion-exchange
process. 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
ion-exchanging properties. Resins containing acidic groups (--COOH, --SO3H) are capable
of exchanging their H+ ions with cations of hard water. Resins containing basic groups
(--NH2, --OH) are capable of exchanging their anions with the anions of hard water.

De-ionizer
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PROCESS: In this process hard water is allowed to pass through two kinds of columns.

The first column is packed with a cation exchange resin (RH) which exchanges H+ ions with
Ca2+, Mg2+ and all other cations present in the water.

2 RH + Ca2+ R2Ca + 2 H+

RH + Na+ RNa + H+

The cation free water is now passed through the second column packed with an anion exchange
resin (ROH) which exchanges OH- ions with Cl-, SO42- and all other anions present in the water.

ROH + Cl- RCl + OH-

2 ROH + SO42- R2SO4 + 2 OH-

The H+ and OH- ions released from the exchangers combine to give water molecules which are
free from all the cations and anions present in the hard water. The ion-free water is called de-
ionized water or de-mineralized water.

REGENERATION: The cation exchanger is regenerated by passing dil.HCl

R2Ca + 2 HCl 2 RH + CaCl2

RNa + HCl RH + NaCl

Similarly, the anion exchanger is regenerated by passing dil.NaOH.

RCl + NaOH ROH + NaCl

R2SO4 + 2 NaOH 2 ROH + Na2SO4

Advantages:
1. This process produces water of hardness nearly 2 ppm.
2. Highly acidic or alkaline water can be softened.

Disadvantages:
1. It is expensive.
2. Highly turbid water cannot be softened.

DESALINATION: Based on the TDS value, the water is classified as fresh water (TDS < 1000
ppm), brackish water (TDS = 1000 – 35000 ppm) and sea water (TDS > 35000 ppm). The water
containing dissolved salts (3.5% of NaCl) with a peculiar salty taste is called brackish water. It is
totally unfit for drinking purpose. Sea water and brackish water can be made available as
drinking water through desalination process. The process of removing common salts (NaCl)
from water is known as desalination. The need for such a method arises due to the scarcity of
fresh water. Desalination can be carried out by the principle of reverse osmosis.

REVERSE OSMOSIS (RO): When a semi-permeable membrane separates two solutions of

different concentrations, flow of solvent takes place from dilute to concentrated solution due to
osmosis. By applying external pressure exceeding osmotic pressure on the concentrated side,

16
the flow of solvent takes place from concentrated to dilute solution. This process is called RO.
It is also known as hyper-filtration / super-filtration.

RO is used in conjunction with one or more activated carbon filters. This combination
removes 99.9 % of undesirable water contaminants. Using RO method pure water is separated
from sea water. The membranes used are cellulose acetate, cellulose butyrate, polysulphone
and polyamides, etc.

Reverse osmosis

Sl.No Internal conditioning External conditioning

1 It can be carried out in the boiler
itself.
2 It includes phosphate, calgon and
carbonate conditioning, etc
3 It is used in low pressure boilers.
4 It is a corrective method
It is carried out before its entry into the
boiler.
It includes lime-soda, ion-exchange
process and zeolite, etc
It is used in high pressure boilers.
It is a preventive method.

SOLVED PROBLEMS
Hint: TLH = Total hardness; PH = Permanent hardness; TH = Temporary hardness.
CH = Carbonate hardnes; NCH = Non-carbonate hardness; HW = Hard water;
SHW = Standard hard water.

1. A sample of water contains 204 mg of CaSO4 and 73 mg of Mg(HCO3)2 per litre. What is the
TH in terms of CaCO3 equivalent?

Solution:

Salt Amount M.Wt Hardness

CaSO4 204 136 (204/136) X 100 = 150

Mg(HCO3)2 73 146 (73/146) X 100 = 50

PH due to the presence of CaSO4 = 150 mg/L

TH due to the presence of Mg(HCO3)2 = 50 mg/L

TLH = 150 + 50 = 200 mg/L

***************

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2. Calculate the TH and PH of water sample containing the following. Mg(HCO3)2 = 146 mg/L,
Ca(HCO3)2 = 81 mg/L, CaSO4 = 68 mg/L, CaCl2 = 11.1 mg/L and MgCl2 = 9.5 mg/L.

Solution:

Salt Amount M.Wt Hardness

Mg(HCO3)2 146 146 (146/146) X 100 = 100

Ca(HCO3)2 81 162 (81/162) X 100 = 50

CaSO4 68 136 (68/136) X 100 = 50

CaCl2 11.1 111 (11.1/111) X 100 = 10

MgCl2 9.5 95 (9.5/95) X 100 = 10

TH is due to the presence of Mg(HCO3)2 & Ca(HCO3)2 . TH = 100 + 50 = 150 mg/L

PH is due to the presence of CaSO4,CaCl2 & MgCl2 . PH = 50 + 10 + 10 = 70 mg/L

TLH = 150 + 70 = 220 mg/L

************
3. Calculate the CH and NCH of a water sample containing dissolved solids (mg/L) given as
follows: Mg(HCO3)2 = 7.3, Ca(HCO3)2 = 40.5, CaSO4 = 13.6, MgCl2 = 21.75 and NaCl = 60
.

Solution:

Salt Amount M.Wt Hardness

Mg(HCO3)2 7.3 146 (7.3/146) X 100 = 5

Ca(HCO3)2 40.5 162 (40.5/162) X 100 = 25

CaSO4 13.6 136 (13.6/136) X 100 = 10

MgCl2 21.75 95 (21.75/95) X 100 = 22.8

NaCl 60 Do not consume any hardness

CH is due to the presence of Mg(HCO3)2 &Ca(HCO3)2. CH= 5 + 25 = 30 mg/L

NCH is due to the presence of CaSO4 & MgCl2. NCH = 10 + 22.8 = 32.8 mg/L

TLH = 30 + 32.8 = 62.8 mg/L

***********************

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4. 50 ml of hard water required 15 ml of EDTA solution for a titration. Calculate the hardness of
the sample of water.

Solution: We know that 1 ml of EDTA = 1 mg of CaCO3 equivalent

Therefore 15 ml of EDTA = 15 mg of CaCO3 equivalent

i.e. 50 ml of hard water contain 15 mg of CaCO3 equivalent

Then the hardness = (15/50) X 1000 = 300 mg/L

******************
5. 50 ml of SHW containing 1 mg of CaCO3 per ml consumed 17 ml of EDTA solution. 50 ml of
sample of HW consumed 12 ml of EDTA solution. Calculate the TLH in ppm.

Solution: 50 ml of standard hard water = 50 mg of CaCO3 equivalent

Therefore 17 ml of EDTA = 50 mg of CaCO3 equivalent

1 ml of EDTA = (50/17) mg of CaCO3 equivalent

12 ml of EDTA = 50 ml of water sample

12 ml of EDTA = 12 X (50/17) mg of CaCO3 equivalent

Thus, 50 ml of water sample contain 12 X (50/17) mg of CaCO3 equivalent.

Therefore hardness = 12 X (50/17) X1000 /50 = 705.88 mg/L

******************
6. 100 ml of a sample of water required 15 ml of 0.01 M EDTA solution for the titration using
EBT indicator. In another experiment, 100 ml of the same sample was boiled to remove the
CH, the precipitate was removed and the cold solution required 8 ml of 0.01 M EDTA solution
using EBT indicator. Calculate TLH, NCH and CH in terms of mg/L of CaCO3 .

Solution: TLH: We know that 1 ml of 1 M EDTA = 100 mg of CaCO3

Then 1 ml of 0.01 M EDTA = 1 mg of CaCO3 equivalent

15 ml of 0.01 M EDTA = 15 mg of CaCO3 equivalent

i.e. 100 ml of water sample contain 15 mg of CaCO3

TLH = (15/100) X 1000 = 150 mg/L

NCH: 1 ml of 0.01 M EDTA = 1 mg of CaCO3 equivalent

8 ml of 0.01 M EDTA = 8 mg of CaCO3 equivalent

i.e. 100 ml of water sample contain 8 mg of CaCO3

NCH = (8/100) X 1000 =80 mg/L ; CH = TLH – NCH = 150 – 80 = 70 mg/L

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 PROBLEMS FOR PRACTICE

1. A sample of water contains 120 mg of MgSO4 per L . Calculate the hardness in terms of CaCO3
equivalent. (Answer: 100 ppm)

2. If a sample of water contain 50 mg of Ca2+ ion per L. Calculate its hardness in terms of CaCO3
equivalent. (Answer: 125 mg/L)

3. Calculate the TH and PH of a water sample containing the dissolved salts in 1 L of HW as given below:
Ca(HCO3)2 = 64.8 mg, Mg(HCO3)2 = 14.6 mg , CaSO4 = 13.6 mg/L and MgCl2 = 50 mg.
(Answer:TH= 50 mg/L, PH= 62.6 mg/L & TLH= 112.6mg/L)

4. Calculate the TH and PH of a water sample having the following data. Mg(HCO3)2 = 73 mg/L ,
Ca(HCO3)2 =162 mg/L, CaSO4 = 136 mg/L, MgCl2 = 95 mg/L and CaCl2 = 111 mg/L. (Answer:
TH= 150 mg/L, PH= 300 mg/L)

5. A sample of water contain the following dissolved salts in mg/L. Mg(HCO3)2 = 73, Ca(HCO3)2 = 81,
CaCl2 = 111 and MgSO4 = 40 . Calculate the TH and PH of the water (Answer: TH= 100 mg/L ,
PH= 133.33 mg/L)

6.100 ml of water sample needs 20 ml of EDTA solution for a titration. a ml of EDTA solution is
equivalent to 1.1 mg of CaCO3. Calculate hardness in ppm. (Answer: Hardness = 220 mg/L)

7. A water sample of 100 ml requires 18 ml of EDTA solution for a titration. 22 ml of the same EDTA
solution was required for the titration of 100 ml of standard hard water containing 1 g CaCO3 per litre.
Calculate hardness of water sample in ppm. (Ans:Hardness=818.18 mg/L)

8. 100 ml of a sample of water required 20 ml of 0.01 M EDTA solution for the titration with EBT indicator.
100 ml of the same sample after boiling and filtering required 10 ml of 0.01 M EDTA solution. Calculate
the TLH, CH and NCH of the sample. (Answer: TLH= 200 ppm, CH = 100 and NCH = 100 ppm)

******************

QUESTION BANK

PART – A
1. Name the different sources of water
2. What is the cause for alkalinity of natural water?
3. List out the hardness producing salts in water.
4. Define: Turbidity, and name the sources for turbidity of water.
5. How do acidity and alkalinity of water are caused?
6. What is the sanitary significance of fluorides in water ?
7. How does colour imparted in water? Give example.
8. How will you remove turbidity and colour from water?
9. Mention the common units used for expressing hardness of water.
10. Define: ppm
11. Distinguish between hard water and soft water.
12. What are the salts responsible for the temporary and permanent hardness of water?
13. Why does hard water consume lot of soap?
14. The simultaneous presence of OH- , HCO3- and CO32- in water is not possible. Give reason.
15. Give a test to identify the hard water.
16. Every soft water is not a demineralized water where as every demineralized water is a soft water.
Justify
17. Define: Hard water and soft water.
18. Define: Hardness of water.
20
19. Distinguish between Temporary and permanent hardness of water.
20. Define: Standard hard water.
21. What happens when temporary hard water is boiled?
22. Why is ammonia buffer solution added during determination of hardness of water by using EDTA?
23. What is the indicator used in EDTA method? What is the end point?
24. Write the structure of EDTA and disodium salt of EDTA.
25. What is boiler corrosion? How it can be prevented?
26. What is caustic embrittlement? How it can be prevented?
27. What is meant by priming and foaming? List out their effects in boilers.
28. What are the problems encountered in boiler feed water?
29. Name the gases dissolved in water that cause corrosion.
30. Differentiate scale from sludge.
31. Why should natural water not be fed in boiler?
32. Why boiled water is not always 100 % safe for drinking purposes?
33. What is meant by softening of water? Mention any two methods of water treatment.
34. Name any two coagulants.
35. In the deionization process, water is usually first passed through the cation exchanger and then
through the anion exchanger. Give reason.
36. How will you regenerate the column in demineralization process?
37. Give few examples for cation and anion exchangers.
38. What is brackish water?
39. What is desalination? Name few methods of converting sea water into fresh water?
40. What is electro dialysis?
41. What is reverse osmosis?
42. What are the advantages of reverse osmosis?
43. Chloramines are better than chlorine for sterilization of water. Why?
44. What is meant by break point chlorination?
45. Calgon conditioning prevents scale formation in boilers. Give reason.
46. Chloramines are preferable to bleaching powder for sterilization of drinking water. Give reason.
47. Calgon treatment is better than phosphate treatment. Why?
48. Why is water softened before using in boiler?
49. Boiled water is not always 100% safe for drinking purposes. Why?
50. What are disinfectants? Give examples.
51. Distinguish between internal and external conditioning of water.
52. What are the requisites of potable water?
53. Write the various steps involved in the domestic water treatment.
54. What is meant by sterilization of water?
55. Name any three examples for sterilizing agents.

PART – B

1. Discuss the estimation of hardness of water by EDTA method?

2. Explain the ion-exchange process of demineralization. Give its merits and demerits.
3. What is desalination? Discuss various methods of desalination of water.
4. What are the problems may arise in boilers due to the usage of hard water? Discuss the causes,
effect and control of any two problems.
5. Define: Boiler feed water, what are the specifications for boiler feed water? Discuss the internal and
external treatment methods of boiler feed water production.
6. Why is sterilization of water necessary? Discuss various methods of sterilization. Briefly explain how
water is treated for domestic purpose?
7. Explain: Break point chlorination.
8. What are the specifications for potable water? Briefly explain the types of impurities present in water
and the process used for their removal.
9. What is alkalinity? Describe the determination of various alkalinities of a given water sample.

21