7.

Water Technology

1 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

7. Water Technology
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Introduction, sources of water, types of impurities in water, hardness of water- temporary and
permanent hardness, units of hardness, disadvantages of hard water. Estimation of hardness by EDTA
method, boiler troubles. Softening methods: Internal treatment, external treatment; zeolite process, ion
exchange process, desalination of brackish water - reverse osmosis.
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Introduction: Water is the driver of nature

Water is our most important foodstuff: An adult should drink at least 2 L of liquid per day. The
recommended drink is water. Because water contains mineral nutrients and trace elements, it is the
perfect drink for meeting our daily fluid requirements. And furthermore, water doesn't contain calories.
The role of water in our body: Roughly 60% of an adult's body is composed of water. This reaches
as much as 70 to 80% in newborns. Quantitatively speaking, this makes water the most important
building block of the human body. It also explains why maintaining a good water balance is particularly
important for our physical and mental health.
Acting as both a means of transport and a solvent, water transports mineral nutrients contained within
our diet (e.g. magnesium, sodium, potassium and calcium) to our cells and removes the unwanted byproducts of metabolic processes through excretion. Chemical reactions continuously take place in our
cells, which can only happen if there is water present, or if water is involved in some way.
Take our body temperature, for example. During physical exercise or in the case of fever, water acts
as a heat conductor and ensures that our temperature returns to normal by sweating.
With this it is clear that life is possible on earth due to the presence of water. Nearly three-fourths of the
earth's surface is covered with water. Water is also found below the earth's surface. It is present in air
in the form of water vapor. About 60% of the human body is water. The bodies of all plants and animals
contain water.
Water is not only essential for lives of animals, plants, but also occupies a unique position in industries.
Probably, it is most important use as an engineering material is in the stream generation. Water is also
used as a coolant in power and chemical industry. In addition all most all industry (textile, paper, sugar,
atomic energy, steel, ice etc) needs water to function.

2 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Although water is natures most wonderful and abundant compound but only less than 1% of the
worlds water resources are available for ready use. Hence it is required to use it carefully and
economically.
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Sources of Water:
Rainwater, oceans, rivers, lakes, streams, ponds and springs are natural sources of water. Dams,
wells, tube wells, hand-pumps, canals, etc, are man-made sources of water.
The natural source of water is divided into two types. 1) Surface water 2) underground water
1) Surface Water:
Water present on the surface of the earth in the form of oceans, rivers, lakes, ponds and streams is
called surface water. The water in rivers and lakes comes from rain and melting of snow on mountains.
Rivers flow into the sea.
i)

Rain Water is probably the purest form of natural water, since it is obtained as a result of
evaporation from the surface water. However, during the journey downwards through atmosphere,
it dissolves a industrial gases (CO2, SO2, NO2 etc) and suspended solid particles.

ii)

River water is obtained from rains and spring waters. River water contains many minerals of the soil
with which have come in contact, in the dissolved form. River water also contains the organic
matter, derived from the decomposition of plants, small parts of sand and rock in suspension.

iii) Lake water has more constant chemical composition. It, usually, contains much lesser amount of
minerals than well water, but contains high concentration of organic matter.
iv) Sea water is the most important form of natural water. Sea water contains about 3.5% of dissolved
slats out of which about 2.6% is NaCl. It is too saline for most industrial uses except cooling.
Surface water contains many impurities, suspended matter, and also disease producing
microorganisms. So the water must be purifying for safety.
2) Underground Water:
Some of the rainwater seeps through the soil onto the non-porous rocks below. This is underground
water. As this water journey downwards, it comes in contact with a number of mineral salts present in
the soil and dissolves some of them.
Sometimes due to high pressure, this water sprouts out in the form of springs. It can be obtained by
digging wells, sinking tube wells, etc.
------------------------------------------------------------------------------------------------------------------------------------3 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Types of impurities in water:

Types of impurities in water

a) Physical impurities
i) Colour
ii) Turbidity
iii) Odour
iv) Taste

b) Chemical impurities

c) biological impurities

1) Dissolved impurities (acidity, gases, inorganic salts)

2) Suspended impurities (inorganic, organic)
3) Colloidal impurities

The natural water is usually contaminated with many types of impurities. The most important are the
following three types
a) Physical impurities

b) Chemical impurities

c) biological impurities

a) Physical impurities: Generally the pure water has no colour, taste and odour.
(i) Colour in water is caused by metallic substances.

Yellowish thing indicates the presence of chromium and appreciable amount of organic matter.

Yellowish red colour indicates the presence of iron,

Red brown colour indicates the presence of peaty matter.

Change in colour of water is not harmful, unless it is associated with any chemical impurities.
(ii) Turbidity is due to the colloidal, extermely fine suspension such as clay, slit, finely divided organic
and inorganic matters and micro organisms etc.
Turbidity in water can be eliminated by sedimentation, followed by coagulation, filtration etc.
(iii) Odour in water is undesirable for domestic as well as industrial use. The cause of odour in polluted
rivers is due to the

presence of organic and inorganic impurities of N, S and P

Industrial effluents containing organic substances such as aldehydes, phenols, esters, ketones
etc.

(iv) Taste is due to the presence of dissolved mineral in water produces taste, but not odour.

Bitter taste: due to the presence of iron, aluminum, manganese, sulphate or excess of lime.

Soapy taste: due to the presence of large amount of sodium bicarbonate.

Brackish taste: due to the presence of unusual amount of salts.

Polatable Taste: due to the presence of dissolved gases and minerals like nitrates in water.

4 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

b) Chemical impurities in water:

1) Dissolved impurities:
(i) Acidity: Surface waters and ground waters attain acidity from industrial wastes like acid, and free
CO2. Acidity is not any specific pollutant and it simply determines the power to neutralize hydroxyl
ions and is, usually expressed in terms of ppm( or mg/L) of calcium carbonate equivalent.
(ii) Gases: generally the dissolved gases are O2, CO2, NH3, H2S etc.
a) All natural waters contain dissolved atmosphere CO2. Its solubility depends upon
temperature, pressure and dissolved mineral content of water.
b) The dissolved oxygen (DO) in water is essential to the life of aquatic organisms
such as fishes. Same time, the water excess of DO promotes corrosion.
c) Dissolved NH3 in water arises due to the decomposition of nitrogenous organic
compounds like urea.
(iii) Inorganic salts: they are released from industrial wastes.
(a) Cations: Ca2+, Mg2+, Na+, K+, Fe2+, Al3+ etc.
(b) Anions: CO3 2-, Cl, SO42-, NO32- etc.
2) Suspended Impurities:
(a) Inorganic: Clay and sand.
(b) Organic: Oil globules, vegetables, and animal material.
3) Colloidal Impurities
Finally divided clay and silica Al(OH)3, Fe(OH)3, organic waste products, colouring matter, amino acids
etc.
c) Biological impurities:
Micro-organisums like Bacteria, algae, fungi, different worms etc grow in water. The source of
these contaminations is discharges of domestic and sewage wastes. The contaminated water is not
only harmful to aquatic animals like fish, but also to human health. The growth of micro-organisms is
more at 20-35 oC. These micro-organisms can be controlled by chlorination.
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5 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

SOURCES OF IMPURITIES IN WATER

Following are the sources of impurities in water:
(i) Gases (O2, CO2 etc.) are picked up from the atmosphere by rainwater.
(ii) Decomposition of plants and animals remains introduce organic impurities in water.
(iii) Water dissolves impurities when it comes in contact with ground, soil or rocks.
(iv) Impurities are also introduced in water when it comes in contact with sewage or industrial waste.

Impurities in various sources of water

River water contains dissolved minerals like chlorides, sulphates, bicarbonates of sodium,
magnesium, calcium and iron. It also contains suspended impurities of sand, rocks and organic matter.
The composition of river water is not constant. The amount of dissolved impurities in it depends on its
contacts of the soil. Greater the duration of contact, more soluble is the minerals of soil in it.
Lake water has high quantity of organic matter present in it but lesser amount of dissolved minerals.
Its chemical composition is also constant.
Rain water is obtaining as a result of evaporation from the surface water. Probably it is the purest form
of natural water. But during its downward journey through the atmosphere it dissolves organic and
inorganic suspended particles and considerable amount of industrial gases like (CO2, NO2, SO2 etc.).
Rain water is expensive to collect and is irregular in supply.
Underground water is free from organic impurities and is clearer in appearance due to the filtering
action of the soil. But it contains large amount of dissolved salts.
Sea water is very impure due to two reasons:
1. Continuous evaporation increases the dissolved impurities content, which is further increased by
the impurities thrown by rivers as they join sea.
2. Due to the excretory impurities released by sea animals.
---------------------------------------------------------------------------------------------------------------------------------------HARDNESS OF WATER
The water consist of excess of minerals (Ca+2/ Mg+2) is called as hard water. Hardness in water is
that characteristics, which prevents the lathering of soap.

6 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Cause of Hardness
Hardness is due to presence of certain salts of Ca+2, Mg+2 and other heavy metal ions like Al3+, Fe3+
and Mn2+ in water.
Mechanism of cause of hardness: It can be explained by the reaction of soap in soft and hard water.
Reaction of soap in soft water
When soft water is treated with soap, lather is produced according to the following reaction:
C17H35COONa + H2O C17H35COOH + NaOH
Soap (Sodium stearate)
Stearic acid
C17H35COONa + C17H35COOH Lather
Reaction of soap in hard water
A sample of hard water, when treated with soap (sodium or potassium salt of higher fatty acid like
oleic, palmitic and stearic acid), does not produce lather, but on the other hand forms insoluble white
scum or precipitate which do not possess any detergent action. This is due to the formation of
insoluble soap of calcium and magnesium. Typical reaction of soap (sodium stearate) with calcium
chloride and magnesium sulphate are shown below.
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl
Calcium stearate (Insoluble scum)

2 C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

Magnesium stearate (Insoluble scum)

-------------------------------------------------------------------------------------------------------------------------------------Types of Hardness
It is of two types. 1) Temporary Hardness 2) Permanent Hardness
1. Temporary Hardness
(a) Temporary hardness is caused by the presence of dissolved bicarbonates of calcium, magnesium
and other heavy metals and the carbonates of iron and other metals also. The main salts responsible
for temporary hardness are Ca(HCO3)2 and Mg(HCO3)2.
(b) Temporary hardness can be largely removed by more boiling of water, when bicarbonates are
decomposed, yielding in soluble carbonates or hydroxides, which are deposited as a crust at the
bottom of vessel.
7 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 Mg(OH)2 + 2CO2
(c) Temporary hardness is also known as carbonate hardness or alkaline hardness.
(d) Temporary hardness is due to the presence of bicarbonates, carbonates and hydroxides of the
hardness producing metal ions. This is determined by titration with HCl using methyl orange as
indicator.
2. Permanent Hardness
(a) It is due to the presence of dissolved chlorides and sulphates of calcium, magnesium, iron and
other heavy metals. Hence, the salts responsible for permanent hardness are CaCl2, MgCl2, CaSO4,
MgSO4, FeSO4, Al2(SO4)3 etc.
(b) Unlike temporary hardness, permanent hardness is not destroyed on boiling.
(c) It is also known as non-carbonate or non-alkaline hardness.
(d) The difference between total hardness and Temporary hardness gives the permanent hardness.
---------------------------------------------------------------------------------------------------------------------------------------Disadvantages of Hard Water or Effect of Hardness
Hardness causing impurities present in the hard water exert following effects:
i)

Effect on domestic uses

ii) Effect on industries

i) Effect on domestic uses:

(a) Washing: hard water reduces the efficiency of soap. Because it does not produces lather freely.
Same time it produces sticky precipitate (i.e. scum) of Calcium stearate or Magnesium stearate.
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl
Calcium stearate (Insoluble scum)

2 C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

Magnesium stearate (Insoluble scum)

The formation of such insoluble sticky precipitates continues till all calcium and magnesium salts
present in water are precipitated. After that, the soap (i.e., sodium stearate) gives lather with water. As
result the consumption of soap is increased. Finally shows effect on economy.
C17H35COONa

+ H2O C17H35COOH + NaOH

Soap (Sodium stearate)

Stearic acid

C17H35COONa + C17H35COOH Lather

Soap (Sodium stearate)

Stearic acid

This causes wastage of lot of soap being used. The sticky precipitate adheres on the fabric giving
spots and streaks. Iron salts may cause staining of cloth.
8 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

(b) Bathing: Hard water does not lather freely with soap solution, but produces sticky scum on the body
and bath-tub. As a result, the cleansing quality of soap depresses and a lot of it is wasted.
(c) Cooking: Due to presence of dissolved hardness producing salts, the boiling point of water
increases. As result, more fuel and time are required for cooking. Certain foods such as pulses, beans
and peas do not cook soft in hard water. Also tea or coffee, prepared in hard water, has an unpleasant
taste and muddy looking extract. Moreover, the dissolved salts are deposited as carbonates on the
inner walls of the water heating utensils.
(d) Drinking: It adversely affects digestive system and increased possibilities of forming calcium oxalate
crystals in the urinary track on drinking.
ii) Effect on industries: Due to presence of dissolved salts, it exerts adverse effects on various
industries like
(i) Textile industries: The Ca+2/Mg+2 adhered on fabrics reduces quality of the colour shade. Further,
these salts may cause coloured spots on fabrics, thereby spoiling their beauty.
(ii) Sugar industries: Difficulties in crystallization of sugar and produced sugar may be deliquescent.
(iii) Dyeing industry: Dissolved salts may react with costly dyes, which give result of impure shade and
spot on fabric being dyed.
(iv) Paper industry: Dissolved salt may react with the chemicals used to give shining to paper. Iron
salts may affect colour of paper being produced.
(v) Effect on laboratories: Hardness causing ions interference in various reactions therefore it is not a
suitable solvent.
(vi) Concrete making: the presence of Cl-, SO42- affects the hydration of cement and finally strength of
the hardened concrete.
(vii) Effect on steam generation in boilers: For steam generation, boilers are widly used in various
industries. If the hard water fed directly to the boilers, there arise many troubles such as: (i) Sludge and
scale formation (ii) caustic embrittlement (iii) corrosion (iv) Priming and foaming, and carry over
--------------------------------------------------------------------------------------------------------------------------------------Softening of Water:
Softening of water means the removal of calcium, magnesium, iron salts and similar other metallic
ions, which would form insoluble metallic soaps. The important industrial methods employed for
softening of water are: i) zeolite process ii) ion exchange process
9 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Zeolite process or Permutit process: Zeolites in Greek it means boiling stone.

Zeolites is hydrated sodium alumino silicate Na2O, Al2O3, xSiO2.yH2O where x = 2-10 and y=2-6).
zeolites are insoluble in water and have the property of exchanging ions(Na+) present in them with the
ions (Ca+2, Mg+2) present in the solution. Zeolite is two types a) natural zeolite and b) Artificial zeolite
Natural zeolite is hard and cannot use for water purification. Example for natural zeolite is
natrolith and its chemical formula is Na2O Al2O3.3SiO2.2H2O. Artificial zeolite used for softening
purpose is permutit. These are porous and glassy and have greater softening capacity than green
sand. They are prepared by heating together with china clay, feldspar and soda ash.
Permutit or zeolites are and a slow stream of hard water is passed through this material. As a result,
Ca+2 and Mg+2 present in hard water are exchanged with sodium ions in the Zeolite. The outgoing
water contains sodium salts, which do not cause hardness.
Method of Softening in zeolite process: Hard water is passed through a bed of zeolite packed in a
suitable container at a specific rate at ordinary temperature; the hardness causing cations i.e., Ca2+ and

Mg2+ are exchanged for Na+ and it is converted to CaZe and MgZe. ( Ze = O, Al2O3, xSiO2.yH2O )
Reactions taking place are:
Na2Ze + Ca(HCO3)2 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 2NaHCO3 + MgZe
Na2Ze + CaSO4 Na2SO4 + CaZe
Na2Ze + CaCl2 2NaCl + CaZe
Regeneration of Zeolite: The process is also commercially successful since the Ca/Mg zeolites formed
by passing hard water through the bed can be easily regenerated into Na2Ze by passing brine through
the bed of inactivated zeolite.
CaZe or MgZe + 2NaCl Na2Ze + CaCl2 (Or MgCl2)
The washings containing CaCl2 or MgCl2 are wasted. The water softened by this process can be used
for laundry purposes.
Advantages:
(i)

Hardness of water can be removed completely up to about 10 ppm;

(ii)

The equipment used is small and easy to handle;

(iii)

It requires less time for softening;

10 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

(iv)

There is no sludge formation, hence the process is clean;

(v)

Easy to regenerate;

(vi)

Any hardness can be removed without any adjustment of the process.

Softening of hard water by permutit / zeolite process

Disadvantages / limitations:
(i)

Coloured water due to Mn+2 and Fe+2 cannot be used as such. Because these ions cause
reacts with zeolite and produces manganese and iron zeolite, which cannot be easily
regenerate.

(ii)

water containing suspended impurities cannot be used before filtration;

(iii)

Water containing acid cannot be used for softening since acid may destroy the zeolite;

(iv)

In this method only Ca2+ and Mg2+ ions are replaced by Na+ ions leaving all acidic ions like
-

HCO3 , CO3 2. When this water is used in boilers on heating liberates CO2, which causes
corrosion in the boilers and hence this soft water is not suitable for boilers.

Ion Exchange Resins

Giant organic molecules having acidic (or) basic groups are known as Ion-exchange resins. It is two
types. i) Cation exchange resins ii) Anion exchange resins.

11 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

(i)

Cation exchange resins (RH+): contain the acid group (- COOH) which exchange their H+ ions
with the cations present in the water i.e., Ca2+ and Mg2+.

(ii)

Anion exchange resins (ROH-): contain basic group (quaternary ammonium) which
exchange their OH- with different anions of water i.e., Cl-, SO42- etc.

Method of Softening in ionexchange resin process:

The hard water is passed first through cation exchange resin, where all the cations like Ca2+, Mg2+ are
removed from the hard water and exchanged with H+ as follows.
-

2RCOO H+ + Ca2+ (RCOO)2Ca + 2H+

After this the hard water is again passed through anion exchange resin, which exchanges all the
anions like SO42 , Cl , HCO3 etc. present in the water with OH . Basic resins, therefore, are also
known as acid exchange resins.
-

2RNH3+OH + Cl RNH3Cl + OH
-

2RNH3+OH + SO42 (RNH3)2SO4 + 2OH

These H+ and OH- combine to form water molecule. Thus the water coming out finally from the two
exchangers is ion free and called deioinized or demineralized water. This is as good as distilled water.
The water becomes soft after this process
-

H+ + OH H2O
Regeneration of Resin:
The inactivated or exhausted cation exchange resin is regenerated by dil. H2SO4/HCl.
12 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

(RCOO)2Ca + 2H+ 2RCOO H+ + Ca2+

Similarly, the exhausted anion exchange resin is regenerated by dil. NaOH
-

(RNH3)2SO4 + 2OH 2RNH3+OH + SO42

The columns are finally washed with deionized water and the washings are discarded.

Ion-exchange process for water softening

Advantages:
i)

This method can used to soften highly acidic or alkaline waters.

ii)

By this method the hardness of the water can bring to low (2 ppm). So this water is good for
high pressure boilers.

Disadvantages:
i)

The equipment is costly and more expensive chemicals are to be used.

ii)

The water used for purification must be free from turbidity.

If Anion exchanger use before cation exchanger in water treatment system then following problem
occured
1. Deposition of sulphate in bed at high pH.
2. Elimination of CO2 gas will not possible at high pH
3. Due to very high pH in Cation unit sludge will be form which is the cause of strainer chocking
& effect to resin quality.
4. Increase possibility of sodium slippage.
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13 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Units of hardness
Both temporary and permanent hardnesses are expressed in ppm as CaCO3. The choice of CaCO3 is
due to the fact that its mol. wt. is 100 and equivalent weight is 50 and it is the most insoluble salt in
water.

Hardness is principally expressed in Parts Per Million (ppm) ubnits: which is defined as the parts of
CaCO3 equivalent per 106 parts of water. i.e. 1 ppm = 1 part of CaCO3 eq hardness in 106 parts of
water.

Other limits include mg/L, meq/L, French degree of hardness (oFr), English degree of hardness or
Clark (oCl).
Relationship between various units:

1 ppm

1 mg/L

0.1 oFr

0.07 oCl

0.02 meq/L

Problems relating to hardness of water: Refer Text book and class note book.
------------------------------------------------------------------------------------------------------------------------------------------------------------------

Estimation of hardness by EDTA method: this is a complexometric determination of hardness of

water. In this method disodium salt of ethylene diamine tetra acetic acid (EDTA) is used as a
complexing agent for Ca 2+, Mg 2+.

Erichrome black T is used as an indicator and pH is maintained at pH 10 using NH4OH/NH4Cl buffer.

Principle: Erichrome black T forms unstable complex with Ca2+, Mg2+ giving wine red colour. When
EDTA added and the total Ca2+, Mg2+ forms complex with it and the indicator becomes free, the colour
of the solution changes from wine red to blue at the end point.
M+2 + EBT M-EBT

(unstable complex-wine red)

M-EBT + EDTA M -EDTA

(stable complex)

+ EBT
(blue)

(where M = Ca or Mg)
14 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Chemicals required:
(a) 0.01 M EDTA solution = Dissolve 4 g EDTA crystals in 1 L distilled water
(b) Buffer solution (pH= 10) = Add 67.5 g NH4Cl to 570 mL NH3 solution dilute to 1 L with distilled
water
(c) EBT indicator = Dissolve 1 g EBT in 200 mL ethanol
(d) Standard hard water: Dissolve 1 g pure dry CaCO3 in 1 L distilled water. i.e 1 mL of the
solution contains 1 mg CaCO3 equivalent hardness.
Procedure:
Standardization of EDTA solution: The burette is rinsed and filled with EDTA solution. 20 mL of
standard hard water is pipette out into a clean conical flask. 2 mL of ammonical buffer and few drops of
EBT indicator are added and then titerated against EDTA solution until the wine red colour changes to
deep blue colour which indicates the end point. Let the volume of EDTA used be V1 mL.
1 mL of standard hard water = 1 mg CaCO3 equivalent
20 mL of standard hard water = V1 mL EDTA
i.e V1 mL of EDTA = 20 mg of CaCO3 equivalent
1 mL EDTA =

mg of CaCO3 equivalent

--------------------------eq.1

Estimation of Total hardness: 50 mL of a given sample of hard water is pipette out into a clean conical
flask. 2 mL of ammonical buffer and few drops of EBT indicator are added and then titerated against
EDTA solution until the wine red colour changes to deep blue colour which indicates the end point. Let
the volume of EDTA used be V2 mL.
20 mL of given hard water = V2 mL EDTA
V2 mL of EDTA =
1mL of hard water =

X V2 mg of CaCO3 equivalent
X

mg of CaCO3 equivalent

1 L (1000 mL) of given hard water =

Total hardness =
15 |Water Technology

(from - eq.1)

x 1000 mg of CaCO3 equivalent

x 1000 mg/L
Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Estimation of permanent hardness: 250 mL of the hard water sample is taken in a beaker, heated
strongly and evaporated nearly 50 mL. As a result all bicarbonates decompose to insoluble CaCO3.
Filter off CaCO3 and make-up the filtrate to 250 mL with distilled water. 20 mL of make-up solution is
pipette out into a clean conical flask. 2 mL of ammonical buffer and few drops of EBT indicator are
added and then titerated against EDTA solution until the wine red colour changes to deep blue colour
which indicates the end point. Let the volume of EDTA used be V3 mL.
20 mL of boiled water = V3 mL EDTA
V3 mL of EDTA =

X V3 mg of CaCO3 equivalent

1mL of boiled water =

mg of CaCO3 equivalent

1 L (1000 mL) of boiled water =

Permanent hardness =

(from - eq.1)

x 1000 mg of CaCO3 equivalent

x 1000 mg/L

Temporary hardness = Total hardness Permanent hardness

2
x 1000
1
3
2
= 1000 1 1
2 3
= 1000
1

3
x 1000
1

Problems relating to hardness of water: Refer Text book and class note book.
-----------------------------------------------------------------------------------------------------------------------------------Boiler troubles

16 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

1 Scale and sludge formation

In boilers, water gets evaporates continuously and the concentration of the dissolved salts
increases progressively. As a result, dissolved salts concentration reach saturation point and at
this stage these dissolved salts thrown out of water in the form of precipitates (scale and sludge)
on the inner walls of their boiler.
i)

Sludge is a soft, loose and slimy precipitate formed with in the boiler. Sludges are fomed by
substances which have grater solubilites in hot water than in cold water. eg: MgCO3, MgCl2,
MgSO4, CaCl2 etc

Disadvantages due to sludge formation:

a) Sludge is a bad conductor of heat, hence it waste a portion of heat generated.
b) Excessive sludge formation reduces the efficiency of the boiler.
Prevention of sludge formation:
a) Sludge can be easily scrapped off with a wire brush and frequent blow-down operation.
b) By using well softened water.

ii)

Scales are hard deposits, which stick very firmly to the inner surfaces of the boiler. Formation
of scales may be due to following reasons:

a) Decomposition of Ca(HCO3)2:
Ca(HCO3)2 CaCO3 + H2O + CO2
(Scale)

But in high pressure boilers, CaCO3 soluble in water and forms soft scale
CaCO3 + H2O Ca(OH)2 + CO2
(soft scale)

b) Deposition of CaSO4
The solubility of CaSO4 in water decrease with rise of temperature, consequently, CaSO4 gets
precipitated as hard scale on the heated portion of the boiler.
c) Hydrolysis of magnesium slats:
Dissolved magnesium slats undergo hydrolysis and forms soft type of scales.
MgCl2 + 2H2O Mg(OH)2 + HCl

17 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

d) Presence of Silica: presence of SiO2 deposits as calcium silicates (CaSiO3) and magnesium
silicates (MgSiO3). This can be removed by using sand filters.
Disadvantages due to scale formation:
i)

Wastage of fuel: scales acts as a band conductors of heat. In order to provide steady supply
of heat to water, excessive heating is done and this causes increase in fuel consumption. The
wastage of fuel depends on the thickness of scale

ii)

Thickness of scale (mm)

0.3

0.6

1.2

2.5

12

Wastage of fuel (%)

10

15

50

80

150

Lowering of boiler safety: due to scale formation over heating is done and due to overheating,
the boiler material becomes soft and weaker. This makes the boiler unsafe to bare the
pressure of the steam.

iii) Decrease in efficiency: scales may some time deposits in the valves of boilers, this result in
decrease in efficiency of the boilers.
iv) Danger of explosion: At high temperature, cracks may be formed on scale and due to the
formation of uneven scales inside the boiler, causes the formation of large amount of steam
suddenly. This develops the high pressure, which may even cause explosion of the boilers.
Removal of scales:
i)
By thermal shocks
ii)
With help of a scraper or piece of wood
iii)
CaCO3 scales can be dissolved by using 5-10%
Prevention of scales formation:
This can be done in two ways. A) external treatment B) internal treatment (sequestration)
A) External treatment: this can be done by zeolite process or by using deionization procedure.
B) Internal treatment: this can be done by adding proper chemicals to the boiler water either i) to
convert scale formed substances into sludge which can be removed by blow-down operation or ii) by
keeping the scale forming substances in soluble state by means of complexation.

i) Colloidal conditioning

ii) Phosphate conditioning

iii) Carbonate conditioning

iv) Calgon conditioning

v) Sodium aluminate conditioning

Colloidal conditioning: organic substances like kerosene and agar-agar are added to the water
to avoid scale formation.

18 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Phosphate conditioning: A phosphate reacts with harness of water forming loose sludge which
can be easily removed by blow-down operation.
3CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

Carbonate conditioning: scale formation can be avoided by adding Na2CO3 to boiler water
CaSO4 + Na2CO3 CaCO3 + Na2SO4

Calgon conditioning: sodium hexa meta phosphate (calgon) is added to boiler water to prevent
the scale formation.
2CaSO4 + Na3(Na4(PO3)6) Na3(Na4(PO3)6) + Na2SO4

Sodium aluminate conditioning: Sodium aluminate (NaAlO2) gets hydrolyzed and so-formed
NaOH precipitates the magnesium present in hard water as Mg(OH)2
NaAlO2 + 2H2O Na + Al(OH)3
MgCl2 + 2NaOH Mg()2 + 2 NaCl
The precipitates Mg()2 + Al(OH)3 formed inside the boiler, traps the finely suspended and
colloidal impurities and the loose precipitates can be removed by blow-down operation.

Caustic embrittlement:
This type of corrosion caused by the NaOH formed in the boilers. Generally, during softening
process of water Na2CO3 is used, as a result usually free Na2CO3 present in small proportion in
the softened water. In boilers these Na2CO3 decomposes to give NaOH.
Na2CO3 + H2O 2 NaOH + 2 CO2
This NaOH passes into the minute hair cracks present on the boiler by a capillary action and
attacks the surrounding area dissolving iron of the boiler as sodium ferroate.
Fe + NaOH Na2FeO2 + H2
This causes the embrittlement of boiler parts particularly at bends, riverts, and joints etc causing
failure of boilers.
Prevention of embrittlement:
a) by using sodium phosphate as softening agent instead of Na2CO3
b) by adding tannin, Na2SO4 to boiler water. Since these materials blocks the hair-cracks

19 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Boiler corrosion
Boiler corrosion is decay of boiler material by a chemical or electrochemical attack by its
environment. This boiler corrosion is due to
i) Dissolved oxygen (DO)

ii) Dissolved CO2

iii) acids from dissolved salts

i) Dissolved oxygen (DO): water usually contains 8 mg/L of dissolved oxygen at room
temperature. It attacks boiler material causing rust formation.
2Fe + 2H2O + O2 2Fe(OH)2
4 Fe(OH)2 + O2 2(Fe2O3.2H2O)
Removal of DO: a) by mechanical de-aeration
b) by adding calculated quantity of Na2SO3 or Na2S or N2H4
Na2SO3 + O2 Na2SO4
Na2S + 2 O2 2 Na2SO4
N2H4 + O2 2 N2 + 2 H2O
ii) Dissolved CO2:- Water contains some dissolved CO2 and the decomposition product of
bicarbonates present in water also produces CO2. This CO2 dissolves in water forming carbonic
acid which causes local corrosion called pitting.
CO2 + H2O H2CO3
Fe + H2CO3 FeCO3 + H2
4FeCO3 + O2 + 10H2O 4Fe(OH)3 + 4H2O + 4CO2
4Fe(OH)3 2Fe2O3 + 6H2O
Removal of dissolved CO2: a) by mechanical de-aeration
b) by adding calculated quantity of ammonia
2 NH4OH + CO2 (NH4)2CO3 + H2O
iii) Acids from dissolved salts:- Water from industrial areas contains acidic waste and also
magnesium salts present in water liberate acids on hydrolysis.
20 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

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

The liberated Hcl reacts with iron in chain like reactions producing HCl again and again. So the
presence of even small amount of MgCl2 can cause corrosion of iron to a large extent. This type
of corrosion may be avoided by neutralization with alkali.
Fe + HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2 HCl

Priming and foaming:- this is also known as wet steam or carry over.
Priming: production of wet steam by rapid boiling of water in boilers is called priming. It may be
due to
a) Very high steam velocity

b) high water level

c) improper boiler design

d) sudden boiling

Priming can be avoided by i) maintaining low water level

iii) fitting mechanical steam purifiers

ii) using softened water

iv) using well designed boiler

Foaming: the production of continuing bubbles or foam in boiler, which do not break easily. It may
be due to
a) The presence of oil or soapy substances

b) more amount of salts

Foaming can be avoided by

i)

By adding antifoaming agents like cotton seed oil and castor oil

ii)

Adding sodium aluminate which coagulates the oily or soapy substances.

---------------------------------------------------------------------------------------------------------------------------------------Desalination of Brackish Water:

The water containing dissolved salts and having very salty taste is called brackish water, like the sea
water and it is not suitable for drinking. The process of removal of common salt from this brackish
water is called desalination. Desalination can be done by the following methods.
(a) Electrodialysis: This method involves the removal of ions from the brine solution by applying direct
current and employing pair of plastic membranes through which ions can pass. When direct current is
21 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

passed through saline water, the Na+ ions move towards the cathode while Cl ions move towards the
anode through the membrane and collect in the two side compartments while the central compartment
contains pure desalinated water.

To make this process more effective, ions-selective membranes are used that allow the passage of
either specific cations or specific anions only. These membranes are selective as they are made up of
materials containing fixed functional groups (Such as RSO3-, RCOO-, R4N+Cl-).
An electrodialysis cell contains a large number of pair of membranes and saline water is passed under
pressure in electric field applied perpendicular to the direction of flowing water. Cations and anions
pass through the membrane pairs and we obtain alternate streams of pure water and concentrated salt
solution.

Electrodialysis cell
22 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Advantages by Electrodialysis:
i) It is most compact unit
ii) The cost of installation of the plant and its operation is economical, if the electricity is
easily available.
(b) Reverse osmosis (RO):

Osmosis describes the flow of solvent from dilute to concentrated

solution through a semipermeable membrane. The pressure is called osmotic pressure. But in reverse
osmosis the flow of solvent is in opposite direction. i.e. from concentrate solution to dilute solution
across the semi-permeable membrane. A hydrostatic pressure which is higher than osmotic pressure
is applied as a result the solvent flow reverse.
Method: in this process, pressure is applied to the sea water to force its pure water out through the
semi-permeable membrane leaving behind the dissolved salts. The semi-permeable membrane is
cellulose acetate or polyamide polymers. Semi-permeable membrane can allow only solvent but not
solute particle.
Advantages by reverse osmosis purification process:
(i)

Removal of ionic, non-ionic, colloidal and high molecular weight solutes from water.

(ii)

Easy replacement of the semi-permeable membrane and life time of membrane is high.

(iii)

Uninterrupted supply of large volume of water for industrial or domestic purpose can be
obtained.

(iv)

Reverse osmosis is largely used for purification of sea water for domestic use.

--------------------------------------------------------------------------------------------------------------------------------------

General information:
Requirements for Drinking Water:
It should be clear and odorless.
It should be devoid of any unpleasant taste.
Suspended matter should not exceed 10 ppm.
It should be devoid of heavy metals and arsenic.
pH should be about 8.
Content of dissolved salts should not exceed 500 ppm.
Lastly, it should be free from pathogenic (disease causing) microorganisms

23 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

Differences between Hard Water and Soft Water

11

Effect
industries

on

Shows bad effect on textile, sugar, paper industries, etc

No bad effects. Moreover,

soft water is used in
these industries.

EXERCISES
1. What is desalination? Name the different methods of desalination and describe any one.
2.

What are boiler troubles? Why are they caused? What are the methods of their elimination?

24 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

3.

Distinguish between:
(a) Temporary and permanent hardness. (b) Sludge and Scale. (c) Softening and demineralization.

4. Write notes on: (i) Caustic embrittlement, (ii) Reverse osmosis, (iii) Priming and foaming, (iv) Boiler
corrosion
5. What is the principle involved in the determination of total hardness of water by EDTA method?
6. Why does hard water consume more soap?
7. During deionization process, water is first passed through cation exchanger and then through anion
exchanger, why?
-----------------------------------------------------------------------------------------------------------------------------------------------

2 hours
Source of water 1) Surface water 2) underground water
Types of impurities in water
Types of impurities in water

a) Physical impurities

b) Chemical impurities

i) Colour
ii) Turbidity
iii) Odour
iv) Taste

c) biological impurities

1) Dissolved impurities (acidity, gases, inorganic salts)

2) Suspended impurities (inorganic, organic)
3) Colloidal impurities

-----------------------------------------------------------------------------------------------------------------------------------2 hours
Hardness of water- temporary and permanent hardness
Disadvantages of hard water
i)

Effect on domestic uses

ii) Effect on industries

-----------------------------------------------------------------------------------------------------------------------------------1 hour
Units of hardness, Estimation of hardness by EDTA method
-------------------------------------------------------------------------------------------------------------------------------------1 hour (in 1 year inter syllabus)
Softening methods: Internal treatment, external treatment; zeolite process, ion exchange process
------------------------------------------------------------------------------------------------------------------------------------1 hour
desalination of brackish water - reverse osmosis
25 |Water Technology

Dr Y.B.Kiran, Sreevidyanikethan Engineering College

8.

Analytical Techniques

----------------------------------------------------------------------------------------------------------------------------------------------------Introduction to spectroscopy. U.V.Visible Spectroscopy: Basic principle, origin of absorption bands,

chromophores and their absorption values. I.R. Spectroscopy: Principle, modes of vibration, group frequencies.
NMR Spectroscopy: Principle, shielding and deshilding of protons, chemical shift and applications of NMR
spectroscopy. Atomic Absorption Spectroscopy: Principle and applications. Flame photometry: Principle
and applications.
----------------------------------------------------------------------------------------------------------------------------------------------------

An analytical technique is a method that is used to determine the concentration of a chemical

compound or chemical element. There are a wide variety of techniques used for analysis.
Spectroscopy is the analysis of the interaction between matter and any portion of the electromagnetic
spectrum.
For this unit better follow class notes and important topics only

Dr Y.
Y. B. Kiran
Assistant professor (SL)
Department of Chemistry
Sree Vidyanikethan Engineering College,
Sree Sainath Nagar, A.Rangampet,
Tirupati, India 517102
drybkiran@gmail.com

26 |Water Technology

1) This material gives you a basic information

2) Refer text book for more details

Dr Y.B.Kiran, Sreevidyanikethan Engineering College