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CHAPTER - 4
WATER TREATMENT
HARD WATER :
Hard water does not produce good lather or form with soap and consume more
soap. The hard water contains bicarbonates chloride and sulphates of calcium &
magnesium.
The hard water when treated with soap i.e. sodium stearate, then no lather will
be formed because sodium stearate of soap reacts with salts of calcium and
magnesium giving insoluble Ca & Mg stearate.

17 35 2 17 35
17 35 2 17 35
2C H COONa CaCl 2C H COOCa 2NaCl
sodium calcium
stearate stearate
2C H COONa MgCl 2C H COOMg 2NaCl
sodium magnesium
stearate stearate
+ +
+ +
SOFT WATER :
The soft water when treated with soap produces more lather and consume less
soap and this is due to the absence of dissolved salts of Ca & Mg in water.

17 35 2 17 35
C H COONa H O NaOH 2C H COOH + +
TYPES OF HARDNESS :
There are two types of hardness.
(1) TEMPORARY HARDNESS
It is due to the presence of only bicarbonate of calcium & magnesium. This
type of hardness can be removed by boiling the water.

Boil
3 2 3 2 2
Boil
3 2 3 2 2
insoluble
insoluble
Ca(HCO ) CaCO CO H O
Mg(HCO ) MgCO CO H O
+ + | +
+ + | +
(2) PERMANENT HARDNESS
This type of hardness is caused by the presence of chloride and sulphates of
calcium & magnesium. It can not be removed by boiling the water.
D:\Science & Humanity Department\Appliedsci.202\Ch.4water- treatmentA.doc
2
Salts producing hardness of water
Temporary Hardness :
Calciumbicarbonate Ca(HCO ) Mol.wt 162gm/ mole
3 2

Magnesiumbicarbonate Mg(HCO ) Mol.wt 146gm/ mole
3 2

Permanent Hardness :

2
Calciumchloride CaCl Mol.wt 111gm/ mole

2
Magnesiumchloride MgCl Mol.wt 95gm/ mole

4
Calciumsulphate CaSO Mol.wt 136gm/ mole

4
Magnesiumsulphate MgSO Mol.wt 120gm/ mole
UNITS OF HARDNESS :
(1) DEGREE CLARK
If in a 7.0 10
4
parts (by weight) of water contains one part (by weight) of
CaCO
3
or equivalent salts of Ca & Mg, then the hardness is said to be one degree
clark.
(2) DEGREE FRENCH
If in a 1 10
5
parts (by wight) of water contain one part (by weight) of CaCO
3
or equivalent salts of Ca & Mg, then the hardness is said to be one degree French.
(3) PPM
If in a 10
6
parts (by weight) of water contain one part (by weight) of CaCO
3
or
equivalent salts of Ca & Mg, then the hardness is said to be one ppm.
Relationship
0.07
0
degree clark = 0.1
0
degree french = 1 ppm

3
3
W Mol. wt.of CaCO
Hardness of solublesalt equivalent toCaCO
Mol. wt.of solublesalt
=

W 100
Mol. wt.of solublesalt
=
Note : The hardness is measured in terms of CaCO
3
because CaCO
3
is less soluble in
water and as the molecular weight of calcium carbonate is 100 gm/mole, it
makes easy in calculation.
Example 1
A water sample contains following dissolved salt.
Ca(HCO ) 8.1mg/lit.
3 2

Mg(HCO ) 29.2mg/lit.
3 2

2
CaCl 11.1mg/ lit.
4
MgSO 6.0mg/ lit.
3
Find out temporary hardness, permanent hardness & total hardness.
3
W 100
Hardness of solublesalt equivalent toCaCO
Mol. wt.of soluble salt
=

8.1 100
Hardness due toCa(HCO ) 5mg/ lit
3 2
162
= =

29.2 100
Hardness due toMg(HCO ) 20mg/ lit
3 2
146
= =

2
11.1 100
Hardness due toCaCl 10mg/lit
111
= =

6.0 100
Hardness due toMgSO 5mg/ lit
4
120
= =

3 2 3 2
Temparary Hardness Hardnessdue Hardness due
toCa(HCO ) toMg(HCO )
= +
= 5 + 20
= 25 mg / lit.

2 4
Permanant Hardness Hardness due Hardness due
toCaCl toMgSO
= +
= 10 + 5
= 15 mg / lit.

Total hardness Temporaryhardness Permanant hardness = +
= 25 + 15
= 40 mg / lit.
To remove hardness from water, three method are used on a large scale.
(1) Soda-lime method
(2) Permutit process
(3) Ion-exchange process
PERMUTIT PROCESS
Permutit is also known as Zeolite. They are capable of exchanging ions
reversibly. The chemical formula for permutit is Na
2
O, Al
2
O
3
SiO
2
6H
2
O. In short it is
written as Na
2
-P or Na
2
-Z.
For softening of water by this method, hard water is percolated at a specified
rate through a bed of zeolite kept in a cylinder. The hardness causing ions (Ca
++
&
Mg
++
) are retained by the permutit as Ca-P & Mg-P. While the out going water
contains sodium salts.
4
Permutit undergo following chemical reaction with temporary hardness forming salt.
Ca(HCO
3
)
2
+ Na
2
-P Ca-P + 2NaHCO
3
Mg(HCO
3
)
2
+ Na
2
-P Mg-P + 2NaHCO
3
permutit undergo following chemical reaction with permanent hardness forming salt.
CaCl
2
+ Na
2
-P Ca-P + 2NaCl
MgCl
2
+ Na
2
-P Mg-P + 2NaCl
CaSO
4
+ Na
2
-P Ca-P + Na
2
SO
4
MgSO
4
+ Na
2
-P Mg-P + Na
2
SO
4
When permutit is completely converted into calcium & magnesium permutit &
it ceases to soften the water. It gets exhausted. At this stage, the supply of hard water
is stopped & the exhausted permutit is regenerated by treating the bed with
concentrated 10% NaCl solution.
Ca-P + 2NaCl Na
2
-P + CaCl
2
Mg-P + 2NaCl Na
2
-P + MgCl
2
The washing with water is led to remove CaCl
2
& MgCl
2
& thus obtained
regenerated permutit can be again used.
ION-EXCHANGE PROCESS :
This is most modern method for softening hard water. By using this method
almost all salts can be removed completely from hard water and the water obtained is
as good as distill water.
In this process two types of resins are used i.e. cation exchange resin & anion
exchange resin, cation exchange resin contains (-COOH, -SO
3
H) function groups and
are capable of exchanging their H
+
ions with cations. While anion exchange resin
contains (-NH
2
, -OH) functional group and are capable of exchanging OH
-
ions with
anions.
5
In the process two columns, one consist of cation exchange resin & another
consist of anion exchange resin are used.
The hard water is first allowed to pass through a column containing cation
exchange resins. Which remove all the cations like Ca
+2
, Mg
+2
etc. and release H
+
ions. Reaction in first column takes place as under.
R-H
2
+ CaCl
2
Ca-R + 2HCl
R-H
2
+ MgCl
2
Mg-R -- 2HCl
R-H
2
+ CaSO
4
Ca-R -- H
2
SO
4
R-H
2
+ MgSO
4
Mg-R + H
2
SO
4
The anions like chloride & sulphates are converted into acid like HCl &
H
2
SO
4
. Which is passed through another column containing anion exchanger i.e. R-
(OH)
2
resin where the following reaction takes place.
R-(OH)
2
+ 2HCl R-Cl
2
+ 2H
2
O
R-(OH)
2
+ H
2
SO
4
R-SO
4
+ 2H
2
O
Water thus obtained is free from all cations and anions & is called soft water
or distill water.
When both resins get fully exhausted then they are regenerated. The acidic
resin is regenerated by passing dilute acid solution (in first column). While basic resin
is regenerated by passing dilute NaOH solution (in second column), followed by
washing with water.
Ca-R + 2HCl R-H
2
+ CaCl
2
in first
Mg-R + 2HCl R-H
2
+ MgCl
2
column
R-Cl
2
+ 2NaOH R-(OH)
2
+ 2NaCl in second
R-SO
4
+ 2NaOH R-(OH)
2
+ 2Na
2
SO
4
column
6
The regenerated acidic and basic resins are again reused for softening
of hard water.
EFFECT OF HARD WATER IN BOILER
The hard water when used for boiler, causes the following effects in boiler.
1. scale or sludge formations
2. priming and foaming
3. caustic embrittlement
4. corrosion.
(1) SCALE OR SLUDGE FORMATION :
The main causes of scale formation are
(1) On boiling water, the bicarbonates are converted into insoluble carbonate & gets
precipitated to form scale.
boil
3 2 3 2
Ca(HCO ) CaCO CO + H O + + |
boil
3 2 3 2 2
Mg(HCO ) MgCO CO H O + + + +
(2) Due to evaporation, the concentration of soluble matter is increased & finally
precipitated.
(3) Colloidal matter such as silica etc., due to high temperature and concentration are
precipitated in to boiler.
Disadvantages of scale or sludge formation :
(1) Sludges are poor conductor of heat, so they tend to waste a portion of heat
generated.
(2) Excessive sludge formation disturbs the working of boiler.
(3) It causes choking of pipes.
(4) Due to scale formation, over heating of boiler is done in order to maintain a
constant supply of steam. The over heating of the boiler tube makes the material
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softer & weaker & this causes distortion of boiler tube & also makes the boiler
unsafe to bear the pressure of the steam.
Prevention of sludge formation
(1) By using soft water
(2) By frequently blow-down operation.
(3) By removing the scale with the help of brush.
(4) By giving thermal shocks. (i.e. heating the boiler & then suddenly cooling with
cold water)
(5) CaCO
3
scale can be removed by passing 5-10% HCl while CaSO
4
scale can be
removed by passing EDTA solution.
(6) By the addition of sodium phosphate (Na
3
PO
4
) or disodium hydrogen phosphate
(Na
2
HPO
4
), which forms a non-adherent & easily removable soft sludge of
calcium & magnesium phosphate.
3CaCl
2
+ 2Na
3
PO
4
Ca
3
(PO
4
)
2
+ 6NaCl
(7) By the addition of calgon [Na
2
{Na
4
(PO
3
)
6
}] (sodium hexa meta phosphate)
sludge or scale formation can be prevented.
(2) PRIMING & FOAMING
(A) PRIMING
When a boiler is producing steam rapidly some particles of the water liquid
carried along with the steam. This process of Wet Steam formation is called
priming.
Causes of Priming
(1) the presence of large amount of dissolved solids
(2) high steam velocities.
(3) sudden boiling
(4) improper boiler design
(5) sudden increase in steam-production rate.
Disadvantages of Priming
(1) Dissolved salt in boiler water are carried out by the wet steam to turbine blades
which reduces their efficiency.
(2) Dissolved salts may enter the parts of other machinery may decrease the life of
the machinery.
(3) Actual height of the water column cannot be judge properly, Thereby making
the maintenance of the boiler pressure becomes difficult.
Prevention of Priming
(1) By improving boiler design.
(2) By fitting mechanical steam purifiers.
(3) By maintaining low water level in boilers
(4) By using soft water.
(5) By decreasing the amount of dissolved salts.
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( B) FOAMING :
It is the production of foam or bubbles in boiler which do not break easily.
Causes of Foaming :
It is due to the presence of oily substances in water.
(1) Low level of water in boiler.
(2) The presence of dissolved salts in water.
(3) Sudden increase in steam production rate.
Disadvantages of foaming :
(1) Actual height of the water column cannot be judge.
(2) Dissolved salts in water carried by the wet steam may damage turbine
blads or machinery parts.
(3) Boiler pressure cannot be maintained.
Prevention of Foaming :
(1) By the addition of anti-foaming chemicals like castor oil, Gallic acid,
tennic acid etc.
(2) removing oil from boiler water by adding compounds like sodium
aluminate.
(3) CAUSTIC EMBRITTLEMENT
It is a type of boiler corrosion caused by using highly alkaline water in the
boiler. The NaOH containing water flows into the minute hair-cracks, bends, joints
rivets causes the failure of the boiler by corrosion.
Caustic embrittlement can be avoided
(i) By using sodium phosphate as softening agent instead of sodium
carbonate.
(ii) by adding tannin or lignin to boiler water
(iii) by adding sodium sulphate to boiler water.
(iv) By adjusting the pH of boiler water to 8.0 8.5.
(4) CORROSION :
Corrosion of boiler takes place by chemical or electro chemical reaction.
(i) Due to dissolved oxygen :
Water usually contains about 8ml. of dissolved oxygen per liter at
room temperature. Dissolved oxygen in water in the presence of prevailing
high temperature, attack the boiler materials.
2 2 2
2Fe 2H O O 2Fe(OH) + + +
2 2 2 3 2
4Fe(OH) O 2(Fe O 2H O) + + +
(ii) Due to dissolved carbon dioxide
The produced carbon dioxide reacts with water to give carbonic acid
CO
2
+ H
2
O H
2
CO
3
which has slow corrosive effect.
9
(iii) Due to acids from dissolved salt
Water containing dissolved magnesium salts liberates acid on
hydrolysis
CaCl
2
+ 2H
2
O Ca(OH)
2
+ 2HCl
MgCl
2
+ 2H
2
O Mg(OH)
2
+ 2HCl
CaSO
4
+ 2H
2
O Ca(OH)
2
+ H
2
SO
4
MgSO
4
+ 2H
2
O Mg(OH)
2
+ H
2
SO
4
the liberaled acid produces corrosion effect.
Prevention :
(1) Corrosion can be prevented by adding alkali to neutralize acidity & anti-oxidant to
remove oxygen
(2) By keeping pH value 8 to 9.
(3) Oxygen is removed from boiler feed-water by adding Na
2
SO
3
.
(4) Oxygen can also removed by treating it with hydrazine hydrate NH
2
NH
2
NH
2
-NH
2
+ O
2
2N
2
+ 2H
2
O
PURIFICATION OF DRINKING WATER BY SCREENING,
SEDIMENTATION, CO-AGULATION & FILTERATION.
Water used for domestic purposes must be free from germs & bacteria. It
should be free from objectionable dissolved gases like H
2
S & dissolved salts like, lead
arsenic & manganese salts. Generally for domestic supply, surface water is used & it
is contaminated with large number of impurities such as, organic matter, suspended
impurities etc. therefore to make it safe for drinking purpose, following treatment
processes are employed.
(1) Screening :
Screening is the process of removing floating materials from water. Raw water
is allowed to pass through a screen having a large number of perforations which
removes the large & small floating matter.
(2) Sedimentation :
It is the process of removing insoluble impurities by allowing the water to stay
undisturbed for sometime. Water is allowed to settle in big tanks or reservoirs for a
number of hours. The suspended materials, other than living organisms which float
due to the gases they produce, settle down at the bottom due to the force of gravity.
The process of sedimentation is generally carried out in continuous flow type tanks in
which water flows continuously in a horizontal, radial or vertical directions at uniform
rate.
Horizontal flow tank consists of a rectangular tank with channel type inlet &
outlet extending throughout the width of the tank. It is provided with buffle walls to
10
reduce the velocity of the incoming water. The sedimented sludge is taken out through
the outlet provided at the bottom.
(3) Co-agulation :
Co-agulation is the process of removing fine sized particles from water with
addition of certain chemicals known as co-agulants.
Actually the fine sized particles present in water either do not settle down at
all or take a long time. In order to facilitate quick settling of these particles, some
chemical agents known as co-agulants are used. The commonly used co-agulants are
the salts of iron & aluminium. e.g. alum [ K
2
SO
4
Al
2
(SO
4
)
3
24H
2
O ], aluminium
sulphate Al
2
(SO
4
)
3
18H
2
O, ferrous sulphate FeSO
4
7H
2
O, ferric chloride FeCl
3
etc.
These salts react with carbonate & bicarbonate radicals present in water & form co-
agulable precipitates (flocks) of hydroxide of these metals. The precipitated
hydroxide absorbs the suspended impurities, bacteria & other micro-organisms &
causes them to settle down.
(4) Filtration :
When sludge etc. after co-agulation has settled down, filteration is carried out
by means of filters. Filtration is the process of removing insoluble, colloidal &
bacterial impurities from water by means of filters. The filters used in water filtration
consist of several layers of sand particles of different size.
Gravity send filter consists of a large rectangular take made of concrete. The
filtering medium in it consists of 3 feet of find send below which 1 feet thick coarser
sand which inturn is supported by 8 inches thick bed of graded gravel. Below the
graded gravels are drain through which filtered water goes out.
11
As the water percolates ( due to gravity ) through the fine sand bed, most of
the objectionable materials are absorbed by it & clear water collects in the under drain
channel, form where it is drawn out.
(5) Removal of Bacterial & Micro-Organisms :
Although most of bacteria & micro-organisms present in water are removed
by co-agulation followed by settling & filtering through sand beds, yet water contains
a small percentage of pathogenic bacteria. These bacteria must be completely
removed particularly from water supplied by municipality for drinking water
purposes. Otherwise water borne diseases may be produced. The process of
destroying these pathogenic bacterial & micro-organisms is known as sterilization or
disinfection.
(i) Chlorination of water :
Chlorine is a commonly used sterilizer in municipal water supply. It can be
used directly as a gas or as chlorine water. Its germicidal action is based on its
reaction with water. It reacts with water to form hypochlorous acid & nascent oxygen
both of which are powerful germicides.
Cl
2
+ H
2
O HOCl + HCl
HOCl HCl + [O]
However, excess of chlorine should be avoided because it produces
characteristic unpleasant taste & odour & irritating effect on mucous membrane. For
filtered water about 0.3-0.5 ppm of chlorine is sufficient. The treated water should not
contain more than 0.1-0.2 ppm of free chlorine.
(ii) Bleaching powder :
Bleaching powder is a good sterilizer for small water works. In practice about
100 liters of water is mixed well with about 1kg of the powder & the resulting
solution allowed to stand for several hours. Hypochlorous acid & nascent oxygen
produced by action of water on bleaching powder are powerful germicides.
12
CaOCl
2
+ H
2
O Ca(OH)
2
+ Cl
2
Cl
2
+ H
2
O HOCl + HCl
HOCl HCl + [O]
Bleaching powder should be used only in calculated amount because excess of
it will give a bad taste & disagreeable odour. While lesser amount of it will not
sterilize the water completely.
13
Question asked in T.E.B. exam
Q.1 Write the chemical reactions involved in permutit process.
Q.2 A sample of hard water gave on analysis the following results. Calculate the
temporary and permanent hardness in ppm.
Ca(HCO
3
)
2
= 81 mg/l CaCl
2
= 11.1 mg/l
Mg(HCO
3
)
2
= 73 mg/l MgCl
2
= 47.5 mg/l
MgSO
4
= 6.0 mg/l CaSO
4
= 6.8 mg/l
Q.3 List the effects of hard water when used in boiler. Explain scale and studge
formation and its prevention.
Q.4 What is Hard water ?
Q.5 What is French degree ?
Q.6 Total hardness of a water sample is 250 ppm. Calculate the hardness of that
water sample in degree clark and degree French.
Q.7 What is co-agulation ?
Q.8 How to prevent foaming in boiler ?
Q.9 Explain zeolite method for softening of water with figure.
Q.10 Explain sedimentation with co-agulant.
Q.11 Explain chlorination.
Q.12 Write bad effects of scale formation in boiler
Q.13 A sample of water on analysis gives the following results. Calculate total
hardness of the given sample of water.
Mg(HCO
3
)
2
- 7.3 mg/l
CaSO
4
- 13.6 mg/l
MgCl
2
- 19.0 mg/l
Q.14 Write only the names and formulas of the salts which produce the hardness of
water
Q.15 A sample of water on analysis give the following results. Calculate the total
hardness of the given sample of water and convert it in to degree French.
Mg(HCO
3
)
2
= 14.6 mg/lit.
MgCl
2
= 19.0 mg /lit.
CaSO
4
= 34.0 mg/lit.
Q.16 What is hard water ? Give the types of hardness.
Q.17 A sample of hard water gave on analysis the following results. Calculate the
temporary and permanent hardness of water in ppm.
Ca(HCO
3
)
2
= 8.1 mg/l MgSO
4
= 6.0 mg/l
Mg(HCO
3
)
2
= 29.2 mg/l MgCl
2
= 47.5 mg/l
CaCl
2
= 11.1 mg/l CaSO
4
= 6.8 mg/l
Q.18 Define caustic Embrittlement and explain how it can be prevented.
Q.19 Write short note on Demineratization of water. (Ion-exchange process)

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