Water

&
Its Treatment

Introduction
For the existence of all living things water is essential. Without water we

cannot survive. Almost all human activities domestic, agricultural and

industrial demand use of water.

Water from any source has to be treated before its use. The treatment to

which it is subjected depends upon its use.

If it has to be used for drinking purposes, the treatment would include

removal of objectionable colour, taste and pathogenic micro organisms,

whereas the water for industrial use require the removal of dissolved salts if
it is used for steam generation.

In this section we will discuss about the analysis of water and treatment of

water for its industrial and domestic use.

Sources of water
Surface water :-The water which comes from surface through

rain. eg :- rain water, river water & sea water.

Underground water :- This water comes from rain that falls on

earths surface & then goes into the ground water & travel down
the impervious (cracks) layers of earth, thus forming ground
water. eg :- spring water & well water.

Impurities in Water

Silica, clay etc

CO2, O2, H2S

Bacteria & other Micro-organisms like algae & fungi

Carbonates, Bicarbonates, Chlorides & Sulphates of Ca,

Mg.

Types Of Water

HARD WATER

SOFT WATER

Hard WATER
water and Soft
waterWATER
HARD
SOFT
Does not form lather with soap Forms lather with soap easily
easily
Contains dissolved salts of Ca
& Mg

Does not contain dissolved

salts of Ca & Mg

More wastage of time & fuel as Less wastage of time & fuel
boiling temp. of water gets
increased due to impurities
More consumption of soap by
hard water

Less consumption of soap by

soft water

Hardness of water
Hardness is the soap consuming capacity of water
Hardness of water is due to the presence of Ca and Mg salts in

it. Other ions responsible for hardness are Al3+, Fe3+ and Mn2+

If Ca and Mg salts are present in water then they react with the

soluble sodium soap to form insoluble salts calcium and

magnesium.

2C17H35COONa + CaSO4--- (C17H35COO)2Ca + Na2SO4

Sodium stearate
Insoluble salt
2C17H35COONa + MgCl2--- (C17H35COO)2Mg + 2NaCl
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Types Of Hardness

TEMPORARY
(Carbonate Hardness)

PERMANENT
(Non- Carbonate Hardness)

Temporary Hardness
Caused by the presence of dissolved bicarbonates of Ca, Mg and. .

This hardness is also known as alkaline hardness.

Easily removed by heating :

Heat

Ca(HCO3)2--------- CaCO3

+ H2O + CO2

Heat

Mg(HCO3)2--------- MgCO3 + H2O + CO2

Permanent Hardness
Due to the presence of sulphates and chlorides of Ca & Mg
Cannot be removed simply by boiling.
Special methods like lime soda process, zeolite process, ion-

exchange method are used for the removal of permanent

hardness.

10

Degree of Hardness in terms of CaCO3

equivalent
Hardness is expressed in terms of CaCO3 equivalents.
Reasons for choosing CaCO3 as the reference standard for

calculating hardness of water is :

mol. wt. is 100 that makes mathematical calculation easier.

The most insoluble salt and can be easily precipitated in water

treatment process.

11

How to calculate harness in terms of

CaCO3 equivalent
Hardness in terms of CaCO3 equivalents

= wt. of hardness producing sub.

mol. mass of CaCO3

mol. mass of hardness producing
sub.

Units of Hardness
a) parts per million

ppm

parts of CaCO3 equivalent hardness per 106 parts of

water.

b) Milligrams per
litre

Mg/l

no. of milligrams of CaCO3 equivalent hardness per

litre of water.

Cl

parts of CaCO3 equivalent hardness per 70,000 parts

of water.

Fr

parts of CaCO3 equivalent hardness per 105 parts of

water.

Degree Clark

c)

.
d) Degree French

Relation between various units of hardness

1ppm = 1mg/l = 0.1Fr = 0.07 Cl

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Boiler feed water

For steam generations, boilers are used
if hard water is fed to the boiler, various problems are faced by

boiler :

Scale and Sludge formation

Priming and Foaming
Boiler corrosion
Caustic embrittlement

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Sludge & Scale

Continous evaporation of water takes place & conc. of dissolved salts gets

increased & at saturation point forms ppts. on the inner walls of the boiler.
Sludges : If loose & slimy ppts formed.
Scales : If sticky, hard & adhernt coat formed.

Sludge

Scale

15

Sludge
FORMATION:
Where flow of water is slow
At colder region
By substances which have greater solubility in the hot water.
MgCO3, MgCl2, CaCl2, MgSO4 etc.

DISADVANTAGES:
Poor conductor of heat hence more consumption of time and fuel.
Disturbs functioning of boiler & settles in the regions of poor water

circulation.

PREVENTION :
By using soft water
By using blow down pipe operation .

16

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

CaCO3 + H2O
Deposition of CaSO4 :

Ca(OH)2 + CO2

Soluble in cold water

As temp.
solubility of CaSO4
hard scale

Hydrolysis of Mg salts
MgCl2 + 2H2O
Presence of (SiO2)

Mg (OH)2 + 2HCl

17

Scale
DISADVANTAGES

Fuel Wastage
Lowering of boiler safety
Decreased efficiency
Danger of explosion

Removal
Using wire brush
By using chemicals :
CaCO3 scales by 5-10% HCl
CaSO4 scales by EDTA
Blow down pipe operation
By giving thermal shocks

18

Scale
Prevention
External Treatment
By using soft water

INTERNAL TREATMENT
Colloidal conditioning :

Addition of organic substances such as tannin, Agar- Agar

Phosphate conditioning :

o CaCl2 +

Na3PO4

Calcium phosphate + 6NaCl

Carbonate conditioning

o CaSO4 + Na2CO3

CaCO3 + Na2SO4

Calgon conditioning

o CaSO4 + calgon
Soluble complexes of Ca ions
Treatment with sodium aluminate :
o NaAlO2 + 2H2O
Al(OH)3 + NaOH
19

Difference between Sludge & Scale

Sludge

Scale

Soft, loose & slimy precipitates.

hard deposits.

Non-adherent deposits & can be

easily removed.

Stick very firmly to the inner surface of

boiler and are very difficult to remove.

Formed by substances like CaCl2,

MgCl2, MgSO4 & MgCO3.

Formed by substances like CaSO4,

Mg(OH)2, CaCO3 & CaSio3.

Formed generally at colder portions

of the boiler.

Formed generally at heated portions of

the boiler.

Decrease the efficiency of boiler but Decrease the efficiency of boiler &
are less dangerous.
chances of explosions are also there.

Priming and Foaming

Priming
process of making wet steam when some of liquid particles are carried

along with steam

Cause
Presence of dissolved salts
high steam velocity
Sudden boiling
Sudden increase in steam production

Foaming
Formation of bubbles in the boiler continuously

Cause
presence of oil that reduces the surface tension

21

Priming & Foaming

Disadvantages
Reduce the efficiency
Difficult to maintain proper pressure
Wastage of fuel
Actual water level can not be accessed

Prevention
Removal of priming foaming substances
Removal of Scale & sludges
Avoid rapid changes in steaming rate
Change of boiler water from time to time
Using antifoaming agents e.g. castor oil
Addition of a chemical NaAlO2 to remove water

22

Boiler Corrosion
The chemical or electro-chemical eating away of metal by its

environment in a boiler
Cause
Dissolved Oxygen :
2Fe +2H2O + O2
2Fe(OH)2 + O2
Dissolved CO2 :
CO2
+ H 2O
H2CO3
Acids from dissolved salts :
MgCl2 + 2H2O
Mg(OH)2 + 2HCl
Fe
+ HCl
FeCl2
+ H2
FeCl2 + 2H2O
Fe(OH)2
+ 2HCl

2(Fe2O3 .2H2O)

23

Boiler Corrosion

Disadvantages

Shortening of boiler life

Leakages of joints and rivets
Increased cost of repairs and maintenance

Removal of boiler corroision :

Removal of O2 :
2Na2SO3 + O2
N2 H4
+ O2
Removal of CO2 :
2NH4OH + CO2
Removal of acids :
By adding alkali

2Na2SO4
N2
+ 2H2O
(NH4)2CO3 + H2O

24

Caustic Embrittlement
formation of brittle and incrystalline cracks in the boiler shell

due to the accumulation of caustic substances

Cause
Presence of alkali-metal carbonates and bicarbonates in feed water
presence of sodium sulphate.
Sodium carbonate is used in softening of water by lime soda process, due to

this some sodium carbonate may be left behind in the water.

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Process
Na2CO3 used for softening of water & some of which remain unreacted

Na2CO3 + H2O 2NaOH + CO2

As Conc. of NaOH increases, water flows into minute hair cracks by

capillary action.
As water evaporates, conc. of NaOH increases further and react with iron of
boiler, (thereby dissolving Iron of boiler as Sodium ferroate), hence cause
Embrittlement.
This causes embrittlement of boiler parts such as bends, joints, reverts etc,
due to which the boiler gets fail.etc.

prevention :
Use of Na3PO4 instead of Na2CO3
By adding tanin & lignin that blocks the hair cracks
By adding NaSO4 that also blocks the cracks

26

Softening Methods
The following methods are used :
Lime soda Process
Zeolite softening process
Ion exchange process

27

Lime Soda Process

Treatment of water with calculated amount of lime Ca(OH) 2 & Soda

(Na2CO3) which results in the formation of insoluble

Mg that can be removed by filteration.

ppts. of Ca &

Cold Lime Soda

Types

Hot Lime Soda

28

Cold lime soda process

29

Hot Lime Soda Process

30

Cold Lime-Soda Method

Hot Lime-Soda Method

Carried out at room temperature.

Carried out at high temperature,almost at b.pt.of

water.

Slow process

Fast process

Coagulant AL2(SO4) is added

No need of Coagulant.

Dissolved gases are not removed .

Dissolved gases are removed .

water obtained is of hardness 60 ppm.

water obtained is soft of hardness 15-20 ppm.

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Impurity

Mol. Wt.

Requirement

Ca(HCO3)2

162

Mg(HCO3)2

146

2L

CaCl2

111

CaSO4

136

MgCl2

95

L+S

MgSO4

120

L+S

Al2(SO4)3

342

3L+3S

H+

L/2 + S/2

CO2

44

H2S

34

NaHCO3

84

L/2 - S/2

NaAlO2

182

-L/2

FeSO4.7H2O

278

L+S

32

74 (Total Lime) (Vol. Of Water)(100% purity

of lime)

Lime Requirement =

100

106(Total Soda) (Vol. Of Water)(100% purity of lime)

Soda Requirement =

100

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Zeolite or Permutit process

Na2OAl2O3 xSiO2 yH2O
Where x = 2 - 10 , y = 2 6
Can be written as Na2Ze where Ze = OAl2O3 xSiO2 yH2O

exchanges reversibly its sodium ions with hardness producing

ions( Ca & Mg) in water.

34

Principle of Zeolite process

Softening Process :
Na2ze + Ca(HCO3)2

CaZe + 2 NaHCO3

Na2ze + Mg(HCO3)2

MgZe + 2 NaHCO3

Regeneration :
CaZe + 2 NaCl

Na2ze + CaCl2

MgZe + 2 NaCl

Na2ze + MgCl2
35

Zeolite process

36

Ion Exchange or De-ionization or Demineralisation process

Hard water is allowed to pass through ion exchangers when soft water, free

from all the minerals and hardness causing as well as the other ions is
obtained.
Cation Exchange Column represented with its H+ ions

Types

Anion Exchange Column represented with its OH- ions

37

Process
Cation Exchange column :
2RH+
+
Ca+2
Cation exchange resin

H. W.

Cation exchange resin

Anion Exchange column :

ROH+
ClAnion exchange resin

2ROH-

H. W.

H. W.

Anion exchange resin

Regneration:
CationExchange column :
R2Ca+2
+
2H+
Saturated Cation exchange resin

R2SO4-2

dil. acidic sol.

2RH+
Regenerated Cation exchange resin

2H+

OH-

S. W.

RClAnion exchange resin

SO4-2

Anion exchange resin

R2Ca+2

S. W.

2OH-

S. W.

Ca+2

washings

Anion Exchange column :

R2SO4-2
Saturated anion exchange resin

2OHdil. Basic sol.

2ROHRegenerated Cation exchange resin

+
washings

SO4-2
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Ion Exchanger

39

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