Applied Chemistry

CODE NO: 07A1BS07/07A1BS04

I B.TECH
CIVIL ENGINEERING
Unit No: II
Nos. of slides: 117
 Applied Chemistry
Water Technology-II
Term: 2008-09

Unit-2 Power Point Presentations

Text Books:
 A text book of Engineering Chemistry
by Jain & Jain,
 Chemistry of Engineering Materials by
C.P. Murthy, C.V. Agarwal and A. Naidu
 INDEX
UNIT-I PPTS
Srl. Module as per Lecture
PPT
No. Session Planner No.
Slide No.
---------------------------------------------------------------------------------------------
----
1. Boiler Troubles L-1,2 L1,2-1
to L1,2-28
2. Water Internal Treatment L-3 L3-1
to L3-18
3. Water External Treatment Lime-Soda Process L-4,5 L4,5-
1 to L4,5-18
4. Zeolite Process L-6 L6-1
to L6-19
5. Ion- Exchange Process L-7 L7-1
to L7-33
6. Numerical Problems L-8,9 L8,9-
1 to L8,9-33
 BOILER
TROUBLES

L1,2-1
 In treatment of water complete
elimination of all the impurities is
not possible. The impurity that
gives rise to certain troubles will
be removed to certain extent. In
modern pressure boilers and
laboratories, water purer than
the distilled water is required.
Some of the boiler troubles
caused by the use of unsuitable
L1,2-2
water are..
 Boiler troubles mainly 4
types
they are..
1. Carryover
2. Scale formation
3. Boiler corrosion
and
4. Caustic
embrittlement
L1,2-3
 Carryover is mainly 2 types

1. Priming
2. Foaming

L1,2-4
 Priming
 Priming may defined as the violent or
rapid boiling of water occurring in the
boiler which results in carrying out of
water with steam in in the form of a spray.
 When a boiler is producing steam rapidly,
some particles of liquid water are carried
along with the steam.
 This process of wet steam formation is
called priming.

L1,2-5
 Priming mainly caused due to
very high water level. The
presence of large amount of
dissolved solids, high steam
velocities, sudden increase in
steam production rate. Sudden
steam demand which leads to
sudden boiling, presence of
excessive foam filling the foam
spare, and due to faulty boiler
design.
L1,2-6
 priming can be controlled by
proper boiler design, fitting
mechanical steam purifier,
avoiding rapid change in steam-
rate, proper evaporation and
adequate heating surfaces,
uniform distribution of fuel and
providing anti priming pipes,
keeping the water level low and
avoid sudden steam demands.
Efficient softening and filtration
of the boiler feed water.
L1,2-7
 Foaming
 Foaming is the formation of small
but stable bubbles above the
surface. The main reason for
foaming is being presence of fatty
acids and other impurities.
 Foaming can be controlled by
using anti-foaming chemicals,
removal of concentrated boiler
water and replacing it by fresh
feed water.
 Removing oil from boiler water by
adding compounds like sodium
L1,2-8
 Scale formation:
 Some hard, sticky, adherent deposits
formed on the inner surface of the
boilers are known as Scales.
 Scales are hard, adhering
precipitates formed on the inner
walls of the boilers. They stick very
firmly on to the wall surface and are
difficult to remove with chisel and
hammer.
 Generally scales are formed due to
decomposition of calcium
bicarbonates, decomposition of
calcium sulphates, presence of silica
and hydrolysis of magnesium salts.
L1,2-9 Scales formation can be prevented by

 Boiler Corrosion:
 The chemical or electro chemical
eating away of metal by its
environment in a boiler is known as
boiler corrosion.
 The main reason for this problem is
the presence of excess of oxygen in
water.
 It can be prevented by mechanical
deaerator, pre-heating and chemical
treatment.
L1,2-
 Caustic Embrittlement
 The formation of brittle and incrystalline
cracks in the boiler shell is called caustic
embrittlement.
 It is a type of boiler corrosion and the main
reason for this, is the presence of alkali-
metal carbonates and bicarbonates in feed
water and also the presence of sodium
sulphate.
 In lime-soda process, it is likely that, some
residual Na2CO3 is still present in the
softened water.
 This Na2CO3 decomposes to give NaOH
and CO2, due to which the boiler water
becomes “Caustic”.
L1,2-
 This caustic water flows inside the
boiler and causes some minutes hair-
cracks, by capillary action.
 On evaporation of water, the
dissolved caustic soda increases its
concentration which attacks the
surrounding area, thereby dissolving
Iron of boiler as Sodium ferroate.
 This causes embrittlement of boiler
parts such as bends, joints, reverts
etc, due to which the boiler gets fail.
L1,2-
 Caustic cracking can be
explained by considering the
following concentration cell
structure..


|
Iron at bends,+ Concentrate | Dilute NaOH solution |-
Iron at joints, reverts NaOH solution

plane surfaces

L1,2-
 caustic embrittlement can
be prevented by
 By maintaining the pH value of
water and neutralization of
alkali.
 By using Sodium Phosphate as
softening reagents, in the
external treatment of boilers.
 Caustic embrittlement can also
be prevented by adding Tannin
or Lignin or Sodium sulphate
which prevents the infiltration of
caustic-soda solution blocking
L1,2-
 FORMATION
OF
SLUDGE IN BOILERS
 Inboilers, because of
continuous evaporation of
water, the concentration
of salts increase
progressively and after
the saturation point is
reached, precipitate form
on the inner walls of
boiler.
 SLUDGE
 Sludge is a soft, loose and slimy
precipitate formed within the boiler. It
is formed at comparatively colder
portions of the boiler and collects in
the area where flow rate is slow.
 These are formed by substances
which have greater solubilities in hot
water than in cold-water.
 Eg. MgCO3, MgCl2, CaCl2, MgSO4.
 DIS-ADVANTAGES

 As the sludge’s are poor conductor of

heat they cause loss of heat.
 The working of the boiler is disturbed
because of chocking of pipes by the
sludge.
 PREVENTION

 By using well softened water.

 By drawing off a portion of
concentrated water frequently.
 ASSIGNMENT

 Write a short notes on sludge

formation in boilers.
 SCALES
Scales are hard, adhering
precipitates formed on the inner
walls of the boilers. They stick very
firmly on to the inner wall surface
and are difficult to remove with
chisel and hammer.
Scale formed inner
side of the water pipe
causes of scale formation
Decomposition of calcium bicarbonate:
 Ca(HCO3)2  CaCO3 + H2O + CO2

 In low pressure boilers, CaCO3 causes scale

formation.
 In High pressure boilers, CaCO3 becomes
soluble.
 CaCO3 + H2O  Ca(OH)2 + CO2
Decomposition of calcium
sulphate:

The solubility of CaSO4 in water

decreases with rise of
Temperature. In super heated
water CaSO4 is insoluble.
This is the main cause in high-
pressure boilers.
Hydrolysis of Magnesium salts

 Dissolved Magnesium salts undergo

hydrolysis forming Mg(OH)2 precipitate.

 MgCl2 + 2H2O - Mg(OH)2 + 2 HCl

 Mg(OH)2so found by hydrolysis of

Magnesium salts is a soft type of scale.
Presence of Silica
Silica present in small quantities
deposits as silicates like CaSiO3
and MgSiO3. These are very
difficult to remove.
Disadvantages
 Wastage of fuel: The scale formation causes
decreases of heat transfer. As a result over
heating is required this causes consumption
of fuel.
 Danger of Explosion: The hot scale cracks
because of expansion and water suddenly
comes in contact with overheated Iron plates.
This causes in formation of large amount o
steam suddenly. This results high pressure
causing boiler to burst.
PREVENTION

 External treatment: Efficient softening of

water is to be carried out.

 Internaltreatment: Suitable chemicals are

added to the boiler water either to precipitate
or to convert the scale into compound
 INTERNAL
TREATEMENT
OF HARD
WATER
 Internaltreatment of boiler water is
carried out by adding proper
chemicals to precipitate the scale
forming impurities in the form of
sludge and to convert the scale
forming chemicals into compounds
which will stay in dissolved form in
water.
 This process is mainly used as a
corrective treatment to remove the
slight residual hardness and also
sometimes to remove the corrosive
 Some of the internal treatment
methods used for the removed
of scale formation in boilers are.
 COLLODIAL CONDITIONING
 PHOSPHATE CONDITIONING
 CARBONATE CONDITIONING
 CALGON CONDITIONING
 SODIUM ALUMINATE
CONDITIONING
 COLLODIAL
CONDITIONING
 The addition of organic substances
such as Kerosene, tannin, Gel etc., to
the surface in low pressure boilers
may prevent the scale formation.
 These substances gets coated over
the scale forming precipitates and
gives a loose and non-sticky
precipitates which can be removed
by using blow-down operation.
PHOSPHATE CONDITIONING
 The addition of sodium phosphate in
hard water reacts with the hardness
causing agents and gives calcium
and magnesium phosphates which
are soft and non-adhere and can be
removed easily by blow-down
operation.
 In this way, scale formation is
removed in high-pressure boilers.
PHOSPHATE CONDITIONING
chemical equation is
3CaCl2 + 2 Na3PO4

Ca3(PO4)2 + 6NaCl
 CARBONATE CONDITIONING
 In low-pressure boilers, scale-formation can
be avoided by adding sodium carbonate to
boiler water, when CaSO4 is converted into
calcium carbonate in equilibrium.
 CaSO4 + Na2SO4  CaCO3 + Na2SO4
 Consequently, deposition of CaSO4 as
scale doesn’t take place and calcium is
precipitated as loose sludge of CaCO3
which can be removed by blow-down
operation.
 CALGON CONDITIONING
 Involvesin adding calgon to
boiler water. it prevents the
scale and sludge formation by
forming soluble complex
compound with CaSO4.

 calgon
= Sodium hexa meta
phosphate
 Calgon formulae is

Calgon= (NaPO3)6

Na2[Na4(PO3)6]
or
2Na+ +[Na4P6O18] -2
 equation
2CaSO4 [ Na4P6O18] -2

[Ca2P6O18] -2
+ 2Na2SO4
SODIUM ALUMINATE CONDITIONING
 Sodium aluminate gets hydrolyzed
yielding NaOH and a gelatinous
precipitate of aluminum hydroxide.
Thus
NaAlO2 + 2H2O  NaOH + Al(OH)3
The sodium hydroxide, so-formed,
precipitates some of the magnesium as
Mg(OH)2, i.e.,
 MgCl2 + 2NaOH  Mg(OH)2 +
2NaCl
The flocculent precipitate of
Mg(OH)2 plus aluminum
hydroxide, produced inside
the boiler, entraps finely
suspended and colloidal
impurities, including oil
drops and silica.
The loose precipitate can be
removed by pre-
determined blow-down
operation
EXTERNAL TREATMENT
OF WATER
EXTERNAL TREATMENT OF WATER
 Water used for industrial purposes such as
for steam generation, should be sufficiently
pure.
 It should, therefore be freed from hardness-
producing salts before put to use.
 The process of removing hardness-producing
salts from water is known as softening of
water.
In industry main three external
methods employed for softening of
water, they are.

1. Lime-Soda process
2. Zeolite process
3. Ion-Exchange process
LIME-SODA PROCESS
In this method,
 The soluble calcium and magnesium salts in
water are chemically converted in to insoluble
compounds, by adding calculated amount of
Lime and Soda.
 CaCO3 and Mg(OH)2 so precipitated, these
precipitates are filtered off.
Lime soda process mainly two
types, they are

 Cold Lime-soda process

 Hot Lime-soda process.
COLD LIME SODA PROCESS
In this method, calculated quantity of chemical
like lime and soda are mixed with water at
room temperature.
 At room temperature, the precipitates formed
are finely divided, so they do not settle down
easily and cannot be filtered easily.
 Consequently, it is essential to add small
amounts of coagulants like alum, aluminum
sulphate, sodium aluminate, etc.
 Which hydrolyze to flocculent, gelatinous
precipitate of aluminum hydroxide, and
entraps fine precipitates. Use of sodium
aluminate as coagulant also helps the
removal of silica as well as oil, if present in
water. Cold L-S process provides water,
containing a residual hardness of 50 to 60
ppm.
 NaAlO2 + 2H2O ---- NaOH + Al(OH)3

 Al(SO4)3 + 3Ca(HCO3)2  2Al(OH)3 +

3CaSO4 + 6CO2
METHOD OF TREATMENT:
 Raw water and calculated quantities of
chemicals ( Lime + soda + Coagulants) are fed
from the top into the inner vertical circular
chamber, fitted with a vertical rotating shat
carrying a number of paddles.
 As the raw water and chemicals flow down,
there is a vigorous stirring and continuous
mixing, whereby softening of water reaches up.
 The softened water comes into the outer co-axial
chamber, it rises upwards.
METHOD OF TREATMENT:
 The heavy sludge or precipitated floc settles
down the outer chamber by the time the
softened water reaches up.
 The softened water then passes through a
filtering media this is usually made of wood
fibres to ensure complete removal of sludge.
 Filtered soft water finally flows out continuously
through the outlet at the top.
 Sludge settling at the bottom of the outer
chamber is drawn of occasionally.
HOT LIME-SODA PROCESS:
 The reaction proceeds faster
 The softening capacity f hot process is increased to
many fold
 The precipitate and sludge formed settle down rapidly
and hence, no coagulants are needed
 Much of the dissolved gases such as CO2 and air
driven out of the water
 Viscosity of softened water is lower, so filtration of
water becomes much easier. this in-turn increases
the filtering capacity of filters, and
 Hot lime-soda process produces water of
comparatively lower residual hardness of 15 to 30
ppm.
 Hot lime-soda plant consists essentially of
three parts
 A ‘Reaction tank’ in which raw water,
chemicals and steam are thoroughly mixed.
 A ‘Conical sedimentation vessel’ in which
sludge settles down, and
 A ‘sand filter’ which ensures completes
removal of sludge from the softened water.
ADVANTAGES OF LIME-SODA
PROCESS:
 It is very economical
 If this process is combined with sedimentation with
coagulation, lesser amounts o coagulants shall be
needed.
 The process increases the pH value of the treated-
water; thereby corrosion of the distribution pipes is
reduced.
 Besides the removal of harness, the quantity of
minerals in the water is reduced.
 To certain extent, iron and manganese are also
removed from
DIS-ADVANTAGES OF LIME-SODA
PROCESS:
 For efficient and economical softening,
careful operation and skilled supervision is
required.
 Disposal of large amounts of sludge or
insoluble precipitates poses a problem.
However, the sludge may be disposed off in
raising low-lying areas of the city.
 This can remove hardness only upto 15 ppm,
which is not good for boilers.
ZEOLITE
PROCESS
Zeolites are also known as
Permutits;
Zeolites are mainly 2
types

Natural zeolites
Synthetic
Zeolites
 Natural zeolites

Natural zeolites are non-

porous,

eg. Natrolite-
Na2O.Al2O3.4SiO2.2H2O.
 Synthetic Zeolites
 Synthetic Zeolites are porous and
possess gel structure. Sodium zeolites
are generally used for softening of
water and are simply represented as
Na2Ze, where ‘Ze’ stands for insoluble
zeolite.
 In the process, when hard water is
passed through a bed of zeolite placed
in an closed cylinder, the hardness
causing ions like Ca+2 and Mg+2 ions
are taken up by the zeolite.
 Sodium salts are released during the
Process:
 Forsoftening of water by
zeolite process, hard
water is percolated at a
specified rate through a
bed retained by the
zeolite as CaZe and MgZe;
while the outgoing water
contains sodium salts.
 The various reactions
taking place may be..

 Na2Ze + Ca(HCO3)2  CaZe +

2NaHCO3
 Na2Ze + Mg(HCO3)2  MgZe +
2NaHCO3
 Na2Ze + MgCl2  MgZe + 2NaCl
 Na2Ze + CaCl2  CaZe + 2NaCl
 Na2Ze + MgSO4 MgZe +
2Na2SO4
 Hence zeolite
process removes
the hardness of
water effectively
 Regeneration
 After some time, the Zeolite is
completely converted into calcium
and magnesium zeolites and it ceases
to soften water, i.e., it gets exhausted.
At this stage, the supply of hard water
is stopped and the exhausted zeolite
is reclaimed by treating the bed with a
concentrated Brine solution (10%
NaCl).
 CaZe + 2 NaCl  Na2Ze + CaCl2
 MgZe + 2 NaCl  Na2Ze + MgCl2
 Advantages
 It removes the hardness completely and
water of about 10 ppm hardness is
produced.
 The equipment used is compact,
occupying a small space.
 No impurities are precipitated, so there is
no danger of sludge formation in the
treated water at a later stage.
 The process automatically adjusts itself for
variation in hardness of incoming water.
 It is quite clean
 It requires less time for softening.
 It requires less skill for maintenance as
well as operation.
 Disadvantages
 The treated water contains
more sodium salts than in
lime-soda process.
 This method causes caustic
embrittlement.
 High turbidity water cannot be
treated efficiently by this
method.
ION- EXCHANGE
PROCESS
 Ion exchange process also
known as demineralization or
de-ionization process.
 In De-ionization process all the ions
present in water are eliminated by
using ion-exchange resins.
 Basically resins with acidic functional
group are capable of exchanging H+
ions with other cations.
 Resins with functional groups are
capable of exchanging OH- ions with
other anions.
 Resins are classified as

 Cation Exchange Resins

 Anion Exchange Resins
 Cation Exchange Resins:
These are mainly styrene
divinyl benzene co-
polymers, which on
sulphonation or
carboxylation.
 These are capable of
exchanging their
hydrogen ions with
cations in water.
AnionExchange
Resins: these are
capable of
exchanging their OH-
ions with anions in
water.
 In ion-exchange process, hard water is
allowed to pass through cation
exchange resins, which remove Ca+2
and Mg+2 ions and exchange
equivalent amount of H+ ions.
 Anions exchange resins remove
bicarbonates, chlorides and sulphates
from water exchange equivalent
amount of Oh ions.
 Thus by passing hard water through
cation hardness is observed by the
following reactions.
 Cation Exchange Resins

 2RH+ + Ca+2 - R2Ca+2 + 2H+

 2RH+ + Mg+2  R2Mg+2 + 2H+
(RH+ = cation exchange resin)
Anion Exchange Resin

R’OH + Ca+2  R’Cl- + OH-

2R’OH- + S-2  R2S-2 +
2OH-
2R’OH + CO-2  R’2CO-2 +
2OH- (R’OH = anion exchange
resin)
 H- And OH- ions, thus released in
water from respective cation and
anion exchange columns, get
combined to produce water
molecules.
 H+ + OH-  H2O
 The water coming out from the
exchanger is ion free i.e., free from
anions and cations. Thus water of
zero hardness is obtained.
 REGENERATION:

 When cation exchanger losses capacity of

producing H+ ions and exchanger losses
capacity of producing OH- ions, they are
said to be exhausted. The exhausted cation
exchanger is regenerated by passing it
through dilute sulphruric acid.
 R2Ca+2 + 2H+  2RH+ + Ca+2
 The exhausted anion exchanger is
regenerated by passing a dilute solution of
NaOH.
 R2SO-2 + 2OH  2R’OH- + SO-2
 Merits of Ion-exchange
process:
 The process can be used to soften
highly acidic or alkaline water.

It produces water of very low hardness (2

ppm
So it is very good for treating water for
use in high-pressure boilers.
 Demerits of Ion-exchange
process:

 The equipment is costly and more

expensive chemicals are needed.
 If water contains turbidity, the output
of the process is reduced. The
turbidity must be below 10 ppm; else
it has to be removed by coagulation
and filtration.
Ion exchange apparatus
Ion exchange
 Ion exchange
chamber internal
view
Numerical problems
 Water technology-2
Problems
 Calculate the lime and soda needed
for softening 50,000 litres of water
containing the following salts: CaSO4
= 136 mg/lit; MgCl2 = 95 mg/lit;
Mg(HCO3)2 = 73 mg/lit; Ca(HCO3)2=
162 mg/lit. Given that the molar
mass of Ca(HCO3)2 is 162 and that
of MgCl2 is 95.
 Water technology-2
Problems
S.No. Constituent Amount MF CaCO3
(mg/lit) equivalent

1. CaSO4 136 100/136 100

2. MgCl2 95 100/95 100

3. Mg(HCO3)2 73 100/146 50

4. Ca(HCO3)2 162 100/162 100

 Water technology-2
Problems
Lime required = 74
---- [ Ca(HCO3)2 + 2 Mg (HCO3)2 + MgCl2]
100
74
= --- [100 + 2 x 50 + 100 + 100]
100
74 400
= --- x ---- = 296 mg/l
100 1
For 50000 lit of water: 50000 x 296 = 14.8 Kg of lime
required.
 Water technology-2
Problems
106
Soda required = ---- [CaSO4 + MgCl2]
100

106 200
= ---- x ---- = 212 mg/l
100 1
For 50000 lit of water: 50000 x 212 = 10.6
kg of soda required.
 Water technology-2
Problems
Calculate the quantities of lime and
soda required in kgs for softening
10,000 lit of water using 82 ppm of
NaAlO2 as coagulant. Analysis of
water was as follows:
Cacl2 = 111 ppm; Mg(HCO3)2 =
146ppm; NaCl = 58.5ppm; KCl =
74.5ppm; Dissolved CO2 = 44ppm.
(At. Wt of Na = 23, Mg = 24, K = 39,
Ca = 40 and Al = 27)
 Water technology-2
Problems
S.No. Constituent Amount(ppm) MF * CaCO3 equivalent

1. CaCl2 111 100/111 100

2. Mg(HCO3)2 146 100/146 100

3. NaCl 58.5 Do not contribute

4. KCl 74.5

5. CO2 44 100/44 100

6. NaAlO2 82 100/164 50
 Water technology-2
Problems
74
Lime required = ---- [Mg2+ + CO2 + NaAlO2]
100

74
= ---- [100 + 100 + 50] = 185
mg/lit.
100
So for 10000 lit = 10000 X 185 = 1850000 mg =
1.85 kg
 Water technology-2
Problems
106
Soda required = ---- [Ca2+ + Mg2+]
100
106
= ---- [100 + 100] = 212 mg/lit
100

For 10000 lit = 10000 X 212 = 2120000

mg = 2.12 kg.