Dr.

Manoj Acharya August 31, 2023

Water is necessary for living beings (Humans, Animals &

Plants.
Water is required in all human activities like domestic,
agriculture and industries.

Chapter-I  Water covers 70% of the Earth i.e.

2/3rd part of the earth.
Types of Impurities in Water  97% of the earth water is salt
water and 3% is Fresh water; 2/3rd of
fresh water is frozen in glaciers and
By: Dr. Manoj Acharya polar ice caps.
VIT, Bhopal  Fresh water is renewable resource.
Copyright © VIT BHOPAL 1 2

Sources of Water Surface Water

Surface Water includes flowing water (Rivers & Streams)
Surface Water and still water (Ponds, Lakes & Reservoirs).
Flowing Water
Frozen Water
Still Water
Underground Water
River Water Streams
Rain Water

Sea Water

3 Pond Lake Reservoir 4

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Dr. Manoj Acharya August 31, 2023

River Water Frozen Water

River water contains dissolved minerals like chlorides, Frozen Water includes Glaciers,
sulphates, bicarbonates of Sodium, Magnesium, Calcium Icebergs.
and Iron. It includes Water from
Underground Water
River water contains suspended impurities of sand and well and springs.
rock and organic matter. Free from organic
The composition of river water is not constant and impurities, clear in
depends on its contact with soil. appearance but
contain large amount
Lake Water
of dissolved salts.
Rain Water
Lake water has high quantity of organic matter and lesser
Rain water is obtained as a
amount of dissolved minerals. Its chemical composition is
result of evaporation from
also constant.
5 surface water. 6

Rain water is the most purest form of water. Sources of Water

Rain water during its downward journey through the Sources of Water
atmosphere it dissolves organic and inorganic suspended
particles and gases like NOX, COX and SOX.
Surface Water Rain Water
Flowing Still Water
Sea Water
Water
Lakes Reservoirs
Sea water is impure due to
Streams River
continuous evaporation Ponds
increases dissolved impurity Sea
content and impurities thrown
by the rivers as they join the Underground Water Sea Water
sea.
Springs Well
Sea water is saline.
7 8

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Dr. Manoj Acharya August 31, 2023

Impurities in Water Impurities in Water

Impurities in Water Suspended Impurities:
 They impart turbidity, colour and
Physical Bacteriological odour to water.
 It may be Inorganic (Clay and Sand)
Suspended Colloidal Bacteria Fungi or Organic (Oil, Vegetable and Animal
Impurities Impurities matter) in nature.
Algae  Suspended Impurities are
Macroscopic . The size of suspended
Chemical
impurities ranges from 0 to 10-3 mm
Dissolved Dissolved Organic Collodial Impurities:
Gases Salts
They impart turbidity, colour and odour to water.
Dissolved It may be Inorganic (Clay and Sand) or Organic (Oil,
Inorganic Salts 9 Vegetable and Animal matter) in nature. 10

Dissolved Impurities: Hardness

These impurities are due to the presence of dissolved salts
like Carbonates, Bicarbonates, Chlorides and Sulphates of Hardness is the characteristic of water which prevents the
Calcium, Magnesium, Iron and Sodium. lathering of soap.

Hardness is due the presence of these salts. Hardness is the soap consuming capacity of water.

Hardness is due to the presence of certain salts of Ca and

Dissolved gases like CO2, O2, etc. also considered as
Mg and other Heavy Metals ions like Al3+, Fe3+, Mn2+
dissolved impurities.
dissolved in it.
Microorganisms:
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
They include bacteria, fungi and algae. Sodium Stearate Hardness Calcium Stearate
These impurities are introduced into water by animal or
vegetable waste and through sewage flowing into the water 2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4
body. 11 Sodium Stearate Hardness Magnesium Stearate 12

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Dr. Manoj Acharya August 31, 2023

Cations which produces insoluble soap with soap solution

will contribute to the hardness.

On the above basis Water is of Two Types; Hard Water and

Soft Water
Hard Water Soft Water
Water which do not produce Water which produce lather with
lather with soap & form white soap
curd/scum.
Contain soluble Calcium & Do not contain dissolved
Magnesium salts Calcium & Magnesium salts
Cleansing quality is depressed Cleansing quality is not
depressed
Due to the dissolved salts boiling Less fuel and time are required
point of water is elevated for cooking of food. 13 14

Types of Hardness Permanent hardness can not be removed by physical

methods like boiling but it can be removed by Chemical
Hardness is of Two Types Methods.
 Temporary Hardness / Alkaline Hardness / Carbonate Units of Hardness
Hardness
 Parts per million (ppm): Parts of calcium carbonate
The temporary hardness is due to the presence of equivalent hardness per 106 part of water.
carbonates and bicarbonates of Calcium & Magnesium. It
 Milligrams per Litre (mg/L): Milligrams of calcium
can be removed by physical methods like boiling.
carbonate equivalent hardness per Litre of water.
 Permanent Hardness / Non-Alkaline Hardness / Non-
 Degree Clark (°Cl): Parts of calcium carbonate equivalent
Carbonate Hardness
hardness per 70,000 part of water.
The permanent hardness is due to the presence of chlorides
and sulphates of Calcium, Magnesium, Salts of heavy metals  Degree French (°Fr): Parts of calcium carbonate
& Acids. It cann’t be removed by physical methods like 15 equivalent hardness per 105 part of water. 16

boiling.

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Dr. Manoj Acharya August 31, 2023

Degree of Hardness
Relationship between the Units of Hardness
 The hardness of water is expressed in terms of 1 ppm = 1 mg/L
equivalent amount CaCO3. 1 ppm = 1 mg/L = 0.07 °Cl = 0.1 °Fr
 The reason for reporting hardness as equivalent Determination of Hardness by
amount of CaCO3 is the ease in calculation as its
Complexometric Method / EDTA Method
Molecular weight CaCO3 is 100 and equivalent weight is
50.
NH4Cl:NH4OH
+
EBT

17 18

Sodium 4-[(1-hydroxynaphthalen-2-yl-hydrazinylidene]-7-nitro-3-oxo-Y-
naphthalene-1-sulfonate
 Ethylene Diammine Tetra Acetic Acid is tetraprotic acid,
due to its limited solubility, it is not used directly.

 Disodium salt of Ethylene Diammine Tetra Acetic Acid is

used (Molecular Weight – 372.24)

EBT  It combines with metal ions in 1:1 ratio in the presence

of NH4Cl:NH4OH buffer solution and Eriochrome Black T is
used as indicator.
Blue to wine red colour
NH4Cl:NH4OH buffer solution is used because the
divalent metal are stable in slightly basic solution (pH=10).
19 20

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Dr. Manoj Acharya August 31, 2023

 The colour of EBT is “Blue” and when it added to hard Calculation of Hardness of water: Unitary Method
water it forms unstable complex of “Wine Red” colour.
Standardization of EDTA solution
NH4Cl:NH4OH
Ca2+ + EBT Ca-EBT Let the strength of Standard Hard Water (SHW) = S mg / L
Free Indicator Metal-Indicator unstable complex
(Blue) EBT
(Red) 1 Liter of SHW contain----------- S mg of CaCO3
 Metal-Indicator unstable complex when titrated with
EDTA to form colourless Metal-EDTA complex. ‘VStd. SHW’ ml of SHW contain-------- (S x VStd. SHW) mg CaCO3
NH4Cl:NH4OH VStd. EDTA ml of EDTA ----------- VStd. SHW ml of SHW
Ca-EBT + EDTA Ca-EDTA + EBT
pH= 10
Metal-EDTA stable Free Indicator VStd. EDTA ml of EDTA ----------- S x VStd. SHW ml of SHW
complex (Blue)
 End point is achieved by the appearance of Blue Colour 1 ml of EDTA contain----------- S x VStd. SHW mg CaCO3
of Free EBT. 21
VStd. EDTA 22

Determination of Total Hardness of Unknown Hard Water Determination of Permanent Hardness of Unknown Hard
Water
VTH. UHW ml of UHW ----------- VTH. EDTA ml of EDTA VPH. UHW ml of Boiled Water ----------- VPH. EDTA ml of EDTA

VTH. UHW ml of UHW -------- VTH. EDTA S x VStd. SHW mg CaCO3 VPH. UHW ml of UHW -------- VPH. EDTA S x VStd. SHW mg CaCO3
VStd. EDTA VStd. EDTA

1 ml of UHW -------- VTH. EDTA S x VStd. SHW mg CaCO3 1 ml of BHW -------- VPH. EDTA S x VStd. SHW mg CaCO3
VTH. UHW VStd. EDTA VPH. UHW VStd. EDTA

1000 ml of UHW -------- 1000 * VTH. EDTA S x VStd. SHW 1000 ml of BHW -------- 1000 * VPH. EDTA S x VStd. SHW
VTH. UHW VStd. EDTA VPH. UHW VStd. EDTA
mg CaCO3
23 mg CaCO
24
3

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Dr. Manoj Acharya August 31, 2023

Determination of Temporary Hardness of Unknown Hard

Water
Temporary Hardness =
1000 * VTH. EDTA S x VStd. SHW
- 1000 * VPH. EDTA S x VStd. SHW
VTH. UHW VStd. EDTA VPH. UHW VStd. EDTA

25 26

Calculation of Hardness of water: Molarity EDTA solution Vs Standard Hard Water

Method SHW EDTA
Calculation of Molarity of Standard Hard Water M1V1 = M2V2
Weight of CaCO3 = W gm
M2 = M1V1
Molecular weight of CaCO3 = 100 V2

Moles of CaCO3 = Weight (W) EDTA solution Vs Sample Hard Water

Molecular Weight
EDTA Sample Water
Volume of water = ‘V’ Litre M2V2 = M3V3
M3 = M2V2
Morality of SHW (M1)= Weight (W) V3
Molecular Weight * V
27 28

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Dr. Manoj Acharya August 31, 2023

Total Hardness = M3 * Molecular Mass of CaCO3 * 1000 Temporary Hardness =

Total Hardness - Permanent Hardness ppm
ppm

EDTA solution Vs Boiled Hard Water Numerical on Hardness Estimation using EDTA Method
EDTA Boiled Sample Water
Annexure- 1
M2V2 = M4V4
M4 = M2V2
V4

Permanent Hardness = M4 * Molecular Mass of CaCO3 * 1000

ppm
29 30

Alkalinity  OH- and CO32-

 HCO3- and CO32-
Alkalinity is a measure of the ability of water to neutralize the
acids.  The possibility of OH- and HCO3- together is ruled out
because they combine to form CO32-ions.
Alkalinity of water means the total content of those
substances which causes an increased hydroxide ion OH- + HCO3- CO32- + H2O
concentration upon dissociation or due to hydrolysis.
 Thus OH- and HCO3- ions can not exist together in water.
Alkalinity of water is due to the presence of
 Hence OH- , CO32- and HCO3- ions can not exist together
 OH- in water.
 CO32-
Caustic Alkalinity Estimation of Alkalinity of water
 Fill the burette with N/50 HCl solution.
 HCO3- Temporary Hardness
31  Pipette out 20 ml of alkaline water sample in conical flask.
32

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Dr. Manoj Acharya August 31, 2023

 Add a drop of Phenolphthalein, then N/50 HCl Calculation

the colour of solution becomes pink. ACID WATER
V1 ml
 Titrate against N/50 HCl till the N1V1 = N2V2
solution becomes colourless. Note OH-, 1/2CO32- N2 or Np = N1V1
down the amount of acid used (V1 ml). V2
 Add a drop of Methyl Orange ; the V2 ml Strength (P) = Normality (N2) x Equivalent weight of CaCO3 x 1000
solution become slightly orange. ppm
HCO3- For the same solution; V1 = V1+V2
Continue the titration against N/50 HCl
till the reappearance of light pink For different solution; V1 = V2
colour (V2 ml).
ACID WATER
OH- + H+ H2O
N1(V1+V2) = N3V3
CO32- + H+ HCO3-
N3 or NM = N1(V1+V2)
HCO3- + H+ CO2 + H2O 33
V3 34

Strength (M) = Normality (N3) x Equivalent weight of CaCO3 x 1000 Boiler

ppm  Boiler is a closed vessel which is used
Condition of Alkalinity to convert water into steam
 Boiler is made up of two parts
S.No. Results of Hydroxide Carbonate Bicarbonate
Furnace: Provides heat by burning fuel.
Titration
Boiler Proper: Chamber where water is
1 P=0 NIL NIL M converted into steam.
2 P=M P or M NIL NIL  Water feed into boiler is known as
3 P= ½ M NIL 2P NIL “Boiler Feed Water”.
4 P> ½ M 2P – M 2 (M – P) NIL  The Chemical Energy
5 P< ½ M NIL 2P M – 2P is converted into Heat
Energy by combustion
Numerical on Alkalinity process which in turn is
Annexure- 2 absorbed by water.
35 36

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Dr. Manoj Acharya August 31, 2023

Boiler Problems  If the pre-treatment of boiler feed water is not done then it
 Essential requirement for boiler feed water:- may lead to “Boiler Problems” like Priming, Foaming, Scale
and Sludge, Boiler Corrosion and Caustic Embrittlement.
It should be free from
Turbidity, Oils, Dissolved Salts
Scale and
Hardness and scale forming salts Sludge
Dissolved O2 and CO2 Caustic
Caustic Alkali Embrittle- Priming
ment
Boiler Problems
 Proper treatment of boiler feed water is an important part
of boiler operation and maintenance system. Boiler Foaming
Corrosion
 As the water is converted into steam, the concentration of
Carry over
dissolved solids increases and starts depositing inside the
boiler thereby reduces boiler efficiency and leads to poor
heat transfer. 37
Boiler Problems 38

Scale and Sludge  If Solubility Product = KSP and Ionic Product = [Ay+]x[Bx-]y
 In the boiler water is continuously evaporated to form  KSP = [Ay+]x[Bx-]y == Solution is Saturated
steam. This increases the concentration of dissolved salts.
 KSP > [Ay+]x[Bx-]y == Solution is Unsaturated
 A stage is reached when ionic product exceeds the
solubility product (Ksp < Ip, supersaturated solution) and  KSP < [Ay+]x[Bx-]y == Precipitation will takes place
hence they are thrown out as precipitates.
Sludge
 If the precipitate formed
is soft loose and slimy is  Sludge is soft, loose and slimy
known as Sludge. precipitate formed within the
boiler.
 If the precipitate formed
is hard and adhering on  Sludge is formed by substance which have higher solubility
the inner wall of the boiler in hot water than in cold water. For example MgCO3, MgCl2,
is known as Scale. 39 CaCl2, MgSO4. 40

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Dr. Manoj Acharya August 31, 2023

 Sludge is formed at the comparatively colder part of the Scale

boiler and get collected at places where the flow rate is slow.  Scale are hard deposits firmly
sticking to the inner wall of the
Disadvantages of Sludge
boiler.
 Sludge is bad conductor of Heat.
Scale is formed due to the following reasons
 Excessive Sludge formation affects the working of boiler
 Decomposition of Calcium Bicarbonate
and causes chocking of pipes.
Ca(HCO3)2 CaCO3 + H2O + CO2
Prevention of Sludge Formation
Scale composed of CaCO3 is soft and main cause of scale
 Use of Soft Water. formation in the low pressure boilers.

 By frequently “Blow Down Operation” i.e removal of In High pressure boiler CaCO3 is soluble due to the formation
concentrated water through tap at the bottom of the boiler of Ca(OH)2.
when extent of hardness becomes high. 41 CaCO3 Ca(OH)2 + CO2 42

 Decomposition of Calcium Sulphate MgCl2 Mg(OH)2 + 2 HCl

The solubility of CaSO4 in water decreases with the increase in
 Presence of Silica
temperature. CaSO4 is soluble in cold water but completely
insoluble in super heated water. Even if small quantity of SiO2 is present then it may deposit as
calcium silicate (CaSiO2) and Magnesium Silicate (MgSiO2).
Low solubility of CaSO4 is due to the increased ionization at These deposit adhere to the inner surface of boiler very
high temperature and less availability of water molecules for firmly. The main source of silica is the Sand Filter.
solvation at high temperature.
CaSO4 precipitates as hard scale on hotter parts of boiler and Disadvantages of Scale
high pressure boilers.  Wastage of Fuel
 Lowering of Boiler Safety
 Hydrolysis of Magnesium Salts
 Decrease of Boiler Efficiency
Dissolved salts of Magnesium hydrolyze at high temperature  Danger of Boiler Explosion
to form a soft Mg(OH)2 scale. 43 44

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Dr. Manoj Acharya August 31, 2023

Removal of Scale Formation Priming

 Removal by Mechanical Methods- Scrapping  When steam is produced rapidly in the boiler, some
droplets of the liquid water are carried along with the steam.
 If scale is brittle, it can be removed by Thermal shocks This process of “Wet Steam” formation is called Priming.
 Priming is caused by
 If the scale is loosely adhering then it can be removed by
“Blow Down Operation” (i.e. Heating the boiler & then  Presence of Dissolved impurities and Suspended
sudden cooling. impurities.

 If the scale is adherent and hard then can be removed by  Steam Velocities high enough to carry droplets of water
dissolving them in chemicals; into the steam pipe.

 CaCO3 scale can be removed by adding 5-10% HCl  Sudden Boiling

 CaSO4 scale can be removed by adding EDTA
45  Faulty design of Boiler 46

 Priming can be avoided by Foaming

 Controlling the rapid change in steaming velocities.  Foaming is the formation of
persistent foam or bubbles at the
 Proper design of the Boiler. water surface in the boiler which do
not break easily.
 Ensuring sufficient softening.  Foaming is caused due to the
presence of Oil and Alkalis in the
 By blowing off the sludge and scale from time to time. boiler feed water.

 Filtration of Boiler Feed Water  Oil and Alkalis reacts to form soaps which greatly reduces
the surface tension of water & increases the foaming
tendency of the water.

47 48

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Dr. Manoj Acharya August 31, 2023

 Foaming can be avoided by Carry Over and Priming & Foaming occurs together and they
are objectionable.
 Addition of Anti-foaming agent which reduces the surface
tension (Like Castor oil). Dissolved Solids or Suspended Solids in boiler water are
carried by the wet steam to super heater or steam turbine
 Removal of foaming agent oil from Boiler feed water. blades where they get deposit as water evaporates.

Dissolved Solids may enter the part of other machinery,

Carry Over
thereby decreasing their life
The phenomenon of carrying of water along with impurities
The maintenance of the boiler pressure become difficult
by steam is called carry over.
because of improper judgement of actual height of water
column.
Carry Over is due to Priming & Foaming.
49 50

Boiler Corrosion Dissolved oxygen reacts with Iron (Fe) in the presence of
 Boiler corrosion is the decay or disintegration of the boiler water to form Ferric Oxide (Rust).
material either due to chemical or electrochemical reaction
with its environment. 4 Fe + 2H2O + O2 4Fe(OH)2
 Boiler Corrosion is caused due to following reasons-
4Fe(OH)2 + O2 2[Fe2O3 . 2H2O]
Dissolved Oxygen:
This is the most common reason of Removal of Dissolved Oxygen
Boiler Corrosion. In boiler the
 By adding Hydrazine or Sodium Sulphite or Sodium Sulphide
oxygen is introduced through the
raw water supply. Water usually
contain 8 ppm of Oxygen at room N2H4 + O2 N2 + 2H2O
temperature. As the water is heated Na2SO3 + O2 2Na2SO4
this dissolved oxygen is set free and Na2S + O2 Na2SO4
boiler starts corroding . 51 52

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Dr. Manoj Acharya August 31, 2023

Hydrazine (N2H4) is the ideal chemical for the removal of  By Mechanical Deaeration
disolved oxygen. It reacts with oxygen to form Nitrogen and
This process consist of spraying of water over preheated
water. Nitrogen is harmless. Hydrazine removes oxygen
perforated plates stacked in a degasifier. Removal of dissolved
without increasing the concentration of dissolved solids.
oxygen is ensured by applying high temperature and vacuum.
Excess amount of Hydrazine (N2H4) must not be taken Dissolved Carbon Dioxide:
because it decomposes to give Ammonia which may cause
corrosion of some alloys like Brass used in condenser tubes. Main source of CO2 in boiler water are dissolved CO2 in raw
3N2H4 4NH3 + N2 water and decomposition of Bicarbonates in water.
Mg(HCO3)2 MgCO3 + CO2 + H2O
If Sodium Sulphite or Sodium Sulphide is used for the
removal of dissolved oxygen then Sodium Sulphate is formed CO2 in the presence of water forms Carbonic acid (H2CO3)
which decomposes in high pressure boilers to form SO2. The which has corrosive effect on boiler material.
SO2 enters into the steam pipes and forms Sulphurous acid CO2 + H2O H2CO3
(H2SO3) in steam condensate. 53 54

Removal of Carbon Dioxide Boiler Corrosion due to Mineral Acids:

 By Mechanical Deaeration Magnesium Chloride if present in boiler feed water
This process consist of spraying of water over preheated undergoes hydrolysis producing HCl.
perforated plates stacked in a degasifier. Removal of dissolved MgCl2 + H2O Mg(OH)2 + 2HCl
carbon dioxide is ensured by applying high temperature and
vacuum. Liberated HCl reacts with Iron (Fe) to form Ferrous Hydroxide
 By Filtering water through Lime Stone which in turn is converted into Rust.
CaCO3 + CO2 + H2O Ca(HCO3)2 Fe + 2HCl FeCl2 + H2
This method increases hardness. FeCl2 + H2O Fe(OH)2 + 2HCl
2Fe(OH)2 + O2 Fe2O3 .2H2O
 By adding Ammonium Hydroxide
Small amount of HCl causes corrosion to larger extent since
2NH4OH + CO2 (NH4)2CO3 + H2O HCl is produced in chain like manner. Hence small amount of
55
MgCl2 causes corrosion of Iron to larger extent. 56

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Dr. Manoj Acharya August 31, 2023

Caustic Embrittlement
Caustic Embrittlement is the phenomenon during which the
boiler material becomes brittle due to the accumulation of
caustic . This type of boiler corrosion is caused by the use of
highly alkaline water in the high pressure boiler.

During softening by Lime-Soda Process, it is likely that some

residual Sodium Carbonate (Na2CO3) may be present in the
soft water.
In high pressure boilers Na2CO3 decomposes to give Sodium
Hydroxide (NaOH) and CO2 thus makes water “Caustic”.

Na2CO3 + H2O 2NaOH + CO2

57 58

This caustic water flow into the minute hair cracks, present in Prevention of Caustic Embrittlement
the inner side of boiler by capillary action.
By adding Sodium Phosphate as softening reagent, instead
On evaporation of water the dissolved caustic soda of Sodium Carbonate in external treatment of boiler water.
concentration increases progressively which attacks the
surrounding area, thereby dissolving Iron of boiler as Sodium By adding Sodium Sulphate to boiler which blocks the hair
Ferroate (Na2FeO2). cracks and prevents the infiltration of caustic soda solution
into these areas.
Na2FeO2 + 4H2O 6NaOH + Fe3O4 + H2
By adding tannin or lignin to boiler which blocks the hair
The Iron surrounded by dil. NaOH acting as Cathode, while cracks and prevents the infiltration of caustic soda solution
the Iron surrounded by concentrated NaOH act as Anode. into these areas.

The Iron in the anodic parts gets corroded.

59 60

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Dr. Manoj Acharya August 31, 2023

Purification of Boiler Water or Water Softening External Method

The hardness causing salts can be removed from water by Lime Soda Process
two ways-
 The basic principle of Lime Soda Process is to chemically
Water Softening convert all the soluble hardness causing impurities into
insoluble precipitates which may be removed by settling or
External Method Internal Method
filtration.
Colloidal Carbonate
Lime Soda Process Zeolite
Conditioning Conditioning  Calculated quantity of milk of lime [Ca(OH)2] and Sodium
Process
Carbonate [Na2CO3] is added.
Intermittent Continuous Calgon Phosphate
Cold L-S Cold L-S Conditioning Conditioning
Process Process  At Room Temperature the precipitate formed is very fine &
Hot L-S do not settle down easily and causes difficulty in filtration.
Process

 Fine precipitate of CaCO3 and Mg(OH)2 result in “after

Ion-Exchange
Process 61 deposition”, later in pipes, boiler tubes producing scales. 62

Batch L-S Process-

 If small amount of coagulants like Alum Reaction takes place at Room
K2SO4.Al2SO4.24H2O; Aluminium Sulphate [Al2(SO4)3] or Temperature.
Sodium Aluminate [NaAlO2] are added, they hydrolyze to High Softening Time
Soft Water with residual hardness of 60
Al(OH)3 which entraps the fine precipitate of CaCO3 & ppm is obtained.
Mg(OH)2. Coagulants are required for the removal
of fine impurities.
NaAlO2 + 2 H2O NaOH + Al(OH)3
Sodium Aluminate Continuous L-S Process-
Reaction takes place at Room
Temperature.
Al2(SO4)3 + 3 Ca(HCO3)2 2 Al(OH)3 + 3CaSO4 + 6 CO2 Low Softening Time compared to Batch
Lime Soda Process.
Soft water rise up & filter through wood-
filter.
Soft Water with residual hardness of 30-40
ppm is obtained.
Coagulants are required for the removal of
63 fine impurities. 64
Dissolved gases are not removed.

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Dr. Manoj Acharya August 31, 2023

Hot L-S Process- Chemistry of Lime Soda Process

Reaction takes place at 94-100°C by passing super heated steam into the reaction
chamber Constituent Reactions Need
Softening rate of water is faster, Processing Time – 15 min. Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + H2O L
Soft Water with residual hardness of 15-30 ppm residual hardness is obtained. CO2 CO2 + Ca(OH)2 CaCO3 + H2O L
No Coagulant is required.
Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + H2O 2L
Quantity of chemicals required for softening is low.
Dissolved gases like CO2 are removed to some extent. CaCl2 CaCl2 + Na2CO3 CaCO3 + NaCl S
CaSO4 CaSO4 + Na2CO3 CaCO3 + Na2SO4
MgCl2 MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 L+ S
CaCl2 + Na2CO3 CaCO3 + NaCl

MgSO4 MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

CaSO4 + Na2CO3 CaCO3 + Na2SO4
NaHCO3 NaHCO3 + Ca(OH)2 CaCO3 + H2O + Na2CO3 L- S
Free Acids HCl + Ca(OH)2 CaCl2 + 2 H2O L+ S
(HCl) CaCl2 + Na2CO3 CaCO3 + NaCl
FeSO4 FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4 L+ S
CaSO4 + Na2CO3 CaCO3 + Na2SO4
65 66

Limitation of Lime Soda Process Calculation of Lime & Soda Requirement

 Its not possible to remove all the hardness from water. In  Ignore all those impurities like NaCl, KCl, K2SO4, Na2SO4,
actual practice about 50-60 ppm will remain as residual SiO2, Fe2O3, Ash which do not causes hardness.
hardness.
 Convert all the hardness causing impurities into their
 Soft water contain appreciable concentration of soluble CaCO3 equivalent.
salts such as calcium sulphate and can not be used in high Equivalent of CaCO3 = w x Molecular weight of CaCO3
pressure boilers. 2 x Equivalent weight of Hardness
producing substance
 We normally tolerate final total hardness on the order of
75-120 ppm as CaCO3 but the Magnesium content should not  Lime Requirement-
exceeds 40 ppm as CaCO3. 74 [ Temp Ca2+ + 2xTemp Mg2+ + Per Mg2+ + Fe2+ + Al3+ + CO2 +
100 H+ + HCO3- -NaAlO2 ] Volume of Water x Purity

67 68

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Dr. Manoj Acharya August 31, 2023

 Soda Requirement- Zeolite Process or Permutit Process

106 [ Per Ca2+ + Per Mg2+ + Fe2+ + Al3+ + H+ - HCO3- ]  Zeolites are naturally occuring
100 Volume of Water x Purity hydrated sodium alumino silicate
(like Na2O.Al2O3. x SiO2.y H2O
 If ‘x’ is the purity of lime & ‘y’ is the purity of soda then where x = 2-10, y = 2-6).
Purity of Lime = 100 / x & Purity of Soda = 100 / y
 Zeolites are porous in nature &
also known as Permutit.
Numerical on Lime Soda Process
 Zeolites are of two types-
Annexure-3 Natural Zeolite
Synthetic Zeolite
 Natural Zeolite: Non porous, Amorphous & Durable.
For e.g.: Natrolite [Na2O.Al2O3. 4 SiO2.2 H2O], Laumonite
[CaO. Al2O3. 4 SiO2.4 H2O], Harmotome [ BaO.K2O Al2O3. 5
69 70
SiO2.5 H2O],

 Synthetic Zeolite
Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3
Porous and posses gel like structure. Mg(HCO3)2 + Na2Ze MgZe + 2NaHCO3
They are prepared by heating together sodium carbonate CaCl2 + Na2Ze CaZe + 2NaCl
(Na2CO3), alumina (Al2O3), silica (SiO2). CaSO4 + Na2Ze CaZe + Na2SO4
Synthetic Zeolite posses higher exchange capacity per unit MgCl2 + Na2Ze MgZe + 2NaCl
weight compared to natural zeolite. MgSO4 + Na2Ze MgZe + Na2SO4

 Process:  Regeneration:
Hard water is percolated at specified rate through bed of After some time the zeolite is completely converted into CaZe
zeolite. & MgZe. The zeolite bed ceases to soften water i.e. it gets
The hardness causing ions Ca2+, Mg2+ etc. are retained by exhausted.
zeolite as CaZe & MgZe respectively and outgoing water The zeolite bed is regenrated by passing concentrated Sodium
contain Sodium Salts. Chloride (Brine) solution
The water becomes free from hardness causing cations i.e. CaZe + NaCl Na2Ze + CaCl2
Ca2+, Mg2+. MgZe + NaCl Na2Ze + MgCl2
71 72

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Dr. Manoj Acharya August 31, 2023

Instead of NaCl, NaNO3, KCl, KNO3 can also be used for  Anions are not removed by this process. The Bicarbonate present
regeneration but NaCl is used due to its low cost & products in hard water get converted to NaHCO3 which goes into the soft
of regeneration (CaCl2 & MgCl2) are highly soluble in water. water. If it is used in high pressure boilers then it dissociates into
NaOH & CO2.
After regeneration the zeolite bed is rinsed with soft water to
NaHCO3 NaOH + CO2
remove excess amount of NaCl, CaCl2 & MgCl2.
Limitation of Zeolite Process  NaOH & CO2 are responsible for Caustic Embrittlement & Boiler
Corrosion respectively.
 If the supplied water is turbid then suspended impurities should be
removed first otherwise it will clog the pores of zeolte bed. Advantages of Zeolite Process
 If the supplied water contain large quantity of Mn2+ or Fe2+ then  The hardness is nearly completely removed.
they must be removed first because these ions produce MnZe & FeZe,  Water of about 10 ppm residual hardness is produced.
which are very difficult to regenerate.  The impurities are not precipitated, so there is no danger of sludge
 If mineral acids are present in the supplied water then they will formation.
destroy zeolite bed. So, supplied water must be neutralised with soda  The process automatically adjust itself to water of different
in advance. 73 hardness. 74

 Ion-Exchange Process Cation Exchange Resins (RH+)

Removal of all the ions present in water is called  They are styrene –divinyl
Demineralization. The demineralization is done by Ion benzene copolymer which
exchange resins.
on sulphonation or
 Ion exchange resin are
carboxylation becomes
insoluble, cross linked, high
molecular weight, long chain capable to exchange their
organic polymer with hydrogen ions with cations
microporous structure. in water.
 The functional groups  They have acidic functional
attached to the chains are group like –SO3H, -COOH or
responsible for ion exchange.
–OH, capable of exchanging
 Ion Exchange resins are of
the cationic portion of
two types-
Cation Exchange Resin (R-H+) minerals with their
Anion Exchange Resin (R+OH- 75 hydrogen ions. 76

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Dr. Manoj Acharya August 31, 2023

Anion Exchange Resins (R’OH-) Process

Cation Exchange
 They are styrene –divinyl
 The hard water is first passed through the cation exchang
benzene or amine
column which removes all the cations present in water
formaldehyde copolymer which
then equivalent amount of H+ ions are released from this
contains basic functional group
column into water.
like amino or quaternary
ammonium (-N+R3) or 2RH+ + Ca2+ R2Ca2+ + 2H+
quaternary phosphonium or 2RH+ + Mg2+ R2Mg2+ + 2H+
tertiary sulphonium groups. Anion Exchange
 After cation exchange column the water is passed
 These after treatment with dil through anion exchange column which removes all the
NaOH becomes capable to anions present in water then equivalent amount of OH-
exchange their –OH anions with ions are released from this column into water.
the anions of water. 77 78

Regeneration
R’OH- + Cl- R’Cl- + OH-
 When capacities of cation and anion exchanger to exchange
R’OH- + SO42- R’SO42- + 2OH- H+ and OH- ions respectively are lost they are said to be
R’OH- + CO32- R’CO32- + 2OH- exhausted.
 The exhausted cation exchange column is regenerated by
 The H+ and OH- ions released from both the column
passing dil HCl or dil H2SO4.
combine to produce water.
H+ + OH- H 2O R2Ca2+ + H+ 2RH+ + Ca2+
R2Mg2+ + H+ 2RH+ + Mg2+
 Thus water coming out of exchanger is free from cations  The exhausted anion exchange column is regenerated by
as well as anions. Ion free water is known as Deionised or passing dil NaOH.
Demineralised water.
R’Cl- + OH- R’OH- + Cl-
R’SO42- + OH- 2 R’OH- + SO42-
79 R’CO32- + OH- 2 R’OH- + CO32-

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Dr. Manoj Acharya August 31, 2023

Advantages of Ions Exchange Process Internal Treatment

 It means treating raw water inside the boiler. Its also known as
 The process can be used to soften highly acidic or alkaline sequestration.
water.  In this process an ion is prohibited to exhibit its original character
by complexing or converting into more soluble salt by adding
 It produces water of very low hardness (~2ppm).
appropriate reagent.

Disadvantages of Ions Exchange Process  Internal treatment methods are-

 Turbidity in water reduces the efficiency of the process.  Colloidal Conditioning

 Installation cost and operating cost is high.  Carbonate Conditioning

 Calgon Conditioning

 Phosphate conditioning
81 82

Colloidal Conditioning  Scale forming salts like CaSO4 is converted into CaCO3,
 Scale formation can be avoided in low pressure boilers by which can be removed easily.
adding substances like Kerosene, tannin, agar-agar etc. CaSO4 + Na2CO3 CaCO3 + Na2SO4
which get adsorbed over the scale formation precipitate,
thereby resulting in non-sticky and loose deposits which
can be removed easily by blow down operation. Calgon Conditioning
 Calgon is Sodium hexa meta phosphate i.e. Na2[Na4(PO3)6].
Carbonate Conditioning
 Calgon converts the scale forming impurity like CaSO4 into
 Its used in low pressure boilers.
soluble compound, which are harmless to boiler.
 For a salt to precipitate the ionic concentration should
Na2[Na4(PO3)6] 2 Na + [Na4 (PO3)6]2-
exceeds the solubility product [Ksp < Ip].
 Scale formation can be avoided by adding Na2CO3 to the [Na4(PO3)6]2- + CaSO4 2 Na2SO4 + [Ca2 (PO3)6]2-
boiler feed water. 83 Soluble Complex84

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Dr. Manoj Acharya August 31, 2023

 At low temperature and pressure, it forms stable and  Scale formation is avoided by adding Sodium Phosphate
soluble complex with calcium salt. which reacts with Ca2+ & Mg2+ salts to form non adherent
 At high temperature and pressure, its converted into and easily removable soft sludge of Calcium and
Sodium orthophosphate which reacts with calcium salts to Magnesium Phosphate.
form calcium orthophosphate. CaCl2 + Na3PO4 Ca3(PO4)2 + 6 NaCl
2 Na2[Na4(PO3)6]2- + 6H2O 2 Na2P2O7 + 6H2 CaSO4 + Na3PO4 Ca3(PO4)2 + 6 Na2SO4

CaSO4 + Na2P2O7 2 Ca2P2O7 + Na2SO4  Choice of Phosphate salt depends upon alkalinity of boiler
Sodium Orthophosphate Calcium Orthophosphate feed water-
Loose Sludge H3PO4

Phosphate Conditioning NaH2PO4 Na2HPO4

 It is applicable to high pressure boilers. Acidic Weakly Alkaline

Na3PO4
85 86
Alkaline

Specification for potable water S.No. Characteristics Desirable Limit (mg/L)

8 Sulphate 400
Water is colourless, odourless, tasteless and universal 9 Nitrate 45
solvent and usually contains several impurities (Gases, 10 Cyannide 0.2
Solids and Colour) 11 Fluoride 1.5
12 Chromium 0.05
Specification for potable water as per Bureau of 13 Lead 0.05
Indian Standards 14 Arsenic 0.05

S.No. Characteristics Desirable Limit (mg/L)

1 Colour, Odour, Taste Colourless, Odourless and Tasteless
2 Turbidity < 10 ppm
3 Alkalinity pH = 7-7.5
4 pH 6.9
5 Dissolved Oxygen ---
6 Chloride 250
7 Total Hardness (as CaCO3) mg/L < 500
87 88

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Dr. Manoj Acharya August 31, 2023

 Drinking Water Treatment Screening

 It is the process of removing floating
 Rivers, Lakes, Well are the most common source of water material like wood pieces, leaves, etc.
and do not confirm the specification of drinking water. from water.
 Actual treatment method to be adopted depends upon the  Raw water is passed through screens
nature of impurities. having holes, when floating matter is
retained by them and water is allowed to
S.No. Impurity Treatment
pass.
Process
1 Floating matter such as leaves, wood pieces etc. Screening Sedimentation
2 Suspended Impurities such as sand, clay etc. Sedimentation  It is the process of removing suspended
3 Fine suspended inorganic matter Sedimentation impurities by allowing the water to stand
with Coagulation undisturbed in big tank for 2-8 hrs.
4 Microorganisms and Colloidal impurities Filtration  Most of the particles settle down at the
5 Pathogenic Bacteria Disinfection bottom of the tank due to gravitational
89
force. 90

Sedimentation with coagulation Filtration

A water filter removes the
 Finely divided silica , clay and organic matter do not settle down
easily and can not be removed by only by sedimentation. impurities by minimizing
contamination of water using fine
 If coagulants (Alum [K2SO4.Al2(SO4)3.24 H2O], Sodium Aluminate
physical barrier, a chemical process
NaAlO2) are added to water which hydrolyse to form gelatinous
or a biological process.
precipitate of Al(OH)3.
 Activated Charcoal is used as
 Colloidal impurities carry negative charge and coagulants give Al3+ decolourising agent.
ions which neutralize the colloidal particles and form flocculate.
Due to force of gravity these bigger particles settle down. Disinfection
 The process of destroying/killing the pathogenic bacteria in
Chemical Coagulants Ideal pH range of use water is known as disinfection.
Al2(SO4)3 6.5-8.5  The process of complete destruction of all living organisms is
NaAlO2 5.5-8.0 known as sterilisation (Like Boiling). Sterilisation kills the
FeSO4 >8.5 bacteria for some time and does not provide any protection
91 92
against future contamination.

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 Methods of Disinfection  By Chlorination

(a) By Bleaching powder (b) By Chlorination Chlorine is used as disinfectant in water treatment. It can
(c ) By Chloramine (d) By Ozone be used directly as gas or in form of concentrated solution
(e) By Ultraviolet radiation (f) By KMnO4 in water.
It produces hypochlorous acid which is germicide.
 Disinfection by bleaching powder
Cl2 + H2O HOCl + H+ + Cl-
Disinfection can be done by adding Bleaching powder (CaOCl2) to the
water Hypochlorous Acid

CaOCl2 + H2O Ca(OH)2 + Cl2 Depending on pH value, hypochlorous acid gets convert
Cl2 + H2O HCl + HOCl (Hypochlorous Acid) into hypochlorite ion
HOCl HCl + [O] (Nascent Oxygen) Cl2 + 2H2O HOCl + H3O+ + Cl-
HOCl + H2O H3O+ + OCl-
Drawbacks-
 Excess of bleaching powder imparts bad taste & smell to water. OCl- Cl- + [O]
 Bleaching powder is not stable so it deteriorates.
 It introduces Calcium in water and thus increases hardness. 93 94

 The disinfection properties of chlorine in water are based on the  Break Point Chlorination / Free Residual Chlorination
oxidising power of oxygen atom & on chlorine substitution
reactions.  It means chlorination of water to such an extent that living organism
as well as other organic impurities in water are destroyed.
 Hypochlorous acid (HOCl) is electrically neutral while Hypochlorite
ion (OCl-) is electrically negative.  It involves addition of sufficient amount of chlorine to oxidise
organic matter, reducing substances and free ammonia in raw water,
 Hypochlorous acid (HOCl) is strong disinfectant than OCl-. HOCl leaving behind free chorine which possesses disinfection action
breaks into HCl and atomic oxygen (O), which is strong disinfectant. against pathogens bacteria.
 By nature the cell wall of pathogenic microorganism is negatively
charged. Hypochlorous acid penetrates cell wall & kills the
microorganisms or suffers reproductive failure.
S.No. pH HOCl OCl-
1 6 80% 20%
2 7.5 50% 50%
3 8 20% 80% 95 96

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Dr. Manoj Acharya August 31, 2023

 Stage-I: Initially for lower chlorine doses of Chlorine, there is no free  Disinfection by Chloramine
chlorine since all the added chlorine gets consumed in the oxidation
 Chloramine has better bactericidal action than chlorine. Its more
of reducing substances present in water.
stable and does not produce any odour.
 Stage-II: As the amount of chlorine dosage is increased, amount of ClNH2 + H2O HOCl + NH3
residual chlorine also steady increases. In this stage formation of (2:1)
chloro-organic takes place without oxidising them. HOCl HCl + [O]

 Stage-III: At higher dose of applied chlorine, oxidation of organic  Disinfection by Ozone

compounds and microorganisms takes place & the amount of
chlorine free chlorine also decreases. When oxidative destruction is  Ozone is made by passing oxygen through ultraviolet light or an
complete it reaches a minima. electrical discharge. Ozone is highly unstable breaks into oxygen and
nasent oxygen.
 Stage-IV: After minima, the added chlorine is not used in any
O3 O2 + [O]
reaction. Thus the residual chlorine keeps increasing in direct
proportion to added chlorine.  Nasent oxygen is powerful oxidising agent and oxidises organic
matter and also kills bacteria. The main advantage of ozonation is
97 lack of taste & odour. 98

 Disinfection by UV Radiation  Reverse Osmosis / Super or Hyper Filtration

 Water is passed in thin layer around the lamp because the  Osmosis is the phenomenon by virtue of which flow of water takes
germicidal action of UV radiation depends on the intensity of the place from a region of low concentration to high concentration,
light, depth of exposure and contact time. when two solutions of different concentration are separated by
 Turbidity & minor traces of Iron reduces the light transmission. semi-permeable membrane. Semi-permeable membrane do not
allow the passage of solute but allows the passage of solvent only.
 Sea Water Treatment
 The flow of solvent continues till the concentration is equal on both
 Water containing high concentration of dissolved solids with the sides of semi-permeable membrane. The driving force for
peculiar salty or brackish taste is called brackish water. For e.g. Sea osmosis is known as Osmotic Pressure.
Water containing 3.5% of dissolved salts.
 The removal of dissolved solids (NaCl) from water is known as
desalination process.
 Methods of Desalination
(a) Reverse Osmosis (b) Distillation
(c ) Electrodialysis (d) Freezing 99 100

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Dr. Manoj Acharya August 31, 2023

 If the hydrostatic pressure in excess of osmotic pressure is applied  Application

on the concentrated side, the flow of solvent reversed; it is forced to
move from concentrated side to dilute side across the membrane.

 Since semi-permeable membrane do not allow the passage of

solute but allows the passage of solvent only. The concentrated
solution becomes more concentrated.

 There are 03 types of R.O. membrane

(a ) Cellulosic (b) Fully aromatic polyamide
(c ) Thin Film Composite
 The pore size of R.O. membrane is around 0.0001 micron. A
pressure of about 15-40 Kg/cm2 is applied for separating water
from contaminants.

101 102

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