Water

Dr. Bharati Choudhari

Asst. Professor- S&H
KJSCE, SVU,
Vidyavihar.
Introduction
1). Like air, water is one of the few basic materials which is of
prime importance for the preservation of life on this earth.

2). All are aware of the uses of water for drinking, cooking,
cooking, bathing & for farming etc.

3). But few know the importance of water as an engineering

material.

4). As an engineering material water is used for producing

steam, in boilers to generate hydro-electric power, furnishing
steam for engines, for construction of concrete structures for
manufacturing purposes & as a solvent in chemical process.
Sources of Water:
The Main Sources Of Water Are:
1). Rain water
2). River water
3). Spring or well water
4). Sea water
Types of impurities in water:
The impurities present in water are classified
as:
1). Dissolved impurities: dissolved impurities
may organic or inorganic.
Inorganic impurities: the carbonates,
bicarbonates, sulphates, chlorides of calcium,
magnesium, iron potassium and aluminium.
Organic impurities: Organic water products,
amino acids, proteins, etc. Gases: O2, CO2,
Oxides of nitrogen and sulphur, H2S etc.
2). Suspended impurities: It is of two types:
1. Inorganic- sand & clay;
2. Organic- vegetable and animal matter.

3) Biological Impurities: Micro-organisms like

pathogenic bacteria, fungi, algae, etc.
DISADVANTAGES OF HARDWATER/ CAUSES OF
HARDNESS:
The following are the disadvantages when hard
water is used for various purpose:
(i) DOMESTIC USE:
(a) Washing and Bathing: Hard water does not
form lather easily with soap, so soap is
wasted
(b) Drinking: Hard water causes bad effects on
our digestive system. Sometimes, stone
formation takes place in kidneys
(c) Cooking: The boiling point of water is
increased due to the presence of salts. Hence,
more fuel and time are required for cooking.
(ii) INDUSTRIAL USE:
(a) Textile Industry: Hard water causes wastage of
soap. Precipitates of calcium and magnesium
soap adhere to the fabrics and cause problem
such difference in color shades, dull shades,
patches, etc.
(b) Paper Industry: Calcium and Magnesium salts
in water may affect the quality of paper.
(c) Sugar Industry: Water containing sulphates,
carbonates, nitrates affects the crystallisation of
sugar.
(d) Pharmaceutical Industry: Hard water may form
some undesirable products while preparation of
pharmaceutical products.
(iii) STEAM GENERATION IN BOILERS: For steam
generation, boilers are employed. If hard water is
used in boilers, It may lead to the following
troubles-
(a) Boiler Corrosion
(b) Scale and Sludge formation.
(c) Priming and Foaming
(d) Caustic embrittlement Pharmaceutical
industry
HARDNESS OF WATER (OR) HARDWATER AND
SOFT WATER:
Hard Water: The water which does not produce
lather (or) very little lather with soap is called
Hard Water.
Soft Water: Soft water readily produces a lot of
lather when mixed with little soap.
The Hardness of water is caused by the presence
of dissolved salts such as Bicarbonates,
Sulphates, Chlorides and Nitrates of bivalent
metal ions like Ca+2 & Mg+2.
Soap is sodium/ potassium salt of higher fatty
acids like stearic, oleic and palmetic acids. When
soap is mixed with soft water lather is produced
due to stearic acid and sodium stearate.
Na – Stearate + H2O 🡪 NaOH + Stearic Acid
[C17H35COOH]
Stearic Acid + Na-Stearate 🡪 Formation of
lather.
When soap comes in contact with HARD WATER,
Sodium stearate will react with dissolved calcium
and magnesium salts and produce calcium
stearate or magnesium stearate which is white
precipitate.
2Na– Stearate + Ca+2 🡪 Ca– Stearate↓ + 2Na+
[2C17H35COONa] + Ca+2 🡪 [(C17H35COO)2Ca]↓ + 2Na+
(Soap) (Soluble) (Insoluble)
(Soluble)
[2C17H35COONa] + Mg+2 🡪 [(C17H35COO)2Mg]↓ + 2Na+
(Soluble) (Soluble) (Insoluble)
(Soluble)
TYPES OF HARDNESS
The hardness of water is of two types-
(1) Temporary hardness (or) Carbonate hardness
(2) Permanent hardness (or) Non-Carbonate
hardness
(1) Temporary Hardness: Temporary hardness is
caused by two dissolved bicarbonate salts
Ca(HCO3)2 and Mg(HCO3)2. The hardness is called
“Temporary Hardness” because it can be
removed easily by means of boiling.
Ca(HCO3)2 + Heating 🡪 CaCO3↓ + H2O + CO2↑
Mg(HCO3)2 + Heating 🡪 Mg(OH)2↓ + 2CO2↑
(2) Permanent Hardness: Permanent hardness of
water is due to the dissolved chlorides,
sulphates and nitrates of calcium and
magnesium. These salts are CaCl2, CaSO4,
Ca(NO3)2, MgCl2, MgSO4, Mg(NO3)2. These
hardness cannot be removed easily by boiling.
Hence it is called “Permanent Hardness”. Only
chemical treatment can remove this hardness.

Total Hardness Of Water = Temporary Hardness + Permanent Hardness

DEGREE OF HARDNESS:
• The Concentration of hardness as well as non-
hardness constituting ions are, usually expressed
in the term of “Equivalent amount of CaCO3”
• Since this mode permits the multiplication and
division concentration, when required.
• The choice of CaCO3 in particular is due to its
molecular weight (m.wt.) is “100” (Equivalent wt.
= 50), and
• Moreover, it is insoluble salt that can be
precipitated in water treatment.
Therefore, 100 parts by weight of CaCO3
hardness must be equivalent to-
• 162 parts by weight of Ca(HCO3)2 hardness
• 146 parts by weight of Mg(HCO3)2 hardness
• 136 parts by weight of CaSO4 hardness
• 111 parts by weight of CaCl2 hardness
• 164 parts by weight of Ca(NO3)2 hardness
• 120 parts by weight of MgSO4 hardness
• 146 parts by weight of MgCl2 hardness
• 148 parts by weight of Mg(NO3)2 hardness
Salt Molar Mass Chemical Equivalent Multiplication Factor
Ca(HCO3)2 162 81 100/ 162
Mg(HCO3)2 142 73 100/ 142
CaSO4 136 68 100/ 136
FeCl2 127 63.5 100/ 127
CaCl2 111 55.5 100/ 111
MgSO4 120 60 100/ 120
MgCl2 95 47.5 100/ 95
CaCO3 100 50 100/ 100
MgCO3 84 42 100/ 84
CO2 44 22 100/ 44
Ca(NO3)2 164 82 100/164
Mg(NO3)2 148 74 100/ 148
HCO3- 61 61 100/ 122
OH- 17 17 100/ 34
CO32- 60 30 100/ 60
Salt Molar Mass Chemical Equivalent Multiplication Factor
NaAlO2 82 82 100/ 164
Al2(SO4)3 342 57 100/ 114
FeSO4.7H2O 278 139 100/ 278
H+ 1 1 100/ 2
HCl 36.5 36.5 100/ 73

The method of calculating degree of hardness is

given by the following formula
•Hardness causing salt in terms of equivalent of
CaCO3= (Amount (Mass) of the hardness
causing salt x 100)/ Molecular weight of
hardness causing salt
UNITS OF HARDNESS:
The 5 different units in which the hardness of
water is expressed as given below-
(1) Parts per million (PPM): PPM is the number of
parts of CaCO3 equivalent hardness per 106 parts
of water.
i.e., 1 PPM = 1 part of CaCO3 equivalent hardness
in 106 parts of water.
(2) Milli grams Per Litre (mg/litre): mg/L is the
number of milligrams of CaCO3 equivalent
hardness present per litre of water.
i.e., 1 mg/L = 1 mg of CaCO3 equivalent hardness in 1L of
water.
But 1 L water weighs = 1 kg of water
1 kg = 1000 gms = 1000 x 1000 mg = 106 mg
∴ 1 mg/L = 1mg of CaCO3 equivalent per 106 mg of water
= 1 part of CaCO3 equivalent per 106 parts of water
∴ 1 mg/L = 1 ppm
(3) Degree Of Clarke (oCl): It is number of grains
(1/7000 lb) of CaCO3 equivalent hardness per
gallon (10 lb) of water.
(or) It is defined as the number of parts of CaCO3
equivalent hardness per 70,000 parts of water.
∴ 1 oCl = 1 grain of CaCO3 eq. hardness per gallon
of water.
(or) 1 oCl = 1 part of CaCO3 eq. hardness per
70,000 parts of water
∴ 1 ppm = 0.07 oCl
(4) Degree Of French (oFr): It is the number of
parts of CaCO3 equivalent hardness per 105 parts
of water.
1 oFr = 1 part of CaCO3 equivalent hardness per
105 parts of water
∴ 0.1 oFr = 1 ppm
Note: The hardness of water can be converted
into all the four units by making use of the
following interconversion formula-
1 ppm = 1mg/L = 0.07oCl = 0.1oFr
1 oCl = 1.43oFr = 14.3 ppm = 14.3 mg/L
(5) Milliequivalent per Litre (meq/L): It is the
number of milliequivalent of hardness present per
litre of water.
1 meq/L= 1 meq of CaCO3 per litre of water
= 10-3 x 50 g of CaCO3 eq. of hardness per
litre of water
= 50 mg of CaCO3 eq. of hardness per litre of
water
= 50 mg/L of CaCO3 eq.
= 50 ppm
∴1 meq/L= 50 ppm
PROBLEM:
(1) A sample of water gives an analysis 13.6 mg/L of
CaSO4 , 7.3 mg/L of Mg(HCO3)2 . Calculate the total
hardness and permanent hardness.
Sol: Salt Quantity M.
(mg/L) Wt.
Multiplication Eq. of
Factor CaCO
Hardnes
3 s
CaSO4 13.6 136 100/ 136 13.6 x P
(100/
136)= 10
Mg(HCO3 7.3 146 100/ 146 7.3 x T
)2 (100/
146)= 5

Total hardness= Temporary hardness + Permanent

Hardness = 5 + 10 = 15 mg/L = 15 ppm
Permanent hardness = 10 ppm
Temporary hardness= 5 ppm
DETERMINATION OF HARDNESS OF WATER BY
EDTA METHOD:-
1. This is a Complexometric titration method
where Ethylenediamine tetraacetic acid
(EDTA) is used.
2. EDTA forms complexes with different metal
ions at different pH.
3. Calcium & Magnesium ions form complexes
with EDTA at pH 9- 10.
To maintain the pH 9- 10 NH4Cl, NH4OH buffer
solution is used.
4. The disodium salt of EDTA is used for
complexation.
5. An alcoholic solution of Eriochrome Black-T
(EBT) is used as an indicator.

EDTA
EDTA disodium salt

Metal-EDTA complex
BASIC PRINCIPLE:
When hard water comes in contact with EDTA,
at pH 9- 10, the Ca+2 & Mg+2 forms stable,
colourless complex with EDTA.
Ca+2 + EDTA + pH 9-10 🡪 Ca-EDTA
Mg+2 + EDTA + pH 9-10 🡪 Mg-EDTA
Working:-
To the hard water sample, the alcoholic blue coloured EBT
indicator is added along with the NH4Cl + NH4OH buffer (pH 9- 10)
solution.
EBT forms an unstable wine-red complex with Ca+2 & Mg+2.
(Ca+2 + Mg+2) + EBT + Buffer (pH 9-10) 🡪 (Ca-EBT + Mg-EBT) complex
(Hard water) (Indicator) (Unstable wine-red complex)

This wine-red coloured [Ca-EBT & Mg-EBT] complex is then

titrated against EDTA; when EDTA replaces EBT from Ca-EBT & Mg-
EBT complex and forms stable colourless [Ca-EDTA] & [Mg-EDTA]
complex releasing the blue coloured indicator EBT into H2O.
[Ca-EBT + Mg-EBT] complex + EDTA 🡪 EBT + [Ca-EDTA + Mg-EDTA] complex
(Unstable wine-red complex) (Blue) (Stable colourless complex)

Hence the colour change at the end point is wine-red to blue

colour.
The titration is carried out in the following steps
1. PREPARATION OF STANDARD HARD WATER:
Dissolve 1gm of pure, dry CaCO3 in minimum
quantity of dilute HCl and evaporate the
solution to dryness on a water-bath. Dissolve
the residue in distilled water to make 1 litre in a
standard flask and shake well.

Molarity of standard hard water solution =

wt. of CaCO3 = 1 = 0.01M
M.wt. of CaCO3 100
(2) PREPARATION OF EDTA SOLUTION:
Dissolve 4 gms of pure EDTA-disodium salt
crystals along with 0.1 gm of MgCl2 in one litre
of distilled water.
(3) PREPARATION OF INDICATOR (EBT):
Dissolve 0.5 gms of Erichrome Black-T in 100 ml
of alcohol.
(4) PREPARATION OF BUFFER SOLUTION: Add
67.5 gm of NH4Cl to 570 ml of concentrated
ammonia solution and dilute with distilled
water to one litre
(5) STANDARDISATION OF EDTA SOLUTION:
Pipette out 20 ml of standard hard water
solution into a conical flask. Add 2- 3 ml of
buffer (pH 9- 10) solution and 2- 3 drops of EBT
indicator. Titrate the wine-red coloured complex
with EDTA taken in a burette after rinsing it with
EDTA solution till the wine red colour changes to
clear blue.
Note the burette reading and let the volume be
“x”ml. Repeat the titration to get concurrent
values.
(6) TITRATION OF SAMPLE HARD WATER (Total) :
Pipette out 20 ml of the water sample into a
250ml conical flask, add 2- 3 ml of buffer (pH 9-
10) solution and 2- 3 drops of EBT indicator.
Titrate the wine-red coloured solution with EDTA
taken in the burette till a clear blue coloured end
point is obtained.
Let the volume of EDTA be “y” ml. Repeat the
titration to get concurrent values
(7) TITRATION FOR PERMANENT HARDNESS:
Pipette out 100 ml of hard water sample in a
beaker and boil till the volume reduces to 20 ml.
All the bicarbonates of Ca++ and Mg++ decomposes
to CaCO3 and Mg(OH)2. Cool the solution and filter
the water into a flask, wash the beaker and
precipitate with distilled water and add the
washing to conical flask. Add 2- 3 ml of buffer (pH
9- 10) solution and 2- 3 drops of EBT indicator and
titrate with EDTA solution taken in the burette till
a clear blue colour end point is obtained.
Note the burette reading. Let the volume be “z”
ml.
CALCULATIONS:
Molarity of standard hard water solution = 0.01 M.
(Calculated in the preparation of standard hard water)
Molarity of EDTA solution (M2 ): V1M1 = V2M2
n1 n2
n1 & n2 are no. of moles of Ca+2 and EDTA = 1 each
i.e., n1=1, n2=1
V1 = volume of standard hard water
M1= Molarity of standard hard water
V2= volume of EDTA
M2= molarity of EDTA
M2 = V1M1 = 20 X 0.01
V2 x (titre value)
Molarity of sample hard water (M3 ):
V2M2 = V3M3
n2 n3
V2= volume of EDTA
M2= molarity of EDTA
V3= volume of sample hard water
M3= Molarity of sample hard water

M3 = V2M2 = M2 x y (titre value)= y x 0.01

V3 20 x
Total Hardness Of Water
= M3 x 100 gms/1 litre
=M3 X 100 X 1000mg/L or ppm= (y/ x) X 1000ppm
Permanent Hardness Of Water:
V2M2 = V4M4 M4= V2M2 = zM2 = z X 0.01
n2 n4 V4 20 x
V2= volume of EDTA
M2= molarity of EDTA
V4 = volume of water sample containing permanent
hardness (100 ml)
M4= Molarity of water sample containing permanent
hardness
Permanent Hardness Of The Water Sample
= M4 x 100 x 1000 ppm
= z/ x X 1000ppm
Temporary Hardness Of The Water Sample
= (Total Hardness – Permanent Hardness)
= (M3 x 100 x1000 – M4 x 100 x1000) ppm
= (M3 – M4) x 100 x1000 ppm
= (y-z) X 1000 ppm
x
Problem:
1 gm of CaCO3 was dissolved in HCl and the
solution was made upto 1 Lit with distilled water.
50 ml of the above solution required 30 ml of
EDTA solution for titration. 50 ml of hard water
sample required 40 ml of the same solution of
EDTA for titration. 50 ml of the hard water after
boiling, filtering, etc. required 30 ml of the same
EDTA solution for titration. Calculate the
temporary hardness of the water.
Soln:
Molarity of CaCO3 (SHW) solution (M1)= 1/100= 0.01 M
Molarity of EDTA solution (M2 ) = V1 M1/ V2
V1= volume of CaCO3 solution = 50 ml
M1= Molarity of CaCO3 solution = 0.01 M
V2= volume of EDTA = 30 ml
M2= 50 x 0.01/ 30 = 0.016 M
Molarity of Hard Water Sample Sol.(M3 )= V2M2/ V3
V2= volume of EDTA = 40 ml
M2= Molarity of EDTA = 0.016 M
V3= volume of hard water sample= 50 ml
M3= 40 x 0.016/ 50 = 0.0128 M
Total Hardness of water
= 0.0128 x 100 x 1000
= 1280 ppm
Permanent hardness of water: = V4 M4 = V2 M2

n4 n2
M4 = V2M2/ V4
n4=1; V2= volume of EDTA = 30 ml
n2=1; M2= molarity of EDTA = 0.016
V4= volume of permanent hardness containing
water = 50
Permanent hardness of water
= 0.0096 x 100 x 1000 = 960 ppm
Temporary hardness
= Total hardness – Permanent hardness
= 1280 – 960 = 320 ppm
20ml of SHW containing 1.2gm CaCO3 per litre required 35ml of EDTA. 50ml of
hard water sample required 30ml of same EDTA. 100ml of hard water sample
after boiling, cooling required 25ml of same EDTA. Calculate the hardness.
Solution: Strength of SHW= 1.2gm/ lit = 1200mg/ lit = 1.2mg/ ml
Volume of SHW= 20ml = 20 x 1.2 = 24mg of CaCO3 equiv hardness
Now, 20ml SHW = 35ml EDTA = 24mg of CaCO3 equiv hardness
i.e. 35ml EDTA = 24mg So, 1 ml EDTA= 24/35 mg CaCO3 hardness

50ml sample water = 30ml EDTA = 30 x 24/35 mg CaCO3 hardness = 20.57mg

Thus, 1 lit = 1000ml = 1000 x 20.57/50 = 411.4mg
So, Total hardness = 411.40ppm

100ml of boiled sample= 25ml EDTA = 25 x 24/35 = 17.14mg CaCO3 hardness

Thus, 1 lit = 1000ml = 1000 x 17.14/100 = 171.4mg
So, Permanent hardness = 171.40ppm

Temporary Hardness = Total hardness – Permanent hardness

411.40 – 171.40 = 240.00ppm
BOILER TROUBLES:
Water finds a great use in various industries
for generation of steam in boilers. When
water is continuously evaporated to generate
steam, the concentration of the dissolved
salts increase progressively causing bad
effects for steam boilers. The following are
the boiler troubles that arise:
(1) Priming and foaming
(2) Caustic embrittlement
(3) Boiler corrosion
(4) Scale and sludge formation
PRIMING & FOAMING:
Priming: When a boiler is steaming rapidly, some
particles of the liquid water are carried along
with the steam. This process of “WET STEAM”
formation is called ‘PRIMING’. Priming is caused
by:
(1) 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
It can be avoided by: (Preventions)
(1) Maintaining low water level
(2) Using softened water
(3) Fitting mechanical steam purifiers
(4) Using a well-designed boiler
(5) Avoiding rapid change in steam rate
(6) Blow-down of the boiler
FOAMING:
Foaming is phenomenon of formation of foam or
bubbles on the surface of water inside the boiler with
the result that the foam may pass along with the steam.
Causes: The presence of large quantity of suspended
impurities and oils lowers the surface tension producing
foam.
Preventions: Foaming can be avoided by-
(1) Adding anti foaming chemicals like castor oil
(2) Removing oil from boiler water by adding
compounds like “NaAlO2 ”
(3) Blow down of the boiler can prevent the foaming
Disadvantages Of Priming & Foaming:
Priming & Foaming may cause the following
boiler troubles:-
(1) The actual height of the water in boiler is not
judged
(2) Wastage of heat with the result that it
becomes difficult to keep up steam pressure
and efficiency of the boiler is lowered
CAUSTIC EMBRITTLEMENT:
Caustic embrittlement is a term used for the
appearance of cracks inside the boiler particularly at
those places which are under stress such as rivetted
joints due to the high concentration of alkali leading to
the failure of the boiler. The cracks have appearance of
brittle fracture. Hence, the failure is called “Caustic
Embrittlement”
Reasons for the formation of Caustic Embrittlement:
The boiler feed water containing carbonates and bicarbonates of
alkali metals, sodium hydroxide (NaOH) and a small quantity of
silica or sodium silicate; it is purified by Lime-Soda Process.
During the softening process by lime soda process, free Na2CO3 is
usually present in small portion in the soft water which
decomposes to give NaOH and CO2 at high pressure of the
boilers.
Na2CO3 + H2O 🡪 2NaOH + CO2
The precipitation of NaOH makes the boiler water “Caustic”
The NaOH containing water flows into the small pits and minute
haircracks present on the inner walls of the boiler.
As the water evaporates, the concentration of caustic soda
(NaOH) increases progressively, creating a “Concentration Cell”
Thus, dissolving the iron of the boiler as Sodium Ferrate.
Fe + 2NaOH 🡪 Na2FeO2 + H2
The cracking of the boiler occurs particularly at stressed parts like
bends, joints, rivets, etc. causing the failure of the boiler.
The iron at plane surfaces surrounded by dilute NaOH becomes
Cathodic; while the Iron at bends, rivets and joints is surrounded
by highly concentrated NaOH becomes Anodic which
consequently decayed or corroded
(Anodic site) Conc NaoH || dil NaoH (Cathodic site)
Iron at Joints &bends Iron at Plane surface

Prevention Of Caustic Embrittlement:

(1) By adding Na2SO4 , tannin, etc. to the boiler water which
blocks hair cracks. There by preventing infiltration of caustic
soda solution
(2) By using sodium phosphate as the softening agent instead of
sodium carbonate
DISADVANTAGES OF CAUSTIC EMBRITLLEMENT:
The cracking or weakening of the boiler metal
causes failure of the boiler

(3) BOILER CORROSION: The decay of boiler

material by chemical/ electro- chemical attack
by its environment is called “Boiler Corrosion”.
Reasons for boiler corrosion are: (a) Dissolved
oxygen (b) Dissolved CO2 (c) Acids from
dissolved salts.
(a) Dissolved Oxygen: Water usually contains about 8
mg/L of dissolved oxygen at room temperature.
Dissolved O2 at high temperature attacks boiler
material.
2Fe + 2H2O + O2 🡪 2Fe(OH)2↓ (ferrous hydroxide)
4Fe(OH)2↓ + O2 🡪 2[Fe2O3.2H2O]↓ (ferric oxide)
Removal of dissolved O2 :
By adding calculated quantity of sodium sulphate (or)
hydrazine (or) sodium sulphide
2Na2SO3 + O2 🡪 2Na2SO4
Sodium Sulphite
N2H4 + O2 🡪 N2 + 2H2O
Hydrazine
Na2S + 2O2 🡪 Na2SO4
(b) Dissolved CO2:
Dissolved CO2 has slow corrosive effect on the materials
of boiler plate. Source of CO2 into water is the boiler
feed water which contains bicarbonates. Under the high
temperature and pressure, maintained in the boiler the
bicarbonates decompose to produce CO2.
Ca(HCO3 )2 🡪 CaCO3 + CO2 ↑ + H2O
Mg(HCO3 )2 🡪 Mg(OH)2 + 2CO2 ↑
The disadvantage of the CO2 is slow corrosive effect on
boiler plates by producing carbonic acid
CO2 + H2O 🡪 H2CO3
Removal of CO2:
By the addition of calculated quantity of ammonia.
2NH4OH + CO2 🡪 (NH4 )2CO3 + H2O

(c) Acids from dissolved salts:

Water containing dissolved Mg-salts liberate acids on
hydrolysis
MgCl2 + 2H2O 🡪 Mg(OH)2↓ + 2HCl
Disadvantages of the acid production is that the acids
react with Iron of the boiler plate in a chain reaction to
produce decay of the metal.
Fe + 2HCl 🡪 FeCl2 + H2
FeCl2 + H2O 🡪 Fe(OH)2 + 2HCl
Fe(OH)2 + H2O + 1/2O2 🡪 Fe2O3 .3H2O (ferric oxide)
Consequently even a small amount of MgCl 2 can cause
corrosion to a large extent.

Preventions:
(1) Softening of boiler water to remove MgCl 2 from the
water
(2) Addition of corrosion inhibitors like sodium silicates,
sodium phosphate & sodium chromate
(3) By frequent blow-down operation i.e., removal of water,
concentrated with dissolved salts and feeding the boiler
with fresh soft water.
(4) Sludges and Scales formation: In boiler, water
evaporates continuously and the concentration reaches
saturation point, they form precipitates (scale or sludge)
on the inner wall of the boiler
SLUDGE: “Sludge is a soft, loose and slimy precipitate formed
within the boiler”. Sludge are formed by substances which
have greater solubility in hot water than in cold water. Salts
like MgCO3 , MgSO4 , MgCl2 , CaCl2 etc., are responsible for
sludge formation in boilers.
Disadvantages:
(a) Sludge is a bad conductor of heat, hence it wastes a
portion of heat generated.
(b) Excessive sludge formation reduces the efficiency of the
boiler.
Prevention:
(a) Frequent blow-down operation should be carried
out.
(b) Use well-softened water.

SCALES: “Scales are the hard, adhering ppt formed on

the inner wall of the boiler”. Very difficult to remove
once they are deposited on Inner wall of the boiler.
They formed due to decomposition of Calcium
bicarbonate, Calcium sulphate etc..,
Ca(HCO3)2 🡪 CaCO3 ↓ + H2O + CO2 ↑
REMOVAL OF SCALES:
(1) Frequent blow-down operation can remove
the scales which are loosely adhering.
(2) By chemical treatment eg: CaCO3 scale
removed by washing with 5-10% of HCl.
(3) By giving thermal shocks.

Prevention: Use soft water.

SOFTENING OF WATER:
The removal of hardness causing salts from
water is called “Softening of water”.
The 3 Industrial methods employed for
softening of water are:
(1) Lime-Soda Process
(2) Zeolite (or) Permutite Process
(3) Ion-Exchange (or) Demineralization process
(1) LIME-SODA PROCESS:
This process is based on converting the soluble
calcium and magnesium salts into Insoluble
calcium carbonate and magnesium hydroxide
precipitates by addition of calculated amount of
lime (Ca(OH)2) and Soda (Na2CO3). The precipitate
are removed by filtration. Any free dissolved CO2
and acids are also removed by this process. The
various chemical reactions involved in this
process are:
(a) For Calcium and Magnesium bicarbonates, only lime
is required
(i) Ca(HCO3)2 + Ca(OH)2 🡪 2CaCO3↓ + 2H2O
(ii) Mg(HCO3)2 + 2Ca(OH)2 🡪 2CaCO3↓ + Mg(OH)2↓ + 2H2O

(b) For MgSO4 & MgCl2 , both lime & soda are required
(iii) MgSO4 + Na2CO3 + Ca(OH)2 🡪 Mg(OH)2↓ + CaCO3↓ + Na2SO4
(iv) MgCl2 + Na2CO3 + Ca(OH)2 🡪 Mg(OH2)↓ + CaCO3 + 2NaCl

(c) For CaSO4 & CaCl2, only Soda is required

(v) CaSO4 + Na2CO3 🡪 CaCO3↓ + Na2SO4
(vi) CaCl2 + Na2CO3 🡪 CaCO3↓ + 2NaCl
(d) Other Reactions: Free acids, CO2 , H2S dissolved iron and
aluminium salts etc are also removed in this process
2HCl + Na2CO3 🡪 2NaCl + H2O + CO2↑
H2SO4 + Na2CO3 🡪 Na2SO4 + H2O + CO2↑
CO2 + Ca(OH)2 🡪 CaCO3↓ + H2O
H2S + Ca(OH)2 🡪 CaS↓ + 2H2O
FeSO4 + Ca(OH)2 🡪 Fe(OH)2↓ + CaSO4
Al2(SO4)3 + 3Ca(OH)2 🡪 2Al(OH)3↓ + 3CaSO4 + H2O
Constituen Reaction Requireme
t nt
Ca+2 (i) CaSO4 + Na2CO3 🡪 CaCO3↓ + Na2SO4 S
(Permanent (ii) CaCl2 + Na2CO3 🡪 CaCO3↓ + 2NaCl
)
Mg+2 (iii) MgSO4 + Na2CO3 + Ca(OH)2 🡪 Mg(OH)2 ↓ + L+S
(Permanent CaCO3↓ + Na2SO4
) (iv) MgCl2 + Na2CO3 + Ca(OH)2 🡪 Mg(OH2 ) ↓ +
CaCO3 + 2NaCl
HCO3- (v) 2NaHCO3 + Ca(OH)2 🡪 CaCO3 + H2O + Na2CO3 L-S
Ca(HCO3)2 (vi) Ca(HCO3 )2 + Ca(OH)2 🡪 2CaCO3↓ + 2H2O L
(Temporary)
Mg(HCO3)2 (vii) Mg(HCO3)2 + 2Ca(OH)2 🡪 2CaCO3↓ + Mg(OH)2↓ 2L
(Temporary) + 2H2O
CO2 (viii) CO2 + Ca(OH)2 🡪 CaCO3↓ + H2O L
H+ (ix) 2HCl + Ca(OH)2 + Na2CO3 🡪 CaCO3 + 2NaCl + L+S
H2O
Coagulants (x) FeSO4 + Ca(OH)2 🡪 Fe(OH)2 + CaSO4 L+S
FeSO4 2Fe(OH)2 + H2O + O2🡪 2Fe(OH)3
CaSO4 + Na2CO3 🡪 CaCO3 + Na2SO4
Al (SO ) (xi) Al (SO ) + 3Ca(OH) 🡪 2Al(OH) ↓ + 3CaSO + L+S
Calculation:
100 parts by mass of CaCO3 are equivalent to 74
parts of Ca(OH)2 and 106 parts of Na2CO3.

(a) Amount of lime required for softening =

74/100 (Temp Ca2+ + 2 x Temp. Mg2+ + Perm.
(Mg+2 + Fe+2 + Al3+) + CO2 + H+ (HCl/H2SO4 ) +
HCO3 - all in terms of CaCO3 equivalent)

(b) Amount of soda required for softening =

106/100 (Perm. (Ca2+ + Mg2+ + Fe+2 + Al3+) + H+
(HCl/H2SO4) + HCO3 - all in terms of CaCO3 eq.)
COLD-LIME-SODA PROCESS:
• In this method the lime & soda are mixed with hard water at
room temperature with constant stirring.
• Generally the precipitates formed by this process are finely
divided and in order to settle the precipitates, coagulants like
alum, ferrous sulphate, etc. are added.
• The hard water to be softened is mixed with calculated quantity
of chemicals (Lime + Soda + Coagulant) from the top into the
inner chamber on vigorous stirring. The chemical reactions takes
place and the hardness producing salts get converted into
insoluble precipitates.
• The sludge is removed from the bottom of the outer chamber
while the softened water passes through a wood fibre filter to
ensure the complete removal of any residual sludge particles.
• The clear softened water is withdrawn from the top of the outer
chamber.
• The softened water from this process contains a residual
hardness of 50-60ppm
HOT-LIME-SODA PROCESS:
• This process is similar to the cold lime-soda process, but no coagulant
is needed.
• Here the process is carried at a temperature of 80o to 150oC. Since the
reaction carried out at high temperature.
(a) The reaction takes place faster
(b) The sludge settles rapidly
(c) Viscosity of soft water is lower, hence filtered easily
(d) The dissolved gases such as CO2, air, etc. driven out of
the water
(e) The residual hardness is low, compared to cold lime- soda
process.
Hot lime soda process consists of three parts-
• “REACTION TANK” in which complete mixing of water, chemicals and
steam takes place and water gets softened.
• “Conical Sedimentation Vessel” where the sludge settle down.
• “SAND FILTER” where sludge is completely removed.
The softened water from this process contains a residual hardness of 15-
30 ppm.
ADVANTAGES OF LIME-SODA PROCESS:
I. This process is economical.
II. Mineral content of the water is reduced.
III. The process increases the pH value of water, which
reduces the content of pathogenic bacteria.
IV. Manganese and Iron salts are also removed by this
process.
V. The process improves the corrosion resistance of
the water.
DISADVANTAGES OF LIME-SODA PROCESS:
1) Due to residual hardness, water is not useful for
high pressure boilers.
2) Large amount of sludge is formed which create
disposal problem.
PROBLEMS:
1) Calculate the quantities of Lime & Soda required to
soften 5000 litres of water containing the following
salts: MgCl2 = 15.5 ppm; Ca(HCO3)2 = 32.5 ppm, CaSO4
= 22.4 ppm; Mg(HCO3)2 = 14.6 ppm; NaCl = 50 ppm
Soln: Calculation of Calcium Carbonate Equivalents:
Impurity M. Wt. CaCO3 eq. Requiremen
mg/L t
MgCl2 = 15.5 95 15.5 x 100 ÷ 95= 16.31 L+S
Ca(HCO3)2 = 162 32.5 x 100 ÷ 162= L
32.5 20.06
CaSO4 = 22.4 136 22.4 x 100 ÷ 136= S
16.47
Mg(HCO3)2 = 146 14.6 x 100 ÷ 146= 10 2L
14.6
NaCl = 50 -
Lime = 74/100 (Temp Ca2+ + 2 x Temp. Mg2+ + Perm.
(Mg+2 + Fe+2 + Al3+) + CO2 + H+ (HCl/H2SO4 ) + HCO3 - all in
terms of CaCO3 equivalent) x (Vol of water/ 1000) x
(100/ %P)

Lime required for litre of water:

= 74/100 (Ca(HCO3)2 + 2 x Mg(HCO3)2 + MgCl2) as CaCO3
eq.
= 74/100 (20.06 + 2x10 + 16.31)
= 74/100 x 56.37
= 41.71 mg

Lime req’d for 5000 litres of water

= 41.71 x 5000 ÷ 1000 = 208.55 g= 0.208 kg
Soda = 106/100 (Perm. (Ca2+ + Mg2+ + Fe+2 + Al3+)
+ H+ (HCl/H2SO4) + HCO3 - all in terms of CaCO3
eq.) x (Vol of water/ 1000) x (100/ %P)

Soda req’d for litre of water

= 106/100 [MgCl2 + CaSO4] as CaCO3 eq.
= 106/100 [16.31 + 16.47]
= 106/100 [32.78]
= 34.74 mg

Soda req’d for 5000 litres of water:

= 34.74 x 5000 ÷ 1000 = 173.70 gm= 0.173 kg
ION EXCHANGE PROCESS/ DEMINERALISATION
PROCESS:
Ion exchange resins are insoluble, cross-linked, long chain
organic polymers.
The functional groups attached to the chains can exchange
hardness producing cations and anions present in the water.
PROCESS: The process involves the following steps:
1) The first chamber is packed with cation exchange resin
(RH+). When the hard water is passed through a bed of cation
exchange resin it exchanges H+ with Ca+2, Mg+2, K+, Na+ etc. of
hard water.
2RH+ + Mg+2Cl2 🡪 R2Mg2+ + 2H+Cl
2RH+ + Ca2+Cl2 🡪 R2Ca2+ + 2H+Cl
Thus, the hardness producing cations (Ca2+, Mg2+ etc) are
removed
 1) The second chamber is packed with anion exchange resin.
The water coming out of the first chamber contains H+, Cl-, SO42-
and HCO3- ions.
It is now passed through anion exchange resin bed which can
exchange OH- ions with anions like Cl-, SO42- and HCO3-
R-OH + Cl- 🡪 RCl + OH-
2R-OH + SO42- 🡪 R2SO4 + 2OH-
Thus, hardness producing anions like Cl-, SO42- and HCO3- are
removed.
3) Thus, H+ ions produced from first chamber combine with OH-
ions produced from second chamber to form water.
H+ + OH- 🡪 H2O
Hence, the water produced from ion-exchange process is
completely free from all cations and anions of salts.
REGENERATION OF RESINS:
The resin bed gets exhausted, when used for a long period and can
be regenerated:
(a) The exhausted cation exchange resin can be regenerated by
passing dil. HCl (H+)
R2Mg2+ + 2H+ 🡪 2RH+ + Mg2+
R2Ca2+ + 2H+ 🡪 2RH+ + Ca2+

(b) The exhausted anion exchange resin can be regenerated by

passing dil. NaOH (OH-)
RCl + OH- 🡪 ROH + Cl-
R2SO4 + 2OH- 🡪 2ROH + SO42-
ADVANTAGES:
1) The softened water by this method is completely
free from all salts and fit for use in boilers.
2) It produces very low hardness nearly 2 ppm.
3) Highly acidic or alkaline water can be treated by this
process.

DISADVANTAGES:
1) The equipment is costly.
2) More expensive chemicals are required for
regeneration.
3) Turbid water cannot be treated by this method.
Numerical
After treating 104 litres of water by ion-exchange, the cationic
resin required 200 litres of 0.1N HCl and the anionic resin
required 200 litres of 0.1N NaOH solutions for regeneration. Find
the hardness of water.
Solution: Hardness of 104 litres of water= 200lit of 0.1N HCl
= 200 x 0.1 Lit x 1 N CaCO3
eq.
= 20 lit of 1N CaCO3 eq.
= 20 x 50 g of CaCO3 eq.
= 1000 g of CaCO3 eq.
So, Hardness in 1lit water= 1000/ 104 g of CaCO3 eq.
= 100 mg of CaCO3 eq.
Thus, hardness of water sample= 100ppm
 BOD and COD
BOD (Biological Oxygen Demand)
• It is a measure of amount of oxygen required for the biological
oxidation of organic matter under aerobic conditions at 20oC
for a period of 5 days.
Organic matter + O2 Micro-organisms CO2 + H2O

• BOD is the direct measurement of extent of pollution in waste

water & industrial effluent.
• Only applicable for bio-degradable pollutants.
• Higher the BOD, higher will be the level of pollutants in
water.
• Drinking water should have BOD less than 1 ppm.
 Principle
• Dissolved oxygen content of diluted waste-water is determined at the
beginning of the reaction by Winkler’s method or by DO meter.
• Same sample of water is kept for incubation in the presence of micro-
organisms for 5 days at 20oC and decrease in the dissolved oxygen content
is determined by Winkler’s method or by DO meter.

BOD = [(DO)Blank – (DO)Incubated ] X Dilution Factor

(DO)Blank = Dissolved oxygen of diluted sample in the beginning of the reaction
(DO)Incubated = Dissolved oxygen of diluted sample after incubation for 5 days at 20 0 C.
 Significance of BOD
1. BOD gives the extent of bio-degradable pollutants
in wastewater sample
2. It also helps in pollution control in water
3. It also express self-purification capacity of any
water body.

BOD Meter
 COD (Chemical Oxygen Demand)

• It is a measure of amount of oxygen required for the chemical

oxidation of organic matter when refluxed in acidified potassium
dichromate in the presence of Ag2SO4 or HgSO4 catalyst for 3
hours.

CxHyOz + (X + Y/4 – Z/2) O2 X CO2 + (Y/2) H2O

(Organic matter) [O]

• COD is the direct measurement of extent of pollution in waste water &

industrial effluent.
• Applicable for both bio-degradable and non bio-degradable pollutants.
• Higher the COD, higher will be the level of pollutants in water.
• Drinking water should have COD less than 1 ppm.
 Principle
• A known volume of waste water sample (say 250 ml) is refluxed with a
known excess of standard potassium dichromate (1 N) and dilute/conc.
sulfuric acid mixture in the presence of silver sulphate catalyst for about 3
hours.
• This oxidases organic matter to CO2, NH3 and H2O.
• The unreacted potassium dichromate is titrated against Ferrous ammonium
sulphate (Mohr’s salt) with ferroin indicator till blue colour changes to
wine red, the reading is (Vt).
• This gives the amount of potassium dichromate consumed (in terms of
equivalent oxygen) required for degradation of organic pollutants.
• Blank titration is performed initially with known volume of distilled water
sample and added acidified standard potassium dichromate titrated against
Ferrous ammonium sulphate (Mohr’s salt) with ferroin indicator till blue
colour changes to wine red, the reading is (Vb) (zero minute reading)
COD Meter
 Principle

Vb = Volume of FAS required for blank titration

Vt = Volume of FAS required for reaction mass after time
Y = Volume of waste water sample taken
 Significance of COD
1. COD gives the extent of pollution caused by bio-
degradable and non bio-degradable pollutants in
wastewater sample

2. It helps in rapid determination of pollutants level in

water compared to BOD

3. It is taken as a basis for calculation of efficiency

and designing of water treatment plants.
 Comparison between BOD and COD
BOD COD
It measures oxygen demand of bio- It measures oxygen demand of bio-
degradable organic pollutants only degradable and non biodegradable organic
pollutants
Less stable measurement technique as More stable measurement technique as no
micro-organisms are susceptible to micro-organisms are used and potassium
variables such as pH and temperature dichromate oxidizes any type of organic
pollutants in water
Slow process, takes 5 days Fast process , takes 3 hours
BOD values are generally less than COD COD values are generally greater than
values BOD values
 Formulae
1. BOD = [(DO)Blank – (DO)Incubated ] x Dilution Factor
(DO)Blank = Dissolved oxygen of diluted sample in the beginning of the reaction
(DO)Incubated = Dissolved oxygen of diluted sample after incubation for 5 days at 20 0 C.

2.

Vb = Volume of FAS required for blank titration

Vt = Volume of FAS required for reaction mass after time
Y = Volume of waste water sample taken