B.

TECH FIRST YEAR

ACADEMIC YEAR: 2020-2021

COURSE NAME: ENGINEERING CHEMISTRY

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Water Technology

1
Water Is one of the abundant commodities in nature,
but is also the most misused one

Earth is a blue planet, 80% of our planet is covered by water.

But, 97.5% of it is locked in the oceans, which is too saline to

drink and other uses.

2.4% water is trapped in polar ice caps and giant glaciers, from
which only 1% water is used by human for various
development, industrial, agricultural and domestic purposes.

80
70%
70
% of total water used

60
50
40
30 22%
20
8%
10
0
Agriculture Domestic Industry
Water uses

2
 Sources of water
Surface Water:
(i) Flowing water e.g. rivers and streams
In general river water contains dissolved minerals from soil such as chlorides,
sulphates, bicarbonates of sodium, calcium or magnesium, iron and organic
matters derived from decomposition of plants, small particles of sand and rocks
in suspensions.
(ii) Still waters e.g. lakes, ponds and reservoirs (Lowland surface
drainage) Lake water has more constant chemical composition.

Underground Water: water from shallow and deep spring and wells
Rain water: It is probably the purest form of natural water
Sea Water: It is probably the most impure form of natural water
5

Types of Impurities Present in water

Dissolved impurities:
(a) Inorganic salts e.g.
(i) Cations: Ca2+, Mg2+, Na+, K+, Fe+2, Al+3, Zn2+, Cu2+
(ii) Anions: Cl-, SO42-, NO3-, HCO3-, F-, NO2-
(b) Gases: CO2, O2, N2, NH3, H2S
(c) Organic salts
Suspended impurities:
(a) Inorganic e.g. clay and sand
(b) Organics e.g. oil globules, vegetable and animal matters
Colloidal impurities:
Clay and finely divided silica colloidal partials of 10-4 – 10-6 mm
size
Micro-organisms:
Bacteria, Fungi, algae and other forms of animal and vegetable life
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3
Effects of Impurities in natural water

 Colour
 Taste and odour
 Turbidity and sediments
 Micro-organisms
 Dissolved minerals matters
(a) hardness
(b) Alkalinity
(c) Total solids
(d) corrosion

 Dissolved gas
 Silica contents

Hardness of water
Hardness of water is originally defined as the soap
consuming capacity of a water sample. The soap consuming
capacity of water is mainly due to the certain salt of calcium,
magnesium and other heavy metals dissolved in it.

The soap generally consists of sodium salts of fatty acids

such as Oleic acid, Palmitic acid and stearic acid. Calcium
and magnesium react with the sodium salts of long chain
fatty acid present in the soap to form insoluble scums of
calcium and magnesium soaps.

4
 Hardness of water
2 C17H35COONa + CaCl2 (C17H35COO)2Ca + NaCl
(Sodium stearate) (Insoluble)

2 C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

(Sodium stearate) (Insoluble)

Other metal ions such as Fe2+, Mn2+, Al3+ also contributing

to hardness, but they are present in water only in traces
CH3(CH2)7CH=CH(CH2)7COOH Oleic acid
CH3(CH2)14CO2H. Palmitic acid
CH3(CH2)16CO2H stearic acid
9

Temporary hardness (carbonate hardness)

Temporary hardness is caused by the presences of dissolved
bicarbonate of calcium and magnesium and other heavy metal ions
Temporary hardness is mostly destroyed by boiling of water. During
boiling bicarbonate are decomposed in the insoluble carbonate and
hydroxide, which are deposited at the bottom of the vessel.
Heat
Ca(HCO3)2 CaCO3 + CO2 + H2O
(Insoluble)

Heat
Mg(HCO3)2 MgCO3 + 2 CO2
(Insoluble)

Permanent hardness (non-carbonate hardness)

This is due the presences of chlorides and sulphates of calcium,
magnesium, iron and other heavy metal ions.

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5
 Hardness is expressed in terms of equivalent of calcium
carbonate because it is the most insoluble salt that can be
precipitated in water treatment.

Equivalent Mass of hardness producing substances x 50

of CaCO3 =
Chemical equivalent of hardness producing substances

or
Equivalent Mass of hardness producing substances x 100
of CaCO3 = Molar mass of hardness producing substances

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Dissolved Molar Chemical Multiplication factor for

salt Mass equivalent converting into
equivalent of CaCO3
Ca(HCO3)2 162 81 100/162
Mg(HCO3)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
MgCO3 84 42 100/84

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6
 Units of Hardness:

ppm
mg/l
Degree Clarke (oCl)
Degree French (oFr)
A Clark degree (°Clark) or English degrees (°e or e) is defined as
one grain (64.8 mg) of CaCO3 per Imperial gallon (4.55 litres) of
water, equivalent to 14.254 ppm.

A French degree (°fH or °f) is defined as 10 mg/L CaCO3,

equivalent to 10 ppm.

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A water sample contains 200 mg of CaSO4 per

liter. Calculate the hardness in terms of CaCO3
equivalent in mg/L, ppm, oCl and oFr.

Molecular weight of CaSO4 is 136.

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7
 Mol. Wt. of CaCO3
Weight of CaSO4 in mg/L X
Mol. Wt. of CaSO4

200x 100/136 = 147.06 mg/L or ppm

1mg/L= 0.1 oFr
1mg/L= 0.07oCl
10.29 oCl
14.71 oFr

15

(i) How many grams of MgCl2 dissolved in 1

liter water will give hardness of 76 ppm?

(ii) A water sample (500 ML) has hardness

equivalent for 50 mL of 0.1 N CaSO4.
What is the hardness in ppm?

Dissolved salt Molar Mass Chemical

equivalent
CaSO4 136 68
MgCl2 95 47.5

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8
(a) Let x mg/ L MgCl2 dissolved in water
gives 76 ppm hardness.

x X 100/95 = 76
x= 72.2

Ans: 0.0722 g

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(i) A water sample (500 ML) has hardness

equivalent for 50 mL of 0.1 N CaSO4.
What is the hardness in ppm?

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9
 Calculate the temporary hardness and permanent
hardness of a sample of water containing: Mg(HCO3)2 =
7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L;
CaSO4 = 13.6 mg/L

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120;
MgCl2 = 95; Al2(SO4)3 = 114; Ca(NO3)2=164

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Three samples A, B and C were analyzed for their salts contents:

Sample A was found to contain 168 mg of magnesium carbonate per L
Sample B was found to contain 820 mg of calcium nitrate per L
Sample C was found to contain 2 g calcium carbonate per 500 ml

Determine the hardness in all above three sample in ppm

Molecular weights:
Ca(NO3)2 = 164; MgCO3=84; CaCO3= 100

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10
Estimation of hardness: Hardness are usually determined by two methods

Soap solution methods:-

soaps gives lather with hard water only after sufficient quantity of soaps is
added to precipitate all the hardness causing metal ions present in water

2 C17H35COONa + CaCl2 or MgCl2 (C17H35COO)2Ca or Mg + NaCl

(Sodium stearate) (Insoluble)

2 C17H35COONa + MgSO4 or CaSO4 (C17H35COO)2Mg or Ca + Na2SO4

(Sodium stearate) (Insoluble)

After precipitation of all the hardness causing ions present in water, further addition
of soap gives lather

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The solutions required are:

1.A standard solution of CaCl2 prepared by dissolving 0.2 gm of pure CaCO3 in a small
quantity of dilute hydrochloric acid. The solution is then evaporated, to dryness to remove
excess acid. The residue is thereafter dis-solved in one liter of distilled water.

2. Standard soap solution: 100 gms of pure dry soap is dissolved in one liter of 80 per
cent alcohol. This solution is diluted with such quantity of 80 per cent alcohol that 6.4 ml when
added to 20 ml of standard CaCl2 solution produces a pertinent lather.

Procedure:
 50 ml of water under test is taken in a stoppered bottle and to it is added standard
soap solution by burette 0.2 ml at a time.
 The mixture is shaken vigorously after each addition until lather formation starts.
 Then the addition of soap. solution is made at the rate of 0.1 ml at a time till a
lather is obtained which persists for 5 minutes when the bottle is kept aside.
 The total soap solution added is read from the burette. The hardness as CaCO3 is
then found out from a standard table.

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11
 Procedure:

For the determination of permanent hardness the water is boiled and then
treated with a measured excess of standard Na2CO3 solution, and the filtrate
treated with a standard acid using Methyl Orange as indicator, and the
volume of Na2CO3. originally added, minus that left over, is the volume
actually consumed in the precipitation of alkaline earth salts, and its CaCO3
equivalent gives the permanent hardness:

CaSO4 + Na2CO3 = CaCO3 + Na2SO4

MgCl2 + Na2CO3 = MgCO3+2NaCl
i.e., 1 ml of 0.1N. Na2CO3 = 0.005 gm CaCO3

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EDTA Method:- NaOOCH2C CH2COONa

N CH2 CH2 N
HOOCH2C CH2COOH

Hard water
+
EBT Indicator
+
10 pH buffer solution

H Ca/M g
H
OO O
O
O O
NaO3S N N
NaO3S N N
NaO 3 S N N

O2N
O2N

O 2N

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12
 WATER SOFTENING
removal of hardness
◦ Hardness is?...

Primarily due to Ca, Mg, as well as Fe, Mn, Sn, Al

How is Softening done?...

Precipitation of Ca and Mg, or

Ion exchange of Ca / Mg with ion such as Na

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Hardness in 300-500 mg/L as CaCO3 range considered excessive

Even > 150 mg/L may result in consumer objection

60-120 mg/L as CaCO3 is considered a moderate amount

high soap consumption

scaling in heating vessels and pipes

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13
 Lime-Soda process
In this process, all the soluble hardness-causing impurities are converted
into insoluble precipitates which may removed by setting and filtration .
In the lime soda process, calculated amount of lime Ca(OH)2 and soda
Na2CO3 is added in the hard water. The soluble calcium and magnesium
salts in water are converted into insoluble compound such as calcium
carbonate and magnesium hydroxide which may removed by setting and
filtration.
(i) Lime removes the temporary hardness:
Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H 2O

Mg(HCO3)2 + 2 Ca(OH)2 Mg(OH)2 + CaCO3 + H 2O

(ii) Lime removes the permanent magnesium hardness:

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2

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

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(iii) Lime removes the dissolved iron and aluminum salts:

FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4

Al2(SO4)3 + 3 Ca(OH)2 2 Al(OH)3 + 3 CaSO4

(iv) Lime removes free mineral acids:
CaCl2 + H2O
2 HCl + Ca(OH)2

H2SO4 + 3 Ca(OH)2 CaSO4 + H2O

(v) Lime removes dissolved CO2 and H2S:

CO2 + Ca(OH)2 CaCO3 + H2O

H2S + 3 Ca(OH)2 CaS + 2 H2O

(vi) Soda removes all calcium permanent hardness:

CaCl2 + Na2CO3 CaCO3 + NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

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14
Now the 100 parts by mass of CaCO3 are equivalent to : (i) 74 part
of Ca(OH)2 and (ii) 106 parts of Na2CO3

Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)

=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or

=
100 H2SO4) - HCO3-]

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Calculate the amount of lime required for softening 50,000 litre of

hard water containing CaCO3=25 ppm; MgCO3=144 ppm;
CaCl2=111ppm MgCl2=95 ppm; Na2SO4= 15 ppm; Fe2O3 = 25 ppm.

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95;
MgCO3 = 84; CaCl2 = 111
Lime required for softening:

74
= [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
100 + CO + H+ (HCl or H SO ) + HCO -]
2 2 4 3

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or

=
100 H2SO4) - HCO3-]
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15
Calculate the amount of lime and soda required for softening 50,000 litre
of hard water containing Ca(HCO3)2= 8.1 mg; Mg(HCO3)2 = 7.5 mg;
CaSO4 = 13.6 mg; MgSO4 = 12.0 mg; MgCl2 = 2.0 mg; NaCl = 4.7 mg.
Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95

Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or
=
100 H2SO4) - HCO3-]
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Explain with chemical equation and calculate the amount of lime

And soda needed for softening 1,00,000 litrs of water containing
Following:
HCL = 7.3 mg/L; Al2(SO4)3 = 34.2 mg/L; MgCl2 = 9.5 mg/L;
NaCl = 29.25 mg/L
Purity of lime is 90% and that of the soda is 98%.
Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95;
Al2(SO4)3 = 114

Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]
Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or

=
100 H2SO4) - HCO3-]

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16
 A water sample on analysis gave the following data:
Ca2+ = 30 mg/L; Mg2+ = 24 mg/L; CO2 = 24mg/L; K+ = 10 mg/L
Calculate the quantities of lime (90%) and soda (94%) required
to soften one million litres of water sample.
Lime required for softening:
74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or
=
100 H2SO4) - HCO3-]

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A water sample have the following impurities : Ca2+ = 20ppm;

Mg2+ = 18 ppm; HCO3- = 183 ppm; SO42- = 24 ppm. Calculate
the amount of lime and soda needed for softening.

Lime required for softening:

74 [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
=
100 + CO2 + H+ (HCl or H2SO4) + HCO3-]

Soda required for softening:

106 [ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or
=
100 H2SO4) - HCO3-]

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Cold lime soda process:
Calculated quantity of lime and soda are mixed with water at
room temperature the precipitates formed are finely divided, so
they do not settle down easily. Therefore, It is essential to add
small amounts of coagulants (like alum, aluminum sulphate,
sodium aluminates etc).

Use of sodium aluminate as coagulant also helps the removal of silica

as well as oil if present in water..

NaAlO2 + 2H2O NaOH + Al(OH)3

Al2(SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

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Continuous cold lime soda softener

Chemicals
Hard water
(soda+lime
feed
+coagulant)
feed
Softened
water
Wood fiber
filter

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2

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18
 Hot lime soda process:
Calculated quantity of lime and soda are mixed with
water at 800C.

Advantages of high temperature:

 The reaction proceeds faster.

 Softening capacity is increased.
 No coagulant needed as the precipitate and sludge formed settle
down rapidly.
 Much of the dissolved gases are driven out of water.
 Viscosity of soften water is lower, so filtration of water becomes
easier.
 This process produces water of comparatively low residual
hardness 15 to 30 ppm.

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Continuous Hot Lime Soda Process

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19
 Advantages of lime soda process:

 It is very economical.

 If the process is combined with sedimentation/coagulation

lesser amounts of coagulants shall be needed.

 The process increases the pH of the treated .

 In addition to the removal of hardness, the quantities of minerals

in the water are reduced.

 Due to alkaline nature of treated water amount of pathogenic

bacteria in water is considerably reduced.

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Disadvantages of lime soda process:

 For efficient and economical softening, careful operation and

skilled supervision is required.

 Disposal of large amount of sludge poses a problem.

 This can remove hardness up to 15 ppm which is not good for

boilers.

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 WATER SOFTENING
Ion exchange or deionization or demineralization
process: Ion-exchange resins are widely used in different separation,
purification, and decontamination processes. The most common examples are
water softening and water purification.
Ion-exchange resins are insoluble, cross linked, long chain organic
polymer with micro porous structure and the functional groups
attached to the chains are responsible for the ion exchange
properties.

Cation Resin after

exchange Resin treatment

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Resins containing acidic functional groups (-COOH, -SO3H) are

capable of exchanging their H+ ions with other cations which comes in
their contacts, known as a cation exchange resins (RH+).
e.g. styrene-divinyl benzene copolymer, which on sulphonation and
carboxylation, become capable to exchange their hydrogen ions with
the cations (Metal ions) in the water.

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21
 Resins containing basic functional groups (-NR3+OH-) are capable of
exchanging their anions with other anions which comes in their
contacts, known as an Anion exchange resins (ROH-).

They are styrene divinyl benzene or amine-formaldehyde

copolymerization which contains quaternary ammonium or quaternary
phosphonium or tertiary sulphonium groups as an integral part of the
resin matrix. These after treated with dil NaOH becomes capable of
exchanging their OH- ions with anions of water.

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Process:- The hard water is passed first through cation exchange

column, which remove all the cations from it and equivalent amount of
hydrogen ions are released from this column to water:

2RH+ + Ca2+ R2Ca2+ + 2H+

2RH+ + Mg2+ R2Mg2+ + 2H+

After cation exchange column the hard water is passed through anion
exchange resin column, which remove all the anions from it and
equivalent amount of hydroxide ions are released from this column to
water :
ROH- + Cl- RCl- + OH-
2ROH- + SO42- R2SO42- + 2OH-

H + + OH- H2O
Thus water coming out from the exchange is free from cations as well as
anions.
Ion free water is known as deionized or demineralised water.
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 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Wastages to
Acid solution for sink Alkaline solution for
regeneration of regeneration of resin
Wastages to
resin sink
pump

Soft water 45

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23
 Regeneration:
Cation exchange column is regenerated by passing a solution of dil
HCl or dil H2SO4. The regeneration can be represented as

R2Ca2+ + 2H+ 2RH + Ca2+

Exhausted anion exchange column is regenerated by passing a

solution of dil. NaOH. The regeneration can be represented as

R2SO42- + 2OH- 2ROH + SO42-

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Advantages:

Can be used to soften highly acidic or alkaline waters.

It produces water of very low hardness.

Disadvantages:
The equipment is costly

Expensive chemicals are needed

Output of the process is reduced if water contains turbidity.(turbidity

must be below10 ppm)

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 Zeolite (Permutit) method of Softening of
water
Zeolite is a Hydrated Sodium Alumino
Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.

The general chemical structure of zeolite

is given below Na2O.Al2O3.xSiO2.yH2O (x
= 2-10 and y = 2-6)

Micro pores of Zeolite Porous Structure of zeolite

 Porosity or cavity size of synthetic zeolite structures can be
controlled by varying the Si/Al ratio
 Ion-exchange process of zeolite structure is associated with sodium ions

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Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

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25
 Process of softening by Zeolite method
For the purification of water by the zeolite softener, hard water is passed through
the zeolite bed at a specified rate. The hardness causing ions such as Ca2+, Mg2+
are retained by the zeolite bed as CaZe and MgZe respectively; while the
outgoing water contains sodium salts. The following reactions takes place during
softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
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Limitations of Zeolite process

1. If the water is turbid: then the turbidity causing particles clogs the
pores of the Zeolite and making it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which
can not be regenerated that easily as both metal ions bind strongly
and irreversibly to the zeolite structure.
3. Any acid present in water (acidic water) should be neutralized with
soda before admitting the water to the plant.

Advantages of Zeolite process

1. Soft water of 10-15 ppm can be produced by this method
2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation
in the treated water
4. It does not require more time and more skill

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 Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions
like HCO3- and CO32- in the softened water (then it may form
NaHCO3 and Na2CO3 which releases CO2 when the water is boiled
and causes corrosion)
3. It also causes caustic embrittlement when sodium carbonate
hydrolyses to give NaOH

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Internal treatment:

In this process, an ion is prohibited to exhibit its original

character by complexing or converted into other more
soluble salt by adding appropriate reagent.

An internal treatment is accomplished by adding a proper

chemical to water either:
(a) To precipitate the scale forming impurities in the form of
sludge, which can be removed.
(b) To convert them into compounds, which will stay in
dissolved form in water and thus do not cause any harm.
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 Important Internal Treatments are:

Phosphate conditioning:
Scale formation can be avoided by adding sodium phosphate which
reacts with hardness of water forming non-adherent and easily
removable soft sludge of calcium and magnesium phosphate.

3CaCl2 + 2Na3PO4 Ca3 (PO4)2 + 6NaCl

The choice of salt depends upon the alkalinity of the boiled water
because calcium cannot be precipitated below a pH 9.5.
 Trisodium phosphate is most suitable for treatment when
alkalinity is low
 Disodium phosphate is used when the water alkalinity is
sufficient.
 Monosodium phosphate is used when the alkalinity of boiler
water is too high.
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Calgon conditioning:

It involves adding calgon (Sodium hexa-meta phosphate (NaPO3)6 to

boiler water. It prevents the scale and sludge formation by forming
soluble complex compound with CaSO4.

[Na6(PO3)6] 2Na+ + [Na4P6O18]2-

2CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

soluble complex ion

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 Scales and Sludges Formation In Boilers:
In boilers, water evaporates continuously and the concentrations of
the dissolved salts increases progressively. when concentrations of
dissolved salts reach saturation point, they form precipitates in form
of loose and slimy, it is called sludge. On the other hand, if the
precipitate matter form a hard adhering crust/coating on the inner
walls of the boiler, it is called scale.

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Scales are hard deposit, which stick very firmly to the inner surface
of boiler. Scales are very difficult to remove.
Formation of scales may be due to

(1) Decomposition of calcium bicarbonate: (In low-pressure boilers)

Ca(HCO3)2 → CaCO3 + H2O + CO2
Scale composed mainly from calcium carbonate is soft and is the
main cause of scale formation in low pressure boiler. But in the high
pressure boiler, calcium carbonate is soluble.
(In high-pressure boilers)
CaCO3 + H2O → Ca(OH) 2 (soluble) + CO2
(2) Deposition of Calcium Sulphate:
Solubility of calcium sulphate in water decrease with rise of
temperature. Hence CaSO4 gets precipitated as hard scale on the
heated portions of the boiler.

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 (3) Hydrolysis of magnesium salts:
Dissolved Mg salts undergo hydrolysis forming magnesium hydroxide
precipitate, which forms a soft type of scale

MgCl2 +2H2O → Mg(OH)2 + 2HCl

(Scale)

(4) Presence of silica:

SiO2 even present in small quantities, deposits as calcium silicate

(CaSiO3) and /or magnesium silicate (MgSiO3). These deposits stick
on the inner side of the boiler surface and are very difficult to remove.

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Disadvantages of scale formation

Wastage of fuel: Scales have a low thermal conductivity, so that
rate of heat transfer from boiler to inside water is greatly
decreased
Lowering of boiler safety: Due to scale formation, over heating
of boiler is done, which causes distortion of boiler tube.
Decrease in efficiency: Scales may deposit in the valve and
condensers of the boiler and choke them partially.
Danger of explosion: When thick scales crack, the water comes
suddenly in contact with over heated iron plates.
Removal of scales
 With the help of scraper or piece of wood or wire brush.
 By giving thermal shocks, if they are brittle.
 By dissolving them by adding chemicals, (5-10% HCl, EDTA) if
they are adherent and hard.
 By frequent blow-down operation, if the scales are loosely adhering.
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Prevention of scales formation
(1) External Treatment: Includes efficient ‘softening of water’
(i.e., removing hardness-producing constituents of water)
(2) Internal Treatment: Accomplished by adding a proper
chemical to the boiler water either:
Important internal conditioning/treatment methods:
(i) Colloidal conditioning: Scale formation can be avoided by adding
organic substances like kerosene, tannin, agar-agar (a gel) etc., which
get coated on over the scale forming precipitate, thereby, yielding
non-sticky and loose deposits.
(ii) Phosphate Conditioning:
(iii) Carbonate Conditioning: In low pressure boilers, scale-formation
can be avoided by adding sodium carbonate to boiler water.
CaSO4 +Na2CO3 → CaCO3 + Na2SO4
(iv) Calgon (calcium gone) Conditioning:. sodium hexametaphosphate
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(v) Treatment with sodium aluminate (NaAlO2): sodium aluminate

gets hydrolyzed yielding NaOH and a gelatinous of aluminum hydroxide
NaAlO2 + 2H2O → NaOH + Al(OH)3
Sod.meta-aluminate (Gelatinous ppt.)
Theses sodium hydroxide precipitates some magenisium
MgCl2 + 2NaOH → Mg(OH) 2 + 2NaCl
The flocculent precipitate of Mg(OH)2 and Al(OH)3 produced inside the
boiler, entraps finely suspended and colloidal impurities, including oil
drops and silica.
(vi) Electrical conditioning: Sealed glass bulbs, containing Hg
connected to a battery, are set rotating in the boiler. when water boils,
mercury bulbs emit electrical discharges which prevents scale forming
particles to adhere/stick together to form scale.
(vii) Radioactive conditioning: Tablets (radioactive salts) are placed
inside the boiler water. Energy radiations emitted by these salts prevent
scale formation
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 Example – 1:
A water sample contains following dissolved salt
Ca(HCO3)2 = 8.1mg/lit. ; Mg(HCO3)2 = 29.2mg/lit
CaCl2 = 11.1mg/ lit.; MgSO4 = 6.0mg/ lit.
Find out temporary hardness, permanent hardness & total
hardness.
Hardness of soluble salt equivalent to CaCO3
= W x 100
Mol. Wt.of soluble salt

Hardness due to Ca(HCO3)2 = 8.1 x 100 = 5mg/lit

162
Hardness due to Mg(HCO3)2 = 29.2 x 100 = 20mg/lit
146

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Hardness due to CaCl2 = 11.1 x 100 =10mg/lit.

111
Hardness due to MgSO4 = 6.0 x 100 =5mg/lit
120
Temporary Hardness = Hardness due to Ca(HCO3)2 + Hardness due to Mg(HCO3)2
= 5 + 20 = 25 mg / lit.

Permanent Hardness = Hardness due to CaCl2 + Hardness due to MgSO4

= 10 + 5, = 15 mg / lit.

Total hardness = Temporary hardness + Permanent hardness

= 25 + 15, = 40 mg / lit.

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 Practice Question

Calculate the temporary hardness and permanent

hardness of a sample of water containing: Mg(HCO3)2 =
7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L;
CaSO4 = 13.6 mg/L

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120;
MgCl2 = 95; Al2(SO4)3 = 114; Ca(NO3)2=164

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Practice Question

Three samples A, B and C were analyzed for their salts contents:

Sample A was found to contain 168 mg of magnesium carbonate per L
Sample B was found to contain 820 mg of calcium nitrate per L
Sample C was found to contain 2 g calcium carbonate per 500 ml

Determine the hardness in all above three sample in ppm

Molecular weights:
Ca(NO3)2 = 164; MgCO3=84; CaCO3= 100

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 NaOOCH2C CH2COONa

Various steps involved in this method N CH2 CH2 N

HOOCH2C CH2COOH

1. Standardization of EDTA solution:

Rinse and fill the burette with EDTA solution. Pipette out V1 ml of standard hard
water (M1) in a conical flask. Add 4-5 ml of buffer solution and 2 drops of EBT
indicator. Titrate with EDTA solution till wine-red colour changes to clear blue.
Let volume used by ‘V2’ ml.

M1.V1 = M2.V2 » M2 = (M1.V1)/V2

Where, M1 = Molarity of Standard Hard water,

V1 = Volume of Standard Hard water,
M2 = Molarity of EDTA,
V2 = Volume of EDTA

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2. Determination of Total Hardness:

Rinse and fill the burette with EDTA solution. Pipette out sample water (V3) in a
conical flask. Add 4-5 ml of buffer solution and 2 drops indicator. Titrate with
EDTA solution till wine-red colour changes to clear blue. Let volume used by ‘V4’
ml.
M3.V3 = M4.V4 » M3 = (M2.V4)/V3

Where, M3 = Molarity of Sample Hard water,

V3 = Volume of Sample Hard water,
M4 = Molarity of EDTA = M2,
V4 = Volume of EDTA

Total Hardness = M3 × Molecular weight of CaCO3 (100) × One Litre (1000ml)

= M3 × 105 ppm

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 3. Determination of Permanent Hardness:

Take 100 ml of sample water in 250 ml beaker. Boil it to remove temporary hardness to
about half of its volume and cool to room temperature, filter through filter paper to remove
insoluble salts.

Make up the volume to the original 100ml by adding distilled water. Now Pipette out this
solution (V3 ml) in a conical flask. Add 4-5 ml of buffer solution and 2 drops indicator.
Titrate with EDTA solution till wine-red colour changes to clear blue. Let volume used by
‘V4’ ml.

M3.V3 = M4.V4 » M3 = (M2.V4)/V3

Where, M3 = Molarity of Permanent Hard water,

V3 = Volume of Permanent Hard water,
M4 = Molarity of EDTA = M2,
V4 = Volume of EDTA

Permanent Hardness = M3 × Molecular weight of CaCO3 (100) × One Litre (1000ml)

= M3 × 105 ppm

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4. Determination of Temporary Hardness:

Temporary Hardness = Total Hardness - Permanent Hardness

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 Problem:

50 ml of standard hard water containing 1 gram of pure CaCO3 per

liter consumed 20 ml of EDTA. 50 ml of hard water consumed 25
ml of same EDTA solution and EBT indicator. Calculate the total
hardness of water sample in ppm.

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 Problem:

0.28 grams of CaCO3 were dissolved in HCl and the solution was
made up to one litre with distilled water. 100 ml of the above solution
required 28 ml of EDTA solution on titration. 100 ml of hard water
sample consumed 33 ml of same EDTA solution EBT indicator. 100
ml of this water after boiling cooling and filtering required 10 ml of
EDTA solution in titration. Calculate the permanent and temporary
hardness of water sample in ppm.

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 Problem: Calculate the amount of lime (84% pure) required for treatment of 20000 litres of
water whose analysis is as follows:

Ca(HCO3)2 40.5 ppm CaSO4 34.0 ppm

Mg (HCO3)2 36.5 ppm CaCl2 27.75 ppm
MgSO4 30.0 ppm NaCl 10.0 ppm

Also calculate the temporary and permanent hardness of the water sample.

Solution: Salt CaCO3 equivalent

Ca(HCO3)2 40.5 x (100/162) = 25 ppm
Mg (HCO3)2 36.5 x (100/146) = 25 ppm
MgSO4 30.0 x (100/120) = 25ppm
CaSO4 34.0 x (100/136) = 25 ppm
CaCl2 27.75 x (100/111) = 25 ppm
NaCl Ignored as it does not contribute to hardness

Temporary hardness = 25 + 25 = 50 ppm

Permanent hardness = 25 + 25 + 25 = 75 ppm

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Lime required for softening:

74
= [ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+)
100 + CO + H+ (HCl or H SO ) + HCO -]
2 2 4 3

74 100
= [ 25 + 2×25 + 25] x X 20000
100 84

= 1761.90 x 103 mg = 1.76 Kg

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 Problem: Calculate the amount of lime required for softening
50,000 litre of hard water containing CaCO3=25ppm;
MgCO3=144ppm; CaCl2=111ppm; MgCl2=95 ppm; Na2SO4= 15
ppm; Fe2O3 = 25 ppm.

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ;
MgCl2 = 95; MgCO3 = 84; CaCl2 = 111

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Problem: Calculate the amount of lime and soda required for

softening 50,000 litre of hard water containing Ca(HCO3)2= 8.1
mg; Mg(HCO3)2 = 7.5 mg; CaSO4 = 13.6 mg; MgSO4 = 12.0
mg; MgCl2 = 2.0 mg; NaCl = 4.7 mg.

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ;
MgCl2 = 95

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 Problem: Explain with chemical equation and calculate the amount
of lime and soda needed for softening 1,00,000 litrs of water
containing Following:
HCL = 7.3 mg/L; Al2(SO4)3 = 34.2 mg/L; MgCl2 = 9.5 mg/L;
NaCl = 29.25 mg/L
Purity of lime is 90% and that of the soda is 98%.

Molecular weights:
Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ;
MgCl2 = 95; Al2(SO4)3 = 114

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Problem: A water sample on analysis gave the following data:

Ca2+ = 30 mg/L; Mg2+ = 24 mg/L; CO2 = 24mg/L; K+ = 10 mg/L
Calculate the quantities of lime (90%) and soda (94%) required
to soften one million litres of water sample.

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 Problem: A water sample have the following impurities:
Ca2+ = 20ppm; Mg2+ = 18 ppm; HCO3- = 183 ppm; SO42- = 24 ppm.
Calculate the amount of lime and soda needed for softening.

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