B.

TECH FIRST YEAR

ACADEMIC YEAR: 2024-2025

Course name: Engineering Chemistry

Course code : CHY 1001

Module no : 2
Credits : 4
Mode of delivery : Hybrid (Power point presentation)
Faculty : Dr. Veena Dhayal
Email-id : [Link]@[Link]
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.

2
 Domestic

80
70%
70
% of total water used

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

3
 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
Rainwater: It is probably the purest form of natural water
Sea Water: It is probably the most impure form of natural water
4
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
5
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

6
 Hard Water
What’s hard water?

Practically speaking, measurement of:

•Calcium (Ca) ions
•Magnesium (Mg) ions

Hardness as calcium carbonate

mg/L (ppm)

Soft 0-17
Moderately hard (Medium) 60-120
Hard 120-180
Very hard 180 & over

7
7
 Why be concerned about Hard Water?
scalepi

Originally, water hardness was defined as the measure of

the capacity of the water to precipitate soap
Hard water does cause soap scum, clogs pipes and clogs
boilers as lime scale

8
8
•
Hardness of Water
Hardness in Water is characteristic that prevents the ‘lathering
of soap’ thus water which does not produce lather with soap
solution readily, but forms a white precipitate is called hard
water.

2 C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl

Sodium stearate Calcium stearate
(Sodiun soap) (insoluble)

2 C17H35COONa + MgCl2 (C17H35COO)2Mg + 2 NaCl

Sodium stearate magnesium stearate
(Sodiun soap) (insoluble)

• Type of Hardness

– Temporary or Carbonate Hardness

– Permanent Hardness or non-carbonate Hardness. 9
9
Temporary Hardness
Temporary Hardness is caused by the presence of dissolved bicarbonate of
calcium, magnesium and other heavy metals.
It is mostly destroyed by more boiling of water, when bicarbonates are
decomposed yielding insoluble carbonates or hydroxides.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Calcium bicarbonate Calcium Carbonate

Mg(HCO3)2 Heat Mg(OH)2 + 2CO2

Magnesium Bicarbonate Magnesium hydroxide

Calcium/Magnesium Carbonates or hydroxides thus formed being almost

insoluble, are deposited as a scale at the bottom of vessel, while carbon
dioxide escapes out.

Permanent Hardness

Non Carbonate Hardness is due to the presence of chlorides, sulfates of

calcium, Magnesium, iron and other heavy metals
10
10
 Units of Hardness

• Parts per million (ppm)

1ppm=1 part of CaCO3 equivalence hardness causing substance present in 106 parts
of water

• Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 equivalence hardness causing substance present in one liter
of water

1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm
• Clarke's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water

• Degree French (oFr)

1o Fr = 1 part of CaCO3 eq per 105 parts of water
Miliequivalent per litre (meq/L)
1 meq/L = 1 meq of CaCO3 per L of water
= 10-3 x 50 g of CaCO3 eq per litre 11
11 of CaCO eq = 50 ppm
= 50 mg of CaCO3 eq per litre = 50 mg/L 3
 Hardness is expressed in terms of equivalent of calcium
carbonate because it is the most insoluble salt that can be
precipitated in water treatment.

Mass of hardness producing substances x 50

Equivalent of CaCO3 =
Chemical equivalent of hardness producing substances

Hardness of soluble salt equivalent to CaCO3 = W x 100

Mol. [Link] soluble

12
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

13
 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.

14
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.

15
 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

16
Estimation of hardness:

Hardness are usually determined by two methods

• EDTA Method
• Soap solution methods (Clarks Method)

17
 Determination of hardness By:
Complexometric Method / EDTA Method

Principle: The determination of hardness is carried out by titrating water

sample with Sodium salt of Ethylene Diamine Tetra Acetic Acid (EDTA)
using Eriochrome Black-T as an indicator and keeping the pH of the water
at 9.0 - 10.0. The end point is the change in colour from wine - red to blue,
when the EDTA solution complexes the calcium and magnesium salt
completely.

18
EDTA Method:- NaOOCH2C CH2COONa

N CH2 CH2 N
HOOCH2C CH2COOH

Hard water
+
EBT Indicator
+
10 pH buffer solution

H Ca/Mg
H
OO O
O
O O
NaO3S N N
NaO3S N N
NaO3S N N

O2N
O2N

O2N
19
Various steps involved in this method

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

20
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

21
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

22
4. Determination of Temporary Hardness:

Temporary Hardness = Total Hardness - Permanent Hardness

23
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.

24
25
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.

26
27
 WATER SOFTENING
Removal of hardness
» Hardness is?...
primarily Ca, Mg, plus Fe, Mn, St, Al

How is Softening done?...

Precipitation of Ca and Mg, or

Ion exchange of Ca / Mg with ion such as Na

28
 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 H2O

Mg(HCO3)2 + 2 Ca(OH)2 Mg(OH)2 + CaCO3 + H2O

(ii) Lime removes the permanent magnesium hardness:

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

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

30
(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

31
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) –NaAlO2 + HCO3-

Soda required for softening:

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

=
100 H2SO4) - HCO3-]

32
33
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

34
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 X 20000
= [ 25 + 2×25 + 25] x
100 84

= 1761.90 x 103 mg = 1.76 Kg

35
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

36
 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
37
37
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.
38
Continuous Hot Lime Soda Process

39
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 water.

➢ 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.

40
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.

41
Calculation of lime and soda required for the softening of hard water by the lime
soda process

Hardness producing Chemical reaction with lime and soda Need

substance

Permanent Hardness
Ca Salts CaCl2 + Na2CO3 CaCO3 + 2NaCl S

Mg salts MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L+S

CaSO4 + Na2CO3 CaCO3 +Na2SO4

Temp. Hardness
Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O L
Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O 2L

Acids
HCl 2H+ + Ca(OH)2 Ca2+ + 2H2O L+S
H2SO4 Ca2+ + Na2CO3 CaCO3 + 2Na+

HCO3- HCO3- + Ca(OH)2 CaCO3 + H2O + CO32- L-S

Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+

FeSO4 Ca2+ + Na2CO3 CaCO3 + 2Na+ L+S

NaAlO2 NaAlO2 + H2O Al(OH)3 + NaOH

- L/2
[2NaOH = Ca(OH)2]
42
Rules
1. If Ca(HCO3)2 and Mg(HCO3)2 are considered as ions (Ca2+ + 2HCO3-) and (Mg2+ + 2HCO3-)
respectively then the calculation result will be the same based on the ability of the ions to take up
bicarbonate ions
2. If treated water found to contain excess of OH- and CO32- ions these are formed from excess
equivalent each of Ca(OH)2 and Na2CO3 and hence these excess amounts should be added to the
calculation (in temp. hardness and perm. hardness)
3. When the impurities are given as CaCO3 and MgCO3 present in water it should be considered as
due to bicarbonates of calcium and magnesium respectively
4. Substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc do not contribute to hardness and therefore,
they do not consume any soda or lime and hence if these present need not be taken in to
consideration during calculation.
5. Soda (Na2CO3) neutralizes only permanent hardness

Molecular weight of lime = 74

Molecular weight of soda = 106
Molecular weight of CaCO3 = 100

Therefore, 100 parts by mass of CaCO3 are equivalent to

(i) 74 parts by mass of Ca(OH)2
(ii) 106 parts by mass of Na2CO3
43
Therefore, Lime requirement for softenening

= 74 T.H of Ca2++ 2 x T.H of Mg2+ + P.H of (Mg2+ + Fe2+ + Al3+) + CO2 + H+ +

100 HCO3- - NaAlO2/2
X Vol .of water (L)

T.H = temporary hardness

P.H = Permanent Hardness

llIly, Soda requirement for softenening

= 106 P.H of (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ - HCO3- X Vol .of water (L)
100

Problem 1
Calculate the amount of lime required for softening 5,000 litres of hard water containing
72 ppm of MgSO4 (mol wt = 120)

44
Solution
Step 1 List out the given data
Given data : Hardness 72 ppm due to MgSO4; water qty = 5000 litres; mol. wt. MgSO4 = 120

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
MgSO4 72 100/120 72 X (100/120) = 60

Step 3 calculation of lime requirement

Lime required = 74/100 (hardness due to MgSO4) x vol. of water

= 74/100 (60 mg/L) x 5000 L

= 222,000 mg
= 222 g

45
Problem 2
Calculate the amount of lime and soda required for softening 50,000 litres of hard water containing:
Mg(HCO3)2 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 = 25ppm and Na2SO4 =
15ppm

Solution

Step 1 List out the given data

Given data : MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 =
25ppm and Na2SO4 = 15ppm

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
Mg(HCO3)2 144 100/84 144 x(100/84) = 171.4
CaCO3 025 100/100 25 x (100/100) = 25.0
MgCl2 095 100/95 95 x (100/95) = 100.0
CaCl2 111 100/111 111 x (100/111) = 100.0
Fe2O3 025 (does not cause hardness)
Na2SO4 015 (does not cause hardness)

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O; Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 ; CaCl2 + Na2CO3 CaCO3 + Na2SO4

46
Step 3 calculation of lime requirement

Lime required = 74/100 ( {2 x MgHCO3} + CaCO3 + MgCl2 in terms of CaCO3 eq) x vol. of water

= 74/100 (2 x 171.4 + 25.0 +100.0) mg/L x 50,000 L

= 74/100 (467.8) mg x 50,000
= 17, 309,000 mg
Answer = 17. 31 kg

Step 4 calculation of soda requirement

soda required = 106/100 ( MgCl2 + CaCl2 in terms of CaCO3 eq) x vol. of water

= 106/100 (100 +100.0) mg/L x 50,000 L

= 106/100 (200) mg x 50,000
= 10, 6,00,000 mg
Answer = 10. 6 kg

47
47
Practice Problems

48
Problem: Calculate the amount of lime required for softening
50,000 litre of hard water containing 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

49
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

50
 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

51
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.

52
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.

53
 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

54
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.

55
Resins containing basic functional groups (-NR3+OH-) are capable of exchanging
their anions with other anions which comes in their contacts, known as a 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.

56
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.

57
 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

58
58 Soft water
59
 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-

60
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)

61
 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 sodium62ions
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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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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
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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

➢ 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:

Its involve in 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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