1 WATER

1.1 INTRODUCTION
Water is the most important substance for the existence of life. It is
the only substance that occurs naturally as a solid (ice), a
liquid and
a gas (water vapor). It covers about 70% of the Earth for a total of
approximately 332.5 million cubic miles. If you're familiar with the
bnes Water, water, everywhere, nor any drop to drink" from the
poem "The Rime of the Ancient Mariner" you'll understand that most
of it- is undrinkable because it's saltwater. Only
of this water -97%
3% of the world's water supply is freshwater, and 77% of that is
frozen. Of the 23% that is not frozen, only a half a percent is
available to supply every plant, animal and person on Earth with all
the water they need to survive.

Water also occupies a distinctive position in industries; used in

hydro power plant for the production of electricity through steam
generation, as coolant in atomic reactors as well as chemical plants.
used in paper industries, textiles, steel and food industries,
It is also
domestic uses such as drinking, bathing, washings, sanitary etc. In
addition to it, water is widely used in irrigation for agricultural

purposes
Pure water (H,0)is colorless, tasteless, and odorless. It is composed
of hydrogen and oxygen. Because water becomes contaminated by the
substances with which, it comes into contact, it is not available for
use in its pure state. To some degree, water can dissolve every
naturally occurring substance on the earth. Because of this property,
water has been termed a "universal solvent." Although beneficial to
 in
1.2 Chemistry Engineerinong

a major threat
mankind, the solvency power of water can pose to
slow
ndustrial equipment. Corrosion reactions cause the dissolutionon

of metals by water. Deposition reactions, which produce scale on

heat transfer surfaces, represent a change in the solvency power ne
water as its temperature is varied. The control of corrosion and scalo
is a major focus of water treatment technology.

1.2 SOURCES OF WATER

The distribution of water over the surface of the earth is not uniform.
Water on the planet is recycled in a process called the hydrologie
or evaporates
cycle. In this cycle, water is used by plants and animals
into the air and then returns to the earth in the form of rain or snow.
There are four basic sources of water:

(1) Surface water: Found on the surface of the earth, either

or still (ponds, lakes etc.)

flowing (rivers and streams)

(2) Ground water : Found underground and generally obtained

from wells and springs.

(3) Rain water

(4) Sea water

1.3 IMPURITIES OF WATER

Water is the universal solvent. In nature, it is never totally pure. No
matter how isolated it is from sources of contamination, it will
always have some chemicals. Gases or minerals in the air, soil
or

rock are dissolved by the water. Some dissolved materials give water
to be
it's characteristic taste- "pure water" is generally considered

flat and tasteless. On the other hand, minerals can cause hardness
and
(calcium or magnesium), color (iron), contamination (arsenic),
(radium, radon) in the water. Humans can cause
radioactivity
contamination through the improper use of pesticides or fertilizers
in
and through the disposal of waste. These impurities can dissolve
the water, causing it to be contaminated. The minerals and impuriues
are normally present in very small concentrations.
as follows
The impurities present in raw waters can be classified
 Water 1.3

(1) Dissolved impurities:

(a) Inorganic salts:

Cations:Ca", Mg",P,As, Ar,Mn',Na',K",Zn*",Cu,Sr" ete.

Anions: HCog. Cl, so, NOg, Co, F etc.

(b) Organie constituents:

Natural impurities from decay of vegetable and animal matter,
leading colouring material and humic and fulvic acids, soaps
to

and detergents, Solvents (benzene, carbon tetrachloride,

aldrin
tetrachlorethane, trichlorethane, chloroform), lindane,
methoxychlor etc.

(c) Gases :
NHg, SO. SOg, NO, NOg, NO, cO, H,S, Cl, etec.
(2) Suspended impurities:
(a) Inorganic impurities:
Natural materials, mostly sand, Clay etc.

(b) Organic impurities:

Plant and animal particles, discharges from food
industrial
processing, papermaking, organic chemical industries, etc..
(c) Colloidal impurities:
Finely divided silica and clay, organic waste products, component
of sewage solids, complex proteins etc.

(3) Living Matter:

(a) Micro-Organism : Fungi, bacteria, algae, viruses etc.

(b) Macro-Organism: Fish, shrimps, worms, larvae, etc.

1.4 HARDNESS OF WATER

Rain water often considered to be the purest form of natural
is

water. But the fact remains that water being a universal solvent; as
it falls, rain water dissolves many gases from the atmosphere and as

it flows on the earth surface dissolves many salts.

The presence of calcium and magnesium salts as bicarbonates,

chlorides and sulphates in water makes the water "hard'. On the
other hand, water free from soluble salts of calcium and magnesium
is called soft water'. Hard water does not produce lather with
soap
solution but forms white insoluble precipitate or scum. Soft water
produces lather with soap solution very easily. (Table No. 1.1)
 1.4 Chemistry in Engineerin

2C7HcOONa + CaCl2 (CH,C00),Ca+ 2NaCI

(Soap) (Scum)
Sodium Stearate Hardness Calcium Stearate
Due to this reaction more soap is required to form lather, hence mora
re
Soap is wasted with hard water during washing.
The soap consuming capacity of water or the measure of the
capacity of water to precipitate soap is known as hardness of
water. Though calcium and magnesium are mainly responsible for
the hardness of water; other metal ions like strontium, iron.
aluminium, zinc and manganese also contribute to its hardness but
Concentration of these ions are very low in natural water.

Hard water is harmful for drinking or potable purposes because it

causes deposition of calcium in the bone, cysts in urinary tracts

system etc. It also damages the boilers by sludge formation, corrosion,
caustic embrittlement. Presence of hardness causing dissolved salts,
boiling point of water is elevated; conssequently lot of fuel is wasted.

Hard water also conveys some benefits to health

by providing
the solubility of
dietary caleium.andMagnesium and reducing
potentially toxic metal ions'such as.lead and copper.
Table 1.1 Difference between Hard water and Soft water
Hard Water Soft Water
Water which does not produce good Water which forms good lather (foam)
lather (foam) with soap is known as with soap is known as soft water.
hard water.

It prevents formation of lather but forms lather very

It easily with soap
produces white curd / scum with soap
solution.

Due to presence .of dissolved salts, Boiling point of this water is 100° C.|
boiling point of water increases.

Cleaning power decreases.

Cleaning power increases.
The consumption of soap is more Washing becomes easy and no SOaP
during washing. is wasted
during washing.
Surface tension decreases. Surface tension increases.

1.4.1 TYPES OF HARDNESS

Hardness water is
caused by a variety of divalent cations, primari
in rily

calcium and magnes1um. These cations have a

tendency to com D
with anions in the water to form stable salts. The type of anionfoun
in these salts distinguishes between the two types of hardness
non-
temporary or carbonate hardness and permanent hardness orno
carbonate hardness. (Table 1.2)
 Water 1.5

1. Temporary or carbonate hardness

It isthe characteristics of water which prevents the lather formation
for the short time and it is caused due to the
presence of bicarbonates
and
carbonates of calcium &
magnesium, called temporary hardness
or carbonate hardness. This type of hardness can be removed
simply
by boiling the water. On boiling, soluble bicarbonates are decomposed
into insoluble carbonates and the insoluble carbonates can
easily be
removed by filtration. This method is not practical for large scale
softening. Temporary hardness can also be removed by the addition
of calculated amount of lime (Clark's method).

Ca(HCO,2 CaCo, + H,0 +C0

soluble insoluble
bicarbonate carbonate

Temporary or Carbonate hardness salts

Calcium Magnesium carbonate (MgCO,)
bicarbonate(Ca(HCO,))
Magnesium bicarbonate (Mg(HCO))Calciumhydroxide (Ca(OH),)
Calcium carbonate (CaCO,) Magnesium hydroxide (Mg(OH),)

From the above table it is clear that, carbonate hardness is caused

by metals combined with a form of alkalinity. Alkalinity is the
capacity of water to neutralize acids and is caused by compounds
such as carbonate, bicarbonate, hydroxide, and sometimes borate,
silicate, and phosphate.

2. Permanent hardness ornon-carbonate hardness

It the characteristics of water which prevents the lather formation
is

permanently and caused due presence of chlorides, sulphates, and

nitrates of calcium, magnesium and other metals called permanent
hardness or non-carbonate hardness. Such hardness can not be
removed simply by boiling the water.

Permanent or Non-carbonate hardness salts

Calcium chloride (CaCl,) Calcium sulfate (CaSO,)

Magnesium chloride (MgCl,) Ma Magnesium sulfate (MgS0,)

Non-carbonate hardness forms when metals combine with anything
other than alkalinity.
1.6 Chemistry in Engineerins

Table 1.2 Difference between Temporary and Permanent Hardness

Temporary Hardness Permanent Hardness

due to presence ae
The hardness due to presence of| The hardness

Mg
lt
bicarbonates
is called

is the
which prevents the
for short time.
and carbonates of Ca and soluble
Temporary Hardness.
characteristics
lather
of
and Mg

water |
|
chlorides
is called
and sulphate of
Permanent Hard.
It is the characteristics
formation|prevents
permanently.
the
ess.

lather
of water which
formation

CalHCOg, Mg(HCO3)2 are responsible CaCl, MgCl2, CaSO4, MgS0, are

salts for temporary hardness. respon-sible salts 1or permanent
hardness.

It is also knownas Carbonate It is also known as Non-Carbonate

Hardness which is the characteristics Hardness which is the characteristics
of water having carbonates and of water not having carbonates and
bicarbonatesof Ca and Mg. bicarbonates of Ca and Mg, but
having
chlorides and sulphatesof Ca and
Mg.
This type of hardness can be removed This type ofhardness can't be removed|
simply by boiling the water. simply by boiling the water.

MHCOs)2
Soluble
McOs+H20+CO MCI,/MSO4 no reaction

where, [M = Ca, Mgl

Insoluble
where, [M
=Ca, Mgl

1.4.2 EXPRESSION FOR HARDNESS

When measuring hardness, we typically total hardnessconsider
which is the sum of all hardness in water, expressed as a
compounds
calcium carbonate equivalent. Total hardness includes both
temporary
and permanent hardness.

Hardness values are usually quoted in terms of equivalent amount

o
CaCO, because
(i) It is the most common cause of scaling.

(ii) The molecular weight of CaC0, is 100 (equivalent

weight
=b0%
which makes mathematical calculations
simpler.

(iii) It is the most insoluble salt, can be

precipitated in wa
treatment processes.

All the compounds or salts causing hardness should be rted

conver
into respective CaCO, equivalent. The CaCO, equivalents for differen
salts are as under
Water
1.7

100 g of CaCO = 162 g of Ca (HCOa), = 146 g of Mg (HCO,)2 = 111 g

of CaCl =95 g of MgCl, = 136 g of CaSO, = 120 g of MgSO,
Now, if x g of
Ca(HCO,2 is present in a water sample, then the
amount of Ca(HCO,)2 present in terms of its
CaCOa equivalent will be
1 g mole of = 1 g mole of CaCO
Ca(HCO)
162 g of
Ca(HCO) = 100 g of CaCO
Ca(HCO)2 = 50 g of CaCO, (the equivalent weights)
81 g of

for x g of Ca(HCO), = x50 (equivalent weight of CaCO)

. CaCO equivalents of hardness

mass of the substance

= x 50
equivalent weight of the substance
To make mathematical calculations
simpler, the above formula may
be presented in terms of molecular
weight.

=0x
.
For xg of 100 (molecular weight of
Ca(HCO)2 CaCO)
162

CaC0, equivalents of hardness

mass of the substance

molecular mass of the substance
x 100

Conversion or multiplication factors of some

factors
commonly
occurring impurities in water are given in table 1.3.
1.8
Chemistry n Engineering
Table1.3:Conversion factors for hardness causing impurities
Salt/Ion Molecular Conversion factor to convert
mass in terms of CaCO, equivalents
Ca(HC03)2 162 100/162
Mg(HCOg) 146 100 146
CaCl2 111 100 /111
CaSO4 136 100 136
MgSO4 120 100 120
MgCl 95 100 /95
Mg(NO3)2 148 100 /148
CaCO3 100 100 /100
MgCO3 84 100/ 84
HCl 100
36.5
36.5 x 2
HSO4 98 100 /98
FeSO4H20 278 100 /278

NaAIO2 100
82
82x2
Al2(S043 342
100/ 114
Caz 40
Mg2 24 100/ 40

100 /24
HCO 61 100
LCO2 44 61x2
OH 17
100 /44

CO 100/34
60
H 100 /60
100 /2
1.5 UNITS OF HARDNESS
All natural water
contains dissolved
in mineral salts, which
pipelines, particularly when depositea
salts are calcium the water is heated. The
and magnesium and commou
expressed either in their
parts per million concentration in water 1
which may vary from (ppm)or in 'degrees of hardness
country to
The following units are country.
used to
express hardness of
(i)
Degree Clark °CI) It is
hardness per 70,000
: the parts of
water:

parts of water. CaCO, equivalene

1°Cl = 1 part
water CacO equivalent hardness
per 70,000 parts of
(ii)
Degree Frence (Fr) : It
hardness per 0.1 millionis the parts of CaCO, lent
(10)parts of water. equival
1°Fr =1 part
CaCOg equivalent hardness
per 10 parts of wa
water
Water 1.9

(iii) Parts per million (ppm) : It is the number of parts by weight

of calcium carbonate (CaCO,) present per million (10)by weight
of water

1ppm =1 part CaCO equivalent hardness per 10 parts of

water

(iv) Milligram per million (mg/L): It is the number of milligrams

calcium carbonate (CaCO,) equivalent
per litre of water.
ot

Img/L = 1mg CaC0, equivalent in 1 L of water

Relationship between the units of hardness

Let us assume 1 part of CaCOg equivalent hardness = x,
As per definition of ppm, °Cl and °Fr
x = 1 ppm x 106 = 1 °Cl x 70,000 = 1 °Fr x 1,00,000 ..(1)

Now divide above equation (1), one by one with 106, 70,000 and
1,00,000

(a) ppm x 105 1°CIx70,000 1° Fr x 1,00,000

10 10 10
1 ppm = 0.07°Cl =0.1°Fr

x 105 1° Clx 70,000. 1° Fr x 1,00,000

(b) ppm
(b 70,000 70,000 70,000

1°C =14.3 ppm = 1.43°Fr

x 10 1°Clx 70,000 1° Fr x 1,00,000

(c) ppm
1,00,000 1,00,000 1,00,000

1°Fr =10 ppm = 0.7°CI

1°Fr
So,

1 ppm Img/L 0.1°Fr 0.07 Cl

1 mg/L 1 ppm 0.1 °Fr = 0.07 Ci

1 °Fr = 10 ppm 10mg/L 0.7 Cl

1 °C1 =1.433 °Fr = 14.3ppm = 14.3 mg/L

Normally accepted classifications for water is given in the Table 1.4.
 in
1.10 Chemistry Engineering

able 1.4 Classification of water according to hardness

Parts per mllion

Degree Clark
(CI) (ppm)
Soft 0 3.5 0 -50

Moderately soft
3.5 7.0 50 100
Slightly hard 7.0- 10.5 100 - 150
Moderately hard 10.5 14.0 150 -200
Hard 14.0 21.0 200 - 300
Very hard over 21.0 over 300

Example-1.l A water sample contains 204 mg of CaS04 per liter.

Caleulate the hardness in terms of CaCO
equivalents.
Solution: The CaCOg equivalent for CaSO4 is
100 g. of CaCOs 136 2 of CaSO4
100
1g. of CaSO4 = 196 8of CaCO3
136

1 mg. of CaSO4 =a mg100

36 of CaCOg

204 mg. of CaSO4 = 204 x 100

mg of CaCO
136
Equivalents of CaCO3 = 150 mg/L or ppm
OR

Equivalents of CaCOg = Mass of the substance

x 100
Molecular mass

Equivalents of CaCO3 = 204 x 100

136

Equivalents of CaCOg = 150 mg/L or ppm

Example-1.2 How many grams of FesO4 dissolved
210.5 ppm of hardness ? per liter gives

Solution:
The molar mass of FeSO, = 152 mole.

Equivalents of CaCO3 = Mass of

FeSO x 100
Molecular mass
Water 1.11

Mass of FeSO,
210.5= x 100
152

Mass of FeSO, = 210.5x152 = 319.96 ppm

100
Mass of FeSO4 required per liter = 319.96 x 10- g/L = 319.96 mg/L
Mass of FeSO4 required per liter = 0.31996 g/L
Example-1.3How many grams of MgCl2 dissolved per litre gives
60 ppm of hardness ?
Solution :

= Mass of MgCl2
Hardness -x Equivalent mass of CaCO
Equivalent Mass of MgCl2

or Mass of MgCl2 = Equivalent Mass of x Hardness MgCl

Equivalent Mass of CaC03!

:
47.5x 60
= 57 mg
50

Example-1.4 A sample of water on analysis is found to contain 8

mg/l Ca(HCO,)2, 4 mg/l
CaSO, and 12 of Calculate
mg/l MgCl2.
totalhardness of water.
Solution:
Calculatior of CaCOs equivalents
Constituent| Quantity Multiplication| CaCOs equivalents
mg/l factor (mg/)
100
Ca(HCO3 8 162 8 x100
169= 4.94
100 100
CaSO 4 136 4X 136 2.94

100 100
MgCl2 12 95 12x 95
12.63
Temporary Hardness =Hardness due to Ca(HCOg)2
= 4.94 mg/l
Permanent Hardness = Hardness due to CaSO4 + MgCl2
=2.94+12.63
15.57 mg/l
Total Hardness = Temporary Hardness +Permanent Hardness

4.94 +15.57
= 20.51 mg/l
 Chemistry in
1.12 Engineerino

A sample of water on analysis was found to

|
Example-1.5 contain
the following impurities in mg/l

Impurity Ca(HCO)2 Mg(HCOa)2 CaSO |MgSO4

Quantity 10 8.5 1212 14
Mol. wt. 162 146 136 120

Caleulate the temporary, permanent and total hardness of

water in mg/L, ppm, °CI and °Fr ?
Solution :
Calculation of CaCO3 equivalents
Constituent Quantity Multiplication CaCO equivalents
mg/L factor (mg/L)

100
Ca(HCO32 10
100/162 162X 10 = 6.17

100
Mg(HCO3)2 8.5 146x 8.5 =5.82
100/146
100
CaSO 12
100/136 136 12 = 8.82
100
MgSO4 14 120
X 14 = 11.67
100/120

Temporary hardness = Hardness due to (Mg(HCO3)2 + Ca(HCO

= 6.17 + 5.82
.
Temporary hardness
Temporary hardness
Permanent hardness
= 11.99 ppm (mg/L)
= Hardness due to (CaSO, + MOO4)
Permanent hardness = 8.82 + 11.67
Permanent hardness =20.49 ppm (mg/L)
The total hardness =Temporary hardness +Permanent hardness
The total hardness = 11.99 + 20.49
The total hardness
= 32.48 ppm (mg/L)
Various units of hardness of water are inter-related as below
1 ppm =0.07°Cl =
0.1°Fr = 1 mg/L

Hardnessin mg/L inppm in Cl in °Fr

|Temporary 11.99 11.99 0.8393 1.199
Permanent 20.49 20.49 1.4343 2.049
Total 32.48 32.48 2.2736 3.248
Watcr 1.13

Example-1.6 A sample of water is found to contain 40.5 mg/L

Ca(HCO3)2, 46.5 mg/L Mg(HCO,)2, 27.6 mg/L MgsO4
32.1 mg/L CaSO, and 22.45 mg/L CaClg. Calculate the
total hardness of water.

Solution:
Calculation of CaCOg equivalents

Constituent Quantity |Multiplication CaCOg equivalents

mg/L factor (mg/L)

Ca(HCO3)2 40.5 10
162 x 40.5 = 25
100/162
100
Mg(HCO3)2 46.5 146X 46.5
= 31.85
100/146
100
MgSO, 27.6
100/120 120 27.6 =23
100
CaSO4 32.1
100/136 136X 32.1 =23.60
100
CaCl 22.45 111x 22.45 =20.22
100/111

Temporary hardness = Hardnessdue to {Mg(HCO3)2 + Ca(HC0g)al

Temporary hardness =31.85 + 25
.Temporary hardness = 56.85 mg/L
=Hardness
(ppm)
Permanent hardness due to (CaSO4 + MgSO,+ CaClal
= 23 + 23.60 + 20.22
.
Permanent
Permanent
The total
hardness
hardness = 66.82 mg/L (ppm)
hardness=Temporary hardness +Permanent hardness
The total hardness = 56.85 + 66.82
The total hardness = 123.67 mg/L (ppm)
Example-1.7 A sample of water on analysis has been found to
contain the following in ppm : Ca(HCOg)2 = 12.5;
CaCl2 = 8.2; MgsO = 2.6.
Calculate the temporary and permanent hardnéss in
ppm and total hardness in degree French ?
1.14 Chemistry in
Engineering

Solution:
Caleulation of CaCOg equivalents
Constitvent Quantityy MultiplicationCaCOs equivalents
mg/L Factor (mg/L)

100
Ca(HCO3)2 12.5
100/162 162
12.5 7.72

|
CaCl2

MgS0
Temporary
8.2

2.6

hardness

Temporary hardness
100/111

100/120
100
111X8.2 =7.39
100
120x 2.6

= Hardness due to Ca(HCO3)2

= 7.72 mg/L
= 2.17

.
.
Permanent
Permanent
Permanent
hardness
hardness
hardness
= Hardness due to (CaCl, + MgSO4}
= 7.39 +2.17
= 9.56 mg/L
The total hardness =Temporary hardness +Permanent hardness
Thetotal hardness = 7.72 +9.56
The total hardness = 17.28 mg/L (ppm)
The relationship between mg/L (ppm) and degree French (°Fr) is
1 ppm =l mg/L = 0.1° FFr.

.
Total hardness
Total hardness

Total hardness
17.28 mg/L
= 17.28x 0.1° Fr.
= 1.728° Fr.
Example-1.8 Complete the following:
Unif of hardness 70°C1 25 ppm 100°Fr
Ppm ?
Cl
Fr ?
Water
1.15

Solution:
Unit ofhardness
Ppm

Cl 70°CI
70°CI

1°Cl = 14.3

70x 14.3
= 1001
ppm

ppm
1
25 ppmn
25

ppm
25x 0.07
ppm
'
100°Fr
1°Fr = 10 ppm
100 x 10
= 1000
= 0.07°CI 1°Fr
ppm
= 0.7°C1
..100x 0.7
= 1.75°Cl = 70°CI
Fr 1°Cl =1.43°Fr I ppm = 0.1°Fr 100 °Fr
70x 1.43 25x0.1
= 100.1 °Fr 2.5 °Fr
Example-1.9 : 60 mg of MgSO4 is present in 1 L water. Calculate
hardness of water equivalent to CaCO3.
Solution: Hardness due to MgSO4 equivalent to CaCO3

amount of MgSO4x 100

Mol. wt. of MgSO4
60x 100
120
= 50 ppm
1.6 ESTIMATION OF HARDNESS OF WATER
Hardness is usually determined by EDTA titration method, using
organic dye indicator called Eriochrome black- T (EBT, also called
organo-metallic indicator) because it is a stable reagent to form
metal complexes. The estimation is based on complexometric
titration. This is a very accurate method to determine the hardness
of water. The efficiency of complex formation with EDTA is affected
by variation of pH of the solution and it is suitable in alkaline
medium only. Therefore, to get better results alkaline buffer solution

(NH,CI + NH,OH) of pH= 10 is used.

Eriochrome black - T (EBT) is used as an indicator for the
extimation, gives a wine red colored unstable complex with Cas* and
Mg2 ions (Ca2 -EBT and Mg2 EBT complex). EDTA takes Ca2+
and Mg* ions from the unstable complex and forms a colorless stable
complex with regeneration of blue dye (BEBT). Thus, the color of blue
dye changes from wine red to original blue color at the end point.
 in
Chemistry Engineerino
1.16

the hardness ot water

Thus the amount of EDTA used corresponds,

HOOCCH2 CHCOOH
N-CH2-CH2-N
HOOCCH CHCOOH
tetraceticacid
Ethylene diamine

OH OH

NaOgS

O)
OIO N=N

O,N Eriochrome Black-T

Sodium 1-1-hydroxy-2-napthylazo)-6 nitro-2-napthol-4-sulphonatel

Fig. 1.1

1.7 ALKALINITY

Alkalinity is the buffering capacity of a water

body. It measures
the ability of water to neutralize acids,
thereby maintaining a fairly
stable pH in aquatic
system and also important during water
softening process. Without this buffering
capacity any acid added
to a lake would
immediately change its pH. Alkalinity is the result
of the presence of bicarbonates

(OH), of calcium, magnesium, and sodium. (CO,

HCOR), carbonates an
hydroxides
chemicals, used in water
Many of the

treatment, such as alum, chlorine, or lime

cause changes in
alkalinity.

Determining alkalinity is required when

for coagulation and water calculating chemical dosage
softening. Alkalinity is also
calculate corrosivity of water and used
estimate the carbonate
(carbonate hardness is hardn
primarily caused by the carbonate
bicarbonate salts of calcium and a
magnesium.)
Alkalinity (in terms

Depending
of
CaCO)
[HCo3]+[co] loH
on the anions which is
equivalent)

present in water
] (HCO,CO or O
Water 1.17

alkalinity is classified respectively as bicarbonate alkalinity,

carbonate alkalinity or hydroxide
alkalinity. With respect to the
constituents causing alkalinity in water, the
following situations
may arise:
(i) hydroxide only iv) hydroxide and carbonate only

(ii) carbonate only (v) carbonate and bicarbonate only.

(iii) bicarbonate only

The of hydroxide (0H) and bicarbonate (HCO

possibility
is ruled out, because of the fact that
together they combined
with each other and forms carbonates
(Co).
OH+ HCO3 CO3
2 +HO
On the basis of same reason, all the three anions bicarbonates
HCO), carbonates (co), and hydroxides (OH) cannot exist
together.

The types of present in water sample determined

alkalinity
by titrating an aliquot of the sample with the standard acid
(HCI or H,SO,), using phenolphthalein and methyl orange
indicators.

The determination is based on the following reactions:

(i)OH+H H,O P
M
(ii)co +H HCO3
ii) HC0+H H,O+CO
The titration of the water
sample against standard acid up to
phenolphthalein end-point (P)the completion of reactions (i) and (ii)
This amount of acid used thus corresponds to
only. plus one-OH
half of the normal carbonates present.

of
On the other hand, the water sample against a standard
titrations
acid to methyl. orange end point (M) marks the completions of
reactions (i), (i) & (ii). Hence the total amount of acid used
represents the total alkalinity.
1.18 Chemistry in
Engineering

The calculation of hydroxides, carbonates and bicarbonates in

the various samples can be made with the help of the following
table 1.5.

Table 1.5: Computing the alkalinity dueto different anions

Result of O alkalinity CO alkalinity HCO alkalinity
Titration as CaCO, asCaCO asCaCOOg
P 0 M
P<M 2P M-2P

P-M 2P 0

P>M M 2P-M 2(M-P)

P= M 0 0
Pis phenolphthalein end-point and M is methyl orange end-point
(total
alkalinity)

Alkalinity due to individual ions can be calculated from the

values of P and M.
Case I P
= 0) : Here the phenolphthalein end point is uzero. This
can happen only when and OH CO
are absent. The alkalinity
is only because of
HCO3 ions present and determined by using
methyl orange indicator. Here bicarbonate alkalinity will be
M
Case II P < 2 M): This can happen when both C0 and HCO
ions present. The end
phenolphthalein point indicates the half
neutralization of CO. Further titration
using methyl orange
corresponds to neutralization of HCO
which is originally present
and other obtained from CO.
Here alkalinity due to is 2P CO
and HC0, is M-2P.

Case II (P = M)
2
: This can happen when only CO ion
present is

in the solution. The phenolphthalein end point indicates the half

neutralization of CO and other half i.e.
HCO, which is obtained
during neutralization of
CO0G ion, be neutralized and which
will

is indicated by methyl orange end point. Here alkalinity is due to

CO and represented as 2P.

1
Case IV (P> M): This can happen when both OH and CO
 Water
1.19

ions present in the solution. The

phenolphthalein end point indicates
both complete neutralization of OH ion and half
neutralization of
CO ion. Further titration
using methyl orange corresponds to

neutralization of HCOwhich is obtained from ion. Here C0

alkalinity due to OH ion (2M-P) and 2 (M-P).
is
CO ion
Case
in
V (P
the
=M)
solution.
:This can happen
The
when only OH° ion is present
phenolphthalein end point indicates the
is

neutralization of OH
ion. While methyl orange end.point indicates
same result as phenolphthalein end point. Hence
alkalinity due to
OH ion is P M.
Example-1.10 : A 10 ml of water sample required 2 ml of N/50 sulfuric
acid using methyl
orange as indicator but failed to develop any
colour with phenolphthalein. What is the
type of alkalinity present?
Find the strength in terms of ppm.

Solution : As P =
0, only HCO ions present in the solution alkalinity
due to bicarbonate is M.
N,V = N,V
N == 0.02
10
x2

0.004 N
Strength in terms of CaCOg equivalent= Ng x eq. wt. of CaCOg
= 0.004 x 50 g/l
= 0.2 g/l
200 mg/l
or 200 ppm
Example-1.11 10 ml water sample on titration with N/50 sulfuric acid
consumed 2 ml up to phenolphthalein end point. On continuation
of titration in présence of methyl orange 4 ml of acid used. Find
the alkalinity of water sample in terms of CaCO3. Also comment
on the type of alkalinity.

Solution: As P = 2 ml and M =4 ml. Hence it in case of P M

=
indicates only CO ion.

From phenolphthalein end point

NV1 = N2V2
2
N 0.02 x
10
= 0.04 N
1.20 Chemistry in
Engineering

Strength in terms of CaCO, equivalent = N2 X eq. wt. of CaCo,

= 0.004x 50 g/l

= 200 mg/l
Similarly, from methyl orange end point
NV = N,V2
0.02 x 4
N2 =
10
= 0.008 N
Strength in terms of CaCOg equivalent = Na x eq. wt. of CaCO0,
0.008 x 50 g/l

= 0.4 g/l
= 400 mg/l
As P M, only CO ions are present.
Thus C03 alkalinity = 2P
2x 200
= 400 mg/l
1.8 SOFTENING OF WATER OR WATER TREATMENT METHODS
Water softeningis the reduction of the concentration of calcium,
magnesium, and other ions in hard water. These hardness
causing
ions can cause a variety of undesired effects
including interfering
with the action of soaps, the build up of scale, and corrosion. Water
softening may be desirable where the source of water is hard.

The three methods are commonly used for softening of

water:
i) lime-soda process (ii) zeolite process and (iii) ion exchange process.

1.8.1 LIME -SODA PROCESS

The basic principle of this process is to convert
chemically all the
soluble hardness causing salts into insoluble precipitates which may
be removed either by settling or by filteration. For this purpose,
requisite or calculated amount of lime, Ca(OH), and soda ash,Na,CO
is added to hard water.

The lime is required for the precipitation of temporary hardness,

permanent magnesium hardness, free mineral acid, carbon dioxide

Water 1.21

ind hydrogen sulphide impurities. Soda removes all the soluble

calcium permanent hardness, which is originally present as well as
which is introduced during the removal of permanent magnesium

hardness, iron salts, free mineral acid impurities. The reactions

involved in the process are:

Reactions with Lime :

(a) Removal of temporary hardness

+ Ca(OH)2 2CaCO + 2H,0
Ca(HCO3)2

Mg(HCO3)2 + Ca(OH)2 MgCO ++ CaCO3 + 2H,0

MgCO3 + Ca(OH)2 Mg(OH)» CaCO3
(b) Removal of permanent Mg hardness .
MgCl2+ Ca(OH)2 Mg(0H)2 + CaCl2
MgSO4 + Ca(OH)2 Mg(OH)2 CaSO4
(c) Removal

FeSO4
of dissolved iron

+ Ca(OH)2
and aluminium

Fe(OH) +
salts:

CaS04
2FelOH2 + H,0 + Og 2Fe(OH)3

Alo(SO)s +3Ca(OH)2 2A1(OH)s + 3CaSO4

(d) Removal of dissolved COg and H,S

HS+Ca(OH)2 CaS+ 2H,0

CO2+ CalOH)2 CaCO3+Hg0
(e) Removal with NaHCO3

2NaHCO3+ Ca(0H)2 NagCOg +CaCOs2H,0

(D Removal of free mineral acids : + 2H,0
2HCI+ Ca(OH)2 CaCl2

H,SO +Ca(OH)2 CaSO +2H,0

Reactions of Soda :

(i) CaCl+NagCOg 2NaCl +CaCO3

(ii) CaSO + Na2CO3 NaSO+ CaCOs
The lime- soda process may be broadly classified as:
 Chemistry in
Engineerino
ng
Cold Lime-Soda Process
In this process, water is treated with calculated amount of lime an
and
soda, at room temperature only. At room temperature, the precipitates
formed are finely divided, so they do.not settle down casily and
cannot be filtered. Therefore in this process coagulant such as sodium
aluminate, alum etc. is essential. Coagulant hydrolyses and entraps
the fine precipitates and precipitates are easily settle down.

NaAlO, + 2H,0. NaOH +Al(OH)

sodium aluminate

Al SO, + 3 CalHCO,)
from hard water
2 Al(OH), + 3 CaSO, +6CO,

This process provides water containing a hardness of 50 to 60 ppm

i.e. it has low water softening capacity.

This process uses to two kinds of softeners

G) Intermittent type softeners (Batch Process): It consists of

a pair of tanks which are used in turn for softening of water.
Raw water is passed from one side and lime, soda and coagulant
in requisite amount is added from another side
of the tanks.

Each tank is provided with mechanical stirrer. When the tank

fills up, the reaction is completed and sludge or precipitate is
allowed to settle down. Softened water is sent to filtering unit
from where filtration occurs and sludge is taken out from the
tank through the sludge outlet. (Fig. 1.1)

Inlet for chemicals

iniet for raw water
(lime +soda + coagulant)

Stme

Softened water

Sludge outlet

Fig.1.1 Intermittent cold limesoda softener

(ii) :
Continuous type softener It consists of a big steel tank with
inner and outer chambers. Raw water, lime, soda and coagulant
in requisite amount are added into the inner chamber from the

top, inner chamber is fitted with paddle stirrer.Vigorous stirrin8

ensures continuous mixing of chemicals with raw water, softening
Water 1.23

takes place. Sludge formed scttles down at the bottom of the

outer chamber while softened water raises upward passes
through a wood-fiber filter. Filtered water finally comes out

continuously through the outlet provided for the purpose. (Fig.

1.2)

Motor
belt
Chemicals (Soda+
Driving Raw
water
lime+coagulant) feed inlet
feed inlet

Filtered softened
water outlet

Wood-fibre
filter

Outer chamber

Stirrer paddles -
nner chamber

Stirrer

Sedimented sludge
[CacOg Mg(OH)2]

Sludge outlet

777777777777777777

Fig. 1.2 Continuous cold lime-soda softener

Hot Lime-Soda Process:

In this process water is treated with lime and soda at a temperature
of 94°C -
100°C. Thus the process is very rapid, boiling temperature
accelerates the chemical reactions and reduces the viscosity of the
water. This increases the rate of aggregation of the particles. Hence,
both the settling rates and fiteration rates are increased. Thus
softening capacity increased by many times. At the higher
temperature, the dissolved gases are driven out. Softened water has
residual hardness of 15-30 ppm. (Fig. 1.3)

This process also uses to two kinds of softeners:

G)
(i) Intermittent type softeners : It is similar to the cold lime
batch process except that heating coils are installed in it for
boiling the water.
1.24 Chemistry in
Engineering

ii) Continuous type softener :

This softener consists of three
parts: (a) reaction tank, (b) conical sedimentation tank and (e)
sand filter.

(a)Reaction tank this tank has three separate inlets one

each for water, steam and chemicals. The component of these
inlets are taken in and are thoroughly mixed. The beginn-
ing and completion of the reaction occurs only in this tank.
(b)Conical sedimentation tank: in this
tank sludge
is formed
and settle down.
(c)Sand filter: ensures complete removal of sludge from the
softened water

Rawwater
feed inlet

Superheated- Chemicals (lime+soda)

steam inlet feed inltee

Reaction tank-

Sand filter

Fine sand layer

Conical
sedimentation Coarse sand layer
tank
Gravel layer
Precipitated

sludge

Precipitated-
sludge outer Filtered
softened water

Fig. 1.3 Continuous hot line soda softener

Advantage of Lime-Soda Process

1. Lime-soda process is very economical
2. Treated water is alkaline in nature and hence has less corrosion
tendencies.

3. Pathogenic bacteria are reduced in water because of alkaline

nature of treated water.
4. It removes not only hardness but also minerals.

Disadvantage of Lime-Soda Process

1. Disposal of large amount of sludge is a problem
Water 1.25

2. Water softened by this process contains appreciable amount of

soluble salts such as sodium salts etc. and cannot be used in
high pressure boiler.
3. Process requires careful operation and skilled supervision for
economical and efficient softening.

4. This process cannot produce water having zero hardness.

1.8.2 ZEOLITE OR PERMUTIT PROCESS

The namezeolite is derived from two greek words, zein +
lithos which
Zeolites are complex, hydrated orthosilicates
mean boiling stone. of
aluminium, calcium, sodium, potassium or iron. They are capable of
exchanging its sodium ions for divalent ions of alkaline earth metals
and for the multivalent ions present in water.

Zeolites act as ion-exchangers, a reversible exchange of ions between

a liquid phase and a solid phase. A certain class of naturally
occuring aluminosilicate minerals called zeolites which are act as
solid phase and are capable of exchanging its cations.

Zeolites find application in softening of water for domestic and

industrial purpose zeolites are commercially known as permutits and
are of twotypes

() Natural zeolites:
Natural zeolites are derived from greensands. Natural zeolites
includes

Natrolite Na20.Al,0,.SiOg.H,0

Thomsonite :NagO.A1,03.3SiO2.2H,0 and

Analcine Na0.Al,0g.4Si0,.3H,0

ii) Syntheticzeolites:
They can be prepared by heating solutions of sodium silicate,
aluminium sulphate and sodium aluminate. Synthetic zeolites
possesses higher exchange capacity compared to thatofnatural
zeolites. They are porous and possess a gel The
structure. most
common artificial zeolite is a white coloured substance prepared
from feldspar, kaolin, clay and soda and is called permutit and
has the general formula

Nag0.Al,03.nSiO2.xH20 where n = 5 -13, a = 3 4.

 1.26 Chemistry in
Engineering

Principle of Water Softening:

Zeolites may be represented as NagZe where, Ze is the insoluble
radical framework. When hard water comes in contact with a bed of
zeolite placed in a large suitable column (NagZe), Ca** and Mg* ions
of the hard water are exchanged for Na* ions of the zeolite. Thus,
sodium zeolite is converted into calcium and magnesium zeolites,
while water comes free from Ca and Mg salts, but is richer in sodium
(Nat) salts. Hence, zeolite is a sodium exchanger. The various
relations taking place may be written as follows:

Ca(HCO3) + NagZe +
CaZe 2NaHCO
Mg(HCOs)2 + NazZe MgZe + 2NaHCO
CaSO + Na2Ze CaZe + NagS04
MgSO4 + NagZe MgZe +NagSO,
CaCl2+ NazZe CaZe + 2NaCl
MgCl2 + Na2Ze MgZe +2NaCl1
Regeneration:
When the zeolite bed exhausted, it loses its sodium exchanging
is

capacity and it may be regenerated by washing the zeolite bed with a

concentrated solution of sodium chloride (brine) which, converts the
exhausted zeoliteback to its original condition. The other solutions like
NaNO2, Na,sO4, KC etc. can also be used in place of NaCl, but NaCl
is cheap and the products formed by regeneration reactions are CaCla
and MgCl2 which are highly soluble and can be washed away from the
zeolite bed.
CaZe 2NaCl NagZe CaCl
Mgle 2NaCl NagZe MgCl2
Exhausted Brine (Reclaimed) Washings
Zeolite solution Regenerated
zeolite

Process:
A zeolite softner consists of a steel tank packed with a thick layer of
permutit (zeolite). The hard water is percolated at a specified rate
through the bed of zeolite. Ca2* and Mg2* present in it are retained
by the zeolite in the form of CaZe and MgZe respectively. The
outgoing water gets riched in sodium salts. The softened water is
collected from the bottom as shown in fig. 1.4.
Water 1.27

Brine tank

Pre-filter

Hard water

Raw water inlet

Gravel

Soft water outlet

Soft water

Fig. 1.4 Zeolite soiiner tank

When mostof the portion of sodium ions in the zeolite has been
replaced by calcium and magnesium ions, it is regenerated by first
washing it with water by reversing the flow and then treating it with
concentrated, NaCI solution. Theoreticaly each mg/L of CaC03
hardness requires 1.17 mg/L of NaCI solution. But thrice the amount
of theoretically required amount of NaCI is used to make
regeneration reaction more efficient.
The soluble CaCl2 and MgCl2 so
formed in regeneration process are washed with soft water and
washings are led to sink.

Limitations
(i) The presence of turbid water reduces the efficiency of zeolite, as
the zeolite bed.
turbidity clogs the pores of
(ii) In presence of large amounts of coloured ions like Mn2* and
Fe, they should be removed first, otherwise it is difficult to
regenerate the Fed* Mn2* ion zeolite.
ii) Water containing mineral acids destroy the zeolite bed, hence water
should be neutralized first before admitting it into the zeolite.
 1.28 Chemistry in
Engineering

Advantages:
(i) Zeolites can remove hardness upto 10 ppm.
Zeolites softner little space.
very
ii) compact, occupying
is

No no sludge is tormed at
(ii) impurities are precipated, hence a
later stage.
operation cost
is quite
Iv) The running, maintenance and less.

(VIt removes iron and manganese from the water.

(vi) It requires less skill for maintenance as well as operation.

Disadvantages:
of sodium salts. The
i) The treated water contains an excess
total
ions'of sodium is
solid content due to the chloride and sulphate
not decreased or removed, and remain in the softned water.
(ii) It leaves all the acidic ions CI, COg as such in the
HCO,
softned water. For example, in boilers NaHCO3 dissociates
formingNaOH and CO2.
NaHCO3 NaOH + CO2
NaOH causes caustic embrittlement of boiler material and CO,
when it goes steam renders the water acidic and corrosive.
raw water should be subjected to boiling to remove
Thus,
temporary 'hardness before it
is led into zeolite. .
(iii) The treated water contains more dissolved salt than treated by
lime-soda process.

A Zeolite softner was completely exhausted and

Example-1.12
was regenerated by passing 100 liters of sodiumn
chloride solution, containing 120 g/L of NaCl. How
many liters of a sample of water of hardness 500
Ppm. can be softened by this' softner ?
Solution:
100 liters of NaCl = 120 g/L x 100 L
= 12,000 g of NaCl

= 12,000 x
= 10256.41
100
58.5x
g of
2 8 of CaCOa
CaCO3 eq.
ea.

Now 500 mg. of hardness is present in = 1 liter of water

10256.41 x 10 mg of CaCOg eq. hardness is present in
1
x 10256.41 x 103
500
500
= 20512.821 L
Hence, the softner can soften 20512.82 liters of hard water.
Water 1.29

Example-1.13 The total hardness »f 1,U0O itre:s of water was

completely removed by a zeolite softner. The
zeolite softner required 30 1iters of sodium
chloride solution, containing 15 g/l, of NaCl for
regeneration. Calculate the harduess of water.
Solution:
1.000 L of hard water = 30 Lof NaCl solution

= 30 L x 15 BofNaCl
Litre
= 450 g of NaCl

100
450 58.5 x 2
of CaC03 eq.

= 384.61g of CaC0g eq.

1 L of hard water = 384.61 g. of CaCO3/1,000
= 0.38461 g. of CaCO3 eq.
= 384.61 mg.' of. CaCO3 eq.
Hardness of water = 384.61 ppm.
Example-1.14 A completely exhausted zeolite requires 120L of
sodium chloride solution having 100 g/L of sodium
chloride. How many liters of a water having
hardness 500 ppm be softened by zeolite softener?
Solution:
1 L of NaCl solution = 100 x 120 =12000 g of NaCl
1200 x 50
1Z00 X g of CaC03 eq. hardness
58.5
500 ppm or 500 mg/L hardless
0.5 g/L
Now 0.5g of hardness present in 1 L of water

12000x50 g of hardness = 1x 12000 x50 L

58.5 58.5 x 0.5
20518L
1.30 Chemistry in
Engineering

Example-1.15 A 10000 of hard water sample was passed through

a zeolite softner. The softner then required 400 7 of brine solution
containing 200 g/l of NaCl for regeneration. Calculate the hardnes

Solution :
of water sample.

400 7 of brine solution =200

= 80000
g/l x 400

g of NaCl

80000 x
= 68376.068 g eq.
F50
S eq. of CaCO

of CaCO3
So, 10000 l of water contains 68376.068 g eq. of CaCO3
68376.068
Therefore, 1 l contains =
10000
= 6.8376 g
6837.6 mg
Thus hardness of water in 6837.6 mg/l of 6837.6 ppm.

Example-1.16: An exhausted zeolite softnerpassingwas regenerated by

1000 7 of solution, having strength of 150 g/l of NaCl. How
NaCl
many litres of water that can be softened by the same softner, if
hardness of water is 1000 ppm.

Solution : 1000 of NaCl solution = 150 x 1000

= 150000 g/l of NaCl

50
= 150000 x 8 eq. of CaCO
58.5
= 128205.12 g eq. of CaC03
or 1.282 x 10$ mg eq. of CacO3
Now, 1000 mg hardness is present in 1 l of water.

Therefore, 1.282 x 10° mg hardness = 1.282 x 10 lof water

1000
Total volume of water = 128200 l of water

1.8.3 ION EXCHANGE OR DEMINERLIZATION OF WATER

The water softening made by zeolite contains anions viz. and SO
remain in the softened water combined with Nat. Demineralized
HCO
water does not contain any softness or hardness producing ions. Tne
1on exchange process enables the total removal of all soluble
Water
1.31

minerals and ionsof water without it to the expensive

subjecting
distillation process.

Ion Exchange Resins

Ton exchange resins consists of a
long cross linked, high molecular
weight organic polymers containing a microporous structure with
attached ionizable
groups. The functional groups attached to the
polymeric chains are responsible for ion exchange.

The resins usually consist of styrene-divinyl benzene

copolymers,
other polymers like methacrylic acid - divinylbenzene or phenol
formaldehyde polymers are also used.
The ion exchamgers
organic may thus be classified as i) cation
exchangers and (ii) anion exchangers.

i) Cation exchange resins

A number of
synthetie resin cation exchangers which contain
carboxylic (-COOH), sulphonic (-SOgH) and phenolic (-OH) aromatic
hydrocarbons are available under different trade names, such as
Dowex and Duolite. A polystyrene cation-exchange resin, obtained
by copolymerizing styrene with divinyl benzene and sulphonating
the resulting polymer, exchanges its H* with the metal ions in
solution. These resins are called H-form cation exchangers. When
exhausted, the resins can be regenerated with either dilHCl or
dilH2sO4. It is also possible to convert the H-form cation exchanger
to Na-form exchanger by using NaCl. Schematically a cation
exchanger. may be represented as (Fig. 1.5)

CH CHa -CH CH2-CH

(o
SOgH SOgH*

CH CH-ÇH2
-CH2 CH CH CH2

(o)
sogH SOgH
Fig. 1.5 Representation of Cation Exchanger
1.32 Chemistry in Engineering

Resins contain SOgH group are termed as strongly acidic resins

whereas containing CoOH group termed as weakly acidic resins
are
The cation exchange resins may be represented as RH°.
(ii) Anion Exchange resins:
These contain amine, substituted amino or quaternary ammonium
groups as ionizable or functional groups. Resins containing -NH2,
= NH group are weakly basic whereas those having quaternary
ammonium salts are strongly basic.
A polystyrene anion exchanger may be obtained by copolymerizing
styrene and divinyl benzene. followed by chloromethylation and
treatment with trimethyl amine. Anion exchange resins are
represented as ROH. Schematically an anion exchanger may be
represented as (Fig. 1.6)

- CH
:
CH2 -CHCH2-CH

[o] [o
CHNROH CHNRgOH
CH2 CH CH2
-CH2 CH CH CH2

CHENRgOH CHNRGOH
Fig. 1.6 of Anion
Representation Exchanger
Process:
The ion exchange unit
consists oftwo tanks as shown in
Hard water is first fig. 1.7.
passed through the cation
removes all the cations like Ca exchanger bed which
2*, Mg2*, Nat etc. and
hydrogen (H*) ions. releases the

2 RH'+
CaSO, R,Ca + HSO (= 2H)
2 RH'+ MgSO
R,Mg + HSO (= 2H)
2RH+ CaCl R,Ca+ 2HCl (= 2H*)
2 RH'+ MgCl2
RMg + 2HCl (= 2H*)
RH+ NaCl RNa
+HCI(=H*)
 Water
1.33

Regenerating
Acid Solutions

Alkali
Degasifier

Raw wate To vacuum

inlet
pump
Cation
Steam jacket
exchanger bed,

Demineralized
water

Softened
water7 777.
Washings
(to sink)

Fig. 1.7 Demineralization Ion-Exchange Process

The anions originally associated with Ca2t or Mg2t will be associated
with H ions. In other words HCl,
HoSO4, H2CO3 are formed in
amounts equivalent to the anions present in raw water. Thus water
after passing through cation
exchanger is free of Ca2t and Mg2* ions.
This water is then passed through an anion -
exchanger bed. Here
the anions like S0;, Cletc. present in water are
exchanged for OH-
ions of the resin.

2 ROH + CO RCO3 +20H

2 ROH + S0 RaSO +20HI
ROH+ CI RCI +OH
The water coming out of the anion exchanger is completely free from

responsible for hardness. It is known as deionized

cations anions
and
water or demineralized water. It is as pure as distilled water.

H released from cation exchanger and released from anion

exchanger combine to form unionized water.

Regeneration
H +OHH- Ho
When the resins are exhausted i.e,, when their capacity to exchange
Hor OH respectively are lost, they are regenerated.
Regeneration of cation exchanger is made by first back washing and
then passing a 2% H2s04 solution through it.

R,Ca2*+ HSO 2RH +CaSO4

R,Mg + HSO 2RH +MgSO4
 Chemistry in
1.34 Engineering

The column then rinsed with soft water

is
to remove CaSO4 and
MgSO. If HCI is used for regeneration:
RCa + 2HC1 2RH +CaCl2
R2Mg +2HCl1 2RH+ MgCl2
are more soluble.
HCl is suited for regeneration since CaCl2 and MgCl2

The anion exchanger is regenerated by back washing and then

or NaCl so formed are
passing a solution of NaOH. The Na2SO4
sink or drain.
rinsed with soft water and washing are led to

RSO4 + 2NaOH 2ROH +NagSO

RCl + NaOH ROHNaCl
The water is finally freed from dissolved gases like CO etc. by
passing it through a degasifier which is heated and connected to a

vacuum pump.

Advantages:
(i) Highly acidic or alkaline water can be softned.
(ii) Water of lowest hardness (about 2ppm) can be produced by this

method.
iii) Anions as well as cations are removed thereby problems like
caustic embrittlement and corrosion are reduced when treated
water is used for boiler feed purposes.

Disadvantages:
(G) Turbid water decreases the efficiency of the process.
ii) is costly.
The equipment Moreover costly chemicals are required
for regeneration.

(iii) Monitoring of the softened water at intervals is required.

The softened water may not be totally free from organic and
(iv)
bacterial impurities.

1.8.4 DESALINATION
Fundamentally there are two approaches to convert salt water to
fresh water. The one is to take out water away from salt and the
other is to take salt out of water. With in this ambience. the

desalting processes are under development in the fields of

distillation, reverse osmosis, freezing, ion
exchange electrodialysis,
chemical methods ete. Desalination technolgies areavailable, but the
energy required makes the economics of desalting unattractive in
almost all circumstances.
 Water
1.35

Desalination of Brackish water

Water containing
high concentrations of dissolved solids is known as
brackish water. The brackish
water is unsuitable for drinking.
Depending upon the amount of dissolved
solids, water is classified as
(i) Fresh water (Less than 1000 of ppm dissolved solids)
(ii) Brackish water (greater than 1000
of dissolved solids)
ppm and less than 3500 ppm
(iii) Sea water (greater than 3500 ppm of dissolved solids)
The process of
eliminating, dissolved solids (NaCl)
known as desalination from water is
process. The fresh water demands can be
solved by converting sea water into fresh water
desalination. Desalination is through
expensive process. Inspite of high price,
desalination has been used at various
places around the world.
1.8.4.1 Electrodialysis Process
Electrodialysis is the process based on, the
anions present in salt water migration of catious or
through ion-selective permeable
membranes under the influence of electric field.

Brackish water

JL
.
Cation-selective-
-
membrane Negative Anion-selective
membrane
.1ons"{
1.
..
Cathode Ppsitive Anode
1Ons (+)

Concentrated Pure water Concentrated

salt water salt water

Fig. 1.8 ElectrodialysisUnit

Electrodialysis unit consist of electrodes (cathode and

anode), and rigid
and thin ion-selectivemembranes which are
permeable to either cations
or anions. The cathode is.
placed near the cation-selective membrane
while anode is placed near the anion-selective
membrane. Under the
influence of controlled electric potential across the
electrodes, cations
migrates towards the cathode and anions migrate towards the anode
through ion-selective membranes. Pure-water or desalinated water
is
drawn out from the middle part while the concentrated
salt water is
drawn from the left and right parts of the unit.
(Figure 1.8)
 Chemistry in
1.36 Engineerino

Advantage :
cost and operationo
(1) The process is economical as per the capital onal

expenses.
(2) The unit is compact.
Disadvantage :
The process will not remove organic impurities il
any present in the

water.

1.8.4.2 REVERSE OSMOSIS:

The popularity of reverse osmosis water (R.O. water) has steadily
grown since it was first introduced as a home water purification
system in the 1970s. Reverse osmosis is a technology that is used to
remove a large majority of contaminants from water by pushing the
water under pressure through a semi-permeable membrane. Reverse
osmosis process is differ from ordinary filters. Ordinary water filters
use a screen to separate only particles of dirt sediment from water.
Reverse osmosis employs a semi permeable membrane that removes
not only particles but also an extremely high percentage of dissolved
contaminants -molecule by molecule from raw tap water.
Pure Water

Salt--

water
Seml
Permeable
Membrane
-Fresh-
oO0- water--

Contaminants

00o-

Direction of water flow

Fig. 1.9 Simple Osmosis
To understand the purpose and
process of Reverse Osmosis we
understand the of
process Osmosis. Osmosis is a must
ring phenomenon and one of themost naturally occu
nature. It is a process important
where a weaker saline processes
solution (lowe
concentralion) will lendl to migrate to a
(higher conceniration). Examples of strong saline soluto
osmosis are when
absorb water fronm the soil and our plant roo
kidneys absorb water from
blood. A solution that is less
concentrated will have a
0
natatural ten
Water 1.37

deney to migrate to a solution with a higher concentration. For

example, if you had a container full of water with a low salt concen-
tration and another container full of water with a high salt concen-
tration and they were separated by a
semi-permeable membrane,
the witlh the lower salt concentration would begin to
then water
migrate towards the water container with the higher salt concentra-
tion (fig. 1.9).

A semi-permeable membrane is a membrane that will allow some

atoms to pass but not others. A simple example is a
or molecules
It allows air molecules to pass through but not pests or
screen door.
anything larger than the holes in the screen door. Another example
is clothing (waterproof, breathable fabric membrane, able to
Gore-tex
repel liquid water while allowing water vapor to pass through, and is
designed to be a lightweight, waterproof fabric for all-weather use)
fabric that contains an extremely thin plastic film into which billions
of small pores have been cut. The pores are big enough to let water
vapor through, but small enough to prevent liquid water from pass-
ing. The domestic membrane consists of several thin layers or sheets
of film that are bonded together and rolled in a spiral configuration
around a plastic tub (This is known as a thin film composite or TFC
membrane.)

The material of the membrane

semi permeable: it allows water
is

molecules pass through while acting as a barrier to dissolved solids

(i.e. minerals chemical contaminants). When the feed water stream
passes across the surface of the membrane, the water molecules
penetrate the membrane surface, working their way around the
spiral and collecting in the center tube. The remaining contaminants
are concentrated and washed from the surface of the membrane
down the drain as rejected stream.
Osmotic Pressure the hydrostatic pressure required to stop the
water flow is called osmotic pressure

Reverse Osmosis the process of osmosis in reverse. Whereas

is

osmosis occurs naturally without energy required, to reverse the

process of osmosis, need to apply energy to the more saline solution.
A reverse osmosis membrane is a semi-permeable membrane that
allows the passage of water molecules but not the majority of dis-
solved salts,organics, bacteria and pyrogens. However, need to'push
the water through the reverse osmosis membrane by applying pres-
sure that is greater than the naturally occurring osmotic pressure in
order to desalinate (demineralize or deionize) water in the process,
allowing pure water through while holding back a majority of con-
taminants (fig. 1.10).
1.38 Chemistry in Engineerino

Applied Pressure Pure Water

Semi-
Permeable.
Salt Membrane
water -Fresh
Ewater

Contaminants

Direction of water flow

Fig. 1.10 Outline the process of Reverse Osmosis

Reverse osmosis, also known as hyper filtration or

superfilteration,
is the finest means. of filtration
available today. It is the most
common treatment technology, used by premium bottled water com-
panies. Reverse osmosis refers the process of forcing water through
to
a semi-permeable membrane under pressure (15-40 kg/cm2).

Reverse osmosis (RO) works by using a high pressure

pump to
increase the pressure on the salt side of the
RO and force the water
across the
semi-permeable RO membrane, leaving almost all (around
95% to 99%) of dissolved salts behind in
the reject stream. The
amount of pressure required depends on the salt
concentration of the
feed water. The more concentrated the
feed water, the more
is required to overcome the pressure
osmotic pressure.

In very simple terms, feed water is

pumped into a Reverse Osmosis
RO) system and end up with two types of
water coming out of the
RO system: good/pure water and
bad/rejected water. The
that comes out of an RO good water
system has the
majority of contaminants
removed and is called
permeate. Permeate is the water
that was
pushed through the RO membrane and
contains very little
nants. The 'bad' water 1s the water contaml
that contains all of
nants that were unable to pass the contaml
through the RO
enown as the concentrate, reject, or membrane and is
brine (fig. 1.11)
Water 1.39

RO Membrane

Feed water
Permeate water
Pump (Low concentration of Salts)

Reject Stream
(High concentration of salts)

Fig. 1.11 Simple schematic diagram of working of RO system

Factors affecting the quantity and the quality of the water pro
duced
There are four major variables to consider:

(i) : the water pressure, the better the

Pressure The greater
of the water produced. Water pressure of
quantity and quality
60 psi ideal.
ii) Temperature 76°F/ 24.4°C is the ideal water temperature for
R.O. 40°F /4.44°C water will cause the production of R.O. water
to fall to half of that at 76°F/ 24.4°C. The maximum water
temperature recommended is 90°F/32.2°C.
(iii) Total Dissolved Solids (TDS) : The higher the amount of
dissolved contaminants in the water, the lower the quantity of
water produced. A
high level of total dissolved solids can be
overcome with additional water pressure.

(iv) Membrane :Different membranes have different characteristics.

Some produce more water than others; some have better
contaminant rejection capabilities;some have greater resistance
to chemical abrasion for longer life. The Thin Film Composite

(TFC)membranes combine the best of these characteristics and

are considered the finest membrane in the world.

Advantages of Reverse Osmosis

(i) RO removes all types of impurities: ionic, non-ionic, colloidal
and organic impurities such as THMs (chloroform), DBCP,
lindane, TCEs (trichloroethylene), PCEs (tetrachloroethylene),
carbon tetrachloride, chlorine and other organic chemicals.

(ii) The RO treated water is not only pure but also great in taste
and smell. This is because the RO system removes about 98% of
chemicals from the tap water. So we do not have to bear with
the taste and smell of chlorine anymore.

(iii) RO performs a separation without a phase change. Thus, the

energy requirements are low. It requires 30% less energy as
compared to other desalination or distillation process.
1.40 Chemistry in
Engineerin.

iv) The time of semipermeable

life membrane 1s quite high
the maintenance cos
extending to about 2 years which reduces
(v) RO systems are compact, and space requirements are less than
With other desalting systems, e.g. distillation.

(vi) RO equipment is standardized - pumps, motors, valves

flowmeters, pressure gages, etc. Thus, the learning curve for

)
unskilled labour is short.

Disadvantages of Reverse Osmosis

RO is usually not applicable for highly concentrated solutions,
(1) RO feed streams must be compatible with the membrane and
other materials of construction used in the devices. If the feed

stream contains incompatible compounds, these must be removed

in or another compatible device and/or membrane
pretreatment,
must be considered.
(iii) Because all RO membranes and devices are susceptible to
fouling,
the RO process usually cannot be applied without
pretreatment.
(iv) While reverse osmosis is effective for
removing a variety of
contaminants in water, the reverse osmosis membrane alone
does not remove volatile
organic chemical (VOCs), chlorine and
chloramines, pharmaceuticals, and a host of other
synthetic
chemicals found in municipal water.
However, some R.O. systems
now have multi-stage filtration
media (in addition to the R.0.
membrane), such as Activated Carbon, which
chlorine and does remove
certain pesticides.
(v) Wastage of water is one of the biggest
osmosis, from an environmental and disadvantages of reverse
financial
RO systems have a waste water to standpoint. Mostly,
purified water ratio of 5:1 (6
parts waste to 1 part purified
water).
Applications of Reverse Osmosis
All over the world, the
technology of reverse
safe drinking water in osmosis, providing
households.
ii) In big and progressive
cities
areas, collected
with reverse osmosis and rainwater is purified
used for
industrial cooling. irrigation of landscapes and

(iii) For big power plants and

petrochemical
Osmosis is used to remove the industries, reverse
boilers. The water has to be minerals from water used in the
pure and free from
leave deposits on the minerals tha
machinery and cause
damages. corrosion and other
Water 1.41

(iv) Reversc osmosis is used in the concentration (thickening) of

food liquids
(orange juice, tomato juice) that lose their nutritional
values if processed with heat.

(v) It is alsoused in the dairy industry in the production of whey

protein powder and the concentration of milk to reduce shipping
and storage costs
(vi) It is also used in wine or industries.
distillery

(vii) Many reef aquarium keepers are now using reverse osmosis
systems to produce water for their artificial mix of seawater.
They found that ordinary tap water often contains excessive
amounts of chlorine, chloramines, heavy metals, and many other
chemicals that are bad for the reef environment in their
aquariums.

(vii) Pharmaceutical and semiconductorindustries also require the

use of pure, clean water for a vàried of reasons. In semiconductor
production lines for example, the use of ultra-pure water as a
final step of some cleaning processes is absolutely necessary.
Any impurities can cause problems with the sensitive nature of
à variety of the products such as semiconductor wafers and
other electronic components. The same can be said with
pharmaceutical applications. The importance of pure water in
creating medicines simply cannot be undermined. Aside from
the production side, industries often utilize clean water produced
from reverse osmosis to clean, disinfect and maintain equipment
and facilities.

(ix) In places where there is limited water, authorities use reverse.

osmosis technology to desalinate the sea for their drinking
water. In the Middle East especially in Saudi Arabia, large
reverse osmosis and multistage flash desalination plants are in
harness. The energy requirements are large, but they are offset
by the fact that these countries are oil-producers

1.9 BOILER FEED WATER AND ITS TREATMENTS

A boiler is device for generating steam, which consists of two
a
principal parts, the furnace. which provides heat, usually by burning
a fuel, and the boiler proper, a device in which the heat changes
water into steam. The steam or hot fluid is then recirculated out of
the boiler for use in various processes in heating applications.
1.42 Chemistry in
Engineering

The boiler receives the feed

water, which consists of varying proportion
of recovered condensed water (return water) and fresh water, which
has been purified in varying degrees (make up water). The make-up
water is usually natural water either in its raw state, or treated by
some process before use. Feed-water composition therefore depends
on the quality of the make-up water and the amount of condensate
returned to the boiler. The steam, which escapes from the boiler,
frequently contains liquid droplets and gases. The water remaining
in liquid form at the bottom of the boiler picks up all the foreign
matter trom the water that was converted to steam. The impurities
must be blown down by the discharge of some of the water from the
boiler to the drains. The permissible percentage of blown down at a
plant is strictly limited by running costs and initial outlay. (Fig. 1.12)

steam
outlet

water
inlet

flue

air and
fuel inlet

Combustion water tubes

chamber

Fig. 1.12
Proper treatment of boiler feed water is an important
part of operating
and maintaining a boiler system. As steam is
produced, dissolved
solids become concentrated and form deposits
inside the boiler. This
leads to poor heat transfer and reduces the
efficiency of the boiler.
Dissolved gases such as oxygen and carbon dioxide will react with
the metals in the boiler system and lead to boiler corrosion. In order
to protect the boiler from these contaminants, they should be
controlled or removed, through external or internal treatment.

A list of the common boiler feed

water contaminants, their effect and
their possible treatment are given in the table 1.6.