2.

TECHNOLOGY OF WATER

2.1 INTRODUCTION

The two main sources of water are

a) Surface water and

b) Underground water.
The surface water includes rain water, lake water, river water and sea water.
Underground water is further divided into well water and spring water.

2.2 Water quality parameters

2.2.1 Turbidity

Turbidity is the measure of lack of water clarity. Turbidity is the result of suspended solids
in water. It can be measured accurately with a turbidimeter. Turbidity is measured in NTUs,
i.e. nephelometric turbidity unit. Turbidity in drinking water should be less than 1 NTU.
Water treatment is required for drinking water when there is excessive turbidity.

2.2.2 Hardness

Water is said to be hard due to the presence of various dissolved salts of calcium,
magnesium and iron. Hardness is expressed as ppm of CaCO 3. Hardness can be classified
into two types, temporary hardness which can be removed by mere boiling and permanent
hardness which can be removed by certain water treatment process like lime-soda process,
zeolite process etc.

2.2.3 PH
It is in general a measure of hydrogen ion concentration of a water sample. The symbol P H
stands for the potential of hydrogen. Water contains both H + ions and OH- ions. Pure
distilled water contains equal number of both the ions and therefore considered to be neutral
(PH = 7). If a water contains more H+ ions than OH- ions then the water sample is said to be
acidic (PH less than 7). If the water contains OH - ions in excess than H+ ions then the water
sample is said to be basic (PH is more than 7). Rain water has a PH of almost 7 surface water
have alkaline PH.
2.2.4 Alkalinity

It is the measure of the quantity of alkaline substances in water. Mostly alkalinity in water is
due to the presence of hydroxide, carbonate and bicarbonate ions present in the water
sample. The possible combinations of ions causing alkalinity are

(i) OH- alone

(ii) CO32- alone
(iii) HCO3- alone
(iv) OH- and CO32- together
(v) CO32 and HCO3- together.
The combination of OH- and HCO3- ions does not exist as they combine to form CO32- ions.
The combination of all the three ions also result in the formation of CO 32- Hence all the three
ions cannot exist together. Alkalinity is measured in ppm or mg/l.

2.2.5 BOD

Biological oxygen demand is the measure of oxygen in the water that is required by the
aerobic organisms. BOD is the measure of decrease in oxygen content in milligrams per litre
of a sample of water kept in the dark at a temperature of 20 degree Celsius over a specified
period of time. The difference between initial DO level of the collected water and the final
DO level is due to the consumption of oxygen brought about by bacterial breakdown of
organic material and the oxidation of chemicals in the water during the storage period.

2.2.6 TDS

It is a measure of total amount of solid particles dissolved in water. The major dissolved
salts are chlorides, sulphates, bicarbonates and carbonates of Na, K, Ca, Mg, & Fe. High
TDS values make water unsuitable for irrigation and agriculture. It may also cause foaming
and corrosion in boilers. TDS values range from 20 to 2000mg /lit in river water and may be
higher in ground water.

2.3 ANALYSIS OFWATER

2.3.1 Alkalinity
Alkalinity can be estimated by titrimetry method in which water sample is titrated against a
standard acid using phenolphthalein and methyl orange as indicator. The various
neutralization reactions are as follows

I) OH- + H+→H2O
II) CO32- + H+ → HCO3-
III) HCO3- + H+→ H2O + CO2

The phenolpthalein end point represents the completion of first two reactions and methyl
orange end point represents the completion of all the three reactions. Hence the amount of
acid used after the phenolphthalein end point corresponds to

neutralization of complete OH- ions and neutralization of one half of the carbonate ions and
methyl orange end point corresponds to another half of the carbonate and all the
bicarbonates. The total amount of acid used after the methyl orange end point corresponds to
the total amount of hydroxide, carbonate and bicarbonate ions, i.e. total alkalinity.

The possible combinations of ions causing alkalinity are

i) OH- alone
ii) CO32- alone
iii) HCO3- alone
iv) OH- and CO32- together
v) CO32 and HCO3- together.
The combination of OH- and HCO3- ions does not exist as they combine to form CO32- ions.
The combination all the three ions also result in the formation of CO 32- ions. Hence all the
three ions cannot exit together.

PROCEDURE:

V ml of water sample is pipetted out into a clean conical flask and 2 or 3 drops of
phenolphthalein indicator is added into the flask. It is then titrated against a standard acid
from the burette. The end point is the disappearance of pink colour. Let the volume of acid
consumed be V1 ml. continue the titration by adding 2 or 3 drops of methyl orange indicator
to the same solution. The end point is the colour change from yellow to pink. Let the volume
of acid consumed be V2 ml.

CALCULATIONS:

Phenolphthalein end point is noted as V1 ml

Methyl orange end point is noted as V2 ml

Phenolphthalein alkalinity in terms of calcium carbonate equivalent

= V1 X Nacid X 50 X 1000

Methyl orange alkalinity in terms of calcium carbonate equivalent

= V2 X N acid X 50 X 1000

Amount of OH-, CO32-, and HCO3 - in ppm can be calculated as follows:

ALKALINITY
CASE OH- CO32- HCO3-

(I) If P = 0 0 0 M

(II) If P = M / 2 0 2P 0

(III) If P < M / 2 0 2P M-2P

(IV) If P > M / 2 2P-M 2(M-P) 0

(V) If P = M M 0 0

From the above table the type and extent of alkalinity is found out.
2.3.2 NUMERICALS BASED ON ALKALINITY

1. A Water sample is not alkaline to phenolphthalein. But 100 ml of sample on

titration with N/50 HCl. Required 16.7 ml to methyl orange end point. What are
types and amounts the alkalinity present in the sample?

Solution:
Given
Volume of Water sample =100ml
Volume of N/50 HCL required to phenolphthalein end point (P) = 0
Volume of N/50 HCL required to methyl orange end point (M) = 16.7ml
Since P=0 the Alkalinity of water sample is only due to HCO 3- ions

Alkalinity due to HCO3-

Volume of acid consumed V1= 16.7 ml

Normality of the acid N1= N/50
Volume of water sample V2= 100ml
Normality of water sample due to HCO3- N2=?
Therefore, According to the Volumetric law V1N1=V2N2
N2= 16.7/100X1/50= 0.00334
Normality of the HCO3- N2= 0.00334

Therefore,
Amount of HCO3 - in terms of CaCO3 equivalent = N2XEq.wt of CaCO3X1000ppm
= 0.00334X50X1000ppm
=167ppm
I.e. Alkalinity of the raw water sample due to HCO3- = 167ppm

2.100ml of water sample, on titration with N/50 H2SO4 gave a titre value of 6.8ml to
phenolphthalein end point and 13.6 ml to methyl orange end point. Calculate the
alkalinity of the water sample in terms of CaCO3 equivalent and comment on the
type of alkalinity present.

Solution
Given
Volume of the water sample =100ml
Volume of N/50 H2SO4 required to phenolphthalein end point (P)= 6.8ml
Volume of N/50 H2SO4 required to methyl orange end point (M)= 13.6 ml

Since P=1/2 M, the alkalinity of water sample is due to CO32- only and not due OH-
and HCO3.-

Alkalinity due to CO32-

The volume of N/50 H2SO4 equivalent to CO32- present in

100ml of the water sample = 2P=(2X6.8)ml

= 13.6 ml
 Volume of the acid consumed V1= 13.6ml
Normality of the acid N1=N/50
Volume of the water sample V2= 100ml
Normality of the water sample due to CO32- N2= ?
∴ According to Volumetric law
V1N1=V2N2
N2 = 13.6/100X1/50= 0.00276

Normality of CO32- N2= 0.00276

∴ Amount of the CO32- interms
of CaCO3 equivalent = N2X Eq.wt of CaCO3X 1000ppm

= 0.00276X50X1000 ppm
Alkalinity of water sample due to CO32- = 136ppm

3. 200ml of water sample required 22ml of N/50 H2SO4 using methyl orange as
indicator but did not give any colourisation with phenolphthalein. What type of
alkalinity is present? Express the same in mg/lit of CaCO3.

Solution
Given
Volume of water sample = 200ml
Volume of N/50 H2SO4 required to methyl orange endpoint= M=22ml
Since P=0, the Alkalinity of the water sample is only due to HCO32- and OH-

Alkalinity due to HCO3-

Volume of the acid consumed V1 = 22ml
Normality of the acid N1 = N/50
Volume of the water V2 = 100ml
-
Normality of the water sample due to HCO3 N2 = ?
∴ According to Volumetric law
V1N1=V2N2
N2= 22/200X1/50 = 0.0022

Normality of the HCO3- =0.0022

Therefore, Amount of HCO3- interms of CaCO3 equivalent
= N2XEq.wt. of CaCO3X 1000ppm
= 0.0022 X 50 X 1000ppm =110ppm
(or) 110mgs/lit
Alkalinity of the raw water sample due to HCO3- = 110mgs/lit

2.3.3 Hardness:
Hardness is the property of water which prevents the formation of lather or foam readily
with soap. Water is said to be hard due to the presence of various dissolved salts of calcium,
magnesium and iron. Hardness is expressed as ppm of .
Hardness can be classified into two types
1) Temporary hardness which can be removed by mere boiling and
2) Permanent hardness which can be removed by certain water treatment
process like lime-soda process, zeolite process etc.
Temporary and permanent hardness
S.No Temporary hardness Permanent hardness

It is due to the presence of It is due to the presence of chlorides

1. bicarbonates of calciumand and sulphates of calcium and
magnesium. magnesium.
It can be removed easily by boiling
2. because bicarbonates are converted It cannot be removed by boiling.
into insoluble carbonates.

Salts which cause permanent

Salts which cause temporary
hardness – calcium chloride,
3. hardness – calcium bicarbonate,
magnesium chloride, calcium
magnesium bicarbonate etc.
sulphate etc.

Expression of Hardness

Hardness of water is expressed in terms of equivalent amount of CaCO 3. The reason for
selecting calcium carbonate as reference is (i) the molecular weight of calcium
carbonate is 100 and equivalent weight is 50 which makes the calculations easier.
(ii) CaCO3 is highly insoluble in water. The mathematical form of expression of
hardness
Hardness in equivalent of CaCO3
= Weight of hardness causing salt x Molecular mass of CaCO 3
Molecular mass of hardness causing salt

2.3.4 DETERMINATION OF HARDNESS (EDTA METHOD)

EDTA is ethylene diamine tetra acetic acid. The structure of EDTA is

Since EDTA is insoluble in water, its sodium salt is used as a complexing agent.
PRINCIPLE:
Estimation of hardness by EDTA method is based on the principlethat EDTA forms
metal complexes with hardness producing metal ions present in water. These complexes are
stable when the pH is maintained between 8-10. In order to maintain the pH, buffer solution
(ammonium chloride + ammonium hydroxide mixture) is added. The completion of the
complexation reaction is indicated by Eriochrome black-T indicator. When this indicator is
added to the sample water it forms indicator-metal unstable complexes of wine red colour.

(Unstable complex) Wine red

When this solution is titrated against EDTA, it replaces the indicator from the indicator
complex. When all the hardness causing ions are complexed by EDTA, the indicator is set
free and the end point is the sharp change in colour from wine red to steel blue. The total
hardness is thus determined.

(Stable complex)Steel blue

The temporary hardness is removed by boiling and after the removal of the precipitate by
filtration; the permanent hardness in the filtrate is determined by titration with EDTA as
before.

Total hardness - permanent hardness = temporary hardness.

EXPERIMENTAL PROCEDURE:

TITRATION I: STANDARDISATION OF EDTA

A known volume of the standard hard water (Vml) is pipetted out and treated with 10 ml of
buffer solution and 2 to 3 drops of EBT indicator .The solution is then titrated against the
standard EDTA solution taken in the burette. The end point is the colour change from wine
red to steel blue.
Let the volume of EDTA consumed be V1 ml.

TITRATION II: ESTIMATION OF TOTAL HARDNESS

A known volume of the sample hard water is pipetted out and treated with 10 ml of buffer
solution and 2 to 3 drops of EBT indicator .The solution is then titrated against the standard
EDTA solution taken in the burette. The end point is the colour change from wine red to
steel blue.

Let the volume of EDTA consumed be V2 ml.

TITRATION III: ESTIMATION OF PERMANENT HARDNESS

250 ml of the sample hard water is taken in a beaker. The solution is boiled till the volume
is reduced to 50 ml. The residue is filtered and the filtrate is made up to 250ml using
distilled water. From this made up solution a known volume is pipetted out and treated with
10 ml of buffer solution and 2 to 3 drops of EBT indicator. The solution is then titrated
against the standard EDTA solution taken in the burette. The end point is the colour change
from wine red to steel blue.

Let the volume of EDTA consumed be V3 ml.

CALCULATION:

STANDARDISATION OF EDTA:
1 ml of std. hardwater = 1mg of CaCO3
50 ml of std. hardwater = 50 mgs of CaCO3 eq.
50ml of std.hard water consumes = V1 ml of EDTA
V1 ml of EDTA
∴ V1 ml of EDTA = 50 mgs of CaCO3 eq. hardwater
(or)
1 ml of EDTA = 50
V1 mgs of CaCO3 eq. hardwater

TOTAL HARDNESS:
50 ml of unknown hard water sample consumes = V2 ml of EDTA.
i.e., V ml of sample hardwater = V2 ml of EDTA.
= V2 x 50/V1 mg of CaCO3eq.
(Since 1 ml of EDTA = V/V1 mg of CaCO3eq.)

∴ 1 ml of sample hardwater = V2X50 mg of CaCO3eq hardness

V1

∴1ml of EDTA=50/V1 mg of CaCO3eq.

1000 ml of sample hard water = V2X50 X1000

V1 50
= 1000X V2
V1 {mgs of CaCO3 eq
hardness}

∴ TOTAL HARDNESS = 1000XV2

V1 ppm
 PERMANENT HARDNESS:

50 ml of the same hard water sample after boiling, filtering, etc, consumes
= V3 ml of EDTA
= V3 x 50/V1 mg of CaCO3eq.
∴ 1000 ml of given hard water = V3/50 x 1000
V1 50
= 1000xV3/V1 mgs of CaCO3 eq hardness
∴ Permanent hardness =1000 xV3/V1 ppm

TEMPORARY HARDNESS
Temporary hardness =Total hardness – permanent hardness
= 1000 X V2 – 1000 X V3
V1 V1

∴ Temporary hardness = 1000 (V2-V3) ppm

V1
2.3.5 NUMERICALS IN HARDNESS
1. Calculate the hardness of water containing 146 mg/l of magnesium bicarbonate.

Hardness in equivalent of CaCO3

= Weight of hardness causing salt x Molecular mass of CaCO3
Molecular mass of hardness causing salt
= 146 x100
146
Hardness = 100ppm
2. 100ml of the water sample required 20ml of 0.01M EDTA for the titration with
Eriochrome Black-T indicator 100ml of the same water sample after boiling and
filtering required 10ml of 0.01M EDTA. Calculate the total, carbonate and non
carbonate hardness of the sample.

Solution We know that

1ml of 1M EDTA =100mgs of CaCO3
1ml 0f 0.01 M EDTA = 1mg of CaCO3
i)Total Hardness

100ml of the sample of water required =20ml of 0.01M EDTA

= 20X1mgs = 20mgs of CaCO3

∴ 1000ml of the sample of water required = 20X1000

100 mgs of CaCO3
= 200mgs of CaCO3
Total hardness = 200mgs/lit or ppm
 ii) Non-Carbonate Hardness (NCH)

100ml of the sample water sample after boiling,

filtering consumes =10ml of 0.01M EDTA
= 10X1mgs
= 10mgs of CaCO3
∴ 1000ml of sample of water is equal to = 10X1000
100 mgs
=100 mgs of CaCO3 equivalent
Permanent hardness of the water sample =100 ppm

iii) Carbonate Hardness (CH)

Carbonate hardness = Total hardness-Non-Carbonate hardness
= 200-100=100ppm

Carbonate hardness =100ppm

3. 100ml of a water sample requires 20ml of EDTA solution for titration. 1ml of
EDTA solution is equivalent to 1.1 mgs of CaCO3. Calculate hardness in ppm.

Given
1ml of EDTA solution = 1.1mgs of CaCO3
Therefore,
20ml of EDTA solution = 20X1.1mgs of CaCO3
= 22mgs of CaCO3
100ml of water sample requires = 22X1000
100 mgs of CaCO3

Hardness = 220mgs/lit or ppm

4. 100ml of a sample of water requires 15ml of 0.01M EDTA for titration using
EBT- indicator. In another experiment, 100ml of the same sample was boiled to
remove hardness, the precipitate was removed and cold solution required 8ml of
0.01 M EDTA using EBT-indicator. Calculate i) Total hardness ii) Permanent
hardness iii) Carbonate hardness in terms of mg/lit of CaCO 3.

(i) Total Hardness

100ml of the sample of water required =15ml of 0.01M EDTA
= 15X1mgs = 15mgs of CaCO3
∴1000ml of the sample of water required = 15X1000
100 mgs of CaCO3
= 150mgs of CaCO3
Total hardness = 150mgs/lit or ppm
 5. 100ml of a sample of water requires 15ml of 0.01M EDTA for titration using
EBT- indicator. In another experiment, 100ml of the same sample was boiled to
remove hardness, the precipitate was removed and cold solution required 8ml of
0.01 M EDTA using EBT-indicator. Calculate i) Total hardness ii) Permanent
hardness iii) Carbonate hardness in terms of mg/lit of CaCO 3.

Solution
We know that

1ml of 1M EDTA = 100mgs of CaCO3

1ml of 0.01 M EDTA = 1mg of CaCO3

i) Total Hardness
100ml of a sample of water required = 15ml of 0.01M EDTA
= 15X1mgs = 15mgs of CaCO3

∴ 1000ml of sample of water in equivalent to =15X1000

100 mgs of CaCO3

= 150 mgs of CaCO3 equivalent

Total hardness = 150mgs/lit or ppm

ii) Permanent Hardness (NCH)

100ml of the same water sample after boiling,
filtering consumes = 8.0ml of 0.01M EDTA
= 8.0X1mgs
= 8.0mgs of CaCO3

∴ 1000ml of sample of water is equal to = 8.0X1000

100
= 80mgs of CaCO3 equivalent
Permanent hardness of the water sample = 80ppm

iii) Temporary Hardness (CH)

Temporary hardness = Total hardness-Permanent hardness
= 70ppm
Temporary hardness = 70ppm
6. 0.28 gm of CaCO3 was dissolved in HCl and the solution was made upto one litre
with the distilled water. 100ml of the above solution required 28ml of EDTA
solution on titration. 100ml of hard water sample required 33ml of same EDTA
solution on titration. 100ml of this water after boiling cooling and filtering
required 10ml of EDTA solution on titration. Calculation the temporary and
permanent hardness of water.

Solution
Given
1000ml of std.hard water contains=0.28gms of CaCO3
i.e., 1000ml of std. hard water contains
= 0.28x1000 mgs of CaCO3
= 280 mgs of CaCO3
∴ 1ml of std.hardwater = 0.28mg of CaCO3

28ml of EDTA = 100ml of the std.hard water

= 100x 0.28 mgs of CaCO3

= 100x0.28
28
1ml of EDTA = 1mgs of CaCO3

i) Total hardness

100ml of std.hardwater = 33ml of EDTA

= 33X1mgs of CaCO3
= 33 mgs of CaCO3
∴ 1000ml of hard water = 33X1000
100
Total hardness = 330mgs/lit (or)ppm

ii) Permanent hardness (NCH)

100ml of the same water after boiling,
Cooling and filtering required = 10ml of EDTA
= 10X1 mgs of CaCO3
= 10mgs of CaCO3
∴ 1000ml of the water = 10X1000 mgs of CaCO3
100
Permanent hardness =100mgs/lit (or) ppm

iii) Temporary hardness (CH)

Temporary hardness =Total hardness-permanent

= 330-100
Temporary hardness = 230mgs/lit (or) ppm
7. A water sample contains 73mgs of Mg (HCO3)2 per litre. Calculate the hardness
interms of CaCO3 equivalents?

Given, Amount of Mg(HCO3)2 = 73mgs/lit

Mol. Wt. of Mg(HCO3)2 = 146
∴ Amount equivalent to CaCO3 = 73X100
146
= 50mgs/lit

8. What is the hardness of a solution containing 0.585grams of MgSO 4 per litre?

Solution

Given i) The amount of NaCl = 0.585 X1000mgs

= 585mgs
ii)The amount of MgSO4 =0.6X1000mgs
= 600mgs
Note: NaCl does not cause hardness, so it is ignored.
Hardness equivalent to CaCO3 = Amount of hardness producing salt X100
Mol. Wt of hardness producing salt
We know that, the mol.weight of MgSO4 =120
∴ Hardness equivalent to CaCO3 = 600X100
120
= 500mgs/lit (or) 500ppm.

9. Calculate the hardness of a water sample containing 2.4 mg of calcium chloride in

500ml of water?

Solution
Given
The amount of CaCl2 = 2.4 mgs/500 ml (or)
The amount of CaCl2 = 4.8mgs/lit

∴ Amount Hardness equivalent to CaCO3 = Amount of hardness producing salt X100

Mol. Wt of hardness producing salt
We know that, the molecular weight of CaCl2 = 111
∴ Amount equivalent to CaCO3 = 4.8X100
111

= 4.324mgs/lit
10. 50ml of sample of hard water required 35ml of 0.01M EDTA in the titration. 50ml
of the same sample of water after boiling required 12ml of 0.01M EDTA. Calculate
total and temporary hardness of water?

Solution
Given
We know that

1ml of 1M EDTA =100mgs of CaCO3

1ml 0f 0.01 M EDTA = 1mg of CaCO3

i) Total Hardness

50ml of the sample of water required =35ml of 0.01M EDTA

= 35X1mgs = 35mgs of CaCO3
∴ 1000ml of the sample of water required = 35X1000/100 mgs of CaCO3
= 350mgs of CaCO3
Total hardness = 350mgs/lit or ppm

ii) Permanent hardness (NCH)

50ml of the sample water sample after boiling,

filtering consumes =12ml of 0.01M EDTA
= 12X1mgs
= 12mgs of CaCO3
∴ 1000ml of sample of water is equal to = 12X1000/100 mgs
=120 mgs of CaCO3 equivalent
Permanent hardness of the water sample =120 ppm

iii) Temporary hardness (CH)

= Total hardness-Non-Carbonate hardness
= 350-120=230ppm

Temporary hardness =230ppm

 2.4 BOILER FEED WATER
The Water fed into the boiler for the production of steam is called boiler feed water. If
hard water obtained from natural sources is fed directly into the boilers, the following
troubles may arise.

Boiler troubles or disadvantages of using hardwater in boilers

1. Sludge and Scale
2. Caustic embrittlement
3. Priming and Foaming
4. Boiler corrosion

2.4.1.Sludge and Scale

S.No Sludge scales

Sludges are soft and non-adherent Scales are hard deposits which stick very
1.
precipitates firmly to the inner surface of the boiler.

2. Sludges can be removed easily. Scales are very difficult to remove.

Sludges can transfer heat to some extent Scales are bad conductors of heat and are
3.
and are less dangerous. more dangerous.

Sludges are formed by substances like Scales are formed by substances like
4. magnesium chloride, calcium chloride calcium sulphate, magnesium hydroxide
etc. etc.

2.4.2 Caustic embrittlement

It is the phenomenon in which the boiler material becomes brittle due to the
accumulation of caustic substances. Boiler water usually contains a small portion of
Na2CO3. In high pressure boilers, this hydrolyses to give sodium hydroxide and makes the
boiler water more alkaline.
 These dilute alkaline boiler water flows into the minute hair cracks and crevices by
capillary action. There the water evaporates and the concentration of caustic soda
increases progressively. The concentrated alkali present in the crevices, cracks, joints,
bents, rivets etc., sets up minute localized electrochemical cells which convert iron in the
boiler plate to brittle sodium ferroate.

2.4.3 Priming and Foaming

During the production of steam in the boiler, due to rapid boiling some particles of
liquid water are carried along with steam. Steam containing droplets of water is called wet
steam. The process of wet steam formation is called as priming.
Priming is due to,

i) Very high water level.

ii) Presence of foam on the surface

iii) High steam velocity

Priming can be prevented by maintaining low water level in the boiler and by removing oily
materials present in the water.

The formation of stable bubbles above the surface of water is called as foaming. It is caused
by the presence of soluble impurities like alkaline metal salts and oil which form soap.
Foaming can be controlled by the action of anti- foaming agents like synthetic poly amides.

2.4.4 Boiler corrosion

Boiler corrosion is the decay of boiler material due to chemical or electrochemical

attack of its environment. The boiler corrosion is due to dissolved oxygen, dissolved
carbondioxide and dissolved acids produced by the hydrolysis of dissolved salts and
dissolved alkali.

i) Corrosion due to dissolved oxygen:

Dissolved oxygen in water is mainly responsible for the corrosion of boiler. The dissolved
oxygen in water attacks the boiler material at high temperature.

2Fe + 2H2O + O2 2Fe (OH) 2

4Fe (OH) 2 +O2 + 2H2O 2[Fe2O3. 3H2O] (yellow rust)

Dissolved oxygen can be removed from water by chemical and mechanical methods.
Sodium sulphites and hydrazine are some of the chemicals used for removing dissolved
oxygen.
2Na2SO3 + O2 2Na2SO4

N2H4 + O2 N2 + 2H2O

Dissolved oxygen can also be removed from water by mechanical deaeration. In this
process, water is sprayed slowly through the perforated plates fitted inside the tower.
Vacuum is applied to this tower and the sides of the tower are also heated. High
temperature and low pressure reduce the quantity of dissolved oxygen in the water.

ii) Corrosion due to dissolved CO2

Dissolved CO2 in water produces carbonic acid which is corrosive in nature.

CO2 + H2O H2CO3

CO2 can be removed from water by chemical or mechanical means. In the chemical
method CO2 is removed by the addition of a calculated quantity of NH4OH.

2 NH4OH + CO2 (NH4)2CO3 + H2O

Dissolved CO2 along with oxygen can be removed by mechanical deaeration.

iii) Corrosion due to dissolved acids:

Acids produced from salts that are dissolved in water during the boiler operations is mainly
responsible for corrosion of boilers. Certain salts like MgCl2, CaCl2 etc. on hydrolysis at
higher temperature produce hydrochloric acid which corrodes the boiler.

MgCl2 + 2H2O Mg (OH) 2 + 2HCl

The liberated acid can produce rust in the following way.

Fe +2HCl FeCl2 + H2

FeCl2 + 2H2O Fe (OH)2 + 2HCl

4Fe (OH)2 +O2 +2H2O 2[Fe2O3.3 H2O] (rust)

Corrosion by acids can be avoided by the neutralization of acids using alkali.

2.5 SOFTENING OR CONDITIONING PROCESSESS:

The process of removing the hardness producing salts from water is known as
softening or conditioning of water.
Softening of water can be done in two methods.
i) External conditioning
ii) Internal conditioning

2.5.1 EXTERNAL CONDITIONING

DEMINERALISATION PROCESS :

PRINCIPLE:

In this process all the cations and anions except H+ and OH- ions present in water
are completely removed by ion exchange resins and hence water of zero hardness can
be produced. Ion exchange resins are cross linked polymeric molecules. The
functional groups attached to these molecules are responsible for the ion exchange
reactions.
Cation exchange resin contains acidic functional groups eg, sulphonic acid and
carboxylic acid. It is generally represented as RH2. They exchange their H+ ions with
cations present in the hard water.
Anion exchange resin contains quaternary ammonium or phosphonium
hydroxides as functional groups. It is generally represented as R’ (OH) 2. They
exchange their hydroxyl groups with anions present in the hardwater.
PROCESS:

The equipment consists of two exchange columns of cation and anion . The natural water is
first fed into the cation exchanger column where it exchanges its hydrogen ion with other
cations present in the water.
R-H2+ CaSO4 → R-Ca + H2SO4

R-H2+ MgCl2 → R-Mg + 2HCl

R-H2+2NaHCO3 → R-Na2 + 2H2CO3

R-H2+Mg (NO3)2 → R-Mg + 2HNO3

The water coming out of the cation exchange column will be highly acidic and it is then
passed through an anion exchange column. It exchanges hydroxyl ions with other anions
present in the water.

The water obtained is free from all sorts of ions and it is called demineralised water or de
ionized water. Demineralised water is soft water and is free from any type of ions.

REGENERATION:

On prolonged use of ion exchangers, it will lose its exchanging capacity due to the
complete removal of hydrogen and hydroxyl ions. In order to regenerate the resins, dilute
solutions of strong acids like HCl or H2SO4 is passed through the cation exchanger and
dilute solutions of strong bases like NaOH is passed through the anion exchanger.
 ADVANTAGES AND DISADVANTAGES:

(i) Water of zero hardness can be produced by this method.

(ii) Highly alkaline or acidic natural water can be treated by this method.

(iii) Turbid water cannot be treated by this method since the active centers will be
blocked by suspended particles.

(iv) The ion exchange resins are costly.

2.5.2 INTERNAL CONDITIONING METHODS

It involves the removal of scale forming substance, which were not completely removed
in the external treatment, by adding chemicals directly into the boiler.

i) COLLOIDAL CONDITIONING:

Scale formation can be avoided by adding chemicals like lignin, agar- agar gel, kerosene
etc. to the boiler water during boiler operations. When scale forming compounds get
precipitated, these chemicals get coated over them and make them loose and slimy
precipitates which settles down and can be removed by blow down operation.

ii)CARBONATE CONDITIONING:

Scale formation can be avoided by addingcalculated quantity of sodium carbonate to

boiler water during boiler operations. The scale forming salts are converted into insoluble
loose precipitates of respective carbonates which can be removed by blow-down operations.
Excess of sodium carbonate added may lead to caustic embrittlement.

CaSO4+ Na2CO3 CaCO3↓ + Na2SO4

(Scale (non scale

Forming salt) forming precipitate)

iii) PHOSPHATE CONDITIONING:

Scale formation can be avoided by adding sodium phosphate. It is used in high pressure
boilers. The phosphate reacts with Ca2+ and Mg2+ salts to give soft sludges of calcium and
magnesium phosphates.
3CaSO4 + 2Na3PO4 Ca3 (PO4)2 + 3Na2SO4
Generally 3 types of phosphates are employed
a.Tri sodium phosphate: Na3PO4 (too alkaline) used to treat too acidic water.
b.Disodium hydrogen phosphate: Na2HPO4 (weakly alkaline)- used for weakly acidic
water.
c.Sodium dihydrogen phosphate: NaH2PO4 (acidic) - used for alkaline water.
iv) CALGON CONDITIONING:

Calgon is sodium hexa meta phosphate Na2 [Na4 (PO3)6]. This substance interacts with
scale forming ions forming a highly soluble complex and thus prevents the precipitation of
scale forming salts.

2CaSO4 + Na2 [Na4 (PO3)6] Na2[Ca2(PO3)6] + 2Na2SO4

The complex Na2 [Ca2 (PO3)6] is soluble in water and there is no problem of sludge
disposal.

2.6 DESALINATION

Desalination is the process of removal of salt from sea water. It is done by either of the
following methods

a) Reverse osmosis or
b) Electro – dialysis.

2.6.1 REVERSE OSMOSIS

This is a desalination method for converting salt water into potable water. By applying
pressure greater than osmotic pressure, the solvent is made to move from higher
concentration side to lower concentration side through a semi permeable membrane. This is
called Reverse Osmosis.
When two solutions of different concentration are separated by means of a semi permeable
membrane, the solvent molecules migrate from the side of lower concentration to that of the

side of higher concentration due to osmotic pressure and this process is known as osmosis. If
the pressure on the higher concentration solution side is increased more than that of the
osmotic pressure then the flow of solvent is reversed i.e. the solvent molecules migrate from
the side of higher concentration to the side of lower concentration through the semi –
permeable membrane.

The equipment consists of two chambers separated by means of semi permeable membrane
usually made of polymethaacrylate, poly sulphone, cellulose acetate etc. sea water is filled
in the upper chamber and the other chamber is filled with pure water. When high pressure is
applied on the sea water side, the pure water molecules passes through the semi permeable
membrane and migrates to the lower chamber.

Advantages
i) The life time of the membrane is high, and it can be replaced within few
mintues.
ii) It removes ionic as well as non-ionic, colloidal impurities.
iii) Due to low capital cost, simplicity, low operating, this process is used for
converting sea water into drinking water.

2.6.2 ELECTRODIALYSIS

The principle of electrodialysis process is that the cations and anions are pulled out from
the sea water under the influence of an electric field using electrodes and ion selective
membranes. Thus when electric current is passed through the saline water, the Na + ions
moves towards the cathode through cation selective membrane and the Cl- ions moves
towards the anode through the anion selective membrane. Thus the concentration of brine in
alternate chamber is reduced. Desalined water is removed while concentrated brine will be
replaced periodically.
 The cation selective membrane is permeable to cations only due to the presence of
negatively charged functional groups such as RCOO - in the membrane. Similarly anion
selective membrane is permeable only to anions due to the presence of positively charged
functional groups such as R4N+ in the membrane. Usually ion selective membranes are
polystyrene based polymers.