WATER

Hardness of water : Hardness of water defined as which prevent the lathering of soap. This is due to presence of in
+2 +2
water of certain salts of Ca , Mg and other Heavy metals dissolved in it.
Soaps are Sodium or Potassium salts of higher fatty acids like Oleic acid or Palmitic acid or stearic acids.
Hardwater: Water which does not produce lather with soap solution is called hard waer.
Soap with hardwater reactions:
2C17H35COONa + CaCl2 (C17H35COO)2 Ca + 2NaCl
Sodium stearate calcium stearate(insoluble)
2C17H35COONa + MgSO4 (C17H35COO)2 Mg + Na2SO4
magnesium stearate(insoluble)

Soft water: Water which produce lather easily on shaking with soap solution is called soft water.
Such a water,does not contain dissolved calcium and magnesium salts in it.
2C17H35COONa + H2O C17H35COOH + NaOH
Sodium stearate stearic acid (Lather)
Degree of hardness: Hardness of water is expressed in terms of calcium carbonate equivalents. The weights of different
salts causing hardness are converted to weight equivalent to that of CaCO 3.
If a sample of water contains two or more than two salts, their quantities are converted in equivalent to that of
CaCO3 and then the sum will give the total hardness. CaCO3 is selected for expression of the degree of hardness,
because the mol.wt. of CaCO3 is 100,. which is easy for calculation and CaCO3 is an insoluble salt. All the dissolved salts
of calcium are precipitated as CaCO3.
Hardness of the water causing salt in terms of CaCO3 = Amount of the hardness causing salt ×100
mol. wt. of the hardness causing salt
Different types of water have different degrees of hardness:

Hardness Name of water

0-70 mg/liter Soft water
70-150 mg/liter Moderate hard water
150-300 mg/liter Hard water
300 mg/liter &above Very hard water
Equivalents of CaC0 3: 100 parts by weight of CaCO3 hardness must be equivalent
162 parts by weight of Ca(HCO3)2 hardness .
146 parts by weight of Mg(HCO3)2 hardness .
136 parts by weight of CaSO4 hardness.
111 parts by weight of CaCl2 hardness.
164 parts by weight of Ca(NO3)2 hardness.
120 parts by weight of MgSO4 hardness.
95 parts by weight of MgCl2 hardness.
148 parts by weight of Mg(No3)2 hardness.
TYPES OF HARDNESS:
Hardness of water is mainly TWO types
1. Temporary Hardness
2. Permanent Hardness
1. Temporary Hardness:It is mainly caused by the presence of dissolved Bicarbonates of Calcium, Magnesium and the
carbonate of Iron.
Temporary hardness of water mainly responsible salts are- 1. Calcium bicarbonate Ca(HCO3)2 2. Magnesium
bicarbonate Mg(HCO3)2
When bicarbonates are decomposed a, yielding insoluble carbonates or hydroxides, which are deposited as a crust at the
bottom of vessel. Heat
Ca (HCO3) 2 CaCO3 + H2O + CO2
Calcium bicarbonate

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

Magnesium bicarbonate
Temporary Hardness can be largely removed by mere Boiling of water.
Temporary Hardness is also known as….Carbonate Hardness or Alkaline Hardness
2. Permanent harness: It is due to the presence of dissolved Chlorides and sulphates of Calcium, Magnesium, Iron and
other metals
Permanent hardness responsible salts are…. CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2 (SO4)3.
Permanent Hardness cannot be removed by boiling , but it can be removed by the use of chemical agents.
Permanent Hardness also known as…. Non-Carbonate Hardness or Non-Alkaline hardness.
DETERMIANATION OF HARDNESS OF WATER: Determination of hardness of water can be done by using 3 methods.
1.ESTIMATION OF HARDNESS BY EDTA METHOD:
The analysis is done by complexometric titration using standard EDTA and EBT as an indicator.
PRINCIPLE: In this complexometric Titration, the water sample is titrated with standard solution of Di sodium salt of EDTA
using EBT indicator. EBT indicator when added to hard water at pH = 10, forms weak complexes with calcium and
magnesium present in hard water. It results in the formation of wine-red Ca-EBT or Mg-EBT complexes which are
unstable. When hard water comes in contact with EDTA, at PH 9-10, Ca+2 and Mg +2 forms stable, colorless complex
with EDTA, releasing the free indicator(blue) so, the colour changes from wine-red to blue at the endpoint.
Ethylene diamaine tetra acetic acid

EDTA can form 4 to 6 dative bonds with cations like Calcium Magnesium.

(Ca2+ & or Mg2+ ) + EBT → [Ca – EBT ] complex & or [Mg – EBT] complex
blue wine-red wine-red

PROCEDURE:
1. Preparation of standard hard water: dissolve 1g of pure, dry CaCO3 in minimum quantity of dil.HCl and then
evaporate the solution to dryness on a water bath. Dissolve the residue in distilled water to make 1 Litre solution. Each ml
of this solution thus contains 1mg of CaCO3 equivalent hardness.
1 mL hard water solution = 1mg of CaCO3 equivalent hardness.

Molarity of standard hard water (M1) = Weight of CaCO3 x 1000

Mol. Wt. Of CaCO3 100

2. Standardization of EDTA solution: - Pipette out 20 ml of standard hard water into a conical flask. Add 5ml of buffer
solution and few drops of Eriochrome Black-T indicator, which is originally blue, would assume a wine red colour. Titrate it
with EDTA solution taken in the burette, till the wine red colour changes to blue.
This is the end point. Let the burette reading be V2 ml
M1V1 = M2V2 n1=n2= 1

n1 n2

Molarity of EDTA (M2) = M1V1

V2
3.Determination of total hardness: - Pipette out 20 ml of tap water into a conical flask. Add 2ml of buffer solution and 2
to 3 drops of EBT indicator. Colour changes to wine red colour. Titrate with EDTA solution. Wine red colour changes to
blue colour. Note burette reading .let the volume of the solution be V2 ml . Repeat the titration 2 or 3 times.

M3V3=M2V2

Molarity of sample water (M3) = M2V2

V3
Total hardness of sample water = M 3 x 100 x 1000 (ppm)
4. Determination of permanent hardness: - Take 100ml of hard water into a conical flask and boil the water till the
volume reduces to 50 ml .Add 50 ml of distilled water to it and pipette out 20 ml of this hard water into a comical flask and
add 2ml of buffer solution,3 drops of EBT indicator. Colour changes to wine red colour. Titrate with EDTA solution wine red
colour changes to blue colour. Note the burette reading at the volume of EDTA solution, V 2 (zml). Repeat the titration 2 or
3 times.

M4V4=M2V2

Molarity of sample water (M4) = M2V2

V4
Permanent hardness of water = M 4 x 100 x1000 (ppm)

Temporary hardness = Total hardness - Permanent hardness

Advantages of EDTA method:

This method is definitely prep arable to the other methods, because of the
1. Greater accuracy
2. Convenience
Numerical Problems refer text book:
BOILER TROUBLES:
Some of the boiler troubles caused by the use of unsuitable water are.
1. Priming and Foaming
2. Caustic embrittlement
3. Boiler corrosion and
4. Sludge and Scale formation
1. Priming: it may defined as the violent or rapid boiling of water occurring in the boiler which results in carrying out of
water with steam in the form of a spray. This process of wet steam formation is called priming.
Causes: Priming is mainly caused by
1. The presence of large amount of dissolved solids,
2. high steam velocities,
3. Sudden increase in steam production rate.
4. Sudden steam demand which leads to sudden boiling,
5. When the water level rises due to foaming and
6. due to defective boiler design and improper operation
Prevention: Priming can be controlled by
1. Fitting mechanical steam purifier
2. Avoiding rapid change in steam-rate
3. keeping the water level low and avoid sudden steam demands.
4. Efficient softening and filtration of the boiler feed water.
5. Proper boiler design
6. Blow-Down of the boiler (replacing the water concentrated with impurities with fresh water)

Foaming: Foaming is the formation of persistent foam or bubbles above the surface which do not break easily.
Causes:
The main reason for foaming is being presence of fatty acids(oils) and alkalies in boiler feed water. Fatty acids react with
alkalies to form soaps which lowers the surface tension of water and thus increase the foaming tendency.
Prevention:
Foaming can be controlled by
1. Using anti-foaming chemicals,
2. Removal of concentrated boiler water and replacing it by fresh feed water by blow down.
3. Removing oil from boiler water by adding compounds like sodium aluminate.

Caustic Embrittlement: The formation of brittle and incrystalline cracks in the boiler shell is called caustic embrittlement.

Cause: It is a type of boiler corrosion and the main reason for this, is the presence of alkali-metal carbonates and
bicarbonates in feed water and also the presence of sodium sulphate. In lime-soda process, it is likely that, some residual
Na2CO3 is still present in the softened water.
This Na2CO3 decomposes to give NaOH and CO2, due to which the boiler water becomes “Caustic”.
Na2CO3 + H2O NaOH + CO2
This caustic water flows inside the boiler and causes some minutes hair-cracks, by capillary action. On evaporation of
water, the dissolved caustic soda increases its concentration which attacks the surrounding area, thereby dissolving Iron
of boiler as Sodium ferroate. This causes embrittlement of boiler parts such as bends, joints, reverts etc, due to which the
boiler gets fail.
Caustic cracking can be explained by considering the following concentration cell:
Iron at bends, joints, reverts etc.| Conc. NaOH solution | Dil. NaOH solution|Iron at plane surfaces

PREVENTION:
1. By maintaining the pH value of water and neutralization of alkali.
2. By using Sodium Phosphate as softening reagents, in the external treatment of boilers.
3. By adding Tannin or Lignin or Sodium sulphate which prevents the infiltration of caustic-soda solution blocking the hair-
cracks.
Boiler Corrosion: The chemical or electro chemical eating away of metal by its environment in a boiler is known as boiler
corrosion. The main reason for this problem is the presence of
a. Dissolved oxygen: Water usually contains about 8 ml of dissolved oxygen per liter at room temperature. Dissolved
oxygen in water, in presence of high temperature, attacks boiler material:
2Fe + 2H2O + O2 2 Fe (OH)2
4 Fe (OH) 2 + O2 2[ Fe2O3.2H2O]
Removal of dissolved oxygen: 1. By adding calculated quantity of sodium sulphite or sodium sulphide.
2Na2SO3 + O2 2Na2SO4
Na2S + O2 Na2SO4
2. By adding hydrazine.
Hydrazine is an ideal internal treatment chemical for the removal of dissolved oxygen. It reacts with oxygen, forming
nitrogen and water. Nitrogen is harmless.
N2H4 N2 + 2H2O
3. By mechanical deaeration: All gases can be removed with the help of degassifier or deaerator.

Water is sprayed through a perforated plate,fitted in the deaeration tower, heated from sides and connected to vacuum
pump.High temperature,low pressure and large exposed surface area reduces dissolved oxygen and other gases in water.
Recently Azamina 8001-RD a poly organic compound, has been employed for degassing of water.

b. Dissolved carbon dioxide: This has a slow corrosive effect on the boiler material. Carbon dioxide is also released
inside the boiler, if water used for steam generation contains bicarbonate,
Heat
Mg(HCO3)2 MgCO3 + H2O + CO2
Disadvantage: carbon dioxide has a slow corrosive effect on the boiler material by producing carbonic acid,
CO2 + H2O H2CO3
Removal of carbon dioxide:
1. By adding calculated quantity of ammonia,
2NH4OH + CO2 (NH4)2CO3 + H2O
2. By mechanical – deaeration process along with oxygen.
c. Acids from dissolved salts: Water containing dissolved magnesium salts liberates acids on hydrolysis.
MgCl2 + 2H2O Mg(OH)2 + 2HCl
The liberated acid reacts with iron in chain – like reactions producing HCl again and again.
Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl
Consequently, presence of even a small amount of MgCl2 will cause corrosion of iron to a large extent.
PREVENTION:
a. By using softened water.
b. by frequent blow down of water
c. addition of inhibitors like sodium silicate, sodium phosphate and sodium aluminate which form a thin film on the surface
of boiler.
4. Sludge and Scale formation:
In boilers, because of continuous evaporation of water, the concentration of salts increase progressively and after the
saturation point is reached, precipitate form on the inner walls of boiler.
SLUDGE: Sludge is a soft, loose and slimy precipitate formed within the boiler. It is formed at comparatively colder
portions of the boiler and collects in the area where flow rate is slow.
These are formed by substances which have greater solubilities in hot water than in cold-water.
Eg. MgCO3, MgCl2, CaCl2, MgSO4.
DIS-ADVANTAGES:
a. As the sludge‟s are poor conductor of heat they cause loss of heat.
b. The working of the boiler is disturbed because of chocking of pipes by the sludge.
PREVENTION:
a. By using well softened water.
b. By blowdown of a portion of concentrated water frequently.
SCALES: Scales are hard, adhering precipitates formed on the inner walls of the boilers. They stick very firmly on to the
inner wall surface and are difficult to remove.
 Causes of scale formation:
a. Decomposition of calcium bicarbonate: In low pressure boilers, CaCO3 causes scale formation.
Ca(HCO3)2 CaCO3 + H2O + CO2
In High pressure boilers, CaCO3 becomes soluble. CaCO3 + H2O Ca(OH)2 + CO2
b. Decomposition of Calcium sulphate: The solubility of CaSO4 in water decreases with rise of Temperature. In super
heated water CaSO4 is insoluble.
c. Hydrolysis of Magnesium salts:
Dissolved Magnesium salts undergo hydrolysis forming Mg(OH)2 precipitate.
MgCl2 + 2H2O Mg(OH)2 + 2 HCl
Mg(OH)2 so found by hydrolysis of Magnesium salts is a soft type of scale.
d. Presence of Silica: Silica present in small quantities deposits as silicates like CaSiO3 and
MgSiO3. These are very difficult to remove.
Disadvantages:
a. wastage of fuel: The scale formation causes decreases of heat transfer. As a result over heating is required this
causes
b. Decrease in efficiency: scales deposited in the valves and condensers of the boiler cause choking which decreases
efficiency of boiler.
c.Danger of Explosion: The hot scale cracks because of expansion and water suddenly comes in contact with
overheated Iron plates. This causes in formation of large amount o steam suddenly. This results in sssssssshigh pressure
causing boiler to burst.
PREVENTION: Efficient softening of water is to be carried out.
Removal of scales:
1. If the scales formed is soft , it can be removed by wire brush,scrapper.
2. 2.by giving thermal shocks: it is done by heating to high temperatures and suddenly cooling with cold water.
3. By giving chemical treatement; CaCO3 scale is removedby wahing with 5-10% Hcl and CaSO4 scale is removed by
washing with EDTA solution.
WATER SOFTENING:
LIME-SODA METHOD: The basic principle of this process is to chemically convert all the soluble hardness causing
impurities into insoluble precipitates, which may be removed by settling and filtration.
For this purpose, a suspension of lime (Ca (OH)2) and sodium carbonate(soda-Na2CO3) is added.proper mixing of
chemicals and water is carried out. Calcium carbonate (CaCO 3) and magnesium hydroxide Mg (OH)2 so precipitated are
filtered off.
There are two different methods of lime-soda process.
Precautions to be followed during the process:

Dissolved Salt Chemical Reaction Treatment Required lime (L)

or soda (S)
As permanent magnesium hardness produces, permanent calcium hardness causing salts into the water, during lime
treatment these salts require both lime and soda treatment.
MgCl2 MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 L+S

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

Mg(NO3)2 Mg(NO3)2 + Ca(OH)2 Mg(OH)2 +Ca(NO3)2 L+S

Apart from hardness causing salts lime reacts with the
following salts.
CO2 + Ca(OH)2 CaCO3 + H2O L
CO2
(Dissolved Gas)
2 HCl + Ca(OH)2 CaCl2 + H2O ½L+½S
HCl and H2SO4 (one mole of lime reacts with ½ mole of HCl) L+S
(Free Acids) H2SO4 + Ca(OH)2 CaSO4 + 2H2O

2NaHCO3 + Ca(OH)2 CaCO3 + Na2CO3 + 2H2O ½ L + (-½ S)

NaHCO3, KHCO3
(bicarbonates) 2KHCO3 + Ca(OH)2 CaCO3 + K2CO3 + 2H2O
 Dissolved Salt Chemical Reaction Treatment Required lime (L)
or soda (S)
1. Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O L
(Temp. Hardness)
2. Mg(HCO3)2 Mg(HCO3)2 + 2Ca(OH)2 Mg(OH)2 + 2CaCO3 2xL
(Temp. Hardness) + 2H2O
(One mole of Mg(HCO3)2 reacts with 2 moles of
lime. Hence twice the amount of lime required.)
Permanent hardness causing calcium salts cannot be treated by lime as they do not react with lime.
only soda treatment is required.
CaCl2 No lime treatment
CaSO4 - do-
Ca(NO3)2 - do-

Soda (Na2CO3) reacts with only permanent hardness causing salts.

CaCl2 + Na2CO3 CaCO3 +NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Ca(NO3)2 + Na2CO3 CaCO3 + 2NaNO3

Substances like NaCl, Kcl, Na2SO4, SiO2, Fe(SO4)3 etc., do not impart any hardness, hence do not consume any
lime or soda. These salts should not be taken for calculation of lime and soda.

Dissolved Salt Chemical Reaction Treatment Required lime (L) or

soda (S)
1) One mole of lime reacts with ½ mole of
sodium bicarbonate, hence ½ the amount of
lime is required.
2) One mole of Potassium carbonate and
sodium carbonate are produced which
should be subtracted from soda treatment .

FeSO4, Al2(SO4)3, NaAlO2 FeSO4 + Ca(OH)2 Fe(OH)2 + CaSO4 L+S

(Coagulants) 2 Fe(OH)2 + H2O + O2 2 Fe(OH)3

Al2(SO4)3 +Ca(OH)2 2Al(OH)3 +3CaSO4+ H2O 3L + 3S

( One mole of Al2(SO4)3 reacts with 3 moles of lime
and produces 3 moles of CaSO4. )

NaAlO2 + 2H2O Al(OH)3 + NaOH -½ L

2 NaOH + CaCl2 Ca(OH)2 +2NaCl
2 NaOH = Ca(OH)2
NaOH Produced reacts with hardness causing salts and produces lime.
Hence its hardness must be subtracted from lime requirement.

Calculation of lime and soda required for the process: The amount of lime and soda required for the process is
calculated based on the chemical reactions involved as given below:
Amount of lime and soda required for softening:

100 parts by weight of CaCO3 = 74 parts by weight of Ca(OH)2 and 106 parts by weight of Na2CO3

Amount of lime required for softening:

2+ 2+ 2+
74 Temp. Ca hardness + (2 x temp. Mg hardness) + Permanent Mg hardness + CO2 + ½ HCl + H2SO4 + ½

100 NaHCO3 + ½ KHCO3 + FeSO4 + (3 x Al2(SO4)3) – ½ NaAlO2.

Hardness- all in terms of CaCO3 equivalence
Amount of Soda required for softening:
2+ 2+
106 Permanent Ca hardness + Permanent Mg hardness + ½ HCl + H2SO4 - ½
100 NaHCO3 - ½ KHCO3 + FeSO4 + (3 x Al2(SO4)3).
Hardness- all in terms of CaCO3 equivalence

COLD LIME-SODA PROCESS:

In this method, calculated quantity of chemicals(lime and soda) are mixed with water at room temperature. The precipitates
formed are finely divided, so they do not settle down easily. They cannot be filtered easily. Hence small amounts of
coagulants(like alum or aluminium sulphate or sodium aluminate)are added, which also helps in the removal of silica and oil.

Method of purification:
→ Raw water along with calculated amounts of chemicals(lime+ soda+ coagulant) are fed from the top into the inner
chamber, fitted with a vertical stirrer carrying a number of paddles.
→ As the water and chemicals flow down the chamber vigorous mixing and softening takes place.
→ Water comes into the outer chamber and rises up and sludge settles at the bottom.
→ The water passes through the wood-fibre filter and flows out from the outlet at the top.
→ The sludge settling at the bottom of the outer chamber is drawn off occasionally.
→ The water sample contains residual hardness of 50-60 ppm.
o o
HOT LIME SODA METHOD: It involves in treating water with softening chemicals at a temperature of 80 to 150 C.
This method consists of 3 parts.
Reaction tank: It has 3 separate inlets, one each for raw water, chemicals and super heated steam. After all these three
are taken in, they are thoroughly mixed. Reaction completes here.
Conical sedimentation tank: From the reaction tank the contents go to this tank, so that sludge settles down.
Sand filter: It has layers of fine and coarse sand which acts as filter and ensures complete removal of sludge form the
softened water.

A soft water with 15-30 ppm of residual hardness is obtained by this process.
Advantages: 1. This process is more rapid.
2. The sludge formed settle down rapidly and hence no coagulant is needed.
3. Quantity of chemicals required for softening is low, hence economical.
4. Besides removal hardness causing salts, minerals, iron and manganese present in water are removed.
Zeolite or Permutit Method:
Zeolites are also known as Permutits;
Zeolites are mainly 2 types:
1. Natural zeolites are non-porous, eg. Natrolite- Na2O.Al2O3.4SiO2.2H2O.
2. Synthetic Zeolites are porous and possess gel structure. They possess higher exchange capacity.They are prepared by
heating together Na2CO3 , Al2O3 and silica.
Process: Sodium zeolites are simply represented as Na2Ze. For softening of water by zeolite process, hard water is passed
+2, +2
at a specified rate through a bed of zeolite, kept in a cylinder. The hardness causing ions like Ca Mg are retained by the
zeolite as CaZe and MgZe; while the outgoing water contains sodium salts.

The various reactions taking place may be

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3
Na2Ze + MgCl2 MgZe + 2NaCl
Na2Ze + CaCl2 CaZe + 2NaCl
Na2Ze + MgSO4 MgZe + 2Na2SO4
Na2Ze + CaSO4 CaZe + 2Na2SO4
Hence zeolite process removes the hardness of water effectively.
Regeneration: After some time, the Zeolite is completely converted into calcium and magnesium zeolites and it gets
exhausted. At this stage, the supply of hard water is stopped and the exhausted zeolite is regenerated by treating the bed
with a concentrated Brine solution (10% NaCl).
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl Na2Ze + MgCl2
Advantages:
a. It removes the hardness completely and water of about 10 ppm hardness is produced.
b. The equipment used is compact, occupying a small space.
c. No impurities are precipitated, so there is no danger of sludge formation in the treated water at a later stage.
d. The process automatically adjusts itself for variation in hardness of incoming water.
e. It is quite clean.
f. It requires less time for softening.
g. It requires less skill for maintenance as well as operation.
Disadvantages:
a. The treated water contains more sodium salts than in lime-soda process.
b. This method causes caustic embrittlement.
c. High turbidity water cannot be treated efficiently by this method.
Limitations:
1. If the supply of water is turbid, the suspended matter must be removed, before the water is admitted to the zeolite bed.
Otherwise the turbidity will clog the pores of zeolite bed, thereby making it inactive.
+2 +2
2. If water contains large quantities of coloured ions such as Mn and Fe they must be removed first, because these
ions produce magnesium and Ferrous zeolites. This cannot be easily regenerated.
3. Mineral acids, if present in water, destroy the zeolite bed and therefore, they must be neutralized with soda, before
admitting the water to the zeolite softening plant.
Ion exchange process :
Ion exchange process also known as demineralization or de-ionization process. Ion-Exchange resins are insoluble.
Cross linked long chain organic polymers with a micro porous structure, and the “functional Groups” attached to the
chains are responsible for the ion-exchanging properties.
In De-ionization process all the ions present in water are eliminated by using ion-exchange resins.
Resins are classified as
1. Cation Exchange Resins
2. Anion Exchange Resins
 1. Cation Exchange Resins: These are mainly styrene divinyl benzene co-polymers, which on sulphonation or
carboxylation. These are capable of exchanging their hydrogen ions with cations in water.
2. Anion Exchange Resins: Anion exchange resins are styrene-divinyl benzene or amine formaldehyde copolymers,
which contains amino, quaternary ammonium groups as an internal parts of the resin matrix. These after treatment with
dilute NaOH solution. Become capable of exchanging their OH- ions with anions in water.
+2 +2
In ion-exchange process, hard water is allowed to pass through cation exchange resins, which remove Ca and Mg
+
ions and exchange equivalent amount of H ions. Anions exchange resins remove bicarbonates, chlorides and sulphates
-
from water exchange equivalent amount of OH ions.
Thus by passing hard water through cation hardness is observed by the following reactions.
Cation Exchange Resins
+ +2 +2 +
2RH + Ca R2Ca + 2H
+ +2 +2 + +
2RH + Mg R2Mg + 2H (RH = cation exchange resin)
Anion Exchange Resins
+2 - -
R’OH + Cl R’Cl + OH
-2 -2
2R’OH- + SO4 R2SO4 + 2OH-
-2 -2
2R’OH + CO3 R’2CO3 + 2OH- (R’OH = anion exchange resin)
+ -
H and OH ions, thus released in water from respective cation and anion exchange columns, get combined to produce
water molecules.
+ -
H + OH H2O
The water coming out from the exchanger is ion free i.e., free from anions and cations. Thus water of zero hardness is
obtained.
REGENERATION: When cation exchanger losses capacity of producing H+ ions and exchanger losses capacity of
producing OH- ions, they are said to be exhausted. The exhausted cation exchanger is regenerated by passing it through
dilute sulphruric acid.
+2 + + +2
R2Ca + 2H 2RH + Ca
The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.
-2 - - -2
R2SO4 + 2OH 2R’OH + SO4
Merits of Ion-exchange process:
a. The process can be used to soften highly acidic or alkaline water.
b. It produces water of very low hardness (2 ppm)
c. So it is very good for treating water for use in high-pressure boilers.
Demerits of Ion-exchange process:
a. The equipment is costly and more expensive chemicals are needed.
b. If water contains turbidity, the output of the process is reduced. The turbidity must be below 10 ppm; else it has to be
removed by coagulation and filtration.
Numerical problems refer text book:
INTERNAL TREATEMENT:
Some of the internal treatment methods used for the removed of scale formation in boilers are -
1. COLLODIAL CONDITIONING: The addition of organic substances such as Kerosene, tannin, Gel etc., to the surface in
low pressure boilers may prevent the scale formation. These substances gets coated over the scale forming precipitates
and gives a loose and non-sticky precipitates which can be removed by using blow-down operation.
2. PHOSPHATE CONDITIONING: The addition of sodium phosphate in hard water reacts with the hardness causing
agents and gives calcium and magnesium phosphates which are soft and non-adhere and can be removed easily by blow-
down operation. In this way, scale formation is removed in highpressure boilers.
3CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6NaCl
3. CALGON CONDITIONING: Involves in adding calgon to boiler water. It prevents the scale and sludge formation by
forming soluble complex compound with CaSO4.
Calgon = Sodium hexa Meta phosphate = (NaPO3)6
+ -
Na2 [Na4 (PO3)6 2Na + [Na4 (PO3)6]
-2 -2
2CaSO4 + [Na4 (PO3)6] [Ca2(PO3)6] + 2Na2SO4
Portable Water:
Specifications:
1. The water should be clear, colourless and odourless.
2. The water must be free from pathogenic bacteria and dissolved gases like H2S.
3. The optimum hardness opf water must be 125 ppm and pH must 7- 8.5.
4. The turbidity in drinking water should not exeed 25 ppm.
5. The recommended maximum concentration of total dissolved solids in portable water must not exceed 500 ppm.

Steps involved in the treatment of portable water:

The treatment includes the removal of suspended impurities, colloidal Impurities and harmful pathogenic bacteria, the
following is the flow diagram of water treatment for domestic purposes and various stages involved in purification are given
as:
 Source of water Screening Aeration Sedimentation Filtration

Storage and Distribution Sterilisation and disinfectation

Flow diagram of treatment of water for municipal supply

1. Screening: The water is passed throughscreens having large number of holes in it to remove floating impurities.
2. Aeration: The water is then subjected to9 aeration which
i) Helps in exchange of gases between water and air
ii) Increase the oxygen content of water
iii) Removes the impurities like Fe and Mn by precipitating as their hydroxides.
3. Sedimentation with Coagulation: The suspended and colloidal impurities are allowed to settle under gravitation.
The basic principle of this treatment is to allow water to flow at a very slow velocity, so that the heavier particles settle
under gravitation. For settling of fine particles, coagulants like Alums, Sodium aluminate and salts of iron are added which
produces gelatinous precipitates like floc. Floc attracts and helps accumulation of the colloidal particles resulting in setting
of the colloidal particles. The following is the sedimentation tank used for the removal of colloidal impurities.

Sedimentation

4. Filtration: It helps in removal of the colloidal and suspended impurities not removed by sedimentation. Usually
sand filters are employed. There are 2 types of sand filters, slow sand filters and rapid sand filters or pressure filters. In
slow sand filter the filter bed consists of 3 layers of sand of different particle size. A fine sand layer on the top supported
by coarse sand layer, which is supported by gravel. The colloidal impurities are retained by the fine sand layer resulting a
very slow filtration of water. The top layers of the fine sand layer is scraped off, washed, dried and introduced into the
filter bed for reuse. Rapid sand filters make use of compressed air for fast filtration.

Slow Sand Filter Rapid Sand Filter

5. Sterilisation and Disinfectation: Distruction of harmful pathogenic bacteria from drinking water is carried out by
streilisation and disinfectation. The following are the methods adopted for this process.
a) Boiling: By boiling water for 15- 20 min, harmful bacteria are killed. This is not [possible for the muncipal supply of
water. This method of sterilisation is adopted for domestic purpose.
b) Passing Ozone: Ozone when passed into water acts as disinfectant. Ozone is an unstable isotope of oxygen,
produced nascent oxygen which is a powerfull disinfectant.
 O3 O2 + (O)
This treatment is costly and ozone is unstable and cannot be stored for long time.
c) Chlorination:The process of utilising chlorine as a powerful disinfectant is called chlorination.They are 3 types of
chlorinating reagents .
i) By passing Chloramines: Chlorine is mixed with ammonia in the ratio 2:1 by volume to form a stable chloramines
which generates hypochlorous acid a powerful disinfectant
Cl2 + NH3 ClNH2 + HCl
ClNH2 + H2O HOCl + NH3
Hypochlorous acid inactivates the enzymes of bacteria and kills bacteria. Chloramine is useful for disinfecting swimming
pools.
ii) By bleaching powder: Bleaching powder contains 80% chlorine. When bleaching powder is used as disinfectant, it
is called hypochlorination because the disinfectation is due to Hypochlorous acid.
CaOCl2 + H2O Ca(OH)2 + Cl2
(Bleaching powder)
Cl2 + H2O HOCl + HCl
(Disinfectant)
iii) Chlorination: The process of applying calculated amount of Chlorine to water in order kill the pathogenic bacteria is
called chlorination. Chlorine also reacts with water and generates Hypochlorous acid, which kills bacteria. Chlorine is a
powerful disinfectant than chloramine and bleaching powder.
Cl2 + H2O HOCl + HCl
(Disinfectant)
Calculated amount of chlorine must be added to water because chlorine after reacts with bacteria and organic impurities
or ammonia, remains in water as residual chlorine which gives bad taste, odour and toxic to humans. The amount of
chlorine required to kill bacteria and remove organic matter is called breakpoint chlorination.

The water sample is treated with chlorine and estimated for the residual chlorine in water and plotted a graph shown
below which gives the breakpoint chlorination.

From Graph it is clear that

„a‟ gms of chlorine added oxidizes reducing impurities of water
„b‟ gms chlorine added forms chloramines and other chloro compounds
„c‟ gms of chlorine added causes destruction of bacteria.
„d‟ gms of chlorine is residual chlorine
„c‟ gms is the breakpoint for the addition of chlorine to water. This is called breakpoint chlorination.
 Advantages of Break point Chlorination:
1. It removes taste, color, and oxidizes completely organic compounds, ammonia and other reducing impurities.
2. It destroys completely all disease producing bacteria.
3. It prevents growth of any weeds in water.

Dechlorination: over chlorination after „Break point‟ produces unpleasant taste, odor, and toxicity to water. The over
chlorination is removed by passing the water through a bed of granular carbon and also by the addition of SO 2 and
sodium thio sulphate.
SO2 + Cl2 + 2H2O H2SO4 + 2HCl
Na2S2O3 + Cl2 + H2O Na2SO4 + 2HCl

Desalination of Brackish water: The process of removing common salt from the water is known as desalination. The
water containing dissolved salts with a peculiar salty taste is called brackish water. Sea water, containing on an average
about 3.5% salts, comes under this category. Commonly used methods for the desalination of brackish water is:
1. Reverse Osmosis & 2. Electrodialysis.
1. Reverse Osmosis: Osmosis is the phenomenon by virtue of which flow of solvent takes place from a region of low
concentration to high concentration when two solutions of different concentrations are separated by a semi-permeable
membrane. The flow continues till the concentration is equal on both the sides. The driving force for osmosis is osmotic
pressure. However, if a hydrostatic pressure in excess of osmotic pressure is applied on the concentrated side, the flow
of solvent reverses as it is forced to move from concentrated side to dilute side across the membrane. This is the basis of
reverse osmosis.

Method of purification:
The reverse Osmosis cell consists of a chamber fitted with a semi-permeable membrane which is made of thin films of
cellulose acetate, polymethyl acrylate and polyamide polymers . Above the semi permeable membrane sea water or
impure water is taken and a pressure of the order of 15-40 kg/cm2 is applied on the sea water for separating the water
from its contaminants. Pure water is forced through semi permeable membrane. The process is also known as super or
hyper filtration.
Advantages:
a. Colloidal SiO2 can be removed by reverse osmosis which even cannot be removed by demineralization.
b. It is simple and reliable process.
c. Capital and operating expenses are low.
d. The life of the semi-permeable membrane is about 2 years and it can be easily replaced within a few minutes, thereby
nearly uninterrupted water supply can be provided.
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