VELAMMAL ENGINEERING COLLEGE,SURAPET, CHENNAI-66

UNIT –I - WATER TECHNOLOGY

SESSION –I

INTRODUCTION

Water is the most important compound for the existence of human beings,
animals and plants. About 80% of the earth’s surface is occupiedby [Link]
sources of water are
1. Rain
2. Rivers and lakes (surface water)
3. Wells and springs (underground water)
4. Sea water.

Among the above sources of water, rain water is the purest form of water but it
is very difficult to collect whereas sea water is the most impure [Link], surface
and ground water are normally used for industrial and domestic [Link] water
must be free from undesirable impurities.

“The process of removing all types of impurities from water and making it fit for
domestic or industrial purposes are called water treatment.”Before treating water
one must know the nature as well as the amount of impurities.

HARD WATER AND SOFTWATER

Hard Water
“Water which does not produce lather with soap solution, but produces white
precipitate(scum) is called hard water”.This is due to the presence of dissolved Ca
and Mg salts.
Eg :Ca(HCO3)2, Mg(HCO3)2,CaCl2,MgCl2,CaSO4,MgSO4 etc.,
2C17H35COONa + Ca ++ → (C17H35COO)2Ca +2Na+
(Water soluble) (Water insoluble)
Soft water:
“Water which produces lather readily with soap solution is called soft
water.”This is due to the absence of Ca and Mg salts.

HARDNESS OF WATER

Hardness is the property or characteristics of water, which does not produce lather
with soap.

How to detect hardness?

Hardness of water can be detected in two ways.

1. When the water is treated with soap solution, if it prevents lathering and forms
white scum, the water contains hardness.

2. Water containing hardness, gives wine red colour with Eriochrome Black-T
indicator at pH 9-10.

TYPES OF HARDNESS
Depending upon the types of dissolved salts present in water, hardness of water
can be classified into two types

1. Temporary hardness.
2. Permanent hardness.

1. Temporary Hardness (or) Carbonate Hardness (CH) (or) Alkaline

hardness:

This is due to the presence of bicarbonates of calcium and magnesium. It can be

removed by
(i) Boiling the water
(ii) Adding lime to the water.
The above two processes convert the bicarbonates into insoluble carbonates and
hydroxides, which can be removed by filtering.

[Link] hardness (or) Non-carbonate hardness (NCH) (or) Non-alkaline

hardness
This is due to the presence of chlorides and sulphates of calcium and
magnesium. It cannot be removed by boiling the water. But, it can be
removed by
(i) Lime-soda process
(ii) Zeolite process.

TOTAL HARDNESS
The sum of temporary hardness and permanent hardness
 SESSION –II

Estimation of hardness in terms of CaCO3 equivalence

Hardness is expressed in CaCO3 equivalence. Because,

i)It is the most insoluble and easily precipitatablesalt.

ii) Its molecular weight is 100 and equivalent weight is 50. As these are
whole numbers,It is very easy to use them in calculations.

Amount Equivalent of CaCO3 = Amount of hardness producing salt ×Molecular weight of CaCO3

Molecular weight of hardness producing salt

(OR)
Amount of hardness producing salt ×Equivalent weight of CaCO3
=
Equivalent weight of hardness producing salt

UNITS OF HARDNESS:

i) Parts per million (ppm)

ii) Milligrams per litre (mg/L)

iii) Degree Clarkes

iv)Degree French

1`Parts per million (ppm):- It is defined as the number of parts of

Calcium carbonate equivalent hardness per 106parts of water.

i.e., 1ppm= 1 parts of Calcium carbonate equivalent hardness in 106 parts of

water.
[Link] per litre (mg/L):-It is thenumber of milligrams of Calcium
carbonate equivalent hardness present per liter of water.

1mg/L=1mg of CaCO3 equivalent hardness of 1L of water=

1kg=1000g=106mg.

∴1mg/L=1mg of CaCO3eq per 106mg of water=1ppm.

[Link]’s degree (0Cl):-
It is the part of CaCO3 equivalent hardness per 70,000 parts of water.

∴10Cl= 1 part of CaCO3eq hardness in 70,000 parts of water

4. Degree French (oFr):-Number of parts of CaCO3 equivalent hardness per

105 parts of water.

∴10Fr= 1 part of CaCO3equivalent hardness in 105parts of water.

Calculation of equivalents of CaCO3:

Salt/ion Molar
mass ChemicalEquivalen Multiplication factorfor
t OrEquivalent converting
Weight intoequivalents ofCaCO3
Ca(HCO3
)2 162 81 100/162
Mg(HCO3
)2 146 73 100/146
CaSO4 136 68 100/136
CaCl2 111 55.5 100/111
MgSO4 120 60 100/120
MgCl2 95 47.5 100/95
 CaCO3 100 50 100/100
MgCO3 84 42 100/84

Problems based on Hardness.

Problem-1.
Awater sample contains 194 mgs CaSO4per litre. Calculate the hardness in
terms CaCO3equivalent..

Solution.
The amount of hardness producing salts = 194 mgs CaSO4
Molecular weight of the CaSO4 = 100mgs/litre

Equivalent of CaCO3 = Mass of Hardness producing salts ×100 / Molecular

weight of the
hardness producing salts
= 194mg/l*100/136

=142.6mg/l

Problem-2:
A sample of water is found to contains following dissolving salts in
milligrams per [Link](HCO3)2 = 73, CaCl2 = 111, Ca(HCO3)2 = 81,
MgSO4 = 40 and MgCl2 = 95. Calculate Carbonate and Non carbonate
hardness and total hardness.

Solution:
Name of the Amount of the Molecular Amounts equivalent
hardness hardness weight of to
causing hardness
causing salts salts(mg/Lit) causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 73 146 73×100/146 = 50

=
CaCl2 111 111 111×100/111 100
Ca(HCO3)2 81 162 81×100/162 = 50

=
MgSO4 40 120 40×100/120 33.3

=
MgCl2 95 95 95×100/95 100

Carbonate hardness = Mg(HCO3)2 + Ca(HCO3)2

=50 + 50 = 100mgs/Lit.
Non carbonate hardness = CaCl2 + MgSO4 + MgCl2
=100 + 33.3 + 100 = 233.3mgs/Lit.
Total hardness = Carbonate hardness + Non carbonate hardness.
=100 + 233.3 = 333.3mgs/Lit.
Problem-3.
A water sample contains following dissolving substances in milligrams
per litre Mg(HCO3)2 = 16.8, MgCl2 = 12.0, MgSO4 = 29.6 and NaCl = 5.0.
Calculate temporary and permanent hardness of water.

Solution:
Name of the Amount of the Molecular Amounts
hardness hardness weight of equivalent to
causing hardness causing
causing salts salts(mg/Lit) salts CaCO3 (mg/Lit)
16.8×100/146 =
Mg(HCO3)2 16.8 146 11.50
12.0×100/95 =
MgCl2 12.0 95 12.63
29.6×100/120 =
MgSO4 29.6 120 24.66
NaCl does not contribute any hardness
NaCl 5.0 to water
hence it is
ignored.

Temporary hardness = Mg(HCO3)2 = 11.50mgs/Lit.

Permanent hardness = MgCl2 + MgSO4 = 12.63 + 24.66 =
37.29mgs/Lit.

Problem-4:

A sample of water is found to contains following analytical data in

milligrams per litre Mg(HCO3)2 = 14.6, MgCl2 = 9.5, MgSO4 = 6.0 and
Ca(HCO3)2 = 16.2. Calculate temporary and permanent hardness of water in
parts per million, Degree Clarke’s and Degree French.

Solution:
Name of the Amount of the Molecular Amounts equivalent
hardness hardness weight of to
causing hardness
causing salts salts(mg/Lit) causing salts CaCO3 (mg/Lit)
Mg(HCO3)2 14.6 146 14.6×100/146 = 10
MgCl2 9.5 95 9.5×100/95 = 10
MgSO4 6.0 120 6.0×100/120 = 5
Ca(HCO3)2 16.2 162 16.2×100/162 =10

Temporary hardness [Mg(HCO3)2 + Ca(HCO3)2] = 10 + 10 = 20mg/Lit =

20ppm
= 20×0.07°Cl = 1.4°Cl = 20×0.1°Fr =
2°Fr

Permanent hardness [MgCl2 + MgSO4] = 10 + 5 = 15mg/Lit

=15ppm
=15×0.07°Cl = 1.05°Cl
=15×0.1°Fr = 1.5°Fr

Problem-5:
Calculate the amount of temporary and permanent hardness of a water
sample in Degree Clarke’s, Degree French and Milligrams per Litre which
contains following impurities.
Ca(HCO3)2 = 121.5 ppm, Mg(HCO3)2= 116.8 ppm, MgCl2 = 79.6 ppm and
CaSO4 = 102 ppm.
Solution:
Name of the Amount of the Molecular Amounts
hardness hardness weight of equivalent to
hardness
causing salts causing salts(ppm) causing salts CaCO3 (ppm)

121.5×100/162
Ca(HCO3)2 121.5 162 = 75
116.8×100/146
Mg(HCO3)2 116.8 146 = 80
79.6×100/95 =
MgCl2 79.6 95 3.37
102×100/136 =
CaSO4 102 136 75

Temporary hardness [Mg(HCO3)2 + Ca(HCO3)2] = 75 + 80 = 155 ppm

= 155×0.07°Cl = 10.85°Cl = 155×0.1°Fr = 15.5°Fr
= 155×1mg/Lit = 155 mg/Lit
Permanent hardness [MgCl2 + CaSO4] = 10 + 5 = 15mg/Lit
=15ppm
=15×0.07°Cl = 1.05°Cl
=15×0.1°Fr = 1.5°Fr

SESSION –III
BOILER FEED WATER
 The water fed into the boiler for the production of steam is called boiler
feed water.
 Boiler feed water should be free from turbidity, oil, dissolved gases,
alkali and hardness causing substances.

Requirements of boiler feed water

 It should have zero hardness.
 It must be free from dissolved gases like O2, CO2, etc.
 It should be free from suspended impurities.
  It should be free from dissolved salts and alkalinity
 It should be free from turbidity and oil.
 It should be free from hardness causing and scale forming
constituents like Ca and Mg salts.

S. Water specification Volume

No.
1 Hardness <0.02
2 Soda alkalinity 0.15-1
3 Caustic alkalinity 0.15-0.45
4 Excess soda ash 0.3-0.55

Ifhard 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. Formation of deposits (Scale and sludge) in boilers.
2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion

FORMATION OF DEPOSITS IN STEAM BOILERS AND HEAT

EXCHANGERS

Sludge and Scale formation in boilers

 When water is continuously converted into steam in boilers or heat

exchangers, the concentration of dissolved salts in water increases
progressively.
 When the concentration of the salts reaches their saturation point, they
are thrown out in the form of precipitates on the inner walls of the
boilers or heat exchangers.
  The least soluble one gets precipitated first

I. Sludge:

 If the precipitate is loose and slimy it is calledsludges.

 Sludges are formed by substances like MgCl2, MgCO3, MgSO4
andCaCl2.
 They have greater solubilities in hot water than coldwater.
II. Scal
e:  If the precipitate forms hard and adherent coating on the inner
walls of the boiler, it is calledscale.
 Scales are formed by substances like Ca(HCO3)2, CaSO4 and
Mg(OH)2.
Disadvantages:
I) Wastage offuels
(i) Scales have low thermal conductivity, so the heat transfer from
boiler to inside water is not efficient.
(ii) In order to provide steady supply of heat to water, overheating
 is done and this causes wastage of fuel.
(iii) The wastage of fuel depends on the thickness and nature of the
scale, which is shown in the table.

II)Decrease inefficiency
Scales sometimes deposit in the valves and condensers of the boiler and
choke them partially. This results in decrease in efficiency of the boiler.
III)Boiler explosion
Sometimes due to over heating the thick scales may crack and causes
sudden contact of high heated boiler material with water. This causes
formation of a large amount of steam and high pressure is developed which
may lead to explosion.

Prevention of Scale Formation

 At the initial stage, scales can be removed using scraper, wire brush etc.
 If scales are brittle, they can be removed by thermal shocks.
 By using suitable chemicals like dil. acids (for CaCO3 scale), EDTA
(for CaSO4 scale) with which they form suitable complexes.
 If the scales are loosely adhering, they can be removed by frequent
blow down operation.

SESSION –IV
PRIMING AND FOAMING (CARRY OVER)

During the production of steam in the boiler, due to rapid boiling, some
droplets of liquid water are carried along with steam. Steam containing
droplets of liquid water is called wet steam.
 These droplets of liquid water carry with them some dissolved salts and
suspended impurities. This phenomenon is called carry over. It occurs due to
priming and foaming.

Priming
Priming is the process of production of wet steam. Priming is
caused by

 High steamvelocity.
 Very high water level in theboiler.
 Sudden boiling ofwater.
 Very poor boilerdesign.

Prevention
Priming can be controlled by

 Controlling the velocity ofsteam.

 Keeping the water levellower.
 Good boilerdesign.
 Using treatedwater.
Foaming

The formation of stable bubbles above the surface of water is called

foaming. These bubbles are carried over by steam leading to excessive
priming.
Foaming is caused by the

 Presence of oil andgrease.

 Presence of finely dividedparticles.
Prevention

Foaming can be prevented by

 Adding coagulants like sodium aluminate, aluminiumhydroxide.
 Adding anti-foaming agents like syntheticpolyamides.

CAUSTIC EMBRITTLEMENT

 Caustic embrittlement means intercrystalline cracking of

boiler metal.
 Caustic embrittlement is a form of corrosion caused by a high
concentration of sodium Hydroxide in the boiler feed water.

Causes of caustic embrittlement:

Boiler water usually contains a small amount of Na2CO3. In high
pressure boilers, Na2CO3 undergoes hydrolysis to produce NaOH.
Na2CO3 + H2O → 2NaOH +CO2
This NaOH flows into the minute hairline cracks present on the boiler
material by capillary action and dissolves the surrounding area of iron as
sodium ferroate, Na2FeO2.
Fe + 2NaOH → Na2FeO 2 +H2
This type of electrochemical corrosion occurs when the concentration of
NaOH is above 100 ppm. This causes embrittlement of boiler parts,
particularly the stressed parts like bends, joints, rivets, etc.

Caustic embrittlement can be prevented by

 Using sodium phosphate as the softening agent instead of
sodiumcarbonate.
 Adding chemicals such as tannin, lignin to the boiler water. They
block the hairline cracks.
.
BOILER CORROSION

Corrosion in boilers is due to the presence of

 Dissolvedoxygen
 Dissolvedcarbondioxide
 Dissolved salts like magnesiumchloride.
Dissolved oxygen
The presence of dissolved oxygen is responsible for corrosion in boilers.
Water containing dissolved oxygen when heated in a boiler, free oxygen is
evolved, which corrodes the boiler material.

4Fe + 6H2O+3O2 → 4 Fe(OH)3

Removal of dissolved oxygen

Dissolved oxygen can be removed by chemical or mechanical methods.

(a) Chemicalmethod
Sodiumsulphite, hydrazines are some of the chemicals used for removing
dissolved oxygen.

Hydrazine is found to be an ideal compound for removing dissolved oxygen

in the water, since the products are water and inert N2gas.

(b) Mechanical de-aeration

Dissolved oxygen can also be removed from water by mechanical de-aeration.
 Mechanical de-aeration of water

In this process, water is allowed to fall slowly on the perforated plates fitted
inside the tower. The sides of the tower are heated, and a vacuum pump is
also attached to it. The high temperature and low pressure produced inside the
tower reduce the dissolved oxygen content of the water.
Dissolved carbon dioxide
When water containing bicarbonates is heated, carbon dioxide is evolved
which makes the water acidic. Carbon dioxide dissolved in water forms
carbonic acid. This leads to intense local corrosion called pitting
corrosion.
Ca(HCO3)2 → CaCO3 + H2O +CO2;

CO2 + H2O →H2CO3

Removal of dissolved Carbon-di-oxide

(a) Carbon- di-oxide can be removed from water by adding a calculated

amount of NH4OH in to water.

(b) Carbon dioxide along with oxygen can also be removed mechanically by
de-aeration method.
Dissolved magnesium chloride
When water containing dissolved magnesium chloride is used in a boiler,
hydrochloric acid is produced. HCl attacks the boiler in a chain-like reaction
producing hydrochloric acid again and again which corrodes boiler severely.

MgCl2 + 2H2O → 2HCl + Mg (OH)2

Fe + 2 HCl →FeCl2 + H2
FeCl2 + 2H2O → Fe (OH)2+ 2HCl
Corrosion by HCl can be avoided by the addition of alkali to the boiler water.

Removal of acids by neutralization

Corrosion by acids can be avoided by the addition of alkali to the boiler water.
HCl + NaOH → NaCl + H2

PREVENTION OF SCALE FORMATION (OR) SOFTENING OF

HARD WATER
The process of removing hardness – producing salts from water is
known as softening or conditioning of water. Since water is a source for
industrial purpose. It is mandatory to soften water to make it free from
hardness producing substances, suspended impurities and dissolved gases, etc.
Softening or conditioning of water can be done by two methods.
1. External treatment.
2. Internaltreatment.
EXTERNAL TREATMENT (OR) EXTERNAL CONDITIONING
PROCESS
It involves the removal of hardness producing salts from the water
before feeding into the boiler. The external treatment can be done by the
following methods.
1. Zeolite (or) Permutit process [Link] (Or) Ion exchange
 process
Zeolite (or) Permutit process

Zeolites are naturally occuring hydrated sodium aluminosilicate

minerals. The chemical formula is Na2O.Al2O3.xSiO2.yH2O.(x=2-
10,y=2-6). The synthetic form of zeolite is called permutit and is
represented by Na2Ze.

In this process the hard water is allowed to perlocate through

sodium zeolite. The sodium ions which are loosely held in this
compound are replaced by Ca2+ and Mg2+ ions.

When zeolite comes in contact with hard water, it exchanges its

sodium ions with calcium and magnesium ions of hard water to form
calcium and magnesium zeolites.

As sodium ions do not give any hardness to water, the effluent will
be soft. The exhausted zeolite is again regenerated by treated with 5 to
10 percent of sodium chloride solution.
 CaCl 2  Na 2 Ze  CaZe  2 NaCl
M gCl 2  Na 2 Ze  Mg Ze  2 NaCl
Ca ( HCO 3 ) 2  Na 2 Ze  Ca Ze  2 NaHCO 3
M g ( HCO 3 ) 2  Na 2 Ze  M gZe  2 Na HCO 3
CaSO 4  Na 2 Ze  Ca Ze  Na 2 SO 4
M gSO 4  Na 2 Ze  M g Ze  Na 2 SO 4

Regeneration
After some time zeolite gets exhausted. The exhausted zeolite is again
regenerated by treating with 10% solution of NaCl.

Advantages
 No sludge is formed during thisprocess.
 Water of nearly zero hardness isobtained.
 This method is very cheap because the generated zeolite
can be usedagain.
 The equipment used is compact and occupies a smallspace.
 Its operation is alsoeasy.
 The process can be made automatic andcontinuous.
Disadvantages

 This process cannot be used for turbid and acidic water as

they will destroy the zeolitebed.
 This treatment replaces only the cations, leaving all the
 anions like bicarbonate and carbonate in the softwater.
 When such water is fed in boilers, CO2 is liberated. Free
CO2 is weakly acidic in nature and extremely corrosive to
boilermetal.
Na2CO3 + H2O→2NaOH + CO2

 Due to the formation of sodium hydroxide, the water

becomes alkaline and can cause caustic embrittlement.
 Water containing Fe, Mn cannot be treated, because
regeneration is verydifficult.
 This process cannot be used for softening brackish water.
Because brackish water also contains Na+ ions. So, the ions
exchange reaction will not take place.

DEMINERALIZATION:

Ion exchange or Demineralisation process

 Ion exchange or demineralization process removes almost all the
ions (both anions and cations) present in the hard water.

 The soft water, produced by lime-soda and zeolite processes, does

not contain hardness producing Ca2+ and Mg2+ ions, but it will
contain other ions like Na+, K+, SO42–, Cl– etc., .On the other hand
demineralised (DM) water does not contain both anions and
cations.
Thus a soft water is not demineralised water whereas demineralised
water is soft water.
 This process is carried out by using ion exchange resins, which are
 long chain, cross linked, insoluble organic polymers with a micro
process structure. The functional groups attached to the chains are
responsible for the ion exchanging properties.
Two types of ion-exchange resins are used throughout the process.
1. Cation exchange resin (or) cation exchanger
2. Anion exchange resin (or) Anion exchanger

(i) ation exchanger

Resins containing acidic functional groups (–COOH, – SO3H) are
capable of exchanging their H+ ions with other cations of hard water.
Cation exchange resin is represented as RH2.

Examples:
 Sulphonatedcoals
 Sulphonatedpolystyrene
R–SO3H; R–COOH ≡RH2
(ii) Anion Exchanger
Resins containing basic functional groups (–NH2, –OH) are capable
of exchanging their anions with other anions of [Link]
exchange resin is represented as R'(OH)2.
Examples:
 Cross-linked quaternary ammoniumsalts.
 Urea-formaldehyderesin.
R–NR3OH; R–OH; R–NH2 ≡ R (OH)2
Process
The hard water first passed through a cation exchange which absorbs all the
cations like Ca2+, Mg2+ Na+, K+, etc. present in the hardwater.
R H 2  C a C l 2  R C a  2 H C l
R H 2  M g SO 4  R M g  H 2 S O 4
R H  N a C l  R N a  H C l
The cation free water is then passed through a anion exchange column, which
absorbs all the anions like Cl–, SO42, HCO 3–, etc., present in the water.
R ' (OH ) 2  2 HCl  R 'Cl 2  2 H 2O
R ' (OH )2  2 H2 SO4  R 'SO4  2 H 2O

The water coming out of the anion exchanger are completely free from cations
and anions.
This water is known as demineralised water or deionised water.
Regeneration
When the cation exchange resin in exhausted, it can be regenerated by passing
a solution of [Link] or dil.H2SO4.
 RCa + 2HCl → RH2 + CaCl2
RNa + HCl → RH + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated
by passing a solution of [Link].
R'Cl2 + 2 NaOH → R'(OH)2 + 2 NaCl

Advantages
 The water is obtained by this process will have very low
hardness.
 Highly acidic or alkaline water can be treated by this process.

Disadvantages
 The equipment is costly.
 More explosive chemicals are needed for this process.
 Water containing turbidity, Fe and Mn cannot be treated,
because turbidity reduces the output and Fe, Mn form stable
compound with the resins.

INTERNAL TREATMENT (or) INTERNAL CONDITIONING (or)

BOILER COMPOUNDS

Internal treatment involves adding chemicals directly to the water in

the boilers for removing dangerous scale – forming salts which were not
completely removed by the external. The added chemicals are also
called boiler compounds.

Treatment for water softening: This method is used to convert scale

to sludge which can be removed by blow-down operation.
  Calgon conditioning
 Carbonateconditioning
 Phosphateconditioning
 Colloidal conditioning

(i) Calgon conditioning

Calgon - sodium hexa meta phosphate -Na2(Na4 (PO3)6).
A highly soluble complex containing Ca is formed by replacing the
sodium ions and thus prevents their formation of scale forming salts like
CaSO4. The reaction is as follows:
2CaSO 4 + Na 2 [Na 4(PO3)6] →Na 2 [Ca 2 (PO3) 6] + 2Na2SO4
Since the complex is highly soluble there is no problem of sludge
disposal.
(ii)Carbonate conditioning
Scale formation due to CaSO4 in low pressure boilers can be
avoided by adding Na2CO3 to the boilers.
CaSO4 +Na2CO3 → CaCO3 + Na2SO4

The forward reaction is favored by increasing the concentration of

CO32-. CaCO3formed can be removed easily.

(iii)Phosphate conditioning
Scale formation can be avoided by adding sodium phosphate. It is
used in high pressure boilers. The phosphate reacts with Ca 2+ and Mg2+
salts to give soft sludges of calcium and magnesium phosphates.

3CaSO4 +2Na3PO4 → Ca3 (PO4)2+2Na2SO4

There are three types of phosphates employed for this purpose.
 (a) Trisodium phosphate – Na3PO4 (too alkaline) - used for too
acidic water.
(b) Di-sodium hydrogen phosphate – Na2HPO4 (weakly alkaline)-Used
for weakly acidicwater.
(c) Mono sodium dihydrogen phosphate NaH2PO4 (acidic) used
for alkaline water.

(iv)Colloidal conditioning
Scale formation can be avoided by addition of colloidal
conditioning agents are kerosene, agar-agar, gelatin, glue, etc. They are
used in low pressure [Link] colloidal substances convert scale
forming substance like CaCO3, CaSO4 into a non-adherent, loose
precipitate called sludge, which can be removed by blow-down
Operation.

(v)Sodium aluminate conditioning

Scales formation can be avoided by adding Sodium aluminate
( NaAlO2) this get hydrolysed first, gives NaOH and a gelatinous white
precipitate of Al(OH)3 & NaOH.

NaAlO +2H O -----> NaOH + Al(OH)

2 2 3

The sodium hydroxide, thus formed, precipitates magnesium as

magnesium hydroxide. The gelatinous precipitates of Al(OH)3 & Mg(OH)2
entrap the colloidal silica and finely divided solids and settled easily. This can
be removed easily by using blow-down operations.
DESALINATION OF BRACKISH WATER
The process of removing common salt (sodium chloride) from the
water is known as desalination. The water containing dissolved salts with a
peculiar salty (or) brackish taste is called brackish water.
 Depending upon the quantity of dissolved solids, water is graded as

(a) Fresh water - It has < 1000 ppm of dissolved solids.

(b)Brackish water- Ithas > 1000 but < 35,000 ppm of dissolved
solids.

(c)Sea water- It has > 35,000 ppm of dissolved solids.

Water containing dissolved salts with a peculiar salty or brackish

taste is called brackish water. It is totally unfit for drinking purpose. Sea water
and brackish water can be made available as drinking water through
desalination process.

The need for such a method arises due to the non-availability of

fresh water. Desalination is carried out either by electrodialysis or by
reverse osmosis.
Electrodialysis

Principle

Electrodialysis is the process of removal of ions from the salt water through ion-
selective membranes by passing direct current.

When direct electric current is passed through saline water, the sodium ions (Na+)
start moving towards negative pole (cathode); while the chloride ions (Cl-) start moving
towards the positive pole (anode) through the [Link] a result, the concentration
of brine decreases in the central compartment; while it increases in two side
[Link] brine (or pure water) is removed from the central
compartment from time to [Link] concentrated brine solution available in side
compartments is replaced by fresh brine sea water.
 In this process ions-selective membrane are [Link] ion-selective
membrane has permeability for only one kind of ions with specific charge.
Cation selective membrane - It permits only cations, Example polystyrene containing
functional groups such as RSO3- or [Link] completely reject anions.
Anion selective membrane- It permits only anions, Example polystyrene containing
functional groups such as R4N+[Link] completely reject cations.

Description of Electrodialysis cell

An electrodialysis cell consist of a large number of paired sets of rigid plastic
[Link] sea water is passed under a pressure of about 5-6 Kg m-2 between
membrane ion pairs and electric field is applied perpendicular to the direction of water
flow.
The fixed positive charges inside the membrane repel positively charged
ions,permit only negatively charged ions to pass [Link] the fixed negative
charges inside the membrane repel negatively charged ions and permit only positive
charged ions to pass [Link] water in one compartment of the cell is
deprived of its salts; while the salt concentration in adjacent compartments is
[Link] it produces alternate streams of pure water and concentrated brine.

Advantages
(i) It is the most compact unit
(ii) The intial cost of setting up the plant and its operation is economical
(iii) Best suited method when electricity is easily available
(iv) Low energy consumption
(v) High conversion unit (Nearly 80%)
(vi) Product water needs only limited pre-treatment.
Dis advantages
(i) Only removes ions, But doesn’t remove organics and colloids.
(ii)Selection of membranes is difficult
(iii)Purity affected by quality of feed water.
Applications
1. Desalination of brackish water
2. Boiler feedwater production
3. Waste and process water treatment
4. Table salt production
5. Desalination of contaminated industrial water for reuse
Reverse Osmosis (RO)
When two solutions of different concentrations are separated by a
semi-permeable membrane, flow of solvent takes place from a region of low
concentration to high concentration until the concentration is equal on both
the sides. This process is called osmosis.

The driving forces in this phenomenon are called osmotic pressure. If a

hydrostatic pressure in excess of osmotic pressure is applied on the higher
concentration side, the solvent flow reverses, i.e., solvent is forced to move
from higher concentration to lower concentration .This is the principle of
reverse osmosis. Thus, in reverse osmosis method pure water is separated
from its dissolvedsolids.

Using this method pure water is separated from sea water. This
process is also known as super-titration. The membranes used are cellulose
acetate, cellulose butyrate, etc.

Advantages

 The life time of the membrane is high.

 It can be replaced within few minutes.
 It removes ionic as well as non-ionic, colloidal impurities.
  Due to simplicity low capital cost, low operating, this process is used for
converting sea water into drinking water.

Difference between Electrodialysis and Reverse Osmosis method

[Link] Electrodialysis (ED) Reverse osmosis (RO)

1. ED is a voltage driven RO is a pressure - driven
process process
2. Electrodialysis is RO is used to remove
usually applied to de- suspended solids, total organic
ionization of aqueous carbon or other contaminants.
solutions.
3. Sometimes pre- Pre-treatment is necessary
treatment is necessary always
4. High conversion ratio Low conversion ratio (nearly
(nearly 80%). 30- 80%)

ESTIMATION OF HARDNESS BY EDTA METHOD:

1. Aim:
To estimate the amount of hardness present in the given water sample.

2. Chemicals required:

a) Standard hard water – 1g CaCO3 + dil. HCl – made up to 1 Lr.

b) EDTA solution – 4 gms of EDTA sodium salt / 1 Lr of distilled water
c) EBT Indicator – 0.5g EBT / 100 ml alcohol
d) Ammonia buffer - 67.5g Ammoniumchloride +570ml Ammonia-- made up
to 1Lr

3. Principle:
The amount of hardness causing ions (Mg2+ and Ca2+) can be estimated by
titrating the water sample against EDTA using EBT indicator at pH 8to 10.

Structure of EDTA:

By nature, Eriochrome Black T indicator is blue in colour. When EBT

indicator is added to water sample, it forms wine red coloured unstable Ca-
Mg-EBT complex.

This reaction is carried out under a basic pH of 8- 10 using ammonia buffer.

When EDTA is titrated against the complex, EDTA replaces all the EBT and
forms a stable Ca / Mg –EDTA complex. The liberated EBT indicates the end
point as steel blue.
So, the end point is the colour change from wine red to steel blue.

Procedure:
Content Titration – Titration – Titration -
I(Standardisation II(Estimation III
of EDTA) of total (Estimation
hardness ) of
permanent
hardness)
Burette EDTA Std. EDTA Std. EDTA
Solution
Pipette 20 ml standard 20 ml of the 20 ml of
Solution hard water hard water boiled and
sample. cooled hard
water
sample.
Additional 5 ml of 5 ml of 5 ml of
solution ammoniacal ammoniacal ammoniacal
buffer solution buffer buffer
solution solution
Indicator 3drops of EBT 3drops of 3drops of
EBT EBT
End point wind red to steel wind red to wind red to
blue steel blue steel blue
Let the volume of Let the Let the
EDTA consumed volume of volume of
be –V1ml EDTA EDTA
consumed be consumed
–V2ml be –V3 ml
 1. Calculation:

Step1 – Standardisation of EDTA

1 ml of Std. Hard water = 1 mg of CaCO3 (Given)

So, 20 ml of Std. Hard water = 20 mg of CaCO3

V1 ml of EDTA is required for = 20 mg of CaCO3

Therefore, 1ml of EDTA = 20 / V1 mg of CaCO3

Step 2: Finding Total hardness:

20ml of sample water required = V2 ml of EDTA

= V2 X 20 mg of CaCO3
V1

Therefore, 1000ml of sample requires = V2 X 20 X 1000 mg of CaCO3

V1 20

Hence, total hardness = V2 X 1000 ppm

V1

Step 3: Finding Permanent hardness:

20ml of boiled water required = V3 ml of EDTA

= V3 X 20 mg of CaCO3
V1

Therefore, 1000ml of boiled sample requires = V3 X 20 X 1000 mg of CaCO3

V1 20

Hence, permanent hardness = V3 X 1000 ppm

V1

Step 4 : Temporary hardness = Total hardness – permanent hardness