Department of Chemistry

School of Advanced Sciences

Vellore Institute of Technology
Vellore, 632014
Module 1 Water Technology
Characteristics of hard water - hardness, DO, TDS in water and their determination – numerical problems in hardness
determination by EDTA; Modern techniques of water analysis for industrial use - Disadvantages of hard water in industries

Module 2 Water Treatment

Water softening methods: - Lime-soda, Zeolite and ion exchange processes and their applications. Specifications of water for
domestic use (ICMR and WHO); Unit processes involved in water treatment for municipal supply - Sedimentation with coagulant-
Sand Filtration - chlorination; Domestic water purification – Candle filtration- activated carbon filtration; Disinfection methods-
Ultrafiltration, UV treatment, Ozonolysis, Reverse Osmosis; Electro dialysis
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art forms, emphasizing Differential
aeration, Pitting, Galvanic and Stress corrosion cracking; Factors that enhance corrosion and choice of parameters to mitigate
corrosion
Water softening methods: Lime-soda, Zeolite and ion exchange
processes and their applications
Specifications of water for domestic use (ICMR and WHO); Unit
processes involved in water treatment for municipal supply -
Sedimentation with coagulant-Sand Filtration -chlorination
Domestic water purification –Candle filtration-activated carbon filtration;
Disinfection methods-Ultrafiltration, UV treatment, Ozonolysis, Reverse
Osmosis; Electro dialysis
Hardness Concentration (mg/l) Degree of Hardness
0-60 Soft
60-120 Moderately hard
120-180 Hard
Over 180 Very hard
Softening: The process of removing hardness producing salts
from water, is known as softening of water. There are three main
methods are available for softening of water
• Lime-soda process
• Zeolite or permutit process
• Ion-exchange or de-ionization or de-mineralization
 Lime soda process
In this method, the soluble calcium and magnesium salts in water are chemically converted into
insoluble compounds, by adding calculated amounts of lime [Ca(OH)2], and soda [Na2CO3].
Calcium carbonate [CaCO3] and magnesium hydroxide [Mg(OH)2], so-precipitated are filtered
off.
 Cold lime-soda (residual hardness: 50 to 60 ppm)
 Hot lime-soda (residual hardness: 15 to 30 ppm)
o There are two types of Cold and Hot Lime-Soda process
• Batch process
• Continuous process
 Zeolite (permutit process, residual hardness: up to10 ppm):
Permutit process is a process in where hard water containing such as Ca++ is filtered through a
natural sand called the zeolite
 Ion-exchange:
• Cation exchange resins (RH+)
• Anion exchange resins (R′OH-)
• Mixed bed ion-exchange
 Principle
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 milk of lime [Ca(OH)2] (L) together with
calculated amount of sodium carbonate Na2CO3 (soda) (S) is added in requisite
amount. CaCO3, Mg(OH)2, Ferric hydroxide Fe(OH)3 and aluminium hydroxide Al(OH)3
so precipitated and filtered off.

 Calcium carbonate (CaCO3) and magnesium hydroxide Mg(OH)2 so precipitated,

are filtered off
 The precipitates [Mg(OH)2 and CaCO3] formed are very small (colloidal) and hence,
produce a super-saturated solution
 This results in “after deposition” in the pipes and tubes producing sludges which
eventually cause blockage and corrosion
 Lime-soda process can be batch process or continuous process
 Use of Coagulants
At room temperature, the precipitates formed are very fine. They do not settle down easily and
cause difficulty in filtration. The precipitates of CaCO3 and Mg(OH)2 eventually results in “after
deposition”, later in the pipes and boiler tubes, producing scales. These in turns,
(a) Cause their corrosion
(b) Clog tubes and valves
(c) Decrease the effective diameters of pipes
These drawbacks partly offset the purpose of water softening
However small amount of coagulants like alum [K2SO4, Al2(SO4)3, 24H2O], aluminium sulphate
[Al2(SO4)3], or sodium aluminate [NaAlO2] are added, they hydrolyse to precipitate of aluminium
hydroxide [Al(OH)3] which entraps the fine precipitate of CaCO3 and Mg(OH)2. Thus, coagulant
helps in the formation of coarse precipitates.
NaAlO2 + 2H2O → NaOH + Al(OH)3↓
Al2(SO4)3 + 3Ca(HCO3)2 → 2Al(OH)3 + 3CaSO4 + 6CO2↑
Two types of lime-soda processes are briefly described below:
Cold lime-soda Process
Hot lime-soda Process
 Cold lime-soda Process:
o In this process, water is treated with lime and soda, at room in the presence of
coagulant
o There are two types of cold lime-soda softeners, which work either in batch process or
in continuous process.
o Intermittent type (Batch process) Cold Lime-Soda softener
o Continuous Cold Lime-Soda softener
Intermittent type (Batch process) Cold
Lime-Soda softener
 It consists of a pair of tanks
 Each tank is equipped with mechanical
stirrer, inlets and outlets
 Raw water and calculated quantity of
chemicals are charged in tank and stirred
well with mechanical stirrer
 Some sludge is added to accelerate the
process
 The sludge formed is allowed to settle
down, and is then removed from the tank
through the sludge outlet
 The softened water is taken out through a
floating pipe
 Continuous Cold Lime-Soda softener
• Occurring at room temperature.
• Calculated amount of L&S mixed with water at room
temperature with stirring
• Precipitate formed are finely formed hence do not
settle down easily
• It is essential to add small amount of coagulant
[aluminium sulphate, sodium aluminate, Alum
(K2SO4.Al2(SO4)3.24H2O)].
• Coagulant hydrolyze to form gelatinous precipitates
and entraps the fine ppt.
• NaAlO2 + H2O → NaOH + Al(OH)3
• The softened water passes through a filtering media
(wood fiber) for complete removal of sludges.
• It provides water with a residual hardness of 50 to 60
ppm
 Hot lime-soda process
In this process, water is treated with chemicals at a temperature of 94 ⁰C to 100 ⁰C . The
softeners used are of the intermittent-type or continuous type
These are briefly discussed below:
(a) Intermittent-type (Batch process) Hot Lime-Soda Softener: It is similar to the
intermittent-type cold softener except that the heating coils are installed in it for
heating water
(b) Continuous-type Hot Lime-soda Softeners: This softener essentially consists of
following three parts:
o Reaction tank
o Conical sedimentation tank
o Sand filter
 Hot Lime-Soda process
• Occurring at 80 °C to150 °C close to
the boiling point of the solution
• Reaction proceed faster, softening
capacity is increased many folds
• The precipitate and sludges formed
settle down rapidly; no coagulant
needed
• Dissolved gases (CO2, O2) are driven
out easily; viscosity of the softened
water is low, so filtration of water is
much easier (filtering capacity of
filters is improved)
• Produces water contain the residual
hardness of 15 to 30 ppm
• The precipitation reaction is almost complete
• Reaction takes place faster
• Sludge settles down rapidly
• No coagulant is needed
• Dissolved gases (which may cause corrosion) are removed
• Viscosity of soft water is lower, hence filtered easily
• Residual hardness is low compared to cold lime-soda process
• The precipitation reaction is almost complete
• Reaction takes place faster
• Sludge settles down rapidly
• No coagulant is needed
• Dissolved gases (which may cause corrosion) are removed
• Viscosity of soft water is lower, hence filtered easily
• Residual hardness is low compared to cold lime-soda process
 Cold lime-soda process Hot lime-soda process
 Done at room temp, 25 to 30 °C  Elevated temperature, 94 to 100 °C
 Slow Process  Rapid process
 Use of Coagulants is must.  Coagulants are not required
 Filtration is not easy  Filtration is easy since the viscosity is
low at high temperature
 Residual hardness is around 60 ppm  Residual hardness is 15-30 ppm
 Dissolved gases are not removed  Dissolved gases like O2and CO2are
removed to some extent
 Low softening capacity  High softening capacity
 Economical operation costs
 If the process is combined with coagulation + sedimentation, less amount of
coagulants shall be needed
 Process increases the pH and hence corrosion of the distribution pipes are reduced.
 Due to alkaline pH, the amount of pathogenic bacteria in water is also reduced
 To certain extent, mineral content in water reduced. Fe and Mn ions are also removed
from water

 Careful operation and skilled supervision is necessary (If not, the excess L- S addition
will cause an increase in hardness levels in the treated water)
 Huge amount of insoluble sludge is formed and its disposal is difficult
 Due to residual hardness of at least (minimum) 15 ppm, the treated water is not
suitable for high pressure boilers
 Requirement of Lime and Soda through Discussion of Various Chemical Reactions
Involved in Lime-Soda Process
 Requirements of Lime-Soda for Calcium Hardness
 A few specific situations are discussed below:

(1) Presence of Temporary calcium hardness:

 Suppose the water sample contain Ca(HCO3)2
 We know that if OH‒ ions are added (from calcium hydroxide) to an water containing
HCO3‒ ions immediately they will chemically react together to form CO32‒
Thus, for the treatment of Ca(HCO3)2, we can add Ca(OH)2. Because their immediate
chemical reaction, insoluble precipitates of CaCO3 will form, which subsequently are
filtered off.
The water softening will occur as per the following reaction:

Ca(HCO3)2 + Ca(OH)2 → 2CaCO3↓+ H2O

(2) Presence of Permanent calcium hardness:
 Suppose the water sample contain CaCl2, CaSO4
 The reaction between lime and permanent hardness producing calcium salts are as
follows
CaCl2 + Ca(OH)2 → CaCl2 + Ca(OH)2

So it is clear that lime can not remove permanent calcium hardness. So for the softening of this
hard water, we need to add sodium carbonate which will lead to the formation of insoluble
precipitate of calcium carbonate as per following chemical reactions

CaCl2 + Na2CO3 → CaCO3↓ + 2NaCl

CaSO4 + Na2CO3 → CaCO3 ↓+ Na2SO4
So it can be conclude that we require one mole of soda for the softening of hard water containing
either one mole of calcium chloride or one mole of calcium sulphate
 Requirements of Lime-Soda for Calcium Hardness
A few specific situations are discussed below:

(3) Presence of Temporary magnesium hardness:

 Suppose the water sample contain Mg(HCO3)2
 Magnesium bicarbonate and calcium hydroxide will immediately react according to the
following reaction:
Mg(HCO3)2 + Ca(OH)2 → Mg(OH)2 ↓+ Ca(HCO3)2
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O

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

We can conclude that we require two moles of lime for the softening of hard water containing one
mole magnesium bicarbonate
(4) Presence of Permanent magnesium hardness:
 Suppose the water sample contain MgCl2
 Magnesium salts must be converted into insoluble magnesium hydroxide precipitates so we
need to add calcium hydroxide
MgCl2 + Ca(OH)2 → Mg(OH)2↓+ CaCl2
MgSO4 + Ca(OH)2 → CaSO4↓ + Mg(OH)2

As per the above reactions, although permanent magnesium hardness has been removed by the
addition of lime but simultaneously we have generated permanent calcium hardness. Thus for
the complete softening , we need to add soda, so that permanent calcium hardness can be
removed.
So we can conclude that we require one mole of lime and one mole of soda for complete
treatment of one mole of permanent magnesium hardness
 Reactions of lime and soda
• Reaction of permanent calcium
Ca2+ + Na2CO3 → 2Na+ + CaCO3↓ S
• Reactions of permanent magnesium
Mg2+ + Ca(OH)2 → Ca2+ + Mg(OH)2 ↓ L+S
Ca2+ + Na2CO3 → 2Na+ + CaCO3 ↓
• Reaction of HCO3‒ (Example: NaHCO3)
2HCO3‒ + Ca(OH)2 → CaCO3 ↓+ CO32‒ + H2O L-S
• Reaction of Ca(HCO3)2
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓+ 2H2O L
• Reaction of Mg(HCO3)2
Mg(HCO3)2 + 2Ca(OH)2 → 2CaCO3 ↓+ 2H2O + Mg(OH)2 ↓ 2L
• Reaction of CO2:
CO2 + Ca(OH)2 → CaCO3↓ + H2O L
• Reaction of H+
2H+ + Ca(OH)2 → Ca2+ + 2H2O L+S
Ca2+ + Na2CO3 → 2Na+ + CaCO3 ↓
• Reactions of coagulants:
Reaction of FeSO4

Fe2+ + Ca(OH)2 → Ca2+ + Fe(OH)2 ↓

H2O+ O2 + Fe(OH)2 → Fe(OH)3 ↓ L+S
Ca2+ + Na2CO3 → 2Na+ + CaCO3 ↓
 Calculate the amount of lime required for softening of 5000 litres of hard water
containing 72 ppm of MgSO4

Given hard water contains MgSO4, so for its softening we require both lime and soda, according
to the following equations:
MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4
CaSO4 + Na2CO3 → CaCO3 + Na2SO4

Requirement of lime for 1 mole of MgSO4 ≡ 1 mole of Ca(OH)2

120 gm of MgSO4 ≡ 74 gm of Ca(OH)2
So requirement of lime for 72 ppm of MgSO4 ≡ 74/120 × 72 ppm or mg/L
Hence, for softening of 1L of water, lime required is 74 × 72/120 mg

Thus for softening of 5000 L of water, lime required is:

74×72×5000/120 = 222000 mg = 222 gm
 Calculate the amount of lime required for softening of 5000 litres of hard water
containing 72 ppm of MgSO4

Given hard water contains MgSO4, so for its softening we require both lime and soda, according
to the following equations:
MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4
CaSO4 + Na2CO3 → CaCO3 + Na2SO4

Requirement of lime for 1 mole of MgSO4 ≡ 1 mole of Ca(OH)2

120 gm of MgSO4 ≡ 74 gm of Ca(OH)2
So requirement of lime for 72 ppm of MgSO4 ≡ 74/120 × 72 ppm or mg/L
Hence, for softening of 1L of water, lime required is 74 × 72/120 mg

Thus for softening of 5000 L of water, lime required is:

74×72×5000/120 = 222000 mg = 222 gm
 What is Zeolite?
• Zeolite is hydrated sodium alumino silicate having a general formula,
Na2O·Al2O3·xSiO2·yH2O (x=2 to 10 and y=2 to 6).
• Also known as Permutits and in Greek it means “boiling stone”. It is
capable of exchanging reversibly its sodium ions for Ca2+ and Mg2+.
Zeolites are of two types:
o (1) Natural Zeolites: These are non-porous having formula
Na2O·Al2O3·4SiO2·2H2O, it is also known as natrolite.
o (2) Synthetic Zeolite: These are porous and possess gel structure.
These are prepared by heating together china clay, faldspar and soda
ash. Such zeolites possess higher exchange capacity per unit weight
than natural zeolites
 Natural Zeolites:
 Natrolite: Na2O. Al2O3.4SiO2.2H2O
 Laumontite: CaO. Al2O3.4SiO2.4H2O
 Harmotome: (BaO.K2O). Al2O3.5SiO2.5H2O
They are capable of exchanging its Na ions.
 Process
 For softening of water by zeolite
process, hard water is percolated at
a specified rate through a bed of
zeolite, kept in a cylinder
 Zeolite holds sodium ions loosely
and can be represented as Na2Ze.
Where Ze = insoluble radical frame
work
 The hardness causing ions(Ca2+
,Mg2+) are retained by the zeolite as
CaZe and MgZe respectively, while  Method of softening:
the outgoing water contains sodium Na2Ze + Ca(HCO3)2→ CaZe + 2NaHCO3
salts. During this process, the water Na2Ze + Mg(HCO3)2→ MgZe + 2NaHCO3
becomes free from Ca2+ and Mg2+ Na2Ze + CaSO4→ CaZe + Na2SO4
ions. Na2Ze + MgCl2→ MgZe + 2NaCl
(Zeolite) (Hardness)
 Regeneration:
 After some time, the zeolite is completely is completely converted into
calcium and magnesium zeolite and it ceases to soften water, i.e., it gets
exhausted
 At this stage, the supply of hard water is stopped and the exhausted
zeolite is reclaimed by treating the bed with a concentrated (10%) brine
(NaCl) solution
CaZe (or MgZe) + 2NaCl → Na2Ze + CaCl2 (or MgCl2)
 The washing (containing CaCl2 and MgCl2) are led to drain and the
regenerated zeolite bed thus-obtained is used again for softening
purpose
 Limitations of zeolite process:
 If water is turbid, the suspended impurities must be removed (by
coagulation, sedimentation, filtration) before the water is admitted to the
zeolite bed; otherwise the turbid particles will clog the zeolite bed and
make it inactive
 Water containing large quantities of color ions such as Mn2+ and Fe2+
must be removed first because these ions produced Mn-zeolite and Fe-
zeolite which cannot be easily regenerated
 Mineral acids, if present in the hard water will destroy the zeolite bed,
and hence must be neutralized with soda (Na2CO3) before sending the
hard water to the zeolite softening plant
 Disadvantages:
 Coloured water or water containing suspended impurities cannot be used before
filtration.
 Water containing acid cannot be used for softening since acid may destroy the zeolite.
 Treated water contains more Na+ ions than in the L-S process.
 Replaces only Ca2+ and Mg2+ ions but leaves the acidic ions (HCO3‒ and CO32‒) as
such in the softened water; HCO3‒ decompose to produce CO2 which causes
corrosion in boilers; CO32‒ hydrolyze to NaOH to cause caustic embrittlement.
 Advantages:
 Residual hardness of water is about 10 to 15 ppm only.
 Equipment is compact, clean, easy to handle.
 It requires less softening time.
 No impurities, no sludge formation and the process is clean.
 The process automatically adjusts itself to remove the hardness of incoming water
 Zeolite can be regenerated easily using brine solution
 Lime-Soda Zeolite (Permutit)
• Residual water hardness: 15 to 60 ppm Residual water hardness:about 10 ppm
• Treated water contains lesser amount of Na+ ions than in Treated water contains large amount of Na+ions than in
original water original water
• Capital cost is lower Cost of plant and material is higher
• Cost of plant and material is higher Operational cost is lower
• No such limitations Cannot be used for treating acid water because the zeolite
material undergoes disintegration
• Plant occupies more space The plant occupies less space
• No such limitations Raw water containing suspended impurities block the pores of
the permutit and the zeolite bed loses its exchange capacity
• Cannot operate under pressure Can operate under pressure, fully automatic
• Involves difficulties in settling, coagulation, filtration and No settling, coagulation, filtration or formation of sludges /
removal of precipitates precipitation
• To be tested for frequent changes in water hardness, Wateranalysis tests only the hardness of treated water
control and adjustment of reagents
• Treated water contains lesser dissolved solids but more Treated water contains more dissolved solids
precipitated solids
 Ion-exchange resins are insoluble, cross-linked, long chain polymers with
micro-porous structure.
 Functional groups present are responsible for ion-exchange properties
 Acidic functional groups (‒COO‒H+, ‒SO3‒H+) exchange H+ for cations.
 Basic functional groups (‒NH2, =NH) exchange OH‒ for anions
 Cation-exchange Resins (RH+):
H H2 H H2 H H2
 Styrene-divinyl benzene C C C C C C
copolymers, which on
sulphonation or carboxylation,
become capable to exchange
their hydrogen ions with the SO3H
SO3H
cations in the water. H2 H2 H
HC C C C C
 The order of affinity for some H2
C CH
common cations is approximately: H2
Hg2+ < Li+<H+<Na+<K+≈ NH4+<
Cd2+ < Cs+< Ag+< Mn2+ < Mg2+ <
Zn2+ < Cu2+ < Ni2+ < Co2+ < Ca2+ < SO3H
Sr2+ < Pb2+ < Al3+ < Fe3+ SO3H
Anion-exchange Resins (ROH-): H2
H H2 H H2 H
• Styrene-divinyl benzene or C C C C C C
amine-formaldehyde
copolymers, which contain
amino or quaternary ammonium
CH2NMe2OH
or quaternary phophonium or CH2NMe2OH
H2 H2 H
tertiary sulphonium groups as HC C C C C
H2
an integral part of the resin C
H2
CH

matrix. These after treatment

with dil. NaOH solution capable
to exchange their OH¯ ions with CH2NMe2OH
the anions in the water CH2NMe2OH
 At cation exchange column:
• The hard water is first passed through cation exchange column, which
removes all the cations like Ca2+, Mg2+, etc and an equivalent amount of
H+ ions are released from this column to water.
 At anion exchange column:
• Removes all anions like SO42-, Cl-, etc present in the water; an equivalent
amount of OH‒ ions are released from this column into the water.
 After cation exchange column and anion exchange column:
H+ + OH‒ → H2O
2RH+ + Ca2+/Mg2+ → R2Ca2+ /R2Mg2+ + 2H+
R′OH + Cl‒ → R′Cl‒ + OH‒
2R′OH + SO42‒ → R′2 SO4 + 2OH‒
2R′OH + CO32‒ → R′2 CO3 + 2OH‒
 Regeneration:
• When the capacity of the ion exchange resins to exchange H+ and OH‒
ions are lost, they are said to be exhausted
 Cation exchange resin regeneration:
• R2Ca2+/R2Mg2+ + 2H+ (dil HCl or H2SO4) → 2RH+ + Ca2+/Mg2+
 Anion exchange resin regeneration:
• R′2 SO42‒ + 2OH‒ (dil NaOH) → 2R′OH‒ + SO42‒

 The regenerated ion exchange resins can be used again

 Another category of ion-exchange resins:
 Ion-exchange resins are special compounds containing Na+ ions.
 Hard water contains soluble calcium and/or magnesium ions.
 Ca2+ and Mg2+ ions in the hard water swap with those on the resin.
 The water comes out with Na+ ions in it.
 Ca2+ and Mg2+ ions remain attached to the resin.
 Na+ ions do not cause hardness.
Advantages:
 The process can be used to soften highly acidic or alkaline water.
 It produces water of very low hardness (below 1ppm).
 Good for use in high-pressure boiler
Disadvantages:
 The equipment is costly and more expensive chemicals are needed.
 If the turbidity of water is >10ppm then the out put of the process is
reduced.
 Colored water or water containing suspended impurities can not be used
before filtration.
 It needs skilled labor.
 Mixed bed ion-exchanger
 In this type of deionizer a single cylinder contains a mixture of both a strongly acidic
cation exchanger and a strongly basic anion exchanger.

 When the hard water is passed through this bed slowly the cations and anions of the
hard water comes in to contact with these two kinds of resins many number of times.
 Hence, it is equivalent to passing the hard water many number of times through a
series of cation and anion exchange resins.
 The soft water from this method contains less than 1 ppm of dissolved salts and hence
more suitable for boilers.
Regeneration:
• When the bed (resins) are exhausted or cease to soften the water, the
mixed bed is backwashed by using compressed air or forcing the water
from the bottom in the upward direction.
 Then the light weight anion exchanger move to the top and forms upper
layer above the heavier cation exchanger.
 Then the anion exchanger is regenerated by passing caustic soda
(NaOH) from the top and then rinsed with pure water.
 The lower cation exchanger bed is then washed with dilute H2SO4
solution and then rinsed.
 These two beds are then mixed again by forcing compressed air to mix
both and the resins are now ready to use.
 Drinking or potable water should be safe to drink and should satisfy the
following requirements:
 Sparklingly clean and odorless
 Pleasant in taste
 Perfectly cool
 Turbidity should not exceed 10 ppm
 Free from dissolved gases like H2S
 Free from minerals like Pb, As, Cr and Mn salts
 Alkalinity should not be too high (pH should be around 8.0)
 Should be reasonably soft
 Total Dissolved Solids (TDS) should be less than 500 ppm
 Free from disease producing pathogenic micro-organisms
 The World Health Organization (WHO) is a specialized agency of the
United Nations that is concerned with international public health. It was
established on 7 April 1948, and is headquartered in Geneva,
Switzerland. The WHO is a member of the United Nations Development
Group. Its predecessor, the Health Organization, was an agency of the
League of Nations.
 The Indian Council of Medical Research (ICMR), the apex body in
India for the formulation, coordination and promotion of biomedical
research, is one of the oldest and largest medical research bodies in the
world. The ICMR is funded by the Government of India through the
Department of Health Research, Ministry of Health and Family Welfare.
Lakes/Reservoirs/
Storage tanks Coagulation
Rivers
Removes dirt and other particles
Multilayer filtration suspended in water. Alum and
using sand, gravel and other chemicals are added for
coagulation through floc
charcoal

Flocculation &
Filtration Sedimentation
Clarification

Calculated Heavy particles (floc)

amount of settle to the bottom and
chlorine is added clear water goes for
filtration

Disinfection Storage in closed Supply through

containers pipelines
 Screening
 Aeration
 Sedimentation and coagulation
 Filtration
 Sterilization and disinfection
 Storage and
S distribution S S

Source of Water Screening Aeration

S S
SSS SSS S
SSS
Sterilizations and
Filtration Sedimentation
Disinfections
with coagulation
S
SSS SSS SSS
Storage and
distribution
SSS
 Screening
o Floating matter in the water can be retained by passing the water through Screens having
a large number of holes
 Aeration
Promotes taste and odour by exchange of gases between the water and atmosphere
• to add or increase the content of oxygen in water
• to remove CO2 , H2S and other volatile substance causing bad taste and odor in
water
• to remove the impurities like Fe and Mn (which are precipitate as their respective
hydroxides)
 Sedimentation with Coagulation
o Suspended and collodial impurities are separated in a sedimentation tank by gravitation
Fine particles take many hours or days to settle down. Coagulation are added Salts of
aluminium (alum, sodium aluminate) and salts of iron (ferrous sulphate, ferric sulphate, ferric
chloride)
 Filtration
Removal of collodial and suspended matter
(remaining after sedimentation) and bacteria by
passing the water through filter beds containing fine
sand, coarse sand and gravel Types: Gravity type
or pressure type
 Sterilization and Disinfection
Harmful bacteria are destroyed to make the water safe for drinking is called
disinfection Chemical used – Disinfectants
 Boiling: When the water is boiled for 15 - 20 minutes, the harmful bacteria are
killed
 Disadvantages:
i. Boiling changes taste of water
ii. It is impractical for large treatment plants
 Sedimentation with Coagulation:
 Sodium Aluminate (NaAlO2):
o Treating water having no significant alkalinity (pH< 7) (Best Range 5.5 to 8)
NaAlO2 + H2O → Al(OH)3↓ + NaOH
MgSO4 + 2NaOH → Mg(OH)2 + Na2SO4

 Copperas or Ferrous sulphate (FeSO4.7H2O):

 Above pH=8.5, if alkalinity is not present, lime should be added.
FeSO4 + Mg(HCO3)2 → Fe(OH)2↓ + MgSO4 + 2CO2↑
4 Fe(OH)2+ O2+ 2H2O → 4 Fe(OH)3↓
 Alum (K2SO4.Al2(SO4)3.24H2O):
 Alum reacts in water in the presence of alkalinity of water. If the water is not
alkaline, sufficient amount of lime should be added.
Al2(SO4)3+ 3 Ca(HCO3)2→ 2 Al(OH)3↓ + 3 CaSO4+ 6CO2
 Sand filtration:
 Filtration is the process of removing colloidal matter, and most of the microorganisms,
etc by passing water through a bed of fine sand and other proper sized granular
materials
 Filtration is carried out by passing water through an inlet through a bed of fine sand,
coarse sand and granular materials
 The irregular pores in the sand filter hold the sediment particles thereby allowing the
filtered water to pass through an underground drain
 When the flow rate of the filtered water becomes slow, the setup is stopped and
about 2 to 3 cm of the top fine sand layer is scrapped off, replaced with clean sand
and the filter is back to use again
 The scrapped sand is washed with water, dried, and stored for reuse at the time of
next scrapping operation
The Candle Filters are, like all pressure filters,
operating on a batch cycle and may be seen in
process lines handling titanium dioxide, fluegas,
brine clarification, redmud, china clay, fine
chemicals and many other applications that
require efficient low moisture cake filtration or
high degree of polishing.
 The Candle Filter consists of three major
components:
 The vessel
 The filtering elements
 The cake discharge mechanism
 Candle Filters are very well suited for
handling flammable, toxic and corrosive
materials
 Advantages:
 Excellent cake discharge.
 Adapts readily to slurry thickening.
 Minimum floor space.
 Mechanically simple since there are no complex sealing glands or
bearings.
 Disadvantages:
 High headroom is required for dismantling the filtering elements.
 The emptying of the vessel in between cake filtration, washing and drying
requires close monitoring of the pressure inside the vessel to ensure that
the cake holds onto the candles.
 The following are the steps of purification:

Removal of suspended Removal of

impurities micro-organisms

Screening By boiling the water

By adding bleaching
powder
Sedimentati
on with By chlorination
coagulation
By using chloramine
(ClNH2)

Filtration Disinfection by ozone

 The process of destroying the disease producing bacteria,
pathogenic microorganisms, etc., from the water and making it
safe for use is called “Disinfection”.
 The chemicals or substances, which are added to water for
killing the bacteria, etc., are known as “disinfectants”.
 Removal of bacteria is sterilization or disinfection. There are several
important sterilization methods.
 Boiling.
 Using ozone(ozonolysis).
 UV treatment.
 Filtration: membrane filtration like ultra filtration, activated carbon
filtration.
 Chlorination
• Passing chlorine gas or solution.
• Adding chloramines salt.
• Adding bleaching powder (CaOCl2)
*It should be noted that chlorine should be always added a little higher than
the break point chlorination for perfect disinfection.
 By Chlorination: Chlorine (gas or in concentrated solution form) produces hypochlorous
acid which is a powerful germicide. Chlorine is more effective as an effective disinfectant at
lower Ph values (below 6.5).
Cl2 + H2O → HOCl + HCl
Germs + HOCl → Germs are killed
 By adding bleaching powder (CaOCl2) :
In small water-works, 1 kg of bleaching powder is added to 1000 Liters of water (1000 ppm)
and allowed to stand for several hours. The chemical action produces HOCl (Hypochlorous
Acid, a powerful germicide).
CaOCl2 + H2O → Ca(OH)2 + Cl2
Cl2 + H2O → HOCl + HCl
Germs + HOCl → Germs are killed
The disinfecting action is due to the chlorine produced from the bleaching powder
 Drawbacks:
• CaOCl2 introduces Ca2+ ions in water, thereby increasing water hardness
• Bleaching powder deteriorates or decomposes within its storage time
• Excess beaching powder gives a bad taste and smell to treated water
Mechanism of Action:
 Enzymes are essential for the metabolic processes of the micro-
organisms. The death of microorganisms, bacteria, etc., resulted from the
chemical reaction between HOCl and the enzymes (in the cells of the
microorganisms). The enzymes are inactivated by HOCl
 Liquid chlorine: Liquid chlorine is widely used as disinfectant
 Most effective when applied to filtered water at such appoint where
adequate mixing is done. Apparatus used for mixing liquid chlorine with
filtered water is called Chlorinator. Chlroine gas or solution bubbling will
kill bacteria
 Chlorinator is used for adding adequate quantity of chlorine (0.3 to
0.5ppm) so that, after the treatment, the residual chlorine will be 0.1 to 0.2
ppm in treated water
Factors affecting efficiency of chlorination
 Time of Contact: The number of micro-organisms destroyed by
chlorine per unit time is directly proportional to number of micro-
organisms that were alive initially. Therefore, the death rate is
maximum at the start and then gradually decreases with time.
 Temperature of water: With increasing water temperature, the
rate of reaction between chlorine and the enzymes increases
thereby increasing the death rate of microorganisms.
 pH of water: Lower pH of water (5 to 6.5) and a small contact
time is required
By Chlorination
 Advantages of chlorine:
 Effective and economical
 Requires very little space for storage
 Chlorine is stable and does not deteriorate unlike CaOCl2
 Can be used at low and high temperatures
 Does not introduce any salt impurities in the treated water
 Most ideal disinfectant
 Disadvantages of chlorine:
 Excess of chlorine produces characteristic taste and odor
 Excess of chlorine causes irritation to mucus membrane
 Residual chlorine should not exceed 0.1 to 0.2 ppm
 It is most effective below pH 6.5 and not very effective at higher pH
 Break-point Chlorination or Free-residual Chlorination
 Breakpoint chlorination is the point where the demand for chlorine has
been fully satisfied in terms of chlorine addition to water. When chlorine is
added to water, a reaction is produced in the compounds present in the water.
These compounds utilize the chlorine, resulting in zero chlorine residual
 The point at which the added chlorine completely removes bacteria, NH3,
organic and inorganic impurities is known as “Breakpoint chlorination”
 The feed water contains: (a) Bacteria, (b) Ammonia, (c) Organic impurity
(sewage), (d) Inorganic salt impurities ( Effluents, H2S, Fe salts).
 It involves the addition of sufficient amount of chlorine to oxidize: (a) organic
matter, (b) reducing substances, and (c) free ammonia in raw water thereby
leaving behind mainly free chlorine which is used for disinfection against
disease-producing pathogenic bacteria
  The addition of chlorine
at the dip or break is
called “break-point
chlorination”
 At this point, the water is
free from color and odor
D
 Any type of pathogenic
B organisms present in
water are destroyed,
C
thereby making the
A
disinfection highly
efficient
 Process (As shown in the diagram):
• When we add chlorine, first it kills bacteria and oxidizes some inorganic
impurities
• The added chlorine is completely consumed (Point A)
• Further addition of chlorine is used to combine with ammonia to form
chloramines compounds. So, the residual chlorine content is increased up to
point B
• As saturation level is attained, the chloramines begin to decompose to release
chlorine which is utilized to remove all the types organic and inorganic
impurities. So, residual chlorine level decreases. (Point C)
• At point C, the added chlorine removes all the types of impurities. So, the point
is known as “ Break point chlorination”
• After this point C, further addition of chlorine is not at all utilized and simply
increases the residual chlorine content.(along CD)
 Advantages of break-point chlorination (Significance)
 Oxidizes completely the organic compounds, ammonia and other
reducing compounds
 Removes bad taste and color in water which was due to the
presence of organic matter
 Destroys completely (100%) all the micro-organisms
 Prevents the growth of any weeds in the water
Dechlorination:
Excess chlorine beyond the break-point produces bad taste and
smell
 Excess chlorine can be removed by passing the excess chlorinated water
through a bed of molecular carbon or activated carbon. Allow a short
reaction time and remove the carbon by filtration
 Adding small quantities of sulphur dioxide (SO2) or sodium sulphite
(Na2SO3) or sodium thiosulphate (Na2S2O3)
SO2 + Cl2 + 2H2O → H2SO4 + 2HCl
Na2SO3 + Cl2+ H2O → Na2SO4 + 2HCl
Na2S2O3 + Cl2 + H2O → Na2SO4 + 2HCl+ S
By using chloramine (ClNH2):
 When chlorine and ammonia are mixed in the ratio of 2:1 by volume,
chloramine is formed.
Cl2 + NH3 → ClNH2 + HCl
 Chloramine is more reactive and longer lasting than chlorine and is a
better bactericidal agent than chlorine
ClNH2 + H2O → HOCl + NH3
 Excess of ClNH2 does not produce any bad smell but imparts good taste
to water
 Advantages of using chloramine for water disinfection:
• It does not tend to react with organic compounds, so water treated with
chloramine does not have the taste and odor problems of chlorine
• It is less aggressive than chlorine and more stable against light than
hypochlorites. It is more stable than chlorine, the disinfectant benefits last
longer and protect against bacterial regrowth in storage tanks and water
mains.
• It is a less expensive disinfectant alternative to chlorine and the
technology is relatively easy to install and operate.
• It does not produce the disinfection by-products that chlorine treatment
produces such as trihalomethanes and trihaloacetic acid, which may
cause adverse health effects at high levels
 Concerns with using chloramine as a disinfectant in drinking water
(disadvantages):
 Its stability makes it difficult to remove from the water, even by boiling or
distilling.
It is toxic to fish and amphibians. There fore, water treated with chloramine
should not be used in fishbowls and aquariums.
 Its vapor can accumulate in the air of small bath rooms, shower stalls and
indoor swimming pools, which may result in respiratory and breathing issues.
 The potential health effects of choramines disinfection by products are
unknown.
 Without proper treatment of the pipes prior to introducing chloramine, this
disinfectant can cause lead to leach from pipes into drinking water potentially
exposing the population to unsafe lead levels in drinking water
 Disinfection by Ozone (ozonolysis):
 Ozone gas is a very good disinfecting agent.
 Produced by passing silent electric discharge through cold and dry oxygen
3O2 → 2O3 (Ozone)
 Ozone is highly unstable and breaks down to give nascent oxygen
O3 → O2 + [O] (Nacent Oxygen)
 Nascent oxygen is a powerful disinfecting agent and kills all the
microorganisms and oxidizes the organic matter present in the water
o Disadvantage: Expensive than chlorine, not employed for municipal water
treatment.
o Advantages: simultaneous removal of color, smell and taste in water without
giving any residue. Excess not harmful, since O3 is unstable and decomposes
to O2
 Good:
• Short half-life in water, works quickly.
• Ozone breaks down Trihalomethane and Total Organic Halide precursors to lower THM and
TOX product ion potentials. This reduces the amount of chlorine required to maintain a
residual (a nice double edged sword).
• Increases biodegradability in humic and fulvic compounds.
• Reduces BOD and COD.
• Initially oxygenates ground water.
• Can prolong filter media life.
• Adds only oxygen to the water.
 Bad:
• Short half-life in water, little residual for distribution systems
• Filtration required in virtually all cases
• Filtration is always recommended with O3 treatment
• Corrosive as a gas and in solution (that's how it works)
• Reputation of being expensive
• Not yet well understood by many designers and regulators
 Ozone treatment is quite efficient and effective in achieving pollution removal
 Ozone breaks down large and long chain molecules in to smaller building blocks. These
smaller molecules are then usually more biodegradable, less dangerous and more readily
recycled or reused in the environment or removable in a filtration process
 Ozone can be used as a disinfectant, decolorizer, deodorizer, detoxifier, precipitant, coagulant
and for removing tastes. Because of this, it can reduce other chemical loading in treatment
facilities
 Ozone production on site, via normal corona discharge, eliminates the problems of
transporting, storing and handling of hazardous and dangerous materials
 For efficiency, ozone is outstanding, as it is the most powerful and effective broad spectrum
microbiological control or disinfecting agent available. Consequently, with ozone, there is less
need to add high concentrations of a long lived poison to the water you will soon be drinking
 This minimizes the potential for producing carcinogenic THM sand helps protect your health.
Ozone is of particular value in water treatment systems because of it's ability to disinfect
without adding other chemicals which may later need to be removed
 Ozone will decompose in "pure“ water by itself (slower than in air), as well as reacting with
almost anything dissolved or carried in the water
 Activated carbon is produced from carbonaceous source materials such as nutshells, coconut husk,
peat, wood, coir, lignite, coal, etc.
֍ Activated carbon is a material derived mostly from charcoal that has been treated with oxygen creating
many tiny pores between the carbon atoms.
֍ Activated carbon is a highly porous material; therefore, it has an extremely high surface area for
contaminant adsorption.
֍ Production of activated carbon comes from different carbonaceous materials like coal (anthracite or
bituminous), wood, coconut shells, etc.
֍ Two types of activated carbon production are physical activation and chemical activation.
"activated by either Steam Activation(800°C-1000°C) or Chemical Activation (a powerful
dehydrating agent like phosphorus pentoxide (P2O5) or zinc chloride (ZnCl2)."
֍ Two basic kinds of carbon filters Granular Activated Carbon (GAC) and Solid Block Activated Carbon
(SBAC).
֍ Activated carbon works via a process called adsorption, whereby pollutant molecules in the fluid to be
treated are trapped inside the pore structure of the carbon substrate.
֍ Carbon filtering is commonly used for water purification. Active charcoal carbon filters are most effective
at removing chlorine, sediment, volatile organic compounds (VOCs), taste, color and odor from water.
֍ They are not effective at removing minerals, salts, and dissolved inorganic compounds.
֍ Typical particle sizes that can be removed by carbon filters range from 0.5 to 50 μm.
 The principal mechanisms by which activated carbon removes contaminants from
water are
(a) Physical removal
(b) Adsorption and
(c) Catalytic-reduction

֍ Physical removal of contaminant particles: Blocking any that are too large to pass
through the pores (obviously, filters with smaller pores are more effective)
֍ Adsorption: By which a variety of dissolved contaminants are attracted to and held
(adsorbed) on the surface of the carbon particles. The characteristics of the carbon
material (particle and pore size, surface area, surface chemistry, density, and
hardness) influence the efficiency of adsorption
Organics are removed by adsorption. Organic material in public water supplies comes
from decaying plant life, which becomes more soluble in water over time and exists as
large, high-molecular weight organic acids
֍ Catalytic reduction: Residual disinfectants removal
 Activated carbon can remove and destroy residual disinfectants (chlorine and
chloramine) through a catalytic reduction reaction
This is a chemical reaction that involves a transfer of electrons from the activated
carbon surface to the residual disinfectant. In other words, activated carbon acts as a
reducing agent
 Activated carbon's removal of chlorine reduces the chlorine to a non-oxidative chloride
ion
The reaction is very fast and takes place in the first few inches of a new activated
carbon bed.(Where removal of organics by activated carbon takes minutes, removal of
chlorine literally takes seconds). Chloramine removal by activated carbon is a much
slower reaction
 The predominant species of chloramine in city water supplies (pH about 7 to 8) is
monochloramine. The reaction with activated carbon and monochloramine also
renders a non-oxidative chloride ion.
 Microfiltration and Ultrafiltration:
 An ultrafiltration filter has a pore size around 0.01 micron.
 A microfiltration filter has a pore size around 0.1 micron, so when water undergoes microfiltration, many
microorganisms are removed, but viruses remain in the water. Ultrafiltration would remove these larger
particles, and may remove some viruses.
 Neither microfiltration nor ultrafiltration can remove dissolved substances unless they are first
adsorbed(with activated carbon) or coagulated(with alum or iron salts).
 Nanofiltration:
 A nanofiltration filter has a pore size around 0.001 micron.
 Nanofiltration removes most organic molecules, nearly all viruses, most of the natural organic matter
and a range of salts.
 Nanofiltration removes divalent ions, which make water hard, so nanofiltration is often used to soften
hard water.
 Reverse osmosis:
 Reverse osmosis filters have a pore size around 0.0001 micron
 After water passes through a reverse osmosis filter, it is essentially pure water. In addition to removing
all organic molecules and viruses, reverse osmosis also removes most minerals that are present in the
water
 Reverse osmosis removes mono valentions, which means that it desalinates the water
A membrane is a selective barrier that permits the separation of certain
species in a fluid by combination of sieving and diffusion mechanisms

 Four common types of membranes:

o Reverse Osmosis (RO)
o Nano filtration (NF)
o Ultra filtration (UF)
o Micro filtration (MF)
 Other applications:
o Gas separation/permeation
o Pervaporation
o Dialysis
o Electrodialysis
 Water containing dissolved salts with a peculiar salty (brackish) taste is brackish
water
 The process of removing common salt from water is desalination
 Electrodialysis consists of a large container with two membrane separators, one
permeable to positive ions (cations) and the other permeable to negative ions
(anions)
 In the outer compartments cathode (-) and anode (+) are arranged to pass DC
Voltage
 When DC voltage/current is passed through the cell, Na+ cation will move towards
cathode and Cl‒ anion will move towards anode through the membrane
 Hence, the concentration of salt decreases in the middle compartment and
increases in the side compartments
 Water from the middle compartment is collected and this water is known as
desalinated water
֍ Transport of salt ions from
one solution to the other
solution through ion
selective membranes
under the influence of
applied electric potential
֍ For efficient separation,
ion-selective membranes
are used which selectively
allow cations or anions to
pass through them
• Electrodialysis cell consists of Large
number of pairs of rigid plastic ion
selective membranes
• Saline water at a pressure of 5-6kg/cm2
is passed through the membrane pairs
• DC current is applied perpendicular to
the direction of water flow

 Advantages are:
 Unit is compact and installation is
economical
 Best suited if electricity is available
 When two solutions of unequal concentrations are
separated by a semi-permeable membrane, solvent will
flow from lower concentration to higher concentration
 This phenomenon can be reversed (solvent flow
reversed) by applying hydrostatic pressure on the
concentrated side
 In reverse osmosis, pressure of 15-40 kg/cm2 is
applied to sea water
 The water gets forced through the semi-permeable
membrane leaving behind the dissolved solids.
 Thus water is separated from the contaminants rather
than removing contaminants from water
 Both ionic and non-ionic impurities as well as colloidal
impurities are left behind
 This process is also called as “Super-filtration” or
“Hyper filtration”
 Osmosis pressure: The amount of pressure required to stop the
process of osmosis in your experimental set-up.

 Theoretical value (Osmosis equation):

π = iMRT
π : osmosis pressure(atm)
i: van 't Hoff factor(for NaCl, i=1.8)
M: molar concentration(mole/liter)
R: ideal gas constant
T: absolute temperature(K)