Water Technology

Objectives
Characteristics of Water
Hardness of water
Estimation hardness in Water
Alkalinity of water
Estimation of alkalinity of water
 Water : An Engineering material

As a transporter of energy: in steam
raising plant (boiler), cooling
systems and heating circuits
(Coolant).

As an integral part of a process: in
brewing and soft drinks
manufacture, chemicals production
and the food industry

As a generator of power:
Hydroelectric power
 Uses of Water
Consumptive Uses
Domestic
Agriculture
Industry
Power generation: Hydroelectric power
Non-consumptive uses: Recreation...
 Sources of water

Surface Water: not Underground water

safe for consumption

Rain River Lake Sea Spring and well

 Purest Fed by rain Contains Most Rain water

form of and spring less amount impure form penetrates into the
natural of dissolved earth
Contains Dissolved
water minerals
dissolved and salt (3.5%) Due to filtering
Contains suspended High action of the soil it
Suspended
dissolved (org, inorg) quantity of appears clear
matter (org)
ind. gases, impurities org. matter
Contain dissolved
solid (org, salts
inorg)suspe
nded High organic purity
particles
 Impurities Present in water

Dissolved impurities Suspended Impurities Bacterial impurities

Inorganic Organic Gases Inorganic Organic Oil, pathogenic

salts salts vegetable and bacteria
Clay and
CO2, animal matter
Cations: humic sand Bacteria,
O2,
Ca, Mg, acid, other micro
oxides
Na, K, Fe, fulvic organism,
of N,
Al, Trace acid, bacteria,
NH3,
of Zn, Cu tannins. H2S algae, fungi

Anions
Cl,SO4,
NO3,
HCO3,F,
NO2
 Characteristics of water

Colourless

Odourless

Tasteless

Universal solvent

High specific heat capacity: It absorbs large amount of
heat energy before it begins to get hot and it releases this
energy when cool down. So it regulates earths climate and
body temp of organism

The solid form of water, ice, is less dense than its liquid form.

Hardness: Soap consuming capacity of water. It prevents
lather formation with soap.

Alkalinity: Buffering capacity of water

pH: Pure water is neutral but rain water is acidic due to
dissolved oxides of C, S and N

Dissolved Oxygen: Important for aquatic life

Chloride content: Over 250ppm impart peculiar taste.
 Classification of Water
1) Hard Water
Water which does not produce lather with soap solution,
but produces white precipitate is called hard water.
This is mainly due to the presence of calcium and
magnesium salts.
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
2) Soft Water
Water, which produces lather readily with soap solution is
called Soft water.
This is due to the absence of calcium and magnesium salts
 Hardness of water
Soap consuming capacity of water
Dissolved mineral salts result in hardness of water
It prevents lathering of soap due to the presence salts of
calcium (Ca2+), magnesium (Mg2+) ions and other
metals(Fe,Zn, Cu,Al) and other dissolved compounds such as
bicarbonates, sulfates,chlorides and silicates.
Calcium usually enters the water as either calcium carbonate
(CaCO3), in the form of limestone and chalk, or calcium
sulfate (CaSO4), in the form of other mineral deposits.
The predominant source of magnesium is dolomite
(CaMg(CO3)2).
Ground water contains more mineral salts than surface water
and its hardness is higher than surface water
 Types of Hardness
Hard water is categorized by the ions found in the water.
They areTemporary' and Permanent' hard water.
1)Temporary Hardness or Carbonate Hardness (CH) or
Alkaline Hardness
This is due to the presence of bicarbonates of calcium,
magnesium, Iron and other metals.
It can be removed by
boiling the water
adding lime to the water
The bicarbonates are converted into insoluble carbonates and
hydroxides, which can be removed by filtering.
Ca (HCO3)2 CaCO3 + H2O + 2 CO2
Mg (HCO3)2 Mg(OH)2 + 2CO2
contd----
 2) Permanent hardness or Non-carbonate
Hardness (NCH) or Non-alkaline Hardness:
Permanent hardness is hardness (mineral content) that
cannot be removed by boiling.
It is usually caused by the presence of
calcium,magnesium, iron and other metal sulfates
and/or chlorides in the water, which become more soluble
as the temperature rises.
Despite the name, permanent hardness can be either
removed or controlled by the addition of chemicals
(Internal Treatment) and by large-scale softening with
zeolite and ion exchange resins (External Conditioning).
 Expression of Hardness
Hardness is expressed in terms of CaCO3 Equivalents because
It is most insoluble salt obtained in water treatment
Its molecular weight is 100
The equivalent of calcium carbonate =
Mass of Hardness producing substance x Equivalent wt
of CaCO3
---------------------------------------------------------------
Equivalent wt of hardness producing substance
ESTIMATION OF HARDNESS BY EDTA:
Ca and Mg ions form complex with the chelating agent,
EDTA.
EBT forms a Meta stable complex with the metal ions,
which is wine red in colour. On treating the EBT complex
with EDTA, a more stable metal EDTA complex is formed
setting the EBT free. This reaction proceeds with a colour
change of wine red to steel blue.
 Unit of hardness
1) Miilgrams per litre(mg/L) : No of mg of calcium carbonate
equivalent hardness per litre
2) Parts per million ( ppm): no of parts of CaCO3 equivalent hardness
present per106 parts of water
3)Clark degrees (Clark)/English degrees (E)
No of part of calcium carbonate in one Imperial gallon(70,000 parts)
of water
4) French degrees (Fr) No of part of calcium carbonate in 105 parts of
water.
5) Milliequivalent per litre(meg/L): No of milli equivalents of hardness
present per litre
1ppm =1mg/L =0.1oF =0.07oCl
 Disadvantages of hard water
I) Domestic
 wastage of soap
 produces soap scum" and 'bathtub ring' that are difficult to
remove
 Produces unsightly spots on dishes, glassware and flat ware
 Increases the risk of diaper rash, rough, red hands, and skin
irritation and discomfort.
 Reduces the taste of ice cubes and boiled foods such as vegetables
 Bad effect on our digestive system- forming Ca.oxalate in urinary
track
II: Industrial
 Textile: Precipitates of Ca and Mg salts adhere to the fabric. Fe
and Mg salts produce coloured spots on fabrics
 Sugar : Cause difficulties in crystallization of sugar due to the
presence of sulphates, nitrates, alkali carbonates, etc.,
 Dyeing: Dissolved Ca, Mg, Fe Salts react with costly dye, ppt and
give shades and spots
 Paper: Ca and Mg salts react with chemicals which are empolyed
to provide a smooth and glossy finish to paper. Fe salts affect the
colour of the paper
 Disadvantages of hard water
 Laundry: Wastage of soaps and Fe salts cause coloration of
cloth
 Concrete: Chlorides and sulphates affect the hydration of
cement and final strength of hardened concrete
 Pharmaceutical: Undesirable pdt
 Electrical appliances : Formation of scale that clogs plumbing
and builds up on the inside of water heaters washing
machines, dishwashers, etc., which can increase gas or
electric bills, and may lead to early failure of the heater and
decreases life expectancy
III) In Boiler
 Priming and Foaming
 Scale and sludge Formation
 Corrosion
 Caustic Embrittlement
 Alkalinity of water
Buffering capacity of water- Ability of water to neutralize
the acid without changing pH due to carbonate-bicarbonate
ions
Soft water has little buffer capacity
Alkalinity is due to presence of
Caustic alkalinity, OH-, CO32-
Temporary hardness HCO3-
Advantages of alkalinity of water:
Minimum quantity, less than 0.2ppm is Essential to absorb the
excess H+ ions and protects water from pH fluctuation
Disadvantages
Causes caustic embrittlement in boiler
High content of alkalinity affects aquatic life
Leads to precipitation of sludge and scales in boiler
 Estimation of alkalinity of water
Acid base titration using phenolphthalein and methyl orange as
indicators
OH- + H+ H 2O P
CO3 + H
2- +
HCO3 - M
HCO3- + H+ H2O + CO2

The possible combinations of ions causing alkalinity in water are

As single ions: OH- or CO32 - or HCO3-
As double ions: OH- & CO32- or CO32- & HCO3-
The ions OH- & HCO3- cannot exist together because they combine
instantaneously to form CO32-
OH- + HCO3- CO32- + H2O
Significances of alkalinity estimation
 To control corrosion
 For calculating the amount of lime and soda required for softening of
water
 To calculate the amount of coagulants like Al sulphate and Fe sulphate
to be added in internal conditioning
 Points to Remember

Salts of Ca, Mg and other metals produce hardness in the water

Hardness prevents water from lather formation

Hard water is categorized by the ions found in the water. They
areTemporary' and Permanent' hard water.
1)Temporary Hardness or Carbonate Hardness (CH) or Alkaline
Hardness: This is due to the presence of bicarbonates of calcium,
magnesium and other metals. It can be removed by boiling the
water or by adding lime to the water
2) Permanent hardness or Non-carbonate Hardness (NCH) or Non-
alkaline Hardness: It is usually caused by the presence of
calcium and magnesium sulfates and/or chlorides in the water.
Permanent hardness can be either removed or controlled by the
addition of chemicals (Internal Treatment) and by large-scale
softening with zeolite and ion exchange resins(External
Conditioning).

Hardness is expressed in terms of CaCO3 Equivalents:
Commonly used unit is Parts per million ( ppm)

Hardness in water alters its properties and makes water
harmful
Boiler Troubles

 Boiler: Transport Heat

Energy
 Hardness and other
impurities in water:
Trouble maker of boiler
 Trouble shooting of boiler
Steam Utilization 1. Turbine drive
for electric
generating
equipment,
blowers and
pumps
2. Process for
direct contact
with products,
direct contact
sterilization and
non contact for
processing
temperatures
3. Heating and air
conditioning for
comfort and
equipment
 Problems due to hardness of water in the boiler
Boiler Feed water: Water fed into the boiler for
the production of steam
Priming and Foaming(Carryover): carrying
of water by steam along with impurities.
Priming: Formation of wet steam in the form
of spray into the steam outlet. Formation of
stable bubbles above the surface of water is
called foaming.
Scale and sludge formation: Evaporation in a
boiler causes salts to concentrate and they are
precipitated. Soft loose and slimy ppt is called
sludge while hard adherent ppt is called scale.
Boiler Corrosion : Due to presence of
dissolved oxygen, CO2, and acids from
dissolved salts.
Caustic embrittlement: Concentration cell
corrosion due to variation in conc of NaOH at
different parts of the boiler
 Priming
When boiler is steaming (producing steam) rapidly, some
particle of the liquid water containing impurities are carried
along with the steam
The process wet steam formation (steam containing droplets of
water) is called Priming
Caused by
 Sudden boiling : Irregular firing of boiler
 High steam velocities
 Improper boiler design: Steaming above design capacity
 Sudden increase in steam production rate: Variable steam demand
or water pressure
 Presence of large amount of non-scaling dissolved salts
Can be avoided by
 Fitting mechanical steam purifiers
 Avoiding rapid change in steaming rate
 Maintaining low water levels in boilers
 Efficient softening and filtration of boiler feed water
 Foaming
Chemical vaporous carry-over
Formation of stable foam or bubbles in boilers which
do not break easily
Due to
Presence of substances like oil, grease which greatly
reduce the surface tension of water in boiler water
High suspended solids
Other organic impurities
Can be avoided by
Adding anti-foaming chemicals like castor oil
Removing oil from water by adding compound like sod.
aluminates
Disadvantages of Priming and Foaming
They occur together
They are very harmful because
1) Dissolved salts in boiler water are carried by wet
steam to the other parts of the machines (heaters and
turbine blades) where they get deposited and hence
reduce the efficiency.
2) Dissolved salts enter other parts of machinery where
steam is being used thereby decreasing the life of
machinery
3) Actual height of the water column cannot be judged
properly, thereby making the maintenance of boiler
pressure becomes difficult
 Sludge Formation
The conc. of dissolved salts increases progressively as water
evaporates in the boiler
The salts start separating out from the water in the order of
their saturation point
Salts like CaCl2, MgSO4 separates in the body of the
liquid in the form of soft deposit which can be flushed out
easily
Such soft, slimy and non-adherent deposits are called
sludge
They form at comparatively colder portions of the boiler
where the flow rate is slow ex., at bends

contd----
Disadvantages and prevention of Sludge
formation
They are poor conductor of heat so they tend to waste a portion
of heat generated
If sludge forms along with scale, then former gets entrapped in
the latter and both get deposited as scales
Excessive sludge settles in the regions of poor water circulation
such as pipe-connection, plug-opening thereby causing even
choking of pipes
Prevention
Frequent blow down operation : Partial removal of hard water
through tap at the bottom of the boiler when the extent of boiler
is so high and addition of fresh softened water to boiler after
blow down operation
Softened water
 Scale formation
Scale is formed by salts like CaSO4, CaCO3, Mg(OH)2, CaSiO3/
MgSiO3 that have limited solubility but are not totally insoluble in
boiler water
These salts reach the deposit site in a soluble form and precipitate
in the form of hard adherent deposits on the inner walls of the
boiler. They are called scale.
Scales are so hard so that it is difficult to remove them even with
the help of hammer and chisel
They are formed by
CaCO3 deposit by decomposition of Ca. bicarbonate in low
pressure boiler
Ca(HCO3)2 CaCO3 + H2O+ CO2
2) Deposition of calcium sulphate as such in the high pressure boiler
8) Mg(OH)2 deposit by hydrolysis of Mg. salts-
MgCl2 +2H2O Mg(OH)2 + HCl
4) Presence of silica: Even present in small quantities it is ppted as
CaSiO3/ MgSiO3. They are very difficult to remove
contd---
 Disadvantages of Scale Formation
Wastage of fuel: Scaled are poor thermal conductor. In order
to provide a steady supply of heat to water, excessive or over
heating is done and this causes increase in fuel consumption
Lowering of boiler safety: because of over heating, the boiler
material become softer and weaker and makes boiler unsafe to
bear the pressure of the steam especially at high pressure
Decrease in efficiency: Scales may deposit in the valves and
condenser of the boiler and choke them partially. This result in
decrease in efficiency of the boiler
Danger of Explosion: When thick scale crack down due to
uneven expansion, the water comes suddenly in contact with
over heated iron plates. This causes in formation of large
amount of steam steadily. The sudden high pressure even
cause the explosion of the boiler
contd-----
 Removal of Scales
Physical Method: With the help of scraper or
piece of wood or wire brush if they are loosely
adhering
Thermal shocks: Heating the boiler and then
suddenly cool with cold water if the scale is brittle
Chemical method: By dissolving them by adding
chemicals if they are adherent and hard
CaCO3 5-10% HCl
CaSO4 EDTA form complex
Mechanical: By frequent blow down operation
 Caustic Embrittlement
Specific form of stress corrosion, results in the irregular inter crystalline
cracking of steel.
Combination of high stress and high caustic concentrations which
eventually led to destructive cracking of the boiler vessel
During softening process by lime-soda addition excess Na2CO3 is usually
added which results in free Na2CO3 in the boiler
In high press boiler, it decomposes to form NaOH which makes the boiler
water caustic
Na2CO3 + H2O 2NaOH + CO2
This alkaline water flows into the minute hair-cracks always present in the
inner side of the boiler by capillary action
When water evaporates the conc of dissolved caustic soda conc increases
progressively
It creates conc cells and iron parts which are under stress such as riveted
seams, bends and joints act as an anode and gets dissolved to form sod.
Ferroate,Na2FeO3
This causes embrittlement of the boiler parts particularly at stressed parts.
(+)
Fe at rivets, bends, joints|DilNaOH||Conc NaOH| (-)Fe at plain (under
stress) surface
Contd------
 Caustic Embrittlement
Can be avoided by
Using sod. Phosphate as softening agent
instead of sod. Carbonate
Adding tannin or lignin as these blocks the
hair cracks thereby preventing infiltration of
caustic soda solution
Adding NaSO4 as it also blocks hair-cracks,
thereby preventing infiltration of caustic soda
solutions.
 Boiler Corrosion
Decay of boiler material by chemical or
electrochemical attack of its environment
Main corrosive agents are
1)Dissolved Oxygen
2)Dissolved Carbon dioxide
3)Acids from dissolved salts
contd---
 1) Dissolved Oxygen
Water contains about8ml/lt of dissolved O2
At high temp it leads to rust formation-Mainly pitting type corrosion
2Fe+ 2H2O +O2 2Fe(OH)2
4Fe(OH)2 +O2 2Fe2O3.2H2O
Removal of dissolved O2

By Chemical means: By adding calculated quantity of Sod.sulphide or
hydrazine or sod. Sulphite which involves addition of chemicals, capable
of combining rapidly with the oxygen in aqueous solution.
2 Na2SO3+ O2 2 Na2SO4
N2H4+ O2 N2+ 2H2O
Na2S + 2O2 Na2SO4
Hydrazine hydrate is ideal because the reaction products are N2 and
water.
Sod. Sulphide and sulphite form sod.sulphate which are liable to
decompose giving SO2
By mechanical deaeration:
Deareater: Spraying water in a perforated plate-fitted tower heated from sides
and connected to vacuum pump
High temp, low press and large surface area reduces the dissolved O2 in water
 Mechanical deaeration: Eliminating oxygen
Deaerater and other corrosive gases like CO2, NH3from
water
Gas removal is accomplished by spraying cold
makeup water into a steam environment.
Heaters in the deaerater release dissolved
gases in the incoming water by reducing it to a
fine spray as it cascades over several rows of
trays.
The steam that makes intimate contact with
the water droplets then scrubs the dissolved
gases by its counter-current flow.
The steam heats the water to within 3-5 F of
the steam saturation temperature and it should
remove all but the very last traces of oxygen.
The deaerated water then falls to the storage
space below, where a steam blanket protects it
from recontamination.
 2) Dissolved Carbon Dioxide
CO2 +H2O HCO3(carbonic acid)
It has slow corrosive effect on the boiler material
Generation of CO2: CO2 is released inside the
boiler if the water used for steam generation
contains bicarbonate
Mg(HCO3)2 MgCO3 +H2O + CO2
Removal of CO2
1)By adding calculated amount of NH3
2NH4OH + CO2 ( NH4)CO3 +H2O
2)By mechanical deaeration process along with O2
 3) Acids From dissolved salts

Water containing dissolved Mg salts liberate

acids on hydrolysis
MgCl2 +2 H2O Mg(OH)2 +2 HCl
The liberated acid reacts with Fe in chain like
reactions producing HCl again and again
Fe + 2HCl FeCl2 +H2
FeCl2 +2H2O Fe(OH)2 +2HCl
Even the presence of small amount of MgCl2
will cause corrosion of Fe to a large extent
Boiler Corrosion
 Requirements of Boiler Feed water
1) Boiler feed water should be free from
b) Turbidity, oil and non-scaling dissolved salts to reduce the
tendency for priming and foaming
c) Hardness causing and scale forming constituents like Ca, Mg
and other metal salts as the formation of scales would result in
wastage of fuel, loss in out put and over heating of the boiler
tubes leading to explosion
d) Dissolved O2 and CO2 in order to prevent corrosion in the
boiler
e) Caustic alkali to remove caustic embrittlement
2)The limit of tolerance for boiler feed water
Maximum hardness < 20 ppm
Maximum TDS ----150-3500 ppm
Maximum Alkalinity ---- 100-700 ppm
TDS: Total dissolved salt
 Boiler water Treatment
Permanent Hardness can
be removed!
How?
 Boiler Water Treatment
Permanent hardness and other impurities can be
either removed or controlled by
External Conditioning: Ex-situ method:
Removal of hardness producing salts from the
water before feeding into boiler
Internal Treatment: In Situ method : By
adding chemicals directly in the boiler to
change the character of the ion by complexing
it into other more soluble salt
External Conditioning (Softening of Water)
Removal of hardness producing salts from the water before
feeding into boiler. The external treatment can be done by the
following methods.
1)Lime Soda process: Insoluble Ca and Mg salts in water are
chemically converted into soluble compds by adding calculated
amts of lime,Ca(OH)2 and soda Na2CO3
CaCO3 and Mg(OH)2 so ppted are filtered off
2) Zeolite Process: Zeolite is hydrated
Na.Al.silicate(Na2O.Al2O3.xSiO2.yH2O) capable of
exchanging reversibly its Na ions for hardness producing metal
ions in water
3) Ion Exchange Process / Demineralization process / de-
ionisation process:
 The process removes all the anions and cations present in the
hard water.
 Ion Exchange resins are insoluble cross linked long chain macro
polymer with micro porous structure and the functional groups
attached to the chains are responsible for the ion exchanging
properties.
ION-EXCHANGE PROCESS (ADSORPTION)-
Deionisation-dimineralisation of water
The process of releasing the cation or anion and adsorbing
another like ion
Synthetic resins are used as ion-exchange resin or ion-exchanger in
ion-exchange process
Insoluble cross-linked, long-chain org polymers with the functional
gp responsible for ion-exchanging properties
They posses one adsorbed ion on it
They release this ion and adsorbs another like ion
TYPES
Cation exchange resin (R-H+):with acidic functional gp(-COOH, -
SO3H, etc) ex. Styrene-divinyl benzene
Anion Exchange Resin (R+OH-)With basic functional gps
(-NH2, =NH as hydrochloride)
Styrene-divinyl benzene contain amino or quaternary ammonium or
quarternary phosphonium or sulphonium gp as an integral part of the
resin matrix
 Cation Exchanger
Capable of exchanging their cation (H+) with other cations present in the
water.
Cation exchange resin is represented as R-H+
Resins containing acidic fn group(- COO-H+, -SO3-H+) are capable of
exchanging their H+ ions with other cations of hard water.
Mainly styrene (divinyl) benzene copolymers which on sulphonation or
carboxylation become cabable to exchange their hydrogen ions with
cations in water
Process:
The hard water is first passed through a cation exchange column, which
removes all the cations like Calcium, Magnesium from it and equivalent
amount of H+ ions are released.
M+ + R-H+ RM + H+
CaCl2 +2 RH R2Ca + 2HCl
NaCl + RH RNa + HCl
Regeneration: when the cation exchange resin is exhausted, it can be
regenerated by passing a solution of dil. HCl or H2SO4:
RNa + HCl RH + NaCl
 Anion Exchanger
Resins containing basic functional groups ( NH2 ) or quaternary
ammonium groups are capable of exchanging their OH- ions with
other anions of hard water.
Anion exchange resin is represented as R+OH-
Anion exchange resin Styrene-divinyl benzene or amine-
formaldehyde copolymers which contain amino or quarternary amm
or quarternary phosphonium or quarternary sulphonium gp as
integral part of resin matrix
When water is then passed through an anion exchange column, which
removes all the anions like chlorides, sulphates etc. and equivalent
amount of OH- ions are released from the column.
X- + ROH RX + OH -
SO42- + 2ROH R2SO4 + 2OH-
Regeneration
The exhausted anion exchanger dil.NaOH can be used.
RCl + NaOH ROH + NaCl
Net result on passing through both cation and anion exchanger:
H+ + OH- H2O (Pure water)
 Deionisation of water
As the metallic ions (cations) in the water affix themselves to the exchange
material, the latter releases its hydrogen ions on a chemically equivalent
basis.
Because of the relatively high concentration of hydrogen ions, the solution is
very acid. deionization process is just half complete.
While the positive metallic ions have been removed, the water now contains
positive hydrogen ions, and the anions originally in the raw water.
The partially treated water now flows through a second unit, this time an
anion exchange material normally consists of replaceable hydroxyl anions
and fixed irreplaceable cations.
The negative ions in solution (the anions) are absorbed into the anion
exchange material. Released in their place are hydroxyl anions.
Contains the positive hydrogen ions released in the initial exchange plus the
negative hydroxyl ions released in the second exchange.
They have combined (positive to negative) to produce water molecules.
H+ + OH- H2O
The result of this two-stage ion exchange process is completely free from
cations and anions. This water is known as Demineral water or deionised
water.
Ion Exchange Process / Demineralization
process / de-ionisation process
Advantages:
1) Used to soften highly acidic or alkaline water
2) Produces water of very low hardness(2ppm)
Disadvantages:
1) The equipment is costly and expensive
2) If water contains turbidity, then the output of the
process is reduced. The turbidity must be below
10ppm.If it is more it has to be removed by
coagulation and filtration.
 Internal Conditioning
Internal Treatment or Sequestration or Boiler compounds
Involves the removal of scale forming substances which are not
completely removed by external treatment
By adding chemicals directly in the boiler to change the character of
the ion by complexing it into other more soluble salt
It is achieved by
Converting scale forming impurities into sludge forming ppt which
can be removed by blow down operation
Converting scale forming impurities into compd which will stay in
dissolved form in water and thus do not cause any harm
Contd-----
Internal Conditioning Methods
Colloidal Conditioning
Phosphate conditioning
Carbonate conditioning
Calgon conditioning
Treatment with Coagulant (sod.aluminate)
 !) Colloidal conditioning:
 Scale formation can be avoided by adding sub like kerosene, tanin, agar-agar
 These substances get coated over by the scale forming ppt, thereby yielding non-
sticky, loose deposit which can be removed easily by blow-down operation
 Applicable for low press boiler
2) Phosphate Conditioning:
 In high press boiler, scale formation can be avoided by adding sod. Phosphate
 It reacts with hardness of water, forming non-adherent and easily removable soft
sludge of Ca and Mg which can be removed by blow down operation
 3CaCO3(Scale) +2Na3PO4 Ca3(PO4)2(sludge) +3 Na2CO3
 3CaCl2(Scale) + 2Na3PO4 Ca3(PO4)2 (sludge) + 6Cl
 The choice of salt depends upon the alkalinity of boiler feed water. The main
phosphate employed are
 Acidic: Used for boiler water with too high alkalinity, Sod.hydrogen phosphate
NaH2PO4
 Weakly Alkaline: If the boiler waters alkalinity is moderate, Na2HPO4
 Alkaine: If the alkalinity of boiler water is low, Na3PO4
 Ca cannot be ppted properly below the pH of 9.5 so select a phosphate that adjust
pH to optimum value (9.5-10.5)
 Contd----
 3) Carbonate Conditioning
In low press boiler, scale formation can be avoided by adding sod.
Carbonate to the boiler water, permanent hardness is converted into
temporary hardness
CaSO4(per)+ Na2CO3 CaCO3 (temp)+ Na2SO4
CaCO3 is ppted as loose sludge which can be removed by blow-down
operation
4) Calgon Conditioning
Involves the addition of calgon, Sod.hexa meta Phosphate (NaPO3)6 or
Na2[Na4(PO3)6]
It prevents the scale and sludge formation by forming soluble compds
with CaSO4
Na2[Na4(PO3)6] 2Na+ + [Na4P6O18] 2-
2CaSO4(scale) + [Na4P6O18]2-
[Ca2P6O18] 2-(aq) + 2Na2SO4
Contd-----
5) Treatment with Coagulant (Sod.aluminate ,NaAlO2)
 Used to remove colloidal impurities including oil drops
and silica
 Sod.aluminate reacts with water forms gelatinous ppt and
NaOH.
 NaAlO2 +2H2O NaOH + Al(OH)3 (gel)
 NaOH+ 2MgCl2 Mg(OH)2(gel) +2NaCl
 The flocculant ppt of Mg(OH)2 and Al(OH)3 produced
inside the boiler entraps finely suspended and colloidal
impurities including oil drops and silica
 The loose ppt can be removed by pre-determined blow-
down operation
 Points to remember
 Mineral salts and other impurities present in the water are the trouble makers of the
boiler.
 They can be either removed or controlled by
1)External Conditioning: Removal of hardness producing salts from the water before
feeding into boiler
Ion Exchange Process / Demineralization process / de-ionisation process:
 The process removes all the anions and cations present by adsorbing them into the
ion exchange material.
Cation exchanger adsorbs cation and releases the positive hydrogen ions while the
Anion exchanger releases negative hydroxyl ions by exchanging it with other anions
present in the water
Positive hydrogen ions and negative hydroxyl ions released as a result of this two-
stage ion exchange process combine to produce water molecules.
This water is known as Demineral water or deionised water.
In mixed-bed deionisers: The cation-exchange and anion-exchange resins are
intimately mixed and contained in a single pressure vessel so that the whole bed can
be regard as an infinite number of anion and cation exchangers in.
Electrical demineralisation of water
The rate of diffusion of ion is increased by passing electric current through the
electrode placed near , ion-selective membranes membrane
2)Internal Treatment: In Situ method : By adding chemicals directly in the
boiler to change the character of the ion by complexing it into other more
soluble salt
It is achieved by
Converting scale forming impurities into sludge forming ppt which can be
removed by blow down operation
Converting scale forming impurities into compd which will stay in dissolved
form in water and thus do not cause any harm
1)Colloidal conditioning: Org sub like kerosene tanin, etc., get coated over the
scale forming ppt, thereby yielding non-sticky, loose deposit
2) Phosphate Conditioning: Scales are converted into non-adherent and easily
removable soft sludge of Ca and Mg by sod.phosphate
The choice of salt depends upon the alkalinity of boiler feed water.
3) Carbonate Conditioning: Permanent hardness is converted into temporary
hardness by adding Na2CO3
4) Calgon Conditioning: Prevents the scale and sludge formation by converting
them into soluble compds with calgon (sod.hexa meta phosphate)
5)Treatment with Sod.aluminate (NaAlO2); Sod.aluminate reacts with water
and forms flocculant ppt of Mg(OH)2 and Al(OH)3 which entraps finely
suspended and colloidal impurities including oil drops and silica
 Desalination
Only about 1% of worlds water resources
can be used by man
How can the large portion(97%) of water
locked in the ocean be used to over come
the water scarcity of the world
What are the economically viable
techniques used to purify the water
 Desalination of Brackish water
(Sea Water)
Brackish water: The water containing salt with
peculiar salty (or brackish) taste
Sea water containing average about 3.5% salt comes
under this category
The process of removing common salt (NaCl) and
other salt from water is known as desalination
Sea water can be converted into fresh water by
1) Membrane Distillation
2) Electro dialysis
3) Reverse Osmosis
Reverse Osmosis
 Reverse Osmosis
If two solutions of different concentration are separated by a semi-permeable
membrane which is permeable to the smaller solvent molecules but not to the
larger solute molecules, then the solvent will tend to diffuse across the
membrane from the less concentrated to the more concentrated solution. This
process is called osmosis.
When a semi permeable membrane separates a dilute solution from a concentrated
solution, solvent crosses from the dilute to the concentrated side of the membrane
in an attempt to equalize concentrations.
Reverse osmosis is a membrane separation process for removing solvent from a
solution in which solvent will flow from the concentrated to the dilute solution.
Pure solvent is separated from its contaminates rather than contaminates from
the water
It is done by applying an opposing hydrostatic pressure to the concentrated
solution.
The magnitude of the pressure required to completely impede the flow of solvent
due to osmosis is defined as the "osmotic pressure".
If the applied hydrostatic pressure exceeds the osmotic pressure flow of solvent
will be reversed, that is, solvent will flow from the concentrated to the dilute
solution.
Also called Super filtration or Hyper filtration
 The salt water is pressurized(15-40kg/cm2) on
Procedure one side of a semi permeable membrane. The
pressure must be high enough to exceed the
osmotic pressure to cause reverse osmotic flow
of water.
The membrane is highly permeable to water,
but essentially impermeable to dissolved
solutes, pure water crosses the membrane
As pure water crosses the membrane, the
concentration of dissolved impurities increases
in the remaining sea water and, as a
consequence, the osmotic pressure increases.
A point is reached at which the applied
pressure is no longer able to overcome the
osmotic pressure and no further flow of
product water occurs. The membrane becomes
fouled by precipitated
Membrane consists of very thin films of
cellulose acetate, metha acrylate or polyamide
polymers
 Advantages of reverse osmosis
Removing ionic as well as non ionic colloidal and high
mol. Wt org matter
Removes colloidal silica which is not removed by
demineralization
The maintenance cost is entirely on the replacement of
semi permeable membrane
The life time of membrane is quite high, 2yrs
Replacement of membrane takes few min thereby
providing nearly uninterrupted water supply
Conversion of sea water into drinking water and for boiler
Drinking water in India

Microbial contamination of the water supply

has led to outbreaks of disease, causing illness
and even death.
How safe is our water?
How is water treated by Municipality and
whats being done to make it safe?
 Requisites of Drinking Water
Drinking or potable water should be
Clear, colorless and odorless
Pleasant in taste
Perfectly cool
Reasonably soft
turbidity not > 10 ppm
Free from objectionable minerals & dissolved
gases
pH ~ 7.5 8.0
TDS < 500 ppm
Free from disease producing microorganisms
Free from Pb, As, Cr, Mn, Fe etc.
Where does the water come from
for Domestic uses?
surface waters (lakes, rivers, and reservoirs)
groundwater (wells).
Domestic water treatment
Municipal water
Treatment Objectives
Sources: Lakes and rivers- do not meet all the
required specifications of drinking water-contain
suspended inorg. and org particles and micro-org
Render water free from these disease producing
organisms and toxic substances.
Make it free from color, turbidity, taste, odors
Does not aim at removing all dissolved salt: Does
not supply softened water
Process Flow
Raw Water
Chart
Screening

sedimentation
1) Removal of
Sedimentation with Coagulation suspended
Impurities
Filtration

Disinfection 2) Removal of
micro organism
Drinking Water
Drinking water treatment plant
Drinking water treatment plant
 1. screening 2.Sedimentation
1.Screening
To remove floating materials
like wood pieces , leaves etc
Water passed thro bar
screens to hold back floating
matter
2.sedimentation
In grit chambers & settling
tanks
Gravity pulls the heavy
particles to the bottom of the
tank & the water is sent to
settling tank
2) Sedimentation: Allow water to stand undisturbed in big, deep
tanks. The retention period ranges from 2-6hrs WATER
FROM
COAGULATION

Coagulated particles fall, by gravity, through water in

a settling tank and accumulate at the bottom of the
tank, clearing the water of much of the solid debris
and clear water moves to filtration.
WATER
TOWARDS
FILTRATION
Sedimentation
3. Coagulation ( Flocculation) and
o
sedimentation
Coagulation removes fine suspended and colloidal impurities and
other particles suspended in water.
o Alum and other chemicals are added to water to form tiny
sticky
particles called floc which attract the dirt particles.
Coagulant like alum , or Fe.sulphate provide Al3+ or Fe3+ ion
which neutralize the ve charge on the clay(SiO3)2- particle
and bring tiny particles together to form bigger particles
o The combined weight of the dirt and the alums (floc)
becomes heavy enough to sink to the bottom during
sedimentation.

WATER
TOWARDS
SEDIMENTATION

Sludge disposal
 Coagulation - Reactions
1) Using Alum [K2 SO4 . Al2(SO4)3 . 24 H2O]
Al2(SO4)3 + Ca (HCO3)2 2Al(OH)3 + Ca SO4+ 6CO2
coagulant water >pH 7 ppt
2)Using Sodium Aluminate(NaAlO2)
NaAlO2 + 2H2O Al(OH)3 + NaOH
water <pH 7 gelt . Floc

NaOH + MgSO4 Mg(OH)2 + Na2SO4

ppt
3) Copperas or Ferrous sulphate(FeSO4.7H2O)
FeSO4 + Mg(HCO3)2 Fe(OH)2 + MgSO4+ CO2 +H2O
water >pH 7
4Fe(OH)2 +O2 +2H2O 4Fe(OH)3
(Heavy floc causes quick sedimentation)
4. FILTRATION: Process of removing colloidal matter and most
of bacteria, micro-organism, etc., by passing water through a
bed of fine sand and other proper sized granular materials
4)Filtration Sand trickling filters

Water then flows through large dual media rapid sand filters
made up of layers of gravel, sand, and anthracite coal
Sand Filter
5. Disinfection: Removal of micro-organism
Process of destroying/killing any disease causing
bacteria and microbes to make water for safe
The chemicals and sub which are used for
disinfection are called disinfectant
Methods of disinfection
i) Boiling
ii) Using UV light
iii) Ozone
iv) Bleaching powder
v) Chlorination
vi) Chloramines
 1) Boiling
Boil water for 10-15 min
Disadvantages
Boiling alter the taste of drinking water
Can kill only existing germ in water at the
time of boiling, does not provide any
protection against future possible
contamination
It is impossible to employ it in municipal
water-works
ii) Using ultraviolet light
 Ultraviolet radiation lies between visible light and
X-rays on the electromagnetic spectrum.
UV light = 1000 4000A . UV light has a
shorter wavelength than visible light
Earth's atmosphere prevents most UV radiation from
space from reaching the ground.
UV-(short wave) is entirely screened out by
stratospheric ozone at around 35 km altitude.
It is germicidal at 200 and 280 nm. I t is used to
sterilize glassware used in medicine and biological
research.
ULTRAVIOLET RADIATION
SOURCE
UV light is emitted as a result of
current flow through the mercury vapor
between the electrodes of the lamp.
The most commonly used UV lamps
(low pressure mercury vapor) produce
the majority of their UV output at
253.7nm, a wavelength which is very
close to the 260 - 265nm wavelengths
which are most effective in killing
microbes.
The germicidal lamp(200-280nm) is
constructed of UV transmitting quartz;
The advantages of UV disinfection
- disinfection without adding chemicals
- no change to the taste and no removal of beneficial
minerals
- minimal maintenance
- immediate treatment without the need for holding
tanks
- ideal compatibility with other technologies for
complete solutions: carbon filtration, water softeners
reverse osmosis
- low power consumption
 iii) Using ozone

-OZONE is the Strongest oxidant/disinfectant available.

-More effective against microbes than chlorination
Ozone production

3O2 2O3 O2 + [O]

Silent electric Unstable

discharge unstable
Nascent oxygen

Advantages
- Does not leave by any residue Kills bacterias &
Removes simultaneously colour, oxidised org
odour and taste substances
-Excess is not harmful
Demerits
- Expensive
- Unstable and can not be stored for
- long time
 Ozone steriliser

Raw water
Ozone inlet

Disinfected water

tank

Contact time : 10 15 mins

Dosage 2-3 ppm
iv) Bleaching Powder

About 1kg of bleaching powder per 1000 kilolitres of

water is mixed
Reactions
CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HCl + HOCl

kill germs by inactivating the

enzymes essential for the metabolic
process of micro-organism

Demerits:
Introduces calcium hardness
Deteriorates on storing
Imparts bad taste /odor if it is added in excess
 v) Using chloramines(ClNH2)

Cl2 & NH3 in the ratio of 2:1

Cl2 + NH3 ClNH2 + HCl
ClNH2 + H2O HOCl + NH3
-
- Inactivates the enzymes essential for the
metabolic process of micro-organism and
and kill them (bacteria and germs)

It is preferred because
Much more lasting than chlorine alone
Does not produce irritating odor
Imparts good taste
 vi) Chlorination

Cl2 + H2O HCl + HOCl

Gas / liquid

chlorinator
-
- Inactivates the enzymes essential for the
metabolic process of micro-organism and
and kill them (bacteria and germs)
Used at low pH values < 6.5

The acid form, HOCl, is a much stronger disinfectant than

the hypochlorite ion, OCl- (found at higher pH)
Free chlorine in treated water should not exceed 0.1 0.2 ppm
Efficiency of chlorination depends upon time of contact,
Temp., & pH of water
Chlorination
Advantages
Effective and economical-The most ideal disinfectant
Little space for storage
Stable & do not deteriorate on standing can be used at low
& high T.
Introduces no salt impurities
Disadvantages
More effective below 6.5 pH & less effective at higher pH
values
Excess chlorine leaves unpleasant odor which produces
irritation on muscus membrane
Break point chlorination
Problem during chlorination
At high pH exists as OCl -
Presence of NH3 can cause problems as chloramines are
formed which have very little disinfecting power
(Chloramines are an effective disinfectant against
bacteria but not against viruses)
Chloramines irritate the skin and eyes and impart
unpleasant odour to the water
Alternatives
Adding sufficient amounts of chlorine would be an
excellent method to oxidise free ammonia along with
org. substances and reducing substances present in water
Excess chlorine would stay as hypochlorous acid
Break point chlorination or free Produce a residual free available
residual chlorination chlorine (HOCl) with no combined
chlorine
Zone I
Zone II Zone IV
Residual chlorine

Zone III

Break point

Chlorine dosage

Zone I: Chlorine is reduced to chlorides by reducing compounds in water

Zone II: Chloramines are formed with ammonia
Zone III: Chloramines are broken down and converted to
nitrogen gas which leaves the system (Breakpoint).
Zone IV: Free residual.
 Reactions / Mechanism
If ammonia is present in the water, then the hypochlorous acid will
react to form one of the three types of chloramines depending on
the pH, temperature, and reaction time.
Monochloramine and dichloramine are formed in the pH range of
4.5 to 8.5, however, monochloramine is most common when the
pH is above 8.
When the pH of the wastewater is below 4.5, the most common
form of chloramine is trichloramine which produces a very foul
odor.
The equations for the formation of the different chloramines are as
follows :
Monochloramine: NH3 + HOCl -> NH2Cl + H2O
Dichloramine: NH2Cl + 2HOCl -> NHCl2 + 2H2O Zone II
Trichloramine: NHCl2 + 3HOCl -> NHCl3 + 3H2O
Contd-----
 The final step is that additional free chlorine reacts with the
chloramine to produce hydrogen ion, water , and nitrogen
gas which will come out of solution- Zone III
Thus, added excess chlorine reduces the concentration of
chloramines in the disinfection process and the remaining
free chlorine(residual chlorine) forms the stronger
disinfectant, hypochlorous acid- Zone IV
De-Chlorination: Over chlorinated water may be passed
thro bed of activated carbon or by addition of SO2 or Na.
Sulphite to remove unpleasant odor/taste
SO2+ Cl2+ H2O H2SO4 +2HCl
Na2SO3 +Cl2+ H2O Na2SO4 +2HCl
 The advantages of Break point
chlorinatiom
Oxidises completely org. compds
Removes colour due to org matter
Destroys 100% pathogenic bacteria
Removes odour and taste
Prevents the growth of any weeds in water
 Points to remember
Natural surface water, from lakes and rivers are main sources for
municipalities
Water is purified at different steps to remove suspended particles,
org matters and pathogenic bacteria to make it for safe for use
Suspended particles are removed by screening, settling and
sedimentation
Fine colloidal particles are removed by converting them into floc by
adding coagulant followed by sedimentation
Filtration is done to remove all org matters and micro-organisms
Complete destroying/killing of pathogenic bacteria and micro-
organism is done by disinfection
Disinfectantants like UV rays, ozone, chloramines, bleaching
powder and chlorination are used to kill bacteria, virus and other
micro-org present in the water
UV light wave length ranges from 200 and 280nm is germicidal
Unstable ozone decomposes and produces nascent oxygen which
kills all micro-org and oxidizes all org compds present in the water
contd---------------
 Bleaching powder, chloramine and liquid/ gaseous
Cl2(chlorination) kill bacteria by forming HOCl which
inactivates the enzymes essential for the metabolic process
of micro-organism and kill them (bacteria and germs)
Insufficient chlorination of water containing NH3 leads to
the formation of mixture of chloramines which irritate the
skin and eyes and impart unpleasant odour to the water
Excess or Sufficient chlorine is added to produce residual
free available chlorine in Break point chlorination
Excess chlorine oxidizes org. substances, reducing
substances and free ammonia present in water
Excess chlorine would stay as hypochlorous acid and
destroys all micro-organisms
Over chlorinated water may be passed thro bed of
activated carbon or by addition of SO2 or Na. Sulphite to
remove unpleasant odor/taste