WATER TECHNOLOGY

Water is life
Save water save life
 Universe comprises of three parts of water and one part of
land.
 Of the earth’s water – 97% is in the ocean .

Of the remaining 3%

1% is available as fresh water in

2% locked in the polar
river,lakes,streams,resevirors,
ice caps and glaciers
ponds and ground water which
(not for ready use)
is suitable for human
consummation.
{ Depends on rain fall}
70% is lost by direct
16% 8%irrigation 4%
evaporation of transpiration 2%
electrical industry
by plants domestic
utilities
use
 Importance of water

Looking at water, you might think that it's the most

simple thing around.

Pure water is colorless, odorless, and tasteless.

But it's not at all simple and plain and it is vital for all
life on Earth.

Where there is water there is life, and where water is

scarce, life has to struggle or just “give up."
Where does the water come from?
surface waters (ocean, sea, lakes, rivers, and
reservoirs)
groundwater (wells).
Ocean and sea water is useless for drinking
Source of drinking water lakes, rivers, ponds and
reservoirs.
SOFT WATER AND
HARD WATER
Soft water:
Water that gives lather
with soap easily and readily is
Known as Soft water.

• Hard water:
• Hard water forms scum when it comes in
contact with soap.
 HARDNESS OF WATER
Hardness of water is that characteristic property which
prevents the lathering of soap easily . This is due to
presence of certain salts of calcium, magnesium and

other heavy metals dissolved in water .

Typical reactions of soap (sodium stearate) with Calcium
chloride and magnesium sulphate

2C17H35COONa + CaCl2 → (C17H35COO)2Ca ↓

+2NaCl
Calcium
Stearate(insoluble)

2C17H35COONa +
MgSO4→(C17H35COO)2Mg+Na2SO4
Magnesium Stearate(insoluble)
TYPES OF HARDNESS
Temporary hardness:
It is caused by the presence of dissolved bicarbonates
of calcium,magnesium and other heavy metals.
Temporary hardness is easily removed by boiling, on
boiling bicarbonates are decomposed into insoluble
carbonates or hydroxides.
Permanent hardness

It is due to the presence of chlorides sulphates and

carbonates of calcium, magnesium and other heavy
metals . Unlike temporary hardness ,permanent
hardness is not removed on boiling
 Equivalents of Calcium carbonate

The choice of CaCO3 is due to its molecular weight 100

(M) (equivalent weight M/2 = 50) and it is the most

insoluble salt that can be precipitated in water treatment.

Units :
 1 ppm = 1 part of CaCO3 present in 106parts of
water
 1 mg/lit = 1 mg of CaCO3 present in 1 lit of
water

Relationship between units:

 1 mg/lit = 1ppm
Determination of hardness of water by EDTA method

EDTA Di Sodium Salt Of EDTA

Ethylene diamine tetra acetic acid (EDTA) in the form of

di sodium salt yields the anion of Ethylene diamine tetra
acetate which forms complex ions with Ca +2 and Mg+2
Principle of EDTA method for the determination of
hardness of water
In order to determine the equivalence point , indicator
eriochrome black – T (EBT) is employed.
EBT forms unstable wine red complex with Ca+2 and
Mg+2 ions

M+2 + EBT → [ M-EBT ] complex

(Ca+2 and Mg+2 ions
of hard water ) wine red
During titration EDTA combines with Ca+2 or Mg+2
ions and forms stable [M-EDTA] complex.

[M-EBT] complex + EDTA → [M-EDTA]complex + EBT

wine red blue

The change of wine red colour to distinct blue colour

marks the end point of titration.
pH 10

Metal–EDTA
complex
PROCEDURE:
Part: 1:
Preparation of Standard Hard water:

Transfer a known mass (about 1gm) of

calcium carbonate into a 1000ml volumetric
flask. Add 40-50 ml(approximately) of water.
Add dilute hydrochloric acid till a clear
solution is obtained. Make up the volume to
the mark by adding water.
Part: 2:
Standardization of EDTA:
Pipette out 10ml of Standard hard water, into
a conical flask. Add 5ml (approx) of buffer and
a few drops of Eriochrome black-T indicator.
The solution attains wine-red colour. Titrate
the contents of the conical flask against the
solution of EDTA solution. Stop the addition of
solution from the burette when the colour of
solution in the conical flask changes from
wine-red to blue. Note the burette reading
and repeat the titration to get concurrent
results. Let the volume of the solution of
EDTA consumed in this titration be ‘V1’ ml.
Part:3:
Determination of Total Hardness of Test
Sample of Water:
Pipette out 10ml of test sample of water in
the conical flask. Add 5ml (approx) of buffer
and 3 to 4 drops of Eriochrome black-T
indicator. The solution attains wine-red
colour. Titrate the contents of the conical
flask against EDTA solution till the colour
changes from wine-red to blue. Note the
burette reading and repeat the titration to get
concurrent results. Let the volume of EDTA
solution consumed in this titration be ‘V2’ ml.
The total hardness of the test sample of water
is calculated as follows:
 BOILER
TROUBLES
Boilers are almost invariably employed in industries for
generation of steam .

When raw water is directly feed into the boilers ,various

physical as well as chemical reactions are induced in
the boiler with the action of the heat.

The ultimate result being the problem such as sludge or

scale formation, caustic embrittlement, priming, forming
and boiler corrosion .
 BOILER TROUBLES
TYPES

1.Carry over( priming and foaming)

2.Boiler corrosion
3. Scale and Sludge
4.Caustic embrittlement
1.Carry over:
The phenomenon of carrying of water along with
impurities by steam is called carry over.

a)PRIMING:

 When boiler is steaming rapidly some particles of

the liquid water are carried along with the steam.
 This process of wet steam formation is called
PRIMING.
 It is caused by the presence of
 large amount of dissolved solids
 high steam velocities
 sudden boiling
 improper boiler design and
 sudden increase in steam production rate
Priming 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 the
boiler-feed water
b) FOAMING:
 It is the production of persistent foam or bubbles in
boilers, which do not break easily.
 It is due to the presence of substances like oils
Foaming can be avoided by
i. adding anti-foaming chemicals like castor oil
ii. removing oil from boiler water by adding
compounds like NaAlO2.
Priming and Foaming occurs together and are
objectionable because dissolved salts in boilers
deposited and reduce the efficiency or decreases
life of machinery or cause difficult to maintain the
pressure.
2.Boiler Corrosion:

Decay of boiler material by a chemical or electro

chemical attack by its environment.
Main sources for boiler corrosion are
a. Dissolved oxygen
b. Dissolved carbon dioxide
c. Acids from dissolved salts
a. Dissolved oxygen
 Water usually contains about 8ml of
dissolved oxygen per lit. at RT.
 It attacks boilers at high temperature.
2Fe +2H2O + O2 2 Fe(OH)2

4Fe(OH)2 + O2 2[Fe2ORust
3.2H2O]
 Removal of dissolved oxygen:

1) By adding sodium sulphite , hydrazine , sodium sulphide

2Na2SO3 + O2  2 Na2SO4
N2H4 + O2  N2 + 2H2O
Na2S + 2O2  Na2SO4

2) By Mechanical De-aeration Process

b.Dissolved carbon dioxide:
The dissolved CO2 in water produces carbonic acid,
which has slow corrosive effect.

This is also produced inside the boiler, if water

contains bicarbonates.
CO2+ H2O  H2CO3
Mg(HCO3)2  MgCO3 + H2CO3

Removal:
a. By adding ammonia:

2NH4OH + CO2 (NH4)2CO3 + H2O

b.By mechanical aeration process along with

oxygen
c. Acids from dissolved salts:
Mineral acids are generated through the
hydrolysis of disolved acidic salts.

The liberated acid reacts with Fe of boiler to

form Fe(OH)2 subsequently get converted into
rust .

Small amount of MgCl 2 will cause corrosion of

Fe to a large extent.

MgCl2 + 2H2O  Mg(OH)2 + 2HCl

2HCl + Fe  FeCl2 + H2

FeCl2 + 2H2O  Fe(OH)2 + 2HCl

Fe(OH)2 + O2  Fe2O3 .2H2O

 Prevention of Acid corrosion :
 i) By addition of inhibitors
 ii) By frequent blow down operation
 iii) By softening of boiler water .
3. SLUDGE & SCALE FORMATION
 In boilers, water evaporates continuously and
concentration of dissolved salts increases. When
it reaches saturation point they will be
precipitated on the inner walls of the boilers.
 If the precipitation takes place in the form of
loose and slimy ppt it is called sludge.
 If the precipitation takes place in the form of
hard, adhering on the inner walls of the boilers it
is called scale.
a)SLUDGE:
 It is formed at colder portions of the boilers.
 It is formed by substances, which have greater
solubility in hot water than cold water. (MgCO3,
MgCl2, MgSO4, CaCl2)
 It can easily scrapped off with a wire brush.
Disadvantages:
 Sludges are poor conductors of heat.
 Disturbs the working of boilers.
Prevention of Sludge Formation:
 By using well-softened water.
 By frequently blow-down operation.( It is nothing
but the removal concentrated water through an out let at
the bottom of the boiler under pressure.)
b)SCALES:
 These are difficult to remove
 The main sources for the formation of
scales are
 Decomposition of calcium bicarbonate

Ca(HCO3)2  CaCO3 + H2O + CO2

 Deposition of calcium sulphate.

 Hydrolysis of Mg salts.
 Presence of silica
 In low pressure boilers CaCo3 causes
scale formation, but high pressure
boilers CaCO3 is soluble
CaCO3 + H2O Ca(OH)2 + CO2

Disadvantages of scale formation:

 Wastage of fuel.
 Lowering of boiler safety.
 Decrease in efficiency.
 Danger of explosion

Removal of scales:
With the help of scraper or brush
By thermal shocks
 By dissolving in chemicals.
4.Caustic Embrittlement:
 Caustic embrittlement is a phenomenon in
which the boiler material becomes brittle due
to accumulation of caustic substances.
 In high-pressure boilers, sodium carbonate is
hydrolyzed to yield NaOH.

 The NaOH concentration increases by

evaporation and attacks the surround area
there by Fe dissolves as sodium ferrate.
 This causes embrittlement of boiler parts
causing even failure of the boiler.
 Caustic Embrittlement can be removed by
 A) Using sodium phosphate as softening reagent
 B) Adding tannin/lignin (these block hair-cracks
in the boiler walls)
 C) Adding Sodium sulphate
 Softening of water
It can be done by 2 methods

1) Internal treatment.
2) External treatment.
Internal Treatment
 In this method, raw water is treated inside the boiler.
Internal treatment means addition of suitable
chemicals to reduce scale and sludge formation and to
convert the scale forming chemicals into sludge which can be
removed by blow down process.
Some of the internal treatment methods used for the removal
of scale formation in boilers are.

A) Phosphate conditioning

B) Carbonate conditioning
C) Calgon conditioning
A) Phosphate conditioning
It is generally applicable to high pressure
boilers. Scale formation is avoided by adding
sod.phospate, which reacts with Mg,Ca salts
forming soft adherent compunds and easily
removed by blow down operation.
3MCl2 + 2Na3PO4  M3(PO4)2 + 6NaCl
3MSO4 + 2 Na3PO4  M3(PO4)2 + 3Na2SO4
Where M= Ca+2 or Mg+2
The choice of Phosphate salt depends on the
alkalinity of water . Na3PO4 is used for alkaline
water where as Na2HPO4 is used in highly
alkaline water and NaH2PO4 is used in acidic
water
B) Carbonate conditioning
In low pressure boilers, scale formation can
be avoided by adding sodium carbonate to
boiler water, when salts like CaSO4 can be
converted into CaCO3 . CaCo3 can be
removed by blow down process.
Na2CO3 + CaSO4  CaCO3 + Na2SO4
C) Calgon conditioning:
It involves in adding Sod. Hexa meta phosphate
(calgon) to boiler water to prevent the scale and
sludge formation .
Calgon converts the scale forming impurity like
CaSO4 into soluble complex compound.

2CaSO4 + Na2[Na4P6O18]  Na2[Ca2P6O18] +

2Na2SO4

Calgon soluble complex

EXTERNAL TREATMENT:
External treatment: This treatment is
given outside the boiler before the feed
water enters in to the boilers for reducing
the concentration of hardness producing
ions.
ION EXCHANGE PROCESS
 It is also called de-ionization or
demineralization.
 Ion exchange resins are in soluble, long chain,
cross-linked polymers with a micro porous
structure.
 Resins containing acid groups (COOH, SO H) are
3
capable of exchanging their H+ ions with other
cations. This is called Cation exchange resin.
Ex: RCOOH, RSO3H

 Resins containing basic groups (OH-, NH -) are

2
capable of exchanging their anions with other
anions. This is called Anion exchange resin.
Ex: R-CH2NMe2OH
Examples of resins:

OHO
OH
Ion exchange process:
The hard water is pass first through cation
exchange column, which removes all the cations
like Ca+2,Mg+2 etc. from it, and equivalent
amount of H+ ions are released from this column
to water thus:
2RH+ + Ca+2  R2Ca+2 + 2H+
2RH+ + Mg+2  R2Mg+2 + 2H+
After cation exchange column, the hard water is
passed through anion exchange column, which
removes all the anions like SO4-2, Cl-etc. present in
the water and equivalent amount of OH- ions are
released from this column thus:
ROH- + Cl-  RCl- + OH-
2ROH- + SO4-2  R2SO4- + 2OH-
H+ & OH- ions get combined to produced
water molecule.
H+ +OH-  H2O
Thus water coming from the exchanger is
free from cations as well as anions.
Regeneration : Exhausted cation resin is
regenerated by dil. HCl , anion by dil.NaOH.
R2Ca +2 + 2 H+  2RH + Ca+2 (washed)
R2SO4 + 2OH-  2ROH- + SO4-2(washed)
Desalination
The process of removal of dissolved salts
(NaCl, KCl) present in water is known as
desalination. Water is divided into three
categories on the basis of salinity:
(a) Sea water: The salinity is greater than
35000 mg/L.
(b) Brakish water: The salinity is in the range
of 1000−35000 mg/L. It has peculiar salty
taste.

Important desalination methods are:

 (i) reverse osmosis,
 (ii) electrodialysis .
Reverse Osmosis Process
Osmosis is the process in which the flow of solvent
takes place from dilute to concentrated solution
through a semi-permeable membrane. In this process,
only solvent can flow but not the solute, which
produces a pressure called osmotic pressure on the
side of more concentrated solution.

When the flow of solvent under pressure from more

concentrated solution to solvent or to the less
concentrated solution through a semi-permeable
membrane takes place is called reverse osmosis.
This method is applicable mainly for the
desalination of sea water.

Reverse osmosis cell

Advantages of the process
1. The process removes ionic as well as non-ionic
dissolved salts easily.
2. It is effective in removing colloidal impurities
in water.
3. The process is economical and convenient. The
process can be carried out at a room
temperature.
4. It is suitable for converting sea water into
drinking water
Disadvantages:
The life time of membrane is quite
high ,which is an average more than a year.
The maintenance cost is only the replacement
of membrane.
 Water Treatment Plant
Stages
Depending on the type of treatment plant and the
quality of raw water, treatment generally proceeds
in the following sequence of stages:
1. Screening
2. Sedimentation
3. Coagulation
4. Filtration
5. Disinfection(chlorination &
ozonization)
• As required, other steps will be added, depending on the
chemistry of the treated water.
isis.csuhayward.edu/alss/Geography/ mlee/geog4350/4350c4f01.ppt
Treatment of municipal water involves
the following:

1. Screening: Water is allowed to pass

through the mesh screens whereby large
floating matters are removed
2. Sedimentation: Water is allowed to
stand undisturbed for 2−5 h in big setting tanks.
Suspended particles settle down due to gravity and clear
water raises which can be drawn out with the help of the
pumps.
Disadvantages
• It requires long big tanks. It takes a long time.
• It removes 70−75% suspended matter.
• If water contains clay and colloidal impurities,
coagulants are added before sedimentation.
3. Coagulation: Colloidal particles from the
water are removed by adding coagulants such
as alum, Al2(SO4)3, NaAlO2, etc., which
produces flocs. Smaller particles gather
together to form bigger flocs. They can be
easily removed by filtration. Some bacteria
and colour are also removed.

Al2 (SO4)3 + 3 Ca (HCO3)2→ 2 Al(OH)3↓+

3CaSO4 + 6 CO2
NaAlO2 + 2 H2O → Al(OH)3↓ + NaOH
FeSO4 + Mg(HCO3)2 → Fe(OH)2 + MgCO3
+ CO2 + H2O
4Fe(OH)2 + O2 + 2H2O → 4 Fe (OH)3
Coagulation
4. Filtration: Colloidal matter, bacteria,
micro-organism are removed. Water is
passed through a large area sand bed. The
filter may be pressure filter or gravity
filter.
5. Sterilization/disinfection: Water after
passing through sedimentation,
coagulation, and filtration still contains a
small percentage of pathogenic micro-
organisms such as bacteria. Its removal
can be achieved by sterilization
 The chemicals used for killing bacteria are called disinfectants.
Water can be sterilized by the following methods:
(a)Boiling: Water is boiled for 10−15 min, where most of the
pathogenic bacteria are killed.
(b)By adding bleaching powder. Bleaching powder in
calculated amount is added to water and allowedto stand for
several hours.

 CaOCl2 + H2O → Ca(OH)2 + Cl2

 Cl2 + H2O → HCl + HOCl
 HOCl + Germs → germs are killed

Disadvantages:
Bleaching powder introduces Ca2+ hardness in water and adds lime
residue.
Excess of it gives bad smell and bad taste. Excess chlorine is irritating to
mucous membrane.
 (c)By chlorination
 Cl2 + H2O → HCl + HOCl
 Bacteria + HOCl → killed bacteria
The quantity of chlorine to be added is important. The disinfection
will not complete if chlorine is insufficient. If excess chlorine is
added, it causes irritation, bad taste, and odour.
Break-point Chlorination (Free residual chlorination):

It involves in addition of sufficient amount

of chlorine to oxidize

a)Organic matter b) Reducing

substances
c) Free ammonia

The dosage of applied chlorine and the

free Chlorine can be depicted graphically
in which appearance of following four
stages occurs:
Break point chlorination
The graph below shows what happens when chlorine (either
chlorine gas or a hypochlorite) is added to water. First
(between points 1 and 2), the water reacts with reducing
compounds in the water, such as hydrogen sulfide. These
compounds use up the chlorine, producing no chlorine
residual.
Next, between points 2 and 3, the chlorine reacts with organics
and ammonia naturally found in the water. Some combined
chlorine residual is formed - chloramines. Note that if
chloramines were to be used as the disinfecting agent, more
ammonia would be added to the water to react with the
chlorine. The process would be stopped at point 3. Using
chloramine as the disinfecting agent results in little
trihalomethane production but causes taste and odor
problems since chloramines typically give a "swimming pool"
odor to water.

In contrast, if hypochlorous acid is to be used as the chlorine

residual, then chlorine will be added past point 3. Between
points 3 and 4, the chlorine will break down most of the
chloramines in the water, actually lowering the chlorine
Finally, the water reaches the breakpoint, shown at point
4. The breakpoint is the point at which the chlorine
demand has been totally satisfied - the chlorine has reacted
with all reducing agents, organics, and ammonia in the
water. When more chlorine is added past the breakpoint,
the chlorine reacts with water and forms hypochlorous acid
in direct proportion to the amount of chlorine added. This
process, known as breakpoint chlorination, is the most
common form of chlorination, in which enough chlorine is
added to the water to bring it past the breakpoint and to
create some free chlorine residual.
De-chlorination
Over chlolrinated water can be de chlorinatede by passing it
through a bed of activated carbon. Excess chlorine can also be
removed by adding SO2 (or) NaSO3.
 SO2 + Cl2 + 2H 2O → H2SO4 + 2HCl
 Na2SO3 + Cl2 + H2O →Na2SO4 + 2 HCl
(d) By using chloramine (NH2Cl): It is obtained by mixing
chlorine and NH3 in 2:1 ratio. It has better bactericidal action
than chlorine. It is more stable and not producing any irritating
odour.
 NH3 + Cl2 → HCl + NH2Cl
 NH2Cl+ H2O → NH3 + HOCl
(e) Disinfection by ozone: O3 is prepared by passing silent
electric discharge through cold, dry O2. It is highly unstable.
 O3→ O2 + (O)
O3 is an excellent, harmless disinfectant. It is highly unstable and
decomposes to give nacent oxygen (O). (O) is a powerful oxidizing
agent. It oxidizes organic matter in water and also kills bacterias.
Methodology and working of mineral water
plant for drinking purpose:
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