MODULE-1

WATER
Introduction:
Water is a natural gift on the earth. Water is the most important compounds for the
existence of human beings, animals and plants. Use of water for drinking, cooking, bathing,
cleaning and washing. About 80% of earth surface occupied by water. The main sources of water
are rain, rivers, lakes, wells and springs (underground water) and sea water. Among the above
sources of water, rain water is the purest form of water but very difficult to collect where as sea
water is more impure form. Surface and underground water are normally used for domestic and
industrial purposes such water must be free from undesirable impurities.

The process of removing of all types of impurities from water and making fit for domestic
or industrial purposes is called Water Technology or Water Treatment.
The main sources of water are,
1. Rain water
2. Surface water (Rivers and lakes)
3. Underground water (wells and springs)
4. Glacier water and
5. Sea water

Impurities in Water

Impurities in water are of three types

1. Physical impurities:
A. Suspended impurities:
B. Colloidal impurities
2. Chemical impurities
A. Dissolved salts
3. Biological impurities
A. Microorganisms

Types of water:
a) Hard Water b) Soft Water
Hard Water: Water, which does not produce lather with soap solution, but produces white
precipitate is called Hard water. This is due to presence of dissolved calcium and magnesium
salts.
2C17H35COONa + Ca2+ (C17H35COO)2Ca + 2NaCl
Soap hardness calcium soap
(Water soluble) Causing (water insoluble)
Substance
Soft water: Water, which produce lather with soap solution is called Soft water. This is due to
the absence of Ca &Mg salts.

Causes for hardness of water

Hardness of water is mainly TWO types
1.Temporary Hardness
2.Permanent Hardness
1.Temporary Hardness mainly caused by the presence of dissolved bicarbonates of Calcium and
Magnesium. Temporary hardness of water mainly responsible salts are Calcium bicarbonate
Ca(HCO3)2, Magnesium bicarbonate Mg(HCO3)2.When bicarbonates are decomposed yielding
insoluble carbonates. Temporary Hardness can be largely removed by mere boiling of water.
Heat
Ca(HCO3) 2 CaCO3+H2O+CO2

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

2. Permanent harness: It is due to the presence of dissolved Chlorides and sulphates of Calcium,
Magnesium, Iron and other metals. Permanent hardness responsible salts are CaCl 2, MgCl2, CaSO4,
MgSO4, FeSO4, Al2(SO4)3.
Permanent Hardness cannot remove by boiling, but it can be removed by the use of chemical agents.

Expression of hardness units

Hardness is usually expressed in terms of equivalent of CaCO3 in order to simplify the
calculations in water analysis. The choice of CaCO3 because is due to the fact that it is the most
insoluble salt in water. Hence, all the hardness causing impurities are first converted in terms of their
respective weights equivalent to CaCO3 by using the relation

CaCO3 Equivalent= Weight of the hardness producing salt Molecular weight of CaCO3
Molecular weight of the hardness producing salt.
The following are the common units used in hardness measurements.
Parts per million (ppm): It is defined as the number of parts by weight of CaCO3 present in
million parts by weight of water.
1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water
1 ppm= 1 part of hardness
106 parts of water

Milligram per litre: It is defined as the number of milligrams of CaCO3 present in one
litre of water.
1 mg/l = 1 mg of CaCO3 equivalent hardness in one litre of water
Since weight of 1 litre of water = 1 kg = 1000 g
= 1000 x 1000 = 106 mg
1 mg/l = 1 mg of CaCO3 per 106 mg of water
= 1 part of CaCO3 per 106 parts of water = 1 ppm
Thus, mathematically both units are equal.
 Clarkes degree : (0Cl) I t is the number of parts of CaCO3 equivalent hardness per 70,000 parts
of water.
1Clarke = 1 part of CaCO3 of hardness per 70,000 parts of water.

Degree French (0Fr): It is number of parts of CaCO3 Eq hardness per 105 parts of water.

Disadvantages of Hard Water: The following are the disadvantages of hard water:
1. Hard water is not useful for various domestic purposes, viz. washing, bathing and drinking. The
hardness producing ions convert soluble soaps to insoluble precipitates. This results in wastage of
soaps in washing and bathing.

2. Hard water is not useful for many industries such as textile, sugar and paper. Dissolved salts
like Ca, Mg, Fe and Mn affect the following properties.
(a) Giving a smooth and glossy finish to paper in paper industry.
(b) Producing good lather in laundry.
(c) Producing good shades and colour to fabrics in textile industry.

3. Hard water is also not suitable for steam raising in boilers, since they produce scales on inner
plates. Corrosion, priming, foaming and caustic embrittlement are the other problems caused by
hard water.
4. Hard water is not suitable for laboratory analysis, because the hardness producing ions interfere
in various reactions.

Estimation of temporary & permanent hardness of water by EDTA method

The hardness of water indicates the quality in terms of Calcium and Magnesium expressed
in terms of CaCO3. The analysis is done by complexometric titration using standard EDTA and
EBT as an indicator.

Principle: In this complex metric Titration, the water sample is titrated with standard solution of
Di sodium salt of EDTA using EBT indicator.

Reactions involved: EBT indicator when added to hard water at pH = 10, forms weak complexes
with calcium and magnesium present in hard water. It results in the formation of Ca-EBT or Mg-
EBT complexes which is wine-red, these are unstable.

(Ca2+ / Mg2+ ) + EBT [Ca EBT ] / [Mg EBT]

blue wine-red color complex

During titration with EDTA, EDTA extracts metal ions from the above complex to give a
colorless and stable complex releasing the free indicator (blue). The color changes from wine-red
to blue at the endpoint.
 [Ca EBT] / [Mg EBT] + EDTA [Ca EDTA] / [Mg EDTA] + EBT
Wine-red complex colorless complex blue

Various steps involved in this method are

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

2. Standardization of EDTA solution: Rinse and fill the burette with EDTA solution.
Pipette out 50 mL of standard hard water in a conical flask. Add 10-15 mL of buffer solution and
4 to
5 drops indicator. Titrate with EDTA solution till wine-red colour changes to clear blue.
Let volume used by V1 mL.
3. Titration of Unknown Hard water: Rinse and fill the burette with EDTA solution. Pipette
out 50 mL of unknown sample hard water in a conical flask. Add 10-15 mL of buffer solution
and 4 to 5 drops indicator. Titrate with EDTA solution till wine-red colour changes to clear blue.
Let volume used be V2 mL.
4. Titration of Permanent hardness: take 250 mL of the water sample in a large beaker. Boil
it. Till the volume is reduced to about 50 mL, filter it, wash the precipitate with distilled water,
collecting filtrate and washing in a 250 mL measuring flask. Finally make up the volume to 250
mL with distilled water. Then, titrate 50 mL of boiled water sample just as in Step (2). Let
volume used by V3 mL.

CALCULATION:
Total hardness of water = 1000 X V2 ppm
V1
Permanent hardness
= 1000 X V3 ppm
V1
Temporary hardness = [Total hardness Permanent hardness]
Temporary hardness = 1000 X (V2- V3) ppm
V1
Boiler Troubles:
The water fed into boiler for the production of the steam is called boiler feed water. Boiler
water should be free from turbidity, oil, dissolved gases, alkali and hardness causing substances. If the
hard water obtained from natural sources is fed directly into the boilers, the following troubles may be
arise.

1. Scale & Sludge Formation.

2. Caustic Embrittlement.
3. Priming & Foaming.
4. Boiler Corrosion.
1. Scale & Sludge Formation in the boilers:
In industries, boilers are continuously used for stream generation. When water is
continuously converted into steam in boilers, the concentration of dissolved salts in water
increases progressively .When the concentration of salts reaches to their saturation point, they are
thrown out in the form of precipitation on the inner walls of the boilers. The least soluble one gets
precipitate first.
Sludge: A loose, soft and slimy precipitate formed within the boiler is called slude. Sludes can
be formed by substances which have greater solubility in hot water and than in cold water. Salts
like MgCO3, MgCl2, MgSO4 and CaCl2 etc are responsible for slude formation in boilers.

Disadvantages:
1. Sludge is bad conductor of heat, hence it wastes a portion of heat generated and leads to
wastage of fuel.
2. Excessive sludge formation reduces the efficiency of the boiler.
3. The working of the boiler is disturbed because of chocking of pipes by the sludge, as sludge
settle in low water circulation areas.
Prevention:
1. By using well-softened water.
2. Frequent blow-down (i.e. drawing out of a fraction of concentrated water) operation should be
carried out.

Scale: On the other hand, if the precipitate is hard and sticky and forms adherent coating on the
inner walls of the boiler, it is called scale. Scales are formed by substance like Ca (HCO 3),
CaSO4 &Mg (OH)2.
Causes of scale formation: Following are the causes

a. Decomposition of calcium bicarbonate:

Ca(HCO3)2 CaCO3 + H2O + CO2
In low pressure boilers, CaCO3 causes scale formation. In High pressure boilers, CaCO3 becomes
soluble. CaCO3 +H2O Ca(OH)2 + CO2
b. Decomposition of calcium sulphate:
The solubility of CaSO4 in water decreases with rise of temperature. In super heated water
CaSO4 is insoluble. This is the main cause in high-pressure boilers.

c. Hydrolysis of Magnesium salts:

Dissolved Magnesium salts undergo hydrolysis forming Mg(OH)2 precipitate.
MgCl2 + 2H2O Mg(OH)2 + 2 HCl
.
d. Presence of Silica: Silica present in small quantities deposits as silicates like CaSiO3 and
MgSiO3. These are very difficult to remove.

Disdvantages:
1. Wastage of fuel. Scale act as a bad conductor of heat. The scale formation causes decreases of
heat transfer. As a result over heating is required this causes consumption of fuel.
2. Decrease in boiler efficiency. Scale formation can reduce the efficiency of boiler.
3. Lowering of boiler safety.
4. Danger of boiler explosion: The hot scale cracks because of expansion and water suddenly comes
in contact with overheated Iron plates. This causes in formation of large amount of steam
suddenly. This results high pressure causing boiler to burst.

Removal of scales:
1. By thermal shocks.
2. With the help of wire brush, wood piece and scraper.
3. Carbonate scales can be removed by 5 to 10% HCl. Sulphate scales can be removed by
dissolving in EDTA.
4. By doing blow-down operation.

Prevention:
1. By Ion Exchange Process or zeolite process or Lime soda process has to be applied
for softening of hard water.
2. Internal Treatment: water is treated with in the boiler ether by converting scale and
sludge forming substances followed by blow down operation etc.

Sludge Scales
1. Sludges are soft, loose and 1. Scales are hard and sticky deposits
slimy precipitate
2. Sludges are non-adherent deposits 2. Scales stick firmly to the inner
and can be removed easily. surface of boiler and are very difficult
to remove.
3. Sludges are formed by substances 3. Scales are formed by substances like
like CaCl2 , MgCl2 , MgSO4 CaSO4 Mg(OH)2 etc.,
,MgCO3 ,etc,
4. Formed at comparatively 4. Generally formed at heated
colder portions of the boiler
portions of the boiler.
5. Decrease the efficiency of boiler but 5. Decrease the efficiency of boiler and
are less dangerous
chances of explosions are also there.
2. Priming and Foaming (Carry Over):

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

Priming: Priming is the process of production of wet stream. Priming is caused by

1. Improper boiler design.

2. Due to high steam velocity.
3. High water level in the boiler.
4. Sudden boiling of water.

Prevention:
1. Controlling the velocity of stream.
2. Maintaining low water level.
3. Proper boiler designing.
4. Using soft water.

Foaming: Foaming is the formation of small stable/persistent bubbles above the surface of water is called
Foaming. It is caused by
1. Presence of fatty acids and other impurities.
2. Presence of oils and grease.
3. Presence of finely divided particles.

Prevention:
1. By adding anti-foaming chemicals like castor oil, cotton seed oil and polyamides.
2. By adding coagulants like sodium aluminate, aluminium hydroxide to remove oils and greases.

Caustic Embrittlement:
The formation of brittle and incrystalline cracks in the boiler shell is called caustic embrittlement. It is
a type of boiler corrosion and the main reason for this, is the presence of alkali-metal carbonates and
bicarbonates in feed water and also the presence of sodium sulphate. In lime-soda process, it is likely
that, some residual Na2CO3 is still present in the softened water. This Na2CO3 decomposes to give
NaOH and CO2, due to which the boiler water becomes Caustic.

Na2CO3+ H2O NaOH + CO2

This caustic water flows inside the boiler and causes some minutes hair-cracks, by capillary action. On
evaporation of water, the dissolved caustic soda increases its concentration which attacks the
surrounding area, thereby dissolving Iron of boiler as Sodium ferroate. This causes embrittlement of
boiler parts such as bends, joints, reverts etc, due to which the boiler gets fail. Caustic cracking can be
explained by considering the following concentration cell:
 Iron at (+) Concentrated Dilute (-)Iron at
Joints,bends, NaOH NaOH plane surfaces
rivets solution solution

This causes brittlement of the boiler parts, especially at the bends, joints and rivets, even
causing failure of boiler. The formation of cracks in the boilers due to increased concentration of
NaOH is called caustic embrittlement.

Caustic embrittlement can be prevented by

1. Using Na3PO4 as softening reagent instead of Na2CO3 in external treatment of boiler water.
2. Adding tannin, lignin to boiler water, which blocks the hair cracks in the boiler walls.
3. Adding Na2SO4 to boiler water to prevent caustic cracking in boiler.
4. Neutralizing alkali with very small quantity of acid.

Treatment of boiler feed water & Softening of water

Internal treatment:
In this method, raw water is treated inside the boiler. Internal treatment of boiler water is carried
out by adding proper chemicals to precipitate the scale forming impurities in the form of sludge and to
convert the scale forming chemicals into compounds which will stay in dissolved form in water. It is
mainly based on the solubility product. If the product of the concentration of ions exceeds the solubility
product, it precipitates. This is a corrective method to remove slight residual hardness and to remove
corrosive nature of water. The main principle involved in internal condition is that scales formed are
converted into sludges.

Some of the internal treatment methods used for the removed of scale formation in boilers are.
1. Phosphate conditioning
2. Carbonate conditioning
3. Calgon conditioning

Phosphate conditioning: Phosphate conditioning is generally applied to high pressure boilers. The
addition of sodium phosphate in hard water reacts with the hardness causing agents and gives calcium
and magnesium phosphates which are soft and non-adhere and can be removed easily by blow-down
operation. In this way, scale formation is removed in high-pressure boilers.

3 CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6NaCl

3 MgCl2 + 2 Na3PO4 Mg3(PO4)2 + 6NaCl

Carbonate conditioning: Scale formation in low pressure boilers can be avoided by adding sodium
carbonate to boiler water, where CaSO4 is converted into calcium carbonate, a sludge which can be
removed by blow down operation.

CaSO4 + Na2CO3 CaCO3 + Na4SO4

By adding Na2CO3, the concentration ratio of carbonate ion to sulphate ion is made greater than the
solubility product ratio of CaCO3 to CaSO4. CaCO3 is a loose sludge which can be scraped off by blow
down operation.
CO3 2/SO4 2 > CaCO3/CaSO4
i.e., the concentration of carbonate ion is greater than concentration of sulphate. Precipitation of
calcium carbonate occurs in preference to calcium sulphate. In high pressure boilers, excess of sodium
carbonate may get hydrolysed to NaOH which causes caustic embrittlement.
Calgon conditioning:
The word calgon means calcium gone, i.e. the removal of Ca2+.
Involves in adding calgon to boiler water. it prevents the scale and sludge formation by forming
soluble complex compound with CaSO4.

Calgon = Sodium hexa Meta phosphate = (NaPO3)6

Na2 [Na4 (PO3)6] ==== 2Na+ + [Na4P6O18]-

2CaSO4 + [ Na4P6O18]-2 [Ca2P6O18]-2 + 2Na2SO4

External treatment
Water used for industrial purposes such as for steam generation, should be sufficiently pure.
It should, therefore be freed from hardness-producing salts before put to use.
The process of removing hardness-producing salts from water is known as softening of water. In industry
main three external methods employed for softening of water are.
1. Lime-Soda process
2. Zeolite process
3. Ion-Exchange process
 Lime-soda process: In this method, the soluble calcium and magnesium salts in water are chemically
converted in to insoluble compounds, by adding calculated amount of Lime and Soda. CaCO3 and
Mg(OH)2 so precipitated, these precipitates are filtered off.
Lime soda process mainly two types, they are
1. Cold Lime-soda process
2. Hot Lime-soda process.

Cold lime soda process:

In this method, calculated
quantity of chemical like lime
and soda are mixed with water at
Room temperature. At room
temperature, the precipitates
formed are finely divided, so they
do not settle down easily and
cannot be filtered easily.
Consequently, it is essential to
add small amounts of coagulants
like alum, aluminum sulphate,
sodium aluminate, etc. Which
hydrolyze to flocculent,
gelatinous precipitate of
aluminum hydroxide, and entraps
fine precipitates.

Use of sodium aluminate as coagulant also helps the removal of silica as well as oil, If
present in water. Cold L-S process provides water, containing a residual hardness of 50 to 60 ppm.

NaAlO2 + 2H2O NaOH + Al(OH)3

Al2(SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

Method: Raw water and calculated quantities of chemicals ( Lime + soda + Coagulants) are
fed from the top into the inner vertical circular chamber, fitted with a vertical rotating shat carrying a
number of paddles. As the raw water and chemicals flow down, there is a vigorous stirring and
continuous mixing, whereby softening of water reaches up. The softened water comes into the outer
co-axial chamber, it rises upwards. The heavy sludge or precipitated floc settles down the outer
chamber by the time the softened water reaches up. The softened water then passes through a filtering
media this is usually made of wood fibres to ensure complete removal of sludge. Filtered soft water
finally flows out continuously through the outlet at the top. Sludge settling at the bottom of the outer
chamber is drawn of occasionally.
Hot lime-soda process:
a. The reaction proceeds faster
b. The softening capacity of the process is increased to many fold
c. The precipitate and sludge formed settle down rapidly and hence, no coagulants are
needed
d. Much of the dissolved gases such as CO2 and air driven out of the water
e. Viscosity of softened water is lower, so filtration of water becomes much easier. this in-turn increases
the filtering capacity of filters, and
f. Hot lime-soda process produces water of comparatively lower residual hardness of 15 to 30ppm.

Hot lime-soda plant consists essentially of three parts

a. A Reaction tank in which raw water, chemicals and steam are thoroughly mixed.
b. A Conical sedimentation vessel in which sludge settles down, and
c. A sand filter which ensures completes removal of sludge from the softened water

Advantages of lime-soda process:

1. It is very economical
2. If this process is combined with sedimentation with coagulation, lesser amounts of coagulants
shall be needed.
3. The process increases the pH value of the treated-water; thereby corrosion of the distribution
pipes is reduced.
4. Besides the removal of harness, the quantity of minerals in the water is reduced.
5. To certain extent, iron and manganese are also removed from the water.
6. Due to alkaline nature of treated-water, amount of pathogenic bacteria in water is
considerably reduced.
 Dis-advantages of lime-soda process:
1. For efficient and economical softening, careful operation and skilled supervision is required.
2. Disposal of large amounts of sludge or insoluble precipitates poses a problem. However, the
sludge may be disposed off in raising low-lying areas of the city.
3. This can remove hardness only up to 15 ppm, which is not good for boilers.

Ion exchange process

Ion exchange process also known as demineralization or de-ionization process.
Ion-Exchange resins are insoluble. Cross linked long chain organic polymers with a micro
porous structure, and the functional Groups attached to the chains are responsible for the ion-
exchanging properties.
In De-ionization process all the ions present in water are eliminated by using ion-exchange
resins. Basically resins with acidic functional group are capable of exchanging H+ ions with other
cations. Resins with functional groups are capable of exchanging OH- ions with other anions.
Resins are classified as
1. Cation Exchange Resins
2. Anion Exchange Resins
1 Cation Exchange Resins: These are
mainly styrene divinyl benzene co-polymers, which
on sulphonation or carboxylation. These are capable
of exchanging their hydrogen ions with cations in
water.

2 Anion Exchange Resins: Anion

exchange resins are styrene-divinyl benzene or amine-
formaldehyde copolymers, which contains amino,
quaternary ammonium or quaternary phosphonium or
tertiary sulphonium groups as an internal parts of the
resin matrix. These after treatment with dilute NaOH
solution. Become capable of exchanging their OH-
ions with anions in water.

In ion-exchange process, hard water is allowed to pass through cation exchange resins, which remove
Ca+2 and Mg+2 ions and exchange equivalent amount of H+ ions. Anions exchange resins remove
bicarbonates, chlorides and sulphates from water exchange equivalent amount of Oh ions. Thus by passing
hard water through cation hardness is observed by the following reactions.
Cation Exchange Resins 2RH+ + Ca+2 -R2Ca+2 + 2H+
2RH+ + Mg+2 R2Mg+2 + 2H+ (RH+ = cation exchange resin)

Anion Exchange Resins

ROH + Cl+2 RCl- + OH-
2ROH- + SO4-2 R2SO4-2 -2
2ROH + CO-32 R2 CO-32 + 2OH- (ROH = anion exchange resin)

H- and OH- ions, thus released in water from respective cation and anion exchange columns, get
combined to produce water molecules.
H+ + OH- H2O

The water coming out from the exchanger is ion free i.e., free from anions and cations. Thus water
of zero hardness is obtained.
 LIME-SODA PROCESS
Water treatment plant occupies more area or place.
Water after treatment has lesser dissolved solids.
This method of water treatment plants is not much
expensive and material used is cheap.
Operation expenses are higher
The cost incurred on softening of water is high.
It cannot operate in under pressure.
It can be used for treating acidic water also.
There is a problem of settling, coagulation and
removal of sludge.
It is not possible.
In order to meet the changing hardness of incoming
water, frequent control and adjustment of reagents
is needed.
Residual hardness is low about 15 to 50 ppm
It is not good for boilers
Skilled persons required
ION-EXCHANGE/RESIN
Water treatment plant occupies less area.
Water after treatment free from dissolved solids
This method of water treatment plants is more
expensive and material used for softening is
expensive.
Operation expenses are higher
The cost incurred on softening of water is high
It can even operate in under pressure.
It can be used for treating acidic and alkaline
water also.
There is problem of turbidity.
This method can be made automatic.
Control test comprises only in checking the
hardness of treated-water.
Residual hardness is low about 0 to 2 ppm
It is very good for treating water for use in high
pressure boilers.
It required less skill for maintenance as well as
operation
Disinfection of surface water / Removal of micro-organisms in water:
Disinfection: The process of destroying/killing the disease producing Bacteria,
microorganisms, etc. from the water and making it safe for use, is called
disinfection.

Disinfectants: the chemicals or substances which are added to eater for killing the
Bacteria. The disinfection of water can be carried out by following methods:

A) Boiling: Water for 10-15 minutes, all the disease-producing bacteria are killed and
water becomes safe for use.

B) Bleaching power: It is used to purify the drinking water from micro organisms.
The purification process is achieved by dissolving 1 kg of bleaching powder in 1000
kiloliters of water. This dissolved water solution is left undisturbed for many hours.
When bleaching powder is mixed with water, the result of chemical reaction produces
a powerful Germicide called Hypochlorous acid. The presence of chlorine in the
bleaching powder produces disinfecting action, kills germs and purifies the drinking
water effectively.
CaOCl2 + H2O Ca(OH)2 + Cl2 H2O + Cl2 HCl +
HOCl
HOCl + Germs Germs are killed water purified.

C) Chlorine: Chlorination is the process of purifying the drinking water by producing

a powerful Germicide like Hypochlorous acid. When this Chlorine is mixed with
water it produces Hypochlorous acid which kills the germs present in water.
H2O + Cl2 HOCl + HCl
Bacteria+HOClBacteria are killed

The death of micro-organisms results from the chemical action of HOCl with the
enzymes in the cell of organisms,etc. since the enzyme is essential for the metabolic
processes of the micro-organisms, so death of micro-organism results due to the
inactivation of enzyme by HOCl.

Chlorine is basic (means pH value is more than 7) disinfectant and is much effective
over the germs. Hence Chlorine is widely used all over the world as a powerful
disinfectant. Chlorinator is an apparatus, which is used to purify the water by
chlorination process.
Advantages
1. It is effective and economical
2. It requires very little space for storage
3. It is stable and does not deteriorate on keeping
 4. It can be used at low as well as high temperatures
5. It introduces no salt impurities in the treated water.
6. It is the most ideal disinfectant.
Disadvantages
1. Excess chlorine if added, produces unpleasant taste and odour
2. Its excess produces irritation on mucous membrane

Break-point chlorination (or free-residual chlorination) involves the

addition of sufficient amount of chlorine to oxidize (a) organic matter (b)
reducing substances (c) Free ammonia; leaving behind free chlorine which
possesses disinfecting action against disease-producing bacteria.

A known volume of sample of water is treated with an increasing

amount of chlorine and then analyzed for the remaining chlorine. When a
graph is plotted between the amounts of residual chlorine against the added
chlorine, a curve is obtained as shown below. The addition of Chlorine at the
dip or break is called break point chlorination. This indicates the point at
which free chlorine begins to appear and resulting in water free from bad
tastes and odor.
D) Ozonisation: Ozone is powerful disinfectant and is readily dissolved in water.
Ozone being unstable decomposes by giving Nascent Oxygen which is capable of
destroying the Bacteria. This nascent Oxygen removes the colour and taste of water
and oxidizes the organic matter present in water.
O3 O2 + [O]
The nascent oxygen is very powerful oxidizing agent and kills all the bacterias as
well as oxidizes the organic matter present in water.
For carrying out the disinfection by ozone, ozone is released/injected into the water
and the two are allowed to come in contact in sterilizing tank. The disinfected water is
removed from the top. The contact period about minutes and the usual dose strength is
2-3 ppm.

Advantages: Disinfection by ozone is costlier than chlorine, but it simultaneously

 removes colour, odour and taste without giving any residue. Its excess is not harmful,
since it is unstable and decomposes into oxygen.
Dis-advantages: this method is quite expensive and hence, not employed for
disinfection of municipal water supply.

Desalination
Desalination: The process of removing common salt from the water,
is known as desalination. The water containing dissolved salts with a peculiar
salty taste, is called brackish water. Sea water, containing on an average
about 3.5% salts, comes under this category. Brackish water is totally unfit
for drinking purpose.
Commonly used methods for the desalination of brackish water is:
1. Reverse Osmosis
2. Electrodyalias
3. Distillation
4. Freezing
Reverse Osmosis: When two
solutions of unequal
concentrations are separated by
a semi permeable membrane,
flow of solvent takes place
from dilute to concentrated
sides, due to osmosis. If,
however, a hydrostatic
pressure in excess of osmotic
pressure is applied on the
concentrated side, the solvent
flow reverse, ie. Solvent is
forced to move from
concentrated side to dilute side
across the membrane. This is
the principle of reverse
osmosis. Thus, in reverse
osmosis (RO) methods, pure
solvent is separated from its
contaminants, rather than
removing contaminants from
the water.
This membrane filtration is also
called super-filtration or
hyper filtration.
 Process: in Reverse osmosis process, pressure (15 to 40 kg cm-2) is applied to the
sea water or impure water to force its pure water out through the semi-permeable
membrane, leaving behind the dissolved solids. The principle of reverse osmosis, as
applied for treating saline or sea water. The membrane consists of very thin films of
cellulose acetate, affixed to either side of a perforated tube. However, mover
recently superior membranes made of polymethacrylate and polyamide polymers
have come into use.

Advantages:
a. Reverse osmosis possesses a distinct advantage of removing ionic as well as non-
ionic, colloidal and high molecular weight organic matter.
b. It removes colloidal silica, which is not removed by demineralization.
c. The maintenance cost is almost entirely on the replacement of the semi permeable
membrane.
d. The life time of membrane is quite high, about 2 years.
e. The membrane can be replaced within a few minutes, thereby providing nearly
uninterrupted water supply.
f. Due to low capital cost, simplicity, low operating cost and high reliability, the
reverse osmosis is gaining ground at present for converting sea water into drinking
water and for obtaining water for very high pressure boilers.

Domestic drinking water treatment

Requirements of drinking (potable) water:
1. Water should be clear and odour less.

2. It should be pleasant to taste

3. It should be perfectly cooled.

4. It should be free from disease producing bacteria

5. Its turbidity should not exceed 10 ppm.

6. It should be free from dissolved gases like H2S.

7. It should be free from minerals such as Pb, As, Cr and Mn salts.

8. pH should be in the range of 7 8.5

9. Chloride and Sulphate content should be less than 250 ppm.

Element/ Symbol/ Normally found in Health based
substance formula fresh water/surface guideline by the WHO
water/ground water 10. F
luoride
content
should
be less
than 1.5
ppm.

World
Health
Oganisa
tion
(WHO)
s
drinkin
g water
standards

WHO's Guidelines for Drinking-water Quality, set up in Geneva, 1993, are the
international
reference point for standard setting and drinking-water safety.
Aluminium Al 0,2 mg/l

Ammonia NH4 < 0,2 mg/l (up to 0,3 No guideline

mg/l in anaerobic
waters)

Antimony Sb < 4 g/l 0.005 mg/l

Arsenic As 0,01 mg/l

Asbestos No guideline

Barium Ba 0,3 mg/l

Berillium Be < 1 g/l No guideline

Boron B < 1 mg/l 0,3 mg/l

Cadmium Cd < 1 g/l 0,003 mg/l

Chloride Cl 250 mg/l

Chromium Cr+3, Cr+6 < 2 g/l 0,05 mg/l

Colour Not mentioned

Copper Cu 2 mg/l

Cyanide CN- 0,07 mg/l

Dissolvedoxygen O2 No guideline

Fluoride F < 1,5 mg/l (up to 10) 1,5 mg/l

Hardness mg/lCaCO3 No guideline

Hydrogen sulfide H2S No guideline

Iron Fe 0,5 - 50 mg/l No guideline

Lead Pb 0,01 mg/l

Manganese Mn 0,5 mg/l

Mercury Hg < 0,5 g/l 0,001 mg/l

Molybdenum Mb < 0,01 mg/l 0,07 mg/l

Nickel Ni < 0,02 mg/l 0,02 mg/l

Nitrate and NO3, NO2 50 mg/l total nitrogen

nitrite

Turbidity Not mentioned

pH No guideline

Selenium Se < < 0,01 mg/l 0,01 mg/l

Silver Ag 5 50 g/l No guideline

Sodium Na < 20 mg/l 200 mg/l

Sulfate SO4 500 mg/l

Inorganic tin Sn No guideline

TDS No guideline

Uranium U 1,4 mg/l

Zinc Zn 3 mg/l
Group Substance Formula Health based
guideline by the
WHO

Chlorinated Carbon tetrachloride C Cl4 2 g/l

alkanes
Dichloromethane C H2 Cl2 20 g/l

1,1-Dichloroethane C2 H4 Cl2 No guideline

1,2-Dichloroethane Cl CH2 CH2 Cl 30 g/l

1,1,1-Trichloroethane CH3 C Cl3 2000 g/l

Chlorinated 1,1-Dichloroethene C2 H2 Cl2 30 g/l

ethenes
1,2-Dichloroethene C2 H2 Cl2 50 g/l

Trichloroethene C2 H Cl3 70 g/l

Tetrachloroethene C2 Cl4 40 g/l

Aromatic Benzene C6 H6 10 g/l

hydrocarbons
Toluene C7 H8 700 g/l

Xylenes C8 H10 500 g/l

 Ethylbenzene C8 H10 300 g/l

Styrene C8 H8 20 g/l

Polynuclear Aromatic Hydrocarbons C2 H3 N1 O5 P1 3 0.7 g/l

(PAHs)

Chlorinated Monochlorobenzene (MCB) C6 H5 Cl 300 g/l

benzenes
Dichlorobenzenes 1,2- C6 H4 Cl2 1000 g/l
(DCBs) Dichlorobenzene
(1,2-DCB)

1,3- C6 H4 Cl2 No guideline

Dichlorobenzene
(1,3-DCB)

1,4- C6 H4 Cl2 300 g/l

Dichlorobenzene
(1,4-DCB)

Trichlorobenzenes (TCBs) C6 H3 Cl3 20 g/l

Miscellaneous Di(2-ethylhexyl)adipate (DEHA) C22 H42 O4 80 g/l

organic
constituents Di(2-ethylhexyl)phthalate (DEHP) C24 H38 O4 8 g/l

Acrylamide C3 H5 N O 0.5 g/l

Epichlorohydrin (ECH) C3 H5 Cl O 0.4 g/l

Hexachlorobutadiene (HCBD) C4 Cl6 0.6 g/l

Ethylenediaminetetraacetic acid C10 H12 N2 O8 200 g/l

(EDTA)
 Nitrilotriacetic acid (NTA) N(CH2COOH)3 200 g/l

Organotins Dialkyltins R2 Sn X2 No guideline

Tributil oxide C24 H54 O Sn2 2 g/l

(TBTO)

Pesticides

Substance Formula Health based

guideline by the
WHO

Alachlor C14 H20 Cl N O2 20 g/l

Aldicarb C7 H14 N2 O4 S 10 g/l

Aldrin and dieldrin C12 H8 Cl6/ 0.03 g/l
C12 H8 Cl6 O

Atrazine C8 H14 Cl N5 2 g/l

Bentazone C10 H12 N2 O3 S 30 g/l

Carbofuran C12 H15 N O3 5 g/l

Chlordane C10 H6 Cl8 0.2 g/l

Chlorotoluron C10 H13 Cl N2 O 30 g/l

DDT C14 H9 Cl5 2 g/l

1,2-Dibromo-3-chloropropane C3 H5 Br2 Cl 1 g/l

2,4-Dichlorophenoxyacetic acid C8 H6 Cl2 O3 30 g/l

(2,4-D)

1,2-Dichloropropane C3 H6 Cl2 No guideline

1,3-Dichloropropane C3 H6 Cl2 20 g/l

1,3-Dichloropropene CH3 CHClCH2 Cl No guideline

Ethylene dibromide (EDB) Br CH2 CH2 Br No guideline

Heptachlor and heptachlor C10 H5 Cl7 0.03 g/l

epoxide

Hexachlorobenzene (HCB) C10 H5 Cl7 O 1 g/l

Isoproturon C12 H18 N2 O 9 g/l

Lindane C6 H6 Cl6 2 g/l

MCPA C9 H9 Cl O3 2 g/l

Methoxychlor (C6H4OCH3)2CHCCl3 20 g/l

Metolachlor C15 H22 Cl N O2 10 g/l

Molinate C9 H17 N O S 6 g/l

Pendimethalin C13 H19 O4 N3 20 g/l

Pentachlorophenol (PCP) C6 H Cl5 O 9 g/l

Permethrin C21 H20 Cl2 O3 20 g/l

Propanil C9 H9 Cl2 N O 20 g/l

Pyridate C19H23ClN2O2S 100 g/l

Simazine C7 H12 Cl N5 2 g/l

Trifluralin C13 H16 F3 N3 O4 20 g/l

Chlorophenoxy 2,4-DB C10 H10 Cl2 O3 90 g/l

herbicides
(excluding 2,4-D Dichlorprop C9 H8 Cl2 03 100 g/l
and MCPA)
Fenoprop C9H7Cl3O3 9 g/l

MCPB C11 H13 Cl O3 No guideline

Mecoprop C10H11ClO3 10 g/l

2,4,5-T C8 H5 Cl3 O3 9 g/l

 Indian Standard for Drinking Water - Specification
BIS (Bureau of Indian Standards) standard for drinking water:

Essential Characteristics

Sr.no Characteristics Requirement.(desirable) Permissible limit in

the absence of an
alternative source
1. Color-Hazen units, maximum 5 25
2 Odor Unobjectionable Unobjectionable
3 Taste Agreeable Agreeable
4 Turbidity 5 10
5 pH value 6.5 to 8.5 No relaxation
6 Total Hardness as CaCo3,max 300 600
Mg/ml
7 Iron as Fe,max mg/l 0.3 1.0

8 Chlorides as Cl,max mg/l 250 1000

9 Residual free Chlorine as Cl, min 0.2 --

Desirable Characteristics
10 Dissolved Solids, mg/l, max 500 2000
11 Calcium as Ca, mg/l,max 75 200
12 Copper as Cu, mg/l,max 0.05 1.5
13 Manganese as Mn, mg/l,max 0.10 0.3
14 Sulphate as SO4,mg/l,max 200 400
15 Nitrate as NO3,mg/l,max 45 100
16 Fluoride as F, mg/l,max 1.5 1.9
17 Phenolic compounds, mg/lit, max 0.001 0.002
18 Mercury as Hg, mg/lit max 0.001 No relaxation
19 Cadmium as Cd, mg/lit , max 0.01 No relaxation
20 Selenium as Se, mg/lit, max 0.01 No relaxation
21 Arsenic as As, mg/lit, max 0.01 No relaxation
22 Cyanide as Cn, mg/lit, max 0.05 No relaxation
23 Lead as Pb, mg/lit, max 0.05 No relaxation
24 Zinc as Zn, mg/lit, max 5.0 No relaxation
25 Anionic detergents, mg/lit, max 0.2 1.0
26 Polynuclear Hydro carbons --- ---
27 Mineral oil, mg/lit ,max 0.01 0.03
28 Pesticides, mg/lit, max Absent 0.001
29 Alkalinity, mg/lit ,max 200 600
30 Aluminum as Al, mg/lit, max 0.03 0.2 0.03 0.2
 Bacteriological Standards:
a) For water entering a distribution system- Coliform count in any sample of 100 ml
should be zero(0).
b) For water in a distribution system (i) E Coli count in 100 ml of any sample must
be zero (0). (ii)Coliform organisms should not be more than 10 per 100 ml in any
sample. (iii) Coliform organisms should not be present in 100 ml of any two
consecutive samples or more than 5% of the samples collected for the year.

Hardness-numerical problems
Q1. 2 liters of water obtained from a bore well in Patencheru near
Hyderabad gave the following analysis for salts. FeSO4=30.4mg,
CaSO4=13.6mg, MgCl2=48mg, Ca(HCo3)2=32.4 , mg(HCo3)2=14.6mg,

CaCO3
S.No Constituent Amount mg/lit MF equivalent
.
1. FeSO4 30.4 100/152 20

2. CaSO4 13.6 100/136 10

3. MgCl2 48 100/95 50
4. Ca(HCO3)2 32.4 100/162 20
5. Mg(HCO3)2 14.6 100/146 10
6. NaCl 11.7 --- --

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

= 10 + 20 = 30 ppm

Permanent hardness = FeSO4 + CaSO4 + MgCl2

= 20 + 10 + 50 = 80 ppm
NaCl=11.7mg. Find the total hardness of water in ppm units, giving
temporary &permanent hardness assuming the at. Mass of Fe=56, Ca=40,
Mg=24, Na=22.

Total Hardness = Temporary hardness + Permanent hardness = 30 + 80 = 110 ppm

One liter of water from Khammam Dist. in Andhra Pradesh showed the
following analysis: Mg(HCO3)2 = 0.0256 gms, Ca(HCO3)2 = 0.0156 gms,
NaCl = 0.0167 gms, CaSO4 = 0.0065 gms, and MgSO4 = 0.0054 gms.
Calculate temporary, permanent and total hardness.
Equivalent of
S.No. Constituent Amount mg/lit MF
CaCO3 (mg/l)
1. CaSO4 6.5 100/136 4.77

2. MgSO4 5.4 100/120 4.5

3. Ca(HCO3)2 15.6 100/162 9.6
4. Mg(HCO3)2 25.6 100/146 17.5
5. NaCl 16.7 -- --

Temporary hardness = Mg(HCO 3)2 + Ca(HCO3)2

= 17.5 + 9.6 = 27.1 ppm

Permanent hardness = CaSO4 + MgSO4

= 4.77 + 4.5 = 9.27 ppm

Total Hardness = Temporary hardness + Permanent hardness = 27.1 + 9.27 = 36.37 ppm

Q3. One litre of water from an underground reservoir in Tirupathi Town in

Andhra Pradesh showed the following analysis for its contents: Mg(HCO3)2
= 42 mg; Ca(HCO3)2 = 146mg; CaCl2 = 71mg; NaOH = 40mg; MgSO4 = 48
mg; organic impurities = 100 mg; Calculate temporary, permanent and
total hardness.

Equivalent of
S.No. Constituent Amount mg/lit MF
CaCO3 (mg/l)
1. CaCl2 71 100/111 65.4

2. MgSO4 48 100/120 40
3. Ca(HCO3)2 146 100/162 90.1
4. Mg(HCO3)2 42 100/146 28.7
5. NaOH 40 -- --

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

= 28.7 + 90.1 = 118.8 ppm

Permanent hardness = CaCl2 + MgSO4 = 105.4 ppm

 = 65.4 + 40

Total Hardness = Temporary hardness + Permanent hardness = 118.8 + 105.4 = 124.2

ppm

Q4. One liter of water from an underground reservoir in Nalgonda Town

in Andhra Pradesh the following analysis. for its contents:: Mg(HCO3)2 =
0.0146 gms; Ca(HCO3)2 = 0.0081 gms; MgSO4 = 0.0012 gms; CaSO4 =
0.0136 gms; NaCl = 0.0585 gms; Organic impurities = 100 mg; Calculate
temporary, permanent and total hardness of this sample of water in
degree French.
Equivalent of
S.No. Constituent Amount mg/lit MF
CaCO3 (mg/l)
1. CaSO4 136 100/136 100

2. MgSO4 12 100/120 10
3. Ca(HCO3)2 81 100/162 50
4. Mg(HCO3)2 146 100/146 100
5. NaCl 585 -- --

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

= 100 + 50 = 150 ppm

Temporary hardness = 150 X 0.1 = 15 0Fr

Permanent hardness = CaSO4 + MgSO4

= 100 + 10 = 110 ppm

Permanent hardness = 110 X 0.1 = 11 0Fr

Total Hardness = Temporary hardness + Permanent hardness = 150 + 110 = 260 ppm

Total hardness = 260 X 0.1 = 26 0Fr