UNIT I Water
UNIT I Water
UNIT I Water
WATER
Wate r Technology: Introduction, sources of water, types of impurities in water, hardness of wate
r- temporary and permanent hardness, units of hardness, disadvantages of hard water. Estimation
of hardness by EDTA method, boiler troubles.
Softening methods: Internal treatment, external treatment; zeolite process, ion exchange process,
desalination of brackish water - reverse osmosis.
Introduction:
Water is nature’s most wonderful, abundant and useful compound. Without food, human can
survivefor a number of days, but water is such an essential that without it one cannot survive.
Water is not only essential for the lives of animals and plants, but also occupies a unique position
in industries.Probably, it’s most important use as an engineering material is in the steam
generation. Water is also used as coolant in power and chemical plants.
Water is widely distributed in nature. It has been estimated that about 75% matter on the earth’s
surface consists of water. Besides visible water on earth, there is large amount of water under
earth to an average depth of over three kilometres. The air consists 12 to 15% of volume of water
vapour. Water is found in living things. The body of human being consists of about 60% of
water. Plants, fruits and vegetables contain 90 to 95% of water.
Sources of water:
(A) Surface water (B) Underground water
Surface water:
1. Rain water:
It is the purest form of naturel water, since it is obtained as a result of evaporation from
the surface water. However, during the journey downwards, through the atmosphere, it dissolves
a considerable amount of gases like CO2, SO2, NO2, etc. and suspended solid particles.
2. River water:
In general, the greater the greater the contact that water has with the soil, or the more
soluble the minerals of the soils with which it has come in contact, the greater is the amount of
dissolved impurities in river water. River water thus contains dissolved minerals of the soil such
as chlorides, sulphates, bicarbonates of calcium, magnesium and iron. River water also contains
the organic matter, derived from the decomposition of plants, and small particles of sand and
rock in suspension. Thus,river water contains considerable amounts of dissolved as well as
suspended impurities.
3. Lake water:
It has a more constant composition. It, usually, contains much lesser amounts of
dissolved minerals than even well water, but quality of organic matter present in it is quite high.
4. Sea water:
It is the most impure form of natural water. It contains, on an average, about 3.5% of
dissolved salts, out of which about 2.6% is sodium chloride. Other salts present are sulphate of
sodium; bicarbonates of potassium, magnesium and calcium etc.
Surface water, generally, contains suspended matter, which often contains the disease producing
bacteria. Hence, such water is not considered to be safe for human consumption.
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Underground water:
A part of the rain water, which reaches the surface of the earth, percolates into the earth.
As this water journeys downwards, it comes in contact with a number of mineral salts present in
the soil and dissolves some of them. Water continues it’s downwards journey, till it meet a hard
rock, when it retreads upwards and it may even come out in the form of spring or well. In
general, it is clear in appearance due to the filtering action of the soil, but contains more of the
dissolved salts. Thus, water from these sources contains more hardness. Usually, underground
water is of high organic purity.
Types of impurities in water:
Natural water is, usually contaminated three types of impurities.
1. Physical impurities. 2. Chemical impurities. 3. Biological impurities.
Physical impurities:
(a) Colour: Colour in water is usually caused by metallic substances like salts of iron,
manganese, peat, industrial effluents. Usually, yellowish tinge indicates the presence of
chromium and appreciable amount of organic matter. Yellowish red colour indicates the
presence of iron; while red-brown colour indicate the presence of peaty matter.
(b) Turbidity: It is due to the colloidal, extremely fine suspension such as clay, slit,
finely divided matter etc. Turbidity expresses the optical properties of water, which scatter light
rather than to transmit in straight lines. Turbidity in water can be eliminated by sedimentation,
followed by coagulation, filtration, etc.
(c) Taste:
Bitter taste can be due to the presence of iron, aluminium, manganese sulphate or excess
of lime.
Soapy taste can be due to the presence of large amount of sodium bicarbonate.
Brackish taste is due to the presence of unusual amount of salts.
Palatable taste is due to the presence of dissolved gases like CO2. (d) Odour:
The causes of odour in polluted rivers are;
Presence of inorganic and organic compounds of N, S and P and the putrefaction of
proteins and other organic materials present in sewage;
Industrial effluents containing organic substances such as alcohols, aldehydes, phenols
etc.flowing into the water bodies.
Chemical impurities:
(a) Acidity:
Surface water and ground water attain acidity from industrial wastes like acid, mine,
drainage,pickling liquors, etc. Usually, acidity is caused by the presence of free CO2,
mineral acids (H2SO4) and weakly dissociated acids. Mineral acids are released when
iron and aluminium salts hydrolyse.
(b) Gases:
All natural waters contain dissolved atmosphere CO2. It solubility depends upon
temperature,pressure and dissolved mineral content of water.
Concentration of dissolved atmosphere O2 in water depends on temperature, pressure
and salt content in water. Dissolved O2 in industrial water is nuisance, since it induces
corrosion reactions. On the other hand, dissolved O2 in water is essential to the life of
aquatic organisms such as fishes.
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Dissolved NH3 in water arises from the decomposition of nitrogenous organic matter.
Polluted water and sewage contains nitrogen in the form of nitrogenous organic
compouds and urea, which are partially converted into NH3.
(c) Mineral matter:
It has origin from rocks and industrial effluents. These include Ca2+, Mg2+, Na+, K+,
Fe2+, CO 3-2 , Mn2+,HCO -3 , Cl-, SO 24, etc. However, from industrial point of view, alkalinity
and hardness are important.
Biological impurities:
These are algae, pathogenic bacteria, fungi, viruses, pathogens, parasite worms etc. The source
of these contamination is discharge of domestic and sewage wastes, excreta, etc.
Micro-organisms are, usually, abundant in surface water, but their count is often quite low or
even nil in deep-well waters. The common type of micro-organisms from the point of treatment
are algae, fungi and bacteria, which often form slime, thereby causing fouling as well as
corrosion. The slime so- formed clogs the spray nozzles and screens of the circ ulating pumps in
air-conditioning and other industrial plants. The growth of micro-organisms takes place at
temperature in between 20 to 350C.In order to control the micro-organisms, chemical treatment
like chlorination is done.
Hardness of water:
The water which does not produce lather with soap is called hard water. Thus, hardness in water
is the characteristic, which “prevents the lathering of soap”. On the other hand, the water which
produce lather easily on shaking with soap solution, is called soft water.
The hardness of water is caused by the presence of dissolved salts such as bicarbonates,
sulphates, chlorides and nitrates of divalent metal ions like calcium and magnesium. Soap is
sodium or potassium salt of higher fatty acids like stearic, oleic and palmetic acids. When soap is
mixed with soft water lather is produced due to stearic acid and sodium stearate.
When soap comes in contact with hard water, sodium stearate will react with dissolved
calcium and magnesium salts and produce calcium stearate or magnesium stearate which is white
precipitate.
The different types of water are commercially classified on the basis of degree of
hardness as follows;
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Hardness Name of water
0-70 mg/L Soft water
Types of Hardness:
The hardness of water is two types;
1. Temporary hardness. 2. Permanent hardness.
1. Temporary hardness or Carbonate hardness:
This hardness is caused by two dissolved bicarbonate salts Ca(HCO3)2 and Mg(HCO3)2. The
hardness is called temporary because, it can be removed easily by boiling. During boiling,
bicarbonates are decomposed to yield insoluble carbonates or hydroxides, which are deposited as
a crust at the bottom of vessel.
WATETECHNOLOGY
2. Permanent hardness or non-carbonate hardness:
This hardness is due to the dissolved chlorides, sulphates and nitrates of calcium and magnesium.
These salts are CaCl2, MgCl2, CaSO4, MgSO4, Ca(NO3)2, Mg(NO3)2. It cannot be removed
easily by boiling. Hence, it is called permanent hardness. Only chemical treatment can remove
this hardness.
Total Hardness = Temporary hardness + Permanent hardness
Expression of hardness:
Hardness of water is expressed in terms of calcium carbonate equivalents. The weights of
different salts causing hardness are converted to weights equivalent to that of CaCO3.
If a sample of water contains two or more than two salts, their quantities are converted in
equivalent to CaCO3 as mentioned above and then the sum will give the total hardness. CaCO3
was selected for expression of the degree of hardness because;
1. The Molecular Weight of CaCO3 is 100, which is easy for calculation.
2. It is an insoluble salt, and all the dissolved salts of calcium are precipitated as CaCO3.
Ca(HCO3)2 162
Mg(HCO3)2 146
CaSO4 136
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CaCl2 111
MgSO4 120
MgCl2 95
Ca(NO3)2 164
Mg(NO3)2 148
Thus, 120 parts by weight of MgSO4 would react with the same amount of soap as 100 parts by
weight of CaCO3. Hence, weight in terms of CaCO3 would be equal to weight of MgSO4 in
water multiplied by 100/120.
The method of calculating hardness will be clear from the following formula.
Hardness of hardness causing salt in terms of CaCO3
= Amount of the hardness causing salt x 100
Molecular weight of hardness causing salt
Units of hardness:
There are five units in which the hardness of water is expressed.
1. Parts per million. 2. Milligrams per litre. 3. Degree Clark. 4. Degree French. 5. meq per litre.
WATER TECHNOLOGY
1. Parts per million (ppm):
It is the parts of calcium carbonate equivalent hardness per 106 parts of water.
i.e. 1ppm = 1 part of CaCO3 eq hardness in 106 parts of water.
2. Milligrams per litre (mg/L):
It is the number of milligrams of calcium carbonate equivalent hardness present per
litre of water.
Thus,
1 mg/L = 1 mg of CaCO3 eq hardness per1 L of water
But 1 L water = 1 kg = 1000g = 106 mg
1 mg/L = 1 mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1 ppm
3. Degree Clark (0Cl):
It is the number of grains of CaCO3 equivalent hardness per gallon of water. (or) It is
the parts CaCO3 equivalent hardness per 70,000 parts of water.
10 Cl = 1 grain of CaCO3 eq hardness per gallon of water
10 Cl = 1 part of CaCO3 eq hardness per 70,000 parts of water
4. Degree French (0Fr):
It is the parts of calcium carbonate equivalent hardness per 10 5 parts of water.
i.e. 10 Fr = 1 part of CaCO3 eq hardness in 105 parts of water.
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Estimation of hardness by EDTA method:
EDTA forms a colourless stable complex with Ca2+ and Mg2+ ions in water at pH10. Ammonia
buffer is used to maintain the pH. In this method EBT (Eriochrome Black-T) is used as an
indicator. Initially EBT forms an unstable complex with Ca2+ and Mg2+ ions, giving wine red
colour to the solution.During the titration EDTA reacts with this complex (Ca-EBT or Mg-EBT
complex), forms a stablecomplex (Ca-EDTA or Mg-EDTA) and releases the blue EBT into the
solution. Hence the end point is wine red to blue colour.
M2+ + EBT pH=10 [M-EBT] complex
--------- (Wine red)
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Various steps involved in this method are;
1. Preparation of standard hard water (1mg of CaCO3 per 1 mL of water).
2. Standardization of EDTA solutions:
Pipette out 50 mL of standard hard water in a conical flask. Add 10-15 mL of buffer
solution and 4 to 5 drops EBT indicator. Titrate with EDTA solution, till wine red
colour changes to clear blue. Let volume used be V1 mL.
3. Titration of unknown hard water:
Titrate 50 mL of water sample just as indicated above. Let the vo lume used be V2 mL.
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3. In steam generation:
For steam generation, boilers are almost invariably employed. If the hard water is fed
directly to the boilers, there arise many troubles such as:
(i) Scale and sludge formation (ii) corrosion (iii) priming and foaming
(iv) caustic embrittlement.
Principle: Alkalinity of water means the total content of those substances in it which causes an
increased OH- ion concentration up on dissociation or due to hydrolysis. The alkalinity of water
is attributed to the presence of (i) Caustic alkalinity (Due to OH- and CO 32-) (ii) Temporary
hardness (Due to HCO 3 2-) Alkalinity is a measure of ability of water to neutralize the acids
Determination of alkalinity OH-, CO 32- and HCO 32- can be estimated separately by titration
against standard acid using phenolphthalein and methyl orange as indicators The determination is
based on the following reactions
The titration of water sample against a standard acid up to phenolphthalein end point (P) marks
the completion of reaction (i) and (ii) only. This amount of acid used thus corresponds to OH -
plus one half of the normal CO 3 2- present On the other hand, titration of the water sample against
a standard acid to methyl orange end point (M) marks the completion of reaction (i), (ii) and (iii).
Hence the total amount of acid used represents the total alkalinity.
1. Pipette out 20 ml of water sample into a conical flask. Add 1-2 drops of
Phenolphthalein indicator.
2. Rinse and fill the burette with N/10 HCl
3. Titrate the water sample in conical flask with N/10 HCl till the pink colour just
disappears.
4. Note down the reading and repeat to get concordant readings.
5. Calculate phenolphthalein alkalinity by using formula given below
Phenolphthalein alkalinity=V1x normality of acid x 50 x 1000
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Part B: Total alkalinity (Methyl orange)
1. Take 20 ml of water sample in conical flask and add methyl orange
indicator to it.
2. Titrate the water sample in conical flask with N/10 HCl taken in the burette till the yellow
orange colour changes to orange red.
3. Note down the reading and repeat to get concordant readings.
4. Calculate total alkalinity by using formula given below.
Total alkalinity=V2x normality of acid x 50 x 1000
Procedure :
2. The size of equipment , chemical requirement storage space and cost of treatment all depend
upon amount CO 2 Present.
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3. CO 2 is an important consideration in estimating chemical requirements for lime or lime soda
ash softening process.
4. Most industrial wastes containing mineral acidity must be eutralized be for they are subjectd
to biological treatment or direct discharge into water course or sewers quantities of chemicals
size of chemical feeders storage space and costs are determined from the laboratory data of
acidity.
CALCULATION:
100
100
Procedure:
Transfer 100ml of water sample into a clean conical flask. Add about 1 ml of
K2CrO4 indicator solution & titrate against standard (say 0.02N) AgNO3 solution until a
reddish brown color persists in the white precipitate. Record the volume of AgNO3 consumed
(Let ‘a’ cm3 ). Perform a blank titration taking 100 ml of distilled water. The volume of AgNO3
consumed Let ‘b’ cm3.
Calculation:
Volume of AgNO3 required for chlorine estimation = (a-b) cm3 = V 1000ml of-
1 N AgNO3 = 35.45g/Cl
1 ml of 1N AgNO3 = 0.03545g/Cl-
V ml of 0.02 N AgNO3 = 0.03545 X V X 0.02 g/Cl-
Cl- content in the sample = 0.03545 X V X 0.02 grams /Cl-100
Cl- content in the sample = 0.03545 X V X 0.02 X 1000 mg/Cl-100
The processes & technologies used to remove the contaminants from water & to improve its
quality is recognized all over the world. The choice of which treatment to use from a great
variety of available processes depends on the characteristics of the water, the type of the water
quality problems to be present, & the costs of different treatments. There are different methods
of water treatment the selection of which depends upon the type of source & purpose of use of
water. Some of the methods are:
a) Screening
b) Plain sedimentation
c) Sedimentation by coagulation
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d) Filtration
e) Disinfection
b) Plain sedimentation : The process of removing big sized suspended solid particles
from water is called as plain sedimentation. In this process, water is stored in big tanks for
several hours. 70% of solid particles settle down due to force of gravity.
c) Sedimentation by coagulation : This is the process of removing fine suspended and colloidal
impurities by adding coagulants like alum(K 2 SO 4 Al2 (SO 4 )3 24 H2 O,FeSO4 ,NaAlO 2 .When
coagulant is added to water, floc formation takes place due to hydroxide formation which can
gather tiny particles together to form bigger particles and settle down quickly.
d) Filtration: The process of passing a liquid containing suspended impurities through a suitable
porous material so as to effectively removed suspended impurities and some microorganisms is
called filtration. It is a mechanical process. When water flows through a filter bed, many
suspended particles are unable to pass through the gaps and settle in the bed.
e) Disinfection or sterilization
The process of killing pathogenic bacteria and other microorganisms is called
disinfection or sterilization. The water which is free from pathogenic bacteria and safe for
drinking is called potable water. The chemicals used for killing bacteria are called disinfectants.
i) By adding bleaching powde r: Water is mixed with required amount of bleaching powder,
and the mixture is allowed to stand for several hours.
The disinfection action of bleaching powder is due to available chlorine in it. It forms
hypochlorous acid which acts as a powerful germicide(disinfectant).
ii) Chlorination:
Chlorine is mixed with water in a chlorinator, which is a high tower having a
number of baffle plates. Water and required quantity of concentrated chlorine solution
are introduced from its top during their passage through the tower. They get
thoroughly mixed and thn sterilized water is taken out from the bottom.
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Cl2 + H2 O -----------> HOCl + HCl
Advantages:
1) Storage requires less space
2) Effective and economical
3) Produce no salts
4) Ideal disinfectant
Disadvantages:
1) Excess of chlorine causes unpleasant taste and odour.
2) More effective at below pH 6.5 and less effective at higher pH values.
iii) Ozonisation:
3O2 -----------> 2O 3
O3 -----------> O2 + (O)
Advantages :
Disadvantages:
Boiler troubles:
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Sludge:
It is a soft, loose and slimy precipitate formed within the boiler. Sludge can easily be scrapped
off with a wire brush. It is formed at colder portions of the boiler. Sludge is formed b y
substances which have greater solubilities in hot water than cold water.
Scale:
These are hard deposits, which stick very firmly to the inner surfaces of the boiler. Scales are
difficult to remove, even with the help of hammer. These are main sources of boiler troubles.
Formation of scales may be due to;
(a) Decomposition of calcium bicarbonate:
Due to high temperature and pressure present in the boilers, the calcium bicarbonate salt
decomposes in to CaCO3, which is an insoluble salt, forms scale.
Ca(HCO3)2--------- CaCO3 + H2O + CO2
(scale)
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(c) Hydrolysis of magnesium salts:
Dissolved magnesium salts undergo hydrolysis to form magnesium hydroxide precipitate,
which forms a soft type of scale.
MgCl2 + 2H2O-------- Mg(OH)2 + 2HCl
(d) Presence of silica:
SiO2, even present in small quantities, deposits as calcium silicate (CaSiO3) and
magnesium silicate (MgSiO3). These deposits stick very firmly on the inner side of the boiler
surface and are very difficult to remove.
Disadvantages of scales:
(a) Wastage of fuel:Scales have a low thermal conductivity, so the rate of heat transfer
from boiler to inside water gradually decreased. In order to provide a steady supply of
heat to water, excessive or over-heating is done and this causes increase in fuel
consumption. The wastage of fuel depends upon the thickness of scale.
Removal of scales:
(i) With the help of scraper or wire brush, we can remove the scales, if they are loosely
adhering.
(ii) By giving thermal shocks, we can remove the scales, if they are brittle.
(ii) Calcium carbonate scales can be dissolved by using 5-10% HCl. Calcium sulphate
scales can be dissolved by adding EDTA, with which they form soluble complexes.
(iv) By frequent blow-down operation, if the scales are loosely adhering.
2. Boiler corrosion:
Boiler corrosion is “the decay of boiler material by a chemical or electro-chemical attack
by its environment”.
Main reasons for boiler corrosion are:
(i) Dissolved oxygen. (ii) Dissolved carbon dioxide. (iii) Acids from dissolved salts.
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Water usually contains about 8 ppm of dissolved oxygen at room temperature. At high
temperature this D.O. can attack boiler material.
2 Fe + 2 H2O + O2----------- 2 Fe(OH)2
4 Fe(OH)2 + O2---------------- 2[Fe2O3.2 H2O] (rust)
Removal of dissolved oxygen:
By adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide. Thus;
2 Na2SO3 + O2-------- 2 Na2SO4
NH2-NH2 + O2---------- N2 + 2 H2O
Na2S + 2 O2 ----------Na2SO4
WATER TECHNOLOGY
(ii) Dissolved carbon dioxide:
CO2 + H2O--------- H2CO3
Carbon dioxide is also released inside the boiler, if water used for steam generation
contains bicarbonates.
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(iii) Maintaining low water levels in boilers.
(iv) Efficient softening and filtration of boiler- feed water.
Foaming:
Foaming is “the production of persistent foam or bubbles in boilers, which do not break
easily”.Foaming is due to the presence of substances like oils, which greatly reduce the surface
tension of water.
Foaming can be avoided by:
(i) Adding anti- foaming chemicals like castor oil.
(ii) Removing oil from boiler water by adding compounds like sodium aluminate.
4. Caustic embrittlement:
Caustic embrittlement is “a type of boiler corrosion, caused by using highly alkaline water in the
boiler”.During softening process of water (in lime-soda process), free Na2CO3 is usually present
in small proportion in the softened water. In high pressure boilers, Na2CO3 decomposes to give
sodium hydroxide and carbon dioxide. This makes the boiler water ‘caustic’.WATER
TECHNOLOGY
Na2CO3 + H2O -------2NaOH + CO2
The NaOH containing water flows into the minute hair-cracks, present in the inner side of
boiler, bycapillary action. Here water evaporates and the dissolved caustic soda (NaOH)
concentration increases progressively. This caustic soda attacks the surrounding area, thereby
corroding the iron of boiler as sodium ferrate.
This causes embrittlement (cracking) of boiler parts, particularly stressed parts (like
bends, joints), causing even failure of the boiler.
Caustic embrittlement can be explained by considering the following concentration cell;
The iron surrounded by the dilute NaOH becomes the cathodic side; while the iron in contact
with concentrated NaOH becomes anodic part, which consequently corroded.
Prevention of caustic e mbrittle ment:
(i) By using sodium phosphate as softening reagent, instead of sodium carbonate.
(ii) By adding tannin or lignin to boiler water, which blocks the hair-cracks, thereby
Preventing infiltration of caustic soda solution in cracks.
(iii) By adding sodium sulphate to boiler water:
Na2SO4 also blocks hair-cracks, thereby preventing infiltration of caustic soda solution
in these cracks. It has been observed that caustic embrittlement can be prevented, if Na2SO4 is
added to boiler water so that the ratio:
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NaOH concentration
Na2SO4concentration
is kept as 1 : 1, 2 : 1 and 3 : 1 in boilers working respectively at pressures up to 10, 20
and above 20 atmospheres.
Softening methods:
Water used for industrial purpose (such as fir steam generation) should be sufficiently
pure. Therefore, it should be freed from hardness producing salts before put to use. The process
of removing hardnessproducing salts from water, is known as softening of water.
In industry, main methods employed for softening of water are two types.
Softening of water
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The hard and strong adherent scales formed due to CaSO4 are avoided by the addition of
sodium carbonate to boiler water and this is called carbonate condition.
CaSO4 + Na2CO3 --------CaCO3↓ + Na2SO4
The CaSO4 is converted to CaCO3, which is loose sludge and it can be removed by blow down.
External treatment
Zeolite process (Or) Permutit process:
Zeolite is hydrated sodium alumina silicate, which is capable of exchanging reversibly its
sodium ions for hardness-producing ions in water. Chemical formula of sodium zeolite may be
represented as;
Na2O.Al2O3.x SiO2.y H2O where x = 2 – 10 and y = 2 – 6
Process:
For softening of water by zeolite process, hard water is percolated at a specified rate
through a bed of zeolite, kept in a cylinder. The hardness causing ions (Ca2+, Mg2+) are retained
by the zeolite as CaZe and MgZe; while the outgoing water contains sodium salts. Reactions
taking place during the softening process are;
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Na2Ze + CaCl2 --------CaZe + 2NaCl
Na2Ze + MgCl2 --------MgZe + 2NaCl
WATER TECHNOLOGY
1 9
Regeneration:
After some time, the zeolite is completely converted into calcium and magnesium
zeolites and it ceases to soften water, i.e. it gets exhausted. At this stage, the supply of water is
stopped and the exhausted zeolite is reclaimed by treating the bed with brine solution (10% NaC l
solution).
CaZe (or MgZe) + 2NaCl --------Na2Ze + CaCl2 (or MgCl2)
The washings (containing CaCl2 and MgCl2) are led to drain and the regenerated zeolite bed
thus obtained is used again for softening purpose.
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Disadvantages of zeolite process:
(1) The treated water contains more sodium salts than in lime-soda process.
(2) The method only replaces Ca2+ and Mg2+ ions by Na+ ions, but leaves all the acidic
Ions (HCO 3 and CO -2 3) as such in the softened water. When such softened water
(containing NaHCO3 and Na2CO3) is used in boilers for steam generation, sodium
bicarbonate decomposes producing CO2, which causes corrosion; and sodium
carbonate undergoes hydrolysis to sodium hydroxide, which causes caustic
embrittlement.
(3) High turbidity water cannot be treated efficiently by this method, because fine
impurities get deposited on the zeolite bed, thereby creating problem for its working.
Ion exchange process (or) de- ionisation (or) de- mineralization 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-
exchange properties. Resins containing acidic functional groups (-COOH, -SO3H) are capable of
exchanging their H+ ions with other cations, which comes in their contact. Resins containing
basic functional groups (amino groups) are capable of exchanging their anions with other anions,
which comes in their contact. Thus, ion-exchange resins may be classified as follows;
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Process:
The hard water is passed first through cation exchange column, which removes the
cations like Ca2+ and Mg2+ etc from it, and equivalent amount of H+ ions are released from the
column to water. Thus;
2RH+ + Ca2+------- R2Ca2+ + 2H+
2RH+ + Mg2+------ R2Mg2+ + 2H+
After cation exchange column, the hard water is passed through anion exchange column, which
removes all the anions like SO 24 , Cl -, CO2 3 etc. present in the water and equivalent
amount of OHions are replaced from this column to water. Thus;
R’OH- + Cl------- R’Cl- + OH-
2R’OH+ SO 24-------------R2’ SO 24+ 2OH-
2R’OH- + CO2 3----------- R2’ CO2 3 + 2OH
WATER TECHNOLOGY
21H+ and OH- ions (released from cation exchange and anion exchange columns respectively)
get combined to produce water molecule.
H+ + OH-------- H2O
Thus, the water coming out from the exchanger is free from cations as well as anions. Ion- free
water is known as deionised or demineralised water.
Regeneration:
When capacities of cation and anion exchangers to exchange H+ and OH- ions
respectively are lost, they are then said to be exhausted.
The exhausted cation exchange column is regenerated by passing a solution of dil. HCl or
dil. H2SO4. The regeneration can be represented as;
R2Ca2+ + 2H+-------- 2RH+ + Ca2+
The exhausted anion exchange column is regenerated by passing a solution of dil. NaOH.
The regeneration can be represented as;
R2’ SO 24 + 2OH- ---------2R’OH- + SO 24
The regenerated ion exchange resins are then used again.
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2. It produces water of very low hardness (about 2 ppm). So it is very good for treating
Water used in high – pressure boilers.
Disadvantages:
1. The equipment is costly and more expensive chemicals are needed.
2. If water contains turbidity, then the output of the process is reduced. The turbidity must
Be below 10 ppm. If it is more, it has to be removed first by coagulation and filtration.
WA TECHNOLOGY
ESTIMATION OF DISSOLVED OXYGEN:
The amount of oxygen present in the water in dissolved state is called dissolved oxygen
PRINCIPLE:
Dissolved oxygen can be determined by iodometric titrations. The dissolved oxygen present in
water oxidizes KI liberating an equivalent amount of Iodine, which is titrated against standard
hypo solution using starch as an indicator. An oxygen carrier like manganese hydroxide must be
used to bring about the reaction between KI and dissolved oxygen because molecular oxygen in
water is not capable of reacting with KI.
PROCEDURE:
Weigh out accurately the given pure crystalline sample of potassium dichromate and
transfer into 100 ml standard (volumetric) flask provided with a funnel.
Dissolve the dichromate in a small quantity of distilled water, and make up to the mark.
The contents in the flask are shaken well for uniform concentration. Calculate the
normality of potassium dichromate.
STEP:II STANDARDIZATION OF SODIUM THIOSULPHATE:
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Rinse the burette and fill it up with hypo solution without any air bubbles. Note the
burette reading.
Take about 20 ml of 10%KI solution in a clean conical flask and add 2 grams of sodium
bicarbonate followed by 5 ml of concentrate HCl gently rotate the flask for mixing the
liquids.
Rinse the pipette with a little of potassium dichromate solution and then transfer 20 ml
of the same to the conical flask. Shake it well, stopper it, and keep it in dark place for 5
minutes.
Titrate the liberate iodine by running down hypo from the burette with constant stirring.
When the solution attains a pale yellow colour add 2 ml of freshly prepared starch
solution.
The colour changes to blue. Continue the titration drop-wise till the colour changes from
blue to light green indicating the end point. Repeat the titration for concurrent values.
STEP: III ESTIMATION OF DISSOLVED OXYGEN:
Collect water sample in 300 ml capacity of BOD bottle and add 2 ml of manganese
sulphate solution.
To this add 2 ml of alkali- iodine–azide solution.
Stopper the BOD bottle immediately.
Appearance of brown precipitate indicates the presence of dissolved oxygen.
Mixed well by inverting the bottle 2-3 times and allow the brown precipitate settle down.
Add 2 ml of Conc H2SO4 to dissolve the precipitate
Take 20 ml of the above solution in to a clean conical flask.
Titrate the liberated iodine with standard hypo solution present in burette.
Add 1 ml of starch solution when the color of the solution becomes blue color.
Note the volume of the Hypo solution(v ml) repeate the titration till concurrent readings
are obtained.
Calculate the amount of dissolved oxygen present in water sample by using the formulae
given below
Dissolved oxygen in the given sample = V x Conc. of HypoX8X1000/20 PPM
The process of removing common salt (sodium chloride) from water, is known as
desalination. The water containing dissolved salts with a peculiar salty (or brackish) 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 are;
1. Electro dialysis (out of syllabus). 2. Reverse osmosis.
Reverse osmosis:
When two solutions of unequal concentrations are separated by a semipermeable
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 reverses, i.e. solvent is forced to move from concentrated side to diluted
side across the membrane. This is the principle of reverse osmosis. Thus, in reverse osmosis
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method, pure solvent is separated from its contaminates, rather than removing contaminates from
water. This membrane filtration is sometimes also called superfiltration or hype r-filtration.
Advantages:
1. This process removes, ionic as well as non- ionic, colloidal and high molecular weight
organic matter.
2. It removes colloidal silica, which is not removed by demineralization process.
3. The life time of membrane is quite high, about 2 years.
4. The membrane can be replaced within a few minutes, thereby providing nearly
uninterrupted water supply.
5. Due to low cost, simplicity and high reliability, the reverse osmosis is gaining ground
at present for converting sea water into drinking water.
Electrodialysis.
Principle: Passage of an electric current through a solution of salt results in migration of cations towards the cathode
& anions towards the anode. The use of semi permeable cat ion or anion exchange memb rane in an electrolytic
vessel permits the passage of only cations or anions respectively in the solution. An electrodialyzer consists of a
chamber carrying a series of compart ments fitted with closely spaced alternate cation (C) & anion (A) exchange
semi permeab le memb ranes between the electrodes. An electrodialyzer un it will have 200 to 1000 co mpart ments.
The feed water is taken in the dialy zer & the electrodes are connected to a source of an electric current.
The anions pass through the anion permeable memb rane towards the anode. However, these ions do not
pass through the next membrane which is permeable only to cations. Similarly the cations moving in the other
direction will pass through the cation exchange memb rane but not the next. These anions & cations collect in
the alternate chambers; the water in these is enriched with salt while that in the other co mpart ments is
desalinated. Micro porous sieves provided near the electrodes prevent the reentry of any deposit, which might
have been formed on the electrodes, into the feed water. The enriched & desalinated waters are withdrawn
separately. The former is rejected & the desalinated water is recycled to further reduce the salt content.
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