Module-1 (Water Analysis)

Lecture-1
1. INTRODUCTION
[Link] technology
The process of removing all types of impurities from water and making it fit for domestic or industrial
purpose is called water technology.
Water is the most useful, wonderful and abundant compound on earth. It’s a vital component of life
forms. One can live without food for many numbers of days but one cannot live without water.
Water is the important constituent of all the body fluids, without which all the cells or organisms are
in crystalline or dead state. (For example, the human body contains 70%, land plants 50–75% and
aquatic plants 95–99%). Water is not only essential for the lives of animals and plants, but also
occupies a unique position in industry.

1.2. Learning Objectives

 To describe the chemical compositions of natural waters, and explain how and why these
compositions vary.

 To describe the main sources of water pollution, the main types of pollutant and how each type may
be controlled.

 To identify the criteria for drinking water acceptability and outline the processes used to treat water
for a public water supply

 To outline how sewage may be treated before discharge to the environment.

1.3. Sources of Water

The chief sources of water supply for industrial use are:

(a) Rainwater: The purest form of water, collected on the roofs. Yet this method is seldom adopted in industry.
(b) Surface waters: Flowing water such as rivers, streams etc. Still water such as lakes, ponds etc.
(c) Ground Water: Water from springs. Water form shallow wells.

(d) Seawater: Its use is very limited as its uses entail very great problems of chemical engineering.

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 1.4. Uses of Water
 Water is used in power generation, as steam in steam turbines and as coolants.
 Blasting and water jet cutters. Very high pressure water guns are used for precise cutting.
 It is also used in the cooling of machinery to prevent over-heating, or prevent saw-blades from over-
heating.
 Industry requires pure water for many applications and utilizes a variety of purification techniques
both in water supply and discharge.
 Water plays many critical roles within the field of food science.
 Water is widely used in the production of steel, rayon, paper, atomic energy, textiles, chemicals, ice and for air-
conditioning, drinking, bathing, sanitary, washing, irrigation and fire-fighting etc.

1.5. Impurities of Water

Source and nature of impurities of water
Water in the form of vapour in clouds is said to be pure. Yet when it condenses as rain and flows on the ground it takes
many impurities from atmosphere and ground. The major situations in which water gets impure are as
followed:
 Dissolved gases: during raining water absorbs much of the gases like oxygen, carbon dioxide,
hydrogen sulphide etc. from atmosphere. The resultant water will be slightly acid.
 Soluble crystalloids: water when flow over the surface of the land (like rivers, streams), dissolved
soluble minerals. The most of the soluble minerals include chlorides, sulphates, bicarbonates of
sodium, calcium, magnesium and iron. Where as in sea water 3.5% of dissolved salts are seen in
which 2.5% include sodium chloride.
 Organic matter: This is derived from the decomposition of plants and small particles of sand and
rock in suspension.
1.6. Characteristics imparted by impurities of water:
As such pure water is odourless, colourless, tasteless, etc., but the presence of impurities imparts various
physical and chemical changes to water nature which are as followed.
 Colour: The metallic substances like humus, tannins, peat, algae, weeds, protozoa, industrial
effluents and salts of iron, manganese in the colloidal form imparts color to water. For example
yellowish tinge is due to the presence of chromium or appreciable amount of organic matter,
yellowish–red colour due to the presence of iron, while reddish brown is due to the presence of peat.
(The intensity of the colour indicates these verity of toxic nature of water).

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  Turbidity: The colloidal, extremely fine suspension particles such as clay, silt, finely divided matter,
micro-organisms etc. increases the turbidity of the water. The turbid water is not fit for either
consumption or industrial purpose.
 Taste: Usually this property is linked to odour. Yet under certain conditions taste is not accompanied by odour.
For example,
o Bitter taste can be due to the presence of iron, aluminum, manganese, sulphate or excess of lime.
o Soapy taste can be due to the presence of large amount of sodium bicarbonate.
o Brackish taste is due to the presence of unusual amount of salts.
o Palatable taste is due to the presence of dissolved gases (CO2) and minerals like nitrates.
 Odour: The odour maybe due to the presence of living organisms, decaying vegetation. The common
disagreeable odour is due to the presence of sulphides. The odour of sewage water is due to the presence of
organic compounds of N, S and P along with the put refaction of proteins and the industrial effluents
like alcohols, aldehydes, phenols, esters, ketones etc. Besides these,
o The presence of algae in water impart strong grassy odour.
o Growth of iron and sulphur bacteria produces offensive odour.
o Sand in finely divided state imparts faint earthy odour.
o When water passes through iron pipes, it gives tarry odour.
The faint odour when the water passes through galvanized iron pipes is due to the impure hydrogen. Rain water
is almost pure (may contain some dissolved gases from the atmosphere). Being a good solvent, when
it flows on the surface of the earth, it dissolves many salts. Presence of calcium and magnesium salts in

the form of bicarbonate, chloride and sulphate [Cations are Ca2+ ion and Mg2+ ion and Anions are

HCO3- ion, Cl- ion, and SO42-Ion] in water makes water ‘hard’.

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 Lecture-2

2. Hard water does not give ready and permanent lather with soap. Water free from soluble salts of
calcium and magnesium is called Soft water. It gives lather with soap easily.

2.1 Hardness of Water: Hardness o f w a t e r i s defined as the soap consuming capacity of a

water sample.
Soap is the sodium salt of higher fatty acids, e.g. sodium stearate. The sodium salt is soluble in water,
but the corresponding calcium and magnesium ions are insoluble in water. When soap is added to soft
water, it dissolves and lathers r e a d i l y .

On adding soap solution to a sample of hard water which contains calcium or magnesium ions, soap is
precipitated as insoluble salts which prevent the formation of lather. This reaction causes the loss of
soap. No lather is obtained until all the ions are removed. So, large amount of soap is consumed
unnecessarily before lather is formed.

2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCI

(Sodium stearate) (Calcium stearate)
2.2. Types of Hardness
The hardness of water is of two types:
(i) Temporary Hardness, and (ii) Permanent Hardness.

(i) Temporary Hardness

Temporary Hardness is due to the presence of calcium and magnesium bicarbonates [Ca(HCO3)2 and
Mg(HCO3)2]. It is also called carbonate hardness (CH). It can be removed by Boiling. During boiling, the
soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2 is changed to insoluble CaCO3.
These insoluble precipitates can be removed by filtration. Filtrate thusobtained will be soft water.

Mg(HCO3)2 → Mg (OH)2 + 2CO2

Mg(HCO3)2 → Mg (OH)2 + 2CO2

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(ii) Permanent Hardness
Permanent hardness is due to the presence of soluble salts of magnesium and calcium in the form of chlorides
and sulphates in water (CaCl2, CaSO4, MgCl2 and MgSO4). Permanent hardness is not removed by boiling. It
is also called non-carbonate hardness (NCH).

Total Hardness:
Total hardness is the summation of temporary and permanent hardness. It is also expressed as the sum of the
concentration of calcium and magnesium ions.
Total Hardness = Temporary Hardness + Permanent Hardness
Total Hardness = [Ca2+] + [Mg2+]
2.3 Units of hardness:
The following are the common units used in hardness measurements.
(i) 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
1ppm =

Both temporary and permanent hardness is expressed in ppm as CaCO3 equivalent. The choice of CaCO3 is
due to the fact that it is the most insoluble salt in water and the molecular mass of CaCO3 is 100.
(ii) 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.
Hardness is usually expressed in terms of equivalent of CaCO3 in order to simplify the calculations in water
analysis. Hence, all the hardness causing impurities are first converted in terms of their respective weights
equivalent to CaCO3 by using the relation

(Or)

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 Substance Molecular Weight Valency Equivalent Weight
Calcium bicarbonate 162 2 81
Magnesium bicarbonate 146 2 73
Calcium Carbonate 100 2 50
Magnesium Carbonate 84 2 42
Calcium sulphate 136 2 68
Calcium Chloride 111 2 55.5
Magnesium sulphate 120 2 60
Magnesium Chloride 95 2 47.5

2.4 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.
2.5. Alkalinity: Alkalinity of water is the measure of the capacity of the water to neutralize the acid and the
water. It is due to the presence of a different kinds of salts of weak acids such as carbonates, bicarbonates,
phosphates, etc., and also due to the presence of weak and strong bases (due to contamination with industrial
wastes). The major portion of alkalinity in natural water is caused by the presence of bicarbonates that are
formed when water containing free carbon dioxide percolates through soils containing calcium carbonate and
magnesium carbonate.
CaCO3 + CO2 + H2O → Ca(HCO3)2
The alkalinity of natural water may be taken as an indication of the concentration of hydroxides, carbonates
and bicarbonates.

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 Lecture-3
3.1. Sludge and Scale Formation in Boilers: In a boiler, water is continuously converted into steam.
Due to this continuous evaporation of water, the concentration of soluble matters increases progressively.
Then the salts start separating out from the solution in the order of their solubility, the least soluble one
separating out first. Some of the salts like MgCI2, CaCl2 and MgSO4 separate in the body of the liquid in
the form of soft deposits which can be flushed out easily (Figure 1.1 a). Such soft and non-adherent
deposits are known as sludges. Highly alkaline water may cause deposition of precipitates and sludges in
boiler tubes and pipes.
Some salts like CaSO4 and Mg(OH)2 form hard adherent deposits on the inner walls of the boiler.
They are called scales (Figure 1.1 b). Scales are so hard and adherent that they are difficult to remove even
with the help of hammer and chisel.

Figure 1.1: (a) Sludge in boiler and (b) scale in boiler

3.2 Disadvantages of scale formation: The following are the disadvantages of scale formation
[1] Scale is a poor conductor of heat and thus it decreases the evaporative capacity of the boiler. So, the
consumption of fuel is much more than usual.
[2] Since the scale acts as a heat insulator, the boiler metal is overheated. Due to overheating, the metal
expands until the scale on it cracks. When thick scales crack, the water suddenly comes in contact with
overheated boiler metal. This causes the formation of a large amount of steam suddenly. This results in the
development of high pressure inside the boiler which may lead to a dangerous explosion.
[3] Due to scale formation, heat available to water is reduced and hence more heat is required to produce
steam. This causes overheating of boiler plates and tubes and thus their life is reduced.

3.3 Caustic Embrittlement: It is the phenomenon during which the boiler material becomes brittle due to
the accumulation of caustic substances. It is a very dangerous form of stress corrosion occurring in mild steel
boiler metals exposed to alkaline solution at high temperatures, resulting in the failure of the metal. Stressed
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parts like bends, joints and rivets are severely affected. Boiler water usually contains a small proportion of
Na2CO3. In high pressure boilers, this breaks up to give NaOH and makes the boiler water more alkaline:

Na2CO3 + H2O → 2NaOH + CO2

This very dilute alkaline boiler water flows into the minute hair cracks and crevices by capillary action. There
the water evaporates and the concentration of caustic soda increases progressively. The concentrated alkali
dissolves iron as sodium ferroate in crevices, cracks, etc. where the metal is stressed. This causes brittlement
of boiler parts particularly stressed parts like: bends, joints and rivets causing even failure of the boiler.
Highly alkaline water may lead to caustic embrittlement.
Caustic embrittlement can be avoided (a) by using sodium phosphate as softening reagent instead of Na2CO3
and (b) by adding tannin or lignin to boiler water which blocks the hair cracks.

3.4. Boiler Corrosion: It is the decay of boiler material due to chemical or electrochemical attack of its
environment. The corrosion in boilers is due to dissolved oxygen, dissolved CO2 and acids produced by the
hydrolysis of dissolved salts. Therefore, removal of these prevents the corrosion of boilers.

3.5. Removal of Dissolved O2: Dissolved oxygen in water is mainly responsible for the corrosion of a boiler.
The dissolved oxygen in water attacks the boiler material at high temperatures.
2Fe + 2H2O + O2 → 2Fe(OH)2
4Fe(OH)2 + O2 + 2H2O → 2[Fe2O3·3H2O] (rust)
Dissolved oxygen can be removed from water by chemical and mechanical means. Sodium sulphite,
hydrazine, etc. are some of the chemicals used for removing oxygen.
2Na2SO3 + O2 → 2Na2SO4
N2H4 + O2 → N2 + 2H2O
Hydrazine is found to be an ideal compound for removing dissolved oxygen since the products are water and
inert N2 gas. It removes oxygen without increasing the concentration of dissolved salts.
3.5.1 Mechanical deaeration method
Dissolved O2 can also be removed from water by mechanical deaeration (Figure 1.2). In this process, water is
allowed to spray slowly by the perforated plates fitted inside the tower. Vacuum is applied to this tower and
the sides of the tower are also heated. High temperature and low pressure reduce the quantity of dissolved O 2
in water.

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 Figure 1.2: Mechanical deaeration of water
3.3.2 Removal of Dissolved CO2: Dissolved CO2 in water produces carbonic acid which is corrosive in
nature: CO2 + H2O → H2CO3
Carbon dioxide can be removed from water by chemical or mechanical means. In the chemical method CO2
is removed from water by the addition of a calculated quantity of NH4OH:
2NH4OH + CO2 → (NH4)2CO3 + H2O
Dissolved CO2 along with oxygen can be removed by mechanical deaeration.

3.3.2 Removal of Acids: Acids produced from salts dissolved in water are also mainly responsible for
corrosion of boilers. Certain salts like MgCI2 and CaCl2 on hydrolysis at higher temperatures produce
hydrochloric acid which corrodes the boiler.
MgCl2 + 2H2O → Mg(OH)2 + 2HCl
The liberated acid can produce rust in the following way.
Fe + 2HCl → FeCl2 + H2
FeCl2 + 2H2O → Fe(OH)2 + 2HCl
4Fe(OH)2 + O2 + 2H20 →2[Fe2O3·3H2O] (rust)
Hence, even a very small amount of MgCI2 can cause considerable corrosion of the boiler metal.
Corrosion by acids can be avoided by the addition of alkali to the boiler water from outside.

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 Lecture-4
Softening of hard water:
The process of removing hardness producing salts from water is known as softening of water.
There are two mode of softening the hard water
i. External Treatment
ii. Internal Treatment
The three important industrial methods used for softening of water externally are:
1. Lime – Soda process
2. Zeolite or permutit process
3. Ion exchange or demineralization process

1. Lime – Soda process:

In this process, the soluble calcium and magnesium salts are chemically converted into insoluble
compounds by adding calculated amounts of lime [Ca(OH)2] and soda [Na2CO3]. Calcium carbonate
[CaCO3] and magnesium hydroxide [Mg(OH)2] so precipitated are filtered off. By this method both
temporary and permanent hardness are removed.

For removing temporary hardness the reactions are:

Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 → CaCO3 + MgCO3 + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3
Hence to remove equivalent amount of Ca and Mg hardness the amount of lime requirement is in the
ration 1:2.
Again for the removal of permanent hardness the reactions are:
CaSO4 + Na2CO3→ CaCO3 + Na2SO4
MgSO4 + Na2CO3 → MgCO3 + Na2SO4
MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3
Hence for the removal of permanent hardness due to Ca-salts, lime is not necessary, But for Mg salts it is
required. Extra addition of Ca(OH)2 causes hardness. So, calculated quantities of lime and soda are to be
added after the determination of actual hardness.
1. LIME-SODA PROCESS:
In this Method, the soluble calcium and Magnesium salts in water are chemically converted into insoluble
Compounds by adding calculated amounts of lime Ca (OH) 2 and soda Na2CO3 calcium carbonate CaCO3
and magnesium hydroxide Mg (OH) 2. So Precipitated, are filtered off.

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A) COLD LIME-SODA PROCESS:
In this Method, Calculated quantity of chemical (lime and soda) is 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 hydrolyse to flocculent, gelatinous precipitate of aluminium
hydroxide, and entraps the 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 + 3 Ca(HCO3)2 → 2Al(OH)3 + 3 CaSO4 + 6CO2

Method:
Raw water and calculated quantities of chemicals ( Lime+soda+coagulant) are fed from the top into the inner
vertical circular chambers, fitted with a vertical rotating shaft 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 takes place. As the softened ware comes into the outer chamber of the lime the softened water reaches
up. The softened water then passes through a filtering media (usually made of wood fibers) to ensure
complete removal of sludge. Filtered soft water finally a flow out continuously through the outlet at the top
sludge settling at the bottom of the outer chamber is drawn off occasionally.

HOT LIME-SODA PROCESS:

Involves in treating water with softening chemicals at a temperature of 80 to 150 o C. Since hot process is
operated at a temperature close to the boiling point of the solution, so (a) the reaction proceeds faster; (b) the
softening capacity of hot process is increased to may fold; (c) the precipitate and sludge formed settle down
rapidly and hence, no coagulants are needed;(d) much of the 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 Produces water of comparatively lower
residual hardness of 15 to 30ppm.
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 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 complete removal of sludge from the softened water.

Advantages of [Link]:
(i) It is a very economical.
(ii) If this process is combined with sedimentation with coagulation, lesser amounts of coagulants shall be
needed.
(iii)The process increased the pH value of the treated water, thereby corrosion of the distribution pipes is
reduced.
(iv) Besides the removal of hardness, the quantity of minerals in the water are reduced.
(v) To certain extent, iron and manganese are also removed from the water.
(vi) Due to alkaline nature of treated- water, amount of pathogenic bacteria’s in water is considerably
reduced.
Disadvantages of [Link]:
For efficient and economical softening, careful operation and skilled supervision is required
(i) Disposal of large amounts of sludge (insoluble precipitate) poses a problem. However, the sludge may
be disposed off in raising low-lying areas of the city.
(ii) This can remove hardness only up to 15ppm, which is not good for boilers.

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 Lecture-5
2) ZEOLITE PROCESS:
Chemical structure of sodium zeolite may be represented as Na2O3, SiO2, YH2O where x=2-10 and y=2-6.
Zeolite is hydrated sodium alumino silicate, capable of exchanging reversibly its sodium ions for hardness,
producing ions in water Zeolite are two types,
(i) Natural zeolites are non porous for Ex; Natrolite Na2Al3O3.4SiO2, 2H2O
(ii) Synthetic zeolites posses gel structure. Synthetic Zeolites posses higher exchange capacity than
natural Zeolites
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 (Ca+2,
Mg+2 etc.) are retained by the zeolite as CaZe and MgZe;
while the outgoing water contains sodium salts. Reactions
taking place during the softening process are
Na2Ze + Ca(HCO3)2 → CaZe +2NaHCO3
Na2Ze + Mg(HCO3)2 → MgZe +2NaHCO3
Na2Ze +CaCl2 (or CaSO4) → CaZe +2NaCl( or Na2SO4)
Na2Ze +MgCl2 (or MgSO4) → MgZe +2NaCl( or Na2SO4)

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 hard water is stopped and the exhausted zeolite
is reclaimed by treating the bed with a concentrated NaCl solution.
CaZe ( or MgZe) + 2NaCl  Na2Ze + CaCl2 (or MgCl2 )
The washings are led to drain and the regenerated zeolite bed thus obtained is used again for softening
process

Limitations:
(i) If the supply of water is turbid in will clog the pores of zeolite led.
(ii) Water contains large quantities of colored ions such as Mn+2 and Fe+2 they may be removed first
because these ions produce Mn and Fe Zeolites, which can’t be easily regenerated.
(iii) Mineral acids destiny the zeolite bed.

ADVANTAGES:
(i) If removes the hardness almost completely

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 (ii) Equipment occupying a small space
(iii)Requires less time
(iv) It is quite clean

DISADVANTAGES:
(i) Treated water contains more sodium salts than in time soda process.
(ii) The method only replaces Ca+2 and Mg+2 ions by Na+ ions leaves all the acidic ions.

3) ION EXCHANGE PROCESS:

Ion exchange resins are insoluble, cross linked long chain organic polymers with micro porous structure, and
the functional groups attached to the chains are responsible for the Ion – exchanging properties resins
containing acidic functional groups (-COOH,-SO3H etc,) are capable of exchanging their H+ ions with other
cations, which comes in their contact where as those containing basic functional groups(-NH2=NH,
hydrochloride) are capable of exchanging their anions with other anions, which comes in their contact Ion
exchange resins may be classified as
(i) Cation exchange resin(RH+) are mainly styrene-divinyl benzene copolymers, which on sulphonation
or carboxylation, become capable to exchange their hydrogen ions with the cat ions in water.
(ii) Anion exchange resins (ROH) are styrene-divinyl benzene or amine-formaldehyde, copdymers, which
contains amino or quaternary ammonium or quaternary phosphonium or tertiary sulphonium groups
as an integral part of the resin matrix these after treatment with dilute .NaOH solutions become
capable to exchange their OH‒ anions with anions.

PROCESS:
The Hard water is passed first through cat ion exchange column, which removes all the cat ions like Ca+2
etc, from it and equivalent amount of H+ ions released from this column to water, thus
2RH+ + Ca2+  R2Ca2+ + 2H+
2RH+ + Mg2+  R2Mg2+ + 2H+

After Cat ion exchange column, the hard water is passed through anion exchange column which removes all
the anions like SO4, Cl- etc present in the water and equivalent amount of OH- ions are released from this
column to water thus:
R’OH- + Cl-  R’Cl- + OH-
2R’OH- + SO42-  R’2SO42- + 2OH-
2R’OH- + CO32-  R’2CO32- +2OH-

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H+ and OH- ions get combined to produce water molecule
H+ + OH-  H2O
The water coming out from the exchanger is deionized or demineralized water.

REGENRATION:
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 cat ion exchange column is regenerated by passing a solution of Diluted HCl or Dilute H2SO4.
The regeneration can be represented as
R2Ca2+ + 2H+  2RH+ + Ca2+
The exhausted anions exchange column is regenerated by passing a solution of diluted NaoH. The
regeneration can be represented as
R’2SO42- + 2OH-  2R’OH- + SO42-

Advantages:
(i) Process used to soften highly acidic or alkaline water
(ii) It produces water of very low hardness
Disadvantages:
(i) The equipment is costly
(ii) If water contains turbidity out-out of the process is reduced

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 Lecture-6

LIME-SODA PROCESS PERMUTIT/ZEOLITE ION-EXCHANGE/RESIN

[Link]
1 Water treatment plant Water treatment plant occupies Water treatment plant occupies
occupies more area or place. less area. less area.

2 Water after treatment has Water after treatment has much Water after treatment free from
lesser dissolved solids. more dissolved solids. dissolved solids

3 This method of water This method of water treatment This method of water treatment
treatment plants is not much plants is more expensive and plants is more expensive and
expensive and material used material used for softening is material used for softening is
is cheap. expensive. expensive.

4 Operation expenses are Operation expenses are low Operation expenses are higher
higher

5 The cost incurred on The cost incurred on softening of The cost incurred on softening of
softening of water is high. water is low. water is high
6 It cannot operate in under It can even operate in under It can even operate in under
pressure. pressure. pressure.
7 It can be used for treating This method of softening the It can be used for treating acidic
acidic water also. water is not used for treating and alkaline water also.
acidic water.
8 There is a problem of There is no problem of settling, There is problem of turbidity.
settling, coagulation and coagulation and removal of
removal of sludge. sludge.

9 It is not possible. This method can be made This method can be made
automatic. automatic.

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10 In order to meet the changing Control test comprises only in Control test comprises only in
hardness of incoming water, checking the hardness of treated- checking the hardness of treated-
frequent control and water. water.
adjustment of reagents is
needed.
11 Residual hardness is low Residual hardness is low about Residual hardness is low about 0
about 15 to 50 ppm 10 to 15 ppm to 2 ppm

12 It is not good for boilers It is not good for boilers It is very good for treating water
for use in high pressure boilers.
13 Skilled persons required It required less skill for It required less skill for
maintenance as well as operation maintenance as well as operation

INTERNAL TREATMENT:
In this process; an ion is prohibited to exhibit its original character by converting it into other more soluble
salt by adding appropriate reagent. An internal treatment is accomplished by adding a proper chemical to the
boiler water either to precipitate the scale forming impurities in the form of sludge, which can be removed by
blow down operations, or to convert them into compounds, which will stay in dissolved form in water and
they do not cause any harm .
Important Internal treatment methods are:
(i) Colloidal conditioning: In low pressure boilers, scale formation can be avoided by adding organic
substances like Kerosene, tannin ,agar-Agar etc; which get coated over the scale firming precipitates,
there by yielding coated non sticky and loose deposits
(ii) Phosphate conditioning: In High pressure boilers, scale formation can be avoided by adding sodium
phosphate which reacts with hardness of water forming non- adherent and easily removable soft
sludge
3CaCl2+2Na3PO4 Ca3(PO4) 2+ 6NaCl
The main phosphates employed are (a) NaH2PO4 (b) Na2HPO4 (c) Na3PO4

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 (iii) Carbonate Conditioning: In low pressure boilers, scale formation can be avoided by adding sodium
carbonate to boiler water, then caSo4 converted into Caco3 in equipment Caco3 forms loose sludge
CaSO4+Na2CO3CaCO3+ Na2SO4

(iv) Calgon Conditioning: Involves in adding calgon [(NaPO3)6] to boiler water then it forms soluble
complex compound with CaSO4.
Na2 [Na4(PO3)6]- 2Na++ [Na4P6O18]2-
2CaSO4 + [Na4P6O18]2- [CaP6O18]+2
(v) Treatment with sodium aluminate (NaAlO2). Sodium aluminate gets hydrolyzed yielding NaOH
and a gelatinous precipitate of aluminium hydroxide
NaAlO2+2H2O NaOH+Al[OH]3
The NaOH, so formed precipitation some of the magnesium as MgOH)2 i.e.;
MgCl2 + 2 NaOH Mg(OH)2 + 2NaCl
The precipitate of Mg(OH)2 and Al(OH)3 produced inside the boiler entraps finely suspended and
Colloidal impurities including oil drops and silica.
Lecture-7
Desalination of Water:
The process of removing common salt (sodium chloride) from the water, is known as desalination.
The water containing dissolved salts with a peculiar salty (or brackish) taste, is called brackish water.
Sea water contains on an average 3.5% salts. Brackish water is not fit for drinking.
Depending upon the quantity of dissolved solids, water is graded as:
o Fresh Water: Contains less than 1000 ppm of dissolved solids.

o Brackish Water: Contains more than 1000 ppm to less than 35000 ppm of dissolved solids.

o Sea Water: Contains more than 35000 ppm of dissolved solids.

Sea water and brackish water can be made available as drinking water through desalination process.
Desalination is carried out either by reverse osmosis or electro dialysis.
Reverse Osmosis:
Reverse Osmosis is a process in which pressure greater than the osmotic pressure is applied on the high
concentration side of the membrane, the flow of solvent move from concentrated side to dilute side across the
membrane.

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Osmosis is the phenomenon by virtue of which flow of solvent takes place from a region of low
concentration to high concentration when two solutions of different concentrations are separated by a semi-
permeable membrane.
In this process pure water is separated from salt water. 15-40 kg/cm2 pressure is applied for separating the
water from its contaminants. The membranes used are cellulose acetate, polymethylmethacrylate and
polyamide polymers. The process is also known as super or hyper filtration.

Advantages:
➢ It is simple and reliable process & Capital and operating expenses are low.

➢ The life of the semi-permeable membrane is about two years and it can be easily replaced within a few
minutes, thereby nearly uninterrupted water supply can be provided.
Electrodialysis process:

Electrodialysis (ED) is used to transport salt ions from one solution through ion-exchange membranes to
another solution under the influence of an applied electric potential difference.

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 Electro dialysis is used whenever solutions, which contain dissolved electrically charged ions, have to be
concentrated or diluted. The electrolyte separation of solutions which contain electrical uncharged molecules,
like e.g. sugar, proteins and so on, is also possible. The electro dialysis process is driven by the electrical
potential.

For conditioning, the solutions are pumped through the membrane stack and at the electrodes, a direct current
voltage will be applied. The positively charged salt ions (cations) follow the electrical field and flow to the
cathode, the negatively charged ions (anions) flow to the anode.

A membrane stack for electro dialysis consists of a series of cells, which are separated from eac h other by
alternating anions and cations exchange membranes. The stack is completed by a anode and a cathode and
fixed in a clamping device which looks similar to a filter press.

The positively charged ions are able to pass the cations exchange membrane, but they cannot pass the
following anions exchange membrane and are retained. Vice versa the negatively charged ions are able to
pass the anions exchange membrane and are retained at the cations exchange membrane. Hence, ions are
concentrated (concentrate) in every second cell whereas the ions of the neighboring cells are removed
(diluate).

By supply and drain connections at the cell frame, the diluate and concentrate flow can be pumped through
the cells of the membrane stack.

Field of application of electrodialysis

 Acid recovery
 High concentration of brines

Water conditioning

 Desalination of brackish water

 Nitrate removal of potable water
 Reduction of operating costs of ion exchanger plants by upstream desalination with electro dialysis
 Conditioning of reverse osmosis concentrate to reach a plant recovery of more than 95%
 Concentration of Sea water for table salt production

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 Lecture-8

Disinfection of water:
The process of destroying /killing the disease producing bacteria, micro-organisms, etc., from the water and
making it safe for the use, is called disinfectation.

a. Boiling: By boiling water for 10-15 minutes, all the disease producing bacteria is killed and the water
becomes safe for use.
b. Adding bleaching powder: In small water works, about 1 kg of bleaching powered per 1000 kiloliter of
water is mixed and allowed to standing undisturbed for several hours. The chemical action produces
hypochlorous acid (a powerful germicide)
CaOCl2+ H2O → Ca(OH)2+Cl2
Cl2+ H2O → HCl+ HOCl
Germs+ HOCl → Germs are killed
c. Chlorination: Chlorination (either gas or in concentrated solution from) produces hypochlorous acid,
which is a powerful germicide.
Cl2+ H2O → HCl+ HOCl
Bacteria+ HOCl → Bacteria are destroyed
d. By adding Chloramine: When chlorine and ammonia are mixed in the ratio 2:1 a compound chloramine
is formed.
Cl2 + NH3 → ClNH2 + HCl
Chloramine
ClNH2 + H2O → NH3 + HOCl (Hypochlorous acid)
HOCl → HCl + [O] nascent oxygen
Chloramine compounds decompose slowly to give nascent oxygen which will be act as good disinfectant
than the Chlorine. Chloramine gives good taste to the treated water.
e. By Ozonization: Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly
unstable and breaks down to give nascent oxygen.
O3 → O2 + [O] nascent oxygen
The nascent oxygen is a powerful oxidizing agent and kills the bacteria.
Disadvantages: This process is costly and cannot be used in large scale, due to unstable of ozone cannot be
stored for long time.

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