Applied Chemistry (2023

(2023-24)
UNIT I - WATER TECHNOLOGY
Syllabus
Water Technology: Impurities of water, Hardness & its determination (EDTA method), Boiler
Troubles & their removal, water softening methods -Lime soda (both hot lime and cold lime),
Zeolite & Ion exchange, Desalination of water — Electro dialysis & Reverse osmosis method,
Chemical analysis of water; chloride and fluoride estimation.

Impurities of water
The application of water in industries depends on the quality of water; therefore direct use of water
sources for industrial applications may not be appropriate. It is necessary to detect and estimate the
amount of impurities in water. Such an analysis is going to help in deciding methods to decrease the
amount of impurities to an optimum leve levell so that water is render fit for use. Natural water carries
different kinds of impurities in dissolved, suspended and colloidal form.
1. Dissolved Minerals: The various properties caused by different minerals are discussed below.
a. Alkalinity: Alkalinity is caused by the dissolved hydroxide, carbonates and bicarbonate salts of
2+ 2+
Na+, Ca and Mg . All natural waters contain some quantity of alkalinity. Alkalinity contributes to
scale formation of calcium carbonate.
b. Hardness: It is the property by
y virtue of which, water does not easily produce lather with soap.
soap The
2+ 2+
sulphates, chloride and nitrate salts of Ca , Mg ions are reason for hardness. Hardness causes
scale deposit in equipments.
c. Iron, Manganese, and Alumina: These dissolved or suspended d metallic elements are present in
water supplies in varying quantities. They are objectionable because they cause metallic taste and
react with oxygen in water exposed to the atmosphere, form oxides which precipitate and cause
cloudiness, or “red water.” This red color, particularly from iron, causes staining of plumbing
fixtures, sinks, and porcelain china and is a cause of common laundry discoloration.
d. Silica: Silica is dissolved sand or silica
silica-bearing
bearing rock (such as quartz) through which the water
flows. Silica is the cause of very hard and tenacious scales that can form in heat-transfer.
heat It is
present as silicate or suspended in very fine, invisible form as colloidal silica.
e. Chlorides: Chlorides are the sum total of the dissolved chloride salts of sodium,
sodium potassium,
calcium, and magnesium present in water. Sodium chloride, which is common salt, and calcium
chloride are the most common of the chloride minerals found in water. Chlorides do not ordinarily
contribute to scale since they are very soluble. Chlorides are corrosive and cause excessive
corrosion when present in large volume, as in seawater.
f. Sulfates. Sulfates are the dissolved sulfate salts of sodium, potassium, calcium, and magnesium in
the water. They are present due to dissolution of sulfate-bearing rock such as gypsum. Calcium and
magnesium sulfate scale is very hard and difficult to remove and greatly interferes with heat
 transfer.
2. Dissolved Gases
a. Oxygen: Oxygen makes up approximately 20 percent of air. However, it is one of the essential
elements in the corrosion process of metals. Therefore, dissolved oxygen in water is important to
us in the study of corrosion.
b. Carbon Dioxide: Carbon dioxide to smaller extent comes from the atmosphere and larger amounts
of carbon dioxide come from the decomposed organic matter in water. Carbon dioxide contributes
significantly to corrosion by making water acidic. This increases its capability to dissolve metals.
Carbon dioxide forms the mild carbonic acid when dissolved in water, as follows:
CO2 + H 2O H2CO3
Carbon di oxide Water Carbonic acid
c. Sulfur Oxides: Sulfur oxide gases are the consequences of combustion of fuels containing sulfur,
such as coal and fuel oil. When dissolved in water, sulfur oxides form acids which create a corrosive
atmosphere.
SO3 + H2O H2SO4
Sulphur trioxide Water Sulphuric acid
d. Nitrogen Oxides: Nitrogen oxides are also present in the atmosphere both naturally and from
combustion of fuels. When absorbed by water, they form acids leading to the corrosion problem.
3NO2 + H2 O 2HNO3 + NO
Nitrogen dioxide water Nitric acid Nitric oxide
e. Hydrogen Sulfide: Hydrogen sulphide gas comes from decaying organic matter and from sulfur
deposits, which possess rotten eggs odor. Hydrogen sulfide is formed when acidic water reacts with
sulfide minerals such as pyrite (FeS), an iron sulfide commonly called “fool’s gold”.

FeS + H+ Fe2+ + H2S

Ferric sulphide acidic solution Hydrogen sulphide
3. Total Dissolved Solids
The total dissolved solids (TDS) are the sum of dissolved minerals including the carbonates,
chlorides, sulfates, and all others that are present. The dissolved solids contribute to both scale
formation and corrosion in heat-transfer equipment.
4. Suspended Matter
Suspended matter is finely divided organic and inorganic substances found in water. It is caused by
clay silt and microscopic organisms (such as, bacteria, fungi, algae) which are dispersed throughout
the water, giving it a cloudy appearance. It is measured in terms of turbidity of water sample, which
is determined by the intensity of light scattered by the suspended matter in the water.

Hardness and its determination

Hardness is the property by virtue of which water does not produce lather with soap. Hardness is
of two types;
1. Temporary hardness
2. Permanent hardness.
1. Temporary or carbonate hardness is caused by the presence of dissolved bicarbonates of
calcium, magnesium and it can be removed by boiling.

2. Permanent or non-carbonate hardness is due to the presence of chlorides, nitrates and sulphates
of calcium, magnesium, iron and other heavy metals. Permanent hardness can be removed by ion
exchange, lime soda, zeolite, reverse osmosis and electrodialysis methods. The sum of both
temporary and permanent hardness is known as total hardness.

Determination of total hardness by EDTA method

Procedure
Preparation of standard solution of disodium salt of EDTA: Weigh accurately the given amount
of disodium salt of EDTA crystals and transfer into a 250 mL standard flask. Dissolve the crystals by
adding 5 mL ammonia solution and then add distilled water up to the mark and shake well for
uniform concentration. This solution is taken in a 50 ml burette.

Estimation of total hardness: 25 mL of given hard water is pipetted out into a clean 250 ml
conical flask. 5 mL of NH4OH – NH4Cl buffer and 2 drops of Eriochrome Black – T indicator are
added. The resulting wine red coloured solution is titrated with EDTA until clear blue solution is
obtained. Titration is conducted slowly near the end-point. Titration is repeated until agreeing value
is obtained. From the volume of EDTA obtained, calculated total hardness of given water sample.
Theory
EDTA (Ethylene diamine tetra acetic acid) forms colorless stable complexes with Ca 2+ and Mg2+
ions present in water at pH = 9-10. To maintain the pH of the solution at 9-10, buffer solution
(NH4Cl + NH4OH) is used. Eriochrome Black-T (E.B.T) is used as an indicator.
The sample of hard water must be treated with buffer solution and EBT indicator which forms
unstable, wine-red colored complex with Ca2+ and Mg2+ present in water.

Observation
Burette : Standard disodium EDTA salt solution
Conical flask: 25 mL of hard water + 5 mL NH4OH – NH4Cl buffer
Indicator : 5 drops of Eriochrome black T
End point : Change of colour from wine red to blue
Wt. of weighing bottle with solid EDTA salt (W1) = --------- g
Wt. of empty weighing bottle (W2) = --------- g
Wt. of EDTA salt dissolved / 250 mL (W1-W2) = -------- g

Molarity of EDTA salt solution = Wt. of EDTA taken X 4

Molecular wt. of EDTA (372.24)

Therefore MEDTA = -----------------M

Trial Final B.R (ml) Initial B.R (ml) Volume of EDTA consumed
(ml)
1
2
3

b. Calculation
1000 cm3 of 1 M EDTA = 100 g of CaCO3 (Mol. wt of CaCO3 is 100)

∴ VEDTA cm3 of X MEDTA = 100 x V x MEDTA

1000 x 1 g of CaCO 3

= --------- g (Y)

25 cm3 of hard water contains = ‘Y’ g of CaCO3

106 cm3 of hard water contains = Y x 106 / 25 ppm of CaCO3

Therefore total hardness of water = -------------- ppm of CaCO 3

Note:
Unit of hardness
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 = 1 part hardness /106 parts
of water
Both temporary and permanent hardness is expressed in ppm as CaCO 3. The choice of CaCO3
because is due to the fact that it is the most insoluble salt in water. It is expressed in terms of
calcium carbonate, because it is the primary component contributing t o hardness.

Why water treatment?

Water is a universal solvent. Whenever it comes in contact with a foreign substance, there is some
dissolution of that substance. Some substances dissolve at faster rates than others, but in all cases a
definite interaction occurs between water and whatever it contacts. It is because of this interaction
that problems occur in equipment such as boilers or cooling-water systems in which water is used
as a heat-transfer medium. In systems open to the atmosphere, corrosion problems are made worse
by additional impurities picked up by the water from the atmosphere.

Boiler troubles and their removal

What is boiler trouble?
The water supplied to boiler for the generation of steam is known as boiler feed water. At thermal
power stations, the feed water is stored and conditioned in a feed water tank and supplied to boilers
through a ‘boiler feed water pump’. Scale in boilers is a direct result of precipitation of the calcium;
magnesium, iron, and silica minerals present in the boiler feed water. Scale can be prevented by
removing a portion of the scale-forming ingredients prior to the boiler with external water-softening
equipment. One of the most troublesome deposits frequently encountered in steam boilers are; iron
and combinations of iron with calcium and phosphate. The iron comes from iron oxide or iron
carbonates which are the corrosion products. Hence a program for preventing scale deposits shall be
included to prevent this troublesome type of sludge deposit.

Boiler Troubles
Natural water contains different kinds of impurities and creates a variety of boiler problems.
The major boiler troubles due to untreated/unsuitable water are;
 Scale and sludge formation
 Priming and foaming (Carry over)
 Boiler Corrosion
 Caustic embrittlement

1. Scale and sludge formation

During steam generation, the concentration of dissolved salts gets saturated and they get
precipitated on the inner walls of the boiler.
If the precipitate ( ppt) is in the form of thick and adherent it is called scale.
If the precipitate is in the form of soft, loose and silky ppt it is called sludge.
The scale or sludge formation depends on the nature of impurities present in water.
a. Scales
The hard and adherent deposits formed on the inner walls of boilers by salts like CaSO4, Ca
(HCO3), Mg (HCO3), MgCl2, and Silica. The formation of scales is more dangerous than sludge
formation as they affect overall functioning of boilers.
The formation of scale can be explained taking example of CaCO 3 and CaSO4
(i) In low pressure boilers, the CaCO3 salt is formed from Ca(HCO3)2 as shown below;
Ca (HCO3)2 CaCO3 + H2O + CO2
(ii) In high pressure boilers, CaCO3 is converted to soluble Ca (OH) 2. But CaSO4 forms very
hard scale as its solubility decreases with increase in temperature. At high pressure the scale of
 CaSO4becomes very hard.
(iii) In the similar way, very hard and insoluble scales like CaSiO 3, MgSiO3 are formed from SiO2
Disadvantages
 Being an insulator, reduces heat transfer leading to fuel wastage and affects boiler
efficiency
 Boiler becomes unsafe, because of overheating.
 The overheating and softening of metallic parts leads to reaction between water soft metal
(Fe) making tube walls thinner.
 At high pressure, the overheated metal parts undergo expansion and the scale develops
cracks. Consequently water enters into the cracks, liberates steam and pressure builds up
and causes boiler explosion.
 Excessive scale formation clogs the tubes and pipe lines.
 Cleaning becomes expensive

Prevention
 Loose scales can be removed by using scrapper, wire brush often.
 By thermal shock- heating and cooling suddenly with cold water for brittle scales.
 By using chemical treatment with 5-10% HCl and by adding EDTA.
b. Sludge
The precipitated salts exist as loose and separate mass in the water body, is known as sludge. These
are easily separable and non-adherent deposits. Sludge generally formed by the salts such as;
MgCO3, MgSO4, MgCl2 and CaCl2 and can be removed by scrapping with brush. These salts
are more soluble in hot water.
Disadvantages
 Sludge is a poor conductor of heat and thus decreases the rate of heat transfer. Therefore it
leads to wastage of fuel and reduction in boiler efficiency.
 Sludge leads to clogging of cooler parts of boiler. Clogging of pipe lines slowdown of
water circulation.
 Cleaning process also becomes expensive.
Prevention
 By using soft water.
 Removal of concentrate water time to time to avoid sludge deposit.

Carry over
When water is boiled, the steam generated may be associated with small droplets of water, known as
‘wet steam’. These droplets of water generally carry some suspended impurities present in the water
along with them and the phenomenon is known as ‘carry over’. The carry over problem is mainly
attributed to priming and foaming.
Priming
“The rapid boiling of water in boiler during which water particles are carried along with steam in the
form of spray into the steam outlet” is known as priming. It is a consequence of feeding improperly
softened water into boiler.
Causes of priming
 Higher the velocity of steam, greater the ability to carry water droplets.
 High water level.
 Presence of excess foam on water surface.
 Sudden demand for steam leading to drop in the pressure.
 Improper boiler design.
Disadvantages of Priming
 Dissolved salt in boiler water are carried out by the wet steam to turbine blades - which
reduces their efficiency.
 Dissolved salts may enter the parts of other machinery may decrease the life of the
machinery.
 Actual height of the water column cannot be judge properly; Thereby making the
maintenance of the boiler pressure becomes difficult.
Prevention of priming
 Good boiler design with proper water evaporation and uniform heat distribution system.
 Low water level maintenance.
 Proper control over steam flow rate.
 Minimizing foaming.
Foaming
“It is the formation of minute and persistent bubbles on the surface of water”

The major reasons for the occurrence of foaming are;

Causes of Foaming
 It is due to the presence of oily and fat substances in water.
 The presence of dissolved salts in water.
 Sudden increase in steam production rate.
 Presence of organic matter, alkalis' and suspended matter.
Disadvantages of foaming
 Dissolved salts in water carried by the wet steam may damage turbine blades or machinery
parts thereby decreases their working efficiency.
 Boiler pressure cannot be maintained.
Prevention of foaming
 Addition of antifoaming agents (castor oil, polyamide) to reduce surface tension of the
surface film and to destabilize the bubbles
 Removing oil from boiler water by adding compounds like sodium aluminate (NaAlO 2).
 Removal of silica using ferrous sulphate.
 Removal of clay and suspended matter using coagulating agent like Al (OH) 3.
3. Boiler corrosion
The various parts of boiler are prone to corrosion due to the presence of dissolved gases and salts.
Here we discuss to some extent corrosion due to the following factors and mainly the boiler tubes,
plates, pipe lines are often suffer from corrosion.
Dissolved gases such as; O2, CO2, H2S are responsible for corrosion
Presence of salts like MgCl2 directly attack the metallic parts in boiler
1. Corrosion due to dissolve oxygen (DO)
Dissolved oxygen at high pressure corrodes metallic parts of the boilers and the relevant reactions
are;
2Fe + 2H2O + O2 → 2Fe (OH) 2
4Fe (OH) 2 + O2 + 2H2O → 2 [Fe2O3. 3H2O] Rust
The above reaction indicates the corrosion in boilers due to DO. When water containing DO is
heated, it liberates oxygen which in turn causes corrosion as mentioned in the above reactions.

Methods for the removal of DO

Dissolved oxygen is eliminated by any of the following methods;
i) Using mechanical deaerators: The solubility of oxygen directly proportional to pressure and
inversely to temperature and this principle is used in mechanical deaerators. In this, hot water is
sprayed to remove DO.
ii) Use of sodium sulfite (Na2SO3): The complete removal of DO is achieved by adding Na2SO3,
which reacts with DO forming sulphates; Na2SO3 + 1/2O2 → Na2SO4
iii) Use of Hydrazine: Hydrazine (N2H4) is used at 40% concentration in aqueous form due to
itsexplosive nature. N2H4 + O2 → N2 + H2O
One of the advantage of using hydrazine is it does not form any salt.

2. Corrosion due to Carbon dioxide

Carbon dioxide is present naturally in the water and also come from bicarbonates. When present in
boiler water, it is carried by steam and dissolves in water forming carbonic acid (H2CO3), during
steam condensation and it causes intense local corrosion called “pitting corrosion” and hence its
elimination is necessary to prevent boiler corrosion.
Methods for the removal of CO2
The dissolved gases such as CO2, DO are eliminated by a process called “mechanical deaeration’.
Procedure
Dissolved O2 and carbon dioxide gases are removed from water by mechanical deaeration method as
shown in the Fig. 1. In this process, water is allowed to trickle down slowly through the perforated
plates fitted inside the chamber. Under the conditions of high temperature and low pressure values, the
dissolved gases are eliminated.
Also the dissolved CO2 can be removed by treating with calculated amount of ammonia, which
forms carbonate on reaction with CO2 as shown below;
CO2 + 2NH3 + H2O → (NH4)2CO3
 Fig. 1 Mechanical deaerator
3. Corrosion due to MgCl2 (Acid corrosion)
This type of corrosion mainly due to the formation of acids when salts like, MgCl 2, CaCl2 are
dissolved in water. These salts, particularly MgCl2 undergo hydrolysis at high temperature (200 °C)
forming HCl in boiler, which leads to corrosion as mentioned in the below reactions;
MgCl2 + 2H2O → Mg (OH) 2 + 2HCl
The HCl liberated, attacks iron and forms rust as follows;
Fe + 2HCl → FeCl2 + H2
FeCl2 + 2H2O → Fe (OH) 2 + 2HCl
4 Fe (OH) 2 + O2 + 2H2O → 2 [Fe2O3. 3H2O], Rust

Water softening methods

Various methods have been adopted in the process of softening water and few of them are;
1. Lime soda method
2. Ion exchange method
3. Zeolite method
1. Lime soda method
In this method all soluble hardness causing salts are chemically converted into insoluble
precipitates which may be removed via filtration and settling. In this process, the combination of
lime Ca (OH) 2 and soda (Na2CO3) is added to hard water and through the following reactions, the
water becomes soft. Usually 10% excess chemicals are introduced into water to quicken the
softening process.
There are two methods of lime soda process, namely;
(a) Cold lime soda processand
(b) Hot lime soda process.

a) Cold lime soda process

In this Method, calculated quantity of chemical (lime and soda) is mixed with water at room
temperature. The precipitates formed at room temperature are finely divided, hence do not settle
down easily and cannot be filtered easily. Consequently, it is essential to add small amounts of
coagulants (Alum, aluminum sulphate, sodium aluminate, Etc.). These coagulants hydrolyzed to
gelatinous precipitate of aluminium hydroxide, which entraps the fine precipitate. 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

Procedure
Raw water and calculated quantities of chemicals (Lime + soda + coagulant) are fed from the top in
to the inner vertical circular chambers, fitted with a vertical rotating shaft carrying a number of
paddles, as shown in the Fig. 2. Raw water and chemicals subjected to vigorous stirring and
continuous mixing for effective softening of water. As the softened water enters into the outer
chamber reaches top, during which the softened water passes through a filtering media (usually
made of wood fibers) for the complete removal of sludge. Finally filtered soft water tapped out
continuously through an outlet and the sludge settled at the bottom of the chamber.

Fig. 2 Cold Lime soda Process

b) Hot lime soda process
The process involves water softening at a temperature of 80 to 150°C.
The advantages of operatingat high temperature are;
(i) The reaction proceeds faster.
(ii) The softening capacity of hot process increases.
(iii) The precipitate and sludge formed settle down rapidly and hence no coagulants are required.
(iv) Gases such as CO2, O2 are driven out.
(v) The lower viscosity of softened water eases filtration, which in turn increases the filtering
capacity of filters
(vi) Hot Lime-Soda Produces water of comparatively lower residual hardness of about 15 to
30ppm.
Procedure
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 chamber’ in which sludge
settles down and (c) a ‘Sand filter’ which ensures complete removal of sludge from the softened
water. The design of the equipment for hot lime soda process is shown in Fig. 3.

Fig. 3 Hot lime soda process

The different reactions that occur during water softening by lime-soda method are mentioned
below;
Lime removes temporary hardness;
Ca (HCO3)2 + Ca (OH) 2 → 2CaCO3↓ + 2H2O
Mg (HCO3)2 + Ca (OH) 2 → Mg (OH) 2 ↓ + CaCO3 + 2H2O
Lime removes permanent magnesium hardness
MgCl2 + Ca (OH) 2 → Mg (OH) 2 + CaCl2
MgSO4 + Ca (OH) 2 → Mg (OH) 2 + CaSO4
Soda removes permanent calcium hardness
CaCl2 + Na2CO3 → CaCO3 + 2NaCl
CaSO4 + Na2CO3 → CaCO3 + Na2SO4

Lime soda also eliminates dissolved mineral acids, gases (CO 2, H2S) and dissolved salts of iron
and aluminium.
Advantages of lime soda Process
 It is a very economical
 Increase in pH value of the treated water, thereby corrosion of the distribution pipes is
reduced.
 Besides the removal of hardness, the quantity of minerals in the water is reduced.
 Due to alkaline nature of treated- water, amount of pathogenic bacteria’s in water is
considerably reduced.
Disadvantages of lime soda Process
 For efficient and economical softening, careful operation and skilled supervision is
required.
 Disposal of large amounts of sludge (insoluble precipitate) poses a problem.
 This can remove hardness only up to 15ppm, which is not good for boilers.
 2. Zeolite method
Zeolites are also known as permutits and are denoted as Na2Z, where Z is an insoluble radical
framework. Zeolites are capable of exchanging basic radicals (Ca2+, Mg2+), hence known as base
exchangers. When hard water is passed through zeolite bed, all the hardness causing basic radicals
like Ca2+, Mg2+ are held by the zeolite releasing equivalent amount of Na+ ions as mentioned in the
following reactions;
Ca(HCO3)2 CaZ + 2NaHCO3
MgSO4 + Na2Z → MgZ + Na2SO4
CaCl2 CaZ + 2NaCl
The following Fig. 4 explains how water becomes soft after passing through zeolite chamber,
during which the above reactions take place leading to soft water.

Fig.4 Purification of water by Zeolite method

Regeneration of Zeolite
After several use, the zeolite becomes deactivated due to the complete exchange of Na + with
calcium and magnesium of water. Hence activation of zeolite is done by feeding NaCl solution,
where all Ca2+ and Mg2+ are replaced by Na+. Thus the activated zeolite is ready for further water
treatment and is represented by the following reaction.
CaZ / MgZ + 2NaCl  Na2Ze + CaCl2 / MgCl2

Advantages
 Hardness is removed almost completely.
 Equipment installation requires little space.
 Requires less time.
Disadvantages
 Treated water contains more sodium salts than obtained from lime soda process.
 The method only replaces Ca+2 and Mg+2 ions by Na+ ions leaving all the acidic ions.

3. Ion exchange method

In the method cation exchangers are used for the exchange of cations and anions by anion
exchangers Fig.5. The materials used for this application are known as ion-exchange resins. Ion
exchange resins are microporous structured organic polymers with cross linking network
containing some specified functional groups which are responsible for the ion exchange properties
of the resins.
The ion exchange resins are classified as
1. Cation exchange resin
2. Anion exchange resin

Cation exchange resin (RH+)

Cation exchange resins are styrene divinyl benzene copolymers are capable of exchanging their
hydrogen ions with equivalent amount of cations like Ca 2+, Mg2+ during water treatment.
The reaction involving exchange of ions between resin and cations of water is given below;

2RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2H+

Resin Hard water exchanged cations

Anion exchange resin (ROH-)

Resins such as styrene divinyl benzene or amine formaldehyde copolymers with quaternary
ammonium salt are capable of exchanging their OH- with anions like Cl-, SO42- during water
treatment.
The reaction involving exchange of ions between resin and anions of water is given below;

2ROH- + Cl-/SO42- 2RCl-/R2 SO42- + 2OH-

Resin Hard water exchanged anions

Fig. 5 Ion exchange process or demineralization of water

Regeneration of ion exchange resins
Once the resin bed is filled with hardness causing anion and cations ions, regeneration of the resins
is carried out using either H2SO4 or HCl for cation exchange resin and NaOH for the regeneration
of anion resin. All bivalent ions are removed in their sulphates or chloride form and the following
 reactions occur during the regeneration of resins.

R2Ca2+/R2Mg2+ + HCl → Ca2+ / Mg2+ + 2RH+

2RCl-/R2SO42 - + NaOH → Cl- / SO42- + 2ROH-

Deactivated resins regenerating solution Removed ions Activated resins

Procedure: The hard water is passed first through cation exchange resin which removes all
cations like Ca2+, Mg2+ etc. from it and equivalent amount of H+ ions are released from the resin.
Then the water is passed through anion exchange resin which removes all anions like Cl -, SO 4 2 - ,
from it and equivalent amount of OH- ions are released from the resin. The H+ and OH- ions
combine and form water. Thus hard water becomes soft upon ion exchange process.
Advantages
 The process can be used to soften highly acidic or alkaline waters.
 It produces water of very low hardness of 1-2ppm. So the treated waters by this method can be used
in high pressure boilers.
Disadvantages
 High Cost of the equipment.
 The water should not be turbid and the turbidity level should not be more than 10ppm.

Desalination of water
The process of removal of salts present in water using suitable ion permeable membrane is known as
desalination process.
There are two methods
1. Electrodialysis
2. Reverse osmosis
Electrodialysis
“The process of decreasing the concentration of salt in saline water using ion selective
membrane under the influence of an EMF is called as electrodialysis.”
The electrodialysis is a separation process, where ions are removed from aqueous solution with the
application of potential.
There are generally two kinds of membranes for electrodialysis: cation selective membranes which
allow the passage of positively charged ions; anion selective membranes that allow the passage of
negatively charged ions. Cation selective membranes contain negatively charged groups like
sulphonic or carboxylic acid groups on the surface of a polymer. Hence negatively charged anions
are repelled by the membrane and vice versa for anion selective membranes. A number of cationic
and anion selective membranes are placed in an alternating sequence between a cathode and an
anode. When an ionic feed solution is pumped through the cell pairs together with an applied direct
current, the positive ions migrate to the cathode and the negative ions migrate to the anode. The
main application of electrodialysis is to remove ions from an aqueous solution. Electrodialysis can
be used either to concentrate the salt or to produce potable water from sea water. The following Fig.
6 explains the separation of ions from saline water via electrolysis.

Fig. 6 Desalination by Electrodialysis process

Reverse Osmosis (RO)

When a semi-permeable membrane is placed between two solutions with different concentrations,
water flows from higher concentration to lower concentration and a pressure difference is
generated called osmotic pressure. When a larger pressure is applied (compared to the osmotic
pressure) on the side which has a lower concentration, the osmotic flow is reversed. This process is
called reverse osmosis (RO). In the RO process, the processing liquid is being transported
through the membrane under high pressure. The membrane retains most of the ions and larger
molecules in the liquid and the process is often used for desalinization to produce high quality
water. RO membranes are made up of cellulose acetate and aromatic polyamide and many more
stable synthetic polymer materials.
PROCESS: Reverse osmosis cell consists of a vessel, a membrane and a high pressure pump.
Reverse osmosis process requires only mechanical force to generate the required hydrostatic
pressure (410-540 psi). When hydrostatic force is applied on the sea water to force its pure water
to flow out through semi permeable membrane, to the pure water compartment both ionic and non
ionic impurities are left behind. Thus in RO, pure water is separated from its contaminants rather
than removing the contaminants from the water.

Reverse Osmosis
 Fig. 7 Reverse Osmosis process

Chemical analysis of water

Chemical analysis of water chemistry needs to be carried out to identify and quantify the chemical
components and other properties of water samples. Generally chemical analysis of water is carried
out on water samples which origin from industrial processes, domestic sector, river water, rain
water and sea water. Water has its own physical properties, chemical composition and biological
properties.

Determination of chloride
Chlorides are present in all types of water resources at a varying concentration depending on the
geo-chemical conditions in the form of CaCl2, MgCl2 and NaCl. Chlorides are introduced into the
water resources from the discharge of effluents from chemical industries, sewage disposal and
seawater intrusion in coastal region. The concentration of chloride ions more than 250 ppm is not
desirable for drinking purpose. The total chloride ions can be determined by argentometric method
(Mohr’s Method).
Estimation of chloride by argentometric method (Mohr’s Method)
Principle
In this method Cl‒ ion solution is directly titrated against AgNO3 using potassium chromate
(K2CrO4) as the indicator.
AgNO3 + Cl‒ AgCl ↓ + NO3 ‒
(White precipitate)
At the end point, when all the chloride ions are removed. The yellow colour of chromate changes
into reddish brown due to the following reaction.
2AgNO3 + K2CrO4 Ag2CrO4 ↓ + 2KNO3
(Yellow) (Reddish brown)
20 ml of the given water sample is pipette out into a clean conical flask. 1 ml of freshly prepared
potassium chromate solution is added as an indicator and titrated against standard AgNO3 solution
taken in the burette. The end point is the change of colour from yellow to reddish brown colour. Repeat
the titration for concordant values.
Determination of Fluoride
Fluorides are naturally occurring minerals. In some hard rock areas, fluoride minerals like Fluorospar
(natural calcium fluoride, CaF2) and Apatite [natural phosphate and fluoride of calcium,
CaF2.3Ca3(PO4)2] occur abundantly. Ground water acquires large quantity of fluoride ions.
Fluoride is an important water quality parameter, as low concentrations (less than 1.0 mg/l) give rise to
dental caries (decay) usually in children, where excessive amount (more than 1.5 mg/l) may cause
dental and skeletal fluorosis. It can produce incorrect dental enamel formation, reduce the functionality
of joints and even affect the bone structure.
Provision of safe drinking water (1 ppm of fluoride) and creating awareness among people of the
dangers of fluorosis are the urgent needs of the hour for prevention of fluorosis.

Removal of fluoride from water

Several methods have been developed for fluoride removal such as
 Fluoride exchangers using Bone charcoal and Ion exchange resins
 Activated carbon treatment
 Treatment with lime and magnesium salts
 Treatment with Aluminium salts and Coagulant aids

Fluoride content in water is measured using Spectrophotometer

Fluorides in water are estimated accurately by colorimetric method. The method employed is called
SPADNS method.
F- and SPADNS (sodium 2-(para sulphophenylazo)-1,8-dihydroxy-3,6 naphthalene disulphonate)
react forming yellow colored dye.
As the amount of the fluoride is increased, the color becomes progressively lighter and of different
shade. This bleaching action is directly proportional to fluoride content due to formation of ZrF6.
Procedure:
 A series of standard solutions of sodium fluoride are taken such that the concentrations of
fluoride in each of these are 0.5 mg, 1.0 mg, 1.5 mg, 2.0 mg, and 2.5 mg respectively in
different beakers.
 A drop of 0.5 % sodium arsenite (NaAsO2) solution is added to remove any residual chloride.
All solutions are diluted to 50 cm3.
 5 cm3 of SPADNS reagent and 5 cm3 of Zirconyl-acid reagent (ZrOCl2. 8H2O and HCl). The
contents of the beakers are thoroughly shaken.
 To the water sample containing unknown concentration of fluoride, all the reagents mentioned
above are added.
 A blank is prepared by adding all reagents except fluoride sample.
 The absorbance of all the prepared solutions is measured at wavelength of 570 nm against
blank.
 The fluoride concentration in the water sample is determined from the graph.