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# UNIT I

WATER TECHNOLOGY
INTRODUCTION

Water is the most important compound for the existence of human beings, animals & plants.
Among the various sources of water surface & underground water are normally used for
domestic & industrial purposes. Such water must be free from undesirable impurities. The
process of removing all types of impurities from water & making it fit for domestic or industrial
purpose is called water treatment.

HARD WATER

Water which does not produce lather freely with soap is called hard water. This is due to the
formation of insoluble soaps of calcium & magnesium.

Calcium stearate

## 2C17H35COONa +MgSO4 (C17H35COO) 2Mg +Na2SO4

SOFT WATER

Water which produce lather freely with so soft water. Hardness is the property of water which
does not produce lather with soap.

TYPES OF HARDNESS

Depending on the type of dissolved salts present in water, hardness can be classified in two types

1) Temporary hardness

2) Permanent hardness

TEMPORARY HARDNESS

The hardness which is removed by boiling of water is called temporary hardness. This is due to
the presence of bicarbonates of calcium & magnesium.

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

PERMANENT HARDNESS

The hardness which is not removed even after boiling of water is called permanent hardness.
This is due to the presence of chlorides and sulphates of Ca & Mg.

## The concentration of hardness is expressed in terms of equivalent amount of CaCO3. CaCO3 is

chosen as a standard because

(i) Its molecular weight (100) & equivalent weight (50) is a whole number, so tee calculations
can be simplified.

## (ii) It is the most insoluble salt.

Amount equivalent to CaCO3 = Amount of hardness producing salt x molecular weight of CaCO3

_______________________________________________________________________________

## Mg (HCO3)2 = 146 CaCl2 = 111 CaSO4 = 136

PROBLEMS BASED ON HARDNESS

PROBLEM 1:

A sample of water is found to contain the following analytical data in mg/lt. Mg (HCO3)2 = 14.6;
MgCl2 = 9.5; MgSO4 = 6.0; Ca (HCO3)2 =16.2 . Calculate the temporary & permanent hardness
of the sample of water.

SOLUTION:

## Name of the Amount in mg/lt. Molecular weights Amount equivalent

hardness producing to
salt CaCO3

_________ =10
146

_________ =10
95

## 6.0 120 6.0 x 100

MgSO4 _________ =5
120
Ca (HCO3)2 16.2 162 16.2 x 100
_________ =10
162

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

=10 + 10 = 20 mgs/lt.

## Permanent hardness = MgCl2+ MgSO4

=10 + 5 = 15 mgs/lt.
PROBLEM 2:

A sample of water is found to contain the following analytical data in mg/lt. Mg (HCO3)2 = 16.8;
MgCl2 = 12; MgSO4 = 29.6; NaCl=5 . Calculate the temporary & permanent hardness of the
sample of water & express it in ppm. (Atomic weight of Mg =24; H = 1 ; C =12 ; O =16; Cl =
35.5; Na = 23; S = 32)

SOLUTION:

## Name of the Amount in mg/lt. Molecular weights Amount equivalent

hardness producing to
salt CaCO3

_________ =11.5
146

_________ =12.63
95

## 29.6 120 29.6 x 100

MgSO4 _________ =24.66
120

NaCl does not contribute any hardness to water & hence it is ignored

## =12.63+ 24.66 = 37.29 mgs/lt.or ppm.

ALKALINITY

Alkalinity is due to presence of soluble hydroxide (OH-), carbonate (CO32-) & bicarbonate
(HCO3-) ions. These can be determined by titrimetry using standard acid, phenolphthalein &
methyl orange as indicators. The determination is based on the following reactions

## (iii) (HCO3-) + (H+) H2O + CO2

Alkalinity is classified into three types based upon the anion present in the water

## Steps involved in the determination of various types of alkalinity ere as follows,

EXPERIMENTAL PROCEDURE

## TITRATION 1: Determination of phenolphthalein alkalinity

Pipette out 100 ml of the given water sample a clean conical flask. Add 2 to 3 drops of a
phenolphthalein indicator & titrate it against N/50 H2SO4 taken in the burette. The end point is
the disappearance of pink colour.Let the volume of acid consumed be V1.

## TITRATION II: Determination of methyl orange alkalinity

To the same solution add 2 to 3 drops of methyl orange indicator and continue the titration
against the N/50 H2SO4 .The end point is appearance reddish orange. Let the volume of acid
consumed be V2.

CALCULATION

## Normality of the acid N1 = N/50

Volume of the water sample V2 =100 ml

## According to volumetric law

V1N1 = V2N2

N2 = V1N1/ V2

N2 = VI/100 X 1/50

=V1 X 50 X 1000

________________

100 X50

P = 100 V1 PPM

## According to volumetric law

V1N1 = V2N2

N2 = V1N1/ V2

N2 =( VI+V2)/100 X 1/50

## Methyl orange alkalinity (M) = N2 X Equivalent wt. of CaCO3 X 1000 PPM

=(V1+V2) X 50 X 1000

________________

100 X50

## M= 10(V1+ V2) PPM

CONCLUSION

(i) When P=O, both OH- & CO32- are absent & alkalinity is due to HCO3- only.

(ii) When P = ½ M, only is CO32- present, half of carbonate neutralization reaction takes place
with phenolphthalein indicator. Complete carbonate neutralization reaction occurs when methyl
orange indicator is used.

## (iii) When P = M, only OH- is present, alkalinity due to OH- = P = M.

(iv) When P > ½ M, besides CO32- , OH- ions are also present.

## Alkalinity due to OH- = (2P – M)

(v) When P < ½ M, besides CO32- , HCO3- ions are also present.

## Results of P & OH- CO32- HCO3- Nature of

M end point ppm ppm ppm alkalinity

carbonate

carbonate

## P=M P=M O O Only hydroxide

PROBLEMS BASED ON ALKALINITY

PROBLEM 1:

A water sample is not alkaline to phenolphthalein. But 100 ml of the sample on titration with
N/50 HCl required 16.7 ml to methyl orange end point. What are the types & amounts of
alkalinity present in the sample.

SOLUTION:

## Volume of N/50 HCl used to methyl orange end point M = 16.7 ml

Since P = O, the alkalinity of the water sample is only due to HCO3- ions.

## According to volumetric law

V1N1 = V2N2

N2 = V1N1/ V2

N2 = 16.7/100 X 1/50

N2 = 0.00334 N

## Amount of HCO3- interms of CaCO3equivalent= N2 X Equivalent wt. of CaCO3 X 1000 PPM

= 0.00334 x 50 x 100

= 167 PPM.

## Alkalinity of the water sample due to HCO3- =167 PPM

PROBLEM 2:

100 ml of a water sample on titration with N/50 HCl gave a titre value of 6.8 ml to
phenolphthalein end point & 13.6 ml to methyl orange end point. Calculate the alkalinity of the
water sample & comment on the type alkalinity present.

SOLUTION:

## Volume of N/50 HCl used to methyl orange end point M = 13.6 ml

Since P = ½ M, the alkalinity of the water sample is only due to CO32- ions.

## According to volumetric law

V1N1 = V2N2

N2 = V1N1/ V2

N2 = 13.6/100 X 1/50

N2 = 0.00276 N

## Amount of CO32- interms of CaCO3equivalent= N2 X Equivalent wt. of CaCO3 X 1000 PPM

= 0.00276 x 50 x 100

= 136 PPM.

## Alkalinity of the water sample due to CO32- =136 PPM

ESTIMATION OF HARDNESS BY EDTA METHOD

This method is based on complexometric titration method. EDTA is Ethylene diamine tetra acetic
acid. The structure of EDTA is

HOOCH2C CH2COOH

N--CH2—CH2—N

HOOCH2C CH2COOH

PRINCIPLE

The amount of hardness causing ions can be estimated by titrating the water sample against
EDTA using Erichrome Black- T indicator at a PH of 8 to 10. In order to maintain the PH buffer

When the EBT indicator is added to the water sample it forms wine red coloured weak complex
with Ca2+ & Mg2+ ions.

Ca2+ PH 8 – 10 Ca

Mg2+ Mg

## Wine red coloured weak complex

When this solution is titrated against EDTA, it replaces the indicator from tee weak complex &
form stable EDTA complex. The colour of the free indicator is steel blue.

Ca PH 8 – 10 Ca

## EBT + EDTA EDTA complex + EBT

Mg Mg steel blue

Preparation of solutions

## EBT: 0.5 gm EBT in 100 ml alcohol

Standard hard water: 1 gm of calcium carbonate is dissolved in minimum amount of dil. HCl
& then made up to 1000 ml using distilled water.

Buffer: 67.5 gms of ammonium chloride & 570 ml of ammonia are dissolved & the solution is
made up to 1000 ml using distilled water.
Experimental procedure

## (i) Standardisation of EDTA

Pipette out 20 ml of standard hard water into a clean conical flask. Add 10 ml of buffer solution
& 5 drops of EBT indicator & titrate it against EDTA.The end point is the change of colour from
wine red to steel blue.

## (ii) Estimation of total hardness of water sample

Pipette out 20 ml of the given hard water sample into a clean conical flask & titrate it against as
before.

## (iii) Estimation of permanent hardness of water sample

Take 100 ml of the same hard water sample in a 250 ml beaker.Boil it for 15 minutes.Cool &
filter the solution and make upto 100 ml in a standard flask by adding distilled water. Pipette out
20 ml of the made up solution into a clean conical flask & titrate it against EDTA as before.

Calculations

## Total hardness = 1000 X V2/V1 PPM

(iii) Estimation of permanent hardness of water sample

## PROBLEMS BASED ON EDTA METHOD

PROBLEM 1:

0.28 gm of CaCO3 was dissolved in HCl & the solution made up to 1 lt. with distilled water. 100
ml of the above solution required 28 ml of EDTA solution on titration. 100 ml of hard water
sample required 33 ml of same EDTA solution on titration. 100 ml of this water after boiling,
cooling & filtering required 10 ml of EDTA solution on titration. Calculate the temporary &
permanent hardness.

SOLUTION:

## Total hardness = 330 mgs/lt (or) PPM

(ii)Permanent Hardness

100 ml of the hard water after boiling cooling & filtering = 10 ml of EDTA

=330 – 100

## Temporary hardness = 230 mgs/lt (or) PPM

CHARACTERISTICS OF WATER

As per the suggestion given by World Health Organization (WHO) & by Indian Council of
Medical Research (ICMR), the following are the important characteristics of potable water.

## 3. It should be free from harmful bacteria & suspended impurities.

4. It should be free from dissolved gases like CO2, H2S etc & poisonous minerals like lead,
arsenic, manganese etc.

## 9. PH of the potable water should be 6.5 to 8.5.

TREATMENT OF WATER FOR DOMESTIC SUPPLY

Rivers & lakes are the most common sources of water & this water should be free from colloidal
impurities, industrial effluents & disease producing bacteria’s.

## Domestic supply of water involves the following stages,

1. Screening

2. Aeration

3. Sedimentation

4. Coagulation

5. Filtration

6. Sterilization

SCREENING

The raw water is allowed to pass through a screen which retains the floating materials like
leaves; wood pieces etc. & allow the water to pass.

AERATION

## It is a process of mixing water with air. The main purpose is

(i) to remove gases like CO2, H2S and other volatile impurities causing bad taste & odour to
water.

(ii) to remove ferrous & manganous salts s insoluble ferric & manganic salts.

SEDIMENTATION

It is a process of removing suspended impurities by allowing the water to stand undisturbed for 2
to 6 hours in a big tank. The suspended impurities settle down at the bottom due to force of
gravity & they are removed. This removes only 75% of the suspended impurities.

COAGULATION

Finely divided clay, silica etc. do not settle down & cannot be removed by sedimentation. Such
impurities are removed by coagulation method. Al2 (SO4)3 is added to water. It gets hydrolyzed to
form a gelatinous precipitate of Al (OH)3 which entraps the finely divided & colloidal
impurities ,settles to the bottom & can be removed easily.
FILTERATION

It is the process of removing bacteria, colour, taste, odour & suspended particles by passing
through filter beds containing fine sand, coarse sand & gravel. When the rate of filtration
becomes very slow, the filtration is stopped & the thick top layer is scrapped off & replaced with
clean sand.

STERILIZATION

1. Boiling

2. by ozonation

## 3. By using ultraviolet radiations.

4. by chlorination

## c) By adding bleaching powder.

When bleaching powder is added to water, it produces HOCl which is a powerful germicide.

Bleaching powder

## Cl2 + H2O HCl + HOCl

(Hypochlorous acid)

## BREAK POINT CHLORINATION

1. Intially the applied chlorine is used to kill bacteria & oxidizes all the reducing substance &
there is no free residual chlorine.

2. As the amount of chlorine increases, the amount of combined residual chlorine increases.
3. At one point on chlorination, the oxidation of chloramines & other impurities starts & there is
a fall in combined chlorine.

4. Thus the combined chlorine decreases to a point and free residual chlorine appears & this
point is known is known as” Break Point Chlorination”.

## BOILER FEED WATER

The water fed into the boiler for the production of steam is called boiler feed water.

BOILER TROUBLES

If hard water obtained from natural sources is fed directly into the boilers, the following troubles
may arise,

## 2. Priming & foaming

3. Caustic embrittlement

4. Boiler corrosion

## Scale & sludge formation

When water is converted into steam in boilers the concentration of dissolved salts in water
increases.

Sludge

If the precipitate is loose & slimy is called sludge. Sludges are formed by substances like
MgSO4, MgCl2, and MgCO3 & CaCl2.

Prevention

## 1. Sludge formation can be prevented by using soft water.

2. They can also be removed by blow down operation .It is a process of removing a portion of
concentrated water by fresh water from the boiler during steam production.
Scale

If the precipitate forms hard & adherent coating on the inner walls of the boiler, it is called
sacle.Scales area farmed by Ca (HCO3)2, CaSO4 & Mg (OH) 2

Prevention

## Priming & Foaming

During production of steam in the boiler, due to rapid boiling, liquid droplets are carried along
with steam.Steam containing liquid droplets is called wet steam. These droplets carry with them
some dissolved salts & suspended impurities. This is called carry over.

Priming

Prevention

## 4. Using treated water.

Foaming

The formation of stable bubbles above the surface of water is called foaming.

Foaming is caused by

Prevention

## 2. Adding antifoaming agents like synthetic polyamides.

Caustic embrittlement

## Na2CO3 + H2O 2NaOH + CO2

This NaOH flows into minute hair cracks by capillary action & dissolves the surrounding area of
iron as sodium ferroate.

## Fe + 2NaOH Na2FeO2 +H2

This causes brittlement of boiler parts causing even failure of the boiler.

Prevention

## 1. Using sodium phosphate as softening agent instead of sodium carbonate.

2. By adding tannin, lignin to the water which blocks the hair cracks.

Boiler corrosion

## Corrosion in boiler is due to

1. Dissolved oxygen

2. Dissolved CO2
3. Dissolved salts

Dissolved oxygen

Removal

## Dissolved oxygen can be removed by chemical or mechanical methods.

a)Chemical method

## Sodium sulphite, hydrazine are used for removing oxygen.

2Na2SO3 + O2 2Na2SO4

## N2H4 +O2 N2 + 2H2O

b) Mechanical method

Water is allowed to fall slowly on the perforated plates fitted inside the tower.

The high temp. & low pressure produced inside the tower reduces the dissolved oxygen content
of the water.

Dissolved CO2

Dissolved CO2 in water produces carbonic acid which is acidic & corrosive in nature.

Removal

## 2NH4OH + CO2 (NH4) CO3 +H2O

Dissolved MgCl2

Salts like MgCl2, CaCl2 undergo hydrolysis at higher temperature to give HCl which corrodes the
boiler.

## MgCl2 + 2H2O Mg (OH) 2 + 2HCl

Fe + 2HCl FeCl2 + H2

## FeCl2 + 2H2O Fe (OH)2 + 2HCl

Removal of acids

Corrosion by acids can be avoided by the addition of alkali to the boiler water.

## HCl + NaOH NaCl + H2O

SOFTENING METHODS

The process of hardness producing salts from water is known as softening or conditioning of
water.

## Softening can be done in two methods

1. External conditioning

2. Internal conditioning

EXTERNAL CONDITIONING

It involves the removal of hardness producing salts from water before feeding into boiler. The
external treatment can be done by Ion exchange process.

## ION EXCHANGE OR DEMINERALISATION PROCESS

This process removes almost all ions present in the hard water. The process is carried out by
using ion exchange resins, which are long chain, cross linked, insoluble organic polymers with a
micro porous structure. The functional groups attached to the chains are responsible for the ion
exchanging properties.

Cation exchanger

Resins containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their H+
ions with other cations of hard water. It is represented as RH2

## Ex: sulphonated coals, sulphonated polystyrene.

Anion exchanger

Resins containing basic functional groups (-NH2, -OH) are capable of exchanging their anions
with other anions of hard water. It is represented as R (OH) 2

## Ex: cross linked quaternary ammonium salts, Urea formaldehyde resin

PROCESS

The hard water first passed through a cation exchanger column which absorbs all the cations like
Ca2+, Mg2+, Na+ & K+ present in the hard water.

## RH2 + MgSO4 RMg + H2SO4

The cation free water is then passed through a anion exchange column which absorbs all the
anions like Cl-, SO42- present in the water.

## R’ (OH) 2 + H2SO4 R’SO4+ 2H2O

The water coming out of the anion exchange is completely free from cations & anions.

Regeneration

When the cation exchange resin is exhausted it can be regenerated by passing dil. HCl.

## INTERNAL CONDITIONING OR BOILER COMPOUNDS

It involves the removal of scale forming substance, which were not removed in the external
treatment, by adding chemicals directly into the boiler.
1. Carbonate conditioning

Scale formation can be avoided by adding Na2CO3 to the boiler water. CaSO4 is converted into
CaCO3 which can be removed easily.

## CaSO4 + Na2CO3 CaCO3 +Na2SO4

2. Phosphate conditioning

Scale formation can be avoided by adding sodium phosphate. The phosphate reacts with Ca2+ &
Mg2+ salts to give soft sludges of Ca & Mg phosphates.

## 3CaSO4 + 2Na3PO4 Ca3 (PO4)2 + 3Na2SO4

3. Calgon conditioning

Calgon is sodium hexa Meta phosphate Na2 (Na4 (PO3)6). This salt interacts with Ca ions forming
a highly soluble complex & prevents the precipitation of scale forming salt.

## 2CaSO4 + Na2 (Na4 (PO3)6) Na2 (Ca2 (PO3)6) + 2Na2SO4

DESALINATION

The process of removing common salt from water is known as desalination. Depending upon the
quantity of dissolved solids, water is graded as

## (i)Fresh water _ contains < 1000 ppm of dissolved solids

(ii)Brackish water _ contains > 1000 but < 35000 ppm of dissolved solids

## Desalination can be carried out either by reverse osmosis or electro dialysis.

REVERSE OSMOSIS

When two solutions of different concentrations are separated by a semi permeable membrane,
solvent flows from a region of lower concentration to higher concentration. This process is called
osmosis & the driving force is called osmotic pressure.

If hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration side,
the solvent flows from higher concentration to lower concentration. Thus in the process of
reverse osmosis pure water is separated from salt water. The membranes used are cellulose
acetate, cellulose butyrate etc.