UNIT – I

WATER TECHNOLOGY
1. INTRODUCTION:
Water is the most important compound for the existence
of human beings.
About 80% of the earth’s surface is occupied by water.
2. MAIN SOURCES OF WATER:
The main source of water is
Rain-Purest form but very difficult to collect.
Surface water (Ex. Rivers and Lakes).
Underground water (Ex. Wells and springs).
Sea water-most impure form.
WATER TECHNOLOGY or WATER TREATMENT:
The process of removing all types of impurities
from water and making it for domestic or industrial
purpose is called water technology or water treatment.
NATURE OF WATER:
HARD AND SOFT WATER (H&S WATER):

a) SOFT WATER:
Water, which produces lather with soap solution, is called soft water.
This is due to the absence of Calcium and Magnesium salts.

b) HARD WATER:
Water, which does not produce lather with soap solution, but
produces white precipitate (SCUM) is called hard water.
This is due to the presence of dissolved Calcium and Magnesium.
Reaction:
2C 17H 35COONa + Ca++ → (C 17H 35COO)2Ca+2Na+
HARDNESS OF WATER:
Hardness is the property or characteristics of water, Which does
not produce lather with soap.

a )Detection of Hardness:
Hardness can be detected in two ways.
 
i)Treating with Soap solution:
When water is treated with soap solution if it not produces
the lathering and forms white precipitate (SCUM), the water
contains hardness.
ii)Test with EB-T Indicator:
Water containing hardness, gives wine red color with
Eriochrome Black-T(EB-T) indicator.
b)Types of Hardness:
Depending upon the types of dissolved salts in water, hardness
classified in two types.
i)Temporary Hardness :( Carbonate hardness (CH) or Alkaline
Hardness)
This is due to presence of Bicarbonates of Calcium and
Magnesium.
The hardness removed by a)Boiling the water b)adding lime to the
water
In the above process, the bicarbonate converted into insoluble
carbonate and hydroxide (which can be removed by filtering).
Reaction:
Ca (HCO3)2→CaCO3 ↓ +H2O+CO2
Mg(HCO 3)2 + 2Ca(OH)2→Mg(OH) 2↓+2CaCO3↓+2H 2O
Permanent Hardness :( Non-Carbonate hardness (NCH)
or Non-Alkaline Hardness)
Due to the presence of Chlorides and Sulphates of
Calcium and Magnesium.
It can’t be removed by boiling the water.
But it can be removed by a .Lime –soda process b.
Zeolite process.
a).Lime-Soda process:
CaCl2+Na2 CO3→CaCO3↓+2NaCl
b).Zeolite Process:
CaSO 4+Na2 Ze→CaZe+Na2SO4
EXPRESSION OF HARDNESS:
Expression of Hardness in terms of equivalents of CaCO3.
 The concentration of hardness producing salts are usually expressed in
terms of an equivalent amount of CaCO3.CaCO3 is chosen as a
standard,
 Because its Molecular Weight is 100 and its Equivalent weight is 50.(is a
whole number. so calculation is simplified)
 It is the most insoluble salt that can be precipitated in water treatment.
Expressed as if the concentration of hardness producing salt is
‘X’mgs/lit, then
According Molecular Weight,

UNIT OF HARDNESS:
 Parts per million (ppm)-Defined as the number of parts of CaCO3 per 106
parts of water.
ESTIMATION OF HARDNESS BY EDTA METHOD
EDTA is Ethylene Diamine Tetra Acetic acid. The structure of
EDTA is

Principle:
The amount of hardness causing ions (Ca 2+ and Mg2+) can be
estimated by titrating the water sample against EDTA using
Eriochrome Block-T indicator (EBT) at p H of 8-10.
In order to maintain the pH, buffer solution (NH 4Cl-NH4OH
mixture) is added.
Only at this pH such a complexation is possible.
When the EBT indicator is added to the water sample, it forms
wine red coloured weak complex with Ca2+ and Mg2+ ions.
Ca 2+/ Mg2+ in water +EBT [Ca/Mg-EBT]
wine red colour

When EDTA titrated against the complex, EDTA replaces the

EBT and forms a stable Ca/Mg-EDTA Complex.
The liberated EBT indicates the end point as steel blue.
Ca 2+/ Mg2+-EBT + EDTA [Ca/Mg-EDTA] + EBT
(Stable) (Steel
blue )
Preparation of Chemicals:
a) Standard hard water- 1g CaCO3+ dil.HCl (min.Qty)-made up to 1 litre of
distilled water.
b) EDTA Solotion-4 g of EDTA in 1litre of distilled water.
C) EBT indicator- 0.5 g EBT/100 ml alcohol.
d) Ammonia Buffer- 67.5 g of NH4Cl + 570 ml of NH3 in 1litre of distilled
water.
Experimental procedure:
Titration-I
i) Standardization of EDTA:
Pipette out 50 ml of standard hard water into a clean conical flask.
Add 10 ml of Buffer solution and 5 drops of EBT indicator
Titrate against EDTA taken in burette.
The end point is from wine red to steel blue.
Let the volume of EDTA is V1 ml
ii ) Estimation of total hardness of water sample:

Pipette out 50 ml of the given water in to conical flask.

Titrate against EDTA as before.
Let the volume of EDTA is V2 ml

iii) Estimation of permanent hardness of water sample:

Take 100 ml of same hard water sample in a 250 ml beaker.

Boil it for 15 min to remove the temporary hardness.
Cool and filter the water.
Make up to 100 ml in a standard flask by adding dis.H 2O
Pipette out 50 ml of the made up solution into a clean conical flask and titrate
it against EDTA solution.
Let the volume of EDTA is V3 ml
5. Calculation:
Step1 – Standardization of EDTA:
 
1 ml of Std. Hard water                   = 1 mg of CaCO3    (Given)
So, 50 ml of Std. Hard water          = 50 mg of CaCO3
V1 ml of EDTA is required for         = 50 mg of CaCO3
Therefore, 1ml of EDTA                  = 50 / V1 mg of CaCO3
 
Step 2:  Finding Total hardness:
50ml of sample water required        = V2 ml of EDTA
= V2 X 1 ml of EDTA
                                                             = V2 X 50 mg of CaCO3
                                                                         V1 
                                                                                                      
Therefore, 1000ml of sample requires = V 2 X  50  X  1000 mg of CaCO3
                                                                          V1         50
 
Hence, total hardness                        =          V2 X 1000 ppm
                                                                     V1
Step 3:  Finding Permanent hardness:
50ml of boiled water required          = V3 ml of EDTA
= V3 X 1 ml of EDTA
                                                            = V3 X 50 mg of CaCO3
                                                                         V 1 
             
 Therefore, 1000ml of boiled sample requires = V3 X  50  X  1000 mg of CaCO3
V1         50
 
Hence, permanent hardness                         = V3 X 1000 ppm
                                                                              V1
 
Step 4:  Temporary hardness = Total hardness – permanent hardness

Characteristics of water:
It should be clear, colourless and odourless.
It should be cool and pleasant to taste.
It should be free from harmful bacteria and suspended impurities
ALKALINITY
1.Introduction
Alkalinity in water is due to the presence of soluble (i) hydroxide (OH-),
(ii) carbonate (CO32-) and iii) bicarbonate (HCO3-) ions.
These can be determined by titrimetry using standard acid and
Phenolphthalein and methyl orange as indicators.
Reaction:
The type and extent of alkalinity in water sample is determined by  first 
titrating it with phenolphthalein endpoint  P and then continuing the titration
to methyl orange endpoint M .The following reactions takes place
     OH- +   H+     ---------> H20                    ----- (1)
 
           CO3 2-   + H+ --------- >H CO3 -                      ------ (2)
 
          H CO3 -     + H+   -------- >H2CO3              ------- (3)
 
2.Types of alkalinity:
Depending upon the anion that is present in water alkalinity is classified into the three types.
1. Hydroxide alkalinity-due to (OH-)

2. Carbonate alkalinity-due to (CO32-)

3. Bicarbonate alkalinity-due to (HCO3-)

Determination Various Types of Alkalinity-Experimental Method:

Step I: Experimental procedure
Titration –I: Determination of Phenolphthalein Alkalinity.
Pipette out 100 ml of the given water sample into a clean conical flask.
Add 2 to 3 drops of phenolphthalein indicator
Titrate it against N/50 H2SO4 taken in the burette.
The end point is disappearance of pink colour.
Let the volume of acid consumed is V1 ml.
Titration-II: Determination of Methyl Orange Alkalinity.
After the titration-I, to the same solution, add 2 to 3 drops of methyl orange indicator.
Continue the titration against the same N/50 H2SO4.
The end point is the reappearance of pink colour
Let the Volume of acid consumed is V2 ml.
Step-II: Calculation.
(i) Calculation of phenolphthalein alkalinity.
Volume of acid used to phenolphthalein end point V1 = -------- ml
Normality of the acid N1 = N/50
Volume of the Water sample V2 = 100 ml
Normality of water sample N2 =?
 
According to volumetric law V1N1 = V2N2
N2

Therefore Phenolphthalein alkalinity (P) in terms of CaCO3 equivalent

= N2 X Eq.wt of CaCO3 x 1000

P ppm

P= 10 V1 ppm
(ii) Calculation of Methyl Orange Alkalinity.
Extra Volume of acid used to methyl orange end point = V2 ml
Total volume of acid used to methyl orange end point = (V1+V2) ml
Let, the volume of acid used to methyl orange end point V1 = (V1+V2) ml

Normality of acid N1 = N/50

Volume of the water sample V2 = 100 ml
Normality of water sample N2 = ?

N2

Therefore Methyl orange alkalinity (M) in terms of CaCo3 equivalents

M = 10 (V1+V2) ppm
TREATMENT OF WATER FOR DOMESTIC SUPPLY:
Rivers and lakes are the most common sources of water used by
municipalities. This water should be free from colloidal impurities,
domestic sewages, industrial effluents and disease producing bacterias.
Domestic supply of water involves the following stages in the purification
process:
 
SCREENING:
It’s a process of removing the floating materials like leaves, wood pieces etc.

AERATION:
It’s a process of removing gases like CO2, H2S and other voltaic
impurities etc.
 
SEDIMENTATION:
It’s a process of removing suspended impurities by allowing water
undisturbed for 2-6 hours in a tank.
 
COAGULATION:
It’s a process of removing finely divided clay, silica etc. In this method,
coagulants like alum, Al2(SO4)3 is added to water to form a gelatinous
precipitate of Al(OH)3. This precipitate entraps the finely divided and colloidal
impurities, settles to the bottom which can be removed easily.
FILTRATION:
It’s a process of removing bacteria, colour, taste, odour etc by passing water through filter
beds containing fine sand, coarse sand and gravel.

STERILISATION:
  The process of destroying the harmful bacteria is known as sterilization.
By boiling:
When water is boiled for 10-15 minute, all the harmful bacterias are killed and water
becomes safe for use.
Disadvantage:
i) Boiling alters the taste of drinking water.
ii) It is impossible to employ in municipal water works.
2. By Ozonation:
Ozone is a powerful disinfectant and is readily absorbed by water.
Ozone is highly unstable and breaks down to give nascent oxygen.
Nascent oxygen is powerful oxidizing agent and kills the bacterias.
Disadvantage:
i) Thus process is costly and cannot be used in large scale.
ii)Ozone is unstable and cannot be stored for long time.
Reaction:
O3 → O2+ [O]
3. By using UV radiation:
UV rays are produced by passing electric current through mercury vapour
lamp.
Useful particularly for sterilizing water in swimming pool.
Disadvantage:
It is costly.
Turbid water cannot be treated.
4. By chlorination:
a) By adding chlorine gas
Chlorine gas can be bubbled in the water as a very good disinfectant.

Reaction: Cl2 + H2O --------→ HCl + HOCl

b) By adding chloramine:
When Cl2 and NH3 are mixed in the ratio 2:1, a compound chloramine is formed.
Reaction:
Cl2 +NH3 → ClNH2 +HCl
(Chloramine)
ClNH2 + H2O → HOCl + NH3

c) By adding bleaching powder:

When bleaching powder is added to water, it produces hypochlorous acid (HOCl).
HOCl is a powerful germicide.
Reaction:
CaOCl2 + H2 O→ Ca (OH) 2 +Cl2
(Bleaching powder)

Cl2 + H2 O → HCl +HOCl

HOCl + Bacterias → Bacterias are killed
BREAK POINT CHLORINATION
 
Water contains the following impurities,
Bacterias
Organic impurities
Reducing substances ( Fe2+ , H2S etc.)
Free ammonia

Chlorine added to water directly as a gas or in the form of bleaching powder.

Chlorine is used to kill the bacterias and oxidizes all the reducing substances.
As the amount of applied chlorine increases, the amount of combined residual chlorine
also increases. This is due to the formation of chloramines and other chloro
compounds.
Thus the combined residual chlorine decreases to a minimum point at which oxidation
of chloramines and other impurities complete and free residual chlorine begins to
appear.
This minimum point is known as, “ Break Point Chlorination”.
BOILER FEED WATER
Water fed into the production of steam is called boiler feed
water.
Boiler troubles
Scale and Sludge formation
Priming and Foaming
Caustic embrittlement
Boiler corrosion
1. Scale and Sludge formation in boilers:
When water is continuously converted into steam in boiler, the
concentration of dissolved salts in water increases progressively.
When the concentration of the salts reaches their saturation
point, they are thrown in the form of precipitates on the boilers.
Scale:
If the precipitate forms hard and adherent coating on the inner
walls of the boiler, it is called scale. Scales are formed by substances
like Ca(HCO3)2, CaSO4 and Mg(OH)2 .
 Sludge:
If the precipitate is loose and slimy, it is called sludge. Sludges
are formed by substances like MgCl2, MgCO3, MgSO4 and CaCl2.
2. Priming and foaming
Steam containing droplets of liquid water is called wet steam. These droplets of liquid water carry
with them some dissolved salts and suspended impurities. This phenomenon is called carry over. It
occur due to priming and foaming.
Priming
Priming is the process of production of wet steam. Priming is caused by
High steam velocity
Very high water level in the boiler
Sudden boiling of water

 Prevention
Priming can be controlled by,
Controlling the velocity of steam
Keeping the water level lower
Foaming
The formation of stable bubbles above the surface of water is called foaming.
It is caused by the
Presence of oil and grease
Presence of finely divided particles
 Prevention
Foaming can be prevented by
Adding coagulants like sodium aluminate, aluminium hydroxide
Adding anti- foaming agents like synthetic polyamides.
3. Caustic Embrittlement
Caustic embrittlement means inter crystalline cracking of boiler metal. In high pressure
boilers, Na2CO3 present in water undergoes decomposition to give NaOH.

Na2CO3 + H2O 2 NaOH + CO 2

This NaOH flows into the minute hair hair cracks and crevices usually present
on the boiler material by capillary action dissolves the surrounding area of iron as sodium
ferroate.

Fe + 2 NaOH Na 2FeO2 + H2
 

This causes brittlement of boiler parts, particularly stressed parts like bends, joints, riverts
etc., causing even failure of the boiler.
Prevention
It can be prevented by,
using sodium phosphate as softening agent instead of sodium carbonate.
by adding tannin, lignin to the boiler water, which blocks the hair cracks.
4. Boiler corrosion
Corrosion in boilers is due to the presence of,
dissolved oxygen
dissolved carbon dioxide
dissolved salts
 
Dissolved oxygen
The dissolved oxygen in water attacks the boiler material at high temperature.

4Fe + 6 H2O + 3O2 4Fe(OH) 3

 
Removal of dissolved oxygen
Dissolved oxygen can be removed by chemical or mechanical methods.
 
Chemical method
Sodium sulphite, hydrazine are some of the chemicals used for removing oxygen.
2 Na2SO3 + O2 2Na 2SO4
 
N2 H 4 + O 2 N2 + 2H2O
 
Dissolved carbon dioxide
Carbon dioxide gas is produced from the decomposition
of bicarbonate salts present in water.
 
Ca(HCO3)2 CaCO3 + H2O + CO2

H2O + CO2 H2CO3

Prevention
Carbon dioxide can be removed from the water by adding
NH4OH into water.
2 NH4OH + CO2 (NH4)2CO3 + H2O
Dissolved MgCl2
When water containing dissolved MgCl2 is used in boiler, HCl is produced.
HCl attacks boiler in a chain like reaction producing hydrochloric acid again
and again which corrodes boiler severely.

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

Fe + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl
 
Prevention
 
Corrosion by acid can be avoided by the addition of alkali to the boiler
water.
 
HCl + NaOH NaCl + H2O
SOFTENING METHODS
The process of removing hardness producing salts from water is known as
“Softening of Water “.
Types of Methods:
Internal Treatment
External Treatment
Internal Treatment (or) Internal Conditioning (or) Boiler Compounds:
  Removal of scale forming substances, by adding chemicals directly in boiler.
This chemicals are Boiler Compounds.

Types of Internal Conditioning

Carbonate conditioning
Scale formation can be avoided by adding Na 2CO3 to the boiler water. It is used
only in low pressure boilers. The scale forming salt like CaSO 4 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. It is
used in high pressure boilers. The phosphate reacts with Ca 2+ and
Mg2+ salts to give soft sludges of calcium & magnesium phosphates.

3 CaSO4 + 2 Na3PO4 Ca3(PO)4 + 3 Na2SO4

3. Calgon conditioning
 
Calgon is sodium hexa meta phosphate Na2[Na4(PO3)6]. This
substance interacts with calcium ions forming a highly soluble
complex and thus prevents the precipitation of scale forming salt.

2 CaSO4 + Na2[Na4(PO3)6] Na 2[Ca2(PO3)6] + 2 Na2SO4

 
2. External Treatment :
Removal of hardness producing salts from water before feeding into the
boiler.

i. Ion- Exchange or Demineralisation Process:

 
This process removes almost all the ions (both anions and cations)
present in hard water.
 
Soft water does not contains Ca2+, Mg2+ ions, but contains Na+,K+, SO4+, Cl-
Demineralised water - does not contain both anions and cations.
Demineralization process:
This 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.
Types of Exchanger:
Cation exchanger :
containing acidic functional groups (-COOH,-SO3H) are exchanging their H+
ions with other cations of hardwater.
Represented as RH2., ex., Sulphonated coals, Sulphonated Polystyrene.
Anion exchanger
containing basic functional groups (-NH2, -OH) are exchanging OH- ions with
other anions of water.
Represented as R(OH)2.ex., Urea formaldehyde resin, cross linked quaternary
ammonium salts.
Process:
Cation exchange column – Hard water passed through this column, it
absorbs all the cations like Ca2+, Mg2+, Na+,K+etc.

RH2 + CaCl2 RCa + 2HCl

RH2 + MgSO4 RMg + H2SO4

 

  Anion exchange column – Cation free water is passed through this

column, which absorbs all the anions like SO42-, Cl-, HCO3- etc.

R’ (OH)2 + 2HCl R’Cl2 +2H2O

R’(OH)2 + H2SO4 R’SO4 + 2H2O

Regeneration :
 
Cation exchange resin can be regenerated by passing a solution of dil.HCl or dil.H2SO4.

RCa + 2HCl RH2 + CaCl2

RNa + HCl RH + NaCl
Anion exchange resin can be regenerated by passing dil.NaOH.
 
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl 
Advantages:
Highly acidic or alkaline water can be treated by this process.
The water obtained by this process will have very low hardness(nearly 2ppm).
 
Disadvantages:
Water containing turbidity, Fe and Mn cannot be treated, because it forms stable
compound with resin.
The equipment is costly and expensive chemicals are needed.
 
DESALINATION OF BRACKISH 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.
 Classification of water based on salt content
 Fresh water – Contains < 1000ppm of dissolved solids.
 Brackish water – Contains >1000 but < 35,000ppm of dissolved solids.
 Sea water – Contains >35,000ppm of dissolved solids.
Methods of desalination
1.Reverse Osmosis (Super filtration)
When two solutions of different concentrations are separated by a semi-
permeable membrane like cellulose acetate, cellulose butyrate, etc. solvent
flows from a region of lower concentration to higher concentration. This
process is called Osmosis and the driving force in this phenomenon is
called Osmotic Pressure.
 If a hydrostatic pressure in excess of osmotic pressure is
applied on the higher concentration side, the solvent flow is
reversed i.e.,solvent flows from higher concentration to lower
concentration. This process is called reverse osmosis. Thus, in
the process of reverse osmosis pure water is separated from salt
water.

Advantages:
Cheap, easy to operate, simple and gives, water of very high
purity.