1.

WATER TECHNOLOGY
Purpose Requirements
Drinking Should not contain more calcium ions.

Cooking Free from hardness producing salts of Ca and Mg.

Bathing Free from hardness producing ions like Ca
2+

and Mg2+ .

Washing 1. Free from Ca and Mg

2. Free from iron salts

2. For Industrial Purpose

Name of the Industry Requirements
Paper and Pulp 1. Free from hardness Fe and Mn salts

Sugar Free from alkali carbonates and sulphates

Beverages Free from alkaline salts
Textile and Dying 1. Free from Ca and Mg salts, iron and
manganese salts

Boiler 1. Free from dissolved gases like O2, CO2

2. Zero percentage of Ca and Mg salts

1.2.1 WATER QUALITY PARAMETERS FOR DRINKING PURPOSES

The World Health Organization (WHO), Bureau of Indian Standards (BIS) and the Indian
Council of Medical Research (ICMR) have identified the parameters which affect the quality
of water.

HARDNESS
Hardness is one of the characteristics of water which does not produce lather with soap solution.

TYPES OF HARDNESS

1.Temporary Hardness (or) Carbonate Hardness

This is due to the presence of dissolved carbonates and bicarbonates of calcium and magnesium.
Temporary or carbonate hardness can be removed by boiling of water,
2. Permanent Hardness (or) Non-Carbonate Hardness

This is due to the presence of dissolved chlorides and sulphates of calcium and magnesium.
EXPRESSION OF HARDNESS
Weight of salt
× 100
Molecular weight of the salt

1.4.4 UNITS OF HARDNESS OF WATER

Parts per million (ppm),Milligrams per litre (mg/l)
 ESTIMATION OF HARDNESS OF WATER - EDTA METHOD

Principle
The basic principle is complexing agent forms stable complex with the ions (Ca2+, mg2+) present in the
sample hard water. When this wine-red coloured solution is titrated against EDTA, it replaces the
indicator from the weak complex and form stable EDTA complex. When all the hardness causing ions
2+ 2+
like Ca and Mg are complexed by EDTA, the indicator is liberated which produce steel blue colour.
pH = 8 – 10

Ca2+ / Mg2+ + EBT [EBT-Ca2+ / Mg2+ ]

less stable complex

Wine red colour

pH = 8 – 10

[ EBT-Ca2+ / Mg2+ ] + EDTA [EDTA-Ca2+ / Mg2+ ] + EBT

Less stable complex colourless more steel blue

stable complex

Procedure

Titration1 Titration 2 Titration 3

Standard hardwater Boiled sample water Vs

Content Vs EDTA Sample water Vs EDTA EDTA solution

Pipette 20 ml boiled filtered

Solution 20 ml Std. hard water 20 ml Sample Water
sample water
Burette
Solution EDTA Solution EDTA Solution EDTA Solution

Indicator 2 drops of 2 drops of Eriochrome 2 drops of Eriochrome

Eriochrome black -T black -T black -T
pH 8-10 8-10 8-10
2-3 ml Ammonium
Buffer 2-3 ml Ammonium Buffer 2-3 ml Ammonium Buffer
Buffer (NH4OH &
(NH4OH & NH4Cl) (NH4OH & NH4Cl)
NH4Cl)
End Wine red to steel Wine red to steel blue Wine red to steel blue
Point blue colour colour colour
ALKALINITY
The alkalinity of a water sample is nothing but the capacity to neutralise an acid.

Determination of Alkalinity of Water by Indicator Method

Principle

The alkalinity of a water sample may be determined volumetrically by titrating it with a standard acid
using phenolphthalein and methyl orange indicators
In the presence of phenolphthalein indicator, complete neutralization of hydroxide and conversion of
carbonate into bicarbonate ( phenolphthalein alkalinity).
− +
OH + H  H2O

CO32− + H+  HCO3−
The titration is continued using methyl orange indicator. The colour change from yellow to red
occurring with further addition of acid corresponds to the complete neutralisation of all the
bicarbonates.
HCO3− + H+  H2O + CO2

Experimental Procedure
Determination of phenolphthalein alkalinity
100 ml of the water sample is taken into a 250 ml conical flask. Two drops of phenolphthalein indicator,
is added. If a pink colour appears then it was titrated with 0.02 N sulphuric acid until the solution
becomes colourless. Let V1 be the volume of sulphuric acid used.
Determination of total (or) methyl orange alkalinity
To the above same solution in which phenolphthalein alkalinity has been determined three drops of
methyl orange indicator is added and the titration is continued against
0.02 N sulphuric acid until the solution becomes light pink in colour. Let the volume of acid used be V2
ml.
Calculation
Phenolphthalein alkalinity (P),

Volume of H 2 SO 4 50 1000

P 
Volume of water sample  50

Total (or) Methyl orange alkalinity (T),

Volume of H 2 SO 4 50 1000
T
Volume of water sample  50
Condition Hydroxide alkalinity Carbonate alkalinity Bicarbonate alkalinity

P=0 0 0 T
P <1/2 T 0 2P T - 2P
P = 1/2 T 0 2P 0
P > 1/2 T 2P - T 2(T - P) 0
P=T T 0 0

Boiler Troubles
Scales Sludges

1. Scales are hard deposits, which Sludges are loose, slimy and non-
adheres very firmly to the inner surfaces adherent precipitate which is
of the boiler. suspended in water.
2. Scale forming substances are CaSO4, Sludge forming substance are MgCO3,
Ca(HCO3)2, Mg(OH)2. CaCl2, MgCl2, MgSO4 etc.,
Diadvantages Diadvantages
Scales have low thermal conductivity Sludges are poor conductors of heat.
and decreasing the efficiency of the Hence they tend to waste a portion of
boiler. heat generated thereby decreasing the
efficiency of the boiler.

Removal Methods Removal Methods

(i) Scale formation can be removed by (i) By frequent “blow-down” operation,
dissolving them in acids like HCl,
H2SO4.
(ii) They can also be removed by using
scrapers or wire brush, applying thermal
shocks and by frequent blow-down
operation.

1.6.2 PRIMING AND FOAMING

Priming
During the production of steam in boilers, some liquid water droplets may be carried out along
with the steam.

Causes

Wet steam production is caused by

1. presence of very high water level in boiler

2. high steam velocity

3. sudden boiling
4. improper boiler design
Control Methods

Priming can be controlled by

1. keeping low water level in boiler
2. good boiler design
Foaming
Foaming is the production of foam or bubbles in boilers, which do not break easily.

Causes

Foaming is caused by the presence of oily or greasy or soapy substances in water.

Control Methods

Foaming can be controlled by

1. Adding anti-foaming chemicals like castor oil, synthetic polyamides.

BOILER CORROSION
Boiler corrosion is the decay of boiler material by a chemical or electrochemical attack by its environment.
Causes

(i) Dissolved oxygen

At high temperature, dissolved oxygen decays the iron of boiler material as rust.
2 Fe + 2 H2O + O2  2 Fe(OH)2 
4 Fe(OH)2 + O2  2 [Fe2O3.2H2O]
(Rust)

Removal Methods

Dissolved oxygen in water can be removed by the following methods

a. Mechanical de-aeration: w ater is sprayed from tower, heated from sides and connected to a
vacuum pump. High temperature, low pressure and large exposed area reduce the dissolved
oxygen in water.
 b. Chemical methods: By adding calculated quantity of sodium sulphite or
sodium sulphide or hydrazine, the dissolved oxygen in water can be removed.
2 Na2SO3 + O2  2 Na2SO4 
Na2S + 2 O2  Na2SO4 

(ii) Dissolved carbon dioxide

Carbon dioxide in water produces carbonic acid which corrodes the boiler material.
CO2 + H2O  H2CO3

Removal Methods

Dissolved carbon dioxide in water can be removed by

a. Mechanical de-aeration: In this method, carbon dioxide is removed along with
oxygen.
b. Chemical methods: By adding ammonia or lime.
2 NH4OH + CO2  (NH4)2CO3 + H2O
Ca(OH)2 + CO2  CaCO3  + H2O

(iii) Dissolved magnesium chloride

The dissolved magnesium chloride salt in water, on hydrolysis produces acid. The acid which
is produced corrodes the boiler.

MgCl2 + 2 H2O  Mg(OH)2  + 2 HCl

CAUSTIC EMBRITTLEMENT

In high pressure boilers, NaOH is produced when water contains Na2CO3.

Na2CO3 + H2O  2 NaOH + CO2 
This NaOH flows into the minute irregular intergranular cracks usually
present in the boiler material and dissolves the surrounding area

Caustic embrittlement can be prevented byUsing sodium phosphate as softening agent instead
of sodium carbonate.

In general, boiler feed water

Should be free from Ca and Mg salts, acids and alkalis, dissolved gases like O2, CO2, oil and
foam

1.7 INTERNAL CONDITIONING METHODS (or) SEQUESTRATION

Treating the water inside the boiler during the production of steam is called internal
 treatment (or) sequestration.

1.7.1 COLLOIDAL CONDITIONING

Scale formation is prevented by adding organic substances like tannin or agar-agar or

kerosene an can be removed by blow-down operation.

1.7.2 PHOSPHATE CONDITIONING

Scale formation is prevented by adding sodium phosphate and the sludge formed can be
removed by blow-down operation.
3 CaCl2 + 2 Na3PO4  Ca3(PO4)2  + 6 NaCl
1.7.3 CALGON CONDITIONING

In this process, sodium hexa metaphosphate (calgon) is added to the boiler water
2 CaSO4 + Na2[Na4(PO3)6]  Na2[Ca2(PO3)6] + 2 Na2SO4
Calgon

1.7.4 CARBONATE CONDITIONING

Scale formation can be prevented by adding sodium carbonate to boiler water and the loose
sludge of calcium carbonate can be removed by blow-down operation.

CaSO4 + Na2CO3  CaCO3 + Na2SO4

ION EXCHANGE (or DEIONIZATION or DEMINERALISATION) PROCESS

In this process, ion-exchange resins are used.

Cation exchange resins

These are obtained by co-polymerisation of styrene and divinyl benzene, followed by

sulphonation.

Anion exchange resins

These are obtained by co-polymerisation of styrene and divinyl benzene with quaternary
ammonium groups.
Principle

The cation exchange resin exchanges all the cations present in the water.

+ 2+ +
2RH + Ca  R2Ca + 2H

2RH+ + Mg2+  R2Mg + 2H+

An anion exchange resin exchanges all the anions present in the water. Anion exchange resin
is generally represented as ROH–.
– – –
ROH + Cl  RCl + OH
 – 2– –
2ROH + SO4  R2SO4 + 2OH

The hard water is first passed through the cation exchange column. Here all the cations Ca2+,
2+ + +
Mg , Na in the water are replaced by an equivalent amount of H ions.

The hard water is first passed through the cation exchange column. Here all the anions Ca2+,
2+ + -
Mg , Na in the water are replaced by an equivalent amount of oH ions.

Regeneration

i) The exhausted cation exchange resin is regenerated by passing a solution of dilute

HCl or dilute H2SO4 through the resin R2Ca +
+ + 2+
R2Ca + 2H 2RH + Ca

R2Mg + 2H+ 2RH+ + Mg2+

ii) The exhausted anion exchange resin is regenerated by passing a solution of dilute
NaOH.
R′Cl + OH–  R′OH + Cl–

R2′SO4 + 2OH–  2R′OH + SO42–

The washings containing the anions are drained out. The regenerated ion-exchange resins
are then used again.

Advantages

1. Softened water is almost completely free of ions

REVERSE OSMOSIS PROCESS
Principle

When a semi-permeable membrane (cellulose acetate, polymethacrylate and polyamide)

separates two solutions of different concentrations, flow of solvent takes place from the dilute
solution to the concentrated solution due to osmotic pressure. But if a pressure of 15 to 40
kg/cm2 is applied to the concentrated solution, the solvent flow is reversed.

Advantages

1. The reverse osmosis process removes both ionic as well as non-ionic, colloidal
impurities.
2. It is used to remove salts from sea water

DOMESTIC WATER TREATMENT

Requirements of Potable Water

1. It should be clear, colourless, odourless and pleasant in taste.

2. It should be free from harmful bacteria and dissolved gases like CO2, H2S, NH3.
4. Hardness should be less than 500 ppm.

Screening

The raw water is allowed to pass through bar screens (to remove large floating matter) and
mesh screens (to remove coarse solids)

Aeration

1. To remove dissolved gases like CO2, H2S, NH3, etc.

2. To remove volatile impurities causing bad taste and odour.

The aerator consists of a tall tower containing several perforated trays. Water flows in from the
top and air is blown at the bottom. Now the air is free from gases like CO2, H2S, NH3, etc.
Sedimentation

The wateris allowed to stand undisturbed for about 6 hours in large tanks . Most of the
suspended particles settle down

Coagulation
In this method, certain chemicals such as alum or aluminium sulphate (Al2(SO4)3 8H2O), etc.
are added to the water. O n adding to water, it gives a gelatinous precipitate which
entraps colloidal particles in water and settles at the bottom

Filtration
Filtration is the process of removing minute insoluble, colloidal and electrical impurities by passing
through sand filters.

Disinfection or Sterilisation
The process of destroying the pathogenic (harmful) bacteria is known as disinfection or sterilisation.

a) By Boiling

When water is boiled for 10-15 minutes, all the harmful bacteria are killed

b) UV radiations

The energetic UV radiations(wavelength, 200 - 400 nm) attack the micro-organisms and
destroy them.

c) Ozone treatment

Ozone is a powerful oxidising agent and can be used for disinfection

O3  O2 + (O)
(nascent oxygen)

The nascent oxygen kills bacteria easily by the oxidation process

d) Chlorination
The process of adding chlorine to water is called chlorination.

i) By adding chlorine gas

The chlorine gas dissolved in water gives hypochlorous acid.

Cl2 + H2O  HCl + HOCl

ii) By adding chloramines

When chloramines are added to water and gives hypochlorous acid

ClNH2 + 2H2O  NH4OH + HOCl
iii) By adding bleaching powder

It produces hypochlorous acid

CaOCl2 + H2O  Ca(OH)2 + HOCl

In all the above cases hypochlorous acid releases nascent oxygen.

O3 O2 + [O]
The released nascent oxygen destroys micro- organisms.

Break point chlorination

The point at which all the impurities are removed and free residual chlorine begins to
appear is called break point chlorination.

A - Chlorine required to oxidise micro-organisms and reducing compounds

B - Chlorine required to react with ammonia to form chloramines
C - Chlorine required to react with organic compounds to form chlorinate
compoundsD - Free residual chlorine after the break point.

From the graph, initially the applied chlorine is used for the bacteria and reducing
compounds. Then the added chlorine forms another source of chlorine, namely chloramine,
with free ammonia. Further chloramines and added chlorine are used for chlorination of
the organic compounds available in the water so that the residual chlorine amount
decreases.