Prof. B.

Nepplian

Course Code: 15CY101

Course Title: Chemistry
 Technology Of Water
Water:
Water is a chemical substance with the chemical formula
H2O.
• Existance on Earth
1. Solid state-ice,
2. Gaseous state (water vapor or steam)
3. Liquid
• Water is not only universal solvent but also an essential material
for engineering applications.
• Prime factor in development
• Water on Earth moves continually through a cycle of evaporation
or transpiration (evapotranspiration),
 Water
• Water has memory. Depending on how you
treat, what kind of emotions and thoughts
you generate, accordingly it behaves in your
body

• Sadhguru
Evotranspiration Process
• Evapotranspiration (ET) is a term used to describe the sum of
evaporation and plant transpiration from the Earth's land surface to
atmosphere.

• Evaporation :-
The movement of water to the air from sources such as
the soil, canopy interception, and water bodies.

• Transpiration :-
The movement of water within a plant and the
subsequent loss of water as vapor through stomata in its leaves.

• An element (such as a tree) that contributes to evapotranspiration

can be called an evapotranspirator.
 Sources of Water
• The source of water are listed under two categories
1. Surface Water
2. Underground Water

A. Surface Waters:
1. Rain Water
2. River Water
3. Lake Water
4. Sea water

B. Underground Water:
1. Spring
2. Well water
 Types Of Impurities
1. Dissolved Impurities:
a) Inorganic salts e.g
sulphates and chlorides of calcium, Magnesium, Iron

b) gases like carbon dioxide, nitrogen , oxygen, hydrogen sulphides

c) organic salts

2. Suspended Impurities:
a) Clay
b) mud
c) Vegetable and animal matters
3. Colloidal Impurities:
a) fine size like silica and alumina, organic wastes etc.

- These are soluble materials, other than gases

- cannot be removed by conventional filters
- referred as TDS which stands for total dissolved solids.

4. Bacterial Impurities:
a) Bacteria, Germs, Pathogens, Microbes, Viruses, Parasites
- include
- algae, beneficial bacteria that decompose wastes
- harmful bacteria such as those that cause cholera.
 1.2 HARD WATER AND SOFT WATER

Hard Water
“Water which does not produce lather with soap solution,
but produces white precipitate is called hard water”.
2C17 H 35 COONa + Ca ++ → (C17 H 35 COO) 2 Ca + 2Na+ Water soluble
Waterinsoluble
This is due to the presence of dissolved Ca and Mg salts.

Soft Water

“Water which produces lather readily with soap solution is

called soft water.”
This is due to the absence of Ca and Mg salts.
• Effects of Impurities:
a) colour of surface water- dissolved organic matters
b) Taste and Odour- formation of compounds
c) Turbidity- suspended Impurities
d) Pathogenicity- micro organisms
Hardness of Water
• Characteristics of water which prevent the Leather Formation.
• due to presence of:- salts like bicarbonates, sulphates,
chlorides of mg and other metals
• Units of Hardness:
1) ppm 2) mg/l 3) ̊Cl 4) ̊Fr
ppm- parts per million,mg/l- Milligram per litre, C ̊ l -Clarkes degree,
F̊ r- Degree French
• Relation - 1ppm = 1mg/l = 0.07 ̊Cl = 0.1 ̊Fr
 Hardness Table
Water Classification Hardness, mg/L Hardness. Grains/Gal Sodium Added mg/L

Soft 0 to 49 0 to 2.9 0 to 22.5

Medium Hard 50 to 149 2.9 to 8.7 23 to 68.5

Hard 150 to 249 8.7 to 14.6 69 to 115

Very Hard 250 to 299 14.6 to 173 115 to 138

Extremely Hard 300 and up 17.5 and up 138 and up

mg/L = milligrams/Liter
 Types of Hardness
1) Temporary:- or Carbonate Hardness
Water that contains bicarbonate of calcium and
magnesium or of both
• removed by boiling
Ca(HCO3)2 → CaCO3 ↓ + CO2 ↑+ H2O
Mg(HCO3)2 → Mg (OH) 2 ↓ + 2CO2 ↑
2) Permanent :- or Non- Carbonate Hardness
Contains chlorides or sulphates of calcium or
magnesium or of both
• Can not be removed by boiling
CaCl2 → Ca+2 + 2Cl-1
MgSO4 → Mg+2 + SO4-2
• Hardness is expressed in terms of CaCO3 equivalent
The concentrations of hardness as well as non-hardness constituting ions are
usually expressed in terms of equivalent amount of CaCO3.

The choice of CaCO3 in particular is due to its molecular weight 100 (equivalent
weight=50) and it is the most insoluble salt that can be precipitated in water treatment.

 Hardness of the hardness causing salt in terms of CaCO3

CaCO3 hardness eq =
[Mass of hardness Producing sub.] X [Eq.Wt. of CaCO3]
[Eq.Wt. of hardness producing substance]

CaCO3 hardness eq =
[Mass of hardness Producing sub.] X 50
[Eq.Wt. of hardness producing substance]
 Disadvantages of Hard Water
(A) Domestic Uses:
1. Washing
When used for washing, it does not produce lather readily with soap, instead
It produces precipitates of calcium and magnesium soaps. Once all the calcium
andMagnesium salts are precipitated, water forms lather with soap
C17 H35 COO Na + H2O→ C17 H35 COOH + NAOH
C17 H35 COOH + C17 H35 COO Na → Lather
Above reactions occur readily when soft water is used
When hard water is used the following reaction takes place
C17 H35 COO Na + CaSO4 → (C17 H35 COO) 2 Ca ↓ + Na2SO2
(in water) (White Scum)
Formation of calcium or magnesium soap causes wastage of soap,. So when
hard water is used for washing exess amount of soap has to be applied
2. Bathing : hard water does not form lather freely with soap it form scum on the body
3. Drinking: hard water may form crystals of calcium oxalate in urinary tracks
4. Cooking: Hardness causing substances enhances the boiling point of water, taste of
the food is affected
 Disadvantages of Hard Water
(B) Industrial Uses:
1. Boiler Feed: water should be soft as possible,
should not contain nitrates and other hardness causing
salts to avoid any damage due to scale and sludge formation,
boiler corrosion
2. Paper Mill:
should not contain iron and lime- destroy resin of soap
3. Sugar industries:
if water is rich in Sulphates and Alkaline carbonates and
especially nitrates is used, crystallisation of sugar is difficult
and also sugar becomes Deliquescent
4. Dyeing Industries:
should not contain iron and hardness
5. Laundries: should be soft
 Estimation Of Hardness
1. EDTA Method 2. O.Herner’s Method
1. EDTA Method:
Ethylene Diamine Tetra Acetic Acid
-OOOCH2 CH2COO-
NCH2.CH2N
-OOOCH2 CH2COO-
Anion forms a complex with Ca2+ and Mg2+ ions
Complex when hard water is titrated against EDTA solution, EDTA forms
complex with Ca2+ and Mg2+ ions O=C O
O C=O

H2C N N CH2
- -
OOCCH2 CH2COO
H2C CH2
Estimation of Hardness- EDTA Method OH OH
• Estimation is by titration method at pH 10 N N

• Using Indicator Eriochrome Black-T + -

Na SO3
Method:
Take 50 ml water in conical flask NO2
Add buffer and few drops of EBT-T indicator Eriochrome black-T
Sodium-1-(1-Hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulphonate

1st Step: The calcium ion coordinates with the indicator (Eriochrome Black T).

Titrate against EDTA

Red colour change to steel blue/violet
2nd Step: The EDTA chelates the calcium ion and releases the indicator.

V1 ml of EDTA = 50 ml STD water x eq. wt of CaCO3

 Determination of Permanent Hardness
• Caused by Chlorides and Sulphates of Calcium and Magnesium
• Can be determined by using Na2CO3 and HCl.
CaCl2+Na2CO3→CaCO3 ↓+ 2NaCl
CaSO4+Na2CO3→CaCO3 ↓ + 2NaSO4

Method:
1. 50 ml hard water + 50 ml Na2CO3 solution
2. Boiled and Evaporated to dryness.
3. Chlorides of Ca and Mg ppt. as carbonates of Ca and Mg.
4. Extract residue with distilled water
5. Add few drops of methyl orange as indicator
6. Titrate against N/50 HCl
7. End point changes colour from yellow to orange.
 Determination of Temporary Hardness:
O.Herner’s Method (0r) Alkali Titration Method
• Bicarbonates of Ca and Mg makes water alkaline and can react with
HCl
Ca(HCO3)2 + 2HCl → CaCl2 + 2CO2 ↑+ 2H2O
Mg(HCO3)2 + 2HCl → MgCl2 + 2CO2 ↑+ 2H2O
• Ca(HCO3)2 and Mg(HCO3)2 decomposes into insoluble carbonates on
boiling the water.
For Temporary Hardness:
1) 50ml sample water in conical flask
2) 2-3 drops of methyl orange indicator
3) Titrated against N/50 HCl
4) Change colour from yellow to orange
5) Take 100 ml of same sample of water
6) Boil until 1/5th volume
7) Make them again 100 ml Distilled water
8) Take 50ml and perform again the above steps
 Determination of Alkalinity in water
Alkalinity: It is due to 1) OH- and CO3-2 2) HCO3-
• Titrate against phenolphthalein and methyl orange
Method
1. 100 ml sample water in conical flask
2. Add 2-3 drops of phenolphthalein indicator
3. Titrate against N/50 H2SO4
4. Continue till pink colour disappear
5. To the same solution add 2-3 drops of methyl orange
6. Titrate till yellow colour changes to red
Reaction Involved:
OH-+H+ → H2O (using phenolphthalein)
CO3-2+ H+→ HCO3- (using phenolphthalein)
HCO3-+H+ → H2O+ CO2 (using methyl orange)
 Present in the
S.No parameter Ions Characteristics
form of salts
CaCO3, The soap
Ca2+ Ca(HCO3)2, consuming
CaSO4, capacity of water
is increased
1 Hardness MgCO3,
mainly due to
Mg(HCO3)2,
Mg2+ these salts
MgSO4

Ca(OH)2, Highly alkaline

OH– Mg(OH)2 water leads to
Na2CO3, CaCO3, boiler troubles like
2 Alkalinity CO32- caustic
embrittlement
Na(HCO3),
HCO3 –
Ca(HCO3)2,
 Boiler problems with hard water
Scale and Sludge
• Troubles met in boiler which are used in steam production.
Scale:
When water is evaporated in boilers to produce steam continuously
the concentration of the salts present in the water increases progressely
As the concentration reaches a saturation point the salts are thrown
over the inner surface of the boiler.
Sludge:
During boiling salts form precipitate of loose slimy form.
Magnesium Chloride
Decomposes to form hydroxide and hydrochloric acids. The former will
produce hard scale and the later lowers the pH.
MgCl2 + 2H2O  2HCl + Mg(OH)2
Magnesium Sulphate
Forms a hard scale on the heating surfaces
Calcium Sulphate
Forms a hard scale on the heating surfaces (solubility decreases with
increasing temp.; solubility 3200 ppm at 15 ⁰ C, 27 ppm at 320 ⁰C

Calcium Bi-carbonate
Decomposes at a low temperature when CO2 is liberated. Remaining
Calcium carbonate deposits on the heating surface as a soft scale.
Ca(HCO3)2  CaCO3 + CO2 + H2O
Sludge Scale

Heat Heat
Boiler wall
 Disadvantages of Scale Formation
1. Wastage of fuel 2. Decreases in Efficiency
3. Lowering of boiler safety 4. Danger of Explosion
5. Corrosion (MgCl2 + Fe + H2O- Mg(OH)2 + FeCl3 + H2)
(0.625 mm scale thickness: 15% more energy, 12 mm 150% energy
waste)
Removal of Scales
1. By scrapping 2. Giving thermal shocks
3. Dissolving by using chemicals e.g CaCO3 by 5-10% HCl
4. Adding complexing agents e.g CaSO4 by EDTA
5. Blow down Process
Disadvantages of Sludge Formation
1. Chocking of pipes
2. Low supply of heat
3. Wastage of fuel
4. Get entrapped in scales
 Prevention of Sludge Formation
1. Blow down Process: Withdrawing portion of sludge containing water
and replacing with fresh water
2. Softening of water
Method of Preventing Scale Formation
1. External Treatment:
Treatment of water before entering into boiler
- Removal of Ca, Mg and Silica
2. Internal Treatment:
Addition of chemicals directly to water in boiler.
- Scale forming substances produces loose precipitate
- Blow down process
- Adding complexing agents: to form soluble complex
 Methods of Preventing Scale Formation
A. Internal Treatment B. External Treatment
Internal Treatment Method
1. Phosphate Conditioning:
- Small amount of phosphate ions are added to precipitate Ca ions
present in the boiled water is precipitated as loose sludge. The
Sludge is removed by blow down operation
3CaCl 2  2Na 3 PO 4  Ca 3 (PO4 ) 2  6NaCl
- Chosen depending on the pH conditions of boiler.
2. Colloidal Conditioning:
- Using kerosine, tannin (polyphenolic biomolecule- many OH groups),
starch, etc
- Get coated over the scale forming particles
- Removed by Blow down Process
3. Carbonate conditioning:
- Na2CO3 is added to precipitate Ca salts as CaCO3
CaCl 2  Na 2 CO 3  CaCO 3  2NaCl
MgSO 4  Na 2 CO 3  MgCO 3  Na 2 SO 4
- Loose form of the precipitate of calcium carbonate is removed by
Blow down Process
- Used in low pressure boilers
4. Calgon Conditioning:When calgon (sodium hexa meta phosphate) is added to
boiler water, it reacts with the calcium and magnesium ions and forms a highly
soluble complex of calcium hexa meta phosphate. This soluble complex settles
down in the bottom as sludges and it can be easily removed by blow down
operation.
- E.g. Sodium Hexameta Phosphate (Na2PO3)6 is added…reacts with Ca and forms Calcium
Hexameta Phosphate (Ca2PO3)6
Na2[Na4(PO3)6 2Na+ + [Na4P6O18]2-
Calgon – sodium hexa
meta phosphate

2CaSO4 (Boiler water) + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

Calgon tablets are used in the cleaning of washing machine drums
5. Radioactive conditioning:
-Adding radioactive tablets
-Emits radiation energy which prevents Scale formation
6. Electrical Conditioning:
-Mercury bulbs placed in boiler
-Emits electrical discharge
-Prevents Scale formation
Q. 1. Define calgon conditioning.
When calgon (sodium hexa meta phosphate) is added to boiler water, it reacts with
the calcium and magnesium ions and forms a highly soluble complex of calcium hexa
meta phosphate. This soluble complex settles down in the bottom as sludges and it
can be easily removed by blow down operation.

Q. 2. Why is calgon conditioning better than phosphate conditioning?

Calgon conditioning forms soluble complex salt
Na2[Na4(PO3)6] + CaSO4 = Na2[Na2 Ca(PO3)6] + Na2SO4
Calgon Soluble complex
whereas phosphate conditioning i.e., treatment with sodium phosphates, precipitates
calcium and magnesium phosphates causing scale in boiler pipes.
 IV. Boiler corrosion

Degradation or destruction of boiler materials (Fe) due to the chemical or

electrochemical attack of dissolved gases or salts is called boiler corrosion

Boiler corrosion is of three types

1. Corrosion due to dissolved O2

2. Corrosion due to dissolved CO2
3. Corrosion due to acids formed by dissolved salts

1. Corrosion due to dissolved oxygen (DO)

2 Fe + 2 H2O + O2 2 Fe(OH)2

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous Rust
hydroxide

35
 Removal of Dissolved Oxygen (DO)

1. By the addition of chemicals

The dissolved oxygen present in the boiler feed water can be removed by the addition of sodium
sulphite or hydrazine and the reactions can be written as below

2 Na2SO3 + O2 2 Na2SO4
Sodium DO Sodium
sulphite sulphate Water feed

Na2S + 2O2 Na2SO4

N2H4 + O2 N2 + 2H2O
O2 To vacuum
Hydrazine Nitrogen

Steam jacket
2. By mechanical deaeration

It comprises of a tall stainless tower with different layers capped

Perforated
with baffles to facilitate multiple equilibration. plate

The entire chamber is vacuumized and also maintained at high

tempt using perforated heating plates on the walls.

Principle: High tempt and low pressure favors lower solubility of Deaerated 36
water
gases in water (Henry’s law)
2. Corrosion due to dissolved CO2

Presence of bicarbonate salts of either magnesium or calcium also causes the release of CO2 inside the
boiler apart from the dissolved CO2

Mg(HCO3)2 MgCO3 + H2O + CO2

CO2 + H2O H2CO3 (causes slow corrosion)

Removal
1. It can be removed by the addition of ammonia
2 NH4OH + CO2 (NH4)2CO3 + H2O

3. Corrosion due to dissolved salts

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

Fe + 2 HCl FeCl2 + H2

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

37
 Other boiler Troubles

Caustic embrittlement :
is a type of boiler corrosion, caused by high
concentration of sodium hydroxide in boiled water ( highly alkaline)
• Sodium carbonate is used in softening of water by lime soda process,
due to this some sodium carbonate maybe left behind in the water.
Na2CO3 + H2O → 2NaOH + CO2
• As Conc. of NaOH increases, water flows into minute hair cracks.
• Water get evaporated and NaOH increases further and react with iron
of boiler, hence cause Embrittlement. ([FeO4]2−)
Prevention:
1. Addition of sodium sulphate or sodium phosphate. Which will block
hair-cracks.
2. Addition of tannin and lignin- blocks the cracks.
3. Excess of Na2SO4 is avoided else it will form CaSO4 scales. Under
theses circumstances, Na3PO4 should be used
 Priming and Foaming
Priming:- When a boiler is heated rapidly some liquid water particles are
carried along with steam, steam containing these liquid water
particles is also called wet steam, and this process of wet steam
production is called priming.
- Leads to deposits of salt crystals
- Lowers the energy efficiency
Causes:-
Normal Bubble
a)Presence of suspended impurities and dissolved salts
b)High steam velocity and sudden boiling
c)High water levels
d)Faulty boiler design
Preventions:
a)Good boiler design
b)Avoid rapid changes in temp.
c)Maintaining low water level
d)Fitting mechanical steam purifier Carry Over
III. Priming and foaming

Foaming
It is the production of continuous foam or hard
bubblers in boilers. Foaming is due to the
presence of substance like oil in boiling water.

Priming
Foaming It is the process in which some particles in
Normal bubble water are carried along with the steam. The
resulting process is called as wet steam or
carry over. The process of formation of wet
steam in boilers is called as priming.

Causes of Priming,
1. Presence of dissolved salts
Priming 2. High velocity steam due to sudden boiling
Carry over bubble
3. Improper boiler design

Disadvantages of Priming and foaming –

refer Jain and Jain Text book
• Foaming: Foaming is the formation of stable bubbles above the surface of
water (or) production of stable bubbles inside the boiler.
• Foaming is due to the presence of oily impurities in the boiler water
and it can be removed by adding antifoaming agents like castor oil.
Causes:
a) Difference b/w conc. of solute and suspended matters.
b) Surface tension lowering substances
c) Oil and grease
Prevention:
a) Adding antifoaming agents e.g. castor oil
b) Removing oily particles using silicic acid and sodium alluminate.
Boiler Corrosion: Decay of material by chemically or electrochemically
Causes:
a) Presence of dissolved gases e.g. O2 , CO2
b) Caustic Embrittlement
c) Acid formation due to Hydrolysis
d) Presence of free acids.
Q. 1. Why do we express hardness of water in terms of CaCO3 equivalent?
Ans. This mode permits easy addition and subtraction of concentration of
hardness-causing constituents, since its mol. wt. is 100. Moreover, it has also been
adopted as standard for expressing hardness.

Q. 2. What are the salts responsible for temporary and permanent hardness
of water?
Ans. Temporary hardness = Ca(HCO3)2 and Mg(HCO3)2
Permanent hardness = Chloride and sulphate of Ca2+ and Mg2+.

Q. 3. Mention the units of hardness. Define them.

Ans. (i) ppm, (ii) degree.
ppm is defined as the parts of hardness salt present in 106 parts of water expressed
in terms of calcium carbonate.
Degree hardness is defined as the parts of hardness salt present in 105 parts of
water expressed in terms of calcium carbonate
Softening of hard water –
External treatment

Attn: Part B Question

43
II External treatment of water – External Conditioning of water
Softening of hard water can be done by the following methods
1. Lime soda process
2. Zeolite methods
3. Ion exchange resin method
4. Mixed bed deionizer method

1. Lime soda process

It is a process in which Lime (Ca(OH)2) and soda (Na2CO3) are added to the hard water to convert
the soluble calcium and magnesium salts to insoluble compounds by a chemical reaction. The
CaCO3 and Mg(OH)2 so precipitated are filtered off and removed easily.

It is further divided in to two types

1. Cold lime soda process
2. Hot lime soda process

44
 Zeolite (Permutit) method of Softening of
water
Zeolite is a Hydrated Sodium Alumino
Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.

The general chemical structure of zeolite

is given below Na2O.Al2O3.xSiO2.yH2O (x
= 2-10 and y = 2-6)

Micro pores of Zeolite Porous Structure of zeolite

 Porosity or cavity size of synthetic zeolite structures can be

controlled by varying the Si/Al ratio
 Ion-exchange process of zeolite structure is associated with sodium ions
45
A. Natural Zeolite:-
Derived from green sand by washing, Heating, treating
with NaOH.
• Non porous in nature.
Natural Zeolites:
1. Natrolite - Na2O. Al2O3 4SiO2 .2H 2O
2. Laumontite - CaO. Al2O3 4SiO2 .4H 2O
3. Harmotome - (BaO.K2O). Al2O3 5SiO2 .5H 2O

B. Synthetic Zeolite: -
Prepared from solution of Sodium Silicate and AlOH
• Higher exchange capacity and porous in Nature.

Why synthetic zeolite is better than natural zeolite for the softening of water?
Ans: Natural zeolites are non-porous
 Zeolite softener
Consist of Steel Tank
Having Thick Layer of Zeolite
When water pass through it
Hard water in
hardness causing ions (Ca, Mg) are
retained by Zeolite.

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

47
Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through
the zeolite bed at a specified rate. The hardness causing ions such as Ca2+, Mg2+
are retained by the zeolite bed as CaZe and MgZe respectively; while the
outgoing water contains sodium salts. The following reactions takes place during
softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3
Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
48
 Advantages
1. Hardness can be completely removed

2. Process can be made automatic and continuous

3. Easy operation. No experts required

4. Less time and no sludge is produced

5. Equipment is compact, only less space is occupied

 Disadvantages
1. Only Ca+ and Mg+ ions can be removed
2. Large amount of Na ions present in treated water.
3. Leaves other acidic ions HCO3- .which causes corrosion
4. When the softened water containing NaHCO3 is used in boilers, NaHCO3
decomposes to form CO2 which causes corrosion
5. Fe 2+ and Mn 2+ containing water can not be treated because Fe and Mn
Zeolite can not be regenerated
6. Water should be free from suspended impurities to prevent clogging on
Zeolite beds.
7. Treated water contains more dissolved solids.
51
 III. Ion-Exchange resin (or) deionization (or) demineralization process

Ion exchange resin

Ion exchange resins are insoluble, cross linked, long

chain organic polymers with a microporous structure,
and the functional groups attached to the chain is
responsible for the “ion-exchange” properties.

Cation Resin after

exchange Resin treatment
52
 In general the resins containing acidic functional groups (-COOH, -SO3H etc) are capable of exchanging
their H+ ions with other cations, which comes in their contact; whereas those containing basic functional
groups ( -NH2, =NH as hydrochlorides) are capable of exchanging their anions with other ions, which
comes in their contact.

Based on the above fact the resins are classified into two types
1. Cation exchange resin (RH+) –
Strongly acidic (SO3-H+) and weakly acidic (COO-H+) cation exchange resins
2. Anion Exchange resin (ROH-) –

Strongly basic (R4N+OH-) and weakly basic (RNH2+OH-) anion exchange resins

Continued… next slide

Examples of ion exchange resins

1. Sulphonated styrene divinyl benzene copolymer
2. Quaternary resins based upon the amination of chloro-methylated styrene
divinyl benzene copolymer
3. Weak base resins based upon the animation the amination of chloro-methylated
styrene Divinyl benzene copolymer
4. Acrylate carboxilyic divinyl benzene copolymer
53
Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin

R = CH3

54
 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Acid solution
for Wastages to
regeneration sink Alkaline solution for
of resin Wastages to
regeneration of resin
sink
pump

Soft water 55
 Process or Ion-exchange mechanism
involved in water softening

Reactions occurring at Cation exchange resin

2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+

Reactions occurring at Anion exchange resin

2 ROH- + SO42- (hard water) R2SO42+ + 2 OH-

2 ROH- + Cl- (hard water) R2Cl- + 2 OH-

At the end of the process

H+ + OH- H2O

57
 Regeneration of ion exchange resins

Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) 2 RH+ + Ca2+ (CaCl2, washings)

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH) 2 ROH- + SO42- (Na2SO4, washings)

Advantages
1. The process can be used to soften highly acidic or alkaline waters
2. 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
1. The setup is costly and it uses costly chemicals
2. The water should not be turbid and the turbidity level should not be more
than 10ppm
58
 IV. Softening of water by Mixed Bed deioniser

Description and process of mixed bed deionizer

1. It is a single cylindrical chamber containing a mixture of anion and cation exchange resins bed
2. When the hard water is passed through this bed slowly the cations and anioins of the hard water
comes in to contact with the two kind of resins many number of times
3. Hence, it is equivalent to passing the hard water many number of times through a series of cation
and anion exchange resins.
4. The soft water from this method contains less than 1ppm of dissolved salts and hence more
suitable for boilers

Hard water

c a c a Anion exchange
resin
c Mixed bed Mixed resin
a deionizer a bed
a
c a cc Cation exchange
resin

Demineralised
water
59
Regeneration of mixed bed deionizer

1. When the bed (resins) are exhausted or cease to soften the water, the mixed bed is back washed by
forcing the water from the bottom in the upward direction
2. Then the light weight anion exchanger move to the top and forms a upper layer above the heavier cation
exchanger
3. Then the anion exchanger is regenerated by passing caustic soda solution (NaOH) from the top and then
rinsed with pure water
4. The lower cation exchanger bed is then washed with dil.H2SO4 solution and then rinsed.
5. The two beds are then mixed again by forcing compressed air to mix both and the resins are now ready
for use
Low
NaOH
density
resin

c a c a c a c a c aa c a
aa a a a a cRegenerated
c Mixed bed c Exhausted Back washed a
a deionizer a a Mixed bed a
Mixed bed

a a ccccc c
deionizer
a
c a cc c a cc c a c c

Back Compressed
wash High air
water density 60
resin
B. Ion Exchange (or) Demineralization (or) Deionization Process.
• mineral ions are removed
• physical process which uses specially-manufactured ion exchange
resins which bind to and filter out the mineral salts from water.
Advantage:
1. Produces soft water
2. Can treat highly acidic or alkaline water
3. Regeneration of ion resins are possible
4. Maintenance cost is low
Disadvantage:
1. Cost of equipment is high
2. Highly turbid water can not be treated
3. Expensive chemicals are required.
3. Mixed Bed Deionization
• This equipment consist of single column which contain mixture of
cation and anion exchangers.
• When water pass through bed, it comes in contact several times with
both exchangers
• Resultant water contain lesser amount of salt.
Regeneration: by back wash
a) anions with dil. NaOH
b) cations with dil. H2SO4
Advantages:
• More convenient and more effective
Disadvantages:
• Regeneration cost is more
• Equipment cost is high
DESALINATION

64
Commonly used methods:
1. Electrodialysis
2. Reverse Osmosis (Pressure membrane process)
Attn: Part B Question
A. Electrodialysis:
• Method of separation of ions from salt water by passing electric
current.
• Semi permeable membranes are placed

• Consist of three compartments containing

1. Sea Water 2. Pair of electrodes 3. Semi permeable membrane
• As current applied Na ions moves towards cathode and Cl moves
towards anode
• As result brine concentration decreases in the middle compartment.
• Pure water is removed from the central compartment.
• Conc. Brines are replaced by fresh brine water.
• Much more effective separation Ion selective membranes are used
 RO

ED
The Processes

Electrodialysis Reverse Osmosis

68
Reverse Osmosis -
a Natural Process
Water is drawn from a low
to a high concentration.
Evapo-transpiration creates
a suction which draws water
up through the root hairs to
the leaves.
In RO systems pressure is
applied to the high
concentration side of the
membrane to induce
osmotic flow of clean water
to the low concentration
side.
 Reverse Osmosis (or) Super Filtration (or) Hyper Filtration
• Movement of solvent molecule from concentrated side to diluted
side.
• If only pressure higher than that of osmotic pressure

Membranes:
Cellulose Acetate, Polymide,
Polymethylmethaacrylate

Thickness:
0.0005 to 0.0000002 µm
• Advantages:
1. Removes both ionic and non ionic and colloidal matters
2. Maintenance cost is low
3. Membrane replacement can be done with in few minutes.
Reverse Osmosis

71
 Reverse Osmosis
~ Pure Water
High Pressure
Higher
Concentration
Flow
Retentate
Polyamide
barrier 0.2 μm Water Salt

Water
Microporous
40 μm
polysulfone

Polyester 120 μm
fabric

Salt

Water
Discarded Permeate
Low Concentration
Feed

http://www.dow.com/PublishedLiterature/
74
 Domestic Treatment of Water
A. Removal of Suspended Impurities
B. Removal of Micro organisms

Removal of Suspended Impurities

1. Screening:
Floating matters are removed by passing through screens.
2. Sedimentation:
- Big tanks are used
- Left undisturbed
- Water settle down due to gravity.
- Supernatent water is drawn with the help of pump
- Takes 2-6 hours
3. Filtration:
Sand Filters are used.
4. Sedimentation with Coagulation:
- Addition of Chemicals (Coagulants) to water. E.g. Alum (Potash Alum
or Ferric Alum), Sodium Aluminate (NaAlO2) ,Ferrous Sulphate
(FeSO4)
- On addition they form an insoluble gelatinous, flocculent precipitate
which absorbs very fine particles and form bigger flocs.
- Due to this tiny particles which have no charge also come closers.
 B. Removal of Micro Organisms
1. Boiling
2. Adding Bleaching Powder:
- 1 kg for 1000 KL
- Mixed and Allowed to stand several hours
CaOCl2 + H2O → Ca (OH)2 + Cl2
Cl2 + HO → HOCl (Hypochlorous Acid) + HCl
HOCl + Germs → Germs Killed
HOCl → HCl+ [O] (Nascent Oxygen)
[O] + Germs → Germs Killed
Disadvantages:
- Excess addition give bad odour and taste.
- Introduces Ca into water and makes it hard
- Disintegrates on storing
3. By Chlorination:
- Chlorine produces Hypochlorous Acid.
- Hypochlorous acid is strong Germicide.
Cl2 + H2O → HOCl (Hypochlorous Acid) + HCl
HOCl + Germs → Germs Killed
- Cl may be used in Gaseous or Concentrated Form.
- Filtered water with 0.3-0.5 ppm Cl is sufficient.
- Lower pH is favourable (5-6.5)

Advantages:
1. Effective and Economical
2. Stable and does not deteriorate on storage
3. No impurities such as salts are introduced.
4. Can be used at high as well as low temp.
 Disadvantages
1. Excess chlorination produces unpleasant taste. (0.1-0.2 ppm only)
2. More effective at low pH.
Breakpoint Chlorination:
- The addition of chlorine in such amount that it Oxidizes the organic
matter, reducing matters and free ammonia in raw water. And leaves
free residual Cl which disinfect Water.
Advantages
1. Oxidizes organic compounds, reducing substances and ammonia.
2. Removes colour and taste.
3. Kill germs.
- Excess of Declorination can be done by
1. Filtering through bed of molecular carbon
2. Addition of SO2 and Na2SO3
SO2 + Cl2 + 2H 2O → H 2SO4+ 2HCl
Na2SO3 + Cl2 + H 2O → Na2SO4 + 2HCl
4. By chloramine:
- Using 2 : 3 ratio of Cl3 and NH3
ClNH2+ H2O → HOCl + NH3
HOCl + Germs → Germs Killed
5. By Ozonization:
- Ozone and raw water are allowed to come in contact with each other
- 10 – 15 min. in 2-8 ppm
3O2 → 2O3 (Highly Unstable)
O3 → O2 + [O]
[O] + Germs → Germs Killed
Advantage: 1. Leaves no residue. Because of unstability
2. Removes odour, colour, Taste.
Disadvantage: Very Expensive
6. By Ultraviolet Radiation:
- Using Electric mercury vapour lamp
 International Standards for water
- Depends on purpose
- Standards Set By:
1. WHO- World Health Organization
2. USPHD- United States Health Service
3. ICMR- Indian Council of Medical Research

Water should be free from

1. Turbidity, Colour
2. Taste, Odour
3. Microbes
4. Toxicity (Organic and Inorganic Metals)
Breakpoint Chlorination
 Disadvantages of Hard Water
(A) Domestic Uses:
1. Washing 2. Bathing 3. Drinking 4. Cooking
C17 H35 COO Na + H2O→ C17 H35 COOH + NAOH
C17 H35 COOH + C17 H35 COO Na → Lather
C17 H35 COO Na + CaSO4 → (C17 H35 COO) 2 Ca ↓ + Na2SO2
(in water) (White Scum)

(B) Industrial Uses:

1. Boiler Feed: should not contain nitrates- scale and sludges
2. Paper Mill: should not contain iron and lime- destroy resin of soap
3. Sugar industries: Sulphates and Alkaline carbonates- Deliquescent
4. Dyeing Industries: should not contain iron and hardness
5. Laundries: should be soft