UNIT - I

WATER TECHNOLOGY

Dr. K. Rajendra Kumar

Department of Chemistry
School of Advanced Sciences
 Molecular Formula of Water

2
Without food, human can survive for number of
days, but water is such an essential that without it
one cannot survive.
Although water is natures most wonderful,
abundant and useful compound yet is also the
most misused one.

3
 Distribution of water

4
 Sources of Water
A) Surface Waters
Rain Water - Pure but contaminated with gases
River Water - High dissolved salts moderate organics
Lake Water - Const. composition but high organics
Sea Water - High salinity, pathogens, organics

B) Underground Waters
Spring/Well Water - Crystal clear but high dissolved
salts and high purity from organics

5
 Classification of Impurities in water

Physical Impurities - Dissolved Solids/Salts

Chemical Impurities - Inorganic & Organic Chemicals
Biological Impurities - Pathogens, algae, fungi,viruses...

1) Acidity (pH)
2) Gases (CO2-
1) Colour
2) Turbidity O2, NH3) 1) Microorganism
3) Taste 3) Minerals 2) Water Bodies
4) Odour 4) pH
5) Conductivity 5) Salinity
6) Alkalinity
6
7) Hardness
Colour
Colour in water is due to metallic salts of Fe, Mn and due to organic

substances like humus, peat, algae, weed

Industrial activities such as textile, paper & pulp, dyeing, tanneries

Turbidity
It is due to colloidal, extremely fine suspension such as clay, silt,
finely divided matters, sometimes microorganisms
It reflects the optical properties of water in terms of light scattering
ability instead of transmitting in straight lines.

Conductivity
The ability of water to conduct electricity, indicates the amount
of dissolved minerals and gases in water.
Conductivity measured in micro mhos/cm or MicroSiemens/cm3
7
Taste
Presence of dissolved salts and gases imparts bitter, soapy, brackish
and palatable taste which normally co-related with odour but it is
not applicable always the case
Bitter (Fe, Al, Mn, SO4, Ca(OH)2)
Soapy (NaHCO3)
Brackish (High salt content - NaCl)
Palatable (CO2 and NO3)

Odour
Domestic and industrial activities cause undesirable odour to water
Industrial effluent of organics, sewage discharge, presence of N, S
and P contains compounds, metal ion pollution like Fe
Substances like algae, peat, bacterias
Grassy odour, peaty odour, offensive odour, tarry and faint odour
8
 pH
(means potential of hydrogen)
pH a measure of hydrogen ion activity is used to
express the intensity of acidic or alkaline condition of a
solution.

The pH scale runs to 0 from 14 with 0 representing

maximum acidity and 14 maximum basicity

pH = -log [H+]

9
 pH values of some liquids encountered in day-to-day life

The optimum pH
for
the body fluids is
7.0

10
www.chemwiki.ucdavis.e
du
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases
Alkalinity

Calcium Bicarbonate Turbidity, silt, mud, dirt and CO2

Magnesium Carbonate other suspended matter H 2S
Hydroxide NH3
Sodium Color, Plankton CH4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

11
 Hard Water
Whats hard water?

Practically speaking, measurement of:

Calcium (Ca) ions
Magnesium (Mg) ions

Hardness as calcium carbonate

mg/L (ppm)

Soft 0-17
Slightly hard 17-60
Moderately hard (Medium) 60-120
Hard 120-180
Very hard 180 & over

12 http://water.usgs.gov/owq/hardness-
alkalinity.html
 Why be concerned about Hard Water?

Originally, water hardness was defined as the measure of

the capacity of the water to precipitate soap

Hard water does cause soap scum, clogs pipes and clogs
boilers as lime scale

13
 Hardness of Water
Hardness in Water is characteristic that prevents the
lathering of soap thus water which does not produce lather
with soap solution readily, but forms a white curd is called
hard water.

Type of Hardness

Temporary or Carbonate Hardness

Permanent Hardness or non-carbonate Hardness.

14
 Temporary Hardness

Temporary Hardness is caused by the presence of dissolved

bicarbonate of calcium, magnesium and other heavy metals and
the carbonate of ion.
It is mostly destroyed by more boiling of water, when
bicarbonates are decomposed yielding insoluble carbonates.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Calcium bicarbonate Calcium Carbonate

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

Magnesium Bicarbonate Magnesium hydroxide

Calcium/Magnesium Carbonates thus formed being almost

insoluble, are deposited as a scale at the bottom of vessel, while
carbon dioxide escapes out.

15
 Permanent Hardness
Non Carbonate Hardness is due to the presence of
chlorides, sulfates of calcium, Magnesium, iron and
other heavy metals
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium Hardness Calcium
stearate stearate
(sodium soap) (Insoluble)
2C17H35COONa + MgSO4 (C17H35COO)2Mg +
2Na 2SO4
Sodium Magnesium
Hardness
stearate stearate
(sodium soap) (Insoluble)

16
 Most Commonly used
Units of Hardness
Parts per million (ppm)
1ppm=1 part of CaCO3 equivalence hardness causing substance present in 10 6
parts of water

Milligrams per liter (mg/litre)

1mg/L=1mg of CaCO3 equivalence hardness causing substance present in one
liter of water

1mg/L=1ppm
Relationship; 1L water = 1Kg = 1000 g = 1000 X 1000 mg = 106 mg
1mg/L = 1mg of CaCO3 eq per 106 mg of water
= 1 part of CaCO3 eq per 106 parts of water = 1ppm

Clarke's Degree(oCl)
1o Clarke= 1part of CaCO3 equivalent hardness in 70000 parts of water

17 Degrees French (oFr)

1o Fr = 1 part of CaCO3 eq per 105 parts of water
 CaCO3 equivalent
hardness
Mass of hardness Molecular weight
producing
X of CaCO3
Calcium carbonate substance
equivalent = Molecular weight of hardness
producing substances
Problem
1
Calculate the calcium carbonate equivalent hardness of a water sample
containing 204mg of CaSO4 per litre

Solution
: 204 X 100
Calcium carbonate equivalent = 150 mg of
hardness = 136 CaCO3/L
= 150 ppm

Note : Mol. Weight of CaCO3 =

100
Mol. Weight of CaSO4 =
136
18
 Calcium carbonate equivalence conversion
during hardness calculation

Hardness Molecular Multiplication factor

producing weight (in terms of CaCO3
substance equivalence)
Ca(HCO3)2 162 100/162 or 50/81
Mg(HCO3)2 146 100/146 or 50/73
CaSO4 136 100/136 or 50/68
CaCl2 111 100/111 or 50/55.5
120 100/120 or 50/60
MgSO4
95 100/95 or 50/47.5
MgCl2
100 100/100 or 50/50
CaCO3 84 100/84 or 50/42
MgCO3 44 100/44 or 50/22
CO2 61 100/61 or 50/61
HCO-3 17 100/17 or 50/17
OH- 60 100/60 or 50/30
CO32-

19
 Problems
1. A water sample from an industry in Bombay had the following data
Mg(HCO3)2 = 16.8mg/L, MgCl2 = 19 mg/L, CaCO3 = 20 ppm, MgSO4 =24.0mg/L
and KOH = 1 ppm. Calculate the temporary, permanent and total hardness of
the water sample.

Solutio
nStep 1 conversion in to CaCO3
equivalent

Constituent quantity Conversion Hardness

present factor
Mg(HCO3)2 16.8 mg/L 100/146 16.8 *100/146 = 11.5ppm
19.0 mg/L 100/95 19.0*100/95 = 20ppm
MgCl2
20.0*100/100 = 20 ppm
CaCO3 20 ppm 100/100
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculatio
n
Temp. Hardness = 31.5 P. Hardness = 40 ppm
ppm

Tot. Hardness =71.5

20 ppm
 Some websites for your reference

water-softening.org website

The Salt Guru on water softening

http://www.feedwater.co.uk/boiler-water-
treatment.php

21
 Interesting facts about water
Roughly 70 percent of an adults body is made up of
water.
At birth, water accounts for approximately 80 percent of
an infants body weight.

Drinking too much water too quickly can lead to water

intoxication. Water intoxication occurs when water
dilutes the sodium level in the bloodstream and causes an
imbalance of water in the brain.

Water intoxication is most likely to occur during periods

of intense athletic performance.
22
 Interesting facts about water
While the daily recommended amount of water is eight cups per
day, not all of this water must be consumed in the liquid form.
Nearly every food or drink item provides some water to the body.

Soft drinks, coffee, and tea, while made up almost entirely of

water, also contain caffeine. Caffeine can act as a mild diuretic,
preventing water from traveling to necessary locations in the body.

Pure water (solely hydrogen and oxygen atoms) has a

neutral pH of 7, which is neither acidic nor basic.
Water dissolves more substances than any other liquid. Wherever it
travels, water carries chemicals, minerals, and nutrients with it.

Somewhere between 70 and 75 percent of the earths surface is

23
covered with water. Much more fresh water is stored under the
ground in aquifers than on the earths surface.
 Draw backs (or) Disadvantages of Hard
Water
Domestic Use Industrial Use

1. Washing 1. Textile Industry

2. Bathing 2. Sugar Industry
3. 3. Dyeing Industry
Drinking
4. Paper Industry
4. Cooking
5. Pharmaceutical
The sticky precipitate
adheres on the fabric/cloth Industry
and gives spots and streaks.
Fe salts stain the cloths. 6. In Steam generation in
Boilers
Produces sticky scum on
the bath tub and the body

Bad to the digestive

system and calcium
oxalate formation is
possible in urinary tracts
Requires more fuel and
time. Certains food dont
cook soft and also gives
24 unpleasant taste
 Boiler feed water
A boiler is a device for generating steam, which consists of
two principal parts:

1) The furnace, which provides heat, usually by burning a

fuel

2) The boiler proper, a device in which the heat changes

water into steam.

The steam or hot fluid is then recirculated out of the boiler

for use in various processes in heating applications.

25
 An Industrial Boiler

26
 Boiler troubles
Proper treatment of boiler feed water is an important part of operating
and maintaining a boiler system.

As steam is produced, dissolved solids become concentrated and form

deposits inside the boiler.

This leads to poor heat transfer and reduces the efficiency of the boiler.

Dissolved gases such as oxygen and carbon dioxide will react with the
metals in the boiler system and lead to boiler corrosion.

In order to protect the boiler from these contaminants, they should be

controlled or removed.

27
 Boiler troubles due to Hard
Water
1. Scale and 1.
Sludge Sludge Slimy loose
precipitate called
2. Caustic embrittlement sludge suspended in
water
3. Priming and
Foaming
4. Boiler wate
corrosion r

Boiler
wall

Sludge is a soft, loose and slimy precipitate formed within the boiler.
It can be easily scrapped off with a wire brush.
It is formed at comparatively colder portions of the boiler and collects in areas of the system,
where the flow rate is slow or at bends.
It is formed by substances which have greater solubility's in hot water than in cold water, e.g.
MgCl2, CaCl2, MgSO4 etc.,

28
 1. Scale
Hard adherent coating
on inner walls of boiler

water

Boiler
wall

Scale is formed by salts that have limited solubility but are not totally insoluble in boiler
water. These salts reach the deposit site in a soluble form and precipitate.

They are hard substances which sticks very firmly to the inner surfaces of the boiler wall.
Scales are difficult to remove even with the help of a hammer and chisel.
Deposits
29 will cause the temperature of the metal to increase until overheating, metal
softening, blistering and failure occurs
 Reasons for formation of scale

1. Presence of Ca(HCO3)2 in low pressure boilers

But in high pressure boilers it

Ca(HCO3)2 CaCO3 + H2O + is soluble by forming Ca(OH)2
CO2
Calcium bicarbonate Calcium Carbonate
2. Presence of CaSO4 in high pressure boilers
(scale)

To C Solubility of CaSO4
4. Presence of SiO2
15 3200 ppm
230 15 ppm It forms insoluble hard
Super heated water Insoluble adherent CaSiO3 and MgSiO3 as
(scale) scales
3. Presence of MgCl2 in high temperature
boilers
MgCl2 + 2 H2O Mg (OH)2 + 2HCl
Magnesium chloride scale

A low-pressure fire-tube boiler can usually

tolerate high feed-water hardness
All impurities must be removed from water
30
used in some modern, high-pressure boilers.
 Disadvantages of scale formation

1. Fuel wastage scales have low thermal conductivity

2. Degradation of boiler material and increases of risk of
accident
3. Reduces the efficiency of the boiler and- deposit on the
valves and condensers
4. The boiler may explode if crack occurs in scale

Removal of scale

1. Using scrapper, wire brush often

2. By thermal shock- heating and cooling suddenly with cold
water
3. Using chemicals 5-10% HCl and by adding EDTA

31
 Boiler pressure and permissible
limits of TDS

TOTAL DISSOLVED ALKALINIT

BOILER PRESSURE
SOLID Y
(PSI)
( TDS) (PPM)

0 - 300 3500 700

301-450 3000 600
451-600 2500 500
601-750 2000 400
751-900 1500 300
901-1000 1250 250
1001-1500 1000 200
1501-2000 750 150
ABOVE 2000 500 100

32 http://www.hacschem.com
 Thickness of scale & Fuel consumption

Thickness of scale Increases in fuel

consumption due to this
scale

1) 1/2 mm 2%

2) 1 mm 4%

3) 2 mm 6%

4) 4 mm (1/8 ") 10 %

5) 8 mm (1/4") 20 %

6) 16 mm (1/2 ") 40 %

7) 30 mm (1") 80 %

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 What problems does scale
cause?
Increased Energy Costs
The scale acts as
insulation, dramatically
reducing heating or
cooling efficiency and
adding to your energy
costs.

Increased Pumping
Costs and Wear
Scale reduces the internal
bore of pipework, which
causes impaired flow

Overheating and Hot-

Spots
Because scale is an
34 insulator, it can cause hot
 Major benefits of boiler water treatment:

Save energy losses or stabilizes fuel

consumption

Increase life of your boiler

Ensures optimum heat transfer

Reduces unnecessary shutdown / maintenance

bills

Saves frequent acid cleaning cost

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

Priming
Foamin It is the process in which some
g Normal bubble particles of liquid water are carried
along with the steam. It is then
called as wet steam and the
process of formation of wet steam
in boilers is called priming.
Priming is due to the
1. Presence of dissolved salts
2. High velocity steam due to sudden
boiling
Priming
Carry over 3. Improper boiler design
bubble
Disadvantages of Priming and
foaming

36
 II. Caustic
embrittlement

It is caused due to the presence of caustic soda (NaOH) in boiler f

water.

NaOH is introduced into water by the use of sodium carbonate

for removal of permanent hardness.

Na2CO3 + H2O 2 NaOH +

CO2

2NaOH + Fe Na2FeO2 + H2
Sodium ferroate
Treatment for caustic embrittlement

By using sodium phosphate as softening agent instead of sodium

carbonate
By adding tannin or lignin to boiler water which blocks the hair cracks
37
 Removal of foaming

By adding anti-foaming agents like castor oil

Avoiding priming

By maintaining low water levels in boilers

Controlling the boiling rate and hardness level of water
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 + 2 H2O + 2
Fe O2 Fe(OH)2
4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
38 Ferrous Rust
hydroxid
 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 D Sodium
sulphit O sulphat Water
e e feed

N2H4 + O2 N2 + 2H2O
O2 To vacuum
Hydrazin Nitroge
e n

2. By mechanical Steam
jacket

deaeration

Perforate
d plate

39 Deaerate
d water
 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 CO 2

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 +
3. Corrosion
H2O due to dissolved
salts
MgCl2 + 2 H2O Mg(OH)2 + 2HCl

Fe + 2 HCl FeCl2 + H2

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

40
 Prevention of scale
formation
Scale formation can be prevented by two methods
1. Internal conditioning or Internal Treatment
2. External conditioning or External treatment- will be discussed later

1. Internal conditioning methods - of boiler water to prevent scale

formation
1. Phosphate conditioning addition of phosphate compound
2. Carbonate conditioning addition of carbonate compound
3. Calgon conditioning addition of calgon

1. Phosphate
conditioning
Scale formation can be prevented by adding sodium phosphate to the boiler water
which reacts with the hardness producing ions and forms easily removable phosphate
salts of respective ions

3CaCl2 (Boiler water) + 2 Na3PO4 Ca3(PO4)2 + 6

NaCl
Calciu Sodium calcium phosphate
m phosphat
chlorid e (non adherent and
e can be removed by
blow down method)

41
 Phosphate compound
selection
Calcium can not be precipitated below a pH = 9.5, hence the selection of
phosphate has to be based on the pH of the boiler feed water.

NaH2PO4 (acidic in nature) ,

Na2HPO4 (weakly alkaline in
nature),
Na3PO4 (Alkaline in nature)

2. Carbonate
conditioning
CaSO4 (Boiler water) + Na2CO3 CaCO3 +
Na 2SO4
Calciu Sodium calcium carbonate
m carbonat
sulfate e (non adherent loose
sludge and can be
removed by blow
down method)

42
 3. Calgon conditioning

Na2[Na4(PO3)6
]
Calgon sodium
hexa meta
phosphate

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

2Na2SO4
Calcium Soluble
sulfate complex ion
of calcium

43
 Softening of hard water

44
 Sectors where water softening is
needed
Hospitals and Healthcare
Commercial Office Blocks and Building
Services
Hotel Water Softeners
Laundry Water Softeners
Industrial Manufacturers
Bakers and Commercial Kitchens
Industrial Food Processing
SteamBoilers
Humidification and Air Conditioning

45
 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

46
 1. Cold lime soda process

Step 1
In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are
mixed with water at room temperature and added to the hard water. The following
reactions takes place depending on the nature of hardness
Chemical reactions

If it is permanent hardness and due to calcium salt

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda) S

slimy suspended precipitate

If it is permanent hardness and due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime) L

slimy suspended precipitate

47
Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda) S
slimy suspended precipitate
 Chemical reactions contd..
If it is Temporary hardness and due to calcium salt

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O (lime) L

slimy suspended precipitate

If it is due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O (2Lime) 2L

Step 2 slimy suspended precipitates

The precipitates CaCO3 and Mg(OH)2 are very fine and forms sludge like
precipitates in the boiler water and are difficult to remove because it does not
settle easily making it difficult to filter and the removal process. Finally reduces
the efficiency of the boiler.

Therefore, it is essential to add small amount of coagulant (such as Alum,

Aluminium sulfate, sodium aluminate etc) which hydrolyses to flocculent
precipitate of Al(OH)3 which entraps the fine precipitates.

NOTE: Particles finer than 0.1 m (10-7m) in water remain continuously in motion due to electrostatic charge
(often negative) which causes them to repel each other. Once their electrostatic charge is neutralized by the use of
coagulant chemical, the finer particles start to collide and agglomerate (combine together) under the influence of
48
Van der Waals's forces. These larger and heavier particles are called flocs.
 When coagulants are added flocculation takes place followed by the
formation of flocculants.

NaAlO2 + 2H2O NaOH + Al(OH)3

Coagulant Flocculent- Gelatinous
precipitate which
entraps the fine
precipitates of CaCO3
and Mg(OH)2

Al2(SO4)3 + 3 Ca(HCO3)2 2Al(OH)3 + CaSO4 + CO2

Aluminium Hard water
sulfate sample Flocculent- Gelatinous
precipitate which
entraps the fine
precipitates of CaCO3
and Mg(OH)2

The Al(OH)3 formed by the addition of coagulants initiates the process of

flocculation and entraps the fine precipitates and becomes heavy. The
heavier flocs then settles at the bottom and filtered off easily.

49
 Continuous cold lime soda softener

Chemicals
Hard water
(soda+lime
feed
+coagulant)
feed
Softened
water
Wood fiber
filter

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2
50
 2. Hot lime soda Process

In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3 (soda) are
mixed with hot water at a temperature range of 80 to 150oC and added to the hard
water. The following reactions takes place depending on the nature of hardness

Advantages of Hot Lime Soda Process

1. The reaction between hardness producing substance and lime soda proceeds at a faster
rate
2. The precipitates and sludges formed are settled at the bottom easily and hence no
coagulants are required
3. The dissolved gases such as CO2 escapes and the water becomes free from dissolved
gases
4. It produces soft water with the residual hardness of 15-30ppm in contrast to the cold lime
soda process which produces soft water with 50-60ppm of residual hardness

Hot lime soda Plant consists of three parts

1. Reaction tank: water, chemicals and steam are mixed

2. Conical sedimentation tank : sludge settles down
3. Sand filter : complete removal of sludge from the soft water is ensured
51
 Continuous Hot Lime soda Process

Hard water feed

Super heated steam

Chemicals feed (lime
and soda)

Reaction tank
Soft water
r
dl aye
Conical sedimentation san
tank Fine laye
r
a nd
r se s
Coa
n
Precipitated sludge t io
a Gravellayer
(CaCO3, Mg(OH)2 ltr
Sludge
Fi nk
ta
outlet

Filtered soft
water

52
 Advantages of Lime soda process

1. It is very economical compared to other methods

2. Iron and manganese salts are also removed by this process
3. It increases the pH of the softened water hence corrosion is minimized
also pathogenic bacteria

Disadvantages of Lime soda process

1. Disposal of large amount of sludge (insoluble precipitates) poses a

problem
2. This can remove hardness to the extent of 15ppm which is not good for
boilers

53
 Calculation of lime and soda required for the softening of hard water by
the lime soda process

Hardness producing Chemical reaction with lime and soda What is

substance needed
(Lime (L) or
Soda (S))

Permanent Hardness
Ca Salts CaCl2 + Na2CO3 CaCO3 + 2NaCl S

Mg salts MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 L+S

CaSO4 + Na2CO3 CaCO3 +Na2SO4

Temp. Hardness
Ca(HCO3)2 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O L
Mg(HCO3)2 2L
Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

Acids
HCl L+S
2H+ + Ca(OH)2 Ca2+ + 2H2O
H2SO4
Ca2+ + Na2CO3 CaCO3 + 2Na+
L-S

HCO3-
2NaHCO3 + Ca(OH)2 CaCO3 + 2H2O + Na2CO3

54
Rules
1. When the impurities are given as CaCO3 and MgCO3 present in water it should be
considered as due to bicarbonates of calcium and magnesium respectively
2. Substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc do not contribute to hardness and
therefore, they do not consume any soda or lime and hence if these present need not be
taken in to consideration during calculation.
3. Soda (Na2CO3) neutralizes only permanent hardness

Molecular weight of lime = 74

Molecular weight of soda = 106
Molecular weight of CaCO3 = 100

Therefore, 100 parts by mass of CaCO3 are equivalent to

(i) 74 parts by mass of Ca(OH)2
(ii) 106 parts by mass of Na2CO3

55
 Students who are uncertain about what to do will
seldom perform well.

To the question, "When will we ever use this?"

there are several answers.

(1) You never know when knowledge and skills

will be useful.

(2) Whether or not you ever use this specific

knowledge is less important than the fact that
you are learning how to learn, learning the
discipline of focusing on a task, learning how
to work on a task that might not be interesting
to you--and perhaps you are learning how to
56 make such tasks interesting
 Therefore, Lime requirement for softening

= 74 T.H of Ca2++ 2 x T.H of Mg2+ + P.H of (Mg2+ + Fe2+ + Al3+) + CO2 + H+ +

100 HCO3- - NaAlO2
X Vol .of water (L)

T.H = temporary hardness

P.H = Permanent Hardness

llIly, Soda requirement for softening

= 106 P.H of (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ - HCO3- X Vol .of water (L)
100

Problem 1
Calculate the amount of lime required for softening 5,000 litres of hard water
containing 72 ppm of MgSO4 (mol wt = 120) Ans = 222g

57
 Solution
Step 1 List out the given data
Given data : Hardness 72 ppm due to MgSO4; water qty = 5000 litres; mol. wt. MgSO4 = 120

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
MgSO4 72 100/120 72 X (100/120) = 60

Step 3 calculation of lime requirement

Lime required = 74/100 (hardness due to MgSO4) x vol. of water

= 74/100 (60 mg/L) x 5000 L

= 222,000 mg
= 222 g

58
 Problem 2
Calculate the amount of lime and soda required for softening 50,000 litres of hard water containing:
MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 = 25ppm and Na2SO4 =
15ppm
Solution

Step 1 List out the given data

Given data : MgCO3 = 144 ppm, CaCO3 = 25 ppm, MgCl2 = 95ppm, CaCl2 = 111ppm, Fe2O3 =
25ppm and Na2SO4 = 15ppm

Step 2 calculate the CaCO3 equivalent

Hardness producing Quantity (ppm) Multiplication factor CaCO3 equivalent

substance hardness (ppm or
mg/L)
MgCO3 144 100/84 144 x(100/84) = 171.4
CaCO3 025 100/100 25 x (100/100) = 25.0
MgCl2 095 100/95 95 x (100/95) = 100.0
CaCl2 111 100/111 111 x (100/111) = 100.0
025 (does not cause hardness)
Fe2O3
015 (does not cause hardness)
Na2SO4
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O; Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 ; CaCl2 + Na2CO3 CaCO3 + Na2SO4

59
Step 3 calculation of lime requirement

Lime required = 74/100 ( {2 x MgCO3} + CaCO3 + MgCl2 in terms of CaCO3 eq) x vol. of water

= 74/100 (2 x 171.4 + 25.0 +100.0) mg/L x 50,000 L

= 74/100 (467.8) mg x 50,000
= 17, 309,000 mg
Answer = 17. 31 kg

Step 4 calculation of soda requirement

soda required = 106/100 ( MgCl 2 + CaCl2 in terms of CaCO3 eq) x vol. of water

= 106/100 (100 +100.0) mg/L x 50,000 L

= 106/100 (200) mg x 50,000
= 10, 6,00,000 mg
Answer = 10. 6 kg

60
 II. 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)

Why synthetic zeolite is better than natural zeolite for the

softening of water?

Micro pores of Zeolite Porous Structure of zeolite

61
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

62
 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 Ca 2+, 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

63
 Limitations of Zeolite process

1. If the water is turbid ---- then the turbidity causing particles clogs the pores of the Zeolite
and makes it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex with zeolite which can not be
regenerated that easily
3. Any acid present in water (acidic water) should be neutralized with soda before admitting
the water to the plant

Advantages of Zeolite process

1. Soft water of 10ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation in the treated water
4. It does not require more time and more skill

Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3- and CO32-
in the softened water (then it may form NaHCO 3 and Na2CO3 which releases CO2 when
the water is boiled and causes corrosion)

64 3. It also causes caustic embitterment when sodium carbonate hydrolyses to give NaOH
 How abo
ut
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ese.

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Loaded
see the n
ext guy
Tak
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&C g
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65
 For your interest

Search the web on the following topics

Working of Household water purifiers

Working model of softeners (can you do it?)

Visit Chemistry lab to use the working model of

combination of

Reverse osmosis and Demineralization method

66
 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
67
 In general the resins containing acidic functional groups (-COOH, -SO 3H etc) are capable of
exchanging their H+ ions with other cations, which comes in their contact; whereas those
containing basic functional groups ( -NH 2, =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+)
2. Anion Exchange resin (ROH-)

68
 Styrene

A small fraction of a polystyrene chain

69
Divinyl benzene (DVB)

70
71
 Structure of Cation and Anion exchange resins

Cation exchange resin Anion exchange resin

R = CH3

72
 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

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

73
Soft water
 Process of 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) R 2Cl- + 2 OH-

At the end of the process

H+ + OH- H 2O

74
 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 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
75 than 10ppm
 Strongly Acidic Cation Exchange
Resins
Functional groupsSO3H+ Sulphonic acid

SO3Na+ Sodium form, they remove hardness

(essentially calcium and magnesium) from water

SO3H+ Hydrogen form, they remove all cations

AmberjetTM1000 Na
DowexTMMarathon C
LewatitTMMonoplus S100
76
 Weakly Acidic Cation Exchange
Resins
Functional groupsCOOH Carboxylic acid

-COOH - Hydrogen form, they remove

preferentially divalent ions (e.g. calcium and
magnesium) from solutions containing
alkalinity

ExamplesAmberliteTMIRC86
DowexTMMAC3
LewatitTMCNP80

77
 Weakly Basic Anion Exchange Resins
Functional groupsN(CH3)3+OH
Quaternary ammonium
N(CH3)3+OH Hydroxyl form, they remove
all anions
N(CH3)3+Cl In chloride form, they remove
nitrate, sulphate and several other ions
Examples
AmberjetTM4200 Cl
DowexTMMarathon A
LewatitTMMonoplus M500
78
 Functional groupsN(CH3)2
Amines
cation exchange, they remove chloride,
sulphate, nitrate, and other anions of
strong acids, but they do not remove weak
acids (SiO2and
CO2)ExamplesAmberliteTMIRA96
DowexTMMarathon MWA
LewatitTMMonoplus MP64

79
 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 anions 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
a deionizer a resin bed
a
c a cc Cation exchange
resin

Demineralised
water
80
 Desalination Reverse
Osmosis

81
 Desalination - Electrodialysis

82
 Trash screens

83
 Settling base
Filter model

84
 High head tank

85
86
 Liquefaction of gases

Gases can be converted to liquids by compressing the

gas at a suitable temperature.

Gases become more difficult to liquefy as the

temperature increases because the kinetic energies of the
particles that make up the gas also increase

87
 Thecritical temperatureof a substance
is the temperature at and above which
vapor of the substance cannot be liquefied,
no matter how much pressure is applied.
Every substance has a critical temperature.

88
 Substance critical temperature(oC)
NH3 132
O2 -119
CO2 31.2
H2O 374

89