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 nature’s most wonderful,
abundant and useful compound yet is also the
most misused one”.

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Distribution of water

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 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

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 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
O2, NH3) 1) Microorganism
2) Turbidity
3) Minerals 2) Water Bodies
3) Taste
4) pH
4) Odour
5) Salinity
5) Conductivity
6) Alkalinity
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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
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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
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 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+]

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

The optimum pH for

the body fluids is
7.0

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www.chemwiki.ucdavis.edu
 MAJOR IMPURITIES OF WATER

Ionic and dissolved

Cationic Anionic Nonionic and undissolved Gases
Alkalinity

Calcium Bicarbonate Turbidity, silt, mud, dirt and CO 2

Magnesium Carbonate other suspended matter H2S
Hydroxide NH3
Sodium Color, Plankton CH 4
Potassium Sulfate Organic matter, O2
Ammonium Chloride Colloidal silica,
Iron Nitrate Microorganisms,
Manganese Phosphate Bacteria

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 Hard Water
What’s hard water?

Practically speaking, measurement of:

•Calcium (Ca) ions
•Magnesium (Mg) ions

Hardness as calcium carbonate

mg/L (ppm)

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

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 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

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 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.

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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.

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 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 stearate Hardness Calcium stearate
(sodium soap) (Insoluble)

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

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)

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 Units of Hardness
Most Commonly used
• Parts per million (ppm)
1ppm=1 part of CaCO3 equivalence hardness causing substance present in 106
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

• Degrees French (oFr)

1o Fr = 1 part of CaCO3 eq per 105 parts of water 17
 CaCO3 equivalent hardness

Mass of hardness Molecular weight

producing substance
X of CaCO3
Calcium carbonate 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 hardness = = 150 mg of CaCO3/L
136
= 150 ppm

Note : Mol. Weight of CaCO3 = 100

Mol. Weight of CaSO4 = 136

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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
MgSO4 120 100/120 or 50/60
MgCl2 95 100/95 or 50/47.5
CaCO3 100 100/100 or 50/50
MgCO3 84 100/84 or 50/42
CO2 44 100/44 or 50/22
HCO-3 61 100/61 or 50/61
OH- 17 100/17 or 50/17
CO32- 60 100/60 or 50/30

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 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.

Solution
Step 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
MgCl2 19.0 mg/L 100/95 19.0*100/95 = 20ppm
20.0*100/100 = 20 ppm
CaCO3 20 ppm 100/100
24.0*100/120 = 20 ppm
MgSO4 24.0 mg/L 100/120

Calculation

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

Tot. Hardness =71.5 ppm

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 Interesting facts about water
Roughly 70 percent of an adult’s body is made up of
water.
At birth, water accounts for approximately 80 percent of
an infant’s 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.
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 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 earth’s surface is

covered with water. Much more fresh water is stored under the 22
ground in aquifers than on the earth’s surface.
 Draw backs (or) Disadvantages of Hard Water

Domestic Use Industrial Use

1. Washing 1. Textile Industry

2. Bathing 2. Sugar Industry
3. Drinking 3. Dyeing Industry
4. Cooking 4. Paper Industry
5. Pharmaceutical Industry
The sticky precipitate adheres
on the fabric/cloth and gives
spots and streaks. Fe salts stain
6. In Steam generation in
the cloths. 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 don’t cook soft
and also gives unpleasant taste
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 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.

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An Industrial Boiler

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 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.

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 Boiler troubles due to Hard Water

1. Scale and Sludge 1. Sludge

Slimy loose precipitate
called sludge suspended
2. Caustic embrittlement in water

3. Priming and Foaming

4. Boiler corrosion water

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.,

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 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. 28
 Reasons for formation of scale

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

Ca(HCO3)2 CaCO3 + H2O + CO2 But in high pressure boilers it is

soluble by forming Ca(OH)2
Calcium bicarbonate Calcium Carbonate (scale)

2. Presence of CaSO4 in high pressure boilers

To C Solubility of CaSO4
4. Presence of SiO2
15 3200 ppm
230 15 ppm
It forms insoluble hard adherent
Super heated water Insoluble (scale) CaSiO3 and MgSiO3 as 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 used in
some modern, high-pressure boilers. 29
 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

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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
Foaming It is the process in which some particles
Normal bubble 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 3. Improper boiler design
Carry over bubble

Disadvantages of Priming and foaming

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

4 Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Ferrous Rust 32
hydroxide
 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

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

2. By mechanical deaeration Steam jacket

Perforated
plate

Deaerated 33
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 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

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 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

Calcium Sodium calcium phosphate
chloride phosphate
(non adherent and can
be removed by blow
down method)

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 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 + Na2SO4

Calcium Sodium calcium carbonate
sulfate carbonate
(non adherent loose
sludge and can be
removed by blow
down method)

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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

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 II. Caustic embrittlement

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

water.

NaOH is introduced into water by the use of sodium carbonate used

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
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Softening of hard water

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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

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 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)
slimy suspended precipitate

If it is permanent hardness and due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime)
slimy suspended precipitate

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

slimy suspended precipitate

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 Chemical reactions contd..

If it is Temporary hardness and due to calcium salt

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O (lime)
slimy suspended precipitate

If it is due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O (2Lime)
slimy suspended precipitates

Step 2

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 µm (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 influence42 of
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.

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 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
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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
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 Continuous Hot Lime soda Process

Hard water feed

Super heated steam

Chemicals feed (lime
and soda)

Reaction tank
Soft water

Conical sedimentation
tank

Precipitated sludge
(CaCO3, Mg(OH)2 Sludge
outlet

Filtered soft
water

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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

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

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

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

48
Rules
1. If treated water found to contain excess of OH- and CO32- ions these are formed from excess
equivalent each of Ca(OH)2 and Na2CO3 and hence these excess amounts should be added
to the calculation (in temp. hardness and perm. hardness)
2. 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
3. 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.
4. 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 49
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 make such tasks interesting

50
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

51
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

52
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
Fe2O3 025 (does not cause hardness)
Na2SO4 015 (does not cause hardness)

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

53
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 ( MgCl2 + 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

54
 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

55
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

56
 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

57
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 NaHCO3 and Na2CO3 which releases CO2 when
the water is boiled and causes corrosion)
3. It also causes caustic embitterment when sodium carbonate hydrolyses to give NaOH 58
59
 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

60
 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 61
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+)
2. Anion Exchange resin (ROH-)

62
 Styrene

A small fraction of a polystyrene chain

63
Divinyl benzene (DVB)

64
65
Structure of Cation and Anion exchange resins

Cation exchange resin Anion exchange resin

R = CH3

66
 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

67
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) R2Cl- + 2 OH-

At the end of the process

H+ + OH- H2 O

68
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
than 10ppm 69
 Strongly Acidic Cation Exchange Resins

– +
• Functional groups—SO 3 H Sulphonic acid

• SO3– Na+ Sodium form, they remove hardness

(essentially calcium and magnesium) from water

• SO3– H+ Hydrogen form, they remove all cations

• AmberjetTM 1000 Na
DowexTM Marathon C
LewatitTM Monoplus S100
70
 Weakly Acidic Cation Exchange Resins

• Functional groups—COOH Carboxylic acid

• -COOH - Hydrogen form, they remove preferentially

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

TM
• ExamplesAmberlite IRC86
TM
Dowex MAC3
TM
Lewatit CNP80

71
 Weakly Basic Anion Exchange Resins
+ –
• Functionalgroups—N(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
• AmberjetTM 4200 Cl
DowexTM Marathon A
LewatitTM Monoplus M500
72
• Functional groups—N(CH3)2
• Amines
• cation exchange, they remove chloride,
sulphate, nitrate, and other anions of
strong acids, but they do not remove weak
acids (SiO2 and
CO2)ExamplesAmberliteTM IRA96
DowexTM Marathon MWA
LewatitTM Monoplus MP64
73
 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
74
Trash screens

75
Settling base
Filter model

76
High head tank

77
 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
78
• The critical temperature of 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.
•

79
• Substance critical temperature(oC)
• NH3 132
• O2 -119
• CO2 31.2
• H2O 374

80