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CY3151 ENGINEERING CHEMISTRY

UNIT I – WATER & ITS TREATMENT
INTRODUCTION
Water is the most important compound essential for the survival of all living
organisms. About 80% of the earth’s surface is covered by water. Besides being a
supporter of life, water plays a unique role in industries. Water is used in the power
generation industry for the production of the electric current through steam
generation. It is also used as a coolant in nuclear power plants and chemicals plants.
Water is widely used in other fields such as production of steel, atomic energy,
textiles, irrigation, etc.
The process of removing of all types of impurities from water and making it
fit for domestic or industrial purposes is called water technology or water
treatment.

SOURCES OF WATER
The main sources of water are
 Surface water
 Underground water
 Sea water
Impurities

1. Physical impurities
(a) Suspended impurities like sand, oil droplets, vegetable and animal matter, impart
turbidity to water.
(b) Colloidal impurities like finely divided silica, clay and organic waste products impart
colour, dour and taste to water.

2. Chemical impurities
(a) Dissolved salts like bicarbonates, sulphates and chlorides of Ca and Mg and
carbonates, bicarbonates of Na and K.
Dissolved Mg and Ca salts in water cause "hardness" whereas alkali salts (bicarbonates,
carbonates of K and Na and bicarbonates of Ca & Mg) make the water "alkaline".
(b) Dissolved gases like O, CO2, H2S, SO2 make the water "acidic". So they accelerate the
rate of corrosion.

3. Biological/Bacterial impurities like fungi, bacteria and other microorganisms cause

diseases.
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WATER QUALITY PARAMETERS

The quality of water is a very important parameter to be determined in order to decide the
type of application or treatment required. The quality of water varies to place to place and
seasons.
The following are some important parameters of quality of water.

Water Quality Parameters

Colour, Odour, Turbidity, pH, Hardness, Alkalinity, TDS, COD and BOD,
Fluoride and Arsenic

COLOUR
Colour is a shade imparted by organic or inorganic material, which change
the appearance of the water. Colour is found mostly in surface water. The colours of
natural water range from pale straw through yellowish-brown to dark brown. The colour
of natural waters is mainly due to the presence of dissolved or colloidal organic or
inorganic materials.
Sources
1. Organic sources : Algae, tannins, humic compounds, organic dyes, etc.
2. Inorganic sources: Fe and Mn compounds, chemicals and inorganie dyes from various
industries.
Significance
1. The colours and the materials which produce colour are often objectionable in
which the water and the manufactured product come into contact.
Ex.: Dyeing, scouring and laundering

2. Variation in colour of water from the same source with time serves as index of
quality of the water.
Ex: (a) Yellowish tinge - indicates the presence of 'Cr and organic matter.
(b) Yellowish red - indicates the presence of iron.
(c) Red-brown - indicates the presence of peaty matter.
Removal of colour
Colour and colour producing materials are removed by coagulation, settling, adsorption
and filtration.
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TASTE AND ODOUR

Taste
Taste is the sensation of flavour perceived in the mouth and throat on
contact with a substance.

Odour
Odour is a smell (or) scent caused by one (or) more volatilized chemical
compounds that are generally found in low concentration.
Sources:
Organic sources: Algae and decaying vegetation, etc.
Inorganic sources: Mercaptans, amines and sulphides, etc.
The tastes and odours observed in chlorinated waters are due to chloro-organic
compounds formed by the reaction between chlorine and organic matter present in the
water.
How to Evaluate the Odour?
It is impossible to isolate and identify clearly the odour causing materials. Evaluation of
dour depends on the olfactory senses of the testing person and on his ability to
distinguish between different types of odours.
Significance
1. Disagreeable odours and tastes are objectionable for various industrial processes
such as food products, beverages, textiles, paper, pulp. Most of the odours in
natural waters are organic in nature, except H2S.
2. Taste helps us to decide what to eat and influences how efficiently we digest these
foods.
3. Senses of smell and taste are vital in identification of valuable nutrients in the
environment.
4. Taste enables the evaluation of foods for toxicity.

Removal of Tastes and Odours

(i) Organic tastes and odours may be removed by aeration (or) activated carbon treatment.
(ii) Inorganic tastes due to HyS (or) Iron may be removed by chemical methods like
oxidation, chlorination (or) precipitation.
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TURBIDITY

Turbidity is the reduction of clarity of natural water due to the presence of finely
divided, insoluble impurities suspended in water.
Sources
I. Inorganic sources
Clay, silt, silica, ferric hydroxide, calcium carbonate, sulphur, etc.
2. Organic sources
Finely divided vegetable or animal matter, oils, fats, greases, micro-organisms, etc.,

Problems Caused by Turbidity

(i) Presence of turbidity and sediments in boiler water and cooling water system cause
problems.
(ii) Water-softening processes cannot be carried out.
(iii) Due to deposition of these organic impurities, disinfection efficiency gets reduced

Significance
(i) Turbidity affects the taste and odour of drinking water.
(ii) As turbidity affects the disinfection process, it must be removed.
(iii) Turbidity have many negative effects on aquatic life, it block light to aquatic plants,
aquatic organisms.
(iv) Turbidity affects the growth rate of algae.
(v) It increases water temperature because suspended particles absorb more heat.

Removal of Turbidity and Sediments

Turbidity of water may be removed by sedimentation followed by
(a) Coagulation and filtering
(b) Coagulation and settling
(c) Coagulation, settling and filtering.

Example
1. Turbidity caused by suspended silt and mud is objectionable in boilers and in
cooling-water systems.
2. Turbidity caused by colloidal or dissolved organic matter will interfere with water-
softening processes.
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pH
The hydrogen ion concentration is represented by the pH value, which is defined as
pH = -log10 [H+]
pH is defined as negative logarithm of hydrogen ion concentration.
The pH value ranges from 0-14 as
0 7 14
Acidic Neutral Basic

• Generally pH of natural waters lies in the neutral range.

• For drinking water recommended pH = 6.5 to 8.5.
• For irrigation recommended pH = 6.0 to 9.0.
• Some surface waters passing over areas rich in sodium and potassium posses
alkaline pH.
• The rain water contaminated by the dissolved gases such as SOx and NOx will have
acidic pH.

Significance of pH
(i) pH determines the solubility (amount that can be dissolved in water).
(ii) It also determines the biological availability (amount that can be utilized by aquatic life).
(iii) A rise (or) fall in pH can indicate chemical pollution (or) acid rain. Many animals cannot
live in water at a pH level below 5 (or) above 9.

HARDNESS OF WATER
Hardness is the characteristic property of water which “prevents the lathering of soap”.
This is due to the presence of certain salts of calcium, magnesium and other
heavy metals dissolved in water.

How to detect hardness?

When a sample of water is treated with soap solution, if it does not produce
lather, but forms a white scum or precipitate, the water contains hardness.
This is due to the formation of insoluble soaps of calcium and magnesium.
C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl
Sodium stearate Hardness causing Calcium stearate (Soap)
substance (insoluble soap)
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TYPES OF WATER
On the basis of hardness, water can be classified into two types:
 Hard Water and Soft Water
HARD WATER
Water which does not produce lather easily with soap solution, but forms a white
precipitate, is called hard water.
SOFT WATER
Water which lathers easily with soap solution, is called soft water.
It does not contain dissolved calcium and magnesium salts.

TYPES OF HARDNESS
 Hardness is classified into two types based on dissolved salts present in water.
They are: Temporary Hardness (or) Carbonate Hardness (CH)
 Permanent Hardness (or) Non-Carbonate Hardness (NCH)

TEMPORARY HARDNESS
Temporary Hardness is due to the presence of dissolved bicarbonates of calcium
and magnesium. Thus the salts responsible for temporary hardness are Ca(HCO3)2
and Mg(HCO3)2.
Temporary hardness is otherwise known as Carbonate Hardness (or) Alkaline
Hardness.
Temporary Hardness can be removed by following two processes:
 Boiling of water
 Adding lime to the water

Boiling of water
Ca(HCO3)2 CaCO3 + H2O + CO2
Mg(HCO3)2 Mg(OH)2 + 2CO2
Adding lime to the water
Mg(HCO3)2 + 2 Ca (OH)2 Mg(OH)2 + 2 CaCO3 + 2H2O
Lime
The above two processes convert the bicarbonates into insoluble carbonates and
hydroxides, these are removed by filtering.
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PERMANENT HARDNESS
Permanent hardness is due to the presence of dissolved chlorides and sulphates of
calcium and magnesium. The salts responsible for permanent hardness are CaCl2,
MgCl2, CaSO4 and MgSO4.
Permanent hardness cannot be removed by boiling.
It can be removed by the following two processes:
 Lime – soda process
 Zeolite process

Lime-soda process:
CaCl2 + Na2CO3 CaCO3 + 2NaCl
(Soda)

Zeolite process:
CaSO4 + Na2Ze Ca-Ze + Na2SO4
Sodium Zeolite
Permanent Hardness is otherwise known as Non-Carbonate Hardness (NCH) (or) Non –
alkaline Hardness.

TOTAL HARDNESS
Total hardness = Temporary Hardness + Permanent Hardness

ALKALINITY
Alkalinity of water is a measure of its acid-neutralising ability. The natural
alkalinity in waters is imparted by the hydroxides, carbonates and bicarbonates.
Sources
1. Hydroxides, carbonates and
Industries like fertilizer,
bicarbonates of alkali metals, detergent, leather and paint.
borates, silicates, phosphates.

Significance
1. Very high values of alkalinity are harmful to aquatic organisms.
2. Alkalinity in boiler feed water causes caustic embrittlement of pipes.

Removal of Alkalinity
Alkalinity in water, can be removed by adding limited amount of HC1.
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TDS
TDS stands for Total Dissolved Solids. It is defined as the measure of all
inorganic and organic substances present, in water.
Significance
(i) TDS impacts the salinity of water.
(ii) TDS in water may not be ideal for your health and must be filtered out before
intake.
(iii) Water with TDS level higher than 300 ppm may not be potable as it can taste salty.
(iv) Water with high level of TDS (>1200) impacts the color, odour and taste
dramatically.
(v) Water with high level of TDS may not be suitable due to excessive scaling caused by
it in water pipes, heaters, boilers and household appliances,

FLUORIDE
Fluoride is found in ground water as a result of dissolution from geologic
formulations. Surface waters generally contain much smaller concentration of fluoride.

Sources
Fluoride containing minerals - Fluorapatite [Ca10 F2 (PO4)6],
Cryolite (Na3AlF6) and igneous rocks containing fluosilicates.

Contaminated domestic sewage, run-off from agricultural lands - Phosphate fertilizers

Significance
1. Optimum fluoride concentrations, prescribed in public water supplies, are in the
range of 0.7 to 1.2 mg / lit.
2. Beneficial health effects have been observed where the fluoride levels are optimum.
3. If the fluoride concentration is low in drinking water it causes dental caries in
children.
4. If the fluoride concentration is high it causes fluorosis.

Removal of fluoride (Defluoridation)

1. Precipitation using aluminum salts in alkaline media.
2. Using strongly basic anion exchange resin.
3. By adsorption on activated carbon.
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ARSENIC
Arsenic is a metallic element that forms a number of poisonous compounds.
It is found in nature at low levels, mostly in compounds, with oxygen, chlorine and sulfur.
Source
Arsenic can get into drinking water from natural deposits (or) runoff from agriculture,
mining and industrial processes.
Significance
(i) Long-term intake of arsenic contaminated water leads to arsenic poisoning with
cancer of skin, bladder, kidney.
(ii) Association of arsenic contaminated water produces diabetes, hypertension and
reproductive disorders.
(iii) Children may have more exposure to arsenic in drinking water. As a result,
children may be at greater risk of illness when higher levels of arsenic are present.

CHEMICAL OXYGEN DEMAND (COD)

COD is defined as, the measure of amount of oxygen required to chemically
oxidise all the oxidisable impurities, present in the sewage using an oxidising
agent like acidified K2Cr2O7.
Significance of COD
(i) Determination of COD is carried out only in 3 hours, but determination of BOD is carried
out after 5 days.
(ii) It measures both the biologically oxidisable and biologically inert organic matter.
(iii) COD test is used to monitor water treatment plant efficiency.
(iv) COD is used to measure pollutants in water, waste water and aqueous hazardous
wastes.
(v)It provides an index to assess the effect of discharged waste water on the environment.

BIOLOGICAL/BIOCHEMICAL OXYGEN DEMAND (BOD)

BOD is defined as, "the amount of free oxygen required by bacteria for the
biological oxidation of the organic matter under aerobic conditions at 20°C for a
period of 5 days".
Significance of BOD
(i) It indicates the amount of decomposable organic matter present in the sewage.
(ii) It enables us to determine the degree of pollution at any time in the sewage stream
(iii) Lesser the BOD, better is the quality of water. ie. sample with BOD >3ppm is
considered as pure water, whereas the water, < 4 ppm is considered as polluted water.
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TREATMENT OF WATER FOR DOMESTIC SUPPLY (or) MUNICIPAL WATER TREATMENT

Rivers and lakes are the most common sources of water used by municipalities. These
water should be free from colloidal impurities, domestic sewages, industrial effluents and
disease producing bacterias. Hence domestic supply of water involves the following stages
in the purification processes.

Sources of Screening Aeration

Water

Sedimentation Coagulation Filtration

Sterilisation
(or)
Disinfection

I Primary Treatment

1. Screening
It is a process of removing the floating materials like, leaves, wood pieces, etc. from
water. The raw water is allowed to pass through a screen, having large number of holes,
which retains the floating materials and allows the water to pass.

2. Aeration
The process of mixing water with air is known as aeration. The main purpose of
aeration is:
(i) to remove gases like CO2, H2S and other volatile impurities causing bad taste and
odour to water.
(ii) to remove ferrous and manganous salts as insoluble ferric and manganic salts.

3. Sedimentation
It is a process of removing suspended impurities by allowing the water to stand
undisturbed for 2-6 hours in a big tank. Most of the suspended particles settle down at
the bottom, due to forces of gravity, and they are removed. Sedimentation removes only
75% of the suspended impurities.
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4. Coagulation
Finely divided clay, silica, etc. do not settle down easily and hence cannot be removed
by sedimentation. Such impurities are removed by coagulation method.
In this method certain chemicals, called coagulants, like alum, Al2(SO4)3 etc., are
added to water. When the Al2(SO4)3 is added to water, it gets hydrolysed to form a
gelatinous precipitate of Al(OH)3. The gelatinous precipitate of Al(OH)3 entraps the finely
divided and colloidal impurities, settles to the bottom and can be removed easily.

5. Filtration

It is the process of removing bacteria, colour, taste, odour and suspended particles,
etc., by passing the water through filter beds containing fine sand, coarse sand and
gravel. typical sand filter is shown in the figure 1.1.
The sand filter consists of a tank containing a thick top layer of fine sand followed by
coarse sand, fine gravel and coarse gravel. When the water passes through the filtering
medium, it flows through the various beds slowly. The rate of filtration decreases slowly
due to the clogging of impurities in the pores of the sand bed. When the rate of filtration
becomes very slow, the filtration is stopped and the thick top layer of fine sand is
scrapped off and replaced with clean sand. Bacterias are also partly removed by this
process.
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II. Sterilisation (or) Disinfection

The process of destroying the harmful bacterias is known as sterilisation or

disinfection. The chemicals used for this purpose are called disinfectants. This process
can be carried out by the following methods.

1. By using ozone
Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly
unstable and breaks down to give nascent oxygen.
O3 O2 + [O]
The nascent oxygen is a powerful oxidising agent and kills the bacterias.
Disadvantages
(a) This process is costly and cannot be used in large scale.
(b) Ozone is unstable and cannot be stored for long time.

2. By using ultraviolet (UV) radiations

UV rays are produced by passing electric current through mercury vapour lamp. This
is particularly useful for sterilizing water in swimming pool.
Disadvantages
(i) It is costly.
(ii) Turbid water cannot be treated.

3. By chlorination
The process of adding chlorine to water is called chlorination. Chlorination can be
done by the following methods.

(a) By adding chlorine gas

Disinfection is done by addition of liquid chlorine or gaseous chlorine.
Chlorine gas can be bubbled in the water as a very good disinfectant.
Chlorine produces hypochlorous acid [HOCl] which kills microorganisms.
Cl2+H2O→HCl+HOCl
HOCl→ H+ +OCl-
HOCl → Kills Germs
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(b) By adding chloramine

When chlorine and ammonia are mixed in the ratio 2:1, a compound chloramines
(NH2Cl) is formed.
Cl2+NH3 → NH2Cl+HCl
Chloramine compounds decompose slowly to give chlorine. It is a better disinfectant than
chlorine.

(c) By adding bleaching powder (CaOCl2)

When bleaching powder is added to water, it produces hypochlorous acid (HOCI).
HOCI is a powerful germicide.
CaOCl2+H2O → Ca(OH)2 + Cl2↑
Cl2 +H2O → HCl + HOCl
HOCl → Kills Bacteria, Germs
Limitations:
(i) It is unstable, difficult to store
(ii) It introduces calcium in water which increases hardness of water when used in excess.

Break Point Chlorination

Chlorine may be added to water directly as a gas or in the form of bleaching powder.
When chlorine is applied to water, the results obtained can be depicted graphically in the
following. The graph shows the relationship between the amount of chlorine added to
water and the residual chlorine. It is observed from the graph that initially the applied
chlorine is used to kill the bacterias and oxidises all the reducing substances present in
the water and there is no free residual chlorine.

As the amount of applied chlorine increases, the amount of combined residual

chlorine also increases. This is due to the formation of chloramine and other chloro
compounds.
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





• It is observed from the graph that initially the applied chlorine is used to kill the
bacteria and oxidises and the reducing substances present in the water and there is no
free residual chlorine.
• As the amount of applied chlorine increases, the amount of combined residual chlorine
also increases.
• This is due to the formation of chloramines and other chloro compounds.
• At particular point, on further chlorination, the oxidation of chloramines and other
impurities starts and there is a fall in the combined chlorine content.
• Break point chlorination is the point at which the combined residual chlorine
decreases to a minimum point where oxidation of chloramine and other
impurities complete and free residual chlorine begins to appear.
• Thus, the break point chlorination eliminates bacterias, reducing substances, organic
substances responsible for the bad taste and odour from the water.
Advantages: Break point chlorination gives idea of amount of chlorine required to add
for chlorination. It,
i) oxidizes completely organic matter, NH3 and reducing agents,
ii) removes colours and odour in water,
iii) destroys completely all the disease producing bacteria,
iv) prevents if any growth of weeds in water.
Disadvantages:
If excess chlorine is added it leave residual or free chlorine which impart bad taste and
odour. Dechlorination must be done in order to remove free chlorine.
Dechlorination: Dechlorination is done by passing SO2 & sodium sulphite (Na2SO3).


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DESALINATION OF BRACKISH WATER

Water containing high concentration of dissolved salts or solids of peculiar salty or

brackish taste is called brackish water. The sea water contains about 3.5% of
dissolved salts. Before the removal of these salts, it is unfit for most of the domestic
and industrial applications.
The process of removing common salt (sodium chloride) from the brackish or saline
water is known as Desalination or Desalting.
Salinity of water is expressed in ppm or mg/L.

Based on the quantity of dissolved salts present, water is graded as:

 FRESH WATER It contains less than 1000 ppm of dissolved salts.
 BRACKISH WATER It contains above 1000 and below 35,000 ppm of dissolved salts.
 SEA WATER It contains above 35,000 ppm of dissolved salts.

Sea water and brackish water can be made available as drinking water through
desalination process. Desalination is carried out either by reverse osmosis or electro
dialysis

REVERSE OSMOSIS
When two solutions of different concentrations are separated by a semi-
permeable membrane, solvent molecules flow from a region of lower concentration
(dilute) to higher concentration side. This process is called Osmosis. The driving
force in this phenomenon is called Osmotic pressure.
If a pressure higher than that of osmotic pressure is applied on the concentrated
side, solvent flow reverses. That is the solvent molecules pass from concentrated side
to dilute side through the membrane. This phenomenon is called Reverse Osmosis.
Using reverse osmosis, pure solvent (water) is separated from salt water. This
membrane filtration is also called Super Filtration or Hyper Filtration.
The membranes consist of very thin film of cellulose acetate and cellulose
butyrate. Polymers like polymethacrylate and polyamide of superior quality are also
being used.
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METHOD:
In this process, pressure of about 15 to 40 kgcm-2 higher than that of osmotic
pressure is applied to sea water so that pure water is forced to move through
semi permeable membrane to pure water side. The membrane consists of very
thin films of cellulose acetate.

ADVANTAGES:

 It removes ionic as well as non-ionic and colloidal impurities.

 Life time of the membrane is high (2 - 3 years) and it can be replaced within few
minutes.
 Maintenance cost is less.
 Capital cost is low and operation is simple.
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BOILER FEED WATER

• The water fed into the boiler for the production of steam is called boiler feed water.
• Boiler feed water should be free from dissolved salts, suspended impurities,
silica, turbidity, oil, alkali and hardness producing substances.

BOILER TROUBLES (OR) BOILER PROBLEMS (OR)

DISADVANTAGES OF USING HARD WATER IN BOILERS
Presence of impurities in boiler feed water may lead to the following problems:
 Sludge and scale formation
 Priming and foaming (carry over)
 Caustic embrittlement
 Boiler corrosion

SLUDGE AND SCALE FORMATION IN BOILERS:

When water is evaporated in boilers to produce steam continuously,
concentration of the dissolved salts present in water increases progressively.

• When the concentration of the salts reaches their saturation point, they are
thrown out of water in the form of precipitates on the inner walls of the boilers.
• The least soluble one gets precipitated first.
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SLUDGE:
• If the precipitate formed inside the boiler is soft, loose and slimy it is known as sludge.
• Sludges are formed by substances like MgCO3, MgCl2, MgSO4 and CaCl2.
• They have greater solubility in hot water than cold water.
Disadvantages:
• Sludges are poor conductors of heat which results in wastage of fuel.
• Excess of sludge formation decreases the efficiency of boiler (i.e.) it disturbs the
functioning of boiler.
Prevention:
• Sludge formation can be prevented by using softened water.
• It can be removed by “blow down operation”. It is a process of removing a portion of
concentrated water frequently from the boiler during steam production.

SCALE:
• Scales are hard deposits formed by the evaporation of hard water in boilers.
• If the precipitate forms a hard and adherent coating on the inner walls of the boiler,
it is known as scale.
• Scales are formed by substances like Ca(HCO3)2, CaSO4 and Mg(OH)2.

S.No Sludge Scale

1 Sludge is a loose, slimy and Scale is a hard, adherent coating
non adherent precipitate
2 The main sludge forming substances The main scale forming substances
are MgCO3, MgCl2 , MgSO4 and CaCl2 are Ca(HCO3)2, CaSO4, Mg(OH)2
etc
3 Disadvantages: Sludges are poor Disadvantages: Scales act as
conductors of heat. Excess of sludge thermal insulators. It decreases the
formation decreases the efficiency of efficiency of boiler. Any crack
boiler. developed on the scale, leads to
explosion.
3 Prevention Prevention
(i) Sludge formation can be prevented (i) Scale formation can be
by using softened water. prevented by dissolving using
acids like HCl, H2SO4
(ii) Sludges can also be removed by
“blow-down operation”. (ii) Scale formation can be
removed by (a) External treatment.
(b) Internal treatment.
(iii) Blow-down operation is a process (iii) They can also be removed by
of removing a portion of concentrated applying thermal shocks, scrapers,
water by fresh water frequently from wire brush, etc
the boiler during steam production.
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DISADVANTAGES OF SCALE FORMATION

1. Wastage of fuel
Scale have low thermal conductivity, so the heat transfer from boiler to inside water
is not efficient. In order to provide steady supply of heat to watt, overheating is done
and this causes wastage fuel. The wastage of fuel depends on the thickness and
nature of the scale, which is shown in the table.

Thickness of scale(mm) 0.325 0.625 1.25 2.5 12

Wastage of fuel 10% 15% 50% 80% 150%

2. Decrease in efficiency
Scales sometimes deposit in the valves and condensers of the boiler and choke.
This results in decrease efficiency of the boiler.

3. Boiler Explosion
Sometimes due to overheating the thick scales may crack and causes sudden
contact of high heated boiler material with water. This causes formation of a large
amount of stem and high pressure is developed which may lead to explosion.

Prevention of scale formation

1. At the initial stage, scales can be removed using scraper, wire brush etc.
2. If scales are brittle, they can be removed by thermal shocks.
3. By using suitable chemicals like dil.acids, EDTA with which form suitable complexes.
4. If the scales are loosely adhering, they can be removed by frequent blow down
operation.

PRIMING
Priming is the process of production of wet steam. Priming is caused by
(i) High steam velocity.
(ii) Very high water level in the boiler.
(iii) Sudden boiling of water.
(iv) Very poor boiler design
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Prevention
Priming can be controlled by
(i) Controlling the velocity of steam.
(ii) Keeping the water level lower.
(iii) Good boiler design.
(iv) Using treated water.

FOAMING

The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried over by steam leading to excessive priming.

Foaming is caused by the

 presence of oil, and grease,
 presence of finely divided particles.

Prevention
Foaming can be prevented by
(i) adding coagulants like sodium aluminate, aluminium hydroxide,
(ii) adding anti-foaming agents like synthetic polyamides.

CAUSTIC EMBRITTLEMENT (INTERCRYSTALLINE CRACKING)

Caustic embrittlement means intercrystalline cracking of boiler metal.

Boiler water usually contains a small proportion of Na2CO3 .
In high pressure boilers this Na2CO3 undergoes decomposition to give NaOH.

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

This causes brittlement of boiler parts, particularly stressed parts like bends, joints,
rivets, etc., causing even failure of the boiler.
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Prevention
Caustic embrittlement can be prevented by
(i) using sodium phosphate as softening agent instead of sodium carbonate.
(ii) by adding tannin, lignin to the boiler water, which blocks the cracks.

BOILER CORROSION
 Corrosion in boilers is due to the presence of
1. dissolved oxygen.
2. dissolved carbon dioxide.
3. dissolved salts.

1. Dissolved oxygen
Dissolved oxygen in water is mainly responsible for the corrosion of boiler. The dissolved
oxygen in water attacks the boiler material at higher temperature.

Removal of dissolved oxygen

Dissolved oxygen can be removed by chemical or mechanical methods.

(a) Chemical method

Sodium sulphite, hydrazine are some of the chemicals used for removing dissolved
oxygen.

Hydrazine is found to be an ideal compound for removing dissolved oxygen in the water,
since the products are water and inert N2 gas.

(b) Mechanical de-aeration

Dissolved oxygen can also be removed from water by mechanical deaeration
In this process, water is allowed to fall slowly on the perforated plates fitted inside the
tower. The sides of the tower are heated, and a vacuum pump is also attached to it.
The high temperature and low pressure produced inside the tower reduce the dissolved
oxygen content of the water.
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2. Dissolved carbon dioxide

 Dissolved carbon dioxide in water produces carbonic acid, which is acidic and corrosive
in nature

 Carbon dioxide gas is also produced from the decomposition of bicarbonate salts
present in water.

Removal of dissolved Carbon dioxide

(a) Carbon dioxide can be removed from water by adding a calculated amount of NH 4OH
into water.
(b) Carbon dioxide along with oxygen can also be removed mechanically by de-aeration
method. (similar to oxygen removal method)

3. Dissolved Salts
 Acids, produced from salts dissolved in water, are also mainly responsible for the
corrosion of boilers.
 Salts like MgCl2, CaCl2, etc, undergo hydrolysis at higher temperature to give HCl,
which corrodes the boiler.

Removal of acids by neutralization

Corrosion by acids can be avoided by the addition of alkali to the boiler water.
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SOFTENING (OR) CONDITIONING METHODS

Water used for industrial purposes (for steam generation) should be free from
dissolved gases and salts, hardness producing substances, suspended impurities,
etc. The methods of removing hardness producing salts from water are known as
water softening or conditioning.
Water Softening can be done by the following two methods:
 Internal conditioning (or) treatment
 External conditioning (or) treatment

INTERNAL CONDITIONING OR INTERNAL TREARMENT OR

BOILER COMPOUNDS
This method involves the removal of scale forming substances and corrosive chemicals
in water, which were not completely removed in the external treatment, by adding
suitable chemicals directly inside the boiler. These chemicals are called boiler
compounds.

i. PHOSPHATE CONDITIONING

Scale formation in high pressure boilers can be avoided by adding sodium phosphate.
The added phosphate reacts with calcium and magnesium salts to produce soft
sludges of calcium and magnesium phosphates.
3 CaSO4 + 2 Na3PO4 Ca3(PO4)2 + 3 Na2SO4
3 CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl
3 MgCl2 + 2 Na3PO4 Mg3(PO4)2 + 6 NaCl
3 MgSO4 + 2 Na3PO4 Mg3(PO4)2 + 3 Na2SO4
Three types of phosphates are employed in phosphate conditioning. They are:
 Trisodium phosphate (Na3PO4)
 Disodium hydrogen phosphate (Na2HPO4)
 Sodium dihydrogen phosphate (NaH2PO4)
The optimum pH for the precipitation of Ca3(PO4)2 is 9.5 to 10.5. The exact choice of the
phosphate salt depends upon the alkalinity of boiler feed water.
 Trisodium phosphate (Na3PO4)
When the alkalinity of boiler feed water is low, it has to be raised to 9.5-10.5 for this
highly alkaline phosphate is preferred. Na3PO4 is highly alkaline, used for strong acidic
water.
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 Disodium hydrogen phosphate (Na2HPO4)

When the alkalinity of boiler feed water is already sufficient for precipitation,
Na2HPO4 is preferred. Na2HPO4 is weakly alkaline, used for weakly acidic water.
 Sodium dihydrogen phosphate (NaH2PO4)
When the alkalinity of boiler feed water is too high, acidic phosphate is preferred. It
reduces the pH to the optimum range. NaH2PO4 is acidic, used for alkaline water.

ii. CALGON CONDITIONING

When calgon (Sodium hexa meta phosphate Na2[Na4(PO3)6] ) is added to boiler water, it
interacts with calcium ions forming a highly soluble complex and thus prevents the
precipitation of sludge and scale forming salts.
2 CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2 Na2SO4
The complexNa2 [Ca2(PO3)6] is soluble in water and there is no problem of sludge disposal.

iii. COLLOIDAL CONDITIONING

Scale formation can be avoided by adding colloidal containing agents like kerosene,
agar – agar, gelatin, etc., It is used in low pressure boilers. These colloidal substances
get coated over the sale forming particles and converted them into non-adherent, loose
precipitate called sludge, which can be removed by blow down operation.

iv. SODIUM ALUMINATE CONDITIONING

Sodium Aluminate (NaAl2O3) undergoes hydrolysis in boiler water to give gelatinous
white precipitate of aluminium hydroxide and sodium hydroxide.
NaAl2O3 + 2H2O Al(OH)3 +NaOH

The sodium hydroxide, thus formed, precipitates magnesium as magnesium hydroxide.

The gelatinous precipitates of aluminum hydroxide and magnesium hydroxide entrap the
colloidal silica and finely divided solids and settled easily. This can be removed easily by
blow down operation.
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EXTERNAL CONDITIONING
External conditioning method involves the removal of hardness causing salts
from the water before feeding into the boiler.
External treatment can be done by:
 Demineralization or ion-exchange process
 Zeolite or Permutit process
 Lime soda process

DEMINERALISATION (OR) ION-EXCHANGE PROCESS

This process removes both cations and anions present in the water. The soft
water produced by lime-soda and zeolite process, does not contain hardness
causing ions Ca2+ and Mg2+, but it may contain other ions like Na+, K+, SO42-, Cl-,
etc. On the other hand, demineralized water (D.M. water) does not contain both
cations and anions. Thus, a soft water is not demineralized water whereas a
demineralized water is soft water.
This process involves the use of ion-exchange resins for softening water.
Ion-exchange resins are insoluble, cross-linked, long chain organic polymers with
micro-porous structure. The functional groups attached to the chains are
responsible for the ion-exchanging properties.

There are two types of ion-exchange resins namely:

 Cation exchange resins and
 Anion exchange resins.

 Cation Exchange Resins:

 Resins capable of exchanging the cations from hard water are called cation
exchange resins.
 It contains acidic functional groups like – COOH,-SO3H or H+ , which can replace
their H+ ions with the cations of hard water.
 It can be represented as RH+ (or) RH2.
Examples:
 Sulphonated coals
 Sulphonated polystyrene
 Phenol formaldehyde resin
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 Anion Exchange Resins:

 Resins capable of exchanging the anions from hard water are called anion
exchange resins.
 It contains basic functional groups like -NH2,-NR3 or OH- , which can
replace their OH- ions with the cations of hard water.
 It can be represented as R‟OH- (or) R‟ (OH)2.
Examples:
 Methyl ammonium hydroxy styrene
 Cross-linked quaternary ammonium salts.
 Urea formaldehyde resin

PROCESS OF DEMINERALISATION:
The hard water is passed first through cation exchange column (containing cation
exchange resins, RH+). All the cations such Ca2+, Mg2+, Na+, K+, etc. present in hard
water are exchanged with H+ ions of the cation exchange resin. That is, it removes all
the cations from hard water.

The water leaving the cation exchange column is now passed through anion exchange
column (containing anion exchange resins, R’OH). All the anions such as Cl-, SO42-,
HCO3-, etc. present in the water are exchanged with OH- ions of anion exchange
resins. So that all the anions are removed from water.
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Thus, the water coming out of the anion exchange column is completely free from
hardness causing cations and anions. This ion free water is known as demineralized
water (or) deionized water.

Regeneration

When all the H+ and OH- ions of the ion exchange columns are exhausted, the ion
exchange resins have to be regenerated.
The exhausted cation exchange column is regenerated by passing dilute HCl or dilutes
H2SO4 through the column. The washing containing Ca2+, Mg2+, etc. is passed to sink.

Similarly the anion exchange column is regenerated by passing dilute NaOH through
the column. Then washing containing SO42-, Cl- , etc. is passed to sink.

The regenerated ion exchange resins are then used again.

Advantages:
 This method produces soft water of very low residual hardness
 Highly acidic and alkaline water can be treated by this process.
 Regeneration of ion-exchange resin is possible.
 Maintenance cost is less.
 No sludge disposal problem arises.

Disadvantages:
 Cost of the equipment is high.
 Highly turbid waters cannot be treated. Turbidity should be less than 10 ppm.
 Expensive chemicals are required.
 Water containing turbidity, Fe and Mn cannot be treated, because turbidity
reduces the output as it blocks the pores and Fe and Mn form stable compound
with the resin which cannot be regenerated.
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ZEOLITE (OR) PERMUTIT PROCESS

 Zeolites are naturally occurring hydrated sodium aluminosilicate. It general
formula is Na2.Al2O3.xSiO2.yH2O (x=2-10, y=2-6).

 Natural zeolite are green sand and non-porous. The synthetic form of zeolite is
known as permutit, which is porous and possess gel like structure, hence it is
generally used for water softening.

 Synthetic zeolite is represented by Na2Ze are replaced by Ca2+ and Mg2+ ions present in
the water.

PROCESS
When hard water is passed through a bed of sodium zeolite (Na2Ze), kept in a cylinder,
it exchanges its sodium ion with Ca2+ and Mg2+ ions present in the hard water to form
Ca2+ and Mg2+ zeolites. The various reactions taking place during softening process are
CaCl2 + Na2Ze CaZe + 2NaCl
MgCl2 + Na2Ze MgZe + 2NaCl
Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3
CaSO4 +Na2Ze CaZe + Na2SO4
MgSO4 + Na2Ze MgZe + Na2SO4

Zeolite process
The softened water is enriched with large amount of sodium salts, which do not cause
any hardness, but cannot be used in boilers.
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Regeneration
After some time zeolite gets exhaust. The exhausted zeolite is again regenerated by
treated with 10% solution of NaCl.
CaZe + 2NaCl Na2Ze + CaCl2
MgZe + 2NaCl Na2Ze + MgCl2
Advantages:
 Water obtained by this process will have only hardness of 1-2 ppm.
 This method is cheap, because the regenerated zeolite can be used again.
 No sludge is formed during this process.
 The equipment used is compact and occupies a small space.
 It operation is easy.

Disadvantages
o Turbidity water can’t treated, because it blocked the porous of zeolite bed.
o Acidic water can’t treated, because it decomposes the structure of zeolite.
o The softened water contains more dissolved sodium salts like NaHCO3, Na2CO3, etc.
o When such water is boiled in boiler, CO2 and NaOH is produced resulting in
boiler corrosion and caustic embrittlement.
o Water containing Fe, Mn can’t be treated, because regeneration is very difficult.
o This process can’t be used for softening brackish water, because brackish water
contains Na+ ions.
o The ion exchange reaction will not occur.

Differences between Zeolite and Demineralisation process

S.No. ZEOLITE DEMINERALISATION

1. It exchanges only cations. It exchange cations as well as
anions
2. Acidic water cannot be treated Acidic water can be treated.
because acid decomposes the
zeolite.
3. The treated water contains The treated water does not
relatively large amount of dissolved contain any dissolved salts.
salts, which leads to priming, Hence there is no priming and
foaming and caustic foaming.
embrittlement in boilers.
4. Water containing turbidity, Fe, Mn Here also water containing
cannot be treated turbidity, Fe, Mn cannot be
treated.
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