Chem Unit 1

Department of Chemistry
KPR Institute of Engineering and Technology
U21CY101
Engineering Chemistry
Unit I
Characteristics of water and its treatment
Unit – I Characteristics of Water and its Treatment
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CHARACTERISTICS OF WATER AND ITS TREATMENT

Introduction:
Water is the most important compound for the existence of human beings, animals and plants
and occupies a unique position in industries. About 75% of the earth’s surface is occupied by
water. The main sources of water are surface water- rain, rivers and lakes, sea water and
underground water- wells and springs etc.
CHARACTERISTICS OF WATER:
Unique Characteristics:
1. Water is polar in nature.
2. It is a good solvent for the ionic compounds and it dissolves almost all substances (solid, liquid
or gas). Hence, it is known as universal solvent.
3. Has High Heat capacity
4. Has High heat of vaporization
5. The density of water is maximum at 40C, which is equal to 1000 kg m-3. It is Less dense as a
solid than as a liquid
6. It exists in three states ie., solid, liquid and gas. The solid form of water is known as ice. It exists
only below 00C. It exists as a liquid between 0 and1000 C and as gas (steam) above 1000C. Hence
the boiling point of water is 1000C (373K) and freezing point is 00C (273K).
7. Pure water is a transparent, colourless, odourless and tasteless liquid.
8. Pure water is a bad conductor of electricity, but acidified water is an electrolyte.
Physical characteristics:
1. Colour: caused by metallic substances like salt of Fe, Mn, algae, weeds etc. The standard unit of
colour is that which is produced by one milligram of platinum cobalt dissolved in one litre of
distilled water. For public supplies, the colour number on cobalt scale should not exceed 20 and
should be preferably less than 10. Colour determined by an instrument is known as tintometer.
2. Turbidity: due to colloidal suspension, finely divided matters. The turbidity is measured by a
turbidity rod or by a turbidity meter with optical observations and is expressed as the amount of
suspended matter in mg/l or parts per million (ppm). For water, ppm and mg/l are approximately
equal. The standard unit is that which is produced by one milligram of finely divided silica
(fuller’s earth) in one litre of distilled water.
3. Taste: it is interlinked directly with odour.
4. Odour: due to presence of living organism, decaying vegetation.
The extent of taste or odour present in a particular sample of water is measured by a term
called odour intensity, which is related with the threshold odour or threshold odour
number. Water to be tested is therefore gradually diluted with odour free water, and the mixture
at which the detection of odour by human observation is just lost, is determined. The number of
times the sample is diluted represents the threshold odour number. For public supplies, the water
should generally free from odour, i.e. the threshold number should be 1 and should never exceed
3.
5. For potable water, temperature of about 100C is desirable. It should not be more than 250C
Department of Chemistry, KPRIET Page 2

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6. The total amount of dissolved salts present in water can be easily estimated by measuring the
specific conductivity of water..
Chemical characteristics:
1. Total Solids and Suspended Solids
Total solids (suspended solids + dissolved solids) can be obtained by evaporating a sample of
water and weighing the dry residue left on the filter paper. The suspended solid can be found by
filtering the water sample. Total permissible amount of solids in water is generally limited to 500
ppm.
2. pH value of Water
pH= - log [H+]

= log [1/ H+]
If H+ concentration increases, pH decreases and then it will be acidic. If H+ concentration

decreases, pH increases and then it will be alkaline.
[H+] + . [OH-]= . 10 -14

pH + pOH = 14 if the pH of water is more than 7, it will be alkaline and if it is less than 7, it
will be acidic.
The alkalinity is caused by the presence of bicarbonate of calcium and magnesium or by the
carbonates of hydroxides of sodium, potassium, calcium and magnesium. Some, but not all of the
compounds that cause alkalinity also cause hardness.
pH Measurement: The pH value of water can be measured quickly and automatically with the
help of a pH meter. The pH can also be measured by indicators as given below:
Permissible pH value for public supplies may range of 6.6 to 8.4.
3. Hardness of Water
Hard waters are undesirable because they may lead to greater soap consumption, scaling of
boilers, causing corrosion and incrustation of pipes, making food tasteless etc.,
Temporary Hardness: If bicarbonates and carbonates of calcium and magnesium are present in
water, the water is render hard temporarily as this hardness can be removed to some extent by
simple boiling or to full extent by adding lime to water. Such hardness is known as temporary
hardness or carbonate hardness.
Permanent Hardness: If sulphates and chlorides of calcium or magnesium are present in water,
they cannot be removed at all by simple boiling and therefore, such water requires special
treatment for softening. Such hardness is known as permanent hardness or non-carbonate
hardness. It is caused by sulphates, chlorides of Ca and Mg.
 One French degree of hardness is equal to 10mg/l of CaCO3.
 One British degree of hardness is equal to a hardness of 14.25mg/l.
 Water with hardness up to 75 ppm are considered soft and above 200 ppm are considered hard
and in between is considered as moderately hard.
 Underground waters are generally harder than surface waters.
 The prescribed hardness limit for public supplies range between 75 to 115 ppm.
4. Chloride Content

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The chloride content of treated water to be supplied to the public should not exceed a value of
about 250 ppm. The chloride content of water can be measured by titrating the water with
standard silver nitrate solution using potassium chromate as indicator.
5. Nitrogen Content
The presence of nitrogen in water may occur in one or more of the following reasons:
Free ammonia: It indicates very first stage of decomposition of organic matter. It should not
exceed 0.15mg/l
Albuminous or Organic Matter: It indicates the quantity of nitrogen present in water before the
decomposition of organic molten has started. It should not exceed 0.3mg/l
Nitrites: Not fully oxidized organic matter in water.
Nitrates: It indicates fully oxidized organic matter in water (representing old pollution).
Nitrite is highly dangerous and therefore the permissible amount of nitrite in water should be nil.
Nitrates in water are not harmful. However the presence of too much of nitrates in water may
adversely affect the health of infants causing a disease called methemoglobinemia commonly
called blue baby disease.
 The nitrate concentration in domestic water supplies is limited to 45 mg/l.
6. Metal and other chemical substances in water:
Iron – 0.3ppm, excess of these cause discolouration of clothes.
Manganese – 0.05ppm Copper – 1.3ppm Sulphate – 250 ppm
Fluoride – 1.5 ppm, excess of this effects human lungs and other respiratory organs.
Fluoride concentration of less than 0.8 – 1.0 ppm causes dental cavity (tooth decay). If fluoride
concentration is greater than 1.5ppm, causing spotting and discolouration of teeth (a disease
called fluorosis).
7. Dissolved Oxygen:
The amount of oxygen dissolved in a given quantity of water at a particular pressure &
temperature. Oxygen gas is generally absorbed by water from the atmosphere but it being
consumed by unstable organic matter for their oxidation. Hence, if the oxygen present in water is
found to be less than its saturation level, it indicates presence of organic matter and consequently
making the waters suspicious.
Significance of DO:
It supports fish & other aquatic life in river water.
Determines whether the biological change is brought about by aerobic or anaerobic micro-
organisms.
Controls river pollution.
Minimum level of DO-4 mg/lit , to support the aquatic life in good condition.
Biological Oxygen Demand

The amount of oxygen required for the biological decomposition of organic matter
present in the water. The extent of organic matter present in water sample can be estimated by
supplying oxygen to this sample and finding the oxygen consumed by the organic matter present
in water. This oxygen demand is known as Biological oxygen demand (BOD). It is not
practically possible to determine ultimate oxygen demand. Hence, BOD of water during the first
five days at 20 0C is generally taken as the standard demand. BOD 5 = BOD of 5 days= Loss of
oxygen in mg/l x dilution factor. The BOD of safe drinking water must be nil.

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Significance of BOD:
The amount of organic matter present in the river water.
Complete oxidation occurs in indefinite period, the reaction period is taken as 5 days at 20˚C.
The rate of oxidation and demand depends on the amount & type of organic matter
present in river water.
Chemical Oxygen Demand

The amount of oxygen required for chemical oxidation of organic matter using some
oxidizing agent like potassium dichromate & potassium permanganate.
Significance of COD:
It is carried out to determine the amount of pollution in river water.
Rapid process & take only 3 hours.
Dissolved Oxygen
Water usually contains about 8 ppm of dissolved oxygen per liter at room temperature. The
dissolved oxygen in water attacks the boiler material at high temperatures.
2Fe +2H2O +O2 2Fe (OH)2 ↓
Ferrous Hydroxide
4Fe(OH) 2+ O2 2[Fe2O3.2H2O]↓
Rust
Removal of dissolved Oxygen

Dissolved Oxygen can be removed from water by two methods. They are,
Chemical Method
Mechanical Method
1. Chemical Method
Sodium sulphite, sodium sulphide and Hydrazine are some of the chemicals used for removing
oxygen.
2Na2SO3+O2 2Na2SO4
Na2S +2O2 Na2SO4
N2H4+O2 N2+2H2O
Hydrazine is an ideal internal treatment chemical for the removal of dissolved oxygen. It results
with oxygen, forming nitrogen and water. Nitrogen is harmless.
2. Mechanical Method De-aeration
Dissolved oxygen can be removed from the water by mechanical de-aeration. 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 considerably reduce the oxygen content of the water.

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MECHANICAL DEAERATOR
TOTAL DISSOLVED SOLIDS

Total dissolved solids (TDS) is a measure of the dissolved combined content of
all inorganic and organic substances present in a liquid in molecular, ionized, or micro-granular
(colloidal sol) suspended form. TDS concentrations are often reported in parts per million (ppm).
Water TDS concentrations can be determined using a digital meter.
The water TDS level which is considered more suitable and acceptable for consumption without
filtration is below 300 PPM
Bacterial and Microscopic Characteristics of Water

Five types of parasitic organisms (i.e. bacteria, protozoa, viruses, worms and fungi) are generally
known to be infective to main and are found in water.
1. Bacteria
These are the minute single cell organisms possessing no defined nucleus and having no green
material to help them manufacture their own food. They are reproduced by binary fusion and
may of various shapes and sizes are 1 to 4 microns, examined by microscope. a) Non-disease
causing bacteria – Non pathogenic bacteria. b) Disease causing bacteria – Pathogenic bacteria.
2. Protozoa
These are single cell animals and are the lowest and the simplest form of animal life. They are
bacteria eaters and thus destroy Pathogens. They are counted by microscope.
3. Viruses
4. Worms
These are the larva of flies.
5. Fungi
These are those plants which grow without sunlight and live on other plants or animals, dead or
alive.

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SPECIFICATIONS OF DOMESTIC WATER (ICMR & WHO)

WHO produces international norms on water quality and human health in the form of guidelines
that are used as the basis for regulation and standard setting, in developing and developed
countries worldwide. The quality of drinking water is a powerful environmental determinant of
health. Assurance of drinking water safety is a foundation for the prevention and control of
waterborne diseases. The guidelines developed by WHO are prepared through a vast global
consultative process involving WHO member states (India is the member state), national
authorities and international agencies, in consultation with the WHO Expert Advisory Panel.
Parameters Standard limits as per WHO guidelines (mg/L)
Ammonia 1.5
Cadmium 0.003
Chloramines 0.5 - 1.5
Chloride 200 - 300
Chlorine 5
Chromium 0.05
Colour in drinking water No visible colour
Copper 2.0
Cyanide 0.07
DDT and metabolites 0.001
Dissolved oxygen No health-based guideline value is recommended
Fluoride 1.5
Iron No health-based guideline value is proposed
Lead 0.01
Manganese 0.4
Mercury 0.006
Molybdenum 0.07
Nickel 0.07
Nitrate 50
Nitrite 3
pH No health-based guideline value is proposed
Sulphate No health-based guideline value has been derived
Total dissolved solids (TDS) No health-based guideline value is proposed
Uranium 0.015

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Parameters Standard limits as per WHO guidelines (mg/L)
Zinc No health-based guideline value is proposed

Water Quality Parameter ( ICMR &WHO)
Indian standards (desirable)

Water quality Unit Analytical method
and recommended agencies
pH pH unit pH meter 6.5–8.5 (BIS/ICMR)
Turbidity NTU Turbidity meter 5 (BIS)
Dissolved oxygen mg/L DO meter 5 (ICMR)
Electrical
µs/cm Conductivity meter 300 (ICMR)
conductivity
Total dissolved
mg/L TDS meter 500 (BIS)
solid
Total suspended
mg/L Gravimetric 500 (WHO)
solid
Degree Portable
Temperature —
Celsius thermometer
Biochemical Winkler azide

mg/L 5 (ICMR)
oxygen demand method
Total hardness CaCO3 mg/L Titrimetric 300 (BIS/ICMR)
Total alkalinity CaCO3 mg/L Titrimetric 120 (ICMR)
Chloride mg/L Argentometric 250 (BIS/ICMR)
Sodium mg/L Flame photometer <20 (WHO)
Potassium mg/L Flame photometer 10 (WHO)
UV
Phosphate Microgram/L —
spectrophotometer
Lead mg/L Atomic absorption 0.05 (BIS)
Copper mg/L Atomic absorption 0.05 (BIS)
Iron mg/L Atomic absorption 0.3 (BIS)

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Zinc mg/L Atomic absorption 5 (BIS)
BIS: Bureau of Indian Standard, WHO: World Health Organization, and ICMR: Indian
Council of Medical Research.
WATER TREATMENT
The process of removing all types of impurities from water and making it fit for domestic or
industrial purposes is called water treatment or water technology.
Hardness of Water
Hardness is the property present in water which prevents lathering of soap.
Water from different sources, differ in taste and odour. This difference is due to the presence of
dissolved salts and minerals. Based on the quality, water can be classified into two types.
They are,
1. Soft water
2. Hard water.
Soft water
Water which gives good foam lather with soap solution is called soft water. This is due to the
absence of ‘Ca’and‘Mg’salts.
Hard water
Water which does not give much foam lather with soap solution is called hard water. On the
other hand, it forms a white scum or precipitate.
Reason for Hardness

The hardness of water is due to the presence of bicarbonates (HCO3-), carbonates (CO32-),
chlorides (Cl-) and sulphates (SO42-) of calcium or magnesium or both.
How to identify Hardness?
Hardness of water can be identified by two ways.
1. Reaction with soap solution.
2. Reaction with EBT indicator.
Reaction with soap solution
When, the water is treated with soap solution, if it does not give much foam lather. This water is
called hardwater.
2C17H35COONa + CaCl2 (C17H35COO)2Ca↓ + 2NaCl
Sodium stearate Calcium chloride Calcium Stearate
2C17H35COONa + MgSO4 (C17H35COO)2Mg↓ + Na2SO4

Sodium stearate Magnesium Sulphate Magnesium Stearate

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Reaction with EBT indicator

When two to three drops of EBT indicator is added to the water, if it gives wine red colour, the
water is hard water.
Classification of Hardness of water
On the basis of dissolved ions, hardness of water can be classified into two types. They are,
1. Temporary hardness (or) Carbonate hardness (or) Alkaline hardness.
2. Permanent hardness (or) Non-carbonate hardness (or) Non-Alkaline hardness.
Temporary hardness (or) Carbonate hardness (or) Alkaline hardness
If bicarbonates of Ca and Mg are present in water, such hardness is called carbonate hardness or
temporary hardness or alkaline hardness.
Removal of Temporary hardness
Temporary hardness of water may be removed by the following methods.
1. Boiling
2. Clark’s process
Boiling
When the temporary hard water is heated strongly, the following reactions take place.
Ca(HCO3)2 CaCO3 ↓ + H2O + CO2
Calcium bicarbonate Calcium carbonate
Mg(HCO3)2 MgCO3 ↓ + H2O + CO2
Magnesium bicarbonate Magnesium carbonate
Calcium bicarbonate and magnesium bicarbonate are decomposed into calcium and magnesium
carbonate. These salts are insoluble in water and settle at the bottom of the vessel. It can be
removed by filtration. The filtrate obtained, is soft water.
Clark’s process
In this process a calculated quantity of slacked lime (calcium hydroxide) is added to temporary
hardness of water. This converts the soluble bicarbonates into insoluble carbonates which are
removed by filtration. Filtered water is thus free from calcium and magnesium bicarbonates and
is soft.
Ca(HCO3)2 + Ca(OH)2 CaCO3↓ + 2H2O
Calcium bicarbonate Calcium hydroxide Calcium carbonate
Mg(HCO3)2 + Ca(OH)2 MgCO3↓ + CaCO3↓ + 2H2O
Magnesium bicarbonate Calcium hydroxide Magnesium carbonate
Permanent hardness (or) Non-carbonate hardness (or) Non-alkaline hardness

If chlorides and sulphates of Ca and Mg are present in water, such hardness is called permanent
hardness or non–carbonate hardness or non–alkaline hardness. It cannot be removed by boiling
the water, because permanent hardness producing salts do not decompose on heating.
But it can be removed by the following methods.
1. Lime–soda (washing soda–sodium carbonate) process
2. Calgon process (Internal conditioning method)
3. Zeolite or Permutit (External conditioning method) process

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4. Ion–exchange or Demineralisation or Deionisation process
Lime– soda process

When washing soda is added to hard water, the chlorides and sulphates of calcium and
magnesium are converted into their respective carbonates.
CaCl2 + Na2CO3 CaCO3↓ + 2NaCl
Calcium Chloride Sod. Carbonate Calcium carbonate
Units of hardness
The following four common units are used in hardness measurements.
1. Milligrams per litre (mg/l)
2. Parts per million (ppm)
3. Degree Clark’s (0Cl)
4. Degree French (0Fr)
Milligrams per litre
It is defined as the number of milligrams of CaCO3 present in one litre of water.
Parts per million
It is defined as the number of parts by weight of CaCO3 present in million (106) parts of water.
Degree Clark’s
It is defined as the number of parts of CaCO3 equivalent hardness per 70,000 parts of water.
Degree French
It is defined as the number of parts of CaCO3 equivalent hardness per 1,00,000 (105) parts of
water.
.
Relation between the hardness units
1 mg/lit=1ppm=0.07 0Cl =0.10F
Disadvantages of using hard water

1. Hard water when used for drinking affects the digestive system and leads to formation of kidney
stones (Calcium oxalate).
2. Hard water is not suitable for laboratory analysis because the hardness producing ions (Ca2+and
Mg2+) interface in various reactions.
3. When hard water is used for cooking, more fuel and time consumption are required. Because of
the presence of salts Ca and Mg, this increases the boiling point of water.
4. When hard water is used for steam production, the boiler affected by the problems like Scale –
Sludge formation, priming and foaming and caustic embrittlement.
5. When hard water is used for concrete making, the hydration of the cement and the strength of the
concrete are affected.
Expression of hardness in terms of equivalents of CaCO3

The concentrations of hardness producing salts are usually expressed in terms of an equivalent
amount of CaCO3.
The reason for choosing CaCO3 as the standard for calculating hardness of water is because,
 Its molecular weight is exactly 100 and equivalent weight is 50, which makes the calculations
easier.

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 It is the most insoluble salt, thus can be easily precipitated in water treatment processes.
Amount equivalent to CaCO3 = Weight of hardness producing salt or ions X Molecular
Weight of CaCO3
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Molecular Weight of hardness producing salt or ions
Molecular weight of some hardness producing salts
Hardness producing Molecular Hardness producing Salt Molecular

salt weight salt weight
Ca(HCO3)2 162 Mg(HCO3)2 146
CaCl2 111 MgCl2 95
CaSO4 136 MgSO4 120
CaCO3 100 MgCO3 84
40 24
Ca2+ Mg2+
Ca(NO3)2 164 Mg(NO3)2 148
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 turbidity, oil, dissolved gases, alkali and hardness causing substances.
If hard water obtained from natural sources is fed directly into the boilers, the following troubles
may arise.
Boiler troubles (or) disadvantages of using hard water in boilers
1. Formation of deposits (Scale and sludge) in boilers.
2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion.
Formation of deposits (Scale and sludge) in boilers.
• When water is continuously converted into steam in boilers or heat exchangers, the concentration
of dissolved salts in water increases progressively.
• When the concentration of the salts reaches their saturation point, they are thrown out in the
form of precipitates on the inner walls of the boilers or heat exchangers.
• The least soluble one gets precipitated first.

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Sludge (Loose deposit)

If the precipitate is loose and slimy it is called sludge. Sludges are formed by substances like
MgCl2, MgCO3, MgSO4 and CaCl2. They have greater solubility in hot water than cold water.
Removal of Sludge
Sludge formation can be removed by
Frequent blow down operation and
Using soft water
Disadvantages of sludge formation
 Wastage of fuel
 Decrease in efficiency and
 Danger of explosion of boiler.
Scale (Hard deposit)
On the other hand, if the precipitate forms hard and adherent coating on the inner walls of the
boiler, it is called scale. Scales are formed by substances like calcium carbonate (CaCO3),
Calcium Sulphate (CaSO4), Calcium Silicate (CaSiO3) and Magnesium hydroxide (Mg (OH)2).
Removal of Scales
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 (for CaCO3 scale), EDTA (for CaSO4 scale) with
which they form suitable complexes.
4. If the scales are loosely adhering, they can be removed by frequent blow down operation.
Disadvantages of scale formation

Wastage of fuel
Decrease in efficiency and
Danger of explosion of boiler.

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Priming and foaming

Priming
During the production of steam in the boiler, due to rapid boiling some droplets of liquid water
are carried along with steam. Steam containing droplets of water is called wet steam. These
droplets of liquid water carry with them some dissolved salts and suspended impurities.
This phenomenon is called carry over. It occurs due to priming and foaming.
The process of wet steam formation is called Priming.
Reasons for priming
Priming is due to
 Some dissolved salts
 High steam velocity and very high water level in the boiler
 Improper design of boiler and
 Sudden boiling of water etc.,
Removal of Priming
Priming can be removed by,
 Controlling the velocity of steam
 Maintaining medium water level
 Removing oily materials present in water
 Good boiler design and
 Using treated water.
Foaming
The formation of stable bubbles above the surface of water is called foaming.
Reasons for Foaming
Foaming is due to
 The presence of oil, grease and
 The presence of finely divided particles.
Removal of Foaming
Foaming can be removed by
 Adding certain anti–foaming chemicals like cotton seed oil, castor oil and synthetic polyamides
etc.,
 Adding coagulants like Sodium aluminates and aluminium hydroxide etc.,
Caustic Embrittlement
Caustic Embrittlement means inter crystalline cracking of boiler metal. It is a type of boiler
corrosion, caused by using highly alkaline water in the boiler. Boiler water usually contains
small amounts of NaHCO3 and Na2CO3. In high pressure boilers, Na2CO3 undergoes hydrolysis
to produce NaOH.
i)2NaHCO3 Na2CO3 + H2O+CO2
ii) Na2CO3+H2O 2NaOH+CO2
The NaOH thus formed flows into the minute hair cracks that are usually present in inner side of
the boiler by capillary action. As water evaporates, its concentration increases and dissolve the

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iron of boiler forming Sodium ferroate.

Fe + 2NaOH Na2FeO2+H2
This type of electrochemical corrosion occurs when concentration of NaOH is above 100 ppm.
This causes embrittlement of boiler parts particularly stressed parts like bends, joints, rivets etc.,
causing even failure of the boiler.
Removal of Caustic embrittlement
Caustic embrittlement can be avoided by
 Neutralizing the alkali with a very small quantity of acid.
 Adding tri sodium phosphate as softening agent for water.
 Adding tannin or lignin which also blocks hair cracks.
Requisites of Boiler feed water
SOFTENING OF WATER
The process of removing hardness producing substances from water is known as softening of
water.
Softening of water can be done in two methods. They are
I. External treatment(or)External conditioning method
II. Internal treatment(or)Internal conditioning method
INTERNAL TREATMENT OF BOILER FEED WATER (OR) BOILER COMPOUNDS

Internal treatment (or) internal conditioning refers to the treatment of water in the boiler itself.
This treatment consists of adding chemicals directly to the water in the boiler for removing
dangerous scale forming salts which were not completely removed by the external treatment for
water softening. These chemicals convert the scale forming substances into insoluble precipitates

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(or) soluble complexes. These chemicals are also called boiler compounds.
Some important internal conditioning methods are
(i) Phosphate conditioning
(ii) Carbonate conditioning
(iii) Calgon conditioning
(iv) Colloidal conditioning
EXTERNAL TREATMENT OF BOILER FEED WATER

In external treatment process, the hardness producing salts are removed before feeding the water
into the boiler. The external treatment process can be done by any one of the following methods.
1. Zeolite (or) Permutit process
2. Ion exchange (or) Deionization (or) demineralization process
3. Soda lime process
The above methods of softening are not only used for boiler feed water but also for domestic and
industrial use.
ZEOLITE PROCESS
Zeolite
Zeolite is hydrated sodium aluminum silicate. Its chemical formula is
Na2.O.Al2O3. XSiO2 YH2O (where X=2–10 and Y=2–6)
It is represented as Na2Ze, which is capable of exchanging reversibly its Na ions for
hardness producing ions in water. It is also known as Permutit.
Classification
They are classified into two types (a).Natural zeolites (b).Synthetic zeolites
Natural zeolites
Natural zeolites are derived from greensand. They are non–porous zeolites.
Example
Netrolite (Na2O.Al2O3.4SiO2.2H2O)
Synthetic zeolites
Synthetics zeolites are porous and gelly structure. It is prepared by heating together china clay,
feldspar and soda ash. These zeolites have higher exchange capacity per unit weight than natural
zeolites.
Process
In this process the hard water is allowed to percolate through a bed of sodium zeolite (Na2Ze).
The hardness causing ions (Ca2+andMg2+) in hard water is replaced by loosely held sodium ions
in zeolite bed.
(i) The outgoing soft water contains sodium ions.
Reaction
Na2Ze+Ca(HCO3)2 CaZe +2NaHCO3
Na2Ze+Mg(HCO3)2 MgZe +2NaHCO3

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Na2Ze+CaCl2 → CaZe +2NaCl

Na2Ze +MgCl2 MgZe+2NaCl
Na2Ze +CaSO4 CaZe+Na2SO4
Na2Ze+MgSO4 MgZe+Na2SO4
Regeneration
After the softening process, the zeolite is completely converted into calcium and magnesium
zeolites and it gets exhausted.
At this stage the hard water supply is stopped and the exhausted bed is regenerated by treating
with a concentrated (10%) NaCl (brine) solution.
CaZe + 2NaCl Na2Ze + CaCl2
MgZe + 2NaCl Na2Ze + MgCl2

Exhausted zeolite regenerated zeolite
Advantages of Zeolite process

(i) It reduces hardness up to 5 ppm.
(ii) The equipment is quite compact.
(iii) It requires less time for softening.
(iv) It requires less skill for maintenance and operation.

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(v) No impurities are precipitated, so there is no danger of sludge formation.

(vi) This method is very cheap because the regenerated permutit can be used again.
Disadvantages of zeolite process
(i) Highly turbid water cannot be treated by this method.
(ii) This process removes only the cations (Ca2+and Mg2+).
(iii) All the acidic ions like HCO3-, CO32-, Cl- and SO42-,etc., are not treated by this method, which
can cause corrosion.
(iv) Acidic water cannot be treated because it decomposes the structure of zeolite.
(v) Brackish water cannot be treated by this method.
DEMINERALIZATION (OR) DEIONIZATION (OR) ION EXCHANGE PROCESS

In this process almost all the ions (both anions (Cl-, SO42-) and cations (Ca2+, Mg2+) present in
hard water are removed. This process is also called demineralization process.
In the demineralization process, the ions present in water are removed by ion exchangers. Ion
exchange resins are insoluble; cross - linked, long chain organic polymers with a micro porous
structure, and the functional groups attached to the chains are responsible for the ion exchanging
properties. They are of two types.
Cation exchangers.
Anion exchangers.
Cation exchangers
Materials capable of exchanging cations are called cation exchangers. Cation exchanger resins
containing acidic groups (-COOH,-SO3H) are capable of exchanging their H+ ions with other
cations (Ca2+,Mg2+) of hard water.
Cation exchange resin is represented as RH2 (or) RH.
Anion exchangers
Materials capable of exchanging anions are called anion exchangers. Anion exchanger resins
containing basic groups (-NH2,-OH) are capable of exchanging their OH-ions with the other
anions of hard water.
Anion exchange resin is represented as R1(OH)2 (or) R1OH.
Process
Water is passed through a tank having cation exchanger which absorbs all the cations present in
water.
RH2+ CaCl2 RCa + 2HCl
RH2+MgSO4 RMg+H2SO4
The cation free water is now passed through another tank having anion exchanger which
absorbs all the anions present in water.
R1 (OH)2+2HCl R1Cl2 + 2H2O
R1 (OH)2+ H2SO4 R1SO4 + 2H2O
The water coming out of the anion exchanger is completely free from cations and anions
responsible for hardness. It is known as deionized water (or) demineralized water. It is as pure as
distilled water.

treatment
Regeneration
Cation exchange resins are regenerated by passing a dilute solution of HCl through them.
RCa+2HCl RH2 + CaCl2
Cation Exchange Resin
Similarly, the anion exchange resins are regenerated by passing a dilute solution of NaOH
through them.
R1Cl2+ 2NaOH R1(OH)2 +2NaCl
Anion Exchange Resin
Advantages of ion exchange process

(i) Highly acidic (or) alkaline water can be treated by this process.
(ii) This produces water of very low hardness nearly 2 ppm.
Disadvantages of ion exchange process
(i) The equipment is costly and more expensive chemicals are needed.
(ii) If water contains turbidity, then the output of the process is reduced. The turbidity must be below
10 ppm.
SODA LIME PROCESS

Lime soda process uses calcium hydroxide and soda ash as reagents. Soluble magnesium and
calcium salts are removed as calcium carbonate and magnesium hydroxide precipitates. After
removal of this precipitate, both temporary hardness and permanent hardness are removed. Before
water treatment, amount of temporary and permanent hardness is calculated and then the amount of

treatment
lime and soda ash to be added is estimated. In case of temporary water hardness the following
reactions are take places:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 → 2CaCO3 + MgCO3 + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3
In case of permanent water hardness the following reactions are take places:
CaSO4 + Na2CO3→ CaCO3 + Na2SO4
MgSO4 + Na2CO3→ MgCO3 + Na2SO4
MgCO3 + Ca(OH)2 → Mg(OH)2 + CaCO3
There are two type lime-soda process : cold lime soda process and hot lime soda process.
Cold lime soda process
In this process, the reactions take place at normal temperature. The raw water and calculated amount
of chemical mixture of Lime, soda, and coagulant are added from the top into the inner vertical
circular chamber, fitted with a vertical rotating shaft carrying a number of paddles. As the mixture of
raw water and chemicals flows down, there is a vigorous stirring and continuous mixing, where by
softening of water takes place. The heavy sludge (or precipitated floc) settles down in the outer
chamber. Cold L-S process gives water containing a residual hardness of 50 to 60 ppm. The cold
lime soda process is not suitable for all purposes. The cold lime soda process is used for municipal
water and cooling water softener systems.
Hot Lime-Soda process:
It involves in treating water with softening chemicals at a temperature of 80 to150oC. Since hot

treatment
process is operated at a temperature close to the boiling point of the solution,

(a) The reaction proceeds faster
(b) The softening capacity of hot process is increased to many folds
(c) The precipitate and sludge formed settle down rapidly and hence no coagulants are needed
(d) Much of the dissolved gases (such as CO2and air) are driven out of the water
(e) Viscosity of softened water is lower, so filtration of water becomes easier. This in-turn
Increases the filtering capacity of filters
(f) Hot lime-soda process produces water of comparatively lower residual hardness of 15 to 30 ppm
Hot lime-soda plant consists essentially of three parts:
(a) a “reaction tank” in which raw water, chemicals and steam are thoroughly mixed
(b) a “conical sedimentation vessel” in which sludge settles down
(c) a “sand filter” which ensures complete removal of sludge from the softened water.
DESALINATION
The process of removal of extra common salt (NaCl) from the water is known as desalination.
Depending up on the quantity of dissolved salts the water is graded as,
1. Freshwater
It contains less than (<) 1000 ppm of dissolved salts
2. Brackish water
It contains1000–35,000 ppm of dissolved salts

treatment
3. Seawater
It contains greater (>) than35,000 ppm of dissolved salts.
Brackish water
Water containing dissolved salts with a peculiar salty (or) brackish taste is called brackish water.
It is totally unfit for drinking purposes. Sea water and brackish water can be made available as
drinking water through desalination process.
Desalination is carried out by the following methods
 Reverse osmosis
 Electro–dialysis
 Freezing method
 Distillation method
REVERSE OSMOSIS
Osmosis
When two solutions of different concentrations are separated by a semi permeable membrane,
flow of solvent takes place from the region of low concentration to high concentration until the
concentration is equal on both the sides. This process is called osmosis. The driving force in this
phenomenon is called osmotic pressure.
Principle of reverse osmosis
If a hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration
side, the solvent flow reverse. That is solvent is forced to move from higher concentration to
lower concentration. This is the principle of reverse osmosis.
Using this method pure water is separated from sea water. This process is also known as super –
filtration (or) hyper– filtration.
Process
In this method, pressure (15 – 40 kg/cm2) is applied to the sea water to force its pure water out
through the semi permeable membrane leaving behind the dissolved salts. Earlier, cellulose

treatment
acetate membrane, cellulose butyrate membrane was used for this purpose. Now – a – days a
number of synthetic semi permeable membranes such as polyamide, polysulphones, etc., are
used.
Advantages
(i) It removes ionic, non–ionic, colloidal and high molecular weight organic matters.
(ii) It also removes colloidal silica which is not removed by demineralization process.
(iii) The process is cheap, simple and does not require skilled labour.
(iv) The maintenance cost depends on the replacement of the semi–permeable membrane, usually
once in three years.
ELECTRODIALYSIS
Principle:
Electro dialysis involves the separation of salt as ions from saline water. The process is based on
the migration of ions towards oppositely charged electrodes through ion selective membrane
under the influence of electric field.
Method
In this method, the ions (of the salt present) are pulled out of the salt water by passing direct
current, using electrodes and thin rigid plastic membrane pair (natural or synthetic).
When direct electric current is passed through saline water, the sodium ions move towards
negative pole (cathode), while the chloride ions start moving towards the positive pole (anode),
through the membrane. As a result, the concentration of brine decreases in the central
compartment while it increases in two side compartments. Pure water is removed from the
central compartment from time to time while concentrated salt is replaced by fresh brine mater in
the side compartment. For more efficient separation, ion selective membranes are employed. An
ion selective membrane has permeability for only one kind of ions with specific charge. For
example, a cation selective membrane is permeable to cations only, because of the presence of
negatively charge fixed (inside the membrane) functional groups reject anions. Similarly anion-
selective membrane has positively charged fixed functional groups.
An electro dialysis cell consists of a large number of paired sets of rigid plastic membranes.
Saline water is passed under a pressure of about 5-6 kg m-2 between membrane pairs and electric
field is applied perpendicular to the direction of water flow. The fixed positive charge inside the
anion selective membrane repel positively charged Na+ ion, yet permit negatively charged Cl-
ion to pass through. Similarly the fixed negative charge in the cation selective membrane repel
negatively charged Cl- ion, yet permit positively charged Na+ ion to pass through. Therefore
water in one compartment of the cell is deprived of salts while salt concentration in adjacent
compartments is increased. Thus, we get alternate streams of pure water and concentrated brine.

treatment
Advantages
It is most compact unit.
The operation of the unit is simple.
The cost of installation of the plant is less.

treatment
TREATMENT OF DOMESTIC WATER (OR) PURIFICATION OF WATER FOR

DRINKING PURPOSE
Drinking water
Water which is safe to drink and fit for human consumption is called drinking water. It is
otherwise called potable water or municipal water.
Essential requirements of drinking water
(i) It should be sparking clear and odourless.
(ii) It should be pleasant in taste.
(iii) It should be perfectly cool.
(iv) Its turbidity should not exceed10 ppm.
(v) It should be free from dissolved gases like H2S, CO2, NH3,etc.,
(vi) It should be free from minerals like lead (Pb), Arsenic (As), Chromium (Cr) and manganese
(Mn) salts.
(vii) It should be free from disease producing micro-organism.
(viii) It’s TDS (Total Dissolved Solids) is less than500 ppm.
(ix) pH of the drinking water should be 6.5–8.5.
The various stages in the treatment of water for domestic supply
Block Diagram
Sources of water
Screening Aeration
(Raw Water)
Sedimentation Sterilisation and

Filteration
and Coagulation disinfection
Storage and
distribution

treatment
Source of water
The main sources of water is,
(i) Surface water
(ii) Under ground water
These untreated waters are called raw water.
Screening
The raw water is passed through screens having large number of small holes, where floating
matters like wood pieces, leaves etc., are removed.
Aeration
The process of mixing water with air is known as aeration
The main purpose of aeration is,
 Increase the content of oxygen in water and makes it fresh and promotes taste.
 Remove unwanted gases like H2S, CO 2and other volatile substances.
 Salts of iron and manganese are also removed.
Sedimentation
It is the process of removing suspended impurities by allowing the water to stand undisturbed for
2-5 hours in a big sedimentation tanks about 5 m deep. Most of the suspended particles are settle
down at the bottom due to forces of gravity and they are removed. Sedimentation process
removes only 75% of the suspended impurities.
Coagulation
In sedimentation process all the impurities cannot be removed. So certain chemicals are added to
fasten the sedimentation and the process is called coagulation.
Alum [Al2(SO4)3] and sodium aluminate (NaAlO 2) are widely used in water treatment plants.
These are called coagulants.
Al2(SO4)3+3Ca(HCO3)2 2Al (OH)3 + 3CaSO4 +6CO2↑
Alum calcium bicarbonate Aluminium hydroxide
(Flocculant.precipitate)
NaAlO2 +2H2O Al(OH)3 + NaOH

ate Aluminium hydroxide(Gelatinous precipitate)
The gelatinous precipitate of Aluminium hydroxide settles to the bottom and can be removed
by filtration method.
*Salts of iron [(FeSO4, FeCl3)] are also used as coagulant.
FeSO4+ Mg(HCO3)2 Fe(OH)2↓ + MgCO3 + CO2 + SO3
Ferrous sulphate Ferrous hydroxide
4Fe (OH)2↓+ O2 + 2H2O → 4Fe(OH)3↓

Ferric hydroxide (Heavy floc)

treatment
Fe(OH)3 is in the form of heavy floc, which causes quick sedimentation.

Filtration
It is the process of removing colloidal matter and most of the bacteria, micro-organisms etc, by
passing water through a bed of fine sand and other proper-sized granular materials.
Generally filtration is carried out by using sand filter.
Sterilization (or) Disinfection

The complete removal of harmful bacteria is known as sterilization. The chemicals (or)
substances used for this purpose are called disinfectants.
This process can be carried out by the following methods.
(a) Boiling method.
(b) Ozonation (By using ozone).
(c) UV Radiation method (By using UV Radiations)
(d) Chlorination method.
 By adding chlorine gas (Cl2).
 By adding chloramines (ClNH2).
 By adding bleaching powder (CaOCl2).
 Break point chlorination (or) free residual chlorination.
Boiling method
Just boiling the water 100oC for 10 to 15 minutes, all the disease producing bacteria are killed
and water becomes safe for use.
Ozonation
Ozone (gas) is an excellent disinfectant. Ozone is produced by passing silent electric discharge
through cold and dry oxygen.
3O2 (Oxygen) 2O3 (Ozone)

treatment
Ozone (O3) is highly unstable and decomposes to give molecular and nascent oxygen [O].
O3 O2 + [O]
Ozone Nascent Oxygen
The nascent oxygen is highly powerful oxidizing agent and kills all the bacteria’s and germs. It
also oxidizes the organic matter present in the water.
Advantages
1. Ozone not only removes bacteria’s but also removes colour, unpleasant taste and bad odour.
2. If present excess in water, it is not harmful, because it is unstable and decomposes to oxygen.
Disadvantages
1. This method is expensive and cannot be employed for municipal water works.
UV Radiation method
UV rays are produced by passing electric current through mercury vapour lamp. This is
particularly used for sterilizing swimming pool water. This process is highly expensive.
Advantages
1. It effectively kills the majority of bacteria, viruses and other harmful microorganisms.
2. It does not introduce any chemicals to the water and produces no by- products.
3. It does not alter the taste, pH or other properties of the water.
Disadvantages
1. This method requires electrical connection
2. Pre filtration is a must for effective disinfection.
Chlorination Method
The process of adding chlorine to water is called chlorination. Chlorination can be done by the
following methods.
By adding chlorine gas
Chlorine (gas or liquid form) produce hypochlorous acid (powerful germicide) with filtered
water.
Cl2 + H2O HOCl+ HCl.
Hypochlorous acid
Bacteria/germs + HOCl Bacteria/germs are killed.
By adding chloramines (ClNH2)

When chlorine and ammonia are mixed in the ratio 2:1 compound chloramines is formed.
Cl2+NH3 ClNH2 + HCl
Chloramine

treatment
ClNH2+ H2O HOCl+NH3

Hypochlorous acid
Chloramine is a better disinfectant than chlorine and it gives good taste to treated water.
By adding bleaching powder (CaOCl2)
When bleaching powder is added to water, it produces hypo chlorous acid, which is a powerful
germicide.
CaOCl2 +H2O Ca(OH)2 + Cl2
Cl2 + H2O HOCl+ HCl
Hypochlorousacid
HOCl +Bacteria/ Germs Bacteria/Germs are destroyed
Hypochlorousacid
Advantages
1. This method is very effective and economical.
2. Storage requires only little space.
3. It can be used at both high and low temperatures.
4. It does not produce any salt impurities in the treated water.
Disadvantages
1. Excess chlorine when added, imparts unpleasant taste and bad odour.
2. It is effective at lower pH (below 6.5) and less effective at higher pH(>6.5).
Break point chlorination or free residual chlorination

This involves in addition of sufficient amount of chlorine to oxidize;
1. Organic matter
2. Reducing substances and
3. Free ammonia in raw water, leaving behind mainly free chlorine, which
possesses disinfecting action against pathogenic bacteria.
When the dosage of applied chlorine to water (rich in organic compounds or ammonia) is
gradually increased, the results are shown in figure. It shows the relationship between the amount
of chlorine added to water and the residual chlorine.
The addition of chlorine at the dip or break is called break point chlorination. This indicates the
point at which free residual chlorine begins to appear. Usually all tastes, odours disappear at
break point resulting in appearance of water free from bad tastes and odour.
It is seen that initially the applied chlorine is used to kill the bacterias and oxidizes all the
reducing substances present in 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 one point,
on further chlorination, the oxidation of chloramines and other impurities starts and there is a fall

treatment
in the combined chlorine content. Thus, the combined residual chorine decreases to a minimum
point at which oxidation of chloramines and other impurities complete and free residual chlorine
begins to disappear. This minimum point is known as break point chlorination.
Advantages
It oxidizes organic compounds reducing substances and free ammonia.
It removes unwanted colour from water, bad odour and taste.
Destroy completely all pathogens.
Disadvantages
Over–chlorination after BPC may lead to unpleasant taste and odour in water.
Break–Point Chlorination Curve

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Department of Chemistry

KPR Institute of Engineering and Technology

CHARACTERISTICS OF WATER AND ITS TREATMENT

Department of Chemistry, KPRIET Page 2

pH= - log [H+]

If H+ concentration increases, pH decreases and then it will be acidic. If H+ concentration

[H+] + . [OH-]= . 10 -14

Department of Chemistry, KPRIET Page 3

Biological Oxygen Demand

Department of Chemistry, KPRIET Page 4

Chemical Oxygen Demand

Removal of dissolved Oxygen

Department of Chemistry, KPRIET Page 5

TOTAL DISSOLVED SOLIDS

Bacterial and Microscopic Characteristics of Water

Department of Chemistry, KPRIET Page 6

SPECIFICATIONS OF DOMESTIC WATER (ICMR & WHO)

Parameters Standard limits as per WHO guidelines (mg/L)

Department of Chemistry, KPRIET Page 7

Parameters Standard limits as per WHO guidelines (mg/L)

Zinc No health-based guideline value is proposed

Indian standards (desirable)

pH pH unit pH meter 6.5–8.5 (BIS/ICMR)

Turbidity NTU Turbidity meter 5 (BIS)

Dissolved oxygen mg/L DO meter 5 (ICMR)

Biochemical Winkler azide

Total hardness CaCO3 mg/L Titrimetric 300 (BIS/ICMR)

Total alkalinity CaCO3 mg/L Titrimetric 120 (ICMR)

Chloride mg/L Argentometric 250 (BIS/ICMR)

Sodium mg/L Flame photometer <20 (WHO)

Potassium mg/L Flame photometer 10 (WHO)

Lead mg/L Atomic absorption 0.05 (BIS)

Copper mg/L Atomic absorption 0.05 (BIS)

Iron mg/L Atomic absorption 0.3 (BIS)

Department of Chemistry, KPRIET Page 8

Zinc mg/L Atomic absorption 5 (BIS)

Reason for Hardness

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

Department of Chemistry, KPRIET Page 9

Reaction with EBT indicator

Permanent hardness (or) Non-carbonate hardness (or) Non-alkaline hardness

Department of Chemistry, KPRIET Page 10

4. Ion–exchange or Demineralisation or Deionisation process

Lime– soda process

Disadvantages of using hard water

Expression of hardness in terms of equivalents of CaCO3

Department of Chemistry, KPRIET Page 11

Molecular weight of some hardness producing salts

Hardness producing Molecular Hardness producing Salt Molecular

BOILER FEED WATER

Department of Chemistry, KPRIET Page 12

Sludge (Loose deposit)

Disadvantages of scale formation

Department of Chemistry, KPRIET Page 13

Priming and foaming

Department of Chemistry, KPRIET Page 14

iron of boiler forming Sodium ferroate.

Requisites of Boiler feed water

INTERNAL TREATMENT OF BOILER FEED WATER (OR) BOILER COMPOUNDS