Engineering Chemistry

Unit 1: Water Treatment Sub code: CH22101

Sources of water
Water is one of the abundantly available substances in nature. Water is essential for the
survival of all living organisms. About 75% of the earth's surface is occupied by water. So, our
planet earth is also called as 'Blue planet'. Water is distributed in nature in different forms such
as;
(1) Rain water
(2) Rivers and lakes (Surface water)
(3) Wells and springs (Underground water)
(4) Sea water
Among the above sources of water, rain water is the purest form and the sea water is the
most impure form. For drinking and industrial purpose, we need water which is free from
undesirable impurities. Surface water contains suspended matters which in turn contains the
disease producing bacteria. So, they are not considered to be good for human consumption.
Underground water is clear due to the filtering action of soil. Such water is safe and fit for
human consumption.
Water treatment
The process that improves the quality of water by removing all type of impurities from
water and making it fit for domestic and industrial purpose is called water treatment.
Before studying the water treatment, we should know the nature and types of impurities
present in water.
Impurities in water
The impurities present in water may be broadly classified as follows.
a) Physical impurities
Physical impurities in water are visible particles or materials that affect the water’s
clarity, taste and other physical properties. The physical impurities are classified into two types;
➢ Suspended impurities (particles in water that are not completely soluble and make the
water appear cloudy)
They are sand, oil droplets, vegetable and animal matters which cause turbidity in water.
➢ Colloidal impurities (very fine dispersed particles and cannot be removed by standard
filtration method)
 They are finely divided silica, clay and organic waste products which imparts colour, odour
and taste to water.
b) Chemical impurities
Chemical impurities are classified in to two types;
➢ Dissolved salts
They are bicarbonates, sulphates and chlorides of Ca and Mg, carbonates and
bicarbonates of Na and K can cause water to harden.
➢ Dissolved gases
They are Oxygen, Carbon dioxide, Hydrogen sulphide, Sulphur dioxide, carbon
monoxide, etc., which makes the water acidic and thereby accelerate the rate of corrosion.
c) Biological impurities

They are fungi, bacteria, coliforms and other microorganisms which spread harmful
diseases.

HARDNESS
Hardness is the property of water which does not produce lather with soap. Hardness is
due to the presence of bicarbonates, sulphates and chlorides of calcium and magnesium.
Types of hardness
Hardness of water is classified in to two types;
1) Temporary hardness
2) Permanent hardness
Temporary hardness
Temporary hardness is caused by the presence of bicarbonates of calcium and
magnesium. This hardness can be removed by boiling.

Permanent hardness
Permanent hardness is caused by the presence of chlorides and sulphates of calcium,
magnesium, iron, aluminium and other heavy metals. This cannot be removed by boiling but it
can be removed by
➢ lime-soda process [This process works by adding lime (Ca(OH)2) and soda ash
(Na2CO3) to water]
➢ Calgon’s method [Water softening method using sodium hexameta phosphate (NaPO3)6]
 ➢ ion-exchange method [This process removes all the ions (both anions and cations)
present in the hard water] and
➢ Zeolite process [Zeolite is a crystalline solid made of silicon, oxygen and aluminium].
Units for hardness
1) milligram/litre (mg/l)
2) parts per million (ppm)
3) degree French (°Fr)
4) Clark's degree (°Cl)
Calcium carbonate (CaCO3) is used as a standard for calculating water hardness because
of its molecular weight (100) and solubility.
➢ milligram/ litre (mg/l)
It is defined as the number of milligrams of CaC equivalent hardness present per litre
of water.
➢ parts per million (ppm)
It is defined as the number of parts of CaC equivalent hardness present per million part
of water
➢ Degree French(°Fr)
It is defined as the number of parts of CaC equivalent hardness present in105 part of
water.
➢ Clark's degree (°Cl)
It is defined as the number of parts of CaC equivalent hardness present in 70,000 part
of water.
Types of water based on hardness
➢ Soft water
Soft water produces lather readily with soap solution. Has low levels of minerals and
dissolved salts and higher levels of sodium salts.
➢ Hard water
Hard water does not produce lather readily with soap solution but it produces white
precipitate. Has high levels of minerals like Ca, Mg and other dissolved salts.
ESTIMATION OF HARDNESS OF WATER BY EDTA METHOD
EDTA METHOD (Complexometric method)
EDTA means Ethylene Diamine Tetra Acetic acid.
The structure of EDTA is

Since EDTA is insoluble in water, its disodium salt is used as a complexing agent.
Principle
The amount of hardness causing ions (Ca2+, Mg2+) can be estimated by titrating water sample
against EDTA using Eriochrome-Black-T indicator at a pH of 8-10. To maintain the pH,
Ammonia buffer [NH4Cl – NH4OH] is added. Only at this pH complexation is possible.
When the EBT indicator is added to the water sample, it forms wine red coloured weak complex
with Calcium and Magnesium ions.

M2+ + EBT [M2+- EBT]

M2+= Ca2+, Mg2+ (Indicator) Unstable wine-red complex
When this solution is titrated against EDTA, it replaces the indicator from the weak
complex and form stable EDTA complex. When all the hardness causing ions are complexed by
EDTA, the indicator is set free. The colour of the free indicator is steel blue. Thus, the end point
is change of colour from wine red to steel blue.
[M2+ - EBT] + EDTA [M2+- EDTA] + EBT
(Unstable wine-red complex (Stable complex) (Indicator)
Preparation of solutions
1. EDTA solution
It is prepared by dissolving 4 grams of EDTA in 1000ml of distilled water.
2. Standard hard water
1gram of pure CaCO3 is dissolved in minimum HCl and then made up to 1000ml using
distilled water.
 1ml of standard hard water =1mg of CaCO3 Equivalent hardness
3. EBT indicator
0.5gms of EBT is dissolved in 100 ml of alcohol.
4. Buffer solution
67.5gms of Ammonium chloride and 570ml of Ammonia are dissolved and the solution is
made up to 1000ml using distilled water.

Experimental Procedure
1. Standardization of EDTA
Pipette out 50ml of standard hard water into a clean conical flask. Add 10ml of Ammonia
buffer solution and 4-5 drops of EBT indicator and titrate it against EDTA solution taken in the
burette. The end point is the change of colour from wine red to steel blue.
Let the volume of EDTA consumed be V1 ml
2. Estimation of Total Hardness of water sample
Pipette out 50ml of the given hard water sample into a clean conical flask and titrate it
against EDTA as before. Let the volume of EDTA Consumed be V2 ml
3. Estimation of Permanent Hardness of water sample
Take 100ml of same hard water sample in a 250ml beaker. Boil it for 15 minutes. During
boiling temporary hardness gets removed. Cool and filter the solution and made up to 100ml in a
standard flask by adding distilled water.
Pipette out 50ml of the made-up solution into a clean conical flask and titrate it against
EDTA as before. Let the volume of EDTA consumed be V3 ml
Calculations
1. Standardization of EDTA
1ml of Standard hard water = 1 mg of CaCO3
50ml of Standard hard water = 50 mg of CaCO3
50ml of Standard hard water consumes = V1 ml of EDTA
V1 ml of EDTA = 50 mg of CaCO3
1 ml of EDTA = 50 mg of CaCO3 equivalent hardness
V1
2. Estimation of total hardness of water sample
50ml of hard water sample consumes = V2 ml of EDTA
50ml of hard water sample = V2 x 50 mg of CaCO3 equivalent hardness
V1
1000ml of hard water sample =1000 xV2 mg of CaCO3 equivalent hardness
V1
Total Hardness = 1000 xV2 ppm
V1
3. Estimation of Permanent hardness of water sample
50ml of boiled hard water sample = V3 ml of EDTA
50ml of boiled hard water sample =V3 x 50 mg of CaCO3 equivalent hardness
V1
1000ml of boiled hard water sample =1000xV3 mg of CaCO3 equivalent hardness
V1
Permanent Hardness = 1000 xV3 ppm
V1
4. Temporary Hardness
Temporary Hardness = Total hardness - Permanent hardness
Temporary Hardness = 1000 x V2 -1000 x V3
V1 V1
Temporary Hardness = 1000 x [V2-V3] ppm
V1
BOILER FEED WATER
In industries, water is used for the generation of steam by using boilers. Water fed in to
the boiler for the generation of steam is called boiler feed water.
Requirements
1) Boiler feed water should be free from turbidity. Turbidity leads to priming and
foaming, caustic embrittlement etc.
2) Boiler feed water should be free from oiliness. It leads to priming and foaming.
3) Boiler feed water should be free from dissolved gases like O2 and CO2. It leads to
boiler corrosion.
 4) Boiler feed water should be free from hardness causing Ca and Mg salts. It leads to
wastage of fuel, loss of efficiency and boiler explosion.
Boiler Troubles
Boiler feed water should be free from impurities and hardness producing salts. If raw
water is supplied directly to the boilers, the following troubles may arise
1) Scale and sludge formation
2) Priming and foaming
3) Caustic embrittlement
4) Boiler corrosion
1) Scale and sludge formation in boilers
When water is continuously converted into steam in boilers, the concentration of
dissolved salts in water increases progressively.

Sludge
If the precipitate is soft, loose and slimy it is called sludge. Sludges are formed by
substances like MgCl2, MgCO3, MgSO4 and CaCl2. They have greater solubilities in hot water
than cold water.
Disadvantages of sludge formation
➢ Sludges are poor conductors of heat. Excess of sludge formation decreases the efficiency of
boiler.
Prevention
1. Sludge formation can be prevented by using softened water.
2. Sludges can also be removed by ''blow-down operation''.
 3. Blow-down operation is a process of removing a portion of concentrated water by fresh
water frequently from the boiler during steam production.
Scale
If the precipitate forms hard and adherent coating on the inner walls of boiler, it is
called scale. Scales are formed by substances like Ca(HCO3)2, CaSO4 and Mg(OH)2.
Disadvantages of scale formation

• Scales act as thermal insulators. It decreases the efficiency of boilers. Any crack
developed on the scale, leads to explosion.
Prevention
1. Scale formation can be prevented by dissolving it by using acids like HCl, S .
2. Scale formation can be removed by (a) External treatment.
(b) Internal treatment.
3. They can also be removed by applying thermal shocks, Scrapers, wire brush, etc.,

Some important terms

Priming: Priming happens when water droplets are carried along with steam during rapid
boiling. It can be caused by, improper boiler construction, sudden fluctuations in steam and
impurities in the boiler water
Foaming: Foaming happens when bubbles or foam form in the boiler. It can be caused by, High
concentration of solids in the boiler water such as alkalis, oils, fats, greases, organic matter and
suspended solids
Boiler explosion: Caused by a buildup of pressure in the boiler, due to low water levels, high
heat or blocked fuel lines
Caustic embrittlement: A type of corrosion caused by a high concentration of NaOH in the
boiler water.
SOFTENING OR CONDITIONING METHODS
The process of removing hardness producing salts from water is known as Softening or
Conditioning of water. It can be done in two methods
1. External treatment
2. Internal treatment
1. EXTERNAL TREATMENT
The process of removing hardness producing salts from water before feeding into the
boiler is known as external treatment of water.
Lime soda process, Zeolite process and demineralization (ion exchange) process are the
most common external water softening methods.
ION EXCHANGE OR DEMINERALISATION PROCESS
 This process removes all the ions (both anions and cations) present in the hard water. A
soft water is not demineralized water whereas demineralized water is soft water.
This process is carried out by using ion exchange resins, which are long chain, cross
linked, insoluble organic polymers with a micro-porous structure. The functional groups
attached to the chains are responsible for the ion exchanging properties.
Cation exchanger

• Materials capable of exchanging cations are called cation exchangers.

• Resins containing acidic functional groups (-COOH,-S H) are capable of exchanging
their H+ with other cations of hard water. Cation exchange resin is represented as RH2
Examples
Phenol-formaldehyde resin
Anion exchanger

• Materials capable of exchanging anions are called anion exchangers.

• Resins containing basic functional groups (-N ,-OH) are capable of exchanging their
anions with other anions of hard water. Anion exchange resin is represented as R(OH
Examples
Urea-formaldehyde resin.
Process

The hard water is passed through a cation exchanger column, which absorbs all the cations like
C ,M ,N , , etc., present in the hard water.

RH2+ CaCl2 RCa + 2HCl

RH2 + MgSO4 RMg +H2SO4
RH + NaCl RNa + HCl
The cation free water is then passed through an anion exchange column, which absorbs all the
anions like C , , etc., present in the water.

R(OH + 2HCl RCl2 + 2H2O

R(OH + H2SO4 R SO4 + 2 H2O

The water coming out from anion exchanger is completely free from cations and anions. This
water is known as demineralised water or deionised water.
Regeneration
When the cation exchange resin is exhausted, it can be regenerated by passing a solution of dil
HCl or H2SO4
RCa + 2HCl RH2 + CaCl2
RNa + HCl RH + NaCl
similarly, when the anion exchange resin is exhausted, it can be regenerated by passing a
solution of dil NaOH.

RCl2 + 2NaOH R(OH + 2NaCl

Advantages of ion-exchange process

(1) Highly acidic or alkaline water can be treated by this process.
(2) The water obtained by this process will have very low hardness (nearly 2 ppm).
Disadvantages of ion-exchange process
(1) Water containing turbidity, Fe and Mn cannot be treated, because turbidity reduces the
output and Fe, Mn form stable compound with resin.
(2) The equipment is more costly and more expensive chemicals are needed.
INTERNAL CONDITIONING (INTERNAL TREATMENT)
The removal of scale forming substances after feeding in to the boiler by adding
chemicals is called internal treatment. The chemicals added are called boiler compounds.
Types of Internal treatment
1) Colloidal conditioning [In low-pressure boilers, scale formation can be avoided by
adding organic substances like kerosene, tannin, agar-agar, etc, which get covered over the
scale forming precipitates thereby yielding loose deposits, which can easily be removed by
blow-down process]
2) Sodium aluminate conditioning
 3) Calgon conditioning
4) Phosphate conditioning
i) Sodium Aluminate Conditioning
Sodium aluminate added to the boiler water gets hydrolyzed yielding sodium hydroxide
and a gelatinous precipitate of Aluminium hydroxide as in the reaction
NaAlO2 + 2H2O NaOH + Al( OH)3
The Sodium hydroxide so formed precipitates some of the Magnesium ions of hard water as
Magnesium hydroxide.
MgCl2 + 2NaOH 2NaCl + Mg(OH)2 ↓
The flocculent precipitates of Aluminium hydroxide and Magnesium hydroxide produced
inside the boiler, entrap finely suspended and colloidal impurities and settles at the bottom.
The loose precipitate can be removed by pre-determined blow-down operation
ii) Calgon conditioning

Calgon is a sodium hexa meta phosphate N [N (P ]. Addition of calgon to boiler

water prevent the sludge and limescale formation is called Calgon conditioning. This substance
interacts with calcium ions forming a highly soluble complex and thus prevents the precipitation
of scale forming salt.

2 CaSO4+ N [N (P ] N [C (P ] + 2N SO4

The complex N [C (P ] is soluble in water and there is no problem of sludge

disposal.
DOMESTIC WATER TREATMENT

▪ Rivers and lakes are the most common sources of water used by municipalities.
▪ This water should be free from colloidal impurities, domestic sewages, industrial
effluents and disease producing bacterias.
▪ Process of removing all types of impurities from water and making it fit for domestic and
industrial purposes.
▪ It involves the following steps:
1. Screening
▪ It is a process of removing the floating materials like. leaves, wood pieces, etc. from
water.
▪ 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 a aeration. The main purpose of aeration is

• to remove gases like CO₂, H₂S and other volatile impurities causing bad taste and
odour to water
• 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.
4. Coagulation
▪ Finely divided clay, silica, etc, 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, course sand and gravel.
▪ A typical sand filter is shown in the
figure
▪ The sand filter consists of a tank
containing a thick top layer of fine
sand followed by course sand, fine
gravel and coarse gravel.
▪ When the water passes through the
filtering medium, it flows through
the various beds slowly.
▪ Bacteria are also partly removed by
this process.
6. Sterilisation or Disinfection
▪ The process of destroying the harmful bacterias is known as sterilization or disinfection.
▪ The chemicals used for this purpose are called disinfectants.
▪ This process can be carried out by the following methods.
By boiling
 When water is boiled for 10-15 minutes, all the harmful bacterias are killed and water
becomes safe for use. Disadvantages of boiling are (i) boiling alters the taste of drinking water
(ii) it is impossible to employ it in municipal water-works.
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 of this process are

(a) This process is costly and cannot be used in large scale.

(b) Ozone is unstable and cannot be stored for long time.
By using ultraviolet 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.
By chlorination
The process of adding chlorine to water is called chlorination. Chlorination can be done
by the following methods.
i)By adding chlorine gas
Chlorine gas can be bubbled in the water as a very good disinfectant.
(ii) By adding chloramine
When chlorine and ammonia are mixed in the ratio 2:1. a compound chloramine is
formed.
Cl2 + NH3 ClNH2 + HCl
Chloramine
Chloramine compounds decompose slowly chlorine. It is a better disinfectant than chlorine.
(iii)By adding bleaching powder
 When bleaching powder is added to water, it produces hypochlorous acid (HOCI). HOCI
is a powerful germicide.
CaOCl₂ + H₂O Ca(OH)₂ + Cl₂
Bleaching powder
Cl₂ + H₂O HC1 + HOCl
Hypochlorous acid
HOCl + Bacteria Bacteria are killed
Break point Chlorination
Water contains the following impurities
(i) Bacterias
(ii)Organic impurities
(iii)Reducing substances (Fe2+, H₂S, etc.),
(iv) Free ammonia
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 Fig. The graph shows the relationship between the amount of chlorine added
to water and the residual chlorine
It is seen 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.
At one point, on further chlorination, the oxidation of chloramines and other impurities
starts and there is a fall in the combined chlorine content Thus the combined residual chlorine
decreases to a minimum point at which oxidation of chloramines and other impurities complete
and free residual chlorine begins to appear this minimum point is known as "break point
chlorination"
Thus, the break point chlorination eliminates bacterias, reducing substances, organic
substances responsible for the bad taste and odour, from the water.
 DESALINATION
The process of removing common salt (sodium chloride) from the water is known as
desalination. The water containing dissolved salts with a peculiar salty or brackish taste is called
brackish water.
Depending upon the quantity of dissolved solids, water is graded as
1. Fresh water - Contains < 1000 ppm of dissolved solids.
2. Brackish water - Contains > 1000 but < 35,000 ppm of dissolved solids.
3. Sea water - Contains > 35,000 ppm of dissolved solids.
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 (RO)
When two different concentrations of solutions are separated by semipermeable membrane, the
solvent is flow from lower Concentration to higher concentration is called osmosis.
The driving force in this
phenomenon is called osmotic
pressure. If a hydrostatic pressure in
excess of osmotic pressure is applied
on the higher concentration side, the
solvent flow is reversed i.e., solvent
flows from higher concentration to
lower concentration. This process is
called reverse osmosis.
Thus, in the process of reverse osmosis pure water is separated from salt water. This process is
also known as super-filtration. The membranes used are cellulose acetate, cellulose butyrate
etc.
Advantages
(i) The life time of the membrane is high, and it can be replaced within few minutes.
(ii) It removes ionic as well as non-ionic, colloidal impurities.
(iii) Due to low capital cost, simplicity, low operating, this process is used for converting sea
water into drinking water.
 Solar desalination method
Solar desalination is a process that uses solar energy to separate salt from saline water, producing
fresh water that can be used for drinking and irrigation. The process is similar to natural rain,
using evaporation and condensation.
There are two main types of solar desalination systems: direct and indirect:
Direct solar desalination
Uses solar energy directly to heat and evaporate saline water, leaving behind salt and other
impurities. A solar still is an example of a direct solar desalination system, where the sun's
energy is trapped to produce fresh water through evaporation and condensation.
Indirect solar desalination
Uses solar energy to power a desalination system, such as multi-stage flash distillation or reverse
osmosis. Solar collectors can capture and transfer solar energy to saline water, or photovoltaic
panels can convert solar radiation into electricity to power the desalination process.
Solar desalination is an area of rapid
technological advancement, especially for
small-scale use in remote locations.
Materials
Stainless steel is the most common material
used in desalination plants, but titanium is
ideal because it doesn't corrode in saltwater.
Benefits
Solar desalination systems are:

• Affordable: They can save up to 70% on

water expenses.
• Sustainable: They use abundant resources
from the sun and sea, and don't use fossil
fuels.
• Easy to operate: They can be automated and remotely monitored.
Applications
Solar desalination systems can be a sustainable solution to water scarcity in areas with limited
access to water, such as remote areas and countries with arid conditions.