Water

• Sources of Water:
Water on earth is classified as surface water & ground water.

1. Surface water includes:

a. Rainwater: Purest form of water obtained from natural evaporation & condensation. So,
rainwater when reaches to earth it dissolves gases like 𝐶𝑂2 , 𝑆𝑂2 & 𝑁𝑂2 etc. & carries
suspended solid particles with it.
b. River Water: River gathers water from rain, springs & glaciers. When water flows over
earth surface it dissolves soluble minerals from soil so, river water thus contain salts like
chlorides, Mg, Fe etc. They also contain some organic matter derived from plant & animal
bodies,
c. Lake Water: This is the water stored above earth’s surface. The water obtained is generally
of good quality & directly used for domestic & industrial purposes. Lake water contains
lower quantities of dissolved salts or minerals than well water.
d. Sea Water: Most impure form of natural water Bcoz Rivers throw all the impurities carried
with water into sea. It generally contains dissolved NaCl.

2. Underground Water: A part rain water which reaches earth surface or water from rivers percolates
into the earth. This water travels downward & during the flow of it, it comes in contact with various
mineral salts present in soil & dissolves some of them. Water continues to flow downward till it
meets the mouth in the form of spring.

The underground water is suitable for domestic use Bcoz it is filtered through soil layers. The water
from wells & springs contains more hardness Bcoz of dissolved salts.

• Impurities in Water:

1. Dissolved Solids: It includes Na, K, Mg, Ca, 𝑁𝐻3 , Fe, Al, Cl, N, Bicarbonates etc.
2. Suspended Impurities: It includes inorganic clay & sand particles which makes water turbid.
3. Colloidal Impurities: Finely divided clay, Silica-Al salts, Ferric hydroxides, organic waste matter,
complex protein, amino acids etc. Particles size smaller than suspended particles.
4. Bacterial Impurities: Bacteria, micro-organisms & other forms of animals produced bacteria. They
are diseases causing germs or viral.

• Types of Water:
1. Soft Water
2. Hard Water
 1. Soft Water: Water which does not contain any of the Ca or Mg salts dissolved in it. It may
contain salts like Na & K dissolved in it. It forms lather or foam with soap.
2. Hard Water: Water containing the dissolved salts of Ca & Mg is called Hard Water. Due to the
presence of these salts hard water cannot produce good lather or foam with soap.

• Hardness in water:
It is that characteristic property of water which prevents the lathering of soap. AA soap is generally a
Na-salt of long chain fatty acids. The soap consuming capacity of water is mainly due to the reaction of
hardness causing Ca & Mg ions with soap. They form insoluble salt of Ca & Mg soaps which do not
have detergent value.

2𝐶17𝐻35 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝑎𝐶𝑙2 → {𝐶17𝐻35 𝐶𝑂𝑂}2 𝐶𝑎 + 2𝑁𝑎𝐶𝑙

Soap Impurities Insoluble salt

in water

2𝐶17 𝐻35𝐶𝑂𝑂𝑁𝑎 + 𝑀𝑔𝑆𝑂4 → {𝐶17 𝐻35 𝐶𝑂𝑂}2 𝑀𝑔 + 2𝑁𝑎2 𝑆𝑂4

• Types of Hardness:
1. Temporary Hardness
2. Permanent Hardness

1. Temporary Hardness: It is the hardness developed in water due to presence of dissolved

bicarbonates of Ca & Mg i.e (𝐶𝑎(𝐻𝐶𝑂)3 )2 & (𝑀𝑔(𝐻𝐶𝑂)3 )2.

The temporary hardness is mostly removed by just boiling of water. Due to boiling of water the
bicarbonates are decomposed & formation of the insoluble Carbonates or Hydroxides takes place
which settles at the bottom & 𝐶𝑂2 gas is evolved out as vent gas.

Heat
(𝐶𝑎(𝐻𝐶𝑂)3 )2 → 𝐶𝑎𝐶𝑂3 + 𝐶𝑂2 ↑

Insoluble
Carbonates
settles down

(𝑀𝑔(𝐻𝐶𝑂)3 )2 → 𝑀𝑔(𝑂𝐻)2 ↓ + 𝐶𝑂2 ↑

 2. Permanent Hardness: It is the hardness due to the presence of chlorides, sulphates of Ca & Mg
& other heavy metals.

The hardness developed due to chlorides & sulphates or salts other than bicarbonates can’t be
removed by boiling. It requires some chemical process or treatment to remove some chemical
process or treatment to remove these salts that is why it is called permanent hardness.

• Units of Hardness & their inter-relations:

The conc. of hardness is expressed in terms of equivalent amount 𝐶𝑎𝐶𝑂3. The choice of 𝐶𝑎𝐶𝑂3 is due
to its molecular weight is 100 & equivalent weight is 50 & also it is insoluble in water & can be easily
precipitated.

Units of Hardness are:

a. 1ppm → 1 part of 𝐶𝑎𝐶𝑂3 equivalent hardness for million parts of water
b. 1mg/lt → 1mg of 𝐶𝑎𝐶𝑂3 equivalent in 1lt
c. 1°𝐶𝑙 (°𝐶𝑙𝑎𝑟𝑘𝑒) → 1 part of 𝐶𝑎𝐶𝑂3 equivalent to 70000 parts of water
d. 1°𝐹𝑟 (°𝐹𝑟𝑒𝑛𝑐ℎ) → 1 part of 𝐶𝑎𝐶𝑂3 equivalent to 105 parts of water

Inter-relations of hardness unit is:

1ppm = 1mg/lt = 0.07°𝐶𝑙 = 0.1°𝐹𝑟

• Estimation of hardness by EDTA method:

• Conditions for Boiler Feed Water & Water Boiler Problems:
Since Boilers are operated at elevated temp. & press., water treatment is more demanding than for
cooling services.

Constituents as ppm 𝑊𝑎𝑡𝑒𝑟 𝑎 𝑊𝑎𝑡𝑒𝑟 𝑏 𝑊𝑎𝑡𝑒𝑟 𝑐

P- alkalinity (𝐶𝑎𝐶𝑂3 ) 0 0 0
M- alkalinity (𝐶𝑎𝐶𝑂3 ) 30 235 120
Chloride (Cl) 25 11 48
Calcium(𝐶𝑎𝐶𝑙3) 19 144 135
Mg 9 96 53
Hardness(𝐶𝑎𝐶𝑂3 ) 28 240 188
Phosphate(𝑃𝑂4 ) 1 1 1
Sodium(Na) 17 5 29
Silica(𝑆𝑖𝑂2 ) 6 6 7
Sulfate(𝑆𝑂4 ) 7 8 84
Nitrate(𝑁𝑂3 ) 5 5 307
TDS 75 250 307
Suspended Solids 40 50 50
pH(25°𝐶) 6.7 7.8 7.5

These guidelines issued in 1975 by ASME research committee for water in thermal power system. They
are somewhat conservative & may be exceeded with careful operation & monitoring.

Water absorbs more heat for a given temp. than any other inorganic substance. It expands 1600 times as
it evaporates to form steam at atm. press. The steam is capable of carrying large qty. of heat. These
unique properties of water make it an ideal raw material for power generating processes. Since water
 impurities cause boiler problems careful considerations must be given to the quality of water used for
generating steam.

i. Water-Boiler Problems:
1) Scale & Sludge problems
2) Priming & Foaming
3) Carryover
4) Boiler corrosion
5) Caustic Embrittlement

➢ Iron & Copper conc. & hardness limit control deposition in the boiler.
➢ The silica limit prevents excessive volatile silica conc. of the steam.
➢ The alkalinity & conductivity limits prevent steam conc. caused by foaming.

1) Scale formation:
When hard water is evaporated in the boiler the soluble salts of Ca & Mg along with other
soluble impurities as silica & aluminium comes in form of residue. This residue settle inside the
boiler & the layer of this residue on metal surface of the boiler is called scales.

• Effects of scales: These scales are hard & bad conductor of heat so when scales are formed,
much heat is lost unnecessarily & regular supply of steam is stopped. But if regular steam is
maintained then extra heat will be given & hence extra fuel will be required. So there will be
wastage of fuel. The wastage depends upon the thickness of scale.

Thickness of scale (cm) Wastage of fuel (%)

0.83 9
0.166 12-16
0.33 20
0.67 60

By giving extra fuel in order to maintain the regular supply of the steam, the boiler is overheated
which may cause following effects:
a. By applying extra fuel, the boiler material which separate water from scale, will be overheated &
may become softer & softer. So, when it will be red hot, the outer surface of it will quickly
combine with atmospheric oxygen & converted into iron oxide. The inner red hot surface may
also react with steam & converted into oxide.

3 𝐹𝑒 + 4 𝐻2 𝑂 → 𝐹𝑒3 𝑂4 + 4𝐻2

The iron oxide the formed is non-adherent, comes down as sludge. So, life of boiler is shorten.
b. By overheating boiler, there will be unnecessary strain on plates and tubes & rivets will be
damaged.
c. Overheating due to unequal coeff. Of expansion, the scale gets cracked. The boiler water will at
once comes in contact of red hot plates of boiler where scale is cracked & will be converted into
 steam with it results that there may be sudden rise of press. Inside the boiler which may result to
dangerous explosion.

• Removal of Scale: Simple & easier method to remove the scale is by use of scraper, knife blade
or a piece of wood. If the scale is brittle, it can be removed by mechanical or thermal shock. The
thermal shock consists of heating of metal & scale & then cooling it suddenly with cold water
the result that it is easily removed.

If the scale is somewhat hard, it can be removed by using some chemical reagent depending
upon the composition of the scale i.e., 𝐶𝑎𝐶𝑂3. Sulfate scales can be removed by use of 5-15 % as
it is readily soluble.

2) Corrosion:
Water containing various impurities is responsible for the inner surface corrosion of boiler. The cause of
corrosion depends upon nature of dissolved substances in water. The dissolved gases such as 𝑂2 , 𝐶𝑂2 ,
𝐻2 𝑆 & other organic matter.

With the presence of these salts, boiler plates & tubes are corroded & then life of the boiler is reduced.

• Causes of Corrosion:

Among dissolved gases, oxygen is most corroding. For boiler operating at high temp, even small
amt. of dissolved oxygen creates a serious corrosion problem.

𝐶𝑂2 is also responsible for the corrosion of boiler material. 𝐶𝑂2 when dissolved in water, behaves as
an acid due to the formation of Carbonic acid.

𝐶𝑂2 + 𝐻2 𝑂 → 𝐻2 𝐶𝑂3

The acid thus formed slowly attack over the metal which is then corroded.

Water containing dissolved 𝐻2 𝑆 is also responsible for corrosion as 𝐻2 𝑆 is very soluble in water.
Water containing dissolved 𝐻2 𝑆 behaves as weak dibasic acid. The corrosion action depends upon
the dissolved 𝐻2 𝑆 content.

• Corrosion due to dissolved salts:

Dissolved salts in water play an important role in the of boiler material. The chlorides of Ca, Mg are
readily hydrolyzed to give acids, which slowly attack the inner surface of boiler & thus reduce the
life of boiler. Magnesium chloride is hydrolyzed to produce HCl acid.

𝑀𝑔𝐶𝑙2 + 𝐻2 𝑂 → 𝑀𝑔(𝑂𝐻)𝐶𝑙 + 𝐻𝐶𝑙

 𝑀𝑔(𝑂𝐻)𝐶𝑙 + 𝐻2 𝑂 → 𝑀𝑔𝑂𝐻2 + 𝐻𝐶𝑙

The HCl acid thus formed reacts on metal of boiler.

𝐹𝑒 + 2𝐻𝐶𝑙 → 𝐹𝑒𝐶𝑙2 + 𝐻2

𝐹𝑒𝐶𝑙2 + 2𝐻2 𝑂 → 𝐹𝑒(𝑂𝐻)2 + 𝐻𝐶𝑙

• Prevention of Corrosion:

1) Degasification: It means the complete removal of dissolved gases such as 𝑂2 , 𝐶𝑂2 , 𝐻2 𝑆 from
water.
2) Chemical Degasification: It consists of use of chemicals to remove gases.
i. Removal of 𝑶𝟐 : It is removed by addition of sodium sulfate(𝑁𝑎2 𝑆𝑂4 ) which combines
with oxygen.
𝑁𝑎𝟐 𝑆𝑂𝟒 + 𝑂𝟐 → 2𝑁𝑎𝟐 𝑆𝑂𝟒
Reaction is very quick at higher temp. & in presence of excess sulfite. This method has a
drawback that it inc. the salt content of water.

Oxygen can also be removed by the action of hydrazine hydrate without any inc. in salt
content of water.
𝑁2 𝐻4 + 𝑂2 → 2𝑁𝑎 + 𝐻2 𝑂
The reaction is quick. However the excess of hydrazine hydrate inc. the pH value of
water.

ii. Removal of 𝑪𝑶𝟐 : It is converted to ammonium carbonate by adding ammonia.

𝐶𝑂2 + 2𝑁𝐻3 + 𝐻2 𝑂 → (𝑁𝐻4 )2 𝐶𝑂3

3) Priming & Foaming

• Priming: It is the phenomenon of very rapid boiling of water inside the boiler which results that
the water particles mixed up with steam. The priming is influenced by following factors:
I. Due to presence of large quantity of dissolved organic oily matter, alkalies &
suspended materials etc.
II. It is also caused due to defective design of boiler & wrong operation. If the steam
gets condensed in outer tube, the press. Outside the boiler in this tube may be
decreased which results water inside the boiler to jump & passes with steam
outside the boiler.
III. Priming also starts when level of water rise due to foaming. So priming is
generally associated with foaming.
• Foaming: It is the phenomenon of formulation of foam or bubbles on the surface of water.

• Disadvantages of priming & foaming:

I. The actual height of water in boiler is not judged.

 II. Wastage of height with the result that it becomes difficult to keep up steam press. & thus
efficiency is lower.
• Prevention of priming & foaming:
Priming and foaming may be prevented by following methods:
i. They can be prevented to some extent by controlling the conc. of impurities inside the
boiler. This is done by complete change of water. This is called blow down of boiler.
ii. They can be reduced by keeping the water level as low as possible.
iii. The addition of antifoam agents is also satisfactory method for foaming. The agents are
easier oil, Gallic acid, tannic acid, cotton oil, tartaric acid, citric acid, etc.

4) Caustic Embrittlement:
It may be regarded as a type of boiler corrosion that is caused by alkaline water in boiler. This
type of corrosion takes place in boiler which operates under high press. When water is soften by
Lime-soda process some free 𝑁𝑎2 𝐶𝑂3 remained in minute amount in soften water decompose in
high press. Boiler & NaOH & CaO are formed as per the reaction.
𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐶𝑂2

The Caustic soda (NaOH) so formed makes the water in boiler alkaline & this alkaline water is
responsible for what is known as Caustic Embrittlement. The NaOH containing in water flows
into the minute hair cracks which are present inner side of boiler Bcoz of capillary action. As a
result of evaporation of water in the boiler conc. of NaOH goes on inc. & this conc. caustic soda
attacks the surrounding areas of the boiler made of iron as a result sodium ferroid is formed &
causes Embrittlement of boiler parts such as joints, bends & other stressed parts.

• Prevention methods:
Caustic Embrittlement may be prevented by:
i. Using Sodium Phosphate as a softening agent in place of 𝑁𝑎2 𝐶𝑂3.
ii. Blocking the hair cracks of boiler unit by adding lignin.
iii. By adding Sodium phosphate to water which also block hair cracks.

5) Carryover:
It is a mechanical entrainment of non-volatile solids caused by incomplete steam/water
separation in the upper drum of the boiler. It results from excessive
i. Dissolved salts for alkalinity in the boiler.
ii. Excessive steam generation or sudden change in rate.

The higher the boiler press., the more frequent the entrainment problems Bcoz of the small
density difference between liq. & vapour & the higher steam release rate per unit of steam drum
area.
 Scale Sludge`
Scale is sufficiently dense deposit which occur Sludge is freeable loose deposit obtained from
on the heating & cooling surface capable of settling, deposition, accumulation & thickening
disturbing the normal operation boiler of suspended substance form with water

• Water softening process: It is the removal of Ca, Mg & certain other metal cations from hard water.
It is usually achieved using lime softening or ion exchange resins. The process of decreasing the
hardness is called softening of water. It involves decreasing the conc. of Ca & Mg salts in water.

a. Preboiling of 𝑯𝟐 𝑶: Generally 𝐻2 𝑂 feed to boilers is passed through heat exchangers & it is reboiled.
During preboiling the dissolved gases are removed. The bicarbonates of Ca & Mg causing the temporary
hardness are decomposed to insoluble carbonates & are removed from 𝐻2 𝑂.
Boiling
Ca(HCO3 )2 → CaCO3 + H2 O + CO2
Mg(HCO3 )2 → MgCO3 + H2 O + CO2

Mass of hardness producing subs. ∗ Chemical equi. of CaCO3 Mass of hardness producing subs. x 50
=> = Chemical equi.of hardness producing subs.
Chemical equi.of hardness producing subs.

➢ External process

b. Lime - soda process: This is most widely used method to 𝐻2 𝑂 softening. In this process all the soluble
hardness causing impurities are chemically converted into insoluble precipitate which can be removed
by settling or filtration.

Inn this method hard 𝐻2 𝑂 is treated with calculated quantities off slaked lime, 𝐶𝑎(𝑂𝐻)2 & soda ash
(𝑁𝑎2 𝐶𝑂3) in reaction tanks provided with stirrer. A slight excess of lime & soda ash are mixed for fast
reaction. The chemicals & 𝐻2 𝑂 are mixed using stirrer. Water gets softened & the precipitates of CaCO3
& MgOH3 settle down as sludge at the bottom of tank. To remove suspended particles, water is filtered.
The chemical rex. taking part are:

i. Lime reacts with free acid to neutria

2𝐻𝐶𝑙 + 𝐶𝑎(𝑂𝐻)2 → 𝐶𝑎𝐶𝑙2 + 2𝐻2 𝑂
𝐻2 𝑆𝑂4 + 𝐶𝑎(𝑂𝐻)2 → 2𝐶𝑎𝑆𝑂4 + 2𝐻2 𝑂

ii. Lime removes temporary hardness

𝐶𝑎(𝐻𝐶𝑂3 )2 + 𝐶𝑎(𝑂𝐻)2 → 2𝐶𝑎𝐶𝑂3 + 2𝐻2 𝑂
𝑀𝑔(𝐻𝐶𝑂3 )2 + 2𝐶𝑎(𝑂𝐻)2 → 2𝐶𝑎𝐶𝑂3 + 𝑀𝑔(𝑂𝐻)2 + 2𝐻2 𝑂
 iii. Lime removes Mg salts
𝑀𝑔𝐶𝑙2 + 𝐶𝑎(𝑂𝐻)2 → 𝑀𝑔(𝑂𝐻)2 + 𝐶𝑎𝐶𝑙2
𝑀𝑔𝑆𝑂4 + 𝐶𝑎(𝑂𝐻)2 → 𝑀𝑔(𝑂𝐻)2 + 𝐶𝑎𝑆𝑂4

iv. Lime removes iron & Al salts

𝐹𝑒𝑆𝑂4 + 𝐶𝑎(𝑂𝐻)2 → 𝐹𝑒(𝑂𝐻)2 + 𝐶𝑎𝑆𝑂4
𝐹𝑒(𝑂𝐻)2 + 𝐻2 𝑂 → 2𝐹𝑒(𝑂𝐻)3
𝐴𝑙2 (𝑆𝑂4 )3 + 𝐶𝑎(𝑂𝐻)2 → 2𝐴𝑙(𝑂𝐻)3 + 𝐶𝑎𝑆𝑂4

v. Lime removes 𝐶𝑂2 & 𝐻2 𝑆

𝐶𝑎(𝑂𝐻)2 + 𝐶𝑂2 → 𝐶𝑎𝐶𝑂3 + 𝐻2 𝑂
𝐶𝑎(𝑂𝐻)2 + 𝐻2 𝑆 → 𝐶𝑎𝑆 + 2𝐻2 𝑂

vi. Soda ash reacts with all Ca salts present in water

𝐶𝑎𝐶𝑙2 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 + 2𝑁𝑎𝐶𝑙
𝐶𝑎𝑆𝑂4 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 + 𝑁𝑎2 𝑆𝑂4

The rexn. Of lime with Ca & Mg salts are slow. They produce very fine particles which require sufficient time
for settling. But water generally obtains large proportions of hardness, which can be effectively removed by
lime. Lime is cheap & doesn’t introduce new soluble salts to water. 𝑀𝑔(𝑂𝐻)2 produced precipitates as
insoluble & rexn. with Ca salts gives 𝐶𝑎𝐶𝑂3 precipitates. These precipitates can be coagulated faster by using
coagulating reagent like sodium aluminate or alum. The precipitates then can be removed by filtration.

The softening of water by lime-soda process can be carried either in cold or hot.

➢ Cold Lime-Soda process:

In this method a calculated quantity of lime & soda ash are mixed with water at room temp.. At this
temp., the precipitates formed are very fine & require more time for setting which may be about 24 hrs.
Also it is not possible to remove them completely by filtration. Some coagulants like alum or sodium
aluminate or Al precipitates of 𝐴𝑙(𝑂𝐻)2 which bring together fine precipitates particles. Use of sodium
aluminate as coagulating agent removes silica & oil present in water.

A. Batch process
This is also known as intermittent process. It consists of 2 tanks used alternately for softening of
water. Each tank is provided with inlets for raw water, inlet for chemicals, outlet for soft water &
outlet for sludge. It is provided with a mechanical stirrer as shown in fig.
 Raw water & calculated quantities of soda & lime are simultaneously added to tank & thoroughly mixed
by the stirrer, calculated quantities of coagulating reagents is added to tanks. When the tank is full, rexn.
is almost complete. The contents of tank are kept undisturbed for few hours which allow coagulation &
setting of precipitates. The clear softened water is collected through a float pipe & sent to filtering unit.
The sludge formed in the tank is removed through sludge outlet. The tank is washed with water & used
for another batch of water.

B. Conventional type continuous process:

In this process the raw water & calculated quantities of chemicals are continuously fed from the
top into an inner chamber of vertical circular tank provided with a paddle stirrer.

The raw water & chemicals flowing down the chamber comes into close contact because of
continuous stirring & the chemical rexn. takes place to soften the water. The sludge formed
settles down to the bottom of the outer chamber from where it is removed through sludge outlet.
The softened water rising up passes through outlet provided for it.

Soft water obtained from cold lime-soda process still contains about 50-60ppm of residual
hardness.

➢ Hot Lime-soda process:

In this process, raw water is treated with softening chemicals at a temp. of 80℃ - 110℃. At this temp.,
the chemical rexn. are much faster than in cold process. Also for the cold process large size
storage tank are essential & process requires some hrs. to complete. The hot lime-soda softeners
are much faster in operation & requires less storage capacity tank. Elevated temp. inc. the rate of
actual chemical rexn., but reduces the viscosity of water & inc. the rate of aggregation of particles.
Thus, rate of settling & filtration is increased. The sludge formed settles down rapidly, hence there
is no need of adding coagulating reagents.
In this process, the dissolved gases are driven out due to high temp.. The hot lime-soda water
softening unit cconsists of rexn. cum settling tank & a filter. The water softened by this process
contains residual hardness of about 15-30ppm.
 Advantages:

a) Very economical.
b) Can be used with lower qty. of coagulants as required.
c) Process inc. pH value which reduces the corrosion of tanks & pipe lines.
d) Removes dissolved salts along with hardness.

c. Ion-Exchange process:
In this process, ion exchange resins are insoluble cross-linked long chain organic polymers with a
microporous structure & the functional groups attached to chains are responsible for the ion-exchanging
properties. The resins containing acid functional groups such as –COOH, -𝑆𝑂3 𝐻 are capable of
exchanging their 𝐻 + ions with the cations coming in their contact & the resins containing groups
−𝑁𝐻2 , ≡ 𝑁𝐻2 are capable of exchanging their anion with other anion coming in their contact. Hence,
there will be 2 types of ion exchange resins in ion-exchange process.

1) Cation exchange resins

2) Anion exchange resins

1) Cation exchange resins:

These are capable of exchanging cations in 𝐻2 𝑂 & 𝐻+ ions. The resins such as sulfonated coals,
tannin formaldehyde represents as 𝑅𝐻2 are the examples. Their exchange rexn. with cation can be
represented as:
𝑅𝐻2 + 𝐶𝑎2+ → 𝑅𝐶𝑎 + 2𝐻+

𝑅𝐻2 + 𝑀𝑔2+ → 𝑅𝑀𝑔 + 2𝐻+

These cation exchanger when exhausted can be regenerated by passing through their bed, an excess
of strong acid solution.
 𝑅𝐶𝑎 + 2𝐻𝐶𝑙 → 𝑅𝐻2 + 𝐶𝑎𝐶𝑙2
𝑅𝑀𝑔 + 2𝐻𝐶𝑙 → 𝑅𝐻2 + 𝑀𝑔𝐶𝑙2

2) Anion exchange resins:

These are capable of exchanging anion in 𝐻2 𝑂 by 𝑂𝐻 − ions. The functional groups in anion
exchangers are −𝑁(𝐶𝐻3 )2 +, −𝑂𝐻𝑁𝐻2 . The −𝑁(𝐶𝐻3 )2 + & − 𝑂𝐻 groups are stable & react fast.
These exchangers are represented by 𝑅(𝑂𝐻)2. Their exchange rexn. with anion can be represented
as:

𝑅′(𝑂𝐻)2 + 𝑆𝑂4 → 𝑅′ 𝑆𝑂4 + 2𝑂𝐻−

𝑅′(𝑂𝐻)2 + 𝐶𝑙4 → 𝑅′ 𝐶𝑙4 + 2𝑂𝐻−

These anion exchangers when exhausted can be regenerated by passing strong alkalies solution
through their bed.

𝑅′𝑆𝑂4 + 2𝑁𝑎𝑂𝐻 → 𝑅 ′ (𝑂𝐻)2 + 𝑁𝑎2 𝑆𝑂4

𝑅′𝐶𝑙2 + 2𝑁𝑎𝑂𝐻 → 𝑅 ′ (𝑂𝐻)2 + 2𝑁𝑎𝐶𝑙

Thus, if the hard 𝐻2 𝑂 is passed first through cation exchange bed & then through anion exchange
bed. The resulting water will be free from both cations & anions i.e., it will be deionized or
demineralized water.

The process of deionization consists of passing hard water first through cation exchange bed where
all the cations like 𝐶𝑎2+ , 𝑀𝑔2+ , 𝑁𝑎+ are replaced by 𝐻+ ions.

𝑅𝐻2 + 𝐶𝑎2+ → 𝑅𝐶𝑎 + 2𝐻+

𝑅𝐻2 + 𝑀𝑔2+ → 𝑅𝑀𝑔 + 2𝐻+

𝑅𝐻2 + 𝑁𝑎+ → 𝑅𝑁𝑎2 + 2𝐻+

d. Zeolite process or permutit process:

In this process water is soften through a natural or artificial zeolite. Permutit is an artificial zeolite called
as hydrate of sodium-aluminium orthosilicate & can be obtained in the form of coarse sand by fusing
together 𝑁𝑎2 𝐶𝑂3, Aluminium(𝐴𝑙2 𝑂3 ) & silica(𝑆𝑖𝑂2 ). Zeolites known as green sand are used for
softening but zeolites known as permutit is more common & has general formula
𝑁𝑎2 𝑂. 𝐴𝑙2 𝑂3 . 𝑛𝑆𝑖𝑂2 (𝑛 = 5 − 15). 𝑛𝐻2 𝑂(𝑛 = 3 − 4). Permutit or zeolite is insoluble in water but can
act as a base exchanger when brought in contact with water containing cations. This method removes
both temporary & permanent hardness.
 Temporary hardness

𝑁𝑎2 𝑍 + 𝐶𝑎(𝐻𝐶𝑂3 )2 → 2𝑁𝑎𝐻𝐶𝑂3 + 𝐶𝑎𝑍

Permanent hardness

𝑁𝑎2 𝑍 + 𝑀𝑔𝑆𝑂4 → 𝑁𝑎2 𝑆𝑂4 + 𝐶𝑎𝑍

𝑁𝑎2 𝑍 + 𝐶𝑎𝐶𝑙2 → 2𝑁𝑎𝐶𝑙 + 𝐶𝑎𝑍

Regeneration of zeolite

𝐶𝑎𝑍 + 2𝑁𝑎𝐶𝑙 → 𝑁𝑎2 𝑍 + 𝐶𝑎𝐶𝑙2

Advantages:
a) Hardness is completely removed. (about 10ppm)
b) Suitable for all type of hard water.
c) Require less time for softening.
d) Lower in cost as chemical consumed is brine only.
e) No problem of sludge formation & removal.
f) No precipitate is formed.
g) Equipment is compact & simple.

➢ Internal process:
1. Phosphate conditioning: This process is used in internal conditioning of boiler water. The
zeolite process & ion exchange methods remove most of the Ca & Mg ions from water. The
traces of these impurities in water may cause scale formation in boiler. In high press. boilers
scale formation can be avoided by addition of phosphate to the boiler water. The soluble
phosphates for this purpose are:
 𝑁𝑎2 𝐻𝑃𝑂4 → Disodium hydrogen phosphate
𝑁𝑎2 𝐻2 𝑃𝑂4 → Disodium dihydrogen phosphate
𝑁𝑎3 𝑃𝑂4 → Trisodium phosphate
𝑁𝑎2 𝑃2 𝑂7 → Sodium ortho phosphate

These sodium phosphates react with Ca & Mg impurities to convert them to their insoluble
phosphates as 𝐶𝑎(𝑃𝑂4 )2 which are deposited & removed as sludge. This avoids scale formation.

3𝐶𝑎𝑆𝑂4 + 2𝑁𝑎3 𝑃𝑂4 → 𝐶𝑎3 (𝑃𝑂4 )2 + 3𝑁𝑎2 𝑆𝑂4

3𝑀𝐶𝑙2 + 2𝑁𝑎3 𝑃𝑂4 → 𝑀3 (𝑃𝑂4 )2 + 6𝑁𝑎𝐶𝑙

For effective phosphate treatment pH of water should be in range 9.5-10.5. Depending upon the
original pH of water sample suitable phosphates are used for treatment.

▪ Phosphate conditioning is just supplement process to the lime-soda process.

➢ Colloidal conditioning: Scale formation can be avoided by the addition of colloidal agents like
kerosene, glue, agar-agar & gelatin. It is used in low press. boiler. The colloidal subs. get coated over the
scale forming particles, convert them by blow down operation.

➢ Carbonate conditioning: Scale formation can be avoided by adding 𝑁𝑎2 𝐶𝑂3 to boiler water. Scale
forming salts like 𝐶𝑎𝑆𝑂4 are converted into 𝐶𝑎𝐶𝑂3 which can be easily removed.

𝐶𝑎𝑆𝑂4 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 + 𝑁𝑎2 𝑆𝑂4

➢ Phosphate conditioning: AN excess of soluble phosphate is added to the boiler water react with Ca
ions & Mg salts to form a non-adherent precipitate of 𝐶𝑎𝑃𝑂4 & 𝑀𝑔𝑃𝑂4 & thus the scale formation is
prevented.
𝐶𝑎𝑆𝑂4 + 2𝑁𝑎3 𝑃𝑂4 → 𝐶𝑎3 (𝑃𝑂4 )2 + 3𝑁𝑎2 𝑆𝑂4
Generally 3 types of phosphate are employed:
a) Trisodium phosphate
b) Disodium hydrogen phosphate
c) Sodium dihydrogen phosphate

➢ Calogen Conditioning: Calogen is sodium hexa meta phosphate 𝑁𝑎2 [𝑁𝑎4 (𝑃𝑂3 )6] or (𝑁𝑎𝑃𝑂3 )6 which
reacts with Ca ions forming a highly soluble Ca hexa meta phosphate complex & thus prevents
formation of scale.
2𝐶𝑎𝑆𝑂4 + 𝑁𝑎2 [𝑁𝑎4 (𝑃𝑂3 )6] → 𝑁𝑎2 [𝐶𝑎4(𝑃𝑂3 )6 ] + 𝑁𝑎2 𝑆𝑂4
• Concept of Soft, Hard & Deionized water
➢ Soft water: It is the Water which does not contain any of Ca & Mg salts dissolved in it. It may contain
salts like Na & K dissolved in it. It forms lather or foam with soap.

➢ Hard water: Water which contains Ca & Mg salts dissolved in it. Due to presence of salts of Ca & Mg
salts. Hard water cannot produce good lather or foam with soap.

➢ Deionized Water: It is often synonymous with demineralized water (DM water). It is the water that has
had almost all of its mineral ions removed such as cations like Na, Ca, Fe & Cu and ions such as
chlorides & sulfates.

Deionized water may contain contamination in the form of bits of ion exchange resins. It is not safe to
drink.

* Deionization or demineralization simply means the removal of ions.

Deionized water is cleaner, safer & great tasting water. It does not contain harmful toxins & chemicals.

*Difference b/w distilled & deionized water

In distilled water only distillation process is used in which only evaporation & condensation is used to
clean the water dissolved salts.

Whereas in deionized water ions are removed by ion exchange & reverse osmosis to remove approx. all
the minerals present.

➢ Distilled Water: It is the water that has had many of its impurities removed by distillation. Distillation
involves boiling the water than condensing the steam into a clean container.

• Mixed Bed Deionizer: This consists of a single cylinder containing an intimate mixture of strongly
acidic cation exchanger. Originally the cation exchanger is in the 𝐻 + form & the anion exchanger is in the
𝑂𝐻 − form when hard water containing say 𝐶𝑎𝐶𝑙2 is poured into the mixed resin bed from the top. Pure
water flow out at the bottom. Each 𝐶𝑎2+ ion displaces one 𝑂𝐻− ions. Exactly equal no. of 𝐻+ & 𝑂𝐻 − are
produced, which combine to form water.

• Regeneration:
To regenerate a mixed bed deionizer, it is first necessary to separate the two resins. The cation exchanger is
regenerated by treatment with a strong base like NaOH.

Thus, it might be obvious that the mixed bed ionizer are comparatively more convenient to use & are more
efficient. But they are most costly too. In many areas, deionization is a simpler & less costly alternative to
distillate & is widely used for purifying water used in laboratories.

In domestic water softening by ion exchange, total deionization is not necessary. Only the cation
responsible for water hardness needs to be removed. So only a cation exchanger is 𝑁𝑎+ form is used. Its
operation is reversible & regeneration is carried out by using readily available, inexpensive NaCl solution
(brine).
 STEAM
• Introduction
Steam is the most important utility for chemical process plant. Mostly steam is used as a heating media in
the reactor where endothermic rexn. takes place. Similarly, for evaporation, drying, distillation etc. Steam
is the only choice which is cheap & safe for chemical process plant.

Steam is a vapour & it is also used in the operation of steam engine & steam turbine. Steam as a vapour
would not obey the law of perfect gases (Ideal gas law) unless it is in a highly dried condition. Steam in
such a dried state is known as superheated steam & it is assumed to behave like a perfect gas when highly
superheated.

Steam is being a mixture of dried steam & moisture. It possesses properties like those of gases namely
press., vol., temp., internal energy, enthalpy, entropy. Properties of steam were first investigated
experimentally by Renault & subsequently investigated by calendar by means of electrical calorimeter.

These properties are also represented on chart. The quantities tabulated in steam tables are:
i. Pressure
ii. Internal Energy
iii. Temperature
iv. Enthalpy
v. Specific Volume
vi. Entropy

Thus, the enthalpy, internal energy & entropy at 0℃ are assumed to be zero.

• Formation of steam at constant pressure

Consider a cylinder fitted with frictionless piston which may be loaded to any desired press.(P) bar.
Assume that there is 1kg of water initially at a temp. of 0℃ in the cylinder under the piston exert a constant
press. of P bar.

Let, Area of piston = 1m2

Vin = Vol. of 1Kg water
Vw = Length of cylinder occupied by water

Now, heat is supplied to the water in the cylinder. The temp. of water will rise when sensible heat is
supplied & the rise in temp. continue until the boiling pt. is reached where it will remain constant. The
temp. at which water boils depends upon the press. on it. For any given press. there is one definite B.Pt.
The B.Pt. called saturation temp.(ts) or the temp. of steam formation.
Ex.: Water boils at 99.6℃ when the press. on it is 1bar & at 184.9℃ when press. on it is 11bar.

Fig.(i) represents the condition before the first stage starts.

When the water is again heated the stage (ii) will be reached. It will be noted that piston is at higher level at
the end of operation.
The next stage represented by fig.(iii) is actual production of steam. If the heating of 1kg of water is
continued after the B.Pt. is reached it will be noticed that there is no further inc. in temp. as the temp. is
maintained constant. But steam begins to form & piston starts to rise in the cylinder, rising higher & higher
as more & more steam is formed. So in fig.(iii) the cylinder has a mixture of water & steam (about 50% of
water & 50% of steam). This mixture of water is called as Wet Steam.

Dry Saturated Steam: When last particle of water in suspension in wet steam disappears.

Fig.(iv) shows the formation of steam is completed. The water is entirely evaporated & the vol. of steam
below the piston is VS m3 (It is the vol. of 1kg of dry saturated steam at press. (P)).

Finally further heat is added to 1kg of dry steam in the cylinder at a constant press.. The temp. of steam
will rise & there will be no further inc. in vol. of steam as shown in fig.(v). This steam is known as shown
in fig.(v). This steam is known as superheated steam.
 Graphically,

The above diagram shows graphically that what happens when heat is added to 1kg of water initially at
0℃. The heat added is plotted along the horizontal axis in kilojoule unit (KJ) while the corresponding
temp. are plotted along the vertical axis in Celsius unit(℃). During first stage of heating the temp. of water
will began to rise until the water boils at temp. known as Saturation temp. which depends upon the press. in
the cylinder. After the boiling temp. is reached steam begins to form during which time temp. remains
constant. A pt. is reached when there is half water & half steam known as Wet steam. When again heat is
added all the water including those particles of water held in suspension will be evaporated. The steam is
said to be dry saturated steam.

As heating continues further the temp. of steam begins to rise again & the steam is now known as
superheated steam & behave more or less as a perfect gas.

• Terms used in Steam

1. Wet Steam:
The steam in the steam space of a boiler generally contains water mixed with it in the form of a fine
water particle such a steam is termed as Wet steam (50% water +50% steam).

2. Dry saturated Steam:

When saturated steam does not contain any water particle then the steam is termed as dry saturated
steam.
 3. Superheated Steam:
When the temp. of steam is greater than the boiling pt. corresponding to the press. of steam
generation then the steam is called superheated steam.

4. Dryness Fraction or Quality of Wet Steam:

The dryness fraction ‘x’ is defined as the ratio of weight of total wet steam.
Mathematically,
𝑚𝑠
𝑥=
𝑚𝑠 + 𝑚

𝑚𝑠 → Wt. of dry steam contained in steam

𝑚 → Wt. of water in suspension in steam

5. Sensible Heat of water(h):

The amount of heat absorbed by 1kg of water is being heated from freezing point (0℃) to the
boiling Pt. (100℃) is known as sensible heat of water or enthalpy of saturated water.

6. Latent heat of vaporization(ℵ):

It is the qty. of heat required to convert 1kg of water at a given temp. (tS)& press. (P) into steam at
the same temp. & press.. It is also known as enthalpy of vaporization.

7. Enthalpy or Total heat of steam:

It is sum of enthalpy of saturated water & enthalpy of evaporation.
𝐻𝑆 = ℎ + ℵ
It is defined as the qty. of heat required to raise the temp. 1kg of water from freezing Pt. to the
temp. of evaporation & then convert it into dry saturated steam at that temp. & press.

* The value of HS of 1kg of dry saturated steam can be directly obtained from the steam tables
corresponding to given value of temp. & press.

8. Specific Vol. of steam(VS):

The vol. in cubic meter per Kg of dry saturated steam is known as specific vol. of dry saturated
steam & is denoted by symbol (VS). The vol. of 1Kg of dry saturated steam of the table.

Sp. Vol. of wet steam = Vol. of dry steam + Vol. of water particles
i.e., Sp. Vol. of wet steam = 𝑥. 𝑉𝑆 + (1 + 𝑥)𝑉𝑤

• Mollier diagram or Enthalpy – Entropy chart

The Mollier dia. is a chart on which enthalpy is the coordinate & entropy is the abscissa. From steam
tables, both the enthalpy & entropy of water & dry saturated steam for any particular press. are obtained
& by plotting these enthalpies against entropies, liq. line & the dry saturated line are obtained. Both these
lines meets at Pt. C, the critical point.

The dia. can be divided into 4 regions:

i. The liq. region,
ii. Wet region,
iii. Superheated region,
iv. At very high deg. Of superheated.
When steam obeys all the gas represented by a horizontal straight line from one specified line from one
specified Pt. to the other, the reversible adiabatic or isotropic process by a vertical straight line from one
specified Pt. to the other & the constant vol. process, constant press. process, & the constant temp. process may
be represented on the lines already plotted.

• Steam Table
Various parameter such as press., saturation temp., sensible heat, latent heat, sp. Vol. & sometime
entropy are determined experimentally & are tabulated called Steam tables. The various terms of steam
tables are given below:
➢ Pressure
➢ Saturation temp. (tS)
➢ Sensible heat Latent heat Total heat of saturated steam(H S)
➢ Sp. Vol. of steam

• Steam Trap
It is a device for removing condensate from all type of steam heated equipment such as coils, kettles,
reboilers, evaporators, -ve vessel, heater, etc.

The purpose or function of steam trap is not to allow condensate to drain but to prevent steam from
blowing out the space drain. There are variety of steam traps as classified:

i. Expansion trap
ii. Bucket trap
iii. Tilt trap

i. Expansion trap
This trap contains a closed metal cartridge A. To one end of this is connected to a collapsible
corrugated tube B. The left hand end of the tube is sealed & too it is attached the steam of value
C. The space b/w the cartridge & corrugated tube is filled with oil. The collection of condensate
against the value, loosing heat by radiation, cools the cartridge, the oil contract, the valve open &
condensate is blow out when the condensate is all discharged & steam enters the trap again, the
cartridge expands & trap closes. This device is very simple & has no moving parts. It is suited for
small capacity & requires rather delicate regulation.
 ii. Bucket trap
A typical bucket trap is shown in fig. The condensate that enters this trap collects in the bucket. A
until a definite wt. has been caught. The bucket then drops pulls down on rod B & opens the valve
C at the top of the trap. This allows the condensate to be blown out. When sufficient water has
been blown from trap, the bucket float & closes the valve. Non-condensate gases may be removed
by opening the petcock in the cover plate from time- to- time. These traps are intermittent & are
not made as return traps.

iii. Inverted Bucket trap

This is the trap with the bucket down & discharge valve open. This is a non-return trap i.e., press.
in the inlet is greater than press. on outlet. If the water comes into the trap it fills the body of the
trap both inside & outside the bucket & is discharged through the valve. If however, all the water
has been discharged & some steam comes in, the steam discharge & some steam comes in steam
displaces water from inside of the bucket & bucket floats & thus closes outlet valve.

This remains closed until the steam inside the bucket has condensed by radiation, when the bucket
will again drop & water can be discharged still further. In order to take care of air that may
accumulate in the bucket, there is very small opening in the top of the bucket through which such
air can escape into upper part of trap body & be discharged along with water. These bucket traps
are in general suitable for extremely large rates of discharge such as occurs in evaporators.

Tilt traps are much more complicated & are less often seen at present time. General opinion is
that if a pump can be used, a trap is not satisfactory.
REFRACTORIES

• Refractories: These are the materials that are capable to withstand extremely high distorted or soften
by virtue of their high B.Pt.
Or
These are ceramic material that can withstand high temp. as well as abrasive & corrosive material action
of slags & gases without deformation in shape.

• Classification of Refractories
➢ Neutral: Graphite, Zirconia(Zr2), SiC refractories
➢ Acid: Alumina, Silica, Fire clay
➢ Basic: Magnosite, Dolomite(𝐹𝑒𝑂2 𝐶𝑟2)

• Characteristics of Refractories
1. A good refractory should have excellent heat, corrosion & abrasion material property.
2. It should possess low thermal conductivity.
3. It should possess high fusion temp.
4. It should able to withstand the over overlying load of structure at operating temp.
5. Expansion or contraction of refractory should not be sudden but uniform.
6. They should be chemically inert.
7. They should not crack at operating temp.

• Properties of refractories
1. Refractoriness: It is the ability of refractory material to withstand heat without appreciable
softening or deformation under suitable condition.

Simply it is the measure of feasibility of refractory (graphite).

Refractory type Name of Refractory Fusion temp.

Neutral Graphite 2500℃
Zirconia 2700℃
SiC 2700℃
Acidic Alumina (𝐴𝑙2 𝑂3 ) 2050℃
Silica (𝑆𝑖𝑂2 ) 1700℃
Fire Clay 1600-1750℃
Basic Magnesia 2200℃

2. Strength or Refractories under load: Temp., resistance & load bearing capacity essential
qualities of refractory. It is due to fact that commercial refractories which are used for lining high
temp. furnace are expected to withstand varying load of the charge. Hence, they should possess
high strength high strength & excellent temp. resistance. This property is imp. Bcoz usually
refractory fails at lower temp. when subjected to load.

3. Thermal Expansion: Fracture or Flaking occurs due to uneven heat stresses or compression
under condition rapid change of temp.. The material subjected to changes in volume. The change
in vol. may cause damage to joints & producing cracks due to which whole structure of furnace
may spoil.
 4. Thermal Conductivity: Refractories having low thermal conductivity are preferred such as in
glass furnace, open hearth furnace. It is the thermal property of refractory material since it
determines the amount of heat transmission due to heat radiant through it.

5. Porosity or Permeability: It is a measure of rate of diffusion of connected pores of refractories.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑝𝑜𝑟𝑒𝑠
Or 𝑃𝑜𝑟𝑜𝑠𝑖𝑡𝑦 = 𝐵𝑢𝑙𝑘 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙𝑠

Higher the porosity of refractory brick the more easily it will penetrate by gases & molten fluxes.
So, good refractory should have low permeability & porosity.

6. Electrical Conductivity: Refractories used for lining electrical furnaces should have low electrical
conductivity.

• Cermets
It is a special type of group of composite material consisting of an intimate mixture of ceramic & metallic
components in the form of powder.
Or
Cermets are hot pressed or sintered material consisting of ceramic & metals.

For e.g. – Molybdenum carbide, Tungsten carbide, Ceramic carbide, Titanium carbide etc.

The composition of most cermets is 80% ceramic & 20% metal.

Cermets are mainly used as high temp. refractories when high temp. as well as high stroke resistance are
required. Thus cermets are used in rocket & jet engine parts of spinning tools for hot metals.

• Insulating Refractories
Refractory material Used to insulate the furnace walls for avoiding excessive heat losses due to
conduction are known as insulating refractories. e.g. Kiesel guhr, asbestos, etc.

• Manufacturing of Refractories
It consists of following imp. step:
1. Crushing
2. Grinding
3. Screening
4. Mineral Dressing
5. Storage
6. Mixing
7. Moulding
8. Drying
9. Firing

1. Crushing: The clay in the form of big lumps is crushed to suitable size in single or double roll crushers.
For crushing harder clays Jaw crushers are most suitable.
2. Grinding: After crushing the lumps down to 25mm in size, the materials are ground in suitable grinding
machines like ball mill & conical mills.

3. Screening: It is carried out in order to separate fine particles from coarse material. After screening the
desired size material is passed on to the brick making machine & oversize material is recycled to
grinding machine in order to get again the particles of desired size. Shaking screens, closed type screens
are used for this purpose.

4. Mineral Dressing: In order to produce good refractories it is most essential that the raw materials
should be as pure as possible. So, in order to purify the raw materials. Material Dressing is used which is
also known as conc. method. Some methods of conc. are:

a) Tapling:- The undesired foreign material present as impurities have different Sp. Gravity from
main raw material. The impurities are therefore separated by air or water table.
b) Settling:- It is carried out in centrifuge & spingers.
c) Floatation
d) Magnetic & Electrical separation: In this strong electrical or magnetic fields are used.

5. Storage: After mineral dressing, the pure raw material is kept in storage bins.

6. Mixing: The function of mixing is the distribution of plastic material so as to coat thoroughly all plastic
constituent. Mixing provides a lubricant during the molding operation & permits the bonding off mass
with minimum voids.
 7. Moulding: Since refractory bricks of greater density, strength & vol. of uniformity are used in large no.
of industries. The dry press. method of moulding is used.

8. Drying: It is carried out to remove moisture from refractories. Drying is performed very slowly under
specified conditions of humidity & temp. depending upon the refractory. Rate of drying should be so
maintained that neither voids nor shrinkage left in the refractory.

9. Firing: The refractories are fired in order to stabilize & strengthen the structure. Firing or burning is
usually carried out in down drought kiln or continuous tunnel kiln. Due to firing the following changes
usually occurs:

➢ Water of hydration no longer exists.

➢ Calcination of carbonates takes place.
➢ Ferrous ions undergo oxidation.
➢ Shrinkage in vol. may be as high as 30%.
➢ Due to shrinkage great stresses may occur in refractories.

• Failure of Refractories
The conditions which leads to failure of a refractory material are:
1. Using a refractory material of higher thermal expansion.
2. Using a refractory material which does not have a required heat, corrosion & abrasion resistance.
3. Using a refractory of refractoriness less than that of operating temp.
4. Using basic refractory in a furnace in which acidic reactants &/or products are being processed &
vice-versa.
5. Using refractories which undergo considerable vol. changes during their use at high temp.

• Carbon Refractories
They are made by mixing either crushed coke with pitch (or tar) or graphite with clay & firing at about
1300-1400℃. The space b/w the bricks is filled with a mixture of sand & powdered coke for minimizing
contact of the bricks with air during firing.

Properties:
i. Carbon & graphite refractories are practically infusible & can withstand temp. fluctuations.
ii. They have high thermal conductivity.
iii. They are excellent refractory materials inn neutral or acidic conditions Bcoz in oxidizing
atmosphere they get readily oxidized particularly at elevated temp.

Applications:
i. Carbon & Graphite bricks are mostly used as construction materials for electrodes.
ii. They are also used linings of chemical resistant equipments, atomic reactors, electric furnaces,
H.T. systems & in Al, Cu & Pb smelting furnaces.
iii. Crucibles are made from graphite are also widely used in industry. The crucible surface is coated
with boric acid, soda ash, sodium silicate, CaCl2 or MgCl2 in order to prevent oxidation.
• Acid Refractories:
2) Fire Clay Refractories: They are made from raw & calcined amino silicate which is known as
fireclay Bcoz they can withstand high temp.. Calcined fire clay, known as the “Grog”, accounts for 50%
or more of the batch mixture. The extra properties of the constituents depend on the type of bricks to be
made. For e.g., feebly acid fir clay bricks contains 35% 𝐴𝑙2 𝑂3 while nearly neutral fire clay bricks
contains 40% 𝑆𝑖𝑂2 & 55% 𝐴𝑙2 𝑂3 . The balance in both of them consists of 𝐾2 𝑂, FeO, CaO & MgO etc.

Properties:
i. Depending on the content of iron oxides, fire clay bricks are light yellow to reddish brown in
color.
ii. Depending on the SiO2 content, the fireclay bricks show acidic character.
iii. Depending on %age of Grog, these materials show resistance to thermal spalling. Greater the
%age of grog, greater will be the resistance to thermal spalling.
iv. They also have high crushing strength crushing strength (about 200Kg/cm2) which goes down
with increasing temp.
v. Properly fixed bricks are as hard as steel.

Applications:
i. Fireclay refractories are mostly consumed by steel industries as these are used for lining of blast
furnaces, open hearths, stoves, ovens, etc.
ii. These are widely used in foundries like continuous ceramic, pottery & metallurgical kilns; glass,
brass & Cu furnaces; cupolas etc.

3) High Lumina Refractories: When the Alumina (Al2O3) content in the fire clay brick reaches above
47.5% then it is called High-Alumina bricks.

It is made by mixing calcined bauxite (Al2O3) with clay bind.

Properties:
Bcoz of high alumina content, these bricks have more refractoriness, better slag resis., inertness upto
1000℃.

Applications:
High alumina refractories having 75% Al2O3 are known as high-duty bricks & find applications in the
hottest zones of cement rotary kilns, combustion zones of oil-fired furnaces, Al melting furnaces etc.

High alumina refractories containing 50-60% Al2O3 are known as ‘medium duty bricks’ & find
applications in linings of Portland cement rotary kilns, soaking pits, reheating furnaces, hearths &
walls, etc., which are subjected to high abrasion.

4) Silica Bricks:
Preparation: The raw materials used for the manufacture of silica bricks are quartz, quartize, sand,
sandstone, ganister etc.. Siliceous rock is first crushed & ground with 2% lime & water. The resultant
thick paste is then made into bricks by machine pressing. After drying, bricks are burnt in kilns. In
about 24hrs., the temp.is slowly raised to about 1500℃. This high temp. is maintained for about
12hrs.. This step is essential since it allows quartize to be converted into cristobalite (allotropic
transformation) careful cooling is then done & it takes about 1-2 weeks. Cristobalite is slowly
changed into tridymite during cooling & in the final brick, the mixture of two results.
 Properties:
i. Silica bricks are yellowish in color with brown specks throughout the body.
ii. These bricks are acidic & are therefore suitable for acidic furnace charges.
iii. Silica bricks are remarkable for their load bearing capacity. They can withstand a load of
about 3.5Kg/cm2 upto about 1600℃.
iv. Silica bricks are not susceptible to thermal spalling at temp. below 800℃.
v. These bricks are light 7 possess high rigidity & mechanical strength.
vi. These bricks do not contract in use.

Applications:
Silica bricks are used in lining roof arches of open hearth furnaces & reverbratory furnaces, gas retort &
walls of coke ovens.
 Refrigerants & Cooling Towers
• Introduction
Any subs. capable of absorbing heat from another required subs. can be used as refrigerants i.e., ice,
water, air or brine (salt solution of NaCl).

In selecting a refrigerant for a particular purpose their thermodynamic, Chemical & safety characteristics
must be considered in addition to their physical characteristics. Refrigerant selection must be made on
the basis of its compatibility with the conditions prevailing at the specific location for required use. A
mechanical refrigerant is a refrigerant which will absorb the heat from source which is at lower temp. &
dissipate/dispose the same to the sink which is at higher temp. than source either in the form of sensible
heat or in the form of latent heat e.g. Ammonia, CO 2, SO2, freons gas, methyl chloride, fluorinated
hydrocarbons.

• Classification of Refrigerants

➢ Primary Refrigerants: Refrigerants which directly takes part in refrigeration system.

i. Halogen compounds
ii. Azeotropes
iii. Hydrocarbons(HC)
iv. Inorganic compounds
v. Unsaturated organic compounds

➢ Secondary refrigerants: Refrigerants which are first cooled with the help of primary
refrigerants & are further used for cooling purposes.

Primary Refrigerants
i. Halogen compounds:
This group of refrigerants was invented & developed by Charles kettering & Dr. Thomas Midley in
1928. These refrigerants are sold in the market under trade names as Freon, Genetron, Isotron & Arcton.
This group includes refrigerants which contain one or more of three halogens, Cl, F & Br.

The most of the refrigerants used for domestic, commercial & industrial purposes are selected from this
group due to their outstanding advantages over the refrigerants from other groups.

Commonly used halocarbon refrigerants:

No. of refrigerant Chemical name Chemical formula
11 Trichloro monofluoro methane CCl3F
12 Dichloro difluoro methane CCl3F2
13 Monohloro trifluoro methane CClF3
21 Dichloro monofluoro methane CHCl3F
22 Monochloro difluoro methane CHClF2
30 Methylene chloride CH2Cl2
40 Methyl chloride CH2Cl
100 Ethyl chloride CH3CH2Cl
113 Trichloro trifluoro ethane C2F3Cl2
114 Tetrafluoro dichloro ethane Cl2F4Cl2
114(a) Dichloro tetrafluoro ethane CCl2F4
152 Difluoro ethane CH3CH2F2
 ii. Azeotropes:
The refrigerants under this group consists of mixtures of different refrigerants which do not
separate into their components with the changes in press. or temp. or both.

Refrigerant ‘500’ which contains 73.8% F & 26.2% F-152 is an e.g. of azeotrope.

iii. Hydrocarbons:
Most of the organic compounds are considered as refrigerants under this group. Many
hydrocarbons are successfully used as refrigerants in industrial & commercial installations. Most
of them possess satisfactory thermodynamic properties but are highly flammable. Few of them
are listed below with their no. & chemical formula:

No. of refrigerant Chemical Name Chemical Formula

50 Methane CH4
100 Ethane CH3CH3
290 Propane CH3CH2CH3

iv. Inorganic Compounds:

The refrigerants under the group were universally used for all purposes before the introduction of
halocarbon group. They are still used for different purposes due to their inherent thermodynamic
& physical properties. The refrigerants under this group are listed below with their number,
chemical formula & specific use.

No. of Refrigerant Name of Refrigerant Chemical Formula Specific use

717 Ammonia NH3 Ice plants

118 Water H2O In steam refrigeration
system
-29 Air - For airplane
refrigeration
-144 Carbon dioxide CO2 Ship refrigeration
-164 Sulfur dioxide SO2 -

v. Unsaturated Organic Compounds:

The refrigerants under this group are mainly hydrocarbon group with ethylene & propylene base.

No. of Refrigerant Name of Refrigerant Chemical Formula

1120 Trichloro ethylene C2H4Cl3

1130 Dichloro ethylene C2H4Cl2
1150 Ethylene C2H4
1270 Propylene C3H6
• Desirable properties of an ideal refrigerant:
These are sub-divided into 3 main groups:
a. Thermodynamic properties
b. Safe working properties
c. Physical properties

a. Thermodynamic properties

i. Boiling point: Low boiling temp. at atmospheric press. of the refrigerant is required for an
efficient refrigerant. It becomes necessary to operate the compressor at high vacuums if the
boiling Pt. of the refrigerants at atmospheric press. reduces the capacity of the system & lowers
the operating cost.

The boiling points of the different refrigerants, which are commonly used are listed below:

Refrigerant B.pt. at 760mm of Hg

NH3 -33.3℃
CH2 -73.6℃
SO3 -10℃
F-11 23.3℃
F-12 -29.8℃
F-22 -41.3℃
Carren-1 40.3℃
Carren-7 -33.3℃
F-112 47.3℃

ii. Freezing point: Low freezing pt. of the refrigerant is necessary Bcoz the refrigerant should not
freeze under required evaporator temp.. The refrigerant must have a freezing point well below
the operating evaporator temp.

The freezing pt. of most of the refrigerants are below -30℃ so that this property is not seriously
considered for normal refrigerant systems. This requirement is taken into consideration for
selecting the refrigerant when used for cryogenic applications. The F.pt. of few are listed below:

Refrigerant F.pt. in ℃ Refrigerant F.pt. in ℃

NH3 -77.8 F-22 -160
CH2 -56.7 F-113 -35
SO3 -75.6 Carren-1 -96.6
F-11 -111 Carren-7 -156
F-12 -157.8

iii. Evaporator & Condenser pressure:

It is always desirable to have opposite in evaporator & condenser for the required temp. but the
press. should not be too high above atmosphere. Too high press. require the robust construction
of the refrigeration system which requires high initial cost & high operating cost also. Positive
press. are necessary to prevent the leakage of air & moisture into refrigeration system. The
 operating press. range is one of the major considerations for the economical working of
refrigeration system.

The press. ranges for different refrigerants are listed below:

Refrigerant Press. in evaporator Press. in Condenser Press. ratio

at -15℃ at -29℃ PO/P
NH3 2.34ata 11.5ata 4.92
F-12 1.8ata 7.32ata 4.07
CO2 23.7ata 71.2ata 3.02
CH2Cl2 69.5 cm of Hg vacuum 21 cm of Hg vacuum 11.56

The above table shows the extreme press. of CO2 & extreme vacuum of CH2Cl2 for the normal
working temp. range. Both refrigerant are not suitable for refrigeration system due to their
extreme press. conditions.

The selection of compressor for a refrigeration system depends upon the selection of the
refrigerant for a particular join (required evaporator temp.)

Reciprocating compressors are commonly used with refrigerants having low Sp. volumes, high
operating press. & used for the refrigerants given below:

NH3, CO2, F-12, F-22 & CH3Cl

Centrifugal compressors are preferred for refrigerants operating under low evaporator &
condenser press. & low press. differentials.

High difference b/w evaporator & condenser press. results in high compression ratio. The power
required to run the compressor increases with increasing press. ratio & that is Bcoz of high
compression ratio which requires more power & gives low volumetric efficiency.

iv. Critical temp. & press.:

The critical temp. of vapour is defined as a temp. above which the vapour cannot be condensed
irrespective of any high press.. The critical temp. of the refrigerant used should be higher than
the temp. consuming within the condenser for easy condensation of the refrigerant vapour. The
critical temp. of all widely used refrigerants are well above the temp. occurring within the
condenser except CO2.

The air cannot be used as cooling medium in CO 2 refrigeration system Bcoz the critical press. of
CO2 at critical temp. is slightly above the required condenser press. of normally operated system.
The condensation of CO2 using air as cooling medium is more or less imposible during summer
when the temp. of atmospheric air is above the critical temp. of CO2. The critical temp. & press.
of few refrigerants are:
 Refrigerants Critical temp. in ℃ Critical press. in Kg/cm2
NH3 132.8 112
CO2 30.5 72.8
SO2 157 77.5
F-11 197.5 43.2
F-12 112.1 40.2
F-22 95.4 48.7
F-112 214 33.6
Carren-1 216 43.5
Carren-9 103 42.7

v. Latent Heat of Refrigerant:

High latent heat of refrigerant at evaporator temp. is desirable Bcoz the refrigerating effect per
Kg of refrigerant required to be circulated in the system per Ton of refrigerant will be low if the
latent heat of refrigerant is high. This also reduces the initial cost of the refrigerant used in the
system. The refrigerant with low latent heats can be used by increasing the fix numbers & speed
of cylinder if other properties are satisfactory.

b. Safe working properties: In the selection of refrigerant at the safe working properties of the
refrigerant are the prime consideration. There are few refrigerants which are highly desirable
from thermodynamic point of view but they find limited use due to unsafe properties. Ammonia
is one of them which is used for limited applications.

1. It should be chemically inert.

2. It should be nonflammable, non-expensive & non-toxic both in pure state & when mixed with
air, in any proportion.
3. It should not react with lubricating oil & with material used in construction of refrigeration
system.
4. It should not have bad effect on the storage material when the leak develops in the system.

i. Toxicity:
The effect of refrigerant on the human body is one of the major considerations in the selection
of the refrigerant & that is Bcoz of the possibility of the leakage of refrigerant from
refrigeration system. Toxic nature of the refrigerant may cause the injury to the human body or
death depending upon its %age in air. It increases suffocation & poisons the air used for
breathing.

This is one of the major considerations in selecting a refrigerant when the refrigeration system
is used for air conditioning, hospital or direct expansion cold storages.

The use of toxic refrigerants is limited for cold storage system as they effect palatable qualities
of many foods. They are used with indirect cooling method in which a secondary coolant such
as water or brine is used in the system.
 Some refrigerants which are non-toxic in nature become toxic when mixed with air with
certain %age. This is particularly true with all fluorocarbon refrigerants.

Refrigerants Qty. & Time required to produce serious results

%age by vol. in air Time (in min.)
NH3 0.5 30
CO2 30 30-60
SO2 0.7 5
F-11 10 120
F-12 30 120
F-21 5 30
F-113 10 60
Methyl Chloride (Methylene 2.5 120
Chloride)

ii. Flammability:
Ideal refrigerant should not have any danger of explosion in the presence of air or in
association with lubricating oil.

Most of the refrigerants commonly used are non-flammable so the danger of explosion does
not exist. Freons & CO2 come under this group. NH3 & CH3Cl burn with certain conc. in air.
The refrigerants of hydrocarbon family are highly flammable. Methane, ethane & propane
come under this group.

iii. Corrosive property:

The chemical rexn. of the refrigerant on the materials used in refrigeration system is not the
prime consideration in selection of the refrigerant but the selected refrigerant decides the
material to be used for the construction of the system. The refrigerant must be non-corrosive in
order to use more common materials.

Refrigerants must be chemically inert with materials as well as they must also remain inert in
the presence of water or air. The freon refrigerant are non-corrosive with all materials such as
brass, Cu, Zn, Fe, Tin, Pb & Al. The refrigerants become acidic in the presence of air & water.
Mg & Al should not be used with freon refrigerants as they are readily attacked by acid. Freons
have high solvent action on natural rubber so that synthetic rubber is used for gasket & other
sealing purposes to avoid this difficulty.

Iron & steel are commonly used with ammonia refrigerant as it acts on Cu, brass & other
Cuprous alloys in the presence of water.

Sulphuric acid is non-corrosive to all metals in the absence of water but it acts on all common
engg. metals in the presence of water & air.

iv. Chemical Stability:

An ideal refrigerant should not decompose at the temp. normally encountered in the system.
Some refrigerant disintegrate forming non-condensing gases which inc. condensing press. &
sometimes cause vapour lock.

Many times the disintegration of the refrigerant is due to the catalytic action of some metal. To
avoid this refrigerant must be inert with all materials used in refrigeration system.
 Freon is unstable above 600℃ & forms corrosive & poisonous products. SO2 does not
decompose below 1600℃, therefore, it is one of the most stable refrigerants. Such high temp.
are never reached under normal conditions in refrigeration systems.

v. Effect on stored products:

The refrigerants used in cold storage plant & in domestic refrigerators should not affect the
equality of the material when it comes in contact with stored products.

Ammonia is readily dissolved in water & becomes alkaline in nature. Most vegetables, fruits &
meat are slightly acidic in nature. Therefore ammonia reacts with these products & spoils the
taste.

SO2 is readily dissolved in water & become acidic in nature. There is no chemical rexn. of SO 2
on foods as most of the foods are acidic in nature. It has bleaching action on flower, plants &
furs. Methyl chloride vapour has effect on flowers, furs or any other household articles. There
is no danger in eating the food & drinking which are exposed to methyl chloride vapors.

Freon has no effect on foods, meat, vegetables, furs & air products. There will not be any
change in color, taste or texture of the materials which is exposed to freon.

c. Physical Properties

i. Specific vol.:
Low Sp. vol. of the refrigerant at the suction into the compressor is always desirable, Bcoz it
reduces the sized of the compressor for the same refrigeration capacity. The reciprocating
compressors are always used with low sp. vol. at suction where the centrifugal compressors are
desirable with high sp. vol. of the refrigerant at suction.

The quantities of vapour press. of refrigeration per hour for different refrigerants are listed
below:

Refrigerant m3/(ton) . (hour) at evaporator temp. of

150℃
NH3 1.36
CO2 3.58
F-11 5.9
F-12 9.45
F-22 5.85
F-113 16.4

ii. Sp. heat of liq. & vapor

Low sp. heat of liq. refrigerant & high sp. heat of vapor refrigerant are desirable Bcoz both tends
to increase the refrigerating effect per Kg of refrigerant. The low sp. heat of liq. refrigerant helps
in increasing the sub-cooling of liq. & high sp. heat of vapor helps in decreasing the superheating
of vapor. A refrigerant having both properties gives considerably high refrigerating effect per Kg
of refrigerant.
iii. Thermal Conductivity:
The thermal conductivity of liquids & gaseous refrigerants are required for finding the heat
transfer coeff. in evaporators & condensers. This data is necessary for designing evaporators &
condensers. High conductivities of refrigerant in both states are desirable.

iv. Viscosity:
This property of refrigerant in both states carries importance of calculating heat transfer coeff. in
evaporators & condensers. This also helps in designing the pumping units of the system. Low
viscosities of refrigerants in both states are desirable for better heat transfer & low pumping
power.