CY6251 Engineering Chemistry II Lecture Notes PDF

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CY6251 - Engineering Chemistry II - Lecture Notes - 2nd semester notes-regulation 2013- rejinpaul.com
Unit I
Water Technology
1.1 INTRODUCTION
The main sources of water are
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Water is essential for the existence of human beings, animals and plants. Though 80%
of the earths surface is occupied by water, less than 1% of the water is available for ready
use.
Rain
rivers and lakes (surface water)
wells and springs (ground water)
sea water
Among the above sources of water, rain water is the purest form of water but it is very
difficult to collect whereas sea water is the most impure form.
Thus, surface and ground water are normally used for industrial and domestic purposes.
Such water must be free from undesirable impurities.
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The process of removing all types of impurities from water and making it fit for
domestic or industrial purposes are called water treatment. Before treating water one must
know the nature as well as the amount of impurities.
1.2 HARD WATER AND SOFT WATER
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Hard Water
Water which does not produce lather with soap solution, but produces white
precipitate is called hard water.
This is due to the presence of dissolved Ca and Mg salts.
2C17 H 35 COONa + Ca ++ (C17 H 35 COO) 2 Ca +2Na+ Water soluble Water

insoluble
Soft Water
Water which produces lather readily with soap solution is called soft water.
This is due to the absence of Ca and Mg salts.
BOILER FEED WATER

In Industry, one of the chief uses of water is generation of steam by boilers. The
water fed into the boiler for the production of steam is called boiler feed water.
Requirements of boiler feed water
It should have zero hardness.
It must be free from dissolved gases like O2, CO2, etc.
It should be free from suspended impurities.
It should be free from dissolved salts and alkalinity.
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It should be free from turbidity and oil.
It should be free from hardness causing and scale forming constituents like Ca and Mg
salts.
FORMATION OF DEPOSITS IN STEAM BOILERS AND HEAT EXCHANGERS
1.5.1 Sludge and Scale formation in boilers
(i) Sludge
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In a boiler, water is continuously converted into steam. Due to this continuous

evaporation of water, the concentration of soluble matters increases progressively. Then the
salts separating out from the solution in the order of their solubility, the lease soluble ones
separating out first.
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If the precipitate is loose and slimy it is called sludges.

Sludges are formed by substances like MgCl2, MgCO3, MgSO4 and CaCl2.
They have greater solubilities in hot water than cold water.
Scale
1) If the precipitate forms hard and adherent coating on the inner walls of the boiler, it
is called scale.
2) Scales are formed by substances like Ca (HCO3)2, CaSO4 and Mg (OH) 2.
1.5.2 Disadvantages
Wastage of fuels
Scales have a low thermal conductivity, so the rate of heat transfer from boiler to
inside water is greatly decreased. In order to provide a supply of heat to water,
excessive or over-heating is done. This causes increase in fuel consumption. The
wastage of fuel depends upon the thickness and the nature of scale.
(i)
(ii) Decrease in efficiency
Scales sometimes deposit in the valves and condensers of the boiler and choke them partially.
This results in decrease in efficiency of the boiler.

Boiler explosion
When thick scales crack due to uneven expansion, the water comes suddenly in contact
with over-heated iron plates. This causes in formation of a large amount of steam
suddenly. So sudden high-pressure is developed, which may even cause explosion of
the boiler.
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1.6 PREVENTION OF SCALE FORMATION (OR) SOFTENING OF HARD

WATER
The process of removing hardness producing salts from water is known as softening
or conditioning of water. Since water is a source for industrial purpose. It is mandatory to
soften water to make it free from hardness producing substances, suspended impurities and
dissolved gases, etc.
Softening of water can be done by two methods.
External treatment
Internal treatment.
EXTERNAL TREATMENT
It involves the removal of hardness producing salts from the water before feeding into
the boiler. The external treatment can be done by the following methods.
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Zeolite (or) Permutit process
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Zeolite (or) Permutit process
Zeolites are naturally occuring hydrated sodium aluminosilicate minerals. The chemical
formula is Na2O.Al2O3.XSiO2.YH2O. The synthetic form of zeolite is called permutit and is
represented by Na2Ze.
In this process the hard water is allowed to perlocate through sodium zeolite. The
sodium ions which are loosely held in this compound are replaced by Ca2+ and Mg2+ ions.
When zeolite comes in contact with hard water, it exchanges its sodium ions with
calcium and magnesium ions of hard water to form calcium and magnesium zeolites.
As sodium ions do not give any hardness to water, the effluent will be soft. The
exhausted zeolite is again regenerated by treated with 5 to 10 percent of sodium chloride
solution.
CaZe + 2 NaCl Na2Ze + CaCl2
MgZe + 2 NaCl
Na2Ze + MgCl2
Advantages
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No sludge is formed during this process.

Water of nearly zero hardness is obtained.
This method is very cheap because the generated permutit can be used again.
The equipment used is compact and occupies a small space.
Its operation is also easy.
The process can be made automatic and continuous.
Disadvantages
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This process cannot be used for turbid and acidic water as they will destroy the
zeolite bed.
This treatment replaces only the cations, leaving all the anions like (HCO3) and
(CO3)2 in the soft water.
When such water is boiled in boilers, CO2 is liberated. Free CO2 is weakly acidic in
nature and extremely corrosive to boiler metal.
Na2CO3 + H2O2NaOH + CO2
Due to the formation of sodium hydroxide, the water becomes alkaline and can
cause cause caustic embrittlement.
Water containing Fe, Mn cannot be treated, because regeneration is very difficult.
This process cannot be used for softening brackish water. Because brackish water
also contains Na+ ions. So, the ions exchange reaction will not take place.
DEMINERALIZATION
1.8.1 Ion exchange or Demineralisation process
Ion exchange or demineralisation process removes almost all the ions (both anions and
cations) present in the hard water.
The soft water, produced by lime-soda and zeolite processes, does not contain hardness
producing Ca2+ and Mg2+ ions, but it will contain other ions like Na+, K+, SO42, Cl etc.,
On the other hand demineralised (DM) water does not contain both anions and cations.
Thus a soft water is not demineralised water whereas demineralised 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 process structure. The functional groups
attached to the chains are responsible for the ion exchanging properties.
(i) Cation exchanger

Resins containing acidic functional groups (COOH, SO3H) are capable of
exchanging their H+ ions with other cations of hard water. Cation exchange resin is
represented as RH2.
Examples:
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Sulphonated coals
Sulphonated polystyrene
RSO3H; RCOOH RH2
(ii) Anion Exchanger
Resins containing basic functional groups (NH2, OH) are capable of exchanging
their anions with other anions of hard water.
Anion exchange resin is represented as R (OH)2.
Examples:
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Cross-linked quaternary ammonium salts.

Urea-formaldehyde resin.
RNR3OH; ROH; RNH2 R (OH)2
Process
The hard water first passed through a cation exchange which absorbs all the cations
like Ca2+, Mg2+ Na+, K+, 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 a anion exchange column, which absorbs
all the anions like Cl, SO42, HCO3, etc., present in the water.
R' (OH) 2 + 2HCl
R'Cl2 + 2H2O
R'(OH) 2 + H2SO4 R'SO4 + 2H2O

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

RH + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated by passing
a solution of dil.NaOH.
R'Cl2 + 2 NaOH R'(OH)2 + 2 NaCl
Advantages
The water is obtained by this process will have very low hardness.
Highly acidic or alkaline water can be treated by this process.
Disadvantages
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The equipment is costly.

More explosive chemicals are needed for this process.
Water containing turbidity, Fe and Mn cannot be treated, because turbidity reduces
the output and Fe, Mn form stable compound with the resins.
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INTERNAL TREATMENT
Internal treatment involves adding chemicals directly to the water in the boilers for
removing dangerous scale forming salts which were not completely removed by the
external
Treatment for water softening. This method is used to convert scale to sludge which can be
removed by blow-down operation.
Calgon conditioning
Carbonate conditioning
Phosphate conditioning
Colloidal conditioning
Calgon conditioning
Calgon is sodium hexa meta phosphate with a
Composition Na2(Na4 (PO3)6). A highly soluble complex containing Ca is formed by
replacing the sodium ions and thus prevents their formation of scale forming salts like
CaSO4. The reaction is as follows:
2CaSO 4 + Na 2 [Na 4 (PO3) 6]
Na 2 [Ca 2 (PO3) 6] + 2Na 2SO4
Since the complex is highly soluble there is no problem of sludge disposal.

Carbonate conditioning
Scale formation due to CaSO4 in low pressure boilers can be avoided by adding
Na2CO3 to the boilers.
CaSO4 + Na2 CO3
CaCO3 + Na2SO4
The forward reaction is favored by increasing the concentration of CO32-.CaCO3

formed can be removed easily.
3CaSO4 + 2Na3 PO4
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Phosphate conditioning
In high pressure boilers, CaSO4 scale whose solubility decrease with increase of
temperature. Such scale can be converted into soft sludge by adding excess of soluble
phosphates.
Ca3 (PO4)2 +2Na2SO4
There are three types of phosphates employed for this purpose.
Tri-sodium phosphate Na3PO4 (too alkaline): used for too acidic water.
Di-sodium hydrogen phosphate Na2HPO4 (weakly alkaline): Used for weakly acidic
water.
Mono sodium di hydrogen phosphate NaH2PO4 (acidic) used for alkaline acidic water.
Colloidal conditioning
The colloidal conditioning agents are kerosene, agar-agar, gelatin, glue, etc. They are
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Used in low pressure boilers.
The colloidal substances convert scale forming substance like CaCO3, CaSO4 into a
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Non-adherent, loose precipitate called sludge, which can be removed by blow-down

Operation.
CAUSTIC EMBRITTLEMENT
Caustic embrittlement is a form of corrosion caused by a high concentration of sodium
Hydroxide in the boiler feed water.
It is characterized by the formation of irregular intergranular cracks on the boiler metal,
Particularly at places of high local stress such as bends and joints.
Causes of caustic embrittlement
Boiler water usually contains a small amount of Na2CO3. In high pressure boilers,
Na2CO3 undergoes hydrolysis to produce NaOH.
Na 2 CO 3 + H 2 O 2NaOH +CO2
This NaOH flows into the minute hairline cracks present on the boiler material by
capillary action and dissolves the surrounding area of iron as sodium ferroate, Na2FeO2.
Fe + 2NaOH Na 2 FeO 2 +H2
This type of electrochemical corrosion occurs when the concentration of NaOH is
above 100 ppm. This causes embrittlement of boiler parts, particularly the stressed parts like
bends, joints, rivets, etc.
Caustic embrittlement can be prevented by
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Using sodium phosphate as the softening agent instead of sodium carbonate.

Adding chemicals such as tannin, lignin to the boiler water. They block the hairline
cracks.
Adjusting the pH of the feed water carefully between 8 and 9.
BOILER CORROSION
Corrosion in boilers is due to the presence of
Dissolved oxygen
Dissolved carbon dioxide
Dissolved salts like magnesium chloride.
Dissolved oxygen
The presence of dissolved oxygen is responsible for corrosion in boilers. Water

containing dissolved oxygen when heated in a boiler, free oxygen is evolved, which corrodes
the boiler material.
Dissolved carbon dioxide
4 Fe (OH)3
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4Fe + 6H2O + 3O2
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When water containing bicarbonates is heated, carbon dioxide is evolved which makes
the water acidic. Carbon dioxide dissolved in water forms carbonic acid. This leads to intense
local corrosion called pitting corrosion.
Ca(HCO3)2
CaCO3 + H2O + CO2
CO2 + H2O H2CO3
Dissolved magnesium chloride
When water containing dissolved magnesium chloride is used in a boiler, hydrochloric

acid is produced. HCl attacks the boiler in a chain-like reaction producing hydrochloric acid
again and again which corrodes boiler severely.
MgCl2 + 2H2O 2HCl + Mg (OH)2
Fe + 2 HCl FeCl2 + H2
FeCl2 + 2H2O Fe (OH)2 + 2 HCl
Corrosion by HCl can be avoided by the addition of alkali to the boiler water.
Prevention of boiler corrosion

Removal of dissolved oxygen and carbon dioxide can be done either chemically or
mechanically.

Chemical method
For the removal of dissolved oxygen, sodium sulphite, hydrazines are used.
2Na2SO3 + O2
N2H4 + O2
2Na2SO4
N2 + 2H2O
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Hydrazine is the ideal compound for the removal of dissolved O2 as it forms only
water and inert nitrogen gas during the reaction.
Dissolved CO2 is removed by the addition of ammonium hydroxide.
2NH4OH + CO2
Mechanical method
(NH4)2CO3 + H2O
Oxygen along with carbon dioxide can be removed mechanically by the de-aeration
method
In this method, water is allowed to fill in slowly on the perforated plates fitted inside
the tower.
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To reduce the pressure inside the tower, the de-aerator is connected to a vacuum pump.
The sides of the tower are heated by means of a steam jacket. This is based on the principle
that the solubility of a gas in water is directly proportional to pressure and inversely
proportional to temperature.
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High temperature, low pressure and a large exposed surface, reduces the dissolved
gases (O2 and CO 2) in water.
The water flows down through a number of perforated plates and this arrangement
exposes a large surface of water for de-aeration.
1.12 PRIMING AND FOAMING (CARRY OVER)
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 liquid 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.
Priming
Priming is the process of production of wet steam. Priming is caused by

High steam velocity.
Very high water level in the boiler.
Sudden boiling of water.
Very poor boiler design.

Prevention
Priming can be controlled by
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Controlling the velocity of steam.

Keeping the water level lower.
Good boiler design.
Using treated water.
Foaming
The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried over by steam leading to excessive priming.
Foaming is caused by the
Presence of oil and grease.

Presence of finely divided particles.
Prevention
Foaming can be prevented by
Adding coagulants like sodium aluminate, aluminium hydroxide.

Adding anti-foaming agents like synthetic polyamides.
DESALINATION
Depending upon the quantity of dissolved solids, water is graded as
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Dissolved solids.
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Fresh water has < 1000 ppm of dissolved solids. Brackish water has > 1000 but <
35,000 ppm of
Sea water has > 35,000 ppm of dissolved solids.

Water containing dissolved salts with a peculiar salty or brackish taste is called
brackish water. It is totally unfit for drinking purpose. Sea water and brackish water can be
made available as drinking water through desalination process.
The removal of dissolved solids (NaCl) from water is known as desalination

process. The need for such a method arises due to the non-availability of fresh water.
Desalination is carried out either by electro dialysis or by reverse osmosis.
1.13.1 Reverse Osmosis
When two solutions of different concentrations are separated by a semi-permeable

membrane, flow of solvent takes place from a region of low concentration to high
concentration until the concentration is equal on both the sides. This process is called
osmosis.
The driving forces in this phenomenon are called osmotic pressure. If a hydrostatic
pressure in excess of osmotic pressure is applied on the higher concentration side, the
solvent flow reverses, i.e., solvent is forced to move from higher concentration to lower
concentration .This is the principle of reverse osmosis. Thus, in reverse osmosis method
pure water is separated from its dissolved solids.
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Advantages
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Using this method pure water is separated from sea water. This process is also known
as super-titration. The membranes used are cellulose acetate, cellulose butyrate, etc.
The life time of the membrance is high.

It can be replaced within few minutes.
It removes ionic as well as non-ionic, colloidal impurities.
Due to simplicity low capital cost, low operating, this process is used for
converting sea water into drinking water.

UNIT 2
ELECTROCHEMISTRY&CORROSION CONTROL
Emf Series / Electrochemical Series:
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Definition
The arrangement of various metals in the order of increasing values of standard
reduction potential is called emf series.
Applications of Emf Series:
o Calculation of Standard emf of the cell
o Relative ease of Oxidation or Reduction
o Displacement of one element by the other
o Determination of equilibrium constant for the Reaction
o Hydrogen Displacement Behaviour
o Predicting Feasibility/ Spontaneity of the cell
1. Calculation of Standard emf of the cell
Using E , the standard emf can be calculated
E ECell = E RHE - E LHE

2. Relative ease of Oxidation or Reduction
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Standard Reduction
Potential
Positive
Negative
Eg. F ( + 2.87V)
Li ( - 3.01V)
Reaction
Reduction
Oxidation
Reduction
Oxidation
Eg. E
2+
/ = + 0.34 V
Cu
Cu
3. Displacement of one element by the other

Metal with more negative reduction potential can displace those metals with less
negative or positive potentials from the solution
4. Determination of equilibrium constant for the Reaction

Equilibrium constant can be calculated using the formula
WKT, G = RT ln K = 2.303 RT log
K Log K = - G
2.303 RT
= nFE
2.303 RT
5. Hydrogen Displacement Behaviour
Metal with negative reduction potential will displace hydrogen from the
solution
Zn + H2SO4
ZnSO4 + H2 ( Ezn
Ag + H2SO4
No Reaction (E Ag
6. Predicting Feasibility/ Spontaneity of the cell
Spontaneity depends on E value
E - Positive ( Reaction Spontaneous)
E - Negative ( Reaction non Spontaneous)
E - Zero (Reaction Equilibrium)

Measurement Of Emf Of A Cell:
Principle:
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Eg.
Poggendorffs Compensation Principle:

Emf of the cell is just opposed or balanced by an emf of standard cell (external emf)
so that no current flows in the circuit.
Diagram: (Refer Book)
Construction:
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Potentiometer consists of a uniform wire AB

A Storage battery(K) is connected to the ends A and B of the wire through a
rheostat(R)
U n k n o w n emf (x) connecting its
Positive to Pole A
Negative to Sliding contact (D) through galvanometer G.
S l i d i n g contact is free to move along the wire AB till no current flows through the
galvanometer.
Emf of unknown cell is directly proportional to the distance AD
Ex
AD
Unknown cell (x) is replaced by a standard cell (s) in the circuit

S l i d i n g contact is again moved, till there is null reflection in the galvanometer
Emf of the standard cell Es is directly proportional to the distance AD
Es
AD
Emf of the unknown cell x = Length AD

Enf of the unknown cell s Length AD
Ex = AD
Es AD
Using this formula EMF of the unknown cell is calculated.

= -0.76 V)
= +0.80 V)
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Eg: Oxides of heavy metals
II Corrosion by H2
Corrosion by H2
Decarburization (high temp)

H2
2H
H + H
H2
Formation of cracks and blisters

on metal surface due to high
pressure of H2 gas
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H2 embrittlement ( ordinary temperature)

Fe + H2S
FeS + 2H
+ 4H
CH4
The process of decrease in

carbon content in steel is
termed as decarburization of
steel
III Liquid metal corrosion

Occurs due to
a) Either dissolution of solid metal by a liquid metal (or)
b) Liquid metal may penetrate into the solid metal
Electrochemical or Wet Corrosion:
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Mechanism:
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Wet corrosion occurs in two conditions

i)
When two dissimilar metals are contact with each other
ii)
When a metal is exposed to varying concentration of oxygen
At Anode
Oxidation occurs
M
M2+ + 2eAt Cathode
Reduction occurs. Depends on nature of the environment
a) Acidic environment:
Hydrogen evolution occurs

2H+ + 2e-
H2
b) Neutral environment:
Hydroxide ion formation takes place
O2 + 2e- + H2O
2OH-
Hydrogen Evolution Type:

All metals above H2 in electrochemical series undergo this type of corrosion
Example:
Iron metal in contact with HCl
At Anode:
Fe
Fe2+ + 2e(Oxidation) At Cathode:

2H+ + 2e-
H2 (Reduction)
Absorption of oxygen or Formation of hydroxide ion type corrosion:

Example:
Iron metal in contact with a neutral solution
Fe2+ + 2e- (Oxidation)
At Cathode:
O2 + H2O + 2eNet Corrosion reaction is
Fe2+ + 2OH-
Electroplating:
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At Anode:
Fe
2OH-
Fe(OH)2 (Reduction)
Principle:
It is the process in which the coating metal is deposited on the base metal by
passing a direct current through an electrolytic solution containing the soluble salt of
coating metal.
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Objectives:
On Metals:
i)
To increase the resistance to corrosion.
ii)
To improve the hardness
On Non-Metals:
i)
To increase strength
ii)
To preserve and decorate the surfaces of wood, glass, plastics etc.,
Process:
Object to be coated first treated with dil.HCl or dil.H2SO4
Object to be coated
Gold foil
AuCl3
Glue, Gelatin
Brightening Agents
60oC
1 10 mA/cm2
Cathode
Anode
Electrolyte
Additives for strong and
adherent coating
To improve brightness
Optimum temperature
Optimum current
density
When current is passed gold dissolves in solution and deposits on the object
Various chemical reactions:
AuCl3 ionises as
AuCl3
Au3+ + 3ClAt Cathode:
Au3+ ions moves to cathode and deposits as Au metal
Au3+ + 3eAu

At Anode:
Free chloride ions moves to the
anode. Au + 3Cl-
AuCl3 + 3e-
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Corrosion Control By Cathodic Protection

a) Sacrificial Anodic protection method:
The metal to be protected is made cathode. It is connected with more active
metal. Corrosion will concentrate only on the active metal. Thus original metal is
protected. Hence this process is known as sacrificial anodic protection method.
Applications:
i)
Used for the protection of ships and boats.
ii)
Protection of underground pipelines, cables from soil
corrosion iii) Calcium metal is employed to minimize soil
corrosion.
b) Impressed current cathodic protection method:
The corroding metal is converted from anode to cathode. This is done
by applying a current in opposite direction of corrosion current.
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Method:
Negative terminal of the battery is connected to the metal. Positive terminal
of the battery is connected to an inert anode. Inert anode used is graphite, platinised
Titanium. The anode is buried in a back fill to provide electrical contact.
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Applications:
Structures like tanks, pipelines, ships etc can be protected.
Corrosion Inhibitors:
Anodic inhibitors:
It prevents corrosion occurring at the anode. It forms an insoluble
Compound with metal ions. These precipitate forms a protective film and
prevents corrosion.
Example:
Chromates, nitrates, phosphates of transition elements.
Cathodic inhibitors:
It prevents corrosion occurring at cathode.
In acidic solution:
Hydrogen evolution occurs.
2H+ + 2eH2
Corrosion can be reduced by
i)
Slowing the diffusion of H+ ions. This is done by adding amines, pyridines.
ii)
Increasing over voltage. This is done by adding antimony and arsenic oxides.
In a neutral solution:
Formation of hydroxide ion occurs.
O2 + 2e- + H2O
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Corrosion can be reduced by
i)
Eliminating O2. Done by adding Na2SO3, N2H4
etc., ii) Eliminating OH-. Done by adding Mg, Zn or Ni salts.
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Vapour Phase inhibitors:

This readily vapourise and form a protective layer on the metal surface.
Example:
Dicyclohexyl ammonium nitrate, benzotriazole etc.,
Differential Aeration Corrosion:
This type of corrosion occurs when a metal is exposed to varying concentration of
O2 or any electrolyte on the surface of the base
metal. Example:
Metals partially immersed in water (or) conducting solution.
Mechanism:
Metal part which is above the solution is more aerated and hence becomes
cathodic.
Metal part which is inside the solution is less aerated and hence becomes anodic.
At Anode:
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Corrosion occurs
M
M2+ +
2e
At Cathode:
Hydroxide ions are produced.
O2 + 2e- + H2O
2OHExample:
Pipeline corrosion:
Pipelines passing from one type of soil example from clay(less aerated) to sand
(more aerated) undergo differential aeration corrosion.
Factors Influencing the Rate of Corrosion:
i) Nature of the metal

a) Position in emf series:
Metals above hydrogen in emf series undergo corrosion easily. Greater the
difference in their position faster is the corrosion
rate.
b) Relative areas of the anode and cathode:
The rate of corrosion will be more when the cathodic area is
larger. c) Purity of the metal:
100% pure metal will not undergo corrosion. Higher the percentage
of impurity, faster is the rate of corrosion.
Example:
%Purity of Zinc
Corrosion Rate
99.999
1
99.99
2650
99.95
5000
d) Nature of corrosion product:


If the corrosion product is soluble in the medium, the corrosion rate will be
faster. If it is volatile, then also corrosion rate will be
faster.
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e) Nature of the surface film

If the surface film is porous and non-protective, it bring about further
corrosion. If the surface film is non-porous and protective, it prevents further
corrosion.
f) Over voltage or over potential:
The over voltage of a metal in the corrosive environment is inversely
proportional to corrosion rate.
ii) Nature of the environment
a) Temperature:
The rate of corrosion is directly proportional to temperature.
b) Humidity:
The rate of corrosion will be more, when the humidity in the environment is high.
c) Presence of corrosive gases:
Acidic gases like CO2, SO2, H2S and fumes of HCl, H2SO4 etc
increases corrosion
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d) Presence of suspended
particles:
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Particles like NaCl, (NH4)2SO4 with moisture increases

corrosion.
e) Effect of pH:
The rate of corrosion will be maximum when the corrosive environment is

acidic i.e. pH is less than 7.
Electroless Plating
Principle
Electro less plating is a technique of depositing a noble metal on a

catalytically active surface of the metal to be protected by using a suitable reducing
agent without using electrical energy.
Metal ions + Reducing Agent
Metal + Oxidized product
Process:
Step 1: Pretreatment and activation of the surface:
The surface to be plated is first degreased by using organic
solvents or alkali, followed by acid treatment.
Example:
The surface of stainless steel is activated by dipping in hot solution of

50% dil.H2SO4
Step 2: Plating bath :
Complexing agent
Buffer
Optimum pH
Optimum
temperature
Name of the
compound
NiCl2
Sodium
hypophosphite
Sodium succinate
Sodium acetate
4.5
93C
Step 3: Procedure
Quantity(g/l)
Function
20
20
Coating metal
Metal ions reduced
15
10
---------------------------
Improves the quality

Control the pH
-------------------------------
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Nature of the
compound
Coating solution
Reducing agent
The pretreated object is immersed in the plating bath for the required time.
At Cathode:
Ni2+ + 2e-
Ni
At Anode:
H2PO3- + 2H+ + 2e-
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H2PO2- + H2O
Ni + H2PO3- + 2H+
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Net Reaction:
Ni2+ + H2PO2- + H2O
Applications:
1. Electro less Ni plating is extensively used in electronic appliances.

2. Electro less Ni plating is used in domestic as well as automotive fields.
UNIT -3
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ENERGY SOURCES
Nuclear fission: It is the nuclear reaction in which heavy

isotopes are split into lighter nuclei on bombardment by
235
neutrons. Fission reaction of U
is given below
92
+0n1
36Kr
56Ba
1
+ 3 0n + energy
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235
92U
141
(Structure of fission reaction)
Nuclear fusion:
Process of combination of lighter nuclei
into heavier nucles with simultaneous liberation of large
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amount of energy. (e.g) solar system

2
2
4
1H + 1H 2 He + Energy
Nuclear fusion reaction occurs in sun.
Differences between fission and fusion reaction

Nuclear Energy
Nuclear fission
It is a process of breaking a
It
heavier nucleous.
combination of lighter
The mass
process
of
nuclei.
It does not emit any kind
of radioactive rays
The mass number and
atomic
elements are lower than
product is higher than
It
number and
is
atomic number of new
It emits radioactive rays
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Nuclear fusion
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S.No
It
occurs
at
ordinary
temperature
gives
rise
number
of
that of starting elements

It
occurs
at
high
Temperature
to
chain
It does not give rise to
reaction
chain reaction
It emits neutrons
It emits positrons
It can be controlled
It canot be controlled
Light water nuclear power plant

Definition
Light water nuclear power plant is one in
235
WhichU
feel rods are submerged in water.
Here thewater acts as coolant and moderator.
The fission reaction is controlled by inserting or

10
automatically
removing the control rods of B
from the spaces I between the fuel rods.

235
The heat emitted by U
in the fuel core is
absorbed by the coolant.
Heat is transferred to sea water and then

converted into steam.
The steam then drives the turbines, generating
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electricity.
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(Str of light water nuclear power plant)
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Breeder reactor
A nuclear reactor with conversion or multiplication factor greater than one is a breeder reactor. A
breeder reactor generates fissionable nuclei from fertile nuclei.
E.g., the fertile material like uranium-238 is converted into fissile
94 Pu239 by using slow neutrons. 94 Pu239 undergoes fission and produces energy.
Working :
`In breeder reactor, 92U235 is used as trigger to produce sufficient neutrons. These are used to
convert 92U235 to Plutonium undergoes fission with the production of three neutrons. One neutron is
used to propagate fission chain. The other two neutrons react with 92U238 to 94 Pu239. Thus breeder
reactor produces two 239 Pu atoms for each 239 Pu consumed. Thus more fissionable material is
produced than consumed. Hence the reactor is called breeder reactor.
Critical Mass:
The minimum amount of fissile material (U235) required to continue the nuclear chain reaction is
called critical mass.
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Photo galvanic cell or Solar cell
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PRINCIPLE:
The principle of Solar cell is based on photovoltaic effect. When light radiation falls on the p-n
junction semi conductor device, charge separation takes place and a potential difference is setup. This
causes flow of electrons and produces electricity.
Working:
When sun rays all on the top layer of p- type semiconductor, electrons from valence band are
promoted to conductance band and cross the p-n junction into the n-type semiconductor. A potential
difference is set up between the two layers. This causes flow of electrons and produces electricity.
When the p and n layers are connected to an external circuit, electrons flow from n layer to p
layer and current is generated.
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Application of Solar Cell

1. Lighting purpose
Now a days electrical street lights are substituted by solar street lights.
2. Solar pumps are run by solar battery

A large number of solar cells are connected in series to form a solar battery. Solar battery produces
enough electricity to run water pump, etc., They are also used in remote areas where conventional
electricity is not available.
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SOLAR BATTERY
3. Solar cells are used in calculators, electronic watches etc.
4. Solar cells are superior to other type of cells, because they are non-polluting and eco-friendly.
5. Solar cells are used to drive vehicles.
6. Silicon solar cells are used as a source of electricity in space crafts and satellites.
Advantages of Solar cells
1. Solar cells are used in remote areas, forests and hilly regions.
2. Maintenance cost is minimum.
3. Solar cells are pollution free.
4. They have long life.
Disadvantages
1. Solar cells are costly.
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2. Storage of energy is not possible with solar cells.
WIND ENERGY
Moving air is called wind. Energy recovered from the forces of wind is called wind energy.
Generation of electricity from wind mill
Wind energy is used to generate electricity with the help of wind mills. The crank of the wind
mill is connected to a dynamo. When the blades of wind mill rotate, they turn the coil of the dynamo
and produce electricity. Usually a number of wind mills are erected side-by-side. The outputs from the
wind mills are coupled to generate electricity for commercial purpose. This type of system is wind
energy farms.
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Condition: Wind speed should be more than 15km/hr.
Advantages of wind energy
(i) It is cheap and economical.

(ii) It is renewable
(iii) It does not cause pollution.
Disadvantages
(i) They produce noise.
(ii) Wind farms erected on the migratory routes of birds create problems.
(iii) Wind turbines interfere with electromagnetic signals.
FUEL CELLS:
Definition
Fuel cell is a voltaic cell. It converts chemical energy of the fuels directly into electricity without
Fuel + Oxygen
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combustion. In these cells, the reactants and electrolytes are continuously supplied to the cell.
Oxidation products + Electricity.
Examples : Hydrogen - oxygen fuel cell.

Hydrogen - oxygen fuel cell
It is the simplest and most successful fuel cell. The fuel-hydrogen and the oxidiser-oxygen and
the liquid electrolyte are continuously supplied to the cell.
Description
The cell has two porous electrodes, anode and cathode. The electrodes are made of
compressed carbon containing a small amount of catalyst (Pt, Pd, Ag). Between the two electrodes an
electrolytic solution, 25% KOH is filled.
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Working
Hydrogen passes through the anode compartment, where it is oxidised. Oxygen passes through the
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cathode compar tment, where it is reduced.
(Hydrogen Oxygen fuel cell)
Cell reactions
At anode:
2H2+4OH- 4H2O +4e-
At cathode:
O2 +2H2O + 4e-
2H2+O 2 2H2O
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Overall cell reaction:
4OH
emf of the cell = 0.8 to 1.0V
Advantages of Fuel Cells
1. They are efficient and instant in operation.

2. They are pollution free.
3. They produce electric current directly from the reaction of a fuel and an oxidiser.
4. They are light in weight
Disadvantages
1. Fuel cells cannot store electric energy.

2. Electrodes are expensive and short lived.
3. H2 should be pure.
Applications
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1. H2 - O2 fuel cells are used in space crafts, submarines to get electricity

2. In H2 - O2 fuel cell, the produt water is a valuable source of fresh water for astronauts
Battery:
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ENERGY STORAGE DEVICES
It is an arrangement of several electrochemical cells

connected in series that can be used as a source of direct
electric current.
Secondary battery or secondary cells
In these cells, the electrode reactions can be reversed by

passing an external energy.
They can be recharged by passing electric current.
They are called storage cells or accumulators.
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Ex: Lead acid storage cell, Nickel- cadmium cell.

Alkaline Battery
Here the powdered zinc is mixed with KOH and MnO2 to get a gel
A Carbon rod acts as cathode. IT is immersed in KOH
The outside cylindrical body is made up of zinc
Cell reactions
At anode :
Zn (s) + 2OH-
At cathode:
2MnO2 + H2O(l) + 2e- 2OH- +Mn2O3

Zn (s) + 2MnO2 + H2O(l)
Zn(OH)2 + Mn2O3
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Overall :
Zn(OH)2 + 2e-
Uses: It is used in calculators, watches etc.,

Lead storage cell
Description:
It consists of number of voltaic cells connected in series
Pb is anode and PbO2 is cathode
Number of Pb plates and PbO2 plates are connected in
parallel.
Plates are separated from adjacent ones by insulators

like rubber or glass fiber.
This arrangement is immersed in dil. H2SO4
Cell reactions
Pb (s) + SO42-
PbSO4 (s) + 2e+

PbO2(s) + SO42- + 4H + 2e- PbSO4 + 2 H2O
At cathode:
Overall reaction:
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At anode :
Pb (s) + PbO2(s) + 2H2SO4 PbSO4 + H2O + energy

Uses:
It is used to supply current mainly in automobiles

such as cars. Buses, trucks, etc.,
It is also used in gas engine ignition, telephone

exchanges, hospitals, power stations.
Nickel Cadmium Battery
Description
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It consists of a cadmium anode.
a metal grid containing a paste of NiO2 acting as a cathode.
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KOH is electrolyte
Ni-Cd battery
Cell reactions
At anode: Cd(s) + 2OH- Cd(OH)2(s) + 2e+Ni(OH)2 (s) + energy
At cathode: NiO2 + 2H2O(l) + 2e- 2OHOverall reaction:
Cd(s) + NiO2 + 2H2O(l) Cd(OH)2(s) + Ni(OH)2 (s) + energy

Uses:
It is used in calculators. Electronic flash units, transistors and cordless appliances.
Lithium Battery
Description
It consists of a lithium anode and a TiS2 cathode.
A solid electrolyte generally a polymer is packed in
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between the electrodes.
The electrolyte permits the passage of ions but not
electrons.
Cell reactions
At anode:
Li(s)
+
Li + e-
TiS2 + e- TiS2-
At cathode:
Overall reaction:
+
Li + TiS2-
Li(s) + TiS2
Li/ MnO2
(ii)
Li/V2O5
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(i)
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Other types of secondary lithium batteries
(iii) Li/MoO2
(iv) Li/Cr3O8
Advantages of Li battery
It is the cell future. Why?
Its cell voltage is high, 3.0V
Since Li is a light weight metal, only 7kg material required

to produce 1mole of electrons.
Since all the constituents of the battery are solids, there is
no risk of leakage from the battery. This battery can be made in a variety of shapes and sizes.

Disadvantages of Li battery
Li battery is more expensive than other batteries
Uses
Button sized batteries are used in calculators, watches,
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cameras, mobile phones, laptop computers.
Lithium Battery
It is a solid state battery. Solid electrolyte is used.

Construction
It has a lithium anode and a TiS2 cathode. A solid electrolyte, a polymer, is packed in
between the electrodes. The polymer electrolyte permits the passage of ions but not that of
electrons.
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Working (Discharging)
The anode is connected to cathode through the polymer electrolyte. Lithium ions and
electrons are produced at the anode . The cathode receives the lithium ions and electrons.
At anode: Li(s)
Li+ + e-
At Cathode: TiS2(s) + e
TiS2
Overall reaction: Li(s) + TiS2(s)
Li+ + TiS2- LiTiS2
Recharging
The battery is recharged by passing an external current, which drives the lithium ions back
to the anode. The overall reaction is

LiTiS2 Li+ + TiS2
This cell has a voltage of 3.oV.
Uses:
It possesses very small size and high energy density. So it is used in calcutors, electronic
flash units, computers, transistors head phones etc.
Advantages
(i) The cell has a voltage of 3.0V.


(ii) Li is a light-weight metal. Just 7g (1 mole) of Li is required to produce 1 mole of
electrons.
(iii) Li has the most negative Eo value. So it gives a higher voltage than other cells.
(iv) It is a total solid state battery. There is no risk of current leakage from the battery.
(v) It is manufactured in a variety of sizes and shapes.
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Disadvantages
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It is more expensive than other batteries.
UNIT 4
ENGINEERING MATERIALS
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REFRACTORIES
Materials that can withstand high temp without softening and deformation in their
shape.
Used for the construction of furnaces, converters, kilns, crucibles, ladles etc.
CHARACTERISTICS
Infusible at operating temp.
Chemically inert towards corrosive gases, liquids etc.
Should not suffer change in size at operating temp.
Should have high refractoriness
Should have high load bearing capacity at operating temp.
CLASSIFICATION
Based on chemical nature
Acidic refractories Eg. Silica and Alumina
Basic refractories Eg. Magnesite and Dolomite
Neutral refractories Eg. Graphite and Carborundum
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Based on refractoriness
Low heat duty refractories
Intermediate heat duty refractories
High heat duty refractories
Super heat duty refractories
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PROPERTIES
Refractoriness
It is the ability to withstand very high temp. without softening or deformation under
particular service condition. Since most of the refractories are mixtures of several metallic
oxides, they do not have a sharp melting point. So the refractoriness of a refractory is
generally measured as the softening temperature and is expressed in terms of pyrometric cone
equivalent.(PCE). Pyrometric cone equivalent is the number which represents the softening
temperature of a refractory specimen of standard dimension (38mm height and 19mm
triangular base) and composition.
Objectives of PCE test
To determine the softening temperature of a test refractory material.
To classify the refractories
To determine the purity of the refractoreies
To check whether the refractory can be used at particular servicing temperature.
Refractoriness is determined by comparing the softening temperature of a test cone with

that of a series of segar cones. Segar cones are pyramid shaped standard refractory of definite
composition and dimensions and hence it has a definite softening temperature.
A test cone is prepared from a refractory for which the softening temperature to be
determined, as the same dimensions of segar cones.

Then the test cone os placed in electric furnace. The furnace is heated at a standard rate of
100C per minute, during which softening of segar cones occur along with test cone. The
temperature at which the apex of the cone touches the base is taken as its softening
temperature.
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RUL Refractoriness Under Load

The temp. at which a std dimensioned specimen of a refractory undergoes 10% deformation
with a constant load of 3.5 or 1.75 Kg/cm2 The load bearing capacity of a refractory can be
measured by RUL test. A good refractory should have high RUL value
Porosity ratio of pore volume to the bulk volume
P = (W- D/W- A) X 100
W weight of saturated specimen in air
D weight of dry specimen
A weight of saturated specimen in water
Porosity reduces strength, corrosion resistance thermal conductivity, thermal spalling and
abrasion resistance
Thermal spalling property of breaking, cracking or peeling of refractory material under

high temp. Thermal spalling may be due to rapid change in temp. or slag penetration
A good refractory should show good resistance to thermal spalling
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Dimensional stability
Resistance of refractory to any volume change when exposed to high temp. over a prolonged
time
Refractories may undergo reversible or irreversible dimensional changes A good refractory
should show minimum level of reversible dimensional changes with temp.
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ALUMINA BRICKS
Contain 50% of aluminium oxide
Manufacture
Calcined bauxite, silica and grog (calcined fire clay) are ground well and mixed with water
The pasty mass is converted into bricks by mechanical pressing or slip casting
The bricks are dried and fired at about 1200 to 14000 C for 6-8 days
MAGNESITE BRICKS
Contain maximum Magnesium oxide
Manufacture
Calcined magnesite, magnesia or iron oxide are ground well and mixed with water
The pasty mass is converted into bricks by mechanical pressing or slip casting
The bricks are dried and fired at about 15000 C for 8 hours then cooled slowly
ZIRCONIA BRICKS
Contain zirconite
Manufacture
Zirconite mineral, colloidal zirconia or alumina are ground well and mixed with water and
made into bricks. Small amount of MgO or CaO is added as stabilizer. The bricks are dried
and fired at about 17000 C
ABRASIVES
Abrasives are very hard substances used for grinding, shaping and polishing other
materials
ABRASIVES - TYPES
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PROPERTIES
Have very high melting point
Chemically inert
High abrasive power (ability to scratch away pr sharp other materials)
Sometimes hard and brittle or soft and flexible
natural abrasives Eg. Diamond, corundum

synthetic abrasives Eg. carborundum, norbide
Hardness is measured in terms of mohs scale.
Diamond is taken as the reference and hardness of other materials are determined
abrasives with Mohrs scale 1-4 are called soft abrasives
NATURAL ABRASIVES
Diamond:
Purest crystalline carbon - Hardest natural substance

Mohrs scale value is 10 -Superior chemical inertness
Used in grinding wheels, drilling tools, cutting glasses, etc
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Corundum
Emery
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Pure crystalline form of alumina - Mohrs scale value is 9 - Used in grinding glass, gems etc.
55-75% alumina, 20-40% magnetite, 12% others - Black and opaque

-Mhos scale value is 8 - Used for making abrasive paper, abrasive cloth, etc.
Quartz
Pure silicone - Mohrs scale value is 7 - Used in painting industries
Garnet
Trisilicates of alumina, magnetite and Fe oxide

Used for the manufacture of abrasive paper and cloth
ARTIFICIAL ABRASIVES
Silicon Carbide (SiC)
Manufacture
Silicon Carbide is manufactured by heating sand (60%)and coke (40%) with some saw dust
and a little salt in an electric furnace to about 1500C
SiO2 + 3C SiC + 2CO
The silicon carbide removed from the furnaces, is then mixed with bonding agent(clay,
silicon nitride) and than shaped, dried and fired.

Properties
1. Silicon carbide possesses a high thermal conductivity, low expansion and high resistance
to abrasion and spalling.
2. They are mechanically strong. Mohrs scale value is 9.
3. Bear very high temp. 1650C
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4. Has thermal conductivity between metals and ceramics
They are electrically intermediate between conductors and insulators.

Uses
1. Silicon carbide are used as heating elements in furnaces in the form of rods or bars.
2. They are also used for partition wall of chamber kilns, coke ovens, muffle furnaces and
floors of heat treatment furnaces.
3. Sic bonded with tar are excellent for making high conductivity crucible.
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Norbide or Boran Carbide (B4C)

Manufacture
It is prepared by heating a mixture of boran oxide (B2O3) and coke in an electric furnace to
about 2700C
B2O3 +7C give B4C + 6CO
Properties
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1. Its hardness is 9 on Mohrs scale.
2. It is light weight and black colored compound.

3. It is highly resistant to chemical attack and erosion.
4. It resists oxidation much better than diamond.
Uses
It is used as hard materials for making grinding dies, and for cutting and sharpening
hard high speed tools.
It is used to prepare scratch and wear resistant coating.
PORTLAND CEMENT
It is defined as an extremely finely ground product.
It is obtained by heating a mixture of argillaceous (clay containing ) and calcareous (lime

containing ) raw materials to about 1500 c. It is then mixed with gypsum to increase the quick setting
and hardening property.

MANUFACTURE OF PORTLAND CEMENT
Raw materials :
(i) Calcareous materials , CaO Ex: Limestone, chalk.
(ii) Argillaceous materials, Al2O3 and SiO2 Ex: clay, slate etc
(iii) Powdered coal (or) fuel oil.
(iv) Gypsum (CaSo4.2H2O)
(i)
Mixing of raw materials
(ii)
Burning
(iii)
Grinding
(iv)
Storage and Packing

(i)
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Manufacture of Portland cement involves the following steps:
Mixing of raw materials:
(a) Dry Process
(b) Wet Process
(a) Dry Process: In dry process, the raw materials like limestone and clay(3:1) are dried, and
mixed in definite proportions
(b) Wet process : In wet process, the raw materials in definite proportions are finely ground with
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water and the slurry ( past like) is fed at the top of the rotary kiln.
(II) Burning
The burning process is usually done in rotary kiln which is a long horizontal steel cylinder
coated with refractory bricks and capable of rotating at 1 rpm 9 Revolution per minute) . The
rotary kiln is set at a slight inclination of about 5-60 in order to allow the raw materials fed at one
end to travel slowly to the firing and discharge exit end.
The slurry of raw materials is allowed to enter from the top end of the rotary kiln.
Simultaneously the burning fuel ( like powdered coal or oil) and air are introduced from the lower
end of kiln . The slurry gradually comes down in the kiln into the different zones ( Drying Zone at

400o :Calcination zone at 700 -1000
C and clinkering zone at 1250-1500
C of increasing
temperatures.
(a) Drying Zone: The upper part of the rotary kiln is known as drying zone ,where
the temperature is about 400 o C . Due to the presence of hot gases in this zone,
water is evaporated from the slurry.
(b) Calcinations zone: The middle part of the rotary kiln is known as calcining zone
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where the temperature ranges from 700 -1000
C. In this zone lime stone is
decomposed into CaO and CO2

CaCO3
700 -1000 o C
Lime Stone
CaO +CO2
Quick lime
(c) Clinkering Zone : The lowest part of the zone is called as clinkering zone, where
the temperature is maintained about 1250-1500 o C. In this zone lime reacts with clay ( Containing
Al2O3, Fe2O3 and SiO2) and forms aluminates and silicates
2CaO+ SiO2 -------- 2CaO.SiO2
Di calcium Silicate
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3CaO+ SiO2 -------- 3CaO.SiO2
Tri calcium Silicate
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The mixture is then finely powdered and fed into the top of the rotary kiln.
3CaO+ Al2O3-------- 3CaO.Al2O3
Tri calcium Aluminate
4CaO + Al2O3 + Fe2O3--------- 4CaO.Al2O3.Fe2O3
(ii)
(iii)
Tetra calcium alumino Ferrate
Cooling : the hot clinker is cooled with atmospheric air and the hot air thus produced
is used for drying the coal before grinding.
Grinding : The cooled clinker is then finely pulverized with 2-6% gypsum acts as a
retarding agent for quick setting of cement.
(iv)
Storage and Packing: The cement coming out from the grinding mills is stored in a
concrete storage silos.
Then the cement is packed in jute bags by automatic machines. Each bag contains 50kgs of cement.

PROPERTIES
Setting and Hardening of cement:
When the cement is mixed with water, hydration and hydrolysis of cement begin, resulting in
the formation of gel and crystalline products.
It is defined as the stiffening of the original plastic mass, due to initial gel formation.
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Setting:
Hardening: It is defined as the development of strength, due to crystallization.
Chemical reactions involved in setting and hardening of cement:
When water is mixed with cement , hydration of tricalcium aluminate occurs rapidly and the
paste becomes quite hard within a short time. This process is known as initial setting of cement.
3CaO.Al2O3 +6H2O-------3CaO.Al2O3.6H2O
Role of gypsum in cement:
The rapid hydration of C3A
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(i) In initial setting process gypsum is added during grinding of cement clinkers to retardt
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Gypsum reacts with C3A to form insoluble calcium sulphoaluminate complex.

C3A + 3CaSO4.2H2O--------C3A.3CaSO4.2H2O
(ii)
After the hydration of C3A,C3S begins to hydrate to give tobermonite gel and crystalline
Ca(OH)2. The hydration of C3S takes place within 7days.
2(3CaO.SiO2) + 6H2O--------- 3CaO.2SiO2.3H2O + 3Ca(OH)2 + 500kj/kg

Dicalcium silicate reacts with water slowly and gets finished 7-28days.
(iii)
3CaO.2SiO2.3H2O +Ca(OH) 2 + 250kj/kg
2(2CaO.SiO2) + 4 H2O --------
(iv)
Hydration of tetra calcium aluminoferritetakesplace initially, the hardening takes place
finally through crystallization along with C2 S.
4CaO.Al2O3.Fe2O3 + 7H2O----------3CaO.Al2O3.6H2O + CaO.Fe2O3.H2O + 420KJ

Crystalline
gel
Thus the final setting and hardening of cement is due to the formation of tobermonite gel
plus crystallization of Ca(OH)2 and hydrated tricalcium aluminate.
SPECIAL CEMENT

Water Proof Cement :
It is obtained by adding water proofing agents like calcium stearate and gypsum with
tannic acid to ordinary Portland cement during grinding.
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Functions of water- Proof cement:

Functions of water- proof cement
(i)
To make concrete impervious to water under pressure.
(ii)
To resist the adsorption of water.
White cement or White Portland cement
It is obtained by heating the raw materials free from iron oxides. It is white in color
due to the absence of ferric oxide.
It issued for making tiles, mosaic works with some coloring agents like yellow
ochre, Venetian red etc.
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It is used for repairing and joining marble pillars and blocks.
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GLASS
Glass is an amorphous, hard brittle, transparent, super cooled liquid of infinite
viscosity.
Glass may be represented as
xR2O.yMO.6SiO2
General Properties of Glass:

1. It is amorphous.
2. It is very brittle.
3. It softens on heating.
4. It has no definite melting point.

5. It is affected by alkalis.
6. It is a good electrical insulator.
7. It can absorb, reflect or transmit light.
8. It is not affected by air water, acids and chemical agents.
Manufacture of Glass
1. Melting :
The raw materials in proper proportions are mixed and finely powdered.

This homogeneous mixture is known as BATCH is fused with some broken glass called
CULLET in the pot of the furnace.
The furnace is heated by burning producer gas and air mixture over the charge.
The cullet melts at a low temp and assists in melting the rest of the charge.
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CaC O3 + Si O2------ CaSiO3 + CO2

Na2C O3 + Si O2----Forming and Shaping
Na2Si O3 + CO2
The molten glass is then worked into articles of desired shapes by either blowing or moulding
or pressing between rollers.
Annealing:
Glass articles are then allowed to cool gradually to room temperature.

Sudden cooling must be avoided, because cracking occurs.
Longer the annealing period, the better is the quality of the glass.
Finishing:
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All glass articles after annealing, are subjected to finishing processes such as
(a) Cleaning (b) grinding (c) polishing (d) cutting (e) sand blasting
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TYPES OF GLASSES
1.Soda-lime or soda glass
(i) Raw materials: Silica , calcium carbonate and soda ash

(ii) Composition: Na2O. CaO. 6SiO2
Properties
They are low in cost.

They are resistant to water
They are attacked by common reagents like acids.
They melt easily
(a)
(b)
(c)
(d)
2. Potash lime or Hard glass

(i)
Raw materials : Silica, CaCO3, K2CO3
(ii) Composition:
K2O. CaO.6SiO2
(iii)
Properties:
(a)
They have high melting point.
(b)
They do not fuse easily.
(c)
They are less acted upon acids alkalis, solvents.
Uses:
Used for manufacturing combustion tubes, chemical apparatus
3. Lead glass or Flint glass

(i) Raw materials: Lead oxide, silicva, K2O
(ii) Composition: K2O.PbO.6SiO2
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(iii) Properties:
(a)
It is bright and lustrous
(b)
It has high specific gravity. (3 to 3.3)
(c)
It is more expensive to manufacture.
(d)
It has a lower softening temperature than soda glass.
(e)
It has higher refractive index.
Uses: (a) These are used for high quality tablewares.

(b) They are used in neon sign tubings, optical lenses, electrical insulators, cathode ray tube.
4. Borosilicate glass or Pyrex glass or Jena glass
(i)Raw materials: Silica, borax with small amount of alumina and some oxides.
in
(ii) Composition : SiO2 (80.5%); B2O3 (13%)

K2O
(3%)
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Al2O3 (3%)
Na2O (0.5%)
(iii) Properties
(i) It possess low thermal coefficient of expansion and high chemical resistance.
(2)It possesses very high softening points and excellent resistivity.

It is used in industry for pipe lines for corrosive liquids, gauge glasses,
Uses:
5. Alumina silicate glass

Raw materials: It has 5% or more alumina
(i)Composition: SiO2 Al2O3, B2O3, MgO, CaO, Na2O K2O
Properties:
They possess high softening temperature.
Uses:
(a)Used in high pressure mercury discharge tubes

(b)Chemical combustion tubes.
6. Optical or Crookes glass

Raw materials: It contains phosphorus, lead silicate with small amount of cerium oxide.
Properties:
Cerium oxide present in the glass absorbs uv light,
(b)
They have low melting point.
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(a)
Uses: optical glasses are used for making lenses.

7. Glass wool
Glass wool is fibrous wool like material It is composed of intermingled fine threads or
filaments of glass.
Properties:
It is a very good heat and fire proof materials

Its electrical conductivity is low.
Uses; It is used for heat insulation purposes
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It is used for electrical and sound insulation.
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ii) Nitrogen Content:

Kjeldahls method:
Con.H2SO4,
Powdered Coal
Ammonium sulphate (clear solution)

K2SO4 Catalyst
NaOH
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Std N/10 HCl
Neutralisation takes place

Reactions :
2N + 3H2+H2SO4
(NH4)2SO4+2NaOH
NH3
(NH4)2SO4
2 NH3 + Na2SO4 +2 H2O NH3 + HCl
From the volume of HCl consumed % of Nitrogen is calculated
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% of N2 in coal = 1.4 x volume of acid consumed x Normality

Weight of coal sample
i) Sulphur Content :
Burnt in
Sulphate
A known amount of coal
Bomb calorimeter
Extracted with water
Extract
BaCl2
Filtered, dried & weighed
BaSO4
From the weight of BaSO4, % of Sulphur is calculated

% of Sulphur = 32 x weight of BaSO4 obtained / 233 x weight of coal sample x 100
iv) Ash content :
Moisture & volatile

matter removed coal
without lid
hr
700 + 500c
Loss in weight of coal is noted
Loss in weight of the coal

% of volatile matter in coal =
x 100
Weight of air-dried coal
v) Oxygen content :
% of Oxygen in coal = 100 - % of ( Carbon + Hydrogen + Sulphur
+ Ash content )
1
2
CONTENTS
High Carbon
& Hydrogen
High Nitrogen
SIGNIFICANCE
i) Increases calorific value of
coal
ii) Helps in the
No calorific value
High
Sulphur
i) Increase calorific value

ii) It produces SO2 , SO3
and corrosion takes place
i) Low calorific value
ii) Increases moisture
holding capacity of coal
High
Oxygen
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S.NO
Draw backs of presence of S in Coal:

1. The combustion products of sulphur, SO2 and SO3 are harmful
and have corrosion effects on equipments
2. The coal containing sulphur is not suitable for the preparation of
metallurgical coke as it affects the properties of the metal.
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A good quality coal has High calorific value. For High calorific value, coal
must contain
1. High Carbon & Hydrogen content
2. Low Nitrogen content
3. Low Sulphur content
4. Low oxygen content
Carbonisation:
The process of conversion of coal into coke by strong heating in the absence of air is
known as carbonization.
Caking and coking coals:

If the product obtained from the carbonization is soft, plastic and coherent mass is
called caking coal, if the product is hard and strong then the coke is called as coking coal.
Significance :
i) Increase the thermal efficiency of the carbonization
process
ii)Recover the valuable by-products
Otto Hoffmann oven consists of no of silica chambers (10 12 m length, 3-4 m

height, 0.4 0.45 m wide) with charging hole at top and iron door at each end.
Coal taken in chambers is heated by preheated air and producer gas at 1200C.
The air and gas are preheated by sending them through 2nd and 3rd hot regenerators.
Hot flue gases produced during carbonization are passed through 1st and 4th
regenerators upto 1000C.
The system of recycling the flue gases to produce heat energy is known as the
regenerative system of heat economy.
After 24 h, when the process is complete the coke is removed and quenched with
water. Yield is about 70% and the valuable by products can be recovered from flue
gas.
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Construction:
Hydrogenation of coal or Manufacture of synthetic petrol:

If coal is heated with hydrogen to high temperature under high pressure, it is
converted to gasoline. Hence, the preparation of liquid fuels from solid coal is called
Hydrogenation of coal.
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There are two methods available for the hydrogenation of coal.

(a) Bergius process (or direct method) (b) Fischer- Tropsch Process (or indirect method)
(a) Bergius process (or indirect method)
in
Process:
Finely powdered coal + heavy oil+ catalyst powder (tin or nickel oleate) is made into
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a paste and pumped along with hydrogen gas into the converter,
Saturated higher hydrocarbons on further decomposition yield mixture of lower

hydrocarbons.
The mixture is led to a condenser, where the crude oil is obtained.

The crude oil is then fractionated to yield. (i) Gasoline (ii) Middle oil (iii) heavy oil
The middle oil is further hydrogenated to yield more gasoline.
The heavy oil is recycled for making paste with fresh coal dust.
The yield of gasoline is about 60% of the coal.
Process:
1200C
Coal Coke
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(b) Fischer-tropics process (or indirect method)
mixed with H2
CO + H2
(Water gas)
Passed through Fe2O3
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H2O
remove H2S
Passed through Fe2O3+Na2CO3

Remove
organic
Sulphur
compounds
Purified gas
Compressor (5-25 atm)
Converter with catalyst bed with mixture of
(100 parts cobalt+5parts thoria + 8 parts
(200-300C)
magnesia +200 parts Keiselghur earth)
Polymerisation
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KNOCKING:
Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.
Improve
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OCTANE NUMBER OR OCTANE RATING:

Thus octane number is defined as The percentage of iso-octane present in a mixture
of iso octane and n-heptane.
CETANE NUMBER OR CETANE RATING:

Cetane number is defined as the percentage of cetane present in a mixture of cetane
and 2-methyl naphthalene which has the same ignition lag as the fuel under test
Producer gas:
Constituents
CO
N2
H2
CO2+CH4
Percentage (%)
30
51 - 56
10 15
rest
Calorific value : 1300kcal/m3

Construction:
It consists of tall steel vessel lined with refractory bricks
It has cup and cone feeder at the top and a producer gas exit
It has inlet pipe at bottom to pass air &steam
Manufacture :
Red hot coke
11000c
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Air + steam
Producer gas
Zones present :
i) Ash Zone :
Lowest zone contains ash
in
Air and steam is preheated

ii) Combustion or Oxidation Zone :
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Zone next to ash zone
Exothermic reactions take place
Temperature of the bed reaches around 11000c

C + O2
CO2
C + O2
iii) Reduction Zone :
CO
Middle zone
C + CO2 2CO
Endothermic reactions take place
C + H2O CO + H2
Temperature of the coke bed falls to 10000c
iv) Distillation or Drying zone

Uppermost layer of the coke bed
Tempertaure : 400 - 8000c
Incoming coke is heated by outgoing gas
Uses :
i) As a reducing agent in Metallurgy
ii) For heating muffle furnace
Water gas:
CONSTITUENT PERCENTAGE(
CO
41
H2
51
N2
4
Calorific value : 2800kcal/m3
REST
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CO2+CH4
Construction:
It consists of tall steel vessel lined with refractory bricks
It has cup and cone feeder at the top and a water gas exit
Manufacture :
Air & steam passed alternatively

Red hot coke
900 10000c
Various Reactions :
Water gas
Endothermic reactions
in
H = +VE
i) Step 1 : Steam is passed through the red hot coke to produce CO & H 2
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( Temperature falls)
C + H2O
CO + H2
ii) Step 2 : Air is blown and steam supply is cut temporarily to raise the temperature
(1000C)
CO2
C + O2
Uses :
ii)In the synthesis of ammonia, and production of H2
ii)In the synthesis of gasoline in Fischer Tropsch Process

In the synthesis of Power alcohol and carburetted water gas
Used as an illuminating gas and a fuel
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The main sources of water are

2C17 H 35 COONa + Ca ++ (C17 H 35 COO) 2 Ca +2Na+ Water soluble Water

BOILER FEED WATER

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In a boiler, water is continuously converted into steam. Due to this continuous

If the precipitate is loose and slimy it is called sludges.

(ii) Decrease in efficiency

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1.6 PREVENTION OF SCALE FORMATION (OR) SOFTENING OF HARD

Zeolite (or) Permutit process

Zeolite (or) Permutit process

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No sludge is formed during this process.

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(i) Cation exchanger

Cross-linked quaternary ammonium salts.

R'(OH) 2 + H2SO4 R'SO4 + 2H2O

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RCa + 2HCl RH2 + CaCl2

The equipment is costly.

Na 2 [Ca 2 (PO3) 6] + 2Na 2SO4

Since the complex is highly soluble there is no problem of sludge disposal.

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The forward reaction is favored by increasing the concentration of CO32-.CaCO3

3CaSO4 + 2Na3 PO4

Ca3 (PO4)2 +2Na2SO4

There are three types of phosphates employed for this purpose.

Used in low pressure boilers.

Non-adherent, loose precipitate called sludge, which can be removed by blow-down

Causes of caustic embrittlement

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Caustic embrittlement can be prevented by

Using sodium phosphate as the softening agent instead of sodium carbonate.

The presence of dissolved oxygen is responsible for corrosion in boilers. Water

Dissolved carbon dioxide

4Fe + 6H2O + 3O2

CaCO3 + H2O + CO2

CO2 + H2O H2CO3

Dissolved magnesium chloride

When water containing dissolved magnesium chloride is used in a boiler, hydrochloric

Prevention of boiler corrosion

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Priming is the process of production of wet steam. Priming is caused by

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Controlling the velocity of steam.

Presence of oil and grease.

Adding coagulants like sodium aluminate, aluminium hydroxide.

Sea water has > 35,000 ppm of dissolved solids.

The removal of dissolved solids (NaCl) from water is known as desalination

1.13.1 Reverse Osmosis