CORROSION AND ITS CONTROL

Corrosion & its Control 1

 Learning Objectives
At the end of the chapter the learner will be able to
1. Understand the terms: Corrosion, Galvanic Series, Inhibition
2. Describe the mechanism of corrosion by electrochemical
theory
3. Describe different forms of corrosion- galvanic, pitting, stress,
and inter-granular
4. Understand the importance of the factors affecting corrosion
5. Know about the different established and modern techniques
to control corrosion
6. Distinguish between galvanizing and tinning, electrochemical
series and galvanic series
7. Unfold the practical aspects of metal corrosion with real life
examples.
Corrosion & its Control
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 Content
❖ Introduction
❖ Corrosion Classification
❖ Galvanic Series
❖ Types of Galvanic Corrosion
❖ Factors affecting Corrosion
❖ Protection against Corrosion
❖ Summary

Corrosion & its Control 3

 Corrosion

Corrosion
(Oxidation)
Metal Metallic
compound + Energy
Metallurgy
(Reduction)

State of Higher Energy State of Lower Energy

Corrosion & its Control 4

❖Rusting of iron 4Fe(s) + 3O2(g) →
2Fe2O3.H2O(s)

❖Tarnishing of silver 4Ag(s) +2 H2S(g) + O2(g) →

2Ag2S(s) + 2H2O(l)

❖Scales on copper 2Cu(s) + H2O(l) + O2(g) +

CO2(g) →Cu2(OH)2CO3(s)
 Corrosion
Classification

Dry or Chemical Wet or

Electrochemical
Corrosion Corrosion
 Comparison Between Dry corrosion and
Wet Corrosion

Dry Corrosion Wet Corrosion

• Involves direct attack of
atmospheric gases
• No need of a corroding
medium
• Types include oxidation
corrosion, liquid metal
corrosion and corrosion by
gases
• Less prevailing
• Occurs due to existence of
separate anodic and
Cathodic areas between
which current flows
through the medium
• Need of a corrosive medium
• Types include galvanic,
pitting, stress and
intergranular
• More common

Corrosion & its Control

9
Electrochemical Theory of Corrosion

Corrosion & its Control 7

• Anodic reaction:

M → Mn+ + ne-
Fe → Fe2+ + 2e-
• Cathodic reactions:

i) Hydrogen evolution:
2H+ (aq) + 2e− → H2 (dearated and acidic medium)
H2 liberation along with OH- ions formation
2H2O + 2e- →H2(g) + 2OH- (aq) ( deaerated and
neutral)
ii) Reduction of oxygen in neutral medium:
O2 (aq) + 2H2O + 4e− → 4OH−(aq) (aerated and
neutral)
Mechanism of Rusting

Corrosion & its Control

8
• At anodic sites [Fe → Fe 2+ + 2e−] x 2
• At cathodic sites O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
• Overall reaction 2Fe + O2 (g) +2H2O (l) →2Fe2+ (aq)+ 4 OH-
• Reactions to the formation of hydrated ferric oxide (rust)
• Fe2+(aq) + 2OH− (aq) → Fe (OH)2
• In presence of enough oxygen, ferrous hydroxide reacts with
moisture and oxygen to give yellow rust.
• 4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] ( Yellow rust)
• If the supply of oxygen is limited, the corrosion product may
be black anhydrous magnetite.
• 6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] ( Black Rust)
• Rust is a brittle substance that easily flakes off the surface to
expose more iron atoms and the process starts over again. It
is too porous to shield the underlying metal from further
oxidation.
 Dry Corrosion Types

Oxidation Corrosion by Liquid Metal

Corrosion gases Corrosion

Corrosion & its Control

6
 Types of Wet
Corrosion

Inter
Galvanic Pitting Stress
granular
Corrosion Corrosion Corrosion
Corrosion
Galvanic Corrosion

Corrosion & its Control 12

• Galvanic corrosion occurs when two dissimilar metals
are in physical contact in an aqueous electrolyte. The
less resistant metal acts as anode (metal with lower
electrode potential) and the more resistant metal
(metal with higher electrode potential) acts as cathode.
• Some real world examples of galvanic corrosion
include:
• *copper piping connected to steel tanks.
• * Zinc coated screws in a sheet of copper,
• *A stainless steel screw in contact with cadmium
plated steel washer.
• * Steel propeller shaft in bronze bearing
 Pitting Corrosion
The important reasons for the pitting
corrosion :
• Surface roughness or non-
uniform finish.
• Scratches or cut edges.
• Local straining of metal
due to non- uniform
stress.
• Deposition of extraneous
matter such as sand, scale,
water drop and dust

Corrosion & its Control

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Inter-granular Corrosion

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14
 Stress Corrosion
Stress corrosion or cracking refers to cracking caused by the
combined effect of a tensile stress & specific corrosive
environment

Corrosion & its Control 15

 Caustic Embrittlement

Iron / Concentrated, Dilute / Iron

NaOH (stressed) (cracks) NaOH (unstressed)
ANODE CATHODE

Reactions Involved :

3 Na2FeO2+ 4 H2O → 6 NaOH+ Fe3O4 + H2

6 Na2FeO2+ 6 H2O + O2 →12 NaOH + 2Fe2O4

Preventive Methods for Caustic Embrittlement

• By adding Na2SO4, tannin or lignin to water

• Boiler can be constructed by welding the

sheets to avoid local stresses

• Caustic embrittlement is minimized by using

demineralized water

Corrosion & its Control 16

 Microbial Corrosion
• Deterioration of metal due to microbial activity is
termed biocorrosion or Microbially Influenced
Corrosion (MIC).

• Insoluble products formed by the microbial activity

can accept electrons from the base metal.

• This sequence of biotic and abiotic reactions

produces a kinetically favored pathway of electron
flow from the metal anode to the universal electron
acceptor, oxygen.
 Prerequisites for MIC

➢ The presence of microorganisms.

➢ An energy source, a carbon source,
➢ An electron donator
➢ An electron acceptor
➢ Water."
 Factors affecting MIC
Microorganisms growing at interfaces can
influence all parameters like :

• Concentration of oxygen,
• Salts, pH value,
• Redox potential,
• and conductivity (which affect corrosion
kinetics)
Sulfate-Reducing Bacteria (SRB)

• SRB is a group of ubiquitous, divers anaerobes that

reduce oxidized sulfur compounds, such as sulfate,
sulfite and thiosulphate, as well as sulfur to H2S.

• Although SRB is strictly anaerobic (obligate anaerobes),

some genera tolerate oxygen and are able to grow in
presence of oxygen.

• Metal-Reducing Bacteria (MRB): Promote corrosion of

iron and its alloys through reactions leading to the
dissolution of corrosion-resistant oxide films on the
metal surface.
 Galvanic Series
Mg Active (more anodic)
Mg alloys
Zn
Al
Cd Mild Steel
Cast Iron Increasingly Increasingly
Active Inert
Stainless steel
.
.
Nickel
Ag
Ti
Graphite
Au
Pt Passive (more cathodic)

Corrosion & its Control 10

Comparison between EC and Galvanic series
Electrochemical series
• Electrode potentials are measured
by dipping pure metals in their salt
solution of 1M concentration
without any oxide film on it.
• Electrode potentials are measured
w.r.t. standard hydrogen electrode.
• The position of a given metal in
electrochemical series is fixed.
• Electrochemical series gives no
information regarding the position
of alloys.
• Metals and non- metals are
included.
Galvanic series
• The galvanic series was developed by
studying corrosion of metals and
alloys in unpolluted sea water,
without their oxide films.
• Electrode potentials in the galvanic
series are measured relative to a
saturated calomel electrode.
• The position of a given metal and its
allou may shift in galvanic series
• Alloys are included in galvanic series
based on their corrosion behavior
• In galvanic series only metals and
alloys are included.

Corrosion & its Control 11

 Factors Affecting
Corrosion

Primary Factors- Secondary Factors-

associated mainly which vary mainly
with the metal with the environment

Nature of metal and Concentration and

relative electrode nature of pH of the medium
potentials of metals electrolytes

Polarization at
Relative Cathodic
Temperature anodic and cathodic
and Anodic area
region

Corrosion & its Control 17

1. Discuss the methods used for cleaning of the metal surface before electroplating.
Define liquid crystals? How do they differ from crystalline state and liquid state?
(3+2)
2. What are the differences between electrochemical series and galvanic series.
Explain the working of Liquid Crystals in Display systems.
(3+2)
3. Explain the mechanism of rusting of iron.
Explain the classification of liquid crystals based on the shape.
(3+2)
4. What is meant by dry corrosion? Why do metals get oxidized on exposure to air?
What are the applications of biomaterials?
(3+2)
5.Distinguish between decorative and hard chromium. Describe the electroplating of
decorative chromium?
What are biomaterials? How they are classified? (3+2)
 Corrosion Control
Methods

Use of
Selection of Change of Change of coatings for
material & design metal environment separating
improvement metal from
environment
 Selection of Material
Material selection principles:

• Pure metals show greater resistance to corrosion than impure one.

• Using an anodic material of larger area and cathodic material of

smaller area cases reduction in the corrosion rate.

• Suitable alloying of metals in some cases improves its corrosion

resistivity.

• Avoid residual stress in fabricated articles by proper heat treatment

• The metals chosen should be very close in the galvanic series.

Proper insulator fitting may be used in between to avoid direct
contact of metals.

Corrosion & its Control 19

 Design Improvement

Proper Design :

Simplify forms
Avoid Crevices
Avoid residual moisture
Avoid sharp corners and sharp bends

Corrosion & its Control 20

 Cathodic protection
Sacrificial anode method
Advantages:
• No external power supply
is necessary.
• Can be used in remote
and difficult to reach
areas.
• Low installation cost.
• Minimum maintenance
cost.
• Replacement is much
cheaper than replacing
the tank/oil pipeline

Corrosion & its Control 21

• Corrosion of a structure can be controlled if the entire
article can be changed into the cathodic part of a
corrosion cell. This is called cathodic protection.

• Ship's steel hulls, offshore drilling platforms, oil and gas

under sea pipelines, containers used to store water and
other liquids are protected by this method.

• Cathodic protection is done by two different methods.

a) Sacrificial anode method
b) Impressed current method
 Cathodic protection

Impressed Current Method:

Advantages:
• Applicable to large structures
Battery – External and long term operations.
power source • Uncoated parts can be
protected.

Anode- Inert electrode
(graphite/Pt)
Disadvantages:
• Larger installation cost.
• Higher maintenance cost.
• High energy consumption
• Localised corrosion may occur
Cathode-Steel if the impressed current is not
storage tank
uniform on the entire surface.

Corrosion & its Control 22

• In this method the metallic structure is made cathode
with the use of impressed current by connecting the
negative terminal of the external DC power source to
the metallic structure to be protected and positive to
an inert anode.
• The anode may be made up of steel, graphite and
platinum group metals.
• The anode may be consumed very slowly or may not
be consumed at all depending on the anode material.
• The anode is surrounded by back film consisting of
coke breeze, gypsum to improve electrical contact
between the anode and the environment if it is a poor
ionic conductor.
 Anodic protection Method

Passivated metal to be
protected-anode

Platinum Calomel
electrode-cathode electrode

Corrosion & its Control 23

 Anodic protection Method
Advantages: Disadvantages:

• Reduced equipment cost-i.e. it • Cannot be applied in case of

is possible to protect two or
more vessels with one controller
• Cost of anodic protection is
generally independent of tank
capacity.
• Applicable in extremely
corrosive environments
• Low current demand
corrosive medium containing
aggressive anions such as
chloride.
• Needs continuous supply of
electric current
• Applicable only to those metals
that show active passive
behavior
• Initial installation cost is high
• It cannot reduce the corrosion
rate to zero.

Corrosion & its Control 24

 Surface Coating

Metallic Coating: Coating of a metal on a substrate metal requiring

protection against corrosion is metallic coating.

There are two types of metallic coating.

• Anodic metal coating – coating the substrate metal with a more

anodic metal eg. Galvanizing

• Cathodic metal coating - coating the substrate metal with a more

cathodic metal eg. tinning

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26
Galvanization

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 Tinning

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 Comparison of Galvanizing and tinning
• A process of coating Zn over • A process of coating Sn over
iron/ steel to prevent it from iron to prevent it from corrosion
rusting (anode metal coating) (cathode metal coating)
• Hot rollers used to wipe excess
coat are not immersed in oil • Hot rollers are immersed in oil
• Galvanized containers cannot be • Tin coated containers can be
used to store acidic foodstuffs used to store foodstuffs because
because zinc reacts with food tin is nontoxic and does not react
acids forming highly toxic zinc
compounds. to cause any food poisoning
• Zinc protects the underlying • Tin protects the base metal iron
iron by sacrificial action due to its noble nature.
• Zinc continues to protect iron • Tin protects the iron till the
by sacrificial action in the event
of puncture/break in coating coating is perfect and any break
causes rapid corrosion of iron
Corrosion & its Control
29
 Organic coatings
Organic coatings are inert barriers (like paints, varnishes,
lacquers, and enamels) applied on a metallic surface for
both corrosion protection and decoration. These involve a
relatively thin barrier between the substrate material and
the environment.

The protective value of such a coating depends on

• i) its chemical inertness to the corrosive environment
• ii) its good surface adhesion
• iii) its impermeability to water, salts and gases and its
proper application method
• Requirements of a good paint:
• It should be fluid enough to be spread easily over the
surface.
• It should form a quite tough, uniform adherent and
impervious film.
• Its film should not crack on drying.
• Its film should be glossy and quite stable.
Constituents of paints:
• Pigment
• Vehicle
• Thinners
• Driers
• Extenders or fillers
• Plasticizers
• Anti-skinning agents
 Inorganic coating:
PHOSPHATE COATINGS
• These are produced by the chemical reaction of base
metal with an aqueous solution of phosphoric acid and
phosphates of iron, zinc, manganese along with copper
salts as accelerators.
• Such coatings are usually applied to iron, steel, and zinc
by either immersion or spraying or brushing.
• The chemical reaction between the phosphating
solution and the base metal results in the formation of
a surface film, consisting of crystalline zinc-iron or
manganese- iron phosphates.
 Anodic Inhibitors.

➢ Substances used to stop anodic reaction.

➢ They form insoluble compounds with the metal ions
formed at the anodic part .
➢ These insoluble compounds form a protective film on
the anode surface.
➢ This film isolates the anode from the electrolyte
medium and stops its corrosion.
➢ The anions such as chromate, tungstate, molybdate,
phosphate etc., are used to arrest anodic process.
➢Effective only when they are added above
their critical concentrations.
➢ If the added inhibitor is insufficient, it cannot
plug all the anodic sites.
➢This leads to severe pitting corrosion.
 Cathodic Inhibitors.
➢ Substances used to retard cathodic reaction.
➢ They form a protective film on cathodic surface and
isolate it from the electrolyte medium thereby
preventing corrosion.
➢ Two major reactions taking place on cathodic
surface depending on the nature of corrosive
environment are:
*Hydrogen evolution type
*Oxygen absorption type
• Hydrogen evolution:
2H+ + 2e- -------->H2 (acid medium)
This reaction can be prevented either by
*Retarding the diffusion of H+ to the
cathode.
*Increasing hydrogen over voltage.
• Addition of certain organic compounds,
containing N or S, retards the diffusion of H+.
• Such substances when added to corroding
environment are adsorbed on the cathodic
sites forming a protective film that suppresses
cathodic reaction.
• Eg: Urea, thiourea, mercaptans and
heterocyclic compounds.
• Substances added deposit as adherent
metallic film on the cathode areas and
thereby prevents the evolution of H2.
• Oxides of Arsenic, antimony or salts like
sodium meta arsenite are used since hydrogen
overvoltage for these metals is quite high.
• Oxygen absorption type: (in neutral or slightly
alkaline medium)
O2 + 2H2O + 4e- -------> 4OH-
• This reaction can be easily stifled either by removing
the oxygen from the corrosive media or by
decreasing the diffusion rate of oxygen to cathode.
• Reducing agents such as N2H4, Na2SO3 etc remove
oxygen from the corroding environment by
combining with it.
N2H4 + O2 ----------> N2 + 2H2O.
• Decreasing the diffusion rate of oxygen is achieved
by adding salts such as ZnSO4,MgSO4,NiSO4 etc., to
the aqueous environment.
• They undergo hydrolysis and form a deposit of their
insoluble hydroxide on the cathodic sites.
Zn2+ + 2OH- -----------> Zn(OH)2.
• The protective film being impermeable to oxygen
prevents its further diffusion to cathodic sites.
• The action of an inhibitor depends on the
nature of the metal to be protected as well as
corrosive environment.
• It is therefore necessary to choose an
appropriate inhibitor for a particular system.
1. a)Explain the phase structures formed by Lyotropic liquid crystals.[2]
b) Explain the theory of electroplating with a suitable example [3]

2. a) What are the differences between thermotropic and lyotropic liquid

crystals? [2]
b) Explain the effect of following factors on the corrosion rate.
i) Hydrogen overvoltage ii) Nature of the corrosion product iii) Conductivity
of the medium [3]

3A.i) Describe the methods of cleaning the metal surface for electroplating. [2]
ii) Why is galvanic series used in corrosion studies rather than electrochemical
series? [1]
3B.Explain the structural characteristics of calamitic and discotic liquid
crystals. [2]

4A. i). Describe the types of dry corrosion and give an example for each. [2]
ii)Write the oxidation and reduction reaction for electroless plating of copper.1
4B. Describe briefly the working of liquid crystals display. [2]
 Summary
• Metallic corrosion is one of the problems often encountered in
our industrialized society, and hence it has to be studied.

• Enormous breadths of engineering systems depend upon

corrosion protection for their reliability, performance and
safety.

• It becomes essential to understand the different forms of

corrosion and factors affecting it.

• Corrosion control techniques include selection of materials and

proper design, cathodic and anodic protection methods, surface
coating and the use of corrosion inhibitors.

Corrosion & its Control

30
 Self Test
1. What is corrosion? Explain the bimetallic corrosion with an
example.
2. Justify : Iron in contact with copper corrodes faster than that
in contact with tin.
3. What is cathodic protection? Explain the sacrificial
anode method of corrosion protection.
4. Explain how the following factors affect the rate of
corrosion.
(i) Hydrogen overvoltage (ii) Nature of the product formed

Corrosion & its Control

31
 References

1. P .C. Jain, M. Jain, Engineering Chemistry, 15th Edn., Dhanpat Rai

and Sons, Delhi, 2006
2. E.Mc. Cafferty, Introduction to Corrosion Science, Springer
Berlin Publication, 2009

Corrosion & its Control 32

Liquid Crystals
LIQUID CRYSTAL

A “double melting” behavior of cholesteryl benzoate.

The crystals of this material melted at 145.5oC into a
cloudy fluid, which upon further heating to 178.5oC
became clear.

They undergo more than a single transition in passing from

solid to liquid through different intermediate states on
heating.

Intermediate state - mesophase

Liquid Crystal – a stable phase of matter characterized by
anisotropic properties without the existence of a 3-dimensional
crystal lattice – generally lying between the solid and isotropic
(“liquid”) phase.

Anisotropy: they exhibit different optical properties when the

light is incident in different directions

Isotropy: Same properties in all directions

Isotropic
Liquids and gases
(uniform properties in all
directions).

vs.
Anisotropic
Liquid Crystals
have orientational order
LC state (mesomorphic state) is characterised by having a long-range
orientational order and possible partial positional order

i.e., the tendency of the molecules (mesogens) to point along a

common axis, called the director.

where theta is the angle between the

director and the long axis of each
molecule.
In a liquid crystal, the molecules possess orientational order, i.e.,
the molecules tend to remain oriented in a particular direction.

Director (n )
The direction of preferred orientation in a liquid crystal

Since the molecules are in constant motion, in liquid crystal phase

they spend more time pointing along the director than along any
other direction.

An average of 0° indicates perfect orientation and can be expected

in solids.
An average of greater than 45° indicates no orientational order and
found in liquids.

liquid crystals a smaller average angle with the director is observed

which indicates orientational order.
A distinct state of matter in which the degrees of molecular ordering
lie intermediate between the ordered crystalline state and the
completely disordered isotropic liquid state
Characteristics of LC

a. Liquid crystalline nature should be at room

temperature and the entire temperature range of the
device operation

b. Chemically, electrochemically, photochemically and

thermally stable

c. Permanent electric dipole, hence either a positive or

negative dielectric anisotropy.

d. Should possess easily polarizable substituents

 Types of LCs
❑ Thermotropic LCs, LC substances undergo transition by
variation in temperature
Mesophase formation is temperature dependent
Ex: p-azoxy anisole
❑ Lyotropic LCs, LC substances undergo transition by
the influence of solvent
Mesophase formation is solvent dependent
Ex: sodium stearate

Amphotropic LCs- exhibit both thermotropic and lyotropic

mesophases
Thermotropic LCs

Classification
Based on the molecular phase structure
Nematic:
Smectic
Columnar
Cubic
Nematic phase:

The least ordered mesophase (the closest to the

isotropic liquid state) is the nematic (N) phase, where
the molecules have only an orientational order
Smectic phases
In smectic (S) phase, in addition to the orientational
order the molecules possess less or more positional
order, such that the molecules organize in layered
structures.
Schematic of alignment in the smectic phases. The smectic A phase
(left) has molecules organized into layers. In the smectic C phase
(right), the molecules are tilted inside the layers.
Smectic B

Smectic B phase has the molecules arranged

within the layers in a hexagonally close-paced
array with the molecular long axes perpendicular
to the layer planes
Columnar Phases

Columnar (Col) phases are more ordered. Here the disc-

shaped cores have a tendency to stack one on the top of
another, forming columns

Arrangement of these columns into different lattice

patterns gives rise to a number of columnar
mesophases, namely columnar rectangular (Colr) and
columnar hexagonal (Colh)
(a) the general structure of Col phases, where the molecules are aligned in the
same orientation and, in addition, form columns,
(b) representation of Colr, and (c) representation of Colh.

Cubic Phase of LCs

This phase exhibited by lyotropic LC
Structures with micellar lattice units
 Thermotropic LCs
The essential requirement for a molecule to be a thermotropic
LC is a structure consisting of a central rigid core (often
aromatic) and a flexible peripheral moiety (generally aliphatic
groups).

1 . Calamitic LCs
2. Discotic LCs
3. Banana shaped LCs
4. Polycatenar LCs
 Calamitic LCs
Calamitic or rod-like LCs are those mesomorphic compounds that
possess an elongated shape, molecular length (l) being significantly
greater than the molecular breadth (b).

Ex:
The general molecular formulae of Calamitic LC s
Discotic LCs
A second type of mesogenic structure, based on discotic (disc-
shaped) molecular structures.

The first series of discotic compounds to exhibit mesophase

belonged to the hexa-substituted benzene derivatives.

Structure comprising a planar (usually aromatic) central rigid core

surrounded by a flexible periphery, represented mostly by pendant
chains (usually four, six, or eight),
Molecular structure of first series of discotic LCs discovered
Benzene hexa n-alkanoate derivatives
 Bent shape or Banana shaped LCs
➢ Mesomorphic compounds characterised by bent
molecular structures
➢ It exhibit both nematic and/or smectic phase.
➢ It consist of two mesogenic groups linked through a
rigid core so as to form bent shaped molecule but not
linear.
Examples of bent LCs
Polycatenar Liquid crystals
➢ Hybrid class of thermotropic LCs
➢ Described with intermediate molecular features between
rod-like and disc-like mesogens.
➢ the central core of polycatenar LCs comprises a
calamitic region.
➢ It exhibit both calamitic (nematics/smectic) and discotic
(columnar) depending on the specific molecular
structure of the components
E.g., the tetracatenar mesogens
The numbers of the flexible end chains of the core can be
indicated by using the term, m,n– polycatenary mesogen.
 Lyotropic LCs

Lyotropic LCs are two-component systems where an

amphiphile is dissolved in a solvent. Thus, lyotropic
mesophases are concentration and solvent dependent.

The amphiphilic compounds are characterized by two

distinct moieties, a hydrophilic polar “head” and a non polar
hydrophobic “tail”.

Examples of these kinds of molecules are soaps and

various phospholipids like those present in cell
membranes
Soap + polar solvent like water- micelle formation

Soap + non polar solvent like hexane – inverted micelle

where the hydrophobic tails shield the hydrophilic head

groups from the non-polar environment. Under certain
conditions, these micelles further aggregate to form
more complicated assemblies, such as lamellar and
hexagonal phases, which generate lyotropic liquid
crystal phases.

Lamellar phases are particularly significant as they form

the structural basis for biological membranes
Micellar aggregates and phases formed by Lyotropic liquid crystals
Application of liquid crystal

Liquid crystal display

Liquid crystal thermometers
In medicine
Optical imaging and recording
Non destructive mechanical testing
Polarization of light

Polarization of light
• When unpolarized light passes through a polarizing filter, only
one plane of polarization is transmitted. Two polarizing
filters used together transmit light differently depending on
their relative orientation.

Online Offline 33
 Construction of
Liquid Crystal Display

▪ Two bounding plates (usually glass slides), each with a

transparent conductive coating (such as indium tin oxide)
that acts as an electrode;
▪ A polymer alignment layer- undergoes a rubbing process
as grooves.
▪ Spacers to control the cell gap precisely

▪ Two crossed polarizers (the polarizer and the analyzer);

 LCD Alignment

When coming into contact with a finely grooved surface (alignment

layer), LC molecules line up parallel along groove due to their
rod-like shape.

[Coating ITO glass with a layer of PVA and rubbing repeatedly

creates these grooves.]
 LCD Orientation

The molecules along the upper plate point in direction 'a'

and those along the lower plate in direction 'b,' thus forcing
the liquid crystals into a twisted structural arrangement./
(figure shows a 90-degree twist) (TN type liquid crystal)
 Unique Properties of Liquid Crystals

The orientation of Liquid Crystals can be affected by…

• Pressure
• Temperature
• Electrical Field
Light movement
Offline (no voltage is applied)

• Light travels through the

spacing of the molecular
arrangement.
• The light also "twists" as it
passes through the twisted
liquid crystals.
• Light bends 90 degrees as it
follows the twist of the
molecules.
• Polarized light pass through
the analyzer (lower polarizer).

38
Molecules movement
Online (voltage is applied)

• Liquid crystal molecules

straighten out of their helix
pattern
• Molecules rearrange
themselves vertically (Along
with the electric field)
• No twisting thoughout the
movement
• Forcing the liquid crystals into
a straight structural
arrangement. (Electric force)

39
 Screen appear dark

Screen appear bright

When voltage is switched on
( LCD TV)
1.Light travels from the back of the TV toward the front from a large bright
light.
2.A horizontal polarizing filter in front of the light blocks out all light waves
except those vibrating horizontally.
3.Only light waves vibrating horizontally can get through.
4.A transistor switches off this pixel by switching on the electricity flowing
through its liquid crystals. That makes the crystals straighten out (so they're
completely untwisted), and the light travels straight through them unchanged.
5.Light waves emerge from the liquid crystals still vibrating horizontally.
6.A vertical polarizing filter in front of the liquid crystals blocks out all light
waves except those vibrating vertically. The horizontally vibrating light that
travelled through the liquid crystals cannot get through the vertical filter.
7.No light reaches the screen at this point. In other words, this pixel is dark.
When voltage is switched off
1.The bright light at the back of the screen shines as before.
2.The horizontal polarizing filter in front of the light blocks out all light waves
except those vibrating horizontally.
3.Only light waves vibrating horizontally can get through.
4.A transistor switches on this pixel by switching off the electricity flowing
through its liquid crystals. That makes the crystals twist. The twisted crystals
rotate light waves by 90° as they travel through.
5.Light waves that entered the liquid crystals vibrating horizontally emerge from
them vibrating vertically.
6.The vertical polarizing filter in front of the liquid crystals blocks out all light
waves except those vibrating vertically. The vertically vibrating light that
emerged from the liquid crystals can now get through the vertical filter.
7.The pixel is lit up. A red, blue, or green filter gives the pixel its color.
Structure of liquid crystal display: 1 – vertical polarization
filter, 2,4 – glass with electrodes, 3 – liquid crystals, 5 –
horizontal polarization filter, 6 – reflector
 Ceramics
“ceramic” - desirable properties of these materials are normally
achieved through a high-temperature heat treatment process called
firing.

Consist of a combination of non –metallic substances mostly

silicates and metal oxides.

Some of the common ceramic materials include aluminum oxide,

silicon dioxide, silicon carbide, silicon nitride

Traditional ceramics - composed of clay minerals as well as cement

and glass.

Withstand a temperature of 1500 to 2000 0 C.

Mechanical behaviour of ceramic materials

Relatively stiff and strong,

Very hard, brittle, highly susceptible to fracture,
Higher stability and higher melting points.

Most of these are insulators like other covalent materials.

Optical characteristics

Ceramics may be transparent, translucent, or opaque.

some of the oxide ceramics (e.g.,Fe3O4) exhibit magnetic

behaviour.
Classification of ceramic materials on the basis of
application

Glasses - products of fusion rapidly cooled to a rigid condition

without crystallization.

Non crystalline silicates that contain other oxides. Optical

transparency is the most desirable properties of these materials.

The most common uses for these materials are as ovenware,

tableware, oven windows because of their strength and excellent
resistance to thermal shock.

Serve as electrical insulators and as substrates for printed circuit

boards and for heat exchangers and regenerators.
Clay products

Principal component of the white wares and structural clay

products.

Stuctural clay products include building bricks, tiles-

applications in which structural integrity is important.

Feldspar and quartz may be added which influence the changes

that occur during firing.

Fire clays are hydrated aluminosilicates of composition

Al2O3.2SiO2.2H2O.
Refractories – fire clay, silica, basic special meterials :

The materials that are employed at elevated temperatures and often in

reactive environments .

Typical applications include furnace linings for metal refining, glass

manufacturing, metallurgical heat treatment and power generation.

Acid refractories:

Consist of mostly acidic materials like alumina (Al2O3) and silica

(SiO2). Not attacked or affected by acidic materials, but easily affected
by basic materials.

Fireclay bricks are used in furnace construction to confine hot

atmosphere and to thermally insulate structures from excessive
temperatures.
Neutral refractories:

Used in areas where slags and atmosphere are either acidic or basic
and are chemically stable to both acids and bases.

The main raw materials belong to, but are not confined to, the M2O3
group. The common examples of these materials are alumina
(Al2O3), chromia (Cr2O3) and carbon.

Basic refractories:

The refractories that are rich in periclase or magnesia (MgO) are

termed basic; they may also contain calcium, chromium, and iron
compounds.

Used on areas where slags and atmosphere are basic; they are
stable to alkaline materials but could react with acids.
Abrasive meterials –

Metal oxides and nitrides, being hard and tough are used to cut,
grind and polish other softer materials.

Diamond, SiC, Tungsten carbide are common examples.

Cements – portland cement:

When mixed with water, inorganic cements form a paste that is

capable of assuming just about any desired shape. Subsequent
setting is a result of chemical reactions involving the cement
particles and occurs at the ambient temperature.

Portland cement is the most common hydraulic cement, the

chemical reaction is one of hydration.
Advanced ceramics

Composite materials, engine rotors, many of our modern

technologies use advanced ceramics because of their unique
mechanical, chemical, electrical magnetic and optical properties and
property combinations.

Examples: ceramic ball bearings, piezoelectric materials.

Properties:

➢ Glass ceramic materials have relatively high mechanical

strength; low coefficient of thermal expansion (to avoid
thermal shock) and high temperature capabilities, good
dielectric properties and good biological compatibility, ease of
fabrication.

➢ In refractories porosity must be controlled .Strength, load

bearing capacity and resistance to attack by corrosive materials
all increase with porosity reduction.

➢ Any residual porosity will have deleterious influence on both

elastic properties and strength.
Mechanical properties of ceramics:

➢ Mechanical properties of ceramics are inferior to Metals.

➢ Energy absorption is low. Strength and melting temperature

vary linearly.

➢ At low temperature, ceramics are brittle while close to its

melting temperature, non-crystalline ceramics becomes
ductile.

➢ The processing method of ceramics decides the strength and

are usually strong in compression than in tension.

.
Brittle fracture

➢ Fracture toughness is the ability of the ceramics to resist the

fracture is directly proportional to applied stress and length of
the crack

➢ When the tensile load is applied on crystalline or non-

crystalline ceramics, fracture takes place, before any
deformation sets in.

➢ Compressive strength is higher than tensile strength.

➢ Flaws in the ceramics behaves like stress magnifiers and forms

the cracks.
Stress-strain behavior

➢ As ceramics are brittle, they tend to fracture before it

reaches plastic deformation state.

➢ Three-point bending apparatus is used to measure stress-

strain behavior.

➢ Flexural or fracture strength σ fs is the stress at fracture

is directly proportional to load at fracture and indirectly
proportional to the thickness of the material
Elastic behavior

➢ Elastic deformation is reversible deformation, while plastic

deformation is permanent deformation.

➢ Elastic deformation can be due to tension / compression / shear

force.

➢ Metals and ceramics usually have linear elastic behavior.

➢ The elastic modulus is directly proportional to load at fracture

and indirectly proportional to the thickness of the material.
Applications of ceramics

➢ Die blanks- Wear resistance properties

➢ Cutting tools – for cutting Silicon wafers, grinding glasses

➢ Sensors – ZrO2 as oxygen sensor ( rapid response of the sensor to

change in oxygen concentration)

➢ Matts for automobile engines.

COMPOSITES

▪ Composite material- material system composed of two or more

macro constituents that differ in shape & chemical composition,
mutually insoluble

▪ It contains two or more physically distinct and mechanically

separable materials( metal, ceramic and polymer)

▪ It is made by dispersing one material in the other in a controlled

way to achieve optimum properties

1
Many composite materials are composed of two phases
▪ matrix phase and dispersed phase.

Matrix
It is a continuous phase in composite which completely surrounds the
other phase (or dispersed phase)
Ex: metal (MMC), polymer (PMC), ceramic (CMC)

Function of matrix phase:

▪ Binds dispersed phase
▪ Acts as medium to transport and distribute the load to dispersed
phase
▪ Protect the dispersed phase from chemical action and keep in
proper position and orientation along the direction of applied load

2
Dispersed phase or reinforcing phase
It is a discontinuous phase that is surrounded by the matrix
phase.
It is the structural constituent which determines the internal
structure of the composite

Ex: fibers (glass or carbon), particulates (small pieces of solid

material)

Function of dispersed phase:

▪ To enhance matrix properties
▪ Increases the strength, used at elevated temperature

3
Ex: i) Wood consists of strong and flexible cellulose fibers surrounded and
held together by a stiffer material called lignin

Synthetic composite: ii) fiberglass, in which small glass fibers are

embedded within a polymeric material (epoxy or polyester).

Properties of composite materials are determined by three

factors.
i) The materials used as component phases (property of two
phases)
ii) Geometry of dispersed phase (particle size, distribution,
orientation)
iii) The amount of phase and the way in which the phases interact
with one another.

4
Classification of composites

i) Particle reinforced:
Large particle
Dispersion strengthened

ii) Fiber reinforced:

Continuous (aligned)
Discontinuous(short)-Aligned and Randomly oriented

iii) Structural: Based on build-up of sandwiches in layered form

Laminates
Sandwich panels

5
Particle reinforced

Based on reinforcement and strengthening

mechanism
i) Large particle:
Concrete
▪ The dispersion phase (particulate) should be harder and stiffer
than matrix phase
▪ The matrix transfer some stress to the particulate, which bears
the major portion of the applied load
▪ Particles can have quite a variety of geometries, but they should
be of approximately the same dimension in all direction.
▪ Particle size is large and present in large concentration.

Ex: concrete where the aggregates ( sand and gravel) are the
particles and cement is the matrix.

6
7
i) Dispersion strengthened

▪ strengthening materials which are very small and hard (usually

less than 0.1 µm) are uniformly dispersed within the matrix
phase
▪ The matrix bears the major portion of an applied load and the
small dispersed particles hinder the motion of dislocations.
▪ Thus plastic deformation is restricted and hardness and strength
increases
▪ Particle size is small and present in small concentration.
▪ The dispersed phase may be metallic or nonmetallic materials

▪ Example: thoria (ThO2) dispersed Ni-alloys.

8
Fiber-reinforced composites

Dispersed phase : fiber (long length to diameter ratio)

Matrix phase: metal, polymer or ceramic
▪ The primary functions of the matrix are to Transfer stresses
between the reinforcing fibers (hold fibers together)
▪ To protect the fibers from mechanical and/or environmental
damages.

Fibre phase:
On the basis of diameter and character, fibres are grouped into
three different classifications as
Whiskers
Fibres
Wires.

9
Whiskers
▪ Thin single crystals that have large length to diameter ratios (lower
than fiber)
▪ Posses high strength due to its small size that have extremely high
degree of Crystallinity
▪ they are very expensive and difficult to incorporate into matrix.

Ex: graphite, silicon carbide, silicon nitride.

Silicon carbide whiskers

10
Fibres : They are either polycrystalline or amorphous and have
small diameters (ex: like glass, ceramic)
High length to diameter ratio
The stiff reinforcing fibres are responsible for carrying load
and ductility, toughened

Glass fiber and glass fiber mat carbon fiber mat

11
Wires: Fine wires have relatively large diameters. Typical
material include steel, molybdenum, tungsten.
Ex: wire mesh

12
The strength of fiber-reinforced composite depends on fiber
orientation and its concentration
a) Parallel alignment of the longitudinal axis of the fibers in a
single direction
c)Totally random alignment

13
Elastic Behavior—Longitudinal Loading
When the load is applied on the composite in the direction of the
orientation of continuous fiber, then its modulus of elasticity is
equal to the summation of the products of the modulus of elasticity
(E) and volume fraction (V) of the respective phases.

i.e., Modulus of elasticity of composite, E = (EV)matrix + (EV)fiber

When the load is applied on the composite perpendicular to the

orientation of continuous fiber, the inverse of the modulus of
elasticity is equal to the summation of the ratio of volume fraction
(V) and modulus of elasticity (E) of the respective phases.

𝟏 𝑽 𝑽
i.e., = +
𝑬 𝑬 𝒎𝒂𝒕𝒓𝒊𝒙 𝑬 𝒇𝒊𝒃𝒆𝒓

14
Structural composites
It composed of composite and homogenous materials.
The properties depend on properties of constituent materials and on
the geometrical design of various structural elements.

Laminar composites:
▪ It is made of two dimensional sheets or panels that have a
preferred high strength direction
▪ Layers are stacked and subsequently cemented together such that
the orientation of high strength direction varies with each
successive layer. Ex: Ply wood

15
Sandwich panels
Consists of two strong outer sheets, or faces separated by a layer of less dense
material or core which has lower stiffness and lower strength
Faces or skin: Laminates of glass or carbon fiber-reinforced thermoplastics or
mainly thermoset polymers
Core:
Polymeric foams like PVC, Polyurethane, PE, PS and synthetic rubber

Foam 16
17
 POLYMER COMPOSITES

Combination of two material- reinforcing material usually in the

form of fiber, sheet or particles,
Matrix is made of polymeric material

Materials used :Fiber- glass, carbon

Matrix: thermoplastic(polyolefines, vinylic polymers) and
thermosetting resines (polyester and epoxides)

18
Polymer matrix materials:

The matrix materials used in composites are polyesters, vinyl esters, epoxies,
polyetheretherketone (PEEK), polyphenylene sulfide (PPS), and polyetherimide
(PEI). PEEK, PPS and PEI are the polymeric resins with potential aerospace
applications.

i) Glass Fiber-Reinforced Polymer (GFRP) Composites,

ii) Carbon Fiber-Reinforced Polymer (CFRP) Composites, and
iii) Aramid Fiber-Reinforced Polymer Composites.
Advantages of polymer composites:
-Light weight.
-High strength to weight ratio.
-More durable than conventional materials like steel and
aluminium.
-Good corrosion resistance.
-High fatigue strength.
-High temperature resistance.

Applications:
-Composites of phenolic resins and nylon are used in heat
shields for space crafts.
-Which are used in automotive and railway applications.
-As structural material in construction industries.
20
Fibre glass or glass-reinforced plastic (GRP)

Matrix: Made by reacting a polyester with carbon-carbon double bonds

in its backbone and styrene- a mix of the styrene and polyester
Fibre: glass fibre

O
CH2

O +
O
O n Cross linked resin

Ex: Used car engines components aeroplane parts and boat hulls
21
Aramid Fiber-Reinforced Polymer Composite:

Aramid fibers - high-strength, high-modulus materials

desirable for their outstanding strength-to-weight ratios, which are

superior to metals.

Materials is known as poly(paraphenylene terephthalamide).

Most common are Kevlar™ and Nomex™.

Kevlar composites

Kevlar is an aromatic polyimide. Chemically it is poly(para

phenyleneterephthalamide).
Matrix: Kevlar
Fibres: carbon fibre or glass fibre as reinforcing agent.

NH
NH

n
O

In Kevlar aramid ring provides thermal stability and para-

structure provides high strength and modulus
para-phenylenediamine and terephthaloyl chloride

Kevlar® 29 is used in the manufacture of body armour (panels) for

lightweight military vehicles. A good example is the US Army’s
‘Bradley Fighting Vehicle’. This has been used extensively in Iraq
and Afghanistan.
Advantages:
-Light weight, high strength, thermally stable
-Resistant to impact and abrasion damage. It can be used as
protective layer on graphite laminates.
-Can be mixed with graphite to provide damage resistance and to
prevent failure.

Disadvantages:

-Fibres themselves absorb moisture, so Kevlar composites are

more sensitive to the environment than glass or graphite
composites.
-Poor compression resistance.

27
ii) Carbon Fiber Reinforced Polymer (CFRP) Composite:
Carbon is a high-performance fiber material that is most commonly
used reinforcement in advanced polymer matrix composites. The
reasons for this are as follows:
1. Carbon fibers have the highest specific modulus and specific
strength of all reinforcing fiber materials.
2. They retain their high tensile modulus and high strength at elevated
temperatures; high-temperature oxidation, however, may be a
problem.
3. At room temperature, carbon fibers are not affected by moisture or
a wide variety of solvents, acids, and bases.
4. These fibers exhibit a diversity of physical and mechanical
characteristics, allowing composites incorporating these fibers to have
specific engineered properties.
5. Fiber and composite manufacturing processes have been developed
that are relatively inexpensive and cost-effective. 28
Carbon-reinforced polymer composites are currently being utilized
extensively in sports and recreational equipment (fishing rods, golf
clubs), filament-wound rocket motor cases, pressure vessels, and
aircraft structural components—both military and commercial,
fixed wing and helicopters (e.g., as a wing, body, stabilizer, and
rudder components).

29
 CHEMICAL FUELS

Definition
Chemical fuel is a combustible carbonaceous material which
on proper burning in air gives large amount of heat that can
be used economically for domestic and industrial purposes.

Eg.- wood, charcoal, coal, kerosene, petrol, diesel,

producer gas, water gas, natural gas, etc.,
❖ During the process of combustion, C and H of the fuel
combine with oxygen of air to form CO2 and H2O
respectively.
❖ Since the heat content of combustion products CO2, H2O,
etc. being lower than that of reactants (C, H, etc. of fuel), the
chemical fuel release heat during their combustion process.

Classification

• Based on their origin: 1) Primary (Natural) fuels

2) Secondary (Derived) fuels

• These are again subdivided into solid, liquid and gaseous

according to the physical state.
 Table-1. Classification of Fuels

Physical state Primary fuel Secondary fuel

Solid Wood, Peat, Charcoal, Coke

Coal, Lignite

Liquid Crude petroleum Petrol, Kerosene,

Diesel, Synthetic
petrol

Gas Natural gas Producer gas,

Water gas, Coal gas,
Biogas, LPG
 Characteristics of a Good Fuel
• High calorific value.
• Moderate ignition temperature.
• Low moisture content
• Low content of non-combustible matter.
• In case of solid fuel, the ash content should be
less and the size should be uniform.
• Readily available in bulk at low cost.
• Products of combustion should not be harmful.
• Combustion should be easily controllable.
• It should be safe, convenient and economical
for storage and transport.
Calorific value
It is defined as “the amount of heat liberated when
unit mass (or unit volume in the case of a gaseous
fuel) of fuel is completely burnt in air or oxygen”

Units
•Solid or Liquid fuels - cal/g or kcal/kg or J/kg
•Gaseous fuels – kcal/m3 or J/m3

•Gross or Higher calorific value (GCV)

It is defined as “the amount of heat liberated when
unit mass / volume of the fuel is burnt completely
in air and the products of combustion are cooled
to room temperature”
• Net or Lower calorific value (NCV)
It is defined as “the amount of heat produced when
unit mass/volume of fuel is completely burnt in air and
the products of combustion are allowed to escape into
the atmosphere”

• GCV = NCV + Latent heat of condensation of steam

• NCV = GCV – 9 × Mass of hydrogen × Latent heat

of steam

•NCV = GCV – 0.09 × % of hydrogen × Latent heat

of steam
 Analysis of coal and its significance

The proximate analysis involves the determination of

moisture, volatile matter, ash, and fixed carbon.

•This gives quick and valuable information regarding

commercial classification and determination of
suitability for a particular industrial use.

The ultimate analysis involves the determination of

carbon, hydrogen, sulphur, nitrogen, oxygen and ash.

•The ultimate analysis is essential for calculating heat

balances in any process for which coal is employed
as a fuel.
 Proximate analysis

i) Moisture: An air-dried coal sample is weighed into a

dry silica crucible and heated for about one hour at
1100 C in an electric hot air-oven. The crucible is
cooled first in air then in a desiccator and then
weighed.
% moisture = Loss in weight × 100
Wt. of coal taken

• Moisture in coal evaporates during the burning of coal and

it takes some of the liberated heat in the form of latent heat
of evaporation.
• Moisture lowers the effective calorific value of coal.
• Lesser the moisture content better is the quality of coal as a
fuel.
 ii) Volatile matter: The dried sample of coal left in the
crucible in step (i) is then covered with a lid and placed
in a muffle furnace, maintained at 9500 C. The crucible
is taken out after 7 minutes of heating. It is cooled first
in air then in a desiccator and finally weighed.

% Volatile matter = Loss in weight × 100

Wt. of coal taken

• A high volatile matter content means that a high proportion

of fuel will distill over as vapour and a large portion of which
escapes unburnt. So, higher % of volatile matter in coal is
undesirable.
• A high volatile matter containing coal burns with a long flame,
high smoke and has low calorific value.
• Lesser the volatile matter, better is the rank of coal.
iii) Ash: The residual coal left in the crucible in step (ii) is
then heated without lid in a muffle furnace at 700-7500 C,
until a constant weight of residue is obtained.

% Ash = Wt. of ash left × 100

Wt. of coal taken

Ash-forming constituents in coal are undesirable

for the following reasons:
• The calorific value of the coal is decreased
• The removal and disposal of ash poses problems
• The ash deposited in the fire bars interferes with
circulation of air
• If the ash fuses to form a clinker on the fire bars, it
hinders air circulation and also promotes corrosion
of the fire bars.
 iv) Fixed carbon: It is reported as the difference
between 100 and the sum of the percentages of
moisture, volatile matter and ash content of a coal
sample.

• Higher the percentage of fixed carbon, greater is its

calorific value and better is the quality of coal.

• Greater the percentage of fixed carbon, smaller is the

percentage of volatile matter. It is the fixed carbon
which burns in the solid state.

• Information regarding the percentage of fixed carbon

helps in designing of the furnace and the fire-box.
 Ultimate Analysis

i) Carbon and Hydrogen: An accurately weighed coal

sample (1-2 g) is burnt in a current of oxygen in combustion
apparatus. As a result C and H of the coal are converted into
CO2 and H2O respectively. These are absorbed respectively
in KOH and CaCl2 tubes of known weights. The increase in
the weights of KOH and CaCl2 tubes corresponds to the
amount of CO2 and H2O formed respectively.

C + O2 → CO2
12 44
2 KOH + CO2 → K2CO3 + H2O

H2 + 1/2O2 → H2O
2 18
CaCl2 + 7 H2O → CaCl2 .7 H2O
 % Carbon = Increase in wt .of KOH tube × 12 × 100
Wt. of coal taken ×44

% Hydrogen = Increase in wt. of CaCl2 tube × 2 ×100

Wt. of coal taken ×18

• C and H in coal directly contribute towards the calorific value

of the coal.
• Higher the percentage of C and H, better is the quality of the
coal and higher is its calorific value.

ii) Nitrogen: Determined by digesting a known quantity (1g) of

powdered air-dried coal sample in a Kjeldhal’s flask with conc.
H2SO4 in the presence of K2SO4 as a catalyst. After the solution
becomes clear, it is treated with excess of NaOH.
The liberated ammonia is distilled into a known volume of
standard acid solution. The volume of unused acid is then
determined by back titration with standard NaOH solution.
From the volume of acid used by ammonia liberated, the
percentage of nitrogen is calculated.

% Nitrogen = Wt. of nitrogen × 100

Wt. of coal taken

Where,
Wt. of nitrogen = Vol. of acid used × Nacid × 14
1000

Thus, % Nitrogen = Vol. of acid used × Nacid ×1.4

Wt. of coal taken
• iii)Sulphur: A known amount of coal
sample is burnt completely in a bomb
calorimeter. Sulphur present in coal
is oxidized to sulphates. The ash left after
combustion from the bomb calorimeter is
extracted with dil. HCl. The acid extract is
then treated with barium chloride solution
to precipitate sulphate as barium
sulphate. The precipitate is filtered,
washed, ignited and weighed.
% Sulphur = Wt. of BaSO4 obtained × 32 × 100
Wt. of coal taken × 233
• Sulphur containing coal is not suitable for
the preparation of metallurgical coke as it
adversely affects the properties of the
metal.
• Oxides of sulphur pollutes the environment
and leads to corrosion.
(iv) Ash: The ash content of coal sample is
determined as described under proximate
analysis.
(v) Oxygen:
% Oxygen = 100 – % (C + H + N + S + Ash)

The lower the oxygen content, the more is the

maturity of coal and greater is its calorific value
 Petroleum refining

The various fractions condensed and collected

at different heights of the column are :
Gases (Boiling range, below 300C),
Petroleum ether (30-700 C),
Gasoline or petrol (40-1200 C),
Naphtha (120-1800 C),
Kerosene (180-2500 C),
Diesel or fuel oil or light gas oil (250-3200C),
Heavy oil (320-4000 C),
Paraffin wax, Asphalt, etc., (above 4000 C).
 Cracking

•Cracking is defined as the process of decomposition of

higher molecular weight hydrocarbons (higher boiling)

into lower molecular weight hydrocarbons (low boiling).

• Cracking process involves breaking of C-C and C-H bonds.

• It produces low boiling alkanes and alkenes.
• A small amount of carbon and hydrogen are also produced.
 Cracking
C10H22 C5H12 + C5H10
Decane Pentane Pentene

Cracking

Thermal Cracking Catalytic Cracking

[Carried out at high temperature [Carried out in the presence of a
and pressure in the absence of catalyst (Al2O3 + SiO2) at a much
catalyst] lower temperature and pressure]
Advantages of fluidized-bed cracking
• A high degree of mixing is achieved and consequently
a good contact is established between the catalyst and
the feed stock vapours.
•This results in a higher yield.
• The regeneration of the inactive catalyst can be
carried out continuously without interrupting the
production of gasoline unlike in fixed-bed catalytic
cracking.
 Reforming of petrol

Catalytic Reforming: It is the process of upgrading gasoline

(increasing its octane number) in presence of a catalyst

•The increase in octane number of straight run gasoline occurs

through structural modifications such as conversions of straight
hydrocarbons into branched, cyclic and aromatic hydrocarbons.

• Reforming Process: The feed stock (straight run gasoline) is

preheated to remove S and N content to acceptable limits to
avoid platinum catalyst being poisoned. The vapours of the
feed stock is mixed with hydrogen and preheated to 5000 C.
The mixture is compressed (15-50 atmosphere) and then fed
into a series of three cylindrical reactors containing the
platinum catalyst supported on alumina-silica base. The
reformed products are fractionated to get stabilized gasoline.
Reforming reactions
• Isomerisation: The conversion of straight chain
hydrocarbons into branched chain hydrocarbons.
H3C (CH2)4 CH3 H3C CH CH2 CH2 CH3
CH3

n-hexane 2-methyl petane

• Dehydrogenation: Dehydrogenation of Cycloalkanes to

produce aromatic compounds.

+ 3 H 2

C y c lo h e x a n e B e z e n e

C H 3
C H 3

+ 3 H 2

M e th y l c y c lo h e a n e T o lu e n e
 • Cyclisation and dehydrogenation: Cyclisation of straight
chain hydrocarbons followed by dehydrogenation to
produce aromatic hydrocarbons.
C H3 ( C H 2)4 C H3 + H 2

n -H e xa n e C y c lo h e x a n e

+ 3H 2

C y c lo h e x a n e Benzene

• Hydro cracking: Hydro cracking of n-Paraffins to produce

light gases that are removed from gasoline fraction.

C
at
C
H 3 (
C H)8 C
2 H 3 +H
2 C
2H (
C H)3 C
2
H 3
3
n
-De
can
e n
-Pe
nta
ne
 SYNTHETIC PETROL
• Synthetic fuel or Synfuel is a liquid fuel obtained from
coal, natural gas, oil shale, or biomass. It may also refer
to fuels to fuels derived from other solids such as plastic
or rubber waste

• Method of producing Synthetic Petrol:

• 1. Polymerisation
• 2. Fischer-Tropsch method
• 3. Bergius process
• There are two type: i) Thermal Polymerization ii)
Catalytic Polymerization
• i) Thermal Polymerization: Thermal polymerization is
carried out at a temperature of about 500- 600 o C and
pressure about 70-350 kg/cm2
• ii) Catalytic Polymerization: It is carried out at a lower
temperature of 150- 200 o C, in low pressure and in the
presence of a catalyst like phosphoric acid. The rate of
reaction is increased. The gasoline obtained is of
improved quality and possess high antiknock properties
than the gasoline obtained from thermal polymerization
process.
 Fischer- Tropsch Process
• The Fischer-Tropsch process is a collection of chemical reactions that convert a
mixture of carbon monoxide and hydrogen into liquid hydrocarbons.

• The water gas is varied with hydrogen, and the combination is purified by
transitory from side to side Fe2O3 and then into a mixture of Fe2O3+Na2CO3.

• The cleanse gas is dense to 5 to 25 atm and then led from side to side a
converter, which is preserved at a temperature of 200-300 oC.

• The converter is provided with a catalyst bed consisting of a mixture of 1000 parts
cobalt, 5 parts thoria, 8 parts magnesia and 200 parts keiselghur earth.

• nCO + 2nH2 = CnH2n+ nH2O

• nCO +(2n+1)H2 = CnH2n+2 + nH2O
 The main advantages of gaseous fuels are:

• It is easier to handle gaseous fuels than solid fuels.

• It can be transported easily through pipelines.
• They do not leave any residue after burning.
• They have higher calorific values than the solid fuels.
• They produce little or no smoke, whereas most of the
solid fuels burn with smoke.
• They have relatively low ignition temperature, and
hence they burn more easily.
 The main disadvantages of gaseous fuels are:

• Very large storage tanks are needed for storing

gaseous fuels.
• The chances of fire hazards in case of leakages are
high as they are highly inflammable.
• They are more expensive than solid or liquid fuels.
 BIO GAS

Biogas is a type of biofuel that is naturally

produced by the decomposition of organic
waste. When organic matter, such as food
scraps and animal waste, break down in an
anaerobic environment (an environment
absent of oxygen) they release a blend of
gases, primarily methane and carbon
dioxide. Because this decomposition
happens in an anaerobic environment, the
process of producing biogas is also known
 Bio-gas composition: Compound
Formula %
• Methane CH4 50–75
• Carbon dioxide CO2 25–50
• Nitrogen N2 0–10
• Hydrogen H2 0–1
• Hydrogen sulfide H2S 0.1 –0.5
• Oxygen O2 0–0.5
• The manure and waste are mixed in the plant's receiving
tank before being heated to 38-52° C and pumped into
the digester in which the biogas is produced. The
biomass stays in the digester for 2-3 weeks, and the
fermented slurry can subsequently be used as crop
fertilizer

• To produce biogas, organic matter ferments with the

help of bacterial communities. Four stages of
fermentation move the organic material from their initial
composite on into their biogas state.
 Knocking
The explosive violent noise coming out from the IC engines
due to instataneous burning of the last portion of the fuel rapily
is known as knocking

• The efficiency of power production in spark ignited

internal combustion (IC) engines is related to the
compression ratio (CR).
• The CR is the ratio of the cylinder volume (V1) at the
end of the suction stroke to the volume (V2) at the
end of the compression stroke of the piston.
• This ratio is always greater than one, since V1 being
greater than V2.
•
The tendency to knock decreases as
follows:
➢ n-alkanes> mono substituted alkanes >
cycloalkanes > alkenes > poly substituted
alkanes > aromatics.
Adverse effects of gasoline knock

• It increases the fuel consumption.

• It results in decreased power output.
• It causes mechanical damage by overheating of the
cylinder parts.
• The driving becomes rather unpleasant.

The knocking in IC engines can be minimized through

the following measures:

• By a suitable change in engine design.

• By using high rating gasoline.
• By using anti-knocking agents.
Octane Number
•Among alkanes, n-heptane knocks severely,
while under
identical conditions, 2,2,4-trimethyl pentane
(iso-octane)has a high resistance to knocking.
• For the scale proposed to indicate the anti-
knock properties of gasoline, n-heptane was
arbitrarily assigned an octane number of zero
and iso-octane was arbitrarily assigned a
value of 100.
•
 Octane number is defined as the percentage
by volume of iso-octane in a mixture of iso-
octane and n-heptane blend,
which has the same knocking characteristics
as the gasoline sample, under the same set
of conditions.
• Thus a gasoline with an octane number of
90, has the same knocking characteristics as a
mixture of iso-octane and n-heptane containing
90% by volume of iso-octane. Since iso-octane
has good anti-knock properties, it is clear that
greater the octane number, greater is the
resistance to knocking.
Anti-knocking Agents
The octane rating of gasoline samples
can be increased by the addition of
certain organometallic compounds
called anti-knocking agents and the
process is called “doping”.
An extensively used anti-knocking
agent is tetraethyl lead (TEL),
Pb(C2H5)4.
Proposed Mechanism:
Pb(C2H5)4 +O2 PbO˚2 +Other products
RCH2O˚ + O2 RCHO + HO˚2
PbO + OH ˚ PbO(OH)
PbO˚2 + RCH2 PbO +RCH2O˚
HO˚2 + PbO OH˚ + PbO2
PbO(OH) + OH˚ PbO2 +H2O
Tetraethyl lead helps to cut self ignition brought
about by compression by generating a smooth
supply of free radicals
Unleaded Petrol

Petrol wherein the enhancement of octane rating is

accomplished without the addition of lead compounds is
referred to as unleaded petrol.

• To improve its octane number, Concentration of high octane

components (like isopentane, isooctane, ethylbenzene,
isopropyl benzene, etc) is increased by the process of
reforming.
• Compounds like methyl tertiary butylether (MTBE) can also
be added to improve octane number of unleaded petrol.

MTBE provides oxygen (of ether group) for combustion of

petrol in IC engines, thereby reducing considerably the
formation of peroxy compounds (which causes knocking).
Advantages of unleaded petrol

• The harmful effects of discharge of poisonous lead and its

compounds through the exhaust of automobiles is avoided.
• One of the major advantages of using unleaded petrol
is that it permits the attachment of a catalytic converter to
the exhaust pipe in automobiles.

Catalytic converter contains rhodium catalyst.

• It converts the toxic gases such as CO and NO to harmless
CO2 and N2.
• It also oxidizes hydrocarbons into CO2 and H2O.

Leaded petrol cannot be used in automobiles equipped with

catalytic converter as the lead present poisons the catalyst
thus destroying the active sites.
 Gaseous Fuels

Liquefied petroleum gas (LPG) or bottled gas or refinery gas

• It is obtained as a byproduct, during the cracking of heavy oils

or from natural gas.
• LPG is dehydrated, desulphurised and traces of odorous
organic sulphides (mercaptans) are added to give warning of
gas leak. It is supplied under pressure in containers under the
trade name like Indane, Bharat gas, etc.
• It has the calorific value of about 25000 kcal /m3.
• LPG consists of hydrocarbons of such volatility that they can
exist as gas under atmospheric pressure, but can be readily
liquefied under pressure.
• The main constituents of LPG are n-butane, isobutene,
butylenes and propene.
• LPG is widely used as a domestic fuel. Used as an
alternative fuel for IC engines, since it permits the
attainment of high compression ratios without producing
knocking

Advantages of LPG over gasoline as a motor fuel

• It is cheaper than gasoline.
• It readily mix with air.
• It is highly knock resistant,
• Residue and oil contamination is less, as it burns cleanly.

Disadvantages of LPG over gasoline as a motor fuel

• Handling has to be done under pressure.
• LPG is advantageous only in engines working under
high compression ratio.
• Its octane number is quite low.
• Its response to blending is very poor.
Water gas
• It is essentially a mixture of combustible gases, CO and H2.
• It is also known as blue gas because it burns with a blue flame
due to the combustion of carbon monoxide.
• The calorific value of water gas is about 10000 -11000 KJ/m3.
• The average composition of water gas is as follows:
CO: 40 – 45% ; H2 : 45 – 50% ; CO2 : 4% ; N2 : 4%

Manufacture: It is produced by passing alternatively steam

and little air through a bed of red hot coke maintained at10000 C.
Principle: When steam is blown through a bed of hot coke
(10000 C) water gas is produced.
C + H2O (steam) → CO + H2 ∆H = 131.4 KJ
• The reaction being endothermic in nature, the temperature
of the coke bed gradually decreases with continuous passage
of steam and the drop in temperature must be prevented. For
this the steam supply is temporarily cut off and air is blown in.
The over all reaction during air blow is the formation of CO.

2C + O2 → 2CO ∆H = - 221.9 KJ

This reaction being exothermic increases the temperature of

the coke bed to about 10000 C. Thus by blowing steam and
air alternatively, the temperature of the coke bed can be
maintained at 10000 C.

Uses
• It is used for the production of hydrogen.
• It is extensively used for the manufacture of methyl alcohol
and synthetic petrol.
• It is used as a fuel in glass and ceramic industries.
• Enriched water gas (mixed with hydrocarbons), which
burns with luminous flame is used as illuminating agent.
Producer gas
• It is essentially a mixture of carbon monoxide and nitrogen.
• It is prepared by passing air mixed with little steam over a
red hot coal or coke bed maintained at about11000 C.
• The average composition of producer gas is as follows:
CO: 25-30% ; N2 : 50-55% ; H2 : 10% ; CO2 : 5%;
Hydrocarbons : 2-3%.
• The calorific value of producer gas is 4000 - 5000 KJ/m3.

Manufacture: The producer is charged with coke from the

top and the charge is heated to about 11000 C. A mixture of
air and steam is passed over red hot coke bed through the
inlet at the bottom. The producer gas goes out through the
outlet at the top.
Reactions that takes place in different zones of the fuel bed

• Oxidation zone: This is the lowest part of the coke bed.

Here, the carbon of the coke burns in presence of excess of
air to give carbon dioxide.
2C + O2 → 2CO2 ∆H = - 393.5 KJ

• Reduction zone: Carbon dioxide produced in the oxidation

zone then rises through the hot bed and is reduced by coke
to CO.
2CO2 + C → 2CO ∆H = - 173.5 KJ
The over all reaction in the formation of carbon monoxide
being exothermic, the fuel bed gets heated up beyond 11000 C.
At high temperature:
- the ash forms clinkers or slag which are rather difficult to
remove.
- the grate bars and refractory lining get distorted.
 In order to avoid these problems in the producer, a
reduction in temperature is achieved by passing air saturated
with steam instead of air alone.
In the reduction zone, steam gets reduced to water gas.
C + H2O (steam) → CO + H2 ∆H = 131.4 KJ
This endothermic reaction brings down the temperature to the
optimum level.

• Distillation zone: This is the upper most part of the fuel bed,
where the distillation of volatile matter of coke / coal occurs.

Uses:- It is used as a fuel in the manufacture of steel, glass,

coal gas, etc.
- It is used as reducing agent in metallurgical operations
 Advantages of catalytic cracking

• The octane number of gasoline produced is high.

• The yield of gasoline is also high.
• The process can be better controlled.
• The product contains a very little amount of undesirable
sulphur.
• There is a saving in production costs since high temper-
atures and high pressures are not needed.
• In catalytic cracking, external fuel is not required.
The necessary heat is obtained by burning off the coke
deposited on the catalyst itself, during the regeneration
process.
• The gasoline formed contains much less gum and gum
forming compounds.
• Catalysts are selective in their action, and therefore, they
permit cracking of only high boiling hydrocarbons.
•Fluidized (moving) bed catalytic cracking:
The finely divided catalyst bed (Al2O3 + SiO2) is fluidized by the
upward passage of feed stock vapours (Heavy oil, gas oil, etc)
in a cracking chamber (called Reactor) maintained at 5500 C.
Near the top of the reactor, there is a centrifugal separator
(called cyclone), which allows only the cracked oil vapours to
pass onto the fractionating column but retains the catalyst
powder in the reactor itself. The catalyst powder gradually
becomes heavier due to the deposition of carbon and settles to
the bottom, from where it is forced by an air blast to the
regenerator (maintained at 6000 C). After cracking, the products
are fractionated into gases, gasoline, gas oils and residual oils.
The heavier oil fractions may be cracked in a second-stage
cracking.
In regenerator, the spent catalyst is stripped of the adsorbed
oil by passing steam and then decarbonized by a hot air blast,
under controlled conditions. The heat liberated during this
regeneration is used to raise steam and to preheat the catalyst.
• H. R. Ricardo, with the help of a variable
compression engine
• showed that in actual practice, the power
increases to a
• maximum and then falls rapidly with further
increase in the
• CR. The CR, corresponding to the maximum
power output, is
• known as highest useful compression ratio
(HUCR).
Mechanism of Knocking
• In IC engines, the gasoline and air drawn into the cylinder is
compressed by the piston and ignited by an electric spark.
• As the flame front travels towards feed end of the combustion
chamber, rapidly expanding combustion gases, compress the
remaining un-burnt fuel ahead of flame front and raise its
temperature.
• If the flame front travels rapidly at optimum speed, the
combustion of un-burnt fuel takes place but smoothly.
• If the flame front travels too slowly, the entire last portion of
the fuel-air mixture may get heated up beyond its ignition
temp. and undergo instantaneous explosive combustion.
This produces thermal shock wave which hits cylinder walls
and piston. This result in emitting of characteristic rattling
sound called knocking or pinking.
 Liquid Fuels

Petroleum (Crude oil)

• An important primary liquid fuel.

• It is a dark colored viscous oil found deep in the earth’s
crust.
• It is believed to have been formed millions of years ago by
anaerobic decay of marine plant and animal life under the
influence of high temperature and pressure.
• It is mainly a complex mixture of hydrocarbons (like straight-
chain paraffins, cycloparaffins, olefins and aromatics) with
small amounts of other organic compounds containing N, O
and S, and traces of inorganic compounds.
• The average composition of crude oil is:
C: 83 - 87%; H: 11 - 15 %; S, N and O: 0.1- 5%.
• The mechanism of the chemical reactions that lead to
knocking is not clear.
• It is believed that chemical reactions that are of importance
are cracking and the oxidation of the hydrocarbons.
• Probably the reactions proceed by a chain reaction.
• It was recognized that the structures of the fuel
hydrocarbons determines largely their knocking tendency.

• The tendency to knock decreases as follows:

n-alkanes> mono substituted alkanes > cycloalkanes >
alkenes > poly substituted alkanes > aromatics.

• The tendency to knock depends not only on the fuel used

but also on the engine design, shape of head, location of
plug, etc., and also upon the running conditions.
• Automobile gasoline's have octane number ranging from 75
• to 95. Aviation gasoline's have a greater knock resistance
• and their octane numbers are greater than 100. In such cases
• the octane numbers are computed using the relationship,

• Octane number = [ Power number –100 ] + 100

• 3
• where, power number is an arbitrary number proportional to
• the power being extracted by the engine.
• About 0.5 ml of TEL per liter is added for motor fuel and about
1 ml of TEL per liter is generally added for aviation petrol.
• It is believed that during combustion of gasoline, TEL forms
Pb and PbO.
• These species act as free-radical chain inhibitors and thus
curtail the propagation of the explosive chain reaction and
thereby minimizing knocking.
• If TEL alone is used, the species Pb and PbO may get
deposited on engine parts and cause mechanical damage.
• The vapours of Pb and PbO may pollute the air.
• In order to minimize the air pollution and damage to engine
parts, TEL is always used along with ethylene dibromide
or ethylene dichloride.
• The functions of these ethylene derivatives is to convert the
less volatile Pb and PbO into more volatile PbBr2 or PbCl2
which escapes into air along with exhaust gases.
 Catalytic Cracking methods

• Fixed-bed catalytic cracking: The catalyst (Al2O3 + SiO2)

in the form of powder or pellets is placed on the grid in the
catalytic chamber. The vapours of the feed stocks (Heavy oil,
gas oil, etc.) are passed through the bed of catalyst main-
tained at 450-5000 C. About 50% of the feed stock is
converted into gasoline together with elemental carbon
which gets deposited on the surface of the catalyst. Cracked
vapours are next subjected to fractionation in a fractionating
column wherein gasoline is separated from un-cracked heavy
oil. The catalyst loses its activity because of the deposition
of carbon and also due to the adsorption of oil vapours.
Accordingly, the catalyst requires regeneration after 8-10
hours. During regeneration time, the cracking process is
interrupted and the adsorbed oil is stripped off by passing
steam while deposited carbon is burnt off by a hot air blast.