Sharma, Shanta S. - Pal, Arpita P. - A Textbook of Applied Chemistry II-Himalaya Pub. House (2009) PDF

ATEXTBOOK OF
APPLIED
CHEMISTRY-II
Dr. Sbanta s. Sbarma

Asst. Professor, SIES Graduate School of Technology,
Nerul, Navi Mumbai.
•
Dr. Arplta Fe Pal
Asst. Professor, A. C. Patil College of Engineering,
Kharghar, Navi Mumbai.
Hm
GJIimalaya GJlublishingGJIouse"
MUMBAI • NEW DELHI • NAGPUR • BANGAlORE • HYDERABAD • CHENNAJ • PUNE • LUCKNOW .. AHMEDABAD· ERNAKULAM
© Authors
No part of this books shall be reproduced, reprinted or translated for any purpose whatsoever without prior
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ISBN : 978-93-5024-362-6
First Edition: 2009
Published by Mrs. Meena Pandey

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CONTENTS
1. CORROSION 1-39
1.1 Introduction
1.1.1 Nernst theory
1.1.2 Standard electrode potential
1.2 Theories of corrosion
1.2.1 Dry or chemical corrosion
1.2.2 Wet or electrochemical corrosion
1.3 Types of electrochemical corrosion
1.3.1 Galvanic cell corrosion
1,3.2 Concentration cell corrosion
1.3.3 Intergranular corrosion
1.3.4 Stress corrosion
1.4 Concept of polarization and over voltage
1.5 Factors affecting rates of corrosion
1,6 Methods to decrease rate of corrosion
1.6.1 Cathodic protection
1,6,2 Anodic protection
1.6.3 Advanced coatings
1,7 Metallic coatings
1.7,1 Methods of applying metallic coatings
1.7.2 Electroplating
1.7,3 Numericals based on Faraday's laws.
1.8 Organic Coatings
1.8.1 Paints
1.8.2 Varnishes
1.8.3 Enamels
1.8,4 lacquers
1.9 Corrosion engineering of electronic and photonic devices
2. ALLOYS AND POWDER METALLURGY 40-50

2.1 Introduction
2.1.1 Types of alloys
2.2 Non-Ferrous alloys
2.2.1 Alloys of Aluminium
2.2.2 Alloys of copper
2.2.2.1 Brass
2.2.2.2 Bronze
2.2.2 Bronzes
2.2.3 Alloys of lead
2.3 Recent advances in alloy related materials
2.3.1 Powder metallurgy
2.3.2 Ceramic powder.
3. FUELS 51-84
3.1 Introduction
3.1.1 Definition
3.1.2 Classification of fuels
3.1.3 Characteristic properties of a good fuel
3.2 Calorific value
3.2.1 Types of calorific value
3.2.2 Dulong's formula and numericals
3.3 Analysis of coal
3.3.1 Proximate analysis
3.3.2 Numericals based on proximate analysis
3.3.3 Ultimate analysis
3.3.4 Numericals based on ultimate analysis
3.4 Numericals based on combustion.
3.5 Liquid fuels
3.5.1 Crude Petroleum Oil
3.5.2 Classification of crude petroleum oil
3.5.3 Mining of petroleum
3.5.4 Refining of petroleum (Crude Oil)
3.6 Cracking
3.6.1 Thermal cracking
3.6.2 Catalytic cracking
3.6.2.1 Fixed bed catalytic cracking
3.6.2.2 Moving bed catalytic
3.6.3 Advantages of catalytic cracking over thermal cracking.
3.7 Knocking
3.7.1 Knocking in petrol engines.
3.7.2 Knocking in desel engines.
3.7.3 Octane number
3.7.4 cetane number
3.7.5 Antoknocking agents
3.7.6 Working of TEL.
3.7.7 catalytic converters and unlended gaso-line
3.7.8 Antiknocking agents in disel fud.
3.8 Diesel
3.8.1 Biodiesel
3.8.2 Transesterification
3.8.3 Production of hydrocarbons from plants (Petrocrops)
3.8.4 Agricultural waste
3.8.5 Producation of ethanol using biomass (Bioethnol
4. COMPOSITE MATERIALS 85-94

4.1 Introduction
4.1.1 Classification
4.2 Matrix phase and dispersed phase
4.2.1 Characteristic Properties of Composite materials
4.3 Fiber reinforced composities.
4.3.1 Large particle composities
4.3.2 Dispersion Strengthned composites.
4.4 Fiber reinforced composites
4.4.1 Continuous and aligned fibre composites
4.4.2 Discontinuous fibre composite.
•
4.5 Structural composites
4.5.1 Laminar composites
4.5.2 Sandwich panels
4.6 Application of composite materials
5. GREEN CHEMISTRY 95-105

5.1 Introduction
5.1.1 Principles of green chemistry
5.1.2 Goals and Significance
5.2 Green chemistry principle of atom economy
5.3 Numericals based on atom economy
5.4 Comparison of conventional route and green route
5.4.1 Synthesis of Indigo
5.4.2 Synthesis of Adipic acid
5.4.3 Fridel Craft's reaction
5.5 Industrial applications of. green chemistry
5.5.1 Waste utilization
5.5.2 Supercritical Liquids
5.5.3 Green fuels and E-green propellants
5.5.4 Dimethyl carbonate- A green regent.
6. CATALYSIS 106-123
6.1 Introduction
6.2 Characteristics of catalytic reactions
6.2.1 Types of catalysts
6.3 Activation energy and catalysis.
6.3.1 Theries of catalysis
6.4 Molecular design for catalysts and adsorbents
6.4.1 Metal complexes.
6.4.2 Metal cluster catalyst
6.4.3 Zeolities and zeotypes
6.4.4 Pillared clays
6.4.5 Metal oxide catalyst.
6.4.6 Carbon membranes
REVISION AT A GLANCE 124-176

Corrosion
1.1 INTRODUCTION
Corrosion is defined as the deterioration or destruction of metal (alloys) by an unwanted
chemical or electrochemical reaction with its environment, starting at its surface.
Note: Corrosion refers only to metals and alloys. Rotting of wood, paper is not corrosion. It
is erosion. Also it refers to chemical or electrochemical attack and not physical or mechanical
wearing of metals.
The most familiar example of corrosio'n is rusting of iron.
The process of corrosion is slow, but the losses incurred are enormous. Some of the social
and economic consequences of corrosion include:
• Plant failure and subsequent shutdown
• Replacement of corroded equipment
• Loss of efficiency
• Contamination or loss of the product (e.g., from corroded container)
• Preventive maintenance
It is estimated that annual loss due to corrosion runs into several billion dollars per annum
all over the world. It is therefore necessary that an engineer must understand the mechanism of
corrosion, if its effects are to be minimized. Also it is more prudent to avoid 'severe corrosion
conditions and provide simultaneous protection against corrosion.
1.1.1 Nernst theory

According to the Nernst theory, no metal is truly insoluble, and all metals have a tendency
to go into solution. If a piece of metal is immersed in water, some metal atoms will shed their
valence electrons and the positively charged metal ions, M+n go into solution. This leaves an
excess of negative charge on the metal electrode and thus a potential difference exists between
the metal and the solution. The positively charged metal ions, M+n, are held near the metal piece
due to electrostatic attraction. Some of the metal ions regain the electrons and get discharged as
metal atom. The process continues until an equilibrium is established and the number of metal
2 Applied Chemistry - 1/
ions getting discharged as metal atoms is equal to the number of metal atoms going into sol·ution
as M+n.
M ~ M+n + ne-
~
Zinc shows a greater tendency to go into solution in water as Zn+2 than Cu and a much
gredter concentration of Zn+ 2 in solution is required for the equilibrium to be established. In
case of sodium, the tendency to go into solution as ions is even greater. This tendency of a metal
to go into solution as ions when dipped in water is explained in terms of electrode potential.
The relation between the electrode potential and the concentration of the metal ion is
given by the Nernst equation:
0.0591 C
E= log-
n K
where C = concentration( activity) of the metal ions in giL, n = the charge or valence of
the ions and K = equilibrium constant. When C = K, the potential is zero.
1.1.2 Standard electrode potential

To determine the potential difference between an electrode and ,a solution, it is necessary
to have another electrode and a solution whose potential difference is accurately known. The
two half cells can then be combined to form a voltaic cell and its e.m.f. measured.
Now, Ecell = Eoxid + Eredn.
Thus the value of the unknown potential can be calculated.
The primary reference electrode is the normal or standard hydrogen electrode (S.H.E.).
S.H.E can be prepared by bubbling hydrogen gas at 1 atmosphere pressure over platinised
platinum, immersed in a solution of hydrochloric acid containing hydrogen ions at unit activity.
By convention, the potential of the S.H.E. is taken as zero volts at all temperatures.
By connecting the S.H.E. with a metal electrode in contact with a solution of its ions of unit
activity, the standard electrode potentials of various metals are determined.
When metals are arranged in the order of their standard electrode potentials, it is called
electrochemical series.
Table 1.1 gives the standard oxidation potential of some of the elements.
A metal will normally displace any other meral below it in the series from solutions of its
salts and precipitate it as metal. Thus Mg will displace AI, Zn will displace Fe, Fe will displace Cu
and so on from solution of its salts.
Corrosion 3
Table 1.1: Standard electrode potentials (reduction) at 25°C.
Metal ion Potential in volts

Li+ +e- ~ Li (BASE) -3.05 (ANODE)
K++e- ~ K -2.93
Ca2++2e- ~ Ca -2.90
Na+ +2e- ~ Na -2.71
Mg2+ + 2e- ~ Mg -2.37
Aj3++3e- ~ AI -1.66
Zn2+ + 2e- ~ Zn -0.76
C~++3e- ~ Cr -0.74
Fe2++2e- ~ Fe -0.44
Nj2+ +2e- ~ Ni -0.23
Sn 2++2e- ~ Sn -0.14
Pb2+2e- ~ Pb -0.13
Fe3++3e- ~ Fe -0.04
H++e- ~ 1/2H 0.00 (Reference)
Cu 2+ + 2e- ~ Cu +0.34
Ag+ +e- ~Ag +0.80
Pt"+ +4e- ~ Pt +0.86
Au+ +e- ~Au + 1.69
1/2F2+e- ~ F- (NOBLE) +2.87 (CATHODIC)
Galvanic series
Although electrochemical series gives very useful information regarding chemical reactivity
of metals, it may not provide sufficient information in predicting corrosion behavior in a particular
set of environmental conditions because-
(i) in practical situations many side reactions may take place which influence the corrosion
reactions
(ii) electrochemical series does not shed light about alloys.
In view of this, oxidation potential measurements of various metals and alloys on common
use have been made using standard calomel electrode as the reference electrode and immersing
the metals and alloys in sea water. These are arranged in the decreasing order of activity and this
series is known as galvanic series ( Table 1.2 ).
4 Applied Chemistry - /I
Tablel.2: Galvanic series.
Active (or anodic) 1. Mg

2. Mgalloys
3. Zn
4. AI
5. Cd
6. AI alloys
7. Mild steel
8. Cast iron
9. High Ni cast iron
10. Pb-Sn solder
11. Pb
12. Sn
13. Iconel
14. Ni-Mo-Fe alloys
15. Brasses
16. Monel(7-Ni, 30-Cu, rest-Fe)
17. Silversolder
18. Cu
19. Ni
20. Cr stainless steel
21. 18-8 stainless steel
22. 18-8 Mo stainless steel
23. Ag
24. Ti
25. Graphite
Noble (or cathodic) 26. Au
27. Pt
1.2. THEORIES OF CORROSION

Corrosion occurs in 2 ways-
(i) Dry or Chemical corrosion
(ii) Wet or EIect ro-chem ical or Immersed corrosion.
1.2.1. Dry or Chemical corrosion

It occurs mainly through-
(i) Direct chemical attack of atmospheric gases like ° 2, H 2 , H 2 S, N02 , etc., on met~ls.
(ii) Action of anhydrous inorganic liquid with the metal surfaces.
02: At ordinary temperature, metals, in general, are very slightly attacked. However, alkali
and alkaline earth metals are attacked by 02 even at low temperatures. At high temperatures, all
metals (except Ag, Au and Pt) are oxidized.
Corrosion 5
2M + nl20 2 ---+M 20 n
The oxidation first occurs at the surface of the metal and the resulting metal oxide forms a
barrier, that tends to restrict further oxidation.
Further oxidation then depends upon the nature of the oxidized product-
(i) Stable- If the oxide film is stable and finely grained in structure, it gets tightly adhered
to the parent metal surface protecting the metal eg., oxide films on AI, Sn, Pb, Cu, Pt.
etc.
(ii) Volatile- If the oxide layer volatalises as soon as it is formed it leaves the underlying
metal surface exposed for further attack. This causes rapid and continous corrosion,
eg., molybdenum'oxide, Mo03 •
(iii) Porous-Ifthe oxide layer is porous or has cracks the oxygen has access to the underlying
metal surface and the corrosion continues unobstructed, eg., .oxides of alkali and
alkaline earth metals.
(iv) Unstable- The oxide layer decomposes back into the metal and oxygen and
consequently oxidation corrosion is not possible in such a case, eg., Ag, Au and Pt do
not undergo oxidation corrosion.
Metal oxide ~ Metal + oxygen
Pilling-Bedworth rule: The rule states that an oxide is protective or non-porous, if the
volume of the oxide is at least as great as the volume of the metal from which it is formed and
vice-versa.
Corrosion by other gases like S02' CO2, C1 2, H 2S, etc., except H 2 : Ltke oxidation, the degree
of attack depends on the formation of protective or non-protective films on the metal surface-
(i) Protective film or non-porous film - e.g. Agel film, resulting from the attack of CI 2 on
Ag. The AgCI film protects the metal from further attack.
(ii) Non-protective or porous film - e.g. SnCI 2 film formed when dry CI 2 gas attacks Sn.
The film is volatile leaving fresh metal surface for further attack. FeS film is porous and
exposes iron or steel to further attack by H2 S.
Corrosion by H 2 :
(i) At ordinary temperatures H2 causes embrittlem~nt. This is caused due to the formation of
atomic hydrogen which is formed as a result of chemical or electrochemical attack on the metal
surface by gases like H 2 S.
H 2S + Fe---+ FeS + 2H
The hydrogen so formed diffuses readily into the voids on the metal surface where it
recombines to form molecular H 2•
H + H---+ H2
6 Applied Chemistry - II
Gradually the pressure of H2 on the metal voids builds up resulting in the formation of
blisters and fissures.
(ii) At high temperatures, hydrogen decomposes to form atomic hydrogen by thermal
dissociation.
H2 heat) H + H
The atomic hydrogen is highly chemically active and diffuses into the metal where it readily
combines with impurities like C, 5, 0, N, etc., usually present in metals in small amounts. The
pressure of the product builds up causing cracking, blistering, etc.
C + 4H~CH4
N + 3H·~ NH3
5+ 2H~H25
Liquid metal corrosion: It is caused due to chemical action of flowing liquid metal at high
temperatures on solid metal or alloy. It occurs by- (i) dissolution of solid metal by liquid metal.
(ii) Penetration of liquid metal into solid metal. Both these causes results in a weakening of the
solid metal.
1.2.2. Wet or Electrochemical corrosion

This type of corrosion occurs in presence of : i) a conducting liquid ii) a single metal/ alloy
is exposed to this liquid or two dissimilar metals/alloys in electrical contact are exposed to this
liquid.
In either case separate anode and cathode areas are formed on the metal surface, between
which the current flows through the conducting solution.
At anode, oxidation takes place, i.e., the metal dissolves in the surrounding electrolyte to
form metal ions.
M~ M+n + ne-
The electrons liberated at the anode migrate to the cathode through the metal. At the
cathode, the electrons are consumed. Usually, the cathode reactions donot affect the cathode
part of the metal, since most metals are already reduced and cannot be reduced further. So,
usually at cathodic part, dissolved constituents in the conducting medium accepts the electrons.
Hence, corrosion always occur at anodic areas and the cathode areas usually remains free
from corrosion.
Cathode reactions:
(i) Acidic environment-In presence of acids the cathodic reactions proceeds with evolution
of H2 gas.
Corrosion 7
For e.g. Consider a metal like Fe, the anodic reaction is dissolution or iron as ferrous ions
with liberation of electrons.
These electrons flow through the metal from anode to cathode, where H+ ions from the
electrolyte and get liberated as hydrogen gas.
2H+ + 2e-~ H21
The overall reaction is: Fe + 2H+ ~ Fe+ 2 + H21
--------~-------------------------------------------
Fig. 1.1 Mechanism of wet corrosion by hydrogen evolution
All metals above hydrogen in the electrochemical series have a tendency to get dissolved
in the acidic solutions with simultaneous evolution of H2 gas.
(ii) Neutral or alkaline environment- In neutral or alkaline environment, the electrons are
accepted by the dissolved oxygen, to form OH- ions.
1
H20 + "2 02 + 2e- ~20H-
For e.g. Consider the corrosion of iron in neutral aqueous solution. At the anodic areas,
iron metal dissolves as ferrous ions with liberation of electrons.
Fe ~ Fe+ 2 + 2e-
Electrons liberated at the anode, migrate to the cathode through the iron metal and are
intercepted by the dissolved oxygen and forms OH- ions.
1
H 20 +"2°2 + 2e-~ 20H-
The metal ions, Fe+ 2 ions, formed at the anode and the OH- ions formed at the cathode
diffuse towards each other and the corrosion product, ferrous hydroxide is precipitated.
Fe+ 2 + 20H-~ Fe(OH)2J..

If there is enough oxygen present, ferrous hydroxide is easily oxidized to ferric hydroxide,
i.e., rust.
4Fe(OH)2 + 02 + 2H 20 ~ 4Fe(OH)3 J.. or 2Fe20 3.2H 20
Rust
The corrosion product is formed more commonly near or at the cathode because the
smaller Fe+ 2 diffuse more rapidly than the larger OH- ions.
:::: ::: :::::::.::-- -AqueOUS neutral ;iluikln -:::::::::: : ::: :::

- - - - - -- - - - - - - - - - of electrolyte -- - - - - - - - - - - - - --.
: : : : : : : : : : : : : : Rust : : : : : : : : : : Rust :;: ~ ~ - ~-: ~ -;:-;H- ::::

---J.!zO,+2e-+H,O+20H --~--- -- ---- ,+ +, ---.
- - - - - - - - - - - - - - - - - Oxide film - - - -
Fig. 1.2 Mechnism of wet corrosion by oxygen absorption
1.3. TYPES OF ELECTRO-CHEMICAL CORROSION
1.3.1 Galvanic cell corrosion

Galvanic corrosion occurs when two dissimilar metals or alloys, e.g., Zinc and Copper, in
electrical contact are exposed to an electrolyte. The metal or alloy higher in the galvanic series
forms the anode and suffers corrosion while the metal or alloy placed below remains free from
corrosion. Hence, in the above example, zinc, placed higher in the galvanic series, forms the
anode and suffers corrosion whereas copper placed below forms cathode and remains free
from corrosion.
Anode:
.............. (oxidation)
Cathode:
In acidic solution. The corrosion occurs by the hydrogen evolution process.
2H+ + 2e-~ H2
Corrosion 9
In neutral or slightly alkaline solution, oxygen absorption occurs resulting in the formation
of OH- ions. .
1 .
2
H0 + "2°2 + 2e-~ 20H- . .............. (reduction)
The larger the potential difference between the two metals, the greater will be the rate of
corrosion.
Some common examples of galvanic corrosion-

(i) Steel screws in a brass marine hardware.
('ij) Lead-antimony solder around copper wire.
(iii) A steel propeller shaft in a bronze bearing.
(iv) Steel pipe connected to copper plumbing.
Electronic current Electrolyte
r----------- -------
----- -------
----fJ-------
-----
----
----- --------
-------
1- ~-- - - - - - - - - - - --- --------
---- ------_.
--------------
I';: (Less noble) : : _-. (More noble . : :~
1.= anode is :. :.:: cathode is .:. :. :
::. attacked ==:
--- Positive ions
~
==:: protected
Current
Cu
Fig. 1.3 Galvanic corrosion
1.3.2 concentration cell corrosion

This type of corrosion is due to electrochemical attack on the metal surface, exposed to-
(i) an electrolyte of varying concentrations, e.g., storage tank of a solution or
(ii) an electrolyte of varying aeration or differential aeration.
(i) Metal in contact with solution of varying concentrations - This may be the result of
local difference in metal ion concentrations, caused by local temperature differences or inadequate
agitation or slow diffusion of metal-ions, produced by corrosion.
(ii) Differential aeration - This is the most common type of concentration cell corrosion. It
occurs when one part of the metal is exposed to higher concentration of air compared to the
other part. This causes a difference in potential between differently aerated areas. The metal
surface exposed to higher concentration of oxygen, becomes cathodic, as oxygen helps in the
consumption of electrons.
The metal surface which is exposed to lower concentration of air becomes anodic.
.
.
The concentration cell can be represented as;
Differential aeration accounts for the corrosion of metals, partially immersed in a solution,
just below the waterline. For e.g., consider a metal plate like Zn partially immersed in dilute
solution of a neutral salt like NaCI. The parts above and closely adjacent to the waterline are
more strongly aerated and hence become cathodic.
On the other hand, parts immersed to greater depth have less access to oxygen become
anodic.
Thus a difference in potential is created, which causes a flow of current between the two
differentially aerated areas of the same metal.
At anode, Zinc will dissolve to form Zinc ions.
Zn ~ Zn +2 + 2e-
The electrons liberated at the anode, is accepted at the cathode by the oxygen to form
hydroxyl ions.
1
-2 0 + H 20 +
2 .
2e- ~ 20H-
More oxygenated
part (cathode)
---+----", ~~!It..;' Nacl soltion
Row of eieotron
Corroding anode
zn~zn2++2e-
(Less oxygeated part)
=Zn2+==---=-"7===
_-=-_-_-_-=-:; Znc~ :,.-=-_-=-_-=-_
-------------
------------
Fig. 1.4 Mechanism of differential aeration attack caused by partial immersion of a metal
Similarly, iron corrodes away under a drop of water or salt solution. Areas underneath the
drop, are less aerated and forms anode compared to the areas at the periphery of the drop and
the remaining areas, which are freely exposed to air and forms cathode.
Metal dissolves at the anodic areas while the OH- ions are formed at the cathode and the
corrosion product, i.e., rust is deposited at the cathodic areas.
Corrosion 11
Air
Rust ring
Rust ring
(iron hydroxide)
(iron hydroxide)
Y2 o2+H20+2e--+20H- Y2 o2+~ O+2e--+20H-
Good access
ofoxyegn
Fig. 1.5 Mechanism of differential aeration attack, caused by the presence of drops of salt solution on the
iron surface. metal dissolves at the less-aerate anodic areas; whereas corrrodsion product (iron hydroxide) is
deposited at the cathodic areas.
Some more examples of differential aeration corrosion:

(i) Corrosion of metal in cracks or crevices are accelerated, as these areas are deficient in
oxygen concentration and consequently behave as anode while the rest of the plain surface of
the metal behaves as the cathode.
Corrosion product
Anode
sand (less oxygenated part)
\ /
Fig. 1.6 Oxygen concentration corrsion. Anode is formed at inaccessible location, where oxygen is less
available. The cathode forms, where oxygen is freely available
Fig. 1.7 Localized corrosion of oxygen-deficient areas

Corrosion of metal is accelerated under the accumulation of dirt, sand, scale or other
contamination. This is because accumulation or rust, scale ·or sand, etc. restricts the access of
oxygen. The portion of the metal under these areas thus behave as anode and the remaining
areas that are clean and free from the impurities form the cathode.
Zt
Fe +20H"" Fe(OHh
r.nlTnQ,inn product
More oxygenated
cathode
Fig. 1.8 Pitting corrosion at the surface of iron
(ii) Metals under block of wood or pieces of glass, which screen that portion of metal from
oxygen access form anode ~hen exposed to a suitable electrolyte.
Corrosion 13
1.3.3. Intergranular corrosion

This type of corrosion occurs along grain boundaries in metal alloys. Metal alloys are finely
grained in structure.
This type of corrosion occurs because of an alloy concentration gradient between the
grains and the grain boundaries and the presence of an electrolyte which possess the selective
character of attacking only at the grain boundaries. This concentration gradient occurs due to
precipitation of certain compounds at' the grain boundaries, thereby leaving the solid metal
solution (alloy) adjacent to the grain boundary, deficient in one constituent. The grain boundary
acts as an anode with respect to the grain centre which becomes the cathode. The precipitated
compound also becomes cathodic.
For e.g., During the welding of stainless steel (alloy of Fe, C and Cr), chromium carbide is
precipitated at the grain boundaries. Thus the region just adjacent to the grain boundaries become
deficient in chromium and is therefore more anodic with respect to the grain centre which is
richer in chromium. It is alsO anodic .to the particles of chromium carbide so precipitated.
This type of corrosion occ.urs on a microscopic scale without any external signs of any
intensive attack. On account of this sudden failure of material occurs (without any pre-warnings)
due to loss of cohesion between grains.
The remedy for such corrosion of alloys is heat treatment followed by rapid quenching to
avoid heterogeneous precipitation, that usually occurs due to .slow cooling.
Protected grain
centre (cathodic)
Improvised grian
boundary (anodic)
1..--~:::====::::- Precipitated compound

(cathodic)
Fig. 1.9 General intergranular attack
1.3.4. Stress corrosion

Stress corrosion is the combined effect of static tensile stresses and the corrosive environment
on a metal.
Stress corrosion is characterized by a highly localized attack when overall corrosion is

negligible. For stress corrosion to occur - (i) the presence of tensile stress and (ii) presence of
specific corrosive environment are necessary. The corrosive agents are highly specific and selective
such as acid chloride solution for stainless steel.
The stress may have been produced during manufacture or fabrication or heat treatment.
The external stress is due to the service condition.
From thermodynamic calculations it has been shown that the atoms under stress are at high
energy levels. These become so chemically active that they are attacked by even mild corrosive
environment. Consequently the points under stress as well as grain boundaries are anodic and
there is a large stress free surface which is cathodic. The path of stress is very narrow and
corrosion is concentrated in a narrow path which is anodic with a large cathodic surface. This
results in the formation of a crack, which grows and propogates in a plant (perpendicular to the
tensile stress), until failure occurs or it may stop, after progressing a finite distance.
Some typical examples of stress corrosion:
(i) Season cracking - It is a term applied to stress corrosion of copper alloys, mainly brasses.
Pure copper is immune to stress corrosion, but presence of small amounts of alloying elements
like P, As, Sb, Zn, AI, Si increases its susceptibility to corrosion. For e.g., alpha brass, when
highly strained, undergo intergrannular cracking in an atmosphere, containing traces of ammonia,
amines. Both Cu and Zn form stable complexes ions in ammonia solutions, Cu(NH 3)4 +2 and
Zn(NH 3)4 +2 respectively. As a result, brass gets dissolved, leading to fissure, that ultimately
propogates to form cracks in the presence of high tensile stress.
(ii) Caustic embrittlement -This is a stress corrosion seen in mild steel exposed to alkaline
solutions at high temperatures and stresses and is the main cause of failure of steam- boilers.
----------_.
- - - -- - -- - --- Aqueous
-
:.:. :. :.:. :.:. ::: - - : solution
Stressed Part ~~~:;:;;::~r- Anode (strained part)

grain boundary where corrosion takes
(anode)where place
corrosion takes place
Cathode---+
Fig. 1.10 Stress corrosion

Corrosion 15
1.4. CONCEPTS OF POLARIZATION AND OVERVOLTAGE

Polaritation: Polarization of a cell can occur due to two mechanism:
(i) Concentration polariz.ation: When a cell is under use, the concentration of the ions
surrounding the electrodes differ from that in the bulk of the electrolyte. These concentration
gradients at the electrodes set up a back e.m.f., and the cell potential drops. This is known as
concentration polarization. It increases with time and current density.
In commonly used dry cell, the effect of polarization is counteracted by adding NH 4 CI to
remove the Zn ions in the form of a complex Zn(NH 3V2 •
(ii) Cas polarization: This is caused by the formation of a resistant film of adhering atoms or
molecules of gas on the electrode. It occurs when 02 or CI 2 is liberated at anodes or when
hydrogen ions are discharged at the cathode liberating H 2.
In a dry cell, cathodic polarization occurs 'at the carbon electrode. The depolarizing agent
employed is Mn02 which reacts with H2 to produce water and lower oxides of manganese.
The more adherent and non-porous the film formed, the more it contributes to the increase
of polarization at an electrode. However, even porous and loosely adherent films may also exert
a considerable effect.
Decomposition voltage: If a small voltage say around 0.5 V is applied between two smooth
platinum electrodes immersed in 1M sulphuric acid solution, the current in the circuit initially
shows that an appreciable amount of current is flowing as seen in the atnmeter placed in the
circuit. However, its strength gradually decreases and falls practically to zero within a short
time.
If the applied voltage is gradually increased, there is a slight increase in the current until,
when the voltage reaches a certain value, the current suddenly increase rapidly with increase in
the e.m.f. The sudden increase in current is accompanied by copious evolution of gas at the
electrodes. The voltage at this point is called the decomposition voltage or decomposition potential
and is defined as the minimum external voltage that must be applied in order to bring about
continuous electrolysis.
If the circuit is broken now, it can be observed that the voltmeter reading which is fairly
steady at first, rapidly falls to zero. This implies that the cell is behaving as a source of current
and is said to exert a back e.mJ. because it acts in a direction opposite to that of the applied
e.m.f.
This back e.m.f. arises due to the accumulation of 02 and H2 at the anode and the cathode
respectively, which consequently act as gas electrodes. The potential difference between them
opposes the applied e.m.f. When the primary current from the battery is cut off, the cell produces
a moderately steady current until the gases at the electrodes are either used up or diffuses away,
and then the voltage falls to zero. This back e.m.f. is present even when the current from the
battery passes through the cell.
Overvoltage or over-potential: It has been experimentally found that the decomposition
voltage of an electrolyte varies with the nature of the electrodes employed for the electrolysis
16 Applied Chemistry - 11
and is in many cases, higher than that calculated from the difference of the reversible electrodes.
This excess voltage over the calculated back e.m.f. is known as overvoltage or over-potential.
The decomposition voltage, Ed, is given by the following relation.
Ed = (Ecathode + Eo) - (Eanode + Eo)

where Eo.c and Eo.a are the overvoltages the cathode and anode respectively.
For example, the e.m.f of a standard chlorine hydrogen cell is 1.36V. But unless one uses a
platinised electrode, the decomposition voltage required to generate hydrogen and chlorine by
electrolysis is considerably greater than 1.36V. This extra voltage above the cell voltage is called
overvoltage or over-potential.
1.5 FACTORS AFFECTING RATE OF CORROSION

The rate and extent of corrosion, depends on the following factors:
• Nature of the metal
• Nature of the environment
Nature of the metal

(i) Position of metal in the galvanic series: When two different metal or alloys in electrical
contact is exposed to an electrolyte, the metal which is placed above in the galvanic series forms
the anode and suffers corrosion while the metal which is placed below forms cathode and
remains free from corrosion.
Greater the difference in the position in the galvanic series, faster is the rate of corrosion.
(ii) Overvoltage: Reduction in the overvoltage of the corroding metal/alloy accelerates the
corrosion rate.
For e.g.,. When Zn is placed partially on 1 N, H 2S0 4, it undergoes corrosion forming a film
and evolving hydrogen gas. The initial rate of reaction is quite slow, because 0 f high overvoltage
of Zn metal (0.7 V). The corrosion is accelerated by adding a few drops of CuS04 , because some
. copper gets deposited on the Zn metal, forming minute copper cathodes, where the hydrogen
overvoltage is only 0.33V.
(iii) Relative are,!s of anode and cathode: Rate of corrosion is directly proportional to the
ratio of the areas of the cathodic part to the anodic part.
Corrosion is more localized and accelerated, if the anodic area is much smaller than the
cathodic area because the demand for electrons by the large cathode is very high and can be
satisfied only by undergoing corrosion more rapidly, eg., a small steel pipe fitted in a large
copper vessel.
(iv) Purity of metal: The rate of corrosion increases with increase in the impurities in the
metal.
Impllrities in a metal, form tiny galvanic cells with the base metal and the anodic part gets
corroded.
Corrosion 17
(v) Physical state of the metal: The rate of corrosion is influenced by the physical state of the
metal (such as grain size, orientation of the crystal, presence of stress, etc.).
The smaller the grain size of the metal or alloy, the greater will be its corrosion. Areas
under stress, even in a pure metal tend to be anodic and corrosion takes place at these areas.
(vi) Nature of the surface film: In aerated atmosphere, practically all metals get covered by
a thin film, a few Angstroms in thickness, of metal oxide. The ratio of the volumes of the metal
oxide to the metal, is known as specific volume ratio.
Rate of corrosion is inversely proportional to the specific volume ratio. The specific volume
ratios of Ni, Cr, and Ware 1.6, 2.0 and 3.6 respectively. Hence the rate of oxidation is the least
in tungsten, even at elevated temperature.
(vii) Solubility of the corrosion products: If the corrosion product is soluble in the surrounding
medium, then corrosion proceeds at a faster rate. On the other hand, if the corrosion product is
insoluble or it forms an insoluble product on reacting with the medium, then it forms a physical
barrier, and protects the metal from further attack by the medium, eg., PbS0 4 formed when Pb
reacts with H 2S04 medium.
(viii) Passive character of metal: Metals like AI, Cr, Ni, Co are passive and exhibits a much
higher resistance to corrosion than expected from their positions in galvanic series.
This occurs due to the formation of a highly stable, but very thin film of the corresponding
metal oxide on the metal surface. Also, the film is self-healing, i.e., if the film is broken, it repairs
itself, on re-exposure to oxidizing conditions. The exceptional corrosion resistance of stainless
steel is due to the presence of a passive chromium oxide film on its surface.
Nature of the environment
(i) Humidity: Iron doesnot corrode in dry air but undergoes rapid corrosion, when exposed
to moist air. In fact the corrosion of all metals become faster in humid atmosphere.
Gases (C0 2, 02' etc.) and vapours dissolve in the moisture, providing the electrolyte,
necessary for setting up of an electrochemical corrosion cell. Also, rain water, helps to wash
away a good part of oxide film from the metal surface, leading to enhanced atmospheric attack,
unless the oxide film is exceptionally adherent (eg., Cr, AI).
(ii) Temperature: The rate of any reaction as well as diffusion reactions, increases with
increase in temperature. Hence the rate of corrosion reaction also increase with increase in
temperature.
(iii) pH: Corrosion reactions involve H+ and OH- ions, hence rate of corrosion reactions
are affected by the pH of the medium.
Acidic media (pH < 7), are more corrosive than alkaline and neutral media. However,
amphoteric metals ( like AI, Zn, Pb) dissolve in alkaline solutions as complex ions and so corrode
even in alkaline medium.
(iv) Presence of impurities in the atmosphere: Atmosphere in the vicinity of industrial areas,
contains corrosive gases like CO2, H2S, S02 and fumes of HCI, H 2 S04 , etc. In the presence of
these gases, the acidity of the liquid, adjacent to the metal surfaces, increases and its electrical
conductivity also increases resulting in increased corrosion.
Corrosion is also a severe problem in marine atmosphere due to the presence of chloride
ions in the environment.
(v) Nature of the ions present: Ions can enhance the rate of corrosion or depress the rate of
corrosion.
Presence of anions like silicate in the medium leads to the formation of insoluble reaction
products which inhibit further corrosion.
Chloride ions, on the other hand, destroy the protective and passive surface film, thereby
exposing the metal or alloy surface for fresh corrosion. Many metals, including iron, undergo
corrosion rapidly, if the corroding medium contains ammonium salts. Presence of even traces of
copper or other noble metals in mine waters, accelerates the corrosion of iron pipes carrying
such waters.
(vi) Conductance of the medium: The conductance of the medium plays a great role in the
corrosion of underground or submerged structures.
Conductance of clay or mineralized soils is higher than that of dry sandy soils. So, stray
currents from power leakages will damage the metal structures buried under soils of higher
conductance to a greater extent than those under dry sandy soils.
(vii) Concentration of oxygen and formation of oxygen concentration cells: The rate of
corrosion increases with increasing concentration of oxygen. Also, hydrogen depolarization
increases under these conditions, further enhancing corrosion.
Differential aeration also promotes corrosion by the formation of oxygen concentration
cell. Corrosion often takes place under metal washers where oxygen cannot diffuse easily.
1.6 METHODS TO DECREASE RATE OF REACTION
1.6.1 Cathodic protection

It is based on the principle that the metal to be protected is forced to behave as a cathode,
and thereby avoid corrosion.
The two types of cathodic protection are:

(i) Sacrificial anode method - The metallic structure, to be protected, is connected by a
metallic wire to a more anodic metal called the sacrificial anode SQ that all the corrosion is
concentrated on this more anodic metal. When sacrificial anode is corroded completely it is
replaced by a fresh one. Examples of sacrificial anode metals- Mg, Zn, 'AI and their alloys.
Uses - This method is used for the protection of buried pipelines, underground cables,
marine structures, ship hulls, water tanks, etc.
Corrosion 19
e
Ground level
: :S9i! : : : : : : : : : : : : : : : : : : : : : : : : : : : :
::::0-:: .... ...

.... .... .... ....
M 2+
: -~ :~,?:
:........ :/.
Fig. 1.11 In cathodic protection, an anode of a more strongly reducing metal is sacrificed to maintain the
integrity of the protected object (e.g. a pipeline, bridge, ship hull or boat)
(ii) Impressed current cathodic protection - An impressed current is applied in opposite

direction to nullify the corrosion current and convert the corroding metal from anode to cathode.
The impressed current is derived from a direct current source like battery with an insoluble
anode like graphite, high silica iron, scrap iron, stainless steel, platinum blackfill (coke).
Uses - This type of protection has been applied to open water-box coolers, water tanks,
buried oil or water pipes, condensers, transmission line towers, marine pliers, laid up ships, etc.
This kind of protection technique is, particularl, useful for large structures for long-term
operations.
-L_ _ _ _-::;;rn~"-----L-L..-......:.I~tFiF==----lnsulated
copper wire
7""":~-:~-_'':. a:==::t:==~:-_Underground
Back fill--:;~~t: pipeline cathode
Graphite or _":;;":;;":;;'"'"l1li
Stainless steel
~~~~tttt~~r~ltt~
Fig. 1.12 In impressed-current cathodic protection, electrons are supplied from an external cell so that the
object itself becomes cathodic and is not oxidized
20 Applied Chemistry - /1
1.6.2 Anodic protection
+1.6
+1.6
+0.8
+0.8
:> :>
ui ui
iii iii 0.0
0.0 E
~ Ql
~
D..
0
D..
Neutralization
Corrosion
-0.8
-0.8
-1.6
-1.6
-2 2 6 10 16 -2 2 6 10 14
pH pH
Fig. 1.13 A & B. Pourbaix diagram
Pourbaix diagram of Iron in neutral water

Certain metals exhibit active-passive behaviour depending on the pH of the medium and
the potential developed in contact with a liquid.
For e.g., iron can be active as well as passive to corrosion in contact with water under the
influence of pH and electric potential. Thus for any given condition, X, of the metal, we can
achieve corrosion protection by cathodic protection, by neutralization or by anodic protection.
Thus anodic protection of iron can be achieved by applying a potential more than 0.1 V (pH = 7)
through an external circuit. This protection method is generally applied in iron, steel, stainless
steel, aluminium, titanium, chromium.
Insulated electrode leads
Ammeter
Vacuum
tube
voltmeter
Potentiostat
Tank to be Protected
Fig. 1.14 Anodic protection system for tanks

Corrosion 21
To protect a structure anodically, a device called as 'potentiostat' is used. A potentiostat is an

electronic device which maintains a metal at constant potential with respect to the reference electrode.
A potentiostat usually has three terminals, one is connected to the tank or structure to be
protected, the other is connected to an auxiliary electrode (a platinum or platinum clad electrode)
and the third to a reference elec..1rode (eg. a calomel electrode). In actual operation, the potentiostat
maintains a constant potential between the tank (or the structure being protected) and the reference
electrode.
The cathode material used must be such that it doesnot suffer much corrosion. Platinum
clad metals or some corrosion resistant alloys are often used.
Cathodic protection Anodic protection
1. The metal to be protected is made cathode. 1 . The metal to be protected is made anode.
2. Method is applicable to all metals. 2. Method is applicable to metals showing active-
passive behaviour.
3. Installation cost is low. 3. Installation cost is higher.
4. Operating cost is high. 4. Operating cost is low.
5. More number of electrodes are required for 5. Fewer electrodes can achieve better corrosion
better corrosion protection. protection.
6. The method can be used where there is no 6. Applicable to wide range of severe corrodents.
source of power by employing sacrificial anodes
1.6.3 Advanced coatings

A coated surface isolates the underlying metal from the corroding environment. It can be
metallic, inorganic or organic.
1.7 METALLIC COATINGS

A coating of one metal or alloy over another metal or alloy is called metallic coating.
It can be divided into-

(i) Anodic coatings.
(ii) Cathodic coatings.
(i) Anodic coatings: These coatings are produced from metals which are anodic to the base
metal to be protected, i.e., metals which lie above in the galvanic series, e.g., Zn, AI, Cd
coati ngs on steel.
If any pores or breaks occur in such coatings, a galvanic cell is formed between the coating
and the exposed part of the base metal. In such a case, since the coating metal is anodic, it
corrodes, leaving the underlying metal unprotected.
Thus the anodic coatings act as 'sacrificial anode'. The corrosion is more uniform and less
severe as the anode surface area is much larger compared to the cathode.
These coatings can be applied by hot dipping, spraying, etc.

: :: : : : :: : :: : : :: : : : : ::: : Corrosive envimoment
: : :: Zinc coating Zinc coating : : : : :
Zn"'Zn2~ 2e- ::::
Fig. 1.15 Functioning of anodic coating. In galvanized steel, Zn serves an anode; while iron of steel serves as
the cathode. Therefore, the iron is protected, even if it is exposed, when a part of the zinc coating is
. scrapped off
(ii) Cathodic coatings: These coatings are produced from metals' which- are cathodic to the
base metal to be protected i.e., metals which lie below in the galvanic series, e.g., Sn, Ni, Cr
coatings on steel.
If any pores or breaks occur in such a coating, a galvanic cell is formed between the
coating a galvanic cell is formed between the coating and the exposed part of the base metal. In
such a case, the base metal being more anodic corrodes.
As the surface area of the anode is much less compared to the cathode, intense corrosion
occurs resulting in severe pitting and perforation of the base metal.
Such coatings are applied by etectroplating because by this method, a more uniform coating
is produced.
: :: ;: : ;:: ::: :: ;:::: :: :: Corrosive envirnoment

....... _.............. ..
Sn coathing
::::::::::::::::::: Exposed Iron part
- - - - - -- -- - - -- - - -- - - becomes anodic and
: : : : : : : : -S~ coathi~g ~ Is attacked Fe-+ Fe"+2e-
Fig. 1.16 Tin-plated steel. The tin protects the iron, when the coating is continuous. When coating is broken,
the iron of the steel becomes the anode and is subjected to accelerated local corrosion.
Corrosion 23
• 1.7.1 Methods of applying metallic coating

Metallic coatings are usually imparted by the following methods: Whatever be the method
chosen for applying the metallic coating, it is necessary that for good adhesion, the surface of the
metal should be thoroughly clean.
1. Hot dipping: This method is used for producing a coating of low-melting metal such as
Zn (m.p. = 419°C), Sn (m.p. = 232°C), Pb, AI, etc., on iron, steel and copper, which have
relatively high melting points.
The process, consists of immersing the base metal in a bath of the molten coating metal,
covered by a molten flux layer.
Functions of flux:
(i) cleans the base metal surface and
(ij) prevents the oxidation of the molten coating-metal.
rltL-----,
Amm.chloride Pair of hot
flux rollers
I sheet I
Galvanized
• ~
;!!CH'<
J
\ I
"+-~;. .:,o.;.;, , liiJ =~
0 ..: (
::::.'::':::::
............ chamber
..... . ....
::: :~~~;~~.:.
air
Water
Dil H,sO. Excess zinc
at 60-90'C bath
Molten zinc removed
at 425-430'c
Fig. 1.17 Galvanizing of sheet steel
Fig. 1.18 Tinning of sheet steel. The steel passes through a layer of flux into the molten tin and then emerges
between pairs of rollers from a layer of palm oil
2. Electroplating: See Section 1.7.2
3. Metal cladding: It is the process by which a dense, homogenoous, layer of coating metal
is bonded firmly and permanently to the base metal on one or both sides.
Cladding is done by arranging thin sheets of the coating metal and the base metal sheet in
the form of a sandwich, which are then passed betw'een rollers where under the action of heat
and pressure, the coating metal gets firmly bonded to the base metal.
Most of the corrosion resisting metals like Ni, Cu, Ag, Pb, etc. and alloys like stainless steel,
Ni alloys, copper alloys, lead alloys etc. are used as cladding materials. Among the base metal
on which cladding is done are mild steel, AI, Cu, Ni and other alloys.
Alclad
sheet
Rollers
Fig. 1.19 The cladding of duralumin
4. Displacement or immersion coating: The process involves immersing the base metal in
an electrolytic solution, containing a salt of the cathodic coating metal. The ions of the nobler
metal are displaced from the salt solution by the ions of the less noble base metal.
Immersion coatings are highly uniform, but they are usually thin. They are often used as a
base coat for other metallic or organic protective coatings, eg., Zn is deposited as a base on AI or
Mg, for further nickel plating.
5. Metal spraying or metallized coatings: The coating metal in the molten state is sprayed
on the base metal surface with. the help of a spraying gun. The metal thus sprayed adheres to the
base metal surface. The sprayed coatings are continuous but porous. So, a sealer-oil or paint is
on such a coating to provide a smooth surface.
6. Cementation or diffusion coating: The method consists of heating the base metal in a
revolving drum containing a powder of the coating metal. Diffusion of coating metal into base
Corrosion 25
metal takes place, resulting in the formation of alloy of varying compC"';ition. The layer just
adjacent to the base metal is an intermediate compound while the outer layers are richer in the
coating metal. This process is suitable for coating small articles of uneven surfaces and intricate
shapes like bolts, screw, threaded parts, valves.
Sheradizing - is the process of cementation, using zinc powder as coating metal. This
method is especially used for coating small steel articles like bolts, screws, nuts, threaded parts,
washers, valves. The advantage is that coating. is uniform, even if the surface is uneven i.e., has
crevices or depression.
1.7.2 Electroplating
Electroplating or Electrodeposition is the process by which the coating metal is deposited
on the base metal by passing direct current through an electrolytic solution, containing the
soluble salt of the coating metal.
The base metal is made cathode. Electrolyte consists of a salt of coating metal. Anode is
either the pure coating metal or an inert conducting material like graphite or insoluble anodes
like Pb or Sb-Pb alloy as used in chromium plating.
Method: The electroplating method depends upon:
(i) the type of metal to be electroplated
(ii) size and type of the articles to be plated

(iii) main objectives
(iv) economics
Brief description of vat plating process

Vat is a rectangular tank.
Busbar
==::::::::::~==~==~===G
----~----~~--~~--@
Cathode Jigs for

ITDUOlng _mal obJec1s
Heatil'Q ~=---::-"""-,,,-7-:..._ AIr _paryer

colla
Plating bath
Fig. 1.20 Vat plating process

(i) Plating tank is a vat made of wood or steel with a ceramic or polymer lining for
thermal insulation.
(ii) Plating bath solution is a highly conducting salt solution ofthe metal to be electroplated
and contains other additives.
(i i i) Heating arrangement. Most electroplating process are carried out at moderate
temperature.
(iv) Convection current arrangement is an air sparger or nitrogen sparger.
(v) DC voltage arrangement: For most plating operations, a voltage of 8-12V at operating
current density of 1 - 200 mNcm2 is required.
(vi) Filters or pumps are employed to filter out regularly the metallic particles (dust or grit)
which otherwise hinder in smooth operations. .
(vii) Power supply to electrodes: Cu, brass or AI bus bars are usually employed for supplying
power to the electrodes. The anodes and the cathodes are suspended alternatively
from the bus bars through the entire width of the tank.
(viii) Pretreatment of surface of substrate (cathode): Inorder to get a good electrodeposit it is
essential to prepare the surface of the substrate properly as follows-
(a) Removal of organic impurities and grease from the surface by employing organic
solvents like trichloroethylene, methylene chloride and (or) hot aqueous alkali.
pH increase by (alkali) hydrolyses the fatty impurities. Alkali treatment can also be
carried out by making the surface of the article cathodic by using a current of 30
- 80 mamp at 60 - 80°C. The hydrogen so liberated on the electrode assists in the
removal of organic impurities.
(b) Acid pickling- excess alkali is then removed by dipping the articles in 10% H 2S04
soln. This treatment also removes the scale or rust.
(c) Polishing- articles are usually polished by using SiC wheels or by sand blasting.
(d) Rinsing in water followed by drying.
Fa~tors that effect the electrodeposit:
(1) Temperature - Most of the electroplating bath solutions should be used at room
temperature. However warm baths are also used because solubility of .electrolyte
increases, thereby concentration of ions increases and hence current density also
increases.
However, at higher temperatures, H2 evolution at the cathode may take place, leading
to corrosion of the equipment.
At moderate temperatures, diffusion is higher than hydrogen evolution. Consequently,
plating temperature is usually kept between 35 - 60°C.
(2) Current density- Uniform deposit takes place at low current density but leads to low
rate of deposit. While high current density results in loose and brittle deposit. Hence,
current density should be optimum.
Corrosion 27
(3) pH - For good deposit pH of bath must be properly maintained. Optimum pH ranges
from 4 to 8.. Lower than optimum pH means stronger H2 evolution resulting in burnt
deposit. Higher than optimum pH means precipitation of hydroxides of the metal on
the electrode surface.
(4) Choice of the electrolyte- Electrolyte should be good conductor and highly soluble,
not undergo oxidation, reduction or hydrolysis, possess sufficient covering power.
However no single electrolyte satisfies all the requirements. So usually a mixture of
two or more electrolyte is used, e.g., in copper plating CuS04 is used along with dilute
H2 S04 ,
(5) Presence of additives and other complexing agents - Presence of organic additives
influence the nature of the deposit, e.g., (i) Brighteners- produce microscopic fine
deposits which reflect light falling on the surface, e.g., coumarin, thiourea. (ii) Levellers-
level any unevenness on the platmg and this results in uniform deposit. (iii) Wetting
agents- are added to release the gas bubbles fom the surface of the cathode, e.g.,
sodiumlaurylsulphate. (iv) Complexing agents- On compexing the metal ion with a
complexing agent, fine grained and more adherent deposits are obtained.
1.7.3 Numericals based.on Faradays laws

(1) Calculate the weight of Cd deposited when a current of 0.8 A strength was passed for
58 mts. through a solution of Cadmium nitrate ( At.wt. 112.41)

Solution:·
Quantity of electricity passed ". it
= 0.8 x 58 x 60 C
.. 2784 C
96500C deposit 56.205 g of Cd
56.25 x 2784
2784 C will deposit
96500
= 1.621 g of Cd
(2) The same quantity of electricity passed through suitable voltameter in series, liberated
3.56 L of H2 at NTP and deposited 2.802 g of the metal.. Calculate the equivalent of the metal
and the quantity of electricity passed.
Solution:
22.4 L of H2 weighs 2g
2x3.S6
3.56 L of H2 would weigh - - - ::: 0.3718g
22.4
Equivalent weight of H Weight of H

_ _ _ _ _ _ _ _-=2'- = 2
Equivalent weight of metal Weight of metal
0.3718 -
------=
Equivalent weight 2.802
Equivalent weight = 7.536
96,500 C of electricity would liberate 11.2 L of H2
96,500 x 3.56
3.56 L of H would be liberated by
2 11.2
= 30673.2C
(3) In a certain experiment the weight of silver deposited was fOIJnd to be 130 mg. What is
the quantity of electricity passed through the solution? (At.wt. of Ag = 107.88)
Solution:
107.88 g of Ag is deposited by 96500C of electricity
'. .' 130 x 10- 3 x 96500

130 x 10-3 g of Ag IS deposited by =116.29C
107.88
(4) A current of strength 5 amperes was passed for 48 mts. through an acidified CuS0 4
solution. Calculate the weight of Cu that would get deposited during the electrolysis. (At.wt. of
Cu = 63.55).
Solution:
q - i x t = 5 x 48 x 60C == 14,400C
,
96,500 C of electricity deposit 31. 775 g of Cu.
31.775 x 14,400
14,400C of electricity would deposit 96,500 = 4.741g
1.8 ORGANIC COATINGS

Organic coatings are inert organic barriers (like paints, varnishes, lacquers, enamels) applied
on metallic surfaces and other constructional materials for both corrosion protection and
decoration. -
1.8.1 Paints
Paint is a mechanical dispersion of one or more pigments in a vehicle. Vehicle is a liquid,
consisting of non-volatile film-forming material, drying oil and a highly volatile solvent, thinner.
Corrosion 29
Constituents of paints:
(i) Pigment: It is the most essential constituent of paint.
- protects the surface from corrosion.

- provides desired colour to the paint film.
- gives protection by reflecting off the harmful ultraviolet rays.

- provide resistance to the paint film against abrasion.
Example: white lead, Zinc oxide- white
Red lead, ferric oxide- red, chromium oxide- green.

(ii) Vehicle or drying oil: It is the film-forming constituent of the paint. These are glyceryl
esters of high molecular weight fatty acids, present'in animal and vegetable oils. Eg. Linseed oil,
soyabean oil, castor oil.
Drying oil supplies to the paint filrrr-

- main film-forming constituent.
- vehicle or medium.
- toughness, adhesion, durability.
- water-proofness.
(iii) Reactions of drying oil: The oil film, absorbs oxygen (from air) at the double bonds,
forming peroxides, diperoxides, hydroperoxides, which isomerise, polymerise and condense to
form a tough, coherent, hard, e;astic, insoluble, highly cross-linked macromolecular film.
Conjugated double bonds

J, J,
CH 2COO(CH 2)7-CH = CH 2-CH = CH-(CH 2)4-CH3
I
n CH.COO(CH2)7-CH = CH-CH 2-CH .. CH-(CH 2)4- CH3
I
CH 2COO(CH)7-CH = CH-CH 2-CH .. CH-(CH 2)4-CH3
1
Glyceride of linolenic acid (drying oil)
Air oxidation and polymerization
CH2·COO(CH2)7-CH-CH-CH2-CH = CH-(CH 2)4-CH3

t t
o 0
J, J,
CH.COO(CH2)7-CH-CH-CH2-CH-CH-(CH2)4-CH3
t t
o 0
J, J,
CH2COO(CH2)7-CH-CH-CH2-CH-CH-(CH)rCH3
Peroxide cross
t t
o 0
link ------+) J, J,
CH2-COO(CH2)7-CH-CH-CH2-CH-CH-(CH)4-CH3
t t
o 0
J, J,
CH 2-COO(CH2)7-CH-CH-CH2-CH-CH-(CH 2)4-CH3
t t
o 0
J, J,
CH 2-COO(CH)7-CH-CH-CH2-CH-CH-(CH)4-CH3
t t
o 0
I I
Peroxide
1
Undergoes isomerization,
polymerization and condensation
Highly cross-linked structured

macromolecular film
Corrosion 31
Oils containing conjugated fatty acid, dry faster than those with non-conjugated saturation.
(iv) Thinners: Thinners are volatile substances which evaporate easily after" application of
paints. Functions:.
- reduce the viscosity of paints to suitable consistency
- dissolve the other additives in the vehicle
- suspend the pigments in the paint.

- help in the drying of the paint film.
- help in increasing the elasticity of the paint film.

E.gs. Turpentine, petroleum spirit, toluol, xylol.
(5) Driers: are oxygen carrier catalysts. They accelerate the drying of the oil film through
oxidation, polymerization and condensation.
E.gs. Resonates, linoleates, tungstates and napthenates of Co, Mn, Pb and In.
(6) Extenders and fillers: These are low refractive undices material generally of white colour.
Functions:
- reduce the cost.
- serve to fill voids.in the film.
- help to reduce the cracking of dry paint.
- act as carriers of the pigment colours.
E.gs. Talc, asbestos, ground silica, BaS04 , CaCO y CaS0 4
(7) Platicisers: They provide elasticity to the film and minimize its cracking.
E.gs. Tricresylphosphate, triphenylphosphate, tributylphosphate.
(8) Anti-skinning agents: Prevent gelling ansi skinning of the paint film.
E.gs. Polyhydroxyphenols.
1.8.2 Varnishes
Varnish is a homogenous colloidal dispersion-solution of natural or synthetic resin in oil or
thinner or both.
There are two main types of varnishes:
(i) Oil varnish- is a homogenous solution of one or more natural or synthetic resins in a
drying oil and a volatile solvent. This type of varnish dries up by the evapouration of
the volatile solvent, followed by oxidation and polymerization of the drying oil. As a
result, such varnishes take a longer time i.e., around 24 hrs. for drying. The film
produced is hard, lustrous and durable.
Example- copal in linseed oil.
(ii) Spirit varnish- is a homogenous solution of resin in a volatile solvent. As no oil is

present, such varnishes dries very rapidly, but the film thus obtained is brittle and has
a tendency to crack or peel off. Such varnishes are used for polishing wooden furnitures,
e.g., shellac in alcohol.
Constituents of a varnish:
(i) Resins: Resins in a varnish provide resistance to weathering, chemical action, durability
and water-proofness. Resins can be both (i) Natural - like shellac, kauri, copal, etc.
(ii) Synthetic -like phenol formaldehyde, urea formaldehyde, terpene polymers, etc.
(ii) Drying oils: help to produce a durable film as they dry by oxidation and
polymerization, e.g., linseed oil, tung oil, soyabean oil, etc.
(iii) Solvents or thinners: help to dissolve the constituents of the varnish and drying of the
varnish film by evapourating. E.g., turpentine, petroleum spirits, kerosene, etc.
(iv) Driers: are added to accelerate the drying of the varnish film. E.g. Pb, Co, Mn linoleates,
napthenates, resinates.
(v) Antiskinning agent: like tert amyl phenol, guiacol, etc., are used to prevent the cracking
or peeling of the varnish film.
Uses:
(i) For protection of articles against corrosion.
(ii) As a brightening coat on painted surface to eliminate the effect of corrosion

(iii) On wooden surfaces for enhancing the ornamental grains on their surface.
1.8.3 Enamels
Enamel is a pigmented-varnish. On drying enamels give a lustrous, hard and glossy finish.
Constituents of enamels:
(i) Pigments: Pigments used may be white (e.g. Titanium dioxide and calcium sulphate
mixtures) or coloured. When coloured pigments are used, the enamels are called
Japans. Black Japan is prepared by dissolving asphalt in linseed oil and turpentine or
spirit. They are used for painting metallic surfaces like bicycles, bed-steads and electrical
devices.
(ii) Vehicle: may be pure resin (e.g. Rosin) or oleoresin (e.g. Synthetic resin like
phenolaldehde and oil like linseed oil, fish oil).
(iii) Driers: used only in oleoresin enamels, ego Resonates and oleates of Co, Mn and Zn.
(iv) Thinners: e.g. Turpentine acetone.
Corrosion 33
1.8.4 Lacquers
A lacquer is a colloidal dispersion of solution of cellulose derivative, resin, plasticizer in
solvent and diluents. Lacquers on drying yield a transparent, hard and water-proof film.
Constituents of lacquers:
(1) Cellulose derivatives: e.g. Cellulose nitrate, cellulose acetate. They provide water-
proofness, hardness and durability to the film.
(2) Resins: used are both natural, e.g. Copal and synthetic, e.g. Phenol aldehyde. Resins
provide the resistance to corrosion, retention of original gloss, sdhesion.
(3) Plasticisers: e.g. Tricresyl phosphate,dibutyl phthalate. They reduce the brittleness and
improve the ductility and flexibility of film. .
(4) Solvents: e.g. Ethyl acetate, butyl acetate. Solvents dissolve the various constituents.
(5) Diluents: e.g. solvent naptha, benzol, toluol are added to reduce the viscosity as well
as reduce the cost.
Uses:
(i) Used for interior decoration like paintings of wood work and furniture.
(ii) Finishing coat for automobiles to provide a glossy finish and additional protection
against corrosion.
(iii) For water-proofing cotton fabrics, preparing artificial leather.
1.9 CORROSION ENGINEERING OF ELECTRONIC AND PHOTONIC

DEVICES
Corrosion in electronic components manifests itself in several ways. Computers, integrated
circuits, and microchips are now an integral part of all technologry-intensive industry products,
ranging from aerospace and automotive to medical equipment and consumer products, and are
therefore exposed to a variety of environmental conditions. Corrosion in electronic components
is insidious and cannot be readily detected; therefore, when corrosion failure occurs, it is often
dismissed as just a failure and the part or component is replaced.
Because of the difficulty in detecting and identifying corrosion failures, the cost of corrosion
is difficult to determine. Also, in the case of consumer electronics, such devices would become
technologically obsolete fong before corrosion-induced failures. In addition, while corrosion-
related user costs due to irretrievably lost data could be staggering, as the electronic information
and data exchange become more intensive, most sensitive information is frequently backed up.
Capital-intensive indu.stries with significant investments in durable equipment with a considerable
number of electronic components, such as the defense industry and the airline industry, tend to
keep the equipment for longer periods of time, so that corrosion is likely to become an issue.
Although the cost of corrosion in the electronics sector could not be estimated, it has been
suggested that a significant part of all electric component failures may be caused by corrosion.
Causes of Corrosion
The most common electronic components include integrated circuits (IC), printed circuit
(PC) boards, and connectors and contacts. Traditional materials used for IC conductors are
aluminum-based alloys, often alloyed with silicon and copper. Major metallic components in
PC boards, such as conductors and connectors, are typically made of copper where soldering is
done with lead-tin alloys. Contacts are commonly manufactured from copper covered with
electroplated nickel or gold for improved corrosion resistance.
As electronic devices become more and more common, they become increasingly exposed
to much harsher conditions than the air-conditioned rooms used to house early computers.
Although the microchip in an automobile, for example, is not directly subjected to the same
hazards as the car body, given the dimensions of the former (silicon-based integrated circuit
elements are spaced less than 0.2 microns), the tolerance for corrosion loss is much smaller (on the
order of picograms (1 0-12g)). Minimum line width in the state-of-the-art PC boards in 1997 was less
than 100 microns. On hybrid integrated circuits (HICs), line spacings may be less than 5 microns.
Submicron dimensions of electronic circuits, high-voltage gradients, and an extremely high sensitivity
to corrosinn or corrosion products present a unique set of corrosion-related issues.
Environmental Contamination (Airborne Contaminants)

One of the most common reasons for electronic failure is environmental contaminants and
conditions. The list of contaminants includes fine and coarse particles of such species as chlorides,
sulfates, sodium, ammonium, potassium, magnesium, and calcium. The single most important
environmental condition affecting the impact of particulate matter and gases (such as sulfur
dioxide and nitrogen oxides) is relative humidity. Coarse particles (2.5 to 15 microns) are typically
formed as a result of human activity or originate from soil. Fine particles (0.1 to 2.5 microns)
come from the combustion of fossil fuels and, at times, from volcanic and geological activity.
In electronic devices, coarse particles may cause malfunctions by interrupting electrical
contact between mating pairs of contacts on connectors or relays.
Forms of Corrosion
Anodic Corrosion
Given the spacing between components of the ICs, when a voltage is applied to a device,
voltaic gradients of the order of 105 to 106 V/cm can exist across surfaces, accelerating
electrochemical corrosion reactions and ionic migration. In ICs, positively biased aluminum
metallizations are susceptible to corrosion. Combination of the electric fields, the atmospheric
moisture, and the contamination by halides leads to corrosion attack on aluminum.
Gold and copper metallizations are also subject to corrosion under these conditions.
Cathodic Corrosion
Negatively biased aluminum metallizations, as with those with the positive bias, can also
corrode in the presence of moisture due to high (basic) pH produced by the cathodic reaction of
water reduction. High pH leads to dissolution of the passive surface layer of oxides and aluminum
substrate with the corresponding increases ,in conductor resistance (up to an open circuit).
Corrosion 35
Electrolytic Metal Migration

Detected early on in electromechanical switches, this problem occurs in relation to the
silver-containing compounds. In the presence of moisture and an electric field, silver ions migrate
to a cathodically (negatively) charged surface and plate out, forming dendrites. The dendrites
grow and eventually bridge the gap between the contacts, causing an electric short and an arc.
Even a small volume of dissolved metal can result in formation of a relatively large dendrite.
Under certain humidity and voltage gradient conditions, a 30-day exposure becomes equivalent
to 4 years of service in a typical office environment. Other materials susceptible to the metal
migration include gold, tin, lead, palladium, and copper.
Pore-Creep in Electrical Contacts and Metallic Joints
To prevent tarnishing of connectors and contacts, a noble metal (e.g., gold) is plated on the
contact surface.
Since the coverage is never complete, the substrate material can corrode at the imperfections.
If the substrate is copper or si Iver, and it is exposed to a sulfu r- or chloride-contain ing envi ronment,
corrosion products can creep out from the pores and over the gold plating, forming a layer with
high contact resistance.
Galvanic Corrosion
Galvanic corrosion occurs when two dissimilar metals, such as aluminum and gold, are
coupled together, as is commonly done for packaged (plastic encapsulated) integrated circuits.
The polymers used for packaging are porous and the gaskets around hermetic covers (such as
ceramic or metal) sometimes leak; therefore, in humid environments, moisture can permeate to
the IC bond pad, creating conditions conducive to galvanic corrosion.
Electronic devices tend to dissipate considerable heat during operation, which leads to
reduced relative humidity.
During power-down or storage periods, the relative humidity rises, which presents more
danger.
Micropitting on Aluminum on IC During Processing
Aluminum metallizations, alloyed with copper, can form intermetallic compounds (such
as AI 2 Cu) along the grain boundaries, which act as cathodic sites relative to the aluminum adjacent
to the grain boundaries. This leads to dissolution of an aluminum matrix in the form of micropitting
during the rinsing step after chemical etching.
Corrosion of Aluminum by Chlorinated/Halogenated Solvents
Both liquid and vapor-phase halogenated solvents used for production of ICs and pes
readily corrode aluminum-containing components. Water contamination of the solvents increases
the time-to-corrosion on the one hand; however, on the other hand, it increases the subsequent
corrosion rate. Dilution of the stabilized solvents with aromatic or alcohol solvents leads to the
breakdown of the halogenated solvent and the formation of chloride ions, which corrode
aluminum and aluminum-copper alloys.
Solder Corrosion
Lead-tin solder alloy's resistance to corrosion in aqueous and gaseous environments is a
function of the alloy composition. It improves significantly when the tin content increases above
two weight percent. Lead forms unstable oxides, which easily react with chlorides, borates, and
sulfates.
Corrosion of Magnetic and Magneto-Optic Devices
Besides electronic circuits, corrosion-related failures can occur in advanced magnetic and
magneto-optic storage devices, where thin-film metal discs, thin-film inductive heads, and
magneto-optic layers are affected.
Corrosion takes place in sites where the depOsited carbon overcoat is lacking due to
intentional roughening of the disc and where the magnetic cobalt-based layer and nickel-
phosphorus substrate become exposed. Given the potential differences 'between the noble
(positive) carbon and the metal substrate, a galvanic couple may form, leading to rapid galvanic-
induced dissolution of the magnetic material. Magneto-optic devices utilize extremely reactive
alloys for the recording media (due to high terbium content). Exposure of magneto-optic films to
aqueous solutions or high-humidity conditions results in a localized attack (pitting), even during
storage in ambient office conditions.
While attempts have been made to mitigate corrosion of electronics by encapsulating the
components in plastics, polymers are permeable to moisture. Hermetically sealed ceramic
packaging is more successful; however, care must be exercised to prevent moisture and other
contaminants from being sealed in. One common approach for mitigating corrosion of circuits
housed inside a relatively large-size chassis includes the use of volatile inhibiting compounds
(requires periodic replacement of the carrier).
Corrosion Costs
The cost of corrosion is very difficult to determine. Arguably, in many instances, particularly
in the case of consumer electronics, the devices would become technologically obsolete long
before corrosion-induced failures occur. Also, while corrosion-related user costs (due to
irretrievably lost data) could be staggering, as electronic information and data exchange become
more and more intensive, most sensitive information is frequently backed up.
Capital-intensive industries with significant investments in durable equipment with a
considerable number of electronic components (e.g., defense, airline, etc.) tend to keep the
equipment for longer periods of time (tens of years), such that corrosion is likely to become an
issue. There is even an opinion that the vast majority, if not all, of the electronic component
failures are caused by corrosion.
Questions
1. Give reasons for the following:
(i) Steel screws in a brass marine hardware corrodes.
(ii) Steel pipe connected to copper plumbing corrodes.

Corrosion 37
(iii) Metal under drop of water undergoes accelerated corrosion.

(iv) Pin holes on tin coated iron is more prone to corrosion of iron than those on zinc
coated iron.
(v) Impure metal corrodes faster than pure metal under identical conditions.
(vi) Small anodic area leads to intense corrosion.
(vii) Rusting of iron is quicker in saline water than in ordinary water.
(viii) Corrosion is accelerated under accumulation of dirt, sand, scale and other
contamination.
(ix) Corrosion of zinc partially immersed in dil H2S04 is accelerated when a drop of
CuS04 is added to it.
(x) Iron corrodes faster than aluminium even though iron is placed below aluminium
in the electrochemical series.
(xi) A part of nail inside the wood undergoes corrosion easily.
(xii) Nickel plated steel articles should be from pores and pinholes.
(xiii) Galvanisation of iron articles is preferred to tinning.
(xiv) Rusting of iron is prevented by galvanization.
(xv) Moderate current density is employed during electroplating.
(xiv) pH is strictly maintained during electroplating.
(xv) Moderate temperature is used during electroplating.
(xvi) Zinc coating on iron is called sacrificial anode.

2. Define corrosion of metals. What are different types of corrosion? Explain the
electrochemical theory of wet corrosion, giving its mechanism.
3. Differentiate between chemical corrosion and electrochemical corrosion.
4. What will happen when stainless steel is immersed in aerated and deaerated sodium
chloride solution?
5. Explain the mechanism of following types of corrosion:
(i) Stress corrosion.
(ii) Differential aeration corrosion.
(iii) Hydrogen evolution type corrosion.
(iv) Intergranular corrosion.
(v) Bimetallic or galvanic corrosion.
(vi) Oxygen absorption.

6. What is sacrificial anode? Mention its role in corrosion control.

7. What is cathodic protection? How is it done by using impressed current and sacrificial
anode?
8. Explain the mechanism of dry corrosion.
9. Explain the mechanism of protecting steel water tank by anodic protection.
10. Explain the effects of the following factors on the rate of corrosion:
(i) pH (ii) ratio of anode to cathode area (iii) polarization of electrodes (iv) nature of
corrosion product (v) humidity (vi) temperature (vii) conductance of the medium
(viii) nature of the ions present.
11. Distinguish between
(i) anodic and cathodic caoating
(ii) paints and varnishes
(iii) Anodic protection and cathodic protection
(iv) Sacrificial anode protection and Anodic protection.

(v) Hot dipping and cementation coating
(vi) Driers and drying oil
12. Explain the mechanism of drying of a paint film.
13. Discuss in detail the process of electroplating.
14. What are metallic coatings? Mention the various methods of applying metallic coatings
and discuss any two methods in brief.
15. Discuss electroplating method in detail.
16. Describe the mechanism of drying of the oil used in a paint.
17. Write a short note on enamels and lacquers.
Numerical problems:
1. Calculate how much current is necessary to produce hydrogen gas at the rate of 1 cc
per second under standard conditions. (8.61 amp)
2. How much time is required for the complete decomposition pf 2 moles of water using"
a current of 2 amp. (53.61 hrs)
3. In the electrolysis of an aqueous solution of Snel 2 solution, 4.48 litres of chlorine (in
standard conditions) is liberated at the anode. Find the mass of tin deposited at the
cathode. (At.wt of Sn = 119, CI = 35.5) (23.8 g)
4. In the electrolysis of an aqueous solution of NaOH, 2.8 litres of oxygen was liberated
at the anode at NTP. How much oxygen was liberated at the cathode? (5.6Iitres).
Corrosion 39
5. The density of copper is 8.49 g per mL. Find the charge in coulombs needed to plate
an area 10 x 10 cm to a thickness of 10-2 cm using CuS0 4 solution as electrolyte.
(27116.5 coulombs)
6. What mass of chlorine can be produced by the electrolysis of molten NaCI with a
current of 1.2 A for 118 min. The electrode reaction is 2CI- ~ CI 2 + 2e- .(Mum 08)
(0.4767 g).
7. Three Faradays of electricity is passed through aqueous solution of AgNO y NiS04 ,
CrCI 3 kept in three vessels using inert electrodes. What is the ratio in moles in which
the metals Ag, Ni and Cr will be deposited.(Mum 08) (3:3/2:1)
•••
Alloys and Powder Metalurgy
2.1 INTRODUCTION
An alloy is a metallic, intimately mixed solid mixture of two or more elements, one of
which is essentially a metal.
Note: Alloys are homogenous in molten state, but mayor may not be homogenous upon
solidification. Hence an alloy in a solid state may be either homogenous or heterogenous.
2.1.1 Types of alloys

Alloys can be classified on the casis of principal constituent into:
(i) Ferrous alloys - iron is the major component
(ii) Non-ferrous alloys - donot contain iron as one of the major component
2.2 NON-FERROUS ALLOYS
2.2.1 Alloys of Aluminium

Recently tremendous development has been made in the field of light alloys. These are
alloys of AI and Mg.
In engineering field a great number of Aluminium alloys are employed. Some of the stronger
. ones reach a tensile strength of 63,000 psi or more. This is comparable to the strength of mild
steel.
The reason for the use of Aluminium alloys is its lightness. Tensile strength of AI is about
1/4th the strength of mild steel and about 1/10th that of tool steel. This disadvantage has been
overcome by alloying small amounts of other elements like Cu, Mg, Mn, Fe, Si, Sn, etc. Thus
retaining the advantage of low specific gravity but adding strength and thus making these alloys
suitable for making pistons, cylinders, parts of aeroplanes, automobiles, household appliance
parts like vaccum cleaner, wahing machine, etc.
Advantages of alluminium alloys:
(i) Low specific gravity
(ij) High thermal and electrlical conductivity
Alloys and Powder Metalurgy 41
(iii) Pleasing appearance
(iv) Acceptable corrosion resistance

The alloys are of two types:
(i) Casting alloys- shaped by casting.
(ii) Wrought alloys- which are worked into different shapes by mechanical operation.They
are further classified into:
(a) Non-heat treatable wrought alloys- Major alloying elements are Mg and Mn.
They can be easily formed and welded. They possess low strength and the strength
can be increased by cold work. They possess high ductility and corrosion resistance.
(b) Heat treatable wrought alloys- These alloys can be strengthened by heat treatment
as well as cold work. They exhibit the property of age-hardening, i.e., they are first
heated to about 500 DC and then rapidly cooled by quenching to low temperature
in water or oil and holding it for definite period. As a result the alloy acquires
sufficient strength and hardness.
Duralumin: It is a heat treatable wrought Aluminium alloy. It is made up of 95% AI + 4%

Cu + 0.5% Mg + 0.5% Mn.
• After age hardening tensile strength approaches that of mild steel (60,000 psi) whereas
specific gravity is only 1/3'd that of mild steel.
• Possess good mechanical properties.
• But corrosion resistance is less than that of pure Aluminium. This drawback is qvercome
by cladding.
Uses: It is used for making aeroplane and automobile part because of low specific gravity
and high strength.
Magnalium: It is made up of 90 to 98% AI + 2 to 10% Mg.
• It is lighter than pure Aluminium and Magnesium.
• Possess better strength.
• Good corrosion resistance.
• Possess mechanical properties comparable to that of brass.
Uses: Used in the construction of trucks, buses, commercial aircraft, hand tools, beams of
chemical balances, scientific instruments, furniture and other appliances for home and industry.
2.2.2 Alloys of copper

The two major alloys of copper are brasses and bronzes.
2.2.2.1 Brass
Brass is an alloy of copper and zinc. Properties of brass varies with the percentage of Zn.
Low percentage of zinc makes it softer while high percentage of zinc makes it harder and important
from an engineering point of view.
Cu-Zn alloy containing upto 20 to 45% Zn are called brasses. Most commercial brasses
contain Zn upto 40% because above brasses with greater than 40% Zn are brittle.
Brasses can be broadly classified into:

(i) Low brasses- with less than 25% Zn. They are softer and used for ornamental and
decorative ware because of their pleasing reddish colour.
(ii) High brasses- contain greater than 25% In. These are cheaper as Cu is costlier than
Zn. It is of great engineering importance. Besides In other elements are added in
small amounts to make brass suitable for specific purpose.
Commercial brass: It is made up of Cu 90% + In 10%.
• It is stronger and harder than copper.
• It is g01den in colour.
Uses: It is used for making rivets, hardware, screws and costume jewellery.
German silver: It is also known as Nickel silver. It is a white alloy with variable quantities of
Cu, Zn and Ni. The approx. composition is Cu 60% + Zn 15% + Ni 25%.
• It has an attractive colour. The colour ranges from white for high Ni alloy to pale
yellow for low N i content. .
• It has good corrosion resistance.
• It has good mechanical properties
• Tensile strength ranges from 25,000 to 60,000 psi.
Uses: On account of its attractive colour, corrosion resistance, these alloys are popular for
tableware and cutlery. It is used as coinage material in many countries. It is used in household
utensils because of its white colour and moderate cost. It is also used for decorative and architectural
purpose. An alloy with 18% Ni is widely used for contact springs in telephone exchanges. It is
used as a base for electroplated articles and making resistance wires and coils.
2.2.2.2 Bronze
Bronze is an alloy of Copper and tin.
Bronzes are stronger and harder than brasses. Bronzes are expensive and superior to brasses.
Tin content varies from 2 to 12%. As Sn content increases upto 20%, tensile strength also
increases and then falls rapidly.
Bronzes containing upto 5% Sn is most ductile, ductility gradually decreases with Sn content.
Most useful bronze contain Sn between 8 to 11 % where it has a combination of maximum

strength, toughness and reasonable ductility.
Bronzes are widely used for the manufacture of pumps, valves, flanges etc. where resistance
to corrosion is required.
Gun metal: A common composition is 80% Cu + 10% Sn and 2% Zn.

• It is hard, tough, strong.
• It gives better castings.
• More corrosion resistant.
Uses: It is used for various engineering purpose such as gears, bearings, marine pumps.
High Phosphor bronze: Phosphor bronze are of two types:
(i) Low phosphor bronze - contains less than 0.4% phosphorous.
(ii) High Phosphor bronze - 0.4 to 1 % phosphorous + Sn 10 to 13% and rest Cu.
• In these bronzes, surplus phosphorous forms a hard and brittle constituent copper
phosphide (Cu 3 P). It is a fatigue resisting alloy and is used in operations where
stresses occur.
• It has good abrasion resistance.
• Possess low co-efficient of friction.
Uses: used for making gears, bearings, marine pumps, bushes, turbine blades, fibres for
moving coil galvanometer, springs.
Brass Bronze
(1) It is an alioy of Cu and Zn. (1 ) It IS an alloy of Cu and Sn.
(2) It is inferior to bronze with re~pect to corrosion (2) It is superior to brasses with respect to
resistance. corrosion resistance
(3) It is cheap on account of the presence of Zn. (3) It is expensive on account of Sn.
(4) Brasses are less stronger and harder than bronze. (4) Bronzes are stronger and harder than brasses.
(5) Brasses are difficult to machine becaJse of its (5) Bronzes are easily machined.
toughness.
2.2.3 Alloys of lead

Solders are an important alloy of lead and tin.They are used for joining two metals. Solders
melt at low temperature than the metals to be joined or soldered.
Tinman's solder: It contains Sn 67 % + Pb 33%.

Melts at 183°C
Uses: Used in tin smith's work where penetration into small openings is often required. It is
used for soldering and tinning.
Wood's metal: Wood's metal contains Bi 50% + Pb 25% + Sn 12.5% + Cd 12.5%.

It melts at 71°C
Uses: It is used for
-making fire-alarms and automatic sprinklers.
-making safety plugs for pressure cookers, milk pots.
-for boiler and electric fuses.
-as solder for joining two metallic pieces.
-as castings for dental works.
2.3 RECENT ADVANCES IN ALLOYS AND RELATED MATERIALS
2.3.1 Powder metallurgy

Powder metallurgy is the art or science of manufacturing useful metallic or alloy articles
by compacting the metal (or alloy constituent) powders and other powders in a die with little or
no melting followed by sintering. When compacting or sintering is done simultaneously, then
the process is called pressure sintering or hot sintering.
Powder metallurgy involves the following steps:
(1) Preparation of metal or alloy powder
(2) Mixing and blending
(3) Compacting
(4) Presintering
(5) Sintering
(1) Methods of powder metal formation:
(a) Mechanical pulverization: involves the use of mechanical pulverisers, consisting of

either counter rotating plates or rapidly moving hammers. Usually pulverization is
followed by ball milling. This method is used for Mg, AI, Pb and Zn.
(b) Atomisation: involves forcing molten metal through a nozzle into a stream of
compressed air or water, when molten metal breaks into a fine powder. E.g. Zn, Pb,
Sn, AI, Cd, Mg.
(c) Chemical reduction: involves heating metal oxide in a current of H2 which reduces "
oxide to get pure spongy metal (e"g. tungsten) powder wh ich is suitable for cold pressing
due to its softness and plasticity.
(d) Electrolytic process: When conventional electrolysis is carried out, a powdery deposit
is obtained on the cathode. The powder is then scrapped, washed, dried and then
pulverized further to get powder of desired size. Eg. powders of Fe, Cu, Zn, Ag, W.
(e) .Decomposition: This method is specially used fo r mak ing Fe and Ni powders from
their carbonyls. These gaseous carbonyls [Fe(CO) s or Ni (CO)4] on decomposition yield
very pure Fe and Ni powders.
(2) Mixing and blending: Metal powders in desired proportions are uniformly mixed. For
special purposes, volatalising agents are also included for homogenous distribution of powder.
(3) Compacting: It is the process of obtaining the desired shape of definite dimension from
the loose powder.
A premeasured quantity of the blended powder is taken in a cavity (female) die. having the
desired shape and dimensions. The powder is compressed with the top (mare) die. Pressure
ranges from 100 to 1000 MNI m 2 • The dies are usually made of high grade hardened steeel with
fine finish . The solid mass is called 'green compact'.
Important compacting methods are:
(i) Cold pressing: The bulk powder with or without small quantities of lubricant or binder
is compacted in rigid dies by axially loaded punch. It is very economical for mass
production of precision. In axial pressing, compact on pressures upto 600 MPa are
used.
Upper punch
Die
Compact
Lower punch
Compressor
Fig. 2.1 Schematic representation of cold pressing principles: (A) Axial pressing (B) Isostatic pressing.
(ii) Powder Injection moulding: The metal powder is converted into a mouldable state or
feed stock by mixing with binder ( most of organic nature). Binder also provides good
satability and green strength of the moulded products. Usually heating is done in·
order to melt and force it thrugh sprue and runner channel.
Uses: Used mainly for parts with very complex shapes from materials like cemented
carbides, tungsten, heavy alloys, ceramics, etc.
Front cavity
parting line
Fig. 2.2 Schematic representation of injection moulding equipment
(iii) Cold powder extrusion: The plasticized powder is forced by a piston or screw into a
forming die so that products of constant cross-section e.g. rods, tubes) are produced.
Plasticisers used in this process are organic binders with medium and high viscosity.
(iv) Roll compaction: It involves passing metal powser in the gap between two rollers. This
technique is used for producing strips, sheets, etc. used in batteries, electronic tubes,
thermosatats, bimetallic applications.
(v) Hot compaction: Compaction is done at higher processing temperature and pressure.
The powder is placed in a rigid die and then compacted using direct resistance heating
or induction currents. The materials used for tooling are graphite, tungsten, cobalt
alloys, fibre reinforced carbon, heat resistant alloy steel.
(A) (8)
Fig. 2.3 Tooling for axial hot pressing

(A) By induction heating (8) 8y direct current heating
(4) Presintering: is the process of heating the 'green compact', to a temperature below the
sintering temperature. The objective is to remove the lubricants and binders added during
blending. It also enhances the strength of the 'green compact'. Presintering is essential for metals
like tungsten (for getting carbide) which cannot be machined after sintering.
(5) Sintering: Compaction doesnot provide cohesiveness and strength. The compacted and
presintered pieces are heated in a furnace to a temperature below, but close to the melting point
of the basic metal, usually in an atmosphere of hydrogen gas. During this process, the metal
particles sinters, i.e., a portion of them partly meet and bond the remaining particles into coherent
bodies.
Applications of Powder Metallurgy

Important products manufactured by Powder metallurgy are -
Porous bearings, filaments of electric bulb of tungsten, electric clocks, sewing machines,
gears, cams, cutting tools, parts of gas turbines, refractory metal composites, diamond impregnated
cutting tools, oil pump gears, bearings for automobiles, clutches, brakes, commutator brushes.
Advantages of Powder Metallurgy

(i) Saves energy.
(ii) Rate of production is high.
(iii) Dimensional accuracy is good.
(iv) Good surface finish.
(v) life of component part is longer.
(vi) Products with relatively much uniform structures (i.e. free of defects like voids, blow
holes, etc.).
(vii) Quite complex shapes can be produced.
(viii) No material loss.
Limitations of Powder Metallurgy

(i) Process is not suitable for manufacturing of small number of components because of
high initial investment on tooling, die cast and other equipment.
(i.i) Process is not suitable for form ing components from metals like Mg, AI, Zr, Ti, etc.
This is because, such metals in powder form may explode and cause fire hazards.
(iii) The desired shape and size of a part is limited by the available press capacity, since
relatively high pressure is required to compact the powder.
(iv) Precision dies used for pressing are very expensive.
2.3.2 Ceramic powders

Ceramics are compounds between metalic and non-metalic elements. They are most
frequently oxides, nitrides and carbides. These are compounds with totally ionic or predomiOnantly ·
ionic with somecovalent charachter. Ceramic is word derived from Greek word 'Keremikos'
meaning burnt stuff. Indicating that desirable properties of these materials are normally achieved
thourgh a high temperature heat treatment process called firing.
The traditional and commonly used silicate ceramics are the naturally occurring raw materials
such as clay, kaolin, etc. However the processing of advanced ceramics requires pure and well
defined powders which are made synthetically.
Ceramic powders are synthesized by employing a wide variety of techniques which yield
powders of varying particle size distribution and varying properties like chemical and phase
composition, purity, compactability and sinterability.
Dense fine grained parts require powders in lower or even submicron range.
Coarse powders are used in abrasives (AL 2 0 y SiC) and in refractories (AL 2 0 3 , Zr0 2)
Some general methods for producing ceramic powders are:-
(1) Solid-state reactions - Many oxide ceramics are produced by thermal decomposition
of hydroxide, carbonates, oxalates, sulfates, by the conventional techniques. Depending
on temperature and reaction time, loose or agglomerated powder or a sintered cake is
produced which can be milled to obtain the desired particle size.
(2) Solid-gas reactions - This method is used for synthesizing oxides, carbides, nitrites by
reacting metals with oxygen, hydrocarbon, nitrogen and ammonia respectively.
(3) Gas phase reactions - This method is useful for producing ceramic powders having
high specific area ( 100m2/g and higher). This process comprises of vapour phase
decomposition or hydrilysis in a flame and is specially used to produce Si02 and Ti0 2
from SiCI 4 and TiCI 4 respectively.
SiCI 4 + 2H 20 ~ Si0 2 + 4HCI
(4) Melting - Ceramic oxides such as AI 20 3 and Zr0 2 are manufactured by arc melting
with subsequent milling to produce the desired particle size. The process is mainly
employed for producing coarse grade powders.
(5) Reaction from solution - Aqueous or non-aqueous solutions of salts is used for a
number of techniques for producing ceramic powders. This process yields very fine
powders and uniformly distributed mixtures. The process can be carried out by any of
the following techniques:-
(i) Precipitation and filtration - of single compound or mixtures.
(ii) Hydrothermal reaction at elevated temperature and pressure - e.g. Zr0 2 from
ZrOCI2 solution.
(iii) Solution combustion - alcohol based organometallic solutions are burnt in air or
02 to produce oxide particulate.
(iv) Solvent vapourisation or dehydration - by direct evapouration or spray drying.
(v) Sol-gel process - The technique comprises of the three dimensional network of
inorganic matter (gel) from colloidal or molecular solutions of the precursor (sol) ..
The reaction can take place in aqueous or non-aqueous media, by diminishing the
water content, by changing the pH or surface charge (zeta potential) of the sol.
Manufacture of some important oxides

(1) Alumina (Al z0 3): Most important oxide ceramic produced in large scale in powder
form and to a wide variety of specifications.
Very high purity aluminas are produced by the decomposition of high purity aluminium
based salts like sulphates, chlorides, nitrites.
Powders of lesser purity are produced from bauxite via the Bayers process. After separating
AI 2 0 3 from Fe 20 3 and other oxides by converting into sodium aluminate, the latter is converted
to AI(OH)3 by hydrolysis and which is then calcined to A1 2 0 3.
It is use din various ceramic applications such as cutting tools, spark plugs, machine parts,
bioceramics, chinaware, special glasses, electronic parts. 99.99% ppure AI 20 3 is used in
Na-vapour lamp tubes to provide necessary translucency.
(2) Silicon carbide (SiQ: Most important non oxide ceramic. SiC exists as hexagonal a-SiC
and cubic ~SiC. The a-SiC which is stable form was first manufactured in 1891 by Acheson
process.
Si0 2 + 3C ~ SiC + 2CO
The starting material is pure sand, petroleum coke, some sawdust to decrease the packing
density and 1-3% NaCI for purification. This is heated with graphite electrodes and a temperature
of 2000 - 2300°C is reached during 30 hour cycle to get good crystallization.
13- SiC is obtained by gas-phase reaction of SiCI 4 with hydrocarbons.
Use: Widely used for abrasives, clay-bonded or porous recrystallized high temperature or
wear resistant materials.
Questions
1. What are light metal alloys? Why have ~hey gain importance in recent years.
2. Write a note on composition, properties and uses of:
(i) Duralumin (ii) Magnalium (iii) Commercial brass (iv) German silver (v) Gun metal
(vi) High phosphorous bronze (vii)Woods metal (viii) Tinmanns solder (ix) Woods
metal
3. Distinguish between brasses and bronze.
4. What are solder alloys? What are their uses?
5. Define powder metallurgy. What are the various steps involved?
6. Describe the various methods for making metal powders.
7. What is compacting in powder metallurgy? Discuss the different methods of compacting.
8. What is the significance of sintering in powder metallurgy? Discuss any two methods
of sintering.
9. Give reasons:
(i) Powder metallurgy is not suitable for forming components from metals like Mg,
AI, Zr, etc.
(ii) Powder metallurgy is not suitable for manufacture of small components.
10. Discuss the uses, advantages and limitations of powder metallurgy.

11. Describe the manufacture of (i) Alumina (ii) Silicon carbide.
12. What are ceramic powders? Discuss in brief some general methods for producing
metal ceramic powders. (Mum 08)
•••
, 3
Fuels
3.1 INTRODUCTION
Fuels are sources of energy. The per capita energy consumption is considered to be the
measures of living standards of people. About 200 years ago, fuels were used mainly for cooking,
heating and lighting purposes. Now-a-days (fuels are used) besides cooking, heating and lighting,
fuels are used in transportation, communication, illimination and various manufacturing
appl ications.
3.1.1 Definition
Fuels are substances which on combustion give out heat energy that can be effectively
utilized for domestic as well as industrial purpose.
3.1.2 Classification of fuels

Fuels are classified in two ways:
1. Based on their availability: They are classified into Primary fuels viz, those which are
available in nature and Secondary fuels viz, those which are derived from primary fuels.
Primary Fue s
Wood, Coal, Crude petroleum, Natural gas etc.
2. Based on their physical state: They are classified into, Solid, Liquid and Gaseous.
Solid Liquid Gaseous
Wood, Coke etc. Petrol, Kerosene etc. Natural gas, LPG etc.
3.1.3 Characteristics of a good fuel

A good fuel should have the following characteristics.
1. High calorific value: The amount of heat given out by the complete combustion of
unit quantity of fuel is known as calorific value. A good fuel should have high heat
output per unit quantity.
2. low moisture content: Higher the moisture content more will be the heat energy
required to drive away the moisture. And as a consequence there will be loss of calorific
value. Lower the moisture content higher will be the calorific value. Hence a good
fuel should have low moisture content.
3. Moderate ignition temperature: The ignition temperature of a fuel is defined as the
minimum temperature to which the fuel is to be heated to start combustion. If the
ignition temperature is too high, it is difficult to start the combustion and if it is too
low it may lead to fire hazards during their handling.
4. Moderate velocity of combustion: If the velocity of combustion is too high, the fuel
will get exhausted soon, before the heat given out by it is properly utilized. On the
other hand, if the velocity of combustion is too low, the highest temperatures may not
be achievable. One can avoid large wastage of a valuable fuel if its velocity of
combustion is properly regulated and its burning can be stopped as and when it is
not required.
5. low contents of non-combustible matter or low ash content: Higher the non-
combustible matters lower will be the calorific value. Again the high ash content
causes disposal problems.
6. Easy availability: A good fuel should be easily available at an affordable rate.
7. Easy transportation and storage: A good fuel should not occupy more space and
sophisticated arrangements for storage and transportation. Further there must be
minimum risks during their storage and transportation.
8. Should not produce any obnoxious/poisonous matter on combustion: A good fuel

should not release harmful combustion products like, CO, 502' NO, H 25 etc. Formation
of these products causes harmful effects on health of living beings. Therefore, a good
fuel should be environmentally friendly.
Units of heat
Calorie: A calorie is defined as the amount of heat required to raise the temperature of one
gram of water through 1°C i.e. from lS.SoC to 16.S oC
Kilo Calorie: A Kilo calorie is defined as the amount of heat required to raise the temperature
of one kilogram of water through 1°C i.e., from lS.S0C to 16.S0C
British thermal unit (B. Th.U.): A B.Th.U. is defined as the amount of heat required to raise
the temperature of one pound of water through 1°F i.e., from 60°F to 61°F.
Centigrade heat unit (C.H.U.): A CH.U. is defined as the amount of heat required to raise
the temperature of one pound of water through 1°C i.e., from lS.S0C to 16.S0C
3.2 CALORIFIC VALUE

It is defined as the amount of heat energy given out when a unit quantity of fuel is completely
burnt. Following are the units of calorific value: .
Calorie/g, K.Calorieikg, B.Th.U'/lb, CH.U. lib, Calorie/CC, K. Calorie./m 3, B.Th.U./ft3.
Fuels 53
3.2.1 Types of calorific value

Most often every fuel consists of Hydrogen as an constituent element. Combustion being an
oxidation process, all the constituent elements of a fuel on combustion form their corresponding
oxides. i.e., carbon on combustion forms CO 2 , Hydrogen on combustion forms H 2 0, Sulphur
on combustion forms 502 etc. The product of combustion like water has latent heat of
condensation associated with it. Depending on whether this is included or not we have two
types of calorific values.
(a) Higher or Gross calorific value (HCV or GCV): It is defined as the amount of heat given
out by the complete combustion of unit quantity of fuel and the products of combustion
are cooled to room temperature, i.e., 16°C or 60°F. (i.e., the products of combustion
are not allowed to escape)
(b) lower or Net calorific value (lCV or NCV): It is defined as the amount of heat given
out by the complete combustion of unit quantity of fuel and the products of combustion
allowed to escape into the atmosphere.
Thus,
HCV = NCV + 9H x Latent heat of condensati on of steam

100
(Because 1 part by weight of H corresponds to 9 parts by weight of H 2 0.

9H
Therefore if a fuel contains H% of hydrogen, it corresponds to - parts by weight of
100
3.2.2 Dulong's formula and numericals

It is possible to calculate the higher calorific value of a fuel, purely based on the theoretical
considerations. It is based on the fact that every element has higher calorific value. And the
Higher calorific value of a fuel is sum of the calorific values of the constituent elements present
in it.
100 8
°
HCV = - 1 [8080C + 34,500 (H - - ) + 2,240 5] calslgm
Where C, H, ° and 5 are expressed in percentages.
Numericals based on Dulong's formula

(1) A coal sample has the following composition.
C=80%;H = 10%,O=2%,S=2%,N = 1.5% and remaining ash. Calculate the HCV and LCV
assuming latent heat of condensation of steam to be 540 cal/g.
1 0
Solution: HCV = - [8080C + 34,500 (H - - ) + 2,240 S] calslgm
100 8
Where C, H, O'and S are expressed in percentages.

1 2
HCV = 100 [8080 x 80 + 34,500 (10 -"8) + 2,240 x 2] cals/gm
9H .
HCV = NCV + - x Latent heat of condensation of steam
100
9xl0
NCV = HCV ---x540
100
(2) A sample of coal has the following composition by mass.
C= 78%, H = 8%, N =2%, S= 1.5%,0= 5% and remaining ash. Using Dulong'S formula,
calculate HCV and NCV. (Latent heat of condensation of steam = 587 calslg)
1 0
Solution: HCV = - [8080C + 34,500 (H - - ) + 2,240 S] calslgm
100 8
Where C, H, 0 and S are expressed in percentages.
1 5
HCV=- [8080 x 78 + 34,500 (8 - - ) + 2,240 x 1.5] calslgm
100 8
HCV = NCV + 9H x Latent heat of condensati on of steam

100
9x8
NCV =HCV ---x540
100
Coal: Coal is a fossil fuel formed by the transformation of wood over a long period of time.
Woo~Peat -----t Lignite -----t Bituminous -----t Anthracite
Table 3.1: shows the Gradation in Properties of DifferentTypes of Coal.
Type Wood Peat Lignite Bituminous Anthracite

Properties
% Moisture content 25 15-25 20 4 1.5
(air dried at 40°C)
% Volatile matter 75 65 50-56 20-45 5-6
% Ash content 5-8 3-6 10-15 7 Low
% Fixed carbon 50 57 65-70 75-85 -95
Calorific value inK.CaIS/Kg. 4800 5400 6000-6700 8000-8500 9000-9500
Fuels 55
3.3 ANALYSIS OF COAL

It is very essential to know the quality of coal before it is used for a particular purpose. This
is done by analysis of coal. There are two ways in which analysis of coal can be done.
3.3.1 Proximate analysis

This gives a rough picture of the quality of coal. This includes determination of,
(i) % moisture
(ii) % volatile matter
(iii) % ash
(iv) % Fixed carbon
Proximate Analysis
(i) % Moisture: A known quantity of air dried coal sample is taken in a crucible and kept in
an electric oven maintained at 105-11 OOC for about 1 hr.Then the coal sample is taken out from
the oven, cooled in a desiccator and weighed again.
1/' Loss in weight of coal

~o mOisture = x 100
wt. of coal (air dried) taken
Significance: This analysis gives us an idea about the calorific value of coal. Higher the
moisture content lower will be the calorific value and vice versa. Again it also gives an insight
into the transportation cost of coal.
(ii) % Volatile matter: This can be done in two ways.

(a) Starting with air dried coal sample: A known quantity of air dried coal sample is taken
in a crucible with vented lid and kept in a muffle furnace maintained at 950 ± 25°C for exactly 7
minutes.(both moisture and volatile matter are lost) After that it is removed, cooled and weighed.
Loss in weight of coal

% Volatile matter moisture = x1 00-% moisture
wt. of coal (ai r dried) taken
(b) Starting with moisture free coal: A known quantity of moisture free coal sample (obtained
from the air dried coal) is taken in a crucible with vented lid and kept in a muffle furnace
maintained at 950 ± 25°C for exactly 7 minutes. After that it is removed, cooled and weighed.
weight of Volatile matter
% Volati Ie matter = x 100
Significance: Coal having volatile matter burns with a long sooty flame. If such a coal is
used in a furnace, the furnace will have to be suitably designed to provide sufficient space for
burning of the volatile matter. If not, the volatile matter will leave the furnace without being
burnt, leading to loss of calorific value. Again sooty flame causes pollution problems.
However, coal containing large volatile matter is useful in the synthesis of coal gas.
(iii) % Ash: A known quantity of air dried coal sample is taken in an open crucible and
burnt in a crucible at 750°C for exactly Y:z an hour. The contents are then cooled and weighed.
weight of residue
% As h = x100
Significance: Higher the ash content more will be the non combustible matter and lower
will be the calorific value. Also, higher ash content is associated with waste disposal problems.
Ash is a useless, non-combustible matter, which reduces the calorific value of coal. Moreover,
ash causes the hindrance to the flow of air and heat, thereby lowering the temperature. Also, it
often causes trouble during firing by forming clinkers (i.e.) fused ash lumps), which block the
interspaces of the grate, on which coal is being burnt. This in-turn causes obstruction to air
supply, thereby the burning of coal becomes irregular. Hence, lower the ash content, better the
quality of coal. The presence of ash (similar to moisture) also increases transporting, handling
and storage costs. It also involes additional cost in ash disposal. The presence of ash also causes
early wear of furnace walls, burning of apparatus and feeding machanism.
(iv) % Fixed carbon: This can be determined as below.
% Fixed carbon = 100 - [% moisture + % volatile matter + % ash]
Significance: Higher the % Fixed carbon, more will be the calorific value. A good quality
coal should have low moisture content, low volatile matter and low ash content, which
automatically leads to more % Fixed carbon.
3.3.2 Numericals based on Proximate analysis

(1) 2.5g of air dried coal sample was kept in an electric oven for 1hr at 110°C. The weight
reduced to 2.355g. Further it was kept in a muffle furnace in a crucible with vented lid at
950±25°C for exactly 7 minutes.
1
The weight of coal reduced to 2.05g. It was then burnt in a furnace at 750°C for "2 hr. The
residue weighed 0.35g. Report the proximate analysis results.
Solution: wt. of airdried coal taken=2.5g.
wt. of coal after lOSing moisture = 2.355g.
:. wt. of moisture = 2.5-2.355

= 0.145g.
wt. of moisture
% moisture = x100
wt. of air dried coal
0.145
- - - x 100
2.S
= 5.B.
Fuels 57
wt. of coal after losing volatile matter
= 2.05g.
:. wt. of volatile matter = 2.35.5-2.05
= 0.305
wt. of volatile matter

% volatile matter · - - - - - - - x 100
wt. of air dried coal
0.305
=--x100
2.5
= 12.2.
wt. of vesidue after burning =0.3.5g.
wt. of vesidue
w h x100
loas = wt. of air dried coal
= 0.35 x100
2.5
=14.
% FixedCarban = 100-[%M+%VM + %ash]
= 100 -[5.8 + 12.2 + 14

= 68.
:. proximate analysis results are
%C %moisture %volatile matter %ash

68 5.8 12.2 14
(2) An air dried coal sample weighing 2.9g was taken for volatile matter determination.
After losing volatile matter the coal sample weighed 1.96g. If it contains 4.5% moisture find out
the % volatile matter in it.
Solution: wt. of air dried coal =2.9g.

wt. of coal after losing volatile matter and moisture= 1.96g.
%moisture=4.5
wt. of volatile matter + moisture=2.9-1.96
=0.94g.
Wt.OfV.M+Wt.OfM ]
%volatile matter= [ .. xl00 -%M
wt. of air dned coal
= -0.94
- x 100 ] - 4.5
[ 2.9
=27.9
:. %volatile matter=27.9
3.3.3 Ultimate analysis

This gives an accurate picture about the quality of coal. This includes determination of,
(i) % Carbon and Hydrogen by combustion method
(ii) % Nitrogen by Kjeldahl's method
(iii) % Sulphur by Bomb-calorimeter method.
Determination of %Carbon and %Hydrogen by combustion method. A known quantity of
coal sample is taken in a platinum boat and the it is kept in the combustion tube as shown in the
figure. The narrow and long combustion tube is made of borosilicate glass. The tube is equipped
with copper oxide gauze. The coal is burnt in air/ oxygen which is made free of moisture and
carbon dioxide. The combustion tube.is connected to a previously weighed tube containing
anhydrous calcium chloride which in turn is connected to a previously weighed bulb containing
KOH solution. After the coal is burnt, the products of combustion i.e. H 20 and CO 2 are made to
absorb in tube containing anhydrous calcium chloride and bulb containing KOH solution
respectively. The increase in their weights is noted.
Coarse
CuO gauge copper oxide
Silver gauge
-. .. . .... -..
Pure
oxygen~
Free from
(Co2 & moisture)
Fig. 3.1 Combustion apparatus

Fuels 59
1
C+ 02~C02: H2 + 202~H20
12 44 2 18
2 KOH + C02~ K2C03 + H 20

CaCI 2 + 7H 20 ~ CaCl 2·7H 20
IncreaseinweightofKOHtubex12x100
:. Percentageo fC =-~----::...---------
Weight of coal sample takenx 44
Increase in weight of CaCI tubex2x 100

:. Percentage of H = 2
Weight of coal sample taken x 18
Significance: Carbon and Hydrogen in the coal directly contribute to the calorific value of
coal. Higher the percentage of carbon and hydrogen greater will be its calorific value and better
will be the quality of coal. Hydrogen is generally associated with the volatile matter and thus
implies the use of coal for the byproduct manufacture or otherwise.
Determination of % Nitrogen by Kjeldahl's method: About 1g. of accurately weighed coal

sample is digested in a Kjeldahl's flask with conc. H 2S04 , K2S0 4 (to elevate the boiling point),
and HgS04 (acts as a catalyst). The nitrogen present in the coal gets converted into Ammonium
Sulphate. The contents of the Kjeldahl's flask are quantitatively transferred to a round bottomed
flask fitted with a thistle funnel. The contents are made alkaline by adding NaOH and refluxed.
Liberated ammonia is collected in a flask containing known quantity of known normal H 2S04 ,
The unreacted H 2S04 is titrated against std. NaOH using phenolphthalein indicator till the colour
changes from colourless to pale pink. A blank titration of the same H2S04 is carried out.
Coal+conc 1-\80. Kjeldahl trap

r
.. Condenser
~~add
Fig. 3.2 Nitrogen estimation by kjeldhal method
Calculations: Let wt. of coal sample taken == w gm.
Let blank titration reading=x ml.

Back titration reading=y ml
:.(x-y) ml of N normal H 2S0 4 is used up.
:.(x-y) ml of N normal NH3 is liberated.
1000 ml of N NH3=149 N.
(x - y)xNx14
:.(x-y) ml of N NH3= 1000 gN
(x -y)xNx14
w g. coal = gN
1000
(x - y)xNx14
:. 100g coal = x 100
1000
. f N Volume of acid usedxNormalityx1.4

:. Percentageo =------------'---
Weight of coal sample taken
Significance: Nitrogen in coal has no significance and hence it is present in very small
amount.( -1 %)
Determination of % Sulphur by 80mb-calorimeter method: The bomb washings obtained

from the combustion of known quantity of coal in a bomb calorimeter experiment contain sulfur
in the form of its sulfates. These washings when treated with barium chloride solution or barium
nitrate solution, barium sulfate gets precipitated. It is filtered and washed with water and dried.
The weight of BaS04 is found. From this S% can be determined.
Mol. wt. of BaS04 = 233; at wt. of S=32
Calculations: Let wt. of coal sample taken = w gm.
wt. of BaS04 ppt. formed =xgm.
233g BaS04 = 32gS
xx32
x g BaSO = --gS
4 233
xx32
w g. of coal = 233 gS
xx32
:.100g coal = --x100
233
Fuels 61
Weight of BaS0 4 obtainedx32xl00

:. Percentage 0 f S :;:: --.....;;-----=!.--------
. Weight of coal sample taken in bomb x 233
Significance: Presence of sulfur in coal contributes to the calorific value of coal but its
combustion products, 502 and S03are highly corrosive to the equipments especially in presence
of moisture.Also the oxides of sulfur cause environmental pollution.
Determination of %ash: Same as proximate analysis.
Oxygen: It is obtained by difference.
3.3.4 Numericals based on Ultimate analysis

(1) 3g coal was heated in Kjeldahl's flask and NH3 gas evolved was absorbed in 40ml of
0.5N H 2S04 , The excess acid required 18.5ml of 0.5N KOH for exact neutralization.
2.3g of the same coal sample in a Bomb-calorimer experiment gave 0.35g Ba504 •
Calculate percentage of Nand 5 in the coal sample.
Solution: (a) wt. of coal taken - 3g.
Blank titration reading ... 40 ml.
Back titration reading -18.5 ml
Normality of H 2S04 -O.5
(x - y) x Normal ity x 1.4
%N = ..:....-~-----=--
wt. of coal taken
(40 - 18.5) x 0.5 x 1.4

3
"" 5.016.
:. % N ... 5.016.
(b) wt. of coal taken-2.3g.
wt. of BaS04 Ppt. = 0.35g.
233g. Ba504 ==32gs.
0.35x32
:.0.35g. BaS04 -
233
... 0.048g.
2.3g coal .. 0.048g.
100 x 0.048
:.100g. coal = 2.3
=2.086g.
:. %5=2.086
(2) In a Kjeldahl's method 3.5g of the coal sample was analyzed. The NH3 gas evolved
was absorbed in 50ml of O.lN H2 S0 4 • The residual H 2S0 4 required 15ml of O.lN
NaOH for neutralization. Calculate the percentage of Nitrogen in the sample.
Solution: wt. of coal taken = 3.5g.
Blank titration reading= 50 ml.
Back titration reading= 15ml.
Normality of H 2S04 =0.1
(x - y) x Normal ity x 1.4

%N---~------~--
wt. of coal taken
(50 - 15) x 0.1 x 1.4

3.5
-1.4
%N ... l.4
(3) 2.3g of coal sample was taken for C and H determination by combustion method. The
increase in weight of tube containing anhydrous CaCI 2 was 2.2g and increase in weight
of bulb containing KOH solution was 0.98g. calculate percentage C and H in the coal
sample.
Solutions: wt. of coal sample taken = 2.3g.
Increase in wt. of CaCI 2 tube=2.2g
Increase in wt. of KOH bulb=5.98g.
To calculate %C:
C+02 )C02
12g. 44g.
44g. CO 2 ''' 12g C.
5.98x12
:.0.98g. CO2 = 44
Now, 2.3g. coal-l.63g C.
100 x 1.63
:.lOOg. coal = - - - -
2.3
... 70.90
:.%C-70.9
To calculate % H:
Fuels 63
1
H 2+"2 °2,--~)H20
2g. 18g.
18g. H20=2g.H
2.2x2
:.2.2g. H20 =
18
=0.244g.H.
2.3g. coal =0.24gH.
0.244xl00
:.100g coal = - - - -
2.3
=10.6
:.%H=10.6
3.4 NUMERICALS BASED ON COMBUSTION

Combustion is basically oxidation process. It involves oxidation of constituents of a fuel to
give the respective oxidation products. In these problems it is assumed that there is complete
combustion and hence no partially oxidized products are formed.These calculations are broadly
classified into
(i) Weight based problems
(ii) Volume based problems
(i) Weight based problems: When the fuel composition is expressed in terms of weight, the
minimum quantity of air/oxygen required for the complete combustion of fuel is done by assuming
air to be a mixture of 77% nitrogen and 23% oxygen.
In general if a fuel consists of Carbon, Hydrogen, Oxygen, Nitrogen and Sulphur, then the
combustion equations of these elements can be given as follows.
C + 02 CO2
12 32 44
H2 + Yz 02 H 2O
2 16 18
5 + 02 5°2
32 32 64
It oxygen is present in the fuel, then it will be deducted from the total quantity of oxygen
required for combustion.
Nitrogen does not undergo oxidation during burning.

From these equations it is possible to calculate the air/oxygen requirement for the combustion
of a given quantity of fuel. The total quantity of air/oxygen required for the complete combustion
of the fuel will be equal to the sum of the quantities of air/oxygen required for the combustion of
the constituent elements present in the given fuel.
Therefore the minimum quantity of oxygen required for the complete combustion of a fuel
will be = [~~ C+ 8H + S- ° ]kg

= [2.67 C + 8H + S - 0] Kg
Where C, H, Sand ° are expressed per Kg.

Assuming air to be a mixture of 77% nitrogen and 23% oxygen, the minimum quantity of
100
air required = - x [2.67 C + 8H + S - 0] Kg
23
Note: If in a problem the composition of air is given, for calculation purpose that data will be used.
(ii) Volume based problems
For volume based problems the composition of air considered to be 21 % oxygen and 79%
nitrogen. Also, the average molecular weight of air is taken to be 28.94.
Boyle's and Charle's laws can be used for reducing the volume of a gas at a given temperature
and pressure to the corresponding volume at any other specified condition of temperature and
pressure with the help of equation.
PV ~v,
-=-
T 1,
Where T and T, are absolute temperature of the gases and P and P, and V and V, denote the
initial and final values of presssures and volumes expressed in identical units.lf the temperature
is iCC then the absolute temperature, T=273+io. Similarly if the temperature is iOF then the
corresponding value in absolute scale is 460+ iO.
For problems based on volume, it is very important to write the combustion equations. The
most frequently encountered combustion equations are as follows.
C + 02 --4 CO2
1 mol 1 mol 1 mol
2C + 02 --4 2CO
2CO + 02 - - 4 2C02
2H2 + 02 - - 4 2H 20
Fuels 65
1 mol 2 mol 1 mol 2 mol
C2H4 + 302 ~ 2C0 2 + 2H20
C2H 2 + 2.5 02 ~ 2C02 + H 20

C2H 6 + 3.5 02 ~ 2C0 2 + 3H 20
Nitrogen does not participate in combustion.For stoichiometry these equations are
considered. for example we can calculate the oxygen required for the complete combustion of
x mols of methane. Since 1 mol of methane requires 2 mols of oxygen (from the conbustion
eqution) x mols of methane will require 2 x mols of oxygen.Simiiarly the requirement of oxygen
for various constituents present in the fuel are calculated and added up. If the fuel contains
oxygen, then equivalent amount of oxygen is deducted from the total oxygen requirement.
Therefore, minimum oxygen required for the complete combustion of fuel = Total oxygen
required for the various constituents - Oxygen present in the fuel(if any).
Solved problems
1. A coal sample has the following composition by weight. C=80%, H = 5%, N = 1.5%,
S=2% 0=3% and remaining ash. Calculate the minimum quantity of air required for
the complete combustion of 5 kg. of this fuel.
Solution:
coal composition per kg.

C-80% 0.8
H-5% 0.05
N-1.5% 0.015
S-2% 0.02
0-3% 0.03
Combastion equations.
C + 02 ) CO 2
12 32
1
H2 +"2 02--~) H 0 2
2 16
Minimum quantity of oxygen required per kg. of coal =
= [~~ C +8H+5-0]
~ [( ~~ xO.B ) +(BxO.OS) + 0.02 - 0.03 ]
= [2.13 + 0.4 + 0.02-0.03]
=2.52 kg.
For 5 kg. coal, oxygen required=2.52x5

= 12.6 kg.
Considering air to be a mixture of 23% oxygen and 77% Nitrogen by wt.,
air required for 5 kg. coal
100
=12.6x-
23
=54.58 kg.
2. A sample of coal has the following composition. C=89%, H=6%, 5=2.5%, 0=2%.
Calculate the minimum quantity of air required for the complete combustion of 3 kg.
of this fuel assuming air to be a mixture of 80% nitrogen and 20% oxygen.
Solution:
Coal composition per kg.
C-89% 0.89
H-6% 0.06
5-2.5% 0.025
0-2% 0.02
(Combustion equations are to be given)

Minimum oxygen required for 3 kg. coal
= 3X[~~ C+8H+5-0J
= 3X[( ~~ xO.89)+(8XO.06)+0.025-0.02]
= 3 x [2.37 + 0.48 + 0.025-0.02]
Fuels 67
=3x2.855
=8.565 kg.
Assuming air to be a mixture of 20% oxygen and 80% nitrogen, the amount of air required.
100
=8.565x -
20
=42.82 kg.
(3) A coal sample has the following composition by weight. C = 76%, H = 8%...,. N = 1.5%,
5=3% 0=8% and remaining ash. Calculate the minimum quantity of air required for
the complete combustion of 5 kg. of this fuel. Express it in volume. (Molecular weight
of air = 28.94)
Solution:
Coal composition per kg.
C-76% 0.76
H-8% 0.08
N-1.5% 0.015
5-3% 0.03
0-8% 0.08
(Combustion equations are to be given). Minimum oxygen required for 5 kg. of coal
= 5X[~~XC+8H+5-0 ]
_ 5X[ (~~ xO.76)+(8XO.08)+0.03- 0.08]

= 5 x [2.03 + 0.64 + 0.03-0.08]
=5x2.62
=13.1 kg.
Assuming air is be a mixture of 23% oxygen and 77% nitrogen.
100
air required ... 13.1x--
23
... 56.95 kg.

To calculate volume of air required, molecular wt. of air=28.94.
28.94 kg. air at NTP occupies 22.4m 3
:.56.95 kg. air at NTP occupies 22.4m 3

56.95 x 22.4
28.94
= 44.08 m3
4. Find the volume of air required for the complete combustion of '1 cu. M. of acetylene
and the weight of air necessary for the combustion of 1 kg of fuel.
Solution: Combustion equation:
C2H 2 + 502 = 4C0 2 + 2H 20
2 vols 5 vols 4 vols 2 vols
2 'vols of C2H 2 require 5 vols of oxygen.
:. Oxygen required per cu.m. of C2H 2 = 2.5 cu.m.
100
:. air required per cu.m. of C2H2 = 2.5x-
21
= 11.9 cu.m.
To calculate weight of air;
2' mols of C2H2 require 5 mols of 02
:. (2 x 26) kg. of C2H 2 requires (5 x 32) kg. 02
(Mol wt. of C2H2= 26 mol wt. of 02 = 32)
160
:. weight of 02 required per kg of fuel = 52' kg.
160 100
Therefore, air required = -x- = 13.378 kg.
52 23
(5) A fuel has the following percentage composition by volume: H 2= 20%, CH 4= 36%
·C2H 4=5%, C2H&=6%, C4HS=2%, CO=7%, CO2=6%, 02=0.5% and rest is nitrogen. Calculate:
(i) the volume of oxygen and air required for complete combustion one kg of fuel burnt (ij) the
wt. of air required for the complete combustion of 1 kg. of fuel.
Fuels 69
Composition % bywt. per kg. of fuel Combustion equation
H2 20 0.2 H2 + 0.502 ------t H 2O

CH • 36 0.36 CH 4 + 202 ------t CO 2 + 2H 2O
4
C2H6 6 0.06 C2H6 + 3.502 ------t 2C0 2+ 3H 2O

C2H4 5 0.05 C2H 4 + 302------t 2C0 2 + 2H 2O
C4 H8 2 0.02 C4 H8 + 602 ------t 4C0 2 + 4H 2O
CO 7 0.07 CO + 0.502 ------t CO2
CO 6 0.06 -
°2 0.5 0.005 -
N2 17.5 0.175 -
(i) The minimum volume of oxygen required for the complete combustion of i cU .m. of
fuel = (02 required for H2 + 02 required for CH 4 + 02 required for C2H 4 + 02 required for C4 H 8
+ 02 required for CO).
= (0.5 x 0.2 + 2 x 0.36 + 3.5 x 0.06 + 3 x 0.05 + 6 x 0.02 + 0.5 x 0.07) - 0.005
= [0.1 +0.72+0.21 +0.15+0.12+0.035] - 0.005

= [1.335 - 0.005]
= 1.33 cU.m.
100
minimum volume of air required = 1.33x-
21
= 6.33 cU.m.
(ii) Mol. wt. of air= 28.94

To calculate minimum weight of air required;
22.4 cu. m. air at NTP weight 28.94 kg.
6.33x28.94
:.6.33 cu. m. air at NTP weight=
22.4
= 8.178 kg.
3.S LIQUID FUELS
3.5.1 Crude Petroleum Oil

The crude petroleum (a fossil fuel) obtained from earth's crust is the main source of other
liquid fuels. Mainly it consists of a complex mixture of aliphatic hydrocarbons with small amount
of other organic compounds contening nitrogen oxygen and sulfur.
3.5.2 Classification of crude petroleum oil

Based on the residue left after fractional distillation, the crude petroleum is classified in to,
• Paraffin based: These mainly consist of saturated paraffinic hydrocarbons (from methane
to solid waxes) together with smaller amounts of naphthenes and aromatic
hydrocarbons. These oils on distillation leave a residue of solid paraffin wax.
• Asphalt based: These mainly consist of non-paraffinic hydrocarbons such as aromatic

and naphthenic hydrocarbons. These oils on distillation leave behind asphalt or bitumen.
• Mixed based: These are intermediate between paraffin and asphalt based oils. These
contain varying proportions of asphaltic, naphthenic and aromatic hydrocarbons.
3.5.3 Mining of petrolium

Petroleum is found underneath the earth's surface at different depths (at about 5000 feet or
more) varying from place to place. The oil is found below the impervious rock floating over salt
water of brine. It is often accompanied with natural gas (mainly methane) which experts pressure
on the oil surface and drive out oil through natural openings, but when the pressure is low, the
oil has to be removed by lift pump.
Mining of oil is done drilling holes in the earth's crust and sinking two coaxial pipes into
the oil bearing strata. The compressed air is forced through the outer pipe when oil comes out
through the inner pipe.
Compressed
gas
Naturalgas_~=~ Crude oil
Fig. 3.3 (a) Mining of crude oil from oil"well (b) Mechanical .pumping of oil
Fuels 71
3.5.4 Refining of Petroleum (Crude oil)

The process by which the crude oil is freed from its impurities, separated into various
fractions having different boiling points, and further treated to remove undesirable tendencies
and to impart specific properties in them is broadly known as "Refining of petroleum".
Steps involved in Refining: The following are the steps involved in refining of petroleum.
Demulsification: The crude oil mined from the earth's crust is in the form of emulsion.
(Water in oil type or oil in water type) demulsification is basically separation of water from oil.
This can be affected by mechanical, thermal, chemical, thermo chemical and electrical methods.
The most widely used method is electrical method. In this method the crude oil is subjected to
an electrical field formed by a high voltage alternating current which destroys the emulsion
films. Droplets of the dispersed phase coalesce to form bigger drops which separate out from oil.
Removal of harmful impurities: The impurities like NaCI and MgCI 2 corrode the refining
equipment and cause scale formation in the heating pipes. Hence these are removed by electrical
desalting and dehydration techniques. The other harmful impurity is sulfur and its compounds.
These are removed by adding CuO which reacts with these impurities to precipitate CuS which
can be separated by filtration.
Fractional distillation: Fractional distillation is essentially a combination of distillation and
rectification.
r;.======
•
C, to C 2 Gases
Fractionating liquefied petroleum
1 column _ _ '_ .... gas
i
1
1OO( (5 to ('5
petrol (gasoline) ~
120°C
C,o to (,. kerosine
• chemicals
petrol for
vehicals
Garaffine oil
~
, ~~:r!~~~
L:J for lighting
and heating
diesel fuels
I··•.. .II,& .~
~
fubricating. oils,
waxes polishes
fuels
..._a·_.It...-
.j .. '' ~'dUIJ1"'"
and~sh~ips-
,i
central
heating
> (70 r e s i o u /
bitumen for roads
and rooling
Fig. 3.4 Fractional distillational crude petroleum

Sr. No. Name of fraction Boiling range Composition Uses

1 Uncondensed gases Upt0200C CI -C4 LPG fuel for domestic purpose
2 Petroleum ether 20-70OC CS-C 6 Petrol engine fuel and aviation
spirit
3 Petrol or Gasoline 80-1200C CS-C7 Vehicular fuel
4 Solvent naphtha lS0-2000C C7-C lO Dry cleaning
5 Kerosene l80-23ODC C I I -C I 2 Fuel for illumination and heating
for domestic and laboratory
purpose
6 Light gas oil (Diesel) 230-30SoC C13-C I7 Diesel engine fuel and for
furnaces
7 Heavy oil 30S-40SoC CIS-C 2S Lubricating oil, Fuel for generating
stations,Feed for Cracking.
8 Paraffin Low melting C2S-C40 Waxes and candles
9 Solid residue (Asphalt) ----- ----- Road making, Water proofing
roofs, Petroleum coke
3.6 Cracking
Definition: Breaking up of higher hydrocarbons with high boiling point to lower
hydrocarbons with low boiling point is called Cracking.
The reactions taking place during cracking are breaking, isomerization, cyclization, and
aromatizition. It is difficult to list the reactions taking place during cracking. In general, cracking
reaction can be represented as below.
Heat & Pressure
Reaction: C H . ) C 7 H 16+ C 7 H14
14 30 Absence of air
Need for Cracking: Less than 20% of world's demand for petrol is met by straight run
petrol. With the increase in vehicles on road, the demand for petrol is increasing at an alarming
rate. So, there is a need for more of petrol. Again, not all fractions of crude petroleum distillation
have same demand. The higher fractions like, heavy oil is not consumed as much as the lower
fractions. Hence the surplus heavy oil is made to undergo 'Cracking' to give more useful lower
fractions, petrol.
Cracking can be done in two ways.
(1) Thermal cracking
(2) Catalytic cracking
3.6.1 Thermal Cracking

The breaking up of higher hydrocarbons is affected thermally. This can be done in two
ways,
(a) Liquid phase
(b) Vapour phase

Fuels 73
Reaction features Uquid phase thermal cracking Vapour phase thermal cracking
Temperature 4000C-550OC 6000C -650oC
Pressure lOOkwcm2 10-20kWcm2
Yield 50-60% Variable
Octane rating 65-70 More than 70
Feed requirement Any type of heavy oil can be used Oi I shou Id be vapourised quickly
Time required Comparatively more Comparatively less
3.6.2 Catalytic cracking

Here the breaking up of higher hydrocarbons into lower hydrocarbons is affected by the
assistance of catalyst. This can be done in two ways,·
(a) Fixed bed catalytic cracking
(b) Moving bed catalytic cracking
3.6.2.1 Fixed bed catalytic cracking

This is a batch method (non continuous). In this method the heavy oil is passed through a
preheater to convert it into vapour state. The vapours are passed through a chamber equipped
with series of alternately arranged plates with catalyst. The vapours undergo cracking and the
cracked vapours are then fractionated to get gasoline. The uncracked vapours are recycled. The
gasoline thus obtained is stabilized to get rid of dissolved lower hydrocarbons. Fig. 3.5 shows the
schematic diagram of Fixed bed catalytic cracking.The catalysts used are crystalline alumino silicate,
bentonite and zeolites. The octane rating of gasoline obtained by this method is about 80-85.
After some time, the catalyst gets deactivated because of deposition of carbon on it. Hence
it is taken out and heated in open to get rid of deposited carbon as CO 2 ,
Heavy oil 450-550°C ) Gasoline

(C12 & Higher) Porous Silica-Alumina (C5-C10)
Zeolite
(catalytic Cracking)
Porus si Iica Active sites in zeolite

alumina zeolite
Heav
oil -4-,,_--J
Pre-Heater
D
(425-450 C)
Catalyst
1Heavy oil
Chamber
Fractionating
{425-450·C Gasoline &
coloumn
Dissolved gases
Fig. 3.5 Fixed-bed catalytic cracking
3.6.2.2 Moving bed catalytic cracking

This method is also known as fluidized bed catalytic cracking. In this method the catalyst is
taken in a finely powdered form. The vapours of the heavy oil are made to pass through a
chamber from bottom in which the catalyst powder is sprayed from top. Since the catalyst is
taken in finely powdered form there is a good contact between the catalyst and the reatant. The
cracking takes place immediately and the 'cracked vapours are taken to the next chamber to
separate it from the catalyst vapour. Further the cracked vapours free from catalyst dust are
fractionated to get gasoline which is stabilized. The catalyst dust which subsequently gets
deactivated is taken for regeneration chamber. In the regeneration chamber hot air is passed
through it which removes the deposited carbon as CO 2 • Thus regenerated catalyst is recycled.
This method is a continuous method.
~~~ Stabilizer
Gasoline
Blower
Fig. 3.6 Moving-bed type catalytic cracking
Fuels 75
3.6.3 Advantages of catalytic cracking over thermal cracking

Thermal cracking Catalytic cracking
No catalyst used catalyst is used
H igher temperature high pressure used Comparatively lower temparature and

pressure used
Yield of gasoline 50-60% Yield of gasoline is more than 70%
Octane rating is 70 Octane rating is 80-85
Cracked vapours contain lesser % age Cracked vapours contain greater % age
of aromatics iso-paraffits & less of gum of aromatics iso-paraffits & less of gum
forming diolifines forming diolifines
Time required is comparatively more Time required is comparatively less
There are other synthetic methods of obtaining petrol to meet the ever increasing demand
for petrol.
3.7 Knocking
This is a term used for abnormal combustion of fuel.
Knocking in case of petrol fuel is defined as the sudden combustion of last traces of fuel
whereas knocking in case of diesel fuel is defined as the time lag during the burning of first part
of fuel.
3.7.1 Knocking in petrol engines

The petrol engine is a spark ignition type of internal combustion engine. In this a mixture of
air and fuel(petrol) is compressed and ignited by an electric spark. Generally, this combustion of
fuel proceeds in a regular and uniform way. Sometimes, the burning of fuel is not uniform, as a
result the combustion is so quick that the mixture explodes and produces a sound called engine
"knock". The power output and the efficiency of an internal combustion engine incre~se with
increase in compression ratio. Compression ratio is defined as the ratio of volume in the cylinder
at the end of suction stroke to the volume at the end of compression stroke of the piston. In other
words the compression ratio is the ratio of the volume of gas above the piston in its bottom dead
centre position to the gas volume above the'top dead centre position.
The otetically, the power output and efficiency of an internal combustion engine increases
with increase in compression ratio. However, in actual practice, the power output increases to
maximum and then falls rapidly with further increa'se' in compression ratio. Using a variable
compression ratio engine, it is possible to determine the critical compression ratio at which a
fuel tends to knock. If a fuel-air mixture is compressed beyond critical compression ratio two
difficulties arise. Firstly, because of high temperature due to higher compression ratio, the fuel
ignites even before the regular spark is introduced. This is called preignition. This is one type of
knocking. Secondly, the first portion of the charge burns in a normal manner but knocking is
produced due to spontaneous ignition of last portion of the fuel almost instantaneously. This
causes a shock wave giving a violent blow to the piston. This is viz, knocking or detonation.
Knocking depends on various factors such as, nature of fuel r design of engine, fuel-air ratio,
shape of piston head etc. Knocking results in loss of efficiency of engine, causing fuel wastage
and increased wear and tear of engine.
3.7.2 Knocking in diesel engines

The diesel engine is a compression ignition engine that uses long straight chain hydrocarbons
having boiling range 180-360°C. Here air is passed into the cylinder and compressed to about
500psi (upstroke). Due to compression the temperature of air rises to about 500°C. The diesel oil
is injected towards the end of the compression stroke in the form of fine droplets into the hot
compressed air. The injected oil droplets absorb the heat from the compressed air, and get
vapourised, attain self ignition temperature and burn spontaneously during the downward stroke.
However the combustion of fuel in the diesel engines is not instantaneous but there exists a time
lag between fuel injection and ignition. This time lag or ignition delay is a measure of knocking
in diesel fuels. If the fuel has a short ignition delay, the fuel injected into the burning mixture
continues to burn at the rate at which it is injected. On the other hand, if fuel has along ignition
delay, then the fuel accumulation occurs in the engine even before ignition. When ignited, an
explosive combustion occurs with sudden increase in pressure. This is called "Diesel knock".
Longer the ignition delay, greater is the diesel knock.
3.7.3 Octane number

History: Edger in 1872 introduced the rating for gasoline. Octane number is defined as the
percentage by volume of iso-octane in a mixture of iso-octane and n-heptane which has the
same knocking characteristics as that of fuel under test.
2 3 4 5 6 7
. CH 3 3 4 5
CH3-CH2-CH2-CH2-CH2--cH2--cH3
I
n-Heptane (Octane number = 0) CH 3- C -CH 2- CH -CH3
I I
CH 3 CH 3
Iso-octane (Octane number= 100)
3.7.4 Cetane number
Is defined as the percentage by volume of cetane in a mixture of cetane and 2-methyl
naphthalene which has the same knocking characteristics as that of fuel under test.
Cetane (Cetane number = 100)
(1- Methyl naphthalene (Cetane number = 0)

FUfI/$ 77
The Table 3.3 illustrates the distinguishing properties between octane rating and cetane
rating.
Octane rating Cetane rating
The percentage by volume of iso-octane in a The percentage byvolume ofcetane in a mixture

mixture of iso-octane and n-heptane which has of cetane and a-methyl naphthalene wh ich has
the same knocking characteristics as that of fuel the same knocki ng characteristics as that of fuel
under test. under test.
Octane rating is used for petrol. Cetane rating is used for diesel.
Octane rating increases in the order,St.chain Cetane rating increases in the orderSt.chain
alkanes> brancherl main alkanes > a1icydics > aromatic alkanes < branchedchain alkanes < a1icyclics < aromatic
hydrocarbons hydlOOlIbons
"The fuel with high octane rating has low cetane The fuel with high cetane rating has low octane
rating. rating.
3.7.5 Antlknocklng agents

The high compression ratio used in the modern internal combustion (IC) engines demands
petrol of high quality with least tendency of knocking. The octane rating of many fuels can be
increased by adding certain antiknock agents to petrol. These compounds which are added to
vehicular or aviation petrol to improve their knocking property are called "Antiknock agents".
The commonly used anti knocking agents are,
(i) Tetraethyl lead

(ii) Tetramethyl lead
(iii) Mixed methylethyl lead
3.7~6 Working of TEL

Among the antiknock agents, TEL (Tetraethyl lead) is the most widely used, since it is
cheap and more effective in increasing the octane rating of fuels. Normally 4cc of TEL is added
per gallon of gasoline. It is highly toxic and has a specific gravity of 2.62. Generally it is used
with ethylene dibromide or ethylene dichloride.
During combustion of gasoline, TEL forms Pb and PbO. These species act as free radical
chain inhibitors and thus prevent the propagation of explosive chain reaction and thereby
minimizing knocking. However, if TEL is used, the species Pb and PbO formed may get deposited
on engine parts and cause mechanical damage. In order to minimize damage caused to the
engine parts, TEL is always used with ethylene dibromide or ethylene dichloride. The function
of these halogen compounds is to convert the less volatile Pb and PbO into more volatile PbBr2
and PbCI 2 which escape into air along with exhaust gases.
3.7.7 CatalytiC converters and unleaded gasoline

Mixing 0.1 % TEL per gallon of gasoline increases the octane rating by 10-15 points. Since
lead is toxic and causes environmental pollution, slowly it has been phased out from gasoline.
Unleaded gasoline is supplied in India to minimize undesirable lead emissions on one hand and
to enable incorporation of catalytic converters with the internal combustion engines.
Catalytic converter is fitted in the exhaust system after the exhaust manifold of petrol driven
vehicles. When the exhaust gases containing partially oxidized carbon, unoxidized hydrocarbons,
and NOx, come into contact with the coated catalyst surface, they get catalytically converted
into CO 2 and H 20. Under suitable conditions of engine operation NOx gets reduced to N 2'
2CO + 2NO ~ 2C0 2 + Nl
HC + NO ~ 2C0 2 + H 20 +N2
2CO + 20 ~ 2C0 2
HC+0 2 ~ CO 2+H 20
Catalysts made of noble metals like Pt and Pd are susceptible to get poisoned by lead and
they are very expensive. Hence leaded petrol can not be used in engines with catalytic converters.
The newly developed catalytic converter technology consists of a ceramic or metallic honeycomb
support coated with a low cost catalyst placed in a suitably designed non-corrosive metallic
housing.
3.7.8 Antiknocking agents in diesel fuel

The cetane number of a diesel fuel can be increased by addition of certain compounds
called dopes or ignition acceleralors. The ignition acceleralors added are ethyl nitrate (C 2H s N0 3 )
ethyl nitrite (C 2 H s NO), isoamyl nitrate [(CH 3)2 CHCH 2 N0 3] and acetone peroxide.
o 0
II II
CH 3- · - C-O-o--C-G H3
These are compounds which when added to-diesel fuel, will reduce the delay period,
besides veducing the flash point of the fuel. Ignition accelerators are added only as small amounts
(about 2%). They are not effectives on diesel fuels having low celane number.
Diesel engines may be classified as low, medium and high speed engines & different types
of diesel oils are used per each engine. The following table illustrates the different types of diesel
oils, and their properties uses.
TYpes of diesel oil Speed in rpm Types of disel engine Uses
Heavy oils with cetane value 25. 100-150 Low speed Ships
Medium oils with cetane value 500-1500 Medium speed Tractors locomotious
25-35 etc.
Light oi Is with cetane val ue 45-50 1500-2000 High speed Buses, trucks etc.
Fuels 79
3.8 DIESEL
3.8.1 Biodlesel
The Indian economy is growing at a blistering pace. Currently the GDP growth is averaging
around 9.4% and with the inflation rate substantially subdued, India is on the fast track of
economic growth. Our industrial secte.: is expanding rapidly with the rise in standards of living.
However to propel this growth further substantial amount of energy needs to be made available.
India is the world's sixth-largest consumer of energy and to sustain its current average annual
growth rate it will need to increase its energy consumption by about 4 per cent annually. Currently,
India imports more than 60 per cent of its annual oil needs. Unless India obtains or develops
alternative sources of energy, in 15 years it will have to import close to 90 per cent of its
petroleum needs. Hence there is an urgent need for an alternative source of renewable energy
such as Biodiesel.
There are 3 ways to run a diesel engine on bio-power, using vegetable oils, animal fats or
both:
(a) Using the oil as it is-this is called SVO (straight Vegatable Oil) fuel.
(b) Mixing with kerosine or diesel or with biodiesel.
(c) Converting to biodiesel.
The use of vegetable oils as such in the conventional diesel engines leads to the following
problems:
(a) The high viscosity of the vegetable oils interface with the fuel injection process and
leads to poor fuel atomization. The inefficient mixing of oil with air leads to incomplete
combustion.
(b) Their low volatility and the consequent high flash point lead to more deposit formtion,
carbonization of injector tips, ring sticking and degradation of the lubricating oil.
(c) There high viscosity coupled with volatility causes poor cold engine start-up, misfire
and ignition delay.
(d) Oxidative and thermal polymerization of vegatable oils cause deposite formation of
the injector and interface with injection.
(e) The incompatability of vegetable oils with conventional diesel fuels causes problems.
(f) The use of vegetable oils as diesel fuel requires modification of the conventional diesel
engine design.
3.8.2 Transesterification
Biodiesel is defined as the mono-alkyl esters of fatty acids derived from vegetable oils or
animal fats. In simple terms Biodiesel is the product you get when a vegetable oil or animal fat
is chemically reacted with an alcohol to" produce a new compound known as a fatty acid alkyl
ester. This reaction requires a catalyst such as sodium or potassium hydroxide and is called as
the Trans-esterification reaction. Glycerol is produced as a byproduct. The approximate

proportions of the reaction are:
CH 2 0COR, catalyst CH 2 0H
I J. I
CHOCOR2 + 3CH 30H <=> 3CH 3COORx + CHOH
I I
CH 20COR3 CH 20H
Triglyceride 3 Methanol Biodiesel Glycerin
(Production of Biodiesel by Trans-esterification method)
Biodiesel being produced from the vegetable oil its raw material requirement is a plant
source. For this various plants can be used which can be categorized into edible oil source
which is the consumable one and the other which is a non-edible oil source which cannot be
consumed.
3.8.3 Production of Hydrocarbons from Plants (Petrocrops)

The latex of some plants contain petroleum like hydrocarbons which can be extracted by
organic solvents as a biocrude analogus to crude petroleum. Biocrude can be hydro
cracked(cracked with hydrogen) to yield oil. Such plants are called petrocrops. These are
lactiferous plants (plants belonging to euphorbiaces, asclepiadaceae and apocynaceae families)
growing in arid and semiarid regions specially in uncultivated lands. These plants secrete milky
latex. The latex can be collected and stored or it can be extracted from the biomass using
organic solvents. This Jatex is a rich source of hydrocrackable hydrocarbons and is called
'biocrude'. This can be converted into petroleum products using metal oxide catalysts. More
than 400 species of petroleum plants belonging to different families are known.
Fuels 81
Petorcrops
I~ l
Essential Oil Exudates & Extracts
+
Edible Oil
+
Non Edible oil
Eucalyi Juvenile
Lamiaceace
1
Latex Beari ng
Jatropha Oi I Cassava Euphorbiaceace
1-
Oil Petroleum Nuts
5
-
Latex
1
Extractives
Hydrocawon Vegetable Phenolic S r

heavy light Oil Wax Compound
1
liquid Fuels UQJFuels PhenoL Resin
Adhesive
1
Alcohol
1
Organic Solvent
Fig. 3.7 Classification of Petrocrops
3.8.4 Agricultural waste

Agricultural waste such as sugar ,ane bagasse is also considered as a viable alternative for
producing diesel fuels. Bagasse is first pyrolysed to produce synthesis gas (CO + H). This synthesis
gas is subjected to catalytic convertion process to yield liquid hydrocarbons from which diesel
oil can be fractioned. India produces over 18 million tones of bagasse every year. It is estimated
that a tonne of bagasse may yiels about 100 gallons of diesel fuel.
3.8.5 Production of Ethanol using Biomass (Bioethanol)

Biomass is a carbonaceous waste of various natural and human activities can be obtained
from numerous sources like by-product of agricultural crops, raw material from the forest, from
sugar industry and wood. The primary advantage of using biomass is that it does not add dangerous
gases like CO to the atmosphere.
Alcohol produced by fermentation of grains, starches, sugars etc is a good alternative as it

is clean burning.
Drawback - low calorific value compared to conventional fuels
- utilizing grains for fermentation to produce alcohols for fuels would lead to grain shortage
and hence malnutrition.
Ethanol from starch. Starchy material e.g. grain are first cooked to a gel consistency,. cooled
and mixed with malt. Malt contains diastase enzyme which has the ability to convert starch to
fermentable sugar(maltose). This is converted by zymase bacteria to ethnol.
Yeast enzyme) C H 0
6 22 6
~zym~
Ethyl alcohol from sugar/molasses. Fermentation of sugar by yeast, is essentially used for the
manufacture of ethanol. Yeast contains the enzyme invertse and zymase. The invertase catalyses
the hydrolysis of sucrose in mash of invert sugar.
Invert sugar are subsequently converted into about equal parts of ethyl alcohol and
carbondioxide by action of zymase enzyme
Microbiological aspects. Presently, large scale ethanol plants use saccharomyces strains.
Most yeast grow well on a variety of amino acids, purines and pyrimidines as the sole source of
nitrogen. Biotin and pantothenate are essential for all strains of saccharomyces. Even if sufficient
nutrients such as sugar, nitrogen and vitamins are present, it is the dissolved oxygen in the
solution which limit the population of yeast in the fermentation medium. Once the dissolved
oxygen is depleted during fermentation the yeast population slows and eventually ceases. Anionic
detergents, sorbic acid, dithyl pyrocarbonate (DEP) and the antibiotics cyclohexamide, antimycin
A and nystalin completely inhibit growth of more common yeasts. In fermentation of lignocellulosic
hydrolysates, acetic acid, furfural and ligninderived phenolics are found to be inhibitory. The
best ethanol yields are generally obtained at pH 4.5-4.7. In lightly buffered media, the optimum
starting value is nearer pH 5.5. After fermentation is complete this falls to about pH 3.5 yeasts
survive in the approximate range of pH 2.0-8.6 The temperature for growth of yeasts is about
25°C. Since yeasts growth and fermentation both produce heat, cooling may be necessary to
maintain the desired temperature.
Questions
1. What are fuels? Give the criteria of good fuel.
2. Give the classification of fuels.
3. What is calorific value? Give the types of calorific value.
Fuels 83
4. What is HCV? How is it different from LCV?

. 5. Give the comparision between solid,liquid and gaseous fuels.
6. Tabulate the gradation in properties of coal.
7. What is cracking? Why is it required? .
8. With a schematic diagram explain Fixed bed catalytic cracking.
9. With a schematic diagram explain Moving bed( Fluidized bed) catalytic cracking.
10. Explain the mining of petroleum.
11. What is refining of petroleum? Give the various steps involved in it.
12. With a schematic diagram explain the Fractional distillation of crude petroleum.
Tabulate the various fractions, their boiling range, composition and uses.
13. What is knocking? Explain Knocking in case of petrol and diesel engines.
14. What are Anti knock agents? Give the mode of action of TEL. Explain why PbBr2 is
added to TEL.
15. Write a note on<'-Antiknock agents.
16. What is Octane rating and Cetane rating?
17. Distinguish between Octane rating and C~tane rating:
18. Write a note on catalytic converters.
19. What is Biodiesel? Compare its properties with that of Diesel obtained from crude oil.
20. What is Trans esterification? Why is it required?
21. What are petrocrops? Explain.
22. How is alcohol obtained from molasses?
Numericals
1. Calculate the HCV and NCV of a coal sample having the following composition.
C=86%, H=6%, 0=4%, $=0.5%,N=2.5% and ash= 2.5%
(Ans: HCV = 8857.5Kcalslkg, NCV = 8540.52Kcalslkg)
2. A sample of coal contains C=76%, H=5%, 0= 16.2% , N= 1.5% , $=0.3% and
remaining ash. Calculate the HCV and NCV.
(Ans: HCV = 7173.89 Kcalslkg, NCV = 6909.225 Kcalslkg)
3. 4 g of coal was burnt in a combustion apparatus and the products of combustion were
collected in a previously weighed bulb containing KOH solution and tube containing
anhydrous CaCI 2 • The increase in weights of KOH bulb and CaCI 2 tube were found to
be 0.88 g and 0.2 g respectively. Calculate the percentage of carbon and hydrogen.
(Ans: %C .. 60, %H .. 5.55)
84 Applied Ohemlstry • 11
4. 1g of coal sample was used for determination of nitrogen by Kjeldahl's method. The
ammonia evolved was passed into 50ml of 0.1 N sulphuric acid. The excess acid
required 42ml of 0.1 N NaOH. for neutralization. Calculate the percentage of nitrogen.
(Ans: %N ... 1.12)
5. A sample of coal was found to have the following composition. C ... 82%, H-6.5%,
0=3%, S=2%,N = 1 % and remaining ash. Calculate the minimum quantity of air
needed for the complete combustion of 2.5 kg. of the above coal. (AnsI 29.32kg)
6. Calculate the weight of needed for the complete combustion of 5kg of coal Having
following composition. C =86%, H =5.5%, S=2.5%,N = 1.5% and remaining oxygen.
(Ans: 59.04kg)
7. A gaseous fuel has the following composition by volume.H 2 -35%, CH .. <=47%,
C2 H6 =4%, CO= 6% and N 2 = 8%. Calculate the minimum amount of air required at
2]OC and 740mm pressure for the complete combustion of 1 cu. M. of the fuel.
(Ans: 6.904 cu.m.)
8. A sample of producer gas has the following composition. H 2 -30%, CO ... 10%,
CH 4 =2%, N2 = 58%. Calculate the volume of air required forthe complete combustion
of 2 cU.m. of this fuel. (Ans: 2.28 cu.m.) .
•••
Composite Materials
4.1 INTRODUCTION
Recent technological advancements in various fields demand for materials with unusual
combinations of properties that can not be met by the conventional metal alloys, ceramics and
polymeric materials. This is especially true for materials that are needed for aerospace, underwater
and transportation applications. For examp~, aircraft engineers are always on the look out for
structural materials that have low densities are strong, stiff, and having more corrosion, abrasion
and impact resistance. This is a rare combination of characteristics, since generally strong materials
are relatively dense; also, increasing the strength and stiffness generally results in a decrease in
impact strength.
Composite materials (or composites for short) are engineered materials made from two or
more constituent materials with significantly different physical or chemical properties and which
remain separate and distinct on a macroscopic level within the finished structure. In simple
words, a composite is considered to be any multiphase material that exhibits a significant
proportion of the properties of both constituent phases such that a better combination of properties
is realized.
The most primitive composite materials were straw and mud combined to form bricks for
building construction. The most advanced examples perform routinely on spacecraft in
demanding environments. The most visible applications pave our roadways in the form of either
steel and aggregate reinforced portland cement or asphalt concrete. Those composites closest to
our personal hygiene form our shower stalls and bath tubs made of fiberglass. Solid surface,
imitation granite and cultured marble sinks and counter tops are widely used to enhance our
living experiences.
4.1.1 Classification
Composite materials are made up of two phases; one is termed the IIMatrix" phase, which
is continuous and surrounds the other phase, often called the IIDispersed" phase. The properties
of composites are dependant on the properties of the constituent phases, their relative amounts,
and the geometry of the dispersed phase namely the shape and size of the particles, their distribution
. and orientation. Based on the type of the dispersed phase and its geometry the composite materials
are classified as follows.
Fiber
Reinforced
Dispersion Continuous Discontinuous Sandwich

strengthened (aligned) (short) panels
4.2 MATRIX PHASE AND DISPERSED PHASE

There are two categories of constituent materials: matrix and reinforcement. At least one
portion of each type is required. The matrix material surrounds and supports the reinforcemen\
materials by maintaining their relative positions. The reinforcements impart their special
mechanical and physical properties to enhance the matrix properties. A synergism produces
material properties unavailable from the individual constituent materials, while the wide variety
of matrix and strengthening materials allows the designer of the product or structure to choose
an optiR1um combination. Engineered composite materials must be formed to shape. The matrix
material can be introduced to the reinforcement before or after the reinforcement material is
placed into the mold cavity or onto the mold surface. The matrix material experiences a melding
event, after which the part shape is essentially set. Depending upon the nature of the matrix
material, this melding event can occur in various ways such as chemi.cal polymerization or
solidification from the melted state.
4.2.1 Charachteristic properties of composite materials

Important advantages of composite materials over the conventional materials like, metal,
polymer, ceramic are:
1. Higher specific strength with lower specific gravity
2. Higher specific stiffness
3. Maintains strength even upto high temperature
4. Better toughness
5. Impact and thermal shock resistance
Composite Materials 87
6. Cheaply and easily fabricable
7. Better creep and fatigue strength

8. Lower electrical conductivity
9. Lower thermal expansion

10. Better corrosion and oxidation resistance.
4.3 PARTICLE REINFORCED COMPOSITES

Particles used for reinforcing include ceramics and glasses such as small mineral particles,
metal particles such as aluminum, and amorphous materials, including polymers and carbon
black. Particles are used to increase the modulus of the matrix, to decrease the permeability of
the matrix, to decrease the ductility of the matrix. Particles are also used to produce inexpensive
composites. Reinforcers and matrices can be common, inexpensive materials and are easily
processed. An example of particle reinforced composites is an automobile tire which has carbon
black particles in a matrix of polyisobutylene elastomeric polymer. Another example is
spheroidiied steel where cementite is transformed into a spherical shape which improves the
machinability of the material. Another example for particle-reinforced composite is concrete
where the aggregtes (sand and grave/) are the particles and cement is the matrix. Particle reinforced
composites support higher tenSile, compressive and shear stresses.
Particle Reinforced Composites
Spheroidized Steel
Matrix: Particle:
Ferrite Fe3C
(a - iron) (cementite)
Ductile Brittle
Matrix: Particle:
Rubber Carbon
(Compliant) (Stiffer)
Automobile Tire
Fig. 4.1 Examples for particle-reinforced composites. (Spheroidized steel and automobile tire)
4.3.1 Large particle composites

Its features are,
1. particulate phase is harder and stiffer than matrix phase
2. there is a restriction of movement of matrix phase surrounding the dispersed phase
3. matrix transfers some of the appl ied stress to the .particles
4. the strength of the bonding between the matrix and dispersed phase at the interface
decides the mechanical properties.
e.g. Concrete; composed of cement matrix and particulates of sand and gravel as dispersed
phase. Other examples are, ceramic - metal composites viz,cermets.
S.No. Material Matrix phase Dispersed phase Properties Uses
1. Concrete Cement Sand and gravel Harder and
stronger than Construction
plain cement. purpose.
2. Cermets
(a) Oxide based Chromium Alumina(Al 20 3) Good strength
and good
thermal and shock
resistance
(b) carbide based Cobalt or Tungsten carbide Very hard with Wiredrawing
Nickel (WC) Or Titanium extremely hard dyes, va Ices and
carbide(TiC) surface machine parts.
Chromium carbide High abrasion Valves, spray
(CrC) and corrosion nozzles and
resistance .. pump parts etc.
3. Modern rubber Vulcanised Carbon black Reinforced rubber Automobile
rubber has improved industry.
mechanical
properties
4.3.2 Dispersion strengthened composites

Its features are,
1. Very small particles of the range 10 to 100 nm are used.

2. The particle-matrix interactions leading to strength are on the atomic or molecular
level. The mechanism of strengthening in this case is similar to that of "precipitation
hardening".
3. Matrix phase bears the major load, the small dispersed particles hinder the motion of
dislocations thereby improving the yield, tensile strength and hardness.
Precipitation hardening: In alloys of A",Jminium, the strength and hardness is imprDved by
the formation of extremely small uniformly dispersed particles of a second phase within the
original phase matrix with the help of appropriate heat treatments. This process is called
precipitation hardening because the small particles of the new phase are termed as "precipitates".
This procedure is also called "Age hardening" because the strength develops with time or as the
alloy ages.
e.g. The high temperature strength of Nickel alloys can be considerably enhanced by adding
about 3% by volume of Thoria(Th0 2) in the form of finely dispersed particles.
4.4 FIBER REINFORCED COMPOSITES

Reinforcing fibers can be made of metals, ceramics, glasses, or polymers that have been
turned into graphite and known as carbon fibers . . Fibers increase the modulus of the matrix
material. The strong covalent bonds along the fiber's length gives them a very high modulus in
this direction because to break or extend the fiber the bonds must also be broken or moved.
Fibers are difficult to process into composites which makes fiber-reinforced composites relatively
expensive. Fiber-reinforced composites are used in some of the most advanced, and therefore
most expensive, sports equipment, such as a time-trial racing bicycle frame which consists of
carbon fibers in a thermoset polymer matrix. Body parts of race cars and some automobiles are
composites made of glass fibers (or fiberglass) in a thermoset matrix.
The arrangement or orientation of the fibers relative to one another, the fiber concentration,
and the distribution all have a significant influence on the strength and other properties of fiber-
reinforced composites. Applications involving totally multidirectional applied stresses normaUy
use discontinuous fibers, which are randomly oriented in the matrix material. Consideration of
orientation and fiber length for a particular composites depends on the level and nature of the
applied stress as well as fabrication cost. Production rates for short-fiber composites (both aligned
and randomly oriented) are rapid, and intricate shapes can be formed' which are not possible
with continuous fiber reinforcement.
::'Oiscontinuous
. .•. ·' drandom 1)/
',,,",',
Fig. 4.2 Fiber orientation in fiber reinforced composites
4.4.1 Continuous and aligned fibre composites

Its features are,
1. The properties are highly anisotropic i.e., they depend on the direction in which they
are measured.
2. The maximum strength and reinforcement are achieved along the alignment
(longitudinal) direction.
3. In the transverse direction, fiber reinforcement is almost nil hence fracture usually
occurs at relatively low tensile stresses.
4. For other directions the strength is in between these two extremes.
4.4.2 Discontinuous fiber composites

Thses are of two types. (1) discontinuous and aligned (2) Discontinuous and randomly
oriented.
Its features are,
1. Reinforcement efficiency is only 1/Sth that of continuous aligned type.

2. Mechanical characteristics are isotropic.
3. Applications involving totally multi-directional applied stresses use these materials.

e.g. Glass-fiber reinforced polymer composites
Fiber glass is a very well known composite made up of glass-fiber, either continuous or
discontinuous, embedded in a polymer matrix. Glass is a popular reinforcement material for the
following reasons,
1. It is easily drawn into high strength fibers from molten state.
2. It is readily available and its conversion into glass reinforced plastic is economical.
3. As a fiber it is strong and when reinforced into a polymer matrix it forms a composite
with high specific strength.
4. When coupled with various plastics it possesses chemical resistance and imparts the
composite corrosion resistance.
Limitations:
1. Inspite of very high strength they are not very stiff and rigid hence can not be used in
construction purpose.
2. They can be used upto a temperature limit of 200°C above this temperature most of
the polymers begin to flow or deteriorate.
Appl ications:
1. Automotive and marine bodies.
2. Plastic pipes, strorage containers and Industrial floorings.

3. Transport industries are increasingly using these to reduce the weigth and there by
increase the fuel efficiencies.
Carbon-fiber reinforced polymer composites

Carbon is a high performance fiber material for the following reasons,
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.(At
extremely high temperatures they undergo oxidation}.
3. At room temperature carbon fibers are not affected by moisture, solvents, acids and
bases.
4. These fibers exhibit diverse physical and mechanical properties there by imparting
their composites these properties.
5. Fiber and composite manufacturing processes are developed that are relatively less
expensive and cost effective.
limitations:
1. At elevated temperatures these undergo oxidation.
2. These are relatively costlier and hence are used for certain specific purpose only.
AppJ ications:
1. Sports and recreational equipments such as, fishing rods, golf clubs etc.
2. Filament wound rocket motor cases, pressure vessels, and spacecraft structural
components both military and commercial.
3. Components of helicopters.
Aramid-fiber reinforced composites
Aramid fibers are high strength, high modulus materials which were introduced in the
early 19705. Most often they used in composites having polymer matrices. Common matrix
materials are the epoxides and polyesters. The features which make them unique are,
1. Outstanding strength to weight ratio.
2. They are superior to metals.
3. Even though they are thermoplastic, they are resistant to combustion and stable to
relatively high temperatures.
4. Chemically they are susceptible to attack by strong acids and bases, but they are
relatively inert in other solvents and chemicals.
limitations:
Cost is the only limitation.
AppJ ications:
1. Bullet proof vests and armors.
2. Sporting goods, tires, ropes, missile cases, pressure vessels.
3. As a replacement for asbestos in automotive brake and clutch linings and gaskets.
4.5 STRUCTURAL COMPOSITES

The properties of structural composites depend on:
1. Constituents
2. Geometrical design
Common structural composite types are:
4.5.1 Laminar Composites

Is composed of two-dimensional sheets or panels that have a preferred high strength direction
such as is found in wood and continuous and aligned fiber-reinforced plastics. The layers are
stacked and cemented together such that the orientation of the high-strength direction varies
with each successive layer. Laminations may also be constructed by using fabric material such as
cotton, paper or woven glass fibers embedded in plastic matrix. Thus a laminar composite has
relatively high strength in a number of directions in the two dimentional plane; however the
strength in any given directions, of course, lower than it would be if all the fibers were oriented
in that direction One example of a relatively complex structure is modern ski and another
example is plywood .
Fig. 4.3 The stacking of successive oriented fiber-reinforced layers for a laminar composite
4.5.2 Sandwich Panels

Sandwich panels, considered to be a class of structural composites are designed to be light-
weight beams or panels having relatively high stiffness and strenghts. They generally thick enough
to withstand tensile and compressive stresses that result from loadimg. A sandwich panel consists
of two strong outer sheets which are called face sheetscmd may be made of aluminum alloys,
fiber reil1torced plastics, titanium alloys; steeL Face sheets carry most of the loading and stresses.
Core may be a honeycomb structure which has less density than the face sheets and resists
perpendicular stresses and provides shear rigidity. Core materials typically fall within three
categories: rigid polymeric foams(Le. phenolics, epoxy, polyurethanes),wood (Le.balasa wood)

and honey combs.
Sandwich panels can be used in variety of applications which include roofs, floors, walls of
buildings and in aircraft, for wings, fuselage and tailplane skins.
Fig. 4.4 Schematic diagram showing the construction of a honeycomb core sandwich panel. (Reprinted
with permission from Engineered Materials Handbook, Vol. 1, Composites ASM International, Metals Park,
OH,1987.)
4.6 APPLICATIONS OF COMPOSITE MATERIALS

Composite materials have gained popularity (despite their generally high cost) in high-
performance products that need to be lightweight, yet strong enough to take harsh loading
conditions such' as aerospace components (tails, wings, fuselages, propellers), boat and scull
hulls, bicycle frames and racing car bodies. Other uses include fishing rods and storage tanks.
The new Boeing 787 Dreamliner structure including the wings and fuselage is composed of over
50 percent composites. .
Carbon composite is a key material in today's launch vehicles and spacecraft. It is widely
used in solar panel substrates, antenna reflectors and yokes of spacecraft. It is also used in payload
adapters, inter-stage structures and heat shields of launch vehicles.
In 2007 an all-composite military High Mobility Multi-purpose Wheeled Vehicle (HMMWV
or Hummvee) was introduced by TPI Composites Inc and Armor Holdings Inc, the first all-
composite military vehicle. By using composites the vehicle is lighter, allowing higher payloads.
In 2008 carbon fiber and DuPont Kevlar (five times stronger than steel) were combined with
enhanced thermoset resins to make military transit cases by ECS Composites creating 30-percent
lighter cases with high strength. Also in 2008, an all-composite recreational vehicle RV was
introduced by Pilgrim International Inc. The shell composed of Cosmo Lite, a thermoplastic
fiber-reinforced composite and the exterior surface SpectraLite which incorporates DuPont Surlyn,
an impact-resistant coating found on golf balls.
94 Applied Chemistry" /I
Questions
1. What are composite materials? Give their characteristic properties.
2. Give the classification of composite materials.
3. What are particle reinforced composites? Give their types.
4. What are Fiber reinforced composites? Give their types.
5. Write short notes on '(i) Fibre glass. (ii) Cement (iii) Aramid fiber composites.
6. What are structural composites? Give their types.
7. With a neat diagram explain (i) Laminar composites (ii) Sandwich panels .
•••
I 5'
Green Chemistry
5.1 INTRODUCTION
Cleaning up the environment, and more importantly, preventing pollution are important
issues in today's world. The chemical industry is traditionally viewed more as a cause than a
solution to pollution. Green Chemistry offer unique solutions in the area of waste prevention.
One of the most fundamental of these solutions is the application of the green chemistry principle
of atom economy to chemical reactions.
5.1.1 Principles of green chemistry

[1] Prevention
It is better to prevent waste than to treat or clean up waste after it has been created.
[2] Atom Economy
Synthetic methods should be designed to maximize the incorporation of all materials
used in the process into the final product.
[3] Less Hazardous Chemical Syntheses
Wherever practicable, synthetic methods should be designed to use and generate
substances that possess little or no toxicity to human health and the environment
[4] Designing Safer Chemicals
Chemical products should be designed to effect their desired function while minimizing
their toxicity.
[5] Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g., solvents, separation agents, etc.) should be made
unnecessary wherever possible and innocuous when used.
[6] Design for Energy Efficiency
Energy requirements of chemical processes should be recognized for their
environmental and economic impacts and should be minimized. If possible, synthetic
methods should be conducted at ambient temperature and pressure.
[7] Use of Renewable Feedstocks

A raw material or feedstock should be renewable rather than depleting whenever
technically and economically practicable.
[8] Reduce Derivatives
Unnecess'ary derivatization (use of blocking groups, protection/deprotection, temporary
modification of physical/chemical processes) should be minimized or avoided if
possible, because such steps require additional reagents and can generate waste.
[9] Catalysis
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
[10] Design for Degradation
Chemical products should be designed so that at the end of their function they break
down into innocuous degradation products and do not persist in the environment.
[11] Real-time analysis for Pollution Prevention
Analytical methodologies need to be further developed to allow for real-time, in-
process monitoring and control prior to the formation of hazardous substances
[12] Inherently Safer Chemistry for Accident Prevention
Substances and the form of a substance used in a chemical process should be chosen
to minimize the potential for chemical accidents, including releases, explosions, and
fires.
5.1.2 Goals and significance

1. A novel approach that blends the application of chemistry with economic growth and
environmental preservation.
2. To develop a strategy for sustainable chemical process industries.
3. Achieve conservation of the limited resources through cost effectiveness and pollution
prevention.
4. Therefore the basic axiom of green chemistry is to design products and processes that
reduce or eliminate the generation of all wastes.
5.2 GREEN CHEMISTRY PRINCIPLE OF ATOM ECONOMY

1. Atom economy means maximising the incorporation of materials from the starting
materials or reagents into the final product.
2. It is essentially pollution prevention at the molecular level.

3. It is synthesizing a product by putting together basic building blocks, rather than breaking
down larger molecules and discard most of it as waste.
Green Chemistry 97
5.3 NUMERICALS BASED ON ATOM ECONOMY
© + 4.5 O2 ~o
~ + 2eo2 + 2H20
~
vp,
"'-"" +30 2 • +3HP
~ + 3.502
V20,
• Iq: +4H2O
Atom Economy For Maleic Anhydride Production
Benzene Oxidation
Q o
+ 2CO,+2H,O
Formula weights
78 4.5x32=144 98
% Atom Economy= 100x98/(78+ 144)= 100x981222 =44.1 %

Butene Oxidation
~ +302 --+. ,Q o
o
+ 3H,O
Formula weights
56 3x32 ... 96 98
% Atom Economy = 100x98/(56+96)= 100x 98/152 =64.5%
• The above illustration is an example of the atom economy concept.
• The conventional benzene oxidation technique, the atom economy is 44.1 % as against
64.5% in the case of oxidation of butane.
A 20% increase in atom economy is achieved along-with zero carbon dioxide (green
house gas) emission.
5.4 COMPARISON OF CONVENTIONAL ROUTE AND GREEN ROUTE
5.4.1 Synthesis of Indigo

Indigo, the dye used to colour Jeans, can be made enzymatically by removal of the side
chain of Tryptophan to give Indole, "Yhich can be dehydroxylated enzymatically, and then
oxidized with oxygen to Idigo. The presently used commercial process starts with highly toxic
aniline and produces considerable amount of waste salts leading to disposal problems.
Conventional route
0- NH,
+ OCH,COOH NaoH
o-
I
NJ 2 NaNH,
OH -,K=O=H'"""N,....;aO""H,....-....
fusion
Aniline
Catalytic route
NH,
~I~
~
Aniline
+ HOOH,OH,oH
EthYlene glycol
Ag Catayst
gas phase
0:>-- Indole H
Alkyl hydrcperoxide
2RO,H/Mo(CO), .
Indigo
1. The convp.ntional route involves caustic fusion at two stages leading to the formation
of large quantities of salts
2. The catalytic route selectively oxidizes indole, which is environmentally benign.

Newer enzymatic process of conversion of glucose seems to be more promising as it is eco-
friendly.
5.4.2 S.\4M+resis of Adipic acid

Significant advances have been made by Frost at Michigan State University in using
alternative feed stocks coupled with biosynthetic methodologies. New synthetic pathways have
been reported for the manufacture of Adipic acid, catechol and hydroquinone using glucose as
starting material in place of traditionally used benzene which is carcinogenic.
Green Chemistry 99
Synthesis of Adipic acid

Traditional pathway
0 OH
@ Ni AI 20
370-BOOpsi
3
)
0 CO-0 2
120-140psi
)
6 +
6
benzene cyelohexane cyclohexanone cyelohexanol
j
H0 2C-(CH 2)4 - C0 2H
Adipic acid
Alternative pathway
;s
OH
~OH E-coli E-coli
HO~OH OH OH
D-glucose 3-d i hyd rosh i k i mate
H02C-(CH2)4C02H
50 psi Adipic acid
cis, cis-muconic acid

Green chemistry principle involved.
1. Traditional path way uses benzenfossil fuel based feedstock.
Alternative pathway uses glucose-a renewable feed stock. (use of renewable feedstocks).
2. Traditional pathway - requires high press & temp (energy).
Alternative pathway - enzymatic - less energy requirement. (design for energy
efficiency).
5.4.3 Fridel Craft's Reaction

Fridel Craft's reaction:
In 1980,
A1C13
reagents --~) product yield < 60%
In 1990,
Pd/C
reagents --~) product yield> 75%
2005 Onwards
ZSM-5
reagents ) product yield> 85%
(1) No corrosive chemical like AICI 3
(2) ZSM-5 can be used in sma" quantity repeatedly to conduct same reaction.
5.5 INDUSTRIAL APPLICATIONS OF GREEN CHEMISTRY
5.5.1 Waste utilization

The best example for waste utilization is conversion of glycerin to propylene glycol. Glycerin
is a waste product obtained in the biodiesel production.
catalyst
J,
CHOCOR2 + 3CH 3 0H <=> 3CH 3 COORx + CHOH
I I
CH 2 0COR3 CH 20H
Triglyceride Methanol Biodiesel Glycerin
Conversion of glycerine to propylene glycol.
CH 2 -OH CH 3
I I
CH-OH CH-OH
I I
CH 2-OH CH 2 - OH
Glycerine Propylene glycol
Copper chromite is used as a catalyst for the conversion of glycerin into propylene glycol.
Propylene glycol produced in this way is cheap and can replace more toxic ethylene glycol that
is the primary ingredient used as automobile antifreeze.
Green Chemistry 101
5.5.2 Supercriticalliquids
A fluid heated to above the critical temperature and compressed to above the critical
pressure is known as a supercritical fluid. Frequently the term, compressed liquid, is used to
indicate a supercritical fluid, a near-critical fluid, an expanded liquid or a highly compressed
gas. The phenomena and behavior of supercritical fluids has been the subject of research right
from 1800's.
Two supercritical fluids are of particular interest, carbon dioxide and water. Carbon dioxide
has a low critical temperature of 304 K and a moderate critical pressure of 73 bar. It is non-
flammable, non-toxic and environmentally friendly. It is often used to replace toxic freons and
certain organic solvents. Further, it is miscible with a variety of organic solvents and is readily
recovered after processing. It is also a small and linear molecule and thus diffuses faster than
conventional liquid solvents.
Water has a critical temperature of 647 K and a critical pressure of 220 bar due to its high
polarity. The character of water at supercritical conditions changes from one that supports only
ionic species at ambient conditions to one that dissolves paraffins, aromatics, gases and salts.
Due to this unique property, research has been carried out on supercritical water for reaction
and separation processes to treat toxic wastewater. Further, the dielectric constant of water
changes from about 78 at room temperature and atmospheric pressure to roughly 6 at critical
conditions, enabling control of reactions that depend on the dielectric constant of the medium.
Supercritical fluids such as water and carbon dioxide are substances that are compatible
with the earth's environment. However, several other supercritical fluids can be used, but the
final choice would depend on the specific application and additional factors such as safety,
flammability, phase behavior and solubility at the operating conditions and the cost of the fluid.
In the following sections, a brief outline of the properties, fundamentals and applications of
supercritical fluids is provided.
Applications and commercial processes of supercritical fluids
Any commercialization of a process that uses supercritical fluids must involve a cost analysis
that should indicate that the advantages in the new process offsets the penalty of high pressure
operations. A variety of supercritical fluid processes have ~een commercialized. Many other
processes have been investigated on a lab or pilot plant scale and have the potential to be scaled
up in the near future.
1. Supercritical Fluid Chromatography
Supercritical fluid chromatography is now often used as an analytical tool. The density is
used as the controlling feature. Separations are based on a user programmed density profile with
the supercritical fluid as the mobile phase. This analytical technique has been successfully used
to separate oligomers and high molecular weight polymers. Supercritical fluids are used as the
extracting solvents for the removal of polyaromatic hydrocarbons from soil. It is now a standard
method for gas chromatography sample preparation because the extraction is considerably faster
than Soxhlet extraction.
2. Fractionation
Supercritical fluids can be used to fractionate low vapor pressure oils and polymers. This
fractionation is difficult to achieve in distillation because the impurities have about the same
volatility as the primary components reducing the overall selectivity. Kerr-McGee Inc. has
developed a commercial process for the separatipn of heavy components of crude oil.
Fractionation with respect to chemical composition is possible and has been investigated to
produce polymer fractions of low polydispersity starting from a parent material of high
polydispersity.
3. Reactions
Supercritical fluids are attractive media for several chemical reactions. The properties of
supercritical fluids mentioned earlier can be used to advantage. By small adjustments in pressure,
the reaction rate constants can be altered by two orders of magnitude. Equilibrium constants for
reversible reactions can also be changed 2-6 fold by small changes in pressure. This dramatic
control over the reaction rates has led to the design of several reaCtions in different areas of
biochemistry, polymer chemistry and environmental science. In bioreactions, increased solubilities
of hydrophobic material and the potential to integrate the separation and reaction steps has led
to research in this area. The use of lipase and synthesis of mondisperse biopolymers holds
commercial promise. Carbon dioxide has also been extensively studied for homogeneous
polymerization of a few polymers such as fluoroacrylates. The feasibility of free radical
polymerization of polystyrene and the polymerization of polyethylene has also been investigated.
Carbon dioxide is also often used as a swel,ling agent for a polymer substrate. Though highly
corrosive and a high critical temperature and pressure, supercritica! water has been one of the
most studied medium for chemical reactions. Supercritical water has the ability to dissolve
many nonpolar organic compounds such as alkanes and chlorinated biphenyls and can dissolve
in several gases. It is thus an attractive media for oxidative reactions and has been used to treat a
wide variety of waste water streams from chemical, petroleum, textile industries. Huntsman
Corporation has commercialized a hydrothermal oxidation unit to treat alcohol and amine
contaminated water.
4. Applications in the material and polymer industry
Supercritical fluids are used extensively in the material and polymer industry. Rapid
expansion from supercritical solutions across an orifice or nozzle is used commercially to
precipitate solids. In this technique, a solute dissolved in supercritical fluid is depressurized
rapidly. By controlling the operating variables carefully, the desired precipitated morphology
can be attained. In an another process, called gas anti-solvent, a supercritical fluid is rapidly
added to a solution of a crystalline solid dissolved in an organic solvent. Since the solute has
limited solubility in the fluid, the supercritical fluid acts as an anti-solvent to precipitate solid
crystals. By varying the density of the fluid, the particle size distribution of final crystals can be
finely controlled. Another process is the precipitation using a compressed fluid anti-solvent. In
this process, the solution is sprayed through a nozzle into a compressed fluid and the solvent
diffuses rapidly into the supercritical fluid while the fluid swells the solution to precipitate the
solute. This process has been used commercially to form nanometric monodisperse microspheres
of polymers. Another process that has been commercialized is the usage of supercritical fluid
carbon dioxide to produce foamed parts. Since supercritical fluids depress the glass transition
Green Chemistry 103
temperature of the polymer, polymer foams can be formed at room temperature by directly
adding the supercritical fluid into the extruder.
5. Food applications
Carbon dioxide is the most common supercritical fluid in the food industry. Due to the
non-toxicity and low critical temperature, it can be used to extract thermally labile food
components and the product is not contaminated with residual solvent. Further, the extract's
color, composition, odor, texture are controllable and extraction by supercritical fluid carbon
dioxide retains the aroma of the product. Supercritical carbon dioxide extraction is used as a
replacement for hexane in extracting soybean-oil and has been tested for extraction from corn,
sunflower and peanuts. Supercritical fluid extraction provides a distinct advantage not only in
the replacement but also extracts oils that are lower in iron and free fatty acid. To satisfy the
consumer's need for 'lighter' foods, developmental work on supercritical extraction of oils from
potato chips and other snack foods are been carried out. In addition, supercritical carbon dioxide
has also been used to extract lilac, essential oils, black pepper, nutmeg, vanilla, basil, ginger,
chamomile, and cholesterol.
A large amount of research has been concentrated on the decaffeination of coffee by

supercritical carbon dioxide. Thus, it is not surprising to note that this was the first process to be
commercialized (in 1978), whose primary step is 5upercritical extraction. Dry carbon dioxide
cannot extract caffeine from dry coffee effectively and that the beans should be pre-wetted by
water. Soaking of about 2 hours is necessary for efficient extraction of caffeine from coffee beans
by supercritical carbon dioxide. Commercial processes for decaffeination of coffee include the
Kraft General Foods in USA and several processes in Germany.
6. Pharmaceutical applications
Since the residual solvent present in the extracted material is of critical importance in the
pharmaceutical industry, supercriticai fluid carbon dioxide has found several applications. The
extraction of vitamin E from soybean oil and a purification method for vitamin E has been well
studied. The latter process avoids the step of vacuum distillation, which usually results in the
thermal degradation of the product. Solubilities and recrystallization of various drugs has been
demonstrated in supercritical fluids.
7. Environmental applications
Due to strict environmental regulations, supercritical fluids are used as replacements for
conventional hazardous chemicals such as hexane. Supercritical fluid extraction has been
proposed as an alternative technique for soil remediation and activated carbon regeneration.
Over 99% of a majority of organics can be removed from contaminated soil. Organics that have
been successfully extracted include PAHs, PCBs, DDT and toxophene. Carbon dioxide has been
used with entrainers for the extraction of highly polar compo'_ nds. A commercial process to
separate oils from refinery sludge and contaminated soil has been developed by CF Systems
Corporation, USA. Chelating moieties that dissolve into carbon dioxide have been developed
for the extraction of heavy metals from soil.
8. Applications in nano-electronics
Supercritical fluids are also finding applications in nano-electronics. In nano-electronics
supercritica! CO 2 can replace ultrahigh purity water because it does not affect nanometric
structures. Moreover, controllable evaporation rates observed when supercritical CO 2 is gradually

moved out of supercriticality render it possible to obtain extremely thin homogeneous films of
photo varnishes. These coating methods are founds to be superior to traditional methods.
5.5.3 Green fuels and E-green propellants

The use of biodiesel as an environmentally friendly fuel, a substitute for fossil fuel is well
known. As an extension the space industry is also using alternative ecofriendly fuels viz; Green
propellants. The challenges involve,
1. Replacing present engines with those which are compatible with the ecofriendly fuels
2. To understand the relevant working conditions of the selected green propellants.
Among the alternative fuels under consideration, hydrogen peroxide (H 20 2) is the most
important one. H 2 0 2 is a clean fuel, i.e. it does not produce any harmful substance and it qualifies
as the 'green propellant' from the point of view of energy balance. There are companies which
produce ultra pure H 20 2 for this purpose. Green propellants and green engines offer great promise
and potential to replace the existing ones in near future.
5.5.4 Dimethyl carbonate- A Green reagent

Dimethyl carbonate (DMC) is a safe methylating agent which can be used in place of
methyl halides and Dimethyl Sulphate (toxic) in the methylation of various compounds. DMC is
made by clean process, it is non toxic, biodegradable and can be used in presence of catalytic
amount of base.
It can be prepared by two routes.
1. From propyleneoxide and carbon dioxide using a catalyst
°
R~ .•
S mectlte
(Mg doped) 9
R
CH30H
Smectite· '(
.)0,-
'(
(Mg doped) CH 3 CH 3
2. Conversion of supercritical CO 2 to DMC by the reaction with methanol in the presence

of catalytic amount of dialkyl tin oxide or its derivatives.
2MeOH + CO 2 Catalyst
Supercritical
Advantages of DMC
1. It is ecofriendly and is an alternative to Dimethyl Sulphate for methylation and Phosgene
for carbonylation reactions.
2. DMC is highly selective towards mono-C and mono-N methylation reactions.
3. DMC mediated reactions are catalytic reactions thereby avoiding the formation of
undesirable inorganic salts as byproducts.
4. DMC is biodegradable.
Green Chemistry 105
Questions
1. What is green chemistry? Give its goal and significance.
2. What are the principles of green chemistry?
3. What is Atom economy? Illustrate with an example.
4. Compare the conventional and green chemistry routes for the following highlighting
the green chemistry principles followed.
(i) Synthesis of Indigo (ij) Synthesis of Adipic acid (iii) Friedel Craft's reaction
5. What are the Industrial applications of green chemistry?
6. Give the application of green chemistry in
(i) waste utilization (ii) green solvents (iii) preparation of some intermediates.
Numericals
1. Calculate the percentage atom economy for the following reaction with respect to methyl
isocyanate.
CH3NH2 + COCl 2 CH 3-N=C=O+2HCI
Methyl isocyanate
(Ans: 43.84%)
2. Calculate the percentage atom economy for the following reaction with respect to
Acetanilide.
C6HSNH2 + (CH3CO)20 ) C6HsNHCOCH3 + CH 3COOH
Acetanilide
(Ans: 69.23%)
3. Calculate the percentage atom economy for the following reaction with respect to
Biodiesel.
CH20COC10H21 catalyst CH 20H
I J. I
CHOCOC 10 H 21 + 3CH 30H ~ 3CH3COOC10H21 + CHOH
I .. I
CH20COC10H21 CH 2 0H
(Ans: 86.79"10)
•••
Catalysis
6.1 INTRODUCTION
The phenomenon of catalysis was discovered by J.j. Berzelius after he reviewed a number
of observations where the rate of a reaction was increased by the presence of some substances
that remained unchanged at the end of the reaction. Berzelius thought that such substances help
to loosen the bonds which hold the atoms in the reacting molecules together. Therefore, he
coined the term 'catalysis' which means in Greek 'kata'-. wholly and 'Iien'- to loosen"
A catalyst is defined' as a substance which alters the rate of a chemical reaction, whije
itself remaining chemically unchanged at the end of the reaction'.
This implies that there can be two types of catalysts.

A catalyst which enhances the rate of a reaction or called a positive catalyst and the
phenomenon positive catalysis or simply catalysis.
E.g. Increased rate of decomposition of KCI0 3 in presence of Mn0 2•

A catalyst which retards the rate of a reaction or called a negative catalyst and the
phenomenon negative catalysis.
E.g. Decreased rate of decomposition of H 2 0 2
in presence of dilute acids or glycerol.
6.2 CHARACTERISTICS OF CATALYTIC REACTIONS

(1) A catalyst remains unchanged chemically at the end of the reaction.
The amount and chemical composition of a catalyst remains unaltered at the end of the
process. However, it may undergo a physical change.
E.gs: (i) Granular Mn0 2 employed to catalyse the decomposition of KCI0 3 changes to a fine
powder at the end of the reaction. (ii) Platinum gauze used as catalyst for the oxidation of NH3
becomes rough after sometime.
(2) A small amount of catalyst is sufficient to catalyse a reaction.

E.gs: (i) Cupric ions even at a concentration of 1 g.ion in 106 liters cause considerable
oxidation of Na2 S03 by oxygen.
(ii) Colloidal platinum present at a concentration of 1 g.atom in 106 liters catalyse the
decomposition of H 2 0 2 •
Catalysis 107
(3) A catalyst does not affect the position of equilibrium in a reversible reaction.
A catalyst affects the forward and backward reactions in a reversible process to the same
extent. Thus it helps in attaining the equilibrium more quickly, although the position of equilibrium
constant remains unchanged.
E.gs: (i) The same position of equilibrium was reached in the reaction of S02 and 02 using
three different catalysts, namely V 20 S' Pt and Fe20 3 •
(ii) In the Haber's process for the manufacture of ammonia, the reaction between N2 and H2
is very slow, but in presence of Fe as catalyst, the equilibrium is reached quickly. However, the
percentage yield remains the same.
A+B
... in presence of catalyst

.
c:
o. .
1
'0 .... "' .. Eqiulibrium
..... ----------~~----------------------
~
,
" ..
................. in absence of catalyst
- - -....~ Time
Fig. 6.1 Effect of catalyst on time taken for establishment of equilibrium
(4) A catalyst is specific in its action.
A catalyst that is effective in altering the rate of a particular reaction, may not necessarily be
effective for another reaction. Also, different products are obtained in presence of different
catalysts although the reactants are the same.
E.gs: (i) Ethanol is converted into ethanal, CH 3CHO, in presence of hot Cu as catalyst while
it gives ethene, C2 H 4 , when passed over hot A1 20 3 •
Cu )CH3CHO
(ii) Carbon monoxide and hydrogen react at high temperature and pressure, to give different
products in presence of different catalysts.
Ni
-----7 CH4 + H20
CO + H2 CO ) mixture of higher paraffins.

(5) The efficiency of a catalyst depends on its physical state.
. A catalyst is found to be far more effective when it is present in a fine state of subdivision as
compared to when used in bulk or in lump form.
E.gs: (i) Finely divided nickel has been found to be more effective than pieces or lumps of
nickel.
(ii) Platinum black, platinised asbestos or finely divided platinum is far more effective than
using lumps of platinum.
(6) Change of temperature alters the rate of a.catalytic reaction.
(7) The activity of a catalyst can be. altered by the presence of a foreign substance.
If this substance increases the activity of catalyst, it is called promoter and if the presence of
the foreign substance inhibits or destroys the catalytic activity, then it is called as poison.
E.gs: (i) Molybdenum acts as a promoter for iron used as catalyst in the manufacture of NH3
by Haber's process.
(ii) Arsenic oxides poison the platinum used as catalyst for oxichtion of S02 to S03 in
contact process for manufacture of H 2S04 ,
6.2.1 Types of catalysis

Catalysis reactions are broadly classified into:
(I) Homogeneous catalysis
(II) Heterogeneous catalysis

(I) Homogenous catalytic reaction:
Both the reactants as well as the· catalyst are in the same phase. The reaction involves
molecules, ions, or free radicals as intermediates.
Homogenous catalysis can occur in gaseous and liquid (solution) phase.
• Examples of homogenous catalysis in gas phase-

Catalysis 109
(i) Oxidation of sulphur dioxide to sulphur trioxide by the oxides of nitrogen.

1
[ NO] + -
2 °2
--7 NO2
gas gas gas
gas gas gas gas

(ii) Decomposition of ozone in presence of nitric oxide.
NO(g) ) 302(g)
• Examples of homogenous catalysis in solution phase
(i) Hydrolysis of esters catalysed by an acid or alkali
(ii) Decomposition of H 20 2 catalysed by iodide ion
(iii) Inversion of cane sugar catalysed by hydrogen ion from a mineral acid
glucose fructose
(II) Heterogeneous catalytic reactions
Reactants and the catalyst are of different phases and the reactions proceed at an interface
between the two discrete phases .
• Heterogeneous catalysis with solid reactants
(i) Decomposition of potassium chlorate in presence of manganese dioxide catalyst
2KC103 (s) + [Mn0 2] (s) ~ 2KCI + 302 + [Mn0 2](s)
• Heterogeneous catalysis with liquid reactants
(i) Decomposition of aqueous solution of hydrogen peroxide in presence of Mn02 as catalyst
2H 20 2(1) + [Mn0 2] (s) ~ 2H 20 + 02 + [Mn02](s)

(ij) Hydrogenation of animal and vegetable oils using Ni as catalyst.
• Heterogeneous catalysis with gaseous reactants
(i) Reaction between sulphur dioxide and oxygen wsing finely divided platinum or vanadium.
pentoxide as catalyst, during the manufacture of sulphuric acid by contact process.
2S0 2 (g) + 02(g) + [Pt or V 20 S](s) ~ ~S03(g) + [Pt or V2 0J(s)
(ii) Oxidation of NH3 in presence of platinum gauze as catalyst used in the manufacture of
nitric acid.
4NH3 + 502 + [Pt](s) ~ 4NO(g) + 6H 20(l) + [Pt](s)
(iii) Synthesis of ammonia by Haber's process using nitrogen and hydrogen in t~e presence
of Fe as catalyst.
N2(g) + 3H 2 + [Fe](s) ~ 2NH3 + [Fe](s).
6.3 ACTIVATION ENERGY AND CATALYSIS

Collision theory of reaction rates, states that a chemical reaction takes place only by
collisions between the reacting molecules. Not all the collisions are effective and only a small
fraction of the collisions bring about a reaction. A collision is fruitful only when colliding molecules
collide with sufficient kinetic energy and with proper orientation.
A chemical reaction takes place by breaking bonds between the atoms of the reactant
molecules and formation of new bonds to produce the molecules of the product. The energy
required for this purpose is obtained from the kinetic energy of the reacting molecules.
At ordinary temperatures, the molecules donot possess adequate energy required for effective
collisions. Only those colliding molecules that have a kinetic energy higher than a certain
minimum energy known as 'activation energy' are able to surmount the energy barrier for the
particular reaction. These activated molecules, on collision form an activated complex or in
other words a transition state momentarily that decompose to give the product.
One method to increase the kinetic energy of the reacting molecules is to increase the
temperature.
Another method by which the reaction can be made to take place is by the use of a suitable
catalyst.
A catalyst lowers the activation energy of the reaction QY providing an alternative new
pathway. Thus, presence of a catalyst causes the reaction to proceed at a faster rate.
CatalySis 111
I
>-
e>
Ql
C
Ql ~ ~
~
i
..................................................................................................... ·············1·············
Reactants ~
I Progress of reaction
Products
Fig. 6.2 Action Dynamics & Catalysis
6.3.1 Theories of Catalysis

Several theories have been put forward to explain the mechanism of action of catalysts.
(1) Intermediate compound formation theory

According to this theory, a catalyst initially combines with one reactants forming an
intermediate compound. This intermediate compound is highly reactive. It reacts with the second
reactant to form the product and thereby the catalyst is regenerated.
A + C ~ [Aq
1st reactant catalyst (highly reactive)
intermediate
[Aq + B ~ AB + c
2nd reactant product regenerated
catalyst
Alternatively, the catalyst can react with both the reactant to form a highly reactive and
transient intermediate state, which requires low activation energy. This complex readily and
spontaneously breaks up to form the product and regenerating the catalyst as the energy of AB is
far lower than that of the intermediate complex. Thus the rate of the reaction is increased because
of the presence of the catalyst.
A + B + C --t [A. ... B.... q

Reactants Catalyst Reactive transient intermediate complex
[ A. ... B.... q --t AB + C
product regenerated
catalyst
Approaching Activated complex or Molecules of the

molecules of the Intermediate state product
reactants
Fig. 6.3 Mechanism of a molecular reation involving the formation of a transient intermediate state of
activated complex
Homogenous catalytic processes in solution generally proceed with the formation of an
intermediate compound followed by its decomposition to yield the product and regenerate the
catalyst.
E.gs: (i) Catalytic oxidation of 502 in presence of NO as catalyst in the chamber process for
the manufacture of sulphuric acid. .
1
NO + "2°2 - - t [N0 2l
catalyst intermediate
[NO; + 502 - - t 503 + NO
regenerated catalyst
(ii) Formation of diethyl ether from ethanol in presence of H 2 S04 as catalyst.
C2H sOH + H 2S04 - - t [C2H sHSOJ + H 20

Catalysis 113
(iii) Reaction between benzene and methyl chloride in presence of aluminium chloride as
catalyst - Friedel-Crafts reaction.
CH 3CI + AICI 3 ---7 [CH 3]+ [AICIJ
[CH 3]+ [AICIJ + C6H6 ---7 C6H sCH 3 ' + HCI + AICI 3
(2) The Adsorption Theory
Heterogeneous catalytic processes, particularly those reactions between gaseous reactants

catalysed by a sol id catalyst.
The reaction is initiated by adsorption of the reactant molecules on the surface of the
catalyst. This occurs as a result of residual fprces on the catalyst surface.
The following steps are involved sequentially:

(i) Adsorption of the reactant molecules on the catalytic surface by weak Vander Waals
forces or by formation of partial chemical bonds (chemisorption).
(ii) Formation of unstable and intermediate activated complex between the adsorbed reactant
species and the catalyst surface.
(iii) Decomposition of the unstable activated complex to form the products.
(iv} Desorption of the stable products formed to release the fresh catalytic surface for fresh
cycle of reaction.
The exothermic nature of the chemisorption process supplies the energy required for
loosening or dissociation of bonds present in the adsorbed reactant molecules.
It is important that the atoms should not be adsorbed so strongly on the catalyst su'lface that
they act as catalyst poison.
Transitional metals of Groups IV, V and VI and Fe are capable of chemisorbing gases like
CO, 02' H 2, and N 2. Co and Ni also can chemisorb the above gases except N 2. The heat of
adsorption of H2 is relatively low for Mi, Pt, Pd, Rh, Ir, and Ru and hence they are used effectively
as hydrogenation catalysts. Also, the heats of adsorption of N2 on Pd, Rh, Ru, etc. are very low
whereas those V and Cr group are quite high, while that on Fe, it is intermediate. In case of
synthesis of ammonia, from N2 and H 2, the catalytic activity of Fe is found to be the best.
For efficient catalytic activity, the crystals of transitional metal should possess electronically
incomplete d-bands i.e., unpaired atomic d-orbitals.
The above mechanism can be illustrated by the following example:
Hydrogenation of ethene to ethane in presence of Ni catalyst.
H H H H
\ / Ni as) I I
C=C +H-H H-C-C-H
catalyst I I
/ \
H H H H
Mechanism
Step-1 H
....... _ ........ _- ......... _- ....... _,H
Adsorption of hydrogen molecules on
, the catalyst surface due to residual
valence bonds of Ni atoms.
Step-2
~""
~atalYSI "8:,,, H
."rtace
H
Since the bond length of H-H bond is
lesser than the bond length of Ni-Ni
bond, the H-H bond is stretched,
-B-----I
weakened, and hence broken into atoms
which are held to the catalyst surface
by chemical bonds.
iii i i i~ ~atalyst surface

i
Step-3 H.......... /H
H/
C,- -----------
,,
--... ,,,C ..........
H The chemisorbed H atoms are attached
to ethene molecules by partial chemical
H bonds, thus forming an unstable
activated complex.
'--- Catalyst surface
Step-4 ~ .......... C C/ ~ The unstable activated complex is

H/ ethane" H decomposed to yield the product
~, "" "a"
(ethane) and the catalyst surface is
released for a fresh cycle of the above
steps.
Catalyst surface I
Catalysis 115
The adsorption theory reasonably explains various observations of catalytic activity as

follows:
(i) Catalyst is more efficient when present in finely divided state than when present in
lumps.
The rate of the reaction increases because of the increase in concentration of the reactants
on the surface of the solid catalyst due to adsorption at the active centers. When the catalyst is
present in a finely divided state, the surface area is increased and hence, the active centres on
the catalyst surface are increased.
(ii) A catalyst is selective in its action.

The catalytic reaction is initiated by the adsorption of the reactant molecules on the surface
of the solid catalyst. The catalytic selectivity is the consequence of the specific manner in which
bond formation, polarization, etc of the reactants take place on the catalyst surface.
(iii) A catalyst is specific in its action.

The affinity of different catalysts for different reactant molecules is different.
(iv) Active centres on catalyst surface.

A catalyst surface contains unbalanced or free bonds, and it is on these that the reactant
molecules are adsorbed. These free valancies are found to be greater in number in cracks, peaks
and corner of catalyst. These spots are called active centres.
(v) Action of a promoter.

A promoter forms a loose compound with the catalyst and increases the number of valence
bonds on the catalyst surface by changin'g the crystal lattice, or increasing the number of peaks,
cracks and corners on the catalyst surface.
(vi) Action of poison.

A poison inhibits or destroys a catalyst by blocking the free valence bonds on its surface by
preferential adsorption.
6.4 MOLECULAR DESIGN FOR CATALYSTS AND ADSORBENTS
6.4.1 Metal complexes

These catalysts are the complexes of metal atoms or ions like Fe, Co, Pt, Pd, Rh (rhodium),
Ru (ruthenium), Re (rhenium), Ir (iridium) etc., ( transition metals) with the ligands.
Ligand is any ion or molecule, having in its structure atom or atoms with unshared electron
pair, which is capable of acting as the donor partner in one or more coordinate bonds.
The catalyst mechanism involves- replacement of a weaker ligand by a stronger ligand,

rearrangement of the ligand to form an intermediate, followed by decomposition of the
intermediate to product.
116 Applied Chemistry w 1/
E.gs: (i) Hydrogenation of unsaturated compounds mostly alkene using (Phl)3RhCI, known
as Wilkinson's catalyst. The mechanism involves dissociation ofthe phosphene ligand(lI), addition
of two hydrogen atoms by oxidative addition to give (111), coordinate bond formation between
the 1t electrons of the alkene and the complex at the vacant site (IV), rearrangement of the
coordination site (V). V undergoes reductive etimination to releas~ the alkane and regenerate II.
L.,RhCI
(I)
L +1 - L H,
L", /L addition of H,
a/Rh'b
14e
(II)
H
L I H
"'Rh/
CI/ "'L6
H I I 16e
L I C-CH (III)
'" /1 I
CI/T"'L~
o L I
H
H
~~ "'Rh/
I
CI/ "'L
/-,
'c-c/
18e PH3 P=L
(IV) Vacant siteD
Fig. 6.4 Catalytic applications of organometallics
(ij) Hydroformylation, i.e., reaction of an alkene with synthesis gas (CO + H 2) to produce
an aldehyde, using cobalt or rhodium compounds, e.g. cobalt carbonyl.
Catalysis 117
1
2 CO.(CO).
-; H.1l +;H.
HCo(CO),
RCH2 CH.CHO + CoR.:... co RCH=CH.
HCO(CO)3
Hydrogenolysis
of Co-acyl
reo
RCH.CH.Co(CO)3
RCH.CH.CCo(CO)3
II
o RCH.CH.Co(CO),
--.. . . .---0
"
Insertion of-G into
Co-alkyl
Fig. 6.5 Mechanism of hydroformylatio.n using Cobalt carbonyl as catalyst
6.4.2 Metal cluster catalyst

In chemistry, a cluster is an ensemble of bound atoms intermediate in size between a
molecule and a bulk solid. Clusters exist of diverse stoichiometries and nuclearities. For example,
carbon and boron atoms form fullerene and borane clusters, respectively. Transition metals and
main group elements form especially robust clusters.
The phrase cluster was coined by F.A. Cotton in the early 1960s as compounds containing
metal-metal bonds. In another definition a cluster compound contains a group of two or more
metal atoms where direct and substantial metal metal bonding is present.
The main cluster types are-
• naked clusters without stabilizing ligands.
• those with ligands. Typical ligands that stabilize clusters include carbon monoxide,
halides, isocyanides, alkenes, and hydrides.
Applications of clusters in catalysis

Synthetic metal carbonyl cluster compounds have been evaluated as catalysts for a wide
range of industrial reactions, especially related to carbon monoxide utilization, but no industrial
applications exist. The clusters Ru 3(CO)'2 and Ir/CO),2 catalyse the Water gas shift reaction, also
catalyzed by iron oxide, and Rh 6(CO)'6 catalyzes the conversion of carbon monoxide into
hydrocarbons, reminiscent of the Fischer-Tropsch process, although again iron-oxide based
heterogeneous catalysts are used industrially.
In general metal centers with large d-orbitals form stable clusters because of favorable
overlap of valence orbitals. Thus, metals with a low oxidation state for the later metals and mid-
oxidation states for the early metals tend to form stable clusters. Polynuclear metal carbonyls are
generally found in late transition metals with low formal oxidation states. Transition metal carbonyl
clusters.
The development of metal carbonyl sompmmds 5Uch dS Ni(CO)4 and -Fe(CO)~ reatjuickly
to tbe_ isQl.ation of Fe2(CO)9 a~d Ft::3(CO~f!;'-Rundle and Dahl discovered that Mn 2(CO),o featured
an "unsupported" Mn-Mn bond, thereby verifying the ability of metals to bond to one another in
molecules. In the 1970's, Paolo Chini demonstrated that very large clusters could be p-repared
from the platinum metals, one example being [Rh,/CO)24H3]2_.
Tran$ition metal halide clusters

Linus Pauling showed that "MoCi/, consisted of M06 octahedra. F. Albert Cotton established
that "ReCI/, in fact features subunits of the cluster Re 3C1 9, which could be converted to a host of
adducts without breaking the Re-Re bonds. Because this compound is diamagnetic and not
paramagnetic the rhenium bonds are double bonds and not single bonds. In the solid state
further bridging occurs between neighbours and when this compound is dissolved in hydrochloric
acid a Re 3CI,/- complex forms. An example of a tetranuclear complex is
hexadecamethoxy1etratungsten W 4 (OCH 3)'2 with tungsten single bonds and molybdenum chloride
(M06C1 s)CI 4 is a hexanuclear molybdenum compound and an example of an ottahedral cluster.
A related group of clusters with the general formula MxM06XS such as PbM06Ss form a Chevrel
phase, which exhibit superconductivity at low temperatures. The eclipsed structure of potassium
octachiorodirhenate(lll), K2 Re2CI s was explained by invoking Quadruple bonding. This discovery
led to a broad range of derivatives including di-tungsten tetra(hpp), the currect (2007) record
holder low ionization energy.
Catalysis 119
6.4.3 Zeolites and Zeotypes

Zeolites are crystalline alluminosilicates comprising corner sharing Si0 4 and A10 4 -
tetrahedral and consisting of a regular system of pores (channels) and cavities (cages) with
diameters of molecular dimensions (0.3 to 1.4 nm). A large number or zeolites are known,
which are naturally occurring, but most of which are synthesized.
Analogus structures containing T0 4 elements, e.g. B, Ga, Fe, Ge, Ti, V, Cr, Mn and Co have
also been synthesized and are called as zeotypes. They include for example AIPOs, SAPOs and
MeAPOs.
As with amorphous aluminosilicates, zeolites contain an extra framework cation, usually

Na+, to maintain electrical neutrality with the A104 - moiety. Since an A10 4 - moiety is unstable
when attached to another A10 4- unit, it is necessary that they are separated by atleast one Si04
unit.
Fig. 6.7 The acid form of zeolites
The most important feature of zeolites (and zeotypes), in the context of catalysis is the
presence of a regular structure containing molecular sized cavities and channels that make them
unique as shape selective catalysts for a wide variety of organic transformations.
Basic units in zeolite

In fig. 6.8 eight T0 4 octahedra are joined together in a ring, commonly referred to as the
eight ring structure as there are eight oxygen atoms in the ring. These basic ring structures are
combined to form three dimensional arrangements which constitute the building blocks for the
zeolite. For ego one of these building unit is sodalite cage, a truncated octahedron with four
membered ri ngs made during truncation and six membered ri ngs as part of the original octahedron.
In zeolites derived from the sodalite unit these cages are joined together through extensions
of either the 4- ring or 6-ring. Zeolite A is an example of the former. The centre of the structure
comprises a supercage with a diameter of 1.14 nm, surrounded by eight sodalite cages. Access
to these cages is via the six mutually perpendicular 8- ring openings having a diameter of 0.42
nm, enabling hydrocarbons to enter.
o
0.35 nm-0.45nm
Fig. 6.8 Sodalite cage
Fujasites are naturally occurring zeolites composed of sodalite cages joined through
. extensions of their 6- ring face. An internal supercage of 1.3 nm diameter is accessed hy four 12-
ring openings with a diameter of 0.74 nm. The latter provide access for relatively large aliphatic
aild aromatic molecules, ego naphthalene. The synthetic zeolites X and T have the same crystal
structure.as fujasite but differ in thir SilAI ratios. In zeolites X and Y the Si/AI ratio is 1-1.5 and 1.5
- 3, resptly: While fujasite has Si/AI ratio of 2.2.
Modernite is a naturally occurring zeolite with Si/AI ratio of 10 and a structure of 12-ring
and B-ring tunnels with diameters of 0.39 nrT'l and 0.7 nm resptly, extending through the entire
framework. Every framework atom forms a part of the walls of these tunnels and is accessible to
substrate molecules diffusing through them.
The synthetic zeolite, ZSM-5, is a highly siliceous material with Si/AI ratio from 25 upto
2000. It consists of a three dimensional network of two intersecting 1O-ring tunnel systems of
0.55-0.6 nm diameter.
6.4.4 Pillared clays

Clays are naturally occurring miner~ds and find a wide variety of applications including
their use as catalysts.
Clays are amorphous, layered (alumino)silicates in which the basic building blocks- Si04
tetrahedra and M0 6 octahedra (M- AI+3, Mg+2, Fe+ 3, Fe+ 2, etc.) polymerise to form two-dimensional
sheets. One of the most commonly used clays is montmorillonite in which each layer is composed
of an octahedral sheet sandwiched between two tetrahedral sheets.
Catalysis 121
Typically the octahedral sheet comprises oxygens att3ched to AI- ; and some lower valence
cations such as Mg+2. The overall layer has a net negative chJrge which is compensated by
hydrated cations occupying interlamellar spaces. Immers ion in water results in swelling of clay
and exposure of the intercalated cations making them accessible for cation exchange.
A serious short coming of clays, however is their limited thermal stability . Heating of
exchanged clays results in a loss of water, accompanied by the co llapse of the interlamellar
region, thereby decreasing the effective surface area.
Fig. 6.9 Schematic representation of layered structure of montmorillonite
This problem was solved by developing the pillared clays. In pillared clays the layered
structure is intercalated with piilaring agents which act as 'molecular props' . Inorganic
polyoxocations such as [AI 13 0 4 (OH)24(H 1 0)1]F+ are popular pillaring agents but a variety of organic
and organometallic pillaring agents have also been u!led. Pillaring with AI+3 provides an
interlamellar space of 0.8 nm, which remains after drying. The major goal of the pillaring process
is to produce novel, inexpensive materials with properties (pore shape and size, acidity, etc.)
complementary to zeolites are known examples of the interiayering materials. Most of these are
thermally stable and hold as pillars to allow a porous structure in the interlayer spac~. The
resulting complexes, often called pillared clays, exhibit attractive properties as catalysts-namely,
large surface area, high porosity, regulated pore size, and high solid acidity.
6.4.5 Metal oxide catalyst

Transition Metals: ,>
Catalytic Properties: Many transition metals and their Compounds are found to act as-
catalysts
For example: Platinum and vanadium pent oxide are employed as catalysts in the
manufacture of sulphuriec acid by contact process.
Mn0 2 is used as a catalyst, during decomposition of hydrogen peroxide H 20 2 solution .
Reason for the catalytic power of transition metals: The catalytic power of transition metals
is probably through the use of the (n-1) d-orbitals or due to the formation of some interstitial
compounds which adsorb and activate the reacting substances. Thus, they act as catalyst, due to
variation in oxidation states. Because of presence of incomplete d-orbitals, they can from unstable
intermediate products with the reactants. Transition metal compounds are believed to operate
as catalyst by providing alternative low energy pathways, either by variation in the oxidation
state of transition metal or by formation of suitable intermediates. Thus during the conversion of
S02 to S03 the catalyst V 20 S is believed to act due to the ability of vanadium to have several
oxidation states. The probable mechanism of this catalyst action is as follows:
(i) Solid V 20 S adsorbs a S02 molecule on its surface and gives it an oxygen atom to form
divanadium tetraoxide. · .
V 20 S + S02 ~ V 20 4 + S03
(ii) The divanadiumtetraoxide in than converted back to VPs by the reaction with oxygen.
2V 20 4
+ 02 ~ 2V 20 S
Also, finer the transition metal used, better is its catalytic activity, since finely divided metal
possess larger surface area and more of free valancies at its surface for the adsorption of free
valancies at its surface for the adsorption of the reactant molecules.
6.4.6 Carbon membranes

Nanoparticles due to their extremely large surface to volume ratio are efficient catalyst.
Application of nanoparticles in catalysis ranges from fuel ceU, to catalytic converter, photocatalytic
devices.
Carbon nanotube membranes consists of a vertically aligned array of carbon nanotube
surrounded by a matrix of silicon nitride or on a silicon chip surrounded by ceramics matrix.
Membranes that have carbon nanotubes as pores could be used in desalination and
dem i n~ral ization.
Salt removal from water, commonly performed through reverse osmosis, uses less permeable
membranes, requires lar~e amounts of pressure and is quite expensive. However, these more
permeable nanotube membranes could reduce the energy costs of desalination by up to 75 per
cent compared to conventional membranes used in reverse osmosis.
Carbon na otube
r Ceramics maIne
•,.I I,.....
'.
between CNT
Porous silicon chip support
Fig. 6.10 Carbon nanotube membrane

Catalysis 123
Carbon nanotubes are a unique platform for studying molecular transport and nanofluidics.
Their nanometer-size; atomically smooth surfaces and similarity to cellular water transport
channels make them exceptionally suited for this purpose.
Another potential application for the membranes is in gas separation. The high gas
permeability and its affinity to hydrocarbons may allow for lower-energy, industrial-gas
separations. Though the membranes have an order of magnitude smaller pore size, the enhanced
flow rate per pore and the high pore density makes them superior in both air and water
permeability compared to conventional polycarbonate membranes.
Questions
1. What is catalysis? Give the various types with one example of each.
2. Explain the adsorption theory of catalysis.
3. How does catalyst affect the establishment of equilibrium state and activation energy
of a reaction? Explain with necessary graphs.
4. Explain- NA catalyst only hastens the approach of equilibrium in a reversible reaction
but doesnot alter the position of the equilibrium N •
5. What is meant by activation energy?
6. What are the characteristics of a catalytic reaction or criteria of a catalyst?
7. Discuss the Intermediate Compound formation theory of catalysis.
8. What are zeolites? Discuss the structure if zeolites in the context of catalysis.
9. What are pillared clays?

10. Write a brief note on pillared clays.
11. What are zeotypes? Discuss the structure.
12. What are metal complexes? Explain the role of metal complex catalyst with the help
of any two examples.
13. What is a metal cluster? Give the structure of metal cluster with suitable examples
14. Explain the role of metal oxide as a catalyst.
15. What are carbon membranes? How do they act as a catalyst?
•••
REVISION AT A GLANCE
CHAPTER 1 CORROSION
What is corrosion?
Corrosion is defined as the deterioration or destruction of metal (alloys) by an unwanted

chemical or electrochemical reaction with its environment, starting at its surface.
Deterioration or disintegration of surface metal due to the attack of environment.
Theories of corrosion:
• Dry theory:
• Electrochemical theory: Necessary conditions for electrochemical corrosion are,
• There should be two dissimilar metals ~n contact with each other. Or there should
be two different areas of the same metal exposed to two different concentrations
leading to the formation of separate anodic and cathodic areas.
• There should be a conducting medium.
• Mechanism of Electrochemical corrosion
• In acidic medium: by evolution of hydrogen
• In alkaline or neutral medium: by absorption of oxygen
• Factors affecting rate of corrosion:
• Nature of metal:
o Position of metal in the electrochemical series

o Purity of metal
o Relative areas of cathode and anode
o Nature of corrosion product
• Nature of environment
o Temperature
o Humidity
o pH of the medium
o Nature of r.:orrosion product
Prevention of corrosion:
Revision at a Glance 125
Cathodic protection: The idea behind this method is to forcibly convert the material to be
protected from corrosion into a cathode, because cathode is the one which does not undergo
corrosion.
Sacrificial anode method:
Ground level
: :.s9i! : : : : " : : : : : : : : : : : : : : : : : : : : : : :
Impressed current method:
-L----';::n~..u..-..J...J"--.......;::.&4IiiJb'iiF==---lnsulated
copper wire
r_":.-_-:..-;:.· .'I:==t::::::::::n:.t--_Underground
Back fill-~~~:: .' pipeline cathode
Graphite or -~~:.;.;jIjI!!22~
~tainless steel
In impressed-cUl, ent cathodic protection, electrons are supplied from an external cell so that the object
. itself becomes cathodic and is not oxidized
Anodic protection: Applicable for metals which show active-passive behaviour.
Distinguish between cathodic and anodic protection
Cathodic protection Anodic protection

1. The metal to be protected is made cathode. 1. The metal to be protected is made anode.
2. Method is applicable to all metals. 2. Method is applicable to metals showing active-
passive behaviour.
3. Installation cost is low. 3. Installation cost is higher.
4. Operating cost is high. 4. Operating cost is low.
5. More number of electrodes are required for 5. Fewer electrodes can achieve better corrosion
better corrosion protection. protection.
6. The method can be used where there is no 6. Applicable to wide range of severe corrodents.
l. _
. _ . <;oc,.:e
__
of power by employing sacrificial anodes.
Protective coatings:
Metallic coatings: These are of two types.

Anodic coating: Coating metal is anodic to base metal. E.g. Galvanising.
Cathodic coating: Coating metal is cathodic to base metal. E.g. Tinning
Distinguish between anodic coating and cathodic coating
(i) Anodic coatings: These coatings are produced from metals which are anodic to the base
metal to be protected, Le., metals which lie above in the galvanic series, e,g., Zn, AI, Cd coatings
on steel.
If any pores or breaks occur in such coatings, a galvanic cell is formed between the coating
and the exposed part of the base metal. In such a case, since the coating metal is anodic, it
corrodes, leaving the underlying metal unprotected.
Thus the anodic coatings act as 'sacrificial anode'. The corrosion is more uniform and less
severe as the anode surface area is much larger compared to the cathode.
These coatings can be applied by hot dipping, spraying, etc.
(ii) Cathodic coatings: These coatings are produced from metals which are cathodic to the
base metal to be protected Le., metals which lie below in the galvanic series, e.g., Sn, Ni, Cr
coatings on steel.
If any pores or breaks occur in such a coating, a galvanic cell is formed between the
coating a galvanic cell is formed between the coating and the exposed part of the base metal. In
such a case, the base metal being more anodic corrodes.
As the surface area of the anode is much less compared to the cathode, intense corrosion
occurs resulting in severe pitting and perforation of the base metal.
Such coatings are applied by electroplating because by this method, a more uniform coating
is produced.
• Application of metallic coatings:
o Hot dipping
o Metal spraying
o Metal cladding
o Electroplating
o Powder metallurgy
• Electroplating:
• Organic coatings:
• . Paints:
Paint is a mechanical dispersion of one or more pigments in a vehicle. Vehicle is a liquid,

consisting of n,on-volatile film-forming material, drying oil and a highly volatile solvent, thinner.
Constituents of paints:
(i) Pigment: It is the most essential constituent of paint.
- protects the surface from corrosion.

- provides desired colour to the paint film.
- gives protection by reflecting off the harmful ultraviolet rays.
- provide resistance to the paint film against abrasion.

Example: white lead, Zinc oxide- white
Red lead, ferric oxide- red, chromium oxide- green.
(ii) Vehicle or drying oil: It is the fiim-forming constituent of the paint. These are glyceryl
esters of high molecular weight fatty acids, present in animal and vegetable oils. Eg. Linseed oil,
soyabean oil, castor oi I.
Drying oil supplies to the paint film-
- main film-forming constituent.
- vehicle or medium.
- toughness, adhesion, durability.
- water-proofness.
Oils containing conjugated fatty acid, dry faster than those with non-conjugated saturation.
(iii) Thinners: Thinners are volatile substances which evaporate easily after application of
paints. Functions:
- reduce the viscosity of paints to suitable consistency
- dissolve the other additives in the vehicle
- suspend the pigments in the paint.

- help in the drying of the paint film.
- help in increasing the elasticity of the paint film.
E.gs. Turpentine, petroleum spirit, toluol, xylol.

(iv) Driers: are oxygen carrier catalysts. They accelerate the drying of the oil mm through
oxidation, polymerization and condensation.
E.gs. Resonates, linoleates, tungstates and napthenates of Co, Mn, Pb and Zn.
(v) Extenders and fillers: These are low refractive undices material generally of white colour.
Functions:
- reduce the cost.
- serve to fill voids in the film.
- help to reduce the cracking of dry paint.
- act as carriers of the pigment colours.
E.gs. Talc, asbestos, ground silica, 8.15° 4, CaCO y CaS0 4
(vi) Platicisers: They provide elasticity to the film and minimize its cracking.
E.gs. Tricresylphosphate, triphenylphosphate, tributylphosphate.
(vii) Anti-skinning agents: Prevent gelling and skinning of the paint film.
E.gs. Polyhydroxyphenols.
Varnishes
Varnish is a homogenous colloidal dispersion-solution of natural or synthetic resin in oil or
thinner or both.
There are two main types of varnishes:
(i) Oil varnish- is a homogenous solution of one or more natural or synthetic resins in a
drying oil and a volatile solvent. This type of varnish dries up by the evapouration of
the volatile solvent, followed by oxidation and polymerization of the drying oil. As a
result, such varnishes take a longer time i.e., around 24 hrs. for drying. The film
produced is hard, lustrous and durable.
Example- copal in linseed oil.
(ij) Spirit varnish- is a homogenous solution of resin in a volatile solvent. As no oil is
present, such varnishes dries very rapidly, but the film thus obtained is brittle and has
a tendency to crack or peel off. Such varnishes are used for polishing wooden furnitures,
e.g., shellac in alcohol.
Constituents of a varnish:
(i) Resins: Resins in a varnish provide resistance to weathering, chemical action, durability
and water-proofness. Resins can be both (i) Natural - like shellac, kauri, copal, etc.
(ii) Synthetic - like phenol formaldehyde, urea formaldehyde, terpene polymers, etc.
(ij) Drying oils: help to produce a durable film as they dry by oxidation and
polymerization, e.g., liflseed oil, tung oil, soya bean oil, etc.
(iii) Solvents or thinners: help to dissolve the constituents of the varnish and drying of the
varnish film by evapourating. E.g., turpentine, petroleum spirits, kerosene, etc.
(iv) Driers: are added to accelerate the drying of the varnish film. E.g. Pb, Co, Mn linoleates,
napthenates, resinates.
(v) Antiskinning agent: like tert amyl phenol, guiacol, etc., are used to prevent the cracking
or peeling of the varnish film.
Uses:
(i) For protection of articles against corrosion.
(ii) As a brightening coat on painted surface to eliminate the effect of corrosion
(iii) On wooden surfaces for enhancing the ornamental grains on their surface.
Enamels
Enamel is a pigmented-varnish. On drying enamels give a lustrous, hard and glossy finish.
Constituents of enamels:
(i) Pigments: Pigments used may be white (e.g. Titanium dioxide and calcium sulphate
mixtures) or coloured. When coloured pigments are used, the enamels are called
Japans. Black Japan is prepared by dissolving asphalt in linseed oil and turpentine or
spirit. They are used for painting metallic surfaces like bicycles, bed-steads and electrical
devices.
(ii) Vehicle: may be pure resin (e.g. Rosin) or oleoresin (e.g. Synthetic resin like
phenolaldehde and oil like linseed oil, fish oil).
(iii) Driers: used only in oleoresin enamels, ego Resonates and oleates of .Co, Mn and Zn.
(iv) Thinners: e.g. Turpentine, acetone.
Lacquers
A lacquer is a colloidal dispersion of solution of cellulose derivative, resin, plasticizer in
solvent and diluents. Lacquers on drying yield a transparent, hard and water-proof film.
Constituents of lacquers:
(1) Cellulose derivatives: e.g. Cellulose nitrate, cellulose acetate. They provide water-
proofness, hardness and durability to the film.
(2) Resins: used are both natural, e.g. Copal and synthetic, e.g. Phenol aldehyde. Resins
provide the resistance to corrosion, retention of original gloss, sdhesion.
(3) Plasticisers: e.g. Tricresyl phosphate,dibutyl phthalate. They reduce the brittleness and
improve the ductility and flexibility of film.
(4) Solvents: e.g. Ethyl acetate, butyl acetate. Solvents dissolve the various constituents.
(5) Diluents: e.g. solvent naptha, benzol, toluol are added to reduce the viscosity as well
as reduce the cost.
Uses:
(i) Used for interior decoration like paintings of wood work and furniture.
(ii) Finishing coat for automobiles to provide a glossy finish and additional protection
against corrosion.
(iii) For water-proofing cotton fabrics, preparing artificial leather.
• Numericals.
• Corl'osion in electronic and photonic devices
Corrosion in electronic components manifests itself in several ways. Computers, integrated
circuits, and microchips are now an integral part of all technology-intensive industry products,
ranging from aerospace and automotive to medical equipment and consumer products, and are
therefore exposed to a variety of environmental conditions. Corrosion in electronic components
is insidious and cannot be readily detected; therefore, when corrosion failure occurs, it is often
dismissed as just a failure and the part or component is replaced.
Because of the difficulty in detecting and identifying corrosion failures, the cost of corrosion
is difficult to determine. Also, in the case of consumer electronics, such devices would become
technologically obsolete long before corrosion-induced failures. In addition, while corrosion-
related user costs due to irretrievably lost data could be staggering, as the electronic information
and data exchange become more intensive, most sensitive information is frequently backed up.
Capital-intensive industries with significant investments in durable equipment with a considerable
number of electronic components, such as the defense industry and the airline industry, tend to
keep the equipment for longer periods of time, so that corrosion is likely to become an issue.
Although the cost of corrosion in the electronics sector could not be estimated, it has been
suggested that a significant part of all electric component failures may be caused by corrosion.
Revision at a GIance 131
Mechanism of wet corrosion by hyd rogen evolution
Aq~eOu-; neu-::::::::: ::: :::::: -- - - - - --

_ of electrolyt tral solution ::: - - - - - - -
___ __ _ ______ e --
________ c _+:'-o~_::!: ::: --:: -:::~ ~::: ~~~~:.~ ~ :.::::::::::.

-- - y,O,+2e-+HO ---- Rust - - - - - -
==::: .
- - - -
,~20H
Oxide film -
---
Electronic current Electrolyte
-i~1~i1~~JJE~
r - - - - - - - - - - - ~--.--~
1-
-----t~- ------.
(Less noble) (More noble
I': anode is :. :. :" cathode is
~ attacked Positive ions : ::: protected
Current ~
Cu
Galvanic corrosion
More oxygenated
part (cathode) ~~!!I!/ Nacl so~ion
Flow of eie6tron
y, O,+H,O+2e- -+20H-
Corroding anode
zn_zn" +2e-
(Less oxygeated part)
------------
Mechanism of differential aeration attack caused by partial immersion of a metal
Air
Rust ring
Rust ring
(iron hydroxide)
(iron hydroxide)
% 02+H"O+2e--.20H- % o2+H,O+2e--+20H-
Mechanism of differential aeration attack, caused by the presence of drops of salt ~olution on the iron
surface. metal dissolves at the less-aerate anodic areas; whereas corrrodsion produc t (iron hydroxide) is
deposited at the cathodic areas,
Co rrosion product
\,
Crack Cathode
Anode
Sa nd (less oxygen ated part)
Cathode
\ /
Oxygen concentration corrsion. Anode is formed at inaccessible location, where oxygen is less available. The
cathode forms, where oxygen is freely available
: : : : : : : : : Conducting solution contanin ig :: : : : : : : : : : : :

- - - - - - - - - disolved oxygen
Direction of - - - - - - - - - - - - - - - - - .-:: Direction of
diffusion of : : : : : : : : : : : : : : : : : : : diffusion of : : :
__ ~e~a~i~n~ ~::~~h~~~X~~:s_~~~
:::::::t.~ ~ ~ ~ ~ ~ ~ ~
------ . -------
:'M(OH) - - : : : : :"-OH- -= :
n ----
::::::
------ - -
corrosion product
l ocalized corrosion of oxygen-deficient areas

Fe 2 '+20H- Fe(OH),
Corrosion product
! More oxygenated
cathode
Pitting corrosion at the surface of iron
Protected grain
centre (cathodic)
L_-':::::==:::::::- Precipitated compound

(cathodic)
General intergranular attack

----------------=
---------
------_ ...
-------
Stressed Part /),._-:::::::0..,.... Anode (strained part)

grain boundary where corrosion takes
(anode)where place
corrosion takes place
Stress ~orrosion
Insulated electrode leads
Vacuum
tube
voltmeter
Reference
electrode Tank to be Protected
Anodic protection system for tanks
+1 .6 ~------------~
+1 .6
Passivation
+0.8
:>
ui
~c: 0.0
~
a. Corrosion
-{l.B
-1 .6
-2 2 6
pH
A & B. Pourbaix diagram
136 Applied Chemistry - "
:.....
: : :. .: ....
: : :....: .: ......
: : : ..............
: : : : : : : :. ..: :. Corrosive envimoment
Zinc coating Zinc coating
Zn -. Zn'~ 2e-
Functioning of anodic coating. In galvanized steel, Zn serves an anode; while iron of steel serves as the
cathode_ Therefore, the iron is protected, even if it is exposed, when a part of the zinc coating is scrapped off
- - - - - - - - - - - - - - - - -- - - - •. Corrosive envimoment
Exposed Iron part Sn coathing

becomes anodic and
: : : : : : :: Sn coathing . Is attacked Fe--. Fe"+2e-
Tin-plated steel. The tin protects the iron, when the coating is continuous. When coating is broken, the Iron
of the steel becomes the anode and is subjected to accelerated local corrosion
rt 11...-_ _---,
Amm.chloride
flux
,
Pair of hot
rollers
1
1
Galvanized
sheet
1
T T
Hot
air
Molten zinc
U;;,l.~,
~oved
at 425-430'C
Galvanizing of sheet steel

\
Tin plated
Palm
oil
~:~:
sheet
Tinning of sheet steel. The steel passes through a layer of flux into the molten tin and then emerges between
pairs of rollers from a layer of palm oil
Aldad
sheet
Rollers
The cladding of duralumin

138 Applied Chemistry -' /I
Busbar
----~~----+---~~---G
C±>
Electrolyte ----+_ _ _ _,
Cathode jigs for

mounting small obJects
Anode bags filled with

anode metal pellets
Heating
coils
o 0 0 0 _ Air sparger
~~~~~~~--r--
Plating bath
Vat plating process

CHAPTER 2 ALLOYS AND POWDER METALURGY

What are alloys?
Alloys are mixture of two or more elements of which at least one has to be a metal. e.g.
Brass= Cu+Zn, Steel = Fe+C.
What is the purpose of making alloys?
• To increase hardness. E.g. Pb is soft. +O.5%As used for bullets. Pure gold is very
soft. +Cu will make it hard to be used for making bangles.
• To improve tensile strength. E.g. Fe i~ soft. +C will :ncrease its tensile strength many
fold.
• To improve corrosion resistance. E.g. Cu is very susceptible for corrosion. + Sn to give

bronze makes it more corrosion resistant. Fe is attacked by atmospheric air. + Cr to
give stainless steel makes it more corrosion resistant.
• To modify colour. E.g. Brass=Cu+Zn is golden yellow. Cu-Red and Zn-White.
• To modify chemical reactivity. Na is very reactive. Its reactivity is reduced by

amalgamation, i.e., mixing with Hg.
• To improve castability. Pure metals when cooled from molten condition shrink whereas
alloys expand. This property IS used in printing.
• To modify malleability and ductility.
• To decrease the melting point. E.g. Solders.

What is the principle of alloying?
• Interstial type of alloys.
• Substitutional type of alloys.

Classification of alloys: Alloys are classified into,
Ferrous alloys - those containing Fe as one of the constituent metal.
Non-ferrous alloys - those do not contain Fe.
Ferrous alloys are discussed in detail in the SEM-1.
Non Ferrous alloys:

Alloys of Copper: Brasses and Bronzes
Distinguish between brasses and bronzes
140 Applied Chemistry - "
Brasses Bronzes
These are alloys of Cu and Zn These are alloys of Cu and Sn
These are cheap because Zn is cheap These are costly because Sn is costly
These are less corrosion resistant These are more corrosion resistant
These are not easily machinable. These are easily machinable.
Brasses
Name of the alloy Composition Properties Uses

German silver 60% Cu25% Ni15% Zn It is also known as On account of its attractive
Nickel silver. It is a colour, corrosion resistance,
white alloy with these alloys are popular for
variable quantities of tableware and cutlery. It is used
Cu, Zn and Ni. The as coinage material in many
approx. composition countries. It is used in
is Cu 60% + Zn 15% household utensils because of
+ Ni 25%. its white colour and moderate
cost. It is also used for
decorative and architectural
purpose. An alloy with 18% Ni
is widely used for contact
spri ngs in telephone exchanges.
It is used as a base for
electroplated articles and
making resistance wires and
coils.
Commercial Brass 90% Cu 10% Zn It is made up of Cu It is used for making rivets,
90% + Zn 10%. hardware, screws and costume
jewellery.
Bronzes
Name of the alloy , Composition Properties Uses

High phosphor 0.4 to 1% phosphorous In these bronzes, surplus used for making gears, bearings,
bronze + Sn 10to 13% and phosphorous forms a hard marine pumps, bushes, turbine
restCu and brittle constituent blades, fibres for moving coil
copper phosphide (Cul). galvanometer, springs.
It is a fatigue resisting
alloy and is used in
operations where stresses
occur.
It has good abrasion
resistance.
Possess low co-efficient of
friction.
Gun metal 80% Cu + 10% Sn It is hard, tough, strong. It is used for various
and 2% Zn It gives better casti ngs. engineering purpose such as
More corrosion resistant gears, bearings, marine pumps.
Alloys of Alluminium:

Duralumin 95% AI After age hardening tensile It is used for making
4% Cu strength approaches that of aeroplane and automobile
mild steel (60,000 psi) part because of low specific
0.5% Mn
whereas specific gravity is gravity and high strength.
0.5% Mg only 1/3rd that of mild steel.
Possess good mechanical

properties.
But corrosion resistance is

less than that of, pure
Aluminium. This drawback
is overcome by cladding.
Magnalium 90 to 98% AI It is lighter than pure Used in the construction of
+ 2 to 10% Aluminium and Magnesium trucks, buses, commercial
Mg. aircraft, hand tools, beams of
Possess better strength
chemical balances, scientific
Good corrosion resistance instruments, furniture and
other appliances for home
Possess mechanical properties and industry.
comparable to that of brass.
Alloys of Lead: Solders

Tinman's solder 5n67% + Pb33%. Melts at 183°C Used in tin smith's work where
penetration into small openings is often
required. It is used for soldering and
tinning.
Wood's metal Bi 50% + Pb 25 It melts at 71°C -making fire-alarms and automatic

% + Sn 12.5% + sprinklers
Cd 12.5%.
-making safety plugs for pressure
cookers, milk pots
-for boiler and electric fuses
-as solder for joining two metallic
pieces
-as casti ngs for dental works.
Powder metallurgy: Steps involved in powder metallurgy:
1. Metal powder formation:
• Mechanical pulverization or metal communition
• Atomization
• Chemical reduction or oxidation
• Electro deposition
2. Mixing and blending
3. Compacting
4. Sintering
Technology of powder metallurgy: Compacting techniques:
Advantages and disadvantages of powder metallurgy
Powder metallurgy is the art or science of manufacturing useful metallic or alloy articles
by compacting the metal (or alloy constituent) powders and other powders in a die with little or
no melting followed by sintering. When compacting or sintering is done simultaneously, then
the process is called pressure sintering or hot sintering.
Powder metallurgy involves the following steps:
(1) Preparation of metal or alloy powder
(2) Mixing and blending
(3) Compacting
(4) Presintering
(5) Sintering
(1) Methods of powder metal fQrmation

(a) Mechanical pulverization: involves the use of mechanical pulverisers, consisting of
either counter rotating plates or rapidly moving hammers. ,Usually pulverization is
followed by ball milling. This method is used for Mg, AI, Pb and Zn.
(b) Atomisation: involves forcing molten metal through a nozzle into a stream of
compressed air or water, when molten metal breaks into a fine powder. E.g. Zn, Pb,
Sn, AI, Cd, Mg.
(c) Chemical reduction: involves hecWng metal oxide in a current of H2 which reduces
oxide to get pure spongy metal (e.g. tungsten) powder which is suitable for cold pressing
due to its softness aRd pla~ticity.
(d) Electrolytic process: When conventional electrolysis is carried out, a powdery deposit
is obtained on the cathode. Tlie powder is then scrapped, washed, dried and then
pulverized further to get powder of desired size. E.g. powders of Fe, Cu, Zn, Ag, W.
(e) Decomposition: This method is specially used for making Fe and Ni powders from
their carbonyls. These gaseous carbonyls [Fe(CO)s or Ni(CO)) on decomposition yield
very pure Fe and Ni powders.
(2) Mixing and blending: Metal powders in desired proportions are uniformly mixed. For
special purposes, volatalising agents are also included for homogenous distribution of powder.
(3) Compacting: It is the process of obtaining the desired shape of definite dimension from
the loose powder.
A premeasured quantity of the blended powder is taken in a cavity (female) die. having the
desired shape and dimensions. The powder is compressed with the top (male) die. Pressure
ranges from 100 to 1000 MNi m2 • The dies are usually made of high grade hardened steeel with
fine finish. The solid mass is called 'green compact'.
Important compacting methods are:
(i) Cold pressing: The bulk powder with or without small quantities of lubricant or binder
is compacted in rigid dies by axially loaded punch. It is very economical for mass
production of precision. In axial pressing, compact on pressures upto 600 MPa are
used.
(ii) Powder Injection mQulding: The metal powder is converted into a mouldable state or
feed stock by mixing with binder ( most of organic nature). Binder also provides good
satability and green strength of the moulded products. Usually heating is done in
order to melt and force it ttlrugh sprue and runner channel.
Uses: Used mainly for parts with very complex shapes from materials like cemented
carbides, tungsten, heavy alloys, ceramics, etc.
(iii) Cold powder extrusion: The plasticized powder is forced by a piston or screw into a
forming die so that products of constant cross-section e.g. rods, tubes) are produceq.
Plasticisers used in this process are organic binders with medium and high viscosity.
(iv) Roll compaction: It involves passing metal powser in the gap between two rollers.
This technique is used for producing strips, sheets, etc. used in batteries, electronic
tubes, thermosatats, bimetallic applications.
(v) Hot compaction: Compaction is done at higher processing temperature and pressure.
The powder is placed in a rigid die and then compacted using direct resistance heating
or induction currents. The materials used for tooling are graphite, tungsten, cobalt
alloys, fibre rei'nforced carbon, heat resistant alloy steel.
(4) Presintering: is the process of heating the 'green compact', to a temperature below the
sintering temperature. The objective is to remove the lubricants and binders added during
blending. It also enhances the strength of the 'green compact'. Presintering is essential for metals
like tungsten (for getting carbide) which cannot be machined after sintering.
(5) Sintering: Compaction doesnot provide cohesiveness and strength. The compacted and
presintered pieces are heated in a furnace to a temperature below, but close to the melting point
of the basic metal, usually in an atmosphere of hydrogen gas. During this process, the metal
particles sinters, i.e., a portion of them partly meet and bond the remaining particles into coherent
bodies.
Applications of powder metallurgy
Important products manufactured by Powder metallurgy are -
Porous bearings, filaments of electric bulb of tungsten, electric clocks, sewing machines,
gears, cams, cutting tools, parts of gas turbines, refractory metal composites, diamond impregnated
cutting tools, oil pump gears, bearings for automobiles, clutches, brakes, commutator brushes.
Advantages of Powder Metall!Jrgy

(i) Saves energy.
(ii) Rate of production is high.
(iii) Dimensional accuracy is good.
(iv) Good surface finish.
(v) life of component part is longer.
Upper punch
Die
Compact
~rpunch
Compressor
Schematic representation of cold pressing principles: (A) Axial pressing (8) Isostatic pressing
Feed stock
Front cavity
... ( . Heater Rear cavity
Heaters
parting line
Schematic representation of injection moulding equipment
(A) (8)
Tooling for axial hot pressing

(A) By induction heating (B) By direct current heating
Ceramic powders
Ceramics are compounds between metalic and non-metalic elements. They are most
frequently oxides, nitrides and carbides. These are compounds with totally ionic or predominantly
ionic with somecovalent charachter. Ceramic is word derived from Greek word 'Keremikos'
meaning burnt stuff. Indicating that desirable properties of these materials are normally achieved
thourgh a high temperature heat treatment process called firing.
The traditional and commonly used silicate ceramics are the naturally occurring raw material s
such as clay, kaolin, etc. However the processing of advanced ceramics requires pure and well
defined powders which are made synthetically.
Ceramic powders are synthesized by employing a wide variety of techniq·ues which yield
powders of varying particle size distribution and varying properties like chemical and phase
composition, purity, compactability and sinterability.
Dense fine grained parts require powders in lower or even submicron range.
Coarse powders are used in abrasives (AL 20 3
, SiC) and in refractories (AL 20 y Zr0 2)
Some general methods for producing ceramic powders are:-
(1) Solid-state reactions - Many oxide ceram ics are prod uced by thermal decomposition
of hydroxide, carbonates, oxalates, sulfates, by the conventional techniques. Depending
on temperature and reaction time, loose or agglomerated powder or a sintered cake is
produced which can be milled to obtain the desired particle size.
(2) Solid-gas reactions - This method is used for synthesizing oxides, carbides, nitrites by
reacting metals with oxygen, hydrocarbon, nitrogen and ammonia respectively.
(3) Gas phase reactions - This method is useful for producing ceramic powders having
hig~ specific area ( 100m2/g and higher). This process comprises of vapour phase
decomposition or hydrilysis in a flame and is specially used to produce Si02 and Ti0 2 from SiCI 4
and TiCI 4 respectively.
SiCl 4 + 2H 2 0 ~ Si0 2 + 4HCI

(4) Melting - Ceramic oxides such as AI 20 3 and Zr0 2 are manufactured by arc melting
with subsequent milling to produce the desired particle size. rhe process is mainly
employed for producing coarse grade powders.
(5) Reaction from solution - Aqueous or non-aqueous solutions of salts is used for a
number of techniques for producing ceramic powders. This process yields very fine
powders and uniformly distributed mixtures. The process can be carried out by any of
the following techniques-
(i) Precipitation and filtration - of single compound or mixtures.
(ii) Hydrothermal reaction at elevated temperature and pressure - e.g. Zr0 2 from
ZrOCI 2 solution.
(iii) Solution combustion - alcohol based organometallic solutions are burnt in air or
02 to produce oxide particulate.
(iv) Solvent vapourisation or dehydration - by direct evapouration or spray drying.
(v) Sol-gel process - The technique comprises of the three dimensional network of
inorganic matter (gel) from colloidal or molecular solutions of the precursor (sol).
The reaction can take place in aqueous or non-aqueous media, by diminishing the
water content, by changing the pH or surface charge (zeta potential) of the sol.
CHAPTER 3 FUELS
What are fuels?
Fuels are substances which on combustion give heat energy which can be utilized for both
domestic as well as industrial purpose.
What are the characteristics/criteria of good fuel?
High calorific value, Low moisture content, Moderate velocity of combustion, Moderate
ignition temperature, Low contents of non combustible matter, Cheap, Easily available, Should
not produce any obnoxious gases on combustion, Low ash content, Easy to transport and storage.
Classification
1. Based on availability (a) Primary (available in nature e.g.coal, crude petroleum, natural
gas. (b) Secondary (derived from primary e.g. Coke, petrol, LPG)
2. Based on physical state (a) Solid b) Liquid (c) Gaseous
Units of Heat - Calorie, K.Calorie, B.Th.U. C.H.U.
Calorific value: Calorific value is defined as the amount of heat given out by the complete
combustion of unit quantity of fuel.
Types of calorific value
1. Higher or Gross calorific value (HCV or GCV): It is defined as the amount of heat given
out by the cO.mplete combustion of unit quantity of fuel and the products of combustion are
cooled to 1S.S0C (products of combustion not allowed to escape)
2. Lower or Net calorific value: (LCV or NCV): It is defined as the amQunt of heat given out
by the complete combustion of unit quantity of fuel and the products of combustion are allowed
to escape.
Relationship between HCY and LCY:
HCY = LCY + 9H/100 (Latent heat of condensation of steam)
Dulong's formula (Theoretical calculations of HCY)
HCY = 1/100 [8080C + 34,SOO(H-O/8) + 22405] cals/gm
Where C.H.O and 5 are in %.

Analysis of coal
Proximate analysis: Rough analysis:
Contents Temperature and Formula Significance

analysed duration
% moisture Air dried coal is Lossin weight of coal Higher the moisture content lower
heated to 100- % moisture = xl00 is the cal.value.Moisture content
110°C in wt. of coal (air dried) taken tells about
% volatile Moisture free coal is %volatile matter moisture- Coal with high volatile matter
matter heated to 950 + 20°C burns with a long sooty flame.
in a muffle furnace Loss in weight of coal Furce wi II have to be designed to
xl 00 - % moisture
with vented Iid for 7 wt. of coal (air dried)taken give lot of space for burning v.m.
minutes Or Air dried otherwise v.m. escapes withoue
coal is heated to being burnt. i.e., loss of cal.value.
%volatile matter
950+20°C in a muffle not eco friend Iy.
weight of coal Volatile matter
= xl00
wt. of coal (air dried) taken -
% ash Air dried coal sample weight of residue Higher the ash content lower will
heated in a crucible to %Ash= xl00 be the calorific val ue. Disposal of
700-750°C without lid. wt. of coal (air dried) taken ash is a problem.
% fixed carbon %C-l00[%moisture+% V.M.+ % ash] Higher the fixed carbon higher will
be the calorific value and better
will be the quality of coal.
::::
Ultimate analysis of coal: Accurate analysis:
Contents Temperature and Formula Significance

analysed duration
%Cand Combustion method; known :. Percentage of C = Higherthe carbon higher will be the
%H quantity of coal sample is burnt in calorific value and better will be the
an atmosphere of air or oxygen free Increase in weight of KOH tube x 12 x 100 quality of coal.
from moisture and CO 2 and the Weight of coal sample taken x 44
combustion products are captured
in previously weighed bulbcotg.
KOH solution and tube contg.
CaCI 2(anhyd)
%N Kjeldahl's method: Coal sample is Percentage of N = No significance. Generally coal

treated with cone. H 2 S0 4 in contains around 2% N.
presence of CuS04 and K2 S04 and Volume of acid used x Normality x1.4
heated strongly. The contents are Weight of coal sample taken
quantitatively transferred to R.B.
flask and treated with NaOH aAd
liberated ammonia is collected in
known quantity os known normal
H 2S04 . Unreacted H 2 S04 is ~ack
titrated.
%S Bomb calorimeter expt. Is done. Percentage of S =
The contents of the bomb are
collected and treated with barium Weight of BaSO obtainedx32x100
4
chloride or barium nitrate solution.
Weight of coal sample taken in bomb x 233
Precipitated barium sulphate is
filtered, dried and weighed.
Numericals
Liquid fuels: Classification: 1. Paraffin based (residue-paraffin wax.) 2. Asphaltic based
(residue-asphlt) 3. Mixed based.
Refining of crude petroleum: The process by which the crude oil is freed from its impurities,
separated into various fractions having different boiling points, and further treated to remove
undesirable tendencies and to impart specific properties in them is broadly known as "Refining
of petroleum".
Steps involved in Refining: The following are the steps involved in refining of petroleum.
Demulsification: The crude oil mined from the earth's crust is in the form of emulsion.
(Water in oil type or oil in water type) demulsification is basically separation of water from oil.
This can be affected by mechanical; ther~al, chemical, thermo chemical and electrical methods.
The most widely used method is electrical method. In this method the crude oil is subjected to
an electrical field formed by a high voltage alternating current which destroys the emulsion
films. Droplets of the dispersed phase coalesce to form bigger drops which separate out from oil.
Removal of harmful impurities: The impurities like NaCI and MgCI2 corrode the refining
equipment and cause scale formation in the heating pipes. Hence these are removed by electrical
desalting and dehydration techniques. The other harmful impurity is sulfur und its compounds.
These are removed by adding CuO which reacts with these impurities to precipitate CuS which
can be separated by filtration.
Fractional distillation: Fractional distillation is essentially a combination of distillation and
rectification. '
Cracking: The process of breaking down of higher hydrocarbons with high boiling point
into lower hydrocarbons with low boiling point is known as Cracking. Since the demand for
middle order fractions is more, heavy oil which is surplus is used to get more of middle order
fractions.
Thermal cracking Catalytic cracking
No catalyst used Catalyst is used
Higher temperature high pressure used Comparatively lower ternparature and

pressure used
Yield of gasoline 50-60% Yield of gasoline is more than 70%
Octane rating is 70 Octane rating is 80-85
Cracked vapours contain lesser % age Cracked vapours contain greater % age
of aromatics iso-paraffits & less of gum of aromatics iso-paraffits & less of gum
forming diolifines forming diolifines
Time required is comparatively more Time required is comparatively less

Octane rating Cetane rating
The percentage by volume of iso-octane in a The percentage by vol ume of cetane in a mixture
mixture of iso-octane and n-heptane which has of cetane and a-methyl naphthalene which has
the same knocking characteristics as that of fuel the same knocking characteristics as that of fuel
under test. under test.
Octane rating is used for petrol. Cetane rating is used for diesel.
Octane rating increases in the order,St.chaln Cetane rating increases in the orderSt.chain
alkanes> branched chain alkanes> alicyclics > aromatic alkanes < branchedchain alkanes < alicycl ics < aromatic
hydrocarbons hydrocarbons
The fuel with high octane rating has low cetane The fuel with high cetane rating has low octane
rating. rating.
Antiknocking agents
The high compression ratio used in the modern internal combustion (lC) engines demands
petrol of high quality with least tendency of knocking. The octane rating of many fuels can be
increased by adding certain antiknock agents to petrol. These compounds which are added to
vehicular or aviation petrol to improve their knocking property are called "Antiknock agents".
The commonly used anti knocking agents are,

(i) Tetraethyl lead
(i i) Tetramethyl lead
(iii) Mixed methylethyl lead
Working of TEL
Among the antiknock agents, TEL (Tetraethyl Lead) is the most widely used, since it is
cheap and more effective in increasing the octane rating of fuels. Normally 4cc of TEL is added
per gallon of gasoline. It is highly toxic and 1:<15 a specific gravity of 2.62. Generally it is used
with ethylene dibromide or ethylene dichloride.
During combustion of gasoline, TEL forms Ph and PbO. These species act as free radical
chain inhibitors and thus prevent the propagation of explosive chain reaction and thereby
minimizing knocking. However, ifTEL is used, the species Pb and PbO formed may get deposited
on engine parts and cause mechanical damage. In order to minimize damage caused to the
engine parts, TEL is always used with ethylene dibromide or ethylene dichloride. The function
of these halogen compounds is to convert the less volatile Pb and PbO into more volatile PbBr2
and PbCI 2 which escape into air along with exhaust gases.
Bio-fuels: Fuels obtained from bio-mass. Bio-mass is any material of plant or animal origin.
1. Bio-diesel
Trans esterification:
CH 2 0COR 1 catalyst CH 2 0H
I -l.- I
CHOCOR 2 + 3CH 30H <=> 3CH 3COORx + CHOH
I I
CH 2 0COR 3 CH 20H
Triglyceride 3 Methanol Biodiesel Glycerin
(Production of Biodiesel by Trans-esterification method)
2. Bio-ethanol: (Gasohol)
Biomass is a carbonaceous waste of various natural and human activities can be obtained
from numerous sources like by-product of agricultural crops, raw material from the forest, from
sugar industry and wood. The primary advantage of using biol1'lass is that it does not add dangerous
gases like CO to the atmosphere.
Alcohol produced by fermentation of grains, starches, sugars etc. is a good alternative as it
is clean burning.
Drawback - low calorific value compared to conventional fuels.
- utilizing grains for fermentation to produce alcohols for fuels would lead to grain shortage
and hence malnutrition.
Ethanol from starch. Starchy material e.g. grain are first cooked to a gel consistency, cooled
and mixed with malt. Malt contains diastase enzyme which has the ability to convert starch to
fermentable sugar(maltose). This is converted by zymase bacteria to ethnol.
Yeast enzyme) C H 0
6 22 6
Zymase) zymase
Ethyl alcohol from sugar/molasses. Fermentation of sugar by yeast, is essentially used for the
manufacture of ethanol. Yeast contains the enzyme invertse and zymase. The invertase catalyses
the hydrolysis of sucrose in mash of invert sugar.
Invert sugar are subsequently converted into about equal parts of ethyl alcohol and
carbondioxide by action of zymase enzyme
Zymase) 2CH CH OH + 2CO

3 2 2
Microbiological aspects. Presently, large scale ethanol plants use saccharomyces strains.
Most yeast grow well on a variety of amino acids, purines and pyrimidines as the sole source of
nitrogen. Biotin and pantothenate are essential for all strains of saccharomyces. Even if sufficient
nutrients such as sugar, nitrogen and vitamins are present, it is the dissolved oxygen in the
solution which limit the population of yeast in the fe rmentation medium . Once the dissolved
oxygen is depleted during fermentation the yeast population slows and eventually ceases. Anionic
detergents, sorbic acid, dithyl pyrocarbonate (DEP) and the antibiotics cyclohexamide, antimycin
A and nystalin completely inhibit growth of more common yeasts. In fermentation of lignocellulosic
hydrolysates, acetic acid, furfural and ligninderived phenolics are found to be inhibitory. The
best ethanol yields are generally obtained at pH 4.5-4.7. In lightly buffered media, the optimum
starting value is nearer pH 5.5. After fermentation is complete this falls to about pH 3.5 yeasts
survive in the approximate range of pH 2.0-8.6 The temperature for growth of yeasts is about
25°C. Since yeasts growth and fermentation both produce heat, cooling may be necessary to
maintain the desired temperature.
Coarse
CuO gauge copper oxide
Silver gauge
Pure
oxygen-.
Free from
(Co2 & moisture)
Combustion apparatus
Coal+conc H2SO. Kjeldahl trap

-y- '
+
H2SO.+catalyst
&
.. Condenser
Standard acid
Nitrogen estimation by kjeldhal method

I----:----;=:....-~Compressed
gas
Natural gas Crude oil
Earth's
crust
Oil
water
Compressed __-+
air
lJt t · '\ r-~-!--::--.-=-=-t-=--::--'-----=-~etroleum
I I ~~t ~ ~
Petroleum + +~§ - ~~
~~~~~~ t t J~ ~~~~~~
==========~~=====
-------------~~====-----
==========~=~~=====
(a) Mining of crude oil from oil-well (b) Mechanical pumping of oil
(, to (2 Gases
Fractionating
.l column
r;=====: liquefied
gas
petroleum
•
I!
! chemicals
!
fract i ons
decreasing
in density
and boiling petrol for
point veh icals
~. ~jelfUel'
• paraffin
for li ghting
and heating
diesel fuels
.& ~ fubricating oils,

• ~ waxes polishes
fuels
6QOO(
M
.Ji"_ _"_~ -l bships
fadorie;
em '
CJ:!rtraI
I~
>(70 resiou~
bi1unen for roads
and rooling
Fractional distillational crude petroleum
Heavy oil 450-550·( ) Gasoline

(e12 & Higher) Porous Siliea-Atumina (e5~(1 0)
Zeolite
(catalytic Cracking)
Pre-Heater Catalyst
(425-450°C) Chamber
Fractionating
o Gasoline &
(425-450 C coloumn
Dissolved gases
Fig. 3.S Fixed-bed catalytic cracking
Petorcrops
I
vegetatle Oil +
Essential Oil
l
Exudates & Extracts
~
Edible Oil
* +
Non-Edible Oil
EucalYPt Juvenile
1
Latex Beari ng
Lamiaceace Euphorbiaceace
Jatropha Oil Cassava
~~~
Oil Petroleum Nuts
Latex
1
Extractives
Hydrocarbon Vegetable Phenolic

heavy light . Oil Wax
comr d
UquJFuelS
j
Liquid Fuels Phenolic Re~n
1
Alcohol
Adhesive
1
Organic Solvent
Classification of Petrocrops
Production of Hydrocarbons from Plants (Petrocrops)

The latex of some plants contain petroleum like hydrocarbons which can be extracted by
organic solvents as a biocrude analogus to crude petroleum. Biocrude can be hydro
cracked(cracked with hydrogen) to yield oil. Such plants are called petrocrops. These are
lactiferous plants (plants belonging to euphorbiaces, asclepiadaceae and apocynaceae families)
growing in arid and semiarid regions specially in uncultivated lands. These plants secrete milky
latex. The latex can be collected and stored or it can be extracted from the biomass using
organic solvents. This latex is a rich source of hydroc r.lCkable hydrocarbons and is called
'biocrude'. This can be converted into petroleum products using metal oxide catalysts. More
than 400 species of petroleum plants belonging to different families are known.
Revis/an at a Glance 157
CHAPTER 4 COMPOSITE MATERIALS

Introduction:
Recent technological advancements in various fields demand for materials with unusual
combinations of properties that can not be met by the conventional metal alloys, ceramics and
polymeric materials. This is especially true for materials that are needed for aerospace, underwater
and transportation applications. For example, aircraft engineers are always on the look out for
structural materials that have low densities are strong, stiff, and having more corrosion, abrasion
and impact resistance. This is a rare combination of characteristics, since generally strong materials
are relatively dense; also, increasing the strength and stiffness generally results in a decrease in
impact strength.
Composite materials (or composites for short) are engineered materials made from two or
more constituent materials with significantly different physical or chemical properties and which
remain separate and distinct on a macroscopic level within the finished structure. In simple
words, a composite is considered to be any multiphase material that exhibits a significant
proportion of the properties of both constituent phases such that a better combination of properties
is realized.
Class ification:
Composite materials are made up of two phases; one is termed the "Matrix" phase, which
is continuous and surrounds the other phase, often called the "Dispersed" phase. The properties
of composites are dependant on the properties of the constituent phases, their relative amounts,
and the geometry of the dispersed phase namely the shape and size of the particles, thei r distribution
and orientation. Based on the type of the dispersed phase and its geometry the composite materials
are classified as follows.
Fiber
Reinforced
Large Dispersion Continuous Discontinuous Laminates I Sandwich

particle strengthened (aligned) (short) panels
Charachteristic properties of composite materials

Important advantages of composite materials over the conventional materials like, metal,
polymer, ceramic are
1. Higher specific strength with lower specific gravity
2. Higher specific stiffness
3. Maintains strength even upto high temperature
4. Better toughness
5. Impact and thermal shock resistance
6. Cheaply and easily fabricable
7. Better creep and fatigue strength
8. Lower electrical conductivity
9. Lower thermal expansion
10. Better corrosion and oxidation resistance.
Particle reinforced composites

Particles used for reinforcing include ceramics and glasses such as small mineral particles,
metal particles such as aluminum, and amorphous materials, including polymers and carbon
black. Particles are used to increase the modulus of the matrix, to decrease the permeability of
the matrix, to decrease the ductility of the matrix. Particles are also used to produce inexpensive
composites. Reinforcers and matrices can be common, inexpensive materials and are easily
processed. An example of particle reinforced composites is an automobile tire which has carbon
black particles in a matrix of polyisobutylene elastomeric polymer. Another example is
spheroidized steel where cementite is transformed into a spherical shape which improves the
machinability of the material. Another example for particle-reinforced composite is concrete
where the aggregtes (sand and gravel) are the particles and cement is the matrix. Particle reinforced
composites support higher tensile, compressive and shear stresses.
Particle Reinforced Composites
Spheroidized Steel
Matrix: Particle:
Ferrite Fe3C
(a - iron) (cementite)
Ductile Brittle
Matrix: Particle:
Rubber Carbon
(Compliant) (Stiffer)
Automobile Tire
Examples for particle-reinforced composites. (Spheroidized steel and automobile tire)

Fiber reinforced composites
Reinforcing fibers can be made of metals, ceramics, glasses, or polymers that have been
turned into graphite and known as carbon fibers. Fibers increase the modulus of the matrix
material. The strong covalent bonds along the fiber's length gives them a very high modulus in
this direction because to break or extend the fiber the bonds must also be broken or moved.
Fibers are difficult to process into composites which makes fiber-reinforced composites relatively
expensive. Fiber-reinforced composites are used in some of the most advanced, and therefore
most expensive, sports equipment, such as a time-trial racing bicycle frame which consists of
carbon fibers in a thermoset polymer matrix. Body parts of race cars and some automobiles are
composites made of gl~ss fibers (or fiberglass) in a thermoset matrix.
The arrangement or orientation of the fibers relative to one another, the fiber concentration,
and the distribution all have a. significant influence on the strength and other properties of fiber-
reinforced composites. Applications involving totally multidirectional applied stresses normally
use discontinuous fibers, which are randomly oriented in the matrix material. Consideration of
orientation and fiber length for a particular composites depends on the level and nature of the
applied stress as well as fabrication cost. Production rates for short-fiber composites (both aligned
and randomly oriented) are rapid, and intricate shapes can be formed which are not possible
with continuous fiber reinforcement.
.. ReinforcedCompo:ites
.~~r?~~. r.~~~~
~¥6nlrM~~~~
;!i;pt~~ontirl'~oUS :; DiscontinuoUS
and random Iy
.::~~::,~::.:-;-':; : ..
.brierj~ed tfi bel's.
• ('.::-..:--:- .... "',·:-F'-'· :-./;,.
Fiber orientation in fiber reinforced composites
Laminar Composites
Is composed of two-dimensional sheets or panels that have a preferred high strength direction
such as is found in wood and continuous and aligned fiber-reinforced plastics. The layers are
stacked and cemented together such that the orientation of the high-strength direction varies
with each successive layer. Laminations may also be constructed by using fabric material such as
cotton, paper or woven glass fibers embedded in plastic matrix. Thus a laminar composite has
relatively high strength in a number of directions in the two dimentional plane; however the
strength in any given directions, of course, lower than it would be if all the fibers were oriented
in that direction. One example of a relatively complex structure is modern ski and another
example is plywood.
The stacking of successive oriented fiber-reinforced layers for a laminar composite

Sandwich Panels
Sandwich panels, considered to be a class of structural composites are designed to be light-
weight beams or panels having relatively high stiffness and strenghts. They generally thick enough
to withstand tensile and compressive stresses that result from loadimg. A sandwich panel consists
of two strong outer sheets which are called face sheets and may be made of aluminum alloys,
fiber reinforced plastics, titanium alloys, steel. Face sheets carry most of the loading and stresses.
Core may be a honeycomb structure which has less density than the face sheets and resists
perpendicular stresses and provides shear rigidity. Core materials typically fall within three
categories: rigid polymeric foams(i.e . phenolics, epoxy, polyurethanes),wood (i.e.balasa wood)
and honey combs.
Sandwich panels can be used in variety of applications which include roofs, floors, walls of
buildings and in aircraft, for wings, fuselage and tailplane skins.
Schematic diagram showing the construction of a honeycomb core sandwich panel. (Reprinted with
permission from Engineered Materials Handbook, Vol. 1, Composites ASM International, Metals Park, OH,
1987.)
CHAPTER 5 GREEN CHEMISTRY

.:. Introduction: Scope and Need of green chemistry: Cleaning up the environment and
more importantly preventing pollution are important issues in today's world . The chemical
industry is traditionally viewed more as a cause than as a solution to pollution. Green chemistry
offers unique solution in the area of waste prevention. Its novel approach blends the application
of chemistry with economic growth and environmental preservation. It tells us to develop a
strategy for sustainable chemical industries. To achieve conservation of the limited resources
through cost effectiveness and pollution prevention . Therefore the basic axiom of green chemistry
is to design products and processes that reduce or eliminate the generation of all wastes .
•:. Twelve Principles of green chemistry
1. Prevention of waste formation

2. Atom economy
3. Less hazardous chemical synthesis
4. Designing safer chemicals
5. Safer solvents and auxiliaries
6. Design for energy efficiency
7. Use of renewable feed stocks
8. Reduce derivatives
9. Catalysis
10. Design for degradation
11. Real time analysis for pollution prevention
12. Inherently safer chemistry for accident prevention •
•:. Green chemistry principle of atom economy: Atom economy means maximizing the
incorporation of materials from the starting materials or reagents into the final product. It is
essentially pollution prevention at the molecular level. It is synthesizing the product by putting .
together basic building blocks, rather than breaking down larger molecules and discard most of
them as waste .
•:. Numericals:
.:. Illustration of application of green chemistry for some reactions.
o Synthesis of Indigo
Indigo, the dye used to colour Jeans, can be made enzymatically by removal of the side
chain of Tryptophan to give Indole, which can be dehydroxylated enzymatically, and then
oxidized with oxygen to Idigo. The presently used commercial process starts with highly toxic
aniline and produces considerable amount of waste salts leading to disposal problems.
Conventional route
NH,
0-
Aniline ~ ~a
+OCH,COOH NaoH 2 NaNH,
KOHNaOH
fusion
- LX>~ H
CataJylic route
NH,
~I"""""
CX>-
AgCatayst
~ + HOOH,OH,OH
gas phase
Aniline Ethyiene glycol Indole H
Alkyl hydroperoxide
2RO,HlMo(CO),
Indigo
1. The conventional route involves caustic fusion at two stages leading to the formation
of large quantities of salts
2. The catalytic route selectively oxidizes indole, which is environmentally benign.
Newer enzymatic process of conversion of glucose seems to be more promising as it is eco-

friendly.
o Synthesis of Adipic acid

Traditional pathway
0 OH
@ Ni AI 20
370-BOOpsi
3
)
0 Co-0 2
)
120-140psi
6 +
6
benzene cyclohexane cyclohexanone cyclohexanol
j
H02C-(CH 2)4 - C0 2H
Adipic acid
Alternative pathway
OH
~OH E-coli E-coli
HO~OH
D-glucose 3-dihydroshikimate
H02C-(CH2)4C02H
50 psi Adipic acid
cis, cis-muconic acid

Green chemistry principle involved.
1. Traditional path way uses benzenfossil fuel based feedstock
Alternative pathway uses glucose-a renewable feed stock. (use of renewable feedstocks)
2. Traditional pathway - requires high press & temp (energy).
Alternative pathway - enzymatic - less energy requirement. (design for energy
efficiency).
o Friedel Craft's reaction

Fridel Craft's reaction:
In 1980,
AICI 3
reagents ) product yield < 60%
In 1990,
Pd/C
reagents - - 4 ) product yield> 75%
2005 Onwards
ZSM-S
reagents --~) product yield> 85 %
(1) No corrosive chemical like AICl 3
(2) ZSM-5 can be used in small quantity repeatedly to conduct same reaction .
•:. Industrial applications.
o In waste utilization
The best example for waste uti Iization is conversion of glycerin to propylene glycol. G Iycer! n
I waste product obtained in the biodiesel production.
CH 2 0COR, catalyst CH 20H
I J, I
CHOCOR 2 + 3CH 30H + CHOH
I I
CH 20COR3 CH 2 0H
Conversion of glycerine to propylene glycol.
CH 2 -OH CH 3
I I
CH-OH CH-OH
I
CH 2-OH CH 2 -OH
Glycerine Propylene glycol
Copper chromite is used as a catalyst for the conversion of glycerin into propylene glycol.
Propylene glycol produced in this way is cheap and can replace more toxic ethylene glycol that
is the primary ingredient used as automobile antifreeze.
o Use of supercritical fluids
A fluid heated to above the critical temperature and compressed to above the critical
pressure is known as a supercritical fluid. Frequently the term, compressed liquid, is used to
indicate a supercritical fluid, a near-critical fluid, an expanded liquid or a highly compressed gas.
Applications and commercial processes of supercritical fluids

1. Supercritical Fluid Chromatography
2. Fractionation
3. Reactions
4. Applications in the material and polymer industry
5. Food applications
6. Pharmaceutical applications
7. Environmental applications
8. Applications in nano-electronics
Dill!ethyl carbonate- A Green reagent

Dimethyl carbonate (DMC) is a safe methylating agent which can be used in place of
methyl halides and Dimethyl Sulphate (toxic) in the methylation of various compounds. DMC is
made by clean process, it is non toxic, biodegradable and can be used in presence of catalytic
amount of base.
It can be prepared by two routes.
1. From propyleneoxide and carbon dioxide using a catalyst
Smectite ~ Smectite
(Mg doped) R (Mg' doped) CH 3 CH 3
2. Conversion of supercritical CO 2 to DMC by the reaction with methanol in the presence

of catalytic amount of dialkyl tin oxide or its derivatives.
2MeOH + CO 2 Catalyst
Supercritical
Advantages of DMC
1. It is ecofriendly and is an alternative to Dimethyl Sulphate for methylation and Phosgene
for carbonylation reactions.
2. DMC is highly selective towards mono-C and mono-N methylation reactions. .
3. DMC mediated reactions are catalytic reactions thereby avoiding the formation of
undesirable inorganic salts as byproducts.
4. DMC is biodegradable.
CHAPTER 6 CATALYSIS
What is catalysH
A catalyst is defined 'as a substance which alters the rate of a chemical reaction, while itself
remaining chemically unchanged at the end of the reaction'.
This implies that there can be two types of catalysts.
A catalyst which enhances the rate of a reaction or called a positive catalyst and the
phenomenon positive cata,ysis or simply catalysis.
E.g. Increased rate of decomposition of KCI0 3 in presence of Mn02 •
A catalyst which retards the rate of a reaction or called a negative catalyst and the
phenomenon negative catalysis.
E.g. Decreased rate of decomposition 9f H 20 2 in presence of dilute acids or glycerol.
What is catalysis?
fraction of the collisions bring about a reaction. A collision is fruitful only when colliding molecules
particular reaction. These activated molecules, on collision form an activated complex or in
One method to increase the kinetic energy of the reacting molecules is, to increase the
temperature.
catalyst.
A catalyst lowers the activation energy of the reaction by providing an alternative new
What are the types of catalysis?
Heterogeneous catalysis
Both the reactants as well as the catalyst are in the same phase. The reaction involves
molecules, ions, or free radicals as intermediates.
Homogenous catalysis can occur in gaseous and liquid (solution) phase.
• Examples of homogenous catalysis in gas phase-
(i) Oxidation of sulphur dioxide to sulphur trioxide by the oxides of nitrogen.

1
[NO] + - 0 ~ N02
2 2
gas gas gas
5°2 + N0 2 ~ 503 + [NO]

gas gas gas gas
(ii) Decomposition of ozone in presence of nitric oxide.
NO(g) ) 302(g)
• Examples of homogenous catalysis in solution phase
(i) Hydrolysis of esters catalysed by an acid or alkali
(ii) Decomposition of H 20 2 catalysed by iodide ion
(iii) Inversion of cane sugar catalysed by hydrogen ion from a mineral acid
glucose fructose
(II) Heterogeneous catalytic reactions
Reactants and the catalyst are of different phases and the reactions proceed at an interface
. between the two discrete phases.
• Heterogeneous catalysis with solid reactants
(i) Decomposition of potassium chlorate in presence of manganese dioxide catalyst
2KCI03 (s) + [Mn0 2] (s) ---7 2KCI + 302 + [Mn0 2](s)
• Heterogeneous catalysis with liquid reactants
(i) Decomposition of aqueous solution of hydrogen peroxide in presence of Mn02as catalyst
2H 20 2(1) + [Mn0 2] (s) ---7 2H 20 + 02 + [Mn0 2](s)

(ii) Hydrogenation of animal and vegetable oils using Ni as catalyst.
Heterogeneous catalysis with gaseous reactants
(i) Reaction between sulphur dioxide and oxygen wsing finely divided platinum or vanadium
pentoxide as catalyst, during the manufacture of sulphuric acid by contact process.
2S02 (g) + 02(g) + [PtorVPs](s)~2S03(g) + [PtorVps](s)
(ii) Oxidation of NH3 in presence of platinum gauze as catalyst used in the manufacture of
nitric acid.
4NH3 + 502 + [Pt](s) ~ 4NO(g) + 6H 20(I) + [Pt](s)

(iii) Synthesis of ammonia by Haber's process using nitrogen and bydrogen in the presence
of Fe as catalyst.
N 2(g) + 3H 2 + [Fe](s) ~ 2NH3 + [Fe](s).

Homogenous catalytic processes in solution generally proceed with the formation of an
intermediate compound followed by its decomposition to yield the product and regenerate the
catalyst.
Egs: (i) Catalytic oxidation of 502 in presence of NO as catalyst in the chamber process for
the manufacture of sulphuric acid.
NO + 1h 02 ~ [N0 2]
[N0 2] + S02 ~ 50 3 + NO
(ii) Formation of diethyl ether from ethanol in presence of H 2S0 4 as catalyst.
C2H sOH + H 2S04 ~ [C 2H sHSOJ + Hp

[C 2H sHS0 4] + C2H sOH ~ C2HpC 2H S + H 2S0 4
Characteristics of a good catalyst:
(1) A catalyst remains unchanged chemically at the end of the reaction.
The amount and chemical composition of a catalyst remains unaltered at the end of the
process. However, it may undergo a physical change.
E.gs: (i) Granular Mn0 2 employed to catalyse the decomposition of KCI0 3 changes to a fine
powder at the end of the reaction. (ii) Platinum gauze used as catalyst for the oxidation of NH3
becomes rough after sometime.
(2) A small amount of catalyst is sufficient to catalyse a reaction.
E.gs: (i) C,upric ions even at a concentration of 1 g.ion in 106 liters cause considerable
oxidation of Na2S0 3 by oxygen.
170 Applied Chemistry· II
(ij) Colloidal platinum present at a concentration of 1 g.atom in 106 liters catalyse the
decomposition of H 20 2.
(3) A catalyst does not affect the position of equilibrium in a reversible reaction.
A catalyst affects the forward and backward reactions in a reversible process to the same
extent. Thus it helps in attaining the equilibrium more quickly, although the position of equilibrium
constant remains unchanged.
Egs: (i) The same position of equilibrium was reached in the reaction of S02 and 02 using
three different catalysts, namely V 20 5, Pt and Fe 20 3 •
(ii) In the Haber's process for the manufacture of ammonia, the reaction between N 2and H2
is very slow, but in presence of Fe as catalyst, the equilibrium is reached quickly. However, the
percentage yield remains the same.
in presence of catalyst
.
.............. Eqiulibrium
••••••....••••• .... -----...;in:3Jab...se-nce-of-ca-ta-IY-st--------
- - -...... Time
Effect of catalyst on time taken for establishment of equilibrium

(4) A catalyst is specific in its action.
A catalyst that is effective in alteril')g the rate of a particular reaction, may not necessarily be
effective for another reaction. Also, different products are obtained in presence of different
catalysts although the reactants are the same.
E.gs: (i) Ethanol is converted into ethanal, CH 3CHO, in presence of hot Cu as catalyst while
it gives ethene, C2 H 4 , when passed over hot A1 2 0 3 •
I
I Progress 01 reaction
Products
Action Dynamics & Catalysis
Cu )CH3CHO
(ii) Carbon monoxide and hydrogen react at high temperature and pressure, to give different
products in presence of different catalysts.
Ni
~CH.+H20
CO + Hz Co ) mixture of higher paraffins.

(5) The efficiency of a catalyst depends on its physical state.
A catalyst is found to be far more effective when it is present in a fine state of subdivision as
compared to when used in bulk or in lump form.
E.gs: (i) Finely divided nickel has been found to be more effective than pieces or lumps of
nickel.
(ii) Platinum black, platinised asbestos or finely divided platinum is far more effective than
using lumps of platinum.
(6) Change of temperature alters the rate of a catalytic reaction.
(7) The activity of a catalyst can be altered by the presence of a foreign substance.
If this substance increases the activity of catalyst, it is called promoter and if the presence of
the foreign substance inhibits or destroys the catalytic activity, then it is called as poison.
E.gs: (i) Molybde'num acts as a promoter for iron used as catalyst in the manufacture of NH3
by Haber's process.
(ii) Arsenic oxides poison the platinum used as catalyst for oxidation of 502 to 50 3 in
contact process for manufacture of H 2S0 4 ,
Activation energy:
fraction of the collisions bring about a reactiol). A collision is fruitful only'when colliding molecules
particular reaction. These activated molecules, ,on collision form an activated complex or in
One method to increase the kinetic energy of the reacting molecules is to increase the
temperature.
catalyst.
A catalyst lowers the activation energy of the reaction by providing an alternative new
Adsorption theory:
Heterogeneous catalytic processes, particularly those reactions between gaseous reactants

catalysed by a solid catalyst.
The reaction is initiated by adsorption of the reactant molecules on the surface of the
catalyst. This occurs as a result of residual forces on the catalyst surface.
The following steps are involved sequentially:
(i) Adsorption of the reactant molecules on the catalytic surface by weak Vander Waals
forces or'by formation of partial chemical bonds (chemisorption).
Revision at a Glance . 173
(ii) Formation of unstable and intermediate activated complex between the adsorbed reactant
species and the catalyst sUrface.
(iii) Decomposition of the unstable activated complex to form the products.
(iv) Desorption of the stable products formed to release the fresh catalytic surface for fresh
cycle of reaction.
The exothermic nature of the chemisorption process supplies the energy required for
loosening or Giissociation of bonds present in the adsorbed reactant molecules.
It is important that the atoms should not be adsorbed so strongly on the catalyst surface that
they act as catalyst poison.
CO, °
Transitional metals of Groups IV, V and VI and Fe are capable of chemisorbing gases like
2
, H , and N • Co and Ni also can chemisorb the above gases except N • The heat of
2 2 2
adsorption of H2 is relatively low for Mi, Pt, Pd, Rh, Ir, and Ru and hence they are used effectively
as hydrogenation catalysts. Also, the heats of adsorption of N2 on Pd, Rh, Ru, etc. are very low
whereas those V and Cr group are quite high, while that on Fe, it is intermediate. In case of
synthesis of ammonia, from N2 and H 2, the catalytic activity of Fe is found to be the best.
For efficient catalytic activity, the crystals of transitional metal should possess electronically
incomplete d-bands i.e., unpaired atomic d-orbitals.
The above mechanism can be illustrated by the following example:
Hydrogenation of ethene to ethane in presence of Ni catalyst.
H H
I I
+H-H
Ni as)
catalyst H-<f-<f- H
H H
Mechahism of catalysis:
Step-1 H
... __ ............ _......H
. Adsorption of hydrogen molecules on
, the catalyst surface due to residual
, valence bonds of Ni atoms.
Step-2
~IIIIII8:II' H
Catalyst surface
H
Since the bond length of H-H bond is
lesser than the bond length of Ni-Ni
, bond, the H-H bond is Stretched,
weakened, and hence broken into atoms
-08::
" I I I I I I I I I I I I I I
' - Catalyst surface

Ii
which are held to the catalyst surface by
chemical bonds.
Step-3
H.......... /H
/ C,"."""."""" .. " " " .............
C The chemisorbed H atoms are attached
H ,, ,,, H
to ethene molecules by partial chemical
H bonds, thus forming an unstable
activated complex.
' - Catalyst surface
Step-4 ~ .......... C C/ ~ THe unstable activated complex is

H/ ethane ......... H decomposed to yield the product
-:0." I I ,all,
(ethane) and the catalyst surface is
released for a fresh cycle of the above
steps.
Catalyst surface
Zeolites and Zeotypes

Zeolites are crystalline alluminosilicates comprising corner sharing Si0 4 and A10 4 -
tetrahedral and consisting of a regular system of pores (channels) and cavities (cages) with
diameters of molecular dimensions (0.3 to 1.4 nm). A large number or zeolites are known,
which are naturally occurring, but most of which are synthesized.
Analogus structures containing T0 4 elements, e.g. B, Ga, Fe, Ge, Ti, V, Cr, Mn and Co have
also been synthesized and are called as zeotypes. They include for example AIPOs, SAPOs and
MeAPOs.
As with amorphous aluminosilicates, zeolites contain an extra frameworK cation, usually

Na+, to maintain electrical neutrality with the A104 - moiety. Since an A104- moiety is unstable
when attached to another A10 4- unit, it is necessary that they are separated by atleast one Si04 unit.
The acid form of zeolites
The most important feature of zeolites (and zeotypes), in the context of catalysis is the
presence of a regular structure containing molecular sized cavities and channels that make them
unique as shape selective catalysts for a wide variety of organic transformations.
Basic units in zeolite

In fig. 6.8 eight T0 4 octahedra are joined together in a ring, commonly referred to as the
eight ring structure as there are eight oxygen atoms in the ring. These basic ring structures are
combined to form three dimensional arrangements which constitute the building blocks for the
zeolite. For e.g. one of these building unit is sodalite cage, a truncated octahedron with four
membered rings made during truncation and six membered rings as part of the original octahedron.
In zeolites derived from the sodalite unit these cages are joined together through extensions
of either the 4- ring or 6-ring. Zeolite A is an example of the former. The centre of the structure
comprises a supercage with a diameter of 1.14 nm, surrounded by eight sodalite cages. Access
to these cages is via the six mutually perpendicular 8- ring openings having a diameter of 0.42 nm,
enabling hydrocarbons to enter.
Transition metal halide clusters

Linus'Pauling showed that "MoCi/ consisted of M06 octahedra. F. Albert Cotton established
that "ReCI3" in fact features subunits of the cluster Re 3CI 9 , which could be converted to a host of
adducts without breaking the Re-Re bonds. Because this compound is diamagnetic and not
paramagnetic the rhenium bonds are double bonds and not single bonds. In the solid state
further bridging occurs between neighbours and when this compound is dissolved in hydrochloric
acid a Re 3CI 1/ - complex forms. An example of a tetranuclear complex is
hexadecamethoxytetratungsten W 4 (OCH3)12 with tungsten single bonds and molybdenum chloride
(Mo6C1 s)CI 4 is a hexanuclear molybdenum compound and an example of an octahedral cluster.

A related group of clusters with the general formula MxMo6XS such as PbMo6Ss form a Chevrel
phase, which exhibit superconductivity at low temperatures. The eclipsed structure of potassium
octachlorodirhenate(lIl), K2 Re2CI s was explained by invoking Quadruple bonding. This discovery
led to a broad range of derivatives including di-tungsten tetra(hpp), the currect (2007) record
holder low ionization energy.
Carbon membranes
Nanoparticles due to their extremely large surface to volume ratio are efficient catalyst. Application
of nanoparticles in catalysis ranges from fuel cell, to catalytic converter, photocatalytic devices.
Carbon nanotube membranes consists of a vertically aligned array of carbon nanotube
surrounded by a matrix of silicon nitride or on a silicon chip surrounded by ceramics matrix.
Membranes that have carbon nanotubes as pores could be. used in desalination and
dem i neral ization.
Salt removal from water, commonly performed through reverse osmosis, uses less permeable
membranes, requires large amounts of pressure and is quite expensive. However, these more
permeable nanotube membranes could reduce the energy costs of desalination by up to 75 per
cent compared to conventional membranes used in reverse osmosis.
Carbon tube
r
I,...
Ceramics maIne
between CNT
Porous silicon chip support
Carbon nanotube membrane

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ATEXTBOOK OF

Dr. Sbanta s. Sbarma

Published by Mrs. Meena Pandey

2. ALLOYS AND POWDER METALLURGY 40-50

4. COMPOSITE MATERIALS 85-94

5. GREEN CHEMISTRY 95-105

REVISION AT A GLANCE 124-176

The most familiar example of corrosio'n is rusting of iron.

• Plant failure and subsequent shutdown

• Replacement of corroded equipment

• Contamination or loss of the product (e.g., from corroded container)

1.1.1 Nernst theory

1.1.2 Standard electrode potential

Table 1.1: Standard electrode potentials (reduction) at 25°C.

Metal ion Potential in volts

Tablel.2: Galvanic series.

Active (or anodic) 1. Mg

1.2. THEORIES OF CORROSION

(i) Dry or Chemical corrosion

(ii) Wet or EIect ro-chem ical or Immersed corrosion.

1.2.1. Dry or Chemical corrosion

(ii) Action of anhydrous inorganic liquid with the metal surfaces.

1.2.2. Wet or Electrochemical corrosion

Fig. 1.1 Mechanism of wet corrosion by hydrogen evolution

Fe+ 2 + 20H-~ Fe(OH)2J..

:::: ::: :::::::.::-- -AqueOUS neutral ;iluikln -:::::::::: : ::: :::

: : : : : : : : : : : : : : Rust : : : : : : : : : : Rust :;: ~ ~ - ~-: ~ -;:-;H- ::::

Fig. 1.2 Mechnism of wet corrosion by oxygen absorption

1.3. TYPES OF ELECTRO-CHEMICAL CORROSION

1.3.1 Galvanic cell corrosion

Some common examples of galvanic corrosion-

Electronic current Electrolyte

Fig. 1.3 Galvanic corrosion

1.3.2 concentration cell corrosion

The concentration cell can be represented as;

Some more examples of differential aeration corrosion:

Fig. 1.7 Localized corrosion of oxygen-deficient areas

Fig. 1.8 Pitting corrosion at the surface of iron

1.3.3. Intergranular corrosion

1..--~:::====::::- Precipitated compound

Fig. 1.9 General intergranular attack

1.3.4. Stress corrosion

Stress corrosion is characterized by a highly localized attack when overall corrosion is

Stressed Part ~~~:;:;;::~r- Anode (strained part)

Fig. 1.10 Stress corrosion

1.4. CONCEPTS OF POLARIZATION AND OVERVOLTAGE

Ed = (Ecathode + Eo) - (Eanode + Eo)

1.5 FACTORS AFFECTING RATE OF CORROSION

• Nature of the metal

• Nature of the environment

Nature of the metal

1.6 METHODS TO DECREASE RATE OF REACTION

1.6.1 Cathodic protection

The two types of cathodic protection are:

::::0-:: .... ...

(ii) Impressed current cathodic protection - An impressed current is applied in opposite

1.6.2 Anodic protection

Fig. 1.13 A & B. Pourbaix diagram

Pourbaix diagram of Iron in neutral water

Fig. 1.14 Anodic protection system for tanks

To protect a structure anodically, a device called as 'potentiostat' is used. A potentiostat is an

1.6.3 Advanced coatings

1.7 METALLIC COATINGS