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Sharma, Shanta S. - Pal, Arpita P. - A Textbook of Applied Chemistry II-Himalaya Pub. House (2009) PDF
Sharma, Shanta S. - Pal, Arpita P. - A Textbook of Applied Chemistry II-Himalaya Pub. House (2009) PDF
APPLIED
CHEMISTRY-II
•
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
permission of the publishers in writing.
ISBN : 978-93-5024-362-6
First Edition: 2009
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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
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
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
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 process of corrosion is slow, but the losses incurred are enormous. Some of the social
and economic consequences of corrosion include:
• Loss of efficiency
• 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.
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.
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
(i) Direct chemical attack of atmospheric gases like ° 2, H 2 , H 2 S, N02 , etc., on met~ls.
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.
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
--------~-------------------------------------------
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.
8 Applied Chemistry - /I
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.
r----------- -------
----- -------
----fJ-------
-----
----
----- --------
-------
1- ~-- - - - - - - - - - - --- --------
---- ------_.
--------------
I';: (Less noble) : : _-. (More noble . : :~
1.= anode is :. :.:: cathode is .:. :. :
::. attacked ==:
--- Positive ions
~
==:: protected
Current
Cu
.
.
10 Applied Chemistry - /I
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.
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
12 Applied Chemistry - /I
(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
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)
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
Cathode---+
(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.
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.
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
18 Applied Chemistry - /I
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.
e
Ground level
: :S9i! : : : : : : : : : : : : : : : : : : : : : : : : : : : :
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)
-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
+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
Ammeter
Vacuum
tube
voltmeter
Potentiostat
Tank to be Protected
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
(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.
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.
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
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. 1.18 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
24 Applied Chemistry - 11
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
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
Busbar
==::::::::::~==~==~===G
----~----~~--~~--@
Plating bath
(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.
.. 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
28 Applied Chemistry - /I
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
(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
1.8.1 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:
- 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.
30 Applied Chemistry - /I
1
Glyceride of linolenic acid (drying oil)
Air oxidation and polymerization
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
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:.
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.
32 Applied Chemistry - 1/
(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.
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.
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.
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
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.
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.
(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.
• 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.
• 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.
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.
2.2.2.1 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.
• 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. .
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.
Alloys and Powder Metalurgy 43
Bronzes containing upto 5% Sn is most ductile, ductility gradually decreases with Sn content.
Bronzes are widely used for the manufacture of pumps, valves, flanges etc. where resistance
to corrosion is required.
Uses: It is used for various engineering purpose such as gears, bearings, marine pumps.
(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.
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.
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.
(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.
46 Applied Chemistry - /I
(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
(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.
Alloys and Powder Metalurgy 47
(A) (8)
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.
(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.
decomposition or hydrilysis in a flame and is specially used to produce Si02 and Ti0 2
from SiCI 4 and TiCI 4 respectively.
(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.
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.
•••
, 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.
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.
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.
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
100 8
°
HCV = - 1 [8080C + 34,500 (H - - ) + 2,240 5] calslgm
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.
54 Applied Chemistry - /I
1 0
Solution: HCV = - [8080C + 34,500 (H - - ) + 2,240 S] calslgm
100 8
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
1 5
HCV=- [8080 x 78 + 34,500 (8 - - ) + 2,240 x 1.5] calslgm
100 8
9x8
NCV =HCV ---x540
100
Coal: Coal is a fossil fuel formed by the transformation of wood over a long period of time.
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.
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.
(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
wt. of coal (air dried) taken
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.
56 Applied Chemistry - 1/
(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
wt. of coal (air dried) taken
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.
0.145
- - - x 100
2.S
= 5.B.
Fuels 57
= 2.05g.
:. wt. of volatile matter = 2.35.5-2.05
= 0.305
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]
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
Coarse
CuO gauge copper oxide
Silver gauge
-. .. . .... -..
Pure
oxygen~
Free from
(Co2 & moisture)
1
C+ 02~C02: H2 + 202~H20
12 44 2 18
IncreaseinweightofKOHtubex12x100
:. Percentageo fC =-~----::...---------
Weight of coal sample takenx 44
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.
.. Condenser
~~add
Fig. 3.2 Nitrogen estimation by kjeldhal method
60 Applied Chemistry - /I
(x -y)xNx14
w g. coal = gN
1000
(x - y)xNx14
:. 100g coal = x 100
1000
Significance: Nitrogen in coal has no significance and hence it is present in very small
amount.( -1 %)
xx32
w g. of coal = 233 gS
xx32
:.100g coal = --x100
233
Fuels 61
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.
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
62 Applied Chemistry - /I
(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
-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
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
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.
64 Applied Chemistry - /I
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
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:
C + 02 ) CO 2
12 32
1
H2 +"2 02--~) H 0 2
2 16
66 Applied Chemistry - /I
= [~~ C +8H+5-0]
~ [( ~~ xO.B ) +(BxO.OS) + 0.02 - 0.03 ]
= [2.13 + 0.4 + 0.02-0.03]
=2.52 kg.
Solution:
Coal composition per kg.
C-89% 0.89
H-6% 0.06
5-2.5% 0.025
0-2% 0.02
= 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 ]
= 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
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
(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
= 1.33 cU.m.
100
minimum volume of air required = 1.33x-
21
= 6.33 cU.m.
6.33x28.94
:.6.33 cu. m. air at NTP weight=
22.4
= 8.178 kg.
70 Applied Chemistry - /I
• 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.
• Mixed based: These are intermediate between paraffin and asphalt based oils. These
contain varying proportions of asphaltic, naphthenic and aromatic hydrocarbons.
Fig. 3.3 (a) Mining of crude oil from oil"well (b) Mechanical .pumping of oil
Fuels 71
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
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.
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
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 ,
Heav
oil -4-,,_--J
Pre-Heater
D
(425-450 C)
Catalyst
1Heavy oil
Chamber
Fractionating
{425-450·C Gasoline &
coloumn
Dissolved gases
~~~ Stabilizer
Gasoline
Blower
Fig. 3.6 Moving-bed type catalytic cracking
Fuels 75
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.
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.
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.
The Table 3.3 illustrates the distinguishing properties between octane rating and cetane
rating.
Octane rating Cetane rating
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.
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'
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.
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
80 Applied Chemistry - /I
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
1
liquid Fuels UQJFuels PhenoL Resin
Adhesive
1
Alcohol
1
Organic Solvent
- 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. 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.
86 Applied Chemistry - II
Fiber
Reinforced
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. 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
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.
::'Oiscontinuous
. .•. ·' drandom 1)/
',,,",',
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.
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. Constituents
2. Geometrical design
Common structural composite types are:
Fig. 4.3 The stacking of successive oriented fiber-reinforced layers for a laminar composite
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.)
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.
© + 4.5 O2 ~o
~ + 2eo2 + 2H20
~
vp,
"'-"" +30 2 • +3HP
~ + 3.502
V20,
• Iq: +4H2O
Benzene Oxidation
Q o
+ 2CO,+2H,O
Formula weights
78 4.5x32=144 98
~ +302 --+. ,Q o
o
+ 3H,O
Formula weights
56 3x32 ... 96 98
% Atom Economy = 100x98/(56+96)= 100x 98/152 =64.5%
• The conventional benzene oxidation technique, the atom economy is 44.1 % as against
64.5% in the case of oxidation of butane.
98 Applied Chemistry - /I
A 20% increase in atom economy is achieved along-with zero carbon dioxide (green
house gas) emission.
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
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
H02C-(CH2)4C02H
50 psi Adipic acid
2005 Onwards
ZSM-5
reagents ) product yield> 85%
(2) ZSM-5 can be used in sma" quantity repeatedly to conduct same reaction.
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.
102 Applied Chemistry - II
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.
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
104 Applied Chemistry - 1/
°
R~ .•
S mectlte
(Mg doped) 9
R
CH30H
Smectite· '(
.)0,-
'(
(Mg doped) CH 3 CH 3
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
Triglyceride Methanol Biodiesel Glycerin
(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'.
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.
(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
- - -....~ Time
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
108 Applied Chemistry - II
(ii) Carbon monoxide and hydrogen react at high temperature and pressure, to give different
products in presence of different catalysts.
Ni
-----7 CH4 + H20
. 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 ,
NO(g) ) 302(g)
(iii) Inversion of cane sugar catalysed by hydrogen ion from a mineral acid
glucose fructose
Reactants and the catalyst are of different phases and the reactions proceed at an interface
between the two discrete phases .
(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.
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
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.
(iii) Reaction between benzene and methyl chloride in presence of aluminium chloride as
catalyst - Friedel-Crafts reaction.
catalyst intermediate
[CH 3]+ [AICIJ + C6H6 ---7 C6H sCH 3 ' + HCI + AICI 3
regenerated catalyst
(2) The Adsorption Theory
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.
(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.
114 Applied Chemistry - /I
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.
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.
~, "" "a"
(ethane) and the catalyst surface is
released for a fresh cycle of the above
steps.
Catalyst surface I
Catalysis 115
(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.
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.
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
(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),
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
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-
• those with ligands. Typical ligands that stabilize clusters include carbon monoxide,
halides, isocyanides, alkenes, and hydrides.
118 Applied Chemistry - /I
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.
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.
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.
120 Applied Chemistry - /I
o
0.35 nm-0.45nm
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.
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.
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.
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
122 Applied Chemistry - /I
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.
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
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.
•••
REVISION AT A GLANCE
CHAPTER 1 CORROSION
What is corrosion?
• Dry theory:
• 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.
• Nature of metal:
• 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.
Ground level
: :.s9i! : : : : " : : : : : : : : : : : : : : : : : : : : : : :
-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
Protective coatings:
(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.
o Hot dipping
o Metal spraying
o Metal cladding
o Electroplating
o Powder metallurgy
• Electroplating:
• Organic coatings:
Revision at a Glance 127
• . Paints:
(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
(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.
Revision at a Glance 129
(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.
130 Applied Chemistry - II
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
Oxide film -
---
132 Applied Chemistry - /I
-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,
Revision at a Glance 133
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
__ ~e~a~i~n~ ~::~~h~~~X~~:s_~~~
:::::::t.~ ~ ~ ~ ~ ~ ~ ~
------ . -------
:'M(OH) - - : : : : :"-OH- -= :
n ----
::::::
------ - -
corrosion product
Fe 2 '+20H- Fe(OH),
Corrosion product
! More oxygenated
cathode
Protected grain
centre (cathodic)
----------------=
---------
------_ ...
-------
Stress ~orrosion
Vacuum
tube
voltmeter
Reference
electrode Tank to be Protected
+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
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
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
\
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
Busbar
----~~----+---~~---G
C±>
Electrolyte ----+_ _ _ _,
Heating
coils
o 0 0 0 _ Air sparger
~~~~~~~--r--
Plating bath
• To improve tensile strength. E.g. Fe i~ soft. +C will :ncrease its tensile strength many
fold.
• To improve castability. Pure metals when cooled from molten condition shrink whereas
alloys expand. This property IS used in printing.
Brasses Bronzes
These are cheap because Zn is cheap These are costly because Sn is costly
These are less corrosion resistant These are more corrosion resistant
Brasses
Bronzes
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:
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.
• Atomization
• 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
(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.
144 Applied Chemistry - 1/
(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
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.
Upper punch
Die
Compact
~rpunch
Compressor
Schematic representation of cold pressing principles: (A) Axial pressing (8) Isostatic pressing
Revision at a Glance 145
Feed stock
Front cavity
... ( . Heater Rear cavity
Heaters
parting line
(A) (8)
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.
146 Applied Chemistry - /I
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)
(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.
(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.
Revision at a Glance 147
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
% 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:
%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)
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
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".
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.
152 Applied Chemistry - /I
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
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
Revision at a Glance 153
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
&
.. Condenser
Standard acid
I----:----;=:....-~Compressed
gas
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
Revision at a Glance 155
(, 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
fuels
6QOO(
M
.Ji"_ _"_~ -l bships
fadorie;
em '
CJ:!rtraI
I~
>(70 resiou~
bi1unen for roads
and rooling
Pre-Heater Catalyst
(425-450°C) Chamber
Fractionating
o Gasoline &
(425-450 C coloumn
Dissolved gases
Fig. 3.S Fixed-bed catalytic cracking
156 Applied Chemistry - /I
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
UquJFuelS
j
Liquid Fuels Phenolic Re~n
1
Alcohol
Adhesive
1
Organic Solvent
Classification of Petrocrops
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
Spheroidized Steel
Matrix: Particle:
Ferrite Fe3C
(a - iron) (cementite)
Ductile Brittle
Matrix: Particle:
Rubber Carbon
(Compliant) (Stiffer)
Automobile Tire
.. ReinforcedCompo:ites
.~~r?~~. r.~~~~
~¥6nlrM~~~~
;!i;pt~~ontirl'~oUS :; DiscontinuoUS
and random Iy
.::~~::,~::.:-;-':; : ..
.brierj~ed tfi bel's.
• ('.::-..:--:- .... "',·:-F'-'· :-./;,.
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.
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.)
162 Applied Chemistry - /I
•:. Numericals:
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.
Revision at a Glance 163
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
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
(2) ZSM-5 can be used in small quantity repeatedly to conduct same reaction .
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
Triglyceride Methanol Biodiesel Glycerin
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.
166 Applied Chemistry - II
Smectite ~ Smectite
(Mg doped) R (Mg' doped) CH 3 CH 3
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.
Revision at a Glance 167
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?
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 by providing an alternative new
pathway. Thus, presence of a catalyst causes the reaction to proceed at a faster rate.
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.
168 Applied Chemistry - /I
NO(g) ) 302(g)
(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.
(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.
(ii) Oxidation of NH3 in presence of platinum gauze as catalyst used in the manufacture of
nitric acid.
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]
catalyst intermediate
[N0 2] + S02 ~ 50 3 + NO
regenerated catalyst
(ii) Formation of diethyl ether from ethanol in presence of H 2S0 4 as catalyst.
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
- - -...... Time
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 •
Revision at a Glance 171
I
I Progress 01 reaction
Products
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
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.
172 Applied Chemistry - 11
(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:
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 reactiol). 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 by providing an alternative new
pathway. Thus, presence of a catalyst causes the reaction to proceed at a faster rate.
Adsorption theory:
(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
174 Applied Chemistry - 11
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
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.
-:0." I I ,all,
(ethane) and the catalyst surface is
released for a fresh cycle of the above
steps.
Catalyst surface
Revision at a Glance 175
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.
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.
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