ENGINEERING CHEMISTRY

FRESHMAN ENGINEERING
INSTITUTE OF AERONAUTICAL ENGINEERING
Dundigal, Hyderabad -500 043.
Electrochemistry and Batteries
 Introduction
 Electrochemistry is the branch of chemistry which deals with the
transformation of electrical energy into chemical energy and vice
versa. It is the study of phenomena at electrode solution interfaces.
 Electrochemistry deals with the 1 relationship between electrical,
chemical phenomena and the laws of interaction of these
phenomena. The branch of electrochemistry is of major technical
importance.
 The laws of electrochemistry form the basis of electrolysis and
electrosynthesis. The knowledge of electrochemistry is of immense
importance to study about the causes of destruction of materials due
to corrosion. In electro-chemistry, there are two processes:
electrolysis and electromotive process. Both these processes are
interrelated.
The two processes above can be summarized as
follows:
1. Electrical energy causing chemical reactions →
Electrolysis (Electrolytic cell)
2. Chemical reactions producing electrical energy →
Electromotive (Galvanic cell)
3. Electromotive → Electron + Motion
 Conductance:
 The substances which allow the passage of electric current
are called conductors. Metals such as copper and silver are
good conductors of electricity. Substances which allow the
electricity to pass through them in their molten states or in
the form of their aqueous solutions are called electrolytic
conductors or electrolytes and this property is known as
electrolytic conductance. Electrolytic conductors conduct
electricity due to the migration of ions. The examples of
electrolytic conductors are sodium chloride, potassium
chloride, etc.
 Electrical conductors are of two types:
1. Metallic conductors and 2. Electrolytic conductors.
 Electrolytic Conductance:
 Electrolysis is the process of decomposition of electrolyte when electric
current is passed through the solution.
 Electrolysis is carried out in an apparatus called electrolytic cell. It
contains a +ve electrode called anode and a –ve electrode called
cathode. The current enters at anode and leaves at cathode.
 Ohm’s law states that the current (I) flowing through a conductor is
directly proportional to the potential difference (E) applied across the
conductor and is inversely proportional to the resistance of the
conductor.
Thus,

where I is the current in amperes and Vis the potential difference

applied across the conductor in volts.
Thus,

where R is the proportionality constant and is known as the resistance

of conductor in ohms. Thus, the re-sistance of a conductor is directly
proportional to the potential difference applied across the conductor
and inversely proportional to the current carried by the conductor.
Specific conductance:
 Specific resistance (r) is defined as the resistance of
an electrolyte solution of 1 cm in length and 1 cm2
cross-section, i.e. resistance of 1 cm3 of the
electrolytic solution. The unit of specific resistance
is ohm centimetre.
 The reciprocal of specific resistance (r) is called
specific conductance. This may be defined as the
conductance of 1 cm3 of a material and is denoted
by K
 Equivalent Conductance:
 Equivalent conductance is of greater importance in case of
electrolytic solution. It is defined as the conductance of an
electrolyte solution containing 1 g equivalent of the
electrolyte. It is usually denoted by L. the relation between
equivalent conductance (Ʌ) and specific conductance is
given as-
Ʌ=V x K
where V is the volume of the electrolyte solution in
millilitres containing 1 g equivalent of the electrolyte. If the
concentration of the electrolyte solution is C gL–1, then
volume containing 1 g equivalent of the electrolyte will be
1/C litres or 1000 C ml .
 Thus, by using the above equation,

 The unit of equivalent conductance is ohm–1 cm2eq–1.

 Molar Conductance:
 Molar conductance is defined as the conductance of an
electrolytic solution containing 1 mol of electrolyte. It
is denoted by λm. If Vm ml is the volume of the solution
containing 1 g-mol of the electrolyte, then
λm = Vm X K
 If m is the concentration of the solution in moles per
litre, then

 The unit of λm is S m2 mol–1 or ohm–1cm2mol–1

Cell Constant:
 It is a constant characteristic of the cell in which the
electrolyte is taken and its value depends on the
distance between the electrodes and the area of cross-
section of the electrodes.

 If the area of cross-section is in cm2 and distance

between the electrodes is in cm, the unit of cell
constant is cm–1.
 Variation of Conductance with Dilution:
 On dilution, the volume of an electrolyte solution increases. Thus, the number of
ions furnished by the electrolyte per unit volume is decreased. Hence, the specific
conductance decreases on progressive dilution.
 Electrolytes are of two types: (i) strong electrolytes (ii) weak electrolytes.
 Strong Electrolytes:
 These electrolytes are completely ionized at ordinary concentration. They show
an increase in conductance at lesser dilutions. For example, salts such as KCl,
NaCl, BaCl2, CaCl2, etc.; acids such as HCl, H2SO4, etc.;and strong bases such as
NaOH, KOH, Ca(OH)2, Mg(OH)2, etc.; have very high equivalent conductance at
ordinary concentration. Since the conductance of a solution of a given electrolyte
depends on the number and speed of ions, these two factors will be considered in
the determination of conductance.
1. Strong electrolytes are completely ionized at ordinary concentration; hence, with
increase in dilution,the number of ions will remain the same as before.
2. In the case of concentrated electrolyte, the speed of ions is very low; but on
dilution, the speed of ions will be more. This is because the interionic forces of
attraction of the oppositely charged ions decrease on dilution. Thus, the
equivalent conductance at infinite dilution reaches its maximum value due to
increase in the speed or mobility of ions but not due to the number of ions in
case of strong electrolytes.
 Weak Electrolytes:
 These electrolytes dissociate into a very small extent at
ordinary concentration.
1. In dilute solution, the interionic attraction forces
between the ions are not significant since the ions
move freely. Thus, on dilution, there is a little or no
effect on the speed of ions in the electrolytic
solution.
2. On dilution, the degree of dissociation increases so
that the number of ions increases. Thus, the
equivalent conductance increases on dilution
because of the increase in the number of ions in the
electrolytic solution.
 Effect of Concentration on Equivalent Conductance
 Let us consider a weak electrolyte AB, which is ionised as

 When the electrolyte solution is diluted, more electrolyte molecules break up

and more ions are formed,i.e., the degree of dissociation is increased. As a
result of which the solution exhibits enhanced conductivity. If the process of
dilution is continued, more and more electrolyte molecules undergo
dissociation. But at some stage of dilution all the electrolyte molecules are
ionised, i.e. ionisation is completed and at that point on further dilution, no
more ions are produced and equivalent conductance does not increase. This
limiting value is known as equivalent conductance at infinite dilution (Ʌ0 or
Ʌ∞).
 Strong electrolytes are completely ionised in solution at all concentrations and
hence one would not expect any variation of equivalent conductance with
concentration (dilution). But it is found that for strong electrolytes, equivalent
conductance (Ʌ) increases with dilution, and the cause of this variation
isfundamentally different from weak electrolytes. The conductivity of an
electrolyte depends on the speed and concentration of ion. The motion of an
ionic species in an electric field is retarded by the oppositely charged ions due
to inter-ionic attraction. On dilution, the concentration of electrolyte
decreases and the retarding influence of oppositely charged ions decreases.
Consequently, the speed of ions increases, and the equivalent conductance of
electrolyte is increased
 Kohlrausch’s law of independent migration of ions
 Kohlrausch’s law states that at infinite dilution,
each ion of an electrolyte makes a definite
contribution to the total equivalent conductance
of the electrolyte, and this contribution is
independent of the presence of other ionic
species.
Kohlrausch’s law is applicable to calculate:
1. Equivalent conductance of weak electrolytes at
infinite dilution.
2. Absolute ionic mobility.
3. Solubility of sparingly soluble salt.
4. Degree of ionization.
5. Ionic product of water.
Calculation of equivalent conductance of weak
electrolytes at infinite dilution
 ‘The equivalent conductance of an electrolyte at
infinite dilution is the sum of the equivalent
conductance of the constituent ions at infinite
dilution’ i.e.
 Calculation of absolute ionic mobility (absolute
velocity):
 The speed of an ion produced by an electrolyte varies with
the applied potential difference. Ionic mo-bility is defined
as the distance travelled by an ion per second under the
influence of a unit potential gradient, i.e. 1 V cm–1. Thus, if
an ion moves a distance equal to x cm in t seconds, when a
potential gradient of v Vcm–1 is applied, its mobility U may
be expressed as
 Galvanic Cell
 A galvanic cell is made of two half cells. One is
oxidation or anodic half cell and the other one is
reduction or cathodic half cell.
 Daniel cell is an example of galvanic cell having
zinc and copper electrodes. The first half cell
consists of zinc electrode dipped in ZnSO4
solution and the second half cell is made of
copper electrode dipped in copper sulphate
solution. Both half cells are connected externally
by metallic conductor (connecting wire) and
internally by a bent glass tube having saturated
solution of a strong electrolyte (KCl) called salt
bridge. It acts as a bridge between the two half
cells.
 A zinc or a copper galvanic cell can be represented as
Zn/ZnSO4 || CuSO4/Cu
 The double bar shows a salt bridge, i.e. electrolyte–electrolyte junction. The chemical reactions taking
place at both electrodes may be written as follows:
At anode: Oxidation takes place with the liberation of two electrons.
Zn → Zn+2 + 2e– (oxidation)
At cathode : Reduction occurs and cuprous ion is reduced to metallic copper.
Cu+2 + 2e– → Cu (reduction)
The overall reaction is
Zn + Cu+2 Zn+2 + Cu
 The electrode showing oxidation reaction is anode and the other electrode where reduction occurs is
cathode. As per IUPAC convention, the anode is always represented on the left and the cathode always
represented on the right side of the cell.
 As the connection is complete, the flow of electrons will be externally from anode to cathode and
internally from cathode to anode through the salt bridge. The flow of current is due to the difference in
electrode potentials of both the electrodes. The potential difference in the cell is called the EMF and is
measured in volts. It can be measured by the potentiometer. The flow of current becomes slow after using
the electrodes for a long time because of the polarization of the electrodes.
Salt bridge: Salt bridge is a U-shaped tube
containing concentrated solution of an inert
electrolyte such as
 KCl, KNO3, and K2SO4 or a paste of inert electrolyte
(whose ions do not take part in redox reaction and do
not react with the electrolyte) in agar–agar medium or
gelatin.
Functions of salt bridge:
 Salt bridge helps to complete the circuit by allowing
the ions to flow from one solution to the other
without mixing the two solutions.
 It helps to maintain electrical neutrality of the
solution in the two half cells.
 Reference Electrodes
 The potential of half cell or single electrode potential is the
potential difference between the metal and its salt solution
in which it is dipped.
 The determination of the potential of a single electrode is
not possible. Since any circuit necessarily contains two
electrodes, a reference electrode is an electrode which has a
stable and well known potential. It is used as half cell to
build an electrochemical cell and to determine the
potential of other electrode.
 A fixed potential difference is applied between the working
electrode and the reference electrode; this potential drives
the electrochemical reaction at the working electrode
surface. The current produced from the electrochemical
reaction at the working electrode is balanced by a current
flowing in the opposite direction at the counter electrode.
The examples of reference electrodes are standard
hydrogen electrode, calomel electrode, silversilver chloride
electrode, etc.
 Standard Hydrogen Electrode (Normal Hydrogen
Electrode:
 It is a redox electrode which is widely used as reference
electrode. It can be used as either anode or cathode
depending upon the nature of the half cell for which it is
used. The SHE consists of a platinum electrode immersed in
a solution with a hydrogen ion concentration of 1.0 M. The
platinum electrode is made of a small square of platinum foil
which is platinised and known as platinum black. [Platinum
black provides a surface on which the hydrogen gas can be in
contact with the hydrogen ions (aq.).]
Nernst equation for a cell reaction:
Quinhydrone Electrode:
 It is a type of redox electrode which can be used to
measure the H+ion concentration of a solution. The
electrode consists of an inert metal electrode (a
platinum wire) in contact with quinhydrone crystals
and a water-based solution. Quinhydrone is slightly
soluble in water, formed by equi–molar mixture of
hydroqui-none and quinone.
 Ion Selective Electrode:
 An ion selective electrode is a sensor
which converts the activity of a specific
ion dissolved in a solution into an
A Glass Electrode
electrical potential which can be
measured by a voltameter or pH-meter,
e.g. glass electrode.
 Glass Electrode: A glass electrode is a
type of ion-selective electrode and
consists of a thin-walled glass bulb
attached to a glass tube. A very low
melting point and high electrical
conductivity glass are used for the
construction of this bulb. The glass tube
contains a dilute solution of constant
pH of HCl (0.1 N) solution. A silver–
silver chloride electrode or platinum
wire is immersed as reference electrode
in the HCl solution.
 ELECTRODE POTENTIAL
 When a metal rod is dipped in its salt solution (electrolyte), the metal atom tends
either to lose electrons (oxidation) or to accept electrons (reduction). The process
of oxidation or reduction depends on the nature of metal. In this process, there
develops a potential between the metal atom and its corresponding ion called the
electrode potential.
Oxidation: M → Mn+ + ne–
Reduction: Mn+ + ne– → M
 The tendency of oxidation results in the dissolution of metal and in the release of
electron density on the surface of metal with respect to electrolyte solution.
Similarly in reduction, the positive charge density is more on the surface of metal
with respect to the solution. Consequently, they attract oppositely charged
particles and form a double layer of charge called the Helmholtz electrical double
layer
 There is a dynamic equilibrium between metal and metal ion, and the potential
difference between the two is called the electrode potential or the equilibrium
potential. It is measured in volts. The potential difference for oxidation reaction is
called the oxidation potential and that of reduction is called the reduction
potential.
Batteries or Commercial Cells
 Definition-
a) A battery is a storage device used for the storage of
chemical energy and for the transformation of
chemical energy into electrical energy.
b) Battery consists of group of two or more electrical
cells connected together electrically in series.
c) Battery acts as a portable source of electrical energy.
 Batteries are of three types, namely,
1. Primary batteries (or) primary cells
2. Secondary batteries (or) secondary cells
3. Fuel cells (or) flow batteries
 Primary Cell:
 In a primary cell, a chemical reaction
proceeds spontaneously and its free
energy is converted into electrical energy.
The production of electrical energy at the
expense of the free energy of the cell is
Dry Cell (leclanche Cell)
called discharging of the cell. But in a
secondary cell, electrical energy is passed
into the cell when a chemical reaction is
induced, and the products remain on the
electrodes. These products react in the
backward direction at our choice and
liberate free energy in the form of
electrical energy. These cells accumulate
electrical energy in the form of chemical
reaction and later on the reaction is
reversed to release electrical energy. This
process is called charging of the cell.
 Examples of primary cells:
Voltaic cells, Daniel cell, Leclanche cell,
Weston cadmium cell, and lithium cell.
Secondary Cells (or) Accumulator Batteries:
 In secondary cells, the cell reaction can be made to
proceed in the reverse direction by passing direct current
through it from an external source. Therefore, it can
operate in both the ways, i.e., it receives electrical en-
ergy and also supplies it. When it supplies electrical
energy, it operates like an electrochemical cell and gets
rundown. The cell needs to be recharged. During
recharging, it operates like an electrolytic cell.
 Example:
 Lead storage battery
 Nickel–cadmium battery
 Lithium-ion cell battery
 Lead–acid battery:
 If a number of cells are connected in series, the arrangement is
called a battery. The lead storage battery is one of the most
common batteries that are used in the automobiles. A 12 V lead
storage battery is generally used, which consists of six cells, each
providing 2 V. Each cell consists of a lead anode and a grid of lead
packed with lead oxide as the cathode. These electrodes are
arranged alternately, separated by a thin wooden piece and
suspended in dil. H2SO4(38%), which acts as an electrolyte.
Hence, it is called lead-acid battery.

Lead–acid battery
Lead Storage Cells:
 To increase the current output of each cell, the cathode
and the anode plates are joined together, keeping
them in alternate positions. The cells are connected
parallel to each other (anode to anode and cathode to
cathode). The cell is represented as Pb|PbSO4(s),
H2SO4(aq.)|PbSO4(s), Pb
 Fuel Cells:
 A fuel cell is an electrochemical cell which
converts chemical energy contained in
readily avail-able fuel oxidant system into
electrical energy.
 Principle: The basic principle of the fuel
cell is same as that of an electrochemical
cell. The fuel cell operates like a galvanic
cell. The only difference is that the fuel and
the oxidant are stored outside the cell. Fuel
and oxidant are sup-plied continuously
and separately to the electrodes at which
they undergo redox reactions. Fuel cells are
capable of supplying current as long as
reactants are replenished.
Schematic diagram of hydrogen–
Fuel+Oxidant OxidationProducts+Electricity oxygen fuel cell
 Examples:
(1) H2– O2fuel cell
(2) Propane – O2fuel cell
(3) CH3OH – O2fuel cell
 THEORETICAL QUESTIONS
 1. What are concentration cells? Explain an electrolyte
concentration cell and its application.
 2. Describe the construction of a glass electrode. How is it
significant in its applications?
 3. Derive Nernst’s equation. How is it useful?
 4. Discuss the working principle of the primary batteries.
 5. What is a galvanic cell? Also describe a Daniel cell.
 6. Differentiate between an electrochemical cell and an
electrolytic cell.
 7. What is electrochemical series? Discuss its three important
applications.
 8. Describe the construction and working of a calomal electrode.
 9. Describe the construction of a galvanic cell. Write down the
electrode reactions and the formula for its EMF.
 10. What are fuel cells? Explain the working of the hydrogen–
oxygen fuel cell?
CORROSION AND ITS CONTROL
 Introduction
 Corrosion is a process of formation of the compound of
pure metal by the chemical reaction between metallic
surface and its environment.
 It is an oxidation process.
 It causes loss of metal. Hence, disintegration of a metal by
its surrounding chemicals through a chemical reaction on
the surface of the metal is called corrosion.
 Thus, corrosion is defined as destruction or deterioration
of metals by chemical reaction.
 Example: Formation of rust on the surface of iron,
formation of green film on the surface of copper.
 The responsible factors for the corrosion of a metal are the
metal itself, the environmental chemicals,temperature and
the design
Causes of Corrosion
 In nature, metals are not found in free state due to
their reactivity. It is the ore from which the metals are
extracted by metallurgical processes. Metallurgy
requires a large amount of heat energy.

 Why metals are not found in their free state? The

answer to this question is that the metals are
thermodynamically unstable in their free state. Since
they are stable in the form of certain compounds, the
extracted metal has higher energy. This is given as:
 Effect of Corrosion
 Corrosion is a slow process, taking place mainly on the surface of the
metals, but the damage caused by it is enormous. The corrosion in
metal objects such as equipments, instruments, chemical plants,
structures, etc., makes them inefficient. In some types of corrosion it is
invisible and seen only when accident occurs. Consequences of
corrosion cause a great loss of economy and life. The following harmful
effects are specific.
1.Corrosion reduces the thickness of the metal, resulting in the loss of
mechanical strength and failure of the structure.
2. Because of the deterioration of appearance, the cost of machine is
reduced.
3. Efficiency of a machine is reduced due to corrosion.
4. Because of corrosion, pipes are blocked and pumps are difficult to
operate.
5 Boilers are damaged because of corrosion.
6. Buildings and historic monuments are damaged due to corrosion
(e.g., Taj Mahal).
 Theories of Corrosion:
 There are three theories of corrosion: (i) acid theory, (ii) dry or
chemical corrosion and (iii) galvanic or electrochemical or wet
corrossion.
 Acid Theory of Corrosion
This theory suggests that corrosion of a metal (iron) is due to the
presence of acids surrounding it. According to this theory, iron is
corroded by atmospheric carbon dioxide, moisture and oxygen.
The corrosion products are the mixture of Fe(HCO3)2,
Fe(OH)CO3 and Fe(OH)3. The chemical reactions suggested are
given below:

 This theory is supported by the analysis of rust that gives the test
for CO3
 2– ion. Further, the process of rusting is reduced by the presence
of lime and caustic soda (these two can absorb CO2, thus
reducing corrosion).
 Dry or Chemical Theory of Corrosion:

 According to this theory, corrosion on the surface of a metal is due to

direct reaction of atmospheric gases such as oxygen, halogens, oxides of
sulphur, oxides of nitrogen, hydrogen sulphide and fumes of chemicals
with metal. The extent of corrosion of a particular metal depends on
the chemical affinity of the metal towards reactive gas. Oxygen is
mainly responsible for the corrosion of most metallic substances when
compared to other gases and chemicals.
Oxidation corrosion (Reaction with oxygen):
Some of the metals react directly with oxygen in the absence of
moisture. Alkali and alkaline earth metals react with oxygen at room
temperature and form corresponding oxides, while some metals react
with oxygen at higher temperature. Metals such as Ag, Au and Pt are
not oxidised as they are noble metals.
 Wet or Electrochemical Theory of Corrosion:
 It is a common type of corrosion of metal in aqueous corrosive
environment. This type of corrosion occurs when the metal
comes in contact with a conducting liquid or when two
dissimilar metals are immersed or dipped partly in a solution.
According to this theory, there is the formation of a galvanic cell
on the surface of metals. Some parts of the metal surface act as
anode and rest act as cathode.
 The chemical in the environment and humidity acts as an
electrolyte. Oxidation of anodic part takes place and it results in
corrosion at anode, while reduction takes place at cathode. The
corrosion product is formed on the surface of the metal between
anode and cathode.
 To understand the wet theory, let us take the example of
corrosion of iron. Oxidation of metal takes place at anode while
the reduction process takes place at cathode. By taking rusting of
iron as an example, the reaction can be explained as that it may
occur in two ways: (i) evolution of hydrogen and (ii) absorption
of oxygen
 Types of Corrosion
Based on the reactions and physical states, there are
different types of corrosions.
 They are
 (a) Galvanic corrossion
 (b) Pitting corrosion
 (c) Stress corrosion
 (d) Crevice corrosion
 (e) Erosion corrosion
 (f ) Soil corrosion
 (g) Micro-biological corrosion
 (h) Water-line corrosion
 (i) Differential aeration corrosion
 (j) Intergranular corrosion
 (a) Galvanic corrosion:
This type of electrochemical corrosion is also called bimetallic corrosion.
When two dissimilar metals are connected and exposed to an electrolyte,
they will form a galvanic cell. The anodic metal will be oxidised and it will
undergo corrosion. Zinc and copper metals connected with each other in
an electrolyte medium form a galvanic cell. Zinc acts as anode and
undergoes corrosion while cathode
 Prevention of galvanic corrosion: Galvanic corrosion can be avoided by
(i) Coupling metals close to the electrochemical series.
(ii) Fixing insulating material between two metals.
(iii) Using larger anodic metal and smaller cathodic metal.
 Examples of galvanic corrosion: steel screws in brass marine hardware;
steel pipe connected to copper plumbing; steel propeller shaft in bronze
bearing; zinc coating on mild steel; and lead–tin solder around copper
wires.

Galvanic corrosion
 (b) Pitting corrosion:
Due to the formation of cracks on the surface of a metal, local
straining of metal, sliding under load, chemical attack, there
is formation of a local galvanic cell. The crack portion acts as
anode and rest of the metal surface acts as cathode. It is the
anodic area which will be corroded and the formation of a pit
is observed. This type of corrosion is thus called pitting
corrosion ,Metals owing to their corrosion resistance to their
passive state show pitting and ultimately result in the
formation of passivity. Presence of external impurities such as
sand, dust, scale embedded on the surface of metals lead to
pitting.
 For example, stainless steel and aluminium show pitting in
chloride solution.

Pitting corrosion at the

surface of iron
 (c ) Stress corrosion:
In a metallic structure if there is a portion under stress,
it will act as anode and rest part of the structure will
act as cathode. It is now a galvanic system and hence
anodic part which is small in area will corrode more.
Stress corrosions are observed in the following system.
 Caustic embrittlement is a type of stress corrosion
occurring in steel tank (boiler) at high temperature
and in alkaline medium. Boiler water has Na2CO3; it
will be hydrolysed at high temperature to give NaOH.
It flows into hair cracks and crevices. There it reacts
with iron and forms Na2FeO2(sodium ferroate) which
decomposes to give Fe3O4 (ferroferric oxide) and
NaOH. The reaction is as follows:
3Na2FeO2 + 3H2O Fe3O4 + H2 + 6NaOH
 (d) Crevice corrosion:
If surface of painted metal is scratched, it will undergo
corrosion. The scratched portion acts as small anode and
the rest part will act as cathode forming a local cell. Crevice
corrosion is formed near joints, rivets and bolts. Changes
in the concentration of oxygen/acidic medium causes
crevice corrosion.
 (e) Erosion corrosion: Due to mechanical wear and tear,
corrosion occurs on the surface of a metal and is called
erosion corrosion.
 (f) Soil corrosion: underground pipes, cables, etc. corrode
due to soil corrosion. It is caused due to moisture, pH of
soil and micro-organisms.
 (g) Microbiological corrosion: Some types of bacteria
consume oxygen and cause differential aeration type of
system which results in corrosion. The corrosion occurs at
the portion poor in oxygen concentration. For example, the
bacillus and algae diatoms.
 Inter-granular corrosion:
This corrosion is observed in case of alloys. The corrosion
product is observed at the boundaries of grains. Externally,
it is not seen. There is a sudden failure of material due to
this corrosion. For example, during the welding of stainless
steel (an alloy of Fe, C, Cr), chromium carbide is
precipitated at the grain boundaries and the region
adjacent to grain boundaries becomes depleted of
chromium composition and is made anodic, and is more
susceptible to corrosion.
It occurs on microscopic scale and follows the path of grain
boundary until the affected grain is completely dislodged.
Thus, it leads to sudden failure without any external
indication of the attack. It can be minimized by preventing
heterogeneous due to slow cooling of alloy.
Rapid quenching after heat treatment of a metal is the
remedy of inter-granular corrosion
 Factors Influencing Corrosion:
 Since corrosion is a process of destruction of metal surface by its
environment, the two factors that govern the corrosion process are:
(i) Metallic and (ii) Environmental
 (i) Nature of metal:
Different properties of a metal are responsible for corrosion. These
properties are as follows:
a) Position of metal in galvanic series:
b) Hydrogen over voltage:
c) Purity of metal:
d) Relative areas of anode and cathode:
e) Physical state of the metal:
f) Nature of oxide film:
g) Volatility and solubility of corrosion product:
 (ii) Nature of environment:
The role of environment in the corrosion of a metal is very important.
Environmental parameters like temperature, humidity, pH, etc. play important role.
The effect is discussed here.
 (a) Temperature: The rate of diffusion increases by rise in temperature, hence the
rate of corrosion is also increased. At higher temperature, passive metals also
become active and undergo corrosion. But higher temperature reduces the
concentration of oxygen and hence corrosion is reduced homogeneous solid
solution, hence no local action and no corrosion.
 (b) Humidity of air: In humidity, gases like CO2, SO2, NOx are dissolved which
form electrolytes. It will cause galvanic corrosion. Some oxides are water soluble,
humidity washes away the corrosion products and metal surface is further corroded.
Other soluble corrosion products can also be washed away by humidity, causing
further corrosion.
 (c )Impurity of atmosphere: Pollutants like H2S, SO2, CO2 and acid vapours cause
more pollution where they dissolve. In sea water (salty in nature which acts as an
electrolyte) corrosion rate increases. Some suspended particles are dissolved in
humidity and form electrolyte which helps in corrosion.
 (d) pH value of the medium: pH value means concentration of H+ (acidic nature).
In acidic medium (pH less than 7), corrosion is faster. Also, in basic medium pH > 7,
some metals such as Pb, Zn, Al, etc. form complexes and hence they corrode.
 Measurement of Corrosion:
 The process of corrosion is a slow chemical reaction. During the
corrosion process, there is loss of weight of the metal. The loss in
mg/dm2 per day or inches per year measures the extent of corrosion.
Rate of corrosion (R) =kw/atd
where w = loss of weight of metal in milligrams
a = area of metal surface in sq. cm
t = exposure time for corrosion in 100th part of an hour or a day
d = density in g/cm2
k = constant of proportionality
 The condition is that the surface of the metal must be uniform.
 There are several units for the measurement of the rate of corrosion
(R), i.e. mg/dm2/day, oz/ft2/day, inch/year or millimetre/year.
 A cleaned metal is taken, weighed and exposed for corrosion. Time
taken in the process is recorded and then the piece of the metal is
taken out; corrosion product is removed and is weighed again. The loss
in the weight of the metal is noted which helps to calculate corrosion
rate.
 Protection from Corrosion
 Metals can be protected from corrosion by various
methods. Some of them are as follows:
 . Proper designing
 . Using pure metals
 . Using corrosion inhibitors
 . Modifying the environment
 . Cathodic protection—sacrificial anode, impressed
current, cathode
 . Heat treatment
 . Applying surface coatings
 Sacrificial Anodic Protection:
 Advantages: It is a simple method. It has low maintenance and installation
cost. It does not require external power; cathodic interferences are minimum.
 Disadvantages: More than one anode is required. Current output is less. It
does not work properly in high corrosive environment. The sacrificial anode
must be replaced periodically as used when it is consumed.
 Due to corrosion, there is a great loss of material and money. Therefore, it is
essential to protect metals from corrosion. Since there are two components
involved in corrosion—the metal and environment—both are considered in
corrosion protection. Following methods have been adopted for the protection
of metal from corrosion:
 (i) If it is unavoidable, the anodic area should be very large as compared to the
cathodic area.
 (ii) Proper designing of the equipment is the best way of controlling corrosion.
The design of the metal should be such that even if corrosion occurs, it is
uniform and does not result in intense and localised corrosion.
 (iii) Two different metals used in the structure should be
such that they are occupying near positions in the galvanic
series.
 (iv) Putting an insulator between two metals resists
corrosion.
 (v) As far as possible, metal used in a structure should be
extremely pure. Small amount of impurity causes
corrosion.
 (vi) While using an alloy, it should be completely
homogeneous.
 (vii) Design or fabricate equipment or metal parts in such a
manner that they have minimised sharp edges and corners
and also avoid, as far as possible, the crevices in joints, etc.
 (viii) The equipment must be supported on legs to allow
the passage of air which prevents differential
 Modifying the Environment
 It can be done either by removing the corrosive agents from the
environment or by neutralising the corrosive effect by adding certain
substances. For example, by deaeration or by deactivation of substance
by the addition of chemicals; to deactivate sodium sulphate, oxygen is
added to sodium sulphate. To neutralise the acidic character of the
corrosive environment due to HCl, CO2 and SO2, bases like lime, NH3
and NaOH are used. The modification of environment also helps in
protection from corrosion.
 (i) Deaeration removes oxygen by adjusting temperature and
mechanical ageing.
 (ii) Deactivation involves addition of chemicals such as Na2SO3, NH2 –
NH2.H2O which absorb oxygen.

 (iii) Dehumidification of environment is done by adding alumina or

silica gel. These chemicals absorb humidity from metallic surface.
In humidity, gases such as CO2, H2S, SO2 and HCl give acidic medium
responsible for corrosion. They are neutralised by NH3 or NaOH or
lime.
 Cathodic Protection:
 There are some chemicals which reduce the rate of corrosion. These
chemicals are called corrosion inhibi-tors. They are of two types,
anodicand cathodic. Phosphate, chromate and tungstate protect
anode. They form sparingly soluble products which are adsorbed on
the surface of metal and hence check corrosion. Cathodic protection is
done by organic amines, mercaptans, thiourea and substituted urea.
The above chemi-cals retard reduction reaction taking place at
cathode. Also, by the use of salts of Mg, Zn or Ni, the insoluble
hydroxides of Mg, Zn or Ni are deposited preventing corrosion.

 For protecting corrosion–electrochemically, there are two methods for

the protection from corrosion:
a) Sacrificial anodic protection:
b) Impressed current cathodic protection:
a) Sacrificial anodic protection:
Underground steel pipes are protected from
corrosion by this method. A magnesium rod is fixed
near the metal under protection (Fe) and both are
connected with a conducting wire. Magnesium is
more positive than iron and, hence, in
electrochemical cell it acts as anode and the iron acts
as cathode. According to the principle of galvanic
cell, it is anode that undergoes oxidation, and, hence,
corrosion occurs at anode saving cathode (iron) from
corrosion. Thus, magnesium sacrifies itself for saving
the iron. Usually, buried pipes and storage tanks
made of steel are connected to Mg blocks. Mg
protects steel sacrificially; Zn or Mg sheets are hung
around the ship hull to protect the steel or iron base
of ship by sacrificial protection.
b) Impressed current cathodic protection:
This is another method for the cathodic protection
of metals. The object or the metal to be protected
(the metal is exposed to soil or other electrolyte) is
made anode by connecting to an external battery.
The battery contains an inert graphite anode which
is buried in a back fill to maintain electrical contact.

Sacrificial anodic protection Impressed current cathodic protection

 Applying Surface Coatings:
 The surface of pure metal is homogeneous and it improves corrosion
resistance. Corrosion resistance de-pends on the nature of the environment.
For example, the corrosion resistance of aluminum is reduced in alkaline
environment.
 Preparation of Surface for Metallic Coatings
 The surface of the metal is covered with rust, oxide scales, oil, grease, dust, etc.
These substances produce porous, discontinuous or non-adherent coatings in
order to get uniform, smooth, cohesive and adhering coat-ing. These unwanted
substances covering the metal should be removed perfectly before giving
protective coating. The methods are as follows:
 Sandblasting: This method is used for removing oxide scales. It is suitable for
large steel surfaces and also useful whenever maximum protection from the
coating is required. The process consists in introducing sand (an abrasive) into
an air steam under pressure of 25 to 100 atmospheres. The blast is imparted on
scales and also causes a certain degree of hardening of the cleaned metal
surface.
 Solvent cleaning: This method is used to remove oils, greases and fatty
substances. The organic solvents like naphtha, chlorinated hydrocarbons,
toluene, xylene and acetone are used in this method. This is followed by
cleaning with steam and hot water containing wetting agents and alkalies. This
treatment provides a metal surface, readily wetted by aqueous which is
particularly required for electroplating.
 Mechanical cleaning: It removes loose rust and other impurities and is done
by hand cleaning with bristle brush plus some abrasive (like sand) and
detergent. Tools such as knife scapers, wire, brushes, grinding wheels and
cutters are also used for removing scales. The remaining dust and loose
particles of dirt are then removed by solvent cleaning followed by steam or hot
water treatment.
 Flame cleaning: It involves heating the metal surface with a hot flame to
remove moisture and loosely adhering scales. This is followed by wire brushing.
 Alkali cleaning: This method is used particularly to remove old paint coating
from metal surfaces. Triso-dium phosphate along with soap and wetting agents
such as caustic soda are used as cleaning agents. This method is followed by
rinsing with water and then immersion in an acidic solution of 0.1% chromic
acid to remove traces of alkalies.Alkali cleaning method can be made more
effective by the application of electric current and making the metal cathodic
in alkali medium.
 Pickling and etching: It is a convenient method to remove scales. It is usually
accomplished by immers-ing the metal (except Al) in an acid pickling solution.
Aluminum is picked in alkaline solution. Acid pickling of steel is done with
dilute sulphuric acid or in cold HCl solution to which some inhibitor is added.
For the cleaning of copper, brass or nickel, dilute HNO3 or a mixture of dilute
HNO3 and dilute H2SO4is used.
If the cleaning operation is carried out in an efficient manner, it provides a
clean, smooth surface for elec-trode deposition. Moreover, the deposit
obtained is adherent, tough, smooth and bright in appearance
Methods of application of metal coatings:
Metallic dipping causes a coat of metal over the base
metal. It is of two types, anodic coating and cathodic
coating.

Functioning of anodic coating. In galvanised steel, Zn serves as 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
 PASSIVITY
 The process in which a metal exhibits higher corrosion resistance
is called passivity. When a very thin, invisible and highly
protective film is formed on the surface of a metal or an alloy, it
is called passivity. This film is insoluble and non-passive. A metal
is passive in a certain environment if its corrosion rate is very
low. By the change of the environment, the passivity of a metal
may change and may become active towards corrosion.
 The formation of a passive film on the metal surface in
determined by the Pourbaix diagram, which depends on the
electrode potential and pH of the medium. Low carbon steel
does not corrode in conc. HNO3 due to protection effect of
passive film. However, in dil. HNO3 it does not form a stable
passive film and therefore dissolves steel. Passive film is formed
on the surface of aluminium, Cr, Si, Ti in air, water and dilute
acids.
 There is a good corrosion and oxidation resistance of stainless
oxide passive layer. A damage of passive film may cause intensive
localised corrosion (pitting corrosion). Passive oxide layers are
dissolved in electrolytes containing SO4 2– and chloride.
Phosphate and chromate ions stabilise passive films, promoting
the regain of its defects.
 Paints:
• A paint is a mechanical dispersion of one or more pigments in medium (liquid, non-
volatile) drying oil and thinner. When a metallic surface is painted, the thinner evaporates
while the drying oil forms a dry pigmented film after oxidising itself.
• A paint has following qualities:
(i) it should be spread easily on the surface,
(ii) it should form a tough, uniform and adherent film,
(iii) the coating of paint should not crack after drying,
(iv) it should have high covering power,
(v) it should neither be oxidised nor reduced in environment and
(vi) the colour due to point should be shining and stable
 Constituents of a paint:
 Pigment: It is a solid substance which is of different colours depending upon the
composition, e.g. zinc oxide, white lead, lithophone, titanium oxide (all are white in
colour). Red lead, ferric oxide, chrome red are of red colour. Chromium oxide is green,
while carbon black is black. Pigments provided (i) strength to point, (ii) protection to
the film by reflecting harmful ultraviolet light, (iii) resistance against abrasion/wear,
(iv) impermeability to moisture and (v) aesthetic appeal to the paint film. A good
pigment should be (i) opaque, (ii) chemically inert, (iii) non-toxic so that there is no
bad effect on the health of a painter as well as an inhabitant, (iv) cheap and (v) freely
mixable with film forming constituent oils.
 Drying oil: It is also called vehicle. It is a film-forming constituent. They are glycerides
of higher fatty acids (saturated or unsaturated), e.g.Drying oil may be vegetable oil.
Drying oil absorbs oxygen and forms peroxides, hydroperoxides, etc. and forms tough,
coherent, insoluble and highly cross-linked structure on the surface. They provide
toughness, durability, adhesion and water proofness to the film. When paint is applied
in the form of a film, the drying oil absorbs oxygen from air and forms peroxides and
hydroperoxides at double bonds. These peroxides isomerise, polymerise condense to
form tough, elastic, insoluble, infusible polymer film.
 Thinner: It is a highly volatile liquid, it reduces viscosity of
the paint and increases its elasticity. It increases the
penetration power of drying oil. The common thinner is
turpentine oil. Other thinners are benzene, mineral spirit,
xylol, kerosene, etc. Some other constituents of paint are—
driers(oxygen carrier catalyst) helpful in drying, e.g.
tungstate, linoleates of Co, Mn, Pb and Zn, turpentine,
mineral spirit, naphtha, methylated naphthalene etc.
 Extenders or fillers: They reduce the cost and increase
durability, e.g. barytes (BaSO4), talc, asbestos, gypsum
(CaSO4)etc. They serve to fill voids in the film and act as
carriers for pigment colour.
 Plasticisers: They are used to increase elasticity and to
minimise cracking, e.g. dibutyl phosphate, tri-cresyl
phosphate, dibutyl tartarate etc.
 Anti-skinning agents prevent skinning and gelling of
paint film, e.g. polyhydroxyphenols.
 THEORETICAL QUESTIONS
 1. What is corrosion? Why do metals corrode?
 2. Why most of the metals are found in the ore form and
not in the pure form? Explain.
 3. Describe the electrochemical theory of corrosion.
 4. Show the reactions involved in the hydrogen evolution
and oxygen absorption types of corrosion.
 5. Describe the factors on which corrosion depends.
 6. Discuss various methods of protection corrosion.
 7. Discuss the wet theory of corrosion.
 8. Explain the rusting of iron with the help of
electrochemical theory of corrosion.
 9. Explain two methods to prevent from corrosion.
 10. Define passivity with an example.
 11. Explain the acid theory of corrosion.
 12. Why rusting of iron is fast in saline water than in
ordinary water?
 13. What is differential aeration corrosion?
 14. What is meant by passivity?
 15. What is cementation?
 16. Give the functions of pigments.
 17. What is electrochemical series?
 18. Explain sacrificial anodic and impressed current
cathodic protection.
 19. Give the characteristic features of paints and their
functions.
 20. Differentiate anodic and cathodic protection methods.
 21. Differentiate galvanising and tinning.
 22. Rusting of iron is quicker in saline water than in
ordinary water. Why?
 23. What is cathodic protection?
 24. State the two conditions for wet corrosion
 Multiple-Choice Questions
 1. Corrosion is a process of
(a) reduction (b) oxidation(c) ozonolysis (d) electrolysis
 2. In the wet theory of corrosion
(a) dry cell is formed (b) galvanic cell is formed (c) concentration cell is
formed(d) none
 3. Which one of the following causes corrosion of iron?
(a) oxygen (b) hydrogen(c) strong base (d) moisture and oxygen
 4. The method in which the base metal is heated with another
powdered metal to prevent corrosion is known as
(a) electroplating (b) metal spraying (c) pack cementation (d) metal
cladding
 5. The method to prevent corrosion of iron by zinc coating is called
(a) galvanisation (b) electrolysis (c) cathode protection (d) anode
protection
 6. The rusting of iron is catalysed by
(a) Zn (b) Fe (c) Al (d) H2O (H+)
 7. A process in which metal is protected from corrosion by
dipping it in molten zinc is known as
(a) tinning (b) galvanisation (c) cladding (d) electroplating
 8. During wet corrosion
(a) the anodic part undergoes reduction
(b) the cathodic part undergoes oxidation
(c) the anodic part undergoes corrosion
(d) none
 9. The chemical composition of rust is
(a) Fe2O3⋅H2O (b) Fe3O4⋅xH2O (c) Fe2O3⋅xH2O (d)
Fe3O4⋅H2O
 10. When the ratio of anodic to cathodic area decreases, the
rate of corrosion
(a) decreases (b) increases (c) has no effec
 POLYMER
Polymers are important engineering materials
which have diversified uses in day-to-day life
Natural polymers such as polysaccharides,
cellulose, starch and proteins have been parts of
every living being since the beginning of life. In
addition, there are numerous man-made
polymers, which have a wide range of applications.
The term ‘Polymers’ is derived from two Greek
words: ‘poly’ means many and ‘mers’ means unit or
part.
A polymer is a high molecular weight compound
formed by the joining of a large number of small
units.
 CLASSIFICATIONS OF POLYMER
Polymers can be classified in several ways.

Based on Structure of Polymers

Based on Tacticity (Configuration)
Based on Synthesis
 Based on Structure of Polymers
On the basis of the structures, polymers can be classified
into three groups.

 Linear chain polymer: In these polymers, monomers are

joined together in a chain. They have high density and high
melting point due to a well-packed structure, e.g.
polyethylene and nylon.
 Branched chain polymer: In these polymers, the chain of
the polymer contains branches of monomers,which
hinders the close packing of polymeric chains, and, hence,
these are less tightly packed in comparison to the linear
chain polymers. They have low melting points and less
density in comparison to the linear chain.
 Cross-linked polymers: In the cross-linked polymers,
monomers are cross-linked together in all the three
dimensions, e.g. bakelite.
 Based on Tacticity (Configuration)
There are three different types of polymers depending upon the relative
geometric arrangement of the functional(side) groups.
 Isotactic polymer: All functional groups are on the same side of the
polymer chain.
 Syndiotactic polymer: All the functional groups are arranged in
regular on alternate sides of the polymeric chain.
 Atactic polymer: All the functional groups are arranged randomly on
both sides of the polymeric chain
Based on Synthesis
On the basis of synthesis, polymers are of two types:
Addition polymers: These are formed by the
polymerisation of monomers without the elimination of
atoms or groups.
Condensation polymers: These are formed by the
polymerisation of monomers with the elimination of
small molecules such as NH3, H2O, CH3 and OH.
 On the basis of Thermal processing behaviour,
polymers may be classified further into two groups-
 Thermoplastic polymers: Thermoplastics are polymers
that soften on heating and become hard on cooling. These
are the polymers in which inter-molecular forces of
attraction are moderate and there are no cross-links
between the chains, e.g. polyethylene, polypropylene, PVC
and nylon-66.
 Thermosetting polymer: On heating, extensive cross-link
is formed in these polymers between the polymeric chains
and, thus, they become hard, e.g. Bakelite, urea–
formaldehyde resin, terylene.
The important Thermoplastics are discussed here.
 Polyethylene (polyethene): Polyethylene (PE) is one of the
most common polymers. It is used for a variety of products, such
as polyethylene bottles, polyethylene bags, sheets, dishes and
coatings on milk cartons. The widespread use of this polymer is
due to the low cost of starting materials.
 Properties:
1. It is a soft flexible polymers.
2. PE is a good electrical insulator.
3. It is resistant to moisture, O2, CO and UV light.
4. It is resistant to acids, alkalis, salt solution at room temperature.
 Polyethylene is of two types:
(a) Low-density polyethylene (LDPE)
(b) High-density polyethylene (HDPE)
 :
 (a) LDPE: It is polymerised at a high pressure of 5000 atmospheres
The presence of branches in the polyethylene molecules does not allow it to
pack close together, and hence, its density is low (0.91–0.94 g cm–3 and is
known as a low density polyethylene.
Properties:
(1) LDPE has a linear structure with extrusive branching.
(2) It has low degree of cystallinity, low tensile strength, stiffness, hardness.
(3) It has poor chemical resistance.
LDPE is chemically inert and a poor electrical conductor. It is used in films for
packing, toys, insulation wires, pipes, etc.
 (b) HDPE: It is polymerised under 6–7 atmospheric pressure at 60–70°C in the
presence of Ziegler–Natta catalyst (AlEt3 + TiCl4) dispersed in an inert solvent.
The polyethylene molecules produced by these methods are linear. The ratio of
the side chain to the main chain is less than 1/200. Since, linear molecules can
pack themselves, the density of these polyethylene molecules is high (0.95–
0.97 g cm–3). HDPE is also chemically inert but it is more stiffer and harder
than LDPE. It is not attacked by chemicals. They are used in toys, pipes, bottles
and in bags for packing. Because of its excellent insulation properties, it is used
for wire and cable coating as well.
Polypropylene:It is prepared by passing propylene
through Ziegler–Natta catalyst (AlR3–TiCl4) at 100°C
at 10 atmospheres.
 Polytetrafluoroethylene (Teflon) (PTFE): It is prepared by
the polymerisation of tetrafluoroethylene under pressure in the
presence of free radical initiator (benzoyl peroxide).
Teflon is also known as fluon.
 Properties:
Because of the presence of highly electronegative fluorine atoms,
there are strong attractive forces between different chains in the
teflon molecules. This strong attractive force is responsible for
high toughness and high chemical resistance towards all
chemicals except hot alkali metal and hot fluorine.
 Engineering applications:
It is used in making seals and gaskets, stopcock for burettes and
impregnating glass fibre, asbestos fibre, etc. which have to
withstand high temperature. It is also used for insulation of
electrical items and for making non-sticky surface coating,
particularly for cooking utensils. It is used for storing corrosive
chemicals.
 Polyvinyl chloride (PVC): It is obtained by heating vinyl chloride in an inert
solvent in the presence of benzoyl peroxide.

PVC is also known as Koroseal.

 Properties:
1. It is due to the presence of electronegative chlorine atom on alternative carbon atoms,
and attraction between different strands takes place due to difference in polarity.
Hence,the polymer will have high softening temperature and is very hard.
2. It is colourless, odourless and non-inflammable.
3. It is resistant to weather, chemicals and oil.
4. Its plasticity can be increased by the addition of a plasticizer (ester of phthalic acid).
 Uses: It is used in making sheets, pipes, raincoats, handbags, table clothes,
plastic dolls, floor covering,electrical insulation and coating on electrical
cables. It is used in preparing bottles to pack food stuff, water and cosmetics.
 PVC is of two types: Rigid PVC and Placticized PVC.
 RUBBER (ELASTOMER)
Rubbers are high polymers capable of returning to their original length, shape or size
after being stretched or deformed. Rubber is also known as elastomer. The rubber
obtained from natural sources is called natural rubber, and the polymers prepared in the
laboratory, which are similar to natural rubber, are known as synthetic rubber. About 200
plants and shrubs have been found to produce latex on tapping. Sapotaceae latex gives
trans-isomer of isoprene; it is called Gutta percha.
 Natural Rubber
 Natural rubber is obtained from nearly 500 different plants, but the main source from
which the commercial natural rubber is obtained is the tree Hovea braziliansis. It is in cis
form known as natural rubber. The rubber is obtained from latex (milky sap) collected
from the cuts made in the bark of the tree. The latex is diluted to 15–20% and filtered to
remove impurities such as leaves, pieces of bark, etc. The obtained latex contains
hydrocarbon with impurities such as fatty acids, proteins and resins in an emulsified
form. The latex is then coagulated with acetic acid or formic acid. The crude or raw
rubber is composed of 95% hydrocarbons, 4% protein and 1% of resins. The latex is
diluted to 15–20% and filtered to remove suspended impurities such as bark, leaves, dirt,
etc. It is treated with acetic acid or formic acid. The rubber coagulates as white coagulum.
It is washed with water and passed between two rollers where rubber comes out as a sheet
resembling crepe paper. It is called crepe rubber, which can be dried and used. In the
second type of process, the rubber sheets are hung in smoked chamber for 3–4 days at
40–50°C. This rubber is called smoked rubber. Destructive distillation of natural rubber
gives isoprene as the main product.
 Vulcanisation of Rubber
 The raw or crude rubber is of very little use because it has very undesirable
properties such as low tensile strength, possesses elasticity only over a
limited range of temperature and becomes softer, more plastic and sticky
on heating and brittle on cooling. Its solubility in organic solvents (such as
CHCl3,benzene and petrol) is of advantage for preparing rubber derivatives
and adhesive solutions. It swells in water and attacked by acids, bases O2.
It reacts with O2 to give epoxide with bad smell.
 In order to give more strength and more elasticity, natural rubber is heated
with sulphur or sulphur compounds at 150°C temperature for a few hours.
 The sulphur combines chemically at double bonds of
different rubber springs and a cross-linked network is
formed. This process is known as vulcanisation of rubber.
The vulcanisation process was invented by Charles
Goodyear in 1839. The vulcanisation can also be
accomplished with certain peroxides, gamma radiation and
several other organic compounds. The vulcanisation
process can be enhanced in the presence of certain organic
substances known as accelerators. The common
accelerators contain nitrogen, sulphur or both.
 Advantages of vulcanised rubber
1. Vulcanised rubber has good tensile strength.
2. The working temperature of vulcanised rubber is enhanced
up to 100°C. The temperature range of raw rubber is 10–60°C.
3. The elasticity of vulcanised rubber is very low.
4. It has good resistance to organic solvents.
5. It acts as good electrical insulator.
6. It has low water absorption tendency.
7. It has good impact resistance.
8. It possesses good resistance, i.e., articles made from it return
to original shape when load is removed.
 Application of natural rubber
1. It is used in tank lining in chemical plant for storing corrosive
chemical.
2. It is used in the manufacture of tyres, toys, sport items etc.
3. In used as sandwitching material between metal surface to
prevent liberation in machine parts.
 Thiokol (polysulphide rubber or GR-P):
 Polysulphide rubbers are the condensation products of ethylene dichloride and sodium tetrasulphide.
Polymers | 109 Thiokol (yellow solid)
 Properties
The properties of polymers depend on the length of the aliphatic groups and the number of sulphur atoms present. The
polymer behaves like elastomer when four sulphur atoms are present per monomer and it does not behave as elastomer
if only two sulphur atoms are present per monomer. Thus, in case of thiokol, four methylene groups should be present
in the dihalide to induce elastic properties. Some of the important properties are:
(i) Thiokol is resistant to the action of oxygen and ozone.
(ii) It is also resistant to the action of petrol lubricants and organic solvents.
(iii) Thiokols show outstanding resistance to swelling by organic solvents, but benzene and its derivatives cause some
swelling.
(iv) Thiokol films are impermeable to gases to a large extent.
(v) Thiokols are vulcanised with metal oxides such as zinc oxide.
(vi) Thiokol has poor heat resistance and low tensile strength. The odour of thiokol is very bad. It tends to lose its shape
under continuous pressure.
 Uses
 Thiokol mixed with oxidising agents is used as a fuel in rocket engine.
 It is used in engine gaskets and other such products that come into contact with oil.
 Thiokols are used for hoses and tank lining for the handling and storage of oils and solvents
 Fibres-:
 Fibres are thin ,long ,thread like materials which are extremely
long compared to its width, atleast hundred times longer than its
width.
 Fibres can be classified into two groups
 Natural Fibre = Natural Fibre naturally occurs in plants and
animals e.g. wood ,silk,cotton
 Manufactured Fibre = It is further classified in to two groups
 Regenerated Fibre = These are made from natural fibres.e.g. rayon
( made from cellulose ), cellulose acetate (made from cellulose )
 Synthetic Fibre = These are made from chemicals e.g. nylons
(polyamide ) ,terylene , polyester etc
 COMPOUNDING OF PLASTICS
 The pure material obtained from the process of polymerisation is
known as polymer. The usefulness of long chain pure polymer is very
little. After adding some materials, polymer becomes useful and
termed as plastic.
 These additives improve the workability of plastics and change the
properties of plastics.
 The following types of additives are found to be present in plastic:
 Fillers: These are substances that increase hardness, tensile strength
and the mechanical properties of plastics. Some important fillers are
carbon-black (C-black), chalk, china clay, cellulose fillers, metallic
oxide (ZnO, PbO, etc.), metal powders (Al, Cu, Pb, etc.), carborundum,
quartz, etc. Fillers also reduce the cost of final compounds.
 Binder (resin): In plastics, binder holds different constituents
together. They are generally low-molecularweight materials and
withstand high temperature.
 Plasticisers: Plasticisers are generally small liquid molecules that are
chemically similar to the polymer and create gaps between polymer
chains for greater mobility and reduced inter-chain interactions.
Commonly used plasticisers are camphor, some phosphate esters
(dioctyl phthalate), etc.
Stabilisers: Stabilisers are used to improve the thermal
stability of plastics, e.g. polyvinyl chloride.
 At moulding temperature, PVC undergoes decomposition and
decolourisation. So during their moulding, stabilisers are used.
The commonly used stabilisers are white lead, lead chromate,
red lead, etc.
 Colouring materials: Organic dyestuffs and inorganic
pigments are used as colouring materials. They give bright
transparent colours. For example, carbon black—black,
anthraquinone—yellow and phthalocyanine
 Liquid Crystal Polymers
Liquid crystal polymers (LCP) are a class of aromatic
polyester polymers. They are also known as super
polymers. Liquid crystallinity in polymers occurs
either by dissolving a polymer in a solvent (lyotropic
liquid crystal polymer) or by heating a polymer above
its glass transition temperature (thermotropic liquid-
crystal polymers). These show the characteristic of
ordinary liquid crystals and also retain the properties
of polymers
 Fabrication of plastic
 The fabrication of plastic is the manufacturing process of
plastic articles. The com-monly used methods for
fabrication of plastic articles are welding, extrusion,
moulding, etc.
 Welding: Similar to metal welding, plastic welding also
involves the use of heat to melt two or more pieces
together. In this method, thermoplastics are used which
are unsuitable for adhesive binding.
 Extrusion: It is a manufacturing process in which plastic
material is melted and formed into a continuous profile.
This method of fabrication is generally used for the
manufacture of pipes, tubes, window frames, rods, etc.
 Moulding Process: The commonly used methods are
 Injection moulding
 Compression moulding
 Transfer moulding
 Blow moulding

Injection moulding

Transfer moulding Compression moulding

Blow moulding
Fibre-Reinforced Plastic (FRP)
 Fibre-reinforced plastics are a category of plastics that
specifically use fibrous material to mechanically
enhance the strength and elasticity of plastics. The
plastic material without fiber reinforcement is known
as matrix. Enhanced strength and elasticity in a fiber-
reinforced plastic depends on the mechanical
properties of both the fibre and the matrix, as well as
the fibre length and orientation within the matrix.
 Mainly fibre-reinforced plastics are classified into two
groups:
 Carbon fibre reinforced plastics (CFRP)
 Glass-fibre reinforced plastics (GFRP)
 There are various methods for producing fibre-
reinforced plastic such as continuous lamination,
pultru-sion, rotational moulding, injection moulding,
hand lay up, etc.
 Application of FRP: They find extensive use in space
crafts, aeroplanes, acid storage tanks, motorcars, and
building materials. Melamine FRP is used for
insulation and in making baskets.
 Advantages of FRP:
1. They are non-inflammable and resistant to
corrosion, chemicals, etc.
2. The cost of production of FRPs is low.
3. They possess low coefficient of thermal expansion
 Biodegradable polymers
 Biodegradable polymers are defined as the degradable
polymers in which degradation is caused by the action of
naturally occurring microorganisms such as algae, fungi,
and bacteria. They are easily compostable. During
compositing, they yield CO2, H2O, inorganic compounds
and biomass at a rate consistent with other compostable
materials without leaving toxic residues.
 They are classified into following groups:
 Naturally occurring biodegradable polymers
 Biosynthetic polymers
 Synthetic biodegradable polymers
 Some important biodegradable polymers of synthetic
polymers are poly alkene esters, polyamide esters, polyvinyl
esters, polyvinyl alcohols, polylactic acid and its copolymers
and polyanhydrides.
 Applications of biodegradable polymers :
 Packaging:Compostable bags help in the disposal of vegetable matter
which gets converted to carbon diox-ide and methane.
 Agriculture:Biodegradable polymers are synthesized from the
materials derived from the processing of crops or from petrochemical
feedstock with conventional processing methods, thereby minimizing
the cost of raw materials. The problem of landfill solid wastes can be
reduced.
 Medical applications: Biodegradable polymers are used as surgical
implants in blood vessels for a long-term drug release and as
absorbable surgical sutures for the treatment of eye. Most commonly
used biocompatible sutures are made of PGA and PLA and their
copolymers are used as a surgical thread. PGA gets absorbed in 15 days.
 Bone-fixation devices: Biodegradable polymers such as PGA, PLA
and polydioxanone are used as bone-fixation devices since they have
high compatibility with bone and ligament compared to metal. When
metal implants are used, the removal of metal may cause weakness of
bone and refractures may occur. But biode-gradable polymers when
used for bone fixation allow free movement of ligaments and bones
THEORETICAL QUESTIONS
 1. What is corrosion? Why do metals corrode?
 2. Why most of the metals are found in the ore form
and not in the pure form? Explain.
 3. Describe the electrochemical theory of corrosion.
 4. Show the reactions involved in the hydrogen
evolution and oxygen absorption types of corrosion.
 5. Describe the factors on which corrosion depends.
 6. Discuss various methods of protection corrosion.
 7. Discuss the wet theory of corrosion.
 8. Explain the rusting of iron with the help of
electrochemical theory of corrosion.
MATERIALS CHEMISTRY
Introduction
 The term engineering materials is used to include a
wide variety of materials used in construction and
fabrication.
 Engineering materials include cementing materials or
binding materials such as lime, cement, gypsum and
ceramics.
 Ceramics includes a variety of materials such as glass,
refractories, clay products, lubricants, rocket
propellants, etc.
 Cement
 Cement is a construction material which possesses
adhesive and cohesive properties and is used for binding
building blocks, bricks, stones, etc.
 Cements are classified into four types based on the
chemical composition. The essential constituents of
cement used for construction are the compounds of
calcium (calcareous and argillaceous; calcium + silicon).
 Classification of Cements-Cements are classified into
various types as follows:
 1. Natural cement
 2. Puzzalona cement
 3. Slag cement
 4. Portland cement
 Natural Cement-Natural cement is made by subjecting the argillaceous limestone
to calcinations at high temperature and then pulverizing the calcinated mass.
Natural cement possesses low strength and hydraulic qualities. It is used in the
preparation of mortars and in the construction of dams and foundations
 Puzzalona Cement-It has been the oldest cement used by Romans for the
construction of domes and walls. Natural puzzalona is a deposit of volcanic ash
produced by rapid cooling of lava mixed with slaked lime. It is a mixture of
aluminium silicate, calcium silicate and silicates of iron. They form hydraulic
cementing materials and possess hydraulic properties. Puzzalona cements are not
used directly but can be used by mixing with Portland cement for various
applications.
 Slag Cement-Slag cement is obtained by mixing blast furnace slag (aluminium
silicate) and calcium, then the mixture is poured into cold water. The granular
cement produced is dried and mixed with lime. The mixture is then pulverised to
fine powder. Slag cements are slow-setting cements. They can be hardened by
adding accelerators such as clay, salt or caustic soda. The strength of slag cement is
less. It is mainly used for making concrete for construction in waterlogged area
where the tensile strength is less important.
 Portland Cement -Portland cement is made by the calcination of calculated
amount of clay and lime, followed by gypsum for retarding calcination. The setting
and hardening properties resemble Portland rock, so it is named as Portland
cement. It is a mixture of calcium silicates and calcium aluminates with small
amount of gypsum. All Portland cements are hydraulic in nature, which are capable
of setting and hardening under water by the interaction of water with the
constituents of cement.
Chemical Composition of Cement:
 Cement contains silica, lime and alumina. The
proportion of these constituents in cements should be
main-tained to get good quality cements.

 (1) MgO should be less than 6%.

 (2) Sulfur content should always be less than 2.75%.
 (3) The ratio of alumina to iron oxide should be 0.65.
 (4) Total loss on ignition should be less than 4%.
 Setting and Hardening of Portland Cement
 The hydration of cement followed by gelation is called setting and the
subsequent crystallisation is called hardening. The strength of cement
depends on the amount of gelation and the extent of crystallisation.
 Cement is mixed with water to produce a plastic cement paste. The
paste is subjected to hydration and gelation and finally crystalline
products are formed.
 1. Initial setting of cement involves hydration of tricalcium aluminate.

 2. Second step of the reaction involves gelation in which tobermonite

gel is formed. It also produces calcium hydroxide and hydrated
tricalcium aluminate.
 3. Crystallisation of tricalcium aluminate takes place. Even
though initial reaction involves the formation of
tetracalcium alumiate, hardening of tricalcium aluminate
takes place finally through crystallisation.

 Final setting and hardening of cement paste may be due to

the formation of tobermonite gel with the
 crystallisation of calcium hydroxide and hydrated calcium
aluminate.
 Mentioned below is the flow chart representing setting and
hardening of cement.
 Complete setting and hardening of cement takes place in 20 days.

1. Hydration of cement takes place in one day

2. Next hydration of C3S is completed in seven days

 The gel of C3A crystallises and dicalcium silicate (C2S) begins to hydrate in 7–28 days. The strength of
cement is increased in 7–28 days due to the gelation of both dicalcium silicate and tricalcium silicate.
Initial setting and final setting are recognised based on the ability of the penetration of vicat needle
into the mass. Initial set takes place when the needle does not penetrate the paste beyond certain
depth; final set takes place when the needle does not penetrate the mass at all.
 For ordinary cements, initial setting should be less than 45 minutes to allow sufficient time for mixing,
transportation and placing between the aggregates. Final setting should not be more than 10 hours.
Quick setting cement requires 5 minutes for initial setting and less than 30 minutes for final setting.
 Hardening involves increasing strength of cement. It depends on the chemical combination of cement
and water and occurs faster in the beginning and goes on decreasing gradually. It is a relatively slow
process.
 The heat of hydration of cement constituents is useful in the formulation of cements for different
purposes. Information regarding heat of hydration helps in preventing freezing water in the cement
paste in winter. It is used in controlling the speed of setting and hardening of cement. The liberated
heat should be quickly dis-sipated, otherwise serious stress crackings occur in concrete constructions.
 Special Cements
 1. Water-proof cement: This cement makes the concrete impervious to
water and resist absorption of water. This type of cement is prepared by
adding water proofing agents like calcium stearate, aluminum stearate,
gypsum and tannic acid to Portland cement during grinding and
powdering process.
 2. High alumina cement: High alumina cements are made by fusing
bauxite and limestone mixture at 1500–1600ºC in rotary kiln and the
resulting mass is subjected to grinding .Setting time is similar to portland
cement but hardening is very rapid. It also has superior resistance to
chemicals.
 3. Acid-resistant cements: They are produced by mixing finely ground
quartzite with silicon in suitable proportions. Sodium silicon fluoride, or
ethyl acetate are used as setting agents; silica gel gets precipitated. On
drying, it becomes very porous and permeable to liquids. Hence, it should
be always kept wet to prevent shrinking of gel.
 4. Barium strontium cements: The calcium in Portland cement is
replaced by barium or strontium.Tribarium and dibarium silicates offer
more resistance to radioactive rays. Hence, they are used in concrete
shields for atomic piles.
 Concrete
 Cement alone cannot be used for construction work,
because it is sensitive to moisture and liable to get internal
stresses. In order to overcome these, concrete is used. It is a
building and structural materials obtained by mixing
binding materials (cement or lime), mineral aggregates
(sand, crushed stone, gravel, broken bricks, slag, etc.) and
water in suitable proportion. It is compact, rigid, strong
and durable. If concrete is to be used in beams, pillars, etc.,
where tensile stresses occur, concrete is reinforced with
steel rods, glass fibres, etc. to improve the strength. The
resulting cement is called RCC (reinforced concrete
construction). RCC possesses greater rigidity, moisture and
fire resistance. Its maintenance cost is practically negligible
 Decay of Cement (Effect of CO2)-The constituents of cements
are likely to be attacked by acids and salts present in water. CO2
in acidic water causes leaching out of pure lime.

 The above cycle of reaction continues to occur till all the CO2 is
consumed. Hydrolysis of silicates and aluminates in the cement
also results in the decay of cement.
 Prevention of Cement Decay
 The decay of cement can be minimized by coating the surface
with epoxy resin paint or using drying oils. As a result, acidic
water fails to enter into cement. When alkaline water is carried
by sewage pipes, the SO2 component of cement is attacked. To
prevent it, the inner surface of concrete pipe is treated with SiF4
which produces insoluble CaF2.
Lubricants
 When one solid surface is sliding past over another
solid surface, friction and wear is developed due to the
relative motion of two contacting surfaces which
results in the loss of energy as heat. As the equipment
gets heated up, it is damaged and sometimes result in
welding or seizure.
 Any substance introduced between the two moving
and sliding surfaces with a view to reduce frictional
resistance is known as ‘lubricant’. ‘Lubrication’ may be
defined as the reduction of friction between two
relatively moving surfaces by the interposition of some
other substance (lubricant) between them.
 Functions of Lubricants
 1.Lubricants help in reducing frictional forces between two
sliding surfaces. Even highly polished and extremely
smooth surfaces show many irregularities and peaks called
asperities when viewed under a microscope; when pressed
together they exhibit high friction and wear. Even highly
polished surfaces can be welded together by the application
of pressure. But when a lubricant is placed, the separation
of two surfaces takes place and interlocking of peaks and
valleys does not occur, and sliding takes place conveniently.
 2. It reduces wear and tear and surface deformation. When
a lubricant is placed between the two sliding surfaces,
direct contact between them is avoided. Without lubricant,
small peaks would be sheared which results in wear and
tear and surface deformation; excessive wear in machinery
or any part result in malfunctioning of entire unit.
 3. It prevents the loss of heat energy produced by
frictional forces between two sliding surfaces and acts
as a coolant. In a machine, frictional heat is produced
at the point of contact between the rubbing parts.
Cool oil which is flowing on a heated surface carries
away the heat.
 4. It reduces running cost and maintenance cost of
machines and tools. A lubricant prevents corrosion
and rusting of machine parts. The rust inhibitor in
lubricant protects the machine parts.
 5.It acts as a seal. In internal combustion engines,
lubricant is used as a seal between the wall of the
cylinder and piston and prevents the leakage of gases
under high pressure from the cylinder.
 6. It prevents the accumulation of dirt and foreign
matter entering the bearing.
 Classification of Lubricants
 Lubricants are classified according to the state of
aggregation as liquid, semi-solid and solid lubricants. Their
use in machinery depends on its working conditions. They
contain 90% base (usually petroleum fractions called
mineral oils) and less than 10% additives.
 1. Liquid lubricants: Lubricating oils are widely used for
the lubrication of machine tools. They act as sealing
agents, corrosion inhibitor and cooling medium. Majority
of them are of petroleum origin; some of them are of
vegetable or animal origin.
 Examples:
 Animal oils: whale oil, lard oil, tallow oil, seal oil, etc.
 Vegetable oils: mustard oil, sunflower oil, cotton seed oil,
etc.
 2. Semi-solid lubricants:
 When a liquid lube oil cannot be maintained, lubrication is
done by a semi-solid lube. Greases are very good semi-solid
lubricant. An automotive wheel bearing is best lubricated
by grease. A semi-solid lubricant is obtained by combining
lubricant oil with thickening agent.
 They are special soaps of sodium, calcium, baricum,
aluminium, etc. Non-soap thicknes are carbon-black, silica
gel, poly urea, etc. They have high resistance to friction
than oils and can support heavier loads at low speeds.
 Semi-solid lubricant are used (a) where oil is not suitable
for machines, (b) when machines are working with heavy
load at low speed and (c) where sealing is required without
dust particles and moisture and contamination is not
acceptable.
 3. Solid Lubricants:
 In certain aero-space devices and some other environments, liquid and
semi-solid lubes cannot be used. Solid lubricates such as MoS2, mica,
chalk, wax, soap, graphite, which can with stand heavy load and low
speed can be used. They consist of a number of layers of atoms held
together by weak van der Waals forces which makes them soft and
smooth to act as lubricant. Because of its slippery touch, non-
inflammability and resistance to oxidation, graphite is a widely used
solid lubricant. It can be used as powder or as colloidal dispersion in
water (aqua dag) oil (oil dag). Graphite is used in IC. engines, lathes,
and air compression engines, but is ineffective in vacuum conditions
and above 370ºC. MoS2 can be used upto 800ºC. It possess very low
coefficient of friction. Hence, it can be used in air frame lubrication
and wire drawing. Other organic solid lubes are copper phthalocyanine
and teflon.
 Gases:
 In recent times, gases have also been used as lubes in precious spindles,
fans, compressors, etc., because of their low viscosity which is
independent of temperature. Hence, the viscous resistance is
minimum and there is no effect of variation in temperature on
lubrication. There is no risk of contamination of gas if enclosed system
is used as lubricant.
 Mechanisms of Lubrication
Three mechanisms have been proposed to explain the action of lubricants.
They are:
 1. Thin film or boundary lubrication
 2. Fluid film or hydrodynamic lubrication
 3. Extreme pressure lubrication

 1. Thin film or boundary lubrication:

In this type of lubrication, a thin film of lubricant is adsorbed on the surface
and held by van der Waals forces. When the lubricant is not viscous enough to
generate a film of sufficient thickness for the separation of surfaces under
heavy loads, friction is reduced by thin film lubrication. Thin film lubrication
is applied when (a) the speed in very low, (b) the shaft moves from rest position
to operation, (c) the load in heavy and (d) the oil has low viscosity. Some peaks
or asperities may have higher thickness than the film of lubricant which results
in wearing and tearing. Hence, the chemical or physical forces on some metal
surfaces would avoid the direct contact of metals and absorb a thin layer of
lubricating oil. In such conditions, lubricant forms a thin layer and gets
adsorbed.

Boundary film lubrication

 2. Fluid film or hydrodynamic lubrication
This type of lubrication is also known as thick film
lubri-cation. It is carried out with the help of liquid
lubricants. In fluid film lubrication, the two sliding
sur-faces are separated by a thick film of about 1000 Å
which is applied to prevent direct surface-to-surface
contact. Wearing and tearing of metals is minimised.

Fluid film lubrication

 3. Extreme pressure lubrication
It involves chemical action on the part of lubricant
Under heavy load and high speed conditions, high
local temperature is generated. The liquid film may
not stick, it may decompose and vapourise. Hence,
special additives called extreme pressure additive are
blended with lubricating oils to form more durable
film to withstand high temperature and pressure.
Chlorinated esters, sulfurised oils and tricresyl
phosphates are used as extreme pressure additives.
 Flash and Fire Point
 Flash point is defined as the minimum temperature at which the
lubricating oil gives off its vapours that ignite for a moment when a
flame is brought near it. Fire point is the lowest temperature at which
the vapours of the oil burn continuously for at least 5 seconds, when a
flame is brought near it.
 The flash point of the lubricating oil is above the operating
temperature, because a good lubricating oil should not volatalise under
the working conditions usually. The fire points are 5 to 40°F higher
than flash points. But the flash and fire points do not have any relation
with the lubricating property of oil. Flash and fire points indicate the
occurrence of fire accident. Before fire occurs flash appears.

Flash point apparatus

Application of Lubricants
 Selection of lubricants for few typical applications is given under.

 Lubricants for IC engines: In internal combustion (IC) engines, the

lubricants are generally exposed to high temperatures. Therefore, they
should possess high viscosity index and should be thermally stable.
Hence, petroleum oils containing additives which produce high VI and
oxidation stability are used in IC engines.
 Lubricants for refrigerators: For refrigeration, the selected lubricant
must possess low pour point, low viscosity and low cloud point.
Maximum limit of pour point is –40ºF for lighter grade and –13ºF for
heaviest grade oils, and viscosity should be 85–325 say bolt universal
seconds at (545) 100ºF. Naphthalene base oils satisfy these conditions
and hence are suitable for refrigeration.
 Lubricants for very high pressure and low speed:
Concrete mixers, lathes, railway joints, tractor rollers,
etc. are exposed to very high temperature and move at
low speed. A film of oil or grease is difficult lathes,
railway joints, tractor rollers, etc. are exposed to very
high temperature and move at low speed. A film of oil
or grease is difficult to maintain. Hence, a dry power of
solid lubricants such as graphite, mica is used.
 Lubricants for gears: The lubricants used in gears are
exposed to extreme pressures, hence thick mineral
lubricating oils are used so that they should stick to
the gear teeth. The oil also should possess high
resistance to oxidation and high tensile strength.
Lubricants should possess good lubricating properties,
non-corrosive nature, and chemical stability.
 Selection of a Lubricant
 The selection of a lubricant depends on the operating conditions. Many conventional
lubricants do not work at lower temperatures, and at higher temperatures, they may
break down. The type of lubricating oil suitable for different conditions is given in Table.

 Table : Types of lubricating oil suitable for different conditions

 Operating condition Types of lubricant oil

 High speed, heavy load Extreme pressure lubricants
 Low speed, heavy load High oiliness boundary film lubricants
 Less load, high speed Oil with low viscosity
 Low temperature High fluidity
 High temperature Oxidation resistance and less volatility
 Refractories
 Refractories are inorganic materials which can withstand very high
temperatures without softening or suffering deformation. Therefore, they are
used for the construction of kilns, ovens, crucibles, retarts, furnaces, etc. The
main function of refractories varies depending on the purpose to which they
are subjected like confining heat within the furnace, transmitting or storing
heat in regenerators. The selection of a refractory for a particular purpose
depends on the service conditions, like working temperature to which it is
exposed, the nature of the materials which come into contact with it,
temperature fluctuations, load applied and the nature of chemical reactions
which occur.
 Characteristics of a Refractory
A good refractory materials should possess
(1) high-temperature resistance under working conditions,
(2) good abrasion resistance by dusty gases and molten metals,
(3) low permeability or ability to contain heat,
(4) high mechanical strength, structural strength and crack resistance to
withstand overlying load,
(5) thermal strength to withstand thermal shock due to rapid and repeated
temperature fluctuations and
(6) high resistance to change in physical, chemical and mechanical properties.
 If a given refractory, materials does not have the above-mentioned
characteristic properties, it will fail in service.
 Factors Affecting refractory materials
 1. Chemical reaction with the environment in which it is working. It should be in a
chemically similar environment. For example, acidic refractories should not be used
in furnace using basic fluxes or slags and vice-versa.
 2. Porous refractory materials causes penetration of slag to greater depths and
consequently destruction of refractory. It also affects the reactions with gases.
 3. Deposition of carbon from carbon monoxide in fireclay refractories in blast
furnace is an important cause of its failure. It results in high internal stresses
resulting in the destruction of bricks.
 4. Rise in temperature beyond safe limit quickly brings about the destruction of
refractory.
 5. Agitation or movement of the materials also causes failure of refractory. If
agitation is on the surface, new surface is quickly exposed to chemical attack and is
destroyed.
 6. Another important cause of failure of a refractory is spalling. It is the breaking or
cracking or peeling of fragments or spalls from the surface of refractory brick.
Spalling may be thermal or mechanical or structural.
 Thermal spalling is due to unequal expansion or contraction caused by difference in
temperature at different parts of furnace or by rapid changes in temperature.
 Mechanical spalling: It is due to carelessness in loading the furnace or due to
removal of materials from the furnace thereby damaging the refractory.
 Structural spalling: It is due to change in composition of the refractory due to
reactions with slag. As a result, the coefficient of expansion changes. Spalling of a
refractory can be reduced by proper design, construction and operation of the
furnace.
 Classification of Refractories
Refractories are broadly classified into three categories.
 1. On the basis of their chemical nature
a. Acidic refractories: They are made from acidic materials such as alumina (Al2O3) and silica
(SiO2). They are resistant to acid slags, but attacked by basic materials such as CaO and MgO.
Examples: Silica, alumina and fire clay refractories (fire clay refractories contain silicate
mineral kaolinite. Silicate refractories which rank next to fireclay refractories are produced
from quartzite and quartz pebbles).
b. Basic refractories: Basic refractories are those which consist of basic materials. They are not
attacked by basic materials, but attacked by acidic materials. They find extensive use in steel-
making open hearth furnaces.
Example: Magnesite, dolomite, chrome magnesite refractories.
c. Neutral refractories: They are not completely neutral in chemical sense. They consist of
weakly basic/ acidic materials such as carbon, zirconia (ZrO2), chromite (FeOCrO2), graphite
and silicon carbide.
 2. On the basis of fusion temperature
a. Normal refractory: Fusion temperature is 1580–1780oC.
Example: Fire clay refractory
b. High refractory: Fusion temperature is 1780–2000oC.
Example: Chromite refractory
c. Super refractory: Fusion temperature is above 2000oC.
Example: Zirconia
3. On the basis of oxide content
a. Single oxide refractory
Examples: Alumina, magnesia and zirconia refractory
b. Mixed oxide refractory
Example: Spinel and mullite
c. Non-oxide refractory
Example: Borides, carbides and silicates
 Properties of Refractories
 Chemical inertness:
The refractory materials used as lining for furnace should be chemically inert. It
should not react with slags, reagents, furnace gases, fuel ashes and products
produced inside the furnace. Acidic refractories should not be in contact with
alkaline product, vice-versa.
Example: Silica bricks being acidic cannot be used in a basic furnace and magnesite
bricks being basic can-not be used in acidic furnace.
 Refractoriness:
It indicates the ability of a refractory to bear its own weight at high temperature.
The refrac-tory materials should not undergo deformation with increase in
temperature. Higher the softening tempera-ture, more valuable is the refractory.
Refractoriness is expressed in pyrometric cone equivalents (PCE). The materials
whose refractoriness is to be tested is taken in the form of cone and a similar sized
standard cone is also taken. Then both the cones are heated uniformly at 10°C per
minute. The standard cones possess definite softening temperature. Standard
cones are given the number 22 to 42 with increasing softening temperature. When
the test cone gets softened and loses its shape, one of the standard cones whose
refractoriness is close to that of the test cone will also soften. The serial number of
that standard cone is noted and this number is the PCE of test cone. The soften-ing
temperature range of this pair is also noted. For example, silica brick has PCE of 33
with a softening temperature range of 1700–1750°C. This indicates that particular
refractory can be used in the temperature range of 1700°C.
 Thermal expansion and contraction:
The expansion and contraction of a good refractory should be negli-
gible with change in temperature. Repeated contractions and
expansions of a refractory materials will lead to the breakdown of
refractory materials. The lower the thermal expansion and contraction,
the better the quality of the refractory.
 Porosity:
Combustible materials like sawdust when used as raw materials for
making bricks make them po-rous. Certain foaming agents are added
to make the refractory porous. The porosity of a refractory is the ratio
of its pore volume to the total or bulk volume. Porosity influences the
strength of a refractory. If it is highly porous, molten reactants, gases,
slags, etc., penetrate and damage the brick. As a result, its abrasion
resistance and mechanical strength decreases. Contrary to it, in a
porous brick the pores act as an insulator for the furnace. Porosity
decreases thermal spalling.
 Thermal spalling: The breaking, cracking, peeling of a refractory can
be reduced by (1) using materials with low porosity and low coefficient
of expansion, (2) avoiding sudden changes in temperatures and (3)
avoiding overfiring during construction and finishing of internal
lining of refractories
 NANO MATERIALS:
Nano materials are the materials of nano-metre (10–9 m)
dimension. The properties of nano materials significantly differ
from bulk materials. For example, the electronic structure of
metals and semi-conductor. crystals greatly differs from those of
isolated atoms and bulk materials. Some of the nano materials
like gold particles of 1–2 nm size exhibit unusual catalytic
properties. Large pieces of gold and silver show inert (noble)
behaviour. Silver is widely used in jewellery because of its inert
nature, but it shows anti-bacterial activity at nano scale. Now-a-
days nano particles of silver are used in wound dressing. The
uniqueness of nano particles is due to two factors:
 1. Smaller particles have a relatively large surface area than their
volume.
 2. Below 100 nm size, quantum effects can change the magnetic
and electronic properties in unpredictable manner.
Nano-particle-reinforced polymeric materials could replace
structural metallic components in the auto-mobile industry.
Widespread use of the nano composites could reduce the
consumption of 1.5 billion litres of gasoline by the fleet of
vehicles in 1 year thereby reducing CO2 emission by about 5
billion kg annually.
 Synthesis of Nano Particles:
A number of methods have been developed for the synthesis of nano particles.
Some of them are:
 Precipitation: In this method, metal salts are dissolved in appropriate solvent and
reducing agents such as alcohols, glycols, metal borobydrides, hydroxy methyl
phosphonium chloride are added. For example, gold hydro sols. of 10–640 A size
can be prepared by reducing chloroaurate ions in sodium borohydride solution.
Semiconductor nano crystals of CdSe, AgI, TiO2, Cus, ZnS, ZnO, etc., are prepared
by kinetic control of precipitation.
 Solvothermal synthesis: In this method, the material is heated in an autoclave at
very high temperature i.e. above the boiling temperature of solvent, and a pressure
above atmospheric pressure are employed. Nano crystals of CdSe have been
prepared by heating a mixture of cadmium stearate and selenium powder in tolu-
ene and in the presence of catalyst tetra hydronaphthalene.
Microwave solvothermal method can be employed for the synthesis of nano
particles of MFe2O4 (M = Mn, Lo, Ni, Zn) by heating ammonical solutions of
metal nitrates in the microwave oven for 4 minutes.
 Thermolysis: In this method, high boiling organic solvents are used to prepare
nano crystals. For example, nano crystals of CdSe have been prepared by reacting
dimethyl cadmium dissolved in tri-n-octyl phosphine with tri-n-octyl phosphine
selenide in hot tri-n-octyl phosphine oxide in 120–300°C range of temperature.
The size of the particle depends on the reaction temperature. Larger particles are
produced at higher temperatures. Other organo-metallic nano crystals like CdSe,
PbSe, InP, ZnSe, GaSn, InSb, etc., have also been prepared by thermolysis. By the
thermal decomposition of selected precursors, alloys of controlled composition
like Cd 1 – x MnSe have been prepared.
 Sonochemical reduction: Ultrasound radiation of 20 kHz
to 10 MHz is used for sonication. When a liquid is exposed
to ultrasound radiation, bubble formation, collapse and
breaking of chemical bond occurs. As a result, nano-sized
particles of crystalline or amorphous nature are produced.
For example, nano particles of copper were obtained by
the sonochemical reduction of copper hydrazine
carboxylate in aqueous solution. If argon gas is used for
sonication, metallic copper and cuprous oxide nano
particles are formed.
 Vapour-phase reductions: In this method, evaporation of
pre-formed semiconductor powders or coevapo-ration of
two components like zinc metal and sulphur to produce
zinc sulfide nano particles takes place.
 Techniques for Characterizing Nano Materials
 There are some optical and electrical techniques to characterize
the nano materials. They are used to study the influence of the
optical structural and surface morphological properties of nano
materials. A commonly used technique for optical
characterization is UV-visible spectroscopy. Optical properties
are important for the films. The measurement of transmission or
reflection of a sample provides to determine absorption edge.
The absorption edge and energy band gap can be determined
from the transmission measurement which shifts with the size of
the nano particle. The absorption of photons takes place and
electrons can be raised when an incident radiation passes
through thin film material with energy equal or greater than that
of the band gap. The material absorbs little and can transmit the
photons with less energy. The ability of a material to absorb
photons of a given wavelength is measured quantitatively by the
optical absorption coefficient measured in units of reciprocal
distance.
 Applications of nano materials
 1. The potential application of nano particles is in the design of new
supercomputers. It includes zero dimensional quantum dots¤, one-dimensional
quantum dot, planar arrays of ordered structures, nano scale circuits, etc.
 2. Nano particles are potential components in the generation of bimetallic nano
structures and nano mechanical device based on DNA.
 3. The magnetic nano metal particles are widely used in magnetic separation,
magnetic drug transport and magneto-optical data storage.
 4. In communication technology, nano wires 20 times thinner and longer than
conventional wires are used.
 5. Nylon nano composites containing small amount of clay are capable of
withstanding high temperature environments and used in automobile air intake
covers.
 6. Catalysts that are stable at high temperatures and can be used in smaller
possible amount have been discovered. For example, Rhodium hydrosols are the
effective catalysts for the hydrogenation of olefins in organic phase. The
complex oxide barium hexa aluminate BaO3Al2O3 retains its catalytic activity at
high temperature. Conventional methods to synthesise the catalyst tend to
reduce the catalytic activity by reducing its surface area, Coordinating polymers
(polyvinyl pyrrolidone) seem to protect nano metal particles in their catalytic
activity towards hydrogenation of olefins and hydration of nitriles.
Nano chemical routes catalyse the chemical reactions at much lower
temperature, pressure and in a very short period of time
 7. A combination of nano materials with enzymes improves the
durability of enzymes, create localised high concentration of proteins
and reduces cost by minimising losses.
 8. In the field of medicine and surgery, nano technology possesses
several potential applications. Mutations in DNA could be repaired and
cancer cells, toxic chemicals, viruses could be destroyed with the help
of nano devices. Sensor systems which detect the emerging diseases in
the body would shift the focus from the treatment of disease to early
detection and prevention. They can perform tasks inside the body that
would otherwise not be possible. For example, nano-scale devices
smaller than 50 nm can easily enter most cells, and those smaller than
20 nm can move through the walls of the blood vessels. As a result, a
nano-scale device can interact with molecules on both the cell surface
and within the cell.
 9. Nano technology significantly improves energy efficiency, storage
and production of solar cells. Solar cells are expensive and nanometre-
sized solar cells provide more energy at a cheaper price. This would
reduce the usage of fossil and nuclear fuels. further, the solar fuel is
cleaner, safer and environment friendly or ecofriendly.
 10. Nano technology can provide a platform for integrating research in
proteomics (study of structure and properties of proteins) including
the way they work and interact with each other inside cells with other
scientific investigations into the molecular nature of cancer.
 11. Nano technology also helps in reducing chemical pollution. By
providing thorough control of matter, nano technology will enable us
to prevent chemical pollution. Any waste atoms could be recycled,
since they could be kept under control. Even immense tonnage of
excess carbon dioxide in the atmosphere (a green house gas) could be
swiftly and economically removed.The smallness of their size coupled
with wireless technology facilitates the development of sensors and
systems of real-time occupational safety and health managenment.
 12. Nano technology based fuel cells, lab-on-chip analysers and opto-
electronic devices have potential to be useful in the safe, healthy and
efficient design of work itself.
 In fuel cells: Hydrogen fuel cells being non-polluting are the great
source of power. Nano materials are used as catalysts in hydrogen
storage systems. Nano particles of platinum are used in hydrogenation.
Nano technology is used to create more efficient ultra-thin
hydrocarbon membranes which allow to build light-weight fuel cells.
These membranes allow only hydrogen ions to pass through, but not
those of oxygen.
 Carbon nano tubes
 Carbon nano tubes are capable of storing hydrogen in fuel cell-powered
cars. They absorb hydrogen just like sponge absorbs water and hold
until it is needed. They can hold about 8% by weight of hydrogen.
Conventionally, hydrogen is stored as compressed gas or as a liquid. To
power a car, a large storage tank to store hydrogen is required. Carbon
nano tubes are efficiently used for the purpose.
 Carbon nano tubes are large molecules of pure carbon that are long,
thin and thousands of nanometres long. Nano tubes are 100-times
stronger than steel. Single-walled carbon nano tube is 1 of nm diameter
and multi-walled carbon nano tube is of 10 nm in diameter. Carbon
nano tubes are prepared by laser evaporation method. In this method,
graphite is mixed with iron and nickel catalyst and heated to about
1200°C and then the material is irradiated with laser.
 Carbon Nano tubes are allotrope of carbon made of graphite carbon
with unique electrical, electronic and mechanical properties. They
found wide application in the field of electronics, information
technology and medical fields. Carbon nano tubes are large molecule
of pure carbon that are long and have tube-like structure. The diameter
ranges from 1–2 nm and 100–1000 nm long. They are hundred times
stronger than steel.
 There are two types of nano tubes:
 1. Single-walled CNT with diameter 1 nm
 2. Multi-walled CNT with diameter 10 nm
 Carbon nano tubes exhibit interesting chemical and physical properties with a wide range of
potential applications. The CNTs are ameanable for opening the closed end and various
substances can be filled. They can be derivatised through various chemical methods. For
example, a multi-walled CNT can be opened by boiling them in concentrated HNO3 and it
can be filled with Ni or Pt or with gases like H2. Halogens, amines when filled in CNT make
it soluble in organic solvents.
 Electrical properties: They vary between semi-conducting to metallic depending on the
diameter and chirality of the tube. Metallic nano tubes have very high electrical conductivity
(about billion amps/cm2) and thermal conductivity since they have negligible amounts of
defects which scatter electrons and they have very low resistance.
 Mechanical properties: These are quite unique. CNTs are stiffest and strongest
materials in terms of elastic modulus and tensile strength which is about 20 times that of
steel. But because of their hollow structure they undergo buckling under compression,
bending stress. Because of their high electrical conductivity, they are poor transmitters of
electromagnetic radiation and applied as light weight shielding materials for protecting
electronic equipment against electromagnetic radiation. They act as storage devices for
storing H2 gas. A CNT can hold 6.5% H2 by weight. For every six carbon atoms of CNT, one
lithium atom can be stored. Hence, CNTs can be used to store charged carrier lithium in
lithium batteries. By using nano tubes filters, it is possible to filter out bacteria and viruses
from water. Only few potential applications are there for inorganic nano tubes. The nano
tubes of MoS2 and WS2 act as semiconductors while those of NbS2 and NbSe2 are metallic
in nature with NbSe2 a super conductor at lower temperatures. Nano tubes are resistant to
oxidation, chemical attack. Thermal conductivity of CNTs is two times higher
 than diamond, whereas electric conductivity is 100 times higher than copper.
 Fullerenes

 Fullerenes are the classic three-dimensional carbon nano materials.

The most common and most stable fullerene is buckminster fullerene,
a spheroidal molecule which resembles soccer ball consisting of 60
carbon atoms. (Buckminster fullerene is the most abundant cluster of
carbon atoms found in carbon soot.) Other fullerenes that contain 70,
76, 84, 90, 96 carbon atoms and those that contain 180, 190, 240 and
540 carbon atoms are also available. The soccer ball-like molecules are
prepared in helium by passing about 150 amps through a carbon rod
and extracting the soot with benzene. The resulting solution contains
C60 and C70, i.e., the systems with appropriate material inside the
fullerene ball are conducting and are of particular interest. For
example, the hollow structure can accommodate a drug molecule,
while outside the ball is resistant to interaction with other molecules in
the body. Thus, they act as safe containers of drug. They can enter
cancer cell without reacting with them. A common method of
producing fullerene is to send a large current between two nearby
graphite electrodes in an inert atmosphere. The resulting carbon
plasma arc between the electrodes cools into a residue is soot from
which many fullerenes have been isolated.
 Use of Fullerenes
 1. They find wide application in the field of drug delivery
system, optical devises.
 2. Fullerenes have been used to produce tiny diamonds and
thin diamond films.
 3. They find use in the preparation of super-conductors,
electronic devices, micro-electric devices, soft ferro-
magnet.
 4. They inhibit the activity of HIV and used in medicine for
the treatment of AIDS.
 5. It leads to the discovery of new coating, lubricants,
catalysts, electronic and optical devices.
 6. They find wide applications in preparing conducting
films, alkali, metal-doped fullerenes and super conductor.
Quantum Dots

 They are also known as artificial atoms. Quantum dots

are semi-conductor with quantum confinement
properties in all three dimensions. They measure from
1–10 nm. They display any chosen colour in UV region
which helps to develop multi colour lasers. Quantum
dots may be metallic such as gold, chalcogenised
compounds, e.g., CdSe2, PbSe, CdS, etc. Quantum
dots find potential application in photo voltaic cell.
They absorb photon from solar radiation and release
electrons to generate electricity. They find use in
cellular imaging and light emitting diodes.
 Insulators
 Insulators are the substances which are capable of retarding the flow of heat or electricity
through them.
Insulators are broadly classified into two types:
o 1. Thermal insulators
o 2. Electrical insulators or dielectrics
 Thermal Insulators
The substances having extremely low thermal conductivity are known as thermal insulators.
Thermal insulators are mainly used to prevent the loss of heat which takes place by
conduction, convection and radiation. Thermal insulators are normally employed when the
flow of heat has to be stopped from outside environment to the equipment which has to be
operated at low temperature and when flow of heat is to be stopped from furnace to the
outer environment. Examples: include, refrigerators, cold storages, furnaces, ovens, boilers,
steam carrying pipes, etc. A good thermal insulator should have large number of fine pores
instead of few large pores (which causes heat transfer by convection). Because of the low
thermal conductivity, air and gases entrapped in pores act as good thermal insulators. The
surface of a thermal insulator should be waterproof and pores should be closer, because if
thermally insulating air in pores is replaced by thermally conducting moisture, the thermal
conductivity increases enormously. Thermal insulators are classified into two types on the
basis of suitability of temperature and range of insulator. They are organic (suitability upto
150°C) and inorganic (suitable for high temperature, i.e., above 150°C).
 Examples: Wool, leather, silk, wood pulp, saw-dust, cotton wool, cattle hair, charcoal
powder, etc. : Asbestos, glass wool, hydrous calcium silicate, mineral wool.
 They can withstand 400–1100°C temperature
Characteristics of a Good Thermal Insulator
 1. Its thermal conductivity is extremely low.
 2. It should be waterproof and fireproof.
 3. It should be chemically stable to the surrounding
conditions of high temperatures.
 4. It should have low density.
 5. It should be mechanically stable and capable of
bearing the load applied on it during working.
 6. It should be odourless during use.
 7. Cost of the thermal insulator should be low.
 Electrical Insulators
 Electrical insulators are those materials through which electrical charges cannot pass through. All the
electrons are bound to the parent molecule in an insulator, and there are no free electrons for
conduction. They are non-metallic materials of high specific resistance. Dielectrics are the materials
whose main function is to store the electrical charges, i.e., they prevent the loss of electricity through
certain parts in an electrical system, whereas the insulators are those materials through which electrical
charges cannot pass through.
Characteristics of Electrical Insulator
 1. The electrical charges cannot pass through the insulator.
 2. They possess low conductivity, i.e. high resistivity (109–1020 ohm-cm at room temperature).
 3. They should have low thermal contraction and expansion.
 4. They should be resistant to chemicals, solvents, acids, alkalis, oils and other organic solvents.
etc.
 5. Dielectrical losses should be minimum for an ideal insulator. The dielectric losses are causes
by
(a) the absorption of electrical energy.
(b) the leakage of current through the material.
 6. The absorption of electrical energy results in dissipation of electrical charge in the insulator.
 7. At high temperature, the leakage of current takes place through the insulating materials due
to conduction.
 8. The electrical properties of the materials should not be altered by change in chemical
composition.
 9. They should have low dielectric constant. Dielectric constant is the ratio of the capacitance of
a capacitor containing dielectric materials to the capacitance of the capacitor with vacuum as
the dielectric.
 10. A good dielectric materials should have low porosity. With increase in porosity, the
moisture-holding capacity increases which adversely affects the electrical properties.
 Superconductors

 Superconductivity was invented by kamerlingh Onnes in 1911 during

his experiments on electrical resistivity of metals and alloys at
sufficiently low temperatures. With decrease in temperature, the
electrical resistivity of many metals decreases. The phenomenon in
which the electrical resistively of the materials suddenly falls to nearly
zero when it is cooled to a very low temperature is known as
‘superconductivity’ and the materials under this condition is called
‘superconductor’. In order to study the phenomenon of
superconductivity, mercury was chosen and it was purified by repeated
distillation. With decrease in temperature, the resistivity is lowered,
and at 4.2 K it becomes zero and the materials become superconductor.
The temperature at which the materials undergoes a phase transition
from a state of normal conductor to superconductor is known as critical
temperature or transition temperature. Above critical temperature, it
exhibits normal conductivity. Such materials in their superconducting
state are diamagnetic and repel the magnetic field. The phenomenon
of exclusion of magnetic field is known as Meissner effect, which is
useful in determining the critical temperature of superconductors.
When a magnet approaches a superconductor, it induces a current in
the superconductor. Since there is no resistance to current, it induces
its own magnetic field.
 Application of Superconductors
1. Some superconductors act as excellent catalysts for industrial processes. For
example, YBa2Cu3O7 – x and related cuprates act as catalysts in oxidation or
dehydrogenation reactions.
2. La2 – x SrxCuO4 is a good sensor for alcohol vapours. On contact with certain
gases, the electrical resistivity of superconductor changes sharply.
3. Because of their speed of operation and efficiency, they replace the conventional
doped metallic conductors and alloy conductors in electronic circuits. Superchips
made of superconductors for computers. These can function 1000 times faster than
silicon chips.
4. Superconducting magnets capable of generating high fields with low power
consumption are being employed in scientific tests and research equipments.
5. Because of their small size and less energy consumption, superconductors are
used in magneto-hydrodynamic power generators to maintain plasma.
6. Superconductors are used in magnetic resonance imaging (MRI) in the field
of medicine as a diagnostic tool. Based on the production of cross-sectional
images, any abnormalities in body tissues and organs can be detected.
Magnetic resonance spectroscopy is used in the chemical analysis of body
tissues.
7. Superconducting cables can be used to transmit electric power over long
distances without resistive losses.
8. High efficiency separating machines are built using superconducting
magnets, which are also used to separate tumour cells from healthy cell by
high-gradient magnetic separation method.
9. They can be used as a memory or storage device in computers, since the
current can flow without any change in its value with time in a superconductor.
10. In Japan., superconducting magnets have been used to levitate an
experimental train above its track and can drive it at a great speed of 500 km/h
with minimum expenditure of energy. A similar magnetic propulsion system
may be used to launch satellites into orbits directly from the earth without the
use of rockets.
11. Using superconducting elements, one can built up an extremely fast and
large scale computer in compact size. It consumes less than 0.5 W power.
 Theoretical Questions
 1. What is the average composition of cement. What are the raw materials used
in the manufacture of Portland cement.
 2. How Portland cement is manufactured? Give a detailed flow diagram.
 3. Explain setting and hardening of cement.
 4. Give an account on the classification of cement and the composition of each
type.
 5. Give physical and chemical reactions involved in setting and hardening of
Portland cement.
 6. (a) Explain the manufacture of cement in detail.
(b) Write notes on setting and hardening of cement.
 7. Write chemical reactions that take place during setting of cement and
explain.
 8. What is meant by lubricant? What are the functions of a lubricant? and
prime requisites of lubricant
 9. Define and explain the cloud point and pour point of a lubricant with a neat
diagram.
 10. State and explain different mechanisms of lubrication with examples.
 11. What are extreme pressure additives? Why these additives are used for
lubrication?
 12. What is the significance of flash and fire points of a lubricant? How are they
determined experimentally?
 13. What is the importance of viscosity and viscosity index of a lubricant?
 14. How are refractory materials classified? Give examples of each.
 15. What are basic refractories and how these differ from acidic refractiories?
 16. What are the characteristics of a good refractory?
 17. (a) What are the causes of failure of refractory?
(b) Which of the following is neutral refractory: (i) fireclay bricks (ii) silica
bricks
 18. What is spalling? Write different types of spalling of refractory.
 19. What are the insulators? How are they classified?
 20. Mention the characteristics of thermal and electrical insulators?
 21. What are super conductors? how YBa2Cu3O7 – x is prepared?
 22. Write the engineering applications of thermal and electrical insulators?
 23. What is super conductivity? Explain the phenomenon of super conductivity.
 24. Discuss the important applications of super conductors.
 25. Differentiate dry and wet process of Portland cement.
 26. Discuss the basic principle of lubrication.
 27. Describe the following properties of refractories: (1) RUL test and (2)
refractoriness.
 28. What is meant by lubrication? Describe the theories of lubrication.
 29. Distinguish between hydrodynamic lubrication and boundary lubrication.
 30. What are nano materials? How are they synthesized?
 31. Write about the applications of nano materials.
 Multiple-Choice Questions
 1. The raw materials for Portland cement are
(a) Lime stone and gypsum (b) Lime stone and alumina
(c) Lime stone, clay, gypsum and coal powder (d) clay and lime stone
 2. Lubricant used in machines working at low temperature should have
(a) high pour point (b) high flash point (c) low flash point (d) low pour
point
 3. Lubricants are used to
(a) reduce corrosion (b) reduce wearing (c) reduce seizure (d) all the
above
 4. For liquid lubricants,
(a) flash point > pour point (b) flash point > fire point (c) flash point =
fire point (d) flash point < fire point
 5. Machine working at high temperature, and loads are lubricated by
(a) liquid lubricant (b) mineral oil (c) solid lubricant (d) grease
 6. With increase in temperature, the viscosity of a lubricating oil
(a) decreases (b) increases (c) remains un altered (d) first increases and
then decreases
 7. A good example for fluid film lubrication is
(a) Hydrocarbon oil (b) Coconut oil + Kerosene (c) Graphite (d) MoS2
 8. The lubricant used in boundary lubrication is
(a) Graphite (b) MoS2 (c) Oil suspension of both (d) All the above
 9. Dolomite is an example of ____________ refractory.
(a) aidic (b) basic (c) neutral (d) amphoteric
 10. Thermal spalling is caused due to
(a) unequal expansion and contraction of furnace due to difference of
temperature
(b) the difference in design of furnace (c) carelessness in loading of furnace
(d) none of the above
 11. Silica and alumina are the examples of
(a) basic refractories (b) acidic refratories (c) neutral refractories (d) none of
the above
 12. Which of the following is a neutral refractory?
(a) Alumina (b) Magnesite (c) Silica (d) Silicon carbide
 13. A good refractory materials should have
(a) thermal strength to withstand high temperature
(b) high mechanical strength
(c) crack resistance
(d) all the above
 14. The porosity of insulators should be
(a) high (b) low (c) moderate (d) cannot be predicted
 40. Which of the following is a neutral refractory?
(a) Graphite (b) Carborundum (c) Both (a) and (b) (d) Diamond
 41. The gas used in electric transformers in insulation is
(a) N2 (b) CO2 (c) SF6 (d) Air
 42. Major component of Portland cement is
(a) CaO (b) MgO (c) 3CaO◊SiO2 (d) SiO2
 43. Which of the following constituents of cement contain least heat of hydration?
(a) C2S (b) C4Af (c) C3A (d) C2A
 44. In the final stage of setting of cement, clinkers are mixed with gypsum
(a) to increase the rate of setting (b) to reduce the rate of setting
(c) to make the cement soft and porous (d) to make the cement more brittle
 45. Tobermorite gel is chemically
(a) hydrated tricalcium aluminate (b) hydrated tricalcium silicate
(c) hydrated tricalcium silicate (d) slaked lime
 46. Which of the following constituent of cement has least setting time?
(a) Dicalcium silicate (b) Tricalcium silicate (c) Tricalcium aluminate (d) Tetracalcium aluminate
 47. The high percentage constituent in cement is
(a) tricalcium aluminate (b) dicalcium aluminate (c) dicalcium silicate (d) tricalcium silicate
 48. The chemical formula for lime stone is
(a) MgCO3 (b) CaCO3 (c) Na2CO3 (d) Li2CO3
 49. The Chemical formula for gypsum is
(a) MgSO4◊H2O (b) CaSO4◊2H2O (c) CaCl2 (d) CaCO3
 50. An inorganic material that can withstand high temperatures without softening or suffering any
deformation in shape is called
(a) cement (b) refractory (c) glass (d) chalk
 Answers
 1. (c) 2. (a) 3. (d) 4. (a) 5. (c) 6. (a) 7. (a) 8. (d) 9. (b) 10. (b)
11. (b)
 12. (d) 13. (d) 14. (b) 15. (d) 16. (a) 17. (d) 18. (b) 19. (a) 20.
(a) 21. (d) 22. (d)
 23. (a) 24. (a) 25. (a) 26. (d) 27. (b) 28. (a) 29. (c) 30. (c) 31.
(d) 32. (a) 33. (a)
 34. (d) 35. (b) 36. (a) 37. (a) 38. (d) 39. (d) 40. (a) 41. (a) 42.
(d) 43. (b) 44. (a)
 45. (a) 46. (c) 47. (a) 48. (a) 49. (b) 50. (b) 51. (a) 52. (c) 53.
(d) 54. (b) 55. (b)
 WATER
 INTRODUCTION
 Water is a natural gift on the earth. It is essential for humans, animals and
plants. Human beings use water for drinking, cooking, bathing, cleaning and
washing.
 Chemically, water consists of two atoms of hydrogen and one atom of oxygen
and hence have the molecular formula H2O. In several chemical reactions,
water is formed along with the main product, e.g., acid reacts with a base to
give salt and water. Alcohol and organic acids react to give ester and water.
 Water is found in three physical states: liquid (water), solid (ice) and gas
(vapour). The freezing point of water is 0°C and the boiling point is 100°C.
Several special behaviours found in water are due to the hydrogen bond present
in it. In nature, water is present in abundance. About 96% of water forms the
oceans, 2.2% forms the ice and snow, 1.2% forms the groundwater and only
0.003% of water is useful for human consumption. It is therefore essential to
use available water carefully and economically, the rest forms the surface water
and the water present in the atmosphere. The various sources of water are
rivers, tanks, reservoirs, seas, oceans, w ells, tubewells, rain, glaciers, etc.
 Hardness of Water
 Water is a very good solvent and even called as the universal
solvent. Most of the inorganic salts are soluble in water. The
water that has calcium and magnesium salts dissolved in it
causes hardness of water. Water passes through rocks and flows
on the ground. The calcium and magnesium salts that are
present in the rocks are dissolved in water and make it hard.
Hard water does not give lather with soap, while soft water easily
gives lather with soap. Hence, the hardness of water is its
characteristic which resists the lathering with soap. Chemically,
it can be understood as follows:
 A soap is a sodium salt of higher fatty acid such as stearic acid
(C17H35COOH). Soap in the absence of Ca2+ and Mg2+ gives
lather with water easily, but in the presence of Ca2+ and Mg2+
reacts with them and forms insoluble soap that appears as
precipitate (formation of scum).
 Reaction
 Disadvantages of Hard Water
 In domestic use
(a) Washing: When hard water is used for washing purposes, it does not produce lather
freely with soap; rather it produces sticky precipitates of calcium and magnesium soaps.
The precipitation continues to take place till all calcium and magnesium salts in water
are precipitated. After that the soap gives lather with water.

As a result, wastage of soap takes place and in the presence of iron salts it may cause
staining of cloth.
(b) Bathing: Hard water forms sticky precipitate with soap on bath tub and body. Thus,
cleaning quality of soap is reduced and a lot of it is wasted.
(c) Cooking: Due to the presence of dissolved hardness producing salts, the boiling
point of water is elevated. Hence, more fuel and time are required for cooking. The
dissolved salts are deposited as carbonates on the inner walls of the utensils.
(d) Drinking: Hard water causes bad effect on our health. Calcium forms oxalate crystals
in urinary tract.
 In industrial use
(a) Textile industry: Hard water produces precipitates of
calcium and magnesium with soap. The fabrics when dyed later
on do not produce exact shades of colour. Iron and magnesium
salts containing water produces coloured spots on the fabric.
(b) Sugar industry: Water containing sulphates, nitrates, alkali
carbonates if used in sugar refining causes difficulties in the
crystallization of sugar. Moreover, the sugar so produced may be
deliquescent.
(c) Dying industry: The dissolved calcium, magnesium and
iron salts in hard water react with costly dyes forming
undesirable precipitates, which yield impure shades and give
spots on the fabric being dyed.
(d) Laundry: Hard water causes wastage of soap. Iron salts cause
colouration of clothes.
(e) Pharmaceutical industry: Hard water if used for the
preparation of pharmaceutical products such as drugs injections,
ointments may produce undesirable products in them.
f) Paper industry: Iron salts affect the colour of the paper.
 Types of Hardness
 Hardness in water is of two types:
(i) Temporary hardness and (ii) Permanent hardness.
 Temporary hardness is due to the presence of bicarbonates of
calcium and magnesium that can be removed by boiling. On
boiling, soluble (Ca+2/Mg+2) (HCO3)2 is converted into
insoluble carbonate that can be removed by filtration.

 Permanent Hardness
 Permanent hardness cannot be removed by boiling. It is due to
the dissolution of CaCl2, CaSO4, MgCl2 and MgSO4 in water.
These salts cannot be removed by boiling. They are removed by
different other methods. Fe+3, Al+3 and Mn+7 also cause hardness
in water but they are rarely found in hard water.
 Meaurement of Hardness
 To estimate hardness, it is essential to know the various units to measure it. The hardness of water is
measured in terms of CaCO3 because it is highly insoluble in water and also its molecular weight is
100 that makes the calculation easier.
 Units of Hardness
 Parts per million (ppm): It is the number of parts of equivalent CaCO3 per 106 part of water. For
example, 50 ppm hardness means 106 parts of water has 50 parts of equivalent CaCO3.
 Milligram per litre (mg/L): It is the number of milligrams of equivalent CaCO3 per litre of water.
One milligram per litre hardness means 1 mg of equivalent CaCO3 per litre of hard water.
1 kg of water = 1000 × 1000 mg = 106 parts
1 ppm = 1 mg/L
 Degree Clarke: It is the number of grams of CaCO3 per gallon of water, i.e., the number of parts of
calcium carbonate equivalent hardness per 70,000 part of water.
Hardness 1°Clarke (1°Cl) means 1 gram equivalent CaCO3 present in 1 gallon of hard water.
Degree French: It is the number of parts of CaCO3 per 105 parts of hard water. Hardness 1°French
(1°Fr) means 1 part of equivalent CaCO3 per 105 parts of hard water.
Relationship among units of hardness:
1 ppm = 1mg/L = 0.1°Fr = 0.07°Cl
Any water sample with hardness less than 150 ppm is good and potable, while beyond 350 ppm is not
suitable for consumption.
 Methods to Determine Hardness:
 Hardness of water is determined by the EDTA method, which involves the
complexometric titration. EDTA is a strong complexing agent. EDTA (ethylene
diamine theoretic acid) is a strong complexing agent whose structure is given
as
 As such it is not very soluble in water; hence, disodium salt of EDTA is used in
complexometry.

 Principle:
The EDTA solution is standardized with a standard solution of calcium
carbonate, prepared by dis-solving a known weight of calcium carbonate in dil.
HCl and then making up the solution to a known volume with distilled water.
The permanent hardness of water can be determined by titrating the water
after boiling well to remove the temporary hardness as carbonates of calcium
and magnesium. When hard water is treated with EBT at pH 10, Ca2+ /Mg 2+
ions form unstable wine red coloured complex. When it is titrated with EDTA
under similar conditions, EDTA extracts metal ions from the complex and
forms a stable colourless complex and releases EBT into the solution. Hence,
the colour of the solution changes to blue at the end point
 EDTA forms complexes with different metal ions at
different pH values (Fig below). Calcium and magne-
sium ions present in water form complexes with EDTA
in a buffer solution of ammonium chloride and
ammonium hydroxide at pH = 10

Metal–EDTA complex
Alkalinity of Water:
 The presence of anions, such as CO3 –2 , HCO3– and
OH–, results in alkalinity of water. The estimation of
alkalinity in water is done by titrating water sample
against standard acid using phenolphthalein and
methyl orange as indicators. In this titration, two
indicators are used as the different anions give end
points at different pH values.
 Out of the three anions CO3 –2 , OH– and HCO3 –, any
two of them can exist in water together.
 Experimental Procedure:
100 ml of water sample is taken in a flask and two drops of phenolphthalein (pH > 10) is
added to it. The colour will become pink due to pH > 10. This water sample of pink
colour is titrated against N/50 HCl solu-tion. At the endpoint, pink colour disappears.
This endpoint is termed as P-endpoint. Now add two drops of methyl orange indicator
to the same water (pH falls below 7). At the endpoint, pink colour reappears. This
endpoint is M-endpoint (methyl orange endpoint).
REACTIONS:

 Calculation
At the phenolphthalein endpoint (at P ml), the alkalinity thus calculated is
phenolphthalein alkalinity in terms of CaCO3 and it is given by

The alkalinity of methyl orange (at M ml) is given by

 Conclusions
 A summary of the conclusions is given in Table

Table: Alkalinity of water in terms of phenolphthaleine (P) and methyl orange

(M) indicators
 Boiler Feed water
 In several industries, boilers are used to produce steam.
The water used for making steam must have the following
 Characteristics:
 1. The pH value should be nearly 7.
 2. It should have very low hardness (less than 0.2 ppm).
 3. Caustic and soda alkalinity should not exceed 0.45 ppm
and 1.00 ppm, respectively.
Boiler feedwater is treated to avoid
(i)carry over (priming and foaming),
(ii) caustic embrittlement,
(iii) boiler corrosion, and
(iv) scale and sludges formation.
 Carry Over
 The phenomenon of carrying of water along with impurities by steam is called carry over.
This is due to priming and foaming. Carry over is undesirable because it decreases the
efficiency and results in some practical difficulties in the successful operation of the
boilers. Foaming of water makes it difficult to know the exact level of water in the boiler.
 Water takes grit along with it at high velocity and damages the walls of the cylinder. A
considerable amount of heat is wasted by the removal of hot boiler water.
 Priming and Foaming
During functioning of the boilers, some water droplets pass with steam. This process of
wet steam formation is called priming. Priming in boilers is due to
 (i) the presence of the suspended and dissolved solids,
 (ii) high of water in boilers,
 (iii) faulty design of boilers and
 (iv) sudden steam demands.
Formation of priming reduces the efficiency of the boilers and causes damage to the
system.
 Priming can be controlled by
1. proper evaporation and using adequate heating surfaces.
2. controlling rapid change in steam velocities.
3. proper design of boilers by maintaining low water levels in the boilers.
4. filtering water before feeding to boilers.
5. by blow down.
 Formation of stable, persistent foam or bubbles at the surface
tension of water in the boiler is called foaming. Foaming is due
to the presence of oil or alkali in boiler feed water. The oil and
alkali react with water to form soap, as a result the surface
tension of water decreases. More foaming will cause more
priming. Oil is introduced into the boiler through lubricants. It
results with the formation of wet steam that harms the boiler
cylinder and turbine blades, etc. Foaming is due to the presence
of oil drops, grease and some suspended solids. Silicic acid and
aluminium hydroxide are used as clarifying agents to minimise
foaming. Oil can be removed by sodium aluminate or alum. It
can also be removed by cataphoresis. Polyamide and castor oil
also act as anti-foaming agents.
 Thus, foaming can be prevented by
1. adding anti-foaming agents which reduces the surface tension, e.g.,
castor oil, prevents foaming.
2. blow down, removing the concentrated boiler water and replace the
water by fresh feed water.
 Caustic Embrittlement
 It is the brittlement of the boiler due to the increased concentration of caustic
alkali in boiler water. It is a type of boiler corrosion caused when excess of
caustic alkali is present in water. In high-pressure boilers, sodium carbonate is
hydrolysed to yield NaOH.

 The NaOH thus formed concentrates after long use. It causes inter-granular
cracks on the boiler walls, especially at the stress points. The concentrated
alkali is dissolved iron as sodium ferroate (NaFeO2) which enter through
minute cracks and causes brittlement of the boiler parts, especially at the
bends, joints and rivets, even causing failure of boiler. The formation of cracks
in the boilers due to increased concentration of NaOH is called caustic
embrittlement. Caustic cracking can be explained by the following
concentration cell.

 i.e., iron at bends and joints is in contact with concentrated alkali and causes
corrosion. The iron at plane surface is in contact with dilute alkali and acts as
cathode.
Caustic embrittlement can be prevented by
 1. using Na3PO4 as softening reagent instead of
Na2CO3 in external treatment of boiler water.
 2. adding tannin, lignin to boiler water, which blocks
the hair cracks in the boiler walls.
 3. adding Na2SO4 to boiler water to prevent caustic
cracking in boiler.
At different pressures, the proportions of sodium
sulphate to NaOH as follows:

 4. neutralizing alkali with very small quantity of acid

 Sludge and Scale Formation
 In industries, boilers are continuously used for stream generation. As a result of
continuous evaporation of water, the concentration of dissolved salts increases. When
the ionic product of the salts exceeds the solubility product, the salts are thrown out of
boiler. These salts may get deposited on the inner walls of the boiler to form scales or they
may float on boiler water as loose and slimy precipitates called sludges. Scales are hard
and sticky deposits formed on the inner walls of the boiler. They are very difficult to
remove. Scales are formed due to the presence of MgCl2, CaSO4, Mg(OH)2, Ca(OH)2
and silica in water.
 Formation of Scales
Decomposition of Ca(HCO3)2: Ca(HCO3)2 decomposes to an insoluble calcium
carbonate salt. In low-pressure boilers, calcium carbonate causes scale formation. In high
pressure boilers, it becomes soluble.

 Hydrolysis of magnesium salts: Magnesium salts dissolved in water undergoes

hydrolysis and form a precipitate of Mg(OH)2.

 Presence of silica: Silica present in water gets deposited as CaSiO3. This is

sparingly soluble in water.
 Decomposition of CaSO4: It is soluble in cold water but solubility decreases with
rise in temperature. At high temperature in boilers, CaSO4 gets deposited as hard scale
which is very difficult to remove. The chemicals found in the sludges and scales are
CaSO4, Ca(OH)2, Mg(OH)2, carbonates of Ca2+ and Mg2+, phosphates and silicates.
 Disadvantages of scale formation:
 1. Wastage of fuel: Scales have poor thermal conductivity so the rate of heat
transfer is reduced. In order to provide a steady supply of heat to water,
overheating is done and this causes increase in fuel consumption.
 2. Lowering of boiler safety: Due to overheating, to maintain steady supply of
heat, the boiler material becomes soft and distortion of boiler tubes takes
place.
 3. Decrease in efficiency: Scales may get deposited in the valves and condensers
of the boiler and choke them there by decreasing the efficiency.
 4. Danger of explosion: When thick scales crack due to uneven expansion,
water suddenly comes in contact with overheated walls and a large amount of
steam is formed instantaneously. Sudden high pressure is developed and
causes explosion of the boiler.
 Removal of scales: Scales can be removed by mechanical and chemical
methods.
 1. Mechanical methods: If scales are loosely adhering, they can be removed
with a scraper or a piece of wood or wire brush. They can also be removed by
blow down. If the scales are brittle, thermal shocks are to be given.
 2. Chemical methods: If scales are hard and adhering, they can be removed by
dissolving in chemicals.
 • Calcium carbonate scales are dissolved in 5−10% HCl.
 • Calcium sulphate complex is highly soluble by adding EDTA.
 • Ca–EDTA complex is highly soluble in water.
 Formation of Sludges
 Sludges are loose and slimy precipitates. They do not stick to the walls
of the boiler. They are formed by substances having more solubility in
hot water. Examples, magnesium carbonate, magnesium sulphate,
magnesium chloride, calcium chloride form sludges. The solubility of
these salts increases with increase in temperature. Sludges are formed
at comparatively colder portions of the boiler such as bends, joints,
rivets, etc.
 Disadvantages of sludges:
 1. Sludges are poor conductors of heat. They tend to waste a portion of
heat generated and decreases the efficiency of boiler.
 2. Sludges settle in regions of poor water circulation such as pipe
connections and plug openings, thereby causing chocking of the pipes.
Sludges and scales in boiler
 Softening of Water
 The process of removing the hardness causing salts from water is called softening of water. Soft water is
essential for many industries such as textiles, laundries, paper, ice, brewing, canning, etc. Water used
for steam generation should be perfectly soft in boilers.
 1. To minimize boiler troubles, the water used must be perfectly soft otherwise loss of efficiency and
of boiler tube takes place.
 2. Hardness causing salts are removed by external and internal treatment methods.
There are two treatment methods for preventing scale formation.
They are
 Internal treatment: In this method, raw water is treated inside the boiler. Internal treatment means
addition of suitable chemicals to reduce scale and sludge formation. It is mainly based on the solubility
product. If the product of the concentration of ions exceeds the solubility product, it precipitates.This is
a corrective method to remove slight residual hardness and to remove corrosive nature of water.
 External treatment: This treatment is given outside the boiler before the feed water enters in. External
treatment methods include lime–soda process, permutit process, ion-exchange process.
Pre-heating: Feed water is heated before it enters the boiler. Hot flue gas leaving the boiler is also used
for pre- heating. Water may be heated in a heat exchanger.
 Advantages of pre-heating is as follows:
1. Fuel will be saved. Instead of feeding boiler with water at atmospheric temperature, it is fed with hot
water.
2. A portion of temporary hardness may be removed
Ca(HCO3)2 CaCO3 + CO2 + H2O
3. Dissolved O2, CO2 are removed when water is heated to 65oC. As these gases have corrosive effect,
their removal is advantageous.
 The main principle involved in internal condition is that scales formed are converted into sludges.
 Internal Treatment Methods
 After feeding water to the boiler for steam generation, scale formation can be
prevented by internal treatment method. The precipitation process applied
includes carbonate conditioning, phosphate conditioning, colloidal conditioning,
calgon process and treatment with sodium alluminate. These reduce the scale and
sludge formation in the boilers.
 Carbonate conditioning: Scale formation in low pressure boilers can be avoided
by adding sodium carbonate to boiler water, where CaSO4 is converted into calcium
carbonate, a sludge which can be removed by blow down operation.
CaSO4 + Na2CO3 CaCO3 + Na4SO4
 By adding Na2CO3, the concentration ratio of carbonate ion to sulphate ion is made
greater than the solubility product ratio of CaCO3 to CaSO4. CaCO3 is a loose
sludge which can be scraped off by blow down operation.
 CO3 2–/SO4 2– > CaCO3/CaSO4
i.e., the concentration of carbonate ion is greater than concentration of sulphate.
Precipitation of calcium carbonate occurs in preference to calcium sulphate. In high
pressure boilers, excess of sodium carbonate may get hydrolysed to NaOH which
causes caustic embrittlement.
 Phosphate conditioning: Phosphate conditioning is generally applied to high pressure
boilers. When sodium phosphate in added to boiler water, it reacts with magnesium and
calcium salt forming soft sludges of Mg3(PO4)2 and Ca3(PO)2.

 Trisodium phosphate is used when the alkalinity of boiler water in 9.5–10.5 and calcium
gets precipitated at pH of 9.5. If alkalinity of boiler water is too high, NaH2PO4 (acidic)
is used, and if the boiler water is slightly alkaline, Na2HPO4 is used.
 Colloidal conditioning: Colloidal substances like kerosene, tannin, agar-agar, etc. are
added to low-pressure boilers. These substances gets adsorbed over the scale forming
precipitates and yield non-sticky, loose deposits which can be easily removed by blow
down.
 Calgon conditioning process: The word calgon means calcium gone, i.e. the removal of
Ca2+. Sodium hexametaphosphate is called calgon. It reacts with calcium ion and forms a
water-soluble compound. Calcium sulphate present in hard water forms sludge which on
drying in boiler changes to scale and, hence, reduces the efficiency of the boiler.
 Treatment with sodium aluminate: When boiler water is heated with sodium
aluminate, it gets hydrolysed to give sodium hydroxide and a gelatinous precipitate of

 The NaOH formed above reacts with MgCl2 to form another flocculant precipitate of
Mg(OH)2. These two precipitate entrap colloidal impurities such as oil drops, sand and
make them settle down at the bottom that can be easily removed.
 External Treatmemt Methods
 Lime–Soda process (L–S Process)
 This is the most important method of chemical water softening. The principle
involved in this process is to convert all soluble hardness causing impurities
into insoluble precipitates which can be removed by settling and filtration.
 In lime–soda process, a calculated amount of lime and soda is added to the
hard water (generally some ex-cess quantity is added). Lime removes the
temporary hardness caused by Ca+2 and Mg+2 and also permanent hardness
caused by Mg+2. It also removes dissolved CO2 and acidity, if any. Soda removes
the permanent hardness caused due to Ca+2.
 Reactions involving soda (Na2CO3):
 Cold lime–soda process: In this process, water is treated with lime
and soda at room temperature. For this purpose, two types of water
softeners are known,
 intermittent type and continuous type.
 Intermittent type: In this type of softener, raw water is mixed with a
calculated amount of lime and soda at room temperature. Inside the
chamber, there is mechanical stirrer. During mixing, stirring is started
and a small amount of precipitate from previous treatment is also
mixed. It accelerates precipitation. After some time stirring is stopped
and chemical reaction completes. Precipitate is collected at the bottom
as sludge which is taken out. Clear water is taken out with the help of
floating pipe

Intermittent type of cold lime–soda softener

 Continuous type: This process provides soft water
continuously. There are two chambers shown in.
 Raw water and soda + lime are continuously allowed in to
the chamber through inlet pipes. The circular vertical
chamber is provided with a shaft containing number of
paddles. Mechanical stirrer is used for mixing. A small
amount of coagulant like alum/aluminium sulphate is
mixed to get heavy precipitate. Sludge settles at the bottom
and softened water from outlet

Continuous cold lime–soda softener

 Hot lime–soda process: In this process, raw water is treated with lime and
soda at about 80°C with raw water. The equipment has a heating coil for
maintaining the temperature. At higher temperature precipitation takes place
and coagulant is not required
 Process: It consists of a big steel tank having an inner circular vertical chamber
containing open bottom. The upper end of which is in the form of a funnel and
the lower end is open. Raw water and chemicals fall in to this funnel and get
mixed. The steam is allowed to get in through the steam inlet. By the time the
mixture goes down, the reaction is complete. When the water rises up in the
tank, the sludge separates and settles down. The sludge can be removed from
the bottom.

Continuous hot lime–soda softener

 Advantages of hot L–S process are as follows:
 1. Precipitation is rapid and completes in 15 min.
 2. The residual hardness (15–30 ppm) is far less than the cold process.
 3. Precipitate and sludge settle down rapidly. Hence, no coagulant is needed.
 4. Lime and soda are required in small quantity.
 5. Little or no coagulant is added.
 6. Pathogenic bacteria are killed in hot L–S process.
 7. Fe and Mn salts are removed. They cause unpleasant odour. Fe causes redness to
water.
 8. Dissolved gases like CO2 are driven out.
 9. The pH value of treated water increases, thereby preventing corrosion of
distribution pipes.
 10. The process is economical.
 Disadvantages of L–S process are as follows:
 1. A large amount of sludge is produced which poses disposal problem.
 2. Softened water contains sodium which is not suitable for boiler feed.
 3. It is not suitable for house-hold purposes because it is difficult to know how
much lime and soda should
 be added and how to filter off precipitate.
 4. It is also not suitable for many industries because it leaves water supersaturated
with CaCO3
 Zeolite Process
 Zeolite is a three-dimensional silicate. In zeolite, Si
(IV) atom is replaced by Al (III) atom and, hence,
changes it into anion. Common zeolite is naturally
occurring aluminosilicate with the general
composition Na2O. Al2O3.xSiO2.yH2O (x= 2 to 10
and y= 2 to 6). Zeolite has a cage-like structure. It is
derived from SiO4 tetrahedron.
 Zeolites are of two types:
 Natural zeolite: They occur naturally and are porous.
Example: natrolite Na2O⋅Al2O3⋅4SiO2⋅2H2O.
 Synthetic zeolite: They can be prepared from feldspar
china clay and soda ash. They are porous and possess
gel structure. They possess high exchange capacity
than natural zeolites.
 Besides natural zeolite, synthetic
zeolite is also prepared with the help
of soda ash, feldspar and china clay
on heating.
The apparatus is made of cylindrical
vessel inside it where zeolite salt is
kept. Raw water bed percolated
inside the apparatus through beds
and, thus, ion-exchange reactions
take place where Na– ions is
replaced by Ca+2/Mg+2ions. After the
use of this process for a certain time,
zeolite is exhausted, i.e. all Na+ of
the zeolites are removed by
Ca2+/Mg2+, and hard water will not
be further softened.Exhausted
zeolite can be regenerated or
reactivated by heating it with brine
solution (10% NaCl solution).
Zeolite softener
 Advantages of zeolite process:
 1. Hardness of water is removed with residual hardness of about 10
ppm.
 2. It is easy to operate.
 3. It occupies less space.
 4. The process can be made automatic and continuous.
 5. This process is very cheap since regenerated permutit is used again.
 Disadvantages of zeolite process:
 1. Since the process is an ion-exchange process in which 2Na+ is
replaced by Ca2+/Mg2+ ion, the soft water obtained by this process
has excess of Na+.
 2. Hard water containing acid destroys the zeolite.
 3. If suspended particles (turbidity) are present, the pores of the zeolite
are blocked and softening is not possible.
 4. Bicarbonate and carbonate ions, if present in water, are not removed
and are present as sodium salt resulting in the alkalinity of water.
 5. The colours present in hard water cannot be removed by this process
 Ion-exchange Process or Demineralisation Process
 Ion exchangers are of two types: anionic and cationic. They are
copolymers of styrene and divinyl benzene. The polymers have
two types of functional groups. The first group has (SO3H) or
COOH group in which H+ ion is replaced by cations such as
Mg2+/Ca2+. The second group contains substituted amino groups,
such as –NH+2 OH or >NH+ OH–or N+OH–, in which OH–is
replaced by anions in water. General representation of cation
and anion exchangers are H–R and R–OH, respectively.
Structures of some cations and anions are shown in Fig.

Structures of (a) cation-exchange resins and (b) anion-exchange resins

 Desalination
The process of removal of dissolved salts (NaCl, KCl)
present in water is known as desalination. Water is divided
into three categories on the basis of salinity:
(a) Sea water: The salinity is greater than 35000 mg/L.
(b) Brakish water: The salinity is in the range of 1000−35000
mg/L. It has peculiar salty taste.
(c) Fresh water: The salinity of water is less than 1000 mg/L.
Brakish water and sea water are not fit for drinking as well
as for industrial purposes. They can be subjected to
desalination to make them suitable for drinking.
 Important desalination methods are:
 (i) reverse osmosis,
 (ii) electrodialysis and
 (iii) distillation.
Reverse Osmosis Process
Osmosis is the process in which the flow of solvent takes place
from dilute to concentrated solution through a semi-permeable
membrane. In this process, only solvent can flow but not the
solute, which produces a pressure called osmotic pressure on the
side of more concentrated solution.
When the flow of solvent under pressure from more
concentrated solution to solvent or to the less concentrated
solution through a semi-permeable membrane takes place is
called reverse osmosis.

Reverse osmosis cell

 This method is applicable mainly for the desalination
of sea water. Sea water and pure water are separated by
a semi-permeable membrane made up of cellulose
acetate fitted on both sides of a perforated tube.
Inventions are in progress to search for better
membrane. Polymethacrylate and polyamides have
been proved to be better membranes.
 The process is very easy. It is used to make pure water.
It removes the ionic and non-ionic substances in the
water. It can also remove suspended colloidal particles.
The life of a membrane is nearly two years, and it
should be replaced after this period. By this process,
sea water is made fit for drinking. Water obtained after
being treated by this process is used in boilers.
 Advantages of the process
 1. The process removes ionic as well as non-ionic dissolved
salts easily.
 2. It is effective in removing colloidal impurities in water.
 3. The process is economical and convenient. The process
can be carried out at a room temperature.
 4. It is suitable for converting sea water into drinking water
 Electrodialysis
 Dialysis is a process in which diffusion of smaller particles takes place through a
semi-permeable membrane. By this process, crystalloids are removed from
colloids. The process has been successfully applied for the purification of sea
water. Sea water is called brackish water (salty water). It has 3.5% salt. Dialysis
removes salt from sea water (brine) through a membrane.
 Principle:
In electro dialysis, ion-selective membrane is used, which permits the passage
of only one kind of ions having specific charge, i.e., cation selective membrane
allows the passage of cations only but not anions and vice versa. When electric
current is passed through saline water enclosed between ion-selective
membranes, cations of the dissolved salt move towards cathode through a
cation-selective membrane. Similarly, anions of the salt move towards anode.
As a result, the concentration of ions in saline water becomes free from
dissolved salts and turn into fresh water. In electro dialysis, two electrodes
(anode and cathode) are dipped in brine, separated by a semi-permeable
membrane Cathode is placed near the cation-exchange membrane, and anode
is placed near the anion exchange membrane. When current is passed through
electrodes, oppositely charged ions present in sea water pass through
membrane towards respective electrodes. Chloride ions pass towards anode,
while sodium ions pass towards cathode. After some time, the water in the
middle chamber becomes pure and is taken out. Cation membranes are
permeable to cations due to the presence of negatively charged functional
groups inside the membrance.
 Line diagram of electrodialysis

 When outer chambers become more concentrated with brine, they

should be replaced by fresh water. Now, different types of semi-
permeable membrane have been developed as per the size of cation
and anion.
 In electro dialysis cell, several pairs of membrane are used. These
membranes are made of synthetic materials (plastics). Electrodes
attract oppositely charged particles shown by arrows. Pure water is
obtained in alternate chambers
 Potable/Domestic/Municipal Water
The water supplied by municipality should be fit for
human consumption. It should satisfy the following
requirements:
 1. It should be colourless, odourless, and pleasant to taste.
 2. Turbidity should not exceed 10 ppm. TDS should not
exceed 500 ppm. It should not be very alkaline (pH 8.0).
 3. It should be free from dissolved gases.
 4. It should be free from objectionable minerals such as Pb,
As, Cs, Mn and dissolved gases such as H2Sand CO2.
 5. It should be free from pathogenic micro-organisms
(coliform bacteria are used as indicator organisms,whose
presence suggests water is contaminated.)
 Treatment of municipal water involves the following:
 1. Screening: Water is allowed to pass through the mesh screens whereby large floating matters are
removed
 2. Sedimentation: Water is allowed to stand undisturbed for 2−5 h in big setting tanks. Suspended
particles settle down due to gravity and clear water raises which can be drawn out with the help of the
pumps.
Disadvantages
• It requires long big tanks. It takes a long time.
• It removes 70−75% suspended matter.
• If water contains clay and colloidal impurities, coagulants are added before sedimentation.
 3. Coagulation: Colloidal particles from the water are removed by adding coagulants such as alum,
Al2(SO4)3, NaAlO2, etc., which produces flocs. Smaller particles gather together to form bigger flocs.
They can be easily removed by filtration. Some bacteria and colour are also removed.
Al2 (SO4)3 + 3 Ca (HCO3)2→ 2 Al(OH)3↓+ 3aSO4 + 6 CO2
NaAlO2 + 2 H2O → Al(OH)3↓ + NaOH
FeSO4 + Mg(HCO3)2 → Fe(OH)2 + MgCO3 + CO2 + H2O
4Fe(OH)2 + O2 + 2H2O → 4 Fe (OH)3
 4. Filtration: Colloidal matter, bacteria, micro-organism are removed. Water is passed through a
large area sand bed. The filter may be pressure filter or gravity filter.
 5. Sterilization/disinfection: Water after passing through sedimentation, coagulation, and
filtration still contains a small percentage of pathogenic micro-organisms such as bacteria. Its
removal can be achieved by sterilization
 The chemicals used for killing bacteria are called disinfectants. Water can
be sterilized by the following methods:
(a)Boiling: Water is boiled for 10−15 min, where most of the pathogenic
bacteria are killed.
(b)By adding bleaching powder. Bleaching powder in calculated
amount is added to water and allowedto stand for several hours.

 CaOCl2 + H2O → Ca(OH)2 + Cl2

 Cl2 + H2O → HCl + HOCl
 HOCl + Germs → germs are killed

Disadvantages:
Bleaching powder introduces Ca2+ hardness in water and adds lime residue.
Excess of it gives bad smell and bad taste. Excess chlorine is irritating to mucous
membrane.
 (c)By chlorination
 Cl2 + H2O → HCl + HOCl
 Bacteria + HOCl → killed bacteria
The quantity of chlorine to be added is important. The disinfection will not
complete if chlorine is insufficient. If excess chlorine is added, it causes
irritation, bad taste, and odour.
De-chlorination
Over chlolrinated water can be de chlorinatede by passing it through a bed of
activated carbon. Excess chlorine can also be removed by adding SO2 (or)
NaSO3.
 SO2 + Cl2 + 2H 2O → H2SO4 + 2HCl
 Na2SO3 + Cl2 + H2O →Na2SO4 + 2 HCl
(d) By using chloramine (NH2Cl): It is obtained by mixing chlorine and NH3
in 2:1 ratio. It has better bactericidal action than chlorine. It is more stable and
not producing any irritating odour.
 NH3 + Cl2 → HCl + NH2Cl
 NH2Cl+ H2O → NH3 + HOCl
(e) Disinfection by ozone: O3 is prepared by passing silent electric discharge
through cold, dry O2. It is highly unstable.
 O3→ O2 + (o)
O3 is an excellent, harmless disinfectant. It is highly unstable and decomposes
to give nacent oxygen (o). (o) is a powerful oxidizing agent. It oxidizes organic
matter in water and also kills bacterias.
 Solved Examples
 Numerical problems based on this chapter can be solved using
the table that gives the equivalence of different salts, ions and
compounds in terms of CaCO3 which is also called the
multiplication factor.
 Theoretical Questions
 1. A water sample contains 408 mg of CaSO4 per litre. Calculate the
hardness of water in terms of CaCO3 equivalent.
 2. Why do we express hardness of water in terms of CaCO3 equivalent?
 3. Write various units of hardness and the relationship between them.
 4. What are zeolites? How do they function in removing the hardness
of water? What are the limitationsof this process?
 5. What is the basic principle applied to remove the hardness of water
by lime–soda process?
 6. What are ion-exchange resins?
 7. What do you understand by the hardness of water? What are its
causes?
 8. Distinguish between temporary and permanent hardness of water.
 9. How is water softened by lime–soda process? Describe its types and
suitable chemical reactions.
 10. What is calgon? What is its application in water treatment?
 11. What is meant by the exhaustion of cation and
anion exchangers? How can they be regenerated?
 12. Why is demineralisation process preferred over
zeolite process for the softening of water for use in
boilers?
 13. How is water analysed for alkalinity? How the
alkalinity due to various ions can be determined?
 14. 250 ml of a sample of water on EDTA titration with
EBT as indicator consumed 13 ml of 0.022 M EDTA till
the endpoint is reached. Calculate the hardness of
water in terms of ppm.
 15. The hardness of 1000 L of a water sample was
completely removed by passing it through a zeolite
softener. The softener then required 30 L of NaCl
solution containing 1.5 g/L of NaCl for regeneration.
Calculate the hardness of the sample of water.
 Multiple-choice Questions
 1. Hardness of water is caused by
(a) CaCl2 (b) NaCl (c) Na2CO3 (d) K2SO4

 2. Hard water contains

(a) Na⊕ (b) Mg2+ (c) Ca2+ (d) both (b) and (c)

 3. The chemical formula of zeolite is

(a) FeSO4.7H2O (b) Al2(SO4)3.18H2O(c) Na2Al2O4 (d) Na2O . Al2O3 . xSiO2 . yH2O

 4. Permanent hardness of water is due to

(a) HCO3– (b) CO3– (c) Cl– (d) Na⊕

 5. Temporary hardness can be removed by

(a) zeolite process (b) ion exchange (c) boiling (d) none
 6. The demineralisation of water is called
(a) zeolite process (b) ion-exchange process (c) lime–soda process (d) none
 7. Which is not the unit of hardness of water?
(a) ppm (b) epm (c) degree Clark (d) none of these
 8. The relation between mg/L and ppm is
(a) 1 mg/L = 1 ppm (b) 10 mg/L = 1 ppm (c) 1 mg/L = 10 ppm (d) 1 mg
 9. In EDTA titration, the colour of the end 15. Calgon is a trade name given to
point is (a) sodium hexametaphosphate (b)
(a) red (b) blue (c) yellow (d) no change magnesium phosphate
 10. The colour of phenolphthalein in acidic (c) calcium silicate (d) sodium sulphate
medium is  16. The phenomenon of carrying of water
(a) colourless (b) pink (c) yellow (d) blue along with impurities by steam is
 11. Tannin, lignin are used for (a) priming (b) carry over (c) foaming (d)
(a) phosphate conditioning (b) carbonate embrittlement
conditioning (c) colloidal conditioning (d) 17. Brakish water mostly contains dissolved
calgon conditioning (a) KCl (b) MgCl2 (c) CaCl2 (d) NaCl
 12. Blow down operation causes the 18. Water can be sterilized by using
removal of (a) Cl2 (b) CCl4 (c) CaCO3 (d) NaOH
(a) sludges (b) scales (c) NaCl (d) acidity  19. pH of alkaline water is
 13. Temporary hardness of water can be
(a) 7 (b) more than 7 (c) less than 7 (d) 0
removed by
 20. Brakish water can be purified by using
a) filtration (b) screening (c) boiling (d)
sedimentation (a) lime–soda process (b) permutit process
 14. Purest form of natural water is
(c) filtration (d) reverse osmosis method
(a) sea water (b) river water (c) rain water
(d) lake water
 21. Hard water contains
(a) Ca+2 and Mg+2 (b) K+ and Na+ (c) CO2 and
O2 (d) NO3– and PO43–
 22. Water containing calcium chloride and
magnesium sulphate causes
(a) temporary hardness (b) permanent hardness
(c) both (d) softness
 23. Best method of removing hardness of water
is
(a) ion exchange (b) permutit (c) lime–soda (d) 
boiling
 24. Hardness of water is expressed in terms of
equivalents of
(a) MgCO3 (b) CaCO3 (c) Na2CO3 (d) K2CO3
 25. Caustic embrittlement is caused due to the
presence of
(a) NaCl (b) NaOH (c) MgCO3 (d) KNO3
 26. Priming and foaming in boilers produce
(a) wet steam (b) dry steam (c) soft steam (d)
hard steam
 27. The exhausted cation exchange resin can be
regenerated by treating with
(a) dil. NaOH (b) dil. HCl (c) distilled water (d)
dil. NaCl
 28. A hard sticky precipitate formed on the inner
surface of the boiler is called
(a) sludge (b) embrittlement (c) coating (d) scale
 29. Which of the following is responsible for
temporary hardness?
(a) MgCl2 (b) NaHCO3 (c) MgSO4 (d) Mg
(HCO3)2
 30. The water which is fit for drinking is called
(a) hard water (b) brakish water (c) potable
water (d) mineral water
31. Which of the following is a curdy precipitate?
(a) sodium stearate (b) calcium stearate (c)
potassium stearate (d) sodium carbonate
 32. Which indicator is used for the
determination of hardness by EDTA method?
(a) methyl orange (b) methyl red (c) EBT (d)
FSB-F
 33. pH of purest water is
(a) 7 (b) 14 (c) 10 (d) 0
 34. Water shows hardness, when it contains
(a) alkalinity (b) acidity (c) dissolved sodium
salts (d) dissolved Ca and Mg salts
 35. Loose and slimy precipitate formed within
the boiler is called
(a) scale (b) sludge (c) priming (d) corrosion
 ENERGY SOURCES
 Introduction
 A fuel is a combustible substance which on proper burning produces a large amount of heat
energy. The heat evolved during combustion can be used economically for industrial and other
uses.
 For example, coal is used in locomotives and as reducing agent in blast furnace. Petrol is
mainly used in internal combustion engines and for doing mechanical work. There are solid,
liquid, and gaseous fuels that are available for firing in boilers, furnaces, and other combustion
equipment. Right type of fuel can be selected depending on various factors such as storage,
availability, handling, pollution, and landed cost of fuel. Combustion is the process of
chemical reaction between fuel and oxygen. During combustion heat and products of
combustion are released. The combustion process is an exothermic chemical reaction, i.e., a
reaction that releases energy as it occurs. Symbolically, combustion can be represented as
 Fuel + Oxidizer (Oxygen) → Products of combustion + Energy
 Heating value of a fuel is the amount of energy or heat released per unit mass during
combustion of that fuel. The main elements of combustion are carbon, hydrogen, sulphur,
oxygen and nitrogen. With the advent of nuclear fuels, which generate heat by nuclear
reaction, the common fuels may be termed as chemical fuels.
 Classification of Fuels
Classification of fuels is based on two factors:
 (i) based on occurrence (natural or primary and artificial or
secondary)
 (ii) physical state of the fuel (solid, liquid, gas) or state of
aggregation. Nuclear fuels are nowadays used for power
generation. It includes 92U235 and 94Pu239.
 Natural Fuels (Primary Fuels)
Some fuels are found in nature and are used in the same
form. These are called natural fuels, e.g. wood, coal, natural
gas and petroleum.
 Artificial Fuels (Secondary Fuels)
The fuels that are derived from natural fuels (primary) are
called artificial or secondary fuels, e.g. petrol, producer gas
and charcoal.
Comparison of solid, liquid and gaseous fuels: advantages and disadvantages
 Characteristics of a Good Fuel
A good fuel has the following features:
 1. It should be cheap and easily available.
 2. It should be dry and should have less moisture content. Dry fuel
increases its calorific value.
 3. It should be easily transportable, otherwise cost of fuel will increase.
 4. It must have high calorific value.
 5. It must leave less ash after combustion. In case of more ash, the fuel
gives less heat.
 6. The combustion speed of a good fuel should be moderate, otherwise
it will not solve the problem of heating.
 7. It must have moderate ignition temperature. Low (burning)/ignition
temperature can cause fire accident.
 8. It should not burn spontaneously to avoid fire hazards.
 9. It should not give harmful gases after combustion.
 10. Its handling should be easy.
 11. The combustion of a good fuel should not be explosive.
 12. The combustion of a good fuel should not result in the release of
toxic gases such as CO, CO2, CH4,etc
 Calorific Value of a Fuel
 The calorific value of any fuel is a very important property. It
measures the heat produced by the fuel. The higher the calorific
value, the better will be the quality of fuel. Calorific value is
defined as “the amount of heat produced by the combustion of
unit mass or unit volume of a fuel”. It is characteristic of every
substance and is important for thermodynamic design and
calculation of combustion system.
 The calorific value is measured in several units of heat; they are
calorie, kilocalorie, British thermal unit and Centigrade thermal
unit (Centigrade heat unit).
 Calorie: The amount of heat which increase the temperature of
one gram of water by 1°C in known as 1 calorie.
 Kilocalorie: The amount of heat that increases the temperature
of 1 kg of water by 1°C (i.e., 15°C to 16°C) is called kilocalorie.
 British thermal unit (BTU): The amount of heat required
to raise the temperature of one pound of water by
 1°F (60°F to 61°F) is BTU.
 1 BTU = 252 cal = 0.252 kcal
 1 kcal = 3.968 BTU
 Centigrade heat unit (CHU): It is the amount of heat
required to raise the temperature of one pound of water
through 1°C.
 1 kcal = 3.968 BTU = 2.2 CHU
Relationship among all the above units of heat is given as
follows:
 1 kcal = 1000 cal = 3.968 BTU = 2.2 CHU
 Joule is also a unit of energy.
 1 cal = 4.18 J
 There are two types of calorific values of a fue
 High Calorific Value (HCV) or Gross Calorific Value (GCV)
It is defined as the amount of heat energy produced by the combustion
of unit mass (unit volume) of a fuel when the combustion products are
allowed to cool at the room temperature. Generally, fuels contain
hydrogen. When the calorific value of hydrogen-containing fuels is
determined experimentally, hydrogen is oxidized to steam; when the
products are cooled to room temperature, steam undergoes
condensation to produce water and releases the latent heat of
condensation of steam which must be included in the measured heat
which is called GCV. Actually, during combustion, the products are not
allowed to escape into the atmosphere and they are cooled to the room
temperature. Hence, the net heat energy recovered on the combustion
of fuel is lower.
 Low Calorific Value (LCV) or Net Calorific Value (NCV)
It is defined as the amount of heat energy produced by the combustion
of unit mass (unit volume) of fuel when the combustion products are
allowed to escape out into the atmosphere. LCV does not include the
latent heat of steam or water vapour formed.
 Relationship Between HCV and LCV

 If hydrogen is present in a fuel, the above-mentioned chemical reaction will

take place and 2 g of hydrogen will produce 18 g of H2O or 1 g of hydrogen will
produce 9 g of H2O. If x gram hydrogen is present in a fuel, it will produce 9x g
of water and 9x g of water vapour that will release 9x × L cal heat on cooling ( L
cal/g is the latent heat of water vapour). So,
LCV = HCV – latent heat of water vapour
LCV = HCV – (mass of hydrogen × 9 × latent heat of steam)
= HCV – (9 × H /100× 587)
= HCV – (0.09 H × 587)
where H is the percentage of hydrogen in the fuel and latent heat of steam is 587
kcal/kg.
 Determination of Calorific Value
 The calorific value of a fuel can be determined by an equipment called
calorimeter. The Bomb and Boy’s calorimeters are the two main methods. Here,
only the Bomb calorimeter has been discussed.
 Bomb Calorimeter
The bomb calorimeter is a device that is used for the determination of calorific
values of the solid and liquid fuels. Since the combustion of fuel is explosive, it
is called the bomb calorimeter. A bomb calorimeter is made of a cylindrical
stainless steel vessel called bomb. It contains a crucible having known mass or
volume of a fuel fixed on a screw. A magnesium fuse wire is connected to the
electrodes and the electrodes are connected to a 6 V battery. A copper
calorimeter envelops the bomb. The calorimeter has a known amount of water
having stirrer and Beckman’s thermometers. There are two jackets around the
calorimeter, i.e. air and water, as shown in Fig. 6.3 to prevent heat radiation. As
battery is connected to the electrodes, current flows through magnesium wire,
which ignites the fuel (cotton or cotton thread is also sometimes used for the
ignition of fuel). The initial and final temperatures of water in the calorimeter
are measured with Beckman’s thermometer.
Calculation of calorific value
Let mass of fuel be m gram. Thus,
Mass of water in calorimeter = W gram
Water equivalent of calorimeter = w gram
Initial temperature of water = T1°C
Final temperature of water = T2°C
Since the system is closed, the calorific value obtained will be an HCV.
 Bomb Calorimeter
 Solid Fuels
 Because of environmental hazards, trees were buried inside the earth.
By the action of temperature, pressure and bacterial actions over a
period of thousands of years, they converted into a brown-black solid
named coal.

 Since wood contains higher carbon percentage in the form of cellulose,

lignocelluloses, they are transformed into the form of coal. The process
of conversion of wood into coal is called coalification. Depending upon
the percentage of carbon, hydrogen, moisture and calorific value, four
different types of coals exist. It is called the ranking of coal.
 Dry wood has the following composition: carbon (48–50%), oxygen
(42–44%), hydrogen (5–6%) and traces of minerals. The calorific value
of wood is 4000–4500 kcal/kg and, thus, is used as a domestic fuel.
 Wood can be converted into charcoal by a process called carbonization
(destructive distillation of wood). Charcoal is used as absorbent of
gases and for de colourisation of sugar.
 Coal
 It is a carbonaceous matter produced by the decomposition
of vegetable and animal matter buried inside the earth’s
crust or under oceans. It is a non-renewable energy source
formed by the decomposition of accumulated vegetation
over a period of millions of years. Coal is one of the major
source of energy in many industries such as steel, cement
and paper, because of its easy availability and least risk of
fire hazards.
 Ranking of Coal
 During coalification of wood, the first stage of coal is peat.
It is ranked the lowest among coals. Other coals are lignite,
bituminous and anthracite. It has been reported that
graphite is also the final stage of coalification.
Wood → Peat → Lignite → Bituminous → Anthracite
 Analysis of Coal
 The analysis of coal is helpful in its ranking. The assessment of the
quality of coal is carried out by these two types of analyses:
(i) proximate analysis and (ii) ultimate analysis.
Proximate Analysis
 Proximate analysis gives information regarding the practical utility of
coal. In this analysis, the percentage of carbon is indirectly
determined. This analysis includes percentage of moisture, volatile
substance, ash content and carbon.
 Moisture: A known mass of finely powdered air-dried coal is taken in a
crucible. It is heated up to 110°C for an hour and cooled to room
temperature in a desiccator. The moisture is removed as water vapour
and the process is repeated. The weight of coal is reported on
moisture% basis till the constant weight is obtained.
Percentage of moisture=Loss of weight of coal/Weight of coal
taken×100
 Volatile matter: Dried sample of coal left in the crucible is
covered with a lid and placed in a muffle furnace maintained at
950°C exactly for 7 minutes. The crucible is then taken out,
cooled in the air and then in desiccator and weighed. The loss in
weight is reported as the percentage of volatile matter
Percentage of volatile matter =
Loss in weight due to removal of volatile matter/Weight of coal taken×100
 Ash content: Coal, free from moisture and volatile matter, is
heated in a crucible at about 700°C in a mufflef urnance in the
presence of air. It undergoes combustion and results in the
formation of ash. Crucible is cooled to room temperature and
weighed. Heating, cooling, weighing is repeated to get constant
weight of the residue. The residue is reported as as h. The mass
of ash is then determined.
Percentage of ash=Mass of ash × 100/Mass of coal
 Carbon: Since the main component of coal is carbon, it can be
determined by subtracting the sum of the percentage of
moisture, volatile substance and ash content from 100.
Carbon % = 100 – (% of moisture + % of volatile matter + % of ash)
 Significance of analysis: Proximate analysis gives quick and
valuable information regarding commercial classification and
suitability of coal for industrial use. It consists of a complex
mixture of gaseous and liquid products resulting from the
thermal decomposition of coal. The amount of decomposition
and yield of V.M. depends on the conditions of heating,
particularly temperature.
 Moisture: A high moisture content in the fuel takes some heat
liberated in the form of latent heat, reduces the calorific value,
increases the cost of transportation and causes wastage of heat.
Hence, the lesser the moisture content, the better is the quality
of a fuel. But moisture up to 10% produces a uniform fuel bed
and less of fly ash.
 Volatile matter: It is due to combustible and non-combustible
gases. A coal containing high volatile matter burns with long
flame, high smoke and low calorific value. volatile matter also
influences the design of the furnace since the higher the volatile
matter, the larger is the combustion space required.
 Ash: Ash is a residual, incombustible matter produced by burning
of coal. It creates cleaning and disposal problem. Ash adds
impurities in metallurgical operations. It obstructs the flow of air
and heat.
 1. Ash reduces heating value of coal.
 2. Ash content increases the cost of transportation,
handling, storage and disposal.
 3. It determines the quality of coal. hence, the
lesser the percentage of ash, the better is the
quality of coal.
 Fixed carbon: The higher the fixed carbon in a
coal, the greater is its calorific value and better is
the quality of coal. It helps in designing the
furnace and shape of fire box. It increases from low
ranking coals such as lignite to high ranking coals
such as anthracite. It helps in designing furnace
and fire box.
 Ultimate Analysis
 It is the elemental analysis of coal. This analysis includes percentages of C, H, O, S, N and ash content
in coal and better quality of CO. The two components can be determined in a single experiment.
 Liquid Fuels (Petroleum)
Petroleum is one of the best primary liquid fuel. It is also known
as crude oil. Petrol, diesel, kerosene are main liquid fuels. They
are secondary liquid fuels derived from petroleum. These fuels
are used for domestic works, auto vehicles and power generation.
The word meaning of petroleum is ‘rock oil’ (petra = rock,
oleum= oil).
Petroleum is dark-brown viscous liquid. Petroleum is a mineral
found deep in earth’s crust. It is a mixture of number of
hydrocarbons (paraffins, olefins, aromatics and naphthalene),
nitrogen, sulphur, oxygen containing optically active compounds
along with traces of compounds of heavy metals such as Fe, Co,
Ni and V. The unpleasant odour of petroleum is due to the
presence of some foul smelling sulphur compounds.
 Petroleum does not have definite composition. Its composition varies with the
place of origin. It is a complex mixture of various hydrocarbons and a small
quantity of optically active compounds of S, N, O and traces of Fe, Cu, V, etc.
Composition of petroleum is given as:
C = 80 to 87.1 %, H = 11.1 to 15.0 %, S = 0.1 to 3.5 %, O = 0.1 to 0.9 %, N = 0.4 to 0.9 %.
 Origin of petroleum
There are two theories to explain the origin of petroleum.
 Carbide theory: This theory is also called inorganic theory or Mendeleev’s
theory. Metals inside the earth react with carbon and form metal carbides.
These carbides are converted into hydrocarbons in the presence of moisture or
steam which on further hydrogenation polymerize to give a complex mixture of
paraffin's, olefins, and aromatic hydrocarbons.
Drawbacks: This theory was unable to explain the presence of nitrogen,
sulphur and optically active compounds found in petroleum.
 Engler’s theory or organic theory: According to this theory, organic matters,
animals, vegetation and marine animals died and accumulated in sea. There,
they were decomposed under high temperature and pressure by anaerobic
bacteria to give a dark viscous liquid called petroleum. This theory is better
accepted. The presence of optically active compounds in petroleum favours
Engler’s theory.
Classification of crude oil
There are three types of petroleum.
 Paraffinic base type crude oil: It has main saturated
hydrocarbons CnH2n + 2(n = 1 to 35) alongwith
naphthalene and aromatics hydrocarbons from
C18H38 to C35H72 are solids, called waxes.
 Asphaltic base type crude oil: It has mainly
naphthalene and cycloparaffins with a small quantity
of aromatic and saturated hydrocarbons. These oils on
distillation leave asphalt as residue.
 Mixed base type: This type of crude oil is a mixture of
above two, paraffinic base type and asphaltic type. It
has high percentage of semisolid waxes.
 Synthetic Petrol (Gasoline)
Petrol is mainly obtained from crude oil from oil wells but can also be
obtained by synthetic processes. Two synthetic processes are given
here, viz.
(i) Fisher–Tropsch process and (ii) Bergius process.
 Fischer-Tropsch process: The Fischer–Tropsch process is a collection
of chemical reactions that convert a mixture of carbon monoxide and
hydrogen into liquid hydrocarbons. The process, a key component of
gas to liquids technology, produces a synthetic lubrication oil,
synthetic fuel from coal, natural gas or biomass. When solid
feedstock—coal—is used, the solid feedstock is converted into gaseous
reactants CO, H2 and alkenes. In the Fisher–Tropsch plant that uses
CH4 as feedstock, steam reforming occurs which converts methane
into CO and H2

 A variety of catalysts such as cobalt, iron, ruthenium and Ni can be

used for the Fischer–Tropsch process. Nickel favours the formation of
methane. Cobalt catalysts are more active when feedstock is natural
gas. Iron catalysts are preferred for lower quality feed stocks such as
coal or biomass. This process was developed in Germany by F. Fisher
and H. Tropsch in 1923. In this process coal is converted into coke. Coke
is then treated with steam to obtain water gas.
 Bergius process:
 This process is the oldest one. In this
process, low ash content coal is taken and
powdered. It is now mixed with heavy oil
to make a paste alongwith a catalyst (Ni or
Sn oleate). This paste is heated with
hydrogen at 450°C and 200–250
atmospheric pressure in a converter. The
process is called hydrogenation. The
hydrocarbons formed in this process are
converted into low boiling liquid
hydrocarbon. The issuing gases are led to
condenser; crude oil is obtained which is
fractionated. The middle oil is
hydrogenated to get more gasoline and
heavy oil is mixed with coal for making
paste. The yield of gasoline by this process
is 60%. A flow diagram of this process is
given in Fig. Nowadays improved Bergius process of hydrogenation
processes are introduced which include of coal to gasoline
Exxon donner solvent (EDS) process. This
process is improved by using suitable
catalyst.
 Refining of Gasoline
Ideal gasoline must be
(i) cheap and readily available,
(ii) it must burn without ash or soot on combustion,
(iii) it should mix easily with air and it should be knock resistant.
 The quantity of petrol available from distillation alone was not
sufficient to meet our requirements. Hence, two processes have
been developed:
(i) rebuilding hydrocarbon molecules called reforming and
(ii) breaking heavier hydrocarbons to lighter molecules called
cracking.
 Reforming:
Reforming of gasoline is mainly aimed at reducing the knocking
of gasoline. The straight run gasoline produced by fractional
distillation of crude oil is subjected to structural modification.
Reforming is carried out thermally or catalytically. These
modifications are essentially a result of rearrangement of
molecules without greatly disturbing the average molecular
weight.
 1. Thermal reforming: It is carried out in a reactor
maintained at 500–600°C at 80 atm pressure. The
straight run gasoline is subjected to heating in the
reactor to give branched alkanes. The products are
cooled by spraying cold oil and then fractionated to
remove residual gasoline. During reforming, cracking
occurs to yield alkenes and alkanes. They may also
undergo de hydrocyclization or dehydrogenation to
yield naphthalene.
 2. Catalytic reforming: Catalytic reforming is carried
out in order to improve the yield and to produce better
quality of gasoline. In this method, platinum metal
supported on alumina in used as catalyst and
reforming is done at 460–530°C and at 35–50 atm
pressure.
3. Chemical reactions during reforming:

Gasoline obtained from fractionation of crude oil or by synthesis contains certain

undesirable chemicals (unsaturated straight chain hydrocarbons and sulphur
compounds). Sulphur compounds lead to the corrosion of internal combution
engines whereas remaining ones are oxidised to form gum and sludge. Refining is
thus needed to obtain high class gasoline.
Cracking
 The quality and yield of petrol produced by the
fractionation of petroleum is low. Hence, the middle
oil and heavy oil fractions are cracked to give petrol.
 Cracking is the process of conversion of bigger
hydrocarbon molecules into smaller hydrocarbons of
lower molecular weights.
 The process of cracking brings about (i) the conversion
of high boiling fractions into low boiling fractions
suitable for automobile and (ii) the production of raw
materials for petrochemical industries.
 Knocking
 In internal combustion engines, diesel or gasoline mixed with air is
used as fuel and ignited in the cylinder. The ignition is brought about
by an electric spark (in petrol engines) and compressing air in diesel
engines. After the ignition is initiated by a spark, the fuel air mixture
must burn smoothly and rapidly and the flame should spread
uniformly throughout the gaseous mixture. The expanding gas drives
the piston down the cylinder due to high pressure and provides power
stroke. The four strokes in petrol engine are:
1. Suction stroke: Here the fuel–air mixture is drawn into the cylinder during
induction.
2. Compression stroke: Fuel–air mixture is compressed in the cylinder.
3. Power stroke: Fuel–air mixture is ignited by electric spark. The hot gases
produced due to combustion increase the pressure and push the piston
down the cylinder.
4. Exhaust stroke: The piston ascends and expels exhaust gas from the cylinder
and the next cycle starts again. The efficiency of an engine is directly
related to compression ration (CR)
 CR is the ratio of the volume of gas in the cylinder at the end of
suction stroke to the volume of gas at the end of compression
stroke. Compression ratio directly governs the efficiency of an
engine. More the CR value, better will be efficiency of the
engine. CR depends upon the type of constituents in gasoline.
But in certain circumstances, the smooth burning of fuel is
interrupted due to the presence of certain impurities. The last
portion of the fuel ignites instantly and produces shock waves. it
results in rattling sound in the engine called knocking. it results
in rattling sound in the engine called knocking.
 Knocking decreases the efficiency of engine. The tendency of
knocking is based on chemical structure of hydrocarbons.
Branched chain alkenes burn more easily than straight chain
alkenes. Lower alkenes (e.g., C4H10) burn easily than higher
alkenes, e.g. C7H16. Also alkenes are better than alkanes and
aromatic hydrocarbons; they burn more easily than cycloalkenes.
Alternatively, the order of knocking tendencies is straight chain
alkenes > cycloalkene > olefins > aromatics. For internal
combustion engine, n-alkanes are not fit for modification.
Knocking is the measure of octane number. Hence, for n-
heptane, octane number is 0, and that of isooctane is 100.
 Octane number or Octane rating
 The anti-knocking value of fuel can be increased by adding
tetraethyl lead (TEL). The oxides of lead formed as
combustion products inhibit freeradical chain reaction
responsible for knocking. Additives like ethylene
dibromide and ethylene dichloride are also added to petrol
to avoid the contamination of atmosphere by vapours of
lead and PbO2. They form lead halides which escape into
the atmosphere. They are not eco-friendly.
 Other additives tricresyl phosphate, 2,4-ditertiarybutyle-4-
methyl phenols act as lead scavengers to prevent the
oxidation of lead. The small quantity of methyl
cyclopentadienyl manganese tercarbonyl (MMT) is also
used nowadays in Canada and European countries in place
of TEL, but results in Mn pollution in air and soil.
Nowadays leaded petrol is used as aviation fuel known as
avgas.
 Prevention of Knocking -Knocking can be prevented by using:
(i) Good quality fuel with higher octane number.
(ii)By adding anti-knocking agents like tetraethyllead, methyl
cyclopentadienyl manganese tricarbonyl (MMT) isooctane, diethyl
telluride, etc.
(iii) By retarding spark plug ignition.
 It has been observed that maximum knocking is from a straight chain alkane n-
heptane and hence its octane number (anti-knocking values) is assigned as zero
while isooctane knocks minimum (say zero), its octane number has been given
hundred. Hence, the octane number of gasoline is the percentage of isooctane
in the mixture of isooctane and n-heptane which has the same knocking as the
gasoline itself. Therefore, octane number 60 of a gasoline sample means, the
mixture of 60% isooctane and 40% n-heptane which passees same knocking as
the gasoline. The higher the octane number, the lower it is knocking. There are
certain compounds which are used as anti-knock compounds. Tetraoctyl lead
(C7H5)4Pb is better anti-knock but lead is dangerous for health. Methyl
cyclopentadicyl manganese is also used as anti-knock but manganese is also
harmful. Organic compounds like methanol, ethanol, methyl t-butylether, etc.
are also inserted as anti-knocking agent blended with gasoline. Aviation
gasoline has octane number even more than 100. The fuel marked 100 + 2
means a mixture of isooctane (100 ml) + TEL (2 ml).
 Cetane Number or Rating
 The knocking characteristics of diesel oils are usually expressed in
terms of cetane number. It is a measure of ignition lag or delay of the
fuel. It is the time period between the start of ignition and start of
combustion of the fuel. For the determination of cetane number, n-
hexadecane and a-methyl naphthalene are taken as standard. (C16H34)
n-hexadecane is a saturated hydrocarbon having a short ignition lag as
compared to any commercial diesel fuel. Its cetane number is 100. It
ignites below compression temperature. α-Methyl naphthalene has a
very long ignition lag as compared to any commercial diesel oil. Its
cetane number is taken as zero.
 In diesel engine, fuel is exploded not by spark but by
temperature and pressure. The suitablity of diesel fuel is
determined by its cetane number.
 Cetane number is the percentage of n-hexadecane in n-
hexadecane and α-methyl naphthalene which has the
same ignition characteristics as that of the sample under
test. Cetane number 60 means, it has the same ignition
characteristics as that of 60 parts of cetane and 40 parts of
α-methyl naphthalene. The order of cetane number for the
following is given as
n-alkanes > napthalenes > alkenes > branched alkanes >
aromatics
 Thus, it is inferred that the hydrocarbons which are poor
gasoline fuels are good diesel fuels. Alkyl and nitrites and
di-tertiary peroxides are used as additives to increase the
cetane number of fuel. They are called pre-ignition dopes.
 Power alcohol: It is an excellent alternative motor
fuel for gasoline IC engines. It can also be used in
combination with gasoline. Blends of alcohol with
gasoline or gasoline with benzol or benzene are used
as fuels. When alcohol is blended to gasoline, then the
anti-knock property of gasoline increases. Alcohol-
blended fuels have lesser starting difficulties. They
burn cleaner than gasoline and do not produce any
toxic emissions. They are biodegradable. The raw
materials for alcohol are derived from sugarcane and
corn which are readily available.
 Gaseous Fuels
 Natural gas is the primary gaseous fuel. A variety of secondary fuels are obtained from coal or
petroleum. They include coal gas, producer gas, water gas derived from coal, and LPG, CNG derived
from natural gas and oil gas formed by cracking of kerosene oil.
 Natural Gas
 Natural gas is primarily methane gas. It is a fossil fuel. It is formed in coal beds (coal bed methane).
Other sources are town gas and biogas. The main source of natural gas is oil fields, and the gas is
called associated natural gas. (The gas formed in natural gas field is called associated gas.) Also,
natural gas formed with petroleum and diesels is called wet gas and that formed with crude ore is
called dry gas. The calorific value of wet gas is higher than the dry gas because of higher percentage of
heavy unsaturated molecules. Composition of natural gas:

 Natural gas contains ethane, propane, butane and pentane alongwith main component methane
Before the use of natural gas, other heavier hydrocarbon, CO 2, N2, He, and H2O are removed.
Commercially natural gas is produced from oil fields and natural gas fields. The gas obtained from oil
wells is also called casing head gas. Town gas is a mixture of city and other gases mainly CO. It is used
similar to the natural gas. The gas is used for cooking and lighting purposes. The waste product
coaltar is used for road making. Biogas is also methane-rich and widely used as domestic fuel.
 The approximate composition of natural gas is
CH4= 70–90%, C2H6= 5–10%, H2= 3%, CO + CO2= 0.7%.
 The calorific value of natural gas is 12000 to 14000 kcal/m3. Sometimes harmful H2S gas flows in
traces which can be removed by 2-amino ethanol
Natural gas has several applications:
 1. It is used as a very good domestic fuel.
 2. It is used in the preparation of ammonia (used for
urea manufacturing).
 3. It is used to prepare carbon-black which is used as
filler for rubber industry.
 4. It is used to prepare synthetic proteins for animal
feed. (Methane on fermentation gives synthetic
proteins used as animal feed.) Natural gas is being sent
to thousands of kilometres through pipes.
 Biomass
 In rural areas, the major fuel sources are wood, agricultural wastes, cattle dung,
dry plants, etc. These fuels cater about 75% of our need. They are called
biomasses. In villages, traditional chullas are used which have poor efficiency
(about 10%). It produces a lot of pollution due to smoke. The biomasses are
primary fuels and can be converted into more efficient secondary fuels. Wood
is converted into charcoal and cattle dung can be converted into biogas. The
remaining part of the sugarcane is called bagasse that is used as fuel and as raw
material for making paper. Rice husk is also one of the important biomass from
which liquid fuel can be extracted.
 Biogas
 Biomasses undergo bacterial fermentation and result into biogases.
Alternatively, biogas is obtained by the anaerobic fermentation of the dung,
plant wastes and household wastes (vegetable waste) in the absence of oxygen
and in the presence of water. The main components of biogas are methane
(55%), CO2 (35%), H2 (7.4%), N2 (2.6%) and H2S (present in traces). The
calorific value of common biogas (gobar gas) is 5300 kcal/m3. The natural gas
may also be considered as a biogas. It is formed by animals and plants and
other vegetations buried inside the earth. Bacterial actions, temperature, high
pressure and water convert them into natural gas.
 Biogas Plant:
Biogas is prepared in an
apparatus called biogas plant.
There are two types of biogas
plants:
(i) floating gas holder type and
(ii) fixed dome type.
 Floating Gas Holder Type
Floating gas holder type plants
were made of metallic sheet
(iron sheet) that rusted and
caused gas leakage.
 Fixed Dome Type Biogas
Plant
 This type of plant is made of
concrete, bricks and cement. It
has underground digester tank.
One side of the tank is
connected with inlet chamber
while the other side is
connected with the overflow
tank. There is a dome connected
with the gas pipe having a valve
(Fig.6.12)
 LPG (liquified Petroleum Gas)
 Nowadays LPG has been a common fuel for domestic work and
also in most of the industries. The main components of LPG or
cooking gas are n-butane, isobutane, butylene and propane
(traces of propene and ethane).
 The hydrocarbon are in gaseous state at room temperature and at
atmospheric pressure but can be liquified under higher pressures
(Fig. 6.13A). The gas can be compressed under pressure in
containers and sold under trade names like Indane, Bharat
Petroleum gas, HP gas, etc.
 LPG is kept in metallic cylinder attached with burner through
pipe. It has two stoppers, one at the cylinder and other at burner.
LPG has special odour due to the presence of organic sulphides
which are added specially for safety measure. The gas can be
compressed under pressure in containers and sold under trade
names like Indane, Bharat Petroleum gas, H. P. gas etc. The gas is
obtained from natural gas or as a byproduct in refineries during
cracking of heavy petroleum products.
 Characteristics of LPG
 1. It has high calorific value: 27800 kcal/m3.
 2. It gives less CO and least unburnt hydrocarbons. So it causes least pollution.
 3. It gives moderate heat which is very good for cooking.
 4. Its storage is simple. It is colourless.
 5. It has the tendency to mix with air easily.
 6. Its burning gives no toxic gases though it is highly toxic.
 7. It neither gives smoke nor ash content.
 8. It is cheaper than gasoline. It burns with little air pollution and leaves no solid residue.
Hence, it is used as fuel in auto vehicles also.
 9. It is dangerous when leakage is there. It is highly knock resistant.
 10. LPG can be extracted from natural gases and also from refining of crude oil. Cryogenic
process is best for the extraction for natural gas.
 Advantages of LPG
 1. LPG is used as domestic fuel and as a fuel for internal combustion engines.
 2. It is used as feedstock for the manufacture of various chemicals and olefins by
pyrolysis.
 3. LPG in used in industries as portable blow lamps, welding, annealing, hardening, steel
cutting, etc.
 Disadvantages
 1. It is difficult to handle as fuel.
 2. Engines working at low compression ratio cannot use LPG as fuel.
 CNG (Compressed Natural Gas)
 Natural gas contains mainly CH4. When natural gas is
compressed at high pressure (1000 atm) or cooled to –160°C, it is
converted into CNG. It is stored in cylinder made of steel (Fig.
6.13B). It is now replacing gasoline as it releases less pollutants
during its combustion. It is environmentally clean alternative to
those fuels which produce toxic pollutants. In some of the metro
cities, CNG-vehicles are used to reduce pollution. LNG (liquified
natural gas) is different from CNG. LNG is costlier than CNG.
 Advantages of CNG
 1. Due to higher temperature of ignition, CNG is better fuel than
petrol and diesel.
 2. Operating cost of CNG is less. Cost of production is less. It can
be easily stored.
 3. It releases least pollutants like CO and unburnt hydrocarbons.
 4. Spark plug of CNG-engines are not carbonified.
 5. It undergoes regular combustion.
 Disadvantages
 1. Response to blending is poor.
 2. Faint odour; leakage cannot be detected easily.
 3. CNG tanks require a large tank space.
 4. Refueling network for CNG is very expensive.
 Combustion Problems
 Theoretical Questions
 1. Define fuel. What are the characteristics of a good fuel?
 2. What is meant by calorific value of fuel? Explain the method of determination of
calorific value of liquid and gaseous fuels.
 3. How do you analyse coal by (a) proximate and (b) ultimate analysis? Give their
significance.
 4. What is octane number?
 5. Explain Fischer–Tropsch’s and Bergius methods for the synthesis of petrol.
 6. What are the advantages of gaseous fuels?
 7. How do you analyse flue gas by Orsat’s methods?
 8. Why tetraethyl lead is mixed with gasoline?
 9. Write notes on LPG, CNG and biogas.
 10. Give an account of the advantages and disadvantages of solid fuels over gaseous fuels.
 11. What is LCV and HCV of fuel? Describe Junker’s method for the determination of
calorific value of gaseous fuels.
 12. Give an account of the classification of the fuels with suitable examples.
 13. Define octone number of gasoline. What is its significance and how is it measured?
Why is ethylene dibromide added when TEL is used as an antiknock reagent?
 14. What is biodiesel? How is it obtained? What are its advantages?
 15. What is petroleum? How is it refined? What are the fractions obtained and their uses?
 16. What is cracking? How gasoline is obtained from fixed bed cetelytic cracking
 Multiple-Choice Questions
 1. A good fuel should possess
(a) high ignition temperature (b) moderate ignition temperature (c) high calorific value (d) both (b)
and (c)
 2. Ignition temperature of a fuel is the
(a) temperature at which the fuel ignites for a moment but does not burn after heat.
(b) temperature attained when the fuel is burnt.
(c) lowest temperature at which the fuel must be pre-heated so that it starts burning smoothly.
(d) temperature at which the fuel can be stored safely.
 3. An example of a secondary fuel is
(a) wood (b) coal (c) natural gas (d) gobar gas
 4. Purest form of coal is
(a) lignite (b) bituminous (c) peat (d) anthracite
 5. Gobar gas contains
(a) CO2 (b) H2 (c) CH4 (d) all of these
 6. Biogas contains
(a) CO2 (b) CH4 (c) C2H4 (d) C2H2
 7. Power alcohol is an example of
(a) liquid fuel (b) artificial fuel (c) secondary fuel (d) all of these
 8. Gross calorific value is also known as
(a) high calorific value (b) low calorific value (c) net calorific value (d) none
 9. The correct relationship between HCV and LCV is
(a) LCV = HCV + 0.9 HL (b) LCV = HCV − 0.09 HL (c) HCV = LCV − 0.09 HL (d) HCV = LCV + 0.9
HL
 10. The most impure form of coal is
(a) anthracite (b) peat (c) wood (d) lignite
 11. One kilogram of cattle dung produces biogas which gives
(a) 1000 kJ of heat (b) 10 kJ of heat (c) 800 kJ of heat (d) 500 kJ
of heat
 12. Bomb calorimeter is used for the determination of calorific
value of
(a) solid fuel (b) liquid fuel (c) gaseous fuel (d) both (a) and (b)
(e) both (b) and (c)
 13. The fuel which has the highest calorific value is
(a) wood (b) petrol (c) methane (d) hydrogen
 14. The optimum temperature for fermentation in biogas plant is
(a) 10–20°C (b) 25–35°C (c) 35–50°C (d) 55–75°C
 15. The calorific value of biogas is
(a) 1500 kcal/m3 (b) 2500 kcal/m3 (c) 5300 kcal/m3 (d) 43
kcal/m3
 16. The other name of biogas is
(a) producer gas (b) gobar gas (c) natural gas (d) none
 17. The highest ranking coal is
(a) lignite (b) peat (c) anthracite (d) bituminous
 18. Natural fuel among the following is
(a) oil gas (b) coke (c) petrol (d) coal
 19. Major constituent of LPG is
(a) methane (b) ethane (c) benzene (d) butane
 20. The calorific value of a fuel is expressed as
(a) kcal/m (b) kcal/kg (c) cal/cm3 (d) kcal/g
 21. The calorific value of a fuel can be theoretically calculated by _________
formula.
(a) Dulong’s (b) Newton’s (c) Avagadro’s (d) Raman’s
 22. Compressed natural gas mainly contains
(a) CO (b) N2 (c) CH4 (d) SO2
 23. The jet engine fuel is ____________.
(a) kerosene (b) petrol (c) diesel (d) petroleum ether
 24. Calorific value of diesel is
(a) 11250 kcal/kg (b) 11000 kcal/kg (c) 11200 kcal/kg (d) 10000 kcal/kg
 25. The greases used for lubrication can be obtained by fractionation of
(a) diesel oil (b) kerosene oil (c) vegetable oil (d) heavy oil
 PHASE RULE
 Introduction
 Phase diagrams are of considerable significance both industrially and
commercially, particularly for steels, alloys, ceramics and semiconductors.
These are the basis of separation procedures in petroleum industry, food
formulations and in the preparation of cosmetics. Phase diagrams are an
important tool to deal with the behavior of heterogeneous systems. Phase rule
helps in predicting the effect of temperature, pressure and concentration on a
heterogeneous system in equilibrium.
 The equilibrium condition for any system is that the chemical potential of each
constituent throughout the system must be the same. If there are several
phases of each constituent, then the chemical potential of each constituent in
every phase must have the same value. For example, if at any temperature and
pressure liquid water is in equilibrium with water vapour and solid ice, then

 Phase diagrams can be discussed in terms of relationships, the phase rule,

derived by Gibbs. We shall derive the rule first, and then apply it to a wide
variety of systems. The phase rule requires a careful use of terms, so we begin
by presenting some definitions.
 Phase
 Phase is a homogeneous system which is separated from other
phases of the system by means of a boundary. It is a physically
distinct and mechanically separable part of a system. The phase
has to fulfill the following conditions:
 1. It should be physically homogeneous. It must have the same
composition and physical properties in all its parts.
 2. It should be separated from other phases of the system at
equilibrium by surfaces of contact.
 3. The phases of a system are in dynamic equilibrium with one
another through the exchange of chemical species.
Common examples of some phases
 1. In a system of water and ice all the ice pieces are in one phase
and water in another phase, so there are two phases.
 2. Two liquids which are completely miscible with each other, e.g.
glucose in water, sodium chloride in water, ethanol and water
possess one phase.
 3. Two liquids immisible in all proportions., e.g., benzene and
water and oil and water contain two phases.
 Component
It is an element or a compound present in a system. The concentration of the
component can undergo independent variation. It does not stand for the total
number of constituents of the system. The number of components of a system
at equilibrium is defined as the minimum number of molecular species in
terms of which the composition of each phase may be expressed quantitatively.
Examples:
 1. In the water system, the phases that occur are ice, liquid water, and water
vapour:

It is a one-component system, as each phase is in a different physical form and

the composition of each of these phases can be expressed in terms of the single
constituent represented by H2O.
 2. Decomposition of CaCO3: There are three molecular species–CaCO3, CaO
and CO2, but the composition of each phase can be expressed in terms of any
two of the species. If any two of the constituents are chosen, the composition
of all the phases can be expressed. For example, if CaO and CO2 are the two
components, then
CaO = CaO + OCO2
CO2 = OCaO + CO2
CaCO3 = CaO + CO2
 Thus, the composition of phases present at equilibrium can be fixed by two
variables. Hence it is a two component system.
 Degree of Freedom
 The degree of freedom or variance (F) is defined as the smallest number
of independent variables such as pressure, temperature, and
concentration that must be specified in order to describe the state of
the system completely. The degrees of freedom of a system may be one,
two, three or zero. Accordingly, the systems are known as uni-variant
(or mono-variant), bi-variant, tri-variant and non-variant systems,
respectively. For example:
 1. Consider a gaseous system containing CO2 and nitrogen. The system
is completely defined when three variables of temperature, pressure
and concentration are specified. Then the system is said to have three
degrees of freedom, i.e., F = 3.
 2. A saturated solution of sodium chloride in equilibrium with solid
NaCl and water vapour.

 The system can be completely defined if temperature is specified. At a

fixed temperature, the other two variables (the composition of NaCl
solution and vapour pressure) have a definite value. So the system has
one degree of freedom, i.e., F = 1.
Uses of Phase Diagrams-The following are the uses
of phase diagrams:
 1. Phase diagrams are useful in understanding the
properties of materials in a heterogeneous equilibrium
system.
 2. The study of low-melting eutectic alloys which are
used in soldering can be carried out using phase
diagrams.
 3. From the phase diagram, it is possible to predict
whether an eutectic alloy or a solid solution is formed
on cooling a homogeneous mixture of two metals.
Phase rule
 Willard Gibbs in 1876 deduced the phase rule from
thermodynamic considerations. This rule gives a
relationship between the number of degrees of
freedom (F), the number of components (C) and the
number of phases (P) in a heterogeneous system at
equilibrium. The relationship is as follows:
 F = C– P +2
 Uses of Phase Rule
 1. Phase rule provides a convenient basis for the
classification of systems with the help of phases,
components and degrees of freedom.
 2. The phase rule indicates that different systems
having the same degrees of freedom behave in a
similar fashion.
 3. It is applied to macroscopic systems, hence
information about the molecular structure is not
required.
 4. The rule considers only the number of phases but
not their amounts.
Limitations of Phase Rule
 1. The phase rule can be applied only for systems in
equilibrium. It is not applicable to systems which
attain equilibrium at a later stage.
 2. All the phases must be present under the same
conditions of temperature and pressure.
 3. Only three degrees of freedom are allowed to
influence the equilibrium system.
 4. The rule considers only the number of phases but
not their amounts.
 One-Component System: The Water System
 Under normal conditions the system ‘water’ is a three-phase, one-component
system. In this system,
water vapour water ice

exist in equilibrium. All the three phases can be represented by one chemical
formula H2O. Hence, it is a one-component system. If three phases exist
together,
 we have P = 3, C = 1 and the phase rule
 F=C–P+2
 =1–3+2
 =0
 The system therefore has no degrees of freedom. It is called a non-variant or
invariant system, i.e. none of the variables, i.e., pressure, temperature,
concentration, can be varied without one of the phases disappearing from the
system. Thus, the three phases can only exist together under one condition of
temperature and pressure. If only two phases exist together, say ice and water
or ice and vapour or water and vapour, the system now has one degree of
freedom and is said to be univariant.
 This means that one of the degrees of freedom, say
temperature, may be varied without causing any
alteration in the number of phases:
F=C–P+2
C = 1, P = 2
F=1–2+2=1
 When pressure and temperature are required to define
the system completely, the system represented by areas
has two degrees of freedom and is bivariant:
F=C–P+2
C=1P=1
F=1–1+2=2
 Curves OA: This curve is known as vapourisation curve as it represents
equilibrium between liquid water and vapour at different temperatures:
Liquid water vapour The curve starts from ‘0’, the freezing point of water
and ends at A, the critical temperature of water, 374°C. Beyond point A, the two
phases, liquid water and vapour, merge into each other, i.e. the number of phases
it takes is two because liquid water and vapour exist along the curve OA. For
any given temperature, there exists a fixed value of pressure and for each
vapour pressure, temperature, has also a fixed value. Thus, the degree of
freedom on any point of this curve is 1 or it is univariant, F = 1. Therefore,
F=C–P+2
=1–2+2=1
Curve OB: OB is the sublimation curve or the vapour pressure curve of
ordinary ice. Along this curve, the two phases of solid ice are in equilibrium
with its vapour. This curve shows vapour pressure of ice at various
temperatures. The curve starts at O and ends at B, i.e. absolute zero (–273°C). At
this phase, no vapour can exist and, therefore, only ice is present. On the other
side of OB, ice is in equilibrium with vapour. Therefore, two phases exist and the
degrees of freedom is 1 each.
F=C–P+2
=1–2+2=1
Vapour pressure can be maintained only at a fixed temperature.
 Curve OC: OC is the melting point curve or fusion curve of ice. It
indicates the effect of pressure on the melting point of ice. The fact that
the curve OC is inclined towards the pressure axis indicates that the
melting point of ice is lowered by an increase in pressure. At any point
on curve OC, ice and liquid water exist in equilibrium. It has one degree
of freedom and the system is univariant. The melting point must have a
definite value.
 Triple Point O- The three curves OA, OB, and OC meet at point O, the
triple point. Here all the three phases, namely, ice, water and vapour co-
exist. Further, P = 3, since there are three phases and one component. So
F=C–P+2
=1–3+2=0
In case of ice at the triple point, the system is non-variant. This occurs
at a temperature of 0.0075°C and pressure 4.5 mm of Hg. Phase would
not exist and one of the phases would disappear if temperature and
pressure are varied from this value.
In the area AOB, only vapour exists and in the area AOC, only water
exists. In the area BOC, three areas are bivariant and in order to locate
any point in the area, temperature and pressure must be defined.
F=C–P+2
=1–1+2=2
 Metastable Equilibrium
Sometimes, water can be cooled below its freezing temperature without separating solid
ice. The vapour pressure curve AO can be extended to the dashed line A by cooling below
its freezing point without separating ice, i.e. water can be super-cooled by carefully
eliminating solid particles. Along the curve OA, the liquid is in metastable equilibrium
with vapour. As soon as a small particle of ice is kept in contact with supercooled liquid,
it changes into ice and the curve merges in ‘OB which lies below OA’.
Metastable systems possess a higher vapour pressure than stable systems at the same
temperature. The supercooled water/vapour system is metastable or unstable. It soon
reverts to the stable system ice/vapour, when there is slight disturbance or when ice
crystal is introduced.
Areas AOC, AOB, BOC
The areas between the curves show the conditions of temperature and pressure under a
single phase–ice water or vapour is capable of stable existence.
Area AOC represents stable conditions for one-phase system, i.e. water. Area AOB
represents conditions for the one-phase system water vapour. The area BOC represents
the condition for one-phase system, i.e. ice. In all the three areas there being one phase
and one component, we have
F=C–P+2
=1–1+2=2
Thus, each system, water, water vapour, or ice, has two degrees of freedom, i.e. the system
is bivariant
 Two-Component System:
When a single phase is present in a two-component system,
the number of degrees of freedom is F= 2 – 1 + 2 = 3, i.e. the
three variables temperature, pressure and concentration of
one of the components must be specified. Construction of
the phase diagram of a two-component system will require
besides temperature, pressure coordinates, the use of one
concentration coordinate, which is possible in the space
model or solid model.
 A two-component system can be simplified by considering
various types of equilibria separately. These are (1) liquid–
gas (2) solid–gas (3) liquid–liquid and (4) solid–liquid
equilibria. Solid–liquid systems are of great importance
because they are connected with all crystallisation
problems. These systems are characterised by the absence
of a gas phase and are little affected by small changes in
pres-sure. Systems where the gas phase is absent are called
condensed systems. The measurement on solid–liquid
equilibrium in condensed systems is carried out at
atmospheric pres-sure. The phase rule takes the form F= C–
P+ 1. The reduced phase rule is more convenient to apply to
a solid–liquid two-component condensed system. The
variables are temperature and conentration of one of the
constitutents. Solid–liquid equilibrium is represented on
temperature composition diagrams.
 Simple eutectic system
 Eutectic means easy to melt. A binary system in which two components react
chemically and each component reduces the freezing point of the other is
called eutectic system. In such a system, the two components are miscible in all
proportions, i.e., eutectic system is a binary system consisting of two different,
totally immis-cible components in solid and miscible in liquid state without
any chemical interaction. The solid solution of a two-component system
having lowest freezing point is called eutectic mixture. The lowest melting
point that can be obtained corresponding to eutectic mixture is known as
eutectic point. The eutectic mixture possesses sharp melting point and
definite composition. But it cannot be regarded as a com-pound, because (1)
the compound does not possess components in stoichiometric proportion and
(2) when the components are examined under a microscope, they appear as
separate crystals of the compound. Consider a two-component system having
two components Aand B. In liquid state, these components are completely
miscible and these solutions on cooling yield pure Aor pure Bas solid phases.
Figure 7.3 consists of
 Curve AC, the freezing point curve of A. On addition of Bto A, the freezing
point of A falls along curve AC. Along this curve, solid Ais in equilibrium with
the liquid solution of Bin A.
 Curve BC,the freezing point curve of B. The curve exhibits decrease in freezing
point by the addition of Ato B. Along this curve, solid Bis in equilibrium with
the liquid solution of Ain B.
When reduced phase rule equation is applied,
F= C– P+ 1 = 2 – 2 + 1 = 1
The degree of freedom is 1, i.e., both equilibria are monovariant.
 Eutectic point C: The curves ACand BCintersect at the eutectic
point C, and the three phases—solid Ag, solid Pb and
solution— are in equilibrium. Applying reduced phase rule to
the system,
F= C– P+ 1 = 2 – 3 + 1 = 0,
i.e., At the eutectic point C, the system Ag/Pb/solution is non-
variant.
Both the variables, temperature (303°C) and composition (97.5%
Pb and 2.5% Ag), are fixed. If the tem-perature is raised above
eutectic temperature, the solid phases Ag and Pb disappear and
if the system is cooled below the eutectic point, only solid Ag/Pb
exists where solution phase is non-existent. Area above
AOC:This region is a single-phase system. The solution of
molten Ag and Pb exists. When condensed/reduced phase rule is
applied,
F= C– P+ 1 = 2 – 1 + 1 = 2.
Thus, Ag/Pb system is bivariant. The area below ACrepresents
the phase Ag+ solution and that below BC, the phase Pb+
solution. The area below 303°C represents solid Ag+ and solid
Pb. All these areas have two phases and one degree of freedom.
F= C– P+ 1 = 2 – 2 + 1 = 1
 Solid Solutions -
These are the solid phases containing more than one
component. The phase rule makes no distinction between the
kind of phase (solid, liquid, gas) that occurs, being concerned
with how many phases are present.
Two general classes of solid solutions can be found on structural
grounds:
(1) substitutional solid solution and (2) interstitial solid solution.
A substitutional solid solution is one in which solute atoms or
molecules are substituted for solvent atoms or molecules in the
crystal structure. For example, nickel has a face-centered cubic
structure; if some nickel atoms are replaced at random by copper
atoms, solid solution is obtained. The substitution is possible
only when they do not differ in size. An interstitial solid solution
is one in which the solute atoms or groups occupy interstices in
the crystal structure of solvent. For example, carbon atoms may
occupy some of the interstices in the nickel structure. Interstitial
solid solutions can occur only when solute atoms are small
compared to the solvent atoms.
 Iron–carbon diagram:
 The discussions on phase diagrams would be
incomplete without the iron–carbon system, which is
the prin-cipal theoritical basis for iron and steel
industry. The phase diagram shown in Fig. 7.5 extends
from pure iron to the compound iron carbide
Fe3C.Pure iron is ductile. Molten iron in pure form
freezes into δ-ferrite at 1537°C.
 Difference Among Melting Point, Triple Point and
Eutectic Point-
 At the melting point, a solid and a liquid having the
same composition are in equilibrium. At the triple
point, three phases are in equilibrium. At the eutectic
point, two solids and liquid are in equilibrium. By
definition,all eutectic points are melting points, but all
melting points need not be eutectic points. Similarly,
all eutectic points are triple points, but all triple points
need not be eutectic points.
Heat Treatment
 Heat treatment is the combined operations of heating
and cooling of a metal or an alloy in solid state in order
to get desired properties. Heat treatment is mainly
aimed at (1) increasing strength, toughness, hardness,
ductility to steel, (2) relieving internal stresses and
strains and (3) normalising steel which has been
already subjected to mechanical (or) heat treatment.
 After heat treatment, the properties of high-carbon
steels are altered to a much greater extent than
lowcarbon steels. The heat treatment methods include
the following processes:
 (1) Hardening:
Many desirable properties of alloys, ceramics and structural
materials depend on the components being in the form of
solid solutions. The hardening and tempering of steel
involve the existence of solid solutions of carbon in
different iron carbon compounds. The solid solution stable
at high temperature is hard, and in order to retain
hardness, proper compositions and temperatures are
obtained as indicated by phase diagrams. The steel is
immediately quenched in oil or water so that it does not
have time to form the solid solution which is stable at lower
temperature. By heating up again at little lower
temperature, partial conversion to softer solid solution
occurs which is stable at lower temperature. In this way, the
steel may be given different degrees of hardening.
(2) Transformation hardening:
 Plain carbon steel on heating to a temperature above
723°C for longer periods of time allows the formation
of austenite phase and the dissolution of more carbon
in fcc structure. The fcc structure is changed to bcc
and excess carbon forms cementite on slow cooling. If
the steel is quenched by plunging into water to 204°C,
the carbon atoms do not have sufficient time to form
cementite, but remain trapped in the bcc lattice.
Excess carbon gets precipitated in the hot metal and
prevents slipping of planes. Thus, quenched steel is
quite hard and strong and has lower ductility. This
heat treatment is called transformation hardening, i.e.,
it involves transformation of austenite to cementite
which is a hard steel.
 (3) Tempering:
The carbon steel in austenite state is quenched by plunging in water (or) brine,
the unstable g-iron in fcc and held carbon in solid soln. is changed to stable a-
iron at that temp. Quenched steel is not useful for construction purpose
because of its brittleness. The quenched steel is then tempered by reheating to
below a-iron to g-iron transition temperature. At elevated temperature, there is
greater atomic mobility. The stresses and strains are relieved and excess carbon
is rejected as Fe2.4C. The sample is then cooled in air, water, oil, etc., to get
resistance to abrasion and the steel is capable of withstanding shock loads.
 (4) Annealing:
 The steel is cooled very slowly so that equilibrium is established and stress-free
steel is obtained. It involves dissolution of carbon in g-iron followed by slow
and controlled cooling. The steel becomes soft, ductile and machineable.
Annealing decreases the hardness and strength of steel. Therefore proper
heating must be done. It depends on the chemical composition of steel and on
the structure and properties of the desired product. If steel is heated to a
higher temperature the grain size increases and the material becomes weak.
This is required only for drawing the metal into a wire. Mild and medium
carbon steel (Hypo-eutectoid is < 0.81% C) are heated to just above upper
critical range. Hard steel (hyper-eutectoid, i.e., 70.8% C) are heated above
upper critical range. Annealing consists of three stages, heating to the right
temperature, soaking (or) keeping at that temperature and slow cooling in a
furnace (or) buried in sand, ash (or) lime.
Advantages
 (a) Annealing removes internal stresses.
 (b) It changes ductility, toughness, electrical and
magnetic properties.
 (c) It removes gases entrapped within the mass.
 (d) It improves machinability.
 5) Normalising:
 Normalsing means to bring back the structure and
properties that are normal for a sample. By normalising,
fine, stronger pearlite is produced. It is a better method for
producing the steel with high tensile strength, yield
strength, impact resistance. Both normalising and
annealing treatments are given for making the steel soft
and homogeneous. Normalising is the corrective treatment
for grain refinement in steel after it has been subjected to
rolling, forging, etc. Hyper-eutectoid steels are rarely
normalised because higher temperatures. are used and
there is a tendency to form coarser grains which reduce the
strength. Normalising differs from annealing in two ways:
 (a) In normalising, cooling is done in still air and not in a
furnace. Therefore, the rate of cooling is faster which
prevents the formation of coarse grains at high
temperature.
 (b) In annealing, hyper-eutectoid steels are heated above
lower critical range, and in normalising, both hyper- and
hypo-eutectoid steels are heated above upper critical range.
 Theoretical Questions
 1. State the phase rule and explain the terms involved with suitable examples.
 2. Discuss the phase diagram of Ag–Pb system and its use in obtaining pure metals.
 3. What are interstitial solid solutions?
 4. Define phase, component and degree of freedom with two examples each.
 5. Describe, in detail, the phase diagram of one-component water system.
 6. Illustrate the number of components in the equilibrium given below:

 7. Why are the number of phases in the following two sets different?
 (a) Oil + Water (b) Alcohol + Water
 8. E xplain the concept of metastable state with the help of a phase diagram of water.
 9. What are the differences between melting point, triple boint and eutectic points?
 10. What is meta-stable equilibrium? Explain with an example.
 11. What is eutectic point?
 12. Discuss the application of phase rule to Ag–Pb system.
 13. Describe the salient features of Fe-C system and its relevance to heat treatment of
steel.
 14. E xplain the terms case hardening, normalizing, nitriding and cyaniding?
 15. What is the significance of Gibbs’ phase rule? Discuss its applications and limitations.
 Multiple Choice questions
 1. For one-component system, the phase rule is
(a) F = 3 – P (b) F = 2 – P (c) F = 1 – P (d) none of these
 2. A saturated solution of NaCl in water has degrees of freedom equal to
(a) 1 (b) 2 (c) 3 (d) 4
 3. At a triple point,
(a) both temperature and pressure are fixed
(b) only temperature is fixed
(c) only pressure is fixed
(d) sometimes temperature and sometimes pressure is fixed
 4. For one-phase and one-component system, the degrees of freedom are equal to
(a) 1 (b) 2 (c) 3 (d) 4
 5. A system with zero degree of freedom is known as
(a) mono-variant (b) bivariant (c) invariant (d) none of these
 6. The reduced phase rule for condensed system is
(a) F = C – P + 2 (b) F = C – P + 1 (c) F = C – P (d) F = C – P + 3
 7. The phase rule is applicable to
(a) homogeneous system (b) reversible system (c) irreversible system (d) heterogeneous system
 8. For a one-component system in a single phase, the degree of freedom is
(a) 0 (b) 1 (c) 2 (d) 3
 9. A one-component system has four phases. Can the four phases co-exist in equilibrium?
(a) No (b) Yes (c) Sometimes (d) None of these
 10. Heat treatment is aimed at
(a) increasing strength, toughness and
 11. Annealing of steel helps to
(a) decrease the hardness (b) decrease machinability
(c) increase internal stresses (d) bring back the original structure
 12. For water system, the maximum number of degrees of
freedom is
(a) 0 (b) 3 (c) 2 (c) 4
 13. Low carbon steels are hardened by
(a) quenching (b) case hardening (c) cyaniding (d) nitriding
 14. A system consists of water in contact with its vapour; the
number of degrees of freedom is
(a) unpredictable (b) one (c) two (d) zero
 15. Phase rule for one-component system is
(a) F = 3-P (b) F = 2 – P (c) F = C – P (d) none of the above
 16. Making hard steel resistant to abrasion is called
(a) annealing (b) tempering (c) case hardening (d) hardening
 17. Low-carbon steels are hardened by
(a) quenching (b) case hardening (c) nitriding
(d) cyaniding
 18. When lead in added to silver progressively, 
the melting point of the resulting alloy is
(a) increased (b) decreased (c) unchanged (d)
cannot be predicted
 19. Strength and hardness of steel is increased by
(a) normalizing (b) annealing (c) quenching (d) 
all of the above
 20. A system consists of water in contact with its
vapour. The degree of freedom is
(a) 0 (b) 1 (c) 2 (d) 3
 21. The hardest structure that appears on the
iron–carbon equilibrium is
(a) ledeburite (b) cementite (c) astenite (d)
pearlite
 22. A system containing liquid water and water
vapour has the number of phases
(a) 0 (b) 1 (c) 2 (d) 3
 23. A saturated solution of NaCl is a
_____________ system. ( b )
(a) one-phase (b) two-phase (c) three-phase (d)
no-phase
 24. The number of components of water system
having three phases—ice, water, and water
vapour—is
(a) one (b) two (c) three (d) four
25. The decomposition of CaCO3 in closed vessel
is represented by CaCO3(s) → CaO(s) + CO2(g).
It has _____________ number of phases and
components, respectively.
(a) 2 and 3 (b) 3 and 2 (c) 2 and 2 (d) 3 and 3
26. The appearance of same substance in more
than one crystalline form is known as
(a) polymorphism (b) metamorphism (c)
racemisation (d) isomerism
 27. For one-phase and one-component system,
the degree of freedom is equal to
(a) 1 (b) 2 (c) 3 (d) 4
 28. _____________ is the temperature at which a
polymer substance changes from one form to
another.
(a) Triple point (b) Transition temperature (c)
Ignition temperature (d) Equilibrium
temperature
 SURFACE CHEMISTRY
 Introduction -Adsorption is the phenomenon of
concentration or assimilation of a gas or liquid on the
surface of a solid or liquid with which it is in contact.
Adsorbent is the material which provides the surface on
which adsorption occurs and the substance adsorbed or
attached is called adsorbate. Examples of adsorbents are
charcoal, silica gel, clay, fullers earth, alumina gel, etc.
Adsorbent molecule (adsorbate)
Fig. 8.1 The adsorption of gas on solid surface
 Differences between absorption and Adsorption
 Adsorption is a surface phenomenon and it is a fast process. In
absorption, diffusion into the interior of matter takes place,
hence it is a slow process. For example, when a blotting paper is
kept in contact with ink, ink is absorbed into the paper. on the
other hand, if a dilute solution of litmus is shaken with animal
charcoal the surface of charcoal takes away some of the litmus
and all the litmus is concentrated on charcoal. In adsorption,
equilibrium is easily attained but in absorption it takes some
time to reach equilibrium. Absorption is a bulk phenomenon but
adsorption is a surface phenomenon.
Adsorption depends on the surface area of adsorbent.
Consequently, it is more rapid on finely divided and on a rough
surface. Such effect is not observed in absorption.
Fig. 8.2 Differences between absorption and adsorption
 Types of Adsorption
 Adsorption is not necessarily a physical phenomenon. It may be a
chemical process involving chemical reaction between the surface atoms
of adsorbent and the atoms of adsorbate. This type of adsorption is
known as chemisorption. It results in surface complex. For example, O2
is chemisorbed by carbon and H2 by nickel under suitable conditions.
Chemisorption differs from physical adsorption in the following respects:
 1. Physical adsorption occurs appreciably at very low temperature, i.e,
below boiling point of adsorbate. chemisorption occurs at all
temperatures.
 2. The magnitude of physical adsorption decreases with rise in
temperature. The magnitude of chemisorption increases with
temperature.
 3. The heat evolved during physical adsorption is very low, i.e., 4–40 kj
mol–1. It is very high (40–400 kj mol–1) in chemisorption.
4. Chemisorption is irreversible as the gas adsorbed cannot be
recovered from adsorbent as such on lowering the pressure of the
system at the same temperature. Physical adsorption is reversible as
the gas adsorbed can be recovered by simply lowering the pressure of
the system.

5. Physisorption may extend beyond a monolayer. Chemisorption

operates within short distance only. It does not extend beyond the
monolayer of gas molecules.
6. In physisorption, the adsorbate molecules are held together by
weak van der Waals forces. Hence, activation energy for disorption in
very low. In chemisorption, adsorbate molecules are held by strong
valence forces and its activation energy for disorption is high.
 Adsorption isotherms-The adsorption of a gas on a solid
adsorbent in a closed vessel is a reversible process. The amount of gas
adsorbed depends on equilibrium pressure (p) and temperature.
Adsorption isotherm is a graph plotted between a given magnitude of
adsorption and pressure at a given temperature. It may be given on a
graphical curve which is known as Freundlich adsorption isotherm
 Freundlich Adsorption Isotherm
 The relation between the magnitude of adsorption and
pressure can be expressed mathematically by an empirical
equation known as Freundlich adsorption isotherm.

 where x/m is amount of gas adsorbed per unit mass of the

adsorbent at pressure P. k and n are variables which depend
on the nature of the solid, gas and the nature of adsorbent.
 The extent of adsorption x/m increases with increase in
pressure (P) and becomes maximum at saturation pressure
P0. At P0, the rate of adsorption becomes equal to the rate
of desorption. Further increase of pressure has no effect on
adsorption.
 From the adsorption isotherm (Fig. 8.4), the following
observations can be made:
Limitations of Freundlich adsorption isotherm
 1. It fails when pressure is high and when the
concentration of adsorbent is very high. It is valid only
 within a limited range of pressure.
 2. The constants k and n change with temperature.
 3. It has no theoretical foundation. It is only an
empirical formula.
 Langmuir’s theory of adsorption (MonoLayer adsorption)
 Langmuir proposed a better equation to explain adsorption
isotherms on the basis of theoretical consideration. Langmuir
proposed that the surface of solid possesses fixed number of
adsorption sites per unit area and each site could adsorb only one
molecule of gas. Therefore, the surface of solid is covered by
mono-molecular gaseous layer. Since the solid surface is
assumed to be homogeneous, the molecular adsorption at each
site is independent of other adjacent sites occupied or vacant.
The adsorbed gas molecules remain localised without any
interaction with neighbouring molecules. One site adsorbs one
molecule. When a uni-molecular layer is formed by the
adsorption of gas, no further adsorption occurs, i.e., saturation is
obtained. In Langmuir’s adsorption, there is a dynamic
equilibrium between adsorbed gas molecules on the surface of
solid and evaporation of adsorbate from the surface of
adsorbent.
 Before adsorption, the surface remains vacant and the rate
of condensation stays maximum. As the surface becomes
covered, the rate of desorption (evaporation) is less in the
beginning and it increases when the surface becomes
covered. At equilibrium, the number of molecules
evaporating/unit time from the same surface, i.e., rate of
adsorption and rate of disorption, is in equilibrium. Based
on the above postulates, the rate of adsorption depends on
the pressure P and the number of vacant sites on the surface
(1 – θ), where q is the fraction of surface occupied by gas
molecules.
 Now, since the rate of adsorption is proportional to the
pressure (P) of the gas as well as uncovered surface (1 – q) of
the adsorbent available for adsorption, thus
 Rate of adsorption α P (1 – θ) = k1P(1 – θ)
 Adsorption of Gases by Solids
 Several methods for determining the adsorption of gases
on solid adsorbent have been derived.
 In one such method, the gas is contained in a vessel of
known volume at a given temperature. The pressure of the
gas is measured by a monometer attached to the vessel.
The adsorbent is slowly introduced into the vessel.
Adsorption takes place quickly and the pressure of the gas
falls which is noted on the monometer. Knowing the fall of
pressure, the quantity of gas adsorbed by solid can be
calculated, assuming Boyle’s law to hold good.
 As a result of adsorption, the residual forces on the surface
of adsorbent decrease. Hence, there is a decreaseof surface
energy which appears as heat. Adsorption is invariably
accompanied by decrease in the enthalpy of the system.
 Factors influencing Adsorption
 The magnitude of gaseous adsorption depends on the following
factors: (1) temperature, (2) pressure,
 (3)nature of the gas and (4) nature of adsorbent.
 Effect of temperature and pressure: Since adsorption is
accompanied by evolution of heat, according to Le Chatelaine's
principle, the magnitude of adsorption should increase with fall in
temperature and increase with increase in pressure.
 Nature of gas and nature of adsorbent: The more readily soluble
and easily liquefiable gases such as ammonia, hydrochloric acid,
chlorine, sulfur dioxide are adsorbed more than permanent gases such
as hydrogen, nitrogen and oxygen. This is because the van der Waal’s
forces involved in adsorption are more predominant in the former
category than the latter category of gases. Since adsorption is a surface
phenomenon, it is evident that the greater the surface area per unit
mass of the adsorbent, the greater is its capacity for adsorption under
the given conditions of temperature and pressure.
 COLLOIDS
 In Greek, kolla means glue and eidos means like. Depending on
their ability to diffuse in liquid medium ,substances are classified
into (1) crystalloids and (2) colloids.
 1. Crystalloids: Crystalloids diffuse rapidly in solution and can
pass very easily through animal and vegetable membranes.
 Examples: urea, sugar and other crystalline substances.
 2. Colloids: Colloids diffuse very slowly in solution and cannot
pass through vegetable and animal membranes.
Examples: Gelatin, starch and proteins.
But according to Graham, every substance irrespective of its
nature can be a colloid or crystalloid under suitable conditions,
e.g., soaps show crystalloid character in alcohol in which they are
freely soluble and show colloidal character in water in which they
are sparingly soluble. Thus, it is not feasible to classify the
substances into crystalloids and colloids. Hence, the term
colloidal substance has been replaced by colloidal state.
 True Solution, Colloidal Solution and Suspension
 A true solution is one in which the particles are invisible and do
not settle on standing, e.g., molecules of sugar in water.
 When the particles settle down on standing and can be separated
very easily from the solvent, such mixtures are called
suspensions. They are large enough to be visible to the naked eye
or under a microscope. They are hetergeneous in nature.
 In between these two limits, there are particles which are bigger
than molecules but smaller than suspension particles. They
cannot be seen under a microscope. Such particles are said to be
in ‘colloidal state’ and when suspended in liquid are referred to
as colloidal solutions.
 A colloidal system is made of two phases. The substance
distributed as colloidal particles is called dispersed phase. The
continuous phase in which the colloidal particles are dispersed is
called dispersion medium, e.g., in a colloidal solution of copper in
water, copper particles constitute dispersed phase and water the
dispersion medium.
 Classification of Colloids or Sols
 Colloids are of two types: (1) lyophilic or reversible and (2) lyophobic or
irreversible. If water is the dispersion medium, the terms hydrophilic
and hydrophobic are used.
 Lyophilic Colloids (Lyo = Liquid, Philic = Love)
 A colloidal system obtained by warming or shaking the substance with
a suitable solvent is known as lyophilic colloid, e.g., gelatin, starch,
protein, gum, rubber. These colloids are reversible in nature. On
evaporating the dispersion medium, the residue can be reconverted
into colloidal state by the addition of liquid. They are stable and cannot
be easily precipitated. The affinity of colloidal particles for the medium
is due to hydrogen bonding with water. If a protein (as in egg) is
considered as dispersed phase, hydrogen bonding would occur
between water molecules and the amino group of protein.
 Lyophobic Colloids (Lyo = Liquid, Phobic = Hate)
 These colloids are not formed easily. Lyophobic
colloids are formed by substances such as As2S3,
Fe(OH)3, gold and other metals which are sparingly
soluble and thus their molecules do not readily pass
through colloidal state. There is no hydrogen bonding
when these colloids are dispersed in water. These
colloids are known as irreversible colloids since the
residue obtained by evaporating dispersion medium
cannot be readily reconverted into colloid by ordinary
means. These sols or colloids are not stable and can be
readily precipitated.
 Examples: Dispersion of gold, iron (III) hydroxide and
sulphur in water.
Characteristics of Lyophilic and Lyophobic
Colloids
 The important properties of lyophilic and lyophobic
colloids are described below.
 Heterogeneous character: Unlike true solutions,
colloidal systems are heterogeneous in nature. They
consist of two phases, viz., dispersed phase and
dispersion medium.
 Ease of preparation: Lyophilic colloids are prepared
by mixing the material (starch, protein) with a suitable
solvent. Lyophobic sols cannot be prepared by simply
mixing the solid material with the solvent.
Charge on particles: Lyophilic colloidal solutions have little or no
charge at all, whereas lyophobic colloids carry positive and negative
charges which give them stability.
Viscosity: Lyophilic sols are viscous in nature. The particle size increases
due to solvation. Viscosity of lyophobic colloid is almost similar to that of
dispersion medium.
Colligative properties: The colligative properties such as osmotic
pressure, lowering of vapour pressure, elevation of boiling point and
depression of freezing point depend on the number of solute particles in
a given weight of solvent. Since the colloidal particles are aggregation of
molecules, the number of particles will be very small as compared to the
number of particles in true solution for a given mass of colloids. Hence,
unlike true solution, colloidal system gives very low osmotic pressure and
shows very small elevation of boiling point and depression of freezing
point.
 Optical properties:
 (1) Tyndall effect: A colloidal solution exhibits Tyndall
effect. When a strong beam of light is passed through a
colloidal solution and observed at right angles, the path of
light shows up as a hazy beam or cone. This is due to the
fact that colloidal particles absorb light energy and emit it
in all directions in space. This phenomenon is known as
Tyndall effect and the illuminated path is known as Tyndall
cone.
 Tyndall effect is due to the scattering of light from the
colloidal surface. The appearance of dust particles in a
semi-darkened room when a sun beam enters or when a
light is thrown from a projector in cinema hall is the well-
known example of Tyndall effect. The dust particles are
large enough to scatter light which makes the path of light
visible.
 Tyndall effect is used to distinguish between a true solution
and a colloidal solution, since the ions of solute molecules
are very small to scatter light and the beam of light passing
through true solution is not visible when viewed from the
side.
 Conditions for the system to show tyndall effect are as
follows:
 (a) The diameter of particles of the dispersed phase must
not be much smaller than the wavelength of light used.
 (b) The difference between the refractive indices of the
dispersed phase and dispersion medium must be
appreciably high. Lyophilic colloids have very small
difference of refractive indices and hence the Tyndall effect
is very small. On the other hand, lyophobic colloids shows
Tyndall effect because they satisfy the above condition.
 (2) Colour: The colloidal sols are often coloured. The
colour of a colloidal solution is not always the same
 as that of the dispersed phase in bulk. It depends on
the size and shape of the dispersed particles. For
example, a gold sol is red when the particles are
extremely fine and in spherical shape, but when the
dispersed particles are bigger and flat it appears blue
in colour.
 (3) Visibility: Even under a powerful microscope,
colloidal particles connot be seen. It is not possible to
see a particle whose diameter is less than half the
wavelength of light used. Thus, the particles of
diameter less than 200 mμ cannot be seen, since the
shortest wavelength of visible light is 400 mμ, e.g.,
gold sol cannot be seen by a microscope.
Kinetic Property of Colloidal Solutions
 Brownian movement
 When a colloidal sol is observed under an ultra
microscope, we can find a continuous, zigzag random
motion of particles (Fig. 8.14). This kinetic activity of
particles of colloid is known as Brownian movement. It
depends on the size of the dispersed phase and
viscosity of the dispersion medium. Brownian
movement is due to molecular impacts from the
medium on all sides of dispersed particles. The
movement of colloidal particles is much slower than
that of molecules of the medium, because colloidal
particles are heavier than molecules of dispersion
medium.
 Fig. 8.14

 Brownian movement proves the existence of molecules

and thermal motion of molecules, since the colloidal
particles acquire almost same energy possessed by the
molecules of the dispersion medium.
Coagulation or precipitation
 The stability of lyophobic solution is due to the
adsorption of positive or negative ions by dispersed
particles.
 The repulsive forces between the charged particles do
not allow the particles to settle down. If by any means
the charge is removed, then the particles get
precipitated and settle down under gravity.
 The settling down or flocculation of discharged
solution particles is called coagulation or precipitation
of sol. Coagulation can be brought about by
(1) the addition of ectrolytes, (2) electrophoresis, (3)
mixing two oppositely charged sols and (4) boiling.
 Addition of electrolytes: When excess of electrolyte is added
to the sol, the dispersed particles get precipitated. Sol particles
adsorb oppositely charged ions and get discharged. Electrically
neutral particles then aggregate and settle down as precipitate. It
depends on the valency of the effective ion. the higher the
valency of the effective ion, greater is its power of precipitation.
 Example: For precipitating As2S3 sol (negative), the
precipitating power of Al+3, Ba+2, Na+ ions is in the order
 Al+3 > Ba2+ > Na+
 For precipitating Fe(OH)3 sol (positive), [Fe(CN)6]3–, SO4 2–,
Cl– have been used. Then the order of precipitating power is
[Fe(CN)6]3– > SO4 2– > Cl–
 The precipitating power of an electrolyte is expressed by its
flocculation value. It is the minimum concentration in millimoles
per litre required to cause the precipitation of a sol in 2 hours.
the smaller the flocculation value, the higher is the precipitating
power of the ion.
 By electrophoresis: The charged particles of colloids
migrate to oppositely charged electrodes. They get
discharged and precipitated soon after they come into
contact with electrode.
 By mixing oppositely changed sol: Positive particles
of one sol are attracted by negative particles of second
sol. Mutual adsorption and precipitation of both the
sols occur.
 By boiling: On boiling, the collision between sol
particles and water molecules removes adsorbed layer,
charges from particles are taken away and
precipitation occurs.
 Protective action of colloids
 Lyophilic colloids are stable and reversible. The stability
depends on the degree of hydration. Lyophobic sols are
easily precipitated when a small amount of the electrolyte
is added. These sols are also stabilised if a small amount of
lyophilic sol is added.
 The property of lyophilic sols to prevent the precipitation
of a lyophobic sol is called protection. The lyophilic sol used
to protect a lyophobic sol. from precipitation is known as
protective colloid.
 Example: When a small amount of gelatin (lyophilic
colloid) is added to a gold sol (lyophobic sol), lyophobic sol
is protected which no longer gets precipitated. It is because
the particles of lyophobic sol adsorb the particles of
lyophilic sol, and the lyophilic colloid forms a protective
cover around lyophobic sol particles.
 The protective power of lyophilic sol is expressed in
terms of gold number. Gold number is defined as the
number of milligrams of a lyophilic colloid that will
just prevent the precipitation of 10 ml of gold sol on
addition of 1 ml of 10% solution of NaCl. The start of
precipitation of gold sol is indicated by a colour
change from red to blue with increase in particle size.
The smaller the gold number, the greater is the
protective action of the lyophilic colloid.
Micelles
 The molecules of colloids at low concentration act as
strong electrolytes. At higher concentration, they form
thermodynamically stable particles of colloidal
dimensions called association colloids or ‘micelles’.
Micelles have lyophobic tails which get congregated
and lyophilic heads which provide protection.
 Example: Colloidal aggregate of soap (sodium oleate,
sodium stearate) or detergent molecules formed in the
solvent. Sphere represents lyophilic groups. Stalks
represent lyophilic groups. The zigzag hydrocarbon
tail is shown by a wavy line and the polar head by a
hollow circle (Fig. 8.15).
 Cleansing Action of Soaps and Detergents
 The cleansing action of soap is due to (a) solubilisation of grease
into the micelle and (b) emulsification of grease.
 Solubilisation:
When soap solution is added to a fabric, the tails of the soap
anions penetrate into the grease stain. The polar heads protrude
from the grease surface and form charged layer around it. The
hydrocarbon tails are in the interior of the micelle and the COO–
ions on the surface. The grease droplets are suspended by mutual
repulsions. The emulsified stains of grease are washed away with
soap solution.
 Emulsification:
When soap or detergent molecules are ionised in water, the
anions are made of oil-soluble hydrocarbon tails and water-
soluble polar heads. The polar heads protrude from grease
surface and form charged layer. By mutual repulsion, the grease
droplets are suspended in water. The emulsified grease stains are
washed away.
 Applications of colloids
 1. Electroplating of rubber: Rubber is a colloidal suspension of negatively charged particles
in water. By electrophoresis, it can be made to deposit on various tools. These negative particles
migrate towards anode and get deposited on it during electrolysis.
 2. Leather tanning: The coagulating ability of colloids is used in leather tanning. Leather is a
positively charged colloid when mixed with wood, mutual coagulation takes place and leather
surface gets hardened.
 3. Chrome tanning: Leather can be subjected to chrome tanning when hydrated chromic
oxide penetrates into leather under the influence of electric field.
 4. Medicine: The ease of adsorption and assimilation of colloids makes their use in a number
of medicinal and pharmaceutical preparations where colloidal gold, iron, calcium, etc., are
administered (orally or injected) to raise the vitality of human system. Trivalent Al+3 and Fe+3
colloids are used in the coagulation of blood. Many skin ointments consist of physiologically
active components dissolved in oil and made emulsion with water. Penicillin and streptomycin
antibiotics are produced in colloidal form suitable for injection. and scatter the light of blue
colour. This is an application of the Tyndall effect.
 5. Food: Many food materials are colloidal in nature. For example, butter-milk (emulsion of fat
in water), cheese, fruit jelly, eggs, whipped cream, protoplasm, blood, etc. Ice cream is a
dispersion of ice in cream. Bread is a dispersion of air in baked dough.
 6. Artificial rain is due to the aggregation of minute colloidal particles. Clouds are
charged particles of water dispersed in air. Electrified sand is thrown into clouds to get rain.
 7. Blue colour of the sky: The outer atmosphere contains colloidal dust particles dispersed in
air. As the rays of the sun strike the colloidal particles, they absorb sunlight
 EXPLOSIVES AND ROCKET PROPELLANTS
 Explosives and rocket fuels are closely related materials, since in
both the cases exothermic chemical reaction resulting in large
amount of energy takes place. The materials which were earlier
used as explosives are now used as rocket fuels.
 An explosive is a substance which when subjected to thermal or
mechanical shock gets oxidized exothermically into the product
of increased volume with sudden release of large amount of
potential energy.
 In explosive reactions, being exothermic, the products get heated
up to very high temperatures and exert high pressure on the
surroundings which can be exploited for constructive or
destructive purposes. When an explosion occurs in a confined
space, the high-pressure conditions developed within the system
shatter the confining walls or if developed under relatively slower
and controlled rate, the energy may be used to propel projectiles.
The quantity of power realizable from a given weight (or volume)
of an explosive is called powerto- weight (or volume) ratio which
is small in case of gases. In order to achieve a better ratio, solids
and/or liquids are used as explosives.
 Classification of Explosives
Explosives are broadly classified into three groups:
 (1) primary explosives or detonators,
 (2) low explosives or propellants and
 (3) high explosives.
 Primary Explosives or Initiating High Explosives or
Detonators
These are highly sensitive explosives which explode under a
slight shock or blow by ignition. They have to be very
carefully handled. They are used in very small quantities to
initiate explosion of less sensitive explosives such as TNT.
Hence, they are called initiating high explosives. Primary
explosives are used in blasting caps and catridges.
Examples of primary explosives include:
 Leade azide (PbN6): Beacause of its low cost,
excellent initiating action, stability in storage lead
azide reacts with brass, hence caps loaded with lead
azide are made of aluminium. It cannot initiate
explosion of TNT
 Tetracene (C2H7N7O): Tetracene ignites easily and
has high heat of explosion and produces large volume
of gases. It has low initiating property hence it is not
used by military. It is only used as a detonator.
 Mercury fulminate [Hg(CNO)2]: It is more sensitive
and expensive and more toxic than lead azide. Hence,
its usage is limited.
 Diazonitrophenol (DDNP): It is quite sensitive and
can initiate explosion in less-sensitive high explosives.
It is widely used in commercial blasting caps.
 Low Explosives or Propellants
 They do not explode suddenly but burn. The chemical
reactions takes place comparatively slowly and burning
proceeds from the surface inwards in layers at
approximately 20 cm/s and the evolved gases disperse
readily without building up pressure.
Examples: Cellulose nitrate, gun powder.
Low explosives are used as propellants (to propel missiles)
and in fire works (i.e., pyrotechniques). Low explosives are
divided into two categories depending on their
applications.
 Millitary explosives: RDX, HMX, TNT, nitrocellulose,
tetryl, picric acid, PETN, DDNP, Lead azide, etc.
 Industrial explosives: GTN, dynamite, etc., are used for
industrial purposes.
 High Explosives
 These explosives are insensitive to mechanical shock and to
the flame i.e.; they do not explode on ignition. They
explode with great violence only when initiated with the
help of detonators. They are stable and possess high energy
content than primary explosives. The rate of explosion is
about 1500 to 10,000 m per second. Under the influence of
high temperature large volume of gases are evolved which
produces shattering effect. High explosives are sub-divided
into 1. Military high explosives, 2. Blasting or industrial
purpose explosives.
Examples:
GTN: Glyceryl trinitrate
RDY: Cyclo trimethylene trinitroamine
PETN: Pentaerythetol tetranitrate
TNT: Trinitrotoluene
 Ammonium nitrate:
 It is half as powerful as TNT (2,4,6 trinitrotoluene) and employed in
making binary explosives. It is dangerous to store near any
inflammable material. It cannot be used in contact with brass, since it
produces a detonator – tetrammino cupric nitrate.
 TNT:
 It is used in shell-firing and under-water explosives. It can be loaded in
containers because of its low melting point (81°C). Because of its (1)
non-hygroscopic nature and (2) inertness to metals, TNT is used as safe
explosive in the manufacture, storage and transportation.
 RDX or cyclonite (cyclotrimethylene trinitroamine):
 It is a powerful high explosive. It is more sensitive and less toxic than
TNT. It is used both in military and industrial purpose explosive.
 Picric acid (or trinitrophenol):
 It is replaced largely by TNT since it forms shock-sensitive picrates with
metals.
Explosives, based on their state of aggregation are classified as solid
(e.g.,TNT), liquid (e.g., nitroglycerine) and gaseous (e.g., mixture of
oxygen and acetylene).
 Requisites of Explosives
 The following are the requisites of explosives:
 1. Any compound to serve as an explosive, must have atleast
one easily breakable chemical bond. Most explosives
contain O-Cl, N-N, N-O, N-Cl bonds. The electronegativity
difference in each of these cases is either marginal or nil. In
order to facilitate cleavage of bonds by thermal or
mechanical shock they should have low energy of
dissociation.
 2. It must be stable in thermal conditions of storage
 3. It must be cheap.
 4.It must undergo decomposition rapidly and
exothermically and release large volume of gaseous
products. With sharp rise in temperature gases expand
rapidly. For example, 1 gram of trinitroglycerine yields
about 40 ml of gases when cold, but occupies about 750 ml
at the temperature of explosion
 Precautions During Storage of Explosives
 Following precautions should be taken while storing the
explosives
 1. All wiring and electrical fittings should be properly insulated
and checked regularly.
 2. Jerks or drops of explosive should not be allowed to take place.
 3. Detonators and explosives should be stored separately.
 4. Different explosives should be stored in separate boxes.
 5. Fire or smoking should be strictly prohibited within the radius
of 50 m from the explosive store (magazine).
 6. Only authorized persons with magazine shoes should be
allowed to the explosive store.
 7. The explosive store should not be within 500m from any
working kiln or furnace.
 8. Lighting conductors should be provided to safeguard the
magazine.
Rocket Propellants
 A rocket engine is a tube-like missile which carries
both the fuel and the oxidant, collectively referred to
as propellant. The propellant is burnt in a combustion
chambers and a hot jet of gases at a pressure of 300 kg
cm–1 and a temperature of 3000oC comes out through
a small nozzle at a supersonic velocity. This act of
pushing of the gases downwards produces an equal
and opposite reaction (Newton’s third law of motion)
causing the rocket to move upward
 Charateristics of a Good Propellant
 1. It should burn at a slow and steady rate.
 2. It should have low ignition lag [it is the time taken by the
propellant to catch fire in the presence of an oxidising agent].
 3. It should possess high density.
 4. It should be stable over a wider range of temperatures.
 5. It should be non-corrosive and non-hygroscopic.
 6. After ignition, a good propellant should not leave any residue.
 7. It should not produce toxic products
 8. It should have high specific impulse [it is the thrust delivered
divided by the rate of propellant burnt].
 9. It should produce high temperatures on combustion.
 10. It should produce low molecular weight products (such as H2,
CO, CO2, N2) during combustion.
 11. It should be safe to handle and store under ordinary
conditions and it should not detonate under shock, heat or
impact.
 Classification of Propellants
The chemical propellants are classified into solid and liquid
categories.
 Solid Propellants
Depending on their physical structure, solid propellants are
divided into two main groups: homogeneous and composite (or
heterogeneous). A solid propellant mixture in which the
propellant mixture is intimately mixed in a colloidal state is
known as homogeneous solid propellant. Examples:
Nitroglycerine and nitro cellulose (gun cotton or smokeless
powder combination). It is an example of single-base propellant.
When a single propellant is employed, it is called a single-base
propellant. In a double-based propellant, 50–55% nitrocellulose
and 40–45% nitroglycerine are present. In order to make it a
homogeneous plastic mass, diethyl phthalate is added as a
solvent cum plasticizer. These propellants give a flame
temperature of 800–1650oC and the volume of gases is about
1500 times the original volume of charge
 Liquid Propellant
They have several advantages over solid propellants.
They are more versatile and possess high specific
impulse. But the engine is more delicate and is less
suitable for rough handling than the engine for solid
propellant.Liquid propellants may be mono-
propellants or bi-propellants. Mono-propellants:
They require single storage tank and one fuel injection
and control system. The fuel as well as oxidizer are in
the same solution. For example hydrogen peroxide,
nitromethane, hydrazine, ethylene oxide, 21.4%
methanol and 78.6% hydrogen peroxide is highly
reactive, metal oxides catalyse the decomposition,
hence storage tanks must be made of special materials.
 Bi-propellants:
Bi-propellants are widely used. Liquid oxygen (LOX),
hydrogen peroxide, ozone, fuming nitric acid, liquid
fluorine are the common oxidizers used in bi-propellants.
In bi-propellants, liquid fuel and oxidizers are kept
separately and injected separately into the combustion
chamber. Ethyl alcohol and 25% water is a good fuel.
Addition of water reduces flame temperature and
molecular mass of combustion gases, which compensates
for reduction in performance. Liquid oxygen is safe, non-
toxic and good oxidant, but it has to be stored under
pressure in insulated containers. Ozone though a powerful
oxidant but explodes at high concentration. Liquid fluorine
is toxic, corrosive, volatile, very reactive, but a good
oxidant. It is difficult to store and handle.
 Blasting Fuses
A fuse is a thin water proof canvas tube containing gun-powder
(or TNT) arranged to burn at a given speed for setting off charges
of explosives. Fuses are of two types: (1) saftey fuse and (2)
detonating fuse.
 1. Safety fuse: It is analogous to the wick of a fire cracker. Safety
fuse is employed in initiating caps, where electrical firing is not
used. It consists of a small core of black powder enclosed in a
convering of wrapper of water-proofed fabric. Its burning speed
is approximately 30 to 40 seconds per foot. While blasting a
sufficient length of the fuse is used so as to allow sufficient time
for the short fires to reach a point of safety.
 2. Detonating fuse: It consists of a charge of high velocity
explosives, such as TNT placed in a small bent tube. The line of
fuse (cordean) is in contact with the charge through-out its
length and this causes instantaneous detonation of the whole
charge, irrespective of its velocity. These fuses are used for
exploding charges of explosives in deep holes.
Applications of Explosives
They can be used for constructive as well as destructive
puposes. They do their work faster, cheaper and more
effective than by any other means.
 1. Destructive uses: They are mainly used for military
purposes during times of war. Explosives ammunitions
include grenades, torpedoes, aerial bombs, rockets,
etc.
 2. Constructive uses: In industry, they are employed
for blasting ores or iron and other metals, breaking
down coal, mining salts, quarrying lime stones (for
road construction) blasting holes in mountains for the
construction of tunnels, excavating earth for dams,
seismic prospecting, dislodging rocks, drilling oil
wells, etc.
 Multiple-Choice Questions
 1. Physical adsorption occurs rapidly
at ____________ temperature.
(a) low (c) absolute zero (b) high (d)
none of these
 2. Physical adsorption generally
____________ with increasing
temperature.
(a) decreases (b) increases
(c) first increases and then decreases
(d) first decreases and then increases
 3. Multi-molecule layers are formed in
(a) absorption (b) physical adsorption
(c) chemisorption (d) reversible
absorption
 4. Freundlich isotherm is not
applicable at
(a) high pressure (b) low pressure (c)
273 K (d) room temperature
 5. The process of adsorption is
(a) exothermic (b) endothermic (c)
both endothermic and exothermic (d)
none of the above
 6. The adsorption of hydrogen on
charcoal is
(a) physical adsorption (b) chemical
adsorption (c) desorption (d) none of
these
 7. In gas masks, the poisonous gases
are removed by
(a) adsorption (b) absorption (c)
catalysis (d) none of these
 8. The process of desorption increases
with ____________ of pressure
(a) decrease (b) increase (c)
sometimes increases, sometimes
decreases (d) none of these.
9. Which of the following is incorrect
in chemisorption?
(a) It is caused by bond formation (b)
It is specific in nature (c) It is
reversible (d) It increases with
increase in temperature
 10. In an adsorption process,
unimolecular layer is formed. It is
(a) chemical adsorption (b) physical
adsorption (c) ion exchange (d) all
the above
 11. The efficiency of absorption increases with
increase in
(a) viscosity (b) surface tension (c) surface area
(d) number of ions
 12. Absorbate is one
(a) where adsorption occurs (b) which
concentrates on the surface (c) which evaporates
from the surface (d) none of these
 13. The adsorption of gases on metal surface is
called
(a) catalysis (b) adsorption (c) occlusion (d)
absorption
 14. At low pressure, the amount of gas adsorbed
is ____________ to pressure
(a) directly proportional (b) inversely
proportional (c) not related (d) none of the
above
 15. A colloidal solution consists of
(a) a dispersed phase (b) a dispersion medium
(c) a dispersed phase in a dispersion medium (d)
a dispersion medium in a dispersed phase
 16. The scattering of light by the dispersed phase
is called
(a) Brownian movement (b) Tyndall effect (c)
adsorption (d) electrophoresis
17. In lyophobic sols, the dispersed phase has no
____________ for the medium or solvent.
(a) repulsion (b) attraction (c) solvation (d)
hydration
 18. The sol in which the dispersed phase exhibits
a definite affinity for the medium or the solvent
is called
(a) lyophobic sols (b) lyophilic sols (c) emulsions
(d) hydro sols
 19. Lyophilic sols are
(a) reversible in nature (b) irreversible in nature
(c) sometimes reversible (d) none of the above
20. ____________ does not show Tyndall effect.
(a) True solution (b) Colloidal solution (c)
Suspension
21. The continuous zig-zag movement of
colloidal particle in the dispersion medium is
(a) Tyndall effect (b) Brownian movement (c)
electrophoresis (d) peptisation
22. The movement of particles under an applied
electric field is
(a) electrophoresis (b) electro-osmosis (c)
electrofiltration (d) none of these
 23. The presence of the double layer in to
colloids accounts for (a) hydrolysis of salt present in soap
(a) kinetic properties (b) electrical (b) ionisation of salt present in soap
properties (c) optical properties (d) (c) high molecular mass of soap (d)
stability of colloids emulsification properties of soap
 24. The precipitating power of Al3+, 28. Which of the following is not a
Na+, Ba2+ is in the order colloidal solution?
(a) Na+ > Ba2+ > Al3+ (b) Ba2+ > Na+ (a) Brine solution (b) Fog (c) Smoke
> Al3+ (c) Al3+ > Na+ > Ba2+ (d) Al3+ (d) Butter
> Ba2+ > Na+  29. The _____________ the gold
 25. The number of milligrams of a number of a hydrophilic colloid, the
hydrophilic colloid that will just greater is its protective power.
prevent precipitation of 10 ml of gold (a) higher (b) lower (c) constant (d)
sol on the addition of 1 ml of 10% NaCl none of these
solution is called
(a) gold number (b) charge nymber (c) 30. The charge on the sol particle is
due to _______________ of ions
absorption number (d) silver number common to the particles from the
 26. Peptisation involves dispersion medium.
(a) digestion of food (b) precipitation (a) selective adsorption (b) selective
of colloidal solution coagulation (c) selective peptisation
(c) hydrolysis of proteins (d) breaking (d) selective absorption
of a precipitate to colloidal state
 27. The cleansing action of soap is due
 31. Milk is an example of
(a) sol (b) gel (c) emulsion (d) true
solution
 32. The blue colour of sky is due to
(a) Brownian movement (b) Tyndall effect
(c) pressure of macro molecules (d)
electrophoresis
 33. Gold numbers gives
(a) the number of gold atoms in one gram
of gold
(b) the number of gold atoms required to
coagulate one gram of colloidal solution 
(c) the number of gold atoms in one gram
of gold alloy
(d) none of the above
 34. Smoke is an example of
(a) solid dispersed in solid (b) solid
dispersed in liquid
(c) solid dispersed in gas (d) gas dispersed
in solid
 35. Which of the following is not a
colloidal solution of gas in liquid?
(a) Froath (b) Foams with tiny bubbles (c)
Mist (d) Whipped cream
36. Dust storm is
(a) dispersion of a solid in gas (b)
dispersion of a gas in solid (c) dispersion
of a solid in solid (d) dispersion of a gas in
liquid
 37. Colloidal solution in which the
dispersed phase has little affinity for the
dispersion medium is called
(a) emulsion (b) lyophobic colloids (c)
lyophilic colloids (d) hydrophilic colloids
38. Clouds, mist, fog, and aerosols are
colloidal systems called
(a) solid in a gas (b) gas in a solid (c) liquid
in a gas (d) gas in a liquid
 39. When the dispersed medium is water,
the colloidal system is called
(a) sol (b) aerosol (c) organosol (d)
aquasol
40. Smoke is an example of
(a) gas dispersed in liquid (b) gas
dispersed in solid (c) solid dispersed in gas
(d) solid dispersed in solid
 40. Smoke is an example of
(a) gas dispersed in liquid (b) gas
dispersed in solid (c) solid dispersed in gas
(d) solid dispersed in solid
 41. The main difference between
crystalloids and colloids is
(a) particle size (b) electrical
conductivities (c) concentration (d)
particle composition
 42. Which of the following colloidal
system contains solid as the dispersed
phase
(a) smoke (b) clouds (c) lather (d) shoe
polish
 43. Which of the following is an example
of solid–solid system?
(a) Smoke (b) Cake (c) Synthetic gems (d)
Pumice stone
 44. Which of the following is correct?
(a) Brownian movement is more
pronounced for small particles.
(b) Sols of metal sulphides are lyophilic.
(c) Hardly–Schulze law states that larger
the size of the coagulation ion, greater is
its coagulation power.
(d) A lyophilic sol is most stable at iso-
electric point.
 45. In colloidal state, particle size range
from
(a) 1–10 Å (b) 20–50 Å (c) 10–1000 Å (d) 1–
280 Å
46. Colloidal systems containing liquid
dispersed in a solid are called
(a) gels (b) sols (c) emulsions (d) solution
47. Charge carried by colloidal particles
can be shown by
(a) Tyndall effect (b) cataphoresis (c)
Brownian moment (d) dialysis
 48. In electrophoresis
(a) particles move and medium rests (b)
medium moves and particles rest
(c) both particles and medium move (d)
particles and medium rest
49. In the coagulation of positively charged
colloidal solution, which of the following
has maximum coagulation power?
(a) SO42– (b) Cl– (c) PO43– (d) [Fe(CN)6]4–
 50. The coagulant frequently added to
water to remove suspended impurities is
(a) Cu(NO3)2 (b) ZnCl2 (c) Na2CO3 (d)
Al2(SO4)3
 Theoretical Questions
 1. Distinguish between absorption and adsorption.
 2. Explain the salient features of physical adsorption and chemical adsorption.
 3. Give an account of the different types of adsorption isotherms observed in the adsorption of gases
on
 solids.
 4. Write a note on the various factors affecting adsorption of gases on solid surfaces.
 5. Write an account of the applications of adsorption.
 6. Define the terms: (a) absorption, (b) adsorption, (c) adsorbate and (d) adsorbent.
 7. Define what is Freundlich’s adsorption. What are the drawbacks of Freundlich’s adsorption
isotherm?
 8. Explain Langmuir adsorption isotherm. What are the advantages and limitations of Langmuir
adsorption
 theory?
 9. Explain BET theory of multilayer adsorption.
 10. Discuss Langmuir theory of adsorption and derive expression for Langmuir monolayer adsorption
isotherm.
 11. What do you understand by the term adsorption? What are the factors which affect adsorption?
 12.
(a) What are colloids? How are they classified?
(b) How do you prepare colloidal solution of (i) gold, (ii) arsenic sulfide and (ii) sulphur?
 13. Describe the functions of a protective colloid.
 14. What are lyophilic colloids? Why are they called reversible colloids.
 15. Write short notes on the origin of charge on colloids.
 16. Differentiate lyophilic and lyophobic colloids.
 INTRODUCTION TO LABORATORY
EXPERIMENTS
 Introduction
 Synthesis, analysis and characterization are important
processes in chemistry. In synthesis, compounds are
prepared. Analysis and characterisation deals with the
composition and the structure of compound, respectively.
There are two general analytical methods: qualitative and
quantitative analysis.
Titrimetry is one of the quantitative analyses. In titrimetry,
one determines the volume of a standard solution that is
required to react with the known volume of the unknown
solution. The volume of the standard solution is measured
with burette, while the volume of unknown solution is
measured with pipette.
Equipments required for titrimetry
 Chemical Balance
 It is an equipment to measure the weight of the
chemicals required to prepare the standard
solution. In place of manual balance, electronic
monopan balance is used nowadays. Weighing is
done in the weighing tube or in the watch glass.
 Glasswares
 The common glasswares used in titrimetry are burette,
pipette, measuring flask, measuring cylinders,
conicalflask, reagent bottles, glass rod, etc. (Fig. 9.2).
Different Types of Solutions
 Standard Solution
The solution of known strength is called the standard
solution. It may be prepared by dissolving known
amount of sample in known amount or volume of the
solvent, e.g. 5 g NaOH dissolved in 100 ml of water.
 Normal Solution
If gram equivalent weight is present in 1 L solution, it
is called as the normal solution, i.e. 1 normal NaOH
means 40 g of NaOH is present in 1000 ml solution
and 0.1 normal H2SO4 means 4.9 g of H2SO4 is
present in 1000 ml solution. Its symbol is N. N/2
solution means half of the gram equivalent weight is
present in per litre of the solution.
Molarity of a solution: A solution will be called one
molar (1 M) if the gram molecular weight (1 g mol) is
present in 1 L solution. For example, if 98 g H2SO4 is
present in 1 L of H2SO4 solution, it will be 1 molar (1
M) solution.
In case of H2SO4, 49 g/L solution = M/2 and also = 1
N; in case of NaOH, 40 g/L solution = 1 M = 1 N.
 Molality: If 1 g mole of a substance is dissolved in 1 kg
of the solvent (100 ml water), it is one molal (1 m).
 For example, 58.5 g NaCl dissolved in 1 kg of water will
be one molal solution (1 m).
 Parts per million (ppm): Concentration of Ca2+ and
Mg2+ in water (hardness) is measured in mg/L or part
per million (ppm) of CaCO3.
 Equivalent weight: It is the law in chemistry that
equivalent weight of ‘A’ will react with the equivalent
weight of ‘B’. The knowledge of the equivalent weight is
essential in titration because the solutions of different
normality can be made only by the equivalent weights.
 The calculations of the equivalent weights of an acid,
base, salt, etc are done as follows
 Endpoint and equivalent point: During titration, the
standard solution reacts with the unknown solution.
When the reaction between the two is complete, the stage
is called the equivalent point or the theoretical endpoint.
The completion of a reaction should be visual and it can be
better judged by the change in colour during reaction. A
chemical that gives the idea of endpoint by changing its
colour is called an indicator. The point of colour change is
called the practical endpoint or simply the endpoint of the
titration.
For an ideal condition, the equivalent point and the
theoretical endpoint are same which is observed by the
change in colour of the indicator. Actually, there is some
negligible difference. The difference between the two will
give titration error. The unknown solution is called titrand
and the known solution is titrant.
Common types of titrations
There are mainly four common types of titrations.
 Neutralisation Titration or Acid–Base Titration:
The reaction between an acid and a base is called the
neutralisation reaction. The titration which involves
this reaction is called the neutralisation or acid–base
titration. It is also called acidimetry or alkalimetry. The
indicators used in these titrations are pH-based.
 Reaction for NaOH/HCl titration:
 The change in colour of indicator is due to the change
of pH. Different theories (Ostwald and Quinonoid)
have given different explanations. Quinonoid theory
suggests that the colour changes in methyl orange can
be explained as follows
 Some indicators and their characteristic pH ranges
 Universal indicator is a mixture of several indicators
that are helpful in determining approximate pH of a
solution in the pH range 3–11. It is a mixture of methyl
red, methyl orange, bromothymol blue and
phenolphthalein.
 Complexometric Titration
 In complexometric titrations, the strength of the metal ion is
determined. A complex is formed during the titration. The titrand is a
metal ion that forms a complex with the titrant. The important
example of this type is Ca2+ titrated against EDTA (ethylene diamine
tetraacetic acid) (used for determining hardness in water). The titrant
is a ligand. Here, EDTA is a hexadentate ligand and forms complex
with Ca2+. Indicator used in this titration is also a ligand. In this
particular case, the indicator is Eriochrome Black-T (EBT, an organic
dye).
 Redox Titrations
 Titrations involving oxidation–reduction reactions are called redox
titrations. For acid–base titration, the change in pH has the same
importance as the change of electrode potentials in redox titrations.
The word redox is made up of two words: Red + Ox. ‘Red’ is taken from
reduction and ‘Ox’ from oxidation.
 The reaction between FeSO4 and KMnO4 is a redox reaction. Here
Fe+2 ions are oxidised to Fe+3 by KMnO4 and Mn+7 is reduced to
Mn+2 by FeSO4. Therefore, KMnO4 is an oxidising agent, also called as
oxidant, while FeSO4 is a reducing agent, also called a reductant
 Selection of Indicator for Redox Titration
 The ideal and suitable indicator for a redox titration will be
a chemical which has its redox potential intermediate
between the electrode potentials of titrand and titrant and
which exhibits sharp colour changes. The potential at the
equivalent point is the mean of the two standard redox
potentials.
 For example, in a titration of 0.1 N Fe+2 against 0.1 N Ce+4
ion, the theoretical equivalence point is at 1.10 V .The
change of ‘ferroin’ takes place at 1.12 V from deep red to
pale blue. Ferroin is an indicator (1,10-phenanthroline Fe+2
complex). During titration, 0.1% extra addition of Ce+4 will
give the endpoint. By adding 0.1% extra Ce+4, the electrode
potential of the system will become 1.27 V and, hence, the
change in the colour is observed.
 THEORETICAL Questions
1. Classify the type of reactions in titrimetric analysis. How is the
completion of the reaction indicated in titrations?
2. Discuss the titrimetric analysis of
(a) a strong base against a weak acid and (b) K2Cr2O7 (in acidic
medium) against ferrous ammonium sulphate.
3. Define the following terms:
(a) Molarity (b) Molality (c) Normality
4. What are complexometric titrations? Discuss the role of EDTA in this
titration.
5. What is difference between the endpoint and equivalence point?
6. What is an indicator? Give two examples of an acid–base indicator.
7. Why is distilled water always used in the preparation of the standard
solution?
8. Define the following terms:
(a) Titration (b) Titrant (c) Titrand
9. Calculate the molality of a solution in which 10 g NaOH is dissolved in
500 g of water.
10. How many millilitres of 5.5 M NaOH are needed to prepare 300 ml of
1.2 M NaOH?
 Multiple-Choice Questions
1. The equivalent weight of KMnO4 in acidic medium is
(a) 31.6 (b) 158 (c) 52.6 (d) 46
2. The equivalent weight of KMnO4 in basic medium is
(a) 31.6 (b) 158 (c) 52.6 (d) 46
3. The oxidation number of Fe in K4[Fe(CN)6] is
(a) +2 (b) +3 (c) +1 (d) +4
4. The equivalent weight of KMnO4 in neutral medium is
(a) 31.6 (b) 158 (c) 52.6 (d) 46
5. The argentometric titration is the precipitation titration in which
(a) Na2S2O3 is used as the standard solution (b) H2SO4 is used as the
standard solution
(c) K2Cr2O7 is used as the standard solution (d) AgNO3 is used as the
standard solution
6. In iodometric titrations
(a) I2 is liberated from iodide (b) I2 solution is used
(c) KI is used as indicator (d) I2 is used as indicator
7. In redox titration, which one of the following is used as the standard solution?
(a) Na2CO3 (b) Na2S2O3 (c) K2Cr2O7 (d) K2CrO4
8. Mohr’s salt is
(a) FeSO4·(NH4)2SO4·H2O (b) FeSO4·(NH4)2SO4·2H2O
(c) FeSO4·(NH4)2SO4·6H2O (d) FeSO4·NH4SO4·6H2O
 8. Molarity of a solution relates to the
a) volume of the solution and the moles of the solute
(b) volume of the solute and volume of the solvent
(c) moles of the solute and the solvents
(d) mole of the solute and mass of the solvent
10. For the preparation of N NaOH solution, the amount of NaOH required to
dissolve in 100 ml water is
(a) 4 g (b) 2 g (c) 3 g (d) 1 g
11. Which of the following 0.1 M solution will turn phenolphthalein pink?
(a) HBr (aq.) (b) CO2 (aq.) (c) LiOH (aq.) (d) CH3OH (aq.)
13. The normality (N) is
(a) No of molesVolume. ×1000 (b) No. of equivalentsVolume×1000
(c) No of molesWeight. ×1000 (d) none
14. When KMnO4 is reduced with oxalic acid in acidic medium, the oxidation
number of Mn changes from
(a) 7 to 4 (b) 6 to 4 (c) 7 to 2 (d) 4 to 2
Experiments
 1. Estimation of Ferrous (Fe+2) Ion by Dichrometry
 2. Estimation of Hardness of Water by EDTA method
 3. Determination of Alkalinity of Water
 4. Estimation of Copper by Complexometry Mineral Analysis
 5. Estimation of Calcium in Limestone
 6. Determination of Percentage of Copper in Brass
 7. Estimation of Iron in Cement
 8 .Estimation of Manganese Dioxide in Pyrolusite
 9. Estimation of copper by Colorimetric Method conductometry
 10. Conductometric Titration of Strong Acid Vs Strong Base
 11. Conductometric Titration of Mixture of Acids Vs Strong Base
Potentiometry
 12. Titration of Strong Acid Vs Strong Base by Potentiometry
 13. Titration of Weak Acid Vs Strong Base by Potentiometry
 14. pH Metric Titration of Acid Vs Base
 15. Potentiometric Titration of Fe+2 with Standard K2Cr2O7
Solution
 16. Determination of pKa Value of a Weak Acid
 17. Determination of Viscosity by Redwood Viscometer
 18. Determination of Surface Tension of Liquid Preparations
 19. Preparation of Aspirin
 20. Preparation of Benzimidazole
 21. Preparation of Thiokol Rubber Kinetics
 22. Determination of Rate Constant of Hydrolysis of ethyl
Acetate Catalyzed by an Acid