Unit I – LASER

1. What is Laser?
LASER stands for Light Amplification by Stimulated Emission of Radiation.
2. What are the characteristics of lasers?
i) High intensity
ii) High directionality
iii) High monochromaticity
iv) High coherence
3. What is the basic principle behind the laser?
Stimulated emission
4. What are spontaneous and stimulated emissions?
Spontaneous emission:
 It is a downward transition process
 An atom in the upper level (E2) spontaneously comes down to E1 and emits a
photon of energy, hν = E2 – E1
Stimulated emission:
 It is a downward transition process triggered by an external aid.
 An atom in the upper level (E2) is triggered to come down to lower lower level E1
 During this process a photon of energy, hν = E2 – E1 is emitted
 The emitted photon has same properties as the triggering photon in all respect
viz. direction, energy, phase, etc.
5. What are the conditions for laser (or) stimulated emission?
i) Stimulated emission
ii) Population inversion
iii) Meta-stable state
6. What are the components of a laser?
i) Active medium
ii) Optical resonator
iii) Pumping source
7. What is meant by active medium in laser
The medium in which laser transition occurs is called active medium.
8. What is optical resonator in laser? Why is it required?
Set of two mirrors (M1 – fully polished & M2 – partially polished) forms optical resonator
in lasers. This strengthens the laser by multiple reflection.
9. Is two level laser possible? Explain.
No. Minimum three energy levels are required to achieve population inversion and
hence laser transitions. A metastable state is necessary below the excited state.
10. What are the types of lasers?
i) Solid state laser
ii) Liquid laser
 iii) Gaseous laser
iv) Semiconductor diode laser
v) Dye lasers
11. What is population inversion?
It is a non-equilibrium condition of a system in which excited state has more atoms than
ground state.
12. Define metastable state.
An excited state which has longer life time (10–3 sec) is called metastable state
13. Why is metastable state necessary for laser?
Metastable state has longer life time of 10−3 sec. Hence, it helps to achieve population
inversion.
14. What is the principle of laser? (OR) What is meant by laser action? (OR) Why population
inversion is necessary to achieve lasing action?
In lasing action, light radiation is amplified by Stimulated Emission. But stimulated
emission is predominant only when population inversion is achieved. Hence, population
inversion is necessary for laser action.
15. What is pumping in laser?
Exciting more atoms to upper energy level is called pumping. Pumping results in
population inversion.
16. What are the types of pumping?
i) Optical pumping
ii) Electric discharge pumping
iii) Direct pumping
iv) Elastic atom – atom collision pumping
17. What are the different modes of vibration of CO2 molecule?
i) Symmetric stretching
ii) Asymmetric stretching
iii) Bending
18. What is the role of N2 and He in CO2 laser?
N2 – populates upper laser level;
He – depopulate lower laser level.
19. Differentiate Spontaneous and Stimulated emissions.
Spontaneous emission Stimulated emission
 It is a downward transition process  It is a downward transition process triggered
 An atom in the upper level (E2) by an external aid.
spontaneously comes down to E1 and emits  An atom in the upper level (E2) is triggered
a photon of energy, hν = E2 – E1 to come down to lower lower level E1
 During this process a photon of energy, hν =
E2 – E1 is emitted. The emitted photon has
same properties as the triggering photon in
all respect viz. direction, energy, phase, etc.
 Unit I – LASERS
PART – B
1. For atomic transitions, derive Einstein’s Coefficients and arrive at the conditions for laser
action.
Consider a system of two energy levels (E1 and E2). When a radiation falls on the system
there can be three processes,
1. Absorption
2. Spontaneous emission
3. Stimulated emission
Let,
N1 – number of atoms in E1
N2 – number of atoms in E2
ρ(ν) – energy density of the radiation
hν = E2 – E1 – energy of the photon
Absorption
 An atom in the ground state (E1) absorbs the photon and get excited to the upper
level (E2).
 Thus, the rate of absorption,
R12 (Ab) α ρ(ν) N1
R12(Ab) = B12 ρ(ν) N1
Spontaneous emission
 An atom in the upper level (E2) spontaneously comes down to E1 and emits a
photon of energy, hν = E2 – E1
 Thus, the rate of spontaneous emission,
R21 (Sp) α N2
R21 (Sp) = A21 N2
Stimulated emission
 The incident photon triggers an upper atom to come down.
 During this process a photon of energy, hν = E2 – E1 is emitted
 Thus, the rate of stimulated emission,
R21 (St) α ρ(ν) N2
R21 (St) = B21 ρ(ν) N2
At thermal equilibrium,
Rate of absorption = Total Rate of emission
R12 (Ab) = R21 (Sp) + R21 (St)
B12 ρ(ν) N1 = A21 N2 + B21 ρ(ν) N2
B12 ρ(ν) N1 − B21 ρ(ν) N2 = A21 N2
ρ(ν) [B12 N1 − B21 N2] = A21 N2
 A21 N2
ρ(ν) =
[B12 N1 − B21 N2 ]
(A21 /B21 )
ρ(ν) = B N ----------------------------------------- (4)
[( 12 ) (N1 ) − 1]
B21 2
By Boltzmann distribution law,
𝑁1
= 𝑒 (𝐸2 − 𝐸1 )/𝐾𝑇 = 𝑒 ℎ𝑣/𝐾𝑇
𝑁2
Substituting in eqn. (4),
(A21 /B21 )
ρ(ν) = B12 ----------------------------------------- (5)
[(B ) 𝑒 ℎ𝑣/𝐾𝑇 − 1]
21
But by Planck’s radiation law,
(8𝜋ℎ𝑣 3 /c3 )
ρ(ν) = -------------------------------------------------- (6)
[𝑒 ℎ𝑣/𝐾𝑇 − 1]
Comparing equations (5) and (6),
𝐴21 8𝜋ℎ𝑣 3
=
𝐵21 𝑐3
𝐵12
=1
𝐵21
where B12, A21 and B21 are Einstein’s coefficients of absorption, spontaneous emission and
stimulated emission respectively.
Condition for Laser action:
Let us compare the rates of spontaneous emission and stimulated emission.
𝑅21 (𝑆𝑝) 𝐴21 𝑁2
=
𝑅21 (𝑆𝑡) 𝐵21 𝜌(𝑣)𝑁2
𝐴21
=
𝐵21 𝜌(𝑣)
ℎ𝑣
= 𝑒 𝐾𝑇 − 1 >> 1
Thus, spontaneous emission predominates stimulated emission.
When the rates of absorption and stimulated emission are compared,
𝑅12 𝐵12 𝜌(𝑣)𝑁1
= 𝐵12 = 𝐵21
𝑅21 (𝑆𝑡) 𝐵21 𝜌(𝑣)𝑁2
𝑁1
= >> 1
𝑁2
Thus, absorption predominates stimulated emission.
Hence, for laser action to take place,
1. Population inversion ( N2 > N1 ) is necessary
2. Input energy density, ρ(ν) must be higher
2. Explain the construction and working of Nd – YAG laser
Nd : YAG – Neodymium doped Yttrium Aluminium Garnet (Y3Al5O12)
It is a four level – solid state laser.
Principle
Nd3+ ions are optically pumped. During stimulated transition from metastable
state, laser of wavelength 1.064 μm is emitted.

Construction
1. Active Medium – Nd3+ ions doped Y3Al5O12 rod
2. Pumping Source – Xenon flash lamp
3. Optical resonator – Mirrors M1 (Fully reflecting) & M2 (partially reflecting)

 The active medium is a Nd3+ ions doped Y3Al5O12 rod of length 5-10 m
 The rod and the flash lamp are kept at the foci of an elliptical reflector cavity
 The mirrors are placed at the ends of the rod

Working

 The xenon flash lamp is switched on.

 Nd3+ ions optically pumped to the levels E3 and E4 by absorption at 0.80 μm and
0.73 μm.
 The ions drop down to the level E2 (metastable state) by fast non-radiative decay.
 Population inversion is achieved between E2 and E1.
 Due to stimulated transition, laser of wavelength 1.064 μm is emitted.
 The laser beam is amplified by reflection at the mirrors and released through M2.
 From E1 the ions fall back to E0 by non-radiative decay.
Applications

 Used for material processing – cutting, welding, drilling holes, annealing, etc.
 Used in medical endoscopes
 Used for generation of various other lasers by passing through NLO materials.
3. Explain the construction and working of CO2 laser
CO2 laser is a molecular gas laser – four level laser.
Principle
The laser transition occurs between vibrational energy levels. N2 excites CO2
molecules by resonant collision. By stimulated transition, laser of wavelength 10.6 μm is
emitted.

Modes of vibrations of CO2 molecule

CO2 is a linear molecule. It can vibrate in three modes

1. Symmetric stretching (vs 0 0)

Oxygen atoms symmetrically move with respect to stationary Carbon atom

2. Bending (0 vb 0)
When Carbon atom moves up the Oxygen atoms move down

3. Asymmetric stretching (0 0 vas)

Oxygen atoms asymmetrically move with respect to Carbon atom

Construction
1. Active Medium – CO2, N2 and He gas mixer
2. Pumping Source – Electric discharge
3. Optical resonator – Concave mirrors M1 (fully reflecting) & M2 (partially reflecting)
 CO2, N2 and He gases are taken in a quartz tube in partial pressure ratio 1:4:5
 The terminals of the tube are closed with NaCl Brewster windows.
 The concave mirrors are placed at the ends of the tube.
Working

 An electric discharge excites N2 molecules to excited state

e – * + N 2 → N 2* + e –
 By resonant collision, N2 excites CO2 molecules to the vibrational state ( 0 0 1)
N2* + CO2 → CO2* + N2
 (0 0 1) is metastable state.
 Hence, population inversion is achieved
 By stimulated transition laser beams are emitted
1) (0 0 1) to (1 0 0) → 10.6 μm
2) (0 0 1) to (0 2 0) → 9.6 μm
 The beam at 10.6 μm alone is amplified by the mirrors and released by M2
 The beam at 9.6 μm is eliminated by NaCl Brewster window
Applications
 Used for bloodless surgery in medicine.
 Used for pollution monitoring and remote sensing
4. Explain the construction and working of semiconductor diode laser
Semiconductor diode laser is a heavily doped p-n junction diode.
Types:
1. Homojunction diode laser – the junction is between same material
2. Heterojunction diode laser – the junction is between different materials
Basic principle:
Under forward bias, holes (in V.B of p region) recombine with electrons (in C.B of n
region) emitting a photon. This photon stimulates further recombination.

Construction:

1. Active Medium – heavily doped GaAs p-n junction diode

2. Pumping Source – direct pumping by Forward bias
3. Optical resonator – Polished side of the diode (mirrors not needed)

 Active Medium – p-region – GaAs doped with Ge

n-region – GaAs doped with Te
 The diode is Forward biased using a battery.
 Two opposite faces of the diode are polished for optical resonator

Working:

No Bias Voltage Under Forward Bias

  Due to heavy doping,
p-region is rich in holes
n-region is rich in electrons
𝐸𝑔
 Under forward bias (voltage = ), electrons and holes are directly injected into the
𝑒
junction (active region) i.e. population inversion is achieved.
 Hence, holes in V.B recombine with electrons in C.B emitting photons
 These photons stimulate further electron-hole recombination
 Hence, a laser of wavelength,

ℎ𝑐
= is emitted.
𝐸𝑔

where, Eg – band gap energy of the diode.

 The laser beam is amplified by reflection at the polished sides and escapes through
partially polished side
 This laser operates in pulsed mode

5. Explain the construction and working of Hetero-junction semiconductor diode laser

Hetero-junction diode laser is a heavily doped p-n junction diode made of different
materials. It has low threshold current density
Basic principle:
Under forward bias, holes (in V.B of p region) recombine with electrons (in C.B of n
region) emitting a photon. This photon stimulates further recombination.

Construction (double layer diode):

 Active Medium – Layer 1 – p-region – heavily doped GaAs

Layer 2 – p-region – heavily doped GaAlAs
Layer 3 – p-region – heavily doped GaAs
Layer 4 – n-region – heavily doped GaAlAs
Layer 5 – n-region – heavily doped GaAs
 The diode is Forward biased using a battery.
 Two opposite faces of the diode are polished for optical resonator
 Working:

 Under forward bias, electrons and holes are directly injected into in the 3 rd layer
(active region) i.e. population is inversion is achieved.
 The many layer structure provides confinement of electrons and holes
 Hence, holes in V.B recombine with electrons in C.B emitting photons
 These photons stimulate further electron-hole recombination
 Hence, a laser of wavelength,

ℎ𝑐
= is emitted.
𝐸𝑔

where, Eg – band gap energy of the diode.

 The laser beam is amplified by reflection at the polished sides and escapes through
partially polished side

6. Discuss medical and industrial applications of lasers.

Industrial Applications:

1. Lasers are used in metrology for surveying and alignment.

2. Laser interferometry measures displacement with an accuracy of micron.
3. High power lasers are user for material processing – cutting, welding and drilling of
hard materials in manufacturing industries (Example: CO2 laser in ICF).
4. Low power CO2 lasers are used for removal of insulation from electrical wires.
5. Very smooth cutting of any desired shape is possible with laser.
6. Lasers are used to drill aerosol nozzles and control orifices.
7. In automotive industry, lasers are used for heat treatment of small portions such as
annealing, work hardening, etc.

Medical Applications:

1. In ophthalmolgy, Ar ion laser is used for welding of retinal detachment.

2. Lasers are used for cataract removal
3. Eye lens-curvature correction is done using UV radiations of Excimer lasers
4. Laser scalpels are used for bloodless surgery
5. In laser angioplasty for removal of artery blocks, Nd:YAG lasers are used
6. In dermatology, blue-green lasers are used to remove freckles, acne and tattoo.
7. Lasers are used in breaking kidney stones and gallstones
8. Lasers are used in cancer diagnosis and therapy.
 FIBER OPTICS

INTRODUCTION:
The development of lasers and optical fiber has brought about a revolution in the field of communication
systems. Experiments on the propagation of information – carrying light waves through an open
atmosphere were conducted. The atmospheric conditions like rain, fog etc affected the efficiency of
communication through light waves. To have efficient communication systems, the information carried
by light waves should need a guiding medium through which it can be transmitted safely.
This guiding mechanism is optical fiber. The communication through optical fiber is known as light
wave communication or optical communication. A light beam acting as a carrier wave is capable of
carrying more information than that of radio waves and microwaves due to its larger bandwidth.
Currently in most part of the world, fiber optics is used to transmit voice, video and digital data signals
using light waves from one place to other place.
QUESTIONS
1. Briefly discuss about an optical fiber.
The optical fiber is a wave guide.
It is made up of transparent dielectrics (glass or plastics).
Fiber Construction:

It consists of an inner cylinder made of glass or plastic called core. The core has high refractive index
n1.This core is surrounded by cylindrical shell of glass or plastic called cladding. The cladding has low
refractive index n2. This cladding is covered by a jacket which is made of polyurethane. It protects the
layer from moisture and abrasion. The light is transmitted through this fiber by total internal reflection.
The fiber guides light waves to travel over longer distance without much loss of energy.
Note: Core diameters range from 5 to 600μm while cladding diameters vary from 125 to 750μm.Core
transmits the light waves. The cladding keeps the light waves within the core by total internal reflection.
R.I: The refractive index or index of refraction of a substance is a measure of the speed of light in that
substance. It is expressed as a ratio of the speed of light in vacuum relative to that in the considered
medium.
2. State the principle of propagation of light in an optical fiber.
The light launched inside the core at one end of the fiber propagates to the other end due to total internal
reflection at the core and cladding interface.
3. Give the conditions to occur total internal reflection in an optical fiber.
1. The refractive index of the core material n1 must be higher than that of the cladding n2 surrounding
it.
2. At the core-cladding interface, the angle of incidence (between the ray and normal to the interface)
must be greater than the critical angle.
4. Define Critical angle.

5. Discuss about light propagation through two different media.

6. Discuss about light propagation through an optical fiber.
 This angle im is called the acceptance angle of the fiber
7. Define acceptance angle and acceptance cone.
Acceptance angle is defined as the maximum angle that a light ray can have relative to the axis of the
fiber and propagate down the fiber. Or the maximum angle at or below which the light can suffer Total
Internal Reflection is called acceptance angle.
Acceptance cone:
An optical fiber accepts only those rays which are incident within a cone having a semi angle im.

The light rays contained within the cone having a full angle 2im are accepted and transmitted along the
fiber. Therefore, the cone is called the acceptance cone. Light incident at an angle beyond im refracts
through the cladding and the corresponding optical energy is lost. It is obvious that the larger the
diameter of the core, the larger the acceptance angle.

8. Define the terms Numerical Aperture and Fractional difference in refractive indices.
Fractional difference in Refractive indices

9. Derive the relation between N.A and 

10. Discuss in detail about the types of optical fibers.

11. Describe the modes of propagation in an optical fiber.

Light propagates as electromagnetic waves through an optical fiber. All waves, having ray directions
above the critical angle will be trapped within the fiber due to total internal reflection. However, all
such waves do not propagate through the fiber. Only certain ray directions are allowed to propagate.
The allowed directions correspond to the modes of the fiber.
In simple terms, modes can be visualized as the possible number of paths of light in an optical fiber.
The paths are all zigzag paths excepting the axial direction. Accordingly, light rays travelling through
a fiber are classified as axial rays or zigzag rays. As a ray gets repeatedly reflected at the walls of the
fiber, phase shift occurs. Waves travelling along the certain zigzag paths will be in phase and intensified.
Waves travelling along certain other paths will be out of phase and diminish due to destructive
interference. The light rays path along which the waves are in phase inside the fiber are called modes.
The number of modes that a fiber will support depends upon the ratio of d/λ where d is the diameter of
the core and λ is the wavelength of the wave being transmitted. Modes are designated by an ‘order’
number ‘m’. In a fiber of fixed thickness, the higher order modes propagate at smaller angles than the
lower order modes.

11. Describe single mode and multimode fibers.

SINGLE MODE FIBERS.
In general, the single mode fibers are step – index fibers. These types of fibers are made from doped
silica. It has a very small core diameter so that it can allow only one mode of propagation and hence
called single mode fibers. The cladding diameter must be very large compared to the core diameter.
Thus in the case of single mode fiber, the optical loss is very much reduced. The structure of a single
mode fiber as shown.

MULTI- MODE FIBERS

The multimode fibers are useful in manufacturing both for step – index and graded index fibers. The
multi-mode fibers are made by multi-component glass compounds such as Glass – Clad Glass, Silica –
Clad – Silica, doped silica etc. Here the core diameter is very large compared to single mode fibers, so
that it can allow many modes to propagate through it and hence called as Multi mode fibers. The
cladding diameter is also larger than the diameter of the single mode fibers. The structure of the
multimode fiber is as shown in the figure.

Here d= core diameter

NA = numerical aperture
λ = Optical wavelength.
Application: Because of its less band width it is very useful in short haul communication systems
12. Distinguish between single mode and multimode fibers.

13. Discuss about Step index fibers.

SINGLE MODE STEP INDEX FIBER
A single mode step index fiber consists of a very thin core of uniform refractive index surrounded by a
cladding of refractive index lower than that of core. The refractive index abruptly changes at the core
cladding boundary. Light travels along a side path, i.e., along the axis only. So zero order modes is
supported by Single Mode Fiber.

MULTIMODE STEP INDEX FIBER

A multimode step index fiber consists of a core of uniform refractive index surrounded by cladding of
refractive index lower than that of the core. The refractive index abruptly changes at the core cladding
boundary. The core is of large diameter. Light follows zigzag paths inside the fiber. Many such zigzag
paths of propagation are permitted in Multi-Mode Fiber. The Numerical Aperture of a Multi-mode fiber
is larger as the core diameter of the fiber is larger.

14. Describe graded index fibers.

GRIN fiber is one in which refractive index varies radially, decreasing continuously in a parabolic
manner from the maximum value of n1, at the center of the core to a constant value of n2 at the core
cladding interface.
In graded index fiber, light rays travel at different speeds in different parts of the fiber because the
refractive index varies throughout the fiber. Near the outer edge, the refractive index is lower. As a
result, rays near the outer edge travel faster than the rays at the center of the core. Because of this, rays
arrive at the end of the fiber at approximately the same time. In effect light rays arrive at the end of the
fiber are continuously refocused as they travel down the fiber. All rays take the same amount of time in
traversing the fiber. This leads to small pulse dispersion.

15. Explain the propagation of light in graded index fibers in detail.

Here, since na > nb the ray gets refracted. Similarly since nb> nc, the ray gets refracted and so on. In a
similar manner, due to decrease in refractive index the ray gets gradually curved towards the upward
direction and at one place , where in it satisfies the condition for total internal reflection, it is totally
internally reflected . The reflected rays travels back towards the core axis and without crossing the fiber
axis, it is refracted towards downwards direction and again gets totally internally reflected and passes
towards upward direction. In this manner the ray propagates inside the fiber in a helical or spiral manner.
16. Describe the role of an optical fiber as a waveguide.
Optical fibers are used as dielectric waveguides for electromagnetic signals of optical frequencies.
Figure shows the block diagram of transmission of sound along the optical fiber and conversion again
to sound at the other end.
Sound is first converted into electrical signal by a microphone. The electrical signals modulate the intensity of
light from laser. Then the information is carried along the fiber in a digital form. Boosters or repeaters are placed
at a distance of about 50km of cable to make up the signal loses occurring due to scattering and absorption. At the
receiving place, a photodiode converts the digital light pulses into corresponding electrical signals. The electrical
signals are then converted into sound by an earphone (receiver)Time division multiplexing system is used to
transmit many thousands of telephone cells through a single optical fiber with the use of digital pulses.
17. Distinguish between Step index fibers and graded index fibers.

18. Explain the fiber optic communication system with help of neat sketch.
 THE FIBER OPTIC COMMUNICATION SYSTEM
Figure shows the schematic diagram of a fiber optic communication system. The major components
of an optical fiber communication system are
1. The optical transmitter
2. The optical fiber
3. Receiver
PRINCIPLE:
Basically, a fiber optic system converts an electrical signal to an infrared light signal. This signal is
transmitted through an optical fiber. At the end of the optical fiber, it is reconverted into an electric
signal.
WORKING:
1. Encoder encodes the information in the binary sequence zeros and ones. a. Encoder is an electric
circuit where in the information is encoded into binary sequences of zeros and one. In the light wave
transmitter each ‘one’ corresponds to an electrical pulse and ‘zero’ corresponds to an absence of a pulse.
These electrical pulses are used to turn a light source on and off very rapidly. The driver converts the
incoming electrical signal into a form that will operate with the light source.
2. These electrical pulses are used to turn a light source on and off rapidly.
3. The optical fiber acts as a wave guide and transmits the optical pulses towards the receiver, by the
principle of total internal reflection.
4. The light detector receives the optical pulses and converts them into electrical pulses. These signals
are amplified by the amplifier.
5. The amplified signals are decoded by the decoder.

19. Discuss about the advantages of fiber optic communication system

ADVANTAGES:
1. Extremely wide bandwidth.
Optical frequencies are very large (1015 Hz) as compared to radio frequencies (106Hz) and microwave
frequencies (1010 Hz). The rate at which information can be transmitted is directly related to signal
frequency. Therefore, a transmission system that operates at the frequency of light can theoretically
transmit information at a higher rate than systems that operate at radio frequencies or microwave
frequencies.
2. Lack of cross talk between parallel fibers.
There is virtually no signal leakage from fibers. Hence, cross-talks between neighboring fibers are
almost absent. This is quite frequent in conventional metallic system
3. Immunity to inductive interference
Since optical fibers are not metallic, they do not pick up electromagnetic waves. The result is noise free
transmission i.e., fiber optic cables are immune to interference caused by lighting or other
electromagnetic equipment.
4. Smaller diameter and light weight cable
Optical fibers, because of their light weight and flexibility, can be handled more easily than copper
cables.
5. Signal security
The transmitted signal through the fibers does not radiate. Further the signal cannot be tapped from a
fiber in an easy manner. Therefore, optical fiber communication provides a hundred percent signal
security hence this system is highly suited to secure communications in defence communication
networks.
6. Economical & Low loss per unit length.
20. Discuss about fiber optic sensors
Optical sensor is a transducer which converts any form of signal into optical signal in the measurable
form. Here optical fibers are used as a guiding media and hence called as wave guides. The block
diagram of a sensor system is as follows.

The optical sources used here are LED/Laser. The optical signal produced by the optical source and is
transmitted through the transmitting fiber in the modulation zone. The optical signals are modulated
based on any one of these properties, viz., Optical intensity, phase, polarization, Wavelength and
spectral distribution. These modulated signals with any one of these properties are received by the
receiving / fiber and is sent to the optical detector.
21. Describe the types of fiber optic sensors.
TYPES OF SENSORS
There are two types of sensors
1. Intrinsic sensors or Active sensors
2. Extrinsic sensors or Passive sensors
INTRINSIC SENSORS OR ACTIVE SENSORS

In intrinsic sensors or active sensors the physical parameter to be sensed directly acts on the fiber itself
to produce the changes in the transmission characteristics.
Example:
i. Temperature /Pressure Sensor (Phase and polarization sensor) and
ii. Liquid level sensor.
EXTRINSIC SENSORS
In extrinsic sensors or passive sensors, separate sensing element will be used and the fiber will act as a
guiding media to the sensors.

Examples:
i. Displacement sensor
ii. Laser Doppler velocimeter sensor
TEMPERATURE SENSOR

Principle:
It is based on the principle of interference between the beams emerging out from the reference fiber and
the fiber kept in the measuring environment.
Description:
It consists of a Laser source to emit light. A beam splitter, made of glass plate is inclined at an angle
450 with respect to the direction of the laser beam.
Two fibers viz,
1. Reference fiber which is isolated from the environment
2. Test fiber kept in the environment to be sensed, are placed as shown in the figure. Separate lens
systems are provided to split and to collect the beam.

Working:
1. A monochromatic source of light is emitted from the laser source.
2. The beam splitter kept at an angle 450 inclination divides the beam emerging from the laser source
into two beams (i) main beam and (ii) splitted beam, exactly at right angles to each other.
3. The main beam passes through the lens L1 and is focused onto the reference fiber which is isolated
from the environment to be sensed.
4. The beam after passing through the reference fiber then falls on the Lens L2.
5. The splitted beam passes through the Lens L3 and is focused onto the test fiber kept in the
environment to be sensed.
6. The splitted beam after passing through the test fiber is made to fall on lens L2.
7. The two beams after passing through the fibers, produces a path difference due to change in
parameters such as pressure, temperature etc in the environment.
8. Therefore a path difference is produced between two beams causing the interference pattern as shown
in the figure.
9. Thus the change in pressure or temperature can be accurately measured with the help of the
interference pattern obtained.
22. Describe the displacement sensor.
Principle:
Light is sent through a transmitting fiber and is made to fall on a moving target. The reflected light from
the target is sensed by a detector. With respect to intensity of light reflected from its displacement of
the target is measured.
Description:
It consists of a bundle of transmitting fibers coupled to the laser source and a bundle of receiving fibers
coupled to the detector as shown in the figure.

The axis of the transmitting fiber and the receiving fiber with respect to the moving target can be
adjusted to increase the sensitivity of the sensor. Working: Light from the source is transmitted through
the transmitting fiber and is made to fall on the moving target. The light reflected from the target is
made to pass through the receiving fiber and the same is detected by the detector. Based on the intensity
of the light received, the displacement of the target can be measured, (i.e.) if the received intensity is
more than we can say that the target is moving towards the sensor and if the intensity is less, we can
say that the target is moving away from the sensor.
 PART-A QUESTIONS
TWO MARK QUESTIONS AND ANSWERS
1. Give four applications of fiber optic sensors.
a) Fiber optic sensors are used as optical displacement sensors, which is used to find the displacement
of a target along with its position.
b) It is used as fluid level detector.
c) It is used to sense the pressure, temperature at any environment.
d) It is also used to measure the number of rotations of the fiber coil using the instrument called a
gyroscope.
2. Explain the basic principle of fiber optic communication.
Total internal reflection is the principle of fiber optic communication.
Principle:
When light travels from a denser to rarer medium, at a particular angle of incidence called the critical
angle, the ray emerges along the surface of separation. When the angle of incidence exceeds the critical
angle, the incident ray is reflected in the same medium and this phenomenon is called the total internal
reflection.
3. Give the application of fiber optical system.
a) It can be used for long distance communication in trunk lines.
b) A large no of telephone signals nearly 15000 can be passed through the optical fibers in a particular
time without any interference.
c) It is used in computer networks especially in LAN.
d) It is also used as optical sensor.
4. Mention any four advantages of LED in electronic display.
a) Very small in size.
b) Different colours of display.
c) Works under a wide range of temperature.
d) It is a very wide range of operation.
5. Mention any four advantages of fiber optic sensors.
a) It has no external interference
b) It is used in remote sensing.
c) Safety of data transfer.
d) It is small in size.

6. Give any four examples of intrinsic sensor.

a) Pressure sensor
b) Liquid level sensor
c) Phase and polarization sensor.
d) Optical fiber flow sensor.
7. Give any four examples of extrinsic sensor.
a) Displacement sensor
b) Laser Doppler velocimter sensor
c) Fluor optic temperature sensor
d) Current measurement sensor
8. State the applications of optical fibers in medical field.
a) Fiber optics endoscopes are used in medical diagnosis
b) It is used to visualize the inner organs of the body
9. Mention the advantages of optical fiber communication over radio wave communication.
a) Optical communication can be made even in the absence of electricity
b) The optical signals are not affected by any electrical signals or lightening
c) Optical fiber communication is free from electromagnetic interference (EMI)
d) This type of communication is suitable to any environmental conditions
e) Easy maintenance, longer life, economical and high quality signal transmission are the additional
features of optical fiber communication.
10. What are the losses that occur during optical fiber communication?
During the transmission of light through the optical fiber, three major losses will occur, viz.,
attenuation, distortion, and dispersion.
Attenuation is mainly caused due to absorption, scattering and radiation of light inside the fibers.
Distortion and dispersion occurs due to spreading of light and also due to manufacturing the defects.
11. What are the conditions of Total Internal reflection?
a) Light should travel from denser medium to rarer medium
b) The angle of incidence (Ф) on core should be greater than critical angle (Фc)
Ф > Фc
c) The refractive index of the core (n1) should be greater than the refractive index of the cladding
(n2). n1 > n2
12. Draw the block diagram of fiber optic communication system.

13.Define acceptance angle and acceptance cone.

Acceptance angle is defined as the maximum angle that a light ray can have relative to the axis of the
fiber and propagate down the fiber. Or the maximum angle at or below which the light can suffer Total
Internal Reflection is called acceptance angle.
 UNIT – III

NON-DESTRUCTIVE TESTING

Part A (2 Marks)

1. Define: Non-Destructive Testing.

Nondestructive testing is an inspection method by which a solid is tested without damage
Examples: 1. Liquid Penetrant Test
2. Ultrasonic Flaw Detection
3. X-Ray radiography & Fluoroscopy
4. Eddy current Test
5. Magnetic particle Test,
6. Thermography, etc.,

2. Give the principle of liquid penetrant method.

Liquid Penetrant Test (LPT) works on the principle of capillary action
A liquid penetrant is applied on the surface of the specimen. The penetrant is drawn
into the surface flaws due to capillary action and this is subsequently revealed by a
developer, under visual inspection.

3. What are the various steps involved in Liquid Penetrant method?

 Cleaning the surface
 Application of the penetrant
 Removal of excess penetrant
 Developing
 Inspection
4. What is a developer?
A developer is liquid / powder used to pull the trapped penetrant material out of the flaw
and spread it on the surface of the specimen.
5. What are the characteristics of a good developer?
• Developer should possess high absorption ability.
• Developer should possess low viscosity.
• It should wet material.
• It should easily available.
• It should easily removable.
• It should have high sensitivity to light.
• It should be a good solvent.
6. What are the characteristics of a penetrant?
• Penetrant should possess low surface tension.
• Penetrant should possess low viscosity.
• It should wet material.
• It should easily available.
• It should easily removable.
• It should have high sensitivity to light.
• It should be good solvent.
 7. What is the principle of X-ray radiography?

When X-rays are passed through a specimen they are differentially absorbed by the
specimen. A photographic film records the transmitted x-rays. The dark and bright shadows
in the developed film reveal defects present in the specimen.
I = I o e − x
Where, I – transmitted intensity
Io – incident intensity
µ - absorption coefficient
x – thickness of the specimen.

8. Give the principle of Ultrasonic flaw detection method.

Whenever there is a change in medium ultrasonic waves are reflected. From the intensity
and time delay of the echo, the nature and position of the flaw can be detected

====================================================================

PART-B (10 Marks)

1. Write down the principle, advantages, disadvantages and applications of liquid penetrant
method.

Principle:

Liquid Penetrant Test (LPT) works on the principle of capillary

A liquid penetrant is applied on the surface of the specimen. The penetrant is drawn into
the surface flaws due to capillary action and this is subsequently revealed by a developer,
in addition with visual inspection.

Advantages:

1) It can be used for all metals and non metals.

2) It can be used for any size and shape of material.
3) It requires less cost.
4) High sensitivity (small discontinuities can be detected).
 Disadvantages

1) It is used only for surface defects.

2) It is not suitable for porous material.
3) Requires expert person.
4) Surface finish and roughness can affect inspection sensitivity.
5) Pre-cleaning is critical since impurities can cover

Applications Of LPT

1) LPT is used to detect surface open cracks in welds (e.g. pipes, turbine, etc.).
2) It is used to detect surface open cracks in forgings (e.g. crank shaft).
3) It is used to detect surface open cracks in castings (e.g. piston head).
4) It is used to detect surface open cracks in rolled products (e.g. rolling stocks).

==================================================================

2. List out the characteristics of i) penetrant, ii) developer.

A Liquid Penetrant is capable of getting trapped into the surface flaw by capillary action

Characteristics of a penetrant

• Penetrant should possess low surface tension.

• Penetrant should possess low viscosity.
• It should wet material.
• It should easily available.
• It should easily removable.
• It should have high sensitivity to light.
• It should be good solvent.

The developer is used to pull the trapped penetrant material out of the flaw and spread it on
the surface of the specimen.

Characteristics of a good developer

• Developer should possess high absorption ability.

• Developer should possess low viscosity.
• It should wet material.
• It should easily available.
• It should easily removable.
• It should have high sensitivity to light.
• It should be a good solvent.

3. Write down the principle, advantages, disadvantages and applications of ultrasonic flaw
detector.

Principle

Whenever there is a change in medium ultrasonic waves are reflected. From the intensity
and time delay of the echo, the nature and position of the flaw can be detected
 Advantages

• Internal defects in metals can be detected due to high depth of penetration

• High accuracy in detection of position, size & shape of defect
• Minimal part preparation
• Simple operation
• High speed
• Easy handling
• Low cost.

Disadvantages

• Special care is needed in coupling ultrasonic Probe to the specimen surface

• Highly skilled & trained manpower is require
• Irregular, rough, coarse grained or non homogenous parts, linear defects
oriented parallel to the beam cannot be inspected
• High noise

Applications

• Quality control & material inspection

• Detection of failure of rail rolling stock axes, pressure columns,
earthmoving equipments, mill rolls, mixing equipments, etc.
• Measurement of metal section thickness
• Thickness measurements – refinery & chemical processing equipments,
submarine hulls, aircraft sections, pressure vessels, etc.
• Inspect pipe & plate welds
• Inspect pins, bolts & shafts for cracks
• Detect internal corrosion

4. Describe the X-ray fluoroscopy technique of nondestructive testing with a neat diagram.

5. Write a note on the following:

i) Destructive Testing
ii) Non-Destructive Testing
iii) Penetrant
iv) Developer

====================================================================
PART-C (15 Marks)

1. Illustrate the procedure of liquid penetrant method of testing with neat diagram.

Principle

Liquid Penetrant Test (LPT) works on the principle of capillary

A liquid penetrant is applied on the surface of the specimen. The penetrant is drawn into
the surface flaws due to capillary action and this is subsequently revealed by a developer,
in addition with visual inspection.

1) Surface Preparation

Pre cleaning of the material is the first step in Liquid Penetrant Test. In this process dirt,
grease, oil, etc. on the surface of the material is removedusing cleaning reagent and cotton
cloths.

2) Application of Dye Penetrant

After cleaning of surface of material a suitable dye penetrant is applied on surface of

material. The dye penetrant slips (enter) into cracks of material. Time required to slips into
the cracks is called dwell time. It is near about 20-30 minutes.

3) Removal of Excess Penetrant

After dwell time excess dye penetrant is removed from surface of material.

4) Application of Developer

A thin layer of developer is applied on surface of material. Due to reverse capillarity dye
penetrant is comes out on surface i.e. developer pulls penetrant on surface.
5) Inspection And Evaluation

The inspection of material is done under white light or UV light depending on penetrant
used. White light is used when visible dye penetrant used and UV light is used when
fluorescent light used.

6) Post Cleaning

After inspection, the material is cleaned using cleaning reagent, and can be used for
intended purpose.

Advantages of LPT

1) It can be used for all metals and non metals.

2) It can be used for any size and shape of material.
3) It requires less cost.
4) High sensitivity (small discontinuities can be detected).

Disadvantages

1) It is used only for surface defects.

2) It is not suitable for porous material.
3) Requires expert person.
4) Surface finish and roughness can affect inspection sensitivity.
5) Pre-cleaning is critical since impurities can cover

Applications Of LPT

1) LPT is used to detect surface open cracks in welds (e.g. pipes, turbine, etc.).
2) It is used to detect surface open cracks in forgings (e.g. crank shaft).
3) It is used to detect surface open cracks in castings (e.g. piston head).
4) It is used to detect surface open cracks in rolled products (e.g. rolling stocks).

Characteristics of Penetrant

Selection of penetrant is depends on following characteristics :

1) Penetrant should possess low surface tension.

2) Penetrant should possess low viscosity.
3) It should wet material.
4) It should easily available.
5) It should easily removable.
6) It should have high sensitivity to light.
7) It should be good solvent.
 Characteristics of Developer

Selection of developer is depends on following characteristics :

1) Developer should possess high absorption ability.

2) Developer should possess low viscosity.
3) It should wet material.
4) It should easily available.
5) It should easily removable.
6) It should have high sensitivity to light.
7) It should be good solvent.
====================================================================

2. Explain the working of ultrasonic flaw detector with a neat diagram.

Ultrasonic flaw detector is a Non Destructive Testing method. The method uses
high frequency ultrasonic waves to test a solid without damaging it. Ultrasonic flaw
detector is used to
• detect flaw
• measure flaw-size & specimen-size
• characterize the material, etc.,
Principle
Whenever there is a change in medium ultrasonic waves are partially reflected.
From the intensity and time delay of the echo, the nature and position of the flaw can be
detected
Block Diagram

Timer Pulse CRO Amplifier

circuit generator

Transducer Specimen Transducer

(Transmitter) (Receiver)

Working-Description

The block diagram shows various components of ultrasonic flaw detector. The
transducer is coupled to the top surface of the specimen without air gap.
• The timer circuit triggers the pulse generator at regular intervals
• The pulse generator sends short pulses of high frequency alternating voltage to the
transducer and is also displayed in CRO (peak A)
 Z
A B

• Accordingly the transducer produces ultrasonic waves. The waves are then passed
through the specimen.
• If there is no defect, the ultrasonic waves are reflected from the bottom surface
• The echo is then received by the transducer; amplified by the amplifier; finally
displayed in CRO as peak B.
• If there is any flaw, ultrasonic waves are reflected form the flaw-surface and
displayed as peak Z between A and B.
• From the time delay ( ) of defect pulse and velocity ( ) of ultrasonic waves, the
depth of defect is calculated using the formula,

Ultrasonic Inspection Modes – Pulse Echo System

Normal Probe Reflection Mode

• Reflected signal is used for detection of flaw

• Preparation of only one surface is enough
• Single transducer acts as both transmitter and receiver
• Coupling loss is minimum
• Depth of defect can be measured

Normal Probe Transmission Mode

• Transmitted signal is used for detection of flaw

• Set of parallel surfaces are needed
• Transmitter and receiver are separate; moved together over the parallel surfaces
• Coupling loss is more
• Only the presence of defect can be known but not the depth

Ultrasonic Scanning Methods-Display Modes

The data collected from the U/S flaw detector can be displayed in a number of different
formats. The three most common formats are,
 1. A-Scan
2. B-Scan
3. T-M Scan or C-Scan
For the specimen in the following figure, the A, B & C Scan displays are discussed below.

1. A-Scan (or) Amplitude Mode Display

• Gives one dimensional information about the specimen
• Single transducer is fixed at a point on the top surface
• The data are displayed as vertical spikes in CRO, taking Signal strength along Y-axis
and Time of travel along X-axis
• When there is,
No defect - only two spikes (A & B) appear in CRO
Any defect - three spikes (A, Z & B) appear
• From the Time delay (t) between pulses A and Z- depth (d) of the defect is calculated
using the relation
d =

• Height of the defect pulse gives nature of the defect.

2. B-Scan (or) Brightness mode display

• Gives two dimensional information
• Data are displayed as bright dots
• In B-Scan, travel time is taken along Y-axis and linear transducer position along X-axis

3. T-M Scan (or) Time-motion mode

• In this mode, a u/s probe scans the specimen in a raster manner.
• The echo signals are recorded as a function of probe-position
• A data acquisition system processes the echoes
• Hence the display provides plane view of the specimen as shaded area & flaw as un-
shaded area
• This display mode can be applied to even moving objects
=====================================================================

3. Explain about the working of X-ray radiography.

It is a nondestructive testing method using high frequency radiations such as X-rays.

In this method, an image of the specimen is formed either on a photographic film or
on a fluorescent screen.

Principle of X-ray Radiographic technique:

When X-rays are passed through a specimen, they are differentially absorbed by the
specimen. The transmitted beam is then made to fall on a photographic film or on a fluorescent
screen.
The dark and light shadows reveal the defects present in the specimen and thus defects
are detected.
Law of absorption of X-rays

According to the law of absorption of X-rays, the intensity of the transmitted X-rays
through a material, is given as,

I = I o e − x

Where μ is material dependent absorption coefficient and x is thickness of penetration

X-ray radiographic technique can be employed in different modes.

(i) Displacement method

Three basic elements

1. X-ray probe (source): X-rays are produced by this.

2. Specimen (test piece) : Plate of uniform thickness containing internal flaw
3. Recording medium: Photographic film.

Principle & Working :

The specimen is exposed to the X-rays by keeping the x-ray source at position ‘A’ and
then at ‘B’ by displacing the source through a certain distance.

The corresponding flaw-images (black spots) are recorded on a single photographic

film at “A” and “B” respectively.

From the displacements of the x-ray tube and the images (P and S), the exact position
of the defect can be determined.

Where, F – distance between X-ray tube and photographic film.

If there is no flaw, there is uniform intensity in the developed spot without black spots.

Figure: Displacement method for measuring the distance of location of flaw

(ii) X- Ray Fluoroscopy

 This method is a fast technique, used widely in industry for immediate inspection of
defect. It can detect small defects in the casting sections less than 50 mm.

Principle and working:

• X-rays are passed through the specimen and then fall on a fluorescent screen.
• Fluorescent material converts the transmitted X-rays into visible light rays.
• Image of the defect is displayed on the fluorescent screen.

Merits

 No need of washing and developing films

 Low cost as it does not require any dark room facilities.
 Image is viewed immediately on screen
 Time consumption is less

Demerits

 Poor resolution and low image contrast

 Electronic image intensifier is required for increasing the contrast
 Size of the equipment is large (not portable) and high cost.
 Defects in thicker casting are not detected.
 Requires maintenance and service
 Vinayaka Mission’s Research Foundation
Aarupadai Veedu Institute of Technology
Department of Chemistry
Engineering Chemistry

Syllabus
UNIT – I: ELECTROCHEMISTRY, BATTERIES AND FUEL CELLS
Electrode potential - Nernst equation – Electrodes (SHE, Calomel and Glass) - cells - EMF
measurement. Primary battery (Daniel and dry cell) – secondary battery (lead Acid storage
battery and Nickel-Cadmium battery) – Fuel cell (H2-O2 fuel cell)
UNIT – II: WATER TECHNOLOGY AND CORROSION
Sources of water – impurities – Hardness and its determination (problems to be avoided) –
boiler troubles – water softening (Zeolite & Demineralisation) – Domestic water treatment –
Desalination (Electrodialysis & ReverseOsmosis).
Corrosion – Definition, causes and effects, Classification, Types of corrosion- dry corrosion,
Wet corrosion, Factors influencing rate of corrosion, Corrosion control methods – Sacrificial
anode method and impressed current cathodic method
UNIT – III FUELS AND CHEMISTRY OF ADVANCED MATERIALS
Classification of Fuels (Solid, Liquid, Gaseous, Nuclear and Bio fuels) – Calorific Value of a
fuel –Non Petroleum Fuels –Non conventional sources of Energy – combustion.
Basics and Applications:-Organic electronic material, shape memory alloys, polymers (PVC,
Teflon, Bakelite)
TEXTBOOK
1.Engineering Chemistry by VMU.
REFERENCES
1. A text book of Engineering Chemistry by S.S. Dara, S.Chand & company Ltd., New Delhi
2. Engineering Chemistry by Jain & Jain, 15th edition Dhanpatrai Publishing Company (P)
Ltd., New Delhi
3. A text book of Engineering Chemistry by Shashi Chawla, Edition 2012 Dhanpatrai & Co.,
New Delhi.
4. Engineering Chemistry by Dr. A. Ravikrishnan, Sri Krishna Publications, Chennai.
UNIT – I: ELECTROCHEMISTRY, BATTERIES AND FUEL CELLS
Electrode potential - Nernst equation – Electrodes (SHE, Calomel and Glass) - cells - EMF
measurement. Primary battery (Daniel and dry cell) – secondary battery (lead Acid storage
battery and Nickel-Cadmium battery) – Fuel cell (H2-O2 fuel cell)
Electrode Potential
At equilibrium, the potential difference between the metal and solution becomes a
constant value and is termed as “electrode potential.”
A metal (M) consists of metal ions with valance electrons. When the metal (M) is
placed in a solution of its own salt, any one of the following reactions will occur.
(i) Positive metal ions may pass in to the solution
M → Mn+ + ne- (Oxidation)
If the positive ions in the metal come in to equilibrium with those in the solution leaving
behind an equivalent number of electrons of the metal, the metal acquires a negative charge.
Example: Zn in ZnSO4 solution.
(ii) Positive metal ions from the solution may deposit over the metal.
Mn+ + ne- → M (Reduction)
If the positive metallic ion from the solution enters the metallic lattices, then metal
acquires a positive charge.
Example: Cu in CuSO4 solution.

When a metal is placed in the solution of its own salt, the chemical reaction (i) or (ii),
takes place and ultimately a dynamic equilibrium is established, because negative or positive
charge developed on the metal attracts the positively or negatively charged free ions in the
solution. Due to this attraction, the positive or negative ions remain quite close to the metal.
Thus, a short of layer (positive or negative ions) is formed, all around the metal. This layer is
called “Helmholtz electrical double layer.”
This layer prevents further passing of the positive ions from or to the metal. A
difference in potential is consequently set up between the metal and the solution. At
equilibrium, the potential difference becomes a constant value, which is known as the
electrode potential of a metal. Thus, the tendency of an electrode to lose electrons is called
the oxidation potential and the tendency of an electrode to gain electrons is called the
reduction potential.
Nernst Equation
According to Nernst theory, no metal was truly insoluble and all metals have a
tendency to pass in to solution. Based on this concept, the Nernst equation is derived with the
help of reversible cell. Consider the redox reaction
Mn+ + ne- ↔ M
In the above reversible reaction the free energy change (ΔG and its equilibrium
constant k) are related by the following equation which is popularly known as Van’t Hoff
reaction isotherm.
ΔG = -RTlnK + RTln (products/reactants)
= ΔG0 + RTln (products/reactants)
 Where, ΔG0 is known as standard free energy. The free energy change is equivalent to
the electrical energy -nFE .
ΔG = -nFE
ΔG0 = -nFE0
Where n = no of electrons
F = Faraday
E = Electrode potential
E0 = Standard Electrode potential
R = gas constant =8.134 J/K/mole
T = Temperature =273K
Now the equation can be written as,
-nFE = -nFE0+ RTln (products/reactants)
= -nFE0+ RT ln(M/M+)
= -nFE0+ RT 2.303log(M/M+)
if the product activity is taken as 1, then equation becomes
= -nFE0+ RT 2.303 log(1/M+)
It can be written as
= -nFE0—RT 2.303 log (M+)
It is divided by –nF, then the equation becomes,
E = E0 + RT 2.303log(M+)/nF
= E0 +0.0591/n log (M+)

Application Nernst equation can be used to calculate

i. Electrode potential (half cell potential) in a given set of conditions.

ii. EMF and polarity of electrodes in an electro chemical cell.
iii. Corrosion tendency of metals in a given set of environmental conditions.

Cells
A cell is a device consisting of two half cells which are connected by means of a wire.
Type of Cells
In electrochemistry, a cell means an assembly of electrodes (Namely the anode and
the cathode) and an electrolyte. Cells are classified in to two types.
i. Electrolytic cells
ii. Electrochemical cells
 i. Electrolytic cell
Electrolytic cells are cells in which electrical energy is used to bring about the
chemical change. The cells used for electrolysis (where electrical energy is converted to
chemical energy) are called electrolytic cells.
The process of chemical decomposition of an electrolyte by the passage of electricity
is called electrolysis. The device used for electrolysis is called electrolytic cell and it consists
of two electrodes, an electrolyte and an external source of battery is shown in figure Fig 2.1

Electrolytic cell

Example: Electrolysis of HCl

The electrolysis of HCl can be carried out by using an aqueous solution of HCl, in
which two electrodes. (Pt, Ag, Cu or Fe) are immersed at a definite distance from each other.
When electric current passes through an electrolyte, it is dissociated in to positively (Cation)
and negatively (Anion) charged ions. During electrolysis, cation move towards cathode at
cathode reduction takes place. Anion move towards anode. At anode oxidation takes place.
As a result of the electrolysis, evolution of Cl2 gas takes place at the anode and H2 gas at the
cathode.
Mechanism
When HCl is dissolved in H2O, it is dissociated in to H+ and Cl- ions.
HCl H+ + Cl-
On passing electric current
At anode: Oxidation takes place
2Cl- Cl2 + 2e-
At cathode: Reduction takes place
 2e- + 2H+ H2
H+ ions move towards the cathode, where they take up electrons and are reduced to H2. The
overall reaction is,
2HCl H2 + Cl2 (Decomposition)
ii. Electrochemical cell
An electrochemical cell is a device to produce electrical energy by means of chemical
change (Redox reaction). An electrochemical cell is also commonly referred to as voltaic or
galvanic cell. The electrode where oxidation occurs is called anode, while the electrode
where reduction occurs is called cathode. [An electrochemical cell is obtained by coupling
half cells (or two electrodes)].
The practical application of an electrochemical or galvanic cell is Daniel cell. It
consists of Zinc electrode, dipping in ZnSO4 solution (where oxidation takes place) and a Cu
electrode dipping in CuSO4 solution (where reduction takes place). Each electrode is known
as a half cell. The two solutions are interconnected by a salt bridge and the two electrodes are
connected by a wire through a voltmeter.

Electrochemical cell

Reactions occurring in the cell

At the anode
Oxidation takes place in Zn electrode by the liberation of electrons, so this electrode
is called anode.
At the cathode
Reduction takes place in the Cu electrode by the acceptance of electrons, so this
electrode is called cathode.
Zn Zn2+ + 2e- (at anode - oxidation)
Cu2+ + 2e- Cu (at cathode - reduction)
Zn + Cu2+ Zn2+ + Cu

The electrons liberated by the oxidation reaction flow through the external wire and
are consumed by the Cu ions at the cathode. The emf of a Daniel cell is 1.1 volts.

Liquid Junction Potential

Liquid junction potential is the one which occurs when two solutions of
different concentrations/compositions are in contact with each other through porous
membrane. It is due to formation of an electrical double layer of positive and negative
charges at the junction of the two solutions as the ions diffuse through membranes.
Salt bridge
Solution of a salt (KCl or KNO3 or NH4NO3) that literally serves as a bridge to
complete the electric circuit, maintain electro neutrality of electrolyte and minimize the
liquid junction potential. For precise measurements of potential, a salt bridge is used.
Difference between Electrolytic Cells and Electrochemical Cells
S. No Electrolytic cells Electrochemical cells
1. In electrolytic cells current is In electrochemical cells, current is produced
passed through an electrolyte from electrolyte solutions.
solution.
2. In electrolytic cells the cathode is In electrochemical cells during discharge of
negative (-) and anode is positive current, the cathode is positive (+) and anode
(+). is negative (-).
3. In electrolytic cells the cathode is In electrochemical cells the half cell with
negative (- ve) and attracts the electrode having reduction reaction is always
cations or positive (+ ve) ions. cathode and positive (+ ve). The half cell with
And attracts the anions or negative electrode having oxidation reaction is always
(- ve) ions. anode which is negative (- ve). This is
applicable for the discharge reaction or
 discharging of current.
4. In electrolytic cells, when current In electrochemical cells two half cells with
is passed through the electrolyte electrode and electrolyte are connected and
solution, movement of ions the flow of electron that produce electric
towards the opposite electrode current. i.e., In one half cell oxidation reaction
takes place. i.e., cations or +ve takes place.
ions moves towards cathode or – M → Mn+ + ne- (Oxidation). In another half
ve electrode. And anions or – ve cell reduction reaction takes place.
ions move towards anode or + Mn+ + ne- → M (Reduction).
electrode.
5. Examples of electrolytic cells are Good examples of electrochemical cells are
mainly mainly
(a) i. Electroplating (a) i. Voltaic cells or Batteries
(b) ii. Extraction or purification of
(b) ii. Corrosion process.
metals.

1.1.6 EMF of a cell

MF of Electrochemical cell: The difference of potential, which causes flow of
electrons from the electrode of higher potential to the electrode of lower potential, is called
electromotive force (EMF). The emf of galvanic cell is calculated from the reduction half-cell
potentials using the following relation.
E(cell) = E(right) – E(left)
Where E(cell) = e.m.f of cell
E(right) = reduction potential of right hand side electrode
E(left) = reduction potential of left hand side electrode
Measurement of EMF of a cell by Poggendorff”s compensation method:
The EMF of an unknown cell can be measured with the help of a potentiometer.
Principle
In this method, the EMF of the cell is compensated or balanced by an external emf, so
that no current flows inside the circuit. At this stage, the applied emf is equal in magnitude to
the emf of the test cell.
Description
 The potentiometer consists of a uniform wire AB of high resistance (Fig 1). A storage
battery is connected to the ends A and B of the wire through a rheostat. A standard cell C,
(cell of known emf) is connected to the end A. At the other end, the C 1 is connected to a
galvanometer (G) through a key K1. The galvanometer is then joined to a sliding contact
which moves on the wire AB.
The cell C2 (unknown cell) whose emf is to be measured is similarly connected with
key K2, the galvanometer and then the sliding contact. By using the key K1, the cell C, is put
in to the along AB. The point of contact X1 is recorded when no current flows through the
galvanometer. Then by using the key K2, the cell C2 is put in to the circuit the procedure is
repeated to find the corresponding X2.

The EMF of the unknown cell C2 is calculated by using the equation.

EMF of the unknown cell (C2) Ex = Distance between AX2

EMF of the standard cell (C1) Es Distance between AX1

Ex AX2
____ = ______

Es AX1
AX2
Ex =_____ ES
AX1
Knowing the emf of the standard cell (ES), EX can be calculated.

Applications of EMF measurement:

1. Potentiometer titrations can be carried out. 2. Transport number of the ions can be
determined. 3. Measurement of pH using hydrogen, quinhydrone and glass electrode. 4. From
the EMF data the free energy changes, equilibrium constant of a reaction can be found out. 5.
Hydrolysis constant can be determined. 6. Solubility of a sparingly soluble salt can be found
out.

Electroctremical Series (EMF series)

The arrangement of metals in the increasing order (downwards) of their standard
(reduction) electrode potential
Application of electrochemical series:
1. Relative ease of oxidation or reduction: The metals on the top are more active, easily
ionized into solution and they are good electron donors.
2. Corrosion: The metal higher in the series is anodic or more active and they are more
prone to corrosion. The metals lower in the series are noble metals and they are less prone to
corrosion.
3. Liberation of Hydrogen: The metal with –ve potential will displace H2 from an acid
solution i.e., active metals are attacked by acids
4. Replacement tendency: The metals which are more active will displace less active ion
from the solution of its salt
5. Calculation of Standard emf of the cell:

6. Predicting the spontaneity of redox reaction: Spontaneity of the redox reaction can be
predicted from the e.m.f value of complete cell reaction. If the value of E cell is +ve , the
reaction is feasible.
If it is -ve the reaction is not feasible. It can predict the direction of oxidation-reduction
reaction.
Electrodes:
Reference Electrodes:
The electrode of standard potential, with which we can compare the potentials of another
electrode, is called a “Reference Electrode”. The best “Primary reference electrode” used is
standard hydrogen electrode, whose electrode potential is taken as Zero.

Batteries:
When two or more electrochemical cells are electrically interconnected, each of which
containing two electrodes and an electrolyte is called a Battery. In everyday usage, “battery”
is also used to refer to a single cell. No one battery design is perfect for every application.
There are many parameters like cost, voltage, duty cycle, dimension, stability with time and
temperature, shelf life, etc., on which a battery is selected for a particular operation. It is
important to prioritize our list of requirements before choosing one and requires compromise.
Here duty cycle refers to conditions the battery experiences during use like, type of discharge
and current drain, e.g. continuous, intermittent, continuous with pulses, etc.
Batteries are classified into two categories depending on their recharging capabilities.
a. Primary batteries
b. Secondary Batteries
Primary batteries: These are non-rechargeable and are meant for a single use and
meant to be
discarded after use.
Primary batteries are non-rechargeable and are less expensive and are often used in
ordinary
gadgets like torch lights, watches and toys. Commercially many kinds of primary
batteries are
available but our discussion only on Leclanche cell, Alkaline cell and Lithium cell.
Secondary batteries:
Secondary batteries are rechargeable and are meant for a multi cycle use. After every
use the electrochemical reaction could be reversed by external application of voltage.
The cycle is reversed till the capacity fades or lost due to leakage or internal short
circuit.
These cells are rechargeable and reusable. A combination of all reversible
electrochemical cells gives secondary batteries. Many kinds of secondary batteries are
available in the market but we are restricting our discussion to Lead-acid cell, Ni/Cd
cells, Ni-Metal hydride cell and Lithium ion
cells.

Fuel Cells
Definition Fuel cell is a voltaic cell. It converts chemical energy of the fuels directly into
electricity without combustion. The reactants flow into the cell, and the reaction products
flow out of it, while the electrolyte remains within it. Fuel cells can operate virtually
continuously as long as the fuels are fed. Examples: Hydrogen - oxygen fuel cell.

Anode H2 gas in porous electrode

Cathode O2 gas in porous electrode
Electrolyte 25% KOH
OCV (open circuit potential) 1.2 V
CCV (closed circuit potential) 1.0 V
Cell representation H2/ H2O // KOH // O2/ OH−

Hydrogen - oxygen fuel cell is the simplest and most successful fuel cell. The fuel hydrogen
and the oxidiser-oxygen with the electrolyte. Other fuels include hydrocarbons and alcohols.
Other oxidants include chlorine and chlorine dioxide.
Description/ Construction
The cell has two porous electrodes, anode and cathode. The electrodes are made of
compressed carbon containing a small amount of catalyst (Pt, Pd, Ag) impregnated in it.
Between the two electrodes an electrolytic solution, 25% KOH is filled.
Cell reactions
At anode: 2H2(g) + 4OH− (aq) −→ 4H2O(l) + 4e –
At cathode: O2(g) + 2H2O(l) + 4e − −→ 4OH−
Net reaction: 2H2(g) + O2(g) −→ 2H2O(l)
Working
Hydrogen is passed through the anode compartment, where it is oxidised. Oxygen is passed
through the cathode compartment, where it is reduced.
Advantages of Fuel Cells
1.They are highly efficient in energy conversion and instant in operation.
2. They are pollution free and noise free.
3. Modular and hence parts are exchangeable.
4. Low maintenance cost.
5. Fuel cell holds promises in the energy scenario, replacing to some extend fossil fuel.
6. Continuous discharge takes place.
Disadvantages
1. High initial cost.
2. Large weight and volume of H2 and O2 gas storage.
3. Porous electrodes are affected by CO2 hence gases should be free from CO2.
4. H2 should be pure
Applications
1. H2 - O2 fuel cells are used as energy source in space vehicles, submarines.
2. In H2 - O2 fuel cell, the product water is a valuable source of fresh water for astronauts.
Cells
A cell is a device in which a redox reaction is utilized to get electrical energy. It consists of
two electrodes and an electrolyte. The electrode where oxidation reaction occurs is called
anode, while the electrode where reduction reaction occurs, is called cathode. Cells are
classified based on the electrical energy utilization or production into two kinds:
1. Electrochemical cell:
Here a spontaneous chemical reaction takes place and produces electrical energy.
2. Electrolytic cell:
Here a electrical energy is supplied for a chemical reaction to take place. Further
electrochemical cell is classified on the basis of their nature of chemical reaction taking place
at electrodes as primary or irreversible cell or secondary or reversible cells.
Primary Cell (or) Irreversible cell
In this cell, the electrode reactions cannot be reversed by passing an external electrical
energy. The reactions occur only once. It is a use and throw type of battery. Examples:
Lachlanche cell (Dry cell), Alkaline battery.
2. Secondary Cells (or) Reversible Cells
In these cells, the electrode reactions are reversed by passing an external electrical energy.
They are recharged by passing electric current and used again and again. They are also called
Storage cells (or) Accumulators. Examples: Lead acid storage cell, Nickel-cadmium cell.
Battery is the arrangement of number of cells in series or parallel. Cells connected in series
leads to increase in potential. Cells connected in parallel, leads to addition of energy density.
Daniel cell or Dry cell
The Daniel cell was a great improvement over the existing technology used in the
early days of battery development.
This cell consists of a Cu-vessel containing a concentrated solution of CuSO4.
A porous pot containing dil.H2SO4 is placed in the Cu-vessel which contains CuSO4 solution.
A Zn-rod is dipped into dil.H2SO4. Zn-rod acts as anode and Cu-vessel acts as cathode.
Electrode reactions and the cell reactions are:
Oxidation at anode: Zn(s) Zn2+(aq) + 2e- Eºzn/zn2+ = + 0.77 V
Reduction at cathode: Cu2+(aq) + 2e- Cu(s) Eºcu/cu2+ = + 0.34 V
Cell reaction: Zn(s) + Cu2+ (aq) Cu(s) + Zn2+(aq)

Daniel Cell
Daniel cell can be represented as,
Zn(s) /Zn2+(aq) // Cu2+(aq) /Cu(s)
Anode Cathode
EMF of this cell = Eºzn/zn2+ + Eºcu/cu2+ = 0.77 V + 0.34 V = 1.11 V
Dry Cell Battery
The dry cell battery is one of the most commonly used types, including AA, 9-volt,
and watch batteries. Dry cell batteries are different from wet cells because their electrolytes
are contained in a low-moisture paste; while a wet cell has electrolytes contained in a liquid,
hence the difference in names.
 The most common type of battery used today is the "dry cell" battery. There are many
different types of batteries ranging from the relatively large "flashlight" batteries to the
miniaturized versions used for wristwatches or calculators. Although they vary widely in
composition and form, they all work on the sample principle. A "dry-cell" battery is
essentially comprised of a metal electrode or graphite rod (elemental carbon) surrounded by a
moist electrolyte paste enclosed in a metal cylinder as shown below.

Dry Cell Battery

In the most common type of dry cell battery, the cathode is composed of a form of
elemental carbon called graphite, which serves as a solid support for the reduction half-
reaction. In an acidic dry cell, the reduction reaction occurs within the moist paste comprised
of ammonium chloride (NH4Cl) and manganese dioxide (MnO2):

2NH4+ + 2MnO2 + 2e- Mn2O2 + 2NH3 + H2O

A thin zinc cylinder serves as the anode and it undergoes oxidation:

Zn(s) Zn+2 + 2e-

This dry cell "couple" produces about 1.5 volts. (These "dry cells" can also be linked
in series to boost the voltage produced). In the alkaline version or "alkaline battery", the
ammonium chloride is replaced by KOH or NaOH and the half-cell reactions are:

Zn + 2OH- ZnO + H2O + 2e-

2MnO2 + 2e- + H2O Mn2O3 + 2OH-
Alkaline Battery
Anode Zn
Cathode MnO2/ Carbon rod
Electrolyte 40% KOH
OCV (open circuit voltage) 1.6 V
CCV (closed circuit voltage) 1.5 V
Cell representation Zn/Zn(OH)2 // KOH(aq) // MnO2/Mn2O3

Construction and Working

Alkaline battery is an improved form of the dry cell, in which the electrolyte NH4Cl is
replaced by KOH. Alkaline battery consists of a zinc cylinder filled with an electrolyte
consist of powdered KOH and MnO2 (active cathodic material) in the form of paste using
starch and water. A carbon rod (cathode) is immersed in the electrolyte in the centre of the
cell for electrical contact for the flow of electrons. The outer cylindrical zinc body acts as
anode.
Cell Reactions
At anode: Zn −→ Zn2+ + 2e − Zn + 2OH− (aq) −→ Zn(OH)2
At cathode : 2MnO2(s) + H2O(l) + 2e − −→ Mn2O3(s) + 2OH−
Net Reaction: Zn(s) + 2MnO2(s) + H2O(l) −→ Zn(OH)2(s) + Mn2O3(s)
In cathode reaction, Mn is reduced from +4 oxidation state to +3 oxidation state. Manganese
dioxide is reduced to manganic oxide.
Advantages of alkaline cell
The main advantages of alkaline cell over dry cell are
1. There is no leakage of cell, since Zn does not dissolve readily in a basic medium.
2. The life of alkaline battery is longer than the dry battery, because there is no corrosion of
Zn.
3. Alkaline battery maintains its voltage, as the current is drawn from it.
Uses
It is used in calculators, watches, torch light, transistors, toys etc.

Lead Storage battery or Lead Accumulator or Acid Storage battery

A lead acid storage cell is a secondary cell. It can operate both as a voltaic cell and an
electrolytic cell. When it acts as a voltaic cell, it supplies electrical energy. When it is
recharged, the cell operates as an electrolytic cell.
Anode Pb
Cathode PbO2/ Pb
Electrolyte H2SO4 (1.2 g/cc)
OCV (open circuit voltage) 2.1 V
CCV (closed circuit voltage) 2.0 V
Cell representation Pb/PbSO4// H2SO4(aq) // PbO2/ PbSO4 Cycle life 250-300
A lead storage battery consists of six voltaic cells connected in series to get a 12V battery.
The anode is made of lead. The cathode is made of lead dioxide PbO2 packed on a grid of
lead. Various plates are separated from the adjacent ones by insulators like rubber or glass
fibre. The entire combination is then immersed in dilute H2S O4 (38% by mass) having a
density of 1.2 g/cc. Electrode reaction while discharging When the lead - acid storage battery
operates, the following reaction occurs during discharge.
At anode: (+ve plate)
Pb(s) ⇋ Pb2+ (aq) + 2e –
Pb2+ (aq) + S O2− 4(aq) ⇋ PbS O4(s)
Pb(s) + S O2− 4 ⇋ PbS O4(s) + 2e –
At cathode: (-ve plate)
PbO2(s) + 2e − + 4H + (aq) ⇋ Pb2+ (aq) + 2H2O(l)
Pb2+ (aq) + S O2− 4(aq) ⇋ PbS O4(s)
PbO2(s) + 2e − + 4H + (aq) + S O2− 4(aq) ⇋ PbS O4(s) + 2H2O(l)
Overall cell reaction during discharge
Pb(s) + PbO2(s) + 2H2S O4(aq) ⇋ 2PbS O4(s) + 2H2O(l)
From the cell reaction it is clear that, PbS O4 is precipitated at both the electrodes and H2S
O4 is used up. As a result, the concentration of H2S O4 decreases. Hence the specific gravity
of H2S O4 falls below 1.2 g/cc. So the battery needs recharging.
Recharging of the Battery
The cell is charged by passing electric current in the opposite direction. The electrode
reaction gets reversed and density of acid increases to 1.2g/cc.
At anode (-ve plate):
2PbS O4(s) + 2H2O ⇋ PbO2(s) + 4H + (aq) + S O2− 4(aq) + 2e –
At cathode (+ve plate):
PbS O4(s) + 2e − ⇋ Pb(s) + S O 2− 4
Overall cell reaction during Charge:
2PbS O4(s) + 2H2O(l) ⇋ Pb(s) + PbO2(s) + 2H2S O4(aq)
Disadvantages of lead-acid batteries
1. Recycling of this battery produces environmental hazards.
2. Mechanical strain and normal bumping reduces battery capacity.
3. It is too heavy for handling.
4. It also leaks at times.
Application
1. The cell is used for automobile starting, lighting and ignition batteries.
2. It is used in large backup power supplies for telephone and computer centers, grid energy
and off-grid household electric power systems.
3. They are used in back-up power supplies for computer systems.
4. They are used as fuel in electric scooters, electric wheel chairs, electrified bicycles, marine
applications, battery electric vehicles or micro hybrid vehicles, and motorcycles.
Applications
1. It is used in calculators, electronic flash units, transistors and cordless appliances.
2. It is used in toys like remote-controlled electric model airplanes, boats, and cars.
3. Larger flooded cells are used for aircraft starting batteries, electric vehicles, and standby
power.
Nickel-Cadmium Battery
 Ni–Cd batteries usually have a metal case with a sealing plate equipped with a self-
sealing safety valve. The positive and negative electrode plates, isolated from each other by
the separator, are rolled in a spiral shape inside the case. This is known as the jelly-roll design
and allows a Ni–Cd cell to deliver a much higher maximum current than an equivalent size
alkaline cell. Alkaline cells have a bobbin construction where the cell casing is filled with
electrolyte and contains a graphite rod which acts as the positive electrode. As a relatively
small area of the electrode is in contact with the electrolyte (as opposed to the jelly-roll
design), the internal resistance for an equivalent sized alkaline cell is higher which limits the
maximum current that can be delivered.

Nickel-Cadmium Cell Battery

The chemical reactions during discharge are:
At cadmium electrode,
Cd + 2OH- Cd(OH)2 + 2e-
At nickel electrode,
2NiO(OH) + 2H2O + 2e 2Ni(OH)2 + 2OH-
The net reaction during discharge is,
2NiO(OH) + Cd + 2H2O 2Ni(OH)2 + Cd(OH)2
During recharge, the reactions go from right to left. It can be used in cordless razors,
ash units and power tools.
Advantages: Lightweight
 Unit – II – Water Technology
Introduction:

Water is the most important compound for the existence of human beings, animals and
plants. About 80% of the earth’s surface is occupied by water. The main sources of
water are
1. rain
2. rivers and lakes (surface water),
3. wells and springs (underground water),
4. sea water.

Among the above sources of water, rain water is the purest form of water but it is very
difficult to collect whereas sea water is the most impure form.

So, surface and underground water are normally used for domestic and industrial
purposes. Such water must be free from undesirable impurities.

The process of removing all types of impurities from water and making it fit for
domestic or industrial purposes is called water technology (or) water treatment.

Before treating the water, we should know the nature as well as the amount of
impurities.

HARD WATER AND SOFT WATER

Hard Water
Water, which does not produce lather with soap solution, but produces white
precipitate (scum) is called hard water.
This is due to the presence of dissolved Ca and Mg salts.

Soft water
 Water, which produces lather readily with soap
solution is called soft water.
  This is due to the absence of Ca and Mg Salts.
HARDNESS OF WATER
 Hardness is the property or characteristics of water, which does not
Produce lather with soap.
How to detect hardness?
 Hardness of water can be detected in two ways.

1.3.1 TYPES OF HARDNESS

o Depending upon the types of dissolved salts present in

water,

hardness of water can be classified into two types

1. Temporary hardness.

2. Permanent hardness.
 1. Temporary Hardness (or) Carbonate Hardness (CH)
(or) Alkaline hardness
 This is due to the presence of bicarbonates of calcium and
magnesium. It can be removed by (i) boiling the water (ii)
adding lime to the water.

 The above two processes convert the bicarbonates

into insoluble carbonates and hydroxides, which can
be removed by filtering.

2. Permanent hardness (or) Non-carbonate hardness (NCH) (or) Non-alkaline

hardness
 This is due to the presence of chlorides and sulphates of calcium
and magnesium. It cannot be removed by boiling the water. But,
it can be removed by
i. Lime-soda process
ii. Zeolite process.

Expression of hardness in terms of equivalents of CaCO3

The concentration of hardness producing salts are usually expressed in terms of an
equivalent amount of CaCO3. CaCO3 is chosen as a standard because,
(i) Its molecular weight (100) and equivalent weight (50) is a whole number, so the
calculations in water analysis can be simplified.
 (ii) It is the most insoluble salt, that can be precipitated in water treatment. If the
concentration of hardness producing salt is x mgs/lit, then
Procedure:
Titration:1
Standardisation of EDTA:

Burette Solution: EDTA

Pipette Solution: 20 ml of standard hardwater + 5 ml of buffer solution
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V1 ml

Titration : 2
Estimation of total hardness:
Burette Solution: EDTA
Pipette Solution: 20 ml of Sample hardwater + 5 ml of buffer solution
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V2 ml

Titration: 3
Estimation of permanent hardness:

Burette Solution: EDTA

Pipette Solution: 20 ml of Boiled hardwater + 5 ml of Ammonical buffer
Indicator : EBT
End point: colour changes from wine red to steel blue

Let the volume of EDTA consumed be V3 ml

Boiler Feed Water
The water fed into the boiler for the production of steam is called boiler feed water.
Boiler feed water should be free from turbidity, oil, dissolved gases, alkali and hardness
causing substances. If hard water obtained from natural sources is fed directly into the
boilers, the following troubles may arise.

1. Formation of Scales and sludges in boilers.

2. Priming and foaming (carry over).
3. Caustic embrittlement.
4. Boiler corrosion.

Formation of Scales and Sludges in boilers

When water is continuously converted into steam in boilers (or) heat exchangers, the
concentration of dissolved salts in water increases progressively. When the
concentration of the salts reaches their saturation point, they are thrown out in the form
of precipitates on the inner walls of the boilers (or) heat exchangers. The least soluble
one gets precipitated first.
Sludge:
If the precipitate is loose and slimy it is called sludge. Sludges are formed by the
substances like MgCl2, MgCO3, MgSO4 and CaCl2. They have greater solubilities in hot
water than cold water.
Scale:
On the other hand, if the precipitate forms hard and adherent coating on the inner
walls of the boiler, it is called scale. Scales are formed by substances like Ca(HCO3)2,
CaSO4 and Mg(OH)2

Comparison of Scales and Sludges

S.No Sludge Scale

1. Sludge is a loose, slimy and Scale is a hard, adherent coating
non-adherent precipitate
2. The main sludge forming The main scale forming substances are
substances are MgCO3, MgCl2, Ca(HCO3)2, CaSO4, Mg(OH)2
MgSO4 and CaCl2 etc
3. Disadvantages : Disadvantages:
Sludges are poor conductors of Scales act as thermal insulators. It decreases
heat. Excess of sludge the efficiency of boiler. Any crack developed
formation decrease the on the scale, leads to explosion
 efficiency of boiler
4. Prevention: Prevention:
(i) Sludge formation can be (i) Scale formation can be prevented by
prevented by using softened dissolving using acids like HCl, H2SO4
water
(ii) Sludges can also be removed (ii) Scale formation can be removed by
by “blow-down operation”. (a) External treatment
(b) Internal treatment
(iii) Blow-down operation is a (iii) They can also be removed by applying
process of removing a portion thermal shocks, scrapers, wire brush etc.
of concentrated water by fresh
water frequently from the
boiler during steam production

2. Priming and Foaming (Carry over)

During the production of steam in the boiler, due to rapid boiling, some droplets of
liquid water are carried along with steam. Steam containing droplets of liquid water is called
Wet steam. These droplets of liquid water carry with them some dissolved salts and
suspended impurities. This phenomenon is called carry over. It occurs due to priming and
foaming.
Priming:
Priming is the process of production of wet steam.
Priming is caused by
(i) High steam velocity
(ii) Very high water level in the boiler
(iii) Sudden boiling of water
(iv)Very poor boiler design
Priming can be controlled by
(i) Controlling the velocity of steam
(ii) Keeping the water level lower
(iii) Modified boiler design
(iv) Using treated water
Foaming:
 The formation of stable bubbles above the surface of water is called foaming. These
bubbles are carried over by steam leading to excessive priming. Foaming is caused by the
presence oil, grease and finely divided particles.
Foaming can be prevented by
(i) Adding coagulants like sodium aluminates, aluminium hydroxide
(ii) Adding anti foaming agents like synthetic polyamides.
Caustic embrittlement
Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler water
usually contains a small proportion of Na2CO3. In high pressure boilers this Na2CO3
undergoes decomposition to give NaOH.
Na2CO3 + H2O 2NaOH + CO2
This NaOH flows into the minute hair cracks and crevices usually present in the boiler
material by capillary action and dissolve the surrounding area of iron as sodium ferrate.
Fe + 2NaOH Na2FeO2 + H2↑
This causes embrittlement of boiler parts, particularly stressed parts like bends, joints,
rivets etc., causing even failure of the boiler.
Prevention
Caustic embrittlement can be prevented by
(i) Using sodium phosphate as softening agent instead of sodium carbonate
(ii) By adding tanning, lignin to the boiler water, which blocks the hair cracks.
4. Boiler corrosion
Corrosion in boiler is due to the presence of
1. Dissolved oxygen
2. Dissolved Carbon dioxide
3. Dissolved salts
(i) Dissolved oxygen:
The dissolved oxygen in water attacks the boiler material at higher temperature.
Dissolved oxygen can be removed by chemical or mechanical methods
4Fe + 2H2O + O2 4Fe (OH)3↓
(a) Chemical method
Sodium sulphite and hydrazine are some of the chemical used for removing oxygen.
2Na2SO3 +O2 2Na2SO4
N2H4+O2 N2 + 2H2O
(b) Mechanical de-aeration
 Dissolved oxygen can also be removed from water by mechanical de-aeration. (In
Figure) In this process, water is allowed to fall slowly on the perforated plates fitted inside
the tower. The sides of the tower are heated, and a vacuum pump is also attached to it. The
high temperature and low pressure produced inside the tower reduce the dissolved oxygen
content of the water.

(ii) Dissolved carbon dioxide

Dissolved carbon dioxide in water produces carbonic acid, which is acidic and
corrosive in nature.
CO2 + H2O H2CO3
Carbon dioxide gas is also produced from the decomposition of bicarbonate salts
present in water.
∆
Ca(OH3)2 CaCO3↓ + H2O + CO2↑
Removal of dissolved Carbon dioxide
(a) Carbon dioxide can be removed from water by adding a calculated amount of
NH4OH into water.
2NH4OH + CO2 (NH4)2CO3 + H2O
(b) Carbon dioxide along with oxygen can also be removed mechanically by de-aeration
method.

(iii) Dissolved MgCl2

Acids produced from salts dissolved in water are also mainly responsible for the
corrosion of boilers. Salts like MgCl2, CaCl2 etc, undergo hydrolysis at higher temperature to
give HCl, which corrode the boiler.
MgCl2 + 2H2O Mg(OH)2↓ + 2HCl
 Fe + 2HCl FeCl2 + H 2↑
FeCl2 + 2H2O Fe(OH)2 + 2HCl
Removal of acids
Corrosion by acids can be avoided by the addition of alkali to the boiler water
HCl + NaOH NaCl + H2O
2.1.3. Softening methods
Water used for industrial purposes should be free from hardness producing
substances, suspended impurities and dissolved gases etc. The process of removing hardness
producing salts from water is known as softening of water.
Softening of water can be done in two methods
1. Internal treatment
2. External treatment
External treatment
It involves the removal of hardness producing salts from the water before feeding in
to the boiler. The external treatment can be done by the following methods.
i. Zeolite or Permutit process
ii. Demineralisation or Ion – exchange process
i. Zeolite or permutit process:
Zeolites are naturally occurring hydrated sodium aluminoSilicate. Its general formula
is Na2O. Al2O3. xSiO2. yH2O. (x = 2 – 10, y = 2- 6). Natural zeolites are green sand and non-
porous. The synthetic form of Zeolite is known as permutit, which is porous and possess gel
structure, hence it is generally used for water softening. Synthetic zeolite is represented by
Na2Ze. The sodium ions which are loosely held in Na2Ze are replaced by Ca2+ and Mg2+ ions
present in the water.
Process
When hard water is passed through a bed of sodium zeolite (Na2Ze), kept in a cylinder
(Fig), it exchanges its sodium ions with Ca2+ and Mg2+ ions present in the hard water to form
calcium and magnesium zeolite. The various reactions taking place during softening process
are
CaCl2 + Na2Ze CaZe + 2NaCl
CaSO4+ Na2Ze CaZe + Na2SO4
Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3
CaCl2 + Na2Ze CaZe + 2NaCl
MgCl2+ Na2Ze MgZe+ 2NaCl
 Mg (HCO3)2 + Na2Ze CaZe + 2MgHCO3

Zeolite process
The softened water is enriched with large amount of sodium salts, which do not cause
any hardness, but cannot be used in boilers.
Regeneration process:
After some time zeolite gets exhausted. The exhausted zeolite is again regenerated by
treating with 10% solution of NaCl.
CaZe + NaCl Na2Ze + CaCl2
MgZe + NaCl Na2Ze + MgCl2
Advantages:
1. It reduces hardness up to 10ppm
2. The equipment is quit compact.
3. Less time for softening.
4. Its operation is easy.
5. No sludge is formed during this process.

Disadvantages:
1. The treated water containing sodium ions, which cannot be used as boiler feed water.
2. Highly turbid water cannot be treated by this method. Because it blocks the pores of the
Zeolite bed.
3. Acidic water cannot be treated, because it decomposes the structure of Zeolite.
4. This process cannot be used for softening brackish water, because brackish water contains
Na+ ions. So the ion exchange reaction will not occur.
5. Water containing Fe, Mn cannot be treated, because regeneration is very difficult.
ii. Ion-exchange or demineralization process
This process removes almost all the ions (both anions and cations) present in the hard
water. The soft water, produced by lime-soda and zeolite processes, does not contain
hardness producing Ca2+ and Mg2+ ions, but it will contain other ions like Na+, K+, SO24-, Cl-
etc. on the other hand D.M. (Demineralised) water does not contain both anions and cations.
Thus a soft water is not demineralised water whereas demineralised water is soft water.
This process carried out by using ion exchange resins, which are insoluble, cross-
linked, long chain organic polymers with a micro porous structure and the “functional
groups” attached to the chains are responsible for the ion-exchanging properties.
Cation exchanger:
Resins containing acidic functional groups (-COOH, -SO3H, etc.) are capable of
exchanging their H+ ions with other cations of hard water. Cation exchange resin is
represented as RH2.
Example
1. Sulphonated coals
2. Sulphonated poly styrene
Anion exchanger:
Resins containing basic functional groups (-NH2, -OH, etc.) are capable of
exchanging their anions with other anions of hard water. Anion exchange resin is represented
as R(OH)2.
Example
1. Cross linked quaternary ammonium salts
2. Urea-formaldehyde resin.
Process
The hard water first passed through a cation exchange column, (Fig) which absorbs all
the cations like Na+, K+, SO24-, Cl-+, etc., present in the hard water.
  The water coming out of the anion exchanger is completely
f ree f rom cations and anions. This water is known as demineralised
water or deionised water.
Sri Krishna Hitech Publishing Com pany Pvt. Ltd.

Demineralization process
RH2 + CaCl2 RCa + 2HCl
RH2 + MgSO4 RCa + 2HCl
RH + NaCl RNa + HCl
The cation free water is then passed through an anion exchange column, which
absorbs all the anions like Cl-, SO42-, HCO3- etc., present in the water.
R’(OH)2 +2HCl R’Cl2 + 2H2O
R’(OH)2 +2H2SO4 R’SO4 + 2H2O
The water coming out of the anion exchanger is completely free from cations, anions
and gases. This water is known as demineralised or deionised water.
Regeneration of resin:
When the cation exchange resin is exhausted, it can be regenerated by passing a
solution of dil.HCl or dil.H2SO4.
RCa + 2HCl RH2 + CaCl2
RNa2 + HCl RH2 + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated by
passing a solution of dil.NaOH.
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl
Advantages:
It produces very pure water of hardness nearly 2ppm.
Highly acidic or alkaline water can be treated by this process.
The softened water is completely free from any salts and fit for use as boiler feed water.
Disadvantages:
1. The equipment is little expensive.
2. This process can not treat highly turbid water.
Comparison between zeolite and ion-exchange process
S.No. Zeolite process Ion-exchange process
1. Only cations are exchanged Cations and anions are removed.
2. Acidic water cannot be treated. Acidic water can be treated.
3. Zero hardness cannot be achieved. Zero hardness can be achieved.
Treated water has more sodium
4. Water is free from sodium ions.
ions.

2.1.4. Domestic water treatment:

Municipal water supply has been one of the most challenging problems of water
technology. Water supplied by municipalities or corporation must be free from pathogenic
bacteria, dissolved salt, suspended impurities, colour and odour. It must be clear and pleasant
taste.
Generally, the treatment of this water involves removal of suspended impurities and
colloidal impurities and microbes. Hence domestic supply of water involves the following
purification processes.
Purification of water:
1. Screening
2. Aeration
3. Sedimentation
4. Coagulation
5. Filtration
6. Sterilisation
1. Screening:
It is a process of removing the floating materials like leaves, wood pieces etc. from
water. The raw water is allowed to pass through a screen, having large number of holes,
which retains the floating materials and allows the water to pass.
2. Aeration
The process of mixing water with air is known as aeration. The main purpose of
aeration is,
(i) To remove gases like CO2, H2S and other volatile impurities causing bad taste and odour.
(ii) To remove ferrous and manganous salts as insoluble ferric and manganic salts.
3. Sedimentation:
Sedimentation is the process of removing the sludge and other solid impurities by
allowing the water to stay undisturbed for few days. Different kinds of sedimentation tanks
are used for the settling of solid impurities.
In the horizontal flow tank the water is released at the bottom of the tank where it has
to come through a series of constricted walls. The solid materials automatically settle down.
The water at the top of the other end of the tank is free from suspended impurities.
There are other kinds of sedimentation tanks like ‘radial flow circular tank’ and
‘vertical flow hopper bottom tank’ which can be effectively used to remove the suspended
impurities.
4. Coagulation:
Finely divided clay, silica etc. do not settle down easily and hence cannot be removed
by sedimentation. Such impurities are removed by coagulation method.
In this method certain chemicals called coagulants like alum, Al2(SO4)3 etc., are
added to water. When the Al2(SO4)3 is added to water, it gets hydrolysed to form a gelatinous
precipitate of Al(OH)3. The gelatinous precipitate of Al(OH)3 entraps the finely divided and
colloidal impurities, settles to the bottom and can be removed easily.
5. Filtration: It is the process of removing bacteria, colour, taste, odour and suspended
particles, etc. by passing the water through filter beds containing fine sand, coarse sand and
gravel.
The sand filter consists of a tank containing a thick top layer of fine sand followed by
coarse sand, fine gravel and coarse gravel. When the water passes through the filtering
medium, it flows through the various beds slowly. The rate of filtration decreases slowly due
to the clogging of impurities in the pores of the sand bed. When the rate of filtration becomes
very slow, the filtration is stopped and the thick top layer of fine sand is scrapped off and
replaced with clean sand. Bacteria are also partly removed by this process.
6. Sterilisation or Disinfection
The process of destroying the harmful bacteria is known as sterilization or
disinfection. The chemicals used for this purpose are called disinfectants. This process can
be carried out by the following methods.
(a) By Boiling
When water is boiled for 10-15 minutes, all the harmful bacteria are killed and water
becomes safe for use. Disadvantages of boiling are
(i) Boiling alters the taste of drinking water
(ii) It is impossible to employ it in municipal water-works.

(b) By using Ozone

Ozone is a powerful disinfectant and is readily absorbed by water. Ozone is highly
unstable and breaks down to give nascent oxygen.
O3 O2 + [O]
The nascent oxygen is a powerful oxidizing agent and kills the bacteria.
Disadvantages of this process are
(i) This process is costly and cannot be used in large scale
(ii) Ozone is unstable and cannot be stored for long time.
(c) By Using Ultraviolet Radiations
UV rays are produced by passing electric current through mercury vapour lamp. This
is particularly useful for sterilizing water in swimming pool.
Disadvantages
(i) It is costly
(ii) Turbid water cannot be treated
(d) By Chlorination
The process of adding chlorine to water is called chlorination. Chlorination can be
done by the following methods.
(i) By adding chlorine gas:
Chlorine gas can be bubbled in the water as a very good disinfectant.
(ii) By Adding Chloramine:
When chlorine and ammonia are mixed in the ratio 2:1 compound chloramines is
formed.
Cl2 + NH3 ClNH2 + HCl
Chloramine compounds decompose slowly to give chlorine. It is a better disinfectant
than chlorine.
(iii) By adding bleaching powder: When bleaching powder is added to water, it produces
hypochlorous acid (HOCl). HOCl is a powerful germicide.
CaOCl2 + H2O Ca(OH)2 + Cl2
Bleaching powder
Cl2 + H2O HCl + HOCl
HOCl + Bacteria Bacteria are killed
Break point chlorination
Water contains the following impurities
(i) Bacteria
(ii) Organic impurities
(iii) Reducing substances (Fe2+, H2S etc)
(iv) Free ammonia
Chlorine may be added to water directly as a gas or in the form of bleaching powder.
When chlorine is applied to water, the results obtained can be depicted graphically in the
following fig. The graph shows the relationship between the amount of chlorine added to
water and the residual chlorine.
It is seen from the graph that initially the applied chlorine is used to kill the bacteria and
oxidizes all the reducing substances present in the water and there is no free residual chlorine.
As the amount of applied chlorine increases, the amount of combined residual
chlorine also increases. This is due to the formation of chloramines and other chloro
compound.
At one point, on further chlorination, the oxidation of chloramines and other
impurities starts and there is a fall in the combined residual chlorine content. Thus the
combined residual chlorine decreases to minimum point at which oxidation of chloramines
and other impurities complete and free residual chlorine begins to appear this minimum point
is known as “break point chlorination”.

Thus, the break point chlorination eliminates bacteria, reducing substances, organic
substances responsible for the bad taste and odour, from the water.

Advantages of break – point chlorination

1. It oxidizes completely organic compounds, ammonia and other reducing compounds.
2. It removes colour in water, due to the presence of organic matters.
3. It destroys completely (100%) all the disease – producing bacteria.
4. It removes both odour and taste from the water.
5. It prevents the growth of any weed in water.
2.1.5. Desalination of brackish water
Removal of common salt from sea water is known as desalination process. The water
containing dissolved salts with a peculiar salty or brackish taste is called brackish water.
Sea water or brackish water can be made available as drinking water through
desalination process. Desalination process can be carried out by reverse osmosis,
electrodialysis, solar distillation, freezing etc. The successful methods are reverse osmosis
and electrodialysis.
Electrodialysis:
Principle:
Electrodialysis is the process of separating ions of the salt from the salt water through
ion-selective membranes by passing direct current.
Description:
 An electrodialysis cell consists of alternate cation (C) and anion (A) selective
membranes. An ion selective membrane has permeability for only one kind of ions with
specific charge. Therefore cation selective membrane is permeable to cations only but not to
anions while anion selective membrane is permeable to anions only but not to cations. The
cathode is placed near the cation selective membrane and the anode is placed near the anion
selective membrane.
Process
Saline water is fed into the electrodialysis cell and direct current is applied through
the electrodes perpendicular to the direction of water flow. As the current passes through the
electrodes, from the centre compartment cations (Na+) move towards the cathode through
cation selective membrane (C) and anions (Cl-) move towards the anode through anion
selective membrane (A). The net result is the decrease of ions (salt) from the centre
compartment while the concentration of ions (Salt) in the adjacent compartments is increased.
Now the centre compartment is filled with pure water and the other compartments are filled
with concentrated brine solution. Thus, the salinity is removed from salt water.

Electrodialysis
Examples for ion selective membranes
Cation selective membrane – Poly styrene containing sulphonic acid group
Anion selective membrane – Poly styrene containing tetra ammonium chloride
Advantages:
(i) It is the most compact unit, the cost of installation and operation is economical.
(ii) If electricity is easily available, this process is best suited.
Reverse osmosis:
 When solutions of different concentrations are separated by a semi-permeable
membrane, solvent flows from a region of lower concentration to higher concentration.
This process is called osmosis. The driving force in this phenomenon is called osmotic
pressure.
If a hydrostatic pressure in excess of osmotic pressure is applied on the higher
concentration side, the solvent flow is reversed. i.e., solvent flows from higher
concentration to lower concentration. This process is called reverse osmosis. Thus, in the
process of reverse osmosis pure water is separated from salt water. This process is also
known as super – filtration. The membranes used are cellulose acetate, cellulose butrate etc.

Reverse Osmosis
Advantages:
1. The life time of the membrane is high and it can be replaced easily.
2. It removes ionic as well as non – ionic and colloidal impurities.
3. Due to low capital cost, simplicity, low operating, this process is used for converting
sea water in to drinking water.
CORROSION
2.2. Introduction:
Most metals (with the exception of noble metal such as Au, Pt etc) exist in nature in
combined forms as their oxides, carbonates, hydroxyl carbonates, sulphides, chlorides and
silicates. These are reduced to their metallic state from their ores, during their extraction
processes. Hence, when metals are put in to use, in various forms, they are exposed to
environment; the exposed metal surfaces begin to decay more or less rapidly, when they
come in contact with gaseous and / or liquid environment.
Metals and alloys are generally used as fabrication or construction materials in
engineering. If the metal or alloy structures are not properly maintained, they deteriorate
slowly by the action of atmospheric gases, moisture and other chemicals. This phenomenon
of deterioration or destruction of metals and alloys is known as corrosion.
Definition
 “Corrosion is defined as the gradual destruction or deterioration of metals or alloys
by the chemical or electrochemical reaction with its environment”.
Consequences of corrosion
1. Plant shut – down
2. Replacement of corroded equipment
3. Preventive maintenance
4. Necessity for over design to allow for corrosion
5. Loss of efficiency
6. Contamination or loss of the product
7. Safety
8. Health
Cause of corrosion:
Metals in the uncombined condition have higher energy and are in an unstable state. It
is their natural tendency to go back to the low energy state, i.e. combined state by
recombining with the elements present in the environment. This is the main reason for
corrosion.
2.2.1 Principles of corrosion:
Acid theory
This theory suggests that the presence of acids (such as carbonic acids) is essential for
corrosion.
This acid theory is particularly applicable to rusting of iron in the atmosphere.
According to this theory, rusting of iron is due to the combined action of moisture, O2 and
CO2 on iron converting the metal into ferrous bicarbonate which is further oxidised to basic
ferric carbonate and finally to hydrated ferric oxide.
2Fe + O2 + 4CO2 + 2H2O 2Fe(HCO3)2
4Fe(HCO3)2 + O2 4Fe(OH)CO3 + 4CO2 + H2O
2Fe(OH)CO3 + 2H2O Fe2O3.3H2O + 2CO2
The acid theory is supported by the fact that rust analysis generally shows the
presence of ferrous and ferric carbonates along with hydrated ferric oxide.
Classification of corrosion
On the basis of medium attack, corrosion can be classified in to two types.
(i) Chemical or Dry corrosion
(ii) Electrochemical or Wet corrosion
(i) Direct chemical attack or chemical or dry corrosion:
 Dry corrosion is due to the attack of metal surfaces by the atmospheric gases such as
O2, H2S, N2, SO2 etc. in the dry environment.
There are three main types of dry corrosion
(a) Oxidation corrosion or corrosion by oxygen
(b) Liquid - Metal corrosion
(c) Corrosion by other gases
(a) Oxidation corrosion or corrosion by oxygen
Oxidation corrosion is brought about by the direct action of oxygen at low or high
temperatures on metal surface in the absence of moisture. Alkali metals (Li, Na, K etc) and
alkaline – earth metals (Mg, Ca, Sn etc) are rapidly oxidized at low temperature, almost all
metals (except, Ag, Au and Pt) are oxidized.
Mechanism of corrosion
Step; 1 Oxidation occurs first at the surface of the metal resulting in the formation of metal
ions (M2+) which occurs at the metal / oxide interface
M M2++2e-
Step; 2
Oxygen changes to ionic form (O2-) due to the transfer of electron from metal, which
occurs at the oxides film / environment interface.
1/2O2+2e- O2-
Step; 3
Oxide ions react with the metal ion to form the metal / oxide film.
M+1/2O2- M2++O2- ≡ MO (Metal – Oxide film)
Once the metal surface is converted to a monolayer of metal – oxide, for further
corrosion (oxidation) to occur, the metal ion diffuses outward through the metal –oxide
barrier. Thus the growth of oxide film commences perpendicular to the metal surface.
Oxidation corrosion is depends on the nature of oxide film.
Nature of oxide film
The nature of oxide film formed on the metal surface plays an important role in
oxidation corrosion.
(1) Stable oxide layer
A stable oxide layer is a fine grained in structure, and get adsorbed tightly to the metal
surface. Such a layer is impervious in nature and stops further oxygen attack through
diffusion. Such a film behaves as a protective coating and no further corrosion can develop.
Example
Oxide of Al, Sn, Cu
(2) Unstable oxide layer
Unstable oxide layer is mainly produced on the surface of noble metals, which
decomposes back in to the metal and oxygen.
Metal oxide Metal+Oxide
Example: Oxide of Pt, Ag etc.
(3) Volatile oxide layer
The oxide layer volatilizes as soon as it is formed, leaving the metal surface for
further corrosion.
Example: MoO3 (Molybdum oxide)

(4) Porous oxide layer

In this case, further corrosion is possible through pore or cracks of the metal oxide.
Example: Oxide of Fe
Pilling Bedworth rule / Protective or Non – productive oxide film
The volume of the oxide layer formed is less than the volume of the metal; the oxide
layer is porous or non-protective.
Example:
The volume of oxides of alkali and alkaline earth metals such as Na, Mg, Ca etc., is
less than the volume of the metal consumed. Hence the oxide layer formed is porous and
non-protective.
On the other hand, if the volume of the oxide layer formed is greater than the volume
of the metal, the oxide layer is non-porous and protective. For example, the volume of oxides
of heavy metals such as Pb, Sn etc., is greater than the volume of the metal. Hence, the oxide
layer formed is non-porous and protective.
Pilling – Bed worth ratio
The ratio of the volume of the oxide formed to the volume of the metal consumed is
called Pilling – Bed worth ratio.
(b) Liquid – Metal corrosion
This is due to the chemical action of flowing liquid metal at high temperature. The
corrosion reaction involve,
1. Either dissolution of a solid metal by a liquid metal
2. Liquid metal may penetrate in to the solid metal
(c) Corrosion by other gases
 Besides oxygen, the dry corrosion is caused by CO2, Cl2, SO2, F2 etc. The extent of
corrosion effect depends on the chemical affinity between the metal and the gases involved.
The gases chemically react with the meal surface forming either the protective oxide
layer or the porous or volatile oxide layer which are non – protective.
Example: Hydrogen corrosion or Hydrogen embrittlement
When metals contact to H2S at ordinary temperature causes evolution of atomic
hydrogen.
Fe+H2S FeS +2H
This atomic hydrogen diffuses readily in to the metal and collects in the voids, where
it recombines to form molecular hydrogen.
H+H H2↑
Collection of these hydrogen gases in the voids develops very high pressure, which
causes cracks and blisters on metal. This process is called hydrogen embrittlement.

(ii) Electrochemical theory or wet corrosion:

This type of corrosion where the conducting electrolytic liquid is contact with metal
or two dissimilar metals or alloy is called electrochemical corrosion.
One part of the metal becomes anode, another cathode. Anodic metal oxidation, takes
place with the liberation of electron where the actual corrosion takes place. Cathodic metal
reduction takes place, with the absorption of electron liberated from the anode.
The main basis of electrochemical corrosion involves the formation of anodic and
cathodic parts in the contact with each other through the presence of a conducting electrolyte
media.
Mechanisms of wet corrosion
Under the above conditions, one part of the metal becomes anode and another part as
cathode
(i) At anode
In anodic part, oxidation or dissolution of metal occurs.
M M2++2e-
(ii) At cathode
In cathodic part reduction reaction occurs, which depends on nature of the corrosive
environment.
1. Acidic environment
 If the corrosive environment is acidic, hydrogen evolution occurs at cathodic part.
2H++2e- H2↑
2. Neutral environment
If the corrosive environment is slightly alkaline or neutral, OH- ion forms at cathodic
part.
1/2O2+ 2e-+H2O 2OH-
Thus, the metal ion (from anodic part) and non – metallic ion (from cathodic part)
diffuse towards each other through conducting medium and form a corrosion product
between anode and cathode.
Galvanic Corrosion
When two different metals are in contact with each other in presence of an aqueous
solution or moisture, galvanic corrosion occurs.
The more active metal (with more –ve electrode potential) acts as anode and the less
active metal (with less –ve electrode potential) acts as cathode.
Fig (a) represents Zn-Fe couple, in which Zn (more active or higher in Emf series)
dissolves in preference to iron (less active metal). i.e., Zn acts as anode and undergoes
corrosion and Fe acts as cathode.

Fig (b) represents Fe – Cu couple, in which iron (more active, when compared to Cu)
dissolves in preference to copper (less active) i.e., Fe acts as anode and undergoes corrosion
and Cu acts as cathode.
Example
(i) Steel screw in a brass marine hardware corrodes.
(ii) Bolt and nut made of same metal is preferred.
Prevention:
Galvanic corrosion can be minimized by providing insulating material between the
two metals.
Differential aeration or concentration cell corrosion:
This type of corrosion occurs when a metal is exposed to varying concentration of
oxygen or any electrolyte on the surface of the base metal.
Example:
Metals partially immersed in water or conducting solution (called water line
corrosion).
If the metal is partially immersed in a conducting solution (in Fig) the metal part
above the solution is more aerated and hence become cathodic. On the other hand, the metal
part inside the solution is less aerated and thus, become anodic and suffers corrosion. A good
example of this kind is a metal like zinc partially dipped in a brackish solution (NaCl + H2O).
The zinc rod above the solution is more strongly oxygenated and hence is a cathode.
On the other hand the zinc rod dipped inside the solution have less access to oxygen and the
poorly oxygenated area acts as an anode. Hence a difference of potential is developed on the
same metal and the flow of electrons takes place from anode producing metal ions or
corrosion.
At anode (less aerated) corrosion occurs
Zn Zn2++2e-
At cathode (more aerated part) OH- ions are produced
1/2O2+ 2e-+H2O 2OH-
 Differential aeration or concentration cell corrosion
Examples for this type of corrosion are
Pitting or localized corrosion
Crevice corrosion
Pipeline corrosion
Corrosion on wire fence
2.2.2. Factors influencing corrosion
Corrosion is a kind of reaction that takes place in the metal by the influence of its
environment. Hence both the nature of the metal and the environment play equal part in the
corrosion of the metal. The following are the factors responsible for the corrosion.
1. Nature of the metal
(i) Position in the galvanic series - Metals higher in the electrochemical or galvanic series
(positive values of electrode potential compared with hydrogen) are less prone to corrosion.
(ii) Relative areas of the anode and cathode - When two different metals are in contact, the
corrosion in the anodic area is directly proportional to the areas of cathode and anode.
Corrosion will be severe if the anodic area is smaller and cathodic area is large. The larger
cathodic area of the cathode will create a great demand of electron which can be met by the
smaller area of the anode only by undergoing more corrosion.
(iii) Over potential - The increase of corrosion is related to decease in hydrogen over
potential. The normal hydrogen over potential of zinc metal when it is dipped in 1M
sulphuric acid is 0.7 volt. By adding few amount of copper sulphate to zinc metal directly, the
hydrogen over voltage is reduced to 0.33 and the increase of the dissolution of the metal (or
corrosion) takes place.
(iv) Purity of metals - Impurities present in the pure metal creates heterogeneity. It causes
galvanic cell type corrosion.
(v) Physical state of metals - Metal parts under stress can become anodes and undergo stress
corrosion. Also the smaller grain size of the metal or its alloy can undergo corrosion easily
since the solubility of the metal is high.
(vi) Nature of the surface film - Metals like Mg, Fe etc form oxides whose specific volume
is less than the volume of the metal. Hence the oxide film formed will be porous and mere
oxygen diffuses through the pores to bring about more corrosion.

Metals like Al, Cr, Ni, W etc form oxides whose specific volume is greater than that
of the metal. Hence the oxide film once formed is compact and impervious for further
diffusion of oxygen through the oxide film and corrosion is prevented.
(vii) Nature of corrosion product If the corrosion product is soluble in the corroding
medium, then further corrosion takes place. On the other hand if the corrosion product is
insoluble (eg. PbSO4), it acts as a barrier between the metal and environment and stops
further corrosion.
Volatile metal oxide film also can produce further corrosion. For example
molybdenum metal forms MoO3 when exposed to atmosphere, molybdenum oxide layer
voltalises immediately and fresh attack of oxygen corrosion continues on the metal.
2. Nature of the environment
(i) Temperature
Increase in temperature increases the reaction rate as well as the diffusion rate so
naturally the rate of corrosion is increased.
(ii) Humidity
Humidity of air is directly related to the corrosion rate. Critical humidity is the relative
humidity above which the atmospheric corrosion rate of the metal increases sharply. The
basic principle of enhancement of corrosion in humid conditions is that atmospheric gases
like CO2, O2 etc., and dissolves in water to produce the electrolyte which is essential for
electrochemical corrosion.
(iii) Presence of corrosive gases
In industrial areas atmosphere is polluted with acidic gases like CO2, SO2, H2S and
fumes of HCl, H2SO4 etc., These gases produces electrolyte which are acidic and increases
the electrochemical corrosion. Similarly in the marine atmosphere, the electrolyte produced
will have more chloride ions (Cl-) which increases the corrosion rate.
(iv) Presence of solid suspended particles or compounds
Particles like NaCl, (NH4)2SO4 along with moisture act as powerful electrolyte and
enhances the electrochemical corrosion.
(v) Effect of pH
Generally acidic medium is more corrosive than alkaline medium. The corrosion of iron
in oxygen free water is very slow up to pH = 5. But in presence of oxygen the corrosion rate
of iron is very high at pH = 5. But at pH = 4 the corrosion rate of iron is considerably
increased due to the change in oxidation states of iron from Fe2+ to Fe3+. Zinc which is
readily corroded in acidic solution suffers very less corrosion in alkaline medium i.e., pH =
11 aluminium has less corrosion at pH = 5.5 while corrodes rapidly at pH = 8.5.
(vi) Nature of ions present
Anions like silicates in the presence of medium leads to the formation of insoluble
reaction products which stops further corrosion. Whereas the chloride ions (Cl-) in the
medium destroy the protective oxide film and expose the metal for further corrosion.
(vii) Formation of oxygen concentration cell
Increase in oxygen in one part of the metal which becomes cathodic and the less
oxygenated part becomes anodic and the oxygen concentration cell is set up resulting, in
corrosion. This is explained by the reaction.
1/2O2+ 4e-+H2O 4OH- (Cathodic reaction)
The reaction takes place with more oxygen concentration (Cathodic reaction)
Fe Fe2++2e-
This reaction causes the ionization of the metal. i.e., corrosion in the anodic region
where there is less oxygen concentration.
Corrosion of buried pipelines, cables etc. passing from one kind of soil to another are
due to the differential aeration in the soil.
2.2.3 Corrosion control methods
Corrosion is a process very harmful for the metals or alloys. Since the metals and
alloys disintegrated or wasted every year through corrosion costs a huge amount. It is
necessary to protect the metals or alloys against corrosion. A few methods of corrosion
control are given below.
1. Proper designing
It is necessary that before the fabrication of machine parts or equipment, proper
selection of metal or alloy and the design part of the engineering system have to be properly
studied according to the environmental conditions.
Important design principles are:
(i) “Avoid the contact of dissimilar metals in the presence of a corroding solution”: If
this principle is not followed, then corrosion is localized on the more active metal
(in the immediate vicinity of contact); while the less active metal remains
protected.
(ii) When two dissimilar metals are to be in contact, the anodic material should have
as large area as possible; whereas the cathodic metal should have as much
smaller are as possible.
(iii) If two dissimilar metals in contact have to be used, they should be as close as
possible to each other in the electrochemical series.
(iv) Whenever the direct joining of dissimilar metals, is unavoidable, an insulating
fitting may be applied in between them to avoid direct metal – metal electrical
contact.
(v) The anodic metal should not be painted or coated, when in contact with a
dissimilar cathodic meal, because any break in coating would lead to rapid
localized corrosion.
(vi) It is desirable that the design allows for adequate cleaning and flushing of the
critical parts (i.e., susceptible to dirt, deposition, etc.) of the equipment. Sharp
corners and recesses should be avoided, because they favour the formation of
stagment areas and accumulation of solids, etc.
(vii) Uniform flow of corrosion liquid is desirable, since both stagnant areas and highly
turbulent flow and high velocities can cause accelerated corrosion. So, it is
practically possible.
(viii) A proper design should prevent condition subjecting some areas of structure to
stress (cold – worked part). Such an area could set up a galvanic couple with non
– stressed (not worked) areas of the metal.
2. Use of pure metals
Impurity metal present in the base metal can act as anode and produces
electrochemical corrosion. Purification of metals like Al, Mg etc. makes them corrosion
resistant by its impervious oxide film formation. But the production of purer metals is costly
as well as the metal looses some of its mechanical properties.
3. By cathodic protection
The principle of this method is that the base metal to be protected turn into cathode by
connecting it to a powerful anode metal plate. There are two kinds of it.
(i) Sacrificial anodic protection
The metallic structure to be protected is connected through a metallic wire to a more
anodic metal. So that all the corrosion will takes place only on the anodic metal. The
artificially made anode thus gradually gets corroded protecting the original metallic structure.
And hence this process is otherwise known as sacrificial anodic protection. Metals commonly
used as sacrificial anodes are Al, Zn, Mg and their alloys.

Sacrificial anodic protection

 This method is used for the protection of ships and boats. Sheets of Mg or Zn are hull
of the ship as in figure. Zn or Mg will act as anode compared to iron (ship or boat is made of
iron), so corrosion concentrates on Zn or Mg. Since they are sacrificed in the process of
saving iron, they are called sacrificial anodes.
Application
1. This method is used for the protection of ships and boats.
2. Sheets of Mg or Zn are hung around the hull of the ship.
3. Copper metal is employed to minimize engine corrosion.
(ii) Impressed current cathodic protection
In this method, an impressed current is applied in the opposite direction of the
corrosion current to nullify it and the corroding metal is converted from anode to cathode.
This can be done by connecting –ve terminal of the battery to the metallic structure to
be protected and +ve terminal of the battery is connected to an inert anode. Inert anodes used
for this purpose are graphite, platinised titanium.
The anode is buried in a ‘‘back fill’’ (containing mixture of gypsum, coke, breeze,
sodium sulphite). The ‘‘back fill’’ provides good electrical contact to anode.

Impressed current cathodic protection

Applications of impressed current protection
1. Structures like tanks, pipelines, transmission line towers and laid – up strips etc.
2. Underground water pipe lines, oil pipelines, ships etc can be protected by this
method.