CHAPTER 3

Corrosion

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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.”

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Metals occur in nature in two different forms.
1. Native state.
2. Combined state.

1. Native state
The metals occur in native (or) free (or) uncombined
state are non-reactive with the environment. They are noble
metals exist as such in the earth crust. They have very good
corrosion resistance.
Example:
Au, Pt, Ag
3.2 Engineering Chemistry

2. Combined state
Except noble metals, all other metals are reactive and
react with environment and form stable compounds, as their
oxides, sulphides, chlorides and carbonates. They exist in
their form of stable compounds called ores and minerals.
Example:
Fe 2O3, ZnO, PbS, CaCO3 etc.,

3.2.1 How and why corrosion occurs?

The metals are extracted from their compounds (ores).
During the extraction, these ores are reduced to their metallic
states. In the pure metallic state, the metals are unstable as
they are considered in excited state ie., higher energy state.
Therefore, as soon as the metals are extracted from their
ores, the reverse process begins and form metal compounds,
which are thermodynamically stable, ie., lower energy state.

Fig. 3.1 Corrosion and oxidation process

Hence, when metals are used in various forms, they

are exposed to environment, (such as dry gases, moisture,
etc.,) the exposed metal surface begins to decay ie.,
conversion into more stable compound. This is the basic
reason for metallic corrosion.
The term corrosion is sometimes also applied to
degradation of plastics, concrete, wood and materials.
Corrosion 3.3

The most familiar example of corrosion is rusting of iron

2Fe  32 O2  xH2O  Fe2O3 . xH2O
Rust

Due to corrosion, some useful properties of metals such

as electrical conductivity, ductility and malleability etc., are lost.

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1. Due to formation of corrosion product over the

machinery, the efficiency of the machine gets lost.
2. The products get contaminated due to corrosion.
3. The corroded equipments must be replaced
frequently.
4. Plant gets failure due to corrosion.
5. It is necessary for over design to compensate
for the corrosion.
6. Corrosion releases toxic products, health hazard, etc.
7. Time is lost in making available parts.
8. The value of the goods is reduced.

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Based on the environment, corrosion is classified into

1. Dry or Chemical corrosion, and

2. Wet or Electrochemical corrosion.

3.4 Engineering Chemistry

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Dry corrosion is due to the attack of metal surfaces
by the atmospheric gases such as oxygen, hydrogen sulphide,
sulphur dioxide, nitrogen, etc.

There are 3 main types of dry corrosion.

1. Oxidation corrosion (or) corrosion by oxygen.

2. Corrosion by hydrogen.

3. Liquid-metal corrosion.

3.5.1. Oxidation corrosion (or) corrosion by

oxygen
Oxidation corrosion is brought about by the direct
attack 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 oxidised at low temperature. At high temperature,
almost all metals (except, Ag, Au and Pt) are oxidised.

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(i) Oxidation occurs first at the surface of the metal
resulting in the formation of metal ions M 2,
which occurs at the metal / oxide interface.
M  M 2  2e

(ii) 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
Corrosion 3.5

(iii) Oxide ions reacts with the metal ion to form

the metal-oxide film.
M  12O2  M 2  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 (Fig. 3.2).

Fig 3.2 Mechanism of Oxidation corrosion

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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
gets adsorbed tightly to the metal surface. Such a layer is
impervious in nature and stops further oxygen attack through
3.6 Engineering Chemistry

diffusion. Such a film behaves as a protective coating and

no further corrosion can develop.
Example:
Oxides of Al, Sn, Pb, Cu, etc., are stable oxide layers.

2. Unstable oxide layer

Unstable oxide layer is mainly produced on the surface
of noble metals, which decomposes back into the metal and
oxygen.

Metal oxide Metal  Oxygen

Example:
Oxides of Pt, Ag, etc., are unstable oxide layers.

3. Volatile oxide layer

The oxide layer volatilizes as soon as it is formed,
leaving the metal surface for further corrosion.
Example:
Molybdenum oxide MoO3 is volatile.

4. Protective (or) Non-Protective oxide film (Pilling-

Bedworth rule)
(i) According to Pilling-Bedworth rule, if the volume
of oxide layer formed is less than the volume of metal, the
oxide layer is porous and 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
metal consumed, the oxide layer formed is porous and
non-protective.
Corrosion 3.7

(ii) On the other hand, if the volume of oxide layer

formed is greater than the volume of metal, the oxide layer
is non-porous and protective.

example:

The volume of oxides of heavy metals such as Pb, Sn,

etc., is greater than the volume of metal, the oxide layer
formed is non-porous and protective.

Pilling-Bedworth ratio
The ratio of the volume of metal oxide formed to
the volume of metal consumed is called “Pilling-Bedworth
ratio”.

Volume of metal oxide

PB ratio 
Volume of metal consumed

If the PB ratio is slightly greater than 1, the metal

oxide layer will be protective and non porous.

3.5.2 Corrosion by hydrogen

1. Hydrogen embrittlement (at ordinary temperature)

When metals contact to H2S at ordinary temperature
causes evolution of atomic hydrogen.

Fe  H2S  FeS  2H

This atomic hydrogen diffuses readily into the metal

and collects in the voids, where it recombines to form
molecular hydrogen.

H  H  H2
3.8 Engineering Chemistry

Collection of these hydrogen gases in the voids

develop very high pressure, which causes cracks and blisters
on metal.

Thus, the process of formation of cracks and blisters

on the metal surface, due to high pressure of hydrogen
gas, is called hydrogen embrittlement

2. Decarburisation (at higher temperature)

At higher temperature atomic hydrogen is formed by
the thermal dissociation of molecular hydrogen.

Heat
H2  2H

when steel is exposed to this environment, the atomic hydrogen

readily combines with carbon of steel and produces methane
gas.

C  4H  CH4

Collection of these gases in the voids develop very

high pressure, which causes cracking. Thus, the process of
decrease in carbon content in steel is termed as
“decarburisation” of steel.

3.5.3 Liquid-metal corrosion

This is due to the chemical action of flowing liquid
metal at high temperature. The corrosion reaction involves

(i) either dissolution of a solid metal by a liquid metal.

(or)
(ii) liquid metal may penetrate into the solid metal.
Corrosion 3.9

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Wet corrosion occurs under the following conditions.
(i) When two dissimilar metals or alloys are in contact
with each other in the presence of an aqueous solution
or moisture.
(ii) When a metal is exposed to varying concentration of
oxygen or any electrolyte.

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Under the above conditions, one part of the metal
becomes anode and another part becomes cathode.

1. At anode
In anodic part, oxidation (or) dissolution of metal
occurs
M  M 2  2e

2. At cathode
In cathodic part reduction reaction occurs, which
depends on nature of the corrosive environment.

(a) Acidic environment

If the corrosive environment is acidic, hydrogen
evolution occurs at cathodic part.

2H  2e  H2

(b) Neutral environment

If the corrosive environment is slightly alkaline (or)
neutral, hydroxide ions are formed at cathodic part.

1
2O2  2e  H2O  2OH
3.10 Engineering Chemistry

Thus, the metal ions (from anodic part) and

non-metallic ions (from cathodic part) diffuse towards each
other through conducting medium and form a corrosion
product between anode and cathode.

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“All metals above hydrogen in the electrochemical
series have a tendency to get dissolved in acidic solution
with simultaneous evolution of hydrogen gas” (Fig. 3.3).

Fig. 3.3 Hydrogen evolution type corrosion

Example

When iron metal contacts with non-oxidising acid like

HCl, H2 evolution occurs.

At anode

Iron undergoes dissolution to give Fe 2 ions with the

liberation of electrons.

Fe  Fe2  2e (oxidation)

Corrosion 3.11

At cathode
The liberated electrons flow from anodic to cathodic
part, where H ions get reduced to H2.

2H  2e  H2 (reduction)

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ch_T R^aa^bX^]
The surface of iron is usually, coated with a thin film
of iron oxide. However, if the oxide film grows, some crack
will form and anodic areas are created on the surface while
the remaining part acts as cathode (Fig. 3.4).
Example:
When iron metal contacts with a neutral (or) slightly
alkaline solution of an electrolyte in presence of oxygen,
OH  ions are formed.

Fig. 3.4 Absorption of oxygen type corrosion

At anode

Iron dissolves as Fe 2 with the liberation of electrons.

Fe  Fe2  2e (oxidation)

3.12 Engineering Chemistry

At cathode
The liberated electrons flow from anodic to cathodic
part through metal, where the electrons are taken up by the
dissolved oxygen to form OH  ions.
1 O
2 2  H2O  2e  2OH

Thus, the net corrosion reaction is

Fe 2  2OH   FeOH2

brown rust
If enough O2 is present, FeOH2 is easily oxidised
to FeOH3, a rust Fe 2O3 . H2O.

4FeOH2  O2  2H2O  4FeOH3 (or)

2Fe 2O3 . 3H2O

Table 3.1 Difference between Chemical and Electro

chemical Corrosion
Sl. Electrochemical
Chemical Corrosion
No. Corrosion
1. It occurs only in dry It occurs in presence of
condition. moisture or electrolyte.
2. It is due to the direct It is due to the set up of
chemical attack of metal a large number of cathodic
by the environment. and anodic areas.
3. Even a homogeneous Heterogeneous surface
metal surface gets (or) Bimetallic contact is
corroded. the condition.
4. Corrosion products Corrosion occurs at the
accumulate in the same anode, while products
place, where corrosion formed elsewhere.
occurs.
Corrosion 3.13

Sl. Electrochemical
Chemical Corrosion
No. Corrosion
5. Chemical corrosion is Electrochemical corrosion
self-controlled. is continuous process.
6. It follows adsorption It follows electrochemical
mechanism. reaction.
Examples Examples
Formation of mild scale Rusting of iron in moist
on iron surface. atmosphere.

3.6.1 Types of electrochemical corrosion

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When two different metals are in contact with each
other in presence of an aqueous solution or moisture,
galvanic corrosion occurs.
Here, the more active metal (with more negative
electrode potential) acts as anode and the less active metal
(with less negative electrode potential) acts as cathode.

Fig. 3.5 (a) & (b) Galvanic corrosion

Example Zn-Fe couple

Fig. 3.5 (a) represents Zn-Fe couple, in which zinc

(more active or higher in emf series) dissolves in preference
3.14 Engineering Chemistry

to iron (less active metal) i.e., Zn acts as anode and

undergoes corrosion and Fe acts as cathode.
Example Cu-Fe couple
Fig. 3.5 (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.

Examples for Galvanic Corrosion

(i) Steel screw in a brass marine hardware corrodes
This is due to galvanic corrosion. Iron (higer position
in electrochemical series) becomes anodic and is attacked
and corroded, while brass (lower in electrochemical series)
acts as cathodic and is not attacked.

(ii) Bold and Nut made of the same metal is preferred

It is preferred in practice, because galvanic corrosion
is avoided due to homogeneous metals (no anodic and
cathodic part).

Prevention
Galvanic corrosion can be minimised by the following
two ways.
1. By providing an insulating material between the
two metals.
2. By selecting two metals as close as possible on
the emf series.

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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.
Corrosion 3.15

Example:
Metals partially immersed in water (or) conducting
solution (called water line corrosion).
If a metal is partially immersed in a conducting
solution (Fig. 3.6) 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.

Fig 3.6 Differential aeration corrosion

At anode (less aerated part): Corrosion occurs

M  M 2  2e

At cathode (more aerated part): OH  ions are produced

1
2O2  H2O  2e  2OH

Examples for Differential aeration corrosion

(a) Pitting or localised corrosion.
(b) Crevice corrosion.
3.16 Engineering Chemistry

(c) Pipeline corrosion.

(d) Corrosion on wire fence.
(a) Pitting corrosion
Pitting is a localised attack, resulting in the formation
of a hole around which the metal is relatively unattacked.

Fig. 3.7 Pitting corrosion

Example
Metal area covered by a drop of water, sand, dust,
scale, etc.
Let us consider a drop of water or aqueous NaCl
resting on a metal surface (Fig. 3.7). The area covered by
the drop of water acts as an anode due to less oxygen
concentration and suffers corrosion. The uncovered area
(freely exposed to air) acts as a cathode due to high oxygen
concentration.
The rate of corrosion will be more, when the area of
cathode is larger and the area of anode is smaller. Therefore,
more and more material is removed from the same spot. Thus
a small hole or pit is formed on the surface of the metal.

At anode

Iron is oxidised to Fe 2 ions

Fe  Fe2  2e

Corrosion 3.17

At cathode
Oxygen is converted to OH  ions.
1 O
2 2  H2O  2e  2OH

Net reaction
O
2 
Fe  2OH  FeOH2  FeOH3

This type of intense corrosion is called pitting.

(b) Crevice corrosion
If a crevice between different metallic objects or
between metal and non-metallic material is in contact with
liquids, the crevice becomes the anodic region and suffers
corrosion. This is due to less oxygen in crevice area. The
exposed areas act as cathode (Fig. 3.8).

Fig. 3.8 Crevice corrosion

(c) Pipeline corrosion

Differential aeration corrosion may also occur in
different parts of pipeline.

Fig 3.9 Pipeline corrosion

3.18 Engineering Chemistry

Buried pipelines or cables passing from one type of

soil to another say, from clay (less aerated) to sand (more
aerated) may get corroded due to differential aeration.
(d) Corrosion on wire-fence
Fig. 3.10 shows a wire fence in which the areas where
the wires cross are less aerated than the rest of the fence
and hence corrosion occurs at the wire crossings, which are
anodic.

Fig. 3.10 Corrosion on wire fence

Other examples for differential aeration corrosion

1. Corrosion occurring under metal washers, where
oxygen cannot diffuse easily.
2. Lead pipeline passing through clay to cinders
undergo corrosion. Since the pipeline under
cinders is more aerated, it gets corroded easily.
Corrosion 3.19

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The rate of corrosion can be controlled by either
modifying the metal or the environment.

3.7.1 Control of corrosion by modifying

the metal
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1. By selection of the metal
Selection of right type of metal is the main factor for
corrosion control. Thus, noble metals are used in ornaments
and in surgical instruments, as they are most immune to
corrosion.

2. By using pure metal

Pure metals have higher corrosion resistance. Even a
small amount of impurity may lead to severe corrosion.

3. By alloying
Corrosion resistance of many metals can be improved
by alloying. For example, stainless steel containing
chromium produce a coherent oxide film, which protects the
steel from further attack.

4. By proper design
Some important rules, to be kept in our mind, for
designing are given below.

(i) Avoid galvanic corrosion

If two different metals are joined, galvanic corrosion
will occur. In such a case galvanic corrosion is prevented
by
3.20 Engineering Chemistry

(a) Selecting the metals as close as possible in the

electrochemical series.
(b) Providing smaller area for cathode and larger area for
anode.
(c) Inserting an insulating material between the two metals
(Fig. 3.11).

Fig. 3.11 Insulation avoids galvanic corrosion

(ii) Drainage affects corrosion

Tanks and other containers must be designed in such
a way that, the whole liquid should be drained off
completely (Fig. 3.12).

Fig. 3.12 Drainage affects corrosion

(iii) Avoid sharp corners and bends

Sharp corners or edges should always be avoided, and
hence erosion corrosion can be avoided by smooth corners
or curved pipe bends (Fig. 3.13).
Corrosion 3.21

Fig. 3.13 Corrosion prevention using curved pipeline

(iv) Avoid crevices

Crevices allow moisture and dirt, which results in
increased electrochemical corrosion. This can be prevented
by filling the crevices with a filler (Fig. 3.14).

Fig. 3.14 Minimizing crevice corrosion

Example
Riveted joints produce crevice corrosion, so welded
joints are preferred.
3.22 Engineering Chemistry

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The principle involved in the electrochemical
protection (or) cathodic protection is to force the metal to
behave like a cathode. The important cathodic protections
are
(i) Sacrificial anodic protection
(ii) Impressed current cathodic protection
1. Sacrificial anodic protection method
In this method, the metallic structure to be protected
is made cathode by connecting it with more active metal
(anodic metal). So that all the corrosion will concentrate only
on the active metal. The artificially made anode thus
gradually gets corroded protecting the original metallic
structure. Hence this process is otherwise known as
sacrificial anodic protection.

Fig. 3.15 Sacrificial anodic protection

Aluminium, Zinc, Magnesium are used as sacrificial anodes.

Applications of sacrificial anodic protection

(a) This method is used for the protection of ships
and boats. Sheets of Mg or Zn are hung around the hull of
Corrosion 3.23

the ship (Fig. 3.16). 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.

Fig. 3.16 Sacrificial anodic protection of ship

Fig. 3.17 Sacrificial anodic protection

(b) Protection of underground pipelines, cables from

soil corrosion (Fig. 3.17(a)).
(c) Insertion of Mg sheets into the domestic water
boilers to prevent the formation of rust
(Fig. 3.17(b)).
(d) Calcium metal is employed to minimize engine
corrosion.
3.24 Engineering Chemistry

2. Impressed current cathodic protection method

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 negative terminal of
the battery to the metallic structure, to be protected, and
positive 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
sulphate). The “back fill” provides good electrical contact
to anode (Fig. 3.18).

Fig. 3.18 Impressed current cathodic protection

Applications of impressed current protection

Structures like tanks, pipelines, transmission line
towers, underground water pipe lines, oil pipe lines, ships,
etc., can be protected by this method.
Corrosion 3.25

Table 3.2 Comparison of Galvanic method (Sacrificial

anode) and Impressed current Cathodic method

Sl. Sacrificial anodic Impressed current

No. method method
1. No external power supply External power supply
is necessary. must be present.
2. This method requires Here anodes are stable and
periodical replacement of do not disintegrate.
sacrificial anode.
3. Investment is low. Investment is more.
4. Soil and microbiological Soil and microbiological
corrosion effects are not corrosion effects are taken
taken into account. into account.
5. This is most economical This method is well suited
method especially when for large structures and
short-term protection is long term operations.
required.
6. This method is suitable But this method can be
when the current practiced even if the
requirement and the current requirement and
resistivity of the the resistivity of the
electrolytes are relatively electrolytes are high.
low.

3.7.2 Control of corrosion by modifying the

environment
1. Deaeration
Presence of increased amount of oxygen is harmful and
increases the corrosion rate. Deaeration involves removal of
dissolved oxygen by increase of temperature together with
3.26 Engineering Chemistry

mechanical agitation. It also removes dissolved CO 2 of

water.

2. Deactivation
Deactivation is a process of removing dissolved
oxygen by adding some chemicals in aqueous solution.

Examples
1. Sodium sulphite: 2Na 2SO 3  O2  2Na 2SO 4
2. Hydrazine: N2H4  O2  N2  2H2O

3. Dehumidification
In this method, moisture from the air is removed by
lowering the relative humidity of the surrounding air. This
is done by adding silica gel (or) alumina, which adsorbs
moisture preferentially on its surface.

4. Alkaline neutralisation
Acidic character of the corrosive environment (due to
presence of H2S, HCl, CO2, SO 2, etc ) can be neutralised by
spraying alkaline neutralizers (like NH 3, NaOH , lime, etc.,)

5. Using Corrosion Inhibitors

A corrosion inhibitor is a substance which reduces the
corrosion of a metal, when it is added to the corrosive
environment.

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1. What is chemical corrosion? Explain the mechanism of

oxidation corrosion. (TCY A.U. June 2009)
Corrosion 3.27

2. Explain chemical corrosion. Also explain the intensity

of corrosion varying with the nature of oxide layer
formation over metal. (Chen A.U. May 2009)
3. Explain the various types of corrosion. (A.U.Dec ’06)
4. Differentiate between Chemical and electrochemical
corrosion. Mention any four factors that affect
electrochemical corrosion. (A.U.Dec 97, 06, May ’01)
5. State and explain pilling-bedworth rule.
(A.U.June 2006, Dec 2006)
6. Discuss the mechanism of electrochemical corrosion.
(TCY A.U. July 2009) (Coim A.U. July 2009) (Dec ’06)
7. (i) Describe the mechanism of electrochemical
corrosion by hydrogen evolution and oxygen absorption.
(A.U.Nov.’01)
(ii) Why steel screws in a brass marine hardware
corrode? Explain.
8. When does the electrochemical corrosion occur?
Describe the mechanism of electrochemical corrosion.
(A.U. Dec 2012)
9. How is Galvanic corrosion occur?
(Anna.univ. (CEG) Nov.2002)
10. Discuss the mechanism of chemical and electrochemical
corrosion. (June 06)
11. Explain the principle of electrochemical corrosion with
suitable example. (Dec. 05)
12. Explain water-line corrosion.
(TCY A.U. July 2009, AU Dec ’06)
13. What should be the nature of corrosion product to
prevent further corrosion? (A.U. Dec.’01)
3.28 Engineering Chemistry

14. Deposition of oil or dust on metal surfaces for a long

period is undesirable. Give reasons.
(Anna.univ. (CEG) Nov.2002)
15. Mention the possible means of rendering a metal
cathodic to protect it from corrosion. (A.U. June 06)
16. Describe the mechanism of differential aeration
corrosion taking pitting as example.
(A.U. June 06, Dec ’06)
17. Write a note on pitting corrosion and cathodic
protection. (A.U.Dec ’05, June ’05, June 06)
18. Why corrosion be prevented? Discuss the methods of
corrosion control. (A.U June 2013)
19. Explain the control of corrosion by the use of sacrificial
anodes and by impressed current cathodic protection.
(TNV A.U. May 2009)(Dec 2009)(May 2008)
20. What is cathodic protection? Explain the sacrificial
anode and impressed current techniques for the
prevention of corrosion. (May ’07)
21. Describe corrosion control through impressed current
method. (TCY A.U. Dec 2009)
22. How is corrosion prevented in shiphulls and
transmission line towers. Explain. (May ’01)
23. Write a brief note on
(i) Cathodic protection by sacrificial anode

(Dec. 2005, June 06, Chen A.U. Dec ’06, Dec 2012)
(ii) Differential aeration corrosion.
(June 06, Dec. 05, Dec 2009)

24. Explain differential aeration corrosion with an example.

(TCY A.U. June, Dec 2009)
Corrosion 3.29

25. What is differential aeration corrosion? Write its

mechanism. Give any illustrations that show differential
corrosion. (Chen A.U. May 2009)
26. Describe the sacrificial anode methods of corrosion
control.
(Coim A.U. July 2009, TCY A.U. July 2009, Dec 2008)
27. Explain differential aeration corrosion and galvanic
corrosion with suitable illustrations. (AU June 2014)
 CHAPTER 4
Energy Sources

#  8=CA>3D2C8>=
For our energy requirement, we mainly depend on the
conventional sources of energy like coal, petroleum, natural
gas, etc., These sources are limited in quantity and can be
exhausted in near future. This is because of their continuous
and rapid use.

To overcome this energy crises, the scientists have

accelerated the search and use of non-conventional
(renewable) sources of energy like wind energy, solar energy,
nuclear energy, etc.

#!  =D2;40A 58BB8>=

When U235 is bombarded by thermal neutron (low

energy neutron), it splits into two approximately equal parts
with the liberation of a large amount of energy.

4.2.1 Definition
Nuclear fission is defined as “the process of splitting
of heavier nucleus into two (or) more smaller nuclei with
simultaneous liberation of large amount of energy”.

4.2.2 Mechanism of nuclear fission

When U235 is bombarded by thermal neutron (slow

moving), unstable U236 is formed. The unstable U236 then
4.2 Engineering Chemistry

divides into two approximately equal nuclei with the release

of neutrons and large amount of energy.

Illustration
Splitting of U235 has been shown below.

Fig. 4.1 The fission process

During the nuclear fission a large amount of energy

is released.
4.2.3 Characteristics of Nuclear Fission
1. A heavy nucleus (U235 (or) Pu 239 ), when
bombarded by slow moving neutrons, split into
two or more nuclei.
Energy Sources 4.3

2. Two or more neutrons are produced by fission

of each nucleus.
3. Large quantities of energy is produced as a result
of conversion of small mass of nucleus into energy.
4. All the fission fragments are radioactive, giving
off  and -radiations.
5. The atomic weights of fission products ranges
from about 70 to 160.
6. All the fission reactions are a self-propagating
chain-reactions because fission products contain
neutrons (secondary neutrons) which further
cause fission in other nuclei.
7. The nuclear chain reactions can be controlled and
maintained steadily by absorbing a desired
number of neutrons. This process is used in
nuclear reactor.
8. Every secondary neutron, released in the fission
process, does not strike a nucleus, some escape
into air and hence a chain reaction cannot be
maintained.
9. Multiplication factor: The number of
neutrons, resulting from a single fission, is
known as the multiplication factor.
When the multiplication factor is less than 1, a chain
reaction does not take place.
4.4 Engineering Chemistry

4.2.4 Advantages and disadvantages of

Nuclear fission energy

Advantages of nuclear fission energy over fossil fuels energy

1. A small amount of nuclear fuel U235  gives a large
amount of energy while, large quantity of fossil fuel
is required to produce large amount of heat.
2. In a nuclear power plant, the nuclear fuel is inserted
once to get energy over a long period of time. But,
in a thermal power plant, fossil fuel is to be supplied
continuously to get the energy.

Disadvantages of nuclear fission energy over fossil fuel

energy
1. Nuclear fission causes more serious pollution problem
than the burning of fossil fuel.
2. The biggest problem of using nuclear fission energy
is the safe disposal of nuclear waste. But no such
problem is faced in the disposal of fossil fuel.

#" =D2;40A 5DB8>=

Nuclear fusion is defined as, “the process of
combination of lighter nuclei into heavier nuclei, with
simultaneous liberation of large amount of energy”.

Illustration
Fusion reaction in the sun
2
1H  1H2  2He 4  energy

2
1H  1H3  2He 4  n10
Energy Sources 4.5

Fig. 4.2 The fusion process

The energy of stars and sun is arised from the fusion

reactions in which hydrogen is converted into helium. The
fusion reactions can start only when the atoms are heated
to very high temperatures. Such a high temperature, required,
is produced by fission reaction.

The combination of these nuclei is very difficult

because all the nuclei are positively charged. To make them
combine, they must move at speed high enough to overcome
the electrostatic repulsion. In fact, the hydrogen to helium
fusion reaction in the sun occur at about 100 million degree
centigrade. Thus, to start fusion reaction, temperature of high
order must be reached. That is why it is called
thermonuclear reactions. Such, a high temperature is
generated by a fission reaction.

Example: In Hydrogen bomb, fusion occurs by the

fission of atom bomb, which acts as trigger.

Disadvantages
Utilization of the fusion energy is problem, because
no known material can withstand such a high temperature.
Thus, design of thermonuclear fusion power plant is very
difficult.
4.6 Engineering Chemistry

4.3.1 Characteristics of Nuclear Fusion

1. Unlike nuclear fission, there is no limit on the amount
of nuclear fusion that can occur.
2. Nuclear fusion is possible only when the distance
between the nuclei is of the order of one Fermi.
3. The amount of energy in fusion is four times more
compared to that of fission.
4. Sufficient amount of kinetic energy must be provided
to facilitate a fusion reaction.
5. As electrostatic repulsion increases with increase in
atomic number of nucli, only lighter nuclei can
undergo nuclear fusion reaction.

4.3.2 Differences between nuclear fission and

fusion
S.
Nuclear fission Nuclear fusion
No.
1. It is the process of It is the process of
breaking of heavier combination of lighter
nucleus. nuclei.
2. It emits radioactive rays. It does not emit any kind
of radioactive rays.
3. It occurs at ordinary It occurs at high
temperature. 6
temperature  10 K.
4. The mass number and The mass number and
atomic number of new atomic number of product
elements are lower than are higher than that of
that of parent nucleus. starting elements.
5. It gives rise to chain It does not give rise to
reaction. chain reaction.
Energy Sources 4.7

S.
Nuclear fission Nuclear fusion
No.
6. It emits neutrons. It emits positrons.
7. It can be controlled. It cannot be controlled.

##  =D2;40A 4=4A6H

The enormous amount of energy released during the
nuclear chain reaction of heavy isotope like U235 (or)
Pu 239 is called nuclear energy.

4.4.1 Definition
The energy released by the nuclear fission (or)
nuclear fusion, is called nuclear energy.
Illustration
The fission of U235 or Pu 239 occurs instantaneously,
producing enormous amount of energy in the form of heat
and radiation.

Fig. 4.3 Nuclear energy

4.8 Engineering Chemistry

4.4.2 Cause of the release of energy

The enormous amount of energy released during the
nuclear fission is due to the loss in some mass, when the
reaction takes place. It has been observed that during nuclear
fission, the sum of the masses of the products formed is
slightly less than the sum of masses of target species and
bombarding neutron. The loss in mass gets converted into
energy according to Einstein equation

E  mc2

 m  M  M

where

c  velocity; m  loss in mass and E  energy.

M  Mass of radioactive substance before emitting radiation

M  Mass of radioactive substance after emitting radiation

4.4.3 Hazards of using nuclear energy

The radiation is harmful to the living organisms. The
long and constant exposure of living organisms to these
radiations causes the following disease.

(i) The nuclear radiation can damage the structure of cells

in the human body.
(ii) It causes diseases like cancer and blindness.
(iii) It causes genetic disorder in a human body.
(iv) It causes sterility in young generation.
Energy Sources 4.9

4.4.4 Applications of nuclear energy

1. Electricity generation
Nuclear energy is an environmental-friendly energy
resource for power generation.

2. Source of pure water

The water discharged from the nuclear reactors is free
from radiation and is clean enough to conserve animals and
aquatic animals.

3. Health care
Radioactive isotopes (nuclear energy) find use in
treatment of cancer by radiotherapy. It is also used for
sterilization to destroy micro-organism.

4. Agriculture
It is used to control of agricultural pests. Nuclear
radiation delays ripening of fruits.

#$  =D2;40A 2708= A402C8>=B

In nuclear fission reaction, the neutrons emitted from
the fission of U235 atom may hit another U235 nuclei and
cause fission producing more neutrons and so on. Thus, a
chain of self sustaining nuclear reactions will be set up with
the release of enormous amount of energy. But the amount
of energy released will be less than expected. Thus the
fission of U235 by slow moving neutrons is a chain reaction.

Reason for less energy

Some of the neutrons, released in the fission of
235
U , may escape from the surface to the surroundings or
4.10 Engineering Chemistry

may be absorbed by U238 present as impurity. This will

result in breaking of the chain and the amount of energy
released will be less than expected.

4.5.1 Definition
A fission reaction, where the neutrons from the
previous step continue to propagate and repeat the reaction
is called nuclear chain reaction.

4.5.2 Criteria for nuclear chain reaction

1. For a nuclear chain reaction to continue, sufficient
amount of U235 must be present to capture the
neutrons, otherwise neutrons will escape from the
surface.

Critical mass
The minimum amount of fissionable material (U235 )
required to continue the nuclear chain reaction is called
critical mass.

The critical mass of U235 lies between 1 kg to 100

kg.

(a) Super critical mass

If the mass of the fissionable material (U235 ) is more
than the critical mass, it is called super critical mass.

(b) Sub-critical mass

If the mass of the fissionable material is smaller than
the critical mass, it is called sub-critical mass.
2. Thus the mass greater or lesser than the critical mass
will hinder the propagation of the chain reaction.
Energy Sources 4.11

Illustration
When U235 nucleus is hit by a thermal neutron, it
undergoes the following reaction with the release of three
neutrons.

U235 1 139 94 1
92  n0  Ba 56  Kr 36  3n0

Fig. 4.4 U235 fission chain reaction

Each of the three neutrons, produced in the above

reaction, strikes another U235 nucleus causing 3  3 9
subsequent reactions. These 9 reactions further give rise to
3  9 27 reactions. This process of propagation of the
reaction by multiplication in threes at each fission is called
chain reaction.
4.12 Engineering Chemistry

#%  =D2;40A A402C>A >A ?8;4

Reactors, which are designed to carry out nuclear
reactions for generation of heat, electricity and radioactive
isotopes are called nuclear reactors.

4.6.1 Definition
The arrangement or equipment used to carry out
fission reaction under controlled conditions is called a
nuclear reactor.
Example:
The energy released (due to the controlled fission of
235
U in a nuclear reactor) can be used to produce steam,
which can run turbines and produce electricity.

4.6.2 Classification of nuclear reactors

Based on the type of neutron energy, fuel used,
moderator and purpose, nuclear reactors may be classified
in different ways.

8 1PbTS ^] ]Tdca^] T]TaVh P]S \^STaPc^a

1. Thermal neutron reactors
In these reactors, nuclear fission reaction is brought
out by slow moving (low energy) neutrons. These are further
classified into various types.

(a) Light water moderated reactors (LWR)

In these reactors, ordinary water is used as moderator
and coolant. These are cheaper and simpler and have
excellent safety and stability when compared to other nuclear
reactors. These are further classified into
Energy Sources 4.13

(i) Boiling water reactors (BWR)

(ii) Pressurized water reactors (PWR)

(iii) Supercritical water reactors (SWR)

(b) Heavy water moderated reactors (HWR)

Here, heavy water is used as moderator.

(c) Graphite moderated reactors (GMR)

Here, graphite is used as moderator. These are further
classified into

(i) Gas cooled reactors

(ii) Water cooled reactors

2. Fast neutron reactors

In these reactors, nuclear fission reaction is brought
out by unmoderated fast moving (high energy) neutrons.
These are generally cooled by liquid metal.

88 1PbTS ^] UdT[ dbTS

1. Burner
Here, nuclear fuel is burnt to produce heat or electrical
energy.

2. Convertor (or) Breeder type reactors

Here, fuel is reproduced.

888 1PbTS ^] _da_^bT

Based on the purpose for which type of reactor is
operated, these are further classified into
4.14 Engineering Chemistry

(a) Power reactor

(b) Breeder reactor

(c) Materials testing reactor.

4.6.3 Components of a nuclear reactor

The main components of the nuclear reactor are

1. Fuel rods
The fissionable materials used in the nuclear reactor
is enriched U235 . The enriched fuel is used in the reactor
in the form of rods or strips.

Example: U235 ; Pu 239

Function: It produces heat energy and neutrons, that starts

nuclear chain reaction.

2. Control rods
To control the fission reaction (rate), movable rods,
made of cadmium (or) boron, are suspended between fuel
rods. These rods can be lowered or raised and control the
fission reaction by absorbing excess neutrons.

If the rods are deeply inserted inside the reactor, they

will absorb more neutrons and the reaction becomes very
slow. On the other hand, if the rods are pushed outwards,
they will absorb less neutrons and the reaction will be very
fast.

Cd 113 1 114
43  n0  Cd 43  ray

B10 1 11
5  n0   B 5  ray
Energy Sources 4.15

Examples

Cd 113 ; B10
Function: It controls the nuclear chain-reaction and avoids
the damage of the reactors.
3. Moderators
The substances used to slow down the neutrons are
called moderators.

Fig. 4.5 Functions of a moderator

When the fast-moving neutrons collide with moderator,

they lose energy and gets slow down.

Example:

Ordinary water, heavy water, graphite, beryllium.

Function: The kinetic energy of fast moving neutrons

(1 meV) is reduced to slow neutrons (0.25 eV).

4. Coolants
In order to absorb the heat produced during fission, a
liquid called coolant is circulated in the reactor core. It enters
the base of the reactor and leaves at the top. The heat carried
by out-going liquid is used to produce steam.
4.16 Engineering Chemistry

Example:
Water (act as moderator & coolant), heavy water,
liquid metal (Na or K), air (CO2).

Function: It cools the fuel core.

5. Pressure vessel
It encloses the core and also provides the entrance and
exit passages for coolant.

Function: It withstand the pressure as high as 200

kg/cm 2.

6. Protective shield
The nuclear reactor is enclosed in a thick massive
concrete shield (more than 10 meters thick).

Function: The environment and operating personnels are

protected from destruction in case of leakage of radiation.

7. Turbine
The steam generated in the heat exchanger is used to
operate a steam turbine, which drives a generator to produce
electricity.

4.6.4 Light Water Nuclear-Power Plant

Definition
Light-water nuclear-power plant is the one, in which
U235 fuel rods are submerged in water. Here the water
acts as coolant and moderator.
Energy Sources 4.17

Fig. 4.6 Light water nuclear power plant

Working
The fission reaction is controlled by inserting or
removing the control rods of B10 automatically from the
spaces in between the fuel rods. The heat emitted by fission
of U235 in the fuel core is absorbed by the coolant (light
water). The heated coolant (water at 300C) then goes to
the heat exchanger containing sea water. The coolant here,
transfers heat to sea water, which is converted into steam.
The steam then drives the turbines, generating electricity.

Pollution
Though nuclear power plants are very important for
production of electricity, they will cause a serious danger
to environments.

Problem on disposal of reactor waste

Disposal of reactor waste is another important problem
because the fission products viz., Ba 139 & Kr 92 are
themselves radioactive. They emit dangerous radiation for
4.18 Engineering Chemistry

several hundred years. So the waste is packed in concrete

barrels, which are buried deep in the sea.

#&  1A4434A A402C>A

Breeder reactor is the one which converts
238 232
non-fissionable material U , Th  into fissionable
material U235 , Pu 239 . Thus the reactor produces or breeds
more fissionable material than it consumes.

Illustration

U238
92  n10   Pu 239
94  2e 
Non fissionable Fissionable

Pu 239 1 1
94  n0  Fission products  3n 0

In breeder reactor, of the three neutrons emitted in the

fission of U235 , only one is used in propagating the fission
chain with U235 . The other two are allowed to react with
U238 . Thus, two fissionable atoms of Pu 239 are produced

Fig. 4.7 Principle of breeder reactor

Energy Sources 4.19

for each atom of U235 consumed. Therefore, the breeder

reactor produces more fissionable material than it uses.
Hence Pu 239 is a man made nuclear fuel and is known as
secondary nuclear fuel.

Significance
1. The non-fissionable nucleides, such as U238 &
Th 232 , called fertile nucleides, are converted
into fissile nucleides.
2. The fissionable nucleides such as U235 &
Pu 239 are called fissile nucleides.
3. As regeneration of fissile nucleides takes place,
its efficiency is more.

#' C7>A8D< 50BC A402C>A

It is not possible to build a nuclear reactor using
Thorium (Thorium-232) alone due its physical
characteristics. Thorium has to be converted to uranium-233
in a reactor before it can be used as fuel.
In a nuclear reactor power generation is fueled
primarily by the nuclear fission of the isotope Uranium-233
produced from the fertile element thorium.

Advantages
1. Thorium is three times as abundant as uranium.
2. It produces much less nuclear waste when thorium is
used as a fuel in a liquid fluoride thorium reactor.
3. It produces nuclear energy with low radio-toxicity
waste.
4. No expensive fuel enrichment is needed.
4.20 Engineering Chemistry

5. Its efficiency is more. One ton of thorium can produce

as much energy as 200 tons of uranium (or) 3,500,000
tons of coal.
6. Mining thorium is safer and more efficient than mining
uranium.

Disadvantages
1. Expensive testing, analysis and licensing work would
be required, requiring business and government
support.
2. The cost of fabrication and reprocessing is higher than
using traditional solid fuel rods.
3. Thorium, when irradiated for use in reactors, makes
uranium-232, which emits gamma rays.

#(   0==0 D=8E4AB8CH @D4BC8>=B

1. State any four characteristics of a nuclear fission
reaction. (TNV. AU. May 2009)
2. Write in brief about chain reaction and nuclear fission
reactions. (May 07)
3. What are nuclear chain reactions? Explain how the
amount of nuclear energy can be improved.
(A.U Jan 2013)
4. Discuss the characteristics of the reaction when uranium
undergoes nuclear fission. (Chen. A.U. June 2009)
5. What are the components of a nuclear reactor? Write
briefly about each component. (Chen. A.U. June 2009)
6. Give an account of Light water nuclear reactor with a
neat diagram. (TNV. AU. May 2009)
7. Explain the power generation from light water nuclear
reactor. (CBE. A.U. Jan 2009)
Energy Sources 4.21

8. Describe using a block diagram the light water nuclear

reactor for power generation.
(Chen AU. Jan 2009)(TNV. AU. Jan 2009)(June 2005)
9. Explain with a neat diagram the parts and functions of
a nuclear reactor.
(Chen A.U. Jan 2010, Jan 2013, TNV A.U. Jan 2010)
10. What is a nuclear reactor? Describe the components of
a light-water nuclear power plant with a suitable block
diagram. (TCY A.U. Jan 2010)
11. Describe the breeder reactor. (Coim A.U. Jan 2010)
 CHAPTER 5
Storage Devices

$   8=CA>3D2C8>=

In electrochemical cells, the chemical energy is

converted into electrical energy. The cell potential is related
to free energy change (G).
G for a reaction is a measure of the maximum useful
work, that can be obtained from a chemical reaction.

Decrease in free energy will be converted to electrical

energy.

G   nFE (or) G  0

Decrease in free energy is indicated by (–)ve sign.

One of the main uses of the galvanic cells is the

generation of portable electrical energy. These cells are
known as batteries.

$! 10CC4AH

A battery is an arrangement of several

electrochemical cells connected in series, that can be used
as a source of direct electric current.

A Cell: It contains only one anode and cathode.

A Battery: It contains several anodes and cathodes.

5.2 Engineering Chemistry

5.2.1 Requirements of a battery

A useful battery should fulfil the following
requirements

1. It should be light and compact for easy

transport.
2. It should have long life both when it is being
used and when it is not used.
3. The voltage of the battery should not vary
appreciably during its use.

5.2.2. Types of Battery

 ?aX\Pah 1PccTah ^a ?aX\Pah RT[[b
          ^a =^]aTeTabXQ[T 1PccTah
In these cells, the electrode and the electrode reactions
cannot be reversed by passing an external electrical energy.
The reactions occur only once and after use they become
dead. Therefore, they are not chargeable.

Examples:
Dry cell, mercury cell.

! BTR^]SPah 1PccTah ^a BTR^]SPah RT[[b

                 ^a ATeTabXQ[T 1PccTah
In these cells, the electrode reactions can be reversed
by passing an external electrical energy. Therefore, they can
be recharged by passing electric current and used again and
again. These are also called Storage cells (or)
Accumulators.

Examples:
Lead acid storage cell, Nickel-cadmium cell.
Storage Devices 5.3

" 5[^f QPccTah ^a 5dT[ RT[[b

In these cells, the reactants, products and electrolytes
are continuously passing through the cell. Here chemical
energy gets converted into electrical energy.

Example:
Hydrogen-oxygen fuel cell.

$"  8<?>AC0=C ?A8<0AH 10CC4AH

5.3.1 Dry Cell (or) Leclanche’s Cell

It is a primary cell, which works without fluid
component.

Description

Anode : Zinc
Cathode : Carbon rod (graphite)
Electrolyte : NH 4Cl  ZnCl2  MnO2  Starch  H2O
paste
Emf : 1.5 V

Construction
A dry cell consists of a zinc cylinder, which acts as
anode. This zinc cylinder is filled with an electrolyte
consisting of NH 4Cl, ZnCl 2 and MnO 2 in the form of paste
using starch and water. A carbon rod (graphite), acts as
cathode, is immersed in the electrolyte in the centre of the
cell. The zinc cylinder has an outer insulation of cardboard
case. During use, the zinc cylinder gets consumed and at
5.4 Engineering Chemistry

Fig. 5.1 Leclanche’s Cell

the end, it will develop holes which are responsible for

leakages.

Working
When the cell is working, zinc loses electrons and
2
Zn ions gets dissolved in the electrolyte. The electrons
pass through the circuit and are consumed at cathode. This
causes discharge of NH 4 ions from the electrolyte.

Cell reactions:

At anode: Zn  Zn2  2e 

At cathode:
NH4 aq  MnO2 s2e  MnOOH   NH3
Storage Devices 5.5

Overall Reaction:
Zn  NH 4 aq  MnO2 s  Zn 2  MnOOH  NH 3

In cathode reaction, Mn is reduced from +4 oxidation

state to +3 oxidation state. The liberation of NH 3 gas, which
disrupts the current flow, is prevented by a reaction of
NH 3 g with Zn 2 (from ZnCl 2.

ZnCl 2  2 NH 3  [ZnNH32] Cl 2s

The voltage of Leclanche’s cell is about 1.5 V.

Advantages
1. The cost of dry cell is cheap and easily available.
2. The compact size of it makes it suitable for powering
small electronic devices.
3. The electrolyte used in dry cell is not harmful and no
leakage.
4. It is easy and safe for transportation.

Disadvantages
1. This dry cell does not have an indefinite life, because
NH 4Cl being acidic corrodes the zinc container, even
if it is not used.
2. When current is drawn rapidly from it, products build
up on the electrodes, so voltage drop occurs.
3. This cell can not be recharged.
4. Voltage decreases with continuous usage.

Uses:
It is used in transistor radios, calculators, Flash lights,
torches etc.,
5.6 Engineering Chemistry

$#  B42>=30AH 10CC4A84B

5.4.1. Nickel-Cadmium Cell (or) NICAD

Battery
This is also a rechargeable battery.

Description
Nickel-cadmium cell consists of a cadmium anode and
a metal grid containing a paste of NiO 2 acting as a cathode.
The electrolyte in this cell is KOH.

It is represented as:

Cd  CdOH2  KOHaq  NiO2  Ni

Working (Discharging)
When the Nicad battery operates, at the anode
cadmium is oxidised to Cd 2 ions and insoluble CdOH2
is formed. It produces about 1.4V.

At anode: Cadmium is oxidised to Cd2 and further it

combines with OH ions to form CdOH2.

dicharging
Cds  2OH  CdOH2 s  2e 
charging

At cathode: NiO 2 is reduced to Ni2 ions which further

combine with OH ions to form NiOH2.

dichar ging
NiO 2 s  2H2O  2e NiOH2 s  2OH 
char ging
Storage Devices 5.7

Overall reaction during use (discharging):

dichar ging
Cds  NiO 2 s  2H2O Cd OH2 s  NiOH2 s
charging
 Energy.

From the above cell reactions it is clear that, there is

no formation of gaseous products, the products CdOH2 and
Ni OH2 adhere well to the surfaces. This can be reconverted
by recharging the cell.

Recharging the Battery

The recharging process is similar to lead storage
battery. When the current is passed in the opposite direction,
the electrode reaction gets reversed. As a result, Cd gets
deposited on anode and NiO 2 on the cathode.

The net reaction during charging is

char ging
CdOH2 s  NiOH2 s  Energy Cd s  NiO 2 s
dischar ging

 2H 2O

Advantage
1. It is smaller and lighter.
2. It has longer life than lead storage cell.
3. Like a dry cell, it can be packed in a sealed
container.

Disadvantage
It is more expensive than lead storage battery.
5.8 Engineering Chemistry

Uses
It is used in calculators, electronic flash units,
transistors and cordless appliances.

5.4.2 Lead - Acid Storage Cell

Storage cell
A lead acid storage cell is a secondary battery, which
can operate both as a voltaic cell and as an electrolytic cell.
When it acts as a voltaic cell, it supplies electrical energy
and becomes “run down”. When it is recharged, the cell
operates as an electrolytic cell.
Description
Anode : Lead
Cathode : Lead dioxide
Electrolyte : H2SO 4
Emf : 12 V
Cell diagram : Pb / PbSO4 // H2SO4 aq / PbO2 / Pb

Fig. 5.2. Lead storage cell

Storage Devices 5.9

Construction
A lead-acid storage battery consists of a number of (3
to 6) voltaic cells connected in series to get 6 to 12 V
battery. In each cell, the anode is made of lead. The cathode
is made of lead dioxide PbO 2 (or) a grid made of lead,
packed with PbO 2. A number of lead plates (anodes) are
connected in parallel and a number of PbO 2 plates (cathodes)
are also connected in parallel. Various plates are separated
from the adjacent one by insulators like rubber (or) glass
fibre. The entire combinations is then immersed in dil.
H2SO 4 (38% by mass) having a density of 1.30 gm/ml.

Working (Discharging)
When the lead-acid storage battery operates, the
following reaction occurs.

At anode: Lead is oxidized to Pb 2 ions, which further

combines with SO 2
4 forms insoluble PbSO 4 .

d ischarging
Pb s  SO 2
4 aq PbSO4 s  2e 
chargin g

At cathode: PbO 2 is reduced to Pb 2 ions, which further

combines with SO 2
4 forms insoluble PbSO 4 .

discharging
PbO 2 s  4H   SO2
4  2e

PbSO 4 s  2H 2O
charging
5.10 Engineering Chemistry

Overall cell reaction during use (discharging):

discharging
Pb s  PbO2 s  2H 2SO 4 aq 2PbSO4 s
charging
 2H 2O  Ener gy

From the above cell reactions it is clear that, PbSO 4

is precipitated at both the electrodes and H2SO 4 is used up.
As a result, the concentration of H2SO 4 decreases and hence
the density of H2SO 4 falls below 1.2 gm/ml. So the battery
needs recharging.

Recharging the Battery

The cell can be charged by passing electric current in
the opposite direction. The electrode reaction gets reversed.
As a result, Pb is deposited on anode and PbO 2 on the
cathode. The density of H2SO 4 also increases.
The net reaction during charging is
char ging
2PbSO 4s  2H 2O  Ener gy Pb s  PbO2 s
dischar ging
 2H 2SO 4 eq

Advantages of lead-acid batteries

(i) It is made easily.
(ii) It produces very high current.
(iii) The self-discharging rate is low when compared to
other rechargeable batteries.
(iv) It also acts effectively at low temperature.

Disadvantages of lead-acid batteries

(i) Recycling of this battery causes environmental hazards.
Storage Devices 5.11

(ii) Mechanical strain and normal bumping reduces battery

capacity.

Uses
1. Lead storage cell is used to supply current mainly in
automobiles such as cars, buses, trucks, etc.,
2. It is also used in gas engine ignition, telephone
exchanges, hospitals, power stations, etc.,

5.4.3 Lithium-ion battery (LIB) (or) Lithium-ion

cell
Lithium-ion battery is a secondary battery. As in lithium
cell, it does not contain metallic lithium as anode. As the name
suggests, the movement of lithium ions are responsible for
charging and discharging.

Components
Lithium-ion cell has the following three components.

 A positive electrode (Layers of lithium-metal oxide)

(cathode)
 A negative electrode (Layers of porous carbon)
(anode)
 An electrolyte (Polymer gel) (separator)

Description

Cathode : Lithium-cobalt oxide LiCoO2 Layers

Anode : Graphite (Porous carbon) layers

Electrolyte : Polymer gel (organic solvent)
5.12 Engineering Chemistry

Construction
The positive electrode is typically made from a layers
of chemical compound called lithium-cobalt oxide
LiCoO2.
The negative electrode is made from layers of porous
carbon (C) (graphite).
Both the electrodes are dipped in a polymer gel electrolyte
(organic solvent) and separated by a separator, which is a
perforated plastic and allows the Li ions to pass through.
Working
Charging
During charging, Li  ions flow from the positive
electrode LiCoO2 to the negative electrode (graphite)

Fig. 5.3 Lithium-ion cell during charging

Storage Devices 5.13

through the electrolyte. Electrons also flow from the positive

electrode to the negative electrode through the wire. The
electrons and Li  ions combine at the negative electrode and
deposit there as Li.

LiCoO 2  C  Li 1  xCoO2  CLi x

Discharging
During discharging, the Li  ions flow back through
the electrolyte from negative electrode to the positive
electrode. Electrons flow from the negative electrode to the
positive electrode through the wire. The Li  ions and
electrons combine at the positive electrode and deposit there
as Li.
Li 1  xCoO2  CLix  LiCoO2  C

Fig. 5.4 Lithium-ion cell during discharging

5.14 Engineering Chemistry

Advantages of lithium-ion batteries

1. It is light in weight.
2. Rate of self-discharge is low.
3. Have higher energy density than other rechargeable
batteries.
4. Have a greater number of charge and discharge cycles.
5. Operates at higher voltage (3.7 V)
6. No liquid electrolyte is used.
7. Easy maintenance.

Disadvantages
1. They are expensive.
2. Availability of lithium is difficult.
3. Difficulties in transportation.
4. Improper disposal leads to environment contamination.
5. It is temperature-sensitive battery and explode at high
temperature.

Applications
1. It is used in portable electronic devices like cellular
phones, digital cameras, tablets and laptop computers.
2. It is used in biomedical implantable devices such as
pace makers.
3. It is currently used in most electric vehicles because
of their high energy per unit mass.
Storage Devices 5.15

$$  5D4; 24;;B

Definition
Fuel cell is a voltaic cell, which converts the
chemical energy of the fuels directly into electricity without
combustion.
Fuel cell converts the energy of the fuel directly into
electricity. In these cells, the reactants, products and
electrolytes pass through the cell.

Fuel  Oxygen  Oxidation products  Electricity .

Example
Hydrogen-oxygen fuel cell.

5dT[ 1PccTah
When a large number of fuel cells are connected in
series, it forms fuel battery.

5.5.1 Hydrogen-Oxygen fuel cell

Hydrogen-oxygen fuel cell is the simplest and most
successful fuel cell, in which the fuel-hydrogen and the
oxidiser-oxygen and the liquid electrolyte are continuously
passed through the cell.

Description

Anode : Porous carbon electrode  Hydrogen H2

Cathode : Porous carbon electrode  oxygen O2

Electrolyte : 25% KOH

Emf : 0.8 to 1.0 V
5.16 Engineering Chemistry

Construction
It consists of two porous electrodes anode and cathode.
These porous electrodes are made of compressed carbon
containing a small amount of catalyst (Pt, Pd, Ag). In
between the two electrodes an electrolytic solution such as
25% KOH (or) NaOH is filled. The two electrodes are
connected through the volt meter.
Working
Hydrogen (the fuel) is bubbled through the anode
compartment, where it is oxidised. The oxygen (oxidiser) is
bubbled through the cathode compartment, where it is
reduced.

Fig 5.5 H2O2 Fuel cell

Storage Devices 5.17

Various reactions

At Anode
Hydrogen gas, passed through the anode, is oxidised
with the liberation of electrons which then combine with
hydroxide ions to form water.

H2  2H   2e 

2H   2OH  2H2O

H2  2OH   2H2O  2e 

Multiply by 2: 2H 2  4OH   4H2O  4e 

At cathode
The electrons, produced at the anode, pass through the
external wire to the cathode where it is absorbed by oxygen
and water to produce hydroxide ions.

O2  4e   2 O2 

2O2   2H2O  4OH 

O2  2H2O  4e   4OH 

Overall cell reaction

At anode: 2H2  4OH  4H2O  4e 

At cathode: O2  2H2O  4e   4OH

2H 2  O2  2H2O
5.18 Engineering Chemistry

 The emf of the cell  0.8 to 1.0 V

Applications of H 2  O 2 fuel cell

1. H2O2 fuel cells are used as auxiliary energy source
in space vehicles, submarines (or) other
military-vehicles.
2. In case of H2O2 fuel cells, the product of water is
proved to be a valuable source of fresh water by the
astronauts.

Advantages of H2  O2 fuel cell

(i) It emits only water vapour and no other harmful
chemicals to the environment.
(ii) Efficiency is more than 75%.
(iii) As hydrogen is the lightest element, it can be
transported easily from one place to another.
(iv) Hydrogen, as a fuel, can replace the use of batteries.
(v) It causes less noise pollution.

Limitations (or) Disadvantages of H2  O2 fuel cell

1. Hydrogen gas is explosive.
2. It is very expensive to be carried out.
3. As hydrogen is a gas, it is difficult to compress into
liquid form.
4. Hydrogen is not present as it is, but always present
in combined form with either oxygen (or) some other
element, so it must be separated first.
5. While using H2  O2 fuel cell in an automobile, a high
pressure must be created inside the engine, which is
risky.
Storage Devices 5.19

5.5.2 Advantage and Disadvantages of Fuel

cells
Advantages of Fuel cells
1. Fuel cells are efficient (75%) and take less time for
operation.
2. It is pollution free technique.
3. It produces electric current directly from the reaction
of a fuel and an oxidiser.
4. It produces drinking water.
Disadvantages of Fuel cells
1. Fuel cells can not store electric energy as other cells do.
2. Electrodes are expensive and short lived.
3. Storage and handling of hydrogen gas is dangerous.

$% <82A>180; 5D4; 24;;B <52B

Definition
Microbial fuel cell is a device that converts chemical
energy to electrical energy by the action of
micro-organisms under anaerobic conditions.
Bioelectricity is generated by the oxidation of organic
waste and renewable biomass using bacteria.
Construction (or) Principle
MFCs are type of electrochemical cells, constructed
using either bioanode and (or) a biocathode. A membrane
separates the compartments of the anode (where oxidation
occurs) and the cathode (where reduction occurs). The
electrons produced during oxidation are transferred directly
to the cathode. The charge balance of the system is
maintained by the ionic movement inside the cell.
5.20 Engineering Chemistry

Components
A typical MFC consists of the following three
compartments.
(i) Anodic compartment
(ii) Cathodic compartment
(iii) Permeable membrane.
(i) Anodic compartment
It consists of microbes suspended under anaerobic
conditions.
(ii) Cathodic compartment
It consists of electron acceptor (oxygen)
(iii) Permeable membrane
Anionic and cationic compartments are separated by a
cation (proton) - exchange membrane.

Fig. 5.6 Microbial Fuel cell

Storage Devices 5.21

Working

At anode compartment
When both the electrodes are connected, at anode,
micro organisms oxidize the organic waste (biomass) and
generates protons, electrons and CO 2

oxidation
Organic waste  H  e   CO2 

At cathode compartment
The electrons move from anode to cathode through the
external circuit. Protons move to the cathode chamber
through proton exchange membrane. At cathode protons and
electrons are combined with oxygen to form water.

4H  4e  O2  2H2O; Eo  1.23 V

Advantages of MFC
1. MFC is an alternative technology for energy
production as no fossil fuel is used.
2. It converts chemical energy of organic waste into
electrical energy, thus minimizes waste.
3. It reduces carbon foot print and environmental pollution.
4. The energy, from MFC, is affordable than fossil and
thermal based sources.

Disadvantages of MFC
1. The initial cost of constructing MFC is high.
2. Power density, generated, is very low.
3. Produces bad odour, as it uses organic wastes.
5.22 Engineering Chemistry

Applications
1. In waste water treatment, MFCs, generate less excess
sludge as compared to the aerobic treatment process.
2. MFCs can be used in river and deep-water
environments, where it is difficult to use batteries.
3. MFCs are used to convert carbon rich wastewater into
methane gas.
4. MFCs are used as convenient biosensor for waste
water streams.
5. MFCs are used in space, especially to operate remotely
operated vehicles.
6. MFCs play an important role in the field of
microbiology, soil chemistry and electrical engineering.
7. Many commercial soil based MFC kits are available
for the purchase on the web and in toy stores.

$&  BD?4A 20?028C>A

Super capacitor is an electronic device that store

large amount of electric charge. They store 10 to 100 times
more energy per unit volume and deliver charge much
faster than batteries.

Unlike ordinary capacitors, super capacitors, do not use

the conventional solid dielectric, but rather they use
electrostatic double-layer capacitance.

Construction (or) Design of super capacitor

Super capacitor consists of two electrodes (made from
metal coated with a porous substance like powdery activated
carbon). Both the electrodes are dipped in an electrolyte
Storage Devices 5.23

solution containing positive and negative ions. Ion-permeable

membrane (separator) separates both the electrodes.

Fig. 5.7 Typical construction of a super capacitor

1. Power source 2. Collector

3. Polarized electrode 4. Helmholtz double layer
5. Electrolyte having positive and negative ions
6. Separator

Working (or) storage principle

When the electrodes are connected to the power
source, one of the electrodes gets positively charged while
the other electrodes gets negatively charged.

The positively charged electrode attracts the negatively

charged ions, present in the electrolyte solution and the
negatively charged electrode attracts the positively charged
ions. This leads to the formation of electrical double layer
at around the electrodes called Helmholtz electric double
layer.
5.24 Engineering Chemistry

This electrical double layer acts as a place of storage

for electric charge. The capacity of storage can be improved
by using activated carbon. As the activated carbon is highly
porous and has many holes in its surface, it stores more
electrical energy at the electrode-electrolyte interface.

5.7.1 Type of super capacitors

Supercapacitors are mainly classified into three types
1. Double layer capacitors
2. Pseudo capacitors
3. Hybrid capacitors

1. Double layer capacitors

It consists of two electrodes with separator and
electrolyte. The electrolyte is the mixture of positive ions
and negative ions dissolved in water. The two electrodes are
separated by a separator.

2. Pseudo capacitors
It stores electrical energy by electron charge transfer
between electrode and electrolyte. This can be done by redox
reaction.

3. Hybrid capacitors
It is developed by using techniques of doubld layer
capacitors and pseudo capacitors. In hybrid capacitor both
double layer capacitance and pseudo capacitance is achieved.
Storage Devices 5.25

Table 5.1: Differences between battery, capacitor and

super capacitor

Super
S.No. Battery Capacitor
Capacitor
1. Can store large cannot store can store large
amount of large amount of amount of charge
charge charge
2. Can not deliver can deliver the can deliver the
the charge very charge quickly charge quickly
quickly

5.7.2 Advantages and disadvantages of super

capacitors
Advantages
1. It is highly safe
2. Its life time is very high (10 to 20 years)
3. It can be cycled millions of time
4. It can be charged in seconds
5. It provides high power density and high load currents
6. Its performance is excellent even at low temperature
 40C

Disadvantages
1. Cost per watt is high
2. It cannot be used as source for continuous power
supply
3. If higher voltage is required, the cells must be
connected in series.
4. High self-discharge, it is higher than most batteries.
5.26 Engineering Chemistry

5.7.3 Applications
Super capacitors are used in many power management
applications like,

1. Voltage stabilization in start/stop system

2. Energy harvesting
3. Kitchen appliances
4. Regenerative braking system
5. Consumer electronics
6. Wind energy
7. Utility meters
8. Remote power for sensors, LEDs, switches
9. Energy efficiency and frequency regulation

$'  0==0 D=8E4AB8CH @D4BC8>=B

1. What is a primary battery. Give an example.

(A.U June 2006)
2. Write a brief note on lead-acid storage cell.
(A.U June 2006)
3. Explain the construction and workings of lead acid
battery.
(A.U June 2006)(Dec. 2005)(Coim AU Jan 2008)
4. What is reversible battery? Describe the construction
and working of lead acid storage battery with reaction
occuring during charging and discharging.
(A.U May 2007)
5. Give the description of lead storage cell and explain
its functioning during discharging and recharging.
(A.U Jan 2013)
Storage Devices 5.27

6. Explain the construction and working of a lead storage

battery. (Coim A.U Jan 2009) (TNV. AU. May 2009)
(Dec 2008, Jan 2013)
7. Describe the principle and functioning (charging and
discharging) of lead acid battery.
(Chen. A.U. June 2009)
8. Explain the construction and working principles of
Lead-acid battery? (TNV A.U. Jan 2010)
9. Explain the construction, working of lead-acid battery,
with relevant sketches. (Coim A.U. Jan 2010)
10. Write notes on Lead acid storage battery.
(TCY A.U. Jan 2010)
11. Explain the construction and working of
Hydrogen-Oxygen fuel cell, giving a neat diagram.
(TNV A.U. Jan 2010)
12. With a neat sketch explain the functioning of
H2  O2 fuel cell. (Coim A.U. Jan 2010)
13. Explain the working of hydrogen-oxygen fuel cell.
(Chen A.U. Jan 2010, Jan 2013)
14. Write short notes on:
Hydrogen-oxygen fuel cell. (TCY A.U. Jan 2010)
15. What are lead accumulators? Explain the constructions
and functioning of a lead accumulator.
(AU June 2014)
16. What is a fuel cell? Explain the working of any one
fuel cell. (AU June 2014)
17. Describe the construction of lead-acid battery with the
reaction occurring during discharge. (A.U Dec 2014)
18. Explain charging and discharging reactions of
lithium-ion cell.
19. Describe the construction and working of
hydrogen-oxygen fuel cell. (A.U Dec 2014)
5.28 Engineering Chemistry

20. Write in detail about lead acid battery.

(AU Dec 2015)
21. Describe the construction of lead-acid battery with
reaction occurring during discharging. (AU June 2016)
22. With a neat diagram, explain the working principle of
H2  O2 fuel cell with cell reaction.
(AU June 2016, May 2017)
23. Write notes on super capacitors.
24. Explain advantages, disadvantages and applications of
super capacitors.