GLOBAL ACADEMY OF TECHNOLOGY

Module-1: Electrode System and Corrosion Chemistry

Electrochemistry: Introduction, Electrode Potential, EMF, Expression of Nernst
equation, Numerical problems on Electrode potential, Ion selective electrode-
definition, construction, working and applications of glass electrode. Determination of
pH using glass electrode. Reference electrode-Introduction, calomel electrode-
construction, working and applications of calomel electrode. Concentration cells-
definition, construction and Numerical problems.
Corrosion Engineering: Definition, Electrochemical theory of corrosion, Types of
corrosion-differential metal, differential aeration corrosion, Factors affecting the rate
of corrosion (ratio of anode and cathode, nature of corrosion product, pH and
temperature), corrosion control-cathodic protection, sacrificial anode and impressed
current method.
Electrochemistry
Electrochemistry is a branch of Chemistry which deals with the interconversion of electrical energy
into chemical energy and vice versa that takes place through red-ox reactions.
Electrochemical cell: An electrochemical cell is a device in which chemical energy is converted into
electrical energy (Galvanic cell) or electrical energy into chemical energy (Electrolytic cell).
The electrochemical cell consists of two half cells connected by a salt bridge and a voltmeter. Metal
dipped in the solution of its own ion is known as half-cell.
Electrode Potential:
The potential developed at the interface between the metal and the solution where the metal is in
contact with its own ions.
Electromotive force (EMF):
The potential difference between two electrodes of a galvanic cell which causes the flow of current
from one electrode (higher potential) to the other (lower potential) is called the EMF.
����� = ����ℎ��� − ������
������ = �����ℎ��� − �������
Expression of Nernst equation:
Consider the reaction,
��+ + ��− ↔ �
The Nernst equation is given by,
2.303��
����� = ������ + log [ ��+ ]
��
Where, ����� - electrode potential of the cell
������ - standard electrode potential of the cell and is given by,
������ = �����ℎ��� − �������
R - universal gas constant and R = 8.314Jmol-1K-1

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 1

 GLOBAL ACADEMY OF TECHNOLOGY

F - Faraday constant and F = 96500C

[M]n+ - concentration of metal ions
At 298K, by substituting the values of R, T and F, the Nernst equation becomes,
0.0591 �+
����� = ������ + [� ]
�
In general, for any electrode, Nernst equation can be written as:
0.0591 [���ℎ���� �������������]
����� = ������ + log
� [������ �������������]
Reference Electrodes:
Reference electrodes are electrodes of known electrode potential with which the electrode potential
of any given electrode can be measured.
Reference electrodes are of two types:
1. Primary reference electrodes: Example- Standard hydrogen electrode (SHE)
2. Secondary reference electrodes: Examples- Calomel electrode, Silver-Silver chloride
electrode
Calomel electrode:
Calomel electrode is a metal-metal salt ion electrode. It consists of mercury, mercurous chloride and
solution of KCl. Mercury is placed at the bottom of the glass tube having a side tube at the top.
Mercury is covered with a paste of mercurous chloride with mercury. A solution of KCl is
introduced through the side tube. A platinum wire sealed into a glass tube is dipped into mercury and
used to provide the external electrical contact. Depending on the concentration of the KCl used it
develops potential. If saturated KCl solution is used it develops a potential of 0.2422V. The
electrode is reversible with chloride ions.

The cell is represented as Hg / Hg2Cl2 / Cl-

The calomel electrode can acts as anode or cathode depending on the nature of the other electrode of
the cell.
 When it acts as anode: 2Hg + 2Cl− → Hg2Cl2 + 2e−

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 2

 GLOBAL ACADEMY OF TECHNOLOGY

 When it acts as cathode : ��2 ��2 + 2�− → 2Hg +2Cl−

Equilibrium reaction: ��2 ��2 + 2�− ↔ 2Hg +2Cl−
The electrode potential is given by,
E = Eo − 0.0591 log [��− ] at 298K
Advantages of Calomel electrode:
1. It has simple construction
2. Cell potential is constant over a longer period
3. The cell potential does not vary with temperature
4. The cell potential is reproducible.
Applications of Calomel electrode:
1. Calomel electrode is used as secondary reference electrode in the measurement of electrode
potential.
2. It is most commonly used as reference electrode in all potentiometric & pH determinations.
Ion selective electrodes/ Membrane electrodes:
Ion selective electrode is the electrode which selectively responds to a specific ion in a mixture and
the potential developed at the electrode is a function of the concentration of that ion in the solution.
Example: a) glass electrode (exchanges H+ ions with the solution)
b) LaF3 electrode for fluoride determination
Glass Electrode:
Glass electrode is a pH sensitive electrode, most widely used for pH determination. The glass
electrode consists of a glass bulb made up of special type of glass (corning glass) with high
electrical conductance. The glass bulb is filled with 0.1M HCl and is inserted with a Ag-AgCl
electrode, which is the internal reference electrode and also serves for the external electrical contact.
The electrode is dipped in a solution containing H+ ions.
The glass electrode can be represented as Ag / AgCl / 0.1M HCl / glass

When dipped in a solution it can be represented as,

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 3

 GLOBAL ACADEMY OF TECHNOLOGY

The exchange of ions by the inner and outer membrane gives rise to a boundary potential. This
boundary potential consists of two potentials E1 and E2 which are associated with the outer and inner
membranes respectively.
�� = �1 − �2
The potential of the glass electrode is given by,
�� = �0� + 0.0591log [�+ ]
Determination of pH by using glass electrode:
In this experiment glass electrode is combined with calomel electrode. Glass electrode acts as
indicator electrode and calomel acts reference electrode. Both the electrodes are connected to a pH
meter and both the electrodes are dipped into the given unknown pH solution.

The cell assembly is represented as

Hg/Hg2Cl2/Cl-//solution of unknown pH/ glass/ HCl(0.1M)/AgCl/Ag
The pH is determined by using following relation,
Ecell = EGlass - Ecalomel ……………. (1)
For glass electrode,
EGlass = EG0 + 0.0591 log[H+] {-log[H+] = pH}
EGlass = EG0 - 0.0591pH ………... (2)
Substituting (2) in (1)
Ecell = E0G –0.0591pH- Ecalomel
(E0G −Ecalomel −Ecell )
pH =
0.0591

Concentration Cells:
Concentration cells are the galvanic cells in which anode and the cathode are made up of similar
metals, which are dipped in the solution of its own ions of different concentrations. The electrode
which is in contact with higher electrolyte concentration acts as cathode and the one with lower
electrolyte concentration acts as anode.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 4

 GLOBAL ACADEMY OF TECHNOLOGY

The EMF of the concentration cells is given by the Nernst equation,

0.0591 [C2 ]
E= log
n [C1 ]
Where C2> C1
Ex: Zinc concentration cell

It consists of anode and cathode made up zinc dipped in zinc sulphate solution of different
concentrations. Both the half cell is internally connected by means of salt bridge and externally by a
wire through an ammeter.
Cell reactions:
Anode: Zn → Zn2+
(c1) + 2�
−

Cathode: Zn2+ −
(c2 ) + 2� → Zn

Cell can be represented as Zn/��2+ 2+

(�1 ) // ��(�2) /Zn

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 5

 GLOBAL ACADEMY OF TECHNOLOGY

Corrosion Engineering
Introduction:
Corrosion is a process of destruction or deterioration of metal by the environment through chemical
or electrochemical reactions.
Most of the metals and alloys undergo corrosion except the noble metals. Corrosion is like “Cancer”
for the metals.
Eg: Rusting of Iron- it is due to the formation of hydrated ferric oxide.

Types of corrosion:

1. Dry Corrosion: Corrosion taking place in the absence of moisture that is the direct chemical
reaction taking place between metal and dry gases.

2. Wet Corrosion: Corrosion taking place in the presence of moisture or aqueous wet environment.

Electrochemical Theory of Corrosion:

Electrochemical theory explains wet corrosion.
According to electrochemical theory, corrosion of metal takes place due to the formation of anodic
and cathodic regions on the same metal surface or when two different metals are in contact with each
other in the presence of a conducting medium.

 When a metal is exposed to the aqueous environment it divides the metal into two parts as anode
and cathode on the same metal surface.
 At anodic region, oxidation takes place where electrons are liberated and corrosion takes place at
the anode.
 Cathodic region is protected as it undergoes reduction where it consumes or accepts liberated
electron.
 Anodic and cathodic reactions are going to take place due to metal impurities in bulk amount
and difference in oxygen concentration on the metal surface.
 Part of the metal with lesser oxygen concentration acts as anode which undergoes oxidation.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 6

 GLOBAL ACADEMY OF TECHNOLOGY

 Part of the metal with higher oxygen concentration acts as cathode undergoes reduction.
Corrosion reactions:
Anodic reaction:
Oxidation of metal takes place where metal gets converted into its ion.
M → ��+ + ��−
Cathodic reaction:
Two types of reactions are occur
1. Liberation of hydrogen in the absence of oxygen:
i. In acidic medium, cathodic reaction is
2�+ + 2�− → �2
ii. In neutral or alkaline medium, hydroxide ions are formed.
2�2 � + 2�− → 2��− + �2
2. Absorption of oxygen:
i. In acidic medium, water is formed.
4�+ + 2�− + �2 → 2�2 �
ii. In neutral medium, hydroxide ions are formed.
1
�2 � + �2 + 2�− → 2��−
2
Example: when the surface of iron is exposed to corrosive environment, the following reactions take
place,
Anodic reaction: Fe → Fe2+ + 2e−
1
Cathodic reaction: �2 � + 2 �2 + 2�− → 2��−

Fe2+ ions and OH- ions defuse towards each other and form ferrous hydroxide (corrosion product),
which undergo further oxidation in presence of oxygen to form rust.
��2+ + 2��− → ��(��)2 (insoluble)
1
2��(��)2 + �2 � + �2 → (��2 �3 . 3�2 �)
2
Rust
Types of corrosion:
Differential metal corrosion (galvanic corrosion):
 Differential metal corrosion occurs when two dissimilar metals having different electrode
potential are in contact with each other and exposed to the corrosive environment.
 The metal with lower electrode potential acts as anode, which undergoes corrosion.
 The metal with higher electrode potential acts as cathode and is unaffected by the corrosion.
 The potential difference between two metals is a driving force for the corrosion.
Eg: When iron is in contact with copper.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 7

 GLOBAL ACADEMY OF TECHNOLOGY

Fe has lower electrode potential when compared to copper. Hence, iron undergoes oxidation and gets
corroded.
Reactions:
At anode: Fe → Fe2+ + 2e−
1
At cathode: �2 � + 2 �2 + 2�− → 2��−

��2+ + 2��− → ��(��)2 (insoluble)

1
2��(��)2 + �2 � + 2 �2 → (��2 �3 . 3�2 �)
Rust
Other examples
1. Steel screws in copper sheet.
2. Steel screws with copper washer.
3. Nut and bolts made of different metals.

Differential aeration corrosion:

 Differential aeration corrosion occurs when a metal surface is exposed different oxygen
concentration.
 Part of the metal exposed to higher oxygen concentration acts as cathode and metal exposed to
lower oxygen concentration acts as anode.
 The anodic region undergoes oxidation and gets corroded.
Eg: When iron rod partially dipped in water.

Reactions:
At anode: Fe → Fe2+ + 2e−
1
At cathode: �2 � + 2 �2 + 2�− → 2��−
��2+ + 2��− → ��(��)2 (insoluble)
1
2��(��)2 + �2 � + �2 → (��2 �3 . 3�2 �)
2
Rust
Eg: a) Part of nail inside the wall undergoes corrosion.
b) Partially buried pipeline in soil undergoes corrosion.

Differential aeration corrosion is divided in to two types:

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 8

 GLOBAL ACADEMY OF TECHNOLOGY

Water line corrosion:

This is due to differential oxygen concentration.

Eg: Water storage Iron tank

When a steel tank partially filled with water for a long time, the inner portion of the tank below the
water line is exposed only to dissolved oxygen whereas the portion above waterline is exposed to
more oxygen. Thus the portion below the water acts as anode and undergoes corrosion. The upper
portion acts as cathode and it is unaffected.

Pitting Corrosion:

When a small dust particle gets deposited on the metal surface, the region below the dust particle is
exposed to less oxygen when compared to remaining part of the metal. Therefore region below dust
particle acts as anode and undergoes corrosion and forms a pit. Here the formation of small anodic
area and large cathodic area results in intense corrosion below the dust particle.

Factors affecting the rate of corrosion:

1. Ratio of anodic and cathodic areas:

The rate of corrosion depends on the size of anodic and cathodic area.
(i) If the metal forms small anodic region and larger cathodic region then corrosion is faster and
intensive at anodic region.
At anode, oxidation takes place and electrons are liberated. At cathode, electrons are consumed.
When anode area is smaller, electrons liberated at anode is rapidly consumed at larger cathodic
area. This process makes anodic reaction to take place at maximum and rate of corrosion increases.
(ii) If cathode area is smaller than anode area, the consumption of electrons will be slower and hence,
the anode reaction becomes slower and rate of corrosion decreases.
Eg: Broken coating of Tin (larger cathodic area) on iron surface (smaller anodic area). It
undergoes rapid corrosion.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 9

 GLOBAL ACADEMY OF TECHNOLOGY

Eg: Broken coating of Tin (larger cathodic area) on iron surface (smaller anodic area).
It undergoes rapid corrosion.

2. Nature of corrosion product:

When the corrosion product is deposited on the surface of the metal,

 If the corrosion product formed is insoluble, stable, uniform and non-porous, it acts like barrier
between the metal and the corrosion atmosphere, which prevents further corrosion.

Eg: Aluminium, Titanium and chromium form a protective film of metal oxide on surface and
prevents further corrosion
 On the other hand, if corrosion product is soluble, unstable, non-uniform and porous, rate of
corrosion is fast and continuous.


Eg: Zinc, Iron and Magnesium corrosion product formed do not form protective film and
corrosion continues.

3. Nature of medium:

 pH of corrosion medium:

At Acidic: pH 2-4
The rate of corrosion is very high, this is because the liberation of hydrogen at cathode and
increases the anodic reaction. (But exceptionfor Al, Zn, shows faster in alkaline medium.)

At Basic: pH 10-13
The rate of corrosion decreases, this is because the formation of a thin layer of metal hydroxide on
the metal surface & acts as a barrier between the fresh metal atoms.

At neutral: pH 7
The rate of corrosion is moderate.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 10

 GLOBAL ACADEMY OF TECHNOLOGY

 Temperature:

In general, the rate of chemical reaction increases with increase in temperature. Corrosion is one
such chemical reaction.

At Higher temp: The ionic conductivity of the corrosion medium is high as a result the movement
of ion increases and hence, the rate of corrosion increases.
At Lower temp: The ionic conductivity of the corrosion medium is low as a result the movement
of ion decreases and hence, the rate of corrosion decreases.
corrosion rate.

Corrosion Control:

Cathodic Protection:

a). Sacrifical anodic method:

In this method, the metal or an alloy buried inside the soil is protected from the corrosion by
converting the metal completely into cathode and no part of the metal is allowed to act as anode.

1. The metal structure to be protected is connected to the metal whose electrode potential value is
less . Eg: Mg, Al, Zn etc or more active metal.
2. The metal structure acts as a cathode.
3. The active metal acts as an anode.
4. These active metals undergo corrosion, protectingthe metal structure.
5. Since the anodic metal is sacrificed to protect the metal structure, the method is called as
Sacrificialanodic method.
6. The exhausted sacrificial anodes are replaced with newone when it is required.
Eg: Mg block connected to a buried pipe tank in wateror soil
Mg block connected to underground oil storage tank.

b) Impressed current method:

1. The metal structure to be protected is connected to the inert material ex. Graphite.
2. Apply direct current larger than the corrosion current.
3. The metal to be protected is made cathode by connecting it to the cathode of an external source
of current.
4. The inert material ex. Graphite is made as Anode by connecting it to the anode of an external
electric sources.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 11

 GLOBAL ACADEMY OF TECHNOLOGY

5. The metal structure being cathode does not undergo corrosion.

6. Anode being inert remains unaffected.
Eg: Platinum, graphite, silicon, iron are used as anodes.

DR. ANU K S, ASSISTANT PROFESSOR, DEPARTMENT OF CHEMISTRY 12