PRINCIPLES OF

CORROSION
Dr. T. K. G. Namboodhiri
(Retd. Professor, Inst. Of Tech. , Banaras
Hindu University)
Consultant-Metallurgy & Corrosion,
Tiruvalla, Kerala


INTRODUCTION
Metallic corrosion reactions are
electrochemical in nature.
An electrochemical reaction is
associated with charge transfer in
addition to mass transfer.
All electrochemical reactions may be
split into two or more partial
oxidation and reduction reactions.
ELECTROCHEMICAL CELL
ANODE REACTIONS
Anode metal corrodes and metal ions
get into solution as:
If steel is corroding,
If Aluminum is corroding,
These reactions are also called
Oxidation reactions.
CATHODE REACTIONS
The cathodic reaction consumes the
electrons generated by the anodic
reaction.
In nature, and neutral or basic
environments containing oxygen, the
cathodic reaction is:
OTHER CATHODE REACTIONS
Hydrogen ion reduction or hydrogen
evolution: 2 H
+

+ 2 e H
2

Oxygen reduction in acid solutions:
O
2
+ 4 H
+
+ 4 e 2 H
2
O
Metal ion reduction:
M
+n
+ e M
+(n-1)

Metal deposition: M
+n
+ ne M


ELECTROCHEMISTRY OF
CORROSION
DISSOLUTION OF ZN METAL IN HYDROCHLORIC ACID,

2 2
2 H ZnCl HCl Zn -------------------- -(1)
Written in ionic form as,
2
2
2 2 2 H Cl Zn Cl H Zn

----------------------(2)
The net reaction being,
2
2
2 H Zn H Zn

------------------------- (3)

Equation (3) is the summation of two partial reactions,
e Zn Zn 2
* 2
-----------------------------------------(4) and
2
2 2 H e H

------------------------------------------(5)
Equation (4) is the oxidation / anodic reaction and
Equation (5) is the reduction / cathodic reaction
CORROSION OF ZINC IN HCl
THERMODYNAMICS IN
CORROSION
THERMODYNAMICS OF
CORROSION
Like any reaction, electrode reactions involved in
corrosion are associated with a decrease in free energy
The free energy change is related to the electrode
potential by the relationship
G = -nFE
Where,
G is the free energy change in joules

n is the number of electrons involved in the
reaction
E is the electrode potential in volts
The single electrode potential is a measure of the
tendency for the reaction to take place. Negative
potentials indicate spontaneous reaction.
STANDARD ELECTRODE
POTENTIAL & POLARIZATION
Standard electrode potential is the
potential developed when all the reactants
have unit activity and the temperature is
25 degree C. Oxidation and reduction
reactions are of equal rate.
When these reactions are not equal, there
will be a net oxidation or reduction and
the potential shifts away from its
equilibrium value. This process is
polarization.

POURBAIX DIAGRAM OF IRON
Pourbaix diagram
is a potential-PH
plot showing the
stability of various
metal compounds
Based on the
stability of the
various phases, we
can predict regions
of corrosion,
immunity,
passivation etc
KINETICS OF CORROSION-
MIXED POTENTIAL THEORY
The mixed potential
theory of Wagner and
Traud consists of two
simple hypotheses,
1) any electrochemical
reaction can be split
into two or more partial
oxidation and reduction
reactions, and
2) there can be no net
accumulation of
electrical charge during
an electrochemical
reaction
Kinetics- Corrosion rate & Potential
Anodic & cathodic
reactions occur
simultaneously at
different parts of the
metal.
Electrode potentials
of the two reactions
converge to the
corrosion potential by
polarization
The current density at
this potential gives
the rate of corrosion
PASSIVATION
Many metals like Cr,
Ti, Al, Ni and Fe
exhibit a reduction in
their corrosion rate
above certain critical
potential because of
the formation of a
protective, thin oxide
film.
Passivation is the
reason for the
excellent corrosion
resistance of Al and
S.S.