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 H2
Oxygen reduction in acid solutions:
O2 + 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,

Zn 2 HCl ZnCl

H 2 -------------------- -(1)

Written in ionic form as,

Zn 2 H 2Cl Zn 2 2Cl H 2

----------------------(2)

The net reaction being,

Zn 2 H Zn 2 H 2

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

Equation (3) is the summation of two partial reactions,

Zn Zn 2* 2e -----------------------------------------(4) and
2 H 2e H 2 ------------------------------------------(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 CORROSIONMIXED 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.