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CHAPTER 2 (ii)

CORROSION PRINCIPLES
Chapter Outlines
2.5 Electrochemical Aspects (cont`)
2.6 Environmental Effects
2.7 Metallurgical and Other Effects
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2.5 Electrochemical Aspects (cont`)


POLARIZATION
The rate of an electrochemical reaction is limited by various
physical and
chemical factors; Hence, an electrochemical reaction is said to be
polarized or
retarded by these environment factors;
What is POLARIZATION
The displacement of the electrode potentials from their
equilibrium
values to a constant potential of some intermediate value
and the
creation of a net current flow;
Polarization can be conveniently divided into two different
types:
(i) Activation polarization
(ii) Concentration polarization
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Polarization can be divided into two (2) different types;


1. Activation Polarization (AP)

AP refers to an electrochemical process/reactions that are


controlled by
a slow step in a reaction sequence at the metal- electrolyte
interface;
That is, there is critical activation energy needed to surmount
the energy barrier associated with the slowest step;
This is easily illustrated by considering hydrogen-evolution
reaction on zinc during corrosion in acid solution;

2. Concentration Polarization (CP)

CP refers to an electrochemical process/reactions that are


controlled by the diffusion of ions in the electrolyte;
This type of polarization is illustrated by considering the
diffusion of hydrogen ions to a metal surface to form hydrogen
gas by the cathodic reaction.

PASSIVITY
The passivation of a metal as it pertains to corrosion refers to the
formation of a protective surface layer of reaction product that
inhibits further reaction;
In other words, the passivation of metals refers to their loss of
chemical reactivity in the presence of a particular environmental
conditions;
There are two (2) main theories regarding the nature of the passive
film:
(i) The oxide-film theory- it is believed that the passive film is always a
diffusion-barrier layer of reaction products (e.g., metal oxides or other
compounds) that are separated the metal from its environment and
slow down the reaction rate;
(ii) The adsorption theory- it is believed that passive metals are covered
by chemisorbed films of oxygen; such a layer is supposed to displaced
the normally adsorbed HO molecules and slow down the rate of
anodic dissolution involving the hydration of metals ions;
The two theories have in common that a protective films forms on the
metal surface to create the passive state, which results in increased
corrosion resistance;
04/02/16

Active region- the behavior of this material is identical to


that of a normal metal;
Passive region- if more oxidizing agent is added, the
corrosion rate shows a sudden decrease, further increases
in oxidizing agents produce little, if any, change in the
corrosion rate of the material;
Transpassive region- at very high concentrations of oxidizers
or in the presence of very powerful oxidizers the corrosion
rate again increase with increasing oxidizer power;
04/02/16

2.6 Environmental Effects

1.
2.
3.
4.
5.

Effect of Oxygen and Oxidizers


Effect of Velocity
Effect of Temperature
Effect of Corrosive Concentration
Effect of Galvanic Coupling
Please refer to Text Book - Fontana

2.7 Metallurgical Aspects


1. Metallic Properties
2. Others (Economic Consideration, Inspection and
Instrumentation)
Metallic Properties- grain boundaries are high-energy
areas and are more active chemically; (e.g., pg 30-31);
Economic consideration- control of corrosion is primary
an economic problem;
Inspection- proper inspection is must-particularly for
critical components operating under hazardous
conditions;
Instrumentation- the revolution brought about by the
introduction of electronic instrumentation into
electrochemistry;

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