CORROSION

Dr. E. Laxminarayana
M.Sc., Ph.D., M.L.I.S., M.I.S.T.E.
Associate Professor of Chemistry,

SNIST-Hyderabad.

Dr. E. Laxminarayana
 CORROSION

 Most of the metals (Except Au, Pt) exist in nature in

combined state as their Oxides due to its reactivity.
 These are reduced to get Metals (Extraction of
metals)
 Extraction of the metals is a reduction process.
 When the metals are exposed to environment
destruction starts at the surface.
 This destruction may be due to direct attack of
chemical or electrochemical
 Reverse of extraction of metals is called Corrosion
 “Any process of destruction or deterioration of metals
through chemical or electro chemical attack by its
environment is called Corrosion”

Dr. E. Laxminarayana
 CORROSION

Types of corrosion:
1. Dry (Chemical or Direct) Corrosion
2. Wet (Electro chemical) corrosion
3. Underground (soil) Corrosion
4. Pitting Corrosion
5. Stress Corrosion
6. Galvanic Corrosion
7. Concentration cell (Deferential aeration)
Corrosion

Dr. E. Laxminarayana
 CORROSION
Dry corrosion or Chemical corrosion:
 This type of corrosion occurs through the direct attack of
chemicals
 There are three main types of chemical corrosion
 Oxidation corrosion
 Corrosion by other gases (SO2, CO2, Cl2 etc.,)
 Liquid metal corrosion
Oxidation corrosion:
 It occurs by the direct attack of oxygen at low or high
temperatures on metals.
 It is caused in absence of the moisture.
 At low temperature alkali and alkaline earth metals are
rapidly oxidized and at high temperature almost all metals
(except Au, Ag, and Pt) are oxidized.

2M 2 M2+ + 2e- (Oxidation)

O2 2 O2- (Reduction)
M + O2 Metal oxide Dr. E. Laxminarayana
CORROSION

Dr. E. Laxminarayana
 CORROSION
Mechanism:
Oxidation occurs first at the surface of the metal and the
resulting metal oxide forms a barrier.
Either metal ion diffuse out side or oxide must diffuse inwards
through the scale.
Diffusion of metal ion out side is much faster than the oxygen
diffusion
Nature of oxide formed: This oxide plays an important role in
oxidation corrosion.
1.Stable:
A stable layer is fine grained and gets adhered to the parent
metal surface.
So, it acts as protective layer
Further corrosion is prevented for these metals.
Ex.: oxides of Al, Sn, Pb, Cu, etc. Dr. E. Laxminarayana
 CORROSION

ii) Unstable: If the oxide formed is unstable,

decomposes back into the metal and oxygen.
So, corrosion is not possible.
Ex.: oxide of Pt
iii) Volatile:
 If the oxide formed is volatile in nature it

volatizes as soon as it is formed.

 So, corrosion rate increases rapidly.

Ex.: oxide of Mo

Dr. E. Laxminarayana
 CORROSION

iv) Porous: i.e., having pores or cracks. This

causes continuous corrosion.
Ex.: oxide of K, Na, etc.
This is explained based on the Pilling-
Berworth Rule
 According to this rule “an anode is protective
or non-porous, if the volume of the oxide is
greater than the volume of metal.”
 It is explained based on the ratio of the
metal oxide volume to the metal volume.
 Porous layers usually contain PBR less than 1
and non-porous layer greater than 1.

Dr. E. Laxminarayana
 CORROSION
Corrosion by other Gases:
 The gases like SO2, CO2, Cl2, H2S etc. may also cause
corrosion.
 The extent of the corrosion depends on the chemical
affinity between metal and the gas.
 The degree of attack depends on the formation of
protective or non-protective films on the metal surface.
Liquid metal corrosion:
 It is due to chemical action of flowing liquid metal at
high temperature on solid metal or alloy.
 It involves either dissolution of a solid metal by a liquid
metal; or internal penetration of liquid metal into the
solid metal

Dr. E. Laxminarayana
 CORROSION

WET OR ELECTROCHEMICAL CORROSION:

This type of corrosion occurs
i. Where a conducting liquid is in conducting with
metal (or)
ii. When two dissimilar metals or alloys are
immersed partially in a solution.
 Two metals act as electrodes and current flows
through the conducting solution.
 At anode oxidation reaction takes place, so
anodic metal is destroyed.
 Hence, corrosion always occurs at anode.
 But the cathode is not affected.
Dr. E. Laxminarayana
 CORROSION
Mechanism of action:
 The stability of the metal ion formed at

anode is stabilized either by

 Evolution of hydrogen (or )

 Absorption of Oxygen.

Evolution of Hydrogen type:

 Usually corrosion occurs in acidic medium

 Fe metal converts into ferrous ions at anode

by liberation of the electrons.

Dr. E. Laxminarayana
 CORROSION

Fe Fe+2 + 2e- (oxidation)

These electrons flow through the metal from anode to cathode

The hydrogen ions present at cathode eliminated as H2 gas.

2H+ + 2e- H2 (Reduction)

+ +2
Fe + 2H Fe + H2

Dr. E. Laxminarayana
 CORROSION
 This type of corrosion causes displacement of H+
ions from acidic solution by metal ions.
 In this type of corrosion anodes are large areas;
where as cathodes are small areas.
Absorption of Oxygen:
 Common example is rusting of iron in neutral
medium (NaCl)
 The surface of iron always coated with iron
oxide. If some cracks are developed on this
metal oxide, anodic areas are created; while the
well metal parts act as cathodes.
 In this type of corrosion anodes are small areas;
where as cathodes are large areas.

Dr. E. Laxminarayana
 CORROSION

At anode:
Fe Fe+2 + 2e- (oxidation)

At cathode:
The liberated electrons are absorbed by dissolved oxygen.

1/2 O2 + H2O + 2e- 2 OH-

The Fe+2 and OH- diffuse and combine to form Fe(OH)2

Fe+2 + 2 OH- Fe(OH)2

Dr. E. Laxminarayana
 CORROSION
 If enough oxygen is present it will be oxidized to
form ferric hydroxide or yellow rust.
 If oxygen is limited the corrosion product will be
black rust / anhydrous magnetite.

Factors influencing the corrosion:

The rate and extent corrosion of corrosion depends
on
 Nature of metal
 Nature of corroding environment

Dr. E. Laxminarayana
 CORROSION
1. Nature of the metal:
Position in galvanic series:
 When two metals are electrical contact in
presence of an electrolyte the more active
metal undergoes corrosion.
 The rate depends on the difference in their
position in galvanic series.
 Greater the difference is the faster the
corrosion of the anode.
Over voltage:
 When a metal, which occupies high position in
galvanic series, is placed in 1N H2SO4 it
corrodes and produces small EMF. If a few
drops of CuSO4 is added corrosion rate
accelerates.
 Relative areas of anodic and cathodic parts:
Corrosion rate is rapid, when anodic areas are
small because of the demand for e-.

Dr. E. Laxminarayana
 CORROSION
Purity of the metal:
Impurities in the metal cause heterogeneity and form
electrochemical cells.
Physical state:
The smaller the grain-size of metal is greater will be
solubility, hence rate of corrosion increases.
Nature of surface film:
It can be explained based on the specific volume
ratio.
Specific volume ratio = vol. of metal oxide / vol. of
metal
Greater the specific volume ratio, lesser the
oxidation.
Solubility: Solubility increases the rate of corrosion.
Volatility: Volatility increases the rate of corrosion.

Dr. E. Laxminarayana
 CORROSION
2. Nature of the corroding medium:
Temperature:
 Corrosion rate increases with increasing temperature.

Humidity:
 As the humidity present in the air increases corrosion rate
increases. Critical humidity is the relative humidity above
which the atmospheric corrosion rate of metal increases
sharply.
Presence of the impurities:
 If the impurities like CO , SO , H S etc. increases rate
2 2 2
corrosion.
 Presence of suspended particles also increases rate
corrosion

Dr. E. Laxminarayana
 CORROSION

pH:
 Acidic media is more corrosive than alkaline
and neutral media.
Formation of O2 concentration cell:

Dr. E. Laxminarayana
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Galvanising

Dr. E. Laxminarayana
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Tinning

Dr. E. Laxminarayana
 CORROSION
Metal cladding:

Dr. E. Laxminarayana
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Electroplating:

Dr. E. Laxminarayana