1. Why metals undergo corrosion?

In nature, metals are not found in free state

due to their reactivity.
It is the ore from which the metals are
extracted by metallurgical process.
2.Why metals are not found in their free
state?
The metals are thermodynamically unstable
in their free state. They are stable in the form
of certain compounds. This is given as:

2. What are different theories of corrosion?

There are three theories of corrosion:
(i) acid theory,
(ii) dry or chemical corrosion
(iii) wet or electrochemical corrosion.

1) Acid theory of corrosion

This theory suggests that corrosion of a metal
(iron) is due to the presence of acids surrounding
it.
According to this theory, iron is corroded by
atmospheric carbon dioxide, moisture and
oxygen.

 The corrosion products are the mixture of

Fe(HCO3)2, Fe(OH)CO3 and Fe(OH)3.
The chemical reactions suggested are given
below

Further, the process of rusting is reduced by the

presence of lime and caustic soda (these two
can absorb CO2, thus reducing corrosion).

 2) Dry or Chemical Corrosion:

The direct chemical action of atmospheric
gases like oxygen, halogen, H2S - solid film
of the corrosion = chemical Corrosion.
A solid film protects the metal from further
corrosion.
If a soluble or volatile corrosion product is
formed, then the metal is exposed to further
attack.

 For example, chlorine attack silver generating a

protective film of silver chloride on the surface.

The extent of corrosion depends on the

chemical affinity of the metal towards reactive
gas.
Oxygen is mainly responsible for the corrosion
of most metallic substances.

 There are three main types of dry corrosion:

(i) Oxidation corrosion (Reaction with
oxygen):
Some of the metals directly react with
oxygen in the absence of moisture.

If diffusion of oxygen across this layer,

further corrosion is possible.

 Thus, the layer of metal oxide plays an important

role in the process of corrosion.
Oxides of Pb, Al and Sn are stable and hence inhibit
further corrosion.
Pilling Bedworth Rule:
If volume of metal oxide on the surface of a metal
is more than or equal to the volume of metal, the
oxide layer will be protective.
For example, for Al2O3, Fe, Ni, Zn, Cr.
It will be non-protective if volume of oxide is less
than volume of metal.

 (ii) Corrosion by other gases:

In dry atmosphere, gases react with metal
and form corrosion products which may be
protective or non-protective.
Dry Cl2 reacts with Ag and forms AgCl which
is a protective layer, while SnCl4 is volatile.
In petroleum industries at high temperatures,
H2S attacks steel forming FeS scale which is
porous and interferes with normal operations.

 (iii) Liquid metal corrosion:

In several industries, molten metal passes
through metallic pipes and causes corrosion
due to dissolution or due to internal
penetration.
For example, liquid metal mercury dissolves
most metals by forming amalgams, thereby
corroding them.

 Nature of the oxide formed play an important

part in oxidation corrosion process:
Metal + O2
product)

Metal oxide (corrosion

Types of oxide films:

Stable
(No further corrosion)
Unstable
(Metal oxide
Metal + O2)
Hence Ag, Au, Pt do not under go oxidation
corrosion.
Volatile
(Frequent attack)
Porous
(Attack till complete corrosion)

 3) Wet or Electrochemical Corrosion:

It is a common type of corrosion of metal in aqueous

corrosive environment.

This type of corrosion occurs when the metal comes in

contact with a conducting liquid or when two
dissimilar metals are immersed or dipped partly in a
solution.

According to this theory, there is the formation of a

galvanic cell on the surface of metals.

Some parts of the metal surface act as anode and rest

act as cathode.

At Anode

M
ne-

Mn+

Metal ion

ion
Metal
Mn+
solution

Dissolves in

Forms compounds such as oxide

The chemical in the environment and humidity acts as

an electrolyte, which flows through the anode and
cathode.

Anode = Oxidation (liberation of free electrons)

So, anodic metal is destroyed, hence corrosion always
starts at anodic area.

Cathode = Reduction (gain of electrons).

Cathode reactions do not affect cathode most metals

cannot be further reduced.

At cathodic part, dissolved constituents in the conducting

medium accept the electron to form some ions (like OH -,
O2-).

The metallic ion (anodic part) & non-metallic ion

(cathodic part) diffuse through each other through
conducting medium and forms corrosion product between
anode & cathode.

On a whole an electrochemical corrosion involves:

Formation of anodic and cathodic areas
Presence of conducting medium
Corrosion of anodic areas only
Formation of corrosion product between A & C area.

 Mechanism:
At anodic area
M
Mn+

+ ne-

Cathodic part may consumes e- by:

1) Evolution of H2 gas or
2) Absorption of O2.
1) Evolution of H2 type corrosion occurs in
acidic environments.
Fe
Fe2+ + 2e(Oxidation)

 These electrons flow through the metals from

anode to cathode, where H+ ions (of acidic
solution) are eliminated as H2 gas.
2H+ + 2e(Reduction)
Over all reaction:
Fe + 2H+

H2 gas

Fe2+

+ H2 gas

 2) Absorption of O2:
Rusting of iron in natural aqueous or basic solution
of electrolytes (like NaCl solution) in the presence
of atmospheric O2 is a common example.
At anodic area: metal dissolve as Ferrous ions with
liberation of e-.
Fe
Fe2+ + 2e(Oxidation)
The liberated e- flow from anodic to cathodic area
through metals, these e- were taken up by
dissolved O2.
O2 + H2O + 2e-

2OH-

 Fe2+ (at anode) and OH- ions (at cathode)

diffuse and lead to the formation of ferrous
hydroxide.
Fe2+

+ 2OH-

Fe(OH)2

Types of
Corrosion

 Galvanic corrosion:
This type of electrochemical corrosion is also
called bimetallic corrosion.
When two dissimilar metals are connected and
exposed to an electrolyte, they will form a
galvanic cell.
The anodic metal will be oxidized and it will
undergo corrosion.
Zinc and copper metals connected with each other
in an electrolyte medium form a galvanic cell.

In acidic solution H2 evolution

M
M2+ + 2e2H+

2e-

H2 gas

(Oxidation)
(Reduction)

May induce H2 gas pressure on metal or metal

hydride

 In neutral or basic solution O2 absorption

M
M2+ + 2e(Oxidation)
O2 + H2O + 2e-

2OH-

OH- ions (at cathode) diffuse and lead to the

formation of Metal hydroxide.

 Concentration Cell Corrosion:

Due to electrochemical attack on metal surface.

Metal exposed to electrolyte of varying concentration

or of varying aeration.

Local difference in metal ion concentration.

Differential aeration corrosion one part of metal is

exposed to different air concentration than the other.

This causes difference in the potential

Less O2 part = Anodic

More O2 part = cathode

Part above the water line (more O2) = cathode, while

part immersed in greater depth = anode.

Here a differential potential is created which causes a

flow of current between the two differentially aerated
areas of same metal.

Zn

O2 + H2O + 2e-

The circuit complete with the migration of electrons

from anode to cathode.

Ex. Iron with drop of water - Corrodes

Zn2+ + 2e-

(Oxidn)
2OH-

(Redn)

 Pitting Corrosion: (Pin hole, Pit, Cavity)

Passivity or Passivation:

Metal or alloy exhibit higher corrosion resistance.

This is nothing but the formation of insoluble,

nonporous, thin, invisible, protective film (0.0004 mm
thick) on the surface of metal.

Ex. of Passive metals are Ti, Al, Cr, wide variety of

stainless steel alloy containing Cr.

Pitting corrosion is a localized accelerated attack.

Cause due to breakdown or cracking of protective film

on a metal at specific point.

This causes small anodic and large cathodic area.

Film breakdown is due to

Surface Roughness, Non-uniform Finish, Scratch, Chemical
Attack

The presence of extraneous impurities like sand, dust,

scale, etc, embedded on the surface of metal also lead
to pitting.

 Water Line Corrosion:

Water in a iron tank corrosion takes place just below

the level of water meniscus.

Above waterline High O2 Cathode

The portion of iron tank just below the water level

(Anode) undergoes corrosion.

It is due to the difference in oxygen concentration.

Corroding portion is poor in oxygen and acts as anode

 Soil corrosion:
Underground pipes, cables, etc. corrode due to soil
corrosion.
It is caused due to moisture, pH of soil and microorganisms.
The differential aeration is also the cause of corrosion.
Microbiological corrosion:
Some types of bacteria consume oxygen and cause
differential aeration type of system which results in
corrosion.
The corrosion occurs at the portion poor in oxygen
concentration.
Ex: The bacillus, algae

Factors Influencing
Rate of Corrosion

 Factors influencing rate of corrosion:

1.Nature of the metal: The tendency of the
metal to undergo corrosion is mainly
dependent on the nature of the metal.
Among two metals or alloys - more reactive more susceptible for corrosion
eg: K, Na, Mg, Zn
where as in case of noble metals like Ag, Au,
Pt their corrosion rate are negligible.

 2. Surface state of the metal(passivity):

If the oxide layer forms on the metal surface
is soluble, unstable and porous in nature and
have an appreciable conductivity, they
cannot control corrosion on the metal surface
for eg: oxide layer formed on metals like Zn,
Fe, Mg etc.
Ex. Ti, Al, Cr, wide variety of stainless steel
alloy containing Cr, can be a better option.

 3. Anodic and Cathodic area:

The rate of the corrosion is greatly influenced by the
relative sizes of cathodic and anodic areas.

If the metal has smaller the anodic area and larger the
cathodic area exposed to corrosive atmosphere, more
intense and faster is the corrosion occurring at anodic area
because at anode oxidation takes place and electrons are
liberated.
At the cathode these electrons are consumed. When anode
is smaller and cathode region is larger all the liberated
electrons at anode are rapidly consumed.
This process makes the anodic reaction to takes place at its
maximum rate thus increasing the corrosion rate.

 If the cathode is smaller and reverse process

takes place decrease rate of corrosion.
For eg: If tin (Sn) coated on iron (Fe) and in that
some area are not covered or some pin holes
are left, there forms smaller anodic area and
larger cathodic area because tin is cathodic with
respect to iron so intense localized corrosion
takes place.
On the other hand if Zn coated to Fe then if
there are some pin holes it will create larger
anodic area and smaller cathodic area because
Fe is cathodic with respect to zinc so that rate of
corrosion is very less.

 4. Purity of Metal:
Small impurity heterogeneity small
electrochemical cell anodic part will corrode.
Ex. Zn metal containing small impurity of Pb or Fe.
5. Physical State of Metal:
It includes grain size, orientation of crystal, stress,
etc.
Smaller grain size more solubility more
corrosion.
Area of metal under stress Anode Corrosion.

 6. Nature of surface film

7. Passive character of metal (Al, Cr, Mg, Ni,
Co).
8. Solubility of corrosion product
9. Volatility of corrosion product (MoO3)

Corrosion Control
Methods

 How to control corrosion?

1) Material Design:
Design should be such that corrosion should be
uniform and should not be intense & localized.
Avoid contact of dissimilar metals in the
presence of corroding solution.
In case of two dissimilar metals the anodic and
cathoidc areas should be in control.
Some insulating fitting may be applied between
them to avoid direct metal-metal contact.

 Anodic part should be painted or coated.

Prevent occurrence of inhomogeneities:
Avoid cavities or gaps.
Use pure metals (avoid impurities).
Use suitable metal alloys to suppress
corrosion. Ag, Au, Pt noble metals resistant
to corrosion.
Alloying with Cr to iron can provide best
protection.

 2) Cathodic protection techniques

Force the metal which need protection to behave like

cathode.
Sacrificial anodic protection
Impressed Current technique

A) Sacrificial Anodic Protection (Mg, Zn, Al):

The metallic structure which need protection is connected by

a wire/block of more anodic metal (more reactive).

Hence all the corrosion is concentrated at this more reactive

part.

The more active metal itself gets corroded, while the parent
structure (cathode is protected).

This more active metal is known as sacrificial anode.

 B) Impressed Current Technique:

Current is applied in opposite direction to nullify the

corrosion current, this convert the corroding metal
from anode to cathode.
(Cathode)
ee-

DC Current

eUnder ground/ dipped area

Metal

(Anode)

Due to this current anode of metal

is forced to act as cathode & thus
prevents oxidation

Alloy which
is inert or less
reactive
(Anode)

 3) Alloying:
Both corrosion resistance and strength of
many metals can be improved by alloying.
e-g. Stainless steels containing chromium
produce a coherent oxide film which protects
the steel from further attack.
The other non-corrosive alloys are German
silver, Aluminium bronze, Nickel bronze,
Duralumin etc.
Imp. Tips Selection of right alloy
% of metals
Homogenous mixing

 4) Protective Coating:
This type of coating will suppress the
exposure of metal to corroding environment.
Limitation of this method service behaviour
of protective coating.
This coating must be inert & must not
promote environmental penetration.

Paint
Enamel
Varnish
Lacquer