CLASSIFICATION OR THEORIES OF CORROSION

Based on the environment, corrosion is classified into

(i) Dry or Chemical Corrosion
(ii) Wet or Electrochemical Corrosion
TYPES OF DRY or CHEMICAL CORROSION:

1. Corrosion by Oxygen or Oxidation corrosion

2. Corrosion by Hydrogen

3. Liquid Metal Corrosion

CORROSION BY OXYGEN or OXIDATION CORROSION:

 Mechanism:
 1) Oxidation takes place at the surface of the metal
forming metal ions Mn+
 M → Mn+ + ne-
 2) Oxygen is converted to oxide ion (O2- ) due to the
transfer of electrons from metal.
 n/2 O2 + 2n e- → n O2-
 3) The overall reaction is of oxide ion reacts with the
metal ions to form metal oxide film.
• 2M + n/2 O2 → 2M n+ + nO2-

• The Nature of the Oxide formed plays an important part in

oxidation corrosion process.

• Metal + Oxygen → Metal oxide (corrosion product) When

oxidation starts, a thin layer of oxide is formed on the metal
surface and the nature of this film decides the further
action. If the film is Metals without significant passivation
tendencies in the actual environment, such as iron, are
liable to this form. Metal + Oxygen → Metal oxide
(corrosion product)

• When oxidation starts, a thin layer of oxide is formed on the

• metal surface and the nature of this film decides the further
action. If the film is

• (i) Stable layer: A Stable layer is fine grained in structure

and can get adhered tightly to the parent metal surface.

• Such a film behaves as protective coating in nature, thereby

shielding the metal surface. The oxide films on Al, Sn, Pb,
Cu, Pt, etc., are stable, tightly adhering and impervious in
nature.
• (ii) Unstable oxide layer: This is formed on the surface of
noble metals such as Ag, Au, Pt. As the metallic state is
more stable than oxide, it decomposes back into the metal
and oxygen. Hence, oxidation corrosion is not possible with
noble metals.

• (iii) Volatile oxide layer: The oxide layer film volatilizes as

soon as it is formed. Hence, always a fresh metal surface is
available for further attack. This causes continuous
corrosion. MoO3 is volatile in nature.
• (iv) Porous layer: The layer having pores or
cracks. In such a case, the atmospheric
oxygen have access to the underlying
surface of metal, through the pores or cracks
of the layer, thereby the corrosion continues
unobstructed, till the entire metal is
completely converted into its oxide.
• Pilling-Bedworth rule: According to it “an oxide is protective
or non-porous, if the volume of the oxide is atleast as great
as the volume of the metal from which it is formed”. On the
other hand, “if the volume of the oxide is less than the
volume of metal, the oxide layer is porous (or non-
continuous) and hence, non-protective, because it cannot
prevent the access of oxygen to the fresh metal surface
below”.

• Thus, alkali and alkaline earth metals (like Li, K, Na, Mg)
form oxides of volume less than the volume of metals.
• Consequently, the oxide layer faces stress and strains,
thereby developing cracks and pores in its structure. Porous
oxide scale permits free access of oxygen to the underlying
metal surface (through cracks and pores) for fresh action
and thus, corrosion continues non-stop. Metals like
Aluminium forms oxide, whose volume is greater than the
volume of metal. Consequently, an extremely tightly-
adhering non-porous layer is formed. Due to the absence of
any pores or cracks in the oxide film, the rate of oxidation
rapidly decreases to zero.
• Corrosion by other gases (by hydrogen):

• 1) Hydrogen Embrittlement:

• Loss in ductility of a material in the presence of hydrogen is

known as hydrogen embrittlement the propagation stage,
metal cations from the dissolution reaction diffuse toward
the mouth of the pit or crevice (in the case of crevice
corrosion), where they react with OH- ions produced by the
cathodic reaction, forming metal hydroxide deposits that
may cover the pit to a varying extent.
• Mechanism: This type of corrosion occurs when a metal is
exposed to hydrogen environment. Iron liberates atomic
hydrogen with hydrogen sulphide in the following way.

• Fe + H2S → FeS + 2H

• Hydrogen diffuses into the metal matrix in this atomic form

and gets collected in the voids present inside the metal.
Further, diffusion of atomic hydrogen makes them combine
with each other and forms hydrogen gas.

• H + H → H2↑

• Collection of these gases in the voids develops very high

pressure, causing cracking of metal.

• 2) Decarburisation: The presence of carbon in steel gives
sufficient strength to it. But when steel is exposed to
hydrogen environment at high temperature, atomic
hydrogen is formed.

• H2 heat 2H

• Atomic hydrogen reacts with the carbon of the steel and

produces methane gas.

• C + 4H → CH4

• Hence, the carbon content in steel is decreases. The

process of decrease in carbon content in steel is known as
decarburization.
• Collection of methane gas in the voids of steel develops
high pressure, which causes cracking. Thus, steel loses its
strength.

• 3) Liquid metal corrosion: This is due to chemical action of

flowing liquid metal at high temperatures on solid metal or
alloy. Such corrosion occur in devices used for nuclear
power. The corrosion reaction involves either:

• (i) dissolution of a solid metal by a liquid metal or (ii) internal

penetration of the liquid metal into the solid metal.

• Both these modes of corrosion cause weakening of the solid

metal.
 WET OR ELECTROCHEMICAL CORROSION :

 (1) Electrochemical corrosion involves:

 i) The formation of anodic and cathodic areas or parts in

contact with each other

 ii) Presence of a conducting medium

 iii) Corrosion of anodic areas only and

 iv) Formation of corrosion product somewhere between

anodic and cathodic areas.

 This involves flow of electron-current between the anodic

and cathodic areas.
• At anodic area oxidation reaction takes place (liberation of
free electron), so anodic metal is destroyed by either
dissolving or forming compounds such as oxide.

• Hence corrosion always occurs at anodic areas

• M (metal) → M n+ + n e

• Mn+ (metal ion) → Dissolves in solution

• → forms compounds such as oxide

• At cathodic area, reduction reaction takes place (gain of

electrons), usually cathode reactions do not affect the
cathode, since most metals cannot be further reduced.

•
• So at cathodic part, dissolved constituents in the conducting
medium accepts the electrons to form some ions like OH-
and O2-

• Cathodic reaction consumes electrons with either by

• (a) evolution of hydrogen or

• (b) absorption of oxygen, depending on the nature of the

corrosive environment

• Hydorgen Evolution Type: All metals above hydrogen in the

electrochemical series have a tendency to get dissolved in
acidic solution with simultaneous evolution of hydrogen. It
occurs in acidic environment. Consider the example of iron
• At anode: Fe → Fe2+ + 2e

• These electrons flow through the metal, from anode to

cathode, where H+ ions of acidic solution are eliminated as
hydrogen gas.

• At cathode: 2 H+ + 2 e- → H2↑

• The overall reaction is: Fe + 2H+ → Fe2+ + H2

• Oxygen Absorption Type: Rusting of iron in neutral
aqueous solution of electrolytes (like NaCl solution) in the
presence of atmospheric oxygen is a common example of
this type of corrosion. The surface of iron is usually coated
with a thin film of iron oxide. However, if this iron oxide film
develops some cracks, anodic areas are created on the
surface; while the well metal parts acts as cathodes.

•
At Anode: Metal dissolves as ferrous ions with liberation of
electrons. Fe → Fe2+ + 2e
• At Cathode: The liberated electrons are intercepted by the
dissolved oxygen. ½ O2 + H2O + 2 e- → 2OH-

• The Fe2+ ions and OH- ions diffuse and when they meet,
ferrous hydroxide is precipitated. Fe2+ + 2OH- → Fe(OH)2

• (i) If enough oxygen is present, ferrous hydroxide is easily

oxidized to ferric hydroxide.

• 4Fe(OH)2 +O2 + 2H2O → 4Fe(OH)3 (Yellow rust Fe2O3

.H2O)

• (ii) If the supply of oxygen is limited, the corrosion product

may be even black anhydrous magnetite, Fe3O4
 Difference between (dry) chemical and (wet) electrochemical corrosion:
Chemical Corrosion Electrochemical Corrosion
1- It occurs in dry condition. 1- Electric current flows by movement
of ions.
2- It is due to the direct chemical 2- It is due to the formation of a large
attack of the metal by the number of anodic and cathodic areas.
environment.
3- Even a homogeneous metal 3- Heterogeneous (bimetallic) surface
surface gets corroded alone gets corroded.
4- Corrosion products accumulate 4- Corrosion occurs at the anode
at the place of corrosion while the products are formed
elsewhere.
5- It is a self controlled process 5- It is a continuous process.

6-It adopts adsorption mechanism. 6- It follows electrochemical reaction.

7- Formation of mild scale on iron 7-Rusting of iron in moist atmosphere
surface is an example. is an example
• TYPES OF ELECTROCHEMICAL CORROSION

• The electrochemical corrosion is classified into the following

two types:

• (i) Galvanic (or Bimetallic) Corrosion

• (ii) Differential aeration or concentration cell corrosion.

• Galvanic Corrosion:

• When two dissimilar metals (eg., zinc and copper) are

electrically connected and exposed to an electrolyte, the
metal higher in electrochemical series undergoes corrosion.
In this process, the more active metal (with more negative
• electrode potential) acts as a anode while the less active
metal (with less negative electrode potential) acts as
cathode.

• In the above example, zinc (higher in electrochemical series)

forms the anode and is attacked and gets dissolved;
whereas copper (lower in electrochemical series or more
noble)acts as cathode. Mechanism: In acidic solution, the
corrosion occurs by the hydrogen evolution process; while in
neutral or slightly alkaline solution, oxygen absorption
occurs. The electron-current flows from the anode metal,
zinc to the cathode metal, copper.
• Zn → Zn 2+ + 2e- (Oxidation)

• Thus it is evident that the corrosion occurs at the anode

metal; while the cathodic part is protected from the attack.

• Concentration Cell Corrosion: It is due to electrochemical

attack on the metal surface, exposed to an electrolyte of
varying concentrations or of varying aeration

• It occurs when one part of metal is exposed to a different air

concentration from the other part.
• This causes a difference in potential between differently
aerated areas.

• It has been found experimentally that poor-oxygenated parts

are anodic.

• Examples: i) The metal part immersed in water or in a

conducting liquid is called water line corrosion.

• ii) The metal part partially buried in soil.

• Explanation: If a metal is partially immersed in a conducting

solution
the metal part above the solution is more aerated and
becomes cathodic. The metal part inside the solution is
less aerated and thus becomes anodic and suffers
corrosion
• At anode: Corrosion occurs (less aerated)

• M → M2+ + 2e-

• At cathode: OH- ions are produced (more aerated)

• ½ O2 + H2O + 2e- → 2OH-

• Examples for this type of corrosion are

• 1) Pitting or localized corrosion

• 2) Crevice corrosion

• 3) Pipeline corrosion

• 4) Corrosion on wire fence