Corrosion
The serious consequences of the corrosion process have become a problem of
worldwide significance.
In addition to our everyday encounters with this form of degradation,
corrosion causes plant shutdowns, waste of valuable resources, loss or
contamination of product, reduction in eficiency, costly maintenance and
expensive overdesign.
Humans have most likely been trying to understand and control corrosion for
as long as they have been using metal objects. The most important periods of
pre-recorded history are named for the metals that were used for tools and
weapons (Iron Age, Bronze Age). With a few exceptions, metals are unstable in
ordinary aqueous environments.
Corrosion has been defined as a destructive
chemical and electrochemical reaction of a
metal with its environment (like O 2,
moisture, CO2 etc.) which disfigures
metallic products leading to reduction in
their thickness and also causes loss of useful
properties such as malleability, ductility,
electrical conductivity and optical
refractivity. Except few metals such as gold,
platinum (called noble metal) are prone to
corrosion.
Metals are electropositive in nature. Except few metals like gold, platinum (noble metal)
other metals are found in nature as their compounds (such as oxides, hydroxides,
carbonates, chlorides, sulphides, phosphates, silicates etc.) which are called their ore.
Metals are thus obtained by extraction from their ores by reduction process.
In nature, when metals exists as their compounds (or ore) they are stable and they are in
the low energy states.
However, during extraction of metals from their ores, free metals are become less stable
and are in the higher energy state than in the ionic state.
So, metals have a tendency to back to the ionic state and hence metal atoms are prone to
get attacked by environment .
This is the main reason for corrosion of metals.
Mineral Extraction Corrosion Corrosion
or Metal
(M) product
ore (Mn+) by reduction -ne
(Mn+)
+ ne
Types Of Corrosion
Dry or Chemical Corrosion
It involves direct chemical attack of atmospheric gases like
CO2, O2, H2S, SO2, halogen, moisture and inorganic acid vapours
on metal. Ex. Turnishing of silver ware in H 2S laden air.
This can be classified as
a. Corrosion by oxygen
b. Corrosion by other gases
c. Liquid –Metal corrosion
Wet or Electrochemical Corrosion
It occurs due to setting up of a large number of tiny galvanic cells
in metals in presence of an impurity as well as in presence of
moisture. Generally impurity (more active metal) act as anode and
original metal act as cathode. so anode is the area where
corrosion occurs. Ex: Rusting of iron in moist atmosphere.
This can be classified as
a. Galvanic corrosion
b. Concentration Cell Corrosion or Differential aeration corrosion
Types of dry corrosion
I. Oxidation corrosion
Due to direct chemical reaction of atm. O2 with metal surface forming metal oxide
Absence of moisture
Increases with increase in temperature.
Mechanism
on exposure to atm., metal gets oxidized to form metal ions
M M2+ + 2e-
Electrons lost by metal are taken up by oxygen to forms oxide ions
1/2O2 + 2e- O2-
M + 1/2O2 2M2+ + O2- MO
Metal Oxide
Types of metal oxide film
I. Stable film II. Unstable film
III. Volatile film IV. Porous film
I. Stable film
Fine grained structure
Formation of Oxide films are impervious in nature
Stop further oxygen attack
Stable film acts as a protective coating. Eg: Al, Pb, Cu, Sn
II. Unstable film
Film produced on the surface of noble metals.
Which decompose reversibly to the metal and the oxide which is liberated in the
form of oxygen.
Here corrosion is a continuous process. Eg: Ag, Au, Pt.
III. Volatile film
The oxide layers formed in some cases is volatile.
Oxide film volatilizes as soon as it is formed.
The fresh metal surface is kept exposed all the time for further attack.
Thus it act as a nonprotective coating. Eg: MoO3 (Molybdenum oxide film)
IV. Porous film
The oxide layers formed in some cases have pores or cracks.
The atmospheric oxygen can easily move into the metal surface through
pores of the layer.
So corrosion is a continuous process. Eg: Alkali metals & alkaline earth metals.
Pilling – Bed Worth Rule
Specific Volume Ratio = Volume of oxide formed
Volume of metal
A protective and Non-Porous metal oxide layer has volume equal to or greater than
the volume of metal from which it is formed. Ex: Oxides of Al, Sn, Pb, Cu, etc.
A Non-Protective and Porous metal oxide layer has volume lesser than the volume of metal from
which it is formed. Ex: Oxides of Li, Na, K, Mg, Ca, Sr, etc.
Types of dry corrosion
II. Corrosion by Other Gases
Other gases such as Cl2,SO2,H2S,F2,CO2 & NOX. In dry atmosphere
these gases react with metal and form corrosion products.
2AgCl + Cl2 AgCl
(Non-Porous layer)
Sn + 2Cl2 SnCl4
(Volatile Layer)
Hydrogen Embrittlement (or) Hydrogen Corrosion
At high temperature
Fe + H 2S FeS + 2H
[H] + [H] H2
FeS is a Porous Layer and corrosion is a continuous process.
Atomic hydrogen penetrates and occupies the voids of the metal. Then
develops pressure which leads to cracking of the metal.
This is known as Hydrogen Embrittlement (or) Hydrogen Corrosion
Decarburisation
Atomic hydrogen is highly reactive and combine with Carbon present in metal forming CH 4 gas
which leads to cracking of the metal surface.
The process of decrease in carbon content in steel is known as decarburation of steel.
C + H CH4
III. Liquid Metal Corrosion
Occurs due to the action of flowing liquid metal at high temp on solid metals
or alloys.
As a result of this corrosion, solid metal becomes weak because it
involves either
Dissolution of a solid metal by a liquid metal (or)
Due to the penetration of the liquid metal into the solid metal
Observed in Nuclear power plant. In nuclear reaction where Na metal used as a
coolant leads to corrosion of Cd.
Wet or Electrochemical or Immersed Corrosion
Occurs
When a metal is contact with moist air or any liquid medium
When two diff. metals are partially immersed in a soln.
Chemically non- uniform surfaces of metals behave like electrochemical cells
in the presence of water containing dissolved O 2 & CO2
Always occurs at anodic areas
Mechanism
Involves oxidation- reduction process
depending on the nature of corroding enviornment, electrons released at anode are
consumed at the cathodic area by two ways:
Evolution of H2
Absorption of O2
Hydrogen evolution Mechanism
This types of corrosion takes place when base metals are in contact
with acidic solutions or the solutions are completely free from
dissolved oxygen.
All metals above hydrogen in the electrochemical series have a
tendency to get dissolved in acidic solution with simultaneous evolution
of hydrogen gas.
Anode :
Fe Fe2+ + 2e- (Oxidation)
Cathode :
2H+ + 2e- H2 (g) (Reduction)
Over all Rxn :
Fe + 2H+ 2Fe2+ + H2 (g)
Oxygen Absorption Mechanism
Base metal are in contact with neutral, aqueous or slightly alkaline solution with
some amount of dissolved oxygen.
Anode :
Fe Fe2+ + 2e- (Oxidation)
Cathode :
1/2O2 + 2e- + 2H2O 2OH- (Reduction)
Over all rxn:
Fe + H2O + 1/2O2 Fe2+ + 2OH- Fe(OH)2
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3 (OR) Fe2O3.3H2O
Difference Between Dry and Wet Corrosion
Dry Corrosion Wet Corrosion
Occurs in the absence of moisture Occurs in the presence of conducting medium
Involves direct attack of chemicals on Involves formation of electrochemical cells
the metal surface
Slow process Rapid process
Corrosion products are produced at Corrosion occurs at anode but product is
the site of corrosion deposited at cathode
Process of corrosion is uniform Depends on the size of the anodic part of the
metal
Eg: Tarnishing of Silver Eg: Rusting of Iron
