13.06.

2022
INTRODUCTION

➢ Corrosion is a process of formation of the compound of pure metal by

the chemical reaction between metallic surface and its environment.

➢ It is an oxidation process. It causes loss of metal.

➢ Hence, disintegration of a metal by its surrounding chemicals through

a chemical reaction on the surface of the metal is called corrosion.

➢ Example: Formation of rust on the surface of iron (Fe3O4)

Formation of green film on the surface of copper (CuCO3 + Cu(OH)2).

➢ The responsible factors for the corrosion of a metal are the metal itself, the
environmental chemicals, temperature and the design.
How metal is responsible?
Electrochemical series What do you understand from this?

In these series a system

with high reduction
potential has a great
tendency to undergo
reduction , where as a
system with a low
reduction potential tend
to oxidize more easily
 Electrochemical theory of corrosion

DIFFERENT THEORIES OF CORROSION

(1) Dry or chemical corrosion

(2) Wet or electrochemical or galvanic corrosion

DRY OR CHEMICAL CORROSION

➢This type of corrosion occurs mainly through the direct

reaction of atmospheric gases like oxygen, halogens,
oxides of sulphur, oxides of nitrogen, hydrogen sulphide
and fumes of chemicals with metal surfaces.

➢The extent of corrosion of a particular metal depends on

the chemical affinity of the metal towards reactive gas.

➢Oxygen is mainly responsible for the corrosion of most

metallic substances when compared to other gases and
chemicals.
There are mainly three types of chemical corrosion.

(i)Oxidation corrosion (Reaction with oxygen)

(ii) Corrosion by other gases

(iii) Liquid metal corrosion

(i)Oxidation corrosion (Reaction with oxygen).

• Some of the metals directly react with oxygen in the

absence of moisture.

• Alkali and alkaline earth metals react with oxygen at

room temperature and form corresponding oxides, while
some metals react with oxygen at higher temperature.

• Metals like Ag, Au and Pt are not oxidized as they are

noble metals.
Mechanism:

OR

• During oxidation of a metal, metal oxide is formed as a thin film on the

metallic surface which protects the metal from further corrosion.
Metal + oxygen → Metal oxide (Corrosion product)
• If diffusion of either oxygen or metal is 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(PbO, PbO2, Pb3O4, Al(Al2O3, Al3O4)
and Sn (SnO2, SnO3) are stable and hence inhibit
further corrosion. They form a stable, tightly adhering
oxide film.

➢ Au, Ag, Pt form unstable oxide layer which decomposes

soon after the formation, thereby preventing further
corrosion.
➢Porous oxide layer is formed by alkali and alkaline earth
metals. Molybdenum forms a volatile oxide film of MoO3
which accelerates corrosion.

➢In case of porous oxide film, atmospheric gases pass

through the pores and react with the metal and the
process of corrosion continues to occur till the entire
metal is converted into oxide.
(ii) Corrosion by other gases (Cl2, CO2, SO2, H2S,
F2 NOx etc.)

➢ In dry atmosphere, these 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.

Amalgum: mixture of silver and mercury which is used as a dental filling

sodium amalgam, an alloy of sodium with mercury
Wet or electrochemical theory of corrosion
galvanic 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.

➢ The chemical in the environment and humidity acts as an

electrolyte. Oxidation of anodic part takes place and it
results in corrosion at anode, while reduction takes place
at cathode. The corrosion product is formed on the
surface of the metal between anode and cathode.
 Electrochemical theory of corrosion by
(a) Hydrogen evolution and (b) oxygen absorption
Evolution of hydrogen: occurs
➢ In acidic environments.
➢ For eg in the corrosion of iron metal the anodic reaction is dissolution of Fe
as ferrous ions with liberation of e-s.
Fe –-----> Fe2+ + 2e- (oxidation).
➢ These electrons flow through the metal from anode to cathode (acidic
region) where H+ ions are eliminated as H2 gas.

2H+ + 2e- –------> H2 reduction.

➢ The overall reaction is

Fe + 2H+ –------> Fe2+ + H2

➢ This type of corrosion causes “displacement of hydrogen ions from the acidic
solution by metal ions.
➢ In hydrogen evolution type corrosion, the anodes are very large areas, where
as cathodes are small areas.
➢ All metals above hydrogen in the electrochemical series have a tendency to
get dissolved in acidic solution with simultaneous evolution of hydrogen.
Mechanism of wet corrosion by hydrogen evolution
Absorption of oxygen type corrosion:
Rusting of Fe in neutral aqueous solution of electrolytes like NaCl in the
presence of atmospheric oxygen is a common example of this type of
corrosion.

Mechanism of wet corrosion by Oxygen absorption

➢ The surface of iron will be usually coated with a thin film of
iron oxide. However if this oxide film develops some cracks,
anodic areas are created on the surface.
➢ While pure metal parts act as cathode.
➢ Thus anodic areas are very small surface parts.
➢ The rest of the surface of the metal forms
cathodes.
➢ Thus at the anodic part iron metal dissolves as
Fe+2 ions with the liberation of e- s.
Fe –-----> Fe+2 + 2e-
➢ The liberated e- s flow from anodic to cathodic
areas through iron metal during which they
interact with dissolved oxygen and moisture.
½ O2 + H2O + 2e- → 2OH-
➢ The Fe+2 ions and OH- ions diffuse and form ferrous
hydroxide precipitate when they meet with each other
Fe2+ + 2OH- –------> Fe(OH)2
➢ If enough O2 is present Fe(OH)2 is easily oxidized to Fe(OH)3
(ferric hydroxide)
4 Fe(OH)2 + O2 + 2H2O –-----> 4Fe(OH)3
The product called yellow rust actually corresponds to
Fe(OH)3.H2O.
➢ If the supply of O2 is limited, the corrosion product may be
even black anhydrous magnetite Fe3O4.
Differences between dry and wet corrosion
Dry corrosion Wet corrosion

• Corrosion occurs in the • Corrosion occurs in presence of

absence of moisture. conducting medium.

• It involves direct attack of • It involves formation of

chemicals on the metal Electrochemical cells.
surface.

• The process is slow. • It is a rapid process.

• Corrosion products are • Corrosion occurs at anode but

produced at the rust is deposited at cathode.
site of corrosion.

• The process of corrosion • It depends on the size of the

is uniform. anodic part of metal.
Factors affecting rate of corrosion:
i) Nature of metals
ii) Nature of the corroding environment.

Nature of metals:
1) Position in galvanic series:-The metal higher in series is more
active and suffers corrosion. The rate and extent of corrosion is directly
proportional to electrode potential difference between them.
2) Over voltage: - when a metal, which occupies a high position in
galvanic series (say Zinc), is placed in H2SO4, it undergoes corrosion
forming a film and hydrogen gas.

The initial rate of reaction is quite slow, because of high over voltage
(0.73 V) of the zinc metal, which reduces the effective electrode
potential to a small value. However, if few drops of copper sulphate
(CuSO4) are added, the corrosion rate of zinc is accelerated, because
some copper gets deposited on the zinc metal forming minute
cathodes, where the hydrogen over voltage is only 0.33 V, thus,
reduction in over voltage of the corroding metal/ alloy accelerates the
corrosion rate.
Zn has over hydrogen voltage due to which the rate of
corrosion of Zn is very slow (Zn rod dipped in ZnSO4). But
when CuSO4 solution is added to H2SO4 Cu gets deposited on Zn
rod and acts as small cathode. For Cu higher over hydrogen
voltage value is less. Hence rate of corrosion of Zn in presence
of cu becomes more. Thus metals for which over voltages are
more get corrode slowly, where as those which have lower over
voltages, the rate of corrosion is high.

Ex: corrosion of Zn rod dipped in H2SO4 is very slow. When

small amount of CuSO4 solution is added to H2SO4 , Cu gets
deposited on the Zn rod and acts as cathode and the rate of
corrosion of Zn increases.
(Over voltage of Zn metal is 0.73)
3) Purity of metal: - Impurity of a metal generally causes heterogeneity
and form minute electrochemical cells and the anodic part gets corroded. For
eg: Zn metal containing impurity such as Pb ( or) Fe undergoes corrosion .
The rate and extent of corrosion increases with extent of impurities.

4) Nature of the surface film: - when metals are exposed to atmosphere,

practically all metals get covered with a thin surface film of metal oxide. The
ratio of the volume of metal oxide to the metal is known as specific volume
ratio. Greater the specific volume ratio, lesser is the oxidation corrosion rate.
For eg: the specific volume ratio of Ni, Cr, W are 1.6, 2.0 and 3.6 respectively.
Consequently the rate of oxidation corrosion is least for (w) tungsten.

5) Nature of the corrosion product:-

a) Solubility of corrosion products : If the corrosion product is soluble
in the corroding medium, then corrosion proceeds at a faster rate otherwise if
it is insoluble, corrosion will be suppressed e.g: PbSO4 formation in case of Pb
in H2SO4.
b)Volatility of corrosion products : - If the corrosion product is volatile ,
it evaporates as soon as it is formed, there by leaving the underlying metal
surface exposed for further attack.
This causes rapid and continuous corrosion.
For eg: Mo forms MoO3 volatile oxide.
6.Passive character of metal

7.Physical state of metal

8.Solubility of corrosion product

9.Volatility of corrosion products

Nature of the corroding environment:-
i) Temperature: With increase of temperature, the corrosion
rate also increases because the reaction as well as diffusion
rate of ions in the corrosion medium increases.

ii) Humidity: The higher the humidity of the atmosphere the

greater is rate and extent of corrosion because the moisture acts
as medium for O2 in air and behaves as an electrolyte.

For eg: atmospheric corrosion of iron is slow in dry air

compound to moist air. Iron combines with O2 and water to
form ferrous hydroxide which combines with atmospheric CO2
to form ferrous bicarbonate.
2Fe + O2 + 2H2O –-------> 2Fe(OH)2
Fe(OH)2 + CO2 –------>Fe(HCO3)2
iii) Effect of pH: - Generally acidic media are more corrosive
than alkaline and neutral media. Hence metals may be
virtually classified according to pH range in which they will be
affected (or) resistant.
However atmospheric metals like Al, Pb etc. are corroded in
alkaline medium and
the corrosion rate of iron in O2 free water is slow, Zn is rapidly
corroded in weakly acidic solutions.

iv) Presence of impurities in atmosphere

v) Presence of suspended particles in atmosphere
vi) Nature of ions present
vii) Conductunce of corroding medium
viii) Formation of oxygen concentration cell
ix) Flow velocity of process steam
x) Plarization of electrodes
How can we control corrosion?

CORROSION CONTROL
1) Cathodic protection : The principle involved in this method
is to force the metal to be protected to behave like a cathode
thereby corrosion doesn’t occur. There are two types of cathodic
protection.
i) Sacrificial anodic protection method: - In this method
the metallic structure to be protected is connected by a wire to a
more anodic metal, so that all the corrosion is concentrated at
this more active metal implies the more active metal itself gets
corroded slowly. While the parent structure which is cathodic is
protected. The more active metal so employed is called
“sacrificial anodic” whenever the sacrificial anode is consumed
completely. It is replaced by a fresh one. Metal commonly
employed as sacrificial anodes are Mg, Zn, Al and their alloys.
Sacrificial anodes are used for the protection of buried pipe
lines underground cables, marine structures, ship hulls, water
tanks etc.
(ii) Impressed current–cathodic protection: - In this method an
impressed current is applied in opposite direction to nullify the
corrosion current and current the corroding metal from anode to
cathode. Usually the impressed current is derived from a direct current
source (like battery or rectifier on ac line) with an insoluble anode, like
graphite, high silica iron, scrap iron, stainless steel or platinum. Usually
a sufficient d.c is applied to an insoluble anode, buried in the soil ( or
immersed in the corroding medium) and connected to the metallic
structure to be protected.

The anode is buried is a backfill such as coke breeze or gypsum to

increase the electrical contact between itself and the surrounding soil.
Applications:- This type of protections is used in buried
structures such as tanks and pipelines, transmission line towers,
marine piers, laid up ships etc.,

Advantages: - They can be automatically controlled which

reduce maintenance and operational costs.