Defence University

College of Engineering
Chemical Engineering
Specialization: Electrochemical Engineering

Advanceed Corrosion Engineering(CE-7341)

Chapter 2: Electrochemical Principles of Corrosion

Instructor: Wondalem Misganaw(PhD., M.Tech, B.Tech)

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 Different Theories of Corrosion
 There are three theories of corrosion:

1. Acid theory

2. Dry or chemical corrosion

3. Galvanic or electrochemical

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 1. Acid Theory
 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
carbondioxide, 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

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 2. Chemical Theory of Corrosion
 According to this theory, corrosion on the surface of a metal is
due to direct reaction of atmospheric gases like oxygen,
halogens, oxides of sulphur, oxides of nitrogen, hydrogen
sulphide and fumes of chemicals with metal.
 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 main three types of chemical corrosion.
i. Oxidation corrosion (Reaction with oxygen)
ii. Corrosion by other gases
iii. Liquid metal corrosion

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 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.
 During oxidation of a metal, metal oxide is formed as a thin film on
the metallic surface which protects the metal from further corrosion.
 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.

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 Oxidation corrosion…
 Oxides of Pb, Al and Sn are stable and hence inhibit further

corrosion. They form a stable, tightly adhering oxide film.

 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.

 Porous oxide layer is formed by alkali and alkaline earth metals.

 Molybdenum forms a volatile oxide film of MoO3 which

accelerates corrosion.

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 ii. Corrosion by other gase (Cl2, SO2, H2S, Nox)
 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.

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 3. Wet or electrochemical theory of 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.

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 Differences between dry and wet corrosion
Dry corrosion Wet corrosion
1. Corrosion occurs in the 1. Corrosion occurs in
absence of moisture. presence of conducting
2. It involves direct attack of medium.
chemicals on the metal 2. It involves formation of
surface. electrochemical cells.
3. The process is slow. 3. It is a rapid process.
4. Corrosion products are 4. Corrosion occurs at anode
produced at the site of but rust is deposited at
corrosion. cathode.
5. The process of corrosion is 5. It depends on the size of
uniform. the anodic part of metal.

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 Factors Influencing Corrosion
 The nature and extent of corrosion depend on the metal and
the environment. The important factors which may influence
the corrosion process are
1. Nature of the metal
2. Environment
3. Concentration of electrolyte
4. Temperature
5. Electrode potential and
6. Over voltage

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 Metallurgical Aspects:
 Polycrystalline would corrode much faster than single crystal.
 This happens due to the presence of grain–boundaries in
polycrystalline grain boundaries are the regions of high energy
therefore their chemical reactivity is higher than the rest of
materials.
 Some of the metallurgical effects are :
1. Effect of Grain boundary
2. Metal purity.
3. Effect of various phases in the alloys presence of phases alloys
have the same effect as Galvanic – coupling in .
4. Different metals.
5. Residual stresses.
6. The strain hardening deformation.

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 Electrochemical Process 12

 For metallic materials, the corrosion process is normally

electrochemical, that is a chemical reaction in which there is transfer
of electrons from one chemical species to another.

 Metal atoms characteristically lose or give up electrons in what is

called an oxidation reaction.

 The site at which oxidation takes place is called the anode; oxidation

is sometimes called an anodic reaction.

 The electrons generated from each metal atom that is oxidized must be

transferred to and become a part of another chemical species in what is

termed a reduction reaction. The location at which reduction occurs is
called the cathode.
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 Corrosion Cell 15

 For Corrosion to take place ,the formation of a corrosion cell is

essential. A corrosion cell essentially comprised of the following four
components.
1. Anode ( -ve of cell ): One of the two dissimilar metal electrodes in an
electrolytic cell. Electrons are released at anode , which is the more
reactive metal .Electrons move through the wire in to the cathode.
2. Cathode ( +ve of cell ) :The other Electrode in the electrolytic cell
.Reduction takes place at cathode and electrons are consumed .
3. Electrolyte ( e.g. salt solution ) : It is the electrically conductive
solution for corrosion to occur. Positive electricity passes from
anode to cathode through the electrolyte as cations .
4. Metallic path : The two electrodes are connected externally by a
metallic conductor. Current flow from (+) to (-) which really
electrons flowing from ( - e ) to ( +e ).
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The corrosion cell can be represented as follows
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Anodic and Cathodic Reactions
1. The anode is the area where metal is lost. At the anode, the
reactions which take place are oxidation reactions.
 It represents the entry of metal ion into the solution, by dissolution,
hydration or by complex formation. It also includes precipitation of
metal ions at the metal surface.
 In anodic reaction: Oxidation of metal to an ion with a charge,
Release of electrons, Shift to a higher valence state.
 The process of oxidation in most metals and alloys represents
corrosion. Hence, if oxidation is stopped, corrosion is stopped.
2. Cathodic reactions are reduction reactions which occur at the
cathode.
 Electrons released by the anodic reactions are consumed at the
cathode surface.
 Unlike an anodic reaction, there is a decrease in the valence state.
 Current flow in an electrochemical cell

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Anodic And Cathodic Reactions

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Types of Corrosion Cells
 There are several types of corrosion cells:
1. Galvanic cells
2. Concentration cells
3. Electrolytic cell
1. Galvanic cell 21

• The galvanic cell may have an anode or cathode of dissimilar

metals in an electrolyte or the same metal in dissimilar
conditions in a common electrolyte.
 Galvanic Cell

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 Conditions for galvanic corrosion
1. Two dissimilar metals in contact
 Two metals in contact may be entirely different in composition ,
e.g. iron pipe carrying water is anodic to copper pipe.
 Galvanic Corrosion with example of Couple between Steel and
Brass.
2. Different Heat Treatment
 Behaviour of the metal depends on the type of heat treatment given
, e . g . Tempered steel is anodic to annealed steel.
 Tempered : increase the hardness and strength of a metal by
quenching or heat treatment.
 Annealed: heat of metal and then gradually cooling.
3. Scratches or Abrasion
 If a piece of metal is scratched or abraded, the scratched or the
abraded area will be anodic to remaining portion .
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 Conditions for galvanic corrosion 24

4. Differential strain
 A strained area is usually anodic to an unstrained area.
5. Differential Grain and Matrix Composition
 Many alloys may consist of heterogeneous phases, which may
have a potential difference. However, no general rule can be
established . For example, in the case of Al-Cu alloy CuAl2
precipitate at the grain boundary is cathode to alpha matrix.
6. Different Grain Size
 Usually the smaller grains are anodic to large ones.
7. Surface condition
 Difference in surface condition may also create a potential
difference. This explains why a new section of pipe when welded
in old line becomes anodic and corrodes.
8. Differential curvature
 If the metal has a curved surface, the more highly convex surface
is anodic to the less convex surface.
 Concentration Cell
 This is similar to galvanic cells except with an anode and
cathode of the same metal in a heterogeneous electrolyte.
 Consider the corrosion of a pipe in the soil. Concentration
cells may be set up by:
1. Variation in the amount of oxygen in soils.
2. Differences in moisture content of soils.
3. Differences in compositions of the soil.
 Concentration cells are commonly observed in underground
corroding structures, such as buried pipes or tanks

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Concentration Cell
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Conditions Concentration Cell corrosion formation
1. Differential Composition of the Electrolyte
 Example of this type of corrosion is : A section of pipe buried in
clay soil is anodic to pipe section buried in loam-soil.
2. Differential Motion of the Electrolyte
 If a structure is subjected to varying velocities of the electrolyte ,
the area of higher velocity will be cathodic .
3. Differential concentration of the electrolyte
 These are also known as salt concentration cells and has two
identical electrodes each in contact with a solution of different
concentration of the same electrolyte.
 The area of the metal in contact with the more dilute solution is
usually anodic and corrodes.
4. Differential Oxygen Concentration
 These are also known as differential aeration cells.
 The electrode in deaerated solution (solution with less oxygen)
becomes anodic and corrodes.
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3. Electrolytic Cells
 This type of cell is formed when
an external current is introduced
into the system.
 It may consist of all the basic
components of galvanic cells and
concentration cells plus an external
source of electrical energy.
 This is the type of cell set up for
electrically protecting the
structures by cathodic protection.
 The polarity of an electrolytic cell
is opposite to that in a galvanic
(corrosion) cell
End of Chapter 2

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