Engineering Chemistry

MODULE-3
Corrosion: causes and electrochemical theory of wet
corrosion

Dr. Priti Singh

(M. Sc., Ph.D.)
KIET Group of Institutions, Ghaziabad
 Contents
❑ Introduction
❑ Types of Corrosion
❑ Factors influencing corrosion
❑ Differences between Wet and Dry corrosion
❑ Difference between Electrochemical and
Galvanic Series
❑ Electrochemical theory of wet corrosion
 Corrosion
Corrosion
Corrosion is a chemical or electrochemical attack of environment on metal
which results in the loss of its metallic properties and it gets destructed.
eg. - rusting of iron
Cause of corrosion
Extraction corrosion
Ore of metal pure metal corroded metal
Thermodynamically Thermodynamically Thermodynamically
stable state unstable state more stable than pure metal
 Types of Corrosion
➢Dry Corrosion/Chemical Corrosion. When metal gets corroded in the
absence of any conducting medium then it is known dry corrosion.

➢Wet Corrosion/ Electrochemical Corrosion / Immersed Corrosion.

When metal gets corroded in the presence of any conducting medium
then it is known as wet corrosion.
Differences between Wet and Dry
corrosion
Dry corrosion Wet corrosion

1 It occurs in dry condition. It occurs in wet condition.

2 If the corrosion takes place due to direct If the corrosion takes place due to
chemical attack (in the absence of moisture), electrochemical attack in presence of moisture
corrosion is known as dry corrosion. or a conducting medium, corrosion is known as
wet corrosion.
3 Explained by chemical mechanism. Explained by electrochemical mechanism.

4 It occurs on both heterogeneous and It occurs only on heterogeneous metal surfaces.

homogeneous surfaces.
5 Corrosion is uniform. Corrosion is not uniform.

6 It is a slow process. It is a fast process.

7 Corrosion products accumulate at the place Corrosion take place at anode but products
where corrosion occurs. accumulate near the cathode.
 Factors influencing corrosion
➢Nature of metal: Rate of corrosion depends upon the position of the metal in
galvanic series. When two metals are in electrical contact in presence of an
electrolyte, the metal positioned above in galvanic series becomes anodic and
corroded.

➢Purity of metal: The rate of corrosion increases with the increase of impurities.
Impurities increases the corrosion due to the formation of small electrochemical
cells.

➢Physical state of the metal: The physical state of metal such as grain structures,
stresses, scratches etc., also influences the rate of corrosion.
 Factors influencing corrosion
➢Nature of the oxide film: The metals are usually covered with an oxide layer in aerated
atmosphere. If the specific volume of the metal oxide layer formed is lesser than the
volume of the metal atom, then the film will be porous. The porosity present in layer easily
allow oxygen to diffuse into metal and causes corrosion.

➢Area effect: If the area of cathode is large as compared to anode then the corrosion of the
anode is fast. This is because; large cathodic area will demand more electrons, which can
be only supply by anodic area, so very rapid corrosion occurs.

➢Solubility of the products of corrosions: If product formed during corrosion is soluble in

the corroding medium then corrosion proceeds at a very fast rate.
Difference between Electrochemical and
Galvanic Series
S. No. Electrochemical Series Galvanic Series

1. The arrangement of metals and non- metals in The arrangement of metals and alloys in
increasing order of their standard reductio n decreasing order of their corroding
potential. tendency.
2. It includes metals and nonmetals. It includes metal and alloy

3 It is based upon electrode potential. It is based on actual corrosion rate.

4 Position of a given metal is fixed in series. Position of a given metal may change.

5 It gives no idea about the position of alloys. It gives clear idea about the position o f
alloys.
6 It provide information about the displacement It provide the relative corrosion tendencies.
tendencies.
 Wet Corrosion / Electrochemical Corrosion /
Immersed Corrosion
This type of corrosion takes place-
• When a conducting liquid is in contact with a metal.
• When two dissimilar metals, immersed partially in conducting medium, are
connected to each other.
This theory involves-
❑ Anode: oxidation of metal at anode resulting in the formation of metallic ions
M → Mn+ + ne- (oxidation)
❑ Cathode: e- liberated from anode are consumed through reduction reaction by-

✓ i. Evolution of hydrogen gas

✓ ii. Absorption of oxygen gas
 OXYGEN ABSORPTION MECHANISM
At anode
Fe → Fe+2 + 2e- X 2
(oxidation)
Aqueous neutral solution of
At cathode
electrolyte Anodic area
O2+ 2H2O+4e →4OH-
(reduction) bare surface of metal
Rust exposed in environment
Overall reaction
2Fe + O2 + 2H2O → ½ O2+2e-+2H2O→2OH- ½ O2+2e-+2H2O→2OH- Oxide layer as
Fe+2 + 4(OH)- cathode

Flow of Flow of
electrons electrons
Iron rod
Small anodic area
Fe→Fe2++2e-
 Now depending on the availability of oxygen in environment, two
types of corrosion products are formed.

❑ in excess supply of O 2 yellow rust is formed.

4Fe(OH)2 + 2H2O + O2 → 4 Fe(OH)3 → 2Fe2O3. xH2O
Yellow rust
❑ in limited supply of oxygen- black rust is formed.
Fe(OH)3 → Fe2O3. FeO. xH2O
Black rust
 HYDROGEN EVOLUTION MECHANISM
At anode
Fe → Fe+2 + 2e-
(oxidation)
At cathode Acidic solution (electrolyte)
2H++2e →H2 ↑(reduction) H+ H+ H+ H+ Cathodic area
Overall reaction
H+ H+ H+ H+
2Fe + 2H+ → Fe+2 + H2↑ 2H++2e-→H2-
Fe→Fe2++2e- Fe→Fe2++2e-
Anodic area Anodic area
Flow of Flow of
electrons electrons
Iron rod
Thank
You