Cummins College of Engineering for Women

B.Tech Sem I
Subject: Applied chemistry( BME2T06)
Unit I(Part B)
Corrosion Technology

Corrosion can be defined decay or destruction of a metal due to unwanted

chemical, electrochemical reaction of the metal with its environment (gaseous or
liquid medium).

Metals have a natural tendency to revert back to combined states. Corrosion is the
reverse process of metallurgy.

corrosion
Metal metallic compound + energy
(unstable state) Metallurgy ( stable state)

Some of the common examples of corrosion in metals are :

1.Rusting of Iron: When exposed to the atmospheric conditions, a layer of reddish
scale and powder of Fe3O2 is formed on the surface of iron.
2.Formation of green film of basic carbonate [CuCO 3 + Cu(OH)2 ] on the surface of
copper

Corrosion is a slow but continues process. It depends upon the nature of metallic
material and environment conditions. Normal metals like sodium, Ca, are corroded to
very high extent.
 Cause of corrosion:

Give reason Corrosion is reverse of extraction metallurgy.(2M)

In nature, generally metals are always found in combined state, i.e in the form metal
compound such as oxides , sulphides, sulphates,carbonates etc. These metal
compounds are at lower energy level, i.e. at high chemical stability.

When metal compounds converted into metal, metals exhibit a natural tendency to go
back to its natural thermodynamically stable state, by combing with the
environmental factors (such as dry gases,moisture,liquid,etc.).Thus the corrosion
starts. During the process of corrosion, metals give out energy and attain stability.

Metallurgical operation environment

Ores Pure metal corroded metal + Energy
Low energy state high energy state Low energy (more stable than pure metal)

 Consequences of corrosion:
1) Plant shut down due to failure
2) Replacement of corroded equipment, which is an expensive time-consuming
proposition.
3) It leads to decrease in production rate hence decrease efficiency of machine
4) It may cause leakage of inflammable gas from the corroded pipe line resulting
in leakage of toxic product.
5) Preventive maintenance such as painting. Increase in maintenance and
production cost.
6) Contamination or loss of the product
7) Harmful to health e.g. From pollution due to corrosion product or due to an
escaping chemical from corroded equipment.
Theories of corrosion

 Chemical or dry or atmospheric corrosion

This type of corrosion occurs due to direct attack of atmospheric gases like
oxygen.CO2, SO2, H2S, moisture, chlorine etc. on metal.
Rate of this type of corrosion depends upon:
i) Chemical affinity between metal and corrosive environment.
ii) ability of metal to form protective film.
The surface of metals are directly attacked by the atmospheric gases of the medium
and gets coated with corresponding compounds like oxides, sulphides, carbonates
etc.
There are three main types of Dry corrosion
1.Corrosion due to Oxygen.
Oxygen present in the atmosphere attacks metal surface resulting in the formation of
metal oxide i.e. corrosion product.
2 M + O2 2MO

2.Corrosion due to other gases

Other gases present in the atmosphere like CO2, SO2, H2S attack the metal.

3.Liquid metal corrosion.

This type of corrosion is due to the chemical action of hot flowing liquid metals at at
temperature on solid metal or alloy.

 Electrochemical or wet corrosion or Immersed corrosion:

Corrosion of a metal in presence of moisture or solution as a conducting medium
with the formation of anodic and cathodic areas is known as wet or electrochemical
corrosion.
This type of corrosion occurs when
1.The conducting liquid is in contact with metal
 2. Two dissimilar metals or a single metal are either immersed or partially dipped in
the conducting medium.
Conducting media - like water, aqueous solution, sea water, and humidity.
Anodic area – undergoes corrosion
Cathodic area –prevent and corrosion product deposited on cathode.

 Mechanism of Electrochemical corrosion

Electrochemical corrosion carried out by two mechanisms
i)Evolution of hydrogen ii)Absorption of oxygen
i)Evolution of hydrogen
If the corroding medium is acidic like industrial waste, solution of non-oxidizing
acid and low concentration of dissolved oxygen, hydrogen evolution takes place.
Eg. A steel tank containing acidic medium and a small copper piece.

Diagram
 Here steel tank acts as an anode and copper piece acts as a cathode in acidic
electrolyte.
The steel portion in contact with copper piece gets corroded as iron (steel)undergo
oxidation and Fe2+ ions pass into the solution.
M →M+n + ne-
e.g. Fe →Fe++ + 2e- (oxidation)

Reaction on cathode (reduction):

H2 liberation: The electrons left on anodic part, flow to cathodic part.H+ from the
acidic medium captures electrons from cathode and there is liberation of H 2 gas.
2H+ + 2e- → 2H → H2↑(Reduction)

The overall reaction will be

Fe+2H +→ Fe+++ H2↑

Thus, all the metals above hydrogen in the electrochemical series have tendency to
get dissolved in acidic solution with evolution of H2.
ii)Corrosion due to O2 absorption:

This type of mechanism takes place when base metal is in contact with neutral or
slightly alkaline corroding medium containing some dissolved oxygen.

E.g. Steel plate having crack in oxide film and drops of water collected on that crack.
Conducting medium -Water drops
Anode –crack.
Cathode- Steel with oxide film.
Diagram

At anode: Fe →Fe2+ + 2e- (oxidation)

At Cathode: Electron flow from anode to cathode and interact with oxygen and
water drop.
1/2O2 + H2O +2e-→2OH-(reduction)
Fe2+ + 2OH- Fe(OH)2↓
Ferrous hydroxide
If enough oxygen is present in medium, then ferrous hydroxide gets oxidized:
4Fe(OH)2 + O2 + 2H2O → 4 Fe(OH)3
(Ferric hydroxide)(Rust)
Here corrosion occurs at anode but the corrosion product get deposited at cathode.
This is because, ionic diffusion through the conducting medium is more for smaller
Fe2+ than OH- .

b) Differential aeration cell corrosion (Concentration cell corrosion):

Whenever a part of the metal is in contact of higher concentration electrolyte or
oxygen than the remaining part on the same metal, there is formation of
concentration cell.
The part of metal in contact with lesser O 2 or lower electrolyte concentration acts as
anode and gets corroded. The remaining part is act as cathode.
The concentration cells formed due to varying O 2 concentration on a metal are called
as differential aeration cells.
The differential cells are formed in following situations:

i) Partial immersion of metal ii) partial burial in ground

iii) Crevices iv) Oxide film on metal surface partially ruptured
i) Partial immersion of metal:
The partial immersion of metal in water causes such cell formation. The immersed
part of metal is poor oxygenated and gets corroded by acting as anode. The metal
part expose to higher concentration air acts as cathode.
e.g. water in metal tank or pot, ship.
Diagram
ii) Partial burial in ground:
A metal partially buried in ground (poles, metallic installation on ground) or metals
kept on ground have aerial part more oxygenated (cathode) and metal in contact of
moist soil poor oxygenated (anode).

iii) Crevices (gap):

When two metal plates or pieces of same metal are not fitted properly, there is a
small gap between them. The metallic surface in gap is poorly oxygenated and gets
corroded.

iv) Oxide film on metal surface partially ruptured

 As long as the nonporous oxide film on a metal surface is uniform, no cell is formed
but if the film gets ruptured partially then open part is more oxygenated and the
covered part is poor oxygenated (anode,corroding)

 Nature of film formed

a)Stable b) Unstable film c) Porous film d) Volatile film.
Stable film (Non porous film) -:
If oxide film is stable, non-porous, strong and adherent to metal surface it can get
stick tightly to the metal surface. So, there is no further penetration of oxygen ions to
the metal part. So further corrosion stops. Thus, the stable film acts as protective
coating.
Eg.Al,Sn,Pb etc

ii)Unstable film.
When the oxide film formed is unstable it decomposes back into the metal and oxygen.
2MO 2M + O2
Metal oxide Metal

Therefore, oxidation is not possible. Eg.Pt,Au etc.

iii) Porous film (non protective film)

If the oxide film is porous oxygen penetrates through pores. So inner metal undergo
corrosion. So in this case corrosion is a continuous process.
Eg.Li,Na,K etc.
iv)Volatile film.

If metal film is volatile. Then its evaporation takes place continuously and fresh
metal exposed to oxygen.

Eg.Molebdenum oxide (MO2O3)

 Pilling- Bedworth rule

This rule gives the idea about the nature of oxide- film, whether it is porous or
nonporous.

The rule states that if the volume of oxide is smaller than the volume of metal
consumed in the metal oxide formation, then the film is porous. If the volume of
metal oxide film formed is greater than the metal consumed during corrosion
the film is nonporous.

Pilling- Bedworth Ratio(P.B.R) = Volume of metal oxide

Volume of metal consumed

If the oxide layer formed is porous & as it cannot cover completely the surface of
metal, it is non protective thus corrosion continues.
e.g. Metals like Al forms oxide, whose volume (Al2O3) is greater than the volume of
metal (Al).
Due to the absence of any pores or cracks in the oxide film, the rate of oxidation
rapidly decreases to zero.
e.g. Alkali and alkaline - earth metals (like Li, K, Na, Mg, Ca) form oxides of
volume less than the volume of metals from which it is formed

 P.B.R or RPB < 1 The oxide coating layer is two thin hence provide no
protection .
 P.B.R or RPB is between 1 to 2 The oxide coating uniformly covers metal
surface so form protective type coating.
 P.B.R or RPB > 2 Because of too much compressive stresses in oxide film, the
oxide coating chips off and provides no protective effect.