MODULE-3: Corrosion

Definition of corrosion: Corrosion is defined as the spontaneous process of

degradation or deterioration of metallic constructions during the course of chemical/
biochemical/ electrochemical interaction with the environment.

Corrosion is also called as extractive metallurgy in reverse.

The familiar examples of corrosion are:

• Rusting of iron (Fe2O3)- a reddish brown scale formation on iron and steel objects.
It is due to the formation of hydrated ferric oxide (Fe2O3 . H2O).

• Green scales formed on copper vessels. It is due to the formation of basic cupric
carbonate. [CuCO3 & Cu(OH)2].

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Types of corrosion: Corrosion can be classified into two types:

1. DRY CORROSION (Direct Chemical Corrosion): Dry corrosion occurs due to

direct chemical reaction between the metal and the gasses present in the corrosive
environment.
Example: Metals when exposed to dry gasses like O2, SO2, CO2, H2S etc.

2. WET CORROSION (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. Wet corrosion can be
explained by the following theory as below:

imp→
Wet or Electrochemical theory of corrosion (iron rod is an example): According to
electrochemical theory, when a metal such as iron is exposed to corrosive environment,
following changes occur.

Fig. 1. Corrosion of iron rod

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Principle: According to electrochemical theory, corrosion of metals take place due to the
formation of anodic and cathodic regions on the same metal surface or when two different
metals are in contact with each other in the presence of conducting medium. At the anodic
region oxidation reaction takes place and the metal gets converted into its ions, liberating
electrons. Consequently, metal undergoes corrosion at the anodic region. At the cathodic
region reduction reaction takes place. Metal does not undergo corrosion at the cathodic
region. The following steps are involved in the corrosion process:

1. Formation of galvanic cells: A large number of tiny galvanic cells with anodic and
cathodic regions are formed.
2. Anodic reaction: Oxidation of metal takes place at the anodic region.
M Mn+ + n e- [genaral reaction]
e.g. Fe  Fe2+ + 2 e-
The Fe2+ ions dissolve, so corrosion takes place at the anodic region.
3. The electrons travel through the metal from the anodic region to cathodic region.
4. Cathodic reaction: Reduction of O2 (absorption of oxygen) or H+ (liberation of
hydrogen) takes place at the cathodic region.

a) Liberation of Hydrogen

i) If the medium is acidic and in the absence of oxygen molecule

2H+ + 2e- H2 ↑
ii) If the medium is basic/neutral and in the absence of oxygen molecule
2H2O + 4e-  2OH- + H2 ↑

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 b) Absorption of oxygen

i) If the medium is acidic and in the presence of oxygen molecule

4H+ + O2 + 4e- 2H2O
ii) If the medium is basic/neutral and in the presence of oxygen molecule
2H2O + O2 + 4e-  4OH-
Reduction of O2 or H+ takes place at the cathodic region.
O2 + 2H2O + ne- 4OH-

The metal is unaffected at the cathodic region.

5. Fe2+ and OH- ions travel through the aqueous medium and form corrosion product.

Diffusion of metallic (from anodic area) and non metallic (from cathodic area) ions comes
together through conducting medium and reacts each other resulting corrosion product,
near the cathodic site

Fe2+ + 2OH- → Fe(OH)2 ferrous hydroxide

This ferrous hydroxide is unstable in oxygenated solutions and oxidised to ferric salt

2Fe(OH)2 +H2O + 1/2O2 → 2 Fe(OH)3 (rust)

4Fe(OH)2 +2H2O + O2 → 2 [Fe2O3 3H2O] (yellow rust)

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If the supply of oxygen is limited we get mixture of Fe(II) and Fe(III) hydrated oxide
product it is black rust.
3Fe(OH)2 + 1/2O2 → Fe3O4 .3H2O (black rust) *****
Galvanic Series (or electrochemical series): The metals and alloys were arranged in the
order of their corrosion tendencies or corrosion resistance.

Fig. 2. Galvanic corrosive table

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Types of corrosion

Metals undergo corrosion by different types depending on the nature of metal, the nature
of corrosion environment and the conditions in which they are undergoing.

Some of the important types of corrosion are;

1) Differential metal corrosion (Galvanic corrosion)
2) Differential aeration corrosion

1. Differential metal corrosion:

This type of corrosion occurs when two dissimilar metals are in contact with each other
and are exposed to a corrosive environment. The two metals differ in their electrode
potentials. The metal with lower electrode potential acts as anode and the other metal
with higher electrode potential acts as cathode.

The anodic metal undergoes oxidation and gets corroded. A reduction reaction occurs at
the cathodic metal. The cathodic metal does not undergo corrosion.

Example 1: Zinc (-0.763) and copper (+0.34)

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 Fig. 3. Differential metal corrosion
In the above case, Zn metal has lower electrode potential (more active metal) acts as
anode and the other metal such as copper has higher electrode potential (less active metal)
acts as cathode. Zn metal undergo oxidation and get corroded and other metal copper
remain unaffected.

The reactions may be represented as follows:

Anodic reaction

M → Mn+ + ne- (oxidation)

Zn →Zn2+ +2e-

Cathodic reaction-depending on the nature of corrosion environment the cathode

reaction may be either hydrogen evolution or oxygen absorption

→ If the solution is acidic 2H+ + 2e- → H2 ↑

→ If the solution is neutral, hydroxyl ions are formed. 2H2O + O2 + 4e- → 4OH-

Zn2+ +2OH- → Zn(OH)2

Zn(OH)2 → ZnO +H2O

Higher the potential difference between the anodic and cathodic metals, higher is the rate
of corrosion.

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Other examples:
• Steel screws in copper sheet.

• Steel screws with copper washer.

• Bolt & nut are made of different metals.

2. Differential aeration corrosion

Iron

More O2, (Cathode)

Less O2, (Anode)

Water

Fig. 4. Differential aeration corrosion

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This type of corrosion occurs when two different parts of the same metal are exposed to
different oxygen concentrations. (E.g. An iron rod partially dipped in water.) The part of
the metal which is exposed to less oxygen concentration acts as anode. The part which is
exposed to more oxygen concentration acts as cathode. The anodic region undergoes
corrosion and the cathodic region is unaffected.

The reactions may be represented as follows:

Cell reactions:
At anode : M Mn+ + ne- (Oxidation of metal M)
At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)

Other examples:

1. Part of the nail inside the wall undergoes corrosion.

2. When a dirt particle sits on a metal bar, the part under the dirt undergoes corrosion.
3. Partially filled iron tank undergoes corrosion inside water.

a) Water line corrosion: This is an example of differential aeration corrosion.

Fig. 6. Waterline corrosion

Fig. 5. Waterline corrosion: (a) Water storage tank and (b) ocean going ship.

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When a steel tank is partially filled with water for a long time, the inner portion of the
tank below the water line is exposed only to dissolve oxygen, whereas, the portion above
the water line is exposed to more oxygen.Thus, the portion below the water line acts as
anode and undergoes corrosion. The upper portion acts as cathode and is unaffected.

A distinct brown line is formed just below the water line due to the deposition of
rust.

The reactions may be represented as follows:

Cell reactions:
At anode : M Mn+ + ne- (Oxidation of metal M)
At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)

Other example: Ships which remain partially immersed in sea water for a long time
undergo water line corrosion.

Mechanism of Waterline corrosion

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b) Pitting corrosion: This is an example of differential aeration corrosion.

Fig. 7. Pitting corrosion

When a small dust particle gets deposited on a steel surface, the region below the dust
particle is exposed to less oxygen compared to the remaining part. As a result, the region
below the dust particle acts as anode undergoes corrosion and forms a pit. The remaining
region of the metal acts as cathode and is unaffected.
The reactions may be represented as follows:

Cell reactions:
At anode : M Mn+ + ne- (Oxidation of metal M)
At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)

Formation of a small anodic area and a large cathodic area results in intense corrosion
below the dust particle.
*****

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Corrosion control

Corrosion is a surface phenomenon, the protection of the surface of the material/ metal is
primary object to prevent corrosion.

Corrosion is spontaneous natural process by which a metal is converted into a more stable
compound. Therefore corrosion control is more practical than corrosion prevention.

There are two components involved in corrosion; the metal and environment both are
considered in corrosion protection.

Following methods have been adopted for the protection of metal from corrosion:

1. Protective coatings (a. metallic coating b. Inorganic coating)

2. Cathodic protection

3. Design and selection of materials

a. Metallic coating
The deposition of protective metal over the surface of base metal is called as metallic
coating.

1. Anodic Metal Coating: It is the process of coating the base metal with more
reactive metals (Zn, Mg, Al, Cd etc) which are anodic to the base metal.

Example: Galvanization of iron and steel objects

imp→

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 Galvanization: Galvanizing is the process of coating a metal surface such as iron with
zinc metal. Galvanizing of iron is an example of anodic metal coating on the surface of a
cathodic metal.

Galvanization is carried out by hot dipping method. It involves the following steps:

Pair of hot
Air drier rollars

Iron sheet Galvanized sheet

Excess of Zn
Dil .H2SO4 Organic Water Molten
Solvent Zinc + NH4Cl(flux)
At 420 -5000C

Fig. 8. Galvanization of iron with Zn metal

Step 1 (Pickling process): The metal surface is washed dilute sulphuric acid to remove
any dirt, rust on the surface. [De-scaling].
Step 2 (degreasing): Oil, grease or fatty substances is removed by washing organic
solvents (CCl4, toluene, benzene).
Step 3: Finally, the article is washed with water and air-dried.
Step 4 (zinc bath treatment). The article is then dipped in a bath of molten zinc at 420
˚C to 500 ˚C (Molten zinc is covered with a flux of ammonium chloride to prevent
the oxidation of molten zinc.).
Step 5. The excess zinc on the surface is removed by passing through a pair of hot rollers.
Finally the article is annealed at 650 ˚C and then cooled slowly to obtain galvanized
Iron.

Applications:
1. Iron is protected with open atmosphere

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2. Galvanization of iron is carried out to produce roofing sheets, fencing wire, Nails,
bolts, nuts, pipes etc. and protecting from atmospheric corroding

Note: Even if the Zn coating falls off at some places, the base metal (Fe) does not
get corroded at those places. (This is because the base metal acts as cathode. In
corrosion process, the cathodic metal always remains unaffected.) And because of
the formation of small cathodic area and larger anodic area corrosion process will
not be there.

(Galvanized articles are not used for preparing and storing food because zinc
dissolves in dilute acids producing toxic zinc compounds)
*****

Cathodic Coating: Coating a base metal with more noble metals which are cathodic to
the base metal (Cu, Ni, Ag)

• Coating metals are less reactive than the base metal and are less susceptible to
corossion
• It is protective only when the coating is undamaged, non-porous and continuous
• An intense localized corrosion occurs when it is discontinuous

b. Inorganic coatings (non metallic coating)

These coating are generally chemical conversion coating. A process in which top layer of
a metal is converted to its oxide, which act a protective barrier and reduces corrosion.

Anodizing of Aluminum: When aluminum metal is made anodic in an electrolytic bath

with H2SO4 or chromic acid (H2Cr2O4) as the electrolyte at 35-40 ˚C, a thin layer of Al2O3

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is formed on the surface. This process is called anodizing of aluminum or anodic
oxidation of aluminum.

Fig. 9. Anodic oxidation of aluminum

Anodizing is carried out as follows: The article is made as anode and steel or copper is
made as cathode. The electrodes are dipped in a solution of 5 – 10% chromic acid, the
temperature of the bath is maintained at 350c. A potential is applied and gradually
increased from 0 to 40V during the first 10 min. Anodizing is carried out for 20 min at
40V. After 20 min, the potential is increased to 50V and held at this potential for 5min.
An opaque layer of 2-8µm thickness is obtained.

Following are the reactions:

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Anodized aluminium is exposed to a corrosive environment, the Al 2O3 layer on the
surface acts as a protective coating. Hence corrosion is prevented.

Other metals such as Mg, Ti etc. can also be anodized.

(Note: On anodizing, Al2O3 is formed on the surface as a porous layer. The layer may be
made compact by sealing, which involves heating with boiling water or steam. During
sealing, Al2O3 is converted into Al2O3.H2O which occupies higher volume. Therefore, the
pores are sealed.)

Applications:

Anodized Aluminium is used in computer hardware, roofs, floor, ceilings, curtains,

escalators and commercial buildings.

2.Cathodic protection:-

In cathodic protection, the metal to be protected is completely converted into a cathode.

Since cathodes do not undergo corrosion, the metal is protected against corrosion.

Sacrificial anode method:

Fig. 10. Sacrificial anode (ocean going ship, underground pipes)

In sacrificial anode method, the metal to be protected is electrically connected to a more

active metal. For example, when steel is to be protected, it may be connected to a block of
Mg or Zn. In such a situation, steel acts as cathode and is unaffected. Mg and Zn act as

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anode and undergo sacrificial corrosion. When the sacrificial anode gets exhausted, it is
replaced with new ones.

Other examples:

1. Mg bars are fixed to the sides of ships to act as sacrificial anode.

2. Mg blocks are connected to buried pipe lines.
3. Mg blocks are connected to underground oil storage tank.

Corrosion penetration rate (CPR)

“The Corrosion penetration rate is the speed at which any metal or alloy
deteriorates in a specific corrosive environment through chemical or
electrochemical reactions”.
It is also defined as the amount of weight loss per year in the thickness of
metal or alloy due to corrosion. The Corrosion penetration rate also referred as
corrosion rate.
Corrosion penetration rate depends on following factors;
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of metal.

The Corrosion penetration rate is calculated using the following formula;

K. W
CPR =
D(ρ). A. T

Where, W is weight loss after exposure time.

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 T is exposure time in corrosive medium.
D(𝛒) is the density of metal or alloy.
A is surface area of exposed specimen.
K is constant.
The CPR is conveniently expressed in terms of either mils per year (mpy) or
millimeters per year (mmpy). K = 534 to give CPR in mpy when surface area of test
specimen is in inch2 and K = 87.6 for CPR in mmpy when surface area of test
specimen is in cm2 Where, 1 mil = 0.001 inch.

Symbol CPR in mpy CPR in mmpy

K 534 87.6
W (wt. loss) mg mg
D(ρ) g/cm3 g/cm3
A Inch2 Cm2
T hrs hrs

Numerical Problems on CPR:

1. A sheet of carbon steel one meter wide by three meters long has lost 40g to
corrosion over the past six months. Convert that mass loss to a penetration rate of
the steel in mmpy units and mpy units. What would be the corrosion rate? (Carbon
steel density =7.8 g/ cm3).

Solution: To calculate CPR in mmpy;

Symbol Given CPR in mmpy

K 87.6
W (wt. loss) 40 g 40x1000 mg

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 D(ρ) 7.8 g/cm3 7.8 g/cm3
A 1mx3m = 3m2 3x100x100 cm2
T 6 months 6x30x24 hrs

K. W
CPR =
D(ρ). A. T

87.6x40x1000
CPR =
7.8x3x100x100x6x30x24

CPR = 3.466x10-3 mmpy

To calculate CPR in mpy;

Symbol Given CPR in mpy

K 534
W (wt. loss) 40 g 40x1000 mg
D(ρ) 7.8 g/cm3 7.8 g/cm3
A 1mx3m = 3m2 3x1550 inch2
T 6 months 6x30x24 hrs

K. W
CPR =
D(ρ). A. T
534x40x1000
CPR =
7.8x3x1550x6x30x24

CPR = 0.136 mpy

2. Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100
2
inch which experiences a weight loss of 485g after one year. (Density of steel =
7.9 g/cm3).

Solution: To calculate CPR in mmpy;

Symbol Given CPR in mmpy

K 87.6
W (wt. loss) 485 g 485x1000 mg
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 D(ρ) 7.9 g/cm3 7.9 g/cm3
A 100 inch2 100x6.45 cm2
T 1 year 365x24 hrs

1 inch2 = 6.45 cm2 ; 1 cm2 = 0.155 inch2

K.W
CPR =
D(ρ).A.T

87.6x485x1000
𝐂𝐏𝐑 =
7.9x100x6.45x365x24

CPR = 0.9518 mmpy

To calculate CPR in mpy;

Symbol Given CPR in mpy

K 534
W (wt. loss) 485 g 485x1000 mg
D(ρ) 7.9 g/cm3 7.9 g/cm3
A 100 inch2 100 inch2
T 1 year 365x24 hrs

K. W
CPR =
D(ρ). A. T

534x485x1000
CPR =
7.9x100x365x24

CPR = 37.424 mpy

3. A piece of corroded steel plate was found in a submerged ocean vessel, it

was estimated that the original area was 10 inch 2 that approximately 2.6kg had
corroded away during the submersion. Assuming a corrosion penetration rate of
200 mpy for this alloy in sea water, estimate the time in years, density of steel was
7.9g/cc.

Solution: CPR = 200 mpy.

Symbol Given CPR in mpy

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 K 534
W (wt. loss) 2.6 kg 2.6x1000x1000 mg
D(ρ) 7.9 g/cm3 7.9 g/cm3
A 10 inch2 10 inch2
T X X hrs

K. W
CPR =
D(ρ). A. T
534x2.6x1000x1000
200 =
7.9x10xT

T = 87873.41 hrs
87873.41
T= = 10.03 yrs
365𝑥24

Home work

4. A thickness of brass sheet of area 400 inch 2 is exposed to air near the ocean.
After two year period it was found to experience a weight loss of 375g due to
corrosion. If the density of brass is 8.73 g/cm3. Calculate CPR in mmpy/year
and mpy.

5. A metal iron plate was found in a vessel containing acidic media, it was
estimated that the original area was 20 inch2 that approximately 1.2kg had
corroded. Assuming a corrosion penetration rate of 400 mpy for this iron in
acidic, calculate time in years, density of iron was 7.87 g/cm3.

6. A piece of corroded aluminum plate was found in a submerged ocean vessel, it

was estimated that the original area was 64 cm2 that approximately 350 g had
corroded away during the submersion. Assuming a corrosion penetration rate of
2.4 mmpy for this alloy in sea water. Calculate the time in years, density of
aluminum 2.7 g/cm3

******

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