CHAPTER: VI

CORROSION
Q. (1). Define “Corrosion”. Explain the factors affecting the rate of Corrosion.

[OR] What is Corrosion. What are the factors that influence the rate of

Corrosion.

CORROSION:

The slow and gradual disintegration of a metal by electrochemical (or) chemical

attack with its environment is called “Corrosion”.

[Corrosion]
[Oxidation]
Metal Metallic Compound + Energy
[Metallurgy]
[Reduction]

Factors Influencing Rate of Corrosion:

The rate and extent of corrosion depends on,
[A]. The Nature of Metal and [B]. The Nature of Environment

[A]. The Nature of Metal:

(i). Position of the Metal in Electrochemical Series [Galvanic Series]:

The metal with higher position in electrochemical series undergoes
corrosion first. Greater the difference in position, faster will be the corrosion of
another metal.

(ii). Purity of Metal:

Pure metals are corrosion resistant. The rate and extent of corrosion of
metals increases with increase of impurities in the metal. Impurities lead to
formation of galvanic cells and leads to metallic corrosion.

Ex.: Zn metal containing impurities like Pb (or) Fe undergoes corrosion

readily.
 (iii). Physical State of the Metal:
[a]. Grain Size:
Smaller the grain size of the metal, greater will be the corrosion.
[b]. Stress:
Stressed area in a metal acts as anode and undergoes corrosion
takes place at this area.

(iv). Relative Areas of Anode & Cathode:

Corrosion is more rapid if the ‘anodic area’ of the metal is smaller.

Area of Cathode
Corrosion α
Area of Anode

Ex.: A small steel pipe fitted in a large copper frame undergoes

corrosion readily.

(v). Solubility [Volatility] of Corrosion Product:

If the corrosion product is soluble [i.e. liberated as gas], then the
underlying surface is exposed for further attack. This causes rapid and
continuous corrosion.
If the corrosion product is insoluble, then the rate of corrosion
decreases.

(vi). Passivity of Metal:

Passivity of the metal decreases corrosion rate by increasing the
corrosion resistance of the metal.

[B]. The Nature of Environment:

(i). Temperature:
The rate of corrosion increases with the increase of temperature.

(ii). Humidity:
Higher the moisture content in the atmosphere greater will be the rate
and extent of corrosion.

(iii). Influence of pH:

The rate of corrosion is higher in acidic environment [i.e. pH ˂ 7].
 (iv). Presence of Impurities in Atmosphere:
Presence of corrosive gases like SO 2, H2S, CO2 and fumes of HCl in the
atmosphere increases the acidity which increases the corrosion.

(v). Concentration of Oxygen:

Due to the difference in the concentration of Oxygen around the surface
of the metal, Anode area undergoes corrosion.

(vi). Presence of Suspended Particles in Atmosphere:

Suspended particles like NaCl etc., in atmosphere absorb the moisture
and act as strong electrolytes and increases the corrosion.

(vii). Nature of Ions Present in Environment:

Chloride ions present in the environment destroy the protective film
and corrode metals. Silicate ions decrease the rate of corrosion.

[OR]

CORROSION:

The slow and gradual disintegration of a metal by electrochemical (or) chemical

attack with its environment is called “Corrosion”.

[Corrosion]
[Oxidation]
Metal Metallic Compound + Energy
[Metallurgy]
[Reduction]

Factors Influencing Rate of Corrosion:

The rate and extent of corrosion depends on,
[A]. The Nature of Metal and [B]. The Nature of Environment

[A]. The Nature of Metal:

(i). Position of the Metal in Electrochemical Series [Galvanic Series].

(ii). Purity of Metal.
(iii). Physical State of the Metal: (a). Grain size & (b). Stress.
(iv). Relative areas of Anode and Cathode.
(v). Solubility [Volatility] of Corrosion Product.
(vi). Passivity of Metal.
 [B]. The Nature of Environment:

(i). Temperature.
(ii). Humidity.
(iii). Influence of pH.
(iv). Presence of Impurities in Atmosphere.
(v). Concentration of Oxygen.
(vi). Presence of Suspended Particles in Atmosphere.
(vii). Nature of Ions Present in Environment.

Q. (2). Explain the “Electrochemical Theory of Corrosion”. Explain “Composition

Cells”, “Concentration Cells” and “Stress Cells” with examples. [OR]
Explain “Electrochemical Theory of Corrosion”. Explain the formation of
“Galvanic Cells” due to different factors. [OR]
Explain “Electrochemical Theory of Corrosion” with the formation of
different “Galvanic Cells”.

Electrochemical Theory of Corrosion:

Corrosion is an Electrochemical Reaction. This type of corrosion occurs due to

electrochemical processes resulting from galvanic cell formation between two
different metals (or) two dissimilar parts of the same metal.
Electrochemical activity of metals depends on its electrode potential. If a metal
having higher electrode potential comes in contact with another metal having lower
electrode potential, a galvanic cell is setup. The metal having higher electrode
potential becomes anode and undergoes oxidation, gets corroded.
The rate of corrosion depends upon the difference in the electrode potential of
the two metals. The greater is the difference in the potentials of the cathode and
anode, greater will be the corrosion.
Mechanism:
Electrochemical corrosion involves flow of electron current between anode and
cathode.
At Anode: [Oxidation Reaction]: M Mn+ + n e-

At Cathode: [Reduction Reaction]: ½ O 2 + H 2O + 2 e - 2 OH-

[Neutral Medium & O2 Absorption]

[OR]
 At Cathode: [Reduction Reaction]: 2 H+ + 2e- H2
[Acidic Medium]

Formation of Different Types of Galvanic Cells [Corrosion Cells] :

Three types of galvanic cells are formed during the electrochemical corrosion.
They are:
[1]. Composition Cell, [2]. Concentration Cell and [3]. Stress Cell.
[1]. COMPOSITION CELL [Galvanic Corrosion]:
A composition cell is formed between two different metals are electrolytically
connected and exposed to an electrolyte. In this cell, the metal with higher position in
electrochemical series [i.e. more reactive metal] acts as an anode and undergoes
corrosion. The other metal with lower position in electrochemical series [i.e. less
reactive metal] acts as cathode. This type of corrosion is called ‘Galvanic Corrosion’.

Ex.: When Zinc [Zn] and Copper [Cu] are electrically connected and exposed
to
an electrolyte, ‘Zn’ which is higher in electrochemical series acts as anode
and undergoes corrosion. ‘Cu’ is less reactive and acts as cathode.

Composition Cell

[2]. CONCENTRATION CELL [Differential Aeration Corrosion]:

A Galvanic cell formed due to difference in the concentration of Oxygen (or)

electrolyte around the metal surface is called “Concentration Cell”. This type of
corrosion is known as ‘Differential Aeration Corrosion’.
 ‘Poor Oxygenated’ part of metal acts ‘Anode’ and undergoes corrosion.
‘Richly Oxygenated’ part of the metal acts as ‘Cathode’, which is resistant to corrosion.
Ex.: When a Zinc [Zn] metal is partially immersed in a dilute NaCl solution, the
part above and adjacent to the water line is richly [more] oxygenated and
acts as cathode. The part immersed below the waterline is poorly [less]
oxygenated becomes anode and undergoes corrosion.

Composition Cell

At Anode: [Oxidation Reaction]: Zn Zn+2 + 2 e-

At Cathode: [Reduction Reaction]: ½ O2 + H2O + 2 e- 2 OH-
Net Cell Reaction: [Redox Reaction]: Zn + ½ O2 + H2O Zn+2 + 2 OH-

[3]. STRESS CELL:

A Galvanic cell is formed between stressed areas and unstressed areas of

same metal due to difference in energy levels are called “Stress Cell”.
The ‘High Stressed Area’ of the metal posses ‘Higher Energy’ and acts as
‘Anode’, undergoes corrosion. The ‘Unstressed Area’ possess ‘Less Energy’ and acts as
‘Cathode’.

Ex.: In a nail, the ‘Head’ and ‘Tail’ parts being stressed parts act as ‘Anode’ and
undergo corrosion. The ‘Body [middle]’ portion of the nail is unstressed
area acts as ‘Cathode’ and is protected from corrosion.
 Stress Cell: Nail
Q. (3). What is “Rust”. Write its Formula and the necessary conditions for “Rusting of Iron”
(or) Factors Influencing the rate of Rusting of Iron. Explain the “Mechanism of Rusting
of Iron with Chemical Equations .

RUST:
The ‘reddish brown’ precipitate formed on the surface of iron when it is exposed
to atmosphere is called “Rust”.

RUSTING:
The process of forming rust is called “Rusting”.

FORMULA:
The formula of rust is “Fe2O3 . X H2O”. [Where, X = 0 to 3].
If X = 3, then rust could be regarded as “Hydrated Ferric oxide” (or) “Ferric
hydroxide”.
Fe2O3 . X H2O 2 Fe(OH)3
[Hydrated Ferric oxide] [Ferric hydroxide]

But, X < 3. Rust is formed from Ferric hydroxide followed by the loss of water to the
atmosphere.
2 Fe(OH)3 Fe2O3 . X H2O + (3 – X) H2O
[Rust]

Necessary Conditions for Rusting of Iron [or]

Factors Influencing the Rate of Rusting of Iron:
(1). Impurities and solid defects in metals.
(2). Moisture present in the atmosphere.
(3). O2 and CO2 present in the atmosphere.
(4). Electrolytes in the atmosphere.
(5). Temperature of surroundings.
(6). pH of the medium [electrolytes].

MECHANISM OF RUSTING OF IRON:

Case: I:
Mechanism of Oxygen Absorption Type of Corrosion:
 This type of corrosion generally occurs in neutral environment. In this type
of corrosion usually the anodic area is small and cathode area is large. In the
presence of sufficient oxygen and neutral aqueous medium, oxygen gas is
absorbed.

At Anode:

The Iron metal oxidizes and liberates electrons, forms Fe +2 [Ferrous] ions.

Fe Fe+2 + 2 e- [Oxidation]
At Cathode:

The electons liberated at anode flows towards cathode. There they are
consumed by the dissolved Oxygen generating OH - [Hydroxyl] ions.

H 2O + ½ O 2 + 2 e - 2 OH- [Reduction]

The Fe+2 ions formed at anode and OH- ions formed at cathode combine to
form ‘Ferrous hydroxide’ as precipitate.

Fe+2 + 2 OH- Fe(OH)2 [Ferrous hydroxide]

If enough oxygen is present ‘Ferrous hydroxide’ is oxidized to ‘Ferric

hydroxide’.

4 Fe(OH)2 + O2 + 2 H2O 4 Fe(OH)3 [Ferric hydroxide]

‘Yellow Rust’ is formed from Ferric hydroxide followed by the loss of water to
the atmosphere.

2 Fe(OH)3 Fe2O3 . X H2O + (3 – X) H2O

[Yellow Rust]
 Mechanism of Rusting of Iron by O2 Absorption

Case: II:

Mechanism of Hydrogen Evolution Type Corrosion:

This type of corrosion occurs in ‘Acidic Environment’. Hydrogen [H 2] gas is

liberated in this gas. In this type of corrosion the anodic area is large and cathodic
area is small.

At Anode:

The Iron metal oxidizes and liberates electrons, forms Fe +2 [Ferrous] ions.

Fe Fe+2 + 2 e- [Oxidation]

At Cathode:
The electrons liberated at anode move towards cathode. There they are
consumed by H+ ions present in the acidic medium and are liberated as H 2 gas.

2 H+ + 2 e - H2 [Reduction]
The Overall Reaction [Redox Reaction]:

Fe + 2 H+ Fe+2 + H2
 Thus Iron undergoes corrosion by dissolving in acid medium with evolution
of Hydrogen gas.

Mechanism of Rusting of Iron by Evolution of H2 Gas

Q. (4). Explain different types of “Protective Coatings” used to prevent corrosion. [OR]
Explain how corrosion is prevented by “Protective Coatings Methods”.

Protecting Coating Methods:

Corrosion can be prevented by covering the surface of the metals with suitable
protective coatings. A coated surface isolates the underlying [base] metal from the
corrosion environment and hence prevents the corrosion.

The following types of protective coatings are used to prevent the metal from
corrosion.
[i]. Metallic Coatings, [ii]. Inorganic Coatings and [iii]. Organic Coatings.

[i]. Metallic Coatings:

The process of covering the base metal with a layer of another metal to
protect the base metal from corrosion is called ‘Metallic Coating’.
 Metallic coatings are divided into two types.
They are: (a). Anodic Coatings and (b). Cathodic Coatings.

(a). Anodic Coatings:

In these coatings more active metal is coated over base metal.
Ex.: Coating of Zinc on Iron [Galvanisation].
(b). Cathodic Coatings:
In these coatings less active metal is coated over base metal.
Ex.: Coating of Tin on Iron [Tinning].

[ii]. Inorganic Coatings [Non-metal Coatings]:

Inorganic Coatings are produced by chemical (or) electrochemical reactions

brought at the surface of the base metal.

Inorganic coatings are mainly three types.

They are: (a). Phosphate Coating, (b). Chromate Coating and (c). Oxide Coating.

(a). Phosphate Coatings:

Phosphate coatings are used to coat metals like Iron [Fe], Steel, Zinc [Zn]
to a lesser extent of Al, Cd and Sn.
Phosphate coating is widely used in the automobile industry, nuts and
bolts, construction materials etc.

(b). Chromate Coatings:

Chromate coatings are used as base for paints and enamels. It is used for
the protection of Zn, Al, Mg, Cd etc.

©. Oxide Coatings:
Corrosion-resistance of steel and copper is increased by oxide coatings.
Oxide coatings act as primers for oil, grease and waxes.

[iii]. Organic Coatings:

Organic compounds like Plastics, Paints, Varnishes and Enamels are applied on
metals to protect them from corrosion.
Q. (5). Write the differences between “Anodic Coatings” and “Cathodic Coatings”. [OR]
Distinguish between “Anodic Coatings” and “Cathodic Coatings”.

Differences Between ‘Anodic Coatings’ and ‘Cathodic Coatings’.

ANODIC COATINGS CATHODIC COATINGS

1 In this method a base metal is coated 1. In this method a base metal is coated
. with more active metal [i.e. anode with less reactive [i.e. higher corrosion
metal]. resistance] and noble metal

2 The electrode potential [SRP] of coated 2. The electrode potential [SRP] of coated
. metal is less than base metal. metal is more than base metal.

3 The coated metal prevents base metal 3. The coated metal protects the base metal
. from corrosion by sacrificial anode from corrosion due to its noble character
method. and higher corrosion resistance.

4 The base metal is not corroded even 4. The base metal undergoes corrosion
. when pores (or) cracks are formed in when pores (or) cracks are formed in
surface coating. surface coating.

Ex.: Coating of Zinc on Iron [Galvanizing] Ex.: Coating of Tin on Iron [Tinning]

Q. (5). Explain “Cathodic Protection” method in controlling corrosion with suitable examples.
[OR] Explain “Sacrificial Anode Method” and “Impressed Voltage Method” with
examples.

CATHODIC PROTECTION:

The principle involved in this method is to force the metal to be protected from
corrosion is made to behave like a cathode by connecting it with another active metal
(or) by impressed current, so that corrosion doesn’t occur.

This is of two types. [A]. Sacrificial Anode Method [Galvanic Protection] and
[B]. Impressed Voltage [Current] Method.
 [A]. Sacrificial Anode Method [Galvanic Protection]:

In this method the metal to be protected from corrosion is made cathode by

connecting it with more active metal [i.e. anodic metal] through a wire. The more
active metal acts as anode and gets corroded slowly. The parent metal acts as
cathode and is protected from corrosion. The more active metal is called as
“Sacrificial Anode”.
The commonly used sacrificial anode metals are Mg, Zn, Al etc.

Ex.: Underground Iron pipes are protected from corrosion by connecting them
with more active metal like Magnesium. ‘Mg’ acts as ‘Sacrificial anode’ and
undergoes corrosion. Thus, Iron pipes are protected from corrosion. ‘Mg’ is
sacrificed in the protection of Iron pipes.

Sacrificial Anode Cathodic Protection [Galvanic Protection]

Applications:

(i). Underground cables and pipelines are protected from soil corrosion.
(ii). ‘Mg bars’ are fitted along the sides of the ships for protecting the
hulls from marine corrosion.
(iii). Formation of rusty water in domestic boilers and water-tankers can
be prevented.

[B]. Impressed Voltage Method:

In this method the metal to be protected is connected to an inert metal like

carbon, graphite etc. and an impressed [external] current is applied in the
opposite
direction to nullify the corrosion current. This converts anode [i.e. metal to be
 protected] into cathode. Usually a sufficient direct current is applied to an inert
anode buried in the soil and connected to the metal to be protected. The anode is
buried usually in backfill such as gypsum to increase the electrical contact with the
surrounding soil. This method used for the large structure for long term operations.

Impressed Voltage [Current] Cathodic Protection

Applications:
(i). Protection of Underground water pipelines, Oil pipelines, Marine pipelines
etc.
(ii). Protection of open water – box coolers.
(iii). Protection of condensers, Transmission line towers, Laid – up ships etc.

Q. (6). Explain the various methods used for prevention of corrosion.

The following are the methods used for control of corrosion.

(i). Using metals of high purity.
(ii). Alloying.
(iii). Modification of the environment.
(iv). Protective coatings.
(v). Cathode protection.
(i). Using Metals of High Purity:
Corrosion-resistance of metals can be increased by increasing its purity.
Ex.: The corrosion-resistance of high purity ‘Al’ metal depends on its film
formation which is highly protective only on the high purity metal.
(ii). Alloying:
Corrosion-resistance of metals can be increased by alloying them.
Ex.: Stainless steel is an alloy of Cr + Ni + Fe + C. This has good
corrosion-resistance.
(iii). Modification of the Environment:
The corrosive nature of the environment can be reduced by the
following methods.
(a). Deaeration (or) Deactivation:
The removal of oxygen prevents corrosion. This is done be
‘Deaeration’ (or) ‘Deactivation’.
Deaeration: Oxygen can be removed by adjusting the temperature with
mechanical agitation.
Deactivation: Oxygen can be removed by adding chemicals.
Ex.: 2 Na2SO3 + O2 2 Na2SO4
N 2H4 + O2 N2 + 2 H 2O

(b). Dehumidification:
In this method the moisture in environment is reduced.
Ex.: Alumina [Al2O3], Silica gels are used to absorb the moisture.

©. Alkaline Neutralization:
In this method the corrosion can be reduced by neutralizing the
acidic character of corrosive environment.
Ex.: Ammonia [NH3], NaOH are used as alkaline neutralizers.

(d). Using Inhibitors:

In this method corrosion can be prevented by spraying inhibitors on
metal surface.
Ex.: Chromates, Phosphates and Tungstates are used as inhibitors.
(iv). Protective Coatings:
A metal can be prevented from corrosion by covering the surface of a metal
with suitable protective coatings.
Types of Protective Coatings:
(a). Metallic Coatings:
(i). Anodic Coatings: Ex.: Coating ‘Zn’ on ‘Fe’. [Galvanizing]
(ii). Cathodic Coatings: Ex.: Coating ‘Sn’ on ‘Fe’. [Tinning].

(b). Inorganic (or) Non-metallic Coatings:

(i). Phosphate Coating, (ii). Chromate Coating and (iii). Oxide Coating.

©. Organic Coating:
(i). Plasting Coating and (ii). Paints & Oils Coating.

(v). Cathodic Protection:

The principle involved in this method is to force the metal to be protected
from corrosion is made to behave like a cathode by connecting it with another active
metal (or) by impressed current, so that corrosion doesn’t occur.

Cathodic Protection of two types.

[a]. Sacrificial Anode Method [Galvanic Protection]:
Ex.: Connecting ‘Mg’ to ‘Fe’. ‘Mg’ serves as a sacrificial anode.
[b]. Impressed Voltage [Current] Method:
Ex.: Connecting insoluble ‘Graphite anode’ buried in the soil, to the metallic
structure.

Dr. G. N. RAMESH, M. Sc., M. Phil., Ph. D.

Lecturer in Chemistry
Dr. Y. C. James Yen Government Polytechnic,
[Department of Technical Education, A.P.]
Kuppam – 517425, Chittoor Dt., A.P.
Mobile: 9989064100; 9182754755
E-mail: [email protected]