Preclass Corr

Engg.
Chemistry II
Pre class- CORROSION AND CORROSION CONTROL
Unit-II CORROSION AND CORROSION CONTROL

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Material prepared by: Chemistry faculty
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Engg. Chemistry II
Do You Know???
1st Recorded information
Plato (Greek philosopher and student of Socrates, 427-347 BC), in Phaedo

wrote: "For this earth, and the stones, and the entire region which surrounds us
are spoilt and corroded, like the things in the sea which are corroded by the
brine ..."
The first article on corrosion was reportedly published by Robert Boyle*
in 1675
An early theoretical electrochemical corrosion publication is a paper
attributed to W.H. Wollaston in 1801, "The Electrochemical Theory of
Acid Corrosion".
First corrosion papers within the famous Electrochemical Society
reportedly delivered in 1903
It was estimated that prior to 1904, not more than half a dozen persons
were (significantly) involved in the subject of corrosion, in the USA.
The first text book on corrosion has been attributed to Ulick Richardson
(U.R.) Evans, "Corrosion of Metals", in 1924.
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Engg. Chemistry II
Syllabus
Corrosion- causes- factors- types chemical, electrochemical corrosion (galvanic, differential
aeration), corrosion control material selection and design aspects - electrochemical
protection sacrificial anode method and impressed current cathodic method.
Paints- constituents and function. Electroplating of Copper and electroless plating of nickel.
Learning Objectives
At the end of the unit student will become conversant with
Definition of Corrosion
Reasons for corrosion
Types of corrosion : dry corrosion and wet corrosion
Mechanism of Chemical and Electrochemical corrosion
Types of Differential aeration corrosion
Factors influencing corrosion : Metallic and Environmental factors
Corrosion control : By design and cathodic protection method
Paints : Constituents and function of paints
Electroplating of copper
Electro less plating of nickel
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Engg. Chemistry II
What is corrosion?
The deterioration of the surface of metals due to its chemical / electro chemical
reaction with the surrounding is called corrosion.
Metal + Surrounding Compound
Metal is oxidized and Surrounding is reduced
Examples:
Rusting of iron(Fe2O3 .3H2O)

Green patina (CuO) on copper sheets
Tarnishing of Ag ( due to the formation of AgS)
Pitting of stainless Steel
Why do metals corrode? / Why Corrosion is spontaneous?

The thermodynamic stability of ores is greater than that of the element.
Hence metals tend to regain their state of stability
During extraction G is positive, corrosion is reverse of extractive
metallurgy hence G is negative
Rusting of iron (Fe2O3.H2O)
Cu develops green patina: CuCO3 Cu(OH)2
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Engg. Chemistry II
Ag article tarnishes and finally goes black in atm.
A can containing acidic fruits.
Do you know how much loss per year because of corrosion?

The corrosion is a slow process on the metal surfaces, but the losses incurred are enormous
waste/destruction of machines, equipment.
Consequences of Corrosion:
Plant shut down due to failure
Replacement of corroded equipment
Maintenance cost
Loss of efficiency
Contamination or loss of product ( from the corroded container)
Safety (fire due to release of toxic product or collapse of construction)
Health (pollution)
Necessity for over design to allow for corrosion
Globally industries are spending billions and billions of dollars to overcome these problems.
So corrosion is called as billion dollar thief.
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Engg. Chemistry II
Corrosion occurs on metals in dry as well as in wet conditions,

At room temp., most metals under go corrosion and form thin oxide layer as a result of
reaction of metals with oxygen.
Wet corrosion occurs in environment where the relative humidity exceeds 60 %.
Based on environment corrosion is classified into Two types.
TYPES OF CORROSION:
1. Dry corrosion or Chemical corrosion
2. Wet corrosions or Electrochemical corrosion.
1. Dry or Chemical Corrosion:

Direct chemical action of environment/atm gases such as O2, H2, halogen, H2S, SO2, NO2
with metal surfaces of immediate proximity.
a. Oxidation Corrosion: Direct chemical action of O2 on metal surface.
The further corrosion depends on the nature of the oxide film formed, if the thin film formed
is protective no further corrosion take place.
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Engg. Chemistry II
PILLING BEDWORTH RULE explains the further corrosion
Pilling Bedworth ratio (or) Specific volume ratio = 1 or > 1, film is protective and
non-porous
Pilling Bedworth ratio < 1, film is non-protective and porous
Nature of the metal-oxide layer or film

i) if it is a stable oxide Layer - protective prevent further corrosion
Ex. Oxides of Al, Sn, Ti, Cr etc
ii) if it is a unstable Oxide layer on noble metals: - protective prevent further corrosion
Ex. Oxides of Au, Pt are not stable, MO immediately break and give Metal and Oxygen.
iii)Volatile Oxide layer Non-protective- corrosion rate increases.
Ex.MoO3 is a Volatile; MoO3 leaves the surface for further corrosion.
iv) Porous Oxide Layer Non-protective - corrosion rate increases
Ex. Alkali and alkaline earth metals, pores provide access for further O2 attack.
b) Corrosion by other gases:
Corrosion by gases like Cl2, SO2, CO2, H2S, F2 etc.

Corrosion by H2:
1.Hydrogen Embrittlement: hydrogen atoms re-combine in minuscule voids of the metal
matrix to form hydrogen molecules, they create pressure from inside the cavity they are in.
1.
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Engg. Chemistry II
2.Decarburisation: The atomic hydrogen combines with carbon of the steel to produce
methane gas.
c) Liquid metal corrosion: Proceeds by

i.
Dissolution of solid metal into the liquid metal
ii.
Penetration of the liquid metal into the solid metal
This type of corrosion is observed in Nuclear power plants, where liquid Sodium is used as a
coolant. The cadmium rods (moderator) are corroded by the coolant (liquid Na)
2. WET or ELECTROCHEMICAL CORROSION
Occurs where a conducting liquid is in contact with same metal with different surface
conditions or two dissimilar metals.
This corrosion may be uniform destruction of the metal surface or localized

destruction.
In wet corrosion, the corrosion take place at anodic part but the corrosion products get
deposited near cathode.
1) Evolution of Hydrogen
2H + + 2eFe + 2H+
H2
Fe 2+ + H2
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Engg. Chemistry II
2. Absorption of Oxygen:
Fe
1/2O2 + H2O +2eFe2+ + 2OH-
Fe2+ + 2e2OHFe (OH)2
1. If a metallic tool is made by two dissimilar metals like iron and copper and exposed to the
moisture, which metal undergo corrosion?
Corrosion will be on iron (anodic metal) - Galvanic Corrosion occurs.
2. If a metal surface is exposed to different metal ion concentration or oxygen concentration Concentration Cell Corrosion or Differential Aeration Corrosion occurs.
Types of Wet or electrochemical corrosion
1. Galvanic Corrosion
2. Concentration Cell Corrosion (Differential Aeration Corrosion).
3. Stress Corrosion.
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Engg. Chemistry II
GALVANIC CORROSION
For galvanic corrosion, the following conditions are essential
Electrochemically dissimilar metals must be present
These metals must be in electrical contact, and
The metals must be exposed to an electrolyte
In galvanic corrosion, galvanic series tells the corroding metal among the two connected
dissimilar metals.
Galvanic Series:
A more practical series have been prepared by studying the corrosion of metals in a
given environment like sea-water.
It gives real and useful information about the corrosion of metals and alloys.
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Engg. Chemistry II
Galvanic series Table
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Engg. Chemistry II
Differential Aeration Corrosion
Common type of concentration cell corrosion occurs when same metallic surface
exposed to different oxygen concentration.
Poor-oxygenated parts become anodic and undergo corrosion.
Different Types of Differential Aeration Corrosion

1). Waterline Corrosion: Maximum corrosion takes place along the line just beneath the
level of water meniscus
2) Pitting corrosion: It is a localized attack at a particular area on the metal surface. Metal
area covered by a drop of water and sand, dust, scale etc. act as anode with poor aeration and
undergo corrosion.
3) Crevice Corrosion: Crevice corrosion is a corrosion occurring in spaces to which the

access of the working fluid from the environment is limited. These spaces are generally
called crevices. Examples of crevices are gaps and contact areas between parts, under gaskets
or seals, inside cracks and seams, spaces filled with deposits and under sludge piles.
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Engg. Chemistry II
If a crevice between different metallic objects or between metal and non-metallic material
is in contact with liquid, the crevice becomes the anodic region and suffers corrosion.
4) Pipe line corrosion: Differential aeration corrosion may also occur at the different parts of
pipeline. Buried pipelines or cables passing from one type of soil to another, from clay soil
(less aerated) to sand (more aerated). Pipelines passing through clay with poor aeration
undergo more corrosion.
5) Wire Fence corrosion: The areas where the wire-cross is less aerated than the rest of the
fence and hence corrosion occurs at wire crossing which are anodic.
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Engg. Chemistry II
The rate and extent of corrosion depends on

1. Nature of the metals (substrate) and
2. Nature of corroding environment
FACTORS INFLUENCING CORROSION

1. NATURE OF METALS (SUBSTRATE)
i)
Position of the metals in the galvanic series
ii)
Over Voltage( Back emf)
iii)
Relative areas of anodic and cathodic parts
iv)
Purity of the metal
v)
Physical state of metals
vi)
Nature of surface film
vii)
Passive character of the metal
viii)
Solubility of corrosion product
ix)
Volatility of corrosion product
2. NATURE OF CORRODING ENVIRONMENT

i)
Temperature of the corroding medium
ii)
Humidity of the air
iii)
Impurities present in the atm
iv)
Presence of suspended particle
v)
Nature of ions present:
vi)
Conductivity of corrosive medium
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Engg. Chemistry II
vii)
Formation of oxygen concentration cell
viii)
Velocity of flowing liqui:
Corrosion control
CONTROL OF CORROSION BY MODIFYING THE SURFACE
1. By painting
2. By metal plating.
a. Anodic coating: Galvanization (coating of Zn on iron or steel).
b. Cathodic coating: Tinning. (coating of Sn (Tin) on iron or steel).
C. Electroplating
D. Electroless plating (without electricity)
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Engg. Chemistry II
Electroless plating will give more smooth coatings than electroplating.
CONTROL OF CORROSION BY MODIFYING THE BASE METAL

1. By alloying with passive metals.
Ex.: Stainless steel: steel alloy with a minimum of 10.5 or 11% chromium content by mass. Cr
enhances the corrosive resistance of stainless steel by forming stable CrO3 layer.
2.Avoiding the contact of dissimilar metals.
3.Selecting pure metal to avoid impurities, which cause heterogeneity and leads to
electrochemical corrosion.
4. By providing proper design in fabrication of metallic tools:
Avoid the contact of dissimilar metals.
Choose high anode area than cathodic area. When the ratio of anodic to cathodic
area increases, the rate of corrosion decreases.
Choose the metals which are close in the emf series.
Insulate the fitting of different metals.
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Engg. Chemistry II
5.Avoiding sharp corners, stressed parts and crevices to avoid stress corrosion.
6. By forcing the metallic structure is to behave like cathode thereby corrosion does not
occur. Then corrosion will concentrate on the second metal (magnesium) is called Cathodic
Protection.
1. The metallic structure (iron) to be protected is connected by a wire to a more anodic metal
like Zn, so that all corrosion is concentrated at this more active metal. So iron become
cathode. This method is called Sacrificial anodic protection method.
3. An impressed current is applied to in opposite direction to nullify the corrosion

current.
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Engg. Chemistry II
CORROSION CONTROL BY MODIFYING THE ENVIRONMENT

1. By Deaeration:
2. Dehumidification.
3. Alkaline Neutralisation.
4. Use of Inhibitors
A substance which when added in small quantities to the aqueous environment effectively
decreases the corrosion of metal.
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Engg. Chemistry II
Check your understanding

Fill in the blank with the right answer:
1. Rusting of iron is more in _____________air than in dry air.
2. If Pilling Bedworth ratio (or) Specific volume ratio is greater than 1, the metal
oxide film is a _____________.
3. In wet corrosion, the corrosion products deposit near _____________.
4. In galvanic corrosion, the metal having relatively _____________ Eo value will
undergo more corrosion.
5. When machinery parts made by iron and copper is placed in moist atmosphere,
then _____________ undergo corrosion.
6. When the ratio of anodic to cathodic area decreases, the rate of corrosion
_____________.
7. Galvanization is an _____________coating.
8. During differential oxygen concentration corrosion, the corrosion occurs at
_____________ oxygenated part.
9. When a buried pipeline is protected from corrosion by connecting to Mg block, it
is called_____________.
[Check the correct answers on page 20.]
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Engg. Chemistry II
Answers to Check your understanding:

1.
2.
3.
4.
5.
6.
7.
8.
9.
Wet
Protective
Cathode
lower
Iron
Increases
Anodic
Poorly
Sacrificial anodic protection method
Summary
On completion of this chapter you have learned that:
1. Metals undergo corrosion to attain the thermodynamically stable state.
2. Corrosion is called as billion dollar thief, as globally industries are spending billions
and billions of dollars to control corrosion.
3. At room temp., most metals under go corrosion and form thin oxide layer as a result
of reaction of metals with oxygen.
4. Wet corrosion occurs in environments where the relative humidity exceeds 60 %.
5. For galvanic corrosion, the following conditions are essential
Electrochemically dissimilar metals must be present
These metals must be in electrical contact, and
The metals must be exposed to an electrolyte
6. Concentration cell corrosion occurs when two or more areas of a metal surface are in
contact with different concentrations of the same solution.
7. When same metallic surface exposed to different oxygen concentration. Pooroxygenated parts are anodic and undergo corrosion.
8. Corrosion can be controlled (i) by modifying the metallic nature (ii) by modifying the
nature of the environment
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Engg. Chemistry II
Suggested Reading books

1. Engineering Chemistry by Jain & Jain.
2. Corrosion Basics: An Introduction, 2nd Edition, by Pierre R. Roberge
4. Corrosion Control Through Organic Coatings (Corrosion Technology) by: Amy Forsgren
5. Corrosion and Corrosion Control, An Introduction to Corrosion Science and Engineering
Fourth Edition by R. Winston Revie.
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Engg.

Pre class- CORROSION AND CORROSION CONTROL

Unit-II CORROSION AND CORROSION CONTROL

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Plato (Greek philosopher and student of Socrates, 427-347 BC), in Phaedo

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Reasons for corrosion

Types of corrosion : dry corrosion and wet corrosion

Mechanism of Chemical and Electrochemical corrosion

Types of Differential aeration corrosion

Factors influencing corrosion : Metallic and Environmental factors

Corrosion control : By design and cathodic protection method

Paints : Constituents and function of paints

Electro less plating of nickel

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Rusting of iron(Fe2O3 .3H2O)

Why do metals corrode? / Why Corrosion is spontaneous?

Cu develops green patina: CuCO3 Cu(OH)2

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Ag article tarnishes and finally goes black in atm.

A can containing acidic fruits.

Do you know how much loss per year because of corrosion?

Plant shut down due to failure

Replacement of corroded equipment

Contamination or loss of product ( from the corroded container)

Safety (fire due to release of toxic product or collapse of construction)

Necessity for over design to allow for corrosion

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Corrosion occurs on metals in dry as well as in wet conditions,

1. Dry or Chemical Corrosion:

a. Oxidation Corrosion: Direct chemical action of O2 on metal surface.

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

PILLING BEDWORTH RULE explains the further corrosion

Pilling Bedworth ratio < 1, film is non-protective and porous

Nature of the metal-oxide layer or film

b) Corrosion by other gases:

Corrosion by gases like Cl2, SO2, CO2, H2S, F2 etc.

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

c) Liquid metal corrosion: Proceeds by

Dissolution of solid metal into the liquid metal

Penetration of the liquid metal into the solid metal

2. WET or ELECTROCHEMICAL CORROSION

This corrosion may be uniform destruction of the metal surface or localized

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Fe2+ + 2e2OHFe (OH)2

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

For galvanic corrosion, the following conditions are essential

Electrochemically dissimilar metals must be present

These metals must be in electrical contact, and

The metals must be exposed to an electrolyte

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL

Galvanic series Table

Material prepared by: Chemistry faculty

Pre class- CORROSION AND CORROSION CONTROL