Chemistry of Corrosion

C 452
By

Prof. Dr. Ashraf Moustafa Abdel-Gaber

Professor of Physical Chemistry

Faculty of Science
Alexandria University
 Contents
I. Definition, importance and classification.
II. Electrochemical mechanism of corrosion.
III. Application of thermodynamics to corrosion.
IV. The kinetics of corrosion reactions.
V. Determination of corrosion rate.
VI. Passivity.
VII. Corrosion prevention.
VIII.Types of corrosion damage.
IX. Oxidation- dry corrosion
X. Metallurgy
I.a. Definition
Corrosion is the destructive attack of a metal by chemical or
electrochemical reaction with its environment.

Deterioration by physical causes is not called corrosion, but is

described as Wear, Galling, or Erosion.

In some Instants chemical attack accompanies physical

deterioration are described by the terms: Corrosion –
Erosion, Corrosion – Wear or Fretting Corrosion

➢ “ Rusting” applies to the corrosion of iron

base alloys with formation of corrosion
products consisting largely of hydrous ferric
oxides Fe2O3. H2O. Non ferrous metals ,
therefore, corrode but do not rust.
• Wear is the damaging, or
deformation of material at
solid surfaces.

• Galling is a form of wear caused by adhesion between sliding

surfaces

• Erosion is a combination of
direct attack of solid materials
to the surface and friction
I.b. Classification
1. Low temperature and high temperature corrosion.
2. Direct combination (Oxidation) and Electrochemical
corrosion.

3. Wet corrosion and Dry corrosion.

➢ Wet corrosion occurs when a liquid is
present. An common example is
corrosion of steel by water.

➢ Dry corrosion occurs in the absence of

a liquid phase and high temperature. An
example is attack on steel by furnace
gases.
➢ The presence of even small amounts of moisture could
change the corrosion picture completely. For example, dry
chlorine is practically non corrosive to ordinary steel, but
moist chlorine is extremely corrosive and attack most of the
common metals and alloys.

I.c. Importance of Studying Corrosion

1. Conservation
2. Safety
3. Economic
- Direct Losses
- Indirect Losses
- Cost of Corrosion
1.Conservation
➢ The world’s supply of metal resources is limited, and the
wastage of them includes corresponding losses of energy and
water reserves associated with the production and
fabrication of metal structures.

➢ Not least important is the accompanying conservation of

human effort entering the design and rebuilding of corroded
metal equipment.
2. Safety
The second area is improved safety of operating equipment
which, through corrosion, may fail leading to catastrophic
consequences.
Examples are pressure vessels, boilers, metallic containers for
toxic materials, bridges, airplane components, and
automotive stirring mechanisms. Safety is a prime
consideration in the design of equipment for nuclear- power
plants and for disposal of nuclear wastes.

Boiler explosion
Boiler
 3. Economic
3.1. Direct Losses
• Replacing corroded structures • Replacement of hot water tanks

• using corrosion-resistant metals

• corroded automobile mufflers and alloys

• galvanizing or nickel plating of steel • adding inhibitors

3.2. Indirect Losses

1. Shutdown: shutdown of the unit while

repairs cost $ 20,000 per hour in lost
production.

2. Loss of Product: Losses of oil, gas, or water

occur through a corroded pipe system until
repairs are made.

3. Loss of Efficiency: weakened heat transfer

through accumulated corrosion products, or
because of the clogging of pipes with rust
needing increased pumping capacity.
3.2. Indirect Losses (Continued)

4. Contamination of Product: A small amount of copper picked

up by slight corrosion of copper pipe or of brass equipment
that is otherwise durable may damage an entire batch of soap.
Copper salts accelerate rancidity of soaps and shorten the time
they can be stored before use.

5. Over design: This factor is common in the design of reaction

vessels, boilers, condenser tubes, buried pipelines, water
tanks, and marine structures. Equipment is often designed
many times heavier than normal operating pressures or
applied stresses would require in order to ensure reasonable
life.
 Cost of Corrosion
➢ The costs attributed to corrosion damages
of all kinds have been estimated to be of the
order of 3-5 % of industrialized countries
gross national product (GNP).

• In USA (1995) corrosion costs $ 300 billion/

year.
• In Saudi Arabia (1996) it costs 7800 million
SR.
• In Kuwait (1996) it costs 320 million KD.

• Application of corrosion resistant materials

and application of the best corrosion related
technical practices could reduce
approximately one-third of these costs.
II. Electrochemical Mechanism of Corrosion
II.1. Local Cell
➢ Corrosion of metals and alloys in
aqueous solution or any other
conducting medium takes place by an
electrochemical mechanism . Metal
➢ The electrochemical corrosion reaction
requires four elements: the anode, the
cathode, the ionic conductor 2+
(electrolyte) and the metallic conductor
Fe Anode
(electrical connector).
➢ In order for electrochemical corrosion H2 2e
to takes place all four elements should
occurs simultaneously.
➢ Absence of any one of the four H+ Cathode
elements prevents corrosion from H+
taking place.
II. Electrochemical Mechanism of Corrosion
II.1.a. Corrosion in Acidic Solutions
➢ If just one anode and one cathode
(local cell) could be seen in a magnified
view of iron in an acid solution, Metal
electrons generated by the formation of
ferrous ions would be observed flowed
through the metal from an anodic to 2+
cathodic area. At the cathodic surface, Fe Anode
the electrons would meet hydrogen
ions from the solution to form H2 2e
hydrogen gas

H+ Cathode
H+
II. Electrochemical Mechanism of Corrosion
II.1.b.Corrosion in Neutral and Alkaline Solutions
➢ Corrosion in neutral and alkaline solution
occurs with the same mechanism except that
at the cathodic sites, electrons meet oxygen
gas (instead of hydrogen ion) that diffused
from the bulk solution.

➢ At the anode metallic ions leave the metal

surface and go into solution. In this process it
leaves electrons behind on the metal surface.
➢ The cathodic reaction consuming
quantitatively the electrons liberated during
the anodic reaction
II. 2. Anodic and Cathodic Reactions
Anodic Reaction M Mn+ + ne-

Cathodic Reactions
Oxygen Reduction O2+ 4H++4e- 2H2O
(Acid Solution)

Oxygen Reduction O2+ 2H2O+4e- 4OH-

(Neutral and Alkaline Solutions)

Hydrogen Evolution 2H+ +2e- H2

Metal Ion Reduction Fe3+ + e- Fe2+

Metal Deposition Cu2+ + 2e- Cu

II.3. Types of Cells
1.Dissimilar Electrode cells
a) A metal containing electrically conducting impurities.
b) A copper pipe connected to an iron pipe.
c) cold worked metal in contact with the same meta annealed.

2.Concentration Cells (Differential Aeration Cells)

This may include two iron electrodes in dilute NaCl solution, the
electrolyte around one electrode being thoroughly aerated
(cathode), and the other deaerated (anode), brought about by
bubbling nitrogen gas. The difference in oxygen concentration
produces a potential difference and causes current to flow.

Low O2 high O2 Dil. NaCl Conc. NaCl

Examples:
a) Crevice corrosion at the interface
of two coupled pipes or at
threaded connections.
(oxygen concentration is lower
within the crevice or at the
threads than else where)

b) Pitting damage under rust.

c) Pitting damage at water line.

3. Differential Temperature Cells

Components of these of these cells are electrodes of the same

metal, each of which is at a different temperatures, immersed
in an electrolyte of the same initial composition.