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Raising a new Generation of Leaders

CHE 431 CORROSION OF

METALS AND ALLOYS
Week 4
Lecturers: OLAYEMI ODUNLAMI
(PhD) AND AJIBOLA OGUNBIYI

PRINCIPLES OF CORROSION

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PRINCIPLES OF CORROSION
Direct Chemical Attack Theory

The Electrochemical Theory

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Direct Chemical Attack Theory

This theory explains the chemical or dry corrosion.
Direct chemical attack of metal by dry gases at
atmospheric temperature is rather uncommon.
Whenever corrosion takes place by direct chemical
attack, a solid film of the corrosion product is
usually formed on the surface of the metal, this film
protects the metal from further corrosion.
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 Alkali and alkaline earth metals on oxidation produce

oxide deposits of smaller volume when compare to the
metals from which they were formed. This results in the
formation of a porous layer through which oxygen can
diffuse to bring about further attack of the metal.
But heavy metals and Al form non-porous oxide layers of
greater volume than the metal from which they were
produced.
Aluminium and Chromium form extremely protective
oxide layers and hence are used in alloying.
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The Electrochemical Mechanism

This theory explains the indirect or wet
corrosion.
It is based on the fact that all metals have a
tendency to pass into solution.

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 Zn/Zn2+ equilibrium
Cu2+/Cu equilibrium
The tendency of a metal to pass into solution
when immersed in a solution of its salt is
measured in terms of its electrode potential.
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Galvanic cell analogy

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 The standard electrode potentials of the various

metals have been determined in comparison
with the standard electrode potential of
hydrogen taken as zero.
If a metal having a higher electrode potential
comes into contact with another metal having a
lower electrode potential, a galvanic cell is set
up and the metal having higher electrode
potential becomes anodic and goes into
solution to a measurable extent.
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The dry cell analogy

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Galvanic cell analogy

(See video on the Moodle)

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(See video on the Moodle)

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Standard Electrode Potentials in Aqueous Solution at 25C

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Definition of terms

Oxidation/Reduction in terms of electron loss.

Reducing agent/oxidizing agent

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Summarizing this on the electrochemical series

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Oxidising or Reducing ability of Metal Using E values

The more negative the value, the stronger
reducing agent the metal is. Such metals easily
undergo electrochemical reaction to get
corroded.
The more positive the value, the stronger
oxidizing agent the metal ion is. Such metals do
not get corroded easily. Infact, corrosion
products are formed at such sites.
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Every electrochemical corrosion cell has:

ANODE
------- the metal that is corroding
CATHODE ------ metal or electronic conductor (which
is built up) whose surface provides sites for the
environment to react.
ELECTROLYTE -------- the aqueous environment
which is in contact with both anode and cathode to
provide a path for ionic conduction.
ELECTRICAL CONNECTION -------- between the
anode and the cathode to allow electrons to flow
between them.
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Definitions of anode and cathode

Cathode
The cathode as the electrode at which current enters from the
electrolyte and remember.
The electrode where reduction takes place. Examples of
reduction reactions:

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Formation of hydroxyl ions:

In the presence of dissolved oxygen and in neutral
or alkaline media.
This is the most common reaction
2H2O + O2 + 4e- 4OH In the presence of dissolved oxygen and in acid
media
4H+ + O2 + 4e- 2H2O Corrosion
process involving O2 are called Oxygen type.
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Anode
The anode as the electrode at which current
leaves to return to the electrolyte.
The electrode where oxidation place. Examples
of oxidation reaction:

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 Direction of current flow in an electrochemical

cell.

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Types of cells
There are three main types of cells that take part in corrosion reactions.
1.

Dissimilar Electrode Cells

Examples:
the dry cell
a metal containing electrically conducting impurities on the surface as a
separate phase,
a copper pipe connected to an iron pipe,
and a bronze propeller in contact with the steel hull of a ship.

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2. Concentration Cells:
These are cells with two identical electrodes, each in contact with a solution of
different composition. There are two kinds of concentration cells.
(a) Salt concentration cell
If one copper electrode is exposed to a concentrated copper sulfate solution,
and another to a dilute copper sulfate solution
The Cu in the dilute solution becomes the anode and plates out on the Cu in
the conc. solution.
These reactions tend to bring the two solutions to the same concentration

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Salt concentration cell

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(b) Differential aeration cell

Example includes two iron electrodes in dilute sodium
chloride solution, the electrolyte around one electrode
being thoroughly aerated (cathode), and the other deaerated (anode) by, for example, bubbling nitrogen
through the solution.

The difference in oxygen concentration

produces a potential difference and causes
current to ow.
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 This type of cell accounts for the pronounced

damage at crevices, which is called
crevice
corrosion.
The oxygen concentration is lower within crevices,
and the areas of lower oxygen concentration (inside
the crevice) are anodic with respect to areas of
higher oxygen concentration (outside crevices).
In any differential aeration cell, the electrode in
contact with lower-pressure oxygen tends to be the
anode, and the electrode in contact with higherpressure oxygen tends to be the cathode.
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Differential aeration cell

Differential aeration cell formed by rust on iron

Differential aeration cell

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Water-line corrosion, showing differential aeration cell.

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3. Differential Temperature Cells.

Components of these cells are electrodes of the
same metal, each of which is at a different
temperature, immersed in an electrolyte of the
same initial composition.
These cells are found in heat exchangers, boilers,
immersion heaters, and similar equipment.
In copper sulphate solution, the copper electrode at
the higher temperature is the cathode, and the
copper electrode at the lower temperature is the
anode.
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 In engineering practice, cells responsible for

corrosion may be a combination of these three
types.

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THERMODYNAMICS: CORROSION
TENDENCY AND ELECTRODE POTENTIALS
A. CHANGE OF GIBBS FREE ENERGY

Corrosion tendency of a metal can be measured by the

Gibbs free energy change, G.

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Consider the following reactions:

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Notes
It should be emphasized that the tendency to
corrode is not a measure of reaction rate.
If G is negative, the reaction rate may be
rapid or slow.

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B. EMF of a cell
The corrosion tendency of a metal can also be expressed in terms of the electromotive force
(emf) of the corrosion cells that are an integral part of the corrosion process.

Since electrical energy is expressed as the product of volts by coulombs (joules, J), the
relation between G in joules and emf in volts, E , is dened by
G

nFE ,

where n is the number of electrons (or chemical equivalents) taking part in the reaction, and
F is the Faraday (96,500 C/eq).

Hence, the more the value of E for any cell, the greater the tendency for the overall
reaction of the cell to go.
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Measuring the emf of a cell

Use of a voltmeter of high impedance
A potentiometer

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CALCULATING THE HALF - CELL POTENTIAL

THE NERNST EQUATION

The Nernst equation expresses the

emf of a cell in terms of the
concentrations of reactants and
reaction products.

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 It expresses the exact emf of a cell in terms of

activities of products and reactants of the cell.
The activity of a dissolved substance is equal to its
concentration in moles per thousand grams of
water (molality) multiplied by a correction factor, ,
called the activity coefcient.
The activity coefcient is a function of temperature
and concentration and, except for very dilute
solutions, must be determined experimentally.
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It is given by:

This applies to a galvanic cell with a general reaction of:

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meaning that l moles of substance L plus m

moles of substance M, and so on, react to form q
moles of substance Q, r moles of substance R,
and so on.

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 Since the emf of a cell is always the algebraic

sum of two electrode potentials or of two half-c
ell potentials, it is convenient to calculate each
electrode potential separately.
For example, for the electrode reaction:

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THE HYDROGEN ELECTRODE AND THE STANDARD

HYDROGEN SCALE
Since absolute potentials of electrodes are not known, it
is convenient to assume arbitrarily that the standard
potential for the reaction is equal to zero at all
temperatures.
By measuring the emf of a cell made up, for example, of
a zinc and hydrogen electrode in zinc salt solution of
known activity of Zn 2+ and H + , the standard potential,
, for zinc can be calculated; the accepted value is
0.763 V.
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Hydrogen Electrode

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Questions

?
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