CORROSION OF METALS

Definition
(a) Destruction or deterioration of a material because of reaction with its environment.
(b) Destruction of materials by means other than mechanical.
Corrosion Damage and cost
- Appearance; a piece is made unattractive to the eyes
- Plant shutdowns
- Contamination of products e.g. canned foods
- Maintenance and operating costs increase e.g. vehicle undercarriage due to salts on roads
during winter.
Classification of corrosion types
1. Wet corrosion liquid present
2. Dry corrosion No liquid phase or atmosphere is above dew point of the environment,
Factors affecting environment
- Concentration
- Velocity e.g. water pipe in contact with flowing salt water
- Temperature
Modern theory: Principles of corrosion
For metallic corrosion, the process is normally electromechanical, such that there is transfer of electrons
from one chemical species to another. Consider the following reaction.

The reaction can be broken up into half-cell reactions.

1 and 2 represent copper zinc electrodes in equilibrium with their ions. (The copper and zinc
electrochemical cell can be represented as below).

Each electrode is in equilibrium with its ions of unit activity equal to concentration of one mole, and
each half cell is called a standard half-cell. The 1.1 volts recorded by the voltmeter represents the energy
associated with the reaction. It is the cell potential.

NB: At equilibrium, the reduction and oxidation rates are equal at each electrode. If the electrodes are
not in equilibrium with their ions, then there will be overall oxidation of copper (anodic reaction) and
reduction of Zinc (cathodic reaction).

The standard EMF Series

Half cells of metal are established in reference to an arbitrary standard half so as to generate the
standard EMF series. For this purpose, a standard hydrogen electrode is used. It consists of an inert
platinum electrode in a one mole solution of H+ ions with hydrogen gas bubbled through the solution at
a pressure of one atmosphere and a temperature of 25 degrees C.
Consider Zinc.

The platinum does not take part in the reaction; it only acts as a surface on which hydrogen atoms are
oxidised or reduced. The electromotive force (emf) series is generated.

Effect of concentration and temperature

Consider the reaction involving the oxidation of metal M1 and the reduction of M2 as

Where V1 and V2 are the standard potentials from the EMF series. The potential for M1 is negative
because M1 is being oxidised.

This is called the overall cell potential. The overall cell potential is based on redox standard potentials of
the EMF series which is highly idealised. Altering the temperature or solution concentration or using
alloy electrodes will change cell potential or even reverse the direction of spontaneous direction,
according to the Nernst equation.

GALVANIC SERIES
Ranking of the reactivity by the EMF series is idealistic (why? it assumes conditions of 1 atm, 25 deg C
and solution of concentration of 1 mole of ions). A practical ranking is by the galvanic series which
represents the relative reactivities of a number of metals and alloys in sea water.
Prediction of corrosion rates
This is by electrode kinetics which takes into account that a corroding system is not at equilibrium.
Consider the short-circuitry of an EMF cell system.

Zinc dissolves rapidly according to:

This is an anodic reaction which is oxidation.

At the platinum electrode, hydrogen is reduced (evolved). This is a cathodic reaction. The potential of
the two electrodes are no longer the equilibrium potentials as per the EMF series. This deviation or
displacement of each electrode potential from its equilibrium value is called POLAROSATION. The
magnitude of the displacement is the OVERVOLTAGE. ().
If the cell potential under non-equilibrium conditions is E and the equilibrium potential is Eo, then;

TYPES OF POLARISATION
1. Activation polarisation: This refers to electrochemical reactions controlled by the slowest
reaction in the reactions sequence.
2. Concentration polarisation: This is where the overvoltage depends on the concentration of the
reduction reactants at the surface of the electrodes. It is diffusion controlled and is found in
reduction reactions only.
The overvoltage of both types of polarisation are expressed in terms of current densities.
Consider the surface of the platinum electrode in H2 half-cell.

There are two reactions occurring; oxidation () and reduction (). These rates can be expressed in terms
of current densities though there is no flow of current.
By Faradys law:

Io is the exchange current density which is the oxidation and reduction rate at equilibrium and it
depends on the metal electrode. The two types of polarisation can be expressed in terms of current
densities.

NOTE: The activation polarisation is found in both the oxidation (+) and reduction (-) processes. Hence
the above + signs.

Concentration Polarisation ()
Diffusion controlled. At high reduction rates a limiting rate is reached and is determined by the diffusion
rate to the electrode. The limiting reduction rate is expressed as a limiting current.

c Concentration of the reactant

x Diffusion layer thickness

(In oxidation, the metal is going into solution).

iL limiting current, is only significant in reduction reactions and is negligible in oxidation reaction.

Combined Polarisation

*** Discuss/write about corrosion of ceramics and distinguish degradation of polymers (From the
Internet).