2

Basic Corrosion Theory

2.1 THERMODYNAMICS
Engineering metals are unstable on this planet. While humans thrive in the
earth's environment of oxygen, water, and warm temperatures, their metal
tools and equipment all corrode if given the opportunity. The metals try to
lower their energy by spontaneously reacting to form solutions or compounds
that have a greater thermodynamic stability.
The driving force for metallic corrosion is the Gibbs energy change, ~G,
which is the change in free energy of the metal and environment combination
brought about by the corrosion. If areaction is to be spontaneous, as
corrosion reactions certainly are, ~G for the process must be negative.
The term ~G is only the difference between the Gibbs energies of the final
and initial states of the reaction and, therefore, is independent of the various
intermediate stages. Therefore, the corrosion reaction can be arbitrarily
divided into either real or hypothetical steps, and the ~G values are summed
up for all the steps to find the true Gibbs energy change for the reaction. The
units of ~G are now commonly given in joules per mole (J/mol) of metal, or
in the older units of calories per mole (cal/mol).
In corrosion measurements, the driving force is more often expressed in
volts (V), which can be found from the equation

E= -~G/nF (2-1)

where E is the driving force (in volts, V) for the corrosion process, n is the
number of moles of electrons per mole of metal involved in the process, and
Fis a constant called the "faraday," which is the electrical charge carried by
a mole of electrons (or 96,490 C). Remember that joules = volts X coulombs.
With ~G being negative and with the minus sign in Eq. 2-1, spontaneous
processes always have a positive voltage, E.

S. A. Bradford, Corrosion Control

© Van Nostrand Reinhold 1993
8 Corrosion Control

2.2 ELECTRODE REACTIONS

Aqueous corrosion is electrochemical. The principles of electrochemistry,
established by Michael Faraday in the early nineteenth century, are basic to
an understanding of corrosion and corrosion prevention.

The Corrosion Cell

Every electrochemical corrosion cell must have four components.

1. The anode, which is the metal that is corroding.

2. The cathode, which is a metal or other electronic conductor whose surface
provides sites for the environment to react.
3. The electrolyte (the aqueous environment), in contact with both the
anode and the cathode to provide a path for ionic conduction.
4. The electrical connection between the anode and the cathode to allow
electrons to flow between them.

The components of an electrochemical cell are illustrated schematically in

Figure 2-1. Anodes and cathodes are usually located quite dose to one
another and may even be on the same piece of metal. If any component were
to be missing in the cell, electrochemical corrosion could not occur. Thus,
analyzing the corrosion cell may provide the clue to stopping the corrosion.

Anode Reactions
Corrosion reactions can be separated into anode and cathode half-cell
reactions to better understand the process. The anode reaction is quite
simple-the anode metal M corrodes and goes into solution in the electro-
lyte as metal ions.

Electrical connection
(electron conductor)

Anode Cathode

Electrolyte
(ion conductor)

FleURE 2-1. The components of an electrochemical corrosion cell.