Aluminum E-pH (Pourbaix) Diagram

The E-pH diagram of aluminum is one of the simplest E-pH diagrams. It

will be used here to demonstrate how such diagrams are constructed
from basic principles. In the following discussion, only four species
containing the aluminum element will be considered: (reference)

 two solid species (Al and Al2O3.H2O)

 two ionic species (Al3+ and AlO2-)

The first equilibrium to consider examines the possible presence of

either Al3+ or AlO2- expressed in equation.

Since there is no change in valence of the aluminum present in the two

ionic species considered, the associated equilibrium is independent of
the potential and the expression of that equilibrium can be derived in
the following expression for standard conditions.

where Q is expressed in equation.

Assuming that the activity of H2O is unity and that the activities of the
two ionic species are equal, one can obtain a simpler expression of the
equilibrium in equation based purely on the activity of H+, equation and
its logarithmic form, equation.
and if G0 is expressed in Joules and the temperature is 25oC or 298 K
equation is even further simplified.

By using the standard thermodynamic data from the literature, it is

possible to calculate that the free energy of reaction is in fact equal to
120.44 kJ mol-1 when both [Al3+] and [AlO2-] are equal. Equation then
becomes equation.

This is represented, in the E-pH diagram shown below, by a dotted

vertical line separating the dominant presence of Al3+ at low pH from
the dominant presence of AlO2- at the higher end of the pH scale.
 E-pH diagram showing the soluble species of aluminum in water at
25oC

The next phase for constructing the aluminum E-pH diagram is to

consider all possible reactions between the four chemical species
containing aluminum retained for this exercise, i.e. Al, Al2O3.H2O, Al3+,
and AlO2-. These reactions are summarized in the following Table.

Possible reactions in the Al-H2O system

A computer program would compare all possible interactions and rank
the chemical species involved in terms of their thermodynamic stability
for all conditions of pH and potential would typically carry out this work.
The following Figure illustrates the results of such computation for
aluminum in the presence of water at 25oC when the activities of all
species considered were set at value unity.
E-pH diagram of solid species of aluminum when the soluble species
are at one molar concentration (25oC)

However, an additional consideration is necessary to make such

diagrams useful for corrosion situations for which the presence of
soluble species in the environment never reaches values of the order of
one molar. The following Figure illustrates the results that were
computed by setting the concentrations of soluble species at decreasing
values of one (100), one hundredth (10-2), one in ten thousand (10-4),
and one in a million (10-6). The apparent stability of the solid species
considered gradually recedes as lower values of soluble species are used
in the calculations.
 E-pH diagram of aluminum with four concentrations of soluble
species (25oC)

It is customary to use the lowest boundary (10-6) as a practical indication

of the corrosion stability of a metal and its solid products (Figure 4.12).
 E-pH corrosion diagram of aluminum at 25oC

The usefulness of this graphical representation of thermodynamic data

for corrosion studies was discussed by Pourbaix who showed three
possible states of a metallic material:

Immunity region: In the conditions of potential and pH of that region a

metal is considered to be totally immune from corrosion attack and safe
to use. Cathodic protection may be used to bring the potential of a
metal closer to that region by forcing a cathodic shift, as shown for
aluminum by the domain specified in the previous Figure (-1.0 to 1.2 V
vs. CCSRE)
Passive region: In such region a metal tends to become coated with an
oxide or hydroxide that may form on the metal either as a compact and
adherent film practically preventing all direct contact between the metal
itself and the environment, or as a porous deposit which only partially
prevents contact between the metal and the environment;

Corrosion region: Thermodynamic calculations indicate that, in such

region of an E-pH diagram, a metal is stable as an ionic (soluble)
product and therefore susceptible to corrosion attack. Experience is
required to find out the extent and form of the corrosion attack that
may occur in the corrosion region(s) of a Pourbaix diagram.