POURBAIX DIAGRAMS

1.1 Introduction
Pourbaix (or Eh-pH) diagrams, named for the originator, are graphical representations
of thermodynamic information appropriate to electrochemical reactions. The presentation
of information in this format facilitates its application to practical problems in a wide variety,
including corrosion, electrodeposition, geological processes and hydrometallurgical
extraction processes. A particular diagram is called ‘the Pourbaix diagram for the iron–water
system’, ‘the Pourbaix diagram for the zinc–water system’, and so on.
The objective is to represent the relative stabilities of solid phases and soluble ions that
are produced by reaction between a metal and an aqueous environment as functions of two
parameters, the electrode potential, E, and the pH of the environment. The information
needed to construct a Pourbaix diagram is the standard electrode potentials, Eo, or the
equilibrium constants, K, as appropriate, for all of the possible reactions considered. The
purpose and construction of these diagrams is best appreciated by considering a particular
system in detail.

1.2 Construction of Diagram

Eh and pH as environmental parameters in the electrochemical equilibrium diagram. Eh-
pH diagrams showing reactions and products at electrochemical equilibrium are often
referred to as Pourbaix diagrams. As shown in Fig. 1. below, there are four regions in the
diagram corresponding to oxidizing (acidic), oxidizing (alkaline), reducing (acidic) and
reducing (alkaline) environments. The basic diagram for aqueous environment involves
upper and lower, stability limits for water, represented by the oxygen (universal oxidizing
agent) and hydrogen (universal reducing agent) reactions.
Fig. 1..

1.2.1 Stability limits of water

a) O2 + 4H+ + 4e = 2H2O E0 = +1.23V
 Eh = 1.23 – 0.059 pH (at Po2 =1)
b) 2H+ + 2e = H2 E0 = 0.00V
Eh = 0-0.059 pH (at pH2 = 1)
These equilibria are plotted in Fig. 2. Above the oxygen line, oxygen liberation occurs. Below
the hydrogen line, hydrogen liberation occurs. Water is stable between the two lines.
In neutral or alkaline solutions, the following reactions hold good.
2H2O + 2e = H2 + 2OH-
O2 + 2H2O + 4e = 4OH-
Electrochemical evolution of hydrogen represents water decomposition. At more positive
potentials, oxygen reduction or water oxidation takes place. Slope of both lines correspond
to 59 mV/pH.

Fig. 2.

1.2.2 Three types of lines in the diagram

a. Those depending only on Eh, but independent of pH (Horizontal to the X-axis).
b. Those dependent only on pH, but independent of Eh (Vertical to the X-axis).
c. Those dependent on Eh and pH (Slanted with definite slopes).
The above types of reactions and general effects of Eh and pH on redox reactions
(oxidation, reduction) are illustrated in Fig .3.
 Fig. 3.

1.2.3 The following aspects are noteworthy:

As the potential increases in the positive (noble) direction

 Loss of electrons is favoured (oxidation).

 Metal dissolution is favoured.
 The system becomes more oxidizing.
 Ratio of [OX]/[Red] increases.

When the potential decreases in the negative direction

 Gain of electrons favoured (reduction).

 The system is more reducing.
 Metal deposition (plating) favoured.
 Ratio of [OX]/[Red] decreases.

Increasing pH favours metal hydroxide precipitation. Still higher pH may lead to

solubilization again (eg: dihypoferrite and aluminate), Consider two redox reactions:
OX1 + n1e= Red1
OX2 + n2e = Red2
OX1 + Red2 = OX2 + Red1
As shown in Fig. 4, through Eh – pH diagrams, one can predict oxidizability and reducibility
of different reactants.
 Fig. 3.

Oxidant OX1 can oxidize Red2 to OX2 while OX1 get reduced to Red1.
Relative positions of various oxidation and reduction reactions in the diagram indicate
possibilities of cell reactions as shown above. Oxidizability of various metals such as gold,
silver, copper, nickel, cobalt and iron by oxidants such as oxygen, hydrogen peroxide, halides
(chloride, bromide, iodide), permanganate and dichromate can be predicted. Similarly,
possibility of using hydrogen (and other reducing agents) to reduce and precipitate metal
ions such as Ag+, Cu++, Ni++, Zn++ and Fe++ can also be predicted based on relative positions
of respective lines in the diagram. For example, all metal-metal ion redox lines which are
placed above the hydrogen line can be thermodynamically reduced by hydrogen.
Iron can be used to displace copper from acidic solutions (cementation).
Cu++ + Fe = Cu + Fe++
E0 for Cu++ / Cu is + 0.34V, while E0 for Fe / Fe++ is -0.44V.

1.3 Construction of Eh – pH Diagrams (Fe - H2O - O2 Diagram)

 Construction of an Eh – pH diagram based on thermodynamic data is illustrated with
respect to Fe-H2O – O2 system. Seven major reactions which are thermodynamically
feasible are illustrated along with calculations leading to simplified Eh – pH relationships
which are plotted on the electrochemical equilibrium diagram. The diagram can be drawn
for a given concentration of the metal ion species. The lines will shift as a function of varying
concentrations.
Assume Fe++, Fe+++ ion concentrations (activity), aH2O = 1, pO2 = 1, pH2 = 1. Room temp
25oC.
Eh – pH diagrams drawn for specific ion activities and partial pressures of gases at room
temperature.
The above Eh – pH relationships as above are plotted on a graph one by one as indicated
below to yield the final Eh – pH diagram depicting all the seven reactions with respect to
stability regions for the various cations and precipitated hydroxide products (Fig. 6.1).
 Fig. 4. Reaction – wise plotting of Eh – pH relationships

1.3.1 Domains of immunity, corrosion and passivation

From the Eh – pH diagram, it can be seen that when Fe++, and Fe+++ are stable, the metal
(Fe) is in the dissolved state, corresponding to regions of metallic corrosion. At more active
potentials, iron is thermodynamically stable and immune to corrosion.
In the regions where corrosion products such as Fe (OH)2 and Fe (OH)3 (or Fe3O4 and Fe2O3)
are stable, the metal is oxidized with a surface film which can protect it from further corrosion
(passivity). Corrosion behaviour of the metal (Fe) in an aqueous aerated solution can then be
represented as a corrosion diagram.

Corrosion diagram for the Fe-H2O – O2 system is given below (Fig. 5.).
 Fig. 5. Corrosion diagram for iron
Regions of corrosion for iron (steels) are not only confined to the acidic region, but also
exist in the high alkaline region (beyond a pH of about 12) where dissolution of iron as HFeO2-
species can occur. Regions of immunity (where metallic iron is stable thermodynamically)
and passivation (stability phases for iron oxides which form a protective passive layer) are
shown.

1.4 Advantages and limitations of Eh – pH diagrams

Electrochemical equilibrium diagram shows conditions of solution oxidizing power
(potential) and acidity or alkalinity (pH) at room temperature for a known activity of
dissolved metal species. Stability regions for various solid (elemental form and precipitated
compounds) and ionized forms are demarcated. This diagram has applications in several
disciplines such as:

 Corrosion prediction and protection

 Extractive metallurgy
 Geology and geochemistry
 Geomicrobiology
 Fuel cell
There are some limitations, such as:

 The diagrams are thermodynamically (theoretically) determined only for 25oC.

Caution should be exercised to predict corrosion behaviour at higher temperatures
using this diagram.
 Only thermodynamic amenability to corrosion and protection predicted. Kinetic
factors are not considered. Corrosion rates cannot be predicted.
 No consideration for extraneous ions and effect of complexation.
  Only pure metals are generally considered. Effects of impurities, alloying and
metallographic phases and heterogeneities are not considered. Unstable phases not
represented.

References
[1] David E.J. Talbot, James D.R. Talbot, 2018, Corrosion Science and Technology, 3th ed, CRC
Press.
[2] D. L. Piron, Potential Versus pH (Pourbaix) Diagrams, École Polytechnique de Montreal,
volume 13 Pages 27-55.
[3] K. A. Natarajan, Advances in Corrosion Engineering, NPTL Web Course,
<https://nptel.ac.in/courses/113108051>.
 Report on:

Pourbaix Diagrams
By: Islam Mohamed Reda

Supervision of:
Dr. Mohamed El-Zekki