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POURBAIX DIAGRAMS (AutoRecovered)
POURBAIX DIAGRAMS (AutoRecovered)
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.
Fig. 2.
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.
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.
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