Pourbaix diagram

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Pourbaix diagram of Iron

In chemistry, a Pourbaix diagram, also known as a potential/pH diagram, maps out possible stable (equilibrium) phases of an aqueous electrochemical system. Predominant ion boundaries are represented by lines. As such a Pourbaix diagram can be read much like a standard phase diagram with a different set of axes.

The diagrams are named after Marcel Pourbaix (1904–1998), the Russian-born chemist who invented them.

Contents

Diagram

Pourbaix diagrams are also known as Eh-pH diagrams due to the labeling of the two axes. The vertical axis is labeled Eh for the voltage potential with respect to the standard hydrogen electrode (SHE) as calculated by the Nernst equation. The "h" stands for Hydrogen, although other standards may be used.

Eh = E^0 + \frac{0.0592}{n} \log\frac{[C]^c[D]^d}{[A]^a[B]^b}

The horizontal axis is labeled pH for the -log function of the H+ ion concentration.

pH = − logH + ]

While such diagrams can be drawn for any chemical system, it is important to note that the addition of a metal binding agent (ligand) will often modify the diagram. For instance, carbonate has a great effect upon the diagram for uranium.

In addition, temperature and concentration of solvated ions in solution will shift the equilibrium lines in accordance with the Nernst Equation.

A simplified Pourbaix diagram indicates regions of "Immunity", "Corrosion" and "Passivity", instead of the stable species.

The Pourbaix diagram for uranium in a non-complexing aqueous medium (eg perchloric acid / sodium hydroxide).1
The Pourbaix diagram for uranium in carbonate solution1

See also

References

  1. ^ a b Ignasi Puigdomenech, Hydra/Medusa Chemical Equilibrium Database and Plotting Software (2004) KTH Royal Institute of Technology, freely downloadable software at [1]
  • Denny A. Jones, Principles and Prevention of Corrosion, 2nd edition, 1996, Prentice Hall, Upper Saddle River, NJ. ISBN 0-13-359993-0 Page 50-52
  • Pourbaix, M., Atlas of electrochemical equilibria in aqueous solutions. 2d English ed. 1974, Houston, Tex.: National Association of Corrosion Engineers.

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