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POURBAIX DIAGRAMS

Presentation · February 2014

DOI: 10.13140/RG.2.2.23520.28167

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Fortunatus R. Jacob
University of Dar es Salaam
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 Outline of Presentation
Introduction

Construction

Examples

Applications

Conclusion

Acknowledgement
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 Introduction
Stability of metals depend on environment

Pourbaix Diagram = Potential (Eh) – pH Diagram

The diagram represents thermodynamic equilibrium

of metal, ions, hydroxides (or, oxides) in aqueous
solution at certain temperature (isothermal)

The boundary of stability regions of metal, ion,

hydroxides (or oxides) are equilibrium lines

Does not reflect reaction kinetics

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 Construction
Three possible types of equilibrium lines:
Horizontal
Vertical
Slope

Horizontal Line: Plotted for equilibrium

reactions that are independent of pH –
Depend on potential only

Vertical Line: Plotted for equilibrium

reactions that are independent of potential –
Depend on pH only
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 Construction …
Slope Line: For equilibrium reactions that depend
on both pH and Potential

Basic equation used: Nernst Equation

G  G  RT ln Q
o
G  nF E & G  nF E
o o

RT RT
E X n E  o
X ln Q E  E  o
ln Q
nF nF
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Example 1: Pourbaix diagram of water
Water has two main equilibrium reactions:
1. Oxidation
2. Reduction

Oxidation reaction:
 
2H  2e  H 2 ; E  0.0V
O

Reduction reaction:
 
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O2  4H  4e  2H 2O; E  1.229V
O
6
 Oxidation Reaction – For H2O
2 H   2e   H 2 ; E O  0.0V

 RT   2
 E   ln  H 
O
EH 
 nF 

 8.314  298  2.303  2 

 log  H 
 
EH   E 
O

 2  96500 

EH   E  0.0513P
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O H
7
 Reduction Reaction – For H2O

O2  4 H   4e   2 H 2O; E o  1.229V

EO2  E 
2.303RT
0

nF 
 4
log  H   PO2 
 2.303  8.314  298 
EO2  E  

0

4  96500


 
logPO2  4 log 
 H 
 

EO2  E 0  0.05912 P H
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 EO2  E 0  0.05912P H

EH   E O  0.0513P H

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Example 2: Pourbaix diagram of Fe-H2O system

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 Applications/Uses
Some interesting uses of such diagrams, which
have been constructed for most metals and a
few alloys, are to;
Predict whether or not corrosion can occur;

Estimate the composition of the corrosion products

formed; and

Predict environmental changes which will prevent or

reduce corrosion attack

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 Conclusion
Pourbaix diagrams have the following limitations:

1. Tell us what can happen, not necessarily what will happen

2. No information on the rate of reaction

3. Limited to pure elements, pure water and 25°C

4. Passivation criteria

 Therefore, one should be careful using Pourbaix diagrams to

predict the behavior and stability of metals
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 Acknowledgement

Prof. Alexander Pogrebnoi

3rd Cohort – MaSE (NM-AIST)

Mrs. Samanya

Mr. Magige Genga

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