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Pourbaix Diagram
Potential-pH diagrams are also called pourbaix diagram after the name of the originator Marcel Pourbaix , a Belgium electrochemist and corrosion scientist.

These diagrams represent the stability of metal as a function of potential and pH. They are analogous to phase equilibrium diagrams, where stability of various phases is shown as a function of tempreture and percentage composition of a metal.

At a particular tempreture and composition a stable phase can be easily determined. Similarly at a particular combination of pH and potential , a stable phase can be determined from POURBAIX DIAGRAM.

These diagrams are plotted for the various equillibria on normal Cartesian coordinates with potential on vertical axis or ordinate and pH on horizontal axis or abssica. Means 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.(this is for room temperature only)

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

The diagram takes account of electrochemical and chemical equillibria of metals in conjunction with water and since there are several such equillibria for each metal , only one metal can be clearly represented on one diagram.

Oxidizing conditions are described by the top part of the diagram (high positive electrode potential).
Reducing conditions are described by the bottom part of the diagram (high negative electrode potential).

A typical diagram for Fe-H2O system is shown:-

The diagram defines the following zones of the equilibrium states:

below the line a-b-j: Solid iron (immunity zone). The electrochemical reactions in this zone proceed in the direction of reduction of iron ions. No corrosion occurs in this zone. a-b-n-c-d-e: Aqueous solution of ion Fe2+ (corrosion zone). Metallic iron oxidizes in this zone. e-d-f-g-k: Aqueous solution of ion Fe3+ (corrosion zone). Metallic iron oxidizes (corrodes) in this zone.

h-f-g-m: Aqueous solution of ion FeO42(corrosion zone). c-d-f-h-i: Solid ferrous oxide Fe2O3 (passivation zone). Iron oxidizes (corrodes) in this zone however the resulted oxide film depresses the oxidation process causing passivation (corrosion protection of the metal due to formation of a film of a solid product of the oxidation reaction). n-c-i-p: Solid oxide Fe3O4 (Fe2O3*FeO) (passivation zone). The oxide film causes passivation b-n-p-j: Solid hydroxide (II) Fe(OH)2 / FeO*nH2O / green rust (passivation zone).

Here are some of the reactions and the corresponding lines of the Fe-H2O Pourbaix diagram:

a-b: Fe(s) = Fe2+(aq) + 2e- Redox reaction independent of PH. The equilibrium occurs at the electrode potential value -0.44V, which is equal to the standard electrode potential of iron (see the Electrochemical series).

e-d: Fe2+(aq) = Fe3+(aq) + e- Redox reaction independent of PH. d-f: 2Fe3+(aq) + 3O2- = Fe2O3(s) Non-redox reaction dependent on PH.

b-n: Fe2+(aq) + 2OH-(aq) = Fe(OH)2(s) Nonredox reaction dependent on PH. c-d: 2Fe2+(aq) + 3H2O = Fe2O3(s) + 6H+(aq) +2e- Redox reaction dependent on PH. b-j: Fe(s) + 2OH-(aq) = Fe(OH)2(s) + 2eRedox reaction dependent on PH.

The horizontal , vertical and the sloping lines in the diagram form the following three types of domains or regions:-

1.} Immunity Domain : This region represents the state in which corrosion is thermodynamically impossible in a particular environment. In this region the activity of metal ion doen not exceed 10-6 gram ion/litre.

2.} Passive Domain: This region represents the state in which the metal is thermodynamically unstable in a particular environment but corrosion is prevented by the modification of the surface due to formation of oxide layer.In this region solid metal compound are thermodynamically stable and in equilibrium with metal ions of 10-6 gram ion / litre activity.

3.} Corrosion Domain: In this region the metal corrosion is thermodynamically possible. The area is separated from the immunity domain by lines with represent solubility equal to 10-6 gram ion / litre. These three domains are shown for Fe in above diagram.

Application of E/pH Diagrams:Potential/pH diagrams are useful in electrometallurgy. The diagrams are particularly important in study of corrosion of metals in aqueous media and electrodeposition of metals and oxides. These diagrams are useful for predicting: 1.} Spontaneous direction of reactions. 2.} Stability and composition of corrosion products. 3.} Environmental changes which will prevent or reduce the corrosive attack.

According to E/pH Diagram for FeH2O system, following methods are used to reduce corrosion:

1.} By lowering the electrode potential down into the region of immunity e.g. by cathodic protection. 2.} By raising the electrode potential up to the region of passivity. E.g by anodic protection.

3.} By raising the pH of the alkanity of solution so that a passive film is formed.

Limitations of E/pH Diagrams:-

1.} These diagrams give no information on corrosion rate since they are based on thermodynamic and not on the kinetic data. 2.} The term passivity in these diagrams is applied to field of existence for oxides , hydroxides or other sparingly soluble substances,irrespective of their protective properties.

An Introduction To Electrometallurgy By Satya Narayan and Rajendra Sharan Corrosion Engineering By Mars. G Fontana An Introduction To Metallic Corrosion and its Prevention by Raj Narayan

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