Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)

NPTEL Web Course

Lecture 6 Construction of Eh pH Diagrams (Fe- H2O O2 Diagram)

Keywords: Iron Diagram, Corrosion Regions, Advantages and Limitations.

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. 1. Fe = Fe++ + 2e E0 = - 0.44V

(Reaction dependent only on Eh, independent of pH) Eh = - 0.44 + log [Fe++]

For aFe++ = 1, Eh= - 0.44V 2. Fe++ + 2H2O = Fe(OH)2 + 2H+ (Reaction dependent only on pH, independent of Eh)
reaction = f(FeOH) 2

+2

F0 f(H+) - F0f(Fe++) - 2

-115.57 + 2(0) (-20.30) 2(-56.69) = 18.11 (k.cal) = - RT lnK = - 1.364 log K

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)

NPTEL Web Course

log K =

= - 13.28
2

H log Fe

= - 13.28

2pH + log [Fe++] = 13.28 Log [Fe++] = 13.28 -2pH pH = 6.64 3. Fe++ = Fe+++ + e E0 = + 0.771V

(Eh dependent, but independent of pH) Eh = 0.771 + 0.059 log Eh = 0.771 (at unit activity) 4. Fe +++ + 3H2O = Fe (OH)3 + 3H+ (reaction dependent only on pH) Log [Fe+++] = 4.81 3pH pH = 1.6 5. Fe + 2H2O = Fe(OH)2 + 2H+ + 2e (dependent both on Eh and pH) First, estimate E0 for this reaction from reaction free energy values. E0 = Eh = - 0.05 + = -0.05V log [H+]2

Eh = - 0.05 0.059 pH 6. Fe(OH)2 + H2O = Fe (OH)3 + H+ + e Eh = 0.27 0.059 pH 7. Fe++ + 3H2O = Fe (OH)3 + 3H+ + e Eh = 1.057 0.177pH 0.059 log [Fe++]
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)

NPTEL Web Course

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. 6.1 Reaction wise plotting of Eh pH relationships

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.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)

NPTEL Web Course

Corrosion diagram for the Fe-H2O O2 system is given below (Fig. 6.2).

Fig. 6.2 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.

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. diagram has applications in several disciplines such as: Corrosion prediction and protection Extractive metallurgy Geology and geochemistry Geomicrobiology Fuel cells
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

This

Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)

NPTEL Web Course

However, there are some limitations, such as: a) The diagrams are thermodynamically (theoretically) determined only for 25oC. Caution should be exercised to predict corrosion behaviour at

higher temperatures using this diagram. b) Only thermodynamic amenability to corrosion and protection predicted. Kinetic factors are not considered. Corrosion rates cannot be predicted. c) No consideration for extraneous ions and effect of complexation. d) Only pure metals are generally considered. Effects of impurities, alloying and metallographic phases and heterogeneties are not considered. Unstable phases not represented. Modified Eh pH diagrams for various metals can be prepared taking into consideration the effect of alloying additions and presence of complexing agents. Combined diagrams which take into consideration two or more

metals simultaneously present would be more useful. For example, effect of chromium addition to steel to increase corrosion resistance can be represented in a modified Fe Cr diagram. Anodic and cathodic protection limits with reference to potentials and pH can be predicted using the Eh pH diagrams. Computer programmes and soft-ware kits are now available to construct EhpH diagrams for various metal systems.

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore