Lecture 5: Eh-pH Diagrams - Fundamental Aspects NPTEL Web Course

Lecture 5

Eh-pH Diagrams Fundamental Aspects

Keywords: Eh-pH Relationship, Water Stability, Oxidation, Reduction.

Eh and pH as environmental parameters in the electrochemical equilibrium diagram.

Eh-pH diagrams showing reactions and products at electrochemical equilibrium are

often referred to as Pourbaix diagrams. As shown in Fig. 5.1 below, there are four
regions in the diagram corresponding to oxidizing (acidic), oxidizing (alkaline),
reducing (acidic) and reducing (alkaline) environments.

The basic diagram for aqueous environment involves upper and lower, stability
limits for water, represented by the oxygen (universal oxidizing agent) and hydrogen
(universal reducing agent) reactions.

Fig. 5.1 Basic regions in a Eh pH diagram

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore
Lecture 5: Eh-pH Diagrams - Fundamental Aspects NPTEL Web Course

Stability limits of water

a) O2 + 4H+ + 4e = 2H2O E0 = +1.23V

Eh = 1.23 0.059 pH (at po2 =1)

b) 2H+ + 2e = H2 E0 = 0.00V

Eh = 0-0.059 pH (at pH2 = 1)

These equilibria are plotted in Fig. 5.2. Above the oxygen line, oxygen liberation
occurs. Below the hydrogen line, hydrogen liberation occurs. Water is stable
between the two lines.

In neutral or alkaline solutions, the following reactions hold good.

2H2O + 2e = H2 + 2OH-

O2 + 2H2O + 4e = 4OH-

Electrochemical evolution of hydrogen represents water decomposition. At more

positive potentials, oxygen reduction or water oxidation takes place. Slope of both
lines correspond to 59 mV/pH.

Fig 5.2. Stability limits of water

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore
Lecture 5: Eh-pH Diagrams - Fundamental Aspects NPTEL Web Course

Three types of lines in the diagram

a) Those depending only on Eh, but independent of pH (Horizontal to the X-
axis).
b) Those dependent only on pH, but independent of Eh (Vertical to the X-
axis).
c) Those dependent on Eh and pH (Slanted with definite slopes).
The above types of reactions and general effects of Eh and pH on redox reactions
(oxidation, reduction) are illustrated in Fig. 5.3.

Fig 5.3. Effects of changes in Eh and pH

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore
Lecture 5: Eh-pH Diagrams - Fundamental Aspects NPTEL Web Course

The following aspects are noteworthy:

As the potential increases in the positive (noble) direction

Loss of electrons is favoured (oxidation).

Metal dissolution is favoured.

The system becomes more oxidizing.

Ox
Ratio of increases.
Re d

When the potential decreases in the negative direction

Gain of electrons favoured (reduction).

The system is more reducing.

Metal deposition (plating) favoured.

Ox
Ratio of decreases.
Re d

Increasing pH favours metal hydroxide precipitation. Still higher pH may lead to

solubilisation again (eg: dihypoferrite and aluminate)

Consider two redox reactions:

OX1 + n1e= Red1

OX2 + n2e = Red2

OX1 + Red2 = OX2 + Red1

As shown in Fig. 5.4, through Eh pH diagrams, one can predict oxidizability and
reducibility of different reactants.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore
Lecture 5: Eh-pH Diagrams - Fundamental Aspects NPTEL Web Course

Fig 5.4 Role of oxidising and reducing agents

Oxidant OX1 can oxidise 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.

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