Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes NPTEL Web Course

Lecture 13 Mixed Potential Theory Activation and Diffusion Controlled Processes

Keywords: Bimetallic Couples, Area Ratio, Exchange Current Density.

Effect of added oxidant

The driving force for corrosion is generally increased by the addition of a strong oxidizer such as ferric ions (ferric ferrous redox couple). Ecorr (corrosion potential) of the active metal is shifted in a nobler direction. Corrosion rate is enhanced. Hydrogen evolution rate decreased in the presence of oxidizer (eg: in acid solution). In the presence of an oxidizer such as the Fe+++/Fe++ couple in an acid medium two possible cathodic reactions, namely, 2H+ + 2e = H2 and Fe+++ + e = Fe++ need be considered. The respective exchange current densities for the above cathodic reductions on the corroding metal will determine the corrosion rate.

If for example, the exchange current density for ferric ion reduction is lower than that for hydrogen evolution, the addition of ferric ion oxidizer will not have any significant effect on the corrosion rate of the anodic metal in an acid medium.

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

Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes NPTEL Web Course

Effect of multiple reducible species on anodic corrosion is shown in Fig. 13.1.

Fig 13.1 Effect of multiple reducible species on the corrosion rate of an anodic metal.

Anodic and cathodic currents are proportional to concentrations of the redox species.

Rate of cathodic reduction can be thus related to concentration of cathodic reactant such as hydrogen, oxygen, ferric ions etc. For example, ic is proportional to [H+]n With increase in pH, hydrogen ion concentration decreases in solution (and vice versa).

= 10

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

Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes NPTEL Web Course

For oxygen, from a solution concentration of about 10 mg/L if through deaeration, it is reduced to 0.01 mg/L, the cathodic reaction rate could be altered by a factor of 103.

Effect of changes in cathodic reactant concentrations on the corrosion rate of an anodic metal is shown in Fig. 13.2.

Fig 13.2 Effect of changes in cathodic reactant concentrations on the corrosion rate of a metal.

Diffusion controlled cathodic processes

If one considers the effect of concentration polarization also along with activation polarization for the cathodic process, effects on anodic oxidation rates need to be seen in a different light.

There are instances when the cathodic process can be diffusion controlled (due to concentration gradients at the solid-solution interface). An example is metallic corrosion in sea water where oxygen diffusion controls the cathodic process. O2 + 2H2O + 4e = 4OH3 Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes NPTEL Web Course

Solution velocity influences the corrosion rate of metals when the cathodic process is diffusion controlled (unlike in activation controlled systems) since limiting (diffusion) current is affected (see Fig. 13.3).

Fig 13.3 Effect of concentration and velocity on diffusion controlled polarization

However at higher solution velocity, the cathodic reduction process becomes activation controlled.

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

Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes NPTEL Web Course

The influence of solution velocity on the corrosion rate of a normal metal under a diffusion controlled cathodic process in depicted in Fig. 13.4.

Fig 13.4 Change of corrosion rate with solution velocity for a normal metal.

Corrosion rate increases with solution velocity as long as the cathodic process is under diffusion control and it becomes independent of velocity at higher velocities when the cathodic reaction is under activation control.

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