ME 472

(Corrosion Engineering)

Kinetics
Part#3
Activation and concentration polarization
Both AP & CP are affected by:

1: Activation Polarization/ charge

transfer polarization

2: Concentration Polarization
1:Activation polarization

For charge transfer reaction in metal/solution interface:

M(in lattice)  Mz+ (hydrated in sol.) + ze-

Actually,. M, lattice
 M,lattice Mz+,sol
M, adsorbed M,ad

Mz+, sol
Effect of Activation and Concentration on Anodic Polarization

Fe  Fe2+ + 2e-

Fig. Ref: McCafferty’s Book

1:Activation polarization

Activation polarization is due to retarding factors that are an inherent part of the
kinetics of all electrochemical reactions.
“when some step in the half cell reaction controls the rate of charge (electron) flow, reaction is
said to be under activation or charge transfer control and activation polarization results”

EXAMPLE
• 2H+ + 2e- → H2 (on M)

• H+ + e- → Hads

• Hads + Hads →H2

Sufficient H2 molecules combine together to nucleate a hydrogen bubble on

the surface
Experimental Polarization diagram (Evans diagram))
2: Concentration polarization

• One of the assumptions in the derivation of the Volmer- Butler eq. is the uniformity of
concentration near the electrode.

• This assumption fails at high current densities because migration of ions towards the electrode
from the bulk is slow and may become rate determining.

• A larger overpotential is then needed to produce a given current because the supply of reducible
or oxidizable species has been depleted.

• This effect is called conc. polarization.

•
2: Concentration polarization

A frequent case of concentration polarization

occurs when the cathodic processes depend on the
reduction of dissolved O2 since it is usually in ppm
concentrations

O2 conc. as a function of distance from the

electrode surface
O2+2H2O+ 4e-----4OH-

 The conc. Near the electrode surface depends

on diffusion process of ions
2: Concentration polarization

c = RT/zF ln (1 - i/iL) = 0.059/z log (1 - i/iL) at 298 K.

See class handouts for equations derivation

Concentration polarization (Limiting current density)
iL is increased by

• higher solution concentration, CB;

• higher temperature which increases diffusivity, D;
• higher solution agitation, which decreases .
Concentration polarization only becomes important when the current density approaches iL

Fig. Ref: DA Jones Book