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F Fo 0.059 pH
This theory holds that the initial corrosion product e.g. a metal
oxide provides the diffusion barrier thus reducing corrosion
The oxide layer virtually separates the metal from the
surrounding environment
Effectiveness of this barrier in reducing corrosion depends on the
nature and the properties of the “protective” film
A visible PbSO4 film on Pb exposed to H2SO4 and FeF2 film on
steel immersed in aqueous HF are two examples of such
protective film
Films formed on Cr or stainless steels by anodic polarization are
too thin and invisible
Theories of Passivity: Adsorption Theory
Some authors do point out that the oxide-film theory and the
adsorption theory are not contradictions, rather they supplement
each other. The adsorbed film while getting thicker gradually
changes to an oxide film. Thus these authors mention a
combined oxide-film adsorption theory of passivity.
Passivity and Chloride Ions
Chloride ions and to a lesser degree other halogen ions break down
passivity or prevent passivation in Fe, Cr, Ni, Co and stainless steels
According to the oxide-film theory, Cl- ions penetrate the oxide film
through pores or discontinuities. Chloride ions may also colloidally
disperse the oxide film thus increasing its permeability.
According to the adsorption theory, chloride ions adsorb on the metal
surface faster than dissolved O2 or OH-. While in contact with the metal
surface, Cl- ions favour hydration of metal ions and help the metal ions
go into solution. Whereas adsorbed O2 decreases the rate of metal
dissolution.
Thus adsorbed Cl- ions increase io, decrease overvoltage for anodic
dissolution of the metal. This is so effective, that iron and the stainless
steels are not passivated in aqueous environments containing
appreciable amount of Cl- ions.
Breakdown of metal passivity by chloride ions is local and hence leads
to pitting type of attack.