Passivity

Metal is passive when its corrosion in course of

chemical or electrochemical reaction is lower at higher affinity of reaction than at lower affinity of chemical or electrochemical process

Concept of Passivity
It is known that certain metals and alloys can exist in 2

states, namely ACTIVE & PASSIVE. In Active state metals and alloys exhibit greater activity w.r.t. certain types of environment than others. In Passive state metals and alloys behave as if they are noble. Passivity is the characteristic of a metal exhibited when that metal does not become active in Corrosion atmosphere. Passivity is caused by build-up of a stable, tenacious layer of metal oxide on the surface of the metal.

Passivity can be defined in 2 ways

Thermodynamically Electrochemically

the phenomenon by which the

metal remains unattacked by a medium in which, thermodynamically a net decrease of free energy is associated with corrosion reaction

the phenomenon by which the

metal, when acting as an anode does not pass into the solution even though the value of equilibrium potential seems to indicate that it should

 Metals such as Zr, Cr, Al and S.S. form thin, tenacious oxide films when exposed to the atmosphere or to pure water at room temperature. In some cases, the film is extremely thin and is almost invisible to eye, but is still effective in

giving these metals a marked PASSIVITY. The metals like Fe, Co, Ni can be rendered passive by heating in air. S.S. and Cr plate provide well known examples of passivity resulting from exposure to air.

Characteristic of Passive State

In general, oxidizing condition is required for passive state while reducing condition for active state.
In passive state, corrosion rate reduces to a very small value. Generally reduction in corrosion rate from active to passive state will be of the order of 104 to 106 In passive state, a metal may fail to displace other metal lower in electrochemical series from its salts.

ELECTROCHEMICAL PASSIVITY
Most metals as anode dissolve when the potential is just

slightly positive than the reversible value in the particular solution used as an electrolyte.
If the current density is increased, a point is, however

reached at which the potential increases suddenly or very rapidly, and there is a corresponding decrease in the current, at the same time the anode practically ceases to dissolve, although its appearance is unchanged. The metal is said to be in Passive State and the phenomenon is called ELECTROCHEMICAL PASSIVITY

Active Passive Region

1) Active Region :- when electrode potential is made nobler the metals follow a typical tafel behaviour & dissolution rate increases exponentially. 2) Passive Region :- the dissolution rate decreases to a very small value and remains independent of potential over a considerable range 3) Transpassive Region :- as potential is further increased further in noble direction, the dissolution rate again increases.

Mechanism of Chemical Passivity

A) Oxide film theory
In the film theory the passivation of a metal is caused by the formation of a thin oxide film on the s/f of the metal, which ceases to interact with the surrounding medium and is thus protected from surrounding.
1) Formation of Salt Layer

2) Removal of Salt Layer

3) Formation of Oxide Layer

B) Adsorption Theory It can be achieved through the retardation of the metal dissolution reaction caused by adsorbed oxygen atoms. The adsorbed oxygen atoms passivate the metal either by forming a continuous monomolecular layer on its s/f or by blocking the most active centers or else by changing the effective potential difference across the metal-solution interface. Also here arises the possibility of passivation by blocking active centers on the s/f of a dissolving metal or by retarding the dissolution p/c electrochemically.

Increase in Passivity
There are two ways of increasing the passivation and the

corrosion resistance of metal systems by alloying, i.e. introducing components which directly facilitate passivity (for instance Cr, Si, Mo when added to iron) or introducing components which lower the cathodic polarization (Pt, Pd and other noble metals for stainless steels and titanium). Experimental data on increasing the passivity and corrosion resistance of metal by means of alloying with cathodic metals and by other methods, in particular by the use of anodic protection, are considered

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