PASSIVITY

AIAS

Introduction to Passivity:

Phenomenon passivity is closely related to protection of

metals from corrosion. Term passivity is first utilized by ‘Schonbein’ in 1836 to
describe the strange behavior of iron in concentrate HNO3. Now it is commonly
accepted this phenomenon to all the metals; a piece of iron when dipped in dilute
HCl evolves H2 gas, replace Ag from AgNO3 and Cu from CuSO4 solution. But if
same piece of iron is first dipped in conc. HNO3 or chromic acid for some time and
then reacted with above reagents, it remain unattacked.

Thus iron by treatment of conc. HNO3 is rendered inert or passive and the
phenomenon is known as ‘Passivity’. “The inertness exhibited by metal under
conditions in which chemical activity is to be expected is called chemical passivity
and the substances which cause this phenomenon are called passivators”.
Common passivators are conc. HNO3, chromic acid, heating in air.
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Alternative Definition of
“Phenomenon in which a metal or an alloy exhibits a much higher corrosion
Passivity:
resistance than expected from it’s position in the electrochemical series”. Passivity
is the result of the formation of highly protective but very thin and quite
invisible film on the surface of metal or of an alloy, which make it noble. Such
film is considered to be insoluble, nonporous and of “Self heating nature” that
when broken will repair itself.

Examples of passive metals and alloys are: Ti, Al, Cr, stainless steel containing Cr.
This material exhibit corrosion resistance in oxidizing environments, but in reducing
environment they become active. Experiment shows passivity of certain metal falls in
order: Ti→Al →Cr→Be →Mo →Mg→Ni→Co→Fe→ Mn→Zn →Cd→Sn→ Pb →Cu.
 Factors which Affect Corrosion
AIAS

The main factors which affect corrosion are:-

1.More the reactivity of metal, the more will be the possibility of the metal getting
corroded.

2.The impurities help in setting up voltaic cells, which increase the speed of corrosion

3. Presence of electrolytes in water also increases the rate of corrosion

4. Presence of in CO2 natural water increase rusting of iron.

5.A rise in temperature (with in a reasonable limit) increases the rate of corrosion.
etc…..

Factors influencing corrosion

(i) Nature of the metal

(ii) Environmental factors

 (I) NATURE OF THE METAL
AIAS

(a) Position in Galvanic Series:-

When two metals are in electrical contact in the presence of an electrolyte, the
metal higher up in galvanic series becomes anodic and suffers corrosion.
Moreover, greater the difference in their positions in the electrochemical series,
faster is the corrosion of the anodic metal.

(b) Purity of the metal:-

The rate of corrosion increases with the extent of impurities, due to the formation
of minute electrochemical cells because of “heterogeneity” caused by them. The
anodic part gets corroded. Example:- very pure Zn will not corrode in very pure
HCl, but Zn metal conataing impurities of Pb or Fe corrodes rapidly.
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(c) Nature of the Oxide film:-

If the specific volume of the metal oxide film formed is lesser than the volume of the
metal atom, then the film will be porous. Example:- Metal such as Be, Mg etc. form
oxides which have smaller volumes than the metals from which they are formed
and hence are easily corroded even at low temperature.

(d) Solubility of the products of corrosion:-

If the corrosion product is soluble in the corrosion medium then corrosion proceeds
at a faster rate.

(e) Volatility of corrosion product:-

If the corrosion product is volatile, it leaves the surface of the metal as soon as it is
formed. Hence it leaves the underlying fresh metal surface exposed to further
attack. This results into excessive corrosion.
 (ii) Environmental factors
AIAS

(b) Humidity:-
(a) Temperature:-
Corrosion increases with the
increase in humidity of the
atmosphere. The relative
humidity above which the
atmospheric corrosion rate of
metal increases sharply is
(c) Presence of impurities in atmosphere:- known as critical humidity.

If air is polluted by smoke or gases like H2S, SO2 .

Example:-
NaCl if present absorb moisture and act as strong electrolytes.
Some dust particles containing charcoal are capable of adsorbing SO2 and so
enhance the corrosion process.

(d) Effect of pH:-

Lower is the pH, greater is the corrosion. This implies that acidic
media having pH less than 7 are more corrosive than alkaline or
neutral media.