1.

Galvanic corrosion It is also called bimetallic corrosion or differential metallic

corrosion. It occurs when two dissimilar metals (for example, Zn and Cu) are electrically
connected and exposed to an electrolyte and then the metal higher in the electrochemical
series undergoes corrosion.
For example, if Zn and Cu are connected, Zn acts as anode and undergoes corrosion,
whereas Cu acts as cathode
Mechanism: In a Zn – Cu couple
At anode Zn Zn2+ + 2e–
The reaction at the cathode depends upon the environment

Acidic environment 2H+ + 2e– H2 (evolution of hydrogen)

Alkaline or neutral environment 1/2O2 + H2O + 2e– 2OH– (absorption of oxygen)

Zn2+ and 2OH– ions interact to form Zn(OH)2. Hence, Zn dissolves and Cu is protected.

Fig. Galvanic corrosion

2. Concentration cell corrosion Concentration cell corrosion takes place when different
areas of a metal surface are in contact with an electrolyte of different concentration or
varying aeration (pitting corrosion, waterline corrosion, corrosion under a block of wood
or a drop of water, etc).
Differential aeration corrosion (DAC) This is the most common type of concentration
cell corrosion. It occurs when one part of the metal is exposed to a different air
concentration than the other. There will be a difference of potential between differently
aerated areas.
Experimental observations have shown that
• Poorly oxygenated areas become anodic and
• Highly oxygenated areas become cathodic.
Corrosion occurs at the anode. Some common examples of differential aeration corrosion
are cited below
(a) Waterline corrosion If a Zn metal is partially immersed in a neutral solution (say
NaCl) and the solution is not stirred, the parts above and close to the waterline are well
aerated and act as cathode. Areas deep inside the solution are anodic, as the concentration
of oxygen is less. Thus, a potential develops that causes a flow of current between two
areas of the same metal. Zn dissolves at the anodic area
(At anode) Zn Zn2+ + 2e–
(At cathode) 1/2O2 + H2O + 2e– 2OH–

Similarly, we can observe rusting along a line just beneath the level of water stored in an
iron tank. This is also waterline corrosion and is because of differential aeration. The area
just above the waterline is well aerated and acts as cathode, whereas the areas below the
waterline are poorly aerated/oxygenated and hence become anodic and get corroded. Try
to write down the reactions involved at cathode and at anode.

Fig. Waterline Corrosion

(b) Pitting corrosion It is also an example of differential aeration corrosion. It is a
localised type of corrosion and occurs in areas of pits, cavities and pinholes that penetrate
deeply within the metals. The pit is oxygen deficient and acts as anode, whereas the plane
surface is oxygen-rich and acts as cathode. As the area of anode is small the rate of
corrosion will be high. Anodic metal dissolves and the pit gradually deepens resulting in
the weakening of the metal in these areas. If the pits are small they may be covered by
corrosion products. Therefore, it is difficult to detect pitting corrosion till sudden failure
of the metal occurs.
Pitting of metal generally occurs because of breakdown or cracking in the protective film
on the metal surface at specific points. It may be due to scratches, surface roughness,
chemical attack, stresses and strains, etc. Pitting is common in aluminium alloys, copper
alloys, stainless steels and some nickel alloys.
Passivity
It is defined as the phenomenon in which a metal or an alloy exhibits a much higher
corrosion resistance than expected from its position in the electrochemical series. In an
electrochemical series, the metals are arranged from top to bottom in the order of their
increasing reduction potentials (or decreasing reactivities). The metal placed higher in the
series is more reactive than the one placed below it. Hence, the metal that is placed higher
in the electrochemical series behaves as an anode and undergoes corrosion. For example,
Zn corrodes faster than Fe, which in turn corrodes faster than Sn. This is because Zn is
placed above Fe, which in turn is placed above Sn in electrochemical series.
However, there are some exceptions. Ti, which is above Ag in the electrochemical series,
is less reactive than Ag. Similarly, in a Zn–Al couple, Zn which is below Al in the
electrochemical series, is corroded. These observations are opposite to those predicted by
the electrochemical series. This is because Ti and Al develop strongly adhering oxide
layers on their surface, thereby making their effective electrode potential more positive
(or less negative). These metals are said to be rendered passive.
Passivity is because of the development of a highly protective, very thin (0.004-mm-thick)
invisible oxide film on the surface of the metal. The film so formed makes the metal
behave as a noble metal. The presence of ample excess oxygen on the metal surface
favours passivation. Common examples of passivation are

• Metals like Cr, Al, Ni, Ti and a wide variety of stainless steel alloys containing Cr show
outstanding corrosion resistance in oxidizing environment. These metals and alloys form
insoluble oxide films on their surface in the presence of oxygen and are rendered passive.
On changing the environment, i.e., in reducing environment these metals become
chemically active and undergo rapid corrosion.
• Iron is readily attacked by dilute HNO3 but in concentrated acid it forms a very thin
protective film and becomes passive or inactive.
• Al becomes passive in concentrated HNO3 due to the formation of thin protective oxide
film.

Significance The phenomenon of passivity has been used to protect metals from
corrosion. Passive oxide films are artificially produced on metals and alloys by treatment
with strong oxidizing agents and hence the metals are protected from being corroded.
Galvanic Series
Owing to passivation, the effective electrode potential of some metals changes and they
become less reactive. Their behavior becomes opposite to that predicted by the
electrochemical series. Hence, a more reliable series for predicting the corrosion behavior
in different environments is the galvanic series. It has been prepared by studying the
corrosion of metals and alloys in a given environment like sea water. Thus, the galvanic
series gives real and useful information for studying the corrosion of metals and alloys.

The galvanic series for sea water is given below:

This series will be different for some different environment i.e. not fixed.
Difference between Electrochemical series and Galvanic series

Sl. Electrochemical Series Galvanic Series

No.
1. Electrode potentials are measured by This series was developed by studying
dipping pure metals in their salt the corrosion rates of metals and alloys
solution of 1M concentration, without in different environments like sea
any oxide film on them water without removing their oxide
films if any
2. The position of metal is fixed in the The position of metal may shift in the
electrochemical series galvanic series depending on the
environment
3. It gives no information regarding the Alloys have also been included and
position of alloys hence their corrosion rates can be
studied from this series
4. This series comprises metals and This series comprises metals and
nonmetals alloys

Factors Influencing Corrosion

The rate and extent of corrosion depend on the following
• Nature of the metal
• Nature of the corroding environment.

Nature of the metal

(i) Position in the galvanic series When two metals or alloys are in contact in the
presence of an electrolyte, the metal that is higher in the galvanic series undergoes
corrosion. The rate and severity of corrosion depends on the difference in their position.
Greater the difference in the position of the two metals greater is the corrosion of the
anodic metal.
(ii) Nature of surface film In the presence of air, all metals are covered with a thin film
of metal oxide. The ratio of the volume of metal oxide to that of the metal is called
“specific volume ratio.” If the specific volume ratio of the metal is greater than one the
metal will be protected from corrosion, and if the specific volume ratio is less than unity
the film will be unstable and the underlying metal will be corroded (Pilling–Bedworth
rule). The specific volume ratios of Ni, Cr and W are 1.7, 2.0 and 3.6, respectively.
Consequently, the rate of corrosion of W is the least even at high temperatures.
(iii) Relative areas of anodic and cathodic parts Rate of corrosion is high if anodic areas
are small and cathodic areas are large. This is because the current density at smaller
anodic areas is much greater. Moreover, if the cathodic areas are large, then it will
demand more electrons, which will be met by the brisk and rapid corrosion of the anodic
area.
(iv) Solubility of corrosion products Corrosion is faster if the corrosion product is
soluble in the corroding medium. If the corrosion product is insoluble in the corroding
medium, or it reacts with the corroding medium to form insoluble product; the product
acts as a physical barrier and suppresses further corrosion. For example, the corrosion of
Pb in H2SO4 proceeds at a much slower rate due to the formation of insoluble PbSO4.
(v) Volatility of the corrosion product If the corrosion product is volatile, it leaves the
surface as soon as it is formed, leaving the underlying metal surface exposed for further
attack. This causes rapid, continuous and excessive corrosion. MoO3 is the volatile
corrosion product formed on the oxidation of Mo. It volatilizes, causing extensive
corrosion of the underlying metal.
(vi) Purity of the metal Pure metals are less prone to corrosion. Impurities in a metal
cause ‘heterogeneity’ and forms minute/tiny electrochemical cells, where the anodic part
gets corroded. For example, very pure and smooth zinc metal will not corrode in very
pure hydrochloric acid. However, zinc metal containing impurities of Fe and Pb corrodes
rapidly.
However it is incorrect to assume that pure metals do not corrode at all . For example in
water saturated with air high purity iron corrodes at almost the same rate as impure
commercial iron . This is because corrosion depends on several other factors like
variation in temperature, availability of oxygen to different parts of the metal which leads
to the setting up of local action cells.

Nature of the corroding environment

(i) Temperature As the rate of all chemical reactions increases with the rise in
temperature, rate of corrosion also increases as temperature rises. At higher temperatures,
even the passive metal can become active and get corroded. However, differential
aeration corrosion slows down at higher temperatures. This is because of the faster
diffusion of O2 into pits and crevices.
(ii) Humidity Corrosion increases with the increase in humidity of the atmosphere.This
is due to the fact that moisture acts as a solvent for O2, H2S, SO2, NaCl, and so on to
furnish the electrolyte for setting up a corrosion cell.
Common examples,
• Atmospheric corrosion of Fe is slow in dry air compared with moist air. Steel parts left
in desert areas remain bright and tarnish free for very long periods of time.
• Gases like H2S and SO2 dissolve in water and increase the acidity of medium and hence
increase the corrosion rate.
• Solids like NaCl dissolve in water to increase its conductivity and hence increase the
rate of corrosion.
(iii)Presence of impurities in atmosphere Gases like H2S, SO2 and CO2 increase acidity
of the liquid closer to the metal surface and hence increases the rate of corrosion. Salts
like NaCl present in marine environment increase the conductivity of the electrolyte, thus
speeding up the corrosion process. Presence of even trace amount of H2S in atmosphere
tarnishes silver (due to formation of Ag2S) and copper (due to formation of a mixture of
Cu2S + CuS + Cu2O)
(iv) Effect of pH Generally, acidic media (pH < 7 ) are more corrosive than alkaline or
neutral media. However, amphoteric metals like Al, Zn, Pb form complexes in alkaline
medium.
(v) Conductance of the corroding medium Conductance of the corroding medium has a
vital role in corrosion. Dry sandy soils have lower conductance compared with clay or
mineralized soils. Hence, metallic structures buried under clay or mineralized soils
undergo corrosion faster than under dry sandy soils.
(vi) Formation of oxygen concentration cell Owing to differential aeration “oxygen
concentration cell” is set up and the anodic parts having less oxygen concentration suffers
corrosion.
(vii) Nature of ions present
• Presence of ions like silicate ions in the medium leads to the formation of insoluble
products (like silica gel), which inhibit further corrosion.
• Chloride ions present in the medium destroy the protective and passive film, thereby
exposing the fresh metal surface for further corrosion.
• Iron undergoes rapid corrosion in an environment containing ammonium salts.