UNIT-III CORROSION 2015-16

1. Introduction: “The phenomenon of deterioration and destruction of matter by unwanted,

unintentional attack of the environment leading to loss of matter starting at its surface is called corrosion”.
Examples are rusting of iron, formation of mill scales, tarnishing of silver, formation of a green film of
basic carbonate (CuCO3 .Cu (OH)2) on the surface of copper etc. The basic reason for corrosion is that
metals are more stable as their minerals/compounds than in pure state with few exceptions like gold etc.
Corrosion is a challenge for engineering materials due to enormous loss of material in corrosion.
2. Theories of corrosion- types
Corrosion is broadly classified into two types.
1. Dry or chemical corrosion 2. Wet or electrochemical corrosion
2.1 Dry or chemical corrosion
This type of corrosion takes place by the direct attack of gases present in atmosphere such as O2,
CO2, H2S, SO2, halogens, etc., with metal surfaces in the immediate vicinity.
Dry corrosion is classified into three types.
i) Oxidation corrosion
ii) Corrosion by other gases
iii) Liquid metal corrosion
2.1.1 Oxidation corrosion: This is brought about by the direct action of oxygen on the metal surface
in the absence of moisture. The oxygen atoms of the air are held close to the surface by means of weak
Vander waal forces. Over a period of time, these forces results in the formation of weak bonds converting
the metal into its corresponding metal oxide. The phenomenon is known as chemisorption.
The following reactions are involved in oxidation corrosion.
2M Mn+ + 2 ne- (Loss of electrons) (Oxidation)
n
O + ne-
2 2 nO2- (Gain of electrons) (Reduction)

2 M + n O2 2 Mn+ + nO2-
2

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Mechanism: Oxidation occurs at the surface of the metal first and forms a layer of deposit (oxide) that
tends to restrict further oxidation. The nature of the oxide film formed plays an important role on the
surface of the metal as it may be stable, unstable, volatile and porous. If a stable layer is formed on the
surface, such a product prevents the exposure of the metal for further corrosion. If unstable oxidation
product is formed, the product decomposes readily and may allow further corrosion.

If the product formed is volatile in nature, it readily volatilizes, leaving behind fresh metal surface. This
leads to rapid and excessive corrosion. Ex: Molybdenum oxide MoO3

It a porous product is formed, an unobstructed and uninterrupted oxidation corrosion reaction takes
place.

2.1.2. Pilling Bedworth Rule: According to this, “an oxide product is protective or non-porous, if the
volume of oxide is at least as great as the volume of metal from which it is formed”. On the other hand, if
the volume of oxide formed is less than the volume of the metal, the oxide layer is porous and non-
protective. Thus smaller is the specific volume ratio (Volume of metal oxide/Volume of the metal),
greater is the oxidation corrosion.
Ex: Alkali& alkaline earth metals (Li, K, Na, and Mg) form oxides having volume less than the
volume of metals. While Al forms oxides which is non-porous and protective. The specific volume ratios
of Ni, Cr and W are 1.6, 2.0 and 3.6 respectively. Hence, the rate of oxidation of tungsten (W) is least,
even at elevated temperatures.
2.1.3 Corrosion by other gases: This type of corrosion takes place by the chemical affinity of gases such
as SO2, CO2, Cl2, H2S, and F2 etc. The degree of attack depends upon the formation of protective or non-

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protective films on the metal surface. Example, AgCl forms the protective films. SnCl4 forms a volatile
product, while attack of Fe by H2S gas forms a porous FeS film.
2.1.4. Liquid metal corrosion: This type of corrosion takes place due to chemical action of a flowing
liquid metal on another solid metal surface or an alloy. Such corrosion occurs in devices used for nuclear
power. The corrosion involves either dissolution of solid metal by a liquid metal or internal penetration
of liquid metal into solid metal, which weaken the solid metal.
2.2. Wet corrosion
This type of corrosion occurs when a conducting liquid is in contact with metal or when two
dissimilar metals or alloys are either immersed or dipped partially in a solution. It involves the formation
of two areas of different potentials in contact with a conducting liquid. One is named as anodic area
where oxidation reaction takes place, the other is referred to as a cathodic area involving reduction. The
metal at anodic area is destroyed either by dissolving or by forming a combined state, such as oxides.
Hence corrosion always occurs at anodic areas. At cathode, the dissolved constituents gain the electrons
forming non-metallic ions. The metallic ions and non-metallic ions diffuse towards each other forming
product somewhere between anode and cathode.
2.2.1. Mechanism of wet or electro chemical corrosion: Electro chemical corrosion involves flow
of electric current between anodic and cathodic areas. At anode, dissolution of metal takes place forming
corresponding metallic ions.
M  Mn+ + ne-
On the other hand, at cathode, consumption of electrons takes place either by
i) Evolution of hydrogen type
ii) Absorption of oxygen type

i) Evolution of hydrogen type: This type

of corrosion occurs if the conducting medium
is acidic in nature. For example, Iron
dissolves and forms ferrous ions with the
liberation of electrons. These electrons flow
from anode to cathode, where H+ ions are
eliminated as hydrogen gas.
Fe  Fe2+ + 2e (Oxidation)
2 H+ + 2 e-  H2 (Reduction)
Fe + 2 H+  Fe2+ + H2

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ii) Absorption of oxygen type: A cathodic reaction can be absorption of oxygen, if the
conducting liquid is neutral or aqueous and sufficiently aerated. Some cracks developed in iron oxide
film cause this type of corrosion. The surface of iron is always coated with a thin oxide film. The crack
developed will create an anodic area on the surface while the well coated metal parts act as cathode. The
anodic areas are small and the cathodic areas are large. Corrosion occurs at the anode and rust occurs in
between anode and cathodic areas. When the amount of oxygen increases corrosion is accelerated.

½ O2 + H2O + 2 e- 2OH- (Reduction)

The Fe2+ ions formed at anode, and OH- ions formed at cathode, diffuse towards each other forming Fe
(OH)2 i.e., Fe2+ + 2 OH- Fe(OH)2
If enough oxygen is present, the Fe (OH)2 is oxidized further to Fe(OH)3. This eventually is
converted in to rust [Fe2O3 x.H2O].
2.2.2. Difference between chemical Corrosion and electrochemical corrosion
Chemical Corrosion Electrochemical Corrosion
1. It takes place in dry condition 1. It takes place in wet condition such as in the
presence of electrolytes.
2. It involves the direct chemical attack of 2. It involves the formation of large number of
environment of the metal. galvanic cells.
3. It takes place on homogeneous and
3. It takes place on heterogeneous surfaces only.
heterogeneous surfaces.
4. Corrosion product accumulates at the same
4. Corrosion product accumulates at cathode, but
place where corrosion is taking place.
corrosion takes place at anode.
5. Uniform corrosion takes place.
5. Non – Uniform corrosion takes place.

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3. Galvanic series
In the electrochemical series the elements are arranged in the
Active 1. Mg
increasing order of their reduction potential values. Galvanic (or anodic) 2. Mg alloys
series or electrochemical series is an arrangement of metals 3. Zn
4. Al
in the increasing order of their reduction potentials. The 5. Cd
6. Al alloys
metals with more anodic character occupy the top positions 7. Mild steel
8. Cast iron
in the series whereas the bottom positions are occupied by 9. High Ni Cast iron
10. Pb-Sn Solder
more cathodic metals. A metal top in the series is more 11. Pb
12. Sn
anodic and undergoes corrosion faster than the metal below 13. Lconel
in the series. 14. Ni-Mo-Fe alloys
15. Brasses
Examples: Mg, Zn, Al, Cd, Duralumin, steel, lead – tin 16. Monel
17. Silver solder
(solder), Pb, Sn, Cu and its alloys, Cupro – Nickel, bronze, 18. Cu
19. Ni
passive stainless steel, Ag, Ti, Graphite, Au, Pt. 20. Cr stainless steel
21. 18-8 stainless steel
The noble character increases down this series. 22. 18-8 Mo stainless steel
23. Ag
24. Ti
25. Graphite
Noble 26. Au
(or cathodic) 27. Pt

Although electrochemical series gives useful information regarding the chemical reactivity of metal it
does not predict the corrosion behaviour of the metal several side reactions may take place which
influence the corrosion reaction hence oxidation potentials of various metals and alloys are determined
with SCE, immersing the metal and alloys in sea water when these oxidation potentials are arranged in the
decreasing order of their activity the galvanic series arises.

3.1 Differences between electrochemical series and galvanic series:

Galvanic series
1. This series was developed by the study
of corrosion of metals and alloys in sea
water without their oxide film.
2. The position of the given metal may shift
3. The corrosion of alloys can be studied
from the series.
4. The position of a metal is different from that
Electrochemical series
1. This was developed by dipping
pure metals in their 1M salt solution
2. The position of the metal is fixed
3. No information regarding alloys.
4. The position of the metal is fixed.

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