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Gases like SO2, CO2, Cl2. H2S and F2 etc. cause corrosion. The extent of corrosion depends on the chemical affinity between metal and the gas involved. The
(degree or attack depends on the formation of protective or non-protective or non protective films on the metal surface.
(i) If the film formed is protective or non porous the extent of attack decreases (e.g., AgCl).
(ii) If the film formed is non-protective or porous, the surface of the whole metal is gradually destroyed e.g., 2CI 2 + Sn ? SnCl4 (Volatile). In petroleum industry H 2S
at high temperature attacks~ steel forming scale, which is porous.
This type, of corrosion occurs due to direct chemical attack of environment or atmospheric gases like oxygen halogens, hydrogen sulphide, sulphurdioxide,
nitrogen or anhydrous inorganic liquid with metal surfaces in immediate proximity.
Dry or chemical corrosion is of three main types as:
(a) Oxidation Corrosion
(b) Corrosion by Other Gases
Erosion Corrosion
Whenever streams of gases, vapours or liquids emerge from an opening and strike with high velocities on the side walls (like tin condenser-tubes, agitators etc.),
the combined effect of the abrading action of turbulent flow and the mechanical rubbing action of particles over a metal surface leads to the breakdown of a
protective film at the point of impingement. This leads to the formation of differential cells at such areas and localized corrosion takes place at the anodic region.
This is called erosion corrosion.
Galvanic Series
The potential difference between metals under reversible or non-corroding conditions forms the basis for predicting corrosion tendencies. The potential between
the metals exposed to solutions containing approximately one gram atomic weight of their respective ions are precisely measured at constant temperature. This is
termed as electromotive force or series. All potentials are referenced against the hydrogen electrode which is arbitrarily defined as zero. Potentials between the
metals are determined by taking the absolute differences between their standard potentials.
Galvanic series:
Magnesium
Magnesium alloys
Zinc
Aluminum
Aluminum alloys
Cadmium
Active or anodic
Low carbon steel
Cast iron
Chromium Stainless steel (13% Cr- active)
Lead-Tin alloys
Lead
Tin
Nickel (active)
Inconel (active)
Brass
Copper
Bronze
Silver solders
Noble or catholic
Copper-Nickel alloys
Chromium Stainless steel (11-30% Cr-Passive)
Silver
Titanium
Graphite
Gold
Platinum
Pitting corrosion
Pitting is a form of extreme localized attack that results in holes in the metal. These holes may be large or small in diameter, but generally they are small. Pits are
Pitting is one of the most destructive forms of corrosion. It causes equipment to fail because of perforation with only a small percent weight loss of entire structure.
It is often difficult to detect pits because of their small size and because the pits are often covered with corrosion products.
The presence of extraneous impurities (like sand, dust) embedded on the surface of metals also leads to pitting. Due to the difference in oxygen, the part
underneath the impurity becomes anodic area and the large part the catholic area. Once a small pit is formed, the rate of corrosion increases.
Oxidation corrosion:
This type of corrosion takes place by the direct action of oxygen at low or high temperature on metals in the absence of moisture. At ordinary temperatures the
metals are only slightly attacked. Alkali and alkaline earth metals are rapidly oxidized at low temperature and almost all metals (except Ag, Au and Pt) are oxidized
at high temperature.
Reactions in oxidation corrosion
2M ? 2Mn+ + 2ne(Loss of electrons)
n/2 02 +2ne- ? n02(Gain of electrons)
Overall reaction
2M + n/2O2 ? 2Mn+ + nO2(Metal oxide)
Mechanism:
Oxidation first occurs at the surface of the metal and the resulting metal oxide forms a barrier which restricts further oxidation. For oxidation to continue, the metal
'must diffuse outwards through the metal oxide layer or oxygen must diffuse inwards through the scale to the underlying metal .Both the transfers occur but the
outward diffusion or the metal is more rapid than inward diffusion of oxygen ,since the metal ion is much smaller than oxygen molecule, thus higher mobility. (fig.
a).
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