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Corrosion by Other Gases

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.

Dry or Chemical Corrosion

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

WET OR ELECTROCHEMICAL CORROSION

This type of corrosion occurs


(i) where a conducting liquid is in contact with a metal or
(ii) When two dissimilar, metals or alloys are either immersed or dipped partially in a solution.
This is due to the existence of separate 'anodic' or 'catholic' areas, between which current flows through the conducting solution. At anodic area, oxidation reaction
(liberation of free elections) takes place so anodic metal is destroyed by either dissolving or assuming combined state (e.g... oxide), thus. Corrosion always occurs
at anodic areas.
Anode:
M ? Mn+ + neMn+ ? dissolve in solution or forms compounds
At catholic areas, reduction reaction (gain of electrons) takes place. Usually cathode reactions do not affect the cathode, since metals are not reduced further.
Thus, dissolved constituents in the conducting medium accept the electrons and form some ions (OH -,O2). Metallic ions (from the anode) and non-metallic ions
(from the catholic part) diffuse through the conducting medium and form corrosion products. The electrons released at the anode flow through the metal and are
consumed m the catholic region. During metallic corrosion, the rate of oxidation equals the rate of reduction.
Thus, in electrochemical or wet corrosion the following observations are made:
(i) Formation of anodic and catholic part or parts in contact with each, other.
(ii) Presence of conducting medium
(iii) Corrosion of anodic areas only.
(iv) Formation of corrosion product between anodic and catholic areas.
Mechanism: Electrochemical corrosion involves the flow of electron current between anodic and catholic regions. The anodic reaction involves dissolution of the
metal as corresponding metallic tops with the liberation of tree electrons.
Anodic area:
M ? Mn+ + ne(Oxidation)
Catholic reaction consumes electrons and .depending on the nature, of corrosive environment the following reactions may take place:
(i) Hydrogen evolution
2H+ + 2e- ? H2
(ii) Oxygen reduction (acidic medium)
O2 + 4H+ + 4e- 2H2O
(iii) Oxygen reduction (neutral or alkaline medium)
O2 + 2H2O + 4e- ? 4OH(iv) Metal ion reduction) M3+ + e- ? M2+
(v) Metal deposition
M+ + e- ? M

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 or Bimetallic Corrosion / Differential Metal Corrosion


A potential difference usually exists between two dissimilar metals when they are immersed in a corrosive or conducting solution. If these metals are placed in
contact, this potential difference produces electron flow between them. Corrosion of the less corrosion resistant metal is usually increased and corrosion of die
more resistant material is decreased, as compared with the behavior of these metals when they are not in contact. The less resistant metal usually becomes
anodic and the more resistant metal catholic. Usually the cathode or catholic metal corrodes very little or none at all. Because of the electric current and the
dissimilar metals involved, "this form or corrosion is called galvanic or two metal corrosion. The driving force for current and corrosion is the potential developed
between the two metals. Example when two dissimilar metals like Zn and Cu are electrically connected and exposed to an electrolyte (Fig. a); the metal higher in
the electrochemical series undergoes corrosion. This is called as galvanic corrosion.
Fig. a. Galvanic corrosion
Zn (higher in die electrochemical series) forms the anode and is attacked and gets dissolved: where Cu (lower in the electrochemical series) acts as cathode.
The potential generated by a galvanic cell consisting of dissimilar metals can change with time. The potential generated causes a flow of current and corrosion to
occur at the anodic electrode. As corrosion progresses, reaction products or corrosion products may accumulate either at the anode or the cathode or both. This
reduces the speed at which corrosion occurs. This is called polarization.
In galvanic corrosion, polarization of the electrode at which reduction reaction takes place usually predominates. The degree of catholic polarization and its
effectiveness varies with different metals and their alloys.
Mechanism: At the anode, Zn undergoes oxidation to form Zn ion. The electron current flow from anode to cathode in acidic solution, hydrogen evolution takes
place, while in neutral or slightly alkaline solution, oxygen absorption occurs. Corrosion occurs at the anode part and the cathode is protected from attack.
Example: [a] Steel screw in brass marine hardware
[b] Steel pipe connected to copper plumbing
[c] Lead-Antimony solder around copper wire
[d] Steel propeller shaft in bronze bearing.

Galvanic corrosion can be minimized by:

(i) Avoiding a galvanic couple


(ii) Providing an insulating material between the two metals,
(iii) Selecting metals close together in the galvanic series
(iv) By avoiding effect due to small anode and large cathode.
(v) Applying coating or adding inhibitors
(vi) Inserting a third metal anodic to both metals in galvanic contact

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

Liquid Metal Corrosion


This type of corrosion is due to the chemical action of flowing liquid metal at high temperature on solid metal or alloy. It takes places by either dissolution or the
solid metal by liquid metal or internal penetration of the liquid into the solid metal. This causes weakening of the liquid metal. It is observed m devices used for
nuclear power plants.

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

Fig. a. Pitting corrosion


Sometimes isolated or so close together that they look like a rough surface. Generally a pit may be described as a cavity or hole with the surface diameter about
the same or less than the depth (Fig. a).

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).

Fig.a. Oxidation corrosion mechanism of metal

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