-0.45 (-0.

62)
whence,

= -0.06 log 10-11 + 0.06 log iANODIC

iANODIC = 6.8 x 10-9 A cm-2

Cathodic Current Density Due to Evolution of Hydrogen:

Applying the Nernst equation yields the equilibrium potential, E`H+:
E`H+ = 0.00 (0.0591/2) log (1/(aH+)2)
= -0.0591 pH = -0.0591 x 7 = -0.414 V SHE
Applying the Tafel equation yields the current due to the discharge of
hydrogen:
CATHODIC (H2) = -b log i0 (H2) + b log iCATHODIC (H2)
E`H2 ECORROSION = -0.12 log 10-10 + 0.12 log iCATHODIC (H2)
-0.414 (-0.45) = -0.12 log 10-10 + 0.12 log iCATHODIC (H2)
whence,

iCATHODIC (H2) = 2 x 10-10 A cm-2

Cathodic Current Density Due to Oxygen Reduction:

At the corrosion potential, the anodic current density due to the dissolution
of iron is equal to the sum of the current densities due to the evolution of
hydrogen and reduction of dissolved oxygen:
O2 + H2O + 2e- = 2OHi.e., iANODIC(Fe2+) = iCATHODIC (H2 evolution) + iCATHODIC (O2 reduction)
6.8 x 10-9 = 2 x 10-10 + iCATHODIC (O2 reduction)
whence: iCATHODIC (O2 reduction) = 6.6 x 10-9 A cm-2
This is more than an order of magnitude greater than the cathodic current
density due to evolution of hydrogen, identifying reduction of oxygen as the
dominant cathodic reaction.
Overpotential for Oxygen Reduction:
For the reaction O2 + H2O + 2e- = 2OH-:
E0 = 0.401 V SHE
Applying the Nernst equation yields equilibrium potential:

E` = E0 (0.0591/z) log ((aOH-)2/(aO2)1/2)

= 0.401 - (0.0591/2) log ((10-7)2/(0.21)1/2)
= 0.805 V SHE
At the corrosion potential the cathodic overpotential for oxygen reduction,
= E` - ECORROSION = 0.805 (-0.45) 1.255 V
This is a very high overpotential for a cathodic current of only 6.6 x 10-9 A
cm-2 and implies strong polarization of the reaction
Thus other effects must predominate over activation polarization as
predicted by Tafel equation. These are:
1. Resistance polarization due to a tendency towards film formation.
2. Concentration polarization due to slow diffusion of oxygen,
depleting its concentration in the bulk of the electrolyte
These effects conspire to make the corrosion process very sensitive to oxygen
concentration
(Refer: David Talbot & James Talbot, Corrosion Science & Technology, CRC
Press, London, 1998 pp. 106-110)
Passivity
An unusual phenomenon observed during the corrosion of certain metals and
alloys.
Definition loss of chemical reactivity under certain environmental conditions.
To illustrate nature of passivity experiment by Faraday in 1840s with
corrosion of iron in HNO3. Fig. 9-24

Points:
1. Corrosion rate is very low. Reduction ~104 to 106 times
2. Passive state relatively unstable and subjected to damage
3. It is the result of surface film < 30 A.U. containing water of hydration
Fe, Cr, Ni, Ti, & alloys containing major amounts of these elements
demonstrate active-passive transitions.
Fig. 9-25 illustrate behaviour of an active-passive metal

One important characteristic anodic current density maximum characterized

by primary passive potential Epp and critical anodic current density for passivity,
i c.
Fig. provides some useful information:
1. Defines active-passive metal or alloy as one which demonstrates S-

shaped dissolution curve.

2. Illustrates - decrease in dissolution rate accompanying the active-topassive transition result of film formation.
3. Transpassive region where dissolution rate again increases with increasing
potential due to destruction of passive film at very positive potentials.
Fig. 9-26 illustrates effect of increasing temp. and acid concentration on the
behaviour of an active-passive metal.

Similar effect upon increasing chloride additions in the case of s.s. and other
ferrous base alloys.
When considering mixed electrodes involving active-passive metal unusual
results.
Fig. 9-27 illustrates three possible cases when active-passive metal is exposed
to a corrosive environment such as acid solution.

Case1 one intersection point, point A active region high corrosion

rate. E.g. Ti in dil. air-free H2SO4 or HCl.
Case 2 Point C is electrically unstable system cannot exist.
Point B active region high corrosion rate D passive region
low corrosion rate.
E.g. Cr in air-free H2SO4 and iron in dil.HNO3.
Case 3 metal or alloy will spontaneously passivate and remain passive.
E.g. Stainless and Ti in acid solutions containing oxidizers
such as ferric salts or dissolved oxygen and also iron in
conc.HNO3.
Case 3 most desirable.
Case 2 least desirable
Case 1 not particularly desirable
Metal or alloy more readily passivated if small critical anodic current density
and active primary passive potential.

Forms of Corrosion
Basis for classification appearance of corroded metal.
Eight forms (1) uniform attack; (2) galvanic corrosion; (3) crevice corrosion; (4)
pitting; (5) intergranular corrosion; (6) selective leaching; (7) erosion corrosion;
and (8) stress corrosion.
1. Uniform Attack
Most common form.
Characterized by chemical or electrochemical reaction, which proceeds
uniformly over entire surface.
E.g. rusting of sheet iron roof, steel tank in abandoned gold smelting plant.
Represents greatest destruction of metal on tonnage basis
Prevented by:
(1) proper materials,
(2) inhibitors,
(3) cathodic protection
2. Galvanic Corrosion
Potential difference exists between two dissimilar metals when immersed in
corrosive solution.
If these metals are in contact, potential difference produces electron flow
between them.
Less resistant becomes anodic and more resistant one cathodic.
Cathodic metal corrodes very little or not at all.

E.g. rusting of sheet iron roof, steel tank in abandoned gold smelting plant
(Figure 3-1)

Represents greatest destruction of metal on tonnage basis

Prevented by:
(1) proper materials,
(2) inhibitors,
(3) cathodic protection
1. Galvanic Corrosion
Potential difference exists between two dissimilar metals when immersed in
corrosive solution.
If these metals are in contact, potential difference produces electron flow
between them.
Less resistant becomes anodic and more resistant one cathodic.
Cathodic metal corrodes very little or not at all.
Driving force for corrosion potential developed between two metals
E.g. dry cell Fig.

Examples:
1. A yacht with Monel (70Ni 30Cu) hull and steel rivets
2. Severe attack occurred on Al tubing connected to brass return
bends
3. Domestic hot water tanks made of steel failed where Cu tubing is
connected
4. Pump shafts and valve stem made of steel or more corrosion
resistant materials failed because of contact with graphite coupling
Potential generated by galvanic cell can change with time. As corrosion progresses,
corrosion products may accumulate reduces speed of corrosion.
Polarization of cathodic reaction predominates
Degree of cathodic polarization varies with metals and alloys necessary to know
polarization characteristics before predicting galvanic corrosion
1.1 Environmental effects
Nature and aggressiveness of environment determine to a large extent the
degree of two-metal corrosion Table 3-3

Galvanic corrosion also occurs in atmosphere. Severity depends on type and

amount of moisture
E.g. Corrosion greater near seashore than in a dry rural atmosphere
Condensate near seashore contains salt and therefore more conductive (and
corrosive)
Galvanic corrosion does not occur when metals are completely dry no
electrolyte to carry current
1.2 Distance effect
Accelerated corrosion greatest near junction
Distance affected depends on conductivity of solution
1.3 Area effect
Unfavourable area ratio large cathode & small anode

1.4 Prevention
1. Select combinations of metals as close together as possible in the
galvanic series
2. Avoid unfavourable area effect
3. Insulate dissimilar metals

4. Apply coatings with caution the more noble metal should be coated
5. Add inhibitors
6. Avoid threaded joints of materials far apart in the series. Wall
thickness is cut away during threading operation. Spilled liquid or
condensed moisture collects in threaded grooves

7. Design for the use of readily replaceable anodic parts or make them
thicker
8. Install a third metal
1.5 Beneficial applications
1. Dry cell and other primary batteries
2. Cathodic protection
E.g. galvanized steel Fig.3-6

3.

Cleani
ng silver stains on Ag due to Ag2S. Place Ag in Al pan
containing water and baking soda. Ag2S reduced to Ag. Rinse
Ag and wash in warm soapy water

3.Crevice Corrosion
Intensive localized corrosion within crevices and other shielded areas.
Associated with small volumes of stagnant solution caused by holes, gasket
surfaces, lap joints, surface deposits and crevices under bolt and rivet heads.

Other names deposit or gasket corrosion

3.1Environmental factors
Deposits causing crevice corrosion sand, dirt, corrosion products and other
solids.
Deposits act as shield and creates stagnant condition
Contact between metal and non-metallic surfaces gasket.
Nonmetals wood, plastics, rubber, glass, concrete, asbestos, wax and fabric
To function as corrosion site, crevice wide enough to permit liquid entry
sufficiently narrow to maintain stagnant zone
Crevice at openings a few microns in width
3.2Mechanism
Consider a riveted plate section of metal M immersed in aerated sea water
Fig.

Overall reaction:
Oxidation: M

M+ + e

Reduction: O2 + 2H2O + 4e

4 (OH)-

Initially - reactions uniform

After a short while O2 within crevice depleted - O2 reduction ceases
Area within crevice small overall rate of O2 reduction remains unchanged.
Rate of corrosion within & without remains equal.
Excess +ve charge in the solution within crevice - Fig.

Balanced by migration of Cl- into crevice

Increased concentration of metal chloride within crevice.
Metal salts hydrolyze in water:
M+Cl- + H2O

MOH

+ H+Cl-

Both chloride and H+ ions accelerate dissolution rate of M.

Increase in dissolution increases migration result autocatalytic process
Fluid within crevices 3 to 10 times as much Cl- as bulk solution pH 2 to 3.
As corrosion within crevice increases, rate of O2 reduction on adjacent surfaces
also increases.
This cathodically protects external surfaces
3.3Combating crevice corrosion
1. Use welded butt joints instead of riveted or bolted joints.
2. Close crevices in existing lap joints by welding or soldering
3. Design vessels for complete drainage, avoid sharp corners and stagnant
areas.

4. Inspect equipment and remove deposits frequently

5. Remove solids in suspension in the process
6. Remove wet packing materials during long shut downs
7. Use nonabsorbent gaskets Teflon
8. Weld instead of rolling in tubes
4.Pitting
- Extremely localized attack
- Result in holes
- Causes equipment to fail because of perforation
4.1 Pit shape and growth
- Pits sharply defined with lack of attack on most of the metal

- Pits grow in the direction of gravity

Intermediate stage between general corrosion and corrosion resistance

- In the corrosion of steel by 5% NaCl brine, pH plays an important role. As

pH is increased, corrosion progresses from general to highly localized
pitting. Beginning at pH 4, pits are covered by a cap of corrosion product. At
pH 12, corrosion products assume an unusual tubular shape and corrosion
rates are 17000 mpy at the bottom of the tube.

4.2 Autocatalytic nature of pitting

- Corrosion pit unique type of anodic reaction
- Autocatalytic process
- Fig. 3-19 - Metal M pitted by an aerated NaCl solution

- Rapid dissolution within pit while O2 reduction takes place on adjacent

surfaces
- Process self-stimulating and self-propagating
- Rapid dissolution within pit tends to produce excess positive charge
migration of Cl- ions to maintain electro-neutrality.
- In the pit high concentration of MCl result of hydrolysis, a high
concentration of H+ ions.
- Both H+ and Cl- stimulate dissolution of most metals and alloys and entire
process accelerates with time.
- Cathodic O2 reduction on surface adjacent to pits tends to suppress
corrosion.
- Pits cathodically protect rest of metal surface.

- Initiation of pitting if, for any reason, rate of metal dissolution

momentarily high at one particular point, Cl- ions migrate to this point.
- This change tends to produce conditions, which are favourable to further
rapid dissolution at this point.
- Locally, dissolution momentarily high because of surface scratch, an
emerging dislocation or other defect or random variations in solution
composition.
- Gravity effect result of autocatalytic nature.
- Since dense, concentrated solution within a pit necessary for its continued
activity, pits most stable when growing in the direction of gravity.
- Also, pits are generally initiated on the upper surfaces because Cl- ions more
easily retained under these conditions.
- Pits with tubular corrosion products Fig. 3-18 grow by mechanism similar
as above.

- At interface between pit and adjacent surface, Fe(OH)2 forms due to

interaction between (OH)- produced and pit corrosion product.
- This is further oxidized by the dissolved O2 in the solution to Fe(OH)3,
Fe3O4, Fe2O3 and other oxides. This rust rim grows in the form of a tube.
4.3 Solution composition
Most pitting failures are caused by Cl- & Cl2 containing ions.
Best explanation acid-forming tendency of Cl- salts and high
strength of its free acid (HCl).
Oxidizing metal ions with chlorides like cupric, ferric, and mercuric
halides are extremely aggressive pitters.
Do not require O2 to promote attack their cations cathodically
reduced:
Cu2+ + 2e = Cu
Fe3+ + e = Fe2+
Pitting prevented by hydroxide, chromate or silicate salts.
4.4 Velocity
Pitting associated with stagnant conditions.
- Liquid trapped in a low part of an inactive pipe system.
- Increasing velocity decreases pitting attack.
- E.g. s.s. pump good service handling sea water if run continuously, pit if
shut down for extended periods.
4.5 Metallurgical variables
Stainless steels are more susceptible to damage. Holding types 304 & 306 in
sensitizing range (500-8000C) decreases pitting resistance.
Austenitic s. s. greatest pitting resistance when solution quenched above 9800C.
Severe cold working increases pitting attack of 18-8 s. s. in FeCl3.

Pitting less likely on polished than on etched or ground surfaces.

Ordinary steel more resistant than stainless steels
4.6 Evaluation of pitting damage
Statistical variation in depth of pits. Pit depth a function of sample size. Figs.

Max. pit depth measurement accurate

4.7 Prevention
Methods for combating crevice corrosion apply

Best procedure material not pit

Type 304 s.s.
Increasing

Type 316 s.s.