Chemistry of Corrosion

C 453
By

Prof. Dr. Ashraf Moustafa Abdel-Gaber

Professor of Physical Chemistry

Faculty of Science
Alexandria University
IV-3-The Oxygen Electrode and Differential Aeration Cells
➢ The oxygen electrode can be represented by

O2 (g) / OH- or Pt / O2 (g), OH-

➢ This electrode is important in differential aeration cells that enter

the mechanism of crevice corrosion and pitting.

➢ Ideally, the equilibrium for such an electrode is expressed as:

½ H2O + ¼ O2 + e- → OH- Eo = 0.401 V

Using Nernest equation: E = Eo – (0.0592/n) log [Product] / [reactant]

EO2 = 0.401 – 0.0592 log [OH-] / PO21/4

➢ Consider two oxygen electrodes in an aqueous solutions, one in

contact with O2 at 1 atm (Left) and other with O2 at 0.2 atm (Right).
IV-3-The Oxygen Electrode and Differential Aeration Cells
O2 (1 atm)

O2 (0.2 atm)
OH-

O2 (g) (1 atm)/ OH- / O2 (g) (0.2 atm)

or Pt / O2 (g) (1 atm), OH- , O2 (g) (0.2 atm) / Pt

Anode cathode
(Oxidation) (reduction)

Right Electrode ½ H2O + ¼ O2(0.2 atm) + e- → OH- EoR = 0.401

Left Electrode OH- → ½ H2O + ¼ O2 (1 atm) + e- EoL= - 0.401
Over all (R-L) ¼ O2 (0.2 atm) → ¼ O2 (1 atm) Eocell = 0.0
For the cell Pt / O2 (g) (1 atm), OH- , O2 (g) (0.2 atm) / Pt

Over all (R-L) ¼ O2 (0.2 atm) → ¼ O2 (1 atm) Eocell = 0.0

Apply Nernest E = Eocell - 0.0592 log(11/4 / 0.21/4)

E = - 0.0592 log(11/4 / 0.21/4) = - 0.0103 V

➢ The -ve value of E indicates that

➢ G for the cell reaction is +ve
➢ Thus the reaction is not spontaneous as written.
➢ The cell must be reversed
Pt /O2 (0.2 atm) / OH- / O2 (1 atm) / Pt
Anode cathode
Corrosion
in any differential aeration cell the electrode in contact
with lower-pressure oxygen tends to be anode
When a similar cell is made up of iron electrodes instead of Pt,

Fe

Fe2+forms at anode
Acts as iron electrode OH- Iron oxide (Fe2O3)
forms at cathode
Eo = -0.440 V O2 Acts as O2 electrode
Aerated solution
Eo = 0.401 V

Fe/Fe2+, OH- , O2 / Fe2O3

Right Electrode ½ O2 + H2O + 2e- → 2 OH- Eo = 0.401

Left Electrode Fe → Fe2+ + 2e- Eo= 0.440

Over all (R-L) Fe + ½ O2 + H2O → Fe2+ + 2OH- Eo = +0.841

When a similar cell is made up of iron electrodes instead of Pt,

For the cell Fe/Fe2+, OH- / O2 / Fe2O3

Over all (R-L) Fe + ½ O2 + H2O → Fe2+ + 2OH- Eo = +0.841

E =Eo – 0.0592/2 log [Fe2+] [OH-]2 / P1/2O2

➢ Assume [Fe2+] = 0.01 pH = 7 and PO2 =0.2 atm

E =0.841 – 0.0592/2 log [Fe2+] [OH-]2 / P1/2O2

E= 0.841 - 0.0592/2 log (0.01) (10-7)2 / (0.2)1/2 = 1.27 V

➢ Thus corrosion at the anode takes place.

III. Application of Thermodynamics to Corrosion
III.1. Free Energy Change
➢ The tendency for any chemical reaction to go, including
the reaction of a metal with environment, is measured by
the Gibbs Free-Energy Change  G.

➢ The more negative the value of  G, the greater is the

tendency for the reaction to go.
For example, consider the following reactions at 25oC:

Mg(s) + H2O(l) + 1/2 O2 → Mg (OH)2  G0 = -596.4 kJ

The large negative value for G0 indicates a high tendency
for Mg to corrode.

Cu (s) + H2O (l) + 1/2 O2 (g) → Cu (OH)2 (s)  G0 = -120.1 kJ

The less negative value of G0 indicates that the corrosion
tendency of Cu is not as high as Mg.
 Au (s) + 3/2 H2O (l) + 4/3 O2 (g) ) → Au (OH)3 (s)  G0 = + 65.9 kJ

The free energy change is positive indicating that gold does

not corrode in aqueous media to form Au(OH)3

➢ It should be noted that the tendency to corrode is not a

measure of reaction rate.

➢ A large negative  G may or may not be accompanied by a

high corrosion rate.

➢ When  G is positive it can be stated with certainly that the

reaction will not go at all under the particular condition
described.
III.2.EMF & Galvanic Series
a) EMF Series
➢ The tendency for a metal to corrode can also be expressed in
terms of the electromotive force (EMF) of the corrosion cell.

➢ Since electrical energy is expressed as the product of volts by

coulombs,
➢ the relation between  G in joules and EMF in volts E, is defined
by
 G = -nEF
E is the oxidation Potential of metal or cell
n is the number of electrons taking part in the reaction, and
F is the Faraday (96500 coulombs/equivalent).

➢ The EMF series is determined by the equilibrium potential of a

metal in contact with ions at a concentration equal unit activity.
EMF Series

Reduction potential
Limitations of EMF Series
1.
It is impossible Because
For some metals to obtain unit restricted
activity solubility

2.

Forms surface
Some metals
films and shift the
In oxidizing Become passive
potential into
environment
noble direction
Limitations of EMF Series
3. The actual activities of ions in equilibrium with a given metal
vary greatly with the environment.
Reduction potential

Cr in the active when coupled with because of the

state (e.g. in HCl Fe, Cr becomes the high oxidation
solution) anode potential

because of a
when coupled with
Cr in air saturated passive film that
Fe, Cr becomes the
aqueous solutions forms over its
cathode
surface

4. EMF Series cannot be defined for alloys.

 B) Galvanic Series
Because of the limitations of EMF Series, and because alloys are not
included, the so-called Galvanic Series has been suggested.

- This series is an arrangement of

metals and alloys in accord with their
actual measured potentials in a given
environment.

- In the Galvanic Series, some metals

occupy two positions, depending on
whether they are active or passive.

- Although only one EMF Series exists,

there can be several Galvanic Series
for each environment. The relative
positions of metals in such series
may vary from environment to
another.
 III.2. Emf & Galvanic Series

Table 1 Standard emf series Table 2 Galvanic Series in Seawater

The emf, or electrochemical
Reaction Eo at 25oC,
(V vs NHE)
series.
Au-Au3+ +1.498  Platinum
Pt-Pt2+ +1.2 Noble or • Ordered by standard reduction
Gold
Ag-Ag+ +0.799 cathodic Silver
potential
Hg-Hg22+ +0.788 18-8 Mo stainless steel (passive)
Cu-Cu2+ +0.337 Nickel (passive)
• The more negative values
Cupronickels (60-90 Cu, 40-10 Ni)
H2-H+ 0.000 correspond
Copper to the more
reactive
Nickel (active)metal
Ni-Ni2+ -0.250 18-8 Mo stainless steel (active)
2+
Fe-Fe -0.440 Steel or iron
• Assumes activity of solution
3+
Cr-Cr -0.744 2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
Zn-Zn 2+
-0.763 species is one
Cadmium
3+
Al-Al -1.662 Active or Commercially pure aluminium (1100)
Mg-Mg 2+
-2.363 anodic • Does not allow for protective
Zinc
 corrosionandproducts
+
Na-Na -2.714 Magnesium magnesium alloys
After de Bethune and Loud from INCO test results
• Cannot be defined for alloys
 III.2. Emf & Galvanic Series
Table 1Standard emf series Table 2 Galvanic Series in Seawater
The galvanic series
Reaction Eo at 25oC,
(V vs NHE)
• Ordered by observed
Au-Au 3+ potential
+1.498  Platinum
2+
in a given
Pt-Pt
+
environment. +1.2 Noble or Gold
Ag-Ag +0.799 cathodic Silver
2+
Hg-Hg2 +0.788 18-8 Mo stainless steel (passive)
• Allows
Cu-Cu 2+ for corrosion products
+0.337 Nickel (passive)
Cupronickels (60-90 Cu, 40-10 Ni)
+
H
•2-H 0.000
Can be defined for alloys Copper
Nickel (active)
Ni-Ni2+ -0.250 18-8 Mo stainless steel (active)
• Different for every -0.440
Fe-Fe 2+ environment Steel or iron
3+
Cr-Cr -0.744 2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
2+
Zn-Zn -0.763 Cadmium
3+
Al-Al -1.662 Active or Commercially pure aluminium (1100)
2+
Mg-Mg -2.363 anodic Zinc
Na-Na +
-2.714  Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results
 III.2. Emf & Galvanic Series
Table 1 Standard emf series Table 2 Galvanic Series in Seawater
Reaction Eo at 25oC,
(V vs NHE)
Au-Au3+ +1.498  Platinum
Pt-Pt2+ +1.2 Noble or Gold
Ag-Ag+ +0.799 cathodic Silver
•Note
2+
Note
Hg-Hg2that
that some alloys
some alloys
can
+0.788 18-8 Mo stainless steel (passive)
Cu-Cu2+ +0.337 Nickel (passive)
appear twice
can appear according to
twice Cupronickels (60-90 Cu, 40-10 Ni)
whether
H2-H+ they
according are active
to whether theyor
0.000 Copper
passive Nickel (active)
are
Ni-Niactive
2+ or passive
-0.250 18-8 Mo stainless steel (active)
Fe-Fe2+ -0.440 Steel or iron
3+
Cr-Cr -0.744 2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
2+
Zn-Zn -0.763 Cadmium
3+
Al-Al -1.662 Active or Commercially pure aluminium (1100)
2+
Mg-Mg -2.363 anodic Zinc
Na-Na +
-2.714  Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results
IV.4. Pourbaix Diagrams

M. Paurbaix

Potential-pH
diagram
Thermodynamic For any metal
data in water

Immunity
Passivity
Corrosion
Pourbaix Diagram of Zinc in Water
2.0
1.6
d e
1.2
0.8
Zn(OH)2
Potential

0.4 stable
ZnO22-
0.0 solid
Zn2+ stable stable in
-0.4 solution
in solution
-0.8 a b
-1.2 c
Zn metal stable
-1.6
0 7 14
pH
 2.0
1.6
1.2
0.8 Zn(OH)2
Potential

stable
0.4
solid ZnO22-
0.0 Zn2+ stable Corrosion is in
stable

-0.4 thermodynamicallysolution
impossible
in solution
-0.8
-1.2
-1.6 Zn metal stable
0 7 14
pH
 2.0
1.6
Corrosion is possible,
1.2
but likely to be stifled by
0.8 solid corrosion product
Zn(OH)
Potential

0.4 stable
solid ZnO22-
0.0 Zn2+ stable stable in
-0.4 solution
in solution
-0.8
-1.2
Zn metal stable
-1.6
0 7 14
pH
 2.0
1.6
1.2

Corrosion
Passivity
0.8
Zn(OH)2
Corrosion
Potential

0.4 stable
solid ZnO22-
0.0
Zn2+ stable stable in
-0.4 solution
in solution
-0.8
-1.2 Immunity
Zn metal stable
-1.6
0 7 14
Pourbaix Diagram of Zinc in Water
Five reactions must be written to describe the possible reactions
2.0
1.6
1.2 d e

0.8 Zn(OH)2
Potential

0.4 stable
ZnO22-
0.0 Zn2+ stable
solid
stable in
-0.4 solution
in solution
-0.8 a b
c
-1.2
Zn metal stable
-1.6
0 7 14
pH
Pourbaix Diagram of Zinc in Water

a. The anode oxidation reaction:

Zn ⇋ Zn2+ + 2e-

b. The formation of insoluble zinc hydroxide:

Zn + 2H2O ⇋ Zn (OH) 2 + 2 H+ + 2e-

c. The formation of a soluble zincate ion:

Zn + 2H2O ⇋ ZnO22- + 4 H+ + 2e-

d. The acidic dissolution of Zn(OH)2

Zn (OH) 2 +2H+ ⇋ Zn2+ +2H2O

e. The formation of zincate from Zn(OH)2:

Zn (OH) 2 ⇋ ZnO22- + 2H+
Construction of Pourbaix Diagram of Zinc
Line (a)
Zn2+ + 2e- ⇋ Zn
➢This reaction is independent of pH variation and
influenced only by variation of potential in accordance with
the Nernst equation. E = Eo Zn2+/Zn+0.0592/2 log aZn2+
➢Substituting the value of aZn2+= 10-6 mol./liter, we can
calculate the potential at which a metal begins to corrode:
E = Eo Zn2+/Zn + 0.0592/2 log (10-6)
E = - 0.760 – 0.177 = - 0.937 V
➢We have thus established that pseudo-equilibrium occurs
at – 0.937 V when the concentration of Zn2+ ions equals 10-6
M.
➢ On a graph of E as ordinate and pH as abscissa we can
draw a horizontal line at – 0.937 V.
Line (b)
➢As the electrolyte becomes more alkaline, the concentration of
hydroxide becomes large enough to cause reaction “b”:
Zn(OH)2 + 2H+ + 2e- ⇋ Zn + 2H2O
E = Eo – 0.0592/2 log ( aZn a2 H2O) /( aZn(OH)2 a2 H+)
E = Eo + 0.0592/2 log a2H+
E = - 0.439 – 0.0592 pH
This equation is the equation of the line “b”. We can confirm its point
of interaction with line “a” by substituting the value of ( –0.937 V) for
E in the equation, thus
pH = (- 0.937 + 0.439) / (-0.059) = 8.44
Line (c)
Line c can be determined in the manner identical to that described for
the line b.

Line (d)
If the equilibrium constant (k) for reaction “d” is known,
Zn (OH) 2 +2H+ ⇋ Zn2+ +2H2O
Thus we can write:
K = ([Zn2+] [H2O] 2) / ([Zn (OH) 2] [H+] 2)

log K = log [Zn2+] + 2 pH

K has been measured by chemical means and found to have the value
7.58 x 1010 and we have defined [Zn+2] = 10-6: therefore substituting
into the equation
log 7.58 x 1010 = log 10-6 + 2 pH
10.88 = -6 + 2 pH
pH = 8.44
Line (e)
As pH is increased still further it is found that the insoluble Zn(OH)2
dissolves to form the so called zincate ion. This occurs at pH= 10.88
Pourbaix Diagram of Fe in Water

2.0
1.6
1.2 Fe3+ Fe(OH)32+
Potential (Volts), vs SHE

0.8
0.4
0.0
Fe2+
-0.4
-0.8
-1.2
Fe
-1.6
-2 0.0 2 4 6 8 10 12 14 16
pH
 Pourbaix Diagram of Fe in Water

2.0
1.6
1.2
Fe3+ Passivation
Potential (Volts), vs SHE

0.8
0.4
0.0
Corrosion
-0.4 Fe2+
-0.8
-1.2
-1.6
FeImmunity

-2 0.0 2 4 6 8 10 12 14 16
pH
Practical Limitations in the Use of Pourbaix Diagrams

➢ E-pH diagram is based on thermodynamic calculations

at assumed standard condition.

➢ Pourbaix diagram supposes equilibrium between the

metal and its ions and between the ions in the solution
and corrosion products containing these ions. In
practical corrosion may be far from equilibrium.

➢ The term passivity in the Pourbaix diagram is applied to

the field of existence for oxides, hydroxides or other
sparingly soluble substances, irrespective of their
protective properties.
➢ It is for pure metal in pure water system.

➢ No kinetic information, corrosion rate, is given.

➢ Effect of other ionic species such as Cl- is ignored.

➢ Effect of flow or velocity on the stability of passivity is

not taken into account.

➢ The pH value referred to in the diagram is the one

prevailing at the surface of the metal considered. This
often varies from point to point and is usually lower at
anode surfaces and higher at cathode surfaces than
the "measured" value in the bulk of the corrosive
solution.