EXPERIMENTAL POLARIZATION CURVES

Reading Material: Chapter 3, Sections 3.4 and 3.5 in

Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

Dr. Ramazan Kahraman

Chemical Engineering Department
King Fahd University of Petroleum & Minerals
Dhahran, Saudi Arabia

Cathodic Polarization
(Polarization of cathodic rxn by shift of potential to a more negative value)
Increase cathodic polarization by c (from c=Ecorr-ec to c=E*-ec) and
plot applied current, iapp, vs potential, E.

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

(Same principle is applied in cathodic protection which is to be studied later)

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Anodic Polarization
(Polarization of anodic rxn by shift of potential to a more positive value)
Increase anodic polarization by a (from a=Ecorr-ea to a=E*-ea) and
plot applied current, iapp, vs potential, E.

ic + iapp = ia
supplies e-

consumes e-

(Same principle is applied in anodic protection (in the case of

active-passive metals) which is to be studied later)
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Experimental Polarization Curves

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

Non-ideal Experimental Polarization Curves

Use of cathodic polarization data to form the anodic polarization curve in the case of
non-linear anodic data (distorted probably by corrosion products at high currents).

Cathodic Polarization

ia = ic - iapp

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

Instrumentation
Controlled current (galvanostatic) technique

Current is applied at a
pre-determined rate
and the potential is
measured through a
reference electrode

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

Instrumentation
Controlled potential (potentiostatic) technique

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

Reactions on the Auxiliary Anode

During Cathodic Polarization
For the working electrode as an anode, metal dissolution reactions of the type
M Mn+ + ne(1)
are of interest in corrosion.
When the working electrode is polarized as cathode (auxiliary electrode as anode),
M must be selected for the auxiliary electrode with a very noble eM/Mn+ to prevent
anodic dissolution, which would contaminate the electrolyte. Either platinum or
carbon/graphite is the usual choice.
In the absence of anodic dissolution at the auxiliary electrode by reaction (1), other
anodic oxidation reactions are possible to liberate electrons. These include
oxidation in a redox reaction such as
Fe2+ Fe3+ + e(2)
And oxygen evolution by
4OH- 2H2O + O2 + 4e(3)
Reactions (2) and (3) both must operate at potentials below eM/Mn+ (e.g. ePt/Pt3+) so
that nobel-metal auxiliary electrode is not dissolved.
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Home Work Problems

Prbs. 10 and 11 of Ch.3

in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

References

Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

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