Dr.
Fathy Shokry
Fathishoukry@[Link]
Lecture (4) Week 5
Polarization
❑When a metal is not in equilibrium with a solution of its
ions, the electrode potential differs from the equilibrium
potential by an amount known as the polarization. Other terms
having equivalent meaning are overvoltage and overpotential.
The symbol commonly used for polarization is .
❑ The change in potential that is caused by the passage of a
current (cathodic polarization ( c ) or anodic polarization ( a )
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polarization refers to the potential shift away from the open circuit potential (free
corroding potential) of a corroding system. If the potential shifts in the "positive"
direction (above Ecorr ), it is called "anodic polarization". If the potential shifts in the
"negative" direction (below Ecorr ), it is called "cathodic polarization".
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[Link] explain why concentration polarization is not normally rate
controlling for oxidation reactions
[Link] polarization is not normally rate controlling for oxidation
reactions because there will always be an unlimited supply of metal atoms at the
corroding electrode interface.
2.(a) Cite the major differences between activation and concentration
polarizations.
(b)Under what conditions is activation polarization rate controlling?
(c)Under what conditions is concentration polarization rate
controlling?
(a) - Activation polarization is the situation wherein a reaction rate is controlled
by one step in a series of steps that takes place at the slowest rate.
-For corrosion, activation polarization is possible for both oxidation and
reduction reactions.
-Concentration polarization occurs when a reaction rate is limited by
diffusion in a solution. For corrosion, concentration polarization is possible
only for reduction reactions.
(b) Activation polarization is rate controlling when the reaction rate
is low and/or the concentration of active species in the liquid solution
is high.
(c) Concentration polarization is rate controlling when the
reaction rate is high and/or the concentration of active
species in the liquid solution is low.
(a)Describe the phenomenon of dynamic equilibrium as it applies to
oxidation and
reduction electrochemical reactions.
(b) What is the exchange current density?
(a)The phenomenon of dynamic equilibrium is the state wherein oxidation and
reduction reactions are occurring at the same rate such that there is no net
observable reaction.
(b)The exchange current density is just the current density which is related to
both the rates of oxidation and reduction (which are equal) according to the
following equation for the dynamic equilibrium state.
3. Zinc experiences corrosion in an acid solution according to the reaction
The rates of both oxidation and reduction half-reactions are controlled by
activation polarization.
(a) Compute the rate of oxidation of Zn
(in mol/cm2-s) given the following
activation polarization data:
(b) Compute the value of the corrosion potential.
setting VH VZn leads to
b)
4- The influence of increasing solution velocity on the overvoltage-
versus-log current density behavior for a solution that experiences
combined activation–concentration polarization is indicated in the
illustrated fig. On the basis of this behavior, make a schematic plot of
corrosion rate versus solution velocity for the oxidation of a metal;
assume that the oxidation reaction is controlled by activation
polarization.
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The corrosion rate initially increases with increasing solution velocity (for
velocities v1, v2, and v3), corresponding to intersections in the concentration
polarization regions for the reduction reaction. However, for the higher solution
velocities (v4 and v5), the metal oxidation line intersects the reduction reaction
curve in the linear activation polarization region, and, thus, the reaction becomes
independent of solution velocity.
5- Lead experiences corrosion in an acid solution according to the
reaction
The rates of both oxidation and reduction half-reactions are controlled by
activation
polarization.
(a) Compute the rate of oxidation of Pb (in mol/cm2-s) given the following
activation polarization data:
(b) Compute the value of the corrosion potential
Final answers
-6.055 -7 2
ic = 10 = 8.81 x 10 A/cm
r = 4.56 x 10 -12 mol/cm 2 - s
Vc = -0.0167 V
6-The corrosion rate is to be determined for some divalent metal M in a
solution containing hydrogen ions. The following corrosion data are
known about the metal and solution:
(a) Assuming that activation polarization controls both oxidation and
reduction reactions, determine the rate of corrosion of metal M (in
mol/cm2-s).
(b) Compute the corrosion potential for this reaction.
Final answers
i c = 6.31 x 10 A/cm
-8 2
r = 3.27 x 10 -13 mol/cm 2 - s
Vc = - 0.42 V
❑ In practical situations, polarization is sometimes defined as
the potential change away from some other arbitrary potential
(often the mixed potential or the free corrosion potential, will be
discussed later).
Polarization can also be expressed by E.
E = E – Ecorr =
❑Polarization is an extremely important corrosion parameter
which enables useful statements to be made about the rates of
corrosion processes.
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