University of Technology Corrosion Engineering Lecturer: Basheer Ahmed

Chemical Engineering Dept. 4th Class

POLARIZATION
The shift of potentials from their equilibrium value on application of an external
current is called polarization.

Activation polarization
Activation polarization is caused by a slow electrode reaction step , the reaction at the electrode
requires an activation energy in order to proceed , the most important example is the hydrogen
ion reduction reaction at a cathode:

2H+ + e- → H2
For this reaction, the polarization is called hydrogen over-potential
Over-potential is defined as the polarization (potential change) of an equilibrium electrode that
results from current flow across the electrode-solution interface.
Hydrogen ion reduction is done by the following steps:
1-adsorption of hydrogen ion from solution to metal electrode
2-electron transfer from zinc to form hydrogen atom
3-cobining of two hydrogen atoms to form a molecule of hydrogen
2H→ H2
4-the coalescence of many hydrogen molecules to form a bubble

Activation polarization

Lecturer
Basheer Ahmed
Chem. Eng. Dept.
University of Technology
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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

Factors affecting activation polarization

1-current density: where activation polarization increases with current density
2- Materials: Activation polarization varies with one metal to another because of the specific
effect of current density.
3- Surface Roughness: Activation polarization is high on a smooth surface compared to a shiny
surface.
4- Temperature: Increased temperatures decrease polarization as less activation energy would
be needed and the exchange current density would be increased.
5- Pressure: Hydrogen over-voltage increases rapidly with decreasing pressure.
6- pH: Over-voltage increase initially and decreases with increased pH value.
7- Agitation: It has no effect on activation polarization, because it is a charge transfer process
involving electrons and not a mass transfer.
8- Adsorption of Ions: The hydrogen overvoltage is decreased by adsorption of anions and
increased by adsorption of cations.
Concentration polarization
Consider the hydrogen evolution reaction at low reduction rate the distribution of hydrogen
ions in the solution adjacent to the electrode surface is relatively uniform ,while at high reduction
rate the region adjacent to the electrode surface will becomes depleted of hydrogen

Effect of various factors on concentration polarization

1-Agitation. By agitation, the thickness of the diffusion layer is decreased, and the rate of
diffusion of ions increases. There is no build up of any concentration gradient between the
corroding surface and bulk electrolyte. The end result is a decrease in concentration
polarization and an increase in the rate of corrosion. As the rate of agitation is increased the
corrosion potential shifts in the noble direction because of a decrease in cathodic over-
potential caused by concentration polarization.
2-Temperature. As the temperature rises, the thickness of diffusion layer is decreased and the
corrosion current is increased.
3-Velocity. The higher the velocity, the less is concentration polarization. At a sufficiently high
velocity, concentration polarization becomes zero because the ionic flux is now sufficient to

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

maintain the surface concentration of ions at the electrode/electrolyte surface equal to the bulk
concentration

Combined polarization
Both activation and concentration polarization usually occur at an electrode, at low reaction rates
activation usually controls, whereas at higher concentration becomes controlling .the total
polarization of an electrode is the sum of them as below>

Lecturer
Basheer Ahmed
Chem. Eng. Dept.
University of Technology

3
University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

Determination of Corrosion Rates by Electrochemical Measurements

1- Tafel Extrapolation Method

2- Linear Polarization ( Polarization Resistance)

1- Tafel Extrapolation Method

In this technique, the polarization curves for the anodic and cathodic reactions are
obtained by applying potentials about 300 mV scE well away from the corrosion potential
and recording the current. Plotting the logarithms of current density (log i) vs potential
and extrapolating the currents in the two Tafel regions gives the corrosion potential and
the corrosion current icon. A hypothetical Tafel plot is shown in Fig. 3.19.

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

The rate of hydrogen reduction is determined by the slowest of the steps. The rate, controlling
step, varies with the metals, current density and environment. There is a critical activation energy
needed to surmount the energy barrier associated with the slowest step. The rate of
transformation is controlled by the magnitude of the energy barrier that an atom or ion must
surmount to transform from metal to ion or from ion to metal. The energy that must be acquired
is the activation energy AG*. The relationship between activation polarization and the rate of
reaction is given by the Tafel equation:

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

where (η) is over-potential. A plot of over polarization (ηact) vs log(i) is linear for both anodic
and cathodic polarization. βa and βC are called the Tafel slopes and io is the exchange current
density (Fig. 3.7).

Figure 3.7 Polarization diagram of zinc in contact with its own ions

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

Figure 3.2 shows a partial polarization diagram and related kinetic parameters. For instance,
both Evans and Stern diagrams are superimposed in order for the reader to understand the
significance of the electrochemical behavior of a polarized metal ( M ) electrode in a hydrogen-
containing electrolyte.

Exchange current density (io)

The exchange current density (io) can be defined as the rate of oxidation and reduction reactions
at equilibrium. Specifically, (io) is the current density at which the rate of oxidation and rate of
reduction are equal in a state of equilibrium. Thus, (io) is just the reversible reaction rate at
equilibrium and it is a kinetic parameter, whereas ΔG is a thermodynamic parameter.
Butler-Volmer equation

…. 3-8

𝑖𝑎𝑝𝑝 𝛽𝑎 𝛽𝑐
𝑖𝑐𝑜𝑟𝑟. = 𝑖𝑜 = ( )
𝛥𝐸 𝛽𝑎 + 𝛽𝑐

Eo = Open circuit potential

Lecturer
Basheer Ahmed
Chem. Eng. Dept.
University of Technology

7
University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

(Tafel equation)

𝑖𝑎
ɳa = βa log
𝑖𝑜

𝑖𝑐
and ɳc = βc log
𝑖𝑜

2.303 𝑅𝑇
where βa = anodic Tafel slop
𝛼𝑛𝐹
−2.303 𝑅𝑇
& βc = (1−α)nF
cathodic Tafel slop

T = 25+273 = 298°K
R = 8.314 J/deg.mol
F = Faraday's constant in coulombs/mole
2.303 is a conversion factor to convert natural log to the base 10
and 2.303RT/F= 0.05916 V.

α = It ranges from 0 to 1 Generally, it is assumed that it is located in the center;

here α = 0.5.

At equilibrium ɳ =0 Lecturer
Basheer Ahmed
And 𝑖𝑎 = - 𝑖𝑐 = 𝑖𝑜 Chem. Eng. Dept.
University of Technology
Im = Ia - Ic

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

The exchange current density (𝒊𝒐 ) :-

Is the current density equivalent to the forward and reverse reactions at the
electrode at equilibrium.

Lecturer
Basheer Ahmed
Chem. Eng. Dept.
University of Technology

9
University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

Example 1 :-

When the electrode is anodically polarized to 0.1 V and cathodically polarized to

0.1 V determine im, given 𝑖𝑜 = 10-2 A/cm2 , βa = 0.1 , βc = - 0.1
𝑖𝑎
ɳa = βa log
𝑖𝑜
Lecturer
𝑖𝑎
0.1 = 0.1 log Basheer Ahmed
10−2
Chem. Eng. Dept.
𝑖𝑎 University of Technology
1 = log
10−2

𝑖𝑎 = 0.1
𝑖𝑐
ɳc = βc log
𝑖𝑜

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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

𝑖𝑐
0.1 = -0.1 log
10−2
𝑖𝑐
-1 =log
10−2
𝑖𝑐 = 0.001 A/cm2
𝑖𝑚 = 𝑖𝑎 – 𝑖 𝑐
= 0.1 - 0.001 = 0.099 A/cm2
Example 2
A univalent metal M has βa= 0.2V, βc=-0.2V , io = 20 mA/M , calculate values
of 𝑖𝑎 , 𝑖 𝑐 when the metal is anodically polarized to 0.2V, then find the measured
current density for the same cathodically polarization.

Example 3:-

Calculate the change in cathodic current density at an univalent electrode when

the potential difference changes from 1 V to 2 V at 250C given that α = 0.5

Example 4 :-

Calculate the change in anodic current density under same circumstance in ex.3.

Example 5 :-

A typical exchange current density for 𝐻+ [ discharge at pt is 0.79 mA/m2] at

250C what is the current density at an electrode when its ɳ is :-

a- 10mv , b- 100mv , c- -5 v (Io=079 mA/m2)

Example 6:-

In a linear polarization experiment, a current increase of 10 μA for a voltage

increase of 4 mV is recorded. The area of specimen is 10 cm2. Calculate the:-

a- Polarization resistance
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University of Technology Corrosion Engineering Lecturer: Basheer Ahmed
Chemical Engineering Dept. 4th Class

b- Rate of corrosion

βa= 0.01 V/ decade , βc= 0.02 V/decade

problem 4:-

The following polarized data were obtained by polarizing a metal in deaerated

acid solution

ɳ = 𝐸 − 𝐸𝑐𝑜𝑟𝑟. mv = 20 10 0 -10 -20

𝑖 = 𝑚𝐴/𝑚2 = 0.1 0.05 0 - 0.09 - 0.14

Find Rp

Lecturer
Basheer Ahmed
Chem. Eng. Dept.
University of Technology

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