Corrosion 5 (3)

Oil & Gas Refining Engineering Corrosion Eng.
Lecture (5): Polarization and Corrosion Rates

4th Class In Petroleum Refinery Asst. Lect.: Zainab D. Mohammed
Polarization and Corrosion Rates

Polarization
When there is no net current flows from an electrode, then this electrode
is at equilibrium state and its potential is the equilibrium potential (E ° ).
When net current flows to or from its surface, the potential changes from
E ° to Ei , the electrode is then said to be polarized and the process is termed
as polarization. Polarization is measured in volts as follows:
η = Ei − E °
η = The overvoltage, and Ei = The polarization potential
The Above Figure shows polarization curves (E vs. log i) for the corrosion
of metal in a reducing acid in which there are two exchange processes

involving oxidation of M/M+ and reducing H+/H2.
1
Oil & Gas Refining Engineering Corrosion Eng. Lecture (5): Polarization and Corrosion Rates
Polarization is divided into three main types:

1. Activation Polarization (𝜼𝒂 )
This polarization is caused by a slow electrode reaction or stated in
another way the reaction at the electrode requires activation energy in order
to go. The most important is that of hydrogen ion reduction at the 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. Combining of two hydrogen atoms to form a molecule of hydrogen
2H→ H2
4. The coalescence of many hydrogen molecules to form a bubble
2
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 rough surface

compared to a smooth 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.
2. Concentration polarization(𝜼𝒄 )
Concentration polarization is obtained when the rate of an electrode

reaction is dependent on mass transfer, i.e. the rate at which the reactant is
transported to the surface of the electrode and the rate at which the product
is transported away from the electrode.
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
3
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.
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 maintain the surface
concentration of ions at the electrode/electrolyte surface equal to the bulk
concentration.
4
3. Combined Polarization (𝜼)

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:
𝜂 = 𝜂𝑎 + 𝜂𝑐
How Polarization Measured?

Polarization can be measured using electrochemical corrosion cell and
potentiostat as shown in Figure (1). Electrical connections are shown in
Figure (2).
Figure (1): Schematic diagram of polarization cell.
5
Figure (2): Schematic of potentiostatic anodic polarization wiring diagram.
Polarization corrosion cell was equipped with several necks, which can be
used according to the test conditions:
1. One for the working electrode (metal or test sample).
2. One for reference electrode (SCE, SHE, etc), for potential

measurements.
3. One for thermometer, for temperature control.
4. Counter electrodes.
6
Corrosion Rate Measurements from Polarization Curve
There are two techniques used in corrosion rate measurements:
1. Linear Polarization Technique

https://youtu.be/_YrCSfhx3Zc
The linear polarization technique in principle is a convenient and rapid

way for determining corrosion rates. The technique was started by Wanger
and Traud who stated that the corrosion process with two coupled
electrochemical reactions under activation control can be represented by:
(1)
Equation (1) is derived and simplified by Stern and Geary for relatively
small increment of the exponent (i.e., for potential within about 10 mV of
the corrosion potential). The slope of this linear polarization is related to
the kinetic parameters of the system as follows:
(2)
Where; ba & bc are the anodic and cathodic Tafel slopes respectively.
The Stern and Geary required both anodic and cathodic slopes. For
accurate measurement, it is necessary to determine the values of ba and bc.
For fast corrosion rate calculation assume the values of Tafel slopes in the
range of 120 mV, then equation (2) reduced to:
7
(3)
The ratio of the derivative of the overpotential to the current.𝜕𝜂/𝑑𝑖 when

𝜂 ⟶ 0, represents the resistance in Ohm’s law and is often termed the
charge-transfer resistance or the polarization resistance Rp.
𝑅𝑝 = 𝑑𝜂/𝑑𝑖
𝑑𝑖 𝛼𝑛𝐹
[ ] = −𝑖 𝑜
𝑑𝜂 𝑅𝑇
Example (1)
8
Solution:
Example (2)
Solution:
9
Example (3)
Solution:
Example (4)
Solution:
2. Tafel Extrapolation Technique
In this technique, the polarization curves for the anodic and cathodic
reactions are obtained by applying potentials about 300mVSCE well away
10
from the corrosion potential and recording the current. Plotting the
logarithms of current (log I) vs potential and extrapolating the currents in
the two Tafel regions gives the corrosion potential and the corrosion
current icorr. A hypothetical Tafel plot is shown in Fig. 3.19.
Knowing icorr, the rate of corrosion can be calculated in desired units by
using Faraday’s law.
The applied current polarization curve indicated by points and a solid
line. At low currents the curve is non-linear; but at higher current it
becomes linear on a semi-logarithmic plot.
Applied cathodic current is related to cathodic and anodic current as:
iapp. = ired. - ioxd.
Figure (3): A hypothetical Tafel plot.
11
Example (5)
Solution:
12
13
Example (6)
Solution:
14

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Oil & Gas Refining Engineering Corrosion Eng.

Lecture (5): Polarization and Corrosion Rates

Polarization and Corrosion Rates

of metal in a reducing acid in which there are two exchange processes

Polarization is divided into three main types:

Hydrogen ion reduction is done by the following steps:

Factors affecting activation polarization:

1. Current density: where activation polarization increases with current

2. Materials: Activation polarization varies with one metal to another

3. Surface Roughness: Activation polarization is high on a rough surface

4. Temperature: Increased temperatures decrease polarization as less

5. Pressure: Hydrogen over-voltage increases rapidly with decreasing

6. pH: Over-voltage increase initially and decreases with increased pH

7. Agitation: It has no effect on activation polarization, because it is a

Concentration polarization is obtained when the rate of an electrode

Effect of various factors on concentration polarization

1. Agitation: By agitation, the thickness of the diffusion layer is decreased,

2. Temperature: As the temperature rises, the thickness of diffusion layer

3. Velocity: The higher the velocity, the less is concentration polarization.

3. Combined Polarization (𝜼)

How Polarization Measured?

Figure (1): Schematic diagram of polarization cell.

Figure (2): Schematic of potentiostatic anodic polarization wiring diagram.

1. One for the working electrode (metal or test sample).

2. One for reference electrode (SCE, SHE, etc), for potential

3. One for thermometer, for temperature control.

Corrosion Rate Measurements from Polarization Curve

There are two techniques used in corrosion rate measurements:

1. Linear Polarization Technique

The linear polarization technique in principle is a convenient and rapid

The ratio of the derivative of the overpotential to the current.𝜕𝜂/𝑑𝑖 when

2. Tafel Extrapolation Technique

Figure (3): A hypothetical Tafel plot.

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