CORROSION ENGINEERING

CHAPTER 5
POLARIZATION

Department of Mechanical & Manufacturing Engineering, MIT, Manipal

 CORROSION ENGINEERING

POLARIZATION

• At an intermediate resistance (disturbance from equilibrium)

in the circuit, some current begins to flow and the potentials
of both half-cell reactions move slightly toward each other.

• This change in potential is called polarization.

• The resistance in the circuit depends on a number of

factors, including the resistivity of the media, surface films,
and the metal itself.

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POLARIZATION

• The relationships between polarization reactions at each

half-cell are represented in figure below.

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POLARIZATION

• The intersection of the two polarization lines (curves) closely

approximates the corrosion current and the combined cell
potentials for the freely corroding situation.

• Once the corrosion current is determined, the corrosion

density can be calculated by determining the surface area.

• Using Faraday’s laws, a corrosion rate in terms of metal

loss per unit time can be determined.

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POLARIZATION

• Polarization data helps in determining corrosion rate and

severity of corrosion.

• As polarization increases, corrosion decreases.

• Because of isolating barriers developing at the interface

between electrode and electrolyte.

• Polarization may be preferable to either cathodic or anodic

reactions.

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POLARIZATION

• Understanding the influence of environmental changes on

polarization can offer insight into controlling corrosion.

• In iron–hydrochloric acid system, hydrogen gas formation at

the cathode can actually slow the reaction.

• Due to increased current resistance by blocking access of

hydrogen ions to the cathode site.

• This results in cathodic polarization and lowers the current

flow and corrosion rate.

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 CORROSION ENGINEERING

POLARIZATION

• If oxygen is bubbled through the solution, the hydrogen is

removed more rapidly by combining to form water and the
corrosion rate increases significantly.

• There are three basic causes of polarization

• activation,

• concentration,

• resistance

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 CORROSION ENGINEERING

ACTIVATION POLARIZATION

• Refers to an electrochemical process that is controlled by

the reaction sequence at the metal electrolyte interface.

• This can be easily illustrated by considering hydrogen

evolution reaction on zinc during corrosion in acid solution.

• Figure shows some of the possible steps in hydrogen

reduction on a zinc surface.

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ACTIVATION POLARIZATION

Steps involved in hydrogen reduction reaction under activation

control

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ACTIVATION POLARIZATION

These steps can also be applied to the reduction of any

species on a metal surface.

• Step 1 – Adsorption of H+ on the surface.

• Step 2 – Reduction of H+ ions.

• Step 3 – Reduced species coming together to form H2

molecule.

• Step 4 – Hydrogen bubbles formed by combination of H2

molecules

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 CORROSION ENGINEERING

ACTIVATION POLARIZATION

• The speed of reduction of the hydrogen ions will be

controlled by the slowest of these steps.

• Activation polarization arises out of a slow step in the

electrode reaction for which an activation energy in the form
of an increment in potential is required for the reaction to
proceed.

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ACTIVATION POLARIZATION

• Either the electron transfer step (step 2) or the formation of

hydrogen molecules (step 3) is deemed the slowest step.

• Hence, in the reaction sequence, the rate of overall reaction

will depend on how fast or slow it proceeds.

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 CORROSION ENGINEERING

ACTIVATION POLARIZATION

• Therefore, to have a higher rate of reaction, expressed in

terms of increased current density, an increase in potential
should be effected.

• The relationship between reaction rate and change in

potential (overvoltage) is expressed by the Tafel equation:

a = ±  log (i / i0)

where ηa is overvoltage polarization (in volts), and β is a constant,
called the Tafel constant (also expressed in volts), and is usually of
the order of 0.1V.
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 CORROSION ENGINEERING

ACTIVATION POLARIZATION

• A graphical representation of the above Equation, as

applied to the hydrogen evolution reaction, with a β slope of
0.1V is shown in the next Figure.

• It can be noted from the graph that 0.1V change in

overvoltage can effect a tenfold increase or decrease in the
reaction rate.

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ACTIVATION POLARIZATION

• Dissolution reactions (anodic) in corrosion are usually

controlled by activation polarization where the solution of
ions is the probable rate-controlling step.

• Hydrogen evolution reactions (cathodic reactions) are

controlled by activation polarization when the concentration
of hydrogen ions is high.

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ACTIVATION POLARIZATION

FACTORS AFFECTING ACTIVATION POLARIZATION

• Current Density: Activation polarization increases with
current density i, in accordance with the equation:

a = ±  log (i / i0)

• Materials: Activation polarization varies with one metal to

another because of the specific effect of current density.

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FACTORS AFFECTING ACTIVATION POLARIZATION

• Temperature: Increased temperatures decrease polarization
as less activation energy would be needed

• Pressure: Hydrogen over-voltage decreases rapidly with

increasing pressure.

• Agitation: It has no effect on activation polarization, because

it is a charge transfer process involving electrons and not a
mass transfer.

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CONCENTRATION POLARIZATION

• A build up or depletion of ions at the electrode surface as a

result of reaction will change the value of the electrode
potential according to the Nernst equation.

• For example, for a corroding zinc electrode, the

concentration of zinc will increase with dissolution in the
vicinity of the electrode.

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• The value of aoxid in the equation increases, causing the

electrode potential to shift in a positive direction.

• For the hydrogen evolution reaction, the higher rate of

discharge of hydrogen ions at the electrode surface brings
down the value of aoxid and the electrode potential,
according to the Nernst equation, shifts in a negative
direction.

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 CORROSION ENGINEERING

CONCENTRATION POLARIZATION

• However, the rate of discharge of hydrogen ions at the

electrode surface depends on the diffusion of hydrogen ions
from the bulk of the solution to the surface.

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 CORROSION ENGINEERING

CONCENTRATION POLARIZATION

• A mathematical expression for concentration polarization

involves il and is given by:

• where ηc is overvoltage due to concentration polarization (in

volts). A graphical representation of the equation is shown in
the next figure.

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CONCENTRATION POLARIZATION

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CONCENTRATION POLARIZATION

• Concentration polarization refers to electrochemical reactions

that are controlled by the diffusion in the electrolyte.

• This is also illustrated in the figure for the case of hydrogen

evolution.

• Here the number of hydrogen ions in the solution is quite small,

and reduction rate is controlled by the diffusion of hydrogen
ions to the metal surface.

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CONCENTRATION POLARIZATION

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CONCENTRATION POLARIZATION

• Concentration polarization generally predominates when the

concentration of the reducible species is small.

• In most instances concentration polarization during metal

dissolution is usually small and can be neglected; it is only
important during reduction reactions.

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CONCENTRATION POLARIZATION

• More often, the reduction process is controlled by a

combined polarization — that is, activation polarization at
lower reaction rates and concentration polarization at higher
reaction rates — as i approaches il.

• A graphical representation of such combined polarization is

shown in the next Figure.

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 CORROSION ENGINEERING

CONCENTRATION POLARIZATION

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 CORROSION ENGINEERING

Polarization

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