ChE 4751

Corrosion Science and Engineering

Md. Jahirul Islam

Lecturer
Department of Chemical Engineering
Dhaka University of Engineering and Technology, Gazipur
KINETICS: POLARIZATION AND
CORROSION RATES

© Md. Jahirul Islam , Lecturer

 What We Already Know…

Thermodynamics –
• The equilibrium between metals and their environment
• Corrosion tendency of metals
• Qualitative picture of what can happen at a given pH and potential

© Md. Jahirul Islam , Lecturer

But…

• Considerations of equilibrium are irrelevant to the study of

corrosion
• Some metals with pronounced tendency to react (such as
aluminum) react so slowly that they meet the requirements of a
structural metal

© Md. Jahirul Islam , Lecturer

 Electrode kinetics

• Electrode kinetics is the study of reaction rates at the interface

between an electrode and a liquid.
• The science of electrode kinetics has made possible many
advances in the understanding of corrosion and the practical
measurement of corrosion rates.

© Md. Jahirul Islam , Lecturer

 What is Polarization

• Polarization is the change of potential of an electrode as a result

of the passage of current through it.
• It also refers to the change in the potential of an electrode during
electrolysis, such that the potential of an anode becomes more
noble, and that of a cathode more active, than their respective
reversible potentials (open-circuit electrode potential )

© Md. Jahirul Islam , Lecturer

 The Polarized Cell

Polarized copper–zinc cell.

Polarization diagram for copper–zinc cell.

© Md. Jahirul Islam , Lecturer

 Causes of Polarization

Depending on the type of resistance that limits the reaction rate,

we are talking about three different kinds of polarization
• Concentration polarization
• Activation polarization and
• Resistance (ohmic) polarization or IR Drop

© Md. Jahirul Islam , Lecturer

 Concentration Polarization

 Sometimes the mass transport within the solution may be rate

determining – in such cases we have concentration polarization.

 Concentration polarization implies either there is a shortage of

reactants at the electrode or that an accumulation of reaction
product occurs

© Md. Jahirul Islam , Lecturer

 Concentration Polarization contd..

If copper is made cathode in a solution of dilute CuSO4 then the potential φ1 in absence
of external current, is given by,

When current flows, copper is deposited on the electrode, thereby decreasing

surface concentration of copper ions to an activity (Cu2+ )s. The potential φ2 is then

The difference of potential, φ2 − φ1, is the concentration polarization, equal to

© Md. Jahirul Islam , Lecturer

 Concentration Polarization contd..

• The larger the current, the smaller the surface concentration of copper ion, or the
smaller the value of (Cu2+ )s , thus the larger the corresponding polarization.

• Infinite concentration polarization is approached when (Cu2+ )s approaches zero at

the electrode surface; the corresponding current density that results in this limiting
lower value of (Cu2+ )s is called the limiting current density.

• In practice polarization can never reach infinity; instead, another electrode reaction
takes hold. In this case, the potential moves to that for hydrogen evolution and
hydrogen gas is liberated while copper is simultaneously plated out

2H + + 2e− = H2

© Md. Jahirul Islam , Lecturer

 Concentration Polarization contd..

• If iL is the limiting current density for a cathodic process and i is the applied current
density, it can be shown that

• As i approaches iL, φ2 − φ1 approaches −∞, that is,

minus infinity. This is shown by the plot of φ2 − φ1
versus I

• The limiting current density (A/cm2) can be evaluated

from the expression

• The limiting current density (A/cm2) can be evaluated

from the expression

© Md. Jahirul Islam , Lecturer

 Concentration Polarization contd..

• Should the copper electrode be polarized anodically, concentration of copper

ion at the surface is larger than that in the body of solution.

• The ratio (Cu2+ )/(Cu2+ )s then becomes less than unity and φ2 - φ1 of (5.3)
changes sign.

• In other words, concentration polarization at an anode polarizes the electrode in the

cathodic or noble direction, opposite to the direction of potential change when
the electrode is polarized as cathode.

© Md. Jahirul Islam , Lecturer

 Activation Polarization

• When current flows through the anode and the cathode electrodes,
their shift in potential is partly because of activation polarization.
• Activation polarization is caused by a slow electrode reaction.
• The reaction at the electrode requires an activation energy in order
to proceed.
• The most important example is that of hydrogen ion reduction at a
cathode, 2H+ + 2e− = H2 . For this reaction, the polarization is called
hydrogen overpotential.

© Md. Jahirul Islam , Lecturer

 Overpotential

• Overpotential is defined as the polarization (potential change) of an

equilibrium electrode that results from current flow across the
electrode – solution interface.
• Overpotential, η, is the difference between the measured potential
and the thermodynamic, or reversible, potential; that is,

• In a galvanic cell the existence of overpotential means less energy is

recovered than thermodynamics predicts.
© Md. Jahirul Islam , Lecturer
 Activation Polarization contd..

 At a platinum cathode, for example, the following reactions are thought to occur in
sequence:
H + + e− = Hads
where Hads represents hydrogen atoms adsorbed on the metal surface.
 This relatively rapid reaction is followed by another reaction, namely, adsorbed
hydrogen atoms combining to form hydrogen molecules and bubbles of gaseous
hydrogen:
2Hads = H2
This reaction is relatively slow, and its rate determines the value of hydrogen
overpotential on platinum. The controlling slow step of H+ discharge is not always
the same, but varies with metal, current density, and environment.
© Md. Jahirul Islam , Lecturer
 Activation Polarization contd..
 The cathode is polarized by the hydrogen atoms producing a film covering the
cathode surface. The film affects the process kinetic: it slows down the reaction
between the electrons and hydrogen ions dissolved in the electrolyte.
 The energy barrier must be overcome to proceed with the process. The needed
activation energy for rising above the barrier makes changes to the electrode
potential.
 Activation polarization, η, increases with current density, i, in accord with the Tafel
equation* :

where β and i0 are constants for a given metal and environment and are both dependent on
temperature. The exchange current density, i0, represents the current density equivalent to the equal
forward and reverse reactions at the electrode at equilibrium.
© Md. Jahirul Islam , Lecturer
 Activation Polarization contd..

 A typical plot of activation polarization or

overpotential for H+ discharge is shown in the
Figure.
 At the equilibrium potential for the hydrogen
electrode (−0.059pH), for example, overpotential
is zero.
 At applied current density, i1 , it is given by η, the
difference between measured and equilibrium
potentials. Although usually listed as positive,
hydrogen overpotential values are negative and,
correspondingly, oxygen overpotential values are
positive on the φ scale.
© Md. Jahirul Islam , Lecturer
 Resistance polarization

 Resistance polarization refers to the potential drop due to either the high
resistivity of the electrolyte surrounding the electrode or an insulation effect of
the film on the electrode surface formed by the reaction products.
Resistance polarization may be expressed by the Ohm’s Law:
ηres = iR
Where, i - electric current; R - electrical resistivity.
 If l is the length of the electrode path of cross sectional area s, k is the specific
conductivity, and i is the current density then resistance,
 iR drop in volts =

© Md. Jahirul Islam , Lecturer

 Combined Polarization

• Total polarization of an electrode is the sum of the individual contributions,

ηT = ηa + ηc + ηr
• If neglect IR drop or resistance polarization is neglected then:
ηT = ηa + ηc
• During anodic dissolution of a metal concentration polarization is not important

• During reduction reaction at an electrode both types of polarization have to be

taken into account

© Md. Jahirul Islam , Lecturer

 Effect of Polarizaton on Corrosion

• 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“
• For all metals and alloys in any aqueous environment, cathodic polarization
always reduce the corrosion rate.
• For a non-passive system (e.g. steel in seawater), anodic polarization
always increases the corrosion rate. For systems showing active-to-passive
transition, anodic polarization will increase the corrosion rate initially and
then cause a drastic reduction in the corrosion rate.

© Md. Jahirul Islam , Lecturer

 Polarization Data and Rates of Corrosion

The corrosion current can be calculated from the corrosion potential and the
equilibrium potential if
 The equation expressing polarization of the anode or cathode is known, and
 If the anode – cathode area ratio can be estimated

© Md. Jahirul Islam , Lecturer

 The Area Effect

Usually cathodic reactions are slower than anodic reactions

 For a cathodic reaction to occur, there must be available sites on the metal
surface. Corrosion cells will not work when the cathodic area is too small
for surface sites
 In a galvanic cell, the anode/cathode area ratio is an important factor for
severity of corrosion attack
 A large cathode causes severe attack on a small anode
 If we cannot avoid situations for galvanic corrosion, we may reduce
thinning by making the anode material of large surface area and cathode
of smaller area.
© Md. Jahirul Islam , Lecturer
The Area Effect

© Md. Jahirul Islam , Lecturer

The Area Effect

© Md. Jahirul Islam , Lecturer