Corrosion Engineering

ChE 3219

Kazi Md Asif
Lecturer, Department of Chemical Engineering ,
KUET.
Polarization
 What is polarization

◎ Previously, our consideration of potentials has dealt with equilibrium

considerations when no current actually existed between the
cathode and the anode.
◎ When a net current to or from an electrode exists, the electrode is
no longer in equilibrium and the measured potential is altered.
The alteration being such as to oppose the current.
◎ All corrosion reactions involve current flow and will
alter the potential of the metal surfaces involved.

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Polarization

◎ The deviation from equilibrium causes an electrical potential

difference between the polarized and the equilibrium
(unpolarized) electrode potential known as over potential
Polarization

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Polarization

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Polarization curve

Note that the potential difference will not

be zero even when the resistor is shorted
since there is internal resistance in the
electrolyte.

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 Exchange current density

◎ At the equilibrium potential of a reaction, a

reduction and an oxidation reaction occur,
both at the same rate.
◎ For example, on the Zn electrode, Zn ions
are released from the metal and discharged
on the metal at the same rate
◎ The reaction rate in each direction can also
be expressed by the transport rate of electric
charges, i.e. by current or current density,
called, respectively, exchange current, Io, and
(more frequently used) exchange current
density, io. 7
 Types of polarization

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

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

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 Activation polarization
◎ When current flows through the anode and the cathode
electrodes, their shift in potential is partly because of activation
polarization
◎ An electrochemical reaction may consist of several steps
◎ The slowest step determines the rate of the reaction which
requires activation energy to proceed
◎ Subsequent shift in potential or polarization is termed activation
polarization
◎ Most important example is that of hydrogen ion reduction at a
cathode, H+ + e- → ½ H2, the polarization is termed as hydrogen
over potential.
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Activation polarization

1. Hydrogen evaluation at
a platinum electrode:
H+ + e- → Hads
2. 2H ads → H2
Step 2 is rate limiting
step and its rate
determines the value of
hydrogen over potential
on platinum

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 Activation Polarization
◎ Activation polarization (η) increases with current density in
accord with Tafel equation

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Activation polarization

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 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

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 Concentration polarization

◎ Because of its low

solubility in seawater,
the amount of
oxygen in contact with the
cathode areas is small and
readily consumed by the
reaction. For the
reaction to continue,
additional oxygen must
therefore diffuse to these
areas
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Concentration polarization
◎ Concentration polarization effects can also occur in the
corrosion of metals in acid solutions. When a chemical species
participating in a corrosion process is in short supply.(Dilute
solution).
◎ The most typical concentration polarization occurs when there
is a lack of reactants, and (in corroding systems) therefore most
often for reduction reactions.
◎ This is the case because reduction usually implies that ions or
molecules are transported from the bulk of the liquid to the
electrode surface, while for the anodic (dissolution) reaction,
mass is transported from the metal, where there is a large
reservoir of the actual reactant
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Concentration polarization

◎ Fick’s Law:

where dn/dt is the mass transport in x direction in mol/cm2s, D is the diffusion

coefficient in cm2/s, and c is the concentration in mol/liter

◎ Faraday’s law:

◎ Under steady state, Mass transfer rate = reaction rate

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 Concentration polarization

◎ Maximum transport and reaction rate are attained when C0

approaches zero and the current density approaches the limiting
current density.

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 Concentration polarization
◎ If copper is made cathode in a solution of dilute CuSO4 in which
the activity of cupric ion is represented by (Cu2+ ), then the
potential φ1 , in absence of external current, is given by the Nernst
equation

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Concentration polarization

◎ When current flows, copper is deposited on the electrode,

thereby decreasing surface concentration of copper ions to an
activity
(Cu2+ )s . The potential φ2 of the electrode becomes:

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Concentration polarization

◎ Since (Cu2+ )s is less than (Cu2+ ), the potential of the polarized

cathode is less noble, or more active, than in the absence of
external current. The difference of potential, φ2 - φ1 , is the
concentration polarization , equal to

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Concentration polarization

◎ Ion transport number, also called the transference number, is

the fraction of the total electrical current carried in
an electrolyte by a given ionic species
current carried in electrolyte by a given ionic species

total current

Differences in transport number arise from differences in electrical

mobility. For example, in an aqueous solution of sodium chloride,
less than half of the current is carried by the positively charged
sodium ions (cations) and more than half is carried by the negatively
charged chloride ions (anions) because the chloride ions are able to
move faster, i.e., chloride ions have higher mobility than sodium
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ions.
Concentration polarization

◎ If charged particles are considered migration will occur in addition

to the diffusion and the previous equation must be replaced by

where t is the transference number of all ions in solution except the

ion getting reduced

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 Concentration polarization

Protection
1)Increase agitation
2)Anodic Protection 23
IR drop

◎ When polarization is measured with a potentiometer and a

reference electrode- Lugging probe combination, the measured
potential includes the potential drop due to the electrolyte
resistance and possible film formation on the electrode surface
◎ The drop in potential between the electrode and the tip of Lugging
probe equals iR.

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IR visualization

the working electrode is the anode where

the metal of corrosion testing is set, the
counter electrode(cathode) is required to
complete the electric circuit. The
reference electrode is a potential sensing
probe inserted in the electrolyte between the
two electrodes.

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 IR drop

◎ If l is the length of the electrode path of cross sectional areas, k

is the specific conductivity, and i is the current density then
resistance

◎ iR drop in volts

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Combined Polarization

◎ Total polarization of an electrode is the sum of the individual

contributions

◎ If neglect IR drop or resistance polarization is neglected then:

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Combined Polarization

◎ 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

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Combined Polarization

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 Combined Polarization
A potentiostat is an electronic
instrument that controls the voltage
difference between a Working
Electrode and a Reference Electrode.
Both electrodes are contained in an
electrochemical cell. The potentiostat
implements this control by injecting
current into the cell through an Auxiliary,
or Counter, electrode.
In almost all applications, the
potentiostat measures the current flow
between the Working and Counter
electrodes. The controlled variable in
a potentiostat is the cell potential and
the measured variable is the cell
current. 30
 Polarization measurement

The potential is set by potentiostat,

different current is measured at different
potential. And graph is generated. The
intersection of the graph gives Ecorr and
Icorr

Firstly different potential is set and

measured current is plotted. Thus firstly
obtaining anodic polarization curve,
changing the potential polarity to
negative region we obtain the cathodic
polarization curve. Theoritical

Fig: Actual and measured polarization curves for active metals

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 Comparison of polarization diagram
Hydrogen anode

H2 as Cathode
Iron as Anode

Zinc as Anode

- - - lines represent polarization

diagram of zinc Iron as cathode

Fig: Comparison of electrochemical parameters for iron and zinc in solution 32

 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.

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Area effect

Fe2+ \Fe= -0.44

Cu2+ \Cu= 0.342
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Area effect

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Area effect

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Influence of polarization on corrosion rate

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 Influence of polarization on corrosion rate
◎ Both resistance of the electrolyte and polarization of the electrodes limit the
magnitude of current produced by a galvanic cell. For local - action cells on the
surface of a metal, electrodes are in close proximity to each other; consequently,
resistance of the electrolyte is usually a secondary factor compared to the more
important factor of polarization.
◎ When polarization occurs mostly at the anodes, the corrosion reaction is said to be
anodically controlled
◎ When polarization occurs mostly at the cathode, the corrosion rate is said to be
cathodically controlled
◎ Resistance control occurs when the electrolyte resistance is so high that the
resultant current is not sufficient to appreciably polarize anodes or cathodes.
◎ It is common for polarization to occur in some degree at both anodes and cathodes.
This situation is described as mixed control.
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Thank you

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