Polarization

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
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
Let us look at a Zn-H Cell
(a)
(b)
The Zn electrode moves away from equilibrium
by the removal of negative charges from the Zn
plate and positive ions are released from the Zn
plate to the liquid (a)
Zn is dissolved at the same rate as electrons are
transported to the Pt plate, where they are
consumed in the hydrogen reaction
The same cell process can be totally obtained on
a Zn plate submerged in a solution containing
hydrogen ions and Zn ions (b)
The reactions are accompanied by the same
changes in free enthalpy and have the same
equilibrium potentials as before
However, there is a higher resistance against the
hydrogen reaction on the Zn plate than on Pt,
and thus the reaction rate will be lower on the Zn
surface
So We Also Need to Know



Electrode kinetics to predict the corrosion
rates for the actual conditions

Polarization and Overpotential
Electrode reactions are assumed to induce
deviations from equilibrium due to the passage of an
electrical current through an electrochemical cell
causing a change in the electrode potential. This
electrochemical phenomenon is referred to as
polarization.

The deviation from equilibrium causes an electrical
potential difference between the polarized and the
equilibrium (unpolarized) electrode potential known
as overpotential
Polarization and Overpotential
Equilibrium potential for cathodic reaction = E
oc


Equilibrium potential for anodic reaction = E
oa


Real potential = E

Cathodic Overpotential
c
= E E
oc
< 0

anodic Overpotential
a
= E E
oa
> 0

The Polarized Cell
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, I
o
, and
(more frequently used) exchange current
density, i
o
.
The net reaction rate and net current density
are zero
How Polarization is Measured
Causes 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
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
-
H
2
, the
polarization is termed as hydrogen overpotential
Hydrogen Overpotential
Hydrogen evaluation at
a platinum electrode:
H
+
+ e
-
H
ads


2H
ads

H
2

Step 2 is rate limiting
step and its rate
determines the value of
hydrogen overpotential
on platinum
Tafel Equation
Activation polarization () increases with
current density in accord with Tafel equation:



The Tafel constant is given by:

o
i
i
log | q =
nF
RT

3 . 2
=
Overpotential
Values
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
Concentration Polarization: reduction of
oxygen
O 2H 4e 4H O
2 2
+ +

Contd..
Ficks Law:

where dn/dt is the mass transport in x direction in
mol/cm
2
s, D is the diffusion coefficient in cm
2
/s, and c is
the concentration in mol/liter

Faradays law:

Under steady state,
mass transfer rate = reaction rate

(1) 10
3
=
dx
dc
D
dt
dn
(2)
nF
i
AnF
I
At
w
= =
(3) 10
3
0

=
o
C C
DnF i
B
Contd..
Maximum transport and reaction rate are
attained when C
0
approaches zero and the
current density approaches the limiting
current density:
(4) 10
3
=
o
C
DnF i
L
Contd..
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

Equations (1) to (4) are valid for uncharged
particles, as for instance oxygen molecules

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
Contd..
(5) 10
3
=
t
C
DnF i
L
o
Overpotential due to concentration polarization

If copper is made cathode in a solution of
dilute CuSO
4
in which the activity of cupric
ion is represented by (Cu
+2
), then the
potential
1
, in absence of external current,
is given by the Nernst equation:

) log(Cu
3 2
0.337
) (Cu
1
log
3 2
0.337
2
2
1
+
+
+ = =
nF
RT .
nF
RT .
|
Contd..
When current flows, copper is deposited on
the electrode, thereby decreasing surface
concentration of copper ions to an activity
(Cu
2+
)
s
. The potential
2
of the electrode
becomes:

S
2
S
2
2
) log(Cu
3 2
0.337
) (Cu
1
log
3 2
0.337
+
+
+ = =
nF
RT .
nF
RT .
|
Contd..
Since (Cu
2+
)
s
is less than (Cu
2+
), the
potential of the polarized cathode is less
noble, or more active, than in the absence of
external current. The difference of potential,

2

1
, is the concentration polarization ,
equal to:

) (Cu
) (Cu
log
3 2
2
S
2
1 2
+
+
=
nF
RT .
| |
Contd..
|
|
.
|

\
|
= =
=
=
+
+ +
L
L
S
i
i
nF
RT
DzF
t i
Cu
DzF
t i
Cu Cu
1 log
3 . 2
) (
) ( ) (
1 2 Conc
2
2 2
| | q
o
o
IR Drop
When polarization is measured with a potentiometer and a
reference electrode-Luggin 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 Luggin
probe equals iR.

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 =
k
l
R =
k
il
k
il
Combined Polarization
Total polarization of an electrode is the sum
of the individual contributions,


If neglect IR drop or resistance polarization is
neglected then:

r c a T
+ + =
c a T
+ =
Combined Polarization

Effect of temperature,
concentration and
velocity of the aqueous
environment on combined
polarization is shown in
the figure
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:
o
diss
i
i
log =
|
|
.
|

\
|
+ =
L o
red
i
i
nF
RT
.
i
i
1 log 3 2 log
Anodic and Cathodic Combined Polarization
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

Contd..
If an active metal M is corroding in a
deaerated acid, the metal surface is usually
covered with H
ads
atoms thus acting mostly
as cathode. The open circuit potential is -
0.059pH and if i
corr
>> i
0
for 2H
+
+ 2e
-
H
2

Tafel equation can be used for cathodic
polarization
Contd..
Stern-Gray Equation:
|
|
.
|

\
|
+
=
a c
a c
appl
corr


.
i
i
3 2
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.
The Area Effect
Copper plates with steel rivets in
seawater
Steel rivets severely attacked
Large cathode/small anode
Steel plates with copper rivets in
seawater
Tolerable corrosion of steel plate
Small cathode/large anode
Influence of Polarization on Corrosion Rate
Lead immersed in H
2
SO
4
Magnesium exposed to
natural waters
Iron immersed in a
chromate solution
Zinc in H
2
SO
4
Iron exposed to natural
waters
Porous insulating covering
a metal surface