Polarization

▪ Thermodynamics –
– the equilibrium between metals and their
environment

– The change in potential that is caused by the

passage of a current
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.
▪ Polarization is a deviation of the electrochemical
process from equilibrium due to an electric current
passing through the galvanic cell.
▪ Polarization may occur either at the cathode
(cathodic polarization) or at the anode (anodic
polarization). Cathodic polarization is common.
Polarization and Overpotential
Equilibrium potential for cathodic reaction = Eoc

Equilibrium potential for anodic reaction = Eoa

Real potential = E

Cathodic Overpotential ηc = E – Eoc < 0

anodic Overpotential ηa = E – Eoa > 0

 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
The Polarized Cell
How Polarization is Measured
▪ The deviation from equilibrium causes an
electrical potential difference between the
polarized and the equilibrium (unpolarized)
electrode potential known as overpotential
▪ There are three types of polarization:

▪ Activation polarization
▪ Concentration polarization
▪ Resistance polarization
▪ Activation polarization
▪ An electrochemical reaction proceeds
through several successive steps.
The reaction rate is controlled by the
slowest step (rate-determining step) of the
process.
An energy barrier of should be overcome for
proceeding the rate-determining step of the
process. The activation energy required for
overcoming the barrier changes the
electrode potential.
▪ Activation polarization is the overpotential
(change of the electrode potential) caused
by overcoming the energy barrier of the
slowest step of the electrochemical reaction
 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 overpotential
 Activation Polarization
– The polarization necessary for the
electrochemical reaction to go at the given rate
– Given by Tafel’s Law:

i
E = Eo + b log
io
E = potential at current i
Eo = potential at current io
b = Tafel slope
▪ Common cause of cathodic activation polarization is the the reaction of
Hydrogen formation and evolution at the cathode surface:

▪ First step: reduction of the hydrogen ions resulted in formation of

atomic hydrogen on the cathode surface.

▪ H + + e- = H
▪ Second step: formation of molecules of gaseous hydrogen.

▪ 2H = H2

▪ Third step: formation of hydrogen bubbles.

▪ H2 + H2 + H2 +H2 + ... = nH2

▪ 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.

At the equilibrium (non-polarized) state the rates of oxidation and

reduction reactions proceeding at any electrode are equal. For
example the ions of Cu are receiving electrons on the electrode surface
and transfer from the electrolyte to the copper deposit. In parallel the
same number of copper atoms give up their electrons and dissolve in
the electrolyte.
▪ Reduction:
Cu++ + 2e- = Cu

Oxidation:
Cu = Cu++ + 2e-

The processes produce two equal electric

currents in opposite directions. The
current passing through the electrode
surface in the equilibrium (non-polarized)
state at any direction is called exchange
current.
▪ The activation polarization overpotential may be calculated
by the Tafel equation:

▪ ηact =-(RT/αnF)ln(i/i0) = 2.3(RT/αnF)log(i/i0) for cathodic

activation polarization
ηact = (RT/αnF)ln(i/i0) = 2.3(RT/αnF)log(i/i0) for anodic
activation polarization
▪ Where
R - gas constant R=8.3143 J/(mol*K);
T - temperature, K;
n - number of electrons transferred by one ion;
F - Faraday constant F=96500 C/mol (C-coulombs);
α - electron transfer coefficient (0<α<1);
i - current density;
i0 - current exchange density.
▪ The factor β = 2.3(RT/αnF) is called Tafel
slope and then activation polarization:

▪ ηact = βlog(i/i0)
 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.
▪ The net reaction rate and net current
density are zero
 Hydrogen Overpotential
▪ Hydrogen evaluation at
a platinum electrode:
– H+ + e- → Hads

– 2Hads → H2

▪ Step 2 is rate limiting

step and its rate
determines the value of
hydrogen overpotential
on platinum
 Tafel Equation
▪ Activation polarization (η) increases with
current density in accord with Tafel
equation: i
 =   log
io

▪ The Tafel constant is given by:

2.3RT
β=
αnF
 E-log i and Evans Diagrams
▪ Plot E against log |i|, then activation
Eo and io for the
polarization gives a straight line
cathodic reaction
Anodic reaction, Tafel slope
Mixed equilibrium
Tafel slope Eis
corr and
occurs icorr for
Cathodic
expressed
when the
sum reaction,
as
of
Electrode Potential

positive corrosion reaction

mV Tafel
all currents slope is
perisdecade
zero
Eo and io for the negative
of current
anodic reaction
mV

log (-i2) - log (-i1)

log |current|
 Concentration Polarization
▪ Sometimes the mass transport within the solution may be
rate determining – in such cases we have concentration
polarization
▪ Concentration polarization of an electrode is a result of
formation of a Diffusion layer adjacent to the electrode
surface where there is a gradient of the ion concentration.
▪ Concentration polarization implies either there is a
shortage of reactants at the electrode or that an
accumulation of reaction product occurs
 Concentration Polarization

▪ Additional polarization caused by drop in

concentration of a reactant at the
electrode surface
▪ As concentration falls, more polarization is
needed to make the current flow
▪ Eventually, no more current can flow
because no more reactant can reach the
metal, and a limiting current is reached
▪ Diffusion of the ions through the layers
controls the electrochemical reaction
(corrosion, Electroplating). The electrode
potential may be calculated according to the
Nernst equation:

E = E0 - (RT/nF)ln(Cion)
▪ Where:
E0 - Standard electrode potential, V;
R - gas constant R=8.3143 J/(mol*K);
T - temperature, K;
n - number of electrons transferred by one
ion;
F - Faraday constant F=96500 C/mol (C-
coulombs);
Cion - molar activity (concentration) of ions.
▪ The concentration within the diffusion layer
changes from Cb (bulk concentration) to Cs
(concentration at the electrode surface).
Correspondingly the electrode potential
changes within the diffusion layer:
from
Eb = E0 - (RT/nF)ln(Cb)
to
Es = E0 - (RT/nF)lnC(s)
▪ The difference between Es and Eb is called concentration
overpotential, which is the measure of the concentration polarization:

ηc = Es - Eb = (RT/nF)ln(Cs/Cb)

The concentration overpotential may be also expressed through the

values of the electric current and limiting electric current passing
through the diffusion layer:

ηc = Es - Eb = (RT/nF)ln(1-i/iL)

Concentration polarization may be lowered by increasing agitation and

rising the electrolyte temperature.
▪ Fick’s Law: dn
= −D
dc
 10 −3 (1)
dt dx
▪ 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
w I i
▪ Faraday’s law: = = (2)
At AnF nF

▪ Under steady state, mass transfer rate =

reaction rate
C B − C0
i = DnF  10 −3 (3)

▪ Maximum transport and reaction rate are
attained when C0 approaches zero and the
current density approaches the limiting
current density:

C −3
iL = DnF 10 (4)

▪ 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

C −3
iL = DnF  10 (5)
t
 Overpotential due to concentration
polarization

▪ If copper is made cathode in a solution of

dilute CuSO4 in which the activity of cupric
ion is represented by (Cu+2 ), then the
potential φ1 , in absence of external current,
is given by the Nernst equation:
2.3RT 1 2.3RT
1 = 0.337 − log 2+
= 0.337 + log(Cu 2+
)
nF (Cu ) nF
 ▪ 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:

2.3RT 1 2.3RT
2 = 0.337 − log 2+
= 0.337 + 2+
log(Cu )S
nF (Cu )S nF
▪ 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:

2+
2.3RT (Cu )S
2 − 1 = log 2+
nF (Cu )
 2+ it
2+
(Cu ) S = (Cu ) −
DzF
2+ iLt
(Cu ) =
DzF

2.3RT  i 
 Conc =  2 − 1 = log1 − 
nF  iL 
 Concentration Polarization
▪ Oxygen reduction is often affected by
concentration polarization
Rate of cathodic oxygen
Rate of cathodic
reduction oxygen
without
Electrode Potential

reduction
concentration with
polarization
Limiting current
concentration density -
polarization
rate of reaction limited by
availability of oxygen at
the metal surface

log |current density|

 Resistance Polarization
▪ If there is a resistance between the anode
and the cathode in a cell, then the current
flowing through that resistance will cause a
potential drop given by Ohm’s Law:
V = IR
▪ This is important for paint films and for high
resistance solutions
▪ 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
il
k

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 = l il
R=
k k
Resistance Polarization
Resistance Polarization
causes potential of anode
and cathode to differ due
to potential drop across
Electrode Potential

solution, hence corrosion

current is reduced

log |current density|

 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
 Combined Polarization
▪ During anodic dissolution of a metal
concentration polarization is not important:
i
ηdiss = β log
io
▪ During reduction reaction at an electrode
both types of polarization have to be taken
into account:
i RT  i 
ηred = − β log + 2.3 log 1 − 
io nF  iL 
 Passivation
▪ When a passive film is formed, this causes a
marked drop in current density due to the
resistance of the film and its effect as a
barrier to diffusion
▪ This effect is seen on the anodic curve
 Passivation
When aRapidThe rate
stable of corrosion
passive film will be
rate of cathodic
has formed, critically
the affected
current has by the
reaction leads to passivation,
Lower
a steady, low cathodic
rate
value of - curve
cathodic
the
and low rate of corrosion
Electrode Potential

But
Current
reaction
passive it slow
may
fallsalso
leads
current as
to the
density lead to and
low
passive
activity,
Very cathodic reaction
film rate
startsofof
corrosion?
torate
form
Active corrosion gives normal
high
leads rate
to low of -corrosion
corrosion the
activation polarizationactive-passive transition

log |current density|

 Ex. Polarization Curves
▪ Iron in hydrochloric acid
Electrode Potential

Anodic iron dissolution

Cathodic hydrogen evolution

log |current density|

 Polarization Curves
▪ Iron in sulphuric acid
Electrode Potential

Anodic iron dissolution (with

active-passive
Oxygen evolutiontransition)
on passive
film (or transpassive corrosion
Cathodic
as metalhydrogen evolution
is oxidised to a
higher oxidation state)

log |current density|

 Polarization Curves
▪ Iron in aerated neutral NaCl solution
Electrode Potential

Cathodic oxygen reduction

Anodic iron dissolution
Cathodic hydrogen evolution

log |current density|

 Effect of pH on reaction rate
▪ Consider hydrogen evolution reaction
2H+ + 2e- → H2
▪ The concentration of hydrogen ions will
influence the rate of the reaction
▪ As the hydrogen ion concentration is
increased (i.e. the solution made more acid),
so the rate of the reaction increases
▪ Similarly the potential will influence the
reaction - the more negative the potential
the faster the reaction
Effect of pH and potential on rate
of hydrogen evolution

Slower

Potential

Faster

pH
 Effect of pH on reaction rate
▪ On platinum no metal dissolution will occur,
but to balance the charge a reaction which
creates electrons must occur
▪ If the solution contains dissolved hydrogen,
the reverse of the hydrogen evolution
reaction can occur:
H2 → 2H+ + 2e-
 Effect of pH on reaction rate
▪ H2 → 2H+ + 2e-

▪ This reaction will go faster in alkaline

solution (since H+ will be removed by H+ +
OH- → H2O)

▪ This reaction will go faster at more positive

potentials (because electrons will be
removed from metal)
Effect of pH and potential on rate
of hydrogen oxidation
Oxidation
Faster Reduction
Slower
Potential

Oxidation
Slower Reduction Rates equal
Faster Electrochemical
Equilibrium
pH