Lecture 3

Lecture 3

The reaction rate of a unit surface electrode is proportional to current density.

Electrochemical Kinetics

Polarization, overvoltage
Polarization: the shift in the voltage across a cell caused by the passage of
current, departure of the cell potential from the reversible (or equilibrium or
nernstian) potential.

Basics
Current density
The rate of a homogeneous reaction, vr:

vr

1 dn

1.

dt

where n and are the amount of material and stoichiometric number of a

reactant or product. The unit for vr is mol s-1. Taking stoichiometric number to
be one,

vr

dn
dt

1 dn
A dt

The unit for v is mol dm-2 s-1.The rate of an electrode process is proportional to
the current density

M z ze - M

the cathodic process is a reduction at a rate jc, cathodic current density, while the
anodic process is an oxidation at a rate ja, anodic current density.
At equilibrium a rest or equilibrium potential e is measured against a proper
reference electrode. When electrochemical equilibrium is established

The reaction rate of a heterogeneous process (e.g., an electrode process )

depends on the surface of the electrode at constant polarization potential. The
rate v refers to unit surface area

For a simple reversible redox reaction

jc j a j 0

the anodic and cathodic current densities are the same and equals to j0, the
exchange current density.
Increasing the negative potential:
jc j a

1 dq
A dt

The current density is proportional to rate of an electrochemical reaction and it

makes rate independent of the area of electrode.
An infinitesimal amount of charge dq is proportional to the amount of material
passed through the interface dq zF dn .
j

zF dn
A dt

From equations 1. and 2. we get

j zF v

Fig. 1. Polarization curves

Lecture 3

Lecture 3

The portion of potential differs from equilibrium potential is called overvoltage

( ).

Reaction mechanisms
1.Fast mass transport but rate limiting electron transfer kinetics.

pol e

4.

Processes at electrodes
The rate constant of forward reaction, kf is characteristic to the cathodic
reduction process. The higher the negative polarization potential, the greater the
rate of cathodic reaction.

2. Fast electron transfer but mass transport rate limiting kinetics

Normal homogeneous kinetics at a temperature is characterized a rate constant
independent of the composition of reaction mixture.
Why can an applied voltage affect the kinetics of a reaction?
Question can be answered at the level of equilibrium electrochemistry

G o RT ln K a
and

G o nFE o

Question can be answered at the level of electrochemical kinetics by using the

transition state theory (TST)
Fig. 2. Heterogeneous process at the electrode surface.

Consider a reduction reaction:

O + ze- R
By TST, the species, O with gain an electron and goes through a transition state.
The energy barrier to forming this is called Gc. The c subscript denotes this to
be a cathodic reaction that is a reduction reaction.
The free energy barrier of an electrochemical reaction is linked to the applied
potential.

Mass transport:

reactants are transported from the bulk of solution to the

electrode surface by diffusion
products are transported from electrode to the bulk by
diffusion

Charge transfer: the electron jump between the metal and liquid phase.
The slowest process determines the net rate of the electrode reaction.
Mass transport and charge transfer are the most important steps in controlling
the rate of electrochemical processes.

Lecture 3

Lecture 3

For the back reaction (oxidation of R) we can write:

Ga (2) = Ga (1-)nF

5.b

The quantity relates to the symmetry of the energy barrier. 0 < <1
We can write the Arrhenius equation for the forward and back reactions:

nFE

For forward (cathodic) reaction:

Ga(2)

Gc(2)
Gc

k f A f exp

Ga

O + ne-

Gc
RT

For backward (anodic) reaction:

R

Ga
k b Ab exp
RT

Reaction coordinate

When a potential is applied, the free energy of reactants (O + ne-) is raised by an

amount zFE where E is the applied potential.
When = 0

Energy to reach transition state = Gc.

When > 0

New energy to transition state = Gc(2)

From 5.a and 5.b we get

Gc = Gc(2) - zF
and

The reaction proceeds faster when a negative polarization potential = pol is

applied. As a result:

Ga = Ga(2) + (1-)zF
So we can write:

Gc(2) < Gc.

The converse is true for the back reaction:

k f A f exp

Gc
zF
exp
RT
RT

k b Ab exp

Ga
1 zF
exp
RT
RT

R O + ne-.
For the reduction reaction:
Gc(2) = Gc + nF

5.a

Remember: cathodic potential is negative.

5

But since the first part of both equations are potential independent we do not
need to consider them further and can write:
k f k 0f exp

zF

6.a

RT
6

Lecture 3

Lecture 3

k 0f A f exp

That is:

j a zF

Gc
RT

The net current j can be given as

1 zF
k 0 exp
b

for an anodic process

The constant area of the electrode can be included in rate constants.

and
kb

1
0
k b cred
A

6.b

RT

Now we have two expressions that relate how the forward and back rate
constants for an electron transfer reaction at an electrode are affected by the
applied potential.

j jc j a

and

0
0
j zF k f cox
kb cred

The polarization curve for charge transfer limiting process, j = f()

The mass transport is fast, therefore the surface concentrations are identical to
the concentrations in the bulk phase.

Recall Eq. 3:

Substituting rate constants from 6.a and 6b.

I
zF v
A

1 zF
zF

0
0
j zF k 0f cox
exp
k b0 cred
exp

RT
RT

The rate of a homogeneous process for reaction O + ne- R, can be given

,

k ,f

This is the Butler-Volmer equation and very important in understanding

electrode kinetics. Apart from thermodynamic activation, the exponential term
shows us the potential dependence of rate constant.

cox

and for a reaction at the electrode surface

v

1
0
k f cox
A

At equilibrium potential the cathodic and anodic reaction proceeds at an equal

rate:
7.

0
where the rate refers to unit surface area, and cox
is the concentration of
oxidized form at the surface.

From equations 3. and. 7.

1
0
jc zF k f cox
A

0
j0 zF k 0f cox
exp

zF 0
RT

0
zF kb0 cred
exp

1 zF 0
RT

The j = f() is called polarization curve, therefore equation 8. should be

transformed
From pol e we have,

for a cathodic process

8.

1 zF e
zF e 0 0

0
j zF k 0f cox
exp
k b cred exp

RT
RT

Lecture 3

which can be separated, (showing only for the cathodic part)

zF
zF e
0
j zF k 0f cox
exp
exp

RT
RT

9.

Recognized in equation 9. the part of exchange current density:

zF

j j0 exp

RT

and

zF
1 zF

j j0 exp
exp

RT
RT

This is the equation of a polarization curve giving a current potential

characteristics of an electrochemical process for a metal electrode of clean
surface, crystal parameters, electrolyte composition concentration are known
and the process is charge transfer controlled.

Current vs overpotential curve, transfer coefficient = 0.5

9