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Electrochemical Kinetics
Basics
Current density
The rate of a homogeneous reaction, vr:
1 dn
vr 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,
dn
vr
dt
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
1 dn
v 1
A dt
The unit for v is mol dm-2 s-1.The rate of an electrode process is proportional to
the current density
1 dq
j
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 .
zF dn
j 2
A dt
j zF v 3
1
Lecture 3
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.
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.
jc j a j0
the anodic and cathodic current densities are the same and equals to j0, the
exchange current density.
jc j a
2
Lecture 3
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.
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.
3
Lecture 3
Reaction mechanisms
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)
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.
4
Lecture 3
Ga(2)
Gc(2)
G nFE
Gc
Ga
O + ne-
Reaction coordinate
R O + ne-.
Gc(2) = Gc + nF 5.a
5
Lecture 3
The quantity relates to the symmetry of the energy barrier. 0 < <1
We can write the Arrhenius equation for the forward and back reactions:
Gc
k f A f exp
RT
For backward (anodic) reaction:
Ga
k b Ab exp
RT
From 5.a and 5.b we get
Gc = Gc(2) - zF
and
Ga = Ga(2) + (1-)zF
So we can write:
Gc zF
k f A f exp exp
RT RT
kb Ab exp
Ga
exp
1 zF
RT RT
But since the first part of both equations are potential independent we do not
need to consider them further and can write:
zF
k f k 0f exp 6.a
RT
6
Lecture 3
Gc
That is: k 0f A f exp
RT
and
kb kb0 exp
1 zF 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.
Recall Eq. 3:
I
j zF v
A
v , k ,f cox
1
v 0
k f cox 7.
A
0
where the rate refers to unit surface area, and cox is the concentration of
oxidized form at the surface.
1
jc zF 0
k f cox for a cathodic process
A
7
Lecture 3
1
ja zF 0
kb cred for an anodic process
A
j jc j a
and
j zF k f cox
0
kb cred
0
The mass transport is fast, therefore the surface concentrations are identical to
the concentrations in the bulk phase.
j zF k 0f cox exp
zF
kb0 cred
1 zF
0 0
exp 8.
RT RT
zF 0 1 zF 0
j0 zF k 0f cox
0
exp zF kb0 cred
0
exp
RT RT
zF e 0 0 1 zF e
j zF k 0f cox
0
exp kb cred exp
RT RT
8
Lecture 3
zF zF e
j zF k 0f cox
0
exp exp 9.
RT RT
zF
j j0 exp
RT
and
j j0 exp
zF
exp
1 zF
RT RT