Evans Diagrams

Where we left off

Tafel Equation
The Tafel slope is an intensive parameter and does not
depend on the electrode surface area.
i
0
is and extensive parameter and is influenced by the
electrode surface area and the kinetics or speed of the
reaction.
Notice that the Tafel slope is restricted to the number of
electrons, n, involved in the charge transfer controlled
reaction and the so called symmetry factor, o.
n is often = 1 and although the symmetry factor can vary
between 0 and 1 it is normally close to 0.5.
This means that the Tafel slope should be close to 120
mV if n = 1 and 60 mV if n = 2. (The latter is normally not the case)


Butler-Volmer Equation



where:
I = electrode current, Amps
I
o
= exchange current density, Amp/m
2

E = electrode potential, V
E
eq
= equilibrium potential, V
A = electrode active surface area, m
2

T = absolute temperature, K
n = number of electrons involved in the electrode reaction
F = Faraday constant
R = universal gas constant
= so-called symmetry factor or charge transfer coefficient
dimensionless
The equation is named after chemists John Alfred Valentine Butler and
Max Volmer
Butler-Volmer Equation High Field Strength
( )
ial overpotent cathodic high at
exp
ial overpotent anodic high at
1
exp
0 `
0 `
(

=
(

=
RT
nF
i i
RT
nF
i i
c
c
a
a
q o
q o
i
a
and i
c
are
the exhange
current
densities for
the anodic
and cathodic
reactions
These equations can be rearranged to give
the Tafel equation which was obtained
experimentally
Butler Volmer Equation - Tafel Equation
( ) ( )
( )
( )n n
b
i
n
a i
n
a
i b a
i
n
i
n
i
n
i
n
i
nF
RT
i
nF
RT
o o
a
c c
a
c
c c
c
c
c c
c
o o
o o
q
o o
q
o o
q
o o
q

= =
+ =

=
=
=
1
059 0
or
059 0
1
059 0
or
059 0

equation Tafel known well the is equation The
reaction anodic C 25 at
1
059 0
1
059 0
reaction cathodic C 25 at
059 0 059 0
0
0
0
0
0
. .
ln
.
ln
.
log
log
.
log
.
log
.
log
.
ln ln
Current Voltage Curves for Electrode Reactions
Without concentration
and therefore mass
transport effects to
complicate the
electrolysis it is possible
to establish the effects of
voltage on the current
flowing. In this situation
the quantity E - E
e
reflects
the activation energy
required to force current i
to flow. Plotted below are
three curves for differing
values of i
o
with = 0.5.



Current Voltage Curves for Single Electrode Reactions
Current
V
o
l
t
a
g
e

Electrochemical reactions
of different i
0
or

degrees
of reversibility


The iE curves from the
previous slide have
been rotated.
Single Chemical Reaction
Only at appreciable over-
potentials does the
reverse reaction become
negligible
At E
e
the forward
and reverse
currents are equal
Electrochemical reaction which has a large exchange
current density, i
0
, This means that a small applied
voltage results in an appreciable increase in current.
Electrode reactions which
have a high exchange current
density are not easily
polarised. Examples are the
hydrogen evolution reaction
on Pt and AgCl + e Ag + Cl
-

The H
+
/H
2
(Pt) and Ag/AgCl
make good reference
electrodes because they are
not easily polarised
11
Electrochemical reaction in which the i
0
value is very
low. This means that it takes an appreciable over-
potential to produce a significant current.
This electrode is
easily polarisable
since a small
current would
result in a
significant change
in voltage
12
At low overpotential the Butler Volmer equation is linear
(Stern Geary equation)









q
RT
nF
i i
o
=
So far we have looked mainly at
single electrochemical reactions
14

KINETICS OF AQUEOUS CORROSION
Anodic and cathodic reactions are coupled at a
corroding metal surface

Schematics of two distinct corrosion processes.
(a) The corrosion process M + O M
n+
+ R showing the separation of anodic and
cathodic sites. (b) The corrosion process involving two cathodic reactions.
Wagner Traud Method
The cathodic and
anodic reactions
are drawn
together on the
same graph to
show how the
currents are equal
at the corrosion
potential
Butler Volmer graphs for two electrochemical reactions
Note in the previous diagram that:
i
a
= i
c
= i
corr
at the corrosion potential E
corr

E
corr
is a mixed potential which lies between (E
e
)
c
and (E
e
)
a
. In this
case it is closer to (E
e
)
a
because the i
0
and the kinetics of the anodic
reaction is faster.
The metal dissolution is driven by the anodic activation overpotential

a
= E
corr
- (E
e
)
a

The cathodic reaction is driven by the cathodic activation overpotential

c
= E
corr
- (E
e
)
c

The thermodynamic driving force
E = (E
e
)
c
- (E
e
)
a

E is usually large enough to put E
corr
in the Tafel region for both
reactions, i.e. the reverse reaction is negligible.
Evans Diagrams
It is convenient to
represent the linear plots
of i and E as log i/E plots
with the negative cathodic
current plotted positively,
i.e. both the anodic and
cathodic current appear in
the positive quadrant.

The linear region gives us
the Tafel slopes

The i
0
for the individual
reactions can be obtained
by extrapolating back to
(E
e
)
a
and (E
e
)
c
if these
values are known.
Evans Diagrams
The intersection of the two curves at E
corr
gives us i
corr

Of course you do not see the portion of the E/logi
c
and E/logi
a

at potentials more positive and more negative of E
corr

respectively.
However, it is important to realise that they exist.
I believe it is worthwhile to look at your Tafel type
measurements as a linear representation of current and
voltage.
The logarithmic plots involve a mathematical manipulation of
data and errors can be introduced.
Nevertheless Evans Diagrams are a convenient way of viewing
electrochemical reactions
Evans Diagrams
In this case the
cathodic reaction
with the higher
oxidation
potential is
controlling the
reaction
Evans Diagrams
In this example
because of the
faster kinetics. the
cathodic reaction
taking place at the
lower oxidation
(+ve)
Potential is
influencing the
corrosion rate
more,
Evans Diagrams
The situation in the previous example often occurs for a metal
corroding in acid, compared with the metal corroding in
dissolved oxygen.
Despite the thermodynamic driving force, E
e
, being greater for
oxygen than H
2
/H
+
, the acid corrosion is faster.
In some cases the oxygen and acid have a synergistic effect.
For example in the case of Ni corrosion. The reaction is quite
slow in sulphuric acid (0.5 M) and it is also slow in water
saturated with air at pH 7. In the latter case a passive
protective oxide film is formed. However, in the presence of
sulphuric acid and air. The corrosion rate is relatively rapid.
The acid dissolves the protective oxide film allowing oxygen to
corrode the metal.
Evans Diagrams
The relative corrosion rates of metals depends on the i
0
and
mass transfer.

With acid corrosion: 2H
+
+ e H
2

i
0
can vary from 10
-3
10
-12
A cm
-2

The Tafel slope ~ 120 mV/decade

For oxygen corrosion O
2
+ H
2
O + 4e 4OH
-

I
0
is difficult to difficult to determine because it is very low, but
it is of the order of <10
-10
A cm
-2
The Tafel slope >120 mV/decade
Exchange Current Densities in 1 Molal H
2
SO
4

Electrode Material -log
10
(A/cm
2

Palladium 3.0
Platinum 3.1
Rhodium 3.6
Nickel 5.2
Gold 5.4
Tungsten 5.9
Niobium 6.8
Titantium 8.2
Cadmium 10.8
Manganese 10.9
Lead 12
Mercury 12.3
Values for Some Reactions
Metal System
Pt Fe
3+
+ e Fe
2+
0.58
Pt Ce
4+
+ e Ce
3+
0.75
Hg Ti
4+
+ e Ti
3+
0.42
Hg 2H
+
+ 2e H
2
0.50
Ni 2H
+
+ 2e H
2
0.58
Ag Ag
+
+ e Ag 0.55
Evans Diagrams
The slowest reaction
controls the rate of
corrosion.
Normally this is the
cathodic reaction.
In this example:
A small changes in
kinetics of cathode have
a large effect on
corrosion rate.
A small changes in
kinetics of anode have
small effect on
corrosion
Mass Transfer Control
If the cathodic reagent at the corrosion site (e.g., dissolved O
2

in the O
2
reduction) is in short supply, mass transfer of the
reagent can become rate limiting.
The cathodic charge-transfer reaction at the metal/solution
interface is fast enough to reduce the concentration of the
reagent at interface (cathodic sites) to a value less than that in
the bulk solution.
This sets up a concentration gradient and the reaction
becomes diffusion controlled.





( )
( )
( )
( )
max Lim corr
b
c
s b
c
i
C nFD
i
C C nFD
i
= =

=
o
o
Mass Transfer Control
When the corrosion rate is limited by mass transfer it can be
increased by:
By altering the bulk concentration
By stirring and reducing the thickness of the Nernst diffusion
layer





( )
( )
( )
( )
layer diffusion Nernst the
ion concentrat surface the
ion concentrat bulk the
constant Faraday the
electrons of number the
current cathodic the
: Where
max Lim
=
=
=
=
=
=
= =

=
o
o
o
s
b
c
corr
b
c
s b
c
C
C
F
n
i
i
C nFD
i
C C nFD
i
Mass Transfer Control
Diffusion or Mass Transfer
Controlled
Activation Controlled
Mass Transfer Control
Increase in corrosion potential, E
corr
, and the corrosion current,
i
corr
, due to an increase in mass transfer caused by stirring.
Mixed Transfer Control
Polarization curve
for the cathodic
process showing:
1. Activation
polarization
2. Joint activation-
concentration
polarization
3. Mass transport-
limited corrosion
control
The cathodic Tafel plot often shows deviation from ideal Tafel
behavior
Evans Diagrams
Anodic
Control
Mixed
Control
Cathodic
Control
Galvanic Corrosion Influence of i
0

Cyclic Voltammetry at a Pt Electrode in Sulphuric Acid Solution
Oxygen
Adsorption Pt-O
Oxygen
Evolution O
2

Reduction of
adsorbed oxide
film (Pt-O)
Hydrogen
Evolution H
2

Reduction of
adsorbed H (Pt-H)
Formation of
adsorbed H (Pt-H)
The peak height of the adsorption/desorption processes is directly proportional to
scan, i.e., the charge iE or area under the curve. This contrasts with a diffusion
process where the peak height is proportional to the square root of the scan rate.