Evans Diagrams

Where we left off

Tafel Equation
 Butler-Volmer Equation

• where:
• I = electrode current, Amps
• Io= exchange current density, Amp/m2
• E = electrode potential, V
• Eeq = equilibrium potential, V
• A = electrode active surface area, m2
• T = absolute temperature, K
• n = number of electrons involved in the electrode reaction
• F = Faraday constant
• R = universal gas constant
• α = 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
 (1 − α ) nFη a 
ia ` = i0 exp  
ia and ic are
 RT  the exhange
at high anodic overpotential current
densities for
 αnFη c  the anodic
ic ` = i0 exp −
 RT  and cathodic
reactions
at high cathodic overpotential

These equations can be rearranged to give

the Tafel equation which was obtained
experimentally
Butler Volmer Equation - Tafel
Equation
RT RT
ηc = ln i0 − ln ic
α c nF α c nF
0.059 0.059
ηc = log i0 − log ic at 25 0 C cathodic reaction
αcn αcn
0.059 0.059
ηa = log i0 − log ia at 25 0 C anodic reaction
(1 − α c ) n (1 − α c ) n
The equation is the well known Tafel equation

η = a + b log i
0.059 0.059
a= ln io or a = ln io
αn (1 − α ) n
0.059 0.059
b= or
αn (1 − α ) n
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 - Ee reflects
the activation energy
required to force current i
to flow. Plotted below are
three curves for differing
values of io with α = 0.5.
Current Voltage Curves for Single Electrode
Reactions

Electrochemical reactions The iE curves from the

of different i0 or degrees previous slide have

Voltage
of reversibility been rotated.

Current
 Single Chemical Reaction
Only at appreciable over-
potentials does the
reverse reaction become
negligible

At Ee the forward
and reverse
currents are equal
Electrochemical reaction which has a large exchange
current density, i0, 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+/H2(Pt) and Ag/AgCl
make good reference
electrodes because they are
not easily polarised
Electrochemical reaction in which the i0 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

11
At low overpotential the Butler Volmer
equation is linear (Stern Geary equation)

nF
i = io η
RT

12
 So far we have looked
mainly at single
electrochemical reactions
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  Mn+ + R showing the separation of
anodic and cathodic sites. (b) The corrosion process involving two
14
cathodic reactions.
Butler Volmer graphs for two electrochemical 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
• Note in the previous diagram that:
• ia = ic = icorr at the corrosion potential Ecorr
• Ecorr is a mixed potential which lies between (Ee)c and
(Ee)a. In this case it is closer to (Ee)a because the i0 and the
kinetics of the anodic reaction is faster.
• The metal dissolution is driven by the anodic activation
overpotential ηa = Ecorr - (Ee)a
• The cathodic reaction is driven by the cathodic activation
overpotential ηc = Ecorr - (Ee)c
• The thermodynamic driving force
• ΔE = (Ee)c - (Ee)a
• ΔE is usually large enough to put Ecorr 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 i0 for the individual

reactions can be obtained
by extrapolating back to
(Ee)a and (Ee)c if these
values are known.
 Evans Diagrams
• The intersection of the two curves at Ecorr gives us icorr
• Of course you do not see the portion of the E/logic and
E/logia at potentials more positive and more negative of
Ecorr 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, Ee, being greater
for oxygen than H2/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 i0 and mass transfer.

• With acid corrosion: 2H+ + e → H2

• i0 can vary from 10-3 – 10-12 A cm-2

• The Tafel slope ≈ 120 mV/decade

• For oxygen corrosion O2 + H2 O + 4e → 4OH-

• I0 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
H2SO4
Electrode -log10 (A/cm2
Material
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
α Values for Some Reactions
Metal System α
Pt Fe3+ + e ↔ Fe2+ 0.58
Pt Ce4+ + e ↔ Ce3+ 0.75
Hg Ti4+ + e ↔ Ti3+ 0.42
Hg 2H+ + 2e ↔ H2 0.50
Ni 2H+ + 2e ↔ H2 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
O2 in the O2 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.

nFD( Cb − C s )
ic =
δ
nFD( Cb )
( ic ) Lim = = ( icorr ) max
δ
 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
nFD( Cb − C s )
ic =
δ
nFD( Cb )
( ic ) Lim = = ( icorr ) max
δ
Where :
ic = the cathodic current
n = the number of electrons
F = the Faraday constant
Cb = the bulk concentrat ion
C s = the surface concentrat ion
δ = the Nernst diffusion layer
 Mass Transfer Control

Activation Controlled Diffusion or Mass Transfer

Controlled
 Mass Transfer Control
Increase in corrosion potential, Ecorr , and the corrosion current,
icorr , due to an increase in mass transfer caused by stirring.
 Mixed Transfer Control
The cathodic Tafel plot often shows deviation from ideal Tafel
behavior

Polarization curve
for the cathodic
process showing:
1.Activation
polarization
2.Joint activation-
concentration
polarization
3.Mass transport-
limited corrosion
control
 Evans Diagrams

Cathodic
Anodic Control
Control

Mixed
Control
Galvanic Corrosion – Influence of i0
Cyclic Voltammetry at a Pt Electrode in Sulphuric
Acid Solution
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.

Oxygen
Formation of Oxygen
Adsorption Pt-O
adsorbed H (Pt-H) Evolution O2 ↑

Reduction of
adsorbed H (Pt-H)
Reduction of
adsorbed oxide
Hydrogen film (Pt-O)
Evolution H2 ↑