Electrochemistry Lecture 2 - Notes

Butler-Volmer Equation
The Butler-Volmer equation is one of the

most fundamental relationships in
electrochemistry. It describes how the
electrical current on an electrode depends
on the electrode potential, considering that
both a cathodic and an anodic reaction
occur on the same electrode:
An analysis of the kinetics of electrode processes using activated
complex theory (see Atkins, for details) gives:
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
= so-called symmetry factor or charge transfer coefficient
dimensionless
The equation is named after chemists John Alfred Valentine Butler
and Max Volmer
j = jc - ja = j0[e(1-)nF/RT - e-nF/RT]
where
jc and ja are the cathodic and anodic current densities;
j0 is the exchange current density at equilibrium, where the
rates of the forward (cathodic reduction) and reverse
(anodic oxidation) reactions are equal (but not zero);
and is the transfer coefficient (usually ca. 0.5)
The charge transfer coefficient signifies the fraction of the interfacial
potential at an electrode-electrolyte interface that helps in lowering the
free energy barrier for the electrochemical reaction. The electroactive
ion present in the interfacial region experiences the interfacial potential
and electrostatic work in done on the ion by a part of the interfacial
electric field. It is charge transfer coefficient that signifies this part that is
utilized in activating the ion to the top of the free energy barrier.
Remember is negative for reduction.
For a redox active species in solution where electron

transfer occurs at an electrode it is possible to
establish the effects of voltage on the current
flowing. In this situation the quantity reflects the
activation energy required to force current i to flow.
a + b = 1
Does the shape of these curves resemble concepts

covered in the previous lecture? (Answer provided in
lecture)
Exchange Current
The exchange current can be viewed as an idle
speed.
If we want to draw a current that is only a small
fraction of the bidirectional idle current (j/j0 <<1), then
a very small overpotential (to unbalance the rates in
the two directions slightly) is required.
If we ask for a net current that exceeds the idle current
significantly (j/j0 >1), we need to drive the system more
by applying a larger overpotential.
Butler Volmer Equation

While the Butler-Volmer equation is valid over the full
potential range, simpler approximate solutions can
be obtained over more restricted ranges of potential.
As overpotentials, either positive or negative,
become larger than about 0.05 V, the second or the
first term of equation becomes negligible,
respectively.
Hence, simple exponential relationships between
current (i.e., rate) and overpotential are obtained
This theoretical result is in agreement with the
experimental findings of the German physical
chemist Julius Tafel (1905), and plots of
overpotential versus log j are known as Tafel lines.
The slope of a Tafel plot reveals the value of the
transfer coefficient; for the given direction of the
electrode reaction.
Small
For x<<1, ex = 1 + x, and the Butler-Volmer
equation becomes
j = j0(nF/RT) or = RTj/nFj0
There is a linear relationship between j and at
small overpotentials (< 10 mV).
This linear region is called "polarization
resistance" due to its formal similarity to Ohms
law
Problem - Small
The exchange current density of a Pt|H2(g)|H+
electrode at 298 K is 0.79 mA cm-2. What
current flows through a standard electrode of
area 5.0 cm2 when the overpotential is 5.0 mV?
Large Oxidation
For large either negative or positive, one of
the exponential terms in the Butler -Volmer
equation becomes negligible.
At large positive potentials (corresponding to
oxidation), the first term predominates and
j = j0e(1-nF/RT
or
lnj = lnj0 + (1- )nF/RT
Large - Reduction
At large negative potentials (for reduction),
j = -j0e-nF/RT
or
ln(-j) = lnj0 - nF/RT
Remember is negative for reduction
Same form as the Tafel equation
= a + b logi
Large
The Tafel form holds when ja/jc < 0.01 (or vice-versa)
i.e., for ||>118/n mV.
If the electrode kinetics are fast (large j0), the current
will be limited by mass transfer by the time such a
large overpotential is applied, and the Tafel
relationship will not be observed.
When electrode kinetics are slow (small j0) and
activation potentials are required, the Tafel equation
holds.
Tafel behaviour is thus an indicator of totally
irreversible kinetics.
Problem - Oxidation
A solution of 1 M KOH is electrolysed at
250C with a Pt electrode to produce O2 at
the anode. At an overpotential of 0.40 V,
the current density is 1.0 x 10-3 A cm-2.
What does j become when = 0.6 V?
Assume = 0.5 and n = 1.
Problem - Reduction
The exchange current density and transfer
coefficient for the reduction of H+ to H2 on Ni
are 6.3 A cm-2 and 0.58. What is the current
density at an overpotential of 200 mV?
Tafel Equation
The overpotential, , increases as the
current flowing through the system
increases.
Tafel (1905) found that the overpotential
is related to the logarithm of the current:
= a + b logi
where a and b are empirical constants.
Tafel Plots
lnj = lnj0 + (1- )nF/RT from Butler Volmer
ln(-j) = lnj0 - nF/RT
from Butler Volmer
A plot of lnj versus has an anodic branch
with slope (1-)nF/RT and a cathodic branch
with slope - nF/RT. Both linear segments
extrapolate to an intercept of lnj0.
The transfer coefficient, , and the exchange
current density, j0, can thus be obtained.
ln|I |
slope =
F/RT
slope =
(1)F/RT
ln{In}
En
Tafel plot: the plot of logarithm of the

current density against the over potential.
Example: The following data are the
cathodic current through a platinum
electrode of area 2.0 cm2 in contact with an
Fe 3+, Fe 2+ aqueous solution at 298K.
Calculate the exchange current density and
the transfer coefficient for the process.
Slope is and intercept is a (=ln i0).
In general exchange currents are large
when the redox process involves no bond
breaking or if only weak bonds are broken.
Exchange currents are generally small
when more than one electron needs to be
transferred, or multiple or strong bonds are
broken.
Transport in Electrochemistry
The rate of redox reactions is influenced by the cell

potential difference.
However, the rate of transport to the surface can also
effect or even dominate the overall reaction rate and in
this class we look at the different forms of mass transport
that can influence electrolysis reactions.
There are three forms of mass transport which can
influence an electrolysis reaction:
Diffusion
Convection
Migration
10
Diffusion
In essence, any electrode reaction is a
heterogeneous redox reaction. If its rate
depends exclusively on the rate of
mass transfer, then we have a masstransfer controlled electrode reaction. If
the only mechanism of mass transfer is
diffusion (i.e. the spontaneous transfer
of the electroactive species from
regions of higher concentrations to
regions of lower concentrations), then
we have a diffusion controlled electrode
reaction.
Diffusion occurs in all solutions and
arises from local uneven concentrations
of reagents.
Diffusion
The rate of movement of material by diffusion can be predicted
mathematically and Fick proposed two laws to quantify the
processes. The first law:
this relates the diffusional flux Jo (i.e. the rate of movement of

material by diffusion) to the concentration gradient and the
diffusion coefficient Do. The negative sign simply signifies that
material moves down a concentration gradient i.e. from regions
of high to low concentration. However, in many measurements
we need to know how the concentration of material varies as a
function of time and this can be predicted from the first law.
The result is Fick's second law:
11
in this case we consider diffusion normal to an electrode

surface (x direction). The rate of change of the
concentration ([O]) as a function of time (t) can be seen to
be related to the change in the concentration gradient.
Fick's second law is an important relationship since it
permits the prediction of the variation of concentration of
different species as a function of time within the
electrochemical cell. In order to solve these expressions
analytical or computational models are usually employed.
How do we apply this to electrochemistry and the oxidation
or reduction of a redox active species at an electrode
surface?
When an electrode is polarised, the surface concentration of the species that is

either being oxidized or reduced falls to zero. Additional material will then diffuse to
the electrode surface towards this region of lower concentration. If the experiment
is carried out in an stirred solution or the electrode is rotated then the resulting
concentration-distance profile at the electrode surface is shown below.
Schematic covered in the lecture
This concept of the diffusion layer was introduced by Nernst in 1904.

is the thickness of the Nernst diffusion layer
12
Diffusion
The thickness of the Nernst diffusion layer varies within the range
0.1-0.001 mm depending on the intensity of convection caused by
agitation of the electrodes or electrolyte.
According to the definition of the Nernst diffusion layer the
concentration gradient may be determined as follows:
Where: C0 - bulk concentration, Cc - concentration of the ions at

the cathode surface; c - thickness of the Nernst diffusion layer.
Therefore the flux of ions toward the cathode surface is:
Each ion possesses an electric charge. The density of

the electric current formed by the moving ions:
Where: F - Faradays constant, F = 96485 Coulombs; z

- number of elementary charges transferred by each
ion.
The maximum flux of the ions may be achieved when
Cc= 0 therefore the electric current density is limited by
the value:
13
Convection
Convection results from the action of a force on the solution.
This can be a pump, a flow of gas or even gravity. There are
two forms of convection the first is termed natural
convection and is present in any solution.
This natural convection is generated by small thermal or
density differences and acts to mix the solution in a random
and therefore unpredictable manner.
In the case of electrochemical measurements these effects
tend to cause problems if the measurement time for the
experiment exceeds 20 seconds.
It is possible to drown out the natural convection effects

from an electrochemical experiment by deliberately
introducing convection into the cell. This form of
convection is termed forced convection.
It is typically several orders of magnitude greater than any
natural convection effects and therefore effectively
removes the random aspect from the experimental
measurements. This of course is only true if the
convection is introduced in a well defined and quantitative
manner.
14
If the flow is controlled, after a smalltime period, the profile will become
stable with no mixing in the lateral direction, this is termed laminar
flow.
For laminar flow conditions the mass transport equation for (1

dimensional) convection is predicted by:
where vx is the velocity of the solution which can be calculated in

many situations by solving the appropriate form of the NavierStokes equations. An analogous form exists for the three
dimensional convective transport.
Migration
The final form of mass transport we need to consider is
migration. This is essentially an electrostatic effect
which arises due the application of a voltage on the
electrodes. This effectively creates a charged interface
(the electrodes). Any charged species near that
interface will either be attracted or repelled from it by
electrostatic forces. The migratory flux induced can be
described mathematically (in 1 dimension) as:
15
Migration or Transport
Is the fraction of current carried by the ions.
For example in a solution of copper sulphate the
transport number of Cu2+ is 0.4 and that of SO42- = 0.6.
t+ + t- = 0.4 + 0.6 = 1
Since the migration current depends on the ionic
strength of the solution it is usually eliminated by addition
of excess of an inert supporting electrolyte (100 1000
fold excess in concentration) why?
The following example shows how the migration current is

eliminated. Pb2+ + 2e Pb0
The supporting electrolyte
Ensures diffusion control of limiting currents by eliminating
migration currents
Table: Limiting currents observed for 9.5 x 10-4 M PbCl2 as a
function of the concentration of KNO3 supporting electrolyte
Molarity
of KNO3
0
Il
A
17.6
0.001
12.0
0.005
9.8
0.10
8.45
1.0
8.45
16
The example shown is for the reduction of Pb2+

at an inert mercury electrode.
Pb2+ + 2e Pb(Hg)
At low inert electrolyte concentration a large
fraction of the total current is due to the
migration current, i.e. the currents due to the
electrostatic attraction of ions to the electrode.
For solution 1 what is the migration current
contribution?
Mass Transport in Electrochemical Cells

To gain a quantitative model of the current flowing at the
electrode we must account for the electrode kinetics, the 3
dimensional diffusion, convection and migration, of all the
species involved. This is currently beyond the capacity of
even the fastest computers - and will be for some time.
However, as we will discover electrochemical cells and
experimental conditions can be employed to cheat the
mass transport equations. We can effectively remove much
(but not all) of the mass transport complexity by carefully
designing and controlling the electrochemical experiment.
17

Electrochemistry Lecture 2 - Notes

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Butler-Volmer Equation

The Butler-Volmer equation is one of the

Remember is negative for reduction.

For a redox active species in solution where electron

Does the shape of these curves resemble concepts

Butler Volmer Equation

Tafel plot: the plot of logarithm of the

The rate of redox reactions is influenced by the cell

this relates the diffusional flux Jo (i.e. the rate of movement of

in this case we consider diffusion normal to an electrode

When an electrode is polarised, the surface concentration of the species that is

Schematic covered in the lecture

This concept of the diffusion layer was introduced by Nernst in 1904.

Where: C0 - bulk concentration, Cc - concentration of the ions at

Each ion possesses an electric charge. The density of

Where: F - Faradays constant, F = 96485 Coulombs; z

It is possible to drown out the natural convection effects

For laminar flow conditions the mass transport equation for (1

where vx is the velocity of the solution which can be calculated in

The following example shows how the migration current is

The example shown is for the reduction of Pb2+

Mass Transport in Electrochemical Cells

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