44 Electrochemical Engineering
Solution:
The reactions of interest are as follows:
Fe2‡ ‡ 2e ˆ Fe; U θ ˆ 0:44 V
Fe3‡ ‡ e ˆ Fe2‡ ; U θ ˆ 0:771 V
where the standard potentials have been provided.
Since no concentration information was given in the
problem statement, and corrections for concentration
are typically small relative to the standard potential,
we will make our assessment with use of the
uncorrected potentials.
We are asked to assess whether ferrous Fe2‡ †
ions will be oxidized or ferric Fe3‡ † ions will be
reduced at an applied potential of 0.44 V versus SHE.
The relevant equilibrium potential is that of the second
reaction, 0.771 V. Since the applied potential is lower
than the equilibrium value, the reduction reaction takes
place. Therefore, ferric ions are reduced. Incidentally,
this would mean that this electrode is the cathode.
Will iron deposition occur? The applied poten­
tial of 0.44 V is well above the equilibrium potential
of 0.44 V. Therefore, iron will not deposit on the Pt
electrode.
Will hydrogen be evolved at the electrode? The
applied potential of 0.44 V is also above the
equilibrium value for hydrogen (0 V). Therefore,
hydrogen will not be evolved.
Having examined qualitatively how the potential
affects the direction of the current in the last section, we
now seek a quantitative expression for the current density
Figure 3.3 The relationship between potential, electron energy,
and the direction of a faradaic reaction.
Figure 3.4 Simple electron transfer reaction at metal electrode.
as a function of potential. To do this, we consider a single-
electron elementary redox reaction (also see Figure 3.4):
O ‡ e $ R; (3.3)
where O is the oxidized species and R is the reduced
species. As already discussed, both the forward (in this
case, reduction) and reverse reactions take place simulta­
neously on the same surface. At the equilibrium potential,
the net rate of reaction is zero, whereas the anodic reaction
dominates at potentials positive of U, and the cathodic
reaction dominates at potentials negative of U. By con­
vention, we define anodic current to be positive.
Similar to chemical reactions that you may have
studied previously in a chemistry class, there is an activa­
tion energy associated with both the forward and reverse
reactions as shown in Figure 3.5. To react, an energy
barrier must be overcome to reach a transition state (i.e.,
activated complex), whose energy corresponds to that at
the top of the energy curve. This activation energy is a
function of temperature, as taught in a beginning chemistry
course. The rate of the forward reaction can be written in
Figure 3.5 Change in energy associated with reaction at an
electrode surface (subscript a = anodic and c = cathodic).
 Chapter 3 Electrochemical Kinetics 45

terms of the reactant concentration and a rate constant, kf, Since the precise values of V2 and V1 are arbitrary, we can
that is a function of ΔGzf , the Gibbs energy difference define a reference potential so that V1 is equal to zero. The
between the initial reactants and the transition state. Assum­ activation energy at the reference potential (ΔGzc V 1 †) can
ing a first-order elementary reaction (see Equation 3.3), then be treated as a constant and be incorporated into the
ΔGzf rate constant k c ˆ k oc exp ‰ ΔGzc 0†=RT†Š. We can also
r ˆ k f cO ˆ kof cO exp ; (3.4) drop the subscript on V2. This convention leaves us with
RT the following expression for the cathodic reaction:
where cO is the concentration of the oxidized species. A βFV
decrease in ΔGzf corresponds to a lower activation energy r c V † ˆ kc cO exp : (3.8)
RT
and will cause the rate of the forward reaction to increase.
A similar expression can be written for the reverse reaction. We can now use this equation to write an expression for the
The same type of model applies to electrochemical cathodic current density. Note that the direction of cathodic
reactions, with one important difference. current is from the solution to the electrode (electrons
We can modify the activation energy of electrochemical move in the direction opposite to the current or, in this case,
reactions by changing the electrode potential, as shown in from the electrode to the species in solution that is
Figure 3.5 for a single-electron reaction. Since we are only reduced). Cathodic current is negative by convention.
interested in energy differences, we have arbitrarily set the Consistent with this convention and the transfer of a single
energy of the reduced state to be the same for the two curves. electron,
The upper curve is at a lower (more negative) potential since ic βFV
a decrease in potential corresponds to an increase in the ˆ r c V † ˆ k c cO exp : (3.9)
F RT
energy of the electrons. Therefore, the energy is higher for
V1 (the lower potential), and ΔV = V2 V1 > 0. Following a similar procedure, we obtain the following for
The reduction reaction represented by Equation 3.3 the anode:
takes place as one moves along the reaction coordinate
ia 1 β†FV
from the left to the right of the diagram. At an electrode ˆ r a V † ˆ ka cR exp : (3.10)
potential of V1, the reduction reaction is favored as the energy F RT
of the reduced state is lower than that of the oxidized state. At the equilibrium potential, U, the net current is zero and
The activation barrier for the reduction is also lower than that the magnitude of the anodic current is equal to that of the
for oxidation (the reverse reaction). However, the situation cathodic current. This value of the current density at
changes when the potential of the electrode is changed from equilibrium is defined as the exchange-current density,
V1 to V2 so that the oxidation reaction becomes favored by io (remember that the net current is zero). Therefore,
the increase in potential (see Figure 3.5).
The potential change from V1 to V2 affects the energy io 1 β†FU βFU
 ka cR exp ˆ kc cO exp :
of an electron in the oxidized state relative to that in the F RT RT
reduced state by FΔV. The activation energies of both the (3.11)
reduction (cathodic) and oxidation (anodic) reactions are
also changed. We define β as the fraction of the total energy If we multiply and divide Equation 3.10 by the anodic
change that impacts the activation energy for the cathodic expression for io, we obtain
reaction and (1 β) as the fraction that impacts the anodic 1 β†FV
activation energy. Therefore, the shift in potential from V1 ka cR exp
ia 1 β†FU RT
to V2 changes the activation energies as follows for the ˆ ka cR exp ;
single-electron reaction under consideration: F RT 1 β†FU
k a cR exp
For the cathodic reaction: RT
(3.12)
ΔGzc V 2 † ˆ ΔGcz V 1 † ‡ FΔV 1 β†FΔV
(3.5)
ˆ ΔGzc V 1 † ‡ βFΔV; which simplifies to
and for the anodic reaction: 1 β†F V U†
ia ˆ io exp : (3.13)
ΔGaz V 2 † ˆ ΔGaz V 1 † 1 β†FΔV; (3.6) RT
where c represents cathodic, a represents anodic, and ΔV is The above procedure yields a similar expression for the
positive since V2 > V1. We can now use Equation 3.5 to write cathodic current density:
an expression for the cathodic reaction at potential V2:
βF V U†
ic ˆ io exp : (3.14)
ΔGzc V 1 † ‡ βF V 2 V 1† RT
rc V 2 † ˆ k oc cO exp : (3.7)
RT
46 Electrochemical Engineering
We now define the surface overpotential, ηs, which is the
driving force for the reaction:
ηs  V U; (3.15a)
where V and U are the potential and equilibrium potential
relative to the same reference electrode located just outside
the double layer. As such, these potentials are measurable
and well defined. ηs is also equal to the difference between
the voltage drop across the double layer at the potential of
interest (not measurable) and the voltage drop across the
double layer at equilibrium (also not measurable). The
choice of reference electrode is arbitrary since both V and
U are referred to the same reference. The surface over-
potential is quite important and will be used repeatedly
throughout the course.
Although the definition of the surface overpotential in
Equation 3.15a is adequate for many problems, it is often
necessary to fix further the value of the potential when
analyzing more complex systems. To facilitate this, it is
useful to further expand our expression for ηs as follows:
ηs ˆ V Uˆ ϕmetal ϕsolution † U ˆ ϕ1 ϕ2 †
(3.15b)
where ϕ1 is the potential of the electrode (e.g., metal) and
ϕ2 is the potential measured by a specific reference elec­
trode located in the solution just outside the double layer. U
is the equilibrium potential defined against that same
reference electrode. Be careful since the value of U will
change with the reference electrode chosen.
We can now write the expression for the net current
density by combining Equations 3.13, 3.14, and 3.15a:
1 β†Fηs βFηs
i ˆ ia ‡ ic ˆ io exp exp
RT RT
(3.16)
This equation is known as the Butler–Volmer (BV) equa­
tion, shown here for an elementary reaction involving the
transfer of a single electron. The value of β for this type of
reaction is typically ∼0.5. A derivation similar to that
provided above can be performed for any elementary
reaction, and procedures have been developed to handle
sets of elementary reactions.
The form of Equation 3.16 is useful for describing a
wide variety of elementary and nonelementary reactions
and is used broadly in electrochemical engineering. It can
be generalized by defining anodic and cathodic transfer
coefficients αa and αc to yield
αa Fηs αc Fηs
i ˆ io exp exp ; (3.17)
RT RT
which is a frequently used form of the BV equation. Note
that αa + αc = n is generally true, where n is the number of
electrons transferred in the reaction of interest.
3.3 USE OF THE BUTLER–VOLMER
KINETIC EXPRESSION
The purpose of this section is to help you understand and
learn how to use Equation 3.17, the Butler–Volmer equa­
tion. The BV equation is a relationship between the current
density (i) and the charge transfer or surface overpotential
(ηs). It contains three parameters: the exchange-current
density (io), the anodic charge transfer coefficient (αa),
and the cathodic charge transfer coefficient (αc). It is
frequently used to represent experimental data by fitting
these three parameters to the data.
The charge transfer overpotential (ηs) is defined by
Equation 3.15, where V represents the difference between
the potential of the electrode (ϕ1, often a metal) and the
potential of a reference electrode located just outside the
double layer (ϕ2). U is the difference between the potential
of the electrode and the reference electrode at equilibrium.
As already mentioned, V and U must be relative to the same
reference electrode, although the precise choice of refer­
ence electrode is not critical as long as it is appropriate for
U ; the system. Note that U = 0 if the reference electrode is the
same as the electrode of interest. For example, U would be
zero for the combination of a zinc electrode and a zinc
reference electrode (Why?). The methods that you learned
in Chapter 2 can be used to calculate U, which is a function
of the concentration at the surface.
The current density (i) is the current per area, with
typical units of mA
cm 2 or A
m 2. In theory, it is based on
the actual area over which the reaction is taking place. The
area, however, can be an issue in practice. For example, if
the measured value of io is based on the superficial or
apparent area in a system where the microscopic area is
: significantly greater than the superficial area, io will not
transfer to another system with a different microstructure
(see Figure 3.6). The surface roughness illustrated in
Figure 3.6b results in a larger surface area for electro­
chemical reaction.
A surface roughness factor, Ra, can be defined as the
ratio of the true surface area and the apparent surface
Figure 3.6 The area of the electrode with a rough surface is much
larger than that of the one with the smooth surface.