Chapter 3
Electrochemical Kinetics
O ne of the real advantages of electrochemical reactions is
that it is possible to control the reaction rate and even the
direction of the reaction by changing the potential. This
control is possible because electron transfer in electro­
chemical reactions takes place through a conductor, and
the potential of a conductor can easily be changed or
controlled. In this chapter we learn about reaction rates
and how to describe those rates quantitatively. Before we
do so, however, we need to look carefully at the interface
between a metal electrode and the adjacent electrolyte
solution. That interface is critical to understanding and
manipulating electrode reactions. In the previous chapter,
we determined the potential of an electrode at equilibrium,
U, in the absence of current. Now we want to find the
potential when current is flowing. The difference between
the potential with current flowing and the equilibrium
potential is called the overpotential.
3.1 DOUBLE LAYER
A metal electrode in an electrolyte solution is typically charged,
even at equilibrium. Excess charge is present on the outer
surface of the electrode, adjacent to the electrode–electrolyte
interface. The amount of charge in the metal electrode is a
measure of the energy of the electrons in the metal and can be
changed by using a power supply to force electrons into or out
of the metal. Excess electrons result in higher energy of
electron because electrons tend to repel each other.
How is the electrolyte solution influenced by this
excess charge? As you might expect, charged species in
the electrolyte solution align themselves at the interface to
balance the excess charge on the metal. The result is the
formation of a double layer, as shown in Figure 3.1. Also
shown in the figure is the diffusion layer; only a portion of
this layer is shown because it is so much larger than the
double layer and too large for a drawing of this scale (see
numbers below). The solution side of the double layer is a
Electrochemical Engineering, First Edition. Thomas F. Fuller and John N. Harb.
 2018 Thomas F. Fuller and John N. Harb. Published 2018 by John Wiley & Sons, Inc.
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region of nonuniform charge and, as it takes enormous
energy to separate charge, it is a region where the electric
field is very large. The potential difference between the
metal and the solution just outside the double layer is
critical to our discussion of electrode kinetics. At the open-
circuit conditions we discussed in Chapter 2, where the
overall current is zero, this potential difference adjusts
itself through the transfer of electrons (i.e., reaction) so that
the rates of the forward and reverse reactions are equal. In
other words, equilibrium is achieved across the interface.
The potential difference between the electrode and the
solution at equilibrium provides a reference point for our
discussion of kinetics later in this chapter.
The actual structure of the double layer is more
complex than the simple arrangement presented above.
A more complete view, along with the common nomen­
clature used to describe it, is shown in Figure 3.2. Note the
importance of the solvent (water in this instance) mole­
cules. Water molecules, which are polar, surround the ions
in solution to form a hydration layer or solvent sheath.
They also tend to align at the interface because of their
dipole nature and the charge on the surface. The inner
Helmholtz plane (IHP) is the position of the centers of ions
or molecules that adsorb directly onto the electrode sur­
face. They may experience van der Waals interactions with
the surface in addition to coulombic interactions.
To adsorb directly on the surface, an ion must at least
partially shed its waters of hydration. Negatively charged
ions (anions) hydrate less strongly than cations and are
more frequently found in the inner Helmholtz plane. They
can even adsorb to a negatively charged surface. As a
general rule, the weaker the solvation of an anion, the more
strongly it tends to undergo specific (direct) absorption to
the surface. The outer Helmholtz plane (OHP) is the plane
of closest approach for solvated ions, where the solvent
sheath prevents specific adsorption. Its position is defined
by the radius, including the waters of hydration, of the
largest solvated ions (∼0.2 nm). The last portion of the
41
42 Electrochemical Engineering
Figure 3.1 Simplified description of electrical double layer.
Source: Adapted with permission from L. Faulkner, J. Chem. Ed., 60,
262 (1983).
double layer is called the diffuse double layer. This layer is
characterized by a balance of Brownian motion and Cou­
lombic forces. This balance is analogous to the one intro­
duced in Chapter 2 in the development of the Debye–
Hückel theory for activity coefficients. Both positive and
negative charges are present, and the amount of excess
charge decreases gradually from the OHP to the solution
side of the diffuse double layer where the solution is
electrically neutral. The thickness of the diffuse double
layer is characterized by the Debye length:
εRT
λˆ 2
(3.1)
F z2i ci;bulk
and is a function of concentration. The diffuse part of the
double layer is important at low concentrations and has a
thickness of about 10 nm at an ionic strength of 1 mM. The
diffuse part of the double layer is typically not as important at
concentrations used in practical electrochemical systems, but
the structure of the double layer is critical to the under­
standing of charge transfer. In contrast to the thin diffuse
double layer, the diffusion layer is on the order of 1 mm; thus,
the diffusion layer is typically orders of magnitude larger than
the thickness of the double layer. The potential drop from the
potential of the metal (ϕm) to the potential of the solution just
outside the double layer (ϕs) is also shown in Figure 3.2. For a
potential difference of 1 V, the electric field is
Δϕ 1 the potential that are positive relative to the equilibrium
 ˆ ˆ 108 ‰V m 1 Š;
λ 1  10 8
which is quite high. There is also a capacitance associated
with the separation of charge across the double layer. In
fact, reference is often made to electrochemical capacitors
or double-layer capacitors. The capacitance, C, is simply
Q
C ; (3.2)
Δϕ
where Q is the charge on the electrode. By adjusting the
potential, this charge can be changed. Here an ideally
polarizable electrode is envisaged, which is an electrode
where an arbitrary potential can be applied without causing
a faradaic reaction to occur. Under these conditions, there
is no faradaic reaction associated with the electrical cur­
rent, only simple movement of the charges. The capaci­
tance is discussed in more detail in Chapter 11, along with
devices that take advantage of this effect. In this chapter,
our focus will be on faradaic reactions, which are reactions
that involve the transfer of electrons across the interface in
order to change the oxidation state of at least one of the
participating species. The half-cell reactions that we wrote
in Chapters 1 and 2 are examples of faradaic reactions.
Faraday’s law applies to faradaic reactions and relates the
current to the amount of a species reacted or formed.
3.2 IMPACT OF POTENTIAL ON
REACTION RATE
Electrochemical reactions take place at the surface of the
electrode as electrons are transferred to and from ions or
neutral species in solution. The rate of reaction is influ­
enced by the potential drop across the double layer. At
open circuit (no external current), this potential drop
reaches an equilibrium value where the forward and
reverse reactions are equal. One of the real advantages
of electrochemical reactions is that the rate of reaction can
be controlled by changing the potential of the metal, which
changes the potential drop across the double layer and,
therefore, the rate of reaction across the interface. By
changing the potential of the metal, we can control the
rate and even the direction of the reaction. The main
purpose of this chapter is to develop a relationship between
the rate, expressed as a current density, and the potential,
and to illustrate how this relationship can be used.
The reference point for our discussion of reaction rate
is the equilibrium potential where the net rate of reaction is
zero. What happens when we increase the potential or, in
other words, make the potential more positive than the
equilibrium potential? Increasing the potential lowers the
energy of electrons in the electrode (remember, electrons
are negatively charged) and makes it easier for molecules
or atoms to lose electrons to the electrode. Thus, values of
potential promote the anodic reaction (oxidation). As you
may have guessed, the opposite is true for potentials lower
than the equilibrium potential. Lowering the potential
increases the energy of electrons in the electrode and
promotes the transfer of electrons from the electrode to,
for example, a species in solution (reduction). Therefore,
the cathodic reaction is favored as the potential is lowered
relative to the equilibrium potential. The situation is
summarized in Figure 3.3 using the reaction of ferric
(Fe3+) and ferrous (Fe2+) ions as an example.

Figure 3.2 (a) Detailed structure of electrical double layer. (b) Sketch of potential across the double layer.
There is one slight problem. The potential difference
(ϕm ϕs) between the metal and the solution just outside
the double layer (see Figure 3.2) cannot be measured
directly. The reason for this is easy to understand.
Potentials are measured between two electrodes. How­
ever, if we put another electrode into solution to measure
ϕs, it will also form its own double layer with its own
potential drop. Therefore, what you end up measuring is
a combination of the potential drop associated with the
two electrodes. Fortunately, this problem is easy to
overcome, as mentioned in Chapter 2. We simply
express all potentials relative to a reference electrode,
which defines our potential scale. Thus, what you
learned about reference electrodes and potential in the
Chapter 3 Electrochemical Kinetics 43
previous chapter provides the needed reference point for
our discussion of kinetics.
ILLUSTRATION 3.1
You have been given a solution containing Fe3+ and
Fe2+ ions at a pH of 3. Two inert Pt electrodes are
placed into the beaker and one of the electrodes is set
at a potential of 0.44 V versus SHE. Will ferrous ions
be oxidized or will ferric ions be reduced at that
electrode? Is there any chance of depositing metallic
iron on the electrode? Your lab partner claims that at
0.44 V you will also evolve hydrogen. Is she correct?