E

ELECTROCHEMICAL THEORY

Contents
Thermodynamics
Double Layer
Kinetics
Electrokinetics
Electrocrystalization
Hydrogen Evolution
Oxygen Evolution
Corrosion
Non Faraday Electrochemical Modification of Catalysts Activity

Thermodynamics
S Panero, Sapienza University of Rome, Rome, Italy
& 2009 Elsevier B.V. All rights reserved.

The Electrical Double Layer and the distribution of charge is known as the electrical double
Formation of Electric Potential at layer, since the total charge excess on the one side of the
Interfaces interface must, for reasons of overall electroneutrality, be
exactly equal and opposite to that on the other side.
The electrochemical cells are of extreme importance in When a metal is immersed in a solution of an electrolyte,
physical chemistry and in everyday life, and several ex- the charge on the metal side of the interface corresponds
amples of the two main types of electrochemical cells are to a surplus or deficit of electrons in the surface atomic
in widespread use in all areas of manufacture and energy layer. In most models, the metal is taken to have a perfect
storage. The electrochemical cell, or galvanic cell, is a planar surface. In practice, there are always grain
device that converts chemical energy into electrical en- boundaries and point defects present. Even in the case of
ergy or vice versa when a chemical reaction is occurring. a perfect single crystal facet, low coordination re-
Typically, it consists of two electronically conducting construction surfaces may occur in order to reduce the
phases (solid or liquid metals and semiconductors) con- surface energy. Such reconstruction may be reversed or
nected by an ionically conducting phase (e.g., aqueous or altered if adsorption of electrolyte components occurs.
nonaqueous solution, molten salt, and ionically con- The structure of the solution side is even more compli-
ducting solid). cated (Figure 1). It can be considered to consist of two
Whenever two phases that have significant electrical regions:
conductivities come into contact, there is generally some
redistribution of charge, for instance, by charge transfer
across the metal–solution interface, by orientation of
• anions
An inner layer, which may contain partially desolvated
that have strong chemical bonding interactions
dipoles near the interface, and by adsorption of charged with the metal, together with oriented solvent mo-
particles at the interface. The region containing this lecular dipoles.

1
2 Electrochemical Theory | Thermodynamics

–qM +qS

+
+
+
_ +
+
+
+ +
+
+
_ +
+
+
+
+ +

Metal Solution

IHP OHP

Figure 1 Structure of the electrical double layer when the metal electrode is negatively charged. The molecular representation of the
double layer shows both ion and solvent dipoles. The inner Helmholtz plane (IHP) is almost empty; balancing cations are in the outer
Helmholtz plane (OHP) and in the diffuse layer.

• tracted
A ‘time-averaged’ diffuse layer where ions are at-
to or repelled from the interface by electro-
chemical potential can be regarded either as the change
in free energy when 1 mol of i is added to an infinite
static forces, but which are also affected by thermal amount of the mixture, so that the mole fractions of all
collisions. The effective depth of the diffusive layer is the components are unaltered, or it can be treated as a
a function of electrolyte concentration, temperature, differential quantity:
dielectric constant of the solvent, etc.
 
@G
The formation of an electrical double layer at a mi ¼ ½2
@ni nj ani ;p;T
metal–solution interface brings about a particular ar-
rangement of atoms, ions, and molecules in the region
near the electrode surface, and an associated variation in where the partial derivative is evaluated with the
electrical potential with distance from the interface. The amounts of all other components, j being maintained
double layer structure may significantly affect the rates of constant. The total free energy of a mixture may be
electrochemical reactions. written as
In the case of electrochemical cells capable of passing X
significant direct currents, the principal mechanism for G¼ ni mi ½3
the formation of the potential differences at the phase i

boundaries within the cell is charge transfer, e.g., electron

transfer between two metals or semiconductors, ion If a reaction occurs in the mixture, then the free energy
transfer between a metal and a solution of its ions, etc. change, assuming that the reaction is taking place in a
When speaking of thermodynamic systems, the large excess of the mixture such that the mole fractions of
chemical potential for the ith component of a mixture is both reactants and products are not sensibly affected, is
defined by the equation: given by
X
mi ¼ m0i þ RT ln ai ½1 DG ¼ ni mi ½4
i
where m0i is the chemical potential of ion i in a solution in
which the ion–ion interactions are assumed to be in- where we assign negative values to those stoichiometric
significant, and ai is the activity of the component. The number ni of the reactants.
 Electrochemical Theory | Thermodynamics 3

At the equilibrium where j(I) and j(II) are the electrostatic potentials in
X the interior of phases (I) and (II), and are referred to as
DG ¼ ni mi ¼ 0 ½5 the Galvani potentials. The expression mI þ ziFji is re-
i ferred to as the electrochemical potential m̃ i . We have
If two mixtures or solutions are in contact with each
m̃ i ¼ mi þ zi F ji ¼ m0 þ RT ln ai þ zi F ji ½8
other such that chemical equilibrium is established be-
tween the phases, the chemical potential for each com- and the condition for electrochemical equilibrium is, as
ponent i present in the two phases: usual,
X
mi ðIÞ ¼ mi ðIIÞ ½6 ni m̃i ¼ 0 ½9
i
If this condition is not fulfilled, then the reaction will take
place spontaneously until the condition is fulfilled. where the ni are taken as positive numbers of the right-
If a metal, such as copper, is placed in contact with a hand side of the equilibrium and as negative numbers on
solution containing the ions of that metal, such as the left-hand side. It should be emphasized that the
aqueous copper sulfate, then we expect an equilibrium to condition for the electrochemical equilibrium is essen-
be set up of the following form: tially a dynamic one. An external probe would reveal no
net current passing between electrode and solution, a
Cu0 $Cu2þ ðaqÞ þ 2e ½I result that can be used as the basis of a quantitative
treatment of electrode kinetics.
At the moment at which the metal is placed in contact The difference in inner potential between two phases
with the solution, the condition reported in eqn [6] will is referred to as the Galvani potential difference, and this
not be fulfilled. In order to satisfy the condition, some can be calculated for the equilibrium case when no net
chemical reactions, either deposition of copper ions onto current flows. If we represent by js the Galvani potential
the metal or dissolution of copper ions into the solution of the solution and by jM the Galvani potential of the
according to the dominant energetic relationships, must metal, then the equilibrium condition for reaction [I] can
take place. However, it can be seen from eqn [I] that be written as
copper reactions (dissolution or deposition) cannot be
treated as a simple chemical reaction in a single phase m̃Cu ðMÞ ¼ m̃Cu2þ ðaqÞ þ 2m̃e ðMÞ ½10
since the process must generate or consume electrical
charge, and this will always be accompanied by the for- from eqn [9]. Assuming the copper atoms in the metal to
mation of a potential difference between the two phases. be neutral, so that m̃ ¼ m, then we have
If the chemical potential of the copper in the metal ex-
ceeds that of the copper ions in solution and electrons in m0Cu ðMÞ þ RT lnaCu ðMÞ ¼ m0Cu2þ ðaqÞ þ RT ln aCu2þ
the metal, then the metal dissolution will take place, and þ 2F js þ m0e ðMÞ
the solution close to the metal will become positively þ 2RT ln ae  2F jM ½11
charged with respect to the metal itself. Then the double
layer is set up and the potential difference established will The concentration of both copper atoms and electrons in
inhibit further dissolution. In a similar way, if the chem- copper metal will be effectively constant, so two of the
ical potential of Cu2þ ions in solution and electrons in the activity terms can be neglected, and we finally have, on
metal exceeds that of copper itself, then there will be a rearranging eqn [11]
tendency for the metal ions to deposit on copper, with the
m0Cu2þ ðaqÞ þ m0e ðMÞ  m0Cu ðMÞ
result that a potential difference of opposite polarity is Dj  jM  js ¼
established, which again acts to inhibit further deposition. 2F
RT
It is clear that we must incorporate the effect of this þ ln aCu2þ ðaqÞ ½12
2F
potential difference into our thermodynamic equations. If
1 mol of z-valent ions is brought from a remote position
to the interior of the solution, in which there exists a RT
¼ Dj0 þ ln aCu2þ ½13
potential j, then the work done will be zFj. This work 2F
term must be added or subtracted from the free energy m where Dj0 is the Galvani potential difference between
depending on the relative signs of the charge and j, and electrode and solution in the case where aCu2þ ðaqÞ ¼ 1,
the condition for equilibrium for component i partitioned and is referred to as the standard Galvani potential dif-
between two phases with potentials j(I) and j(II) is ference. Now, the Galvani potential inside the metal
cannot be treated as independent of the potential in the
mi ðIÞ þ zi F ji ðIÞ ¼ mi ðIIÞ þ zi F ji ðIIÞ ½7 solution. Unfortunately, it is impossible to measure the
4 Electrochemical Theory | Thermodynamics

Galvani potential of a single phase or the Galvani po- where n is the number of moles of electrons transferred
tential difference between two phases of different com- in 1 mol of reactants. Obviously the value of d can be
position. Thus, it is not particularly instructive to made as small as desired, so that the maximum work that
develop further the concept of individual electric po- may be obtained from the cell for 1 mol of reactants is
tential differences at phase boundaries within a galvanic
cell. Instead, the relationship between the measurable wmax ¼ nFE ½15
cell voltage and the properties of the chemical processes
with the running of the complete cell will now be By definition, wmax ¼  DG, where DG is the free energy
considered. change associated with 1 mol of reactants and hence

DG ¼ nFE ½16
Thermodynamics of Galvanic Cells

An electrochemical cell is said to act reversibly if the net In practice, the passage of any finite amount of electricity
cell reaction is reversed when the current through the results in a certain degree of irreversibility as some of the
cell is made to flow in the opposite direction. When no electrical energy is dissipated as joule heat in the internal
current is being drawn, such a cell is in a true equilibrium resistance of the cell, or at the electrodes where the ap-
state. When no current is being drawn from a reversible plication of a potential difference is required to drive the
cell, the potential difference across its terminal, or open- current at the desired rate. Galvanic cells can only supply
circuit potential, is known as the electromotive force or electric work equal to the free energy change of the cell
emf of the cell. The emf of any particular reversible cell reaction when the current flowing tends to zero. The cell
is a quantitative measure of the tendency of the cell re- voltage under load is always smaller than the open-cir-
action to occur and may be related to the free energy cuit voltage (VOC), so that only part of the thermo-
change for this process. dynamically available work can be utilized. The various
Let the emf of a reversible cell be balanced by a causes of internal resistance or ‘polarization’ of the cells
Poggendorff potentiometer (Figure 2). are considered later.
At the balance point, where no current is flowing in The enthalpy change associated with a cell reaction is
the cell, the voltage E applied by the potentiometer is just a state function and hence is independent of whether the
sufficient to stop the cell reaction. Let the applied voltage reaction is being carried out reversibly or not. If an
now be reduced to (E  d). Under these circumstances, exothermic reaction is carried out completely irrevers-
current flows and the work done (in joules) by the cell as ibly, the total enthalpy change DH will appear as given
1 mol of reactants are converted to products would be out to the surroundings:
equal to the product of the change driven through the
applied voltage (say nF coulombs) and the value of this Heat given out ¼ qout ¼ DH ½17
potential difference (E  d) (volts):
On the other hand, if some work is done by the cell (e.g.,
by turning an electric motor in order to lift a weight)
w ¼ nF ðE  dÞ ½14
then

ðwout Þ þ ðqout Þ ¼ DH ½18

The second law of thermodynamics determines how

much work can be extracted from a process. For max-
imum work output there is an associated minimum heat
A Sidewire B
output:

+ −
ðwout Þmax þðqout Þmin ¼ DH ½19

The term (qout)min may be identified with  TDS, where

Cell DS is the entropy change of the cell reaction. If DS is
positive, the cell will cool down as it operates, or take in
Figure 2 The Poggendorff potentiometer: A circuit that permits
the electromotive force (emf) of a cell to be backed off so that the
heat from the surroundings. If the same cell operates
spontaneous cell reaction can be allowed to proceed, to be irreversibly, it will cool down less, or take in less heat
exactly halted (galvanometer at zero) or to be reversed. from the surroundings.
 Electrochemical Theory | Thermodynamics 5

Schematic Representation of a Galvanic which describes the nonspontaneous charging reaction:

Cell
Zn2þ ðaqÞ þ CuðsÞ-ZnðsÞ þ Cu2þ ðaqÞ ½V
A galvanic cell may be represented by writing the
composition of the individual phases of which it is In practice, the first of these alternatives is generally
composed in the order in which they are connected. A used. The implication of this is that galvanic cells are
convenient notation is to indicate each phase boundary written with the positive electrode on the right, electron
by a vertical line. The zone of contact of two solution flow in the external circuit is from left to right, and in the
phases is indicated by a double vertical line. This latter solution phase, cation flow is left to right and anion flow
region is usually associated with a small nonequilibrium from right to left (Figure 3).
potential difference caused by charge separation re- It is convenient to introduce the terms anode and
sulting from the unequal rates of diffusion of ions across cathode. A cathode is defined as the electrode to which
it. The accepted convention is for the cell diagram to be electrons flow from the external circuit, i.e., as the elec-
drawn so that the cell reaction under consideration, trode at which reduction takes place. Conversely, elec-
whether spontaneous or not, takes place when positive trons flow from the anode to the external circuit:
charge flows through the cell from left to right. The cell oxidation takes place at the anode. The point of difficulty
emf, Ecell, is positive when the cell reaction proceeds rests in the fact that in a galvanic cell under spontaneous
spontaneously on connecting the two terminals together. discharge, the cathode is the positive electrode, whereas
Thus, if m1 and m2 refer to the molal concentration of in an electrolytic cell, it is the negative electrode.
Zn2þ(aq) and Cu2þ(aq), respectively, it is equally correct
to write for the Daniell cell either
  
ZnðsÞZn2þ ðaqÞ; m1 Cu2þ ðaqÞ; m2 CuðsÞ VOC ¼ þ1:1 V ½II Dependence of Electromotive Force on
Concentration (Nernst Equation)
which describes the spontaneous discharge process:
The dependence of emf on activities or concentration of
ZnðsÞ þ Cu2þ ðaqÞ-Zn2þ ðaqÞ þ CuðsÞ ½III
the products and reactants of a cell reaction follows
or directly from a consideration of the relationship between
   emf and free energy change. For the cell reaction,
CuðsÞCu2þ ðaqÞ; m2 Zn2þ ðaqÞ; m1 ZnðsÞ
VOC ¼ 1:1 V ½IV nA A þ nB B þ y-nP P þ nQ Q þ ? ½20

_ +
→ Electrons →
salt bridge
→

Zinc ions Sulfate ions

Zinc electrode Copper electrode

Anode Cathode

Zinc sulfate Oxidation Reduction Copper(II) sulfate

Figure 3 Ion and electron flow in a schematic Daniell cell.

6 Electrochemical Theory | Thermodynamics

if ni is the stoichiometric number and mi the chemical Table 1 Standard potentials of electrode reactions at 298 K
potential of a species involved, then Electrode reaction E1 (V) Electrode reaction E1 (V)
X X   Liþ þ e#Li  3.01 Tlþ þ e#Tl  0.34
DG ¼ ni mi ¼ ni m0i þ RT ln ai ½21 Rbþ þ e#Rb  2.98 Co2þ þ 2e#Co  0.27
i i Csþ þ e#Cs  2.92 Ni2þ þ 2e#Ni  0.23
Kþ þ e#K  2.92 Sn2þ þ 2e#Sn  0.14
where m0i is the chemical potential of i in its standard Ba2þ þ 2e#Ba  2.92 Pb2þ þ 2e#Pb  0.13
state and ai its molal activity. This equation can be recast Sr2þ þ 2e#Sr  2.89 Dþ þ e#1/2D2  0.003
in the form known as the van’t Hoff reaction isotherm: Ca2þ þ 2e#Ca  2.84 Hþ þ e#1/2H2 0.000
Naþ þ e#Na  2.71 Cu2þ þ 2e#Cu 0.34
" n # Mg2þ þ 2e#Mg  2.38 1/2O2 þ H2O þ 2e#2OH 0.40
aPnP aQQ y Ti2þ þ 2e#Ti  1.75 Cuþ þ e#Cu 0.52
DG ¼ DG1 þ RT ln ½22 Be2þ þ 2e#Be Hg2þ þ 2e#Hg
aAnA aBnB y  1.70 0.80
Al3þ þ 3e#Al  1.66 Agþ þ e#Ag 0.80
Mn2þ þ 2e#Mn  1.05 Pd2þ þ 2e#Pd 0.83
Hence the emf of a cell is given by Zn2þ þ 2e#Zn  0.76 Ir3þ þ 3e#Ir 1.00
" n nQ # Ga3þ þ 3e#Ga  0.52 Br2 þ 2e#2Br 1.07
RT aPP aQ y Fe2þ þ 2e#Fe  0.44 O2 þ 4Hþ þ 4e#2H2O 1.23
E ¼ E1  ln nA nB ½23 Cd2þ þ 2e#Cd  0.40 Cl2 þ 2e#2Cl 1.36
nF aA aB y In3þ þ 3e#In  0.34 F2 þ 2e#F 2.87

E1 is the standard emf of the cell and is the equilibrium

voltage when all the cell components are in their
standard states: solution species have unit molal activities,
gases have pressures of 1 bar, and solid phases are in their the cell potential is 0.799 V and silver is positive. Thus the
most stable form. Equation [23] is known as the Nernst standard potential of the Ag|Agþ couple is þ 0.799 V
equation for a galvanic cell. In an approximate form of versus NHE. Therefore, one can condense the electro-
this equation, molal activities are replaced by molar static and thermodynamic information into one list by
concentrations to give tabulating electrode potentials and writing the half-cell
 nP  reactions as reductions. Table 1 provides a listing of
RT ½P  ½Q nQ y some frequently encountered reactions.
E ¼ E1  ln ½24
nF ½AnA ½B nB y

The values of the standard emf in eqns [23] and [24] are Dependence of Electromotive Force on
slightly different. Temperature and Pressure
The emf of a reversible cell can be regarded either as
a function of the free energy change associated with the From the identity:
overall cell reaction or as a sum of the Galvani potential
differences between phases within the cell. As noted dG ¼ SdT þ V dp ½25
above, the individual Galvani potential differences be-
tween nonidentical phases could not be measured and it it is seen that
is impossible to resolve a cell emf into its interphase    
components. It is therefore convenient to combine half- @DG @E DS
¼ DS or ¼ ½26
cells with a single half-cell and thus obtain a series of @T p @T p nF
related emf values compared to the reference half-cell
value taken as zero. The universally accepted primary    
@DG @E DV
reference half-cell is the standard hydrogen electrode. It ¼ DV or ¼ ½27
@p T @p T nF
consists of a noble metal (platinized platinum) dipping
into a solution of hydrogen ions at unit activity and Cell emf values may therefore have positive or negative
saturated with hydrogen gas at 1 bar. In practice such a temperature coefficients, depending on the sign of the
standard electrode cannot be realized, but the scale it entropy change associated with the cell reaction. An
defines can be. example for which DS Z 0 is the partial combustion of
The electrode potential is defined as the potential carbon to form carbon monoxide:
difference between the terminal of a cell constructed of
the half-cell in question and a standard hydrogen elec- 1
C þ O2 -CO ½VII
trode (NHE), and assuming that the terminal of the latter 2
is at zero voltage. For example, in the system It can be easily seen that if the change in entropy is
positive, then not only can the reaction enthalpy be
Pt jH2 ða ¼ 1ÞjHþ ða ¼ 1ÞjjAgþ ða ¼ 1ÞjAg ½VI converted into electrical energy, but in addition the
 Electrochemical Theory | Thermodynamics 7

amount of heat TDS can be extracted from the en- Voc open-circuit voltage
vironment and converted to electrical energy. V H2 molar volume of hydrogen
For cell reactions involving only condensed phases, w work
the emf can be regarded as virtually independent of wmax maximum work
applied pressure. However, when there is a change in the wout work output
number of moles of gas during a cell reaction the volume (wout)max maximum work output
change DV cannot be neglected: zi charge number of ion i
Z li chemical potential of the species
p
1 involved (J mol-1)
Ep ¼ Ep 0  DV dp ½28
nF p0 li0 chemical potential of ion i in a
solution with insignificant ion-ion
where p0 represents the standard pressure. For a cell such
interaction
as
l̃ electrochemical potential (J mol  1)
l̃i chemical potential for the ith
PtðsÞ; H2 ðgÞ; pjHClðaqÞ; mjAgClðsÞj AgðsÞ ½VIII
component of a mixture
for which the cell reaction is d cell voltage altered from the
equilibrium value (V)
1 DG change in Gibbs free energy (J
H2 ðgÞ þ AgClðsÞ-Hþ ðaqÞ þ AgðsÞ þ Cl ðaqÞ ½IX
2 mol  1)
DG1 standard change in free energy (J
1 mol  1)
DV ¼  V̄ H2 ½29
2 DH change in enthalpy (J mol  1)
where V̄ H2 is the molar volume of hydrogen. For pressure DS change in entropy (J K  1 mol  1)
up to some tens of atmospheres it can be assumed that DV change in volume (L)
the ideal gas law holds, so that Du0 Galvani potential difference between
the electrode and solution
RT Vi stoichiometric number of the
DV ¼  ½30
2p reactants
uM Galvani potential of the metal
Hence us Galvani potential of the solution
Z p Abbreviations and Acronyms
RT dp RT
Ep ¼ Ep 0 þ ¼ Ep 0 þ lnp ½31 emf electromotive force (V)
2nF p0 p 2nF
IHP inner Helmholtz plane
At higher pressures more accurate equations of state are NHE standard hydrogen electrode
required and DV generally becomes a more complex OHP outer Helmholtz plane
function of the pressure.

Nomenclature See also: Batteries: Capacity; Electrochemical Theory:

Symbols and Units Double Layer; Kinetics.
a molality (mol kg  1)
ai activity of the component
E cell voltage Further Reading
E1 standard cell voltage (V)
Bard AJ and Faulkner LR (2001) Electrochemical Methods, 2nd edn.
Ecell cell emf New York: John Wiley & Sons.
F Faraday constant Bockris JO’M, Reddy AKN, and Gamboa-Aldeco ME (2001) Modern
G total free energy Electrochemistry 2A. Fundamentals of Electrodics, 2nd edn. New
York: Kluwer Academic/Plenum Publishers.
p pressure Hamann C, Hamnett A, and Vielstich W (1998) Electrochemistry.
p0 standard pressure Weinheim: Wiley-VCH.
qout heat given out Rockwood AL (1986) Absolute half-cell thermodynamics: Electrode
potential. Physical Review A 33(1): 554--559.
(qout)min minimum heat output The Southampton Electrochemistry Group (1985) Instrumental
R universal gas constant Methods in Electrochemistry. Chichester: Ellis Horwood Publisher.
S entropy Vincent C and Scrosati B (1997) Modern Batteries. An Introduction to
Electrochemical Power Sources 2nd edn. Oxford: Butterworth-
T absolute temperature Heinemann/Elsevier Science Publishers.