ChemTexts (2014) 1:2

DOI 10.1007/s40828-014-0002-9

LECTURE TEXT

Crossing the bridge between thermodynamics

and electrochemistry. From the potential of the cell reaction
to the electrode potential
György Inzelt

Received: 18 September 2014 / Accepted: 8 October 2014

Ó Springer International Publishing 2014

Abstract Thermodynamics plays a similar role in physical technological relevance. Another field of exceptional
chemistry like mathematics in science, however, the inherent interest in the 19th century was electrochemistry. The
link between thermodynamics and electrochemistry is not generation of electricity, the use of the current to induce
entirely obvious. Less attention is paid to such physical chemical changes was something very new for the scien-
quantities as pressure, volume, enthalpy, chemical potential tists. New elements were discovered by the help of elec-
etc. in electrochemistry; on the other hand new quantities trolysis which opened up new vistas in chemistry. At the
(charge, current, electric potential etc.) and terms (galvanic second half of the 19th century—due to the development of
cell. electrode, ion etc.) appear. It is the main goal of this both disciplines—a bridge was established between ther-
lecture to present a systematic thermodynamical treatment modynamics and electrochemistry in which Walther Nernst
regarding the electrochemical cells; and to give the defini- (1864–1941), Josiah Willard Gibbs (1839–1903) and others
tions accepted presently for physical quantities, e.g., poten- played an outstanding role. Nevertheless, thermodynamics
tial of the cell reaction, electrode potential, electrochemical and electrochemistry are—in a certain extent—still treated
potential as well as terms such as electrode. separately at the universities. Thermodynamics applied in
chemistry and called chemical thermodynamics is taught in
Keywords Electrochemical cells  Potential of the cell the course of physical chemistry. It mainly covers phase
reaction  Electrodes  Electrode potential  Interfacial and chemical equilibria, the spontaneous transformations
equilibria  Electrochemical potentials of one phase to another or the direction of spontaneous
chemical reactions. Electrochemistry is either a separate
part of this course or being held as an individual lecture.
Introduction The reason for this lies in the special treatment necessary to
describe the systems of charged species or interphases.
The term thermodynamics was introduced by William First, at least one or two additional work terms appear in
Thomson (1824–1907, from 1892 Lord Kelvin) in 1849 in the fundamental equation of thermodynamics, i.e., beside
order to emphasize the dynamic nature of heat, while the heat and mechanical work as well as the conversion of
working on the problem of conversion of heat to components due to a chemical reaction; electrical work and
mechanical energy which had a high scientific and surface work should be considered. However, the real
problem is caused by the electroneutrality principle. From
this follows that an individual electrode potential, indi-
Electronic supplementary material The online version of this vidual activity coefficients of ions, hydration energy of a
article (doi:10.1007/s40828-014-0002-9) contains supplementary
material, which is available to authorized users. single ion etc. cannot be determined. Further problems also
arise, e.g., regarding the accurate determination of the
G. Inzelt (&) equilibrium cell potential (electromotive force) due to the
Department of Physical Chemistry, Institute of Chemistry,
junction potential at liquid–liquid interfaces or the surface
Eötvös Loránd University, Pázmány Péter sétány 1/A,
Budapest 1117, Hungary stress of solid electrodes. (We will return to these problems
e-mail: [email protected] later). The separate teaching of electrochemistry is also due

123
2 Page 2 of 11 ChemTexts (2014) 1:2

to the fact that several new terms have to be introduced and

defined. The latter seems to be an easy task, however, it is
not. Perhaps it is enough to mention the exact and perfect
definition of the term electrode.
The chemical reaction occurring in a flask and an elec-
trochemical cell is the same chemical reaction, consequently
the possible maximum work produced under the same con-
ditions (temperature, pressure etc.) should be the same.
Therefore, we can take this as a starting-point. In fact, this
idea serves as the inherent link between the ‘‘classical’’
thermodynamics and electrochemical thermodynamics.

Definition of an electrochemical cell

Electrochemical cells consist of at least two (usually metallic)

electron conductors in contact with ionic conductors (elec-
trolytes). Beside metals the electron conductor can be also
different forms of carbon, semiconductor materials etc. (see Fig. 1 Galvanic cell from a hydrogen electrode (left) and a calomel
later), while the electrolyte usually an aqueous or nonaqueous electrode (right). Hydrogen electrode: platinized platinum 1 electro-
solution of compounds which dissociate into ions in the sol- lyte, e.g., HCl (aq) 2 Calomel electrode: (Hg (liq) |Hg2Cl2 (s)| KCl
(aq): metal wire (1), calomel [Hg2Cl2] (2), Hg (liq) (3) and KCl (aq)
vent and which provides by this ionic conductivity. Melts, solution (4) connected with an electrolyte. V is a high resistance
ionic liquids and solid electrolytes are also used as electro- voltmeter. Cell reaction (spontaneous direction): Hg2Cl2 ? H2 
lytes. For the sake of simplicity we restrict our examples to 2Hg ? 2HCl
aqueous electrolyte solutions below. The current flows
through the electrochemical cells may be zero or non-zero.
Electrochemical cells with current flow can operate either as
galvanic cells, in which chemical reactions proceed sponta-
neously and chemical energy is converted into electrical
energy, or they are operated as electrolytic cells (also called
electrolysis cells), in which electrical energy is converted into
chemical energy. In both cases part of the energy becomes
converted into (positive or negative) heat [1–7] (Figs. 1, 2).

The reaction occurring in electrochemical cells: the cell

reaction and its thermodynamic description

If we drop a piece of zinc into the aqueous solution of

CuSO4 the following chemical reaction will take place
spontaneously
CuSO4 þ Zn  Cu þ ZnSO4 ð1Þ
We will see that copper deposits on the surface of the Fig. 2 Electrolysis cell from a hydrogen electrode (left) and a
zinc granule. Eventually all the metallic zinc will be dis- calomel electrode (right). Hydrogen electrode: platinized platinum
solved, and copper metal deposit will appear instead if (1), electrolyte, e.g., HCl (aq) (2). Calomel electrode: metal wire (1),
calomel [Hg2Cl2] (2), Hg (liq) (3) and KCl (aq) solution (4). E is a
CuSO4 is added at high excess. During this process an power source (battery or potentiostat) Cell reaction (forced direction):
increase of temperature of the solution (heat evolution) can 2Hg ? 2HCl  Hg2Cl2 ? H2
be measured. There is no useful work, the energy liberated
will be converted into heat. In an electrochemical cell the The general form of an stoichiometric equation of a
same reaction can be executed in such a way that electrical chemical reaction—which is called cell reaction if it
energy (work) can be generated beside heat (see Fig. 3 later proceeds in an electrochemical cell—can be written as
as well as Figs. 4–8 in the Supplementary material). follows [2]:

123
ChemTexts (2014) 1:2 Page 3 of 11 2

XX
DG ¼ mai lai ¼ nFEcell ð5Þ
a i

where n is the charge number of the cell reaction, F is

the Faraday constant, and Ecell is the potential of the cell
reaction (SI unit is V). The charge number which is the
number of electrons transferred in the cell reaction—
which is generally mi, since it is the stoichiometric
number of the electron in the electrode reaction—depends
on the way of the formulation of the cell reaction. For
instance,

AgCl þ 1=2 H2  Ag þ HCl n ¼ 1 ð6Þ

2AgCl þ H2  2Ag þ 2HCl n ¼ 2 ð7Þ
Please note that Ecell always has the same value inde-
Fig. 3 The Daniell cell. Processes occurring during the measure- pendent of the formulation of the reaction, while DG is
ments of the cell voltage with a high resistance voltmeter or when the proportional to the amount of substances involved. The
two electrodes are connected by a salt bridge and a metal wire minus (–) sign in Eq. (5) is a convention, i.e., for a
spontaneous reaction, where DG is negative, Ecell is
XX
mai Aai ¼ 0 ð2Þ positive. The expression, ‘‘cell reaction’’ is used almost
a i exclusively for the spontaneous reactions occurring in
galvanic cells. However, also in electrolysis cells chemical
where Ai is for the chemical formula of ith species par-
transformations take place, when current is passed through
ticipating in the reaction and mi is the respective stoichi-
the cell from an external source. Evidently, we may also
ometric number which is negative for reactants and
speak of cell reactions even in this case, albeit additional
positive for the products, and a denotes the phases. For
energy is needed for the reaction to proceed since
instance, for reaction (1) Ai represents CuSO4 with mi =
DG [ 0. The cell reaction in a galvanic cell is spontane-
-1, Zn with mi = -1. Cu with mi = 1 and ZnSO4 with
ous, i.e., DG is negative. The reaction equation should be
mi = 1, respectively, where the salts are in the same
written in such a way that DG \ 0 when it proceeds from
aqueous phase while the metals form the respective solid
left to right. The peculiarity of the cell reaction is that the
metallic phases (Cu and Zn). In the case of the Daniell cell
oxidation and reduction take place spatially separated at
(see later), where the same reaction occurs, the components
the electrodes in such a way that they are interconnected
and their respective stoichiometric numbers are the same,
by the ion transport through the solution separating the
however, CuSO4 and ZnSO4 solutions form two different
two electrodes. They are called half-reactions or electrode
liquid phases, and the metals are spatially separated.
reactions. Oxidation takes place at the anode, and reduc-
Homogeneous reactions occur in a single phase a, while
tion at the cathode.
heterogeneous reactions involve two or more phases (a, b, c
Taking into account the relationship between li and the
etc.). Because electrochemical cell reactions belong to the
relative activity of species i, ai, i.e.,
latter category, it is useful to consider the general case. The
Gibbs energy of the (cell) reaction [1–4] can be expressed as li ¼ li þ RT ln ai ð8Þ
  XX
oG where li is the standard chemical potential of species i, R
¼ DG ¼ mai lai ð3Þ
on p;T a
is the gas constant and T is the thermodynamic tempera-
i
ture, it follows that (for the sake of simplicity neglecting
where DG is the Gibbs energy (free enthalpy) of the the indication of phases further on)
reaction and lai is the chemical potential of ith species in
phase a. At equilibrium between each contacting phases for 1 X  RT X
Ecell ¼  mi li  mi ln ai
the common constituents holds the relation: nF X nF
XX RT
¼ Ecell

 mi ln ai ð9Þ
mai lai ¼ 0 ð4Þ nF
a i
Now we have the relationship between the potential of
If we consider a cell without liquid junction [8]—which the cell reaction (Ecell ) and the composition of the chemical
is in fact nonexistent but the effect of the liquid junction system, and introduced the standard potential of the cell
potential can be made negligible—we may write as follows reaction (Ecell

) [1–7, 9–11].

123
2 Page 4 of 11 ChemTexts (2014) 1:2

Ecell

can be calculated from the standard molar Gibbs also the cathode of lead acid batteries) can be used for the
energy change (DG ) for the same reaction with a simple measurements of electromotive force (emf or EMF & Ecell)
relationship: of high accuracy, however, the usual preparation methods
DG RT yield a two-phase mixture of tetragonal and orthorhombic
Ecell

¼ ¼ ln K ð10Þ PbO2 (cr), with the tetragonal form being the predominat-
nF nF
ing phase. This causes a variation in the Ecell 
values
where K is the equilibrium constant of the reaction. determined in different laboratories by 1 mV or more. We
It means that Ecell

can be calculated from the data of also assume that no chemical reactions occurs in either
caloric measurements or if the equilibrium constant of the phase. If we immerse a piece of copper in an aqueous
reaction is known. Of course, DG can also be determined CuSO4 solution, we can observe two phenomena: disso-
by electrochemical measurements, however, the exact lution of Cu or deposition of Cu from the solution. How-
determination of Ecell

is somewhat problematic since the ever, very soon an equilibrium will be established,
measured quantity is the so-called electromotive force, macroscopically no more copper deposition or dissolution
emf. (The name electromotive force and the symbol emf occurs. The equilibrium is dynamic in nature, i.e., the
are no longer recommended by IUPAC, since it is a amount of Cu ions that enters the solution is equal to the
potential difference and not a force, however, it is still used amount of copper deposited at the solid copper phase. This
by electrochemists). The electromotive force is the limiting can be detected by radioactive labelling of copper. There-
value of the electric potential difference of a galvanic cell fore, if we fabricate a cell from two electrodes, i.e., Cu
when the current through the external circuit of the cell metal in contact with CuSO4 solution and Zn metal in
becomes zero, all local charge transfer equilibria across contact with ZnSO4 solution, and let the two solutions be
phase boundaries—except at electrolyte | electrolyte junc- contacted, but not the two terminal metals, we have two
tions—and local chemical equilibria within phases being equilibrium electrodes provided that the diffusion of ions is
established [1]. slow, and there is no metallic contact between the two
different metals. Due to the relative slowness of the dif-
fusion we can measure a relatively stable potential by using
The question of equilibrium the compensation technique or a high resistance voltmeter
for a long duration of time, however, eventually the
According to Eqs. (4) and (5) if the whole cell is at equi- respective ions will reach the other metal, and react there.
librium, i.e., the cell reaction reaches its equilibrium The potential difference will decrease, and eventually will
DG = Ecell = 0, i.e., no further work can be extracted from become zero. It is called the self-discharge of the cell.
the cell and no current will flow if we connect the elec-
trodes by using a conductor. We mentioned above that emf
can be measured if no current flows through the cell, and The cell diagram
all local charge transfer and chemical equilibria being
established. However, it is valid for a functioning cell, and It is useful to represent a cell by a diagram [1]. For the cell
practically no current flows because either the potential described above we may give the following diagram. It is
difference of the cell under study is compensated by the well-known Daniell cell [12] which was constructed in
another galvanic cell or the resistance of the external 1836 by an English scientist, John Frederic Daniell (1790–
conductor (the input resistance of the voltmeter) is several 1845). It was used in telegraph systems as a power source.
orders of magnitude higher than the internal resistance of
Cu(s) j Zn(s) j ZnSO4 ðaqÞ jj CuSO4 ðaqÞ j Cu(s) ð11Þ
the galvanic cell. The equilibria are related to the processes
occurring at the interfaces, i.e., to the electron or ion Sometimes the activity or concentration, and gas pres-
transfers, within the electron conducting part of the elec- sure are also indicated.
trodes and the electrolyte, ionically conducting phase. A single vertical bar (|) should be used to represent a
What does this mean? For instance, in an amalgam elec- phase boundary, a dashed vertical bar (pp) to represent a
trode, the deposited metal is homogeneously distributed in
junction between miscible liquids, and double, dashed
the mercury or Li? ions are evenly distributed in the whole
graphite phase in the case of Li-ion electrodes. The dif- vertical bars (pppp) to represent a liquid junction, in which the
ferent phases are at equilibrium related to the given con- liquid junction potential has been assumed to be eliminated
ditions (T and p), e.g., LixCy phases in the latter system. [1, 13].
Another example is the widely used PbO2 (s, cr) |PbSO4 (s, It is recommended to construct the cell diagram in such
cr) reversible electrode, where s indicates solid, cr indicates a way that reduction takes place at the electrode displayed
crystalline phases. Cells containing this electrode (e.g., it is on the right-hand side, i.e., it is cathode, the electron

123
ChemTexts (2014) 1:2 Page 5 of 11 2

consuming electrode. Consequently, the electron releasing The electrode consists of two or more electrically con-
anode is placed left. The positive charge (electricity), i.e., ducting phases switched in series between which charge
the ionic flow, is flowing from left to right. However, it is carriers (ions or electrons) can be exchanged, one of the
not always easy to do because sometimes a slight change of terminal phases being an electron conductor and the other
the electrolyte concentration causes the change of the an electrolyte.
direction of the charge transfer processes. The electrode can be schematically denoted by these
Rules for the definite description of an electrochemical two terminal phases, e.g., Cu(s) | CuSO4(aq), disregarding
cell were defined in 1953 by the Stockholm convention [1, all other phases that may be interposed. However, in cer-
14]. It was established that, if the direction of current flow tain cases more phases are displayed, e.g., Ag(s) | AgCl(s) |
coincides with the direction upon short-circuiting the cell, KCl(aq) or Pt(s) | Polyaniline(s) | H2SO4(aq) since the
the electrical potential difference will be counted positive. consideration of those phases are essential regarding the
It is of importance to keep in mind when we want to equilibria and the thermodynamic description.
measure the potential difference of an electrochemical cell The electrodes can be classified in several ways. The
by a voltmeter since sign of the voltage measured depends electrode on which reduction occurs is called cathode, on
on the way of connection of the electrodes to the voltmeter. which oxidation takes place is called anode. The positive
It should be mentioned that this potential difference is well electrode is the cathode in a galvanic cell and the anode is
defined only if it is measured between two pieces of in an electrolytic cell. In a galvanic cell the negative
material of the same composition. In the cell diagram (11) electrode is the anode, while in an electrolytic cell it is the
copper pieces are attached to both the left-hand and the cathode. According to the nature of species participating in
right-hand electrodes. Otherwise the different contact electrochemical equilibria and the realization of the equi-
potential differences influence the measured potential libria we may speak of electrodes of the first kind, elec-
values. trodes of the second kind, electrodes of the third kind,
redox electrodes, and membrane electrodes.
When more than one electrode reaction takes place
Definition of electrodes simultaneously at the interface, the electrode is a mixed
electrode. (A typical example of it is the spontaneous
There are currently two usages for the term electrode, corrosion, when metal dissolution and oxygen reduction or
namely either (i) the electron conductor connected to the hydrogen evolution occur simultaneously at the same
external leads or (ii) the half-cell between one electron electrode). Another important distinction is based on
conductor and at least one ionic conductor [1, 2, 4, 5, 15]. whether charged species cross the interface or not. In the
The latter version has usually been favored in electro- former case, when the charge transfer is infinitely fast, the
chemistry. The half-cell, i.e., the electrode may have a electrode is called ideally non-polarizable electrode. When
rather complicated structure. In the simplest case a pure no charge transfer occurs through the interface and the
solid metal is in contact with an electrolyte solution con- current (charge) that can be measured merely contributes to
taining its own ions. However, the electronic conductor the establishment of the electrical double layer, the term is
may be also an alloy (e.g., an amalgam), carbon (e.g., ideally polarizable electrode.
graphite, glassy carbon), boron-doped diamond, a semi- There are also names which express the function of the
conductor (e.g., a metal oxide, metal salt, doped silicon, electrode and refer to the whole construction including
germanium alloys), metal oxides (e.g., iridium dioxide, mechanical parts of the electrode, e.g., dropping mercury
titanium covered with ruthenium dioxide). It should also be or hanging mercury drop electrodes, rotating disk elec-
mentioned that even when a pure metal is immersed into an trode, combination glass electrode, optically transparent
electrolyte solution, its surface may be covered, e.g., with electrodes, photoelectrodes. Electrodes with different
an oxide layer. Typical examples are magnesium or alu- properties can be constructed by using the same element
minium, however, even the surface of platinum is covered or compound for the solid phase, however, in various
with oxides when it is stored in air or at higher positive crystal forms, morphology, surface structure, with or
potentials. Beside the spontaneously formed surface layers, without additives. For instance, carbon electrodes are
the surface of metals or other substances is often modified made of various materials, such as graphite of spectral
on purpose to obtain electrodes for special functions. When purity, graphite powder with liquid or solid binders,
a metal surface covered by an electrochemically active glassy carbon, carbon fibers, highly oriented pyrolytic
polymer layer we speak of polymer modified (or polymer graphite, paraffin-impregnated graphite (PIGE), or dia-
film) electrodes which become an important class of elec- mond. Platinum might be polycrystalline or in forms of
trodes [16]. A satisfactory definition, which includes the different single crystals (well-defined electrodes). The
factors and problems mentioned above, may be as follows. electrode geometry plays also an important role. We may

123
2 Page 6 of 11 ChemTexts (2014) 1:2

classify electrodes according to their forms such as: inlaid In is useful to define a scale, i.e., to select a reference
disk, sphere, cylinder, sheet, net, spiral wire, sponge, electrode, and fix its potential. For this purpose the stan-
inlaid ring, inlaid plate, ring-disk etc. The electrode size dard hydrogen electrode (SHE) was chosen, i.e., the ref-
is also an important factor, and consequently macroelec- erence system is the oxidation of molecular hydrogen to
trodes, microelectrodes, and ultramicroelectrodes are solvated (hydrated) protons [1–3, 9, 11, 18–25]. In aqueous
distinguished. solutions:
The functional grouping is as follows. The electrode 1=2 H2 ðgÞ ! Hþ ðaqÞ þ e ð12Þ
which is under study is called working electrode in vol-
tammetry or indicator electrode in potentiometry. The The notation H? (aq) represents the hydrated proton in
electrode the potential of which is practically constant and aqueous solution without specifying the hydration sphere.
used to make comparison of electrode potentials, i.e., to Therefore, on the basis of Eq. (9) we may write that
define the value of the potential of the electrode on the 1    1 X 
scale based on standard hydrogen electrode, is called a Ecell

¼ lHþ  0:5lH2  mi li ð13Þ
F nF
reference electrode [17]. The electrode that serves to
maintain the current in the circuit formed with the working The standard electrode potential of the hydrogen elec-
electrode in voltammetric experiments in three-compart- trode is chosen as 0 V. Thermodynamically it means that
ment cells is the auxiliary (or counter) electrode. In two- not only the standard free energy of formation of hydrogen
electrode cells the same electrode serves as reference and (lH2 ) is zero—which is a rule in thermodynamics since the
auxiliary electrode. formation standard free energy of elements is taken as
zero—but that of the solvated hydrogen ion, i.e., lHþ ¼ 0
at all temperatures which is an extra-thermodynamic
From the potential of a cell reaction to the potential assumption. In contrast to the common thermodynamic
of an electrode reaction (electrode potential) definition of the standard state, the temperature is ignored.
The zero temperature coefficient of the SHE corresponds to
The electrode potential, E (SI unit is V) is the electric the conventional assumption of the zero standard entropy
potential difference of an electrochemical cell (including of H? ions. This extra-thermodynamic assumption induces
the condition when current flows through the cell), and the the impossibility of comparing the values referred to the
left-hand electrode in the diagram of the galvanic cell (cell hydrogen electrodes, in different solvents.
diagram) is at virtual equilibrium, and hence acting as a Prior to 1982 the old standard values of E were cal-
reference electrode. In electrolysis cells the potential of the culated by using p = 1 atm = 101,325 Pa. The new ones
working electrode is compared to a reference electrode are related to 105 Pa (1 bar). It causes a difference in
which is practically at equilibrium. The liquid junction potential of the standard hydrogen electrode of
potential is assumed to be eliminated. When the right-hand ?0.169 mV, i.e., this value has to be subtracted from the
electrode is also at equilibrium the measured potential is E values given previously in different tables. Since the
the equilibrium electrode potential. In this case we measure large majority of the E values have an uncertainty of at
the electromotive force of the cell. least 1 mV, this correction can be neglected.
A knowledge of the electrode potential is of utmost When all components are in their standard states (ai = 1
importance in order to design any electrochemical device and p = 1 bar) Ecell ¼ Ecell

¼ E . However, ai is not
or to carry out any meaningful measurement. For instance, accessible by any electrochemical measurements, only the
the rate, the product and the product distribution of elec- mean activity (a±) can be determined as we will show
trode reactions depend on the electrode potential. When below. Nevertheless, in practice, aH? is as taken 1 in
current flows through an electrochemical cell the potential 1 mol dm-3 HClO4, H2SO4 and HCl aqueous solutions.
of one of the electrodes should remain practically con- Let us investigate the cell represented by the cell
stant—it is the reference electrode—in order to have a diagram
well-defined value for the electrode potential of the elec- Cu ðsÞjPt ðsÞjH2 ðgÞjHCl ðaqÞjAgCl ðsÞjAg ðsÞjCu ðsÞ
trode under investigation or to control its potential. An ð14Þ
ideally non-polarizable electrode or an electrode the
behavior of which is close to it may serve as a reference p = 1 bar c = 1 mol dm-3
electrode. The choice and the construction of the reference This cell is usually considered as a cell without liquid
electrode depend on the experimental or technical condi- junction. However, this is not entirely true since the elec-
tions, among others on the current applied, the nature and trolyte is saturated with hydrogen and AgCl near the Pt and
composition of the electrolyte (e.g., aqueous solution, non- Ag | AgCl electrodes, respectively (see above). In order to
aqueous solution, melts), and temperature. avoid the direct reaction between AgCl and H2 a long

123
ChemTexts (2014) 1:2 Page 7 of 11 2

distance is kept between the electrodes or the HCl solution measurements were easier or more reliable. On the other
is divided into two parts separated by a diaphragm. hand, E values displayed in the mentioned tables have
In this case the cell reaction is as follows been determined mostly by calorimetric measurements
AgCl þ 1=2 H2  Ag þ Cl þ Hþ ð15Þ since in many cases—due to kinetic reasons, too slow or
too violent reactions—it has been impossible to collect
From Eq. (15) these data by using the measurement of the electric
RT potential difference of a cell at suitable conditions. In other
Ecell ¼ EAg=AgCl

 ln aHþ aCl ð16Þ cases, its application is limited by chemical reaction with
F
the solvent.
where aHþ aCl ¼ a2 ¼ ðc cHCl =c Þ2 , and
The tables compiled usually contain E values for
a and c are called as the mean ionic activity and the
simple inorganic reactions in aqueous solution mostly
mean ionic activity coefficient, respectively. These quan-
involving metals and their ions, oxides and salts, as well as
tities were introduced because only their values can be
some other important elements (H, N, O, S and halogens).
determined, since neither the individual activity nor the
Many values of DG , DH , DS and E that can be found
activity coefficient of an ion is experimentally measurable.
in these sources are based on rather old reports. The ther-
modynamic data have been continuously renewed by the
US National Institute for Standards and Technology (NIST,
Determination of the standard potential
earlier NBS = National Bureau of Standards and Tech-
nology) and its reports supply reliable data which are
As we already mentioned the standard potential of a cell
widely used by the scientific community [25]. The
reaction (Ecell

) can be calculated from the standard molar
numerical values of the quantities have also been changed
free (Gibbs) energy change (DG ) for the same reaction
due to the variation of the standard states and constants.
with a simple relationship: see Eq. (10).
Therefore, it is not surprising that E values are somewhat
However, Ecell
is not the standard potential of the elec-
different depending on the year of publication of the books.
trode reaction (or sometimes called half-cell reaction)
Despite the—usually slight—difference in the data and
which are tabulated in the tables [18–25], but it is the
their uncertainty, E values are very useful for predicting
standard potential of that electrode reaction (abbreviated as
the course of any redox reactions including electrode
standard electrode potential), E , in which the molecular
processes.
hydrogen is oxidized to solvated protons as the balancing
reaction of the reduction reaction. This means that E
always refers to a system like Ox ? 1/2H2  The formal potential (E0

c )
Red- ? H?. It means that the species being oxidised is
always the H2 molecule and E is always related to the Beside Ecell

and E the so-called formal potentials (E0

cell
reduction of Ox. This is the reason why we speak of and E0
c ) are frequently used. The purpose of defining for-
reduction potentials. In the opposite case the numerical mal potentials is to have ‘‘conditional constant’’ that takes
value of E would be the same but the sign would be into account activity coefficients and side reaction coeffi-
opposite. It should be mentioned that in old books, e.g., cients (chemical equilibria of the redox species), since in
[19], the other sign convention was used, however, the many cases it is impossible to calculate the resulting
International Union of Pure and Applied Chemistry (IU- deviations because neither the thermodynamic equilibrium
PAC) has introduced the unambiguous and authoritative constants are known, nor it is possible to calculate the
usage in 1974 [1, 4]. activity coefficients. Therefore, the potential of the cell
Although the standard potentials, at least in aqueous reaction and the potential of the electrode reaction are
solutions are always related to electrode reaction described expressed in terms of concentrations:
in Eq. (12), i.e., the standard hydrogen electrode. It does
RT X ci
not mean that other reference systems cannot be used or Ecell ¼ E0
cell;c  mi ln  ð17Þ
DG of any electrochemically accessible reaction cannot nF c
be determined by measuring the emf. One may think that RT X ci
E ¼ E0 
c  mi ln  ð18Þ
DG and E values in the tables of different books are nF c
determined by calorimetry and electrochemical measure- where
ments, respectively. It is not so, the way of tabulations
RT X
mentioned serves practical purposes, only. Several ‘‘ther- E0
 

cell;c ¼ Ecell  mi ln ci ð19Þ
modynamic’’ quantities (DG , DH , DS etc.) have been nF
determined electrochemically, especially when these and

123
2 Page 8 of 11 ChemTexts (2014) 1:2

RT X In this case the equilibrium potential is as follows:

E0
 

c ¼ E  mi ln ci ð20Þ
nF RT cML
pH2
E ¼ E0

c;ML=M þ ln v ð27Þ
when SHE is the reference electrode ðaHþ ¼ ¼ 1Þ. zF cL
p
Equation (18) is the well-known Nernst-equation: where cML and cL are the concentrations of the complex and
the ligand, respectively, and E0

c;ML=M is the formal potential
RT pcmoxox
E ¼ E0

c þ ln red ð21Þ of reaction (26). At certain conditions (cM? \\ cL) the
nF pcmred
stability constant (K) of the complex and m can be estimated
where p is for the multiplication of the concentrations of from the E vs. ln cL plot by using the following equation:
the oxidised (Ox) and reduced (red) forms, respectively. RT RT
The Nernst-equation provides the relationship between E ¼ E0

c  ln K  ln cvL ð28Þ
zF zF
the equilibrium electrode potential and the composition of
the electrochemically active species. Note that the Amalgam formation shifts the equilibrium potential of a
Nernst-equation can be used only at equilibrium condi- metal (polarographic half-wave potential, E‘) into the
tions! The formal potential is sometimes called as con- direction of higher potentials due to the free energy of the
ditional potential indicating that it relates to specific amalgam formation (DGamal)
conditions (e.g., solution composition) which usually DGamal RT cþ
deviate from the standard conditions. In this way, the E ¼ E0

c  þ ln M ð29Þ
nF nF cM
complex or acid–base equilibria are also considered since
DGamal RT
the total concentrations of oxidised and reduced species E1=2 ¼ E0

c  þ ln cM ðsatÞ ð30Þ
in question can be determined e.g., by potentiometric nF nF
titration, however, without a knowledge of the actual where cM (sat) is the saturation concentration of the metal
compositions of the complexes. In the case of potentio- in the mercury. It is assumed that aHg is not altered, and
metric titration the effect of the change of activity Dred = DOx, where Dred and DOx are the respective diffu-
coefficients of the electrochemically active components sion coefficients.
can be diminished by applying inert electrolyte in high In principle, E0

c can be determined by the widely-used
concentration (almost constant ionic strength). If the electroanalytical techniques (e.g., polarography, cyclic vol-
solution equilibria are known from other sources, it is tammetry). The combination of the techniques is also useful.
relatively easy to include their parameters into the
respective equations related to E0 
c . The most common
equilibria are the acid–base and the complex equilibria.
Application of the Gibbs–Helmholtz equation
In acid media a general equation for the proton transfer in electrochemistry
accompanying the electron transfer is
The Gibbs–Helmholtz equation
Ox þ ne þ mHþ  Hm RedðmnÞþ E0

c ð22Þ    
oDG oDG
Hm RedðmnÞþ  Hm1 Redðmn1Þþ þ Hþ Ka1 ð23Þ DG ¼ DH þ T ; DS ¼ ; ð31Þ
oT p oT p
Hm1 Redðmn1Þþ  Hm2 Redðmn2Þþ þ Hþ Ka2 ð24Þ
where DG, DH and DS are the Gibbs energy, the enthalpy
etc. For m = n = 2 and the entropy change of the reaction, respectively, T is
  the temperature, p is the pressure, is frequently used in
RT cox 1 þ Ka1 aHþ þ a2Hþ
E ¼ E0
c þ ln ð25Þ thermodynamics. Taking into account Eq. (5) we may
nF cred Ka1 Ka2 substitute DG by Ecell, which gives
 
The complex equilibria can be treated in a similar DH oEcell
manner, however, one should not forget that each stability Ecell ¼  þT ð32Þ
nF oT p
constant (Ki) of a metal complex depends on the pH and
ionic strength. For exothermic and endothermic reactions DH \ 0 and
The simplest and frequent case when metal ions (Mz?) DH [ 0, respectively.
can be reduced to the metal which means that all the Before 1897 there had been no experimental evidence
ligands (Lp-) will be liberated, i.e., that endotherm reaction can proceed spontaneously when
István Bugarszky (1868–1941) discovered a galvanic cell
MLðmzmnÞþ ðaqÞ þ ze  ¼ MðsÞ þ mLp ðaqÞ ð26Þ where the cell reaction was endothermic:

123
ChemTexts (2014) 1:2 Page 9 of 11 2

þ Hg jHg2 Cl2 jKCljKOHjHg2 OjHg  ð33Þ of Ecell) by utilizing the interfacial equilibria for a Daniell
cell (Fig. 3).
2 HgCl þ 2 KOH  Hg2 O þ H2 O þ KCl DH
¼ 3;280 cal=mol e d bc a
..
ð34Þ Cu(s)jZn (s)jZnSO4 ðaqÞ.CuSO4 ðaqÞjCu(s)

Such cells when (qEcell/qT)p [ 0 absorb heat from the We have two identical copper metal terminal phases,
surroundings if thermostatted or it cools down. therefore E can be obtained from the difference of the
electrochemical potentials of electron (ze =  1 and in any
metals l~ae ¼ le  FUa ) as follows:
Thermodynamic equilibria at charged interfaces l~ae  l~ee ¼ F ðUa  Ue Þ ¼ FE ð37Þ

It is of importance to investigate the equilibria at interfaces. or by using Cu and Cu0 (for the left-hand side copper metal)
For all mobile species, i.e., for species present in the notations for the two copper terminal phases, i.e., the
contacting phases the equilibrium condition is concrete case
0  0
l~ai ¼ l~bi ; ð35Þ l~Cu
e l ~Cu
e ¼ F UCu  UCu ¼ FE ð38Þ
l~ai þ zi FUa ¼ l~bi þ zi FUb ð36Þ Because
where andl~ai l~bi are the electrochemical potentials (SI unit lCu

e
0
¼ lCu

e ð39Þ
is J) [2, 5, 26] of the ith species in phase a (e.g., in the
metal phase) and phase b (solution), respectively, zi is the i.e., the chemical potentials can be cancelled from Eq. (40),
charge number of the species, Ua and Ub are the inner l~Cu ~Cu Cu
 0
 FUCu  lCu

þ FUCu
0 0
e le ¼ le e ð40Þ
electric potentials of the respective phases, and F is the
Faraday constant. For a neutral entity (solvent or salt This was the very reason why we used identical terminal
molecules) l~i ¼ li , where li is the chemical potential. phases.
The difference of inner electric potentials of the con- Considering phase equilibria (see Eq. 35) we can write
tacting phases Dba U = Ub  Ua is called as Galvani the respective equations for the equilibria of electrons and
metal ions.
potential difference. zi F Dba U is the electrostatic compo-
Electrons are the common components in the contacting
nent of the work term corresponding to the transfer of
metal phases, i.e., at equilibrium
charged species i across the interface between the phases a
0
and b whose inner electric potentials are Ua and Ub , l~Cu
e ¼ l~Zn
e ð41Þ
respectively. From Eq. (36) we can derive an equation
Because zinc ions are present in both the zinc metal and
similar to the Nernst equation, however, because the inner
the contacting zinc sulphate solution, similarly copper ions
potentials or their difference between contacting phases
are present in both the copper metal and the contacting
cannot be measured or calculated, i.e., the absolute or
copper sulphate solution, therefore at equilibrium
single electrode potential cannot be measured, we measure
the electric potential difference of a galvanic cell (cell l~Zn ~ZnSO4
Zn2þ ¼ lZn2þ ð42Þ
voltage), Emeas, which is the difference of electric potential
between a metallic terminal attached to the right-hand l~Cu
Cu2þ
¼ l~CuSO
Cu2þ
4
ð43Þ
electrode in the cell diagram and identical metallic terminal For a single phase we may write
attached to the left-hand electrode. The electrical potential
drop can be measured only between the points of con- l~ZnSO
ZnSO4
4
¼ l~ZnSO
Zn2þ
4
þ l~ZnSO
SO2
4
ð44Þ
4
tacting phases, whose chemical composition is the same,
l~CuSO 4
~CuSO
CuSO4 ¼ l
4
þ l~CuSO 4
ð45Þ
i.e., lbi ¼ lai . It is the very reason why copper pieces were Cu2þ SO2 4

attached to the electrode metals in (11). Zinc and copper are pure phases, therefore

 Zn
l~Zn ~Zn
Zn ¼ l ~Zn
Zn2þ þ 2le ¼ lZn ð46Þ
Derivation of the potential of the cell reaction by using 
 Cu
l~Cu ~Cu
Cu ¼ lCu2þ
þ 2l~Cu
e ¼ lCu ð47Þ
interfacial equilibria
It is evident that the inner potential does not influence any
Now we will show below the derivation of the potential of dissociation equilibria in an electrolyte phase because the
the cell reaction (for the sake of simplicity we use E instead respective terms cancel each other, e.g., for the CuSO4 solution:

123
2 Page 10 of 11 ChemTexts (2014) 1:2

l~CuSO CuSO4 CuSO4

þ lCuSO  2FUCuSO4 Cu2? ? Zn  Zn2? ? Cu, since the charge tranfer is
CuSO4 ¼ lCu2þ þ 2FU
4 4
SO2 4
interesting for the electrochemists. However, in this way,
¼ lCuSO CuSO4 CuSO4
CuSO4 ¼ lCu2þ þ lSO2
4
ð48Þ
4 the terms refers to the junction potential does not appear in
Combining Eqs. (43), (45) and (46) we have the derivation.

2l~Cu
e ¼ lCu ~CuSO
Cu  lCu2þ
4
¼ lCu CuSO4
~CuSO
Cu  lCuSO4  lSO2
4
ð49Þ
4
Conclusions
similarly for the zinc electrode [Eqs. (42), (44) and (46)],
0
It is of the utmost importance to use the consistent terms
2l~Zn ~Cu
e ¼ 2le ¼ lZn ~ZnSO
Zn  l Zn2þ
4
¼ lZn ZnSO4
~ZnSO
Zn  lZnSO4  l SO2
4
4 and definitions in science. Because of historical reasons
ð50Þ electrochemists have been using a different language than
scientists working in the field of thermodynamics do.
Combining Eqs. (38), (49) and (50) we have the fol-
Electrochemistry appeared earlier in the sky of science, and
lowing equations
started to use such terms as ion, voltage, current. The
1  Cu  1 
central theory of electrochemistry was also established by
FE ¼ lCu  lCuSO
CuSO4 
4
lZn ZnSO4
Zn  lZnSO4
2  2 Alessandro Volta (1745–1827) based on the contact
1 CuSO4 ZnSO4
þ l~SO2  l~SO2 ð51Þ potentials between different metals. More than 60 years
2 4 4
later Walther Nernst elaborated the chemical-thermody-
The first term relates to the copper electrode, while the namical model of the galvanic cell. He derived the famous
second one relates to the zinc electrode. equation which was named after him. However, his
Rearranging Eq. (51) we obtain ‘‘osmotic model’’ was inappropriate from a modern point
    of view. Albeit his ideas has survived during the next
CuSO4 ZnSO4
2FE ¼  lZn þ l þ l Cu
þ l 70–80 years, the discovery of electron, the appropriate
 Zn CuSO4
 Cu ZnSO4
CuSO4 ZnSO4
þ l~SO2  l~SO2 ð52Þ explanation of the redox electrodes and electrodes of sec-
4 4 ond kind needed new ideas. The present thermodynamical
It is evident that approach concerning electrochemical cells has been
    developed mostly in 1970s, and it has permanently been
ZnSO4 CuSO4
lCu Zn
Cu þ lZnSO4  lZn þ lCuSO4 ¼ DG ð53Þ improved by the refinement of the original ideas, by
including theories of new discoveries e.g., semiconductor
for the reaction of photoelectrodes. The fundamentals are summarized herein.
CuSO4 þ Zn  Cu þ ZnSO4 ð54Þ In the second lecture the relationship between the surface
thermodynamics and electrochemistry will be discussed.
Consequently, Supplementary material contains an additional figure
 
2FE ¼ DG þ l~CuSO 2
4
 l
~ZnSO4
2 ð55Þ and several photos that can be used to this lecture as
SO SO
4 4
illustrations.
The last term relates the liquid–liquid junction poten-
tial (UCuSO4  UZnSO4 ). If other anions beside sulphate
ions were present, the electrochemical potentials of those
ions would also appear in this term. Furthermore, it fol- References
lows that the liquid junction potential can practically be
eliminated by adding an inert salt of high concentrations 1. Cohen ER, Cvitas T, Fry J et al (eds) (2007) IUPAC quantities,
units and symbols in physical chemistry, 3rd edn. RSC Publish-
in both electrode compartments since in this case the ing, Cambridge, p 73
difference of the electrochemical potentials of anions will 2. Inzelt G (2013) Electrode potentials. In: Inzelt G, Lewenstam A,
always be close to zero, and the concentration change Scholz F (eds) Handbook of reference electrodes. Springer,
occurring when current flows or even at open-circuit Berlin Heidelberg, pp 1–24
3. Inzelt G (2012) Galvanic cell (or galvanic element). In: Bard AJ,
condition due to the diffusion will be minor even for a Inzelt G, Scholz F (eds) Electrochemical Dictionary, 2nd edn.
long period of time. It is of importance to draw the Springer, Berlin Heidelberg, pp 394–395
attention to that in Eq. 54 we used the real chemical 4. Parsons R (1974) Pure Appl Chem 37:503–516
substances, since the starting materials are CuSO4 and Zn, 5. Bard AJ, Faulkner LR (2001) Electrochemical methods, 2nd edn.
Wiley, New York, pp 1–86
the products are ZnSO4 and Cu. In the majority of books 6. Inzelt G (2012) Electrochemical cells. In: Bard AJ, Inzelt G,
including textbooks the ion reactions can be found, which Scholz F (eds) Electrochemical Dictionary, 2nd edn. Springer,
is in this case: Berlin Heidelberg, p 254

123
ChemTexts (2014) 1:2 Page 11 of 11 2

7. Stojek Z (2012) Electrochemical cells (practical aspects). In: 16. Inzelt G (2012) Conducting polymers. A new era in electro-
Bard AJ, Inzelt G, Scholz F (eds) Electrochemical dictionary, 2nd chemistry. In: Scholz F (ed) Monographs in electrochemistry, 2nd
edn. Springer, Berlin Heidelberg, pp 254–256 edn. Springer, Berlin Heidelberg
8. Holze R (2012) Liquid junction. In: Bard AJ, Inzelt G, Scholz F 17. Inzelt G, Lewenstam A, Scholz F (eds) (2013) Handbook of
(eds) Electrochemical Dictionary, 2nd edn. Springer, Berlin reference electrodes. Springer, Berlin Heidelberg
Heidelberg, pp 562–563 18. Petrii OA, Tsirlina GA (2002) Electrode potentials. In: Bard AJ,
9. Inzelt G (2006) Standard potentials. In: Bard AJ, Stratmann M, Stratman M, Gileadi E, Urbakh M (eds) Encyclopedia of elec-
Scholz F, Pickett CJ (eds) Inorganic electrochemistry, vol 7a., trochemistry, vol 1. Wiley-VCH, Weinheim, pp 1–23
Encyclopedia of electrochemistryWiley, Weinheim, pp 1–15 19. Latimer WM (1952) Oxidation potentials. Prentice-Hall, Engle-
10. Scholz F (2010) Thermodynamics of electrochemical reactions. wood Cliffs
In: Scholz F (ed) Electroanalytical methods, 2nd edn. Springer, 20. Milazzo G, Caroli S (1977) Tables of Standard Electrode
Berlin, pp 11–31 Potentials. Wiley-Interscience, New York
11. Bard AJ, Parsons R, Jordan J (1985) Standard potentials in 21. Antelman MS, Harris FJ (eds) (1982) The encyclopedia of
aqueous solutions. Marcel Dekker, New York chemical electrode potentials. Plenum Press, New York
12. Holze R (2012) Daniell cell. In: Bard AJ, Inzelt G, Scholz F (eds) 22. Parsons R (1985) Redox potentials in aqueous solutions: a
Electrochemical dictionary, 2nd edn. Springer, Berlin Heidelberg, selective and critical source book. Marcel Dekker, New York
pp 188–189 23. Bratsch SG (1989) J Phys Chem Ref Data 18:1
13. Inzelt G (2012) Cell diagram. In: Bard AJ, Inzelt G, Scholz F 24. Inzelt G (2006) Standard potentials. In: Bard AJ, Stratmann M,
(eds) Electrochemical dictionary, 2nd edn. Springer, Berlin Hei- Scholz F, Pickett CJ (eds) Inorganic electrochemistry. Encyclo-
delberg, pp 111–112 pedia of electrochemistry, vol 7a. Wiley, Weinheim, pp 17–75
14. Holze R (2012) Stockholm convention. In: Bard AJ, Inzelt G, 25. Case Jr MW (1998) NIST-JANAF Thermodynamical Tables.
Scholz F (eds) Electrochemical dictionary, 2nd edn. Springer, Am. Chem. Soc. Am. Inst. Phys., NIST
Berlin Heidelberg, pp 884–885 26. Tsirlina G, Petrii OA (2012) Electrochemical potential. In: Bard
15. Inzelt G (2012) Electrode. In: Bard AJ, Inzelt G, Scholz F (eds) AJ, Inzelt G, Scholz F (eds) Electrochemical Dictionary, 2nd edn.
Electrochemical dictionary, 2nd edn. Springer, Berlin Heidelberg, Springer, Berlin Heidelberg, p 262
pp 273–277

123