J Solid State Electrochem (2017) 21:1847–1859
DOI 10.1007/s10008-017-3619-y
REVIEW
Wilhelm Ostwald’s role in the genesis and evolution
of the Nernst equation
Fritz Scholz 1
Received: 10 April 2017 / Revised: 20 April 2017 / Accepted: 24 April 2017 / Published online: 13 June 2017
# Springer-Verlag Berlin Heidelberg 2017
Abstract The historical origin of the Nernst equation can
be traced back to Helmholtz’ treatment of the thermody-
namics of galvanic cells and to Gibbs’ masterwork BOn
the Equilibrium of Heterogeneous Substances^. However,
Nernst himself used a model of the metal/solution inter-
face based on Arrhenius’ dissociation theory, together
with some aspects of van’t Hoff’s osmotic pressure theo-
ry. Bancroft performed some initial studies of redox
chains (cells) in Ostwald’s laboratory. Peters has advanced
these studies and published an equation correctly describ-
ing the potential of an inert electrode in a solution con-
taining a dissolved reversible redox pair. Riesenfeld has
treated interfaces of immiscible electrolyte solutions and
the partition equilibria of ions. Luther has shown how
standard potentials of elements possessing several redox
states are related. Fredenhagen was the first to understand
that the series of standard potentials are solvent depen-
dent. Nernst, Bancroft, Peters, Luther and Fredenhagen
were pupils of Ostwald; Riesenfeld and Fredenhagen were
students of Nernst. Indeed, the presiding genius of the
whole endeavour was clearly Friedrich Wilhelm
Ostwald. This new survey of the genesis and evolution
of what we now call Nernst equation reveals the influence
of Ostwald’s ideas on the theorizing process, and it is
concluded that his share in the development of the mod-
ern theory deserves greater recognitions.
* Fritz Scholz
fscholz@uni-greifswald.de
1
Institute of Biochemistry, University of Greifswald,
Felix-Hausdorff-Str.4, 17487 Greifswald, Germany
Introduction
The Nernst equation is one of the main pillars of modern
electrochemistry. Its importance cannot be overestimated.
Without it, we could not understand batteries, fuel cells, elec-
trochemical sensors, bioelectrochemical sensors, membrane
potentials, ion partition, etc.
The term Nernst equation is used in contemporary lit-
erature [1–5] for describing three cases: (a) the equilibri-
um potential (difference of Galvani potentials) of an elec-
trode possessing an interface at which an electron current
is converted to an ion current (e.g. a redox electrode, or a
metal/metal ion electrode), for describing (b) the potential
(voltage, electromotive force) of a cell reaction of an elec-
trochemical cell, and for describing (c) the equilibrium
potential (difference of Galvani potentials) of an electrode
possessing an interface at which ions partition:
In case (a), assuming the following electrochemical equi-
librium at an electrode,
Ox þ ne− ⇄Red
(charges of oxidized and reduced forms are omitted), the re-
spective Nernst equation is as follows:
RT aOx
E eq: ¼ E ⊖
electrode þ ln ð1Þ
nF aRed
where Eeq is the equilibrium potential, E ⊖
electrode is the standard
electrode potential versus a standard electrode, R is the gas
constant, T is the absolute temperature, n is the number of
electrons transferred in the electrode reaction, F is the
Faraday constant and a is the equilibrium activity of the oxi-
dized and reduced forms.
1848
For case (b), assuming the electrochemical cell reaction:
n2 jν Ox1 jOx1 þn1 jν Red2 jRed2 ⇄n2 jν Red1 jRed1 þn1 jν Ox2 jOx2
with the single equilibria
jν Ox1 jOx1 þ n1 e− ⇄jν Red1 jRed1
and
jν Ox2 jOx2 þ n2 e− ⇄jν Red2 jRed2
and the relations and n1n2 = z, the respective Nernst equation
is as follows:
n2 jν Ox1 j n1 jν Red2 j
RT aOx1 aRed2
E eq:;cell ¼ E⊖ þ ln
cell
zF n2 jν Red j n1 jν Ox j
aRed1 1 aOx2 2
(E e q . , c e l l is the equilibrium potential (voltage,
electromotive force) of the cell reaction, E ⊖
cell is the standard
potential of cell reaction; all other symbols have the same
meaning as in Eq. 1).
In case (c), assuming the interfacial equilibrium Xz(α) ⇄
z
X (β), where z is the charge of the ion X, the respective
Nernst equation is as follows:
RT aXz ðαÞ
E eq: ¼ E ⊖
Xz þ ln
ðβÞ∣ðαÞ zF aXz ðβÞ
where Eeq is the equilibrium potential, E ⊖
Xz ðβÞ∣ðαÞ is the standard
potential of ion transfer at the interface, z is the charge of the
ion X, α and β denote the two phases having a common
interface at which the ions partition; all other symbols have
the same meaning as in Eq. 1. Here is not the place to discuss
the problems of choosing and defining the standard electrode
potentials, and the problems involved in defining and deter-
mining equilibrium activities of the chemical species, espe-
cially when nonaqueous or even solid ion conductors consti-
tute the two phases forming the electrode interface.
Case (b), i.e. an electrochemical cell, is of course only
distinguished from cases (a) and (c) by the fact that the second
electrode is not a reference electrode. Implicitly, also the cases
(a) and (c) relate to the potential of an electrochemical cell. In
a more strict sense, the term Nernst equation should be applied
only to Eqs. (1, 3), as these equations describe one electrode
(the second is implicitly involved due to the reference system,
and the physical background is that single Galvani potential
differences are not directly measurable); however, a more re-
laxed use is now common.
J Solid State Electrochem (2017) 21:1847–1859
As the most fundamental form of the Nernst equation, one
can regard the relation between the Galvani potential differ-
ence at an interface and the activities of the charge carriers that
are in equilibrium at that interface.
There are many other variants of Eqs. 1 to 3, e.g. those in
which formal potentials are used instead of standard poten-
tials, and all are also called Nernst equation; so in the most
general meaning, this term describes the equilibrium electrode
potential (voltages) of a single electrode or a combination of
two electrodes (an electrochemical cell) as a function of the
equilibrium activities of the involved chemical species.
Modern textbooks on electrochemistry usually start with
the derivation of the Nernst equation and then use it to ratio-
nalize the oxidation and reduction potentials of chemical spe-
cies. The standard derivation is based on the idea that thermo-
dynamic equilibrium requires equality of electrochemical po-
tentials for species present in both phases. Then, the standard
hydrogen electrode is introduced for defining standard
ð2Þ potentials and building up a galvanic series of standard poten-
tials of half-cells. This is followed by the calculation of the
voltage of a galvanic cell as the potential difference of two
half-cells. Although scientifically correct, this was not the his-
toric path of theory evolution, because the concept of electro-
chemical potential was not available to early researchers. The
actual path was more tortuous, and it involved many of the
leading physical chemists of the day, including Hermann von
Helmholtz, Josiah Willard Gibbs, Walther Nernst, Vladislav
von Türin, Georg Meyer, Rudolf Peters, Robert Thomas
Dietrich Luther, Ernst Hermann Riesenfeld and Karl
Fredenhagen.
ð3Þ
Hermann von Helmholtz 1847
In the beginning was the galvanic cell, i.e. the combination of
two half-cells, as this combination was (and still is) the only
experimentally accessible arrangement, since the Galvani po-
tential difference at a single interface is not accessible to an
external observer. Another, equally important, reason for
analysing galvanic cells was that the mechanism of potential
formation was unknown.
In 1847, the first attempt to understand the electromotive
force of a galvanic cell was made by Hermann von Helmholtz
(Fig. 1) in his famous booklet BÜber die Erhaltung der Kraft^
(BOn the conservation of force^) [6], where he argued that the
potential difference of a galvanic cell is simply given by the
difference in heats evolved at the two electrodes. This idea
was later supported by measurements of William Thomson
(the later Lord Kelvin) using a Daniell cell [7], and so this
idea became known as the BThomson-Helmholtz rule^.
According to this rule, the chemical energy of the reaction
proceeding in a galvanic cell could be completely converted
to electrical energy.
J Solid State Electrochem (2017) 21:1847–1859
Fig. 1 Hermann Ludwig Ferdinand von Helmholtz (1821-1894)
Hermann von Helmholtz 1877
In 1877, Hermann von Helmholtz, published his paper BUeber
galvanische Ströme, verursacht durch Concentrations-
Unterschiede; Folgerungen aus der mechanische
Wärmetheorie^ (BOn galvanic currents caused by concentra-
tion differences; conclusions following from the mechanical
theory of heat^) [8] in BMonatsberichte der königlich
preussischen Akademie der Wissenschaften^. The paper was
re-published by Max Planck in the booklet BAbhandlungen
zur Thermodynamik von H. Helmholtz^ in 1902 [9]. There he
dissociated himself from his previous view and advanced a
treatment which is in agreement with the second law of ther-
modynamics. Helmholtz treated the potential difference of a
galvanic cell constituted of two Cu2+/Cu half-cells with dif-
ferent concentrations of Cu2+ at the cathode and the anode.
His idea was, when this galvanic cell discharges, the Cu2+
concentration will finally be the same on both electrodes.
From a thermodynamic point of view, the result of discharge
must be the same as if the concentrations are equalized by the
transfer of water from the less concentrated to the more con-
centrated solution. So, Helmholtz arrived at the equation (in
the original notation):
qa
Pk −Pa ¼ bV 0 ð1−nÞlog ð4Þ
ak
where Pk − Pa is the potential difference between the cathode
and anode, b is the constant which depends only on the type of
electrolyte (it is a constant introduced by Adolf Wüllner
(1835–1908) for the proportionality between the salt
1849
concentration and solvent vapour pressure, V0 is the molar
volume of pure water at a certain temperature, qa and ak are
the amounts of water in which a certain (equal) amount of salt
is dissolved in the anode and cathode compartments, respec-
tively, i.e. the ratio qaak is the inverse of the concentration ratio.
In modern notation, Eq. 4 can be written as follows:
cc
ΔE ¼ klog ð5Þ
ca
where ΔE is the potential difference, k is the unknown con-
stant (although experimentally accessible via vapour pressure
measurements and determination of transference numbers),
and ccca is the ratio of concentrations of the potential determin-
ing ion.
Josiah Willard Gibbs 1878
One year later, in 1878, Josiah Willard Gibbs (Fig. 2) pub-
lished [10] the complete thermodynamic theory of a galvanic
cell based on the second law of thermodynamics. For the
voltage of an ideal (reversible) galvanic cell, he has derived
the following equation (in the original notation given in
Ostwald’s translation [11]):
0 dε dη dW g dW p
V ″ −V ¼ − þt þ þ ð6Þ
de de de de
V″ − V′is the difference of the electric potentials of the an-
ode and cathode, ε is the energy, e is the electric charge pass-
ing through the cell, η is the entropy, dWg is the gravity work, t
is the temperature and dWp is the work done by outer pressure.
When the gravity work and work of outer pressure is zero, this
equation reduces to:
0 dε dη
V ″ −V ¼ − þt ð7Þ
de de
In modern notation, this equation reads as follows:
ΔEnF ¼ −ΔH þ T ΔS ¼ −ΔG ð8Þ
with ΔE with being the potential difference between anode
and cathode (the voltage of the cell), nF the product of number
n of transferred electrons and Faraday constant F, ΔH the
change of enthalpy, T the absolute temperature, ΔS the change
of entropy, and ΔG the change of free energy (Gibbs energy).
Gibbs publication was not noticed neither by the scientific
community nor by the German physicists and chemists, to
whom it became accessible only after Wilhelm Ostwald
1850
Fig. 2 Josiah Willard Gibbs (1839-1903)
published a German translation in 1892 [11]. It is interesting to
see that Gibbs criticized the assumption put forward by
Helmholtz in his booklet BÜber die Erhaltung der Kraft^
(BOn the conservation of force^) [6], but he did not refer to
the Helmholtz publication of 1877, probably because this par-
ticular journal was not readily available in the USA.
Walther Nernst 1889
On the occasion of the 100th birthday of Helmholtz in 1921,
Walther Nernst (Fig. 3) published an account of Helmholtz con-
tributions to electrochemistry, though not without succumbing
to the temptation of displaying his own work in a flattering light
[12]. Nernst started with a discussion of Helmholtz’s mistake
made in his booklet BÜber die Erhaltung der Kraft^ (BOn the
conservation of force^) [6] and then remarked that
B…by the way, this is probably the only mistake of any
consequence, which Helmholtz made in this famous
work, and we may add, that this was not a trivial mis-
take, a clear sign of the unique standing of the author,
but a mistake of almost historic importance, that curi-
ously even now can be found implicitly or explicitly in
many publications.^ (Freely translated by F. Sch.).
After finishing his PhD in 1887 in Graz, Nernst joint the
research group of Wilhelm Ostwald in Leipzig, where he fin-
ished his Habilitation thesis in 1889. This thesis was entitled
BÜber die elektromotorische Wirksamkeit der Jonen^ and was
J Solid State Electrochem (2017) 21:1847–1859
published in Zeitschrift für physikalische Chemie [13].
Ostwald recalls his time with Nernst and wrote in his autobi-
ography [14]:
BSoon after Nernst found the line of thought in which
his enormous special talents were to bloom.
The theory of electromotive force. Within the small
group of the laboratory we constantly discussed the the-
ories of van’t Hoff and Arrhenius whose full value be-
came apparent when they were combined. It was hard
for most to grasp that indeed dissolved materials and the
ions they gave rise to behaved like gases within the
volume of the solution and in particular that they could
exert the strong pressure which had been calculated. At
that time none of us had seen Pfeffer’s experiments
which directly demonstrated this pressure and permitted
its measurement. Later on Pfeffer built an osmotic cell
for our edification and let us read the manometer for
ourselves. Why don’t the molecules fly out of the solu-
tion when they hit the surface? As we were aware the
Viennese physicist Stefan had provided the answer: on
leaving the surface strong forces amounting to several
atmospheres drive them back. But, said Nernst, if one
got around this force by forming a layer of pure solvent
over the salt solution, then the molecules in the salt
solution must immediately fly into the solvent layer.
That’s what they do, I replied, because diffusion starts
right away. The objection was that a gas fills the empty
Fig. 3 Walther Hermann Nernst (1864-1941)
J Solid State Electrochem (2017) 21:1847–1859
space in just a few moments while diffusion takes weeks
and months. I countered that the empty space provides
no hindrance to movement while the liquid solvent
gives rise to a considerable frictional resistance which
will slow the solutes movement.
I left it at that, but in Nernst’s mind the phenomenon
grew into a picture which he analysed further and which
ended with his discovery of the electromotive force of
ions.
(Footnote in original): Of course I can’t claim that this
conversation in the corner room of the old institute,
which is still fresh in my memory, provided the first
seeds of this idea. Yet I had the impression that at that
time Nernst found these thoughts hard to accept.
After a few months he published the basic idea which
soon led to his theory of the electromotive force of a
voltaic cell.^
From these lines, it is clear that the scientific discussions were
guided by Ostwald, who was enthusiastically interested in
Arrhenius’ dissociation theory and Pfeffer’s osmosis experi-
ments. This combination formed the intellectual basis for
Nernst’s attempts to understand the physical origin of
electromotive force, as everybody was aware that Helmholtz’s
treatment could not give an answer because it was purely phe-
nomenological. Nernst’s first contribution to the theory of poten-
tial differences was an equation for diffusion potentials, or as
they were called at that time galvanic potentials of liquid chains
(cells) (in German: Flüssigkeitsketten). The respective paper had
the title BZur Kinetik der in Lösung befindlichen Körper^ [15]
(BOn the kinetics of dissolved compounds^). In this paper,
Nernst considered the difference of mobilities of cations and
anions as the origin of a potential difference along a concentra-
tion gradient during the process of diffusion, when a concentrat-
ed and diluted solution are in contact. Later, Planck [16] gener-
alized the theory since Nernst had only considered 1:1 monova-
lent ion electrolytes. This theory relates to the origin of potential
differences inside electrolytes caused by the kinetics of ion
movement in a concentration gradient, i.e. diffusion. In another
paper [17], which is in fact Nernst’s habilitation thesis [18], he
tackled the establishment of a potential difference at a metal
electrode in conjunction with a solution containing the ions of
the metal, i.e. he developed the theory for calculating the
Bpotential difference at the interface of a reversible electrode^
(in the German original Bdie an der Grenzfläche umkehrbarer
Elektroden wirkende Potentialdifferenz^). The basic idea of
Nernst was to use van’t Hoff’s theory of osmotic pressure [19]
which is based on treating dissolved particles like gases, so that
they possess a pressure which is proportional to their volume
concentration, i.e. assuming that molecules dissolved in a solvent
behave like gases and obeying the gas laws. Of course, Nernst
was well aware of the reasons for deviations from the ideal gas
behaviour, i.e. solute and solvent have molecular interactions.
1851
However, he saw the possible deviations as being minor in rela-
tion to the main effects resulting from the osmotic pressure.
Further, Nernst based his theory on the finding of Arrhenius that
salts dissociate in solutions [20, 21].
It is very important to realize that Nernst’s ideas matured
inside the Institute of Physical Chemistry of Wilhelm Ostwald
in Leipzig. Ostwald later wrote in his autobiography about the
osmotic theory of van’t Hoff:
Bvan’t Hoff’s brilliant idea had now seen the light of
day, but it had been born with a defect that was almost
fatal. Though it could be generally applied to the large
group of neutral molecules it did not apply to the more
important group of salts including acids and bases. In
order to encompass them van’t Hoff had had to add into
the equations a mysterious factor i which was greater
than one and which seemed to obey laws for which no
rational explanation was available. This was the situa-
tion when, in Leipzig, I received the other manuscript. It
was from Arrhenius and carried the title: BConcerning
the dissociation of chemicals in water.B^ [22]
Ostwald has put the pieces together and derived his well-
known dilution law [23]. Nernst reasoning in [17] went as follows:
BIf we succeed to calculate the work, which is needed to
transport a certain amount of silver out of the electrode
into the solution, we shall have the potential difference
between the electrode and the solution, as this is equal to
the work, necessary to transport the amount of electricity
+1 of the amount of silver (=0.01118 g), because it is
known that it needs the work (P2–P1)ε to bring this
amount of electricity from the potential P1 to P2.
Given that E is the potential difference between the met-
al and the solution, and p the osmotic pressure of the
metal ions in the electrolyte, the work E is necessary to
transfer the electricity +1 from the solution to the metal.
If p is changes to p + dp, E becomes E + dE, and the
increment dE can be easily calculated when we com-
press the amount of electricity +1 of the cations from p
+ dp to p. It follows that dE = –Vdp. ^
Finally, Nernst writes the following formula:
P
E ¼ 0:860T ln  10−4 Volt ð9Þ
p
where p is the osmotic pressure of metal ions, T the absolute
temperature and P is a constant which he interpreted as the
Bdissolution tension of the metal^, a constant typical for each
1852
metal. Now, it was possible to calculate the potential difference
of two electrodes, i.e. the potential difference of a galvanic cell,
and it was clear that the constant k of Helmholtz is RT
nF . Although
one can certainly argue that the Bmodel idea^ of metal ions
applying an osmotic pressure to the metal, and the metal
possessing a Bdissolution tension^ is physically wrong, it must
be admitted that the theory is thermodynamically correct (as
thermodynamics does not care for mechanisms), and it boosted
the further development of electrochemistry. Later, it was realized
by Johannis Jacobus van Laar (1860–1938) (Fig. 4) [24] that it is
necessary to use the difference of chemical potentials of the metal
ions and metal to account for the potential difference [25].
The fact that Nernst used the model based on osmotic pres-
sure is, perhaps, somewhat surprising, as he could just as
easily have made a derivation based on Gibbs energies how-
ever, the van’t Hoff’s osmotic pressure theory was newer and
had a simpler notation. Unfortunately, the modern derivation
in terms of electrochemical potentials was not possible for
Nernst, as that concept was introduced much later, i.e. in
1929 by Guggenheim [26].
Unfortunately, Nernst’s use of van’t Hoff’s osmosis theory
[27] resulted [28] and still results [29] in oversimplified, strictly
speaking wrong, discussions of the nature of electrode poten-
tials in terms of Belectron pressure (or tension)^ or Bmetal dis-
solution tension^. Now, it is well known that molecules or ions
in solutions do not exercise a pressure like gas molecules
against the wall of a gas container. The absurdity of the Btension
theory^ is obvious when some authors believe they could mea-
sure with ion selective electrodes concentrations down to
10−15 mol L−1 [30] and even down to 10−45 mol L−1 [31].
(This also points to another misinterpretation of electrode po-
tentials: thermodynamic data do not tell what ions determine
Fig. 4 Johannis Jacobus van Laar (1860-1938)
J Solid State Electrochem (2017) 21:1847–1859
the electrode potential. In a 10−2 mol L−1 Ag+ solution, a silver
sulphide electrode responds to the silver ions, not to the calcu-
lated sulphide concentration!) The osmosis theory of van’t Hoff
was criticized from the beginning [32, 33], but arguments were
turned down by him, and ascribing osmosis to a tension of the
solute is obviously of longevity. It is also curious that Nernst
gave in his Nobel Lecture in 1921 still the osmotic interpreta-
tion of his equation, although he should have known better.
Finally, it may be noted that Bockris has in his famous textbook
a paragraph with the heading BThe Equilibrium Condition:
Nernst’s thermodynamic Treatment^ [1], where the author
gives the usual derivation based on electrochemical potentials,
what exactly was NOT Nernst’s treatment (although Nernst’s
treatment was of course a thermodynamic one) (Fig. 5).
Vladislav Aleksandrovich von Türin 1890
In 1890, the Russian physicist Vladislav Aleksandrovich von
Türin (Владислав Александрович Тюрин, english transliter-
ation: Tyurin) (Fig. 5) published a paper in Ostwald’s journal
Zeitschrift für physikalische Chemie [34], in which he derived
an equation for two galvanic cells: (i) one having a pure mer-
cury electrode and a mercury amalgam electrode in a solution
of the metal ions forming the amalgam and (ii) a cell with two
amalgam electrodes of different metal content. For the cell (i),
he derived the following equation:
 m  T 
E volt ¼ 3:456  10−4 ð10Þ
V 273
Fig. 5 Vladislav Aleksandrovich von Türin (1862-1907) (Владислав
Александрович Тюрин)
J Solid State Electrochem (2017) 21:1847–1859
where m is the BZahl der Kilogrammoleküle^ (=number of
kilo moles) and V the volume of amalgam in m3. For the cell
(ii), his formula is as follows:
 
h2
E1 2
0 ¼ 1:9108Tqlog ð11Þ
h1
where h is the ratio of number of mercury atoms to number of
dissolved metal atoms, T is the absolute temperature, q is the
electrochemical equivalent of the metal = mass of the element
reduced or oxidized by 1 coulomb. In a follow-up paper [35],
he gave some corrections and refinements of his equations. It is
very remarkable that von Türin based his derivation on
Arrhenius’ dissociation theory of electrolytes and van’t Hoff’s
osmotic theory, very much like Nernst. Obviously, he did not
know the paper of Nernst of 1889, which is readily understand-
able because he lived in St. Petersburg, where the German
journal was probably not so readily available, or not seen by
Türin because he had no regular position.
It may interest the reader to know some details of his life:
Vladislav Aleksandrovich von Türin was born on 19 April
1862 in S. Petersburg. Until the age of 16, he was taught by
his mother Yulia L’vovna Tyurina (neé Gryunberg=Grünberg),
a very educated woman. Vladislav taught himself mathematics,
and at the age of 16, he entered the next to last year of the
gymnasium end finished that school after 2 years with a gold
medal. In 1880, he entered the Faculty of Physics and
Mathematics of S. Petersburg University, where he graduated
in 1884 with a candidate-thesis (equivalent of a PhD) for which
he received the Ivanovskiy Award. After several unsuccessful
attempts to obtain a position at the university, he published
some articles in journals devoted to the popularizing of science.
Ivan Fyodorovich Shreder (Schröder) (1858–1918), the writer
of his obituary [36] wrote the following:
BValdislav Aleksandrovich, shy, bashful, ambitious, un-
communicative, but equipped with a bright intellect,
completely devoid of experimental opportunities,
attracted the attention of only those people who made
the effort to recognize his inner values. For such rea-
sons, his attempts to work in the laboratory of D. I.
Mendeleyev, where I met him, failed also. Parallel to
his publication activity, Vladislav Aleksandrovich, dili-
gently studied physical chemistry, which at that time
flourished. The ideas of Maxwell, van’t Hoff and
Ostwald (energetics), which, for that epoch have given
the most important generalisations, attracted his atten-
tion and motivated him to study the fundamentals and to
come up with some conclusions.B
Later Shreder noted that he failed to reach the high stan-
dards expected of him only because he was deprived of
1853
experimental data and discussions at the highest international
level. Shreder wrote:
BWilhelm Ostwald, who did know him only from two
little papers in Z. Phys. Chem., understood this very
well and he asked me (i.e. Shreder) in summer 1898 to
convince von Türin to come to Leipzig and to work in
Ostwald’s laboratory. On my remark that von Türin
would be no help in experimental work, Ostwald smiled
and said BThis is a bagatelle for a laboratory like ours,
where so many hands are at work, while a head like von
Türin’s will be always useful.^^
When Ostwald was informed by Shreder of von Türin’s
passing away, Ostwald wrote the following:
BHe was an unusual original thinker, who, most proba-
bly, under more convenient circumstances would have
achieved something superior^.
For family reasons, von Türin could not travel to Leipzig. It
is surprising that Ostwald, who carefully reviewed all manu-
scripts submitted to his journal, did not draw the attention of
von Türin on Nernst’s paper published a year before.
Probably, he valued von Türin’s contribution so highly that
he wanted to see it published in its submitted form. It is sad
that von Türin did not receive the due recognition, although
his papers were properly discussed in the exhaustive review of
Kremann and Müller [37]. Although published a year after
Nernst’s seminal paper, von Türin achieved the same goal.
His ultimate target was to determine the molar mass of metals.
Here is not the place for a full evaluation of von Türin’s
achievements, and it may only be added, that in a certain
period it was customary in the Soviet Union to use the name
Tyurin-Nernst equation [38] in an attempt to stress the contri-
butions of Russian scientists. Even in Russian, there has been
published only one paper in a scientific journal commemorat-
ing von Türin [39].
Georg Meyer 1891
In 1891, Georg Meyer (Fig. 6), University of Freiburg,
Germany, published a paper on the determination of the mo-
lecular mass of metals using galvanic cells. He derived the
following equation (Fig. 6):
q c1
E¼ 1:908T log ð12Þ
M c2
1854 J Solid State Electrochem (2017) 21:1847–1859

Wilhelm Ostwald 1893/94

On September 13, 1893, Wilhelm Ostwald (Fig. 8) [43]

Fig. 6 Georg Meyer (1859–1950) (Copyright: 2016 Universität
Freiburg)
for an amalgam chain (cell): metal amalgam (c1) |metal
solution|metal amalgam (c2); metal is less noble than mercury,
c is the metal concentration in amalgam, q is the mass of metal
in amalgam and M is the molecular mass of metal. Meyer
explicitly referred to von Türin’s papers and mentioned that
he performed determinations of molecular masses of metals
already before von Türin’s publication. The same statement he
made in his paper in Annalen der Physik of 1890 [40], where
he also noted that he has just seen the von Türin paper and that
he has performed determinations of molecular masses of
metals before von Türin. Georg Meyer was a physicist and
made his Habilitation in 1890 with Emil Warburg in Freiburg,
and in 1898, he became the first Professor of Physical
Chemistry at the University of Freiburg.
gave a talk at the BVersammlung deutscher Naturforscher
und Ärzte^ in Nürnberg, which was entitled BDas
Chemometer^ (the chemometer) [44]. This talk and the
respective paper illustrate very well the genius and the
far-reaching ideas of Ostwald: Ostwald starts with
recollecting the Bmeters^, i.e. measuring instruments used
in physics, thermometers for temperature, manometers for
pressure, galvanometers for potentials, etc., and then asks
the question whether in chemistry there may exist a sim-
ilar meter allowing to decide whether there exists equilib-
rium between two compounds, or whether a chemical re-
action will occur when they are brought into contact.
After a lengthy discussion of the thermodynamic founda-
tions, he concluded that the BElektrometer^, i.e. a galva-
nometer, can serve as such a meter when potential differ-
ences are measured in a reversible galvanic cell.
Correctly, he stressed that chemical and electrical equilib-
rium must be established in such measurements. This talk
and publication demonstrate that Ostwald’s scientific
BWeltanschauung^ was based on a deep understanding
of thermodynamics and the ability to envisage the possi-
bilities arising from that basis. It makes clear that all the
contributions from his research group, i.e. those of Nernst,
Peters, and Luther would have been impossible, at least at
that time, without his guiding thinking.

Wilder Dwight Bancroft 1893

Bancroft (Fig. 7) was a student of Ostwald staying with him in

Leipzig from 1890 to 1893 [41]. He started measuring the
voltage of galvanic cells of redox chains (cells) using elec-
trodes in Bpure^ reductant and oxidant solutions, missing the
fact that the electrode potential depends on the ratio of both
oxidation states, and also disregarding the reversibility of the
systems [42]. Thus, his results gave only qualitative informa-
tion. His work may certainly has affected Ostwald’s thinking
about electromotive forces. Fig. 7 Wilder Dwight Bancroft (1867–1953)
J Solid State Electrochem (2017) 21:1847–1859
Fig. 8 Friedrich Wilhelm Ostwald (1853-1932) (original postcard in
possession of the author)
Further proof that Ostwald has understood the thermody-
namics of electrochemical cells can be seen in his complete-
ly correct discussion of a gas chain (cell), e.g. two Pt elec-
trodes exposed to two different hydrogen pressures p1 and
p2: without reference to any original publications, he gives
in 1893 in his BLehrbuch der allgemeinen Chemie^ [45]
(Textbook of general chemistry) the correct equation for
the voltage between the two electrodes as proportional to
logpp1 . His discussion of redox cells refers to Bancroft, but
2
not yet to Peters, as Peters started his work only later after
Ostwald’s suggestion.
Rudolf Peters 1898
Georg Rudolf Peters was a PhD student of Wilhelm Ostwald
in Leipzig. He published his PhD thesis in 1898 as a separate
printing [46], and also as a paper in Ostwald’s Zeitschrift für
physikalische Chemie [47]. At the end of his thesis, he explic-
itly wrote that he has performed the work Bauf Anregung von
Herrn Professor Dr. Ostwald^ (i.e. following a suggestion of
Ostwald). Peters derived the equation for the potential of an
inert metal electrode in a solution containing species in two
oxidation states, e.g. Fe(II) and Fe(III) ions. Thus, he expand-
ed the Nernst equation toward so-called oxidation and
1855
reduction chains (cells). He gives the following equation (in
the original notation):
RT cFe3þ
π¼Aþ ln ð13Þ
F cFe2þ
where π is the symbol for potential. For a long time, equa-
tions of this type were distinguished in the German scientific
literature from the Nernst equation and were referred to as
BPeters equation^. The term BNernst equation^ was confined
to metal/metal ions electrodes.
Peters was born on July 30, 1869, in Dresden, where he
went to a Gymnasium and then started an apprenticeship as
pharmacist. In 1892, he started studying pharmacy at the
University of Leipzig. From letters which he wrote to
Ostwald in 1900, which are now kept in the BArchiv der
Berlin-Brandenburgischen Akademie der Wissenschaften^,
it is known that Peters, after finishing his PhD, worked as a
chemist in a zinc factory in Stollberg (Westphalia, Germany)
and then in Spain for Real Compañia Asturiana in Renteria
(Gipúscoa). In these letters, he explained that he was unsatis-
fied with the work in Spain and he asked Ostwald to give him
a reference letter for applications in Germany. In a letter from
1901, he thanked Ostwald for the reference letter and told him
that he had got the position of a BHülfsarbeiter im
Laboratorium der des Königlichen Hauptzollamts Dresden I
mit dem Titel und Rang eines Zollassistenten (vorläufig!)
B(Assistant at the Royal Customs Office Dresden I in the rank
of Customs Assistant, provisional!). Peters later published a
book BChemistry for Customs Officers^ [48]. In 1919, he was
awarded the title Professor because he had trained more than
600 customs officers. Unfortunately, he also suffered from a
mental disorder which severely afflicted his four marriages,
his children and his work colleagues. He was hospitalized in
mental homes from 1931 to 1937, he became incapacitated in
1932, and he died on December 18, 1937, in a retirement
home in Großenhain (records 19116 and 10823 of the
Sächsisches Staatsarchiv, Dresden).
Robert Luther 1900, 1901
Robert Thomas Dietrich Luther (Fig. 9) [49, 50] was at
Ostwald’s Institute in Leipzig. In 1900 and 1901, he published
the very basic relations between the standard potentials of redox
systems possessing several redox states [51, 52]. On the basis of
thermodynamics and the fact that the free energy (Gibbs energy)
is a state function, he derived the following relations (in modern
notation): For metal species involved in the equilibria
(a) Me⇄Men1 þ þ n1 e‐ ,
(b) Men1 þ ⇄Meðn1 þn2 Þ þ þ n2 e‐ , and
(c) Me⇄Meðn1 þn2 Þ þ þ ðn1 þ n2 Þe‐ ,
1856 J Solid State Electrochem (2017) 21:1847–1859

Fig. 10 Ernst Hermann Riesenfeld (1877-1957) (Courtesy of Johan

Riesenfeld, Uppsala)
Fig. 9 Robert Thomas Dietrich Luther (1868-1945)

the following relations hold for the standard Gibbs free ener-
gies and the standard potentials: becomes clear that Nernst had the guiding ideas for
Riesenfeld’s work.
ΔG⊖
M=Mn1 þ
þ ΔG⊖ n ¼ ΔG⊖ ð14Þ
M 1 þ =Mðn1 þn2 Þþ M=Mðn1 þn2 Þþ

and
Bugarszky 1997
n1 FE⊖
M=Mn1 þ
þ n2 FE⊖ n
M 1 þ =Mðn1 þn2 Þþ
István (Stefan or Stephan) Bugarszky (1868–1941) (Fig. 11)
¼ ðn1 þ n2 ÞFE ⊖ ð15Þ [57, 58] was a Hungarian chemist who discovered the first
M=Mðn1 þn2 Þþ
endothermic galvanic cell in 1897 [59, 60], thus verifying
These relations are known as Luther’s rule. As with Nernst’s the thermodynamic theory of Gibbs and Helmholtz. This
work, it is clear that also Luther’s could only have been obtain-
ed in the intellectual environment of Ostwald’s Institute.

Ernst Riesenfeld 1901

Riesenfeld (Fig. 10) was a PhD student of Nernst in Göttingen

[53]. In his PhD, he studied interfaces of two immiscible elec-
trolyte solutions and showed that the potential drop at the
interface can be described by a BNernst equation^ [54, 55].
This was an important step forward as he presented an elec-
trode consisting of two ionic conductors (without the involve-
ment of a metal). Riesenfeld’s studies are based on Nernst’s
treatment of ion partition at interfaces, published previously in
1892 [56]: The title of this paper BÜber die Löslichkeit von
Mischkrystallen^ (about the solubility of mixed crystals)
hides to some extend the message that he treated ion partition
at an interface as a source of potential drop. From this, it Fig. 11 István (Stefan or Stephan) Bugarszky (1868-1941)
J Solid State Electrochem (2017) 21:1847–1859
Fig. 12 Karl (Carl) Fredenhagen (1877-1949)
study was performed in Nernst’s laboratory in Göttingen and
on Nernst’s suggestion.
Karl Fredenhagen 1927
Fredenhagen (Fig. 12) [61], completed his PhD in 1901 with
Nernst in Göttingen, worked 1903/1904 in Ostwald’s labora-
tory in Leipzig, from 1906 to 1912 as Privatdozent, and from
1912 to 1923 as extraordinary Professor. From 1923 to 1945,
he was Professor at the University of Greifswald. He
pioneered chemical and electrochemical studies in nonaque-
ous solutions, especially in pure HF. In 1927 [62], he reported
that in different solvents the series of standard potentials differ
(Fig. 12).
Conclusions
In modern textbooks of chemistry, physical chemistry,
electrochemistry, biochemistry, etc. [63, 64], the term
Nernst equation is used in a very general sense, describing
the difference of Galvani potentials (equilibrium potential)
at an interface, at which charged species are in equilibri-
um, be that an interface at which an electron current is
converted to an ion current, or an interface at which ions
partition resulting in a distribution potential [65], and also
for the equilibrium potential (voltage, electromotive force)
of an electrochemical cell. Thus, the scope of what we
now call the Nernst equation is much greater than that
1857
of the equation derived by Nernst in 1889. Our under-
standing has deepened, Nernst’s derivation has been over-
thrown, but the label Nernst equation has survived. This
short survey of the development of the thermodynamic
theory of galvanic cells and the struggle to derive the
Nernst equation also reveals, that Wilhelm Ostwald
played a central role in this story: first, it was Ostwald
who recognized the importance of Gibbs’ work and made
it accessible to the world, then it was Ostwald who gath-
ered together Nernst, Bancroft, Peters, Fredenhagen and
Luther at his Institute in Leipzig, and finally, it was
Ostwald who focussed their attention on the theory of cell
potentials. Interestingly, Ostwald did not co-author any of
the important papers mentioned here, but it is beyond
doubt that he was actively involved in their genesis, as
one can easily deduce from his visionary paper on the
Chemometer [44]. The fact that Ostwald did not co-
author at least some of the important papers of his pupils
is probably due to publishing customs at that time, al-
though it may also be an indication of his generosity.
Today, Ostwald’s share in the development of electro-
chemistry can hardly be overestimated: his role was much
more than an organizer of science. Ostwald paved his own
way into electrochemistry by writing an exhaustive histo-
ry of the subject [66] which armed him with all the
knowledge prior to 1896. The many fundamental contri-
butions from his Institute, made under his supervision are
a clear indication that he was the Spiritus Rector. This
becomes even more clear looking at his American pupils
who, after advancing electrochemistry in Ostwald’s
Institute, became leading figures in Physical Chemistry
in the USA. Just to name a few: Arthur Amos Noyes
(1866–1936), Olin Freeman Tower (1872–1945),
Theodore William Richards (1868–1928) and Morris
Loeb (1863–1912) [67]. Until 2007, 25 Nobel Laureates
can trace back their scientific pedigree to Ostwald [68].
Thus, the story of the Nernst equation seems to support
the complain made recently by a science historian that
BDespite his tremendous energy and activity in his long
career, Wilhelm Ostwald is a neglected figure in the his-
tory of science. There is not even a decent biography.
Among historians of chemistry, there seems to be a con-
sensus which tends to deny Ostwald’s creativity.^ [69].
Finally, it needs mentioning that there have been
many attempts over the years to derive equations which
are similar to or identical with what we call the Nernst
equation, some based on thermodynamics, some based
on electrode kinetics [37]. In his well-known textbook
of electrochemistry [70], Gustav Kortüm avoided the
term Nernst equation, although he extensively discussed
its thermodynamic derivation, and he also put Nernst’s
term electrolytic dissolution tension in quotation marks,
obviously to express his well-reasoned distaste.
1858
Despite all well-founded criticism, the term Nernst equa-
tion is nowadays an electrochemical trademark; however, it is
necessary to know more about its background than is usually
offered in textbooks.
Acknowledgements I am very thankful to Professor Stephen Fletcher
(Loughborough, UK) and Professor György Inzelt (Budapest, Hungary)
for most valuable suggestions and comments, and to Dr. Elza Arminovna
Zakharova (Tomsk, Russia) for providing copies of papers published by
von Türin in Russian journals and for providing the obituary of von Türin,
published by Shreder.
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