Article

Cite This: J. Chem. Educ. 2018, 95, 1794−1800 pubs.acs.org/jchemeduc

Electrochemical Reaction Gibbs Energy: Spontaneity in

Electrochemical Cells
Tomasz Pacześniak,* Katarzyna Rydel-Ciszek, Paweł Chmielarz, Maria Charczuk,
and Andrzej Sobkowiak
Department of Physical Chemistry, Rzeszow University of Technology, al. Powstancow Warszawy 6, 35-959 Rzeszow, Poland
*
S Supporting Information

ABSTRACT: Spontaneity criteria for processes with useful (especially

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

electrical) work have been discussed based on total differentials of

thermodynamic functions. Reaction Gibbs energy (ΔrG) and electrochemical
reaction Gibbs energy (ΔrG̃ ) have been juxtaposed. Three-dimensional
Downloaded via UNIV DE ALICANTE on October 14, 2022 at 15:58:25 (UTC).

graphs showing the dependencies of ΔrG̃ on the extent of reaction (ξ) and
the cell voltage (φR − φL), in connection with their sections, enable both
coherent and intuitive discussion of equilibrium in electrochemical systems. It
was clearly indicated that important, commonly known dependencies can be
justified and illustrated using these graphs.

KEYWORDS: Upper-Division Undergraduate, Physical Chemistry, Misconceptions/Discrepant Events, Analogies/Transfer,

Electrochemistry, Equilibrium, Electrolytic/Galvanic Cells/Potentials

■ INTRODUCTION
It is a frequently used procedure to use a reaction Gibbs energy
(ΔrG) for considerations on spontaneity in closed systems, not
only in chemical but also in electrochemical processes at
constant temperature and pressure.1 Nevertheless, one should
be careful when applying this function, as a naive usage (which
disregards the presence of a useful work) can lead to confusion.
For example:
• How can one explain the course of the process, for
helpful in understanding electrochemical equilibrium and
reaction spontaneity. Parallel discussion of G-family thermody-
namic parameters (G and ΔrG) and their electrochemical
counterparts (G̃ and ΔrG̃ ) enables us to draw both general and
more specific conclusions concerning chemical and electro-
chemical equilibria. We believe that our model, based on
elementary thermodynamic principles, and illustrated by
relevant graphics of electrochemical reaction Gibbs energy
surfaces, can be a method of choice for teaching undergraduate
students about electrochemical equilibrium.

■
which ΔrG > 0, occurring in electrolytic cells? Does one
really experience unspontaneous phenomena? MODEL DESCRIPTION
• Or why, despite the fact that ΔrG < 0 in open Gibbs Energies in Electrochemical Systems and
electrochemical cells, does the reaction not proceed? Spontaneity
• Or why can electrolysis actually proceed in electro- It is a tempting but erroneous procedure to use the chemical
chemical cells in chemical equilibrium, for which ΔrG = spontaneity condition1a−c
0?
dG < 0 (1)
While some authors aptly point out the sources of students’
misconceptions related with electrochemistry,2 the difference where G is Gibbs energy, as an analogous criterion for the
between chemical and electrochemical equilibrium has scarcely processes with useful work at constant temperature and
been discussed.3 Even then the authors usually do not invoke pressure. Notwithstanding, adding useful work term −dw̅ gives
electrochemical reaction Gibbs energy when discussing (see Supporting Information, section SI1)
electrochemical spontaneity. dG − dw̅ < 0 (2)
In contrast to considerations based on ΔrG, electrochemical
reaction Gibbs energy (ΔrG̃ ) analysis provides an elegant and which is a correct spontaneity indicator of the process with
coherent approach to electrochemical equilibria. Many popular useful work;1b therefore it is also valid for electrochemical
physical chemistry or electrochemistry textbooks do not
mention ΔrG̃ . However, some authors have recently given Received: November 14, 2017
attention to this function.4 In this article we demonstrate how Revised: July 1, 2018
the concept of electrochemical reaction Gibbs energy can be Published: July 18, 2018
© 2018 American Chemical Society and
Division of Chemical Education, Inc. 1794 DOI: 10.1021/acs.jchemed.7b00871
J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education Article

Table 1. ΔrG̃ Compared to ΔrG in Derivation of Reaction (van ’t Hoff) Isotherm

Chemical Reaction Gibbs Energy, ΔrG Electrochemical Reaction Gibbs Energy, ΔrG̃

As follows from denotation recommended by IUPAC6, Δr ≡ ( )

∂
; therefore the definitions are

i ∂G y i ∂G̃ y
∂ξ

Δr G = jjjj zzzz Δr G̃ = jjjj zzzz

T ,P

k ∂ξ {T , P (10a) k ∂ξ {T , P (10b)

Single component parameter

μi = μi 0 + RT ln ai (11a) μĩ = μi 0 + RT ln ai + ziFφi (11b)

For the system at T = const, P = const

k k
G= ∑ niμi G̃ = ∑ niμĩ
i=1 (12a) i=1 (12b)

After differentiation (νi = dni/dξ)

k k
Δr G = ∑ νi μi Δr G̃ = ∑ νi μĩ
i=1 (13a) i=1 (13b)

Reaction parameter (νizi = νe; Supporting Information section SI4)

Δr G = Δr G° + RT ln Q (14a) Δr G̃ = Δr G° + RT ln Q + νeF(φR − φL) (14b)

processes. The left side of the expression is then called the
“electrochemical Gibbs energy” and denoted dG̃ :
dG̃ = dG − dw̅ (3)
Therefore, the electrochemical spontaneity criterion can also
be expressed as
dG̃ < 0
The spontaneity criteria for chemical (eq 1) and electro-
chemical (eq 4) processes are respectively equivalent to the
conditions (section SI2)
Δr G < 0
where ΔrG is the reaction Gibbs energy, and
Δr G̃ < 0
ΔrG̃ is the electrochemical reaction Gibbs energy.
Electrochemical Gibbs energy and electrochemical reaction
Gibbs energy are related to electric properties of the system.
The differential of electric work can be expressed by (section
SI3)
R L
dw̅ = −νeF(φ − φ ) dξ
where νe is stoichiometric number for electrons, F is the
Faraday constant, ξ is the extent of reaction, and (φR − φL) is
the cell voltage1b (also known as a cell potential;1a,5 however,
the former name is frequently used in a non-equilibrium
sense4b and will be used here to stress this possible meaning).
We should remember that cell voltage is always related to two
individual processes occurring at different electrodes.
Combining eq 3 and eq 7 gives
dG̃ = dG + νeF(φR − φL) dξ
Differentiating eq 8 with respect to ξ results in
Δr G̃ = Δr G + νeF(φR − φL)
As follows from eq 9, electrochemical reaction Gibbs energy
differs from reaction Gibbs energy by cell-voltage-related
factor. ΔrG̃ can also be related to system composition. The
intensive thermodynamic parameters of the system’s compo-
nents, the chemical potentials (μi), need to be replaced by
electrochemical ones (μ̅ i) when discussing equilibrium in
electrochemical systems.
(4) In Table 1, starting from the definitions, ΔrG and ΔrG̃
functions have been juxtaposed, and their relations with system
compositions, represented by the reaction quotients Q have
been derived.
For electrochemical systems the resulting equation (eq 14b)
(5) corresponds to eq 9 and relates electrochemical reaction Gibbs
energy (ΔrG̃ ) to Q and to cell voltage (φR − φL).
Composition-related reaction quotient (Q) can be converted
to a function of an extent of reaction (ξ). The form of this
(6) simple relation follows from a given process stoichiometry
(section SI5).
Electrochemical Reaction Gibbs Energy (ΔrG̃ ) Surface and
Its Section with ΔrG̃ = 0 Plane: Nernst Equation and
Reason for Reaction
The spontaneity of electrochemical processes and the
classification of electrochemical systems can be discussed in
(7) a way that appeals to visual perception by analysis of three-
dimensional graphs showing the dependence of electro-
chemical reaction Gibbs energy (ΔrG̃ ) on cell voltage (φR −
φL) and the extent of reaction (ξ) (Figure 1a). The presented
graphs were obtained after conversion Q to ξ in eq 14b for
simple model reaction A + B = C + D (section SI5) and can be
constructed by addition of two-dimenssional (ΔrG̃ vs ξ)
precursors at different (φR − φL) (section SI6). To the best of
our knowledge, a graph of this kind, i.e., displaying an
electrochemical reaction Gibbs energy surface, has neither
(8) been presented in the literature nor proposed for educational
purposes.
As follows from eq 6 the electrochemical spontaneity
criterion is ΔrG̃ < 0. Consequently, the condition ΔrG̃ = 0
(9) defines equilibrium. Out of the infinitely many cell voltages
1795 DOI: 10.1021/acs.jchemed.7b00871
J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education Article

RT
E = E0 − ln Q
νeF (21)
The equilibrium state is characterized by the absence of
effective changes. It should be emphasized that every
electrochemical cell, regardless of its composition or open
cell voltage can be in electrochemical equilibrium provided
that the cell is open.
The most rudimentary application of the graphics presented
is to help to answer the question: what makes the reaction
proceed in an electrochemical cell? We choose any extent of
reaction (e.g., ξx in Figure 2) corresponding to an initial system

Figure 1. Dependence of electrochemical reaction Gibbs energy

(ΔrG̃ ) on cell voltage (φR − φL) and extent of reaction (ξ) (a) and
two-dimensional representation of section of ΔrG̃ surface with ΔrG̃ =
0 plane (b). ξe, equilibrium extent of reaction; ξe,ch, equilibrium
chemical extent of reaction; emf, electromotive force.
Figure 2. Electrochemical reaction Gibbs energy surface and the
reason for reaction.
(φR − φL) possible for any system composition (defined by ξ),
each composition has only one specific cell voltage (emf,
electromotive force) that corresponds to equilibrium con- composition. In the open cell, for the given extent of reaction,
ditions (ΔrG̃ = 0). The values of emf are determined by the the cell voltage is (φR − φL) = emf and ΔrG̃ = 0. Due to the
line of intersection of the ΔrG̃ = 0 plane with the ΔrG̃ surface shape of the electrochemical reaction Gibbs energy surface,
(Figure 1a). The relation emf = f(ξe) (Figure 1b) is invertible. after diminishing the cell voltage (i.e., connecting the
It is important that emf corresponds to only one particular cell electrodes by an external circuit in a galvanic cell or using an
voltage for every extent of the reactionthe one related to external power source in an electrolyzer) also ΔrG̃ decreases
electrochemical equilibrium7 and ΔrG̃ = 0 conditions. (line a). This spurs the process in the forward direction (line
Consequently substituting 0 for ΔrG̃ and emf for (φR − φL) b), because, as shown previously (eq 6), negative ΔrG̃
into eq 14b gives corresponds to a spontaneous process. It is characteristic,
0 = Δr G° + RT ln Q + νeF emf (15) that the ΔrG̃ < 0 condition is equivalent to (φR − φL) < emf. It
is also obvious from the picture that any process at (φR − φL)
therefore, > emf is thermodynamically forbidden, because then ΔrG̃ > 0.
0 = Δr G + νeF emf (16) Section of Electrochemical Reaction Gibbs Energy (ΔrG̃ )
Surface with (φR − φL) = const Planes. Chemical vs
which leads to a popular1a−c equation, Electrochemical Conditions and Electrochemical
Δr G = −νeFemf (17) Equilibrium
The condition (φR − φL) = 0 is inherent in any chemical
or for standard conditions,
reaction. For zero value cell voltage eq 14b converts into eq
Δr G° = −νeFemf 0 (18) 14a and ΔrG̃ = ΔrG. The section of ΔrG̃ surface with the plane
corresponding to (φR − φL) = 0 condition (Figure 3a) results
In turn rearranging eq 15 gives in the two-dimensional dependence ΔrG̃ = f(ξ) (Figure 3b,
Δ r G° RT curve 0) identical to the graph presented customarily for
emf = − − ln Q chemical reactions.1a Consequently, in this case the zero value
νeF νeF
of ΔrG̃ corresponds to chemical equilibrium with chemical
(19)

Next, using emf0 for

Δ G°
− νr F (according to eq 18) leads to the equilibrium extent of reaction, ξe,ch. In view of the above,
e chemical equilibrium can thus be perceived as a specific case of
Nernst equation: an electrochemical equilibrium.
RT In closed systems, various cell voltages (φR − φL) create
emf = emf 0 − ln Q different equilibrium outcomes during electrolysis, in the same
νeF (20)
way as an extent of reaction defines the equilibrium cell voltage
The cell voltage (φ − φ ) is the most frequently denoted
R L
in a galvanic cell. Thus, (Figure 3b, curve 1) positive (φR −
E;1,4,5,8 therefore, in (and only in) equilibrium conditions, for φL) corresponds to diminished (with regard to ξe,ch)
which (φR − φL) = emf, one can also write equilibrium extent of reaction (ξe,1). Negative cell voltage
1796 DOI: 10.1021/acs.jchemed.7b00871
J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education Article

equilibrium constant (K̃ ) is also cell-voltage-dependent.

Inserting 0 for ΔrG̃ and emf for (φR − φL) into eq 14b
gives for equilibrium

0 = Δr G° + RT ln K̃ + νeF emf (22)

therefore,

K̃ = e−ΔrG° / RT e−νeF emf/ RT = K e−νeF emf/ RT (23)

where K is the value of K̃ for emf = 0, i.e., chemical equilibrium

constant.8d Therefore, a chemical equilibrium constant is a
specific example of an electrochemical equilibrium constant.
By analogy to K̃ , an electrochemical reaction quotient Q̃ can
be expressed by eq 24:
R
− φL)/ RT
Q̃ = Q e−νeF(φ (24)

The electrochemical reaction quotient Q̃ is therefore a

general system-composition-defining parameter for equilibrium
and non-equilibrium and electrochemical and non-electro-
chemical conditions:
R
̃ − φL)/ RT
Q̃ = eΔrG / RT e−ΔrG° / RT e−νeF(φ (25)

For ΔrG̃ = 0 (equilibrium), an electrochemical reaction

Figure 3. Electrochemical reaction Gibbs energy surface: sections of
ΔrG̃ surface with (φR − φL) = const planes (a) and two-dimensional
representation of sections as ΔrG̃ = f(ξ) dependencies (b).
(Figure 3b, curve 2) corresponds to increased equilibrium
extent of reaction (ξe,2). Consequently the electrochemical
quotient Q̃ reduces to K̃ , whereas, for (φR − φL) = 0 (chemical
system), it becomes Q. When both conditions are fulfilled, Q̃
turns out to be a chemical equilibrium constant K. We believe
that electrochemical reaction quotient has never been defined,
but it deserves definition to make the equilibrium description
complete.

Figure 4. Electrochemical reaction Gibbs energy surface: sections of ΔrG̃ surface with ξ = const planes (a) and two-dimensional representation of
sections as ΔrG̃ = f [(φR − φL)] dependencies (b−d).

1797 DOI: 10.1021/acs.jchemed.7b00871

J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education
Sections of Electrochemical Reaction Gibbs Energy (ΔrG̃ )
Surface with ξ = const Planes. Relations between emf,
ΔrG̃ , and ΔrG for Various Electrochemical Systems
The planes corresponding to selected values of ξ cross the ΔrG̃
surface giving two-dimensional, linear ΔrG̃ = f(ξ) depend-
encies (Figure 4). The graphics enable us to discuss the
relations between emf, ΔrG̃ , and ΔrG in different electro-
chemical systems.
The nonhatched, “spontaneity areas” in Figure 4b−d
correspond to ΔrG̃ < 0 condition; i.e., they relate to a negative
electrochemical reaction Gibbs energy for a forward reaction.
Zero of a ΔrG̃ function match emf. The function ΔrG̃ has
constant value, independent of the cell voltage and character-
istic of the specific ξ.
Section 1 of Figure 4a,b is typical of a reactant-rich system
(ξ < ξe,ch) for which emf > 0 and ΔrG < 0. A negative ΔrG̃
condition can be implemented by connecting electrodes with
an external circuit of finite resistance (galvanic cell, effectuating
0 < (φR − φL) < emf relation), short-circuiting the electrodes
(chemical-like system, then (φR − φL) = 0) or using an
external power source, which diminishes the cell voltage (φR −
φL) < 0 and additionally boosts the reaction.
Section 0 of Figure 4a,c) corresponds to a discharged
galvanic cell (ξ = ξe,ch), for which emf = 0 and ΔrG = 0. To
make the reaction spontaneous, it is necessary to apply an
external power source and decrease ΔrG̃ . This results in (φR −
φL) < 0 relation, which turns the system into an electrolyzer.
Section 2 (Figure 4a,d) corresponds to a product-rich
system (ξ > ξe,ch), for which emf < 0 and ΔrG > 0. It is only
possible to make ΔrG̃ be negative by using an external power
source and enforcing a (φR − φL) < emf relation. The system is
a typical example of an electrolyzer. It is characteristic that the
ΔrG̃ < 0 spontaneity condition always correlates with the
relation (φR − φL) < emf.
The red part of the ΔrG surface in Figure 4a and the hatched
areas in Figure 4b−d are the realms of a reverse reaction;
however, the discussion of the reverse reaction thermody-
namics has been deliberately omitted here.
Reaction Spontaneity in Different Types of
Electrochemical Systems
It is possible to formulate the cell-voltage-based spontaneity
criterion for an electrochemical process. Based on eq 17 one
can write
dG = −νeF emf dξ (26)
Inserting eq 26 and eq 7 into eq 3 and rearranging gives
dG̃ = −νeF[emf − (φR − φL)] dξ (27)
and after differentiation
Δr G̃ = −νeF[emf − (φR − φL)] (28)
Finally, as an alternative to a quite general (and a little
abstract for a chemistry student) spontaneity criteria for
electrochemical process (eq 4 or eq 6), it is possible to
formulate a more concrete and conceptually easier one (by
combining eq 28 with eq 6):
(φR − φL) < emf (29)
Any electrochemical process is spontaneous if the cell
voltage is less (i.e., less positive or more negative) than the
electromotive force of the cell.
1798
Article
It is also possible to analyze the electrochemical spontaneity
using the single, informative graphic. Based on the presented
consideration one can distinguish several types of electro-
chemical systems, depending on their location on the
electrochemical reaction Gibbs energy surface. The surface
can be divided by three characteristic planes into six areas
(Figure 5).
Figure 5. Dependence of electrochemical reaction Gibbs energy
(ΔrG̃ ) on cell voltage (φR − φL) and extent of reaction (ξ).
Characteristic areas, important for the discussion of equilibrium and
spontaneity.
The dividing planes are as follows:
• P1the plane corresponding to ΔrG̃ = 0 condition
(equilibrium, open cells), separating spontaneous and
unspontaneous (i.e., spontaneous in the forward
direction) processes;
• P2the plane corresponding to the (φR − φL) = 0
condition (chemical processes), differentiating electro-
chemical cells into those exploiting and those not
exploiting an external power source;
• P3the plane corresponding to the ξ = ξe,ch condition
(chemical equilibrium), sectioning off the “external
power source areas” into those “absolutely requiring an
external power” (to enforce the reaction) and those
“nonabsolutely requiring an external power” (to realize
the reaction). The latter ones could actually settle for a
wire connection.
More details concerning the specific parts of the graphic
presented in Figure 5 are given in (section SI7).
The regions outlined by the above-mentioned planes are as
follows:
• F1the area corresponding to a spontaneous reaction
(because ΔrG̃ < 0) after connecting the electrodes with a
wire of a finite resistance [the reaction would also be
spontaneous in chemical conditions (because ΔrG < 0 in
this region)];
• F2the area corresponding to a spontaneous reaction
(because ΔrG̃ < 0) after connecting to an external power
source [the reaction would also be spontaneous in
DOI: 10.1021/acs.jchemed.7b00871
J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education
Table 2. ΔrG̃ and Spontaneity/Unspontaneity Criteria for Electrochemical Process
parameter spontaneous
ΔrG̃ ΔrG̃ < 0
(φR − φL) (φR − φL) < emf
ξ ξ < ξe
chemical conditions (because ΔrG < 0) and so, in fact,
could also proceed after the electrodes were connected
by a wire];
• F3−the area corresponding to a spontaneous reaction
(because ΔrG̃ < 0) after connecting to an external power
source [the reaction is nonspontaneous in chemical
conditions (because ΔrG > 0 in this region) and the
usage of an external power source is a necessary
condition for running the forward process];
• R1, R2, and R3the nonspontaneity regions (unavail-
able for a forward reaction).
Analysis of the characteristic features of the particular
regions of the ΔrG̃ surface, detailed in Table SI1 , leads to
general spontaneity criteria for electrochemical systems. For
every spontaneous process, ΔrG̃ < 0. The other conditions
follow from this one. The distinction of the systems with
regard to spontaneity is summarized in Table 2.
Therefore, for example, we can claim that the process is a
spontaneous one if the cell voltage is less than the
electromotive force or if the extent of reaction is less than
the equilibrium (electrochemical) one. Additionally, because
any chemical system can be regarded as a special case of an
electrochemical one (when (φR − φL) = 0), a chemical
equilibrium is a special case of an electrochemical equilibrium.
Consequently, inserting zero for the cell voltage in the third
column of Table 2 transforms the electrochemical equilibrium
indicators to chemical ones: ΔrG = 0, emf = 0, and ξ = ξe,ch.
■ CONCLUSIONS
The collective answer to each of the questions raised at the
beginning of the article is: it is the ΔrG̃ , and not the ΔrG
function, that determines the spontaneity in closed electro-
chemical systems. That is why even chemically nonsponta-
neous reactions (ΔrG > 0) can proceed in electrolyzers
provided ΔrG̃ < 0. Similarly an open galvanic cell (ΔrG < 0)
will not work, since ΔrG̃ = 0. Discharged galvanic cells (ΔrG =
0) will readily realize a forward reaction, provided ΔrG̃ < 0
condition is assured by harnessing an external power source.
It was demonstrated, that basic thermodynamics parameters
related to electrochemical equilibrium follow from dG̃ = dG −
dw̅ condition (eq 3) and the ΔrG̃ = ΔrG° + RT ln Q + νeF(φR
− φL) (eq 14b) relation. Three-dimensional graphics of ΔrG̃
surfaces enable convenient discussion of rudimentary electro-
chemical principles ruling electrochemical equilibrium and
visualization of spontaneity in electrochemical cells. Both
chemical system or equilibrium conditions correspond to just
one of many possible 2-D sections of the three-dimensional
ΔrG̃ surface.
The presented model provides not only a visual stimulus for
the students, frequently bored with equation-based instruction,
but also helps to discern the meeting points of apparently
disparate equations, enforces general thinking, and prevents
the flawed temptation of applying the chemical equilibrium
rules to electrochemical systems.
1799
Article
equilibrium nonspontaneous
ΔrG̃ = 0 ΔrG̃ > 0
(φR − φL) = emf (φR − φL) > emf
ξ = ξe ξ > ξe
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available on the ACS
Publications website at DOI: 10.1021/acs.jchemed.7b00871.
Derivation of the equations and details of the graphic
illustrating the electrochemical reaction Gibbs energy
surface (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: tompacz@prz.edu.pl.
ORCID
Tomasz Pacześniak: 0000-0002-9877-4826
Paweł Chmielarz: 0000-0002-9101-6264
Notes
The authors declare no competing financial interest.
■
REFERENCES
(1) (a) Atkins, P. W.; de Paula, J. Atkins’ Physical Chemistry, 9th ed.;
Oxford University Press: Oxford; New York, 2010. (b) Mortimer, R.
G. Physical chemistry, 3rd ed.; Academic Press/Elsevier: Amsterdam;
Boston, 2008. (c) Chang, R.; Thoman, J. W., Jr. Physical chemistry for
the chemical sciences; University Science Books: Mill Valley, CA, USA,
2014. (d) Monk, P. M. S. Physical chemistry: Understanding our
chemical world; Wiley: Chichester, England; Hoboken, NJ, USA, 2004.
(2) (a) Bonicamp, J. M.; Clark, R. W. Textbook error: Short
circuiting an electrochemical cell. J. Chem. Educ. 2007, 84 (4), 731−
734. (b) Sanger, M. J.; Greenbowe, T. J. Students’ misconceptions in
electrochemistry: Current flow in electrolyte solutions and the salt
bridge. J. Chem. Educ. 1997, 74 (7), 819−823. (c) Sanger, M. J.;
Greenbowe, T. J. An analysis of college chemistry textbooks as
sources of misconceptions and errors in electrochemistry. J. Chem.
Educ. 1999, 76 (6), 853−860. (d) Ozkaya, A. R. Conceptual
difficulties experienced by prospective teachers in electrochemistry:
Half-cell potential, cell potential, and chemical and electrochemical
equilibrium in galvanic cells. J. Chem. Educ. 2002, 79 (6), 735−738.
(3) (a) Birss, V. I.; Truax, D. R. An Effective Approach to Teaching
Electrochemistry. J. Chem. Educ. 1990, 67 (5), 403−409. (b) Thomp-
son, R. Q.; Craig, N. C. Unified electroanalytical chemistry:
Application of the concept of electrochemical equilibrium. J. Chem.
Educ. 2001, 78 (7), 928−934.
(4) (a) Girault, H. H. Analytical and physical electrochemistry; EPFL,
Marcel Dekker: Lausanne, Switzerland,;New York, NY, USA, 2004.
(b) Bard, A. J.; Inzelt, G. R.; Scholz, F. Electrochemical dictionary, 2nd
rev. & extended ed.; Springer: Heidelberg, Germany, 2012.
(5) (a) Brett, C. M. A.; Brett, A. M. O. Electrochemistry: Principles,
methods, and applications. Oxford University Press: Oxford, U.K.; New
York, 1993. (b) Linder, B. Elementary physical chemistry; World
Scientific: Hackensack, NJ, USA, 2011; DOI: 10.1142/7690.
(6) Cohen, E. R.; Cvitas, T.; Frey, J. G.; Holmström, B.; Kuchitsu,
K.; Marquardt, R.; Mills, I.; Pavase, F.; Quack, M.; Stohner, J.; Strauss,
H. L.; Takami, M.; Thor, A. J. Quantities, units, and symbols in physical
chemistry, IUPAC Green Book, 3rd ed.; IUPAC & RSC: Cambridge,
U.K., 2007.
(7) Bagoŝkiĭ, V. S. Fundamentals of electrochemistry, 2nd ed.; Wiley-
Interscience: Hoboken, NJ, USA, 2006.
DOI: 10.1021/acs.jchemed.7b00871
J. Chem. Educ. 2018, 95, 1794−1800
Journal of Chemical Education Article

(8) (a) Rogers, D. W. Concise physical chemistry, Wiley: Hoboken,

NJ, USA, 2011. (b) Zoski, C. G., Ed. Handbook of Electrochemistry, 1st
ed.; Elsevier: Amsterdam; Oxford, 2007. (c) Scholz, F.; Bond, A. M.
Electroanalytical methods: guide to experiments and applications, 2nd,
rev. and extended ed.; Springer: Heidelberg; New York, 2010.
(d) Oldham, K. B.; Myland, J. C. Fundamentals of electrochemical
science; Academic Press: San Diego, 1994.

1800 DOI: 10.1021/acs.jchemed.7b00871

J. Chem. Educ. 2018, 95, 1794−1800