Laboratory Experiment

pubs.acs.org/jchemeduc

Understanding the Nernst Equation and Other Electrochemical

Concepts: An Easy Experimental Approach for Students
Francisco J. Vidal-Iglesias, José Solla-Gullón,* Antonio Rodes, Enrique Herrero, and Antonio Aldaz
Instituto de Electroquímica, Universidad de Alicante, Apartado 99, 03080 Alicante, Spain
*
S Supporting Information

ABSTRACT: The goal of the present laboratory experiment is to deepen

the understanding of the Nernst equation and some other concepts that
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are essential in electrochemistry. In this practical laboratory session,

students first learn that the equilibrium potential of an electrode is related
to the difference between two equilibrium inner electric potentials (also
called Galvani potentials), namely, ϕM (inner electric potential of the
metallic phase) and ϕsol (inner electric potential of the solution phase).
Second, the concept of overvoltage is defined and the method to measure
it is described. Finally, it is shown how and why the inner potential of a
solution changes with the distance to the working electrode when a current
flows through the solution and how the potential difference is distributed
in an electrochemical cell when a current is flowing through it.
KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction, Physical Chemistry,
Hands-On Learning/Manipulatives, Misconceptions/Discrepant Events, Electrochemistry, Electrolytic/Galvanic Cells/Potentials

T he Nernst equation is one of the most, if not the most,

quoted electrochemical equation.1−5 For an ion−metal
electrochemical equilibrium such as Mn+ + ne− ⇌ M, the
Assuming that the contact potential difference between the two
solutions (ϕsol − ϕsol,ref) is zero

equation is normally introduced to students as E Mn+/M = (ϕM − ϕM,ref )

RT a Mn+ = (ϕM − ϕsol) − (ϕM,ref − ϕsol,ref ) (3)

E Mn+/M = E° + ln
nF aM (1) The nature of the reference electrode employed in the
measurement of the potential is indicated by the sentence
where aMn+ and aM are the activities of the oxidized Mn+ and “referred to the saturated calomel electrode”, for example.
reduced M species, respectively, E stands for the electrode However, it is also clear from eq 2 that if both inner potentials,
potential, R for the gas constant, T for the absolute ϕM and ϕsol, change, but their difference remains constant, the
temperature, and F for Faraday’s constant. However, if the activities of the species involved in the electrochemical
equation is presented in this way, it is not clear to students that equilibrium must also remain constant (or at least their
the magnitude given by EMn+/M (which depends on the ratio). Similarly, if the activities remain constant, the inner
activities of the species involved in the equilibrium) is related to potentials ϕM and ϕsol can change but in such a way that their
the difference between two inner electric potentials,6 the difference must remain constant.
potential of the metal phase of the electrode ϕM, and the Another important electrochemical concept, which is
potential of the solution phase ϕsol measured versus a reference fundamental to understand the behavior of an electrochemical
electrode. system, is the overvoltage (also called overpotential), η, which
However, because experimentally the measurement of E is is defined as the shift of the potential of an electrode from its
carried out versus a reference electrode, the magnitude equilibrium value when a current I flows through the system
measured is the difference between the potential of the metallic η = EI ≠ 0 − EI = 0 (4)
phases M and Mref; that is,
where EI≠0 stands for the electrode potential for I ≠ 0 and
RT a M n+ EI=0for the equilibrium condition, that is, I = 0.
o
E Mn+/M = E M n+
/M + ln = (ϕM − ϕM,ref ) Valuable information about the kinetics of the electro-
nF aM chemical reaction taking place on the electrode surface can be
obtained from the dependence of the current density on
= (ϕM − ϕsol) + (ϕsol − ϕsol,ref )
overvoltage, and consequently, its correct measurement is very
+ (ϕsol,ref − ϕM,ref )
(2) Published: April 13, 2012
© 2012 American Chemical Society and
Division of Chemical Education, Inc. 936 dx.doi.org/10.1021/ed2007179 | J. Chem. Educ. 2012, 89, 936−939
Journal of Chemical Education Laboratory Experiment

important. The overvoltage depends on the current density, j, importance of the position of the reference electrode in the
defined as measurement of potential differences in an electrochemical
system through which a current is flowing, and (iv) how the
I
j= potential difference between two electrodes is distributed inside
A (5)
an electrochemical device.
where A is the electrode surface area. According to the IUPAC
criteria, the current density is negative for a cathodic
(reduction) process and positive for an anodic (oxidation)
■ EXPERIMENTAL PROCEDURE
This is a 4-h experiment (one lab session) performed with 24
one. The measurement of the potential Ej≠0 must be carried out students working in couples. Students have to prepare, outside
when a current is passing through the electrolyte and that can of the lab, a lab report of the experiment which should include a
pose a problem to students, who will find that the value of the detailed response to the questions proposed in the Supporting
electrode potential strongly depends on the position of the Information.
reference electrode. In this experiment, three containers, made of glass or
In addition, when current flows through an electrochemical transparent PVC, are filled with a 1 M CuSO4 solution. The
cell, the potential needed for this flow is distributed through the central container is a cell with dimensions of 15 × 5 × 5 cm, in
cell. Thus, in the electrolyte phase, the inner potential, ϕsol, which a graph paper was fixed on one of the borders. Six 5 × 5
changes with the distance to the electrodes and it is more cm copper (Cu) pieces are introduced into the solutions and
positive near the anode than near the cathode. Thus, there is a Cu pieces 2 and 3 and 4 and 5 are connected by Cu wires as
potential drop through the electrolyte solution that is normally shown in Figure 1A. The cell is filled with 250 mL of the
called the ohmic drop, IR, where R is the resistance of the
electrolyte between both electrodes. For a homogeneous
parallel field distribution, R is
l
R=ρ
A (6)
where ρ stands for the resistivity of the solution and l for the
distance between the electrodes. Because ϕxsol changes with
distance, so does the potential difference (ϕM − ϕM,ref)x. Thus,
the electrode potential E measured versus a reference electrode
placed at a distance x from the electrode is
Ex = (ϕM − ϕM,ref )x
x=0 x=0 x
= (ϕM − ϕsol ) + (ϕsol − ϕsol ) + (ϕsol,ref − ϕM,ref )
(7)
For this homogeneous potential distribution and taking ϕxsol =
ϕsol,ref (i.e., taking the contact potential as zero):
x x=0
ϕsol = ϕsol − IRx (8)
x
where R is the resistance at distance x in the solution. Here, I is
taken as positive (or negative) for the measurement of the Figure 1. (A) Experimental setup. (B) Potential difference measure-
potential of the anode (or cathode). ment with a capillary connected to the reference electrode.
Thus, the measured electrode potential depends on the
position of the reference electrode when a current is circulating
through the system. Consequently, the true value of the CuSO4 solution, giving a liquid height of 3.3 cm. Thus, the Cu
electrode potential is that measured when the distance between electrodic area is 5 cm × 3.3 cm = 16.5 cm2. Initially, the
the metallic phase of the electrode and the reference electrode potentials of the six Cu2+/Cu electrodes, 1−6, are measured
is zero (IR → 0). However, the position of the reference using a KCl/AgCl/Ag reference electrode with the help of a
electrode has to fulfill two opposite conditions. On the one Luggin capillary placed near the electrode, the potential of
hand, it has to be far from the metallic phase of the electrode to which is going to be measured, Figure 1B. The measured values
avoid perturbations of the electric potential distribution. On the should be obviously the same for the six electrodes and should
other hand, it should be as close as possible to the metallic be about 109 mV. Differences among these values, measured
phase of the electrode to reduce the IR potential drop. These with the same reference electrode, bigger than ±3 mV can be
two requirements can be partially overcome employing a ascribed to a bad treatment of the surface of the Cu metals (the
Luggin capillary (see the Supporting Information). Therefore, it surface can be partially oxidized or contaminated). In addition,
is important to show students that the measurement of an the potential differences between Cu(1) and Cu(2) (E1 − E2),
electrode potential when current is flowing is not as simple as it between Cu(5) and Cu(6) (E5 − E6), and between Cu(1) and
seems and that some experimental precautions must be taken Cu(6) (E1 − E6), as well as the potential difference between
into account. solution I and solution III using two reference electrodes are
The aim of this laboratory experiment is to help the students also measured, which in all cases must obviously be zero or near
to understand (i) the electrochemical concepts involved in the zero (slight difference in the potential of the two reference
Nernst equation, (ii) the concept of overvoltage, (iii) the electrodes may exist).
937 dx.doi.org/10.1021/ed2007179 | J. Chem. Educ. 2012, 89, 936−939
Journal of Chemical Education Laboratory Experiment

Then, Cu(3) is connected to the positive pole of a power change in such a way that the difference between them is kept
source and Cu(4) to the negative one. A voltage of 1.00 V is constant.
applied between both electrodes and the electrode potentials Moreover, students have to measure the potentials for
for electrodes Cu(3) and Cu(4) are measured by placing the electrodes Cu(3), E3, and Cu(4), E4, while applying the
capillary of the reference electrode at different distances from potential difference of 1.00 V between electrodes Cu(3) and
the Cu piece. A graph E versus distance is drawn and the values Cu(4), by placing the capillary of the reference electrode at
of the two electrode potentials extrapolated at x = 0 are noted. different distances from the corresponding Cu piece. The E
The experimental data is used to complete a figure in the versus distance representation should be similar to that shown
Supporting Information (Figure LD8). Again, the potential of in Figure 2.
the electrodes placed in beakers I and III, the potential
difference between solution I and solution III, and the potential
differences between Cu(1) and Cu(2) (E1 − E2), between
Cu(5) and Cu(6) (E5 − E6), and between Cu(1) and Cu(6)
(E1 − E6) are measured and noted filling Figure LD8 in the
Supporting Information.

■ HAZARDS
None of the products is dangerous. However, the wastewater
from the experiment should be treated to remove Cu2+ ions.

■ RESULTS AND DISCUSSION

According to the Experimental Procedure, students should
measure the potential differences between Cu(1) and Cu(2)
(E1 − E2), between Cu(5) and Cu(6) (E5 − E6), and between
Cu(1) and Cu(6) (E1 − E6), as well as the potential difference
between solutions I and III using two reference electrodes both
before and after the 1.00 V is applied between Cu(3) and
Figure 2. Electrode potentials of Cu(3) (black solid squares) and
Cu(4) pieces. Students will find that the values E1 − E2, and E5
Cu(4) (red open circles) measured placing the reference electrode at
− E6 remain zero after connecting Cu(3) and Cu(4) to the different distances from the corresponding Cu surface.
power source. On the other hand, a potential difference of 1.00
V will be measured between E1 − E6, and also between solution
I and III. But, how is that possible if solutions I and III are
This representation also allows provides the real values of the
identical? Because of the applied voltage, the inner metal two electrode potentials by extrapolating at x = 0 the measured
potentials, ϕCu, of Cu(3) and Cu(4) have changed. Moreover, potentials at different distances. From the intercepts, the anode,
because of the connections between the copper pieces, Cu(3)− Cu(3) 122 mV, and cathode, Cu(4) 85 mV, potentials were
Cu(2) and Cu(4)−Cu(5) have the same voltage, ϕCu(3) = obtained. It should be pointed out that before the connection
ϕCu(2) and ϕCu(4) = ϕCu(5). According to the Nernst equation, to the power source, these potentials (equilibrium potentials)
since the activity of Cu2+ ions in solutions I and III has not were equal to 109 mV.
changed (no current is flowing through solutions I and III), Consequently, because of the flux of current, an overpotential
ϕCu(2) − ϕsol,I and ϕCu(5) − ϕsol,III should remain constant. (η) appears, which is positive for the anode, Cu(3), η3 = 122 −
However, ϕCu(2) is now more positive (connected to the + 109 = 13 mV and negative for the cathode, Cu(4). η4 = 85 −
pole) than before connection and consequently, to keep the 109 = −24 mV. These values were obtained from the intercept
difference ϕCu(2) − ϕsol,I constant, the potential ϕsol,I must also of the linear adjustment. This finding shows students that the
increase in the same amount. In a similar way, ϕCu(5) is now less potential of an electrode changes when a current flows through
positive (connected to the − pole) than before connection, and the interphase, shifting to more positive (or negative) values
thus, ϕsol,III should decrease in the same amount. For the same than the equilibrium potential when the current is anodic (or
reason, the change of ϕsol,I and ϕsol,III forces ϕCu(1) and ϕCu(6) to cathodic). The former values change if electrode contact areas
change to maintain the differences ϕCu(1) − ϕsol,I and ϕCu(6) − are different from those mentioned in the Experimental
ϕsol,III also constant. This potential reorganization results in a Procedure or if the distance between electrodes Cu(3) and
potential difference of 1.00 V between Cu(1) and Cu(6) and Cu(4) is not 15 cm.
between solutions I and III. Figure 2 also shows a clear dependence of the measured
Thus, this simple experiment will help students to under- electrode potential as a function of the position of the reference
stand that the equilibrium potential of an electrode, defined by electrode. The applied potential of 1.00 V is distributed in
the Nernst equation, is in fact related to the difference between container II as follows: 1 = E3 − E4 + IRtotal, where E3 and E4
two equilibrium inner potentials (electrode and solution). This are the electrode potential of electrodes Cu(3) and Cu(4) at x
difference is controlled by the activities of the compounds = 0 and IRtotal is the potential drop caused by the passage of
involved in the electrode reaction. If these activities are current I through the resistance Rtotal of the electrolyte between
constant, the value of the difference of the inner potentials at both electrodes. IRtotal can be obtained from the slope of
the electrode interphase remains constant, irrespective of the straight lines in Figure 2. These slopes reflect how the potential
particular value of each inner potential. That is to say, if any of changes with distance and are, obviously, the same but with
the inner potentials change, the other potential must also opposite sign, positive for the anode and negative for the
938 dx.doi.org/10.1021/ed2007179 | J. Chem. Educ. 2012, 89, 936−939
Journal of Chemical Education Laboratory Experiment

cathode (average slope = 65 mV cm−1). One V ≅ 122 mV − 85

mV + (65 mV/cm ×15 cm)
When current flows, the inner potential of the solution, ϕsol,
changes with the distance to the electrode. Thus, the measured
potential of the anode will be more positive as the distance
between the anode and the reference electrode increases and
the cathode potential will be less positive when the distance of
the reference electrode to the cathode increases. Experimen-
tally, a better measurement of the real (corrected) potential of
the electrode can be obtained directly by placing the capillary
tip of the Luggin capillary as near as possible to the cathode or
anode.

■ SUMMARY
These results will help students to realize that the inner
potential of an electrolyte solution, ϕsol, changes when current
flows through it and that due to the fact that the electrolyte has
non-negligible electrical resistance, the electrode potential
measured depends on the position of the reference electrode.

■
*
ASSOCIATED CONTENT
S Supporting Information

Experimental procedure for the students; student handouts;

instructor notes. This material is available via the Internet at
http://pubs.acs.org.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
Notes
The authors declare no competing financial interest.

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(4) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, 2nd ed.; John
Wiley & Sons, Inc.: New York, 2001.
(5) Compton, R. G; Sanders, G. H. W. Electrode Potentials, 1st ed.;
Oxford University Press: Oxford, 1996.
(6) IUPAC Gold Book. http://goldbook.iupac.org/I03046.html
(accessed Mar 2012).

939 dx.doi.org/10.1021/ed2007179 | J. Chem. Educ. 2012, 89, 936−939