In the Laboratory
The Solubility Product of PbCl2 from Electrochemical W
Measurements
Jimmy S. Hwang* and Ghassan A. Oweimreen
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia;
*jimmy@kfupm.edu.sa
Electrochemical cell measurements have been used to
determine the thermodynamic properties of chemical reac-
tions (1, 2). The experiment presented in this article is not
found in physical chemistry laboratory textbooks; however,
it reinforces material often discussed in lectures. The experi-
ment illustrates how thermodynamic properties such as the
change in the standard Gibbs energy, ∆G°, and the equilib-
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rium constant of a reaction are related to the emf, at different
temperatures, of electrochemical cells in which the reaction
takes place. The experiment is an application of a metal–
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insoluble salt electrode to determine the solubility of a spar-
ingly soluble salt, PbCl2.
PbCl2 Pb2+ + 2Cl−
Ksp = [Pb2+][Cl−]2
It is suited for a second- or third-year physical chemistry labo-
ratory. The students learn to use equipment for temperature
control and to freshly prepare a Ag|AgCl electrode.
Experiment
The following items are needed for the experiment.
• Two standard (sat. KCl)|AgCl(s)|Ag(s) electrodes
(Corning Glass)
• A high impedance voltmeter (Hewlett-Packard 34420
Nano Volt/Micro Ohm Meter)
• Magnetic stirrers
• Two potassium nitrate salt bridges
• An RCS Lauda Temperature Controller/Circulating
System
• Specially designed beakers with jackets for circulation
of thermostated water to control the temperatures of
the solutions in the half-cells (Figure 1)
• Silver electrode
• Platinum electrode
• 1.5-V battery
Two cells were used in the emf measurements at identi-
cal temperatures and with identical 1 M KNO3 salt bridges.
These cells, numbered 1 and 2 respectively are:
Ag(s) AgCl(s) Cl − (a = ?) (sat. KCl) AgCl(s) Ag(s)
Ag(s) AgCl(s) Cl − (1m KCl) (sat. KCl) AgCl(s) Ag(s)
The right side electrode is common to both cells. The left
side electrode in cell 2 is a standard reference Ag|AgCl(s)
JChemEd.chem.wisc.edu • Vol. 80 No. 9 September 2003 • Journal of Chemical Education
1 M KNO3 salt bridge
thermometer
AgAgCl electrode
AgAgCl sat KCl
electrode
rubber stopper
thermostated
water out
internal
saturated PbCl2 beaker
solution
PbCl2 crystals 1 M AgNO3
magnetic stirrer thermostated
water in
Figure 1. Diagram of the cell 1. Cell 2 is very similar to cell 1; the
only difference is that the saturated PbCl2 is replaced by 1 m KCl.
electrode dipped in 1 m KCl. The left side electrode of cell 1
is a Ag|AgCl(s) electrode dipped in a saturated PbCl2 solu-
tion. The diagram of cell 1 is shown in Figure 1.
The difference between the emf values of these cells mea-
sured at the same temperature T permits the calculation of
Ksp at T:
∆E = E 2 − E 1 = (RT兾F )ln aCl᎑
Ksp = a3Cl᎑兾2
The metal–insoluble salt electrode is a second-order
indicator electrode since it is used to measure the Cl −
activity, which is not directly involved in the electron-
transfer process (3).
Hazards
Powdered PbCl2 is harmful if swallowed; avoid breath-
ing the PbCl2 dust. It is toxic if absorbed through the skin.
Concentrated nitric acid is toxic and may be fatal if swal-
lowed or inhaled. It is extremely corrosive. Contact with skin
or eyes may cause severe burns and permanent damage.
Hydrochloric acid (1M) is corrosive. Inhalation of vapor is
harmful and ingestion may be fatal. Liquid can cause severe
damage to skin and eyes. Potassium nitrate is harmful if swal-
lowed and may cause reproductive disorders.
Results
Typical values obtained in an experimental run in the
physical chemistry laboratory are shown in Table 1. The
variation of ln Ksp with the inverse of the temperature is pre-
sented linearly in Figure 2 and quadratically in Figure 3. The
thermodynamic values calculated from the slope and inter-
cept of the graphs are listed in Table 2.
1051
 In the Laboratory

Table 1. A Typical Set of Student Data for Cells 1 and 2 Discussion

T/°C Ecell 1/mV Ecell 2 /mV To our knowledge this is the first variable-temperature
20.6 134.13 64.60 experiment in which simultaneous emf measurements were
25.3 134.58 65.31 made on two cells at identical temperatures and using two
identical salt bridges. This approach eliminates the need to
29.8 136.23 66.71
correct for the temperature dependence of the two standard
34.8 137.56 68.47 reference electrodes and minimizes errors arising from junc-
39.7 139.65 70.11 tion potentials across the salt bridge.
46.0 142.26 72.73 In the last 20 years, a number of solubility product ex-
50.3 144.03 74.45 periments have been published (4–16). None deal with the
57.0 147.28 77.39
determination of the solubility products through electro-
chemical measurements. Some of the articles deal with the
60.1 148.38 78.31
effect of ionic strength on solubility, a few deal with the com-
mon ion effect, and one deals with the determination of equi-
Table 2. Thermodynamic Quantities at 25 °C librium constant of some complex silver ions.
Obtained from ln Ksp versus T ᎑1 Least-Squares Fits The experiment was easily carried out within a three-
∆H°/ ∆S°/ ∆G°/ hour lab period and the students enjoyed both the practical
Least-Squares Fits
(kJ mol᎑1) (J mol᎑1 K᎑1) (kJ mol᎑1) aspect of the experiment and its relevance to their theory class.
Linear 18.8 ᎑10.2 21.8 It is recommended to freshly prepare the salt bridge a few
days prior to the experiment.
Quadratic 21.7 ᎑0.5 21.8
W
Supplemental Material
-7.8
The background, relevant theory, and details of the ex-
perimental procedure are available in this issue of JCE On-
-8.0
line.
8.2
Acknowledgments
-8.4
ln Ksp

The authors acknowledge support for this work from the

-8.6
chemistry department at King Fahd University of Petroleum
and Minerals. The technical help of Nasrullah Baig in the
-8.8 physical chemistry laboratory is also acknowledged.

-9.0 Literature Cited

-9.2 1. Laidler, K. L.; Meiser, J. H. Physical Chemistry, 3rd ed.;
2.9 3.0 3.1 3.2 3.3 3.4 3.5
Houghton Mifflin Co.: Boston, 1999; pp 344–346.
T ⴚ1/ (10ⴚ3 Kⴚ1) 2. Alberty, R. A.; Silbey, R. J. Physical Chemistry, 1st ed.; J. Wiley
& Sons, Inc.: New York, 1992; pp 255–260.
Figure 2. A linear least-squares fit of ln Ksp versus T ᎑1. 3. Skoog, R. A.; West, D. M. Fundamentals of Analytical Chem-
istry, 3rd ed.; Holt, Rinehart and Winston: New York, 1976;
-7.8 pp 382–383.
4. Lehman, T.; Everett, W. W. J. Chem. Educ. 1982, 59, 132.
-8.0 5. Sawyer, A. K. J. Chem. Educ. 1983, 60, 416.
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280.
-8.4 8. Wruck, D. B.; Rechstein J. J. Chem. Educ. 1989, 66, 515–
ln Ksp

516.
-8.6 9. Rice, G. W.; Hall, C. D. J. Chem. Educ. 1990, 67, 430–431.
10. Scaife, C. W.; Hall, C. D. J. Chem. Educ. 1990, 67, 605–606.
-8.8 11. Gotlib, L. J. J. Chem. Educ. 1990, 67, 937–938.
12. Thomsen, M. W. J. Chem. Educ. 1992, 69, 328–329.
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13. Silbermann, R. G. J. Chem. Educ. 1996, 73, 426–427.
14. Green, D. B.; Rechsteiner, G.; Honodel, A. J. Chem. Educ.
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2.9 3.0 3.1 3.2 3.3 3.4 3.5
1996, 73, 789–792.
15. Marzzacco, C. J. J. Chem. Educ. 1998, 75, 1628–1629.
T ⴚ1/ (10ⴚ3 Kⴚ1)
16. Thompson, M. L.; Kateley, L. J. J. Chem. Educ. 1999, 76,
Figure 3. A quadratic least-squares fit of ln Ksp versus T ᎑1. 95–96.

1052 Journal of Chemical Education • Vol. 80 No. 9 September 2003 • JChemEd.chem.wisc.edu