In the Laboratory
The Nernst Equation: Determination of Equilibrium
Constants for Complex Ions of Silver
Martin L. Thompson and Laura J. Kateley
Department of Chemistry, Lake Forest College, 555 N. Sheridan Road, Lake Forest, IL 60045
The formation of metal complexes is discussed in most
introductory chemistry courses and several reports of methods
for the determination of their equilibrium constants have
appeared. These often involve a titration, followed by graphical
analysis (1–4). A more direct approach for determining such
values utilizes a concentration cell and the Nernst equation.
Described previously as a demonstration (5–7), it can readily
be adapted as a laboratory exercise in an introductory course.
The experiment requires only simple equipment and inex-
pensive chemicals, and excellent results can be obtained in a
relatively short time.
This method can be extended to include equilibria
involving a host of metal–ligand complexes, as well as the
determination of Ksp values for relatively insoluble salts.
General Background
The formation of a metal complex in an aqueous solution
can be written
Mx+(aq) + nL y ᎑(aq) → ML n(x+)+n(y ᎑)(aq)
where the overall formation constant is
Kform = [ML n (x+)+n(y᎑) x+ y᎑
(aq)]/ [M (aq)] [L (aq)] n
In the specific example described below, where x = 1 and
y = 0, these equations can be abbreviated as
Ag+ + 2 NH3 → Ag(NH3)2+
and
Kform = [Ag(NH3) 2+]/[Ag +] [NH 3] 2
A knowledge of the three equilibrium concentrations
clearly yields Kform.
The determination in this experiment makes several as-
sumptions:
1. The formula of the newly formed complex is known (i.e.,
the value of n, the coordination number, is known);
2. The reaction reaches equilibrium quickly (i.e., no kinetic
complications occur);
3. All activity coefficients are assumed to be one and junc-
tion potentials are negligible;
4. A large excess of the ligand is added to the aquated
metal ion; thus, its concentration is diminished negli-
gibly in creating the complex;
5. The overall formation constant, Kform, has a relatively
large value, so the equilibrium value of [Ag(NH3)2]+
is practically the same as the concentration of the sto-
ichiometrically deficient Ag + created in preparing the
sample solution;
6. Concentrations of intermediate species (those contain-
ing both water and the new ligand in the coordina-
tion sphere) are negligibly small.
Because the ligand is in large excess, the equilibrium
concentration of the newly formed complex is defined by the
millimoles of Ag+ used and the final volume. The concentra-
JChemEd.chem.wisc.edu • Vol. 76 No. 1 January 1999 • Journal of Chemical Education
tion of the remaining free ligand can then be determined from
the balanced chemical equation.
The low equilibrium concentration of the aquated metal
ion is the only missing datum to determine Kform, and it can be
obtained using a concentration cell and the Nernst equation.
The emf (voltage) of a cell depends on the concentrations
(or activities) of each species involved in the cell reaction.
The Nernst equation (named for Walter Hermann Nernst,
who derived it in 1889) relates the concentrations in a cell
to the cell’s emf:
E = E ° – [RT /nF ] ln Q (5)
where E is the emf difference between the electrodes in a cell;
E ° is the standard reduction potential for the cell in volts; R
is the gas constant (8.314 J mol᎑1 K ᎑1); T is the temperature;
F is Faraday’s constant, which is 9.6437 × 104 J V᎑1mol ᎑1; n
is the number of moles of electrons transferred through the
external circuit by molar amounts indicated in the balanced
equation; and Q is the reaction quotient. At 25 °C, this re-
(1) duces to
E = E ° – [(0.0591)/n] log Q (6)
(2) In this experiment, the cell used is a concentration cell;
that is, the two half-cells are constructed of the same materials
but differ in concentration. Using silver electrodes and Ag+
ion, the half-reactions are
(3)
oxidation (anode): Ag° → Ag+(dil) + e᎑
reduction (cathode): Ag+(conc) + e᎑ → Ag°
(4)
overall: Ag+(conc) → Ag+(dil) (7)
Since E° = 0 for such a cell, the Nernst equation reduces to
Ecell = ᎑(0.0591 V) log {[Ag+(dil)]/[Ag+(conc)]} (8)
Students check the validity of this equation by using
known concentrations in both half-cells and comparing the
observed and calculated voltages. Then the equation is used to
calculate [Ag+(dil)] when this dilute solution at the anode con-
tains an equilibrium mixture of silver ion, ligand, and complex
ion. This concentration, [Ag+(dil)], is the missing piece of
information needed to calculate Kform in the experiment.
Experimental Procedure
A voltmeter that reads in millivolts with a precision of
± 1 mV (or a good pH meter set to record voltage) is adjusted
to read zero using the zero, calibration, or standardization
knob. A 1.35-V mercury battery is used to check the voltage
readings.
Several types of salt bridges can be used to conduct
the internal circuit of the voltaic cell. A simple one that
works adequately is a strip of porous paper soaked in
1 M KNO 3(aq). This moistened paper is handled with forceps.
Its two ends are dipped into small beakers containing the
reference solution and the one to be tested. A short piece of
95
In the Laboratory
silver wire is placed in each beaker and connected via the
plastic-covered electrode clips to the voltmeter.
To check the validity of the Nernst equation, several read-
ings are observed and recorded by each student:
1. About 20 mL of 0.010 M AgNO3 is placed in one of
two small (50-mL) beakers and one of the silver wires
is immersed in the solution.
CAUTION : Avoid contact of skin and clothing
with silver-ion solutions. Fresh stains can be re-
moved by prompt treatment with sodium thio-
sulfate solution, followed by washing.
A similar volume of the same 0.010 M AgNO3 solution
is added to the other beaker containing its electrode
and the voltage recorded. (To avoid erratic readings,
the electrodes should not be in contact with the paper
salt bridge.) In accord with eq 8 above, students find
that the voltmeter reads nearly zero.
2. The solution in one of the beakers is poured into an-
other container and a 5.0-mL portion of this is added
to a 150-mL beaker, along with 45.0 mL of deionized
H2O. The Ag wire and salt bridge are reassembled as
above and an additional reading is made, which should
be about 59 mV. Students are asked to define the cath-
ode and anode and to rationalize the electrode polarities
with those of the voltmeter.
3. One additional dilution (a more extreme one, decided
by each student) is made, and the is voltage measured as
described. The result is compared with that calculated.
The Kform for the diammine silver(I) complex is deter-
mined by adding a large but known excess of ammonia to a
known amount of aqueous AgNO3. This is done as follows.
The reference half-cell is left undisturbed. Into a clean, dry
50-mL beaker is added 15.0 mL of 0.100 M aqueous ammo-
nia and 15.0 mL of 0.010 M AgNO 3. The salt bridge is
reassembled and the voltage generated is measured. The
concentration of the Ag+(aq) ion remaining in the beaker is
determined from the Nernst equation. The millimoles of the
complex formed and the free ammonia remaining, along with
the final volume of the solution, yield the molarities of these
two species at equilibrium.
Students are asked to repeat the above procedure with
different volumes of the Ag+ and NH3 solutions and obtain a
second value of this formation constant. They are then asked to
repeat the above procedure, using 0.10 M sodium thiosulfate
as a ligand in place of ammonia. After the calculations are
made for these two sets of formation constants, all solutions
are discarded in the waste bottles provided.
Results and Discussion
Surprisingly good results are obtained with this simple
procedure. Values for Kform for Ag(NH3) 2+ cluster around
96 Journal of Chemical Education • Vol. 76 No. 1 January 1999 • JChemEd.chem.wisc.edu
1.2 × 107 (reported value = 1.6 × 107) (8). The precision of
student results are reported as logarithms of Kform values; the
standard deviation is then 0.23, with an accepted value of
log Kform = 7.20.
The Kform values for the Ag(S2O3) 23᎑ complex averaged
1.5 × 1013, ranging from 0.20 × 1013 to 2.2 × 1013. Reported
values range from 0.43 × 1013 (9) to 2.0 × 1013 (8). When
logs of Kform values are used, the average result obtained was
13.18 (corresponding to a Kform of 1.5 × 1013), with a standard
deviation of 0.30.
These results are quite acceptable, considering that activity
coefficients are ignored, dilutions are done with imprecise
graduated cylinders, and initial concentrations are approximated.
(The last is most serious with aqueous NH3, owing to vaporiza-
tion; better results can be obtained by titrating the ammonia
with standard HCl to affirm its initial concentration.)
A knowledge of the values of stepwise equilibrium constants
confirms the relatively low concentration of intermediate
species, justifying assumption (6 ) above. In the case of
Ag(NH3)2+, the two values are similar: K1 = 2.1 × 103 and
K2 = 8.2 × 103. In the first determination described, the cal-
culated equilibrium concentrations are
[Ag(NH3)+] = 1.5 × 10 ᎑5 M
[Ag(NH3)2+] = 5.0 × 10᎑3 M and
[Ag +] = 1.8 × 10᎑7 M
Thus at equilibrium, the concentrations of the monoammine
complex and the Ag+ are respectively 0.3% and 4 × 10᎑3%
that of the diammine.
The experiment illustrates nicely the power of the Nernst
equation. Calculations are straightforward and the results are
satisfying to students. Finally, the data can be collected in an
abbreviated laboratory session, an especially desirable aspect
of an experiment in an honors or advanced placement course
at the high school level, where time is always a concern.
Literature Cited
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1980, 57, 813.
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