In the La bor a tory
La ecuación de Nernst: Determinación de constantes de equilibrio para
iones complejos de plata
La formación de complejos metálicos se discute en la mayoría de
los cursos de química introductoria y han aparecido varios
informes de métodos para la determinación de sus constantes de
equilibrio. Estos a menudo implican una titulación, seguida de un
análisis gráfico (1–4). Un enfoque más directo para determinar
tales valores utiliza una celda de concentración y la ecuación de
Nernst. Descrito anteriormente como una demostración (5-7),
puede adaptarse fácilmente como un ejercicio de laboratorio en
un curso introductorio. El experimento solo requiere equipo
simple y productos químicos económicos, y se pueden obtener
excelentes resultados en un tiempo relativamente corto.
Este método puede extenderse para incluir equilibrios que
involucren una gran cantidad de complejos metal-ligando, así
como la determinación de los valores de Ksp para sales
relativamente insolubles.
Fondo general
La formación de un complejo metálico en una solución
acuosa se puede escribir.
Mx+(aq) + nLy–(aq)  MLn(x+)+n(y–)(aq) (1)
donde la constante de formación global es
Kform = [MLn(x+)+n(y–)(aq)]/ [Mx+(aq)][Ly–(aq)]n (2)
En el ejemplo específico que se describe a continuación,
donde x = 1 y y = 0, estas ecuaciones se pueden abreviar
como
Ag + 2 NH 3 
+
Ag(NH 3) 2+ (3)
y ion, the half-reactions are
Un conocimiento de las tres concentraciones de equilibrio
da claramente Kform.
La determinación en este experimento hace varias
suposiciones:
1. La fórmula del complejo recién formado es
conocida (es decir, se conoce el valor de n, el
número de coordinación);
2. La reacción alcanza el equilibrio rápidamente (es
decir, no se producen complicaciones cinéticas);
3. Se supone que todos los coeficientes de actividad
son uno y los potenciales de unión son depreciables;
4. Se agrega un gran exceso del ligando al ion
metálico acuado; por lo tanto, su concentración se
ve disminuida de manera insignificante en la
creación del complejo;
5. La constante de formación general, Kform, tiene
un valor relativamente grande, por lo que el valor de
equilibrio de [Ag (NH3) 2] + es prácticamente el
mismo que la concentración de Ag +
estequiométricamente deficiente creada en la
preparación de la solución de muestra;
6. Las concentraciones de especies intermedias
(aquellas que contienen tanto agua como el nuevo
ligando en la esfera de coordinación) son
insignificantes.
Debido a que el ligando tiene un gran exceso, la
concentración de equilibrio del complejo recién formado se
define por los milimoles de Ag + utilizados y el volumen
final. La concentración del ligando libre restante se puede
determinar a partir de la ecuación química equilibrada.
La baja concentración de equilibrio del ion metálico
acuoso es el único dato faltante para determinar Kform, y
se puede obtener utilizando una celda de concentración y
la ecuación de Nernst.
La fem (voltaje) de una célula depende de las
concentraciones (o actividades) de cada especie
involucrada en la reacción celular. La ecuación de Nernst
(llamada así por Walter Hermann Nernst, quien la derivó
en 1889) relaciona las concentraciones en una célula con
la fem de la célula:
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-
duces to
E = E  – [(0.0591)/n] log Q (6)
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+
oxidation (anode): Ag  Ag+(dil) + e–
reduction (cathode): Ag+(conc) + e–  Ag
overall: Ag+(conc)  Ag+(dil)
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

JChemEd.chem.wisc.edu • Vol. 76 No. 1 January 1999 • Journal of Chemical Education 95

In the La bor a tory
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
H 2 O. 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 NH 3 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(NH )3+2cluster 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(NH 3 )2 +, the two values are similar: K 1 = 2.1  103 and
3
K2 = 8.2  10 . 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
1. Wolfenden, J. H. J. Chem. Educ. 1959, 36, 490.
2. King, L. C.; Cooper, M. J. Chem. Educ. 1965, 42, 464.
3. Guenther, W. B. J. Chem. Educ. 1967, 44, 46; 1967, 44, 427.
4. Schultz, F. A. J. Chem. Educ. 1979, 56, 62.
5. Schwenck, J. R. J. Chem. Educ. 1959, 36, 45.
6. Shakhashiri, B. Z.; Direen, G. E.; Juergens, F. J. Chem. Educ.
1980, 57, 813.
7. Anderson, R. H. J. Chem. Educ. 1993, 70, 940.
8. Stability Constants, 2nd ed.; Sillen, L. G., compiler of Part I;
London Chemical Society Special Publication No. 17; London
Chemical Society: London, 1964; p 226.
9. Stability Constants, Supplement No. 1; Sillen, L. G., compiler;
London Chemical Society Special Publication No. 25; London
Chemical Society: London, 1971; p 132.