Questions 6 and 7 bring to the discussion the relationship
between solubility and solubility product, which has been
dealt with in various articles in this Journal (e.g., refs 16–21).
They emphasize the difference between the values of the solubility
of salts in water obtained using the Ksp algorithm and
the values obtained experimentally. This is due to effects such
as ionic strength, incomplete dissociation, and the formation
of complex ions, all of which augment the solubility of the
salts. Question 6 allows us to confirm whether the students
consider these effects and differentiate among them.
Dissolved ions exert electrostatic forces among themselves
that produce deviations from ideal behavior, and this necessitates
the calculation of activity coefficients with solutions
more concentrated than 103 M. Because of this effect of ionic
interaction, if another salt that does not contain a common ion
is added to the saturated solution, the solubility of the salt
increases. For example, the solubility of the AgCl in water at
25 °C increases by 12% with the addition of 0.01 mol/L of
KNO3(aq) and by 25% with a concentration of 0.1 mol/L.
In question 7 one hopes that the students distinguish two
opposite effects on the solubility of the AgCl: common ion
and ionic strength, which respectively reduce and augment
the solubility of the salt. Therefore, the students would have
to draw a greater number of dissolved ions than in the initial
situation.
The formation of ionic pairs of univalent electrolytes is
limited in solvents of high dielectric constant such as water,
because the electrostatic attraction between the two dissolved
ions depends on the charges and the distance between them.
Nevertheless, for a solution saturated with a salt of very low
solubility such as AgCl, the concentration of undissociated
salt [Ag+Cl] is similar to that of the silver ion [Ag+] (17).
This effect is more significant when both ions are divalent
(16, 18, 20), as for example in CaSO4.
The formation of complex ions is common in aqueous
solutions of transition metal halides. For the silver chloride
system, when chloride is added to the solution, the formation
of the complex ion AgCl2
occurs (19). A procedure for calculating
the solubility considering also the presence of complex
ions is shown by Ramette (21) for a solution of silver acetate.
On the other hand, it is known that the solubility of the silver
chloride increases with the addition of NH3(aq) owing to the
formation of the complex ion Ag(NH3)2
+.
Finally, a student might suggest the occurrence of hydrolysis
with the formation of Ag(OH). But this effect is negligible;
hydrolysis is only significant with very small ions of high charges
such as Al3+, Cr3+, Fe3+, Bi3+, and Be2+. The case of CaCO3 is
given as an example by Hawkes (19), in which the hydrolysis
of the carbonate contributes more to the solubility than the
equilibrium represented by the solubility product.
In the drawings utilized to evaluate comprehension at the
microscopic level, students must be capable of associating the
particles with models and analogies (5). It is important to
discuss with them what the model is about and, as with all
models, to present its limitations. For example, the model used
is two dimensional and static, and it represents a reduced
number of particles.
During the resolution of this problem the students prove
highly motivated and actively participate in the discussion
of both their own answers and those of their peers.