Chapter 33

Dependence of the Solubility on the Solution’s

Ionic Strength and on the Presence of Common
Ions: Superimposition of Several Precipitation
Equilibria

As we could have predicted, solubility depends on the solution’s ionic strength. The
ionic strength of the solution may be due to the presence of ions differing from
those constituting the electrolyte whose solubility is under study. This influence is
investigated in the first section of the chapter. The ionic strength may also be due
to the addition of ions that constitute the electrolyte itself. In this case, an effect
analogous to the preceding one occurs, but, in addition, another effect, which is
far stronger than the preceding one, arises: the common ion effect. It is due to the
shift of an equilibrium. This is the subject of Sect. 33.2. Finally, we investigate the
superimposition of two precipitation equilibria.

33.1 Influence of the Ionic Strength on the Solubility

First, let’s notice that the ionic strength of the solution influences the solubility of
ions. We have indeed seen that the activity of a molecular species does not change
with the ionic strength of the solution, provided the latter does not exceed about
0.1 mol/L. Therefore, in this section, we are interested only in its influence on the
ionic solubility.
It is an experimental fact that the solubility of an electrolyte increases slightly
when the ionic strength increases. Figure 33.1 gives the solubility changes of silver
iodate as a function of the concentration of potassium nitrate present in the solution.
Quite evidently, the ionic strength of the solution increases with the concentration
of potassium nitrate. [To be rigorous, we must notice, however, that in this example
the ionic strength is not due only to K+ and NO− + −
3 , but also to Ag and IO3 ions
−7.52
resulting from the dissolution of silver iodate (Ks = 10 )].
We can easily explain the increase in solubility with the ionic strength if we
remember that solubility products, defined in terms of activities, do not vary with the
ionic strength as other thermodynamic constants do. Expressing solubility products
in terms of concentrations and activity coefficients such as

Ks = [M+ ][X− ]γ± 2

J.-L. Burgot, Ionic Equilibria in Analytical Chemistry, 619

DOI 10.1007/978-1-4419-8382-4_33, © Springer Science+Business Media, LLC 2012
620 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .

Solubility
of AgIO3 0,20
(m.mol/L)

0,18

Concentration KNO3
(m.mol/L)

0 2 4 6 8 10 12 14 16

Fig. 33.1 Effect of the addition of potassium nitrate on the silver iodate’s solubility

immediately shows that since activities decrease (at least in a first stage) when the
ionic strength increases, the concentrations [M+ ] and [X− ] must simultaneously
increase for the Ks value to remain constant.
This example provides the occasion to recall that only the constants defined in
terms of concentrations, that is, the formal or apparent constants, exhibit values that
change with the ionic strength of the solution. Moreover, formal solubility products
Ks defined as follows:
 z  y
Ks app = M+y X−z

are seldom used for a simple reason: The values of the apparent and thermodynamic
constants are identical to the concentrations at which the concept of solubility product
is useful. Indeed, it is because these concentrations are very low.
From the standpoint of physical chemistry, the measurement of the solubility S
at different ionic strengths I (whose values are imposed by the addition of a foreign
electrolyte in judicious concentrations) permits us to determine both the thermody-
namic solubility product and the mean activity coefficient. This determination can be
carried out in a geometric or algebraic way. Let’s consider the case of a one-to-one
electrolyte 1.1. According to the preceding considerations, we can write

Ks /γ± 2 = S 2 ,
log Ks = 2 log γ± + 2 log S.

At weak ionic strengths, according to Debye–Hückel’s limiting law (see Chap. 3),
 √ 
log γ± = − Az+ z− I ,
1  √ 
log S = log Ks + Az+ z− I .
2
33.1 Influence of the Ionic Strength on the Solubility 621
√
Drawing the diagram of log S as a function of I permits us to determine Ks .
Alternatively, combining two values S1 and S2 , determined at two different ionic
strengths I 1 and I 2 , permits us to obtain Ks through the preceding√ relation. The
better process is probably to draw the best straight line of log S/ I. It presents the
advantage of taking all of the experimental data (i.e., all the couple values Si /I i ) into
account. For example, the solubility at null ionic strength of silver iodate and its
solubility product value have been determined in this way. They are

S(AgIO3 ) = 1.733 × 10−4 mol/L,

Ks (AgIO3 ) = S 2 ,
Ks (AgIO3 ) = 3.00 × 10−8 .

Then the calculation of the mean activity coefficient is immediate by using a couple
of data Si /I i . Indeed, we can write
Ks
γ± 2 = .
Si 2
√
It is interesting to notice that the graph of log γ± / I is actually a straight line, in full
accordance with Debye–Hückel’s law. This fact signifies that the part of the ionic
strength due to the concentrations [IO− +
3 ] and [Ag ] is negligible compared to that
due to the foreign electrolyte, since it is on this assumption that the straight line is
drawn.
Exercise 1 The solubility at 25◦ C of thallium chloride in pure water is S =
1.64 × 10−2 mol/L. What are its solubility into a solution of potassium nitrate 2.5 ×
10−2 mol/L and its solubility product value (A = 0.509)?
One can write for the solution in pure water
1 √ 
log S = log Ks + Az+ z− 1.64 × 10−2 .
2
If S  is the desired solubility in the potassium nitrate solution, the ionic strength of
the solution is
 
I = S  + 2.50 × 10−2 mol/L,

from which we find

1 √ 
log S  = log Ks + Az+ z− 2.5 × 10−2 + S  .
2
Combining the relations giving log S and log S  gives
 
S √    √ 
log = Az+ z− S + 2.50 × 10−2 − 1.64 × 10−2 .
S
622 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .

At 25◦ C
 
S √   √ 
log   = 0.509 S  + 2.50 × 10−2 − 1.64 × 10−2
1.64 × 10−2
or S  = 1.80 × 10−2 mol/L.

We notice that passing from an ionic strength equal to 1.64 × 102 mol/L to another
equal to 4.14 × 10−2 mol/L induces a change in solubility from 1.64 × 10−2 mol/L
to 1.80 × 10−2 mol/L, that is, a change of + 9.8%. The calculation of the solubility
product is immediate. For example, using the values found for the solubility of
thallium chloride in pure water, we can write
  1 √ 
log 1.64 × 10−2 = log Ks + 0.509 1.64 × 10−2 ,
2
Ks = 1.99 × 10−4 .

33.2 The Common Ion Effect

In this section, we consider the influence of the presence of an ion identical to one of
the ions constituting the electrolyte whose solubility is under study. For example, we
study the influence of the presence of sodium sulfate in a solution upon the solubility
of barium sulfate in the same solution. Of course, the added common ion influences
the solubility through its contribution to the ionic strength, as the previous section
described. This is not the phenomenon under study in this section. Here we study
the common ion effect, which can be far more important than the preceding one.
For example, let’s study the solubility of barium sulfate. Once its precipitation
occurs, the solubility-product relation is satisfied:
 2+  
Ba SO4 2− = Ks (saturation).

If the barium or sulfate ion concentration is increased by adding barium chloride or

sodium sulfate (which are fairly soluble themselves), the barium sulfate precipitation
is more pronounced since its solubility is decreased, as we can see now.
If S is the barium sulfate’s solubility in a solution of barium chloride at concen-
tration C, the relations that are satisfied once the saturation is attained are (by mixing
activities and concentrations)
 2+  
Ba SO4 2− = Ks ,
 2+ 
Ba = S + C,
 
SO4 2−
= S.

The barium sulfate’s solubility is equal here to the sulfate ion concentration at satu-
ration. In other words, the solubility S is the maximum number of moles of barium
33.2 The Common Ion Effect 623

Fig. 33.2 Solubility S of

barium sulfate in solutions of 10
sodium sulfate at analytical 9
concentrations C 8

S, micromoles/liter
7
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70 80 90
C, micromoles/liter

sulfate that can be dissolved in 1 L of a barium chloride solution at concentration C.

The above mathematical system is soluble since there are three equations for three
unknowns, [Ba2+ ], [SO4 2− ], and S. By mixing activities and concentrations, we’ve
reduced the system to the second-order equation

S(S + C) = Ks .

If there is a large excess of common ions,

SC
Ks
and S ≈ .
C
Exercise 2 Calculate the barium sulfate’s solubility in a 1.0 × 10−2 mol/L barium
chloride solution.
 2+  
Ba SO4 2− = 1.1 × 10−10 ,
 2+ 
Ba = S + 1.0 × 10−2 ,
 
SO4 2− = S,
 
S S + 1.0 × 10−2 = 1.1 × 10−10 ,
S = 1.1 × 10−8 mol/L.

The solubility is considerably decreased compared to the case of pure water (in
this case, S = 1.05 × 10−5 mol/L). In French, this phenomenon is called recul de
precipitation (“solubility decrease”). From another standpoint, we can verify that,
actually, S  C in the term within brackets. Figure 33.2 shows the solubility changes
of barium sulfate with the concentrations C of sodium sulfate.
These determinations may also be performed with logarithmic diagrams taking
the different concentrations into account (activities and concentrations being mixed).
624 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .

Fig. 33.3 Logarithmic 0

representation of a divalent
ion solubility product –1
SO42–
–2

log[Ba2+] or log(SO42–)
Ba2+
–3
–4
–5 S = 1,05 × 10–5

–6
–7
–8
–9
0 1 2 3 4 5 6 7 8 9 10 11 12
pSO4

For example, in the case of divalent metal sulfates, they are diagrams log(M2+ )/pSO4
with pSO4 = − log (SO4 2− ). Starting from the solubility-product expression:
 2+  
M SO4 2− = Ks ,
we find
 
log M2+ = log Ks + pSO4 .
The fact that the solubility product is obeyed results in a straight line with slope +1
and intercept log Ks (Fig. 33.3).
Now, if we draw the straight line log(SO4 2− )/pSO4 , with slope –1, on the same
diagram, it intersects the preceding for
   
log M2+ = log SO4 2− ,
that is, for
   
M2+ = SO4 2− = S.
S is the solubility in pure water. On the left side of the diagram and below, the follo-
wing inequality holds: [SO4 ]2− [M2+ ]. It is the area of the weakest concentration
of the metallic ion M2+ . This results from the common ion effect. It is the inverse for
the upper area located on the right of the diagram in which [M2+ ]  [SO4 2− ]. Such
diagrams permit us to simplify solubility calculations immediately. For example, the
solubility of BaSO4 in a 10−2 mol/L solution of BaCl2 is obtained by drawing the
horizontal straight line [Ba2+ ] = 10−2 mol/L on the diagram. The horizontal line in-
tersects the straight line log[Ba2+ ]/pSO4 for pSO4 ≈ 8, namely, for S = 10−8 mol/L.
We can remark that this determination process implies that S can be neglected com-
pared to 10−2 mol/L, as in the previous case in the algebraic calculation. Hence, this
is confirmed in the present case by the graphical result
S = 10−8 mol/L  1.0 × 10−2 mol/L.
33.2 The Common Ion Effect 625

In the same manner, we could find the value 1.0 × 10−7 mol/L for the barium sulfate’s
solubility in a 1.0 × 10−3 mol/L sodium sulfate solution.
The graphical determination has been of little interest for the simple cases studied
until now. However, the contrary is true for more complicated cases, such as those in
which complex(es) as well as precipitates form, for example. Such diagrams permit
us to immediately visualize species whose concentrations can be negligible in the
calculations. As a result, the latter are simplified.
Exercise 3 Calculate the magnesium fluoride’s solubility MgF2 in a 10−4 mol/L
magnesium nitrate solution. Ks (MgF2 ) = 10−8.18 .
If S is the unknown solubility, we can write at saturation
 2+   
Mg = S + 1.0 × 10−4 mol/L,
[F− ] = 2S.

By mixing activities and concentrations, we find

  
Ks = 4S 2 S + 1.0 × 10−4 = 10−8.18 ,
S 3 + 10−4 S 2 − 1.65 × 10−9 = 0,
S = 1.08 × 10−3 mol/L.

This is a case in which the solubility is higher than the added ion concentration.
Exercise 4 We want to precipitate thallium(I) as chloride. What is the volume
of a 1 mol/L hydrochloric acid solution that must be added to a 10.0-ml solution
containing 383 mg of thallium(I) for its precipitation to be total at the 99.5% extent?

Ks (TlCl) = 10−3.72 and M(Tl) = 204.37 g/mol.

The number of moles of Tl(I) in the solution is (383 × 10−3 )/(204.37) = 1.874 ×
10−3 mol. Let V be the unknown volume. The total concentration of Tl (i.e.,
precipitated and remaining in solution) is
 
 + 1.874 × 10−3 × 1000
Tl o = mol/L,
(10 + V )
1.874
[Tl+ ]o = mol/L,
(10 + V )
[Tl+ ]o = [Tl+ ] ↓ +[Tl+ ].

The maximum concentration that must remain in solution is

  
0.5 1.874 9.37 × 10−3
[Tl+ ] = = mol/L
100 (10 + V ) (10 + V )
 
1.874 − 9.37 × 10−3 1.865
and [TlCl ] ↓= = mol/L.
(10 + V ) (10 + V )
626 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .

The total concentration of chloride ions is

(V × 1)
[Cl− ]o =
(10 + V )
and that remaining in solution after precipitation is
(V × 1) 1.865
[Cl− ] = − .
(10 + V) (10 + V)
Just at the end of the dissolution, the solubility product is still satisfied:
   
9.37 × 10−3 (V − 1.865)
× = 10−3.72 ,
(10 + V) (10 + V)
V = 10 ml.

Exercise 5 Let’s consider the ionic salt Mz Xy and let So be its solubility in pure
water. Show that its solubility in a solution containing the salt Na3 X of analytical
concentration C is always lower than So .
The dissolution equilibrium is

Mz Xy ↓ zMy+ + yXz− ,
Ks = (zSo )z (ySo )y (pure water).
 y+ 
Since M = zSo ,
 z− 
X = ySo .

In the presence of X2− ,

Ks = (zS)z (yS + C)y .

The comparison of both expressions of Ks immediately shows that S < So since the
concentration C is positive.
The common ion effect is of great interest in gravimetry by precipitation (see
Chap. 38). If we add a suitable excess of the precipitating reagent, the solubility of
the precipitate becomes almost null and, as a result, losses by solubility also become
null. For the same reason, the washing of the precipitates is very often carried out with
a solution containing an ion that is common with one of the ions of the precipitate.
Exercise 6 In a gravimetric determination, 0.451 g of silver chloride is washed
before ignition and weighed. Calculate the precipitate fraction lost during the
washing:
1. with 2 ml of pure water,
2. with, successively, 150 ml of a 0.10 mol/L ammonium chloride solution and 50 ml
of pure water.

M(AgCl) = 143.323 g/mol and Ks (AgCl) = 10−9.75 .

33.2 The Common Ion Effect 627
√
3. The solubility into pure water is 10−9.75 × 143.323 g/L. The part dissolved in
200 ml of pure water is

(10−4.875 × 143.323 × 200)

= 3.82 × 10−4 g.
1000
The answer to the first question is (3.82 × 10−4 )/0.451 = 0.086%.
4. In the ammonium solution at saturation, we can write

S(S + 0.1) = 10−9.75 ,

S = 1.78 × 10−9 mol/L,
or equivalently, 1.78 × 10−9 × 143.323 = 2.549 × 10−7 g/L,

and for 150 ml,

150
2.549 × 10−7 × = 3.823 × 10−8 g.
1000
During the final washing with 50 ml of pure water, we find a loss of 9.556 × 10−5 g.
(The principle of the calculation is the same as in question 1.) For the entirety of
question 2, the loss is

9.556 × 10−5 + 3.823 × 10−8 = 9.56 × 10−5 g,

 
9.56 × 10−5
i.e., = 0.021%.
0.451
We notice that the loss occurring during the washing with 50 ml of pure water is far
higher than that occurring during the washing with 150 ml of the ammonium chloride
solution that contains the ion Cl− , which is also engaged within the precipitate.
The process of mixing two solutions, each containing one ion that gives a very
insoluble precipitate with the ion of the other solution, is a particular case of the
preceding one. It is interesting because it is encountered in titrations by precipitation
(see Chap. 36).
Let’s take the example of the mixing of 50 ml of a 3×10−5 mol/L barium chloride
solution with 100 ml of a 4.5 × 10−5 mol/L sodium sulfate solution. The problem is
to determine the fraction of barium precipitated. Let’s call P the number of moles
of precipitated barium sulfate per liter of solution. The mass balance relations on
Ba2+ , SO4 2− together with the solubility-product expression provide a system of
three equations in three unknowns: [Ba2+ ], [SO4 2− ], and P:
 
 2+  50
Ba + P = 3.0 × 10−5 mol/L,
(100 + 50)
 
  −5 100
SO4 2−
+ P = 4.5 × 10 mol/L,
(100 + 50)
 2+  
Ba SO4 2− = 1.1 × 10−10 .
628 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .

The second-order equation resulting from this system leads to

 2+ 
Ba = 4.5 × 10−6 mol/L,
P = 5.5 × 10−6 mol/L,

and the precipitated fraction is

 
5.5 × 10−6
100 = 55%.
1.0 × 10−5
Again, starting from these considerations, it is easy to show that the presence of a
common ion decreases the solubility of the salt.

33.3 Superimposition of Two Precipitation Equilibria:

Separation by Precipitation

The case of the superimposition of two precipitation equilibria is of practical im-

portance in analysis since it occurs when the separation of two ions by precipitation
is carried out. More precisely, the operation consists of preferentially precipitating
one of the present ions in the admixture by adding an appropriate reagent. Of course,
in this process, the markedly weaker solubility of one of the ions in the presence of
the reagent is taken into account. Simple calculations based on the consideration of
solubility products permit us to predict the maximum extent of the separation.
For example, let’s consider a solution containing 10−2 mol/L of barium chloride
and 10−2 mol/L of strontium chloride. A saturated solution of sodium sulfate is
added to it. The problem is to calculate the concentration of the remaining ion (the
most insoluble) when the second begins to precipitate. The solubility products are
Ks (BaSO4 ) = 1.1 × 10−10 and Ks (SrSO4 ) = 2.8 × 10−7 . An examination of the
solubility products shows that barium ions precipitate first. Just at the beginning of
the strontium precipitation, both solubility products are satisfied simultaneously and
[Sr2+ ] = 10−2 mol/L. Therefore, we can write
 2+  
Ba SO4 2− = 1.1 × 10−10 ,
 2+  
Sr SO4 2− = 2.8 × 10−7 ,
 2+ 
Sr
from which we find  2+  = 2.5 × 10−3
Ba
 2+ 
since Sr = 10−2 mol/L,
 2+ 
Ba = 3.8 × 10−6 mol/L.

This is the concentration of the remaining Ba2+ . Until this point, barium sul-
fate precipitated in the pure state, in principle. Its “precipitated concentration” is
33.3 Superimposition of Two Precipitation Equilibria: Separation by Precipitation 629

(10−2 − 3.8 × 10−6 ) mol/L. However, this is an assertion based only on theoreti-
cal principles. In practice, in several examples, a phenomenon of coprecipitation
also exists, which consists of an entrapment of the solution within the precipitate.
Moreover, an adsorption of ions that are not those engaged in the precipitate may
occur at the precipitate’s surface. Eventually, the formation of a solid solution is also
possible.
Exercise 7 A total of 200 ml of a 10−2 mol/L sodium sulfate is added to 100 ml of
a solution containing 10−2 mol/L of barium chloride and 10−2 mol/L of strontium
chloride. What is the fraction of each ion precipitated in the pure state?

Ks (BaSO4 ) = 1.10 × 10−10 ; Ks (SrSO4 ) = 2.8 × 10−7 .

Barium precipitates first as sulfate. At the beginning of the precipitation of strontium

sulfate, we have
 −2 
 2+  10 × 100
Sr = = 3.33 × 10−3 mol/L,
(100 + 200)
  2.80 × 10−7
SO4 2− =   = 8.40 × 10−5 mol/L.
3.33 × 10−3

The concentration of the remaining barium is

 2+  1.1 × 10−10
Ba =  = 1.31 × 10−6 mol/L.
8.40 × 10−5

The fraction of precipitated barium is:

 −2 
10 − 1.31 × 10−6
  ≈ 1.
3.33 × 10−3

Strontium cannot be obtained in a pure state.

Exercise 8 A solution contains 10−2 mol/L of sodium chloride and 10−3 mol/L of
sodium bromide. A concentrated solution of silver nitrate is added to it. What is the
maximum purity that can be reached by the solution of remaining chloride ions after
the precipitation of silver bromide?

Ks (AgBr) = 10−12.28 ; Ks (AgCl) = 10−9.75 .

We’ll begin by setting up the problem on qualitative grounds. Silver bromide preci-
pitates first. As a result, the solution is purer in chloride ions when silver chloride
begins to precipitate. However, once this point has been reached, silver bromide
continues to precipitate together with silver chloride.
When silver chloride begins to precipitate, both solubility products are satisfied:
 +  − 
Ag Br = 10−12.28 ,
630 33 Dependence of the Solubility on the Solution’s Ionic Strength . . .
 +  − 
Ag Cl = 10−9.75 ,
 −
Br
from which we find  −  = 10−2.53 .
Cl

Just at the beginning of the precipitation of chloride ions, [Cl− ] = 10−2 mol/L. As
a result,
 −
Br = 10−2 × 10−2.53 = 2.95 × 10−5 mol/L.

For 10−2 mol/L of chloride ions, 2.95 × 10−5 mol/L of bromide ions remain, that is,
0.3%. The purity of chloride ions is 100 − 0.3 = 99.7%.
Exercise 9 A total of 1.15 mg of PbSO4 is stirred with 100 ml of a 0.1 mol/L solution
of potassium iodate KIO3 until the equilibrium is reached. What is the fraction of
PbSO4 that has been converted into solid lead iodate, Pb(IO3 )2 ?

Ks (PbSO4 ) = 10−7.8 , Ks (Pb(IO3 )2 ) = 10−12.59 , M (PbSO4 ) = 303.25 g/mol,

M (Pb(IO3 )2 ) = 556.99 g/mol.

Let’s set up the hypothesis that at equilibrium, both precipitates PbSO4↓ and
Pb(IO3 )2↓ coexist. A total of 1.15 mg of PbSO4 corresponds to 3.79 × 10−6 mol. The
relations that are satisfied are
 
n(PbSO4 ) + n (Pb(IO3 )2 ) + Pb2+ 0.1 = 3.79 × 10−6 ,
 
0.1 IO3 − + 2n(Pb(IO3 )2 ) = 0.1 × 0.1,
 
n(PbSO4 ) + SO4 2− 0.1 = 3.79 × 10−6 ,
 2+  
Pb SO4 2− = 10−7.8 ,
 2+  − 2
Pb IO3 = 10−12.59 ,

where n(PbSO4 ) and n (Pb(IO3 )2 ) are, respectively, the number of moles of PbSO4
and Pb(IO3 )2 that have precipitated. The first three equations are expressed in mole
numbers rather than in concentrations. They represent the mass balances on Pb2+ ,
IO− 2−
3 , and SO4 , respectively. The system leads to the equilibrium concentration
[Pb2+ ] = 10−10.59 mol/L and consequently to the value [SO4 2− ] = 102.79 mol/L.
This is an absurd value. The starting hypothesis was false.
Now we’ll set up the hypothesis that lead exists only as lead iodate. At first sight,
this hypothesis seems to be in accordance with intuition since lead iodate’s solubility
product is lower than that of lead sulfate. The system
 
n(Pb(IO3 )2 ) + Pb2+ 0.1 = 3.79 × 10−6 ,
 
0.1 IO3 − + 2n(Pb(IO3 )2 ) = 0.1 × 0.1,
 2+  − 2
Pb IO3 = 10−12.59
33.3 Superimposition of Two Precipitation Equilibria: Separation by Precipitation 631

leads to the concentration:

 
Pb2+ = 1.90 × 10−7 mol/L,
n(Pb(IO3 )2 ) = 3.79 × 10−6 − 1.90 × 10−7 10−1
= 3.77 × 10−6 mol.

These results are in accordance with the problem’s data. Lead sulfate is totally
converted into lead iodate.
Note that in some cases, separation by precipitation may be made selective by a
judicious choice of the pH value (see Chap. 34).