19.

3 EQUILIBRIA OF SLIGHTLY SOLUBLE IONIC COMPOUNDS

In this section, we explore the aqueous equilibria of slightly soluble ionic compounds,
which up to now we’ve called “insoluble.” In Chapter 13, we found that most solutes, even
those said to be “soluble,” have a limited solubility in a given solvent; if we add more than
this amount, some solute remains undissolved. In a saturated solution at a particular
temperature, equilibrium exists between the undissolved and dissolved solute. Slightly soluble
ionic compounds have a relatively low solubility, so they reach equilibrium with relatively
little solute dissolved. At this point, it would be a good idea for you to review the solubility
rules listed in Table 4.1 (p. 121).

When a soluble ionic compound dissolves in water, it dissociates completely into ions.
In this discussion, we will assume that the small amount of a slightly soluble ionic compound
that does dissolve in water also dissociates completely into ions. In reality, however, this is
not the case. Many slightly soluble salts, particularly those of transition metals and heavy
main-group metals, have metalnonmetal bonds with significant covalent character, and their
solutions often contain other species that are partially dissociated or even undissociated. For
example, when lead(II) chloride is thoroughly stirred in water, a small amount dissolves, and
the solution contains not only the Pb 2+(aq) and Cl-(aq) ions expected from complete
dissociation, but also undissociated PbCl2(aq) molecules and PbCl 2(aq) ions. In solutions of
some other salts, such as CaSO4, there are no molecules, but pairs of ions exist, such as Ca 2+
SO42-(aq). These species increase the solubility above what we calculate assuming complete
dissociation. For these reasons, it is best to treat the results of our calculations here as first
approximations.

The Ion-Product Expression (Qsp) and the Solubility-Product Constant (Ksp)

If we make the assumption that there is complete dissociation of a slightly soluble ionic
compound into its component ions, then equilibrium exists between solid solute and aqueous
ions. Thus, for example, for a saturated solution of lead(II) sulfate in water, we have

As with all the other equilibrium systems we’ve looked at, this one can be expressed by
a reaction quotient:
 As in previous cases, we incorporate the constant concentration of the solid, [PbSO4],
into the value of Qc, which gives the ion-product expression, Qsp:

And, when solid PbSO4 attains equilibrium with Pb2+ and SO42- ions, that is, when the solution
reaches saturation, the numerical value of Qsp attains a constant value, called the solubility-
product constant, Ksp. The Ksp for PbSO4 at 25°C, for example, is 1.6 x 10-8.

As we’ve seen with other equilibrium constants, a given Ksp value depends only on the
temperature, not on the individual ion concentrations. Suppose, for example, you add some
lead(II) nitrate, a soluble lead salt, to increase the solution’s [Pb 2+]. The equilibrium position
shifts to the left, and [SO42-] goes down as more PbSO4 precipitates; so the Ksp value is
maintained. The form of Qsp is identical to that of the other reaction quotients we have
written: each ion concentration is raised to an exponent equal to the coefficient in the balanced
equation, which in this case also equals the subscript of each ion in the compound’s formula.
Thus, in general, for a saturated solution of a slightly soluble ionic compound, M pXq,
composed of the ions Mn+ and Xz-, the equilibrium condition is

At saturation, the concentration terms have their equilibrium values, so we can write the
ion-product expression directly with the symbol Ksp. For example, the equation and ion-
product expression that describe a saturated solution of Cu(OH)2 are

Insoluble metal sulfides present a slightly different case. The sulfide ion, S 2-, is so basic
that it is not stable in water and reacts completely to form the hydrogen sulfide ion (HS -) and
the hydroxide ion (OH-):
 For instance, when manganese(II) sulfide is shaken with water, the solution contains
Mn2+, HS-, and OH- ions. Although the sulfide ion does not exist as such in water, you can
imagine the dissolution process as the sum of two steps, with S 2- occurring as an intermediate
that is consumed immediately:

Therefore, the ion-product expression is

SAMPLE PROBLEM 19.5

Writing Ion-Product Expressions for Slightly Soluble Ionic Compounds

Problem Write the ion-product expression for each of the following compounds:
(a) Magnesium carbonate
(b) Iron(II) hydroxide
(c) Calcium phosphate
(d) Silver sulfide
Plan We write an equation that describes a saturated solution and then write the ion-product
expression, Ksp, according to Equation 19.2, noting the sulfide in part (d).

Solution (a) Magnesium carbonate:

Check Except for part (d), you can check by reversing the process to see if you obtain the
formula of the compound from Ksp.

Comment In part (d), we include H2O as reactant to obtain a balanced equation.

FOLLOW-UP PROBLEM 19.5 Write the ion-product expression for each of the following
compounds: (a) Calcium sulfate (b) Chromium(III) carbonate (c) Magnesium hydroxide (d)
Arsenic(III) sulfide

The value of Ksp indicates how far to the right the dissolution proceeds at equilibrium
(saturation). Table 19.2 presents some representative Ksp values. (Appendix C includes a
much more extensive list.) Even though the values are all quite low, they range over many
orders of magnitude.

Calculations Involving the Solubility-Product Constant

In Chapters 17 and 18, we described two types of equilibrium problems. In one type, we
use concentrations to find K, and in the other, we use K to find concentrations. Here we
encounter the same two types.
 Determining Ksp from Solubility The solubilities of ionic compounds are determined
experimentally, and several chemical handbooks tabulate them. Most solubility values are
given in units of grams of solute dissolved in 100 grams of H2O. Because the mass of
compound in solution is small, a negligible error is introduced if we assume that “100 g of
water” is equal to “100 mL of solution.” We then convert the solubility from grams of solute
per 100 mL of solution to molar solubility, the amount (mol) of solute dissolved per liter of
solution (that is, the molarity of the solute). Next, we use the equation for the dissolution of
the solute to find the molarity of each ion and substitute into the ion-product expression to
find the value of Ksp.

SAMPLE PROBLEM 19.6 Determining Ksp from Solubility

Problem (a) Lead(II) sulfate (PbSO4) is a key component in lead-acid car batteries. Its
solubility in water at 25°C is 4.25 x 10 -3 g/100 mL solution. What is the Ksp of PbSO4? (b)
When lead(II) fluoride (PbF2) is shaken with pure water at 25°C, the solubility is found to be
0.64 g/L. Calculate the Ksp of PbF2.

Plan We are given the solubilities in various units and must find Ksp. For each compound, we
write an equation for its dissolution to see the number of moles of each ion, and then write the
ion-product expression. We convert the solubility to molar solubility, find the molarity of each
ion, and substitute into the ion-product expression to calculate Ksp.

Solution (a) For PbSO4. Writing the equation and ion-product (Ksp) expression:

Converting solubility to molar solubility:

Determining molarities of the ions: Because 1 mol of Pb 2+ and 1 mol of SO42- form when 1
mol of PbSO4 dissolves, [Pb2+] = [SO42-] = 1.40 x 10-4 M. Calculating Ksp:
(b) For PbF2. Writing the equation and Ksp expression:

Converting solubility to molar solubility:

Determining molarities of the ions: 1 mol of Pb 2+ and 2 mol of F- form when 1 mol of PbF2
dissolves, so we have

Check The low solubilities are consistent with Ksp values being small. (a) The molar
solubility seems about right:

Squaring this number gives 1.7 x 10-8, which is close to the calculated Ksp. (b) We check the

final step: , close to the calculated Ksp.

Comment 1. In part (b), the formula PbF2 means that [F -] is twice [Pb2+]. Then we square this
value of [F-]. Always follow the ion-product expression explicitly. 2. The tabulated Ksp values
for these compounds (Table 19.2) are lower than our calculated values. For PbF2, for
instance, the tabulated value is 3.6 x 10-8, but we calculated 7.0 x10 -8 from solubility data.
The discrepancy arises because we assumed that the PbF2 in solution dissociates completely
to Pb2+ and F-. Here is an example of the complexity pointed out at the beginning of this
section. Actually, about a third of the PbF2 dissolves as PbF +(aq) and a small amount as
undissociated PbF2(aq). The solubility (0.64 g/L) is determined experimentally and includes
these other species, which we did not include in our simple calculation. This is why we treat
such calculated Ksp values as approximations.
FOLLOW-UP PROBLEM 19.6 When powdered fluorite (CaF2) is shaken with pure water
at 18°C, 1.5 x 10-4 g dissolves for every 10.0 mL of solution. Calculate the Ksp of CaF2 at
18°C.

Determining Solubility from Ksp The reverse of the previous type of problem involves
finding the solubility of a compound based on its formula and Ksp value. An approach similar
to the one we used for weak acids in Sample Problem 18.8 is to define the unknown amount
dissolved—molar solubility—as S. Then we define the ion concentrations in terms of this
unknown in a reaction table, and solve for S.

SAMPLE PROBLEM 19.7 Determining Solubility from Ksp

Problem Calcium hydroxide (slaked lime) is a major component of mortar, plaster, and
cement, and solutions of Ca(OH)2 are used in industry as a cheap, strong base. Calculate the
solubility of Ca(OH)2 in water if the Ksp is 6.5 x 10 -6. Plan We write the dissolution equation
and the ion product expression. We know Ksp (6.5 x 10 -6); to find molar solubility (S), we set
up a reaction table that expresses [Ca2-] and [OH-] in terms of S, substitute into the ion product
expression, and solve for S. Solution Writing the equation and ion-product expression:

Substituting into the ion-product expression and solving for S:

Check We expect a low solubility from a slightly soluble salt. If we reverse the calculation,
we should obtain the given Ksp: 4(1.2 x 10-2)3 = 6.9 x 10-6, close to 6.5 x 10-6.

Comment 1. Note that we did not double and then square [OH-]. 2S is the [OH-], so we just
squared it, as the ion-product expression required.
2. Once again, we assumed that the solid dissociates completely. Actually, the solubility is
increased to about 2.0 x 10-2 M by the presence of CaOH+(aq) formed in the reaction

Our calculated answer is only approximate

because we did not take this other species into account.

FOLLOW-UP PROBLEM 19.7 A suspension of Mg(OH)2 in water is marketed as “milk of

magnesia,” which alleviates minor symptoms of indigestion by neutralizing stomach acid. The
[OH-] is too low to harm the mouth and throat, but the suspension dissolves in the acidic
stomach juices. What is the molar solubility of Mg(OH)2 (Ksp = 6.3 x 10-10) in pure water?

Using Ksp Values to Compare Solubilities The Ksp values provide a guide to relative
solubility, as long as we compare compounds whose formulas contain the same total number
of ions. In such cases, the higher the Ksp, the greater the solubility. Table 19.3 shows this
point for several compounds. Note that for compounds that form three ions, the relationship
holds whether the cation/anion ratio is 1/2 or 2/1, because the mathematical expression
containing S is the same (4S3) in the calculation (see Sample Problem 19.7).

The Effect of a Common Ion on Solubility

The presence of a common ion decreases the solubility of a slightly soluble ionic
compound. As we saw in the case of acid-base systems, Le Châtelier’s principle helps explain
this effect. Let’s examine the equilibrium condition for a saturated solution of lead(II)
chromate:
 At a given temperature, Ksp depends on the product of the ion concentrations. If the
concentration of either ion goes up, the other must go down to maintain Ksp. Suppose we add
Na2CrO4, a soluble salt, to the saturated PbCrO 4 solution. The concentration of the common
ion, CrO42-, increases, and some of it combines with Pb 2+ ion to form more solid PbCrO 4
(Figure 19.10, next page). The overall effect is a shift in the position of equilibrium to the left:

FIGURE 19.10The effect of a common ion on solubility. When a common ion is added
to a saturated solution of an ionic compound, the solubility is lowered and more of the
compound precipitates. A, Lead(II) chromate, a slightly soluble salt, forms a saturated
aqueous solution. B, When Na2CrO4 solution is added, the amount of PbCrO4(s) increases.
Thus, PbCrO4 is less soluble in the presence of the common ion CrO42.

After the addition, [CrO42-] is higher, but [Pb2+] is lower. In this case, [Pb 2+] represents
the amount of PbCrO4 dissolved; thus, in effect, the solubility of PbCrO4 has decreased. The
same result is obtained if we dissolve PbCrO4 in a Na2CrO4 solution. We also obtain this
result by adding a soluble lead(II) salt, such as Pb(NO3)2. The added Pb 2+ ion combines with
some CrO42-(aq), thereby lowering the amount of dissolved PbCrO4.

The Effect of pH on Solubility

The hydronium ion concentration can have a profound effect on the solubility of an ionic
compound. If the compound contains the anion of a weak acid, addition of H3O+ (from a
strong acid) increases its solubility. Once again, Le Châtelier’s principle explains why. An
especially interesting case occurs with calcium carbonate. In a saturated solution of CaCO3,
we have
Adding some strong acid introduces a large amount of H3O +, which immediately reacts with
CO32- to form the weak acid HCO3-:

Thus, more CaCO3 dissolves. In this particular case, the effect is increased by gas formation.
If enough H3O+ is added, further reaction occurs to form carbonic acid, which decomposes
immediately to H2O and CO2, and the gas escapes the container:

As this sequence of changes shows, the net effect of added H3O is a shift in the equilibrium
position to the right:

In fact, this example illustrates a qualitative field test for carbonate minerals because the CO2
bubbles vigorously (Figure 19.11).

In contrast, adding H3O+ to a saturated solution of a compound with a strongacid

anion, such as silver chloride, has no effect on the equilibrium position:

Because Cl- ion is the conjugate base of a strong acid (HCl), it can coexist in solution with
high [H3O+]. The Cl- does not leave the system, so the equilibrium position is not affected.
SAMPLE PROBLEM 19.9 Predicting the Effect on Solubility of Adding Strong Acid
Problem Write balanced equations to explain whether addition of H3O+ from a strong acid
affects the solubility of these ionic compounds: (a) Lead(II) bromide (b) Copper(II) hydroxide
(c) Iron(II) sulfide

Plan We write the balanced dissolution equation and note the anion: Weak-acid anions react
with H3O+ and shift the equilibrium position toward more dissolution. Strong-acid anions do
not react, so added H3O+ has no effect.

Br- is the anion of HBr, a strong acid, so it does not react with H3O+

OH- is the anion of H2O, a very weak acid, so it reacts with the added
H3O+:

We noted earlier that the S2 ion reacts immediately with water to form HS and OH–. The
added H3O reacts with both of these weak-acid anions:
FOLLOW-UP PROBLEM 19.9 Write balanced equations to show how addition of HNO3(aq)
affects the solubility of these ionic compounds: (a) Calcium fluoride (b) Zinc sulfide (c) Silver
iodide

Predicting the Formation of a Precipitate: Qsp vs. Ksp

In Chapter 17, we compared the values of Q and K to see if a reaction had reached
equilibrium and, if not, in which net direction it would move until it did. In this discussion,
we use the same approach to see if a precipitate will form and, if not, what changes in the ion
concentrations will cause it to do so. As you know, Qsp = Ksp when the solution is saturated.
If Qsp is greater than Ksp, the solution is momentarily supersaturated, and some solid
precipitates until the remaining solution becomes saturated (Qsp = Ksp). If Qsp is less than
Ksp, the solution is unsaturated, and no precipitate forms at that temperature (more solid can
dissolve). To summarize,

 Qsp = Ksp: solution is saturated and no change occurs.

 Qsp > Ksp: precipitate forms until solution is saturated.
 Qsp < Ksp: solution is unsaturated and no precipitate forms.

Sample Problems 19.10 and 19.11 show how to predict formation of a precipitate, first using
concentration data and then using molecular scenes.

Applying Ionic Equilibria to the Acid-Rain Problem

The effect of industrial society on the environment is especially apparent in the

problem of acid rain; the underlying chemistry applies several principles of ionic equilibria.
Acidic precipitation—rain, snow, fog, or dry deposits on particles—has been recorded in all
parts of North America, the Amazon basin, Europe, including Russia, much of Asia, and even
at the North and South Poles. Three major substances are involved:

1. Sulfurous acid. Sulfur dioxide (SO2) from the burning of high-sulfur coal forms
sulfurous acid in contact with water. Oxidizing air pollutants, such as hydrogen
peroxide, convert sulfurous acid to sulfuric acid:
2. Sulfuric acid. Sulfur trioxide (SO3) forms through the atmospheric oxidation of SO2
and becomes H2SO4 in contact with water.
3. Nitric acid. Nitrogen oxides (denoted NOx) form when N2 and O2 react. NO is
produced during combustion in car engines and electric power plants, and then forms
NO2 and HNO3. At night, NOx are converted to N2O5, which hydrolyzes to HNO3 in
water.
Figure 19.12 illustrates some of the main sources of the two strong acids.

FIGURE 19.12 Formation of acidic precipitation. A complex interplay of human

activities, atmospheric chemistry, and environmental distribution leads to acidic
precipitation and its harmful effects. Car exhaust and power plant waste gases contain
lower oxides of nitrogen and sulfur. These are oxidized in the atmosphere to higher
oxides (NO2, SO3), which react with moisture to form acidic rain, snow, and fog. In
contact with acidic precipitation, many lakes become acidified, whereas limestone-
bounded lakes form a carbonate buffer that prevents acidification.
Unpolluted rainwater is weakly acidic (pH = 5.6) because it contains dissolved
CO2:

In contrast, the average pH of rainfall in much of the United States was 4.2 as
early as 1984; rain with a pH of 2.7 (about the same as vinegar) has been observed in
Sweden and with a pH of 1.8 (between lemon juice and stomach acid) in West
Virginia. These 10- to 10,000-fold excesses of [H 3O+] are very destructive to fish
(many species die at a pH below 5) and to forests. The aluminosilicates that make up
most soils are nearly insoluble. But contact with H3O+ dissolves some of the bound
Al3+, which is extremely toxic to fish, and many ions that act as nutrients for plants and
animals are dissolved and carried away.
 Acid rain also dissolves the calcium carbonate in the marble and limestone of
buildings and monuments. Ironically, the same process that destroys these structures
saves lakes in limestone-rich soil. As we discussed previously, added H 3O+ shifts the
following equilibrium to the right to dissolve more limestone and form more
bicarbonate:

With time, limestone-bounded lakes become enormous HCO3-/CO3-2 buffers

that maintain a relatively stable pH as they absorb additional H3O +. Lakes in
limestone-poor soils can be treated with limestone. Sweden spent tens of millions of
dollars during the 1990s to add limestone to about 3000 lakes. This method provides
only temporary improvement, however, and the lakes become re-acidified. More
effective approaches reduce SO2 and NOx at the source. SO2 is removed from power-
plant emissions with limestone or, in a newer method, it is partially reduced to H2S
and then converted to sulfur:

Coal can also be converted into gaseous and liquid low-sulfur fuels. The
catalytic converter in an automobile exhaust system reduces NOx to N2 and NH3, and
in power plants, NOx is removed from the hot stack gases with ammonia:

Amendments to the Clean Air Act to further curb NOx emissions and help
states meet ozone standards will reduce HNO3 in the process.
SECTION 19.3 SUMMARY
As an approximation, the dissolved portion of a slightly soluble salt dissociates
completely into ions. • In a saturated solution, the ions are in equilibrium with the
solid, and the product of the ion concentrations, each raised to the power of its
subscript in the compound’s formula, has a constant value (Qsp = Ksp). • The value of
Ksp can be obtained from the solubility, and vice versa. • Adding a common ion
lowers an ionic compound’s solubility. • Adding H3O+ (lowering the pH) increases a
compound’s solubility if the anion of the compound is that of a weak acid. • If Qsp >
Ksp for an ionic compound, a precipitate forms when two solutions, each containing
one of the compound’s ions, are mixed. • Lakes bounded by limestone-rich soils form
buffer systems that prevent harmful acidification by acid rain.