HCI (College) / H2 Chemistry / 2013 Students’ Version

Lecture 18
Solubility Equilibria
CONTENT
1. Introduction
2. Solubility and Saturated solutions
3. Ionic Product
4. Solubility Product
4.1 Using IP and Ksp to predict the occurrence of precipitation
4.2 Selective Precipitation of Ions
5. Solubility vs. Solubility Product
5.1 Calculation of Ksp from Solubility
5.2 Calculation of Solubility from Ksp
6. Factors Affecting Solubility
6.1 Common Ion Effect
6.2 Complex Formation
6.3 Effects of pH
7. Summary

LEARNING OUTCOMES

Candidates should be able to:

(i) show understanding of, and apply, the concept of solubility product, Ksp
(ii) calculate Ksp from concentrations and vice versa
(iii) show understanding of the common ion effect

REFERENCES

1. Martin Silberberg. Chemistry: The molecular nature of Matter and Change, 2002.
2. Peter Cann, Peter Hughes. Chemistry for Advanced Level, 2002.

1 INTRODUCTION

Equilibria involving ions in aqueous solution are important in industrial, analytical and
biological processes. The principles and characteristics of these ionic equilibria are very
similar to those in other systems in chemical equilibrium.

The dissolving and precipitating of compounds are phenomena that occur both within us and
around us. E.g. the dissolving of enamel in teeth in acidic solutions causes tooth decay; the
precipitation of certain salts in our kidneys produce kidney stones; the precipitation of
calcium carbonate from underground water to form stalactites and stalagmites inside caves.

In this section, we will explore the aqueous equilibria of sparingly soluble ionic compounds or
salts.

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2 SOLUBILITY AND SATURATED SOLUTIONS

Before we can talk about the equilibria of sparingly soluble ionic salts, we must first
understand the concept of solubility and saturated solutions.

The following table shows the solubility of some common ionic salts that you should have
come across in your secondary school science syllabus. It provides a good starting point to
discuss the concept of solubility.

Ions Solubility
–
NO3 All nitrates are soluble.
Cl –, Br –, I– All halides are soluble except Ag+ and Pb2+

SO42– All sulfates are soluble except Pb2+, Ba2+ and Ca2+.

CO32– All carbonates are insoluble except Na+, K+ and NH4+

All oxides are insoluble except Na+ and K+
O2–
Ba2+ and Ca2+ are sparingly soluble.
All hydroxides are insoluble except Na+ and K+
OH–
Ba2+ and Ca2+ are sparingly soluble.

DEFINITION
Solubility of a salt is the number of moles of solute (salt) that can be dissolved in 1 dm 3 of
solvent to form a saturated solution at a given temperature.

The solubility of NaCl in water at 25oC is 359 g (6.102 mol) per dm3 of water.

This is the maximum mass or amount of NaCl that can be dissolved in water to give a
saturated solution at 25oC. When this occurs, no further amount of NaCl will dissolve in the
solution.

Note:
• The units for solubility are usually in g dm–3 or mol dm–3 (molar solubility)
• The solubility of a compound is defined for a given temperature. It changes with
changing temperatures.

A supersaturated solution is a solution that contains a greater amount of solute than that
needed to form a saturated solution.
• They can be prepared by saturating a solution at high temperature followed by slow
cooling to a temperature at which the solute is less soluble.
• Addition of a small crystal of the solute to the supersaturated solution will often lead
to crystallization of the salt.

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3 IONIC PRODUCT

Typically for any ionic compound, as more solute is dissolved in a solvent, the concentration
of the solute particles (ions) in the solution increases, but this cannot occur indefinitely. For
most solutes, they have a limited solubility in a particular solvent. At a given temperature,
when this upper limit is reached, the solution is said to be saturated. Additional solute will not
dissolve when added to such a solution. A dynamic equilibrium is set up between the
dissolved solute and the undissolved solute. Thus, there is a constant dissolution of the
excess undissolved solute and a constant precipitation of the solid solute from the ions
formed by the already dissolved solute; these two processes take place at the same rate.

Sparingly soluble ionic compounds (e.g. silver chloride, barium sulfate, and iron(III)
hydroxide) have low solubilities, so they reach equilibrium with relatively little solute
dissolved.
AgCl (s) Ag+ (aq) + Cl – (aq)

Discussion of this type of equilibrium begins with a theoretical measure of the amount of ions
present in the solution.

DEFINITION
The ionic product (IP) of a salt is the product of the molar concentrations of the constituent
ions in the solution, raised to the appropriate powers.

• Given that AgCl is a sparingly soluble salt, dissolution of AgCl is a reversible process
that can be expressed as follows:
AgCl (s) Ag+ (aq) + Cl – (aq)

• The ionic product of AgCl is therefore given by:

IP = [Ag+][Cl–]

• The ionic product is a measure of the amount of ions present in solution at a given
temperature at the instant of mixing of the ions. It simply tells us how much ions are
currently in the solution just upon mixing, regardless of whether the solution is saturated
or otherwise.

• Other examples:
o In a solution of BaSO4, IP = [Ba2+][SO42–]
o In a solution of PbCl2, IP = [Pb2+][Cl –]2

What are the units of the ionic products of these solutions?

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Example 1
1.00 × 10–3 mol dm–3 solution of Ca2+ ions is mixed with an equal volume of 1.00 × 10–3 mol
dm–3 solution of SO42– at 25 oC. Calculate the ionic product of the solution.

[Ca2+] = [SO42–] = 10–3 ÷ 2 = 5.00 × 10–4 mol dm–3

The concentration of each ion is halved since volume has doubled.

IP = [Ca2+][SO42–] = (5.00 × 10–4)2 = 2.50 × 10–7 mol2 dm–6

4 SOLUBILITY PRODUCT

Now, consider the same AgCl system when it is at equilibrium. At equilibrium, it is a

mixture of the dissolved ions at saturation with some of the undissolved solid.

AgCl (s) Ag+ (aq) + Cl – (aq)

We can write an expression for the equilibrium constant, Kc, as follows:

[Ag+ ][Cl − ]
Kc =
[AgCl ]

However, [AgCl] represents the ‘concentration’ of a pure solid, and is therefore a constant.

Thus,

Kc x [AgCl] = [Ag+][Cl –]

Ksp = [Ag+][Cl –]

o The new equilibrium constant, Ksp, is called the solubility product of AgCl.
o In other words, the solubility product is the ionic product of a sparingly soluble
salt when the system is at equilibrium.
o Ksp indicates the maximum concentration of ions of the salt in the solution.
o Units of Ksp of AgCl: mol2 dm–6

DEFINITION
Solubility product (Ksp) of a sparingly soluble salt is the product of the molar
concentrations of the constituent ions in a saturated solution, raised to the appropriate
powers at a given temperature.

• Using the general formula AxBy for a sparingly soluble salt,

AxBy (s) xAy+ (aq) + yBx− (aq)

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the general expression for the solubility product is given by

Ksp = [Ay+]x [Bx−]y

• The solubility product concept is only valid for sparingly soluble salts.

• For soluble salts such as NaCl, CuSO4 and AgNO3, the use of the Ksp concept is
inappropriate. (Why?)

• As such, for sparingly soluble salts, the numerical value of Ksp is always very small,
rarely exceeding 10–4 and can be as low as 10–40.

• Like all other equilibrium constants, the value of Ksp will change only with temperature.

• In effect, the solubility product of a salt tells us the maximum amount of ions that can dissolve
in a solvent.

An Experimental Investigation of Solubility Product

Consider the following experiment:

AgBrO3 (s) ⇌ Ag+ (aq) + BrO3– (aq)

Fixed volumes of AgNO3 (aq) and KBrO3 (aq), both of concentration 0.100 mol dm–3 were
added to 200 cm3 of deionised water at 25 oC. The [Ag+] and [BrO3–] at equilibrium were then
measured and shown in the table below.

Vol. of AgNO3 Vol. of KBrO3 [Ag+]eqm [BrO3–]eqm [Ag+]eqm x [BrO3–]eqm

added / cm3 added / cm3 / mol dm–3 / mol dm–3 / mol2 dm–6
40.0 10.0 0.0144 0.0024 3.45 x 10–5
30.0 20.0 0.0081 0.0041 3.32 x 10–5
25.0 25.0 0.0058 0.0058 3.36 x 10–5
20.0 30.0 0.0042 0.0082 3.44 x 10–5
10.0 40.0 0.0033 0.0102 3.37 x 10–5

Notice that the ionic product of the concentrations of Ag+ (aq) and BrO3–- (aq) in all 5 sets of
experiments are almost constant.

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If we plot the graph of [Ag+]eqm against [BrO3 –]eqm, the following graph will be obtained.

Hence, [Ag+][BrO3–] = Constant at a given temperature

= 3.39 x 10–5 mol2 dm–6 at 25 oC

This value of [Ag+][BrO3–] is the solubility product of AgBrO3 at 25 oC.

It is independent of the amount of Ag+ and BrO3– added to the solution, provided that the
resulting solution is saturated. (i.e. some undissolved AgBrO3 is in contact with the solution.)

4.1 USING IP AND Ksp TO PREDICT THE OCCURRENCE OF PRECIPITATION

By comparing the value of the ionic product against the solubility product of a salt, it is
possible to predict the occurrence of precipitation.

Precipitation is said to occur when two solutions upon mixing produce an insoluble solid
(called the precipitate).

Ionic
Is the solution saturated? Is there precipitation?
Product
• The solution is not saturated • No precipitation can occur yet
IP < Ksp • More AgCl can dissolve in the
solution until IP = Ksp
• The solution is just saturated This is the point where:
• The solution contains the • The precipitate just dissolves or
IP = Ksp
maximum amounts of Ag+ and • The first trace of precipitate just
Cl– without precipitating disappears
• The solution is still saturated. In • Precipitate of AgCl occurs.
fact the concentrations of Ag+ AgCl (s) Ag+ (aq) + Cl – (aq)
and Cl– are the same here as • Equilibrium shifts to the left, forming
IP > Ksp that in the second case. The precipitate until IP = Ksp.
solution already contains the
maximum amounts of Ag+ and
Cl–.

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Note that when a sparingly soluble salt dissolves, the concentrations of the ions in solution
are in a ratio determined by the formula of the salt. For example, when a sample of solid
CaF2 is placed in water, the concentration of the F– ions would be twice that of the Ca2+ ions.
The following equation illustrates this:

CaF2 (s) ⇌ Ca2+ (aq) + 2F– (aq)

Example 2
Given that the numerical value of Ksp of CaSO4 is 2.40 × 10–5 at 25 oC, will a precipitate of
CaSO4 form when a 1.00 × 10–3 mol dm–3 solution of Ca2+ ions is mixed with an equal
volume of 1.00 × 10–3 mol dm–3 solution of SO42– at 25 oC?

Immediately after mixing equal volumes of the two solutions and before
any precipitation occurrs, the concentration of each ion is halved since
volume has doubled.

10−3
[Ca2+] = [SO42–] = = 5.00 x 10–4 mol dm–3
2

IP = [Ca2+][SO42–] = (5 x 10–4)2 = 2.5 x 10–7 mol2 dm–6

Since IP < Ksp, no precipitation occurs.

Exercise 1
Will a precipitate form when 100 cm3 of 3.00 × 10–3 mol dm–3 Pb(NO3)2 is added to
400 cm3 of 5.00 × 10–3 mol dm–3 Na2SO4? [Given that the numerical value of Ksp of PbSO4 is
1.60 × 10–8]

Pb(NO3)2 (aq)  Pb2+ (aq) + 2NO3− (aq)

In 0.100 dm3 –3
3.00 x 10 mol dm–3
3.00 x 10–3 mol dm–3

Na2SO4 (aq)  2Na+ (aq) + SO42− (aq)

In 0.400 dm3 5.0 x 10–3 mol dm–3 5.0 x 10–3 mol dm–3

Pb2+ (aq) + SO42− (aq) ⇌ PbSO4 (s)

The insoluble salt produced in 0.500 dm3 is PbSO4.

0.1
[Pb2+] = 3.0 x 10–3 x = 6.0 x 10–4 mol dm–3
0.5

0.4
[SO42–] = 5.0 x 10–3 x = 4.0 x 10–3 mol dm–3
0.5

Ionic Product of PbSO4 = [Pb2+][SO42–]

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= (6.0 x 10–4)(4.0 x 10–3)

= 2.4 x 10–6 mol2 dm–6 > 1.6 x 10–8 mol2 dm–6
(Ksp of PbSO4)

Since IP > Ksp, precipitation occurs and white precipitate of BaSO4 forms.

Exercise 2
What is the minimum concentration of Ca2+ that must be added to a 2.00 × 10–4 mol dm–3
MgSO4 before a precipitate of CaSO4 can be formed? [Given that the numerical value of Ksp
of CaSO4 is 2.40 × 10–5] -3
(0.120 mol dm )

To just precipitate CaSO4 from the solution, IP = Ksp.

[Ca2+]min [SO42–] = 2.40 × 10–5 mol2 dm–6

From 2.00 × 10–4 mol dm–3 MgSO4,

[SO42–] = 2.00 × 10–4 mol dm–3

2.40 × 10 −5
[Ca2+]min = = 0.120 mol dm–3
2.00 × 10 −4

4.2 SELECTIVE PRECIPITATION OF IONS

• Ions can be separated from each other based on the different solubilities of their salts.
• Selective precipitation: separation of ions in an aqueous solution by using a reagent that
forms a precipitate with one or a few of the other ions but not all.

Exercise 3
A solution contains 1.00 × 10–2 mol dm–3 Ag+ and 2.00 × 10–2 mol dm–3 Pb2+. When Cl– is
added to the solution, both AgCl and PbCl 2 precipitate from the solution.

The numerical value of the Ksp for AgCl is 1.80 × 10–10 while that for PbCl 2 is 1.60 × 10–5.

(a) What concentration of Cl – is necessary to begin precipitation of each salt?

-8 -3 -2 -3
(1.80 x 10 mol dm & 2.83 x 10 mol dm )

For AgCl to be precipitated, [Ag+][Cl–]min = 1.8 x 10–10 mol2 dm–6

(1.0 x 10–2) [Cl–]min = 1.8 x 10–10

[Cl–]min = 1.8 x 10–8 mol dm–3

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For PbCl2 to be precipitated, [Pb2+][Cl–]2min = 1.6 x 10–5 mol3 dm–9

(2.0 x 10–2) [Cl–]2min = 1.6 x 10–5

[Cl–]min = 2.83 x 10–2 mol dm–3

(b) Which salt precipitates first and why?

AgCl. This is because it takes a lower [Cl–] concentration to precipitate

AgCl.

(c) How can Ag+ be separated from Pb2+? Is the separation effective?

When [Cl– ] = 2.83 × 10–2 mol dm –3, PbCl2 is just about to precipitate out.

To separate the two ions, add enough Cl– so that [Cl– ] = 2.83 × 10–2 mol
dm–3. Filter the AgCl precipitate formed. The filtrate will contain Pb2+.

At this point, we can calculate the concentration of Ag+ left in solution:

[Ag+](2.83 × 10–2) = 1.80 × 10–10

1.80 × 10 − 10
[Ag+] = = 6.36 × 10–9 mol dm –3
2.83 × 10 − 2

6.36 × 10 −9
% of Ag+ left in solution = x 100 = 6.36 × 10-5 %
1.00 × 10 −2
Separation is very effective.

Note: Often to ensure that PbCl2 does not precipitate at all, we may add just
a little less Cl– so that [Cl– ] a little less than 2.83 × 10–2 mol dm–3.

5 SOLUBILITY VS. SOLUBILITY PRODUCT

Solubility of Molar solubility Molar

compound of compound concentration of Ksp
(g/dm3) (mol/dm3) ions

• Solubility and Solubility product are different

• Ksp can be calculated from the solubility of the salt and vice versa.

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5.1 CALCULATION OF Ksp FROM SOLUBILITY

Example 3
The solubility of silver chloride at 18 oC is 1.46 × 10–3 g dm–3. What is the solubility product of
silver chloride at this temperature? [Mr of AgCl = 143.5]

AgCl (s) Ag+ (aq) + Cl– (aq)

1.46 × 10−3
Molar solubility of AgCl = = 1.02 × 10−5 mol dm–3
143.5

AgCl(s) ⇌ Ag+(aq) + Cl–(aq)

[ ]eqm /mol dm–3 1.02 × 10−5 1.02 × 10−5

Ksp = [Ag+][Cl–] = (1.02 × 10–5)2 = 1.04 × 10–10 mol2 dm–6

Example 4
Calculate the Ksp of Ag2SO4 given that its solubility is 4.47 g dm–3. [Mr of Ag2SO4 = 312.1]

4.47
Solubility of Ag2SO4 = = 0.0143 mol dm–3
312.1

Ag2SO4(s) ⇌ 2Ag+(aq) + SO42–(aq)

[ ]eqm /mol dm–3 2 × 0.0143 0.0143

i.e. [Ag+] = 2 × 0.0143 mol dm–3 and [SO42–] = 0.0143 mol dm–3

Ksp = [Ag+]2 [SO42–] = (0.0286)2(0.0143) = 1.17 × 10–5 mol3 dm–9

Exercise 4
Given that the solubility of Ag2CO3 at 20 oC is 1.25 x 10–4 mol dm–3, find its solubility product
at this temperature. (7.81 x 10–12 mol3 dm–9)

Ag2CO3(s) ⇌ 2 Ag+(aq) + CO32–(aq)

Ksp = [Ag+]2[CO32–] = (2 x 1.25 x 10–4)2 (1.25 x 10–4) = 7.81 x 10–12 mol3 dm–9

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5.2 CALCULATION OF SOLUBILITY FROM Ksp

Example 5
If the numerical value of Ksp of PbF2 is 7.10 × 10–8, find the solubility of PbF2 in mol dm–3 and
in g dm–3. [Mr of PbF2 = 245.0]

Let the solubility of PbF2 = s mol dm–3

PbF2(s) ⇌ Pb2+(aq) + 2 F–(aq)

–3
[ ]eqm / mol dm s 2s

Ksp of PbF2 = [Pb2+][F–]2 =(s)(2s)2

7.10 × 10–8 = 4s3
s = 2.61 x 10–3 mol dm–3

s = 2.61 x 10–3 x 245.0 = 0.639 g dm–3

Exercise 5
A suspension of Mg(OH)2 in water is sold as "milk of magnesia" to alleviate minor stomach
disorders 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? –4 –3
(5.40 x 10 mol dm )

Let the solubility of Mg(OH)2 be s mol dm–3

Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH–(aq)

[ ]eqm /mol dm–3 s 2s

Ksp = [Mg2+][OH–]2
6.3 x 10–10 = (s)(2s)2
= 4s3
s = 5.40 x 10–4 mol dm–3

The molar solubility of Mg(OH)2 is 5.40 x 10–4 mol dm–3.

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6 FACTORS AFFECTING SOLUBILITY OF A SALT

The solubility of a salt at a given temperature may be changed by shifting the position of the
equilibrium. Movement of the equilibrium position to the right hand side would cause the
solubility to increase while movement to the left hand side would reduce the solubility.
Factors affecting the solubility of a salt include the following:

- Presence of a common ion

- Complex formation
- Changes to the pH of the solution
- Temperature (which changes the Ksp of the salt)

6.1 COMMON ION EFFECT

Consider a saturated solution of CaF2 (i.e. containing solid CaF2 and its ions in solution). The
following equation illustrates this:

CaF2 (s) ⇌ Ca2+ (aq) + 2F– (aq)

If a water-soluble solute containing Ca2+ or F– is added, e.g. CaCl2 or NaF, by Le Chatelier’s

Principle, the position of equilibrium will shift to the left, thus reducing the solubility of CaF2.

In other words, the solubility of a sparingly soluble salt decreases in the presence of a
second solute that contains a common ion.

Exercise 6
Given that the numerical value of Ksp of AgCl is 2.00 × 10–10 at 25 oC,

(a) What is the solubility of AgCl in water? (1.40 x 10-5 mol dm-3)

Let s be the solubility of AgCl in water

AgCl (s) Ag+ (aq) + Cl– (aq)

[ ]eqm / mol dm–3 s s

Ksp = [Ag+][Cl–] = s2 = 2.00 × 10–10 mol2 dm–6

s = 1.40 × 10–5 mol dm–3

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(b) Calculate the solubility of AgCl in 0.100 mol dm3 NaCl. (2.00 x 10-9 mol dm-3)

A sample of 0.100 mol dm-3 NaCl will be fully dissociated as it is a soluble salt.

NaCl (aq) Na+ (aq) + Cl– (aq)

–3
[ ] / mol dm 0.100 0.100

Let s’ be the solubility of AgCl in 0.100 mol dm3 NaCl

AgCl (s) Ag+ (aq) + Cl– (aq)

[ ]eqm / mol dm–3 s’ s’ + 0.100

Total concentration of Cl – = s’ + 0.100

Ksp = [Ag+][ Cl –] = (s’)(s’ + 0.100)

Assume that s’ << 0.1, thus (s’ + 0.100) ≈ 0.100

(s’ )(0.100) = 2.00 x 10–10 mol2 dm–6

s’ = 2.00 x 10–9 mol dm–3

The solubility of the AgCl has decreased in the presence of Cl –, the common ion.
This is known as the common ion effect.

6.2 COMPLEX FORMATION

Some metal ions can act as electron pair acceptors (they have electron orbitals of the right
energy to accept these electrons) towards neutral molecules or anions which act as
electron–pair donors (usually lone pairs), thereby forming complex ions.

When aqueous NaOH is added to a colourless solution of Al3+, a white precipitate, Al(OH)3,
is first formed which then dissolves on adding excess NaOH. The dissolution of the white
precipitate is due to the formation of an aluminium-containing complex, [Al(OH)4]–. The
overall chemical equation may be represented as follows:

Al3+ (aq) + 4OH– (aq) [Al(OH)4]– (aq)

So what actually happens?

• As the value of the Ksp of Al(OH)3 is very small, addition of a small amount of NaOH will
result in the IP easily exceeding Ksp. This means that [Al3+][OH–] > Ksp.

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• To counter IP > Ksp, the precipitate of Al(OH)3 starts forming. The precipitation process
may be represented by the equation below:

Al3+ (aq) + 3 OH– (aq)  Al(OH)3 (s)

This reduces both the Al3+ and OH– concentrations until IP = Ksp. At this point, the
precipitation stops, and the amount of undissolved solid accumulated does not increase
further.

• On addition of more NaOH, [OH–] increases. To maintain IP = Ksp, further precipitation

occurs which reduces [Al3+] until almost all the Al3+ ions in solution has been precipitated
as Al(OH)3.

• At this point, the equilibrium between the precipitated Al(OH)3 and its ions in solution
may be represented as follows:

Al(OH)3 (s) Al3+ (aq) + 3 OH– (aq) ––––––––– (1)

This equilibrium between the solid and its aqueous ions is also present earlier when
Al(OH)3 was first precipitated. In fact, for sparingly soluble salts, as long as there is
excess solid in contact with its solution, this equilibrium will be present.

• When even more NaOH is added at this point (excess), the complex ion [Al(OH)4]– is
formed. The formation of the complex may be represented as follows:

Al3+ (aq) + 4OH– (aq)  [Al(OH)4]– (aq)

• Formation of the complex ion removes Al3+ from the solution, causing IP < Ksp. This shifts
equilibrium (1) to the right and solid Al(OH)3 dissolves. When enough excess NaOH is
added, the equilibrium position may be shifted so far to the right hand side such that all
the precipitated Al(OH)3 dissolves, leaving behind a colourless solution of [Al(OH)4]–.

• Thus complex ion formation increases the solubility of a sparingly soluble salt.

Example 6
The solubility of PbCl2 decreases in dilute HCl but increases in concentrated HCl. Explain.

PbCl2 (s) ⇌ Pb2+ (aq) + 2Cl– (aq) –––––– (1)

HCl (aq)  H+ (aq) + Cl– (aq)

In dilute HCl, solubility of PbCl2 decreases due to the common ion effect of Cl–.

Increase in [Cl–] causes position of the equilibrium in (1) to shift to the left therefore
less PbCl2 dissolves.

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Pb2+ (aq) + 4 Cl– (aq) ⇌ [PbCl4]2– (aq) –––––– (2)

In concentrated HCl, Pb2+ will form soluble complex, [PbCl4]2– with Cl–.

Formation of the complex ions removes Pb2+ from solution, causing IP < Ksp

Equilibrium (1) shifts to the right to produce more Pb2+ and PbCl2 dissolves

6.3 EFFECTS OF pH

Changes to the pH of a solution may affect the solubility of a sparingly soluble salt. This
factor only affects salts which contain either acidic or basic ions.

For example, the solubility of Mg(OH)2 is increased considerably as the pH of the solution
drops.

• A saturated solution of Mg(OH)2 may be represented as follows:

Mg(OH)2 (s) Mg2+ (aq) + 2 OH– (aq)

• Addition of strong acid like HCl will neutralise the OH– ions to form water. The loss of
OH– will cause the IP < Ksp. According to Le Chatelier’s principle, the system will react
such that the equilibrium position shifts to the right hand side to offset the decrease of
OH– ions.

• This causes Mg(OH)2 to dissolve. Thus the solubility of Mg(OH)2 increases as the pH of
the solution decreases.

• The solubility of salts formed from weak acids are usually affected by changes in pH as
they are basic. Some basic anions include CO32–, PO43–, CN– and S2–.

Example 7
Why does a decrease in pH affect the solubility of CaF2 significantly but not CaSO4?

The F– anion is the conjugate base of a weak acid, i.e. F– is a stronger base than
water. On the other hand, SO42– is the conjugate base of a strong acid, i.e. SO42– is
a weaker base than water.

Since F– is tends to accept protons and form HF, [F–] decreases as [H+] increases.
This results in the equilibrium shifting to the right and increasing solubility of
CaF2, i.e. solubility increases as pH decreases. SO42– is a weak base and tends to
remain ionized. Thus, a change in pH does not affect the concentration of SO42–
and hence the solubility of CaSO4 remains unchanged.

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HCI (College) / H2 Chemistry / 2013 Students’ Version

Exercise 7
A saturated solution of Mg(OH)2 has a pH of 10.52. (Ksp of Mg(OH)2 = 1.8 × 10–11 mol3 dm−9)

(a) Calculate the solubility of Mg(OH)2. (1.64 x 10-4 mol dm-3)

pOH = 14.0 – 10.52 = 3.48

[OH–] = 10–3.48 mol dm–3

Ksp = [Mg2+][OH–]2 = 1.8 × 10–11

1.8 × 10 −11
[Mg2+] = = 1.64 × 10–4 mol dm–3
(10 −3.48 ) 2
Therefore solubility of Mg(OH)2 = 1.64 × 10–4 mol dm–3

(ii) Calculate the solubility of Mg(OH)2 if the saturated solution in (a) is mixed with a
solution buffered at pH 9.0. (0.180 mol dm-3)

pOH = 14.0 – 9.0 = 5.0

[OH–] = 10–5 mol dm–3

Ksp = [Mg2+][OH–]2 = 1.8 × 10–11

1.8 × 10 −11
[Mg2+] = −5 2
= 0.18 mol dm–3
(10 )

7 SUMMARY

• Ionic product, IP, is a measure of the amount of ions in the solution.

• Solubility product, Ksp, indicates the maximum amount of ions that can dissolve in a
solution.

• The value of IP can vary depending on the concentrations of the ions that make up the
solution.
o When IP < Ksp , solution is not saturated, more solute can be dissolved
o When IP = Ksp , solution is just saturated, no further solute can be dissolved
o When IP > Ksp , solution is saturated, precipitation will occur.

• Solubility is a measure of the amount of solute that can be dissolved in a given amount
of solvent.

• Common ion effect reduces solubility.

• Complex formation increases solubility

• pH changes may affect solubility.

Teo ME / Sim WH / Soh SK / Wee CS 16

HCI (College) / H2 Chemistry / 2013 Students’ Version

SUPPLEMENTARY EXERCISES
1 Which expression represents the solubility product of iron(III) hydroxide?

A [Fe3+][OH–]3 B [Fe3+]3[OH–]

C 3 3
Fe3+  OH-  Fe3+  OH- 
   D    
Fe ( OH)  Fe ( OH) 
 3  3

2 Which one of the following affects the value of the solubility product, Ksp, of silver sulfide
when it is precipitated by passing hydrogen sulfide into aqueous silver nitrate?

2AgNO3 (aq) + H2S (g)  Ag2S (s) + 2HNO3 (aq)

A An increase in temperature.
B The presence of excess acid.
C The pressure of hydrogen sulfide.
D The addition of aqueous silver nitrate.

3 Public swimming pools are often chlorinated to kill bacteria. As an alternative to

chlorination, silver ions can be used in a concentration of not more than 10–6 mol dm–3
and not less than 10–7 mol dm–3.

Which compound would, in a saturated solution, provide the necessary concentration of

silver ions?

Compound Solubility Product

A AgBr 5 × 10–13 mol2 dm–6
B AgCl 2 × 10–10 mol2 dm–6
C AgIO3 2 × 10–8 mol2 dm–6
D Ag2CO3 5 × 10–12 mol3 dm–9

4 Which of the following statements are true about the solubility of calcium phosphate,
Ca3(PO4)2, a sparingly soluble salt?

1) The solubility of calcium phosphate increases as the concentration of H+ increases.

2) Addition of calcium nitrate, Ca(NO3)2, reduces the solubility of calcium phosphate.

3) More calcium phosphate can be dissolved by cooling the saturated solution.

A 1,2 and 3 are correct

B 1 and 2 only are correct
C 2 and 3 only are correct
D 1 only is correct

AAAB

Teo ME / Sim WH / Soh SK / Wee CS 17