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Solubility


Solubility
 Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

7 Equilibria
This topic illustrates that many chemical reactions are reversible and involve an equilibrium process.
The consideration of the many factors that can affect an equilibrium is an important aspect of physical
chemistry.
Cambridge International AS and A Level Chemistry 9701 syllabus Syllabus content

Learning outcomes
Candidates should be able to:

7.1 Ionic
7.2 Chemical equilibria:
equilibria a) show
a) explain, in terms of rates
understanding of the
of, and use,forward and reverse reactions,
the Brønsted-Lowry theory of what
acids is
reversible reactions; meant by a reversible reaction and dynamic equilibrium
and bases, including the use of the acid-I base-I, acid-II base-II concept
dynamic equilibrium b) state Lequalitatively
Chatelier’s the
principle and apply it to deduce qualitatively
b) explain differences in behaviour between strong and
(from appropriate information) the effects of changes
weak acids and bases and the pH values of their aqueous in temperature,
solutions in
concentration
terms or pressure
of the extent on a system at equilibrium
of dissociation
c) explain
c) state whether changes
the terms pH, Kin ,temperature, concentration or pressure or the
a pKa and Kw and use them in calculations
presence of a catalyst affect the value of the equilibrium constant for a
d) calculate [H+(aq)] and pH values for strong and weak acids and
reaction
strong bases
d) deduce expressions for equilibrium constants in terms of concentrations,
e) explain the choice of suitable indicators for acid-base titrations,
Kc , and partial pressures, Kp (treatment of the relationship between Kp
given appropriate data
and Kc is not required)
f) describe the changes in pH during acid-base titrations and explain
e) calculate the values of equilibrium constants in terms of concentrations
these changes in terms of the strengths of the acids and bases
or partial pressures from appropriate data
g) (i) explain how buffer solutions control pH
f) calculate the quantities present at equilibrium, given appropriate data
(ii)
(suchdescribe and explain
calculations the uses
will not require theofsolving
buffer of
solutions,
quadraticincluding
equations)the
–
role of HCO3 in controlling pH in blood
g) describe and explain the conditions used in the Haber process and the
h) calculate the pH as
Contact process, of examples
buffer solutions, given appropriate
of the importance data
of an understanding of
i) show
chemicalunderstanding
equilibrium inof,
theand use, the
chemical concept of solubility product,
industry
Ksp
j) calculate Ksp from concentrations and vice versa
k) show understanding of the common ion effect

7.3 Partition coefficients a) state what is meant by partition coefficient; calculate and use a
partition coefficient for a system in which the solute is in the same
molecular state in the two solvents

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7. 1 Definition
Solubility product is the product of the concentrations of
each ion in a saturated solution of a sparingly soluble salt
at 298 K, raised to the power of their relative
concentrations.

Solubility is affected by temperature and hence the value

of Ksp depends on temperature.

7. 2 Ksp calculation example 1

The solubility product of a salt can be obtained from its
solubility. A saturated solution of silver chloride contains
1.46 × 10−3 g dm−3 at 18 °C. What is the Ksp?

Step 1: Find the solubility of salt in moldm-3

The solubility of silver chloride at 18°C = 1.46 × 10−3 g

dm−3

7. 3 Ksp calculation example 1

Step 1: Find the solubility of salt in moldm-3

The solubility of silver chloride = 1.46 × 10−3 g dm−3

Molar mass = 143.5 g mol—1

7. 4 Ksp calculation example 1

Step 2: Use the ICE table to find the [Ag+] and [Cl—],
from the amount that dissolves.

AgCl(s) ⇌ Ag+(aq) + Cl—(aq)

Initial
Change
Equiibrium

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7. 5 Ksp calculation example 1

Step 3: Place the values of [Ag+] and [Cl—] in Ksp
expression.

7. 6 Ksp calculation example 2

A saturated solution of magnesium fluoride, MgF2, has a
solubility of 1.22 × 10–3 mol dm–3. Calculate the Ksp?

MgF2(s) ⇌ Mg2+(aq) + 2F—(aq)

Initial
Change
Equiibrium

7. 7 Ksp calculation example 2

7. 8 Skill check
Calculate the Ksp of a saturated aqueous solution of
cadmium sulfide, CdS (solubility = 1.46 × 10–11 mol dm–3)

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7. 9 Skill check
Calculate the Ksp of a saturated aqueous solution of
calcium fluoride, CaF2, containing 0.0168 g dm–3 CaF2

7. 10 Calculating solubility from Ksp 1

Solubility products can be used to calculate the solubility
of compounds.

Calculate the solubility of copper(II) sulfide in mol dm–3


(Ksp for CuS = 6.3 × 10–36 mol2 dm–6)


Step 1: Write down the equilibrium equation.

CuS(s) ⇌ Cu2+(aq) + S2—(aq)

7. 11 Calculating solubility from Ksp 1

Step 2: Find equilibrium concentrations.
CuS(s) ⇌ Cu2+(aq) + S2—(aq)

Initial
Change
Equiibrium
If x is the amount of CuS that dissolves, then [Cu2+] = x and

[S2—] = x

7. 12 Calculating solubility from Ksp 1

Step 3: Subsititute the value of Ksp and x into the Ksp
expression.

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7. 13 Calculating solubility from Ksp 2

Given that the solubility product constant of Ni(OH)2 is
6.5 × 10−18 mol3 dm−9 at 298 K, calculate the solubility of
nickel(II) hydroxide in water.

7. 14 Skill check
Calculate the solubility in mol dm–3 of zinc sulfide, ZnS. 

(Ksp =1.6 × 10–23 mol2 dm–6)


7. 15 Skill check
Calculate the solubility of silver carbonate, Ag2CO3. 

(Ksp = 6.3 × 10–12 mol3 dm–9)

7. 16 Predicting precipitation
The solubility product can be used to predict whether
precipitation will occur when two solutions are mixed.

For example: will we get a precipitate when we mix a

solution of barium chloride, BaCl2, with a very dilute
solution of sodium carbonate?

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7. 17 Predicting precipitation
Both barium chloride and sodium carbonate are soluble
salts, but barium carbonate is relatively insoluble. We
must consider the equilibrium for the insoluble salt
dissolving in water:

BaCO3 (s) ⇌ Ba2+ (aq) + CO32— (aq)

7. 18 Predicting precipitation
The solubility product is given by:

Ksp = [Ba2+] [CO32–] = 5.5 × 10–10 mol2 dm–6

If [Ba2+] [CO32–] is greater than 5.5 × 10–10 mol2 dm–6 a

precipitate will form.

If [Ba2+] [CO32–] is less than 5.5 × 10–10 mol2 dm–6 no

precipitate will form.

7. 19 Predicting precipitation example

Will a precipitate form if we mix equal volumes of
solutions of 1.00 × 10–4 mol dm–3 Na2CO3 and 5.00 × 10–
5 mol dm–3 BaCl2?

[Ba2+] = 1/2 x 5.00 × 10–5 = 2.50 × 10–5 mol dm–3

[CO32–] = 1/2 x 1.00 × 10–4 = 5.00 × 10–5 mol dm–3

[Ba2+] x [CO32–] = ? 


7. 20 Predicting precipitation example

[Ba2+] x [CO32–] = 1.25 × 10—9 mol2dm—6

This value is greater than the solubility product, so a

precipitate of barium carbonate forms.

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7. 21 Common ion effect

Adding a common ion, (one which is already present in the
solution), will result in the precipitation of a sparingly soluble
ionic compound.

Definition: The common ion effect is the reduction in the

solubility of a dissolved salt achieved by adding a
solution of a compound which has an ion in common
with the dissolved salt. This often results in
precipitation.

7. 22 Common ion effect

Adding NaCl to a saturated solution of AgCl will result in
the precipitation of AgCl.

AgCl(s) ⇌ Ag+(aq) + Cl—(aq)

Adding NaCl to a solution of AgCl increases the

concentration of Cl—(aq). Cl—(aq) is a common ion as it is
already in solution.

7. 23 Common ion effect

NaCl(s) → Na+(aq) + Cl—(aq)

The extra Cl— ions means that the solubility product is

exceeded. To reduce the value of [Ag+][Cl—] below the
Ksp, some ions are removed from solution by
precipitating.

Ksp = [Ag+][Cl—] = 1 × 10–10 mol2 dm–6

7. 24 Common ion effect

The effect of increasing or decreasing the concentration
of one of the ions in equilibrium with the sparingly soluble
salt may be predicted qualitatively using Le Chatelier’s
principle.

AgCl(s) ⇌ Ag+(aq) + Cl—(aq)

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7. 25 Common ion effect

AgCl(s) ⇌ Ag+(aq) + Cl—(aq)

The addition of either of Ag+(aq) or Cl—(aq) into the above

system in equilibrium would displace the equilibrium to
the left causing the precipitation of AgCl.

7. 26 Common ion effect

In other words when either M+(aq) or X—(aq) is added the
ion product will exceed the solubility product and MX will
be precipitated until the value of the Ksp is restored.

7. 27 Common ion effect example 1

Since the Ksp [Ag+] [Cl—] = 1x10—10 mol2 dm—6

[Ag+] = [Cl—] = 1x10—5 moldm-3

When [Cl—] is raised to 0.01 moldm-3 by adding either NaClthe [Ag+]

must decrease to 1x10–8 moldm-3

as Ksp = [Ag+][Cl—]

= 1x10—8 x 0.01 = 1x10—10

7. 28 Common ion effect

In calculations of solubility in solutions containing common ion, the
concentration of the ion from the sparingly soluble salt is usually
negligible in comparison to the concentration of the common ion.

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7. 29 Common ion effect example 2

Solubility of BaSO4 in 0.1 mol dm−3 Na2SO4(aq)

Ksp(BaSO4) = 1 × 10−10 mol2 dm−6

Solubility of BaSO4 in 0.1 M Na2SO4(aq) = w

BaSO4 (s) ⇌ Ba2+ (aq) + SO42— (aq)

7. 30 Common ion effect example 2

Na2SO4(s) → 2Na+(aq) + SO42—(aq)

[Ba2+] = w & [SO42—] = (w + 0.1)

but as w is much less than 0.1

[SO42—] = (w + 0.1) ≅ 0.1

Ksp = [Ba2+] [SO42—] = w x 0.1 = 1 × 10−10 mol2 dm−6

7. 31 Common ion effect example 3

How is the solubility of an ionic compound affected when
the compound is dissolved in a solution that already
contains one of its ions? For example, what is the
solubility of CaF2 in a solution that is 0.100 M in NaF?

Ksp of CaF2 = 1.46 x 10—10 mol3 dm—9

7. 32 Common ion effect example 3

Step 1: Begin by writing the reaction by which solid
CaF2 dissolves into its constituent aqueous ions.
Write the corresponding expression for Ksp.
CaF2(s) ⇌ Ca2+(aq) + 2F—(aq)

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7. 33 Common ion effect example 3

Step 2: Use the ICE table to find the concentrations of
the ions from the sparingly soluble salt (CaF2).

7. 34 Common ion effect example 3

Step 3: State the total concentrations of the ions from
the sparingly soluble salt (CaF2) accounting for the
common ion (F from NaF)

7. 35 Common ion effect example 3

Step 4: Plug in the values in the Ksp expression to find
the value of the solubility of CaF2 in NaF.

7. 36 Skill check
Calculate the mass of calcium hydroxide that will
dissolve in 100 cm3 of 0.1 moldm-3 sodium hydroxide
solution at 25oC. Ksp of Ca(OH)2 = 2.12 x10-4 mol3 dm—9

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7. 37 Skill check
Ksp of PbBr2 is 6.6 x 10–6 mol3dm—9. An excess of PbBr2
is stirred with 0.4 moldm-3 KBr solution, and excess
PbBr2 filtered off. Calculate the [Pb2+] in the remaining
solution.

7. 38 Skill check
The solubility of lead chloride is 4.75 gdm—3 at 25oC.
What mass of lead chloride will be precipitated if 5.85 g
of sodium chloride is added to 1 dm3 of saturated
solution of lead chloride?

7. 39 Skill check
The Ksp for Ca(OH)2 at 298K is 4.78× 10–5. Calculate the
[Ca2+] in the saturated solution.

5 dm3 of a saturated solution of was made. To this was

added 0.1 moldm-3 of NaOH. What mass of Ca(OH)2 will
precipitate?

7. 40

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