CAPE Chemistry – UNIT 1 – Chemical Principles and Applications I

Module 2 – Kinetics and Equilibria Lecture Notes 12

Solubility Product Constant (Ksp)

The solubility product constant (Ksp) is the equilibrium constant for the solubility equilibrium of a sparingly
soluble ionic compound.
When ionic compounds dissolve in water, they go into solution as their ions. When the solution becomes saturated
with ions, the excess solid settles out to the bottom of the container and an equilibrium is established between the
undissolved solid and the dissolved ions.
Consider the equilibrium of a saturated solution of calcium carbonate (CaCO3):

NB. - Solids are omitted from the equilibrium constant expression of a heterogeneous equilibria.
- The larger the Ksp, the more soluble the salt is. Therefore the smaller the Ksp the more insoluble the salt.
- Solids are not included in the Ksp expression.

Write the Ksp expression for the following sparingly soluble salts.
1. PbI2
2. Ba(OH)2
3. AgCl
4. PbCl2
5. BaSO4
6. CaC2O4
Calculating Ksp from Solubility

Question 1. The molar solubility of calcium fluoride (CaF2) at 35 oC is 1.24 x 10-3 moldm-3. What is the Ksp at
this temperature?

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Question 2: The solubility of silver chloride, AgCl, is 1.9 x 10-3 gdm-3. Calculate its Ksp.

Practice Questions:
1. A saturated solution of PbI2 contains 0.076g of PbI2 in 100 g of solution. Calculate the Ksp for PbI2. (Molar
mass of PbI2 = 461 gmol-1)

2. The solubility of lead (II) aresenate, Pb3(AsO4)2, is 3 x 10-5 gdm-3. Calculate its Ksp. (Molar mass of
Pb3(AsO4)2 = 899.44 gmol-1)

3. Calculate the Ksp for Ca(OH)2 given that the solubility if Ca(OH)2 in 0.93 gL-1. (Molar mass of Ca(OH)2
= 74 gmol-1)

4. It is found that 1.10 x 10-2 g of SrF2 dissolves per 100 mL of aqueous solution at 25oC. Calculate the
solubility product of SrF2. (Molar mass of SrF2 = 125.62 gmol-1)

Calculating Solubility from Ksp

Question 1: Calculate the solubility in moldm-3 of calcium sulphate given that the Ksp of CaSO4 is 2 x 10-5 mol2
dm-6.

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Practice Questions:
1. If the solubility product of silver carbonate, Ag2CO3, at 20 oC is 8 x 10-12 mol3 dm-9, calculate the solubility
of Ag2CO3.

2. The Ksp of barium iodiate, Ba(IO3)2, at 25 oC is 6 x 10-10 mol3 dm-9. What is the molar solubility of
Ba(IO3)2?

3. Lead iodide, PbI2, is a dense golden-yellow insoluble solid used in bronzing and on metal work requiring
a golden colour. Calculate the molar solubility of PbI2 in water at 25 oC given that the Ksp of PbI2 at this
temperature is 7.1 x 10-9 mol3 dm-9.

4. Calcium fluoride is a toothpaste additive used to enhance the performance of toothpastes. Given that the
Ksp of CaF2 is 4 x 10-11 mol3 dm-9, calculate the solubility of CaF2.

The Common Ion Effect and Precipitation of Sparingly Soluble Salts

The common ion effect refers to the shift in equilibrium that is caused by the addition of a solution having an ion
in common with a dissolved substance. Consider the saturated AgCl solution:
AgCl (s) ↔ Ag+ (aq) + Cl- (aq)
Where Ksp = [Ag+][Cl-]
If AgNO3 is added to the solution, the [Ag+] increases and so the system is no longer at equilibrium. To re-establish
equilibrium, the reaction shifts to the left, according to Le Chatelier’s Principle. This results in the precipitation of
AgCl(s), hence decreasing the solubility of the salt.
Generally: The addition of a common ion, decreases the solubility of the salt.

Predicting Precipitation

To determine if a precipitate will form when a common ion solution is added to a saturated solution of the ions,
the ionic product (solubility quotient, Qc) is found and compared to the Ksp. The ionic product of the salt has the
same form as the solubility product constant expression but the concentrations are not necessarily equilibrium
values, rather they are the concentrations at the start of the reaction.
Generally:
 If Qc < Ksp, no precipitation occurs, equilibrium shifts right.
 If Qc = Ksp, the mixture is at equilibrium and a saturated solution forms.
 If Qc > Ksp, precipitation occurs, equilibrium shifts left.

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Question 1: Will a precipitate form when an aqueous solution containing 6 x 10-5 M BaCl2 is added to an equal
volume of 1.2 x 10-5 M Na2SO4, given that the Ksp of BaSO4 is 1 x 10-10 mol2 dm-6?

Practice Questions:
1. A solution has the following concentrations of Ca2+ and SO42- respectively, 0.0052 M and 0.0041 M. If
these concentrations were doubled by evaporating half the water in the solution, would precipitation of
CaSO4 occur, given that the Ksp for CaSO4 is 2.4 x 10-5 mol2 dm-6?

2. A solution of 1.6 x 10-4 M lead (II) nitrate, Pb(NO3)2, was poured into 450 mL of 0.00023 M sodium
sulphate, Na2SO4. Would a precipitate of lead (II) sulphate, PbSO4, be expected to form if 255 mL of the
Pb(NO3)2 solution were added? (Ksp for PbSO4 = 1.7 X 10-8 mol2 dm-6)

3. Will a precipitate form if 10 mL of 1 x 10-6 moldm-3 FeCl2 is added to 20 mL of 3 x 10-3 Ba(OH)2 (Ksp
Fe(OH)2 = 4.9 X 10-7 mol3 dm-9)?

4. A typical [Ca2+] in sea water is 0.01 moldm-3. Will a precipitate of Ca(OH)2 form if the [OH-] is maintained
at 0.04 moldm-3? (Ksp Ca(OH)2 = 5.5 X 10-6 mol3 dm-9)

5. A solution is prepared by adding 750 mL of 4 x 10-3 moldm-3 Ce(NO3)3 to 30 mL of 2 x 10-2 moldm-3 KIO3.
Will Ce(IO3)3 (Ksp = 1.9 x 10-10 mol3 dm-9) precipitate for this solution?

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 6. A solution is prepared by mixing 100 mL of 1 x 10-2 moldm-3 Pb(NO3)2 and 100 mL of 1 x 10-2 moldm-3
NaF. Will PbF2 (s) (Ksp = 4 x 10-8 mol3 dm-9) precipitate?

7. A solution contains 2 x 10-4 moldm-3 Ag+ and 1.5 x 10-5 Pb2+. If NaI is added, will AgI (Ksp = 8.3 x 10-17
mol2 dm-6) or PbI2 (Ksp = 7.9 x 10-9 mol3 dm-9) precipitate first?

8. Some BaCl2 is added to a solution that contains both K2SO4 (0.05 moldm-3) and Na3PO4 (0.02 moldm-3).
Will BaSO4 (Ksp = 1.08 x 10-10 mol2 dm-6) or Ba3(PO4)2 (Ksp= 3.4 x 10-23 mol5 dm-15) precipitate first?

Experiment used to determine Ksp of Ca(OH)2

 Prepare a saturated solution of Ca(OH)2 and allow to stand for 2 days before filtering.
 Filter the excess solid Ca(OH)2.
 Titrate 25 mL of the saturated Ca(OH)2 solution against 0.05 moldm-3 HCl using a methyl orange indicator.
 Repeat titration 3 times.

Question: In an experiment to determine the solubility product of calcium hydroxide, 25 cm 3 of saturated

Ca(OH)2 solution was titrated against 22 cm3 of 0.05 moldm-3 hydrochloric acid. Use this
information to calculate the Ksp of Ca(OH)2.

Practise Questions:

1. Write dissociation equations to represent the equilibrium present for a saturated solution of each ionic
compound and write the solubility product (Ksp) expression for each of the following equilibrium systems.
a) Al2(SO4)3

b) FeCO3

c) Co2(SO4)3

d) Na3PO4

2. A beaker containing 100.0 mL of saturated BaCO3 solution weighs 159.60g. The beaker is evaporated to
dryness and weighs 56.36g. The empty beaker weighs 24.33g. Calculate the solubility in units of g/100
mL; g/ L; and M. (Molar mass BaCO3 = 197.34 g mol-1)

3. Which is more soluble in pure water, silver chloride, AgCl(s) (Ksp = 1.8 x 10-10 mol2 dm-6), or silver
chromate, Ag2CrO4(s) (Ksp = 1.8 x 10-12 mol3 dm-9)? Explain your answer.

4. The solubility of GaBr3 is 15.8 g/100.0 mL. Calculate the Ksp. (Molar mass GaBr3 = 309.435 g mol-1)

5. If the Ksp for Al2O3 is 2.8 x 10-8 mol5 dm-15, calculate [Al3+] and [O2-] in mol dm-3.

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6. At a certain temperature, a 40.00 mL sample of a saturated solution of barium hydroxide, is neutralized by
29.10 mL of 0.300 M HCl. Calculate the Ksp of Ba(OH)2.

7. If 3.78 L of 0.960 M sodium fluoride solution is added to 6.36 L of 0.550 M calcium nitrate solution, what
is the resulting [Ca+2] and [F-]?

8. Will a precipitate form if 200.0 mL of 0.00020M Ca(NO3)2 is mixed with 300.0 mL of 0.00030M Na2C03?
(Ksp (CaCO3) = 4.96 X 10-9 mol2 dm-6)

9. In a titration 26.5ml of 0.100M Pb(NO3)2 was used to precipitate out all of the Cl- in a 30.0 mL sample of
water. Calculate the [Cl-] in the water sample.

10. Silver ions are slowly added to a solution containing both chromate ions and bromide ions of equal
concentrations (0.200 M). What compound will precipitate first and why? (Ksp (Ag2CrO4) = 1.1 X 10-12
mol3 dm-9) (Ksp (AgBr) = 5.4 x 10-13 mol2 dm-6)

11. Will a precipitate form if you mix 27.00 mL of 0.000258 M lead (II) nitrate with 13.00 mL of 0.000784 M
magnesium iodide? (Ksp (PbI2) = 8.5 X 10-9 mol3 dm-9)

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