LECTURE 6 - Solubility Product and Common Ion Effect-2019

Mulungushi University
- Pursuing the frontiers of

knowledge
Lecture 6:
Solubility product and common ion
Effect
By A. Mbozi
School Of Science, Engineering

and Technology
05/04/24 1
OUTLINE
• Solubility
• Solubility Product
• Common ion effect
05/04/24 2
Solubility Product
• Solubility product constant, Ksp is defined
as the product of the molar concentrations
of the constituent ions, each raised to the
power of its stoichiometric coefficient in
the equilibrium equation.
• Ksp can be found on a chart at a specific
temperature
05/04/24 3
SOLUBILITY OF IONIC COMPOUNDS
• ionic compounds tend to be insoluble in non-polar solvents

• ionic compounds tend to be soluble in water
• water is a polar solvent and stabilises the separated ions
05/04/24 4
SOLUBILITY OF IONIC COMPOUNDS
• ionic compounds tend to be insoluble in non-polar solvents

• ionic compounds tend to be soluble in water
• water is a polar solvent and stabilises the separated ions
• some ionic compounds are very insoluble (AgCl, PbSO4, PbS)

• even soluble ionic compounds have a limit as to how much dissolves
05/04/24 5
SATURATED SOLUTIONS
• solutions become saturated when solute no longer dissolves in a solvent

• solubility varies with temperature
• most solutes are more soluble at higher temperatures
05/04/24 6
SATURATED SOLUTIONS

Ionic crystal lattices can dissociate

(break up) when placed in water. The
ions separate as they are stabilised
by polar water molecules.
05/04/24 7
SATURATED SOLUTIONS

Ionic crystal lattices can dissociate Eventually, no more solute dissolves

(break up) when placed in water. The and the solution becomes saturated.
by polar water molecules. There is a limit to the concentration
of ions in solution.
05/04/24 8
SATURATED SOLUTIONS

Ionic crystal lattices can dissociate Eventually, no more solute dissolves

(break up) when placed in water. The and the solution becomes saturated.
by polar water molecules. There is a limit to the concentration
of ions in solution.
05/04/24 9
SOLUBILITY PRODUCT
Even the most insoluble ionic compounds dissolve to a small extent.

An equilibrium exists between the undissolved solid and its aqueous ions;
(i) MX(s) M+(aq) + X¯(aq)
(ii) BaSO4(s) Ba2+(aq) + SO42-(aq)
(iii) PbCl2(s) Pb2+(aq) + 2Cl¯(aq)
05/04/24 10
SOLUBILITY PRODUCT
Even the most insoluble ionic compounds dissolve to a small extent.

An equilibrium exists between the undissolved solid and its aqueous ions;
(i) MX(s) M+(aq) + X¯(aq)
(ii) BaSO4(s) Ba2+(aq) + SO42-(aq)
(iii) PbCl2(s) Pb2+(aq) + 2Cl¯(aq)
Applying the equilibrium law to (i) and assuming the concentration of

MX(s) is constant in a saturated solution.
[M+(aq)] [X¯(aq)] = a constant, Ksp
[ ] is the concentration in mol dm-3
Ksp is known as the SOLUBILITY PRODUCT

05/04/24 11
SOLUBILITY PRODUCT
AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]
BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]
PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2
Notice that the concentration of Cl¯(aq) is raised to the

power of 2 because there are two Cl¯(aq) ions in the equation
05/04/24 12
SOLUBILITY PRODUCT
Notice that the concentration of Cl¯(aq) is raised to the power of 2
Complete the equilibrium equation and write an expression for Ksp for…
PbS(s) Pb2+(aq) + S2-(aq) Ksp = [Pb2+(aq)] [S2-(aq)]
Fe(OH)2(s) Fe2+(aq) + 2OH¯(aq) Ksp = [Fe2+(aq)] [OH¯(aq)]2
05/04/24 13
SOLUBILITY PRODUCT
05/04/24 14
SOLUBILITY PRODUCT
05/04/24 15
SOLUBILITY PRODUCT
05/04/24 16
SOLUBILITY PRODUCT
Units The value of Ksp has units and it varies with temperature
AgCl Ksp = [Ag+(aq)] [Cl¯(aq)] units of… mol2 dm-6
BaSO4 Ksp = [Ba2+(aq)] [SO42-(aq)] mol2 dm-6
PbCl2 Ksp = [Pb2+(aq)] [Cl¯(aq)]2 mol3 dm-9
05/04/24 17
SOLUBILITY PRODUCT
Work out the units of Ksp for the following…
PbS Ksp = [Pb2+(aq)] [S2-(aq)]
Fe(OH)2 Ksp = [Fe2+(aq)] [OH¯(aq)]2
Fe(OH)3 Ksp = [Fe3+(aq)] [OH¯(aq)]3
05/04/24 18
SOLUBILITY PRODUCT
Work out the units of Ksp for the following…
PbS Ksp = [Pb2+(aq)] [S2-(aq)] mol2 dm-6
Fe(OH)2 Ksp = [Fe2+(aq)] [OH¯(aq)]2 mol3 dm-9
Fe(OH)3 Ksp = [Fe3+(aq)] [OH¯(aq)]3 mol4 dm-12
05/04/24 19
17.4 Solubility Equilibria
Solubility Product Expression and Ksp
The solubility of ionic compounds is important in

industry, medicine, and everyday life.
The compounds described as “insoluble” are actually

very slightly soluble.
The Ksp is called the solubility product constant. It

allows for quantitative predictions about how much of a
given ionic compound will dissolve in water.
20
Solubility Product
• Calculations involving can be done in
three ways;
a) Calculating solubility from
b) Calculating from solubility data
c) Solving problems dealing with precipitation
05/04/24 21
Solubility Product Expression and Ksp
Ksp is equal to the concentrations of products over the

concentrations of reactants, each raised to its coefficient
from the balanced chemical equation.
The smaller the Ksp, the less soluble the compound.
22
Calculations Involving Ksp and Solubility
There are two ways to express the solubility of a

substance:
1.The molar solubility: number of moles of solute in 1 L

of a saturated solution (mol/L).
2.The solubility: number of grams of solute in 1 L of a

saturated solution (g/L).
Both of these refer to concentrations at a particular
temperature (usually 25°C).
23
To calculate molar solubility from Ksp :
The procedure is as follows:
1.Construct an equilibrium table.

2.Fill in what we know.
3.Figure out what we don’t know.
24
The Ksp of silver bromide (AgBr) is 7.7 × 10 ‒13.
Let s be the molar solubility (in mol/L) of AgBr.
At equilibrium: [Ag+] = [Br‒] = s
25
The equilibrium expression is
Therefore,
26
The molar solubility of AgBr is 8.8 × 10 ‒7 M.
Express this solubility in g/L by multiplying the molar

solubility by the molar mass of AgBr:
27
17.7
Calculate the solubility of copper(II) hydroxide [Cu(OH) 2]

in g/L.
Setup
The equation for the dissociation of Cu(OH) 2 is
Ksp = [Cu2+][OH‒]2
Ksp for Cu(OH)2 = 2.2 × 10‒20.
The molar mass of Cu(OH)2 is 97.57 g/mol.

28
17.7
Solution
Therefore,
Remember to raise an entire term to the appropriate

power!
29
17.7
The molar solubility of Cu(OH)2 is 1.8 × 10‒7 M.
Multiplying by its molar mass gives:
30
17.8
The solubility of calcium sulfate (CaSO4) is measured

experimentally and found to be 0.67 g/L. Calculate the
value of Ksp for calcium sulfate.
Setup
The molar mass of CaSO4 is 136.2 g/mol.
The molar solubility of CaSO4 is
31
17.8
Solution
This is a relatively large Ksp value.
32
Predicting Precipitation Reactions

We use the reaction quotient (Q) to predict when a
precipitate will form.
Q has the same form as Ksp except the concentrations of

ions are not equilibrium concentrations.
33
Predicting Precipitation Reactions

If we mix a solution containing Ag+ ions with one
containing Cl‒ ions, we write:
where “i” denotes initial concentrations
If Q ≤ Ksp no precipitate will form
If Q > Ksp AgCl will precipitate
34
17.4 Example
Q = [Ba2+][SO42‒] = (0.0011)(0.0058) = 6.4 × 10‒6
Q > Ksp (1.1 × 10‒10)
BaSO4 will precipitate.
35
17.9
Predict whether a precipitate will form when each of the

following is added to 650 mL of 0.0080 M K2SO4:
(a)250 mL of 0.0040 M BaCl2
(b)175 mL of 0.15 M AgNO3
(c)325 mL of 0.25 M Sr(NO3)2 (Assume volumes are
additive.)
Setup
The compounds that might precipitate and their Ksp
values are
a)BaSO4, Ksp = 1.1 × 10‒10

b)Ag2SO4, Ksp = 1.5 × 10‒5
c)SrSO , K = 3.8 × 10‒7 36
17.9
Solution
(a) Concentrations of the constituent ions of BaSO 4 are:
Q = [Ba2+][SO42‒] = (0.0011)(0.0058) = 6.4 × 10‒6
Q > Ksp (1.1 × 10‒10)
BaSO4 will precipitate.

37
17.9
(b) Concentrations of the constituent ions of Ag 2SO4 are:
Q = [Ag+]2[SO42‒] = (0.032)2(0.0063) = 6.5 × 10‒6
Q < Ksp (1.5 × 10‒5)
Ag2SO4 will not precipitate.

38
17.9
(c) Concentrations of the constituent ions of SrSO 4 are:
Q = [Sr2+][SO42‒] = (0.083)(0.0053) = 4.4 × 10‒4
Q > Ksp (3.8 × 10‒7)
SrSO4 will precipitate.

39
THE COMMON ION EFFECT
Adding a common ion, (one which is present in the solution), will result in the
precipitation of a sparingly soluble ionic compound.
eg Adding a solution of sodium chloride to a saturated solution of

silver chloride will result in the precipitation of silver chloride.
05/04/24 40

Adding the ionic compound MA to a

solution of MX increases the
concentration of M+(aq). M+(aq) is a
common ion as it is already in solution.
05/04/24 41

Adding the ionic compound MA to a The extra M+ ions means that the
solution of MX increases the solubility product is exceeded. To
concentration of M+(aq). M+(aq) is a reduce the value of [M+(aq)][X-(aq)]
common ion as it is already in solution. below the Ksp, some ions are removed
from solution by precipitating.
If the value of the solubility product is exceeded, precipitation will
05/04/24 42
occur.
Problem
05/04/24 43
Initial - 0 0.5
Change - +x +2x
Equilibrium - x 0.5+2x
05/04/24 44
Initial - 0 0
Change - +x +2x
Equilibrium - x 2x
05/04/24 45
About Common ion effect
Common ion effect is a special case of
LeChatelier principle
Addition of a common ion is equivalent
to adding a stress to the system.
The system responds to the stress by

reducing the solubility of one of the ions
and keeping the Ksp constant.
05/04/24 46
Calculate the molar solubility of lead iodide PbI 2,
from its Ksp in water at 25C
PbI2 (s) Pb2+ (aq) + 2I-(aq)

s 1×s 2×s
K sp  Pb 2 1
I   2
K sp  1 s  2  s 
1 2
K sp  (1s )  (2 s )  (2 s )
K sp  (1  2  2)  ( s  s  s )
K sp  4s
05/04/24 3 47
K sp  4s 3
But , K sp  7.9  10 9
7.9  10  4 s
9 3
7.9  109
s 3
4
1.97  10  s9 3
s  1.97  10  1.3  10 M
3 6 3
05/04/24 48
in 0.1 M NaI solution
PbI2 (s) Pb2+ (aq) + 2I-(aq)
s 1×s 2×s
K sp ( PbI 2 )  7.9  10 9
NaI (s) Na+ (aq) + I-(aq)
0.1M 0.1M
K sp  Pb 2 1
I 
 2
Common
7.9  10  1 s  (2  s )  0.1
9 1 2 ion
05/04/24 49
in 0.1 M NaI solution
7.9  10  1 s  (2  s )  0.1
9 1 2
7.9  10  (1s )2 s  0.1

9 2
Because the Ksp of PbI2 is really small, the solubility s is going

to be really small. Hence we can make a simplification.
2s  0.1  0.1
7.9  10  (1s )0.1
9 2
7.9  109
05/04/24 s  7.9  107 M 50
0.01
A comparison of solubility of PbI2
With and without common ion
With common ion Without common ion
s= 1.3 × 10-3 M s= 7.9 × 10-7 M
Solubility decreases because of the presence of
common ion
05/04/24 51

LECTURE 6 - Solubility Product and Common Ion Effect-2019

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Mulungushi University

- Pursuing the frontiers of

School Of Science, Engineering

• ionic compounds tend to be insoluble in non-polar solvents

• ionic compounds tend to be insoluble in non-polar solvents

• some ionic compounds are very insoluble (AgCl, PbSO4, PbS)

• solutions become saturated when solute no longer dissolves in a solvent

• solutions become saturated when solute no longer dissolves in a solvent

Ionic crystal lattices can dissociate

• solutions become saturated when solute no longer dissolves in a solvent

Ionic crystal lattices can dissociate Eventually, no more solute dissolves

• solutions become saturated when solute no longer dissolves in a solvent

Ionic crystal lattices can dissociate Eventually, no more solute dissolves

Even the most insoluble ionic compounds dissolve to a small extent.

(iii) PbCl2(s) Pb2+(aq) + 2Cl¯(aq)

Even the most insoluble ionic compounds dissolve to a small extent.

(iii) PbCl2(s) Pb2+(aq) + 2Cl¯(aq)

Applying the equilibrium law to (i) and assuming the concentration of

[M+(aq)] [X¯(aq)] = a constant, Ksp

[ ] is the concentration in mol dm-3

Ksp is known as the SOLUBILITY PRODUCT

AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]

BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]

PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2

Notice that the concentration of Cl¯(aq) is raised to the

AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]

BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]

PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2

Notice that the concentration of Cl¯(aq) is raised to the power of 2

PbS(s) Pb2+(aq) + S2-(aq) Ksp = [Pb2+(aq)] [S2-(aq)]

Fe(OH)2(s) Fe2+(aq) + 2OH¯(aq) Ksp = [Fe2+(aq)] [OH¯(aq)]2

Fe(OH)3(s) Fe3+(aq) + 3OH¯(aq) Ksp = [Fe3+(aq)] [OH¯(aq)]3

AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]

BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]

PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2

Notice that the concentration of Cl¯(aq) is raised to the power of 2

PbS(s) Pb2+(aq) + S2-(aq) Ksp = [Pb2+(aq)] [S2-(aq)]

Fe(OH)2(s) Fe2+(aq) + 2OH¯(aq) Ksp = [Fe2+(aq)] [OH¯(aq)]2

Fe(OH)3(s) Fe3+(aq) + 3OH¯(aq) Ksp = [Fe3+(aq)] [OH¯(aq)]3

AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]

BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]

PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2

Notice that the concentration of Cl¯(aq) is raised to the power of 2

PbS(s) Pb2+(aq) + S2-(aq) Ksp = [Pb2+(aq)] [S2-(aq)]

Fe(OH)2(s) Fe2+(aq) + 2OH¯(aq) Ksp = [Fe2+(aq)] [OH¯(aq)]2

Fe(OH)3(s) Fe3+(aq) + 3OH¯(aq) Ksp = [Fe3+(aq)] [OH¯(aq)]3

AgCl(s) Ag+(aq) + Cl¯(aq) Ksp = [Ag+(aq)] [Cl¯(aq)]

BaSO4(s) Ba2+(aq) + SO42-(aq) Ksp = [Ba2+(aq)] [SO42-(aq)]

PbCl2(s) Pb2+(aq) + 2Cl¯(aq) Ksp = [Pb2+(aq)] [Cl¯(aq)]2

Notice that the concentration of Cl¯(aq) is raised to the power of 2

PbS(s) Pb2+(aq) + S2-(aq) Ksp = [Pb2+(aq)] [S2-(aq)]

Fe(OH)2(s) Fe2+(aq) + 2OH¯(aq) Ksp = [Fe2+(aq)] [OH¯(aq)]2

Fe(OH)3(s) Fe3+(aq) + 3OH¯(aq) Ksp = [Fe3+(aq)] [OH¯(aq)]3

AgCl Ksp = [Ag+(aq)] [Cl¯(aq)] units of… mol2 dm-6

BaSO4 Ksp = [Ba2+(aq)] [SO42-(aq)] mol2 dm-6

PbCl2 Ksp = [Pb2+(aq)] [Cl¯(aq)]2 mol3 dm-9

AgCl Ksp = [Ag+(aq)] [Cl¯(aq)] units of… mol2 dm-6

BaSO4 Ksp = [Ba2+(aq)] [SO42-(aq)] mol2 dm-6

PbCl2 Ksp = [Pb2+(aq)] [Cl¯(aq)]2 mol3 dm-9

Work out the units of Ksp for the following…

PbS Ksp = [Pb2+(aq)] [S2-(aq)]

Fe(OH)2 Ksp = [Fe2+(aq)] [OH¯(aq)]2

Fe(OH)3 Ksp = [Fe3+(aq)] [OH¯(aq)]3

AgCl Ksp = [Ag+(aq)] [Cl¯(aq)] units of… mol2 dm-6