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VJC Chemistry Department

2012 Tutorial for Ionic Equilibrium : Solubility Equilibria

(H2 Only)

Supplementary Questions
Which pair of 0.1 mol dm-3 aqueous solutions is most likely to give a precipitate when
added together?

1.

A
B

KBr and MgSO4

NaNO3 and CaCl2

C
D

NH3 and BaCl2

MgSO4 and SrCl2

[N00/III/13]]
SrSO4 is insoluble and is precipitated when solutions of MgSO 4 and SrCl2 are
mixed together

2.

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

chlorination, silver ions can be used in a concentration no more than 10-6 mol dm-3
and not less than 10-7 mol dm-3 of silver ions.
Which compounds would, in saturated solution, provide the necessary concentration
of silver ions?

A
B
C
D

compound

solubility product

AgBr
AgCl
AgIO3
Ag2CO3

5 x 10-13 mol2 dm-6

2 x 10-10 mol2 dm-6
2 x 10-8 mol2 dm-6
5 x 10-12 mol3 dm-9
[N00/lll/10]

Let solubility of salt be y mol dm-3.

For AgBr, y2 = 5 x 10-13 y = 7.07 x 10-7 mol dm-3 (between 10-6 and 10-7)
Thus, [Ag+] in a saturated soln of AgBr = 7.07 x 10-7 mol dm-3.
Using similar calculations,
[Ag+] in a saturated soln of AgCl = 1.41 x 10-5 mol dm-3
[Ag+] in a saturated soln of AgIO3 = 1.41 x 10-4 mol dm-3
For Ag2CO3, 4y3 = 5 x 10-12 y = 1.07 x 10-4 mol dm-3
[Ag+] in a saturated soln of Ag2CO3 = 2 x 1.07 x 10-4
= 2.14 x 10-4 mol dm-3

3.

Hydrangeas are flowering plants which commonly have pink flowers. They produce
blue flowers only in soils which contain high concentrations of Mg 2+(aq). The pH of
well limed soil is 9, whereas the pH of peat-based soil is 6.5. The numerical value of
the solubility product, Ksp, of magnesium hydroxide is 1.8 x 10-12.

(a) (i) Write an expression for the Ksp of magnesium hydroxide.

Mg(OH)2(s) Mg2+(aq) + 2OH-(aq)
Ksp = [Mg2+][OH-]2
(ii) Calculate the theoretical maximum value of [Mg2+(aq)] in well-limed soil.

pOH = 14 9 = 5
[OH-] = 1.0 x 10-5 mol dm-3

1.8x1012
[Mg ] =
= 1.8 x 10-2 mol dm-3
5 2
(1.0x10 )
2+

(iii) Calculate the theoretical maximum value of [Mg2+(aq)] in a peat-based soil.

pOH = 14 6.5 = 7.5
[OH-] = 3.16 x 10-8 mol dm-3
[Mg2+] =

1.8x1012
(3.16x108 )2

= 1803 mol dm-3

(iv) Deduce which of these types of soil favours good cultivation of blue hydrangeas.
Peat-based soil
[N99/II/2]
4(a)

Calculate the solubility of lead(II) chloride, PbCl2 , in the following:

(i) pure water;
Let the solubility of PbCl2 be x mol dm-3 in pure water
PbCl2(s) Pb2+(aq) + 2Cl-(aq)
Ksp = [Pb2+][Cl-]2
1.7 x 10-5 = (x)(2x)2 = 4x3
thus, x = 1.62 x 10-2 mol dm-3
(ii) 0.10 mol dm-3 aqueous lead(II) nitrate.
Let the solubility of PbCl2 be z moldm-3 in 0.10 mol dm-3 of Pb(NO3)2
Pb(NO3)2(aq) Pb2+(aq) + 2NO3-(aq)
Complete dissociation: [Pb2+] from Pb(NO3)2 = 0.10 mol dm-3
Ksp
= [Pb2+][Cl-]2
1.7 x 10-5 = (z + 0.1)(2z)2
= (0.1)(4z2) since z << 0.1
thus, z = 6.52 x 10-3 mol dm-3
Note: (1) z = 6.52 x 10-3 << 0.1 (Assumption is valid)
(2) Solubility of PbCl2 is much smaller in Pb(NO3)2 than that in pure
water
(Ksp of PbCl2 = 1.70 x 10 5 mol3 dm-9)

(b)

Using the above results, explain the term common ion effect.
PbCl2 (s) Pb2+ (aq) + 2Cl- (aq)

--- (1)

The common ion effect is the effect on an equilibrium system caused by the
addition of a substance containing an ion, in this case Pb2+(aq) or Cl-(aq), that is
common with one in equilibrium (1).
Addition of Pb2+(aq) or Cl-(aq) will cause equilibrium (1) to shift to the left by Le
Chateliers Principle. Hence the solubility of the salt is decreased due to
common ion effect.
(c)

Hence, explain why the pink colour of phenolphthalein in aqueous ammonia

disappears when sufficient ammonium chloride is added.
NH3 + H2O NH4+ + OH-

--- (2)

Production of OH- in aqueous NH3 causes phenolphthalein to turn pink.

Addition of NH4Cl establishes the following:
NH4Cl NH4+ + Clof common ion NH4+ causes position of equilibrium in (2) to shift to the left by Le
Chatelier's Principle. The degree of ionisation of weak base aqueous ammonia thus
decreases due to this common ion effect. [OH-] decreases to such an extent that the
pink colour of phenolphthalein disappears when sufficient solid NH4Cl is added.

5.

Predict whether precipitation will occur when 50.0 cm3 of 0.0001 mol dm-3
magnesium nitrate solution is added to 200 cm3 of 0.001 mol dm-3 sodium hydroxide
solution. (Ksp of Mg(OH)2 = 1.20 x 10 11 mol3 dm-9)
[Mg2+] in mixture upon mixing =

[OH-] in mixture upon mixing =

50.0x0.0001
= 2.0 x 10-5 mol dm-3
250
200x0.001
= 8.0 x 10-4 mol dm-3
250

Ionic product of Mg(OH)2 = [Mg2+][OH-]2

= (2.0 x 10-5)(8.0 x 10-4)2
= 1.28 x 10-11 mol3 dm-9
Since ionic product is greater than the Ksp of Mg(OH)2, there will be precipitation of
Mg(OH)2.
6.

View the following video and answer the following questions.

Video: http://vimeo.com/13480502 (Password: vjcchemistry)
Procedure
Add aqueous NH3 to a dilute solution of CuSO4 dropwise until it is in excess.
Describe and explain your observations.
Hydrolysis of ammonia generates OH- ions. When aqueous NH3 is added to aqueous
CuSO4, the concentration of OH- ions increases to the extent that the ionic product of
Cu(OH)2 exceeds its Ksp value. Hence, a blue ppt of Cu(OH)2 is formed initially.
NH3 + H2O

NH4+ + OH-

Cu2+(aq) + 2OH-(aq)

Cu(OH)2(s) ----- (1)

When aq. NH3 is added in excess, blue ppt of Cu(OH)2 dissolves to form a dark blue
solution due to complex ion formation as shown.
Cu2+(aq) + 4NH3(aq)

Cu(NH3)42+(aq)
dark blue

As Cu2+ ions are removed to form the soluble complex Cu(NH3)42+, equilibrium (1)
above shifts to the left to counteract the removal of Cu2+ ions, in accordance to Le
Chateliers Principle.
Thus, ionic product of Cu(OH)2 becomes smaller than its Ksp value. Hence, blue ppt
of Cu(OH)2 dissolves.
2012 leekl@vjc