Suggested Solutions to Solubility Equilibria

Standard Questions
Question 1
(a) Ksp = [Ca2+ (aq)][OH (aq)]2
(b) (i) HC (aq) + NaOH(aq) NaC (aq) + H2O()

[1]

amt of NaOH present = amt of HC required = 0.050 x

= 0.0010 mol

= 0.040 mol dm 3

[OH ] =

[]

Note: [OH ] is the total [OH ] present in the solution, NOT just the [OH ] from Ca(OH)2.

Amt of OH from NaOH = 0.010 mol dm 3 x

dm3 = 0.00025 mol

Amt of OH from Ca(OH)2 = 0.0010 0.00025 = 0.00075 mol

Amt of Ca2+ = x Amt of OH from Ca(OH)2 = x 0.00075 = 0.000375 mol

[Ca2+] =

= 0.015 mol dm 3

[]

= 0.015 (mol dm 3) x [0.040 (mol dm 3)]2 = 2.4 x 10 5 (mol dm 3)3

Ksp

(ii) pOH = log [OH ] = log (0.040) = 1.4

pH = 14 1.4 = 12.6

[1]

[1]

(c) [Ca2+] = x 0.010 = 0.0050 mol dm 3

[OH ] =

= 0.06928 mol dm 3

[1]

Let the volume of each solution used be V dm3.

Amt of OH required for precipitation = 0.06928 x (2V) = 0.1386V mol

Amt of OH from Ca(OH)2 = 2 x 0.01 x V = 0.02V mol

Amt of OH from NaOH = 0.1386V 0.02V = 0.1186V mol

[1]

= 0.119 mol dm 3

[1]

(d) (i)When temperature increases, Ksp decreases

[1]

[OH ] required =

(Extra info: dissolution of Ca(OH)2 is exothermic, Hsoln < 0)

(ii) No effect.

[1]

(However, solubility of Ca(OH)2 decreases. Less Ca(OH)2 can dissolve as Ksp is reached
more quickly.)

(e) Reducing acidity of soil.

[1]

Question 2
AgC(s)
Ag+(aq) + C (aq)
Let the solubility of AgC be s.

(a) Ksp = [Ag+][C ] = s2 = 1.2 x 10 10 mol2 dm 6

[1]

s = 1.095 x 10 5 mol dm 3

[1]

(b) Ksp = [Ag+][C ] = s(0.20+s) = 1.2 x 10 10 mol2 dm 6

Assuming s << 0.20; hence 0.20 + s 0.20

[1]

Ksp = 1.2 x 10 10 s x 0.20

s 6.0 x 10 10 mol dm 3

[Check: 6.0 x 1010 << 0.20 i.e. assumption is valid]

[1]

(c) Initial solubility = 1.095 x 10 5 mol dm 3

New solubility = s mol dm 3

Amt of C from NaC =

= 0.0100 mol

[C ] from NaC = 0.01/1 = 0.0100 mol dm 3

Ksp = [Ag+][C ] = s(0.01+s) = 1.2 x 10 10 mol2 dm 6

Assuming s << 0.01; hence 0.0100+ s 0.0100

Ksp = 1.2 x 10 10 0.010 s

s 1.2 x 10 8 mol dm 3

[1]

[Check: 1.2 x 10 << 0.10 i.e. assumption is valid]

[1]

In 1 dm3,
Amt of C precipitated = 1.095 x 10 5 1.2 x 10 8 = 1.094 x 10 5 mol

Mass of AgC precipitated = 1.094 x 10 5 x (108 + 35.5) = 0.00157 g

[1]

Note: The precipitation is (1.094 x 10 /1.095 x 10 ) x 100% = 99.9% complete. This is expected
since the solubility product of AgC is very low.

Question 3
(a) [Ag+] required to precipitate AgC =
[Ag+] required to precipitate AgI =

= 1.2 x 10 8 mol dm 3

[1]

= 8.5 x 10 15 mol dm 3

[1]

Since [Ag+] required to precipitate AgI is lower, AgI will precipitate out first.

[1]

(b) When AgC starts to precipitate, [Ag+] = 1.2 x 10 8 mol dm 3

[I ] =

[1]

= 7.08 x 10 9 mol dm 3

[1]

(c)When AgC starts to precipitate, [I ] has decreased from 0.010 mol dm 3 to 7.08 x 10 9 mol
dm 3 (> 99% decrease). Hence, separation of I and C by AgNO3 (aq) is feasible.
[1]

% of I removed as AgI = 1

= 99.9999%

(d) Step 1: Add excess AgNO3(aq) to precipitate AgI(s) as a yellow ppt and AgCl as a white
ppt.
Ag+(aq) + I (aq)
AgI(s) (1)
[1]
+
Ag (aq) + CI (aq)
AgCI(s) (2)
[1]
Step 2: Filter the mixture to obtain the ppt. Dissolve the AgCI(s) in excess aq ammonia
to release CI (aq).
Ag+(aq) + 2NH3(aq)
[Ag(NH3)2]+(aq) (3)
[1]

Step 3: Filter the mixture to remove AgI (s). To the filtrate, add dilute nitric acid to
regenerate the AgCl ppt, by removing the ammonia present.
NH3 (aq) + HNO3 (aq) NH4NO3 (aq)
Question 4
(a) NH3 is weak base and it produces OH in water.
NH3(aq) + H2O()
NH4+(aq) + OH (aq) (1)

This causes equilibrium (2) to shift to the right and white ppt of Mg(OH)2 is formed.
[1]
2+
Mg (aq) + 2OH (aq)
Mg(OH)2(s) (2)
When NH4C is added, [NH4+] increases. By common ion effect, equilibrium (1) shifts to
the left and [OH ] decreases.
[1]

This in turn causes equilibrium (2) to shift to the left and hence Mg(OH)2 dissolves.

[1]

(OR the ionic product of Mg(OH)2 is less than Ksp.)

(b) The Ksp of BaCrO4 is low so that on addition of K2CrO4 (aq) to BaCl2 (aq), the ionic
product of BaCrO4 exceeds its Ksp value and a yellow ppt of BaCrO4 is observed.
Ba2+ (aq) + CrO42 (aq)
BaCrO4 (s) (1)
[1]

On addition of dilute nitric acid, H+ reacts with CrO42 to give orange Cr2O72 so that
[CrO42 ] decreases.

2CrO42 (aq) + 2H+ (aq)

Cr2O72 (aq) + H2O() (2)
The ionic product of BaCrO4 decreases and becomes less than Ksp.

[1]

Hence, BaCrO4 dissolves to restore the ionic product to the Ksp value. When sufficient H+
is added, the yellow ppt of BaCrO4 dissolves completely and an orange solution (due to
Cr2O72 ) is formed.
[1]

OR Addition of HNO3 causes position of equilibrium in (2) to shift right so that [CrO42 ] decreases. To
increase [CrO42 ], position of equilibrium in (1) shifts left so that BaCrO4 dissolves.

(c) CO2 from the atmosphere dissolves in water to form carbonic acid, H2CO3(aq), which
undergoes further dissociation to give CO3 ions.
[1]
+
+
2
H2CO3(aq)
H (aq) + HCO3 (aq)
&
HCO3 (aq)
H (aq) + CO3 (aq)
2

Ba2+(aq) + CO32 (aq)

BaCO3(s) (2)

Due to the low Ksp of BaCO3, IP exceeds Ksp easily and a white deposit of BaCO3(s) is
observed on the surface of the solution.
[1]
Optional Question
(a)(i) pH = 12.3; At 25 oC, pOH = 14 12.3 = 1.7
[OH (aq)] = 1.0 x 10 1.7 = 2.0 x 10 2 mol dm 3

Ca(OH)2(aq) Ca2+(aq) + 2OH (aq)

[Ca2+] = [OH ] = ()(2.0 x 10 2) = 1.0 x 10 2 mol dm-3
Solubility of Ca(OH)2 = [Ca2+] = 1.0 x 10 2 mol dm 3

[1]

Molar mass of Ca(OH)2 = 40.1 + (2)(17.0) = 74.1 g mol 1

Solubility of Ca(OH)2 = (1.0 x 10 2)(74.1) = 0.741 g dm 3

[1]

(ii) Ksp of Ca(OH)2 = [Ca2+][OH ]2 = (1.0 x 10 2)(2.0 x 10 2)2 = 4.0 x 10 6 mol3 dm 9

(b)

[1]

At 32 oC, Kw = 1.70 x 10-14; pKw = logKw = 13.77

pH = 11.7 Hence pOH at 32 oC = 13.77 11.7 = 2.07
[OH ] at 32 oC = 1.0 x 10 2.07 = 8.51 x 10 3 mol dm 3

[1]

From 7ai, [OH ] at 25 oC = 2.0 x 10 2 mol dm 3

From the data, [OH ] is lower at higher temperature. This indicates that with increasing
temperature, the equilibrium position of the reaction below shifts left in an attempt to
absorb the heat energy added in accordance to Le Chateliers Principle.
[1]

Hence for Ca(OH)2(s) + aq

Ca2+(aq) + 2OH (aq), the backward reaction has to
be endothermic and the forward dissociation reaction is exothermic.
[1]

(c)

Let the required concentration of NaOH be y mol dm-3.

Upon mixing equal volumes of this NaOH solution and a 0.10 mol dm-3 CaCl2 solution
and assuming no precipitation,
initial [OH ] in the resultant solution = y/2 mol dm 3
initial [Ca2+] in the resultant solution = 0.10/2 = 0.050 mol dm 3

For the solution to be saturated,

Ionic product of Ca(OH)2 = Ksp of Ca(OH)2 = [Ca2+][OH]2 = 4.0 x 10-6 mol3 dm 9
(0.050)(y/2)2 = 4.0 x 10 6
y = 1.79 x 10-2
Hence the required concentration of NaOH = 1.79 x 10 2 mol dm 3

(d)

[1]
[1]

pH
1 1.7 2

6.8 8

[2]
V

At infinite dilution, pH of solution approaches that of pure water at the same temp.
Such that [H+] [OH]
Kw = [H+][OH] = 1.70 x 1014 mol2 dm6 (at 32 oC)
[H+]2
=
+
[H ] = 1.304 x 107 mol dm3
pH = 6.88

Note: pH of a neutral solution at 32 oC < 7!!