CHAPTER 4

SOLUBILITY &
COMPLEX ION EQUILIBRIA
 Solubility Product Constant, Ksp

 The Solubility Product, Ksp is the equilibrium constant for the

equilibrium that exists between a slightly soluble salt and its
ions in a saturated solution.
 Ksp is independent of what else is dissolved in solution.
 The solubility of a substance can be calculated from its Ksp.

Example:
AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+] [Cl-]

 Solubility & Molar Solubility
 Solubility (unit: g/L) is the number of grams of solute
dissolved in 1 L of a saturated solution.
 Molar solubility (unit: mol/L) is the number of moles of
solute dissolved in 1 L of a saturated solution.

Solubility of Molar [ ] of cation & Ksp of

compound solubility anion compound

Ksp of [ ] of cation & Molar Solubility of

compound anion solubility compound
Example 1: The molar solubility of AgCl in water is 1.3 x 10-5
mol/L at 25 oC. What is the solubility product, Ksp of AgCl?

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+] [Cl-]

Ksp = (1.3 x 10-5 ) (1.3 x 10-5 )

= 1.7 x 10-10
Example 2: At 25 0C the solubility of CaF2 in water is 1.69 x 10-2 g/L.
Determine the Ksp for CaF2.

CaF2 (s) Ca2+ (aq) + 2F- (aq)

Ksp = [Ca2+] [F-]2

Molar solubility = 1.69 x 10-2 g/L = 2.16 x 10-4 M
78 g/mol

[Ca2+] = 2.16 x 10-4 M

[F-] = 2 x 2.16 x 10-4 M = 4.32 x 10-4 M

Ksp = (2.16 x 10-4)( 4.32 x 10-4)2

= 4.03 x 10-11
Example 3:The solubility product of calcium fluoride is 4.03 x 10 –11.
Calculate solubility in g/L

CaF2 (s) Ca2+ (aq) + 2F- (aq)

Initial (M) 0 0
change –s +s +2s
Eq (M) s 2s

Ksp = [Ca2+] [F-]2 = 4.03 x 10–11

 EXERCISE

1. The solubility of calcium sulfate is 0.67 g/L. Calculate the

value of Ksp for calcium sulfate.

Ksp = 2.4 x 10-5

2. Calculate the solubility of copper(II) hydoxide in g/L

Molar solubility = 1.8 x 10-7 mol/L

Solubility = 1.8 x 10-7 mol/L x 97.6 g/mol
= 1.8 x 10-5 g/L
 The Common Ion Effect & Solubility

 The solubility equilibrium of AgCl is:

AgCl (s) Ag+ (aq) + Cl- (aq)

 Suppose we added some AgNO3 to the solution.

 According to Le Chatelier principle, the equilibrium will be

shifted to the left and this will cause more of the solid AgCl
appeared in the solution.
 Thus the solubility of AgCl is reduced.
 Example: Calculate the solubility (g/L) of AgCl in a 6.5 x 10-3 M
AgNO3 solution.

Solution:
 This is the common-ion problem. The common ion here is Ag+,
which is supplied by both AgCl and AgNO3.
 Remember that the presence of the common ion will affect only the
solubility of AgCl (in g/L), but NOT the Ksp value (why?)

Step 1: Determine the [Ag+] and [Cl-]

AgNO3 is a strong electrolyte. So it dissociates completely:
Step 2: Ksp = [Ag+] [Cl-]
1.6 x 10-10 = (6.5 x 10-3 + s) (s)
s = 2.5 x 10-8 M

Step 3: at equilibrium
[Ag+] = (6.5 x 10-3 + 2.5 x 10-8)  6.5 x 10-3 M
[Cl-] = 2.5 x 10-8 M

 Because all the Cl- ions must come from AgCl, the amount of
AgCl dissolved in AgNO3 solution is also 2.5 x 10-8 M. So we
can calculate the solubility of AgCl as follows:
 Predicting PrecipitationReaction

MA (s) M+ (aq) + A- (aq)

Ksp = [M+] [A-] at eq

Q = [M+] [A-] at t

Q < Ksp  unsaturated solution (no precipitation)

Q = Ksp  saturated solution (no precipitation)

Q > Ksp  supersaturated solution (precipitation occur)

 Example: Exactly 200 mL of 0.004 M BaCl2 are mixed with exactly
600 mL of 0.008 M K2SO4. Will a precipitate form?

BaCl2 (aq) + K2SO4 (aq)  BaSO4 (aq) + 2KCl (aq)

Answer:
Moles of Ba2+ in the original 200 mL of solution
= 0.004 mol/L x 200 x 10-3 L = 8.0 x 10-4 mol
Moles of SO42- in the original 600 mL of solution
= 0.008 mol/L x 600 x 10-3 L = 4.8 x 10-3 mol

Total volume = 800 mL = 0.800 L

[Ba2+] = 8.0 x 10-4 mol = 1.0 x 10-3 M
0.800 L
[SO42-] = 4.8 x 10-3 mol = 6.0 x 10-3 M
0.800 L
Q = [Ba2+] [SO42-] = (1.0 x 10-3) (6.0 x 10-3)
= 6.0 x 10-6

Q > Ksp  the solution is supersaturated, so the

precipitate will form

 some of the BaSO4 will precipitate out of solution until

[Ba2+] [SO42-] = 1.1 x 10-10
 EXERCISE

1. The Ksp for zinc hydroxide is 3.0 x 10-16. Determine the

solubility of this compound in g/L
Solubility = 4.2 x 10-4 g/L

2. If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M

CaCl2, will a precipitate form?
Q = 1.6 x 10-8
Q < Ksp  no precipitate will form

3. 0.100 L of 0.003 M Pb(NO3)2 is added to 0.400 L of 0.005 M

Na2SO4. Will PbSO4 precipitate? Ksp=1.6x10-8

Q = 2.4 x 10-6
Q > Ksp  the precipitate will form