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Unit 1 Mod 2 Solubility Product Ksp page 1 of 7

Solubility product

The Solubility product is related to SPARINGLY SOLUBLE SALTS


ONLY!!!!! Examples are silver chloride, lead(II) chloride, calcium
sulphate (in other words, it deals with salts commonly called insoluble
salts)

Consider a sparingly soluble salt MX

Imagine the reaction that occurs when the solid is placed in water

aMX (s) + H2O aMn+ (aq) + bXm- (aq)

The equilibrium expression would be [Mn+]a [Xm-]b


[MX]a [H2O]
However the concentrations of both the solid AND the water are
constants, so a new equilibrium expression called Ksp is derived

Ksp = [Mn+]a [Xm-]b

Note: The product of the concentration of ions of a sparingly soluble salt


in water OTHER than at equilibrium is called the IONIC PRODUCT

Example 1. AgCl Ag+ + Cl- Ksp = [Ag+][Cl-]

Example 2 Cu(OH)2 Cu2+ + 2OH- Ksp = [Cu2+][OH-]2

Checkpoint A

Write the Ksp expressions for the sparingly soluble salts below

a. AgF b. HgCl2 c. Cu(OH)2


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Common ion effect

The solubility of one salt is reduced by the presence of another salt


having a common ion.

For example consider the reaction AgCl (s) Ag+ (aq) + Cl- (aq)

The ions present in solution are Ag+ and Cl- from the salt silver chloride.

Imagine a soluble salt such as ammonium chloride is added to the


solution, with reference to Le Chatelier’s Principle, what would
happen??

The addition of more chloride ions would increase the [Cl -] in the
equilibrium shown above and the system would then try to decrease the
[Cl-] by shifting the equilibrium to the LEFT.

By shifting to the left, this causes an increase in the amount of solid


silver chloride formed, i.e. the solubility of the silver chloride decreases
in the presence of ammonium chloride. What would be observed is an
increased amount of precipitation when the salt ammonium chloride
(or any salt containing a common ion) is added to a solution containing
silver chloride.

Checkpoint B

Imagine the sparingly soluble salt PbSO4 is added to water

a) First write the equilibrium reaction that would occur when the salt is
added to water.

b) Tick the salt(s) below which via the common ion effect would cause
an increased amount of precipitation if it is added to the water already
containing PbSO4

i) CaCO3 ii) Pb(NO3)2 iii) MgSO4 iv) Na2SO4 v) NaCl


Unit 1 Mod 2 Solubility Product Ksp page 3 of 7

How to calculate the solubility product of a sparingly soluble salt

If the molar solubility of CaI2 at 25 °C is 7.9 x 10-7 mol dm-3, what would
be its Ksp value?

Step 1 Write the equilibrium expression CaI2 Ca2+ + 2I-

Step 2 Write the Ksp expression [Ca2+][I-]2

Step 3 Determine the # of moles of each ion present


ratio of CaI2 : Ca2+ : I- = 1 : 1 : 2
therefore # of moles of Ca2+ = 7.9 x 10-7
and # of moles of I- = 7.9 x 10-7 x 2 = 1.58 x 10-5

Step 4 Use the # of moles of each ion to determine the Ksp value
Ksp = 7.9 x 10-7 x (1.58 x 10-5)2 = 1.97 x 10-16

To calculate the molar solubility from the Ksp value

Ksp PbI2 is 1.39 x 10-8. What is its molar solubility?

Step 1 Write the equilibrium expression PbI2 Pb2+ + 2I-

Step 2 Use the letter “a” to represent the # of mol of PbI 2


then a moles of PbI2 gives a moles of Pb2+ and 2a moles of I-

Step 3 Write the Ksp expression using the algebraic terms


Ksp = [Pb2+][I-]2 = a * (2a)2 = 4a3  1.39 x 10-8 = 4a3

Step 4 Solve for a


3
√(1.39 x 10-8) = 0.0015
4

Step 5 Give molar solubility


molar solubility of PbI2 is 0.0015 mol dm-3
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How to determine the decrease in solubility of a sparingly soluble


salt via common ion effect

If the molar solubility of CaI2 is 7.9 x 10-7 mol dm-3 in water and then
0.1M NaI is added to the solution, what would be the new solubility of
the CaI2?

Step 1 Write the Ksp value & expression of CaI2 (taken from previous
example)
Ksp = [Ca2+][I-]2 = 1.97 x 10-16

Step 2 Substitute the concentration of the common ion with the value
given
NaI is a soluble salt which dissociates FULLY therefore the
concentration of I- = 0.1 (ignore the I- ions coming from the
sparingly soluble salt.)

Step 3 Determine the concentration of Ca2+


Ca2+ = Ksp = 1.97 x 10-16 = 1.97 x 10-14 That is a 40
[I-]2 0.12 MILLION fold
decrease in
Step 4 Determine molar solubility solubility!!!
ratio of Ca2+ : CaI2 = 1 : 1
therefore # of moles of CaI2 = molar solubility
= 1.97 x 10 -14 mol dm-3
therefore the solubility of CaI2 decreases from 7.9 x 10-7 to approx 2 x 10-14

Checkpoint C
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Checkpoint D
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Unit 1 Mod 2 Solubility Product Ksp page 7 of 7
Real life illustrations of solubility product

Kidney stones are crystals of calcium oxalate. When the concentrations


of calcium ions and oxalate ions are too high, the Ksp of calcium oxalate
is exceeded and this causes the precipitation of calcium oxalate crystals.

CaC2O4(s) <-------> Ca2+(aq) + C2O42-(aq)


Note kidney stones are generally of the order 3 millimetres or more to
cause obstruction of the urethra and eventually pain. By minimising the
uptake of oxalate ions and to a lesser extent calcium ions, this reduces
the risk of kidney stone formation.

Qualitative analysis also exploits the principle of solubility product of


sparingly soluble salts. For a precipitate to be formed, the ionic product
must exceed the solubility product. Then precipitation occurs until the
ionic product no longer exceeds the Ksp value.

Reagents used for qualitative analysis must be of a certain minimum


concentration, if not, the ionic product would not be enough to equal the
Ksp value and no precipitate would be seen and a wrong conclusion of
the ion present would occur.