Solubility Equilibrium

Saturated solution – one in which the solution is in contact with undissolved solute.

(i.e. there is excess solute present in the solution)

e.g. A saturated solution of BaSO4 has some solid BaSO4 present in the solution:

saturated BaSO4 solution

solid BaSO4

BaSO4 is an ionic compound therefore it is an electrolyte and produces Ba2+ and SO42- ions in
aqueous solution.

An equilibrium is readily established between the undissolved solid and its hydrated ions in
the solution.

e.g. BaSO4 (s) Ba2+ (aq) + SO42- (aq)

An equilibrium constant Ksp, can then be defined for the dissolution of the solid.

Ksp is called the solubility product constant.

Ksp is formally defined as the measure of the number of dissolved ions present in a saturated
solution.

Ksp indicates how soluble a solid is in water. The greater the Ksp value, the more soluble the
solid.

It should be noted however that Ksp is used when referring to the dissolution of SPARINGLY
SOLUBLE solids, i.e. solids that dissolve only to a small extent in aqueous solution.
In general, the solubility product (Ksp) of a compound is equal to the product of the
concentrations of the ions involved in the equilibrium, each raised to the power of its
coefficient in the equilibrium equation.

e.g. For: BaSO4 (s) Ba2+ (aq) + SO42- (aq)

Ksp = [Ba2+][SO42-]

The value of Ksp for BaSO4 is 1.1 x 10-10 M2 at 25oC, which is a very small value. This indicates
that only a very small amount of solid BaSO4 will dissolve in water at this temperature.

e.g. Write the expression for the solubility product for CaF2.

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

Ksp = [Ca2+][F-]2

Solubility and Ksp

It is important to distinguish between solubility and solubility product (Ksp).

Solubility of a substance is the quantity that dissolves to form a saturated solution. Solubility is
often expressed as grams of solute per liter of solution (i.e. g L-1).

Molar solubility is the number of moles of the solute that dissolve in forming a liter of saturated
solution (i.e. mol L-1).

Solubility product (Ksp) is the equilibrium constant for the equilibrium between an ionic solid
and its saturated solution.

i.e. Solubility concerns the solid, solubility product concerns the ions produced in solution.

Solubility of a substance can change considerably as the concentrations of other solutes also
present in the solution change. e.g. The solubility of Mg(OH)2 depends highly on pH (i.e. the
presence of H+ ions in the solution).

Solubility is also affected by the concentrations of other ions present in the solution. e.g. The
solubility of Mg(OH)2 is affected by Mg2+ ions already present in the solution from another
source.

In contrast, solubility product (Ksp) has only 1 value for a given solute at a specific temperature.
Calculation of Ksp from solubility

e.g. (1) The solubility of Ca(OH)2 in water is 2.78 g L-1 at 20oC. What is the solubility product?

solubility of Ca(OH)2 = 2.78 g L-1

Molar Mass of Ca(OH)2: 74 g mol-1

Molar solubility of Ca(OH)2 = 2.78/ 74 = 0.0375 mol L-1

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

1 mol Ca(OH)2 produces 1 mol Ca2+ and 2 mol OH-

0.0375 mol Ca(OH)2 produce 0.0375 mol Ca2+ and 0.0751 mol OH-

Ksp = [Ca2+][OH-]2

Ksp = (0.0375 mol dm-3)(0.0751 mol dm-3)2

Ksp = 2.12 x 10-4 mol3 dm-9

Calculating solubility from Ksp

e.g. (2) The Ksp for CaF2 is 3.9 x 10-11 M3 at 25oC. Calculate the solubility of CaF2 in g L-1.

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

Let the molar solubility of CaF2 be x. [The molar solubility is really the initial concentration of
CaF2.]

CaF2 Ca2+ F-
Initial conc./ M x 0 0
Change in conc./ M -x +x + 2x
Equil. conc./ M 0 x 2x

Ksp = [Ca2+][F-]2

Ksp = (x)(2x)2 = 4x3

3.9 x 10-11 = 4x3

x3 = 9.75 x 10-12

x = 2.1 x 10-4

molar solubility = 2.1 x 10-4 mol L-1

Molar Mass of CaF2: 78 g mol-1

Solubility of CaF2 = 2.1 x 10-4 x 78 = 0.016 g L-1

 Factors affecting solubility

Generally, the solubility of a substance is affected by:

Temperature – increasing temperature usually increases solubility

The presence of other solutes

Pressure (applicable to gases only) – increasing pressure increases solubility (increasing

pressure forces more gas into the solution)

The solubility of ionic compounds is affected by the:

 presence of common ions

 pH of the solution
 presence of complexing agents

The ‘Common-Ion effect’

The solubility of a slightly soluble solid is decreased by the presence of a second solute which
contains an ion common to both solutes. This is referred to as the common-ion effect.

e.g. Consider: CaF2 (s) Ca2+ (aq) + 2F- (aq)

The presence of either Ca2+ or F- already present in a solution will shift equilibrium position to
the left (Le Chatelier’s Principle) thereby reducing the solubility of CaF2.
Calculating the effect of a common ion on solubility

e.g. (3) Calculate the molar solubility of CaF2 at 25oC in a solution of 0.010 M Ca(NO3)2.

The common ion is Ca2+.

Ca(NO3)2 (s) Ca2+ (aq) + 2NO3- (aq)

0.010 M Ca(NO3)2 produce 0.010 M Ca2+ ions

[This means 0.010 M of Ca2+ ions are already present in the solution & we are adding CaF2 to it.]

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

Let the molar solubility of CaF2 be x.

CaF2 Ca2+ F-
Initial conc./ M x 0.010 0
Change in conc./ M -x +x + 2x
Equil. conc./ M 0 0.010 + x 2x

Ksp = [Ca2+][F-]2

Ksp = (0.010 + x)(2x)2

Assumption: Since x is very small, 0.010 + x ≈ 0.010

Ksp = (0.010)(2x)2

Ksp = 0.040x2

3.9 x 10-11 = 0.040x2

x2 = 9.75 x 10-10

x = 3.1 x 10-5

molar solubility of CaF2 = 3.1 x 10-5 mol L-1

Comparing this value with the value in question (2): 2.1 x 10-4 mol L-1 (i.e. the solubility of CaF2
in pure water), the solubility of CaF2 has decreased due to the presence of Ca2+ in the solution.
e.g. (4) Calculate the molar solubility of CaF2 at 25oC in a 0.010 M NaF solution.

The common ion is F-.

NaF (s) Na+ (aq) + F- (aq)

0.010 M NaF produce 0.010 M F- ions

[This means 0.010 M of F- ions are already present in the solution & we are adding CaF2 to it.]

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

Let the molar solubility of CaF2 be x.

CaF2 Ca2+ F-
Initial conc./ M x 0 0.010
Change in conc./ M -x +x + 2x
Equil. conc./ M 0 x 0.010 + 2x

Ksp = [Ca2+][F-]2

Ksp = (x)(0.010 + 2x)2

Assumption: Since x is very small, 0.010 + 2x ≈ 0.010

Ksp = (x)(0.010)2

Ksp = 0.0001x

3.9 x 10-11 = 0.0001x

x = 3.9 x 10-7

molar solubility of CaF2 = 3.9 x 10-7 mol L-1

Comparing this value with the value in question (3): 3.1 x 10-5 mol L-1 (i.e. the solubility of CaF2
in a 0.010 M Ca(NO3)2 solution), solubility has decreased even further due to the presence of F-
in the solution.
Solubility and pH

The solubility of slightly soluble solids containing basic anions increases as pH decreases or
becomes more acidic (i.e. as [H+] increases).

The more basic the anion, the more solubility is influenced by pH.

e.g. Consider: Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)

A saturated solution of Mg(OH)2 has a calculated pH of 10.52 and has a [Mg2+] = 1.7 x 10-4 M.

Suppose Mg(OH)2 is added to a solution of pH 9.0, what would be its [Mg2+]? (Ksp = 1.8 x 10-11)

If pH = 9.0, then pOH = 5.0, therefore [OH-] = 1.0 x 10-5 M

Ksp = [Mg2+][OH-]2 pH 9.0 is a

Ksp = [Mg2+](1.0 x 10-5)2 more acidic pH
than 10.52
1.8 x 10-11 = [Mg2+](1.0 x 10-5)2

[Mg2+] = 0.18 M

Comparing the two [Mg2+] values, 1.7 x 10-4 M and 0.18 M, Mg(OH)2 is more soluble at pH 9.0.

In general, if a compound contains a basic/ alkaline anion, its solubility will increase if the
solution becomes more acidic. Examples of basic anions – OH-, F-, CO32-

e.g. The solubility of CaF2 increases as solution acidity increases because F- is a weak base.

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

In acidic soln.: 2F- (aq) + 2H+ (aq) 2HF (aq) (II)

Overall equ.: CaF2 (s) + 2H+ (aq) Ca2+ (aq) + 2HF (aq) [equ. (I) + equ. (II)]

Le Chatelier’s Principle applies: As H+ ions remove the F- ions (equ. II), equilibrium position
shifts to the right in equ. I. This increases the solubility of CaF2 (more ions go into the solution).
Formation of complex ions

A characteristic property of metal ions is their ability to act as Lewis acids when dissolved in
water, which acts as a Lewis base. Other Lewis bases besides water can also interact with these
metal ions and this can drastically affect the solubility of metal salts.

e.g. AgCl, Ksp = 1.8 x 10-10 M2 is much more soluble in the presence of aqueous ammonia (NH3)

than in pure water because Ag+ interacts with the Lewis base NH3.

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

In aq. NH3: Ag+ (aq) + 2NH3 (aq) Ag(NH3)2+ (aq) (II)

Overall equ.: AgCl (s) + 2NH3 (aq) Ag(NH3)2+ (aq) + Cl- (aq) [(I) + (II)]

Le Chatelier’s Principle applies: The presence of NH3 removes the Ag+ ions (equ. II), shifting
equilibrium position to the right in equ. I. This increases the solubility of AgCl.

NH3 interacts more strongly with Ag+ than water molecules thereby increasing the solubility of
AgCl in aqueous ammonia. NH3 is a stronger Lewis base than water.

Precipitation and separation of ions

When two solutions are mixed, a parameter defined as Q, the reaction quotient, determines
whether precipitation of ions or dissolution of ions will occur.

Q is calculated using the same formula as for Ksp, however it uses the initial ion concentrations,
not the equilibrium concentrations (which is done for Ksp).

Comparison of the value of Q to Ksp will then determine if precipitation will occur:

If Q > Ksp then precipitation occurs

If Q = Ksp then the system is at equilibrium

If Q < Ksp the no precipitation occurs i.e. any solid product formed dissolves
Predicting whether a precipitate will form

e.g. (5) Will a precipitate form when 100 mL of 8.0 x 10-3 M Pb(NO3)2 is added to 400 mL of

5.0 x 10-3 M Na2SO4? (Ksp of PbSO4 = 6.3 x 10-7 M2)

Pb(NO3)2 (aq) + Na2SO4 (aq) PbSO4 (s) + 2NaNO3 (aq)

[The precipitate will be the PbSO4.]

No. of mol Pb2+ = 8.0 x 10-3 x 100/ 1000 = 8.0 x 10-4 mol

No. of mol SO42- = 5.0 x 10-3 x 400/ 1000 = 2.0 x 10-3 mol

Total volume of solution = 100 + 400 = 500 mL

[Pb2+] = 8.0 x 10-4/ 500 x 1000 = 1.6 x 10-3 M

[SO42-] = 2.0 x 10-3/ 500 x 1000 = 4.0 x 10-3 M

Q = [Pb2+][SO42-] = (1.6 x 10-3)(4.0 x 10-3) = 6.4 x 10-6

6.4 x 10-6 > 6.3 x 10-7

Q > Ksp Therefore, PbSO4 will precipitate out of the solution

Calculating the ion concentration required for precipitation

e.g. (6) A solution contains 1.0 x 10-2 M Ag+. What concentration of Cl- is necessary to begin

precipitation of AgCl (Ksp = 1.8 x 10-10 M2)?

Ksp = [Ag+][Cl-]

1.8 x 10-10 = (1.0 x 10-2) [Cl-]

[Cl-] = 1.8 x 10-8 M

This is the maximum concentration of Cl- that can be present in the solution before precipitation
occurs.

If [Cl-] > 1.8 x 10-8 M, precipitation will definitely occur, therefore at least 1.8 x 10-8 M of Cl-
ions must be present to begin precipitation of AgCl.
Selective precipitation of ions

Ions can be separated from each other based on the solubility of their salts.

e.g. A solution contains both Ag+ and Ca2+. If HCl is added, the Ag+ ions will precipitate out as
AgCl (s) leaving the Ca2+ ions in solution. (CaCl2 is significantly more soluble than AgCl).
[Refer to the solubility table below]

i.e. To a solution of Ag+ and Ca2+, add HCl then filter the mixture. The residue collected in the
filter paper will be solid AgCl and the filtrate in the conical flask will be the Ca2+ ions in
solution. Using this method, the Ag+ and Ca2+ ions have been separated.

Many other ionic mixtures can be separated according to their solubility using this method.

Separation of ions in an aqueous solution by using a reagent that forms a precipitate with
one or a few of the ions is called selective precipitation.

Solubility of compounds:

Compound Solubility

Nitrates All soluble

Chlorides, bromides & iodides All soluble except silver (Ag) and lead (Pb);
PbCl2 and PbBr2 are soluble in hot water

Sulfates All soluble except for barium (Ba) and lead (Pb)
CaSO4 and Ag2SO4 are slightly soluble

Carbonates All insoluble except Na, K and NH4+

Hydroxides All insoluble except Na & K;

Ba(OH)2 and Ca(OH)2 are slightly soluble