Solubility Equilibrium

• In saturated solutions dynamic equilibrium

exists between undissolved solids and ionic
species in solutions
• Solids continue to dissolve and ion-pairs
continue to form solids.
• The rate of dissolution process is equal to the
rate of precipitation.
 Solubility Product Constant
• General expression:
• MmXn(s) ⇄ mMn+(aq) + nXm-(aq)
• Solubility product, Ksp = [Mn+]m[Xm-]n
 Solubility and Solubility Products

Examples:
• AgCl(s) ⇌ Ag+(aq) + Cl-(aq)
• Ksp = [Ag+][Cl-] = 1.6 x 10-10
• If s is the solubility of AgCl, then:
• [Ag+] = s and [Cl-] = s
• Ksp = (s)(s) = s2 = 1.6 x 10-10
• s = 1.3 x 10-5 mol/L
 Solubility and Solubility Products

• Ag2CrO4(s) ⇌ 2Ag+(aq) + CrO42-(aq)

• Ksp = [Ag+]2[CrO42-] = 9.0 x 10-12

• If s is the solubility of Ag2CrO4, then:

• [Ag+] = 2s and [CrO42-] = s
• Ksp = (2s)2(s) = 4s3 = 9.0 x 10-12
• s = 1.3 x 10-4 mol/L
 Solubility and Solubility Products

• More Examples:
• Ca(IO3)2(s) ⇌ Ca2+(aq) + 2 IO3-(aq)
• Ksp = [Ca2+][IO3-]2 = 7.1 x 10-7

• If the solubility of Ca(IO3)2(s) is s mol/L, then:

• Ksp = 4s3 = 7.1 x 10-7
• s = 5.6 x 10-3 mol/L
 Solubility and Solubility Products

• Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH-(aq)

• Ksp = [Mg2+][OH-]2 = 8.9 x 10-12

• If the solubility of Mg(OH)2 is s mol/L, then:

• [Mg2+] = s mol/L and [OH-] = 2s mol/L,
• Ksp = (s)(2s)2 = 4s3 = 8.9 x 10-12
• s = 1.3 x 10-4 mol/L
 Solubility and Solubility Products

• More Examples:
• Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq)
• Ksp = [Ag+]3[PO43-] = 1.8 x 10-18

• If the solubility of Ag3PO4 is s mol/L, then:

• Ksp = (3s)3(s) = 27s4 = 1.8 x 10-18
• s = 1.6 x 10-5 mol/L
 Solubility and Solubility Products

• Cr(OH)3(s) ⇌ Cr3+(aq) + 3 OH-(aq)

• Ksp = [Cr3+][OH-]3 = 6.7 x 10-31

• If the solubility is s mol/L, then:

• Ksp = [Cr3+][OH-]3 = (s)(3s)3 = 27s4 = 6.7 x 10-31
• s = 1.3 x 10-8 mol/L
 Solubility and Solubility Products

• More Examples:
• Ca3(PO4)2(s) ⇌ 3Ca2+(aq) + 2PO43-(aq)
• Ksp = [Ca2+]3[PO43-]2 = 1.3 x 10-32
• If the solubility is s mol/L, then:
• [Ca2+] = 3s, and [PO43-] = 2s
• Ksp = (3s)3(2s)2 = 108s5 = 1.3 x 10-32
• s = 1.6 x 10-7 mol/L
 Factors that affect solubility
• Temperature
– Solubility generally increases with temperature;
• Common ion effect
– Common ions reduce solubility
• Salt effect
– This slightly increases solubility
• pH of solution
– pH affects the solubility of ionic compounds in which the
anions are conjugate bases of weak acids;
• Formation of complex ion
– The formation of complex ion increases solubility
 Common Ion Effect

• Consider the following solubility equilibrium:

• AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10;

• The solubility of AgCl is 1.3 x 10-5 mol/L at 25oC.

• If NaCl is added, equilibrium shifts left due to
increase in [Cl-] and some AgCl will precipitate out.
• For example, if [Cl-] = 1.0 x 10-2 M,
• Solubility of AgCl = (1.6 x 10-10)/(1.0 x 10-2)
• = 1.6 x 10-8 mol/L
 Effect of pH on Solubility
• Consider the following equilibrium:
Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq);

• If HNO3 is added, the following reaction occurs:

H3O+(aq) + PO43-(aq) ⇌ HPO42-(aq) + H2O
• This reaction reduces PO43- in solution, causing more
solid Ag3PO4 to dissolve.
• In general, the solubility of compounds such as
Ag3PO4, which anions are conjugate bases of weak
acids, increases as the pH is lowered by adding nitric
acid.
 Effect of pH on Solubility
• Consider the following equilibrium:
Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH-(aq);

• Increasing the pH means increasing [OH-] and

equilibrium will shift to the left, causing some of
Mg(OH)2 to precipitate out.
• If the pH is lowered, [OH-] decreases and equilibrium
shifts to the right, causing solid Mg(OH)2 to dissolve.
• The solubility of compounds of the type M(OH) n
decreases as pH is increased, and increases as pH is
decreased.
 Formation of Complex Ions on Solubility

• Many transition metals ions have strong affinity for

ligands to form complex ions.
• Ligands are molecules, such as H2O, NH3 and CO, or
anions, such as F-, CN- and S2O32-.
• Complex ions are soluble – thus, the formation of
complex ions increases solubility of slightly soluble
ionic compounds.
 Effect of complex ion formation on solubility
• Consider the following equilibria:
• AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10
• Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) ; Kf = 1.7 x 107

• Combining the two equations yields:

• AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq);
• Knet = Ksp x Kf = (1.6 x 10-10) x (1.7 x 107)
= 2.7 x 10-3
• Knet > Ksp implies that AgCl is more soluble in
aqueous NH3 than in water.
 Solubility Exercise #1

• Calculate the solubility of AgCl in water and in 1.0 M

NH3 solution at 25oC.

• Solutions:
Solubility in water = (Ksp)
= (1.6 x 10-10) = 1.3 x 10-5 mol/L
 Solubility Exercise #1

• Solubility of AgCl in 1.0 NH3:

• AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq)

• [Initial], M - 1.0 0.0 0.0
• [Change] - -2S +S +S
• [Equilm.] - (1 – 2S) S S


[Ag(NH 3 ) 2 ][Cl - ] S2
K net    2.7 x 10 -3

[ NH 3 ]2 (1 - 2 S ) 2
 Solubility Exercise #1
• Solubility of AgCl in 1.0 NH3 (continued):
S
 2.7 x 10 -3  0.052
(1 - 2 S )
• S = 0.052 – 0.104S;
• S = 0.052/1.104 = 0.047 mol/L
• AgCl is much more soluble in NH3 solution than in
water.
 Predicting Formation of Precipitate
• Qsp = Ksp  saturated solution, but no precipitate
• Qsp > Ksp  saturated solution, with precipitate
• Qsp < Ksp  unsaturated solution,

• Qsp is ion product expressed in the same way as Ksp

for a particular system.
 Predicting Precipitation

• Consider the following case:

20.0 mL of 0.025 M Pb(NO3)2 is added to 30.0 mL of 0.10
M NaCl. Predict if precipitate of PbCl2 will form.
(Ksp for PbCl2 = 1.6 x 10-5)
 Predicting Precipitation

• Calculation:
• [Pb2+] = (20.0 mL x 0.025 M)/(50.0 mL) = 0.010 M
• [Cl-] = (30.0 mL x 0.10 M)/(50.0 mL) = 0.060 M
• Qsp = [Pb2+][Cl-]2 = (0.010 M)(0.060 M)2
• = 3.6 x 10-5
• Qsp > Ksp  precipitate of PbCl2 will form.
 Practical Applications of Solubility Equilibria

• Qualitative Analyses
– Isolation and identification of cations and/or anions in
unknown samples
• Synthesis of Ionic Solids of commercial interest
• Selective Precipitation based on Ksp
 Qualitative Analysis

• Separation and identification of cations, such as Ag +,

Ba2+, Cr3+, Fe3+, Cu2+, etc. can be carried out based on
their different solubility and their ability to form
complex ions with specific reagents, such as HCl,
H2SO4, NaOH, NH3, and others.
• Separation and identification of anions, such as Cl -,
Br-, I-, SO42-, CO32-, PO43-, etc., can be accomplished
using reagents such as AgNO3, Ba(NO3)2 under
neutral or acidic conditions.
 Selective Precipitation
(Mixtures of Metal Ions)

• Use a reagent whose anion forms a precipitate

with only one or a few of the metal ions in the
mixture.
• Example:
 Solution contains Ba2+ and Ag+ ions.
 Adding NaCl will form a precipitate with Ag+
(AgCl), while still leaving Ba2+ in solution.
Separation of Cu2+ and Hg2+ from Ni2+ and
Mn2+ using H2S

• At a low pH, [S2–] is relatively low and only

the very insoluble HgS and CuS precipitate.
• When OH– is added to lower [H+], the value
of [S2–] increases, and MnS and NiS
precipitate.
Separation of Cu2+ and Hg2+ from Ni2+ and
Mn2+ using H2S
Separating the Common Cations by
Selective Precipitation
 Synthesis of Ionic Solids

• Chemicals such as AgCl, AgBr, and AgI that are

important in photography are prepared by
precipitation method.

• AgNO3(aq) + KBr(aq)  AgBr(s) + KNO3(aq)

 Selective Precipitation

• Compounds with different solubility can be

selectively precipitated by adjusting the concentration
of the precipitating reagents.
• For example, AgCl has a much lower Ksp than PbCl2
• If Ag+ and Pb2+ are present in the same solution, the
Ag+ ion can be selectively precipitated as AgCl,
leaving Pb2+ in solution.
 Complex Ion Equilibria

• Complex ions are ions consisting central metal ions

and ligands covalently bonded to the metal ions;
• Ligands can be neutral molecules such as H2O, CO,
and NH3, or anions such as Cl-, F-, OH-, and CN-;
• For example, in the complex ion [Cu(NH3)4]2+, four
NH3 molecules are covalently bonded to Cu2+.
 Formation of Complex Ions

• In aqueous solutions, metal ions form complex ions

with water molecules as ligands.
• If stronger ligands are present, ligand exchanges
occur and equilibrium is established.
• For example:
Cu2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4]2+(aq)

2
[Cu(NH 3 ) 4 ]
Kf   1.1 x 1013

[Cu 2 ][ NH 3 ]4
 Stepwise Formation of Complex Ion
• At molecular level, ligand molecules or ions combine with
metal ions in stepwise manner;
• Each step has its equilibrium and equilibrium constant;
• For example:
(1) Ag+(aq) + NH3(aq) ⇌ Ag(NH3)+(aq)
[Ag(NH 3 )  ]
K f1   2.1 x 10 3

[Ag  ][NH 3 ]

(2) Ag(NH3)+(aq) + NH3(aq) ⇌ Ag(NH3)2+(aq);


[Ag(NH 3 ) 2 ]
Kf 2   8.2 x 10 3

[Ag(NH 3 )  ][NH 3 ]
 Stepwise Formation of Complex Ion
Individual equilibrium steps:
(1) Ag+(aq) + NH3(aq) ⇌ Ag(NH3)+(aq); Kf1 = 2.1 x 103

(2) Ag(NH3)+(aq) + NH3(aq) ⇌ Ag(NH3)2+(aq); Kf2 = 8.2 x 103

Combining (1) and (2) yields:

• Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq);

[Ag(NH 3 ) 2 ]
Kf   K f1 x K f2  1.7 x 10 7

[Ag  ][NH 3 ]2
Stepwise complex ion formation for Cu(NH 3)42+
Individual equilibrium steps:
1. Cu2+(aq) + NH3(aq) ⇌ Cu(NH3)2+(aq); K1 = 1.9 x 104
2. Cu(NH3)2+(aq) + NH3(aq) ⇌ Cu(NH3)22+(aq); K2 = 3.9 x 103
3. Cu(NH3)22+(aq) + NH3(aq) ⇌ Cu(NH3)32+(aq); K3 = 1.0 x 103
4. Cu(NH3)32+(aq) + NH3(aq) ⇌ Cu(NH3)42+(aq); K4 = 1.5 x 102

Combining equilibrium:
• Cu2+(aq) + 4NH3(aq) ⇌ Cu(NH3)42+(aq);
2
[Cu(NH 3 ) 4 ]
Kf 
[Cu 2 ][NH 3 ]4

• Kf = K1 x K2 x K3 x K4 = 1.1 x 1013
 Complex Ions and Solubility

• Two strategies for dissolving a water–

insoluble ionic solid.
 If the anion of the solid is a good base, the
solubility is greatly increased by acidifying the
solution.
 In cases where the anion is not sufficiently basic,
the ionic solid often can be dissolved in a solution
containing a ligand that forms stable complex
ions with its cation.
 Concept Check
(a) Calculate the solubility of silver chloride in 10.0 M
ammonia given the following information:
Ksp (AgCl) = 1.6 x 10–10
Ag+ + NH3 AgNH3+ K = 2.1 x 103
AgNH3+ + NH3 Ag(NH3)2+ K = 8.2 x 103

(b) Calculate the concentration of NH3 in the final

equilibrium mixture.

Answers: (a) 0.48 M; (b) 9.0 M