Chem 17

V.

Solubility Equilibria

A. Homogeneous and Heterogeneous Equilibria

Homogenous equilibria - all the species are dissolved to the system
Heterogeneous equilibria pertain to reactions in which the components are in more than one phase
The Common Ion Effect the shifts in equilibrium caused by the addition of a compound having an
ion in common with the dissolved substance.
Let a HA (weak acid) NaA solution:
HA(aq)

H2O(l)

H3O+(aq)

A-(aq)

Ionization constant, Ka,

Ka

[ H ][ A ]
[ HA]

Henderson-Hasselbalch eqtn:

pH pK a log
Solution Equilibria
Recall:
solubility

[ A ]
[ HA]

max. amt. of solute that can dissolve in a given solvent at a specific

temperature
stated in units of concentration
IUPAC Defn.: the analytical composition of a saturated soln expressed as
a proportion of a designated solute in a designated solvent.
Unsaturated, saturated, supersaturated
E.g. SolubilityNaCl 36.0 g / 100mL

Equilibrium between saturated solute and undissolved solute and its ions

MA(s)

Mn+(aq)

An-(aq)

Molar solubility
- number of moles of a solute that dissolves to form hydrated ions in 1.0 L sat. soln.
- moles MA dissolved in 1.0 L
- molar solubility of MA = [Mn+] = [An-]
B. Solubility Product Constant
AgCl(s) Ag+(aq) + Cl-(aq)
Moles of AgCl dissolved in 1.0 L = molar solubility of AgCl = [Ag+] = [Cl-]
Ksp = [Ag+] [Cl-]
Ksp (AgCl) = 1.25 x 10-5 M
Solubility Product the product of the molar concentrations of the constituent ions, each raised to the
power of its stoichiometric coefficient in the equilibrium equation.
Ksp values in comparing solubilities
- Compounds to be compared should have similar formulas (i.e. AgCl and ZnS, or CaF 2 and
Fe(OH)2)
Compound

Ksp

Cation (Mn+)

Anion (An-)

Ksp

AgCl

[Ag+][Cl-]

x2

K sp

BaSO4

[Ba2+][Cl-]

x2

K sp

Ag2CO3

[Ag+]2[CO32-]

2x

4x3

PbF2

[Pb2+][F-]2

2x

4x3

Al(OH)3

[Al3+][OH-]3

3x

27x4

Ca3(PO4)2

[Ca2+]3[PO43-]2

3x

2x

108x5

K sp
4
K sp
4
K sp
27
K sp
108

Ion Product (Qsp)

Qsp = [Mn+]0 [An-]0
Literally the product of the concentration of the ions at any moment in time

Predicting Precipitates
Ksp

Qsp

saturated soln

Ksp

>

Qsp

unsaturated soln

Ksp

<

Qsp

saturated soln + precipitate (supersaturated and subs. will ppt. out until
Ksp is reached)

Solubility of
compound

Molar
solubility of
compound

Concentration
s of cations
and anions

Ksp of
compound

Fractional/Selective Precipitation
- A technique in which 2 or more ions in solution, each capable of being precipitated by the same
reagent are separated by the proper use of that reagent
- one ion is precipitated out while the other(s) remain in solution
- less soluble salt, precipitate first
- more soluble salt, precipitate out as more common ion is added
- Ksp ,most soluble , last to precipitate
- Ksp ,least soluble , first to precipitate
Silver halide salts
Ksp
AgCl
1.6 10-10
AgBr
7.7 10-13
AgI
8.3 10-17
+
- Increasing the Ag ion from other compounds like AgNO3 in the reaction:
AgCl Ag+(aq) + Cl-(aq)
would induce the precipitation of AgCl.

Most soluble
Least soluble

Complex-Ion Equilibria
Complex ion- an ion containing a central metal cation bonded to one or more molecules or ions.
Ligand a molecule or an ion having a lone pair of e-s that can be donated to the metal ion to form a
covalent bond
- e.g common ligands H2O, NH3, Cl-, CN-, I-

Coordination number no. of ligands attached to the metal ion

Co(H2O)62+

CoCl42-

Cu(NH3)42+

Ag(NH3)2+

Formation constant, Kf also called the stability constant

- the equilibrium constant for the complex ion formation
- Kf, more stable the complex ion is
- thus [Cu2+] is low
Cu2+(aq)

4NH3 (aq)

Kf

Cu(NH3)42+(aq)

[Cu( NH 3 ) 24 ]
[Cu 2 ][ NH 3 ]4

Appendices
Table 1.1 Solubility Rules for Common Ionic Compounds in Water at 25C.
Soluble Compounds containing ff. ions
Li , Na+, K+, Rb+, Cs+, NH4+
NO3-, CH3COO-, HCO3-, ClO3-, ClO4Cl-, Br-, ISO42Insoluble Compounds containing ff. ions
CO3-, PO43-, CrO42-, S2OH+

Insoluble w/ cmpd. w/ ff.

none
none
Halides of:
Sulfates of:
Soluble w/ cmpd. w/ ff.
Alkali metal ions and NH4+
Alkali metal ions and Ba2+

Exceptions
None
None
Ag+, Hg22+, Pb2+
Ag+, Ca2+, Sr2+, Ba2+, Hg22+, Pb2+
Exceptions
Li+, Na+, K+, Rb+, Cs+, NH4+
Li+, Na+, K+, Rb+, Cs+, Ba2+