Precipitation equilibria

An example: Hg2Cl2
Hg2Cl2 (s) ⇌ Hg22+(aq) + 2Cl−(aq)

' [Hg22 ][ Cl ]2

K sp   K sp  [Hg22 ][ Cl ]2
[Hg2Cl2 ]

Solubility product: Ksp (or L)

BnAm ⇌ nBm+ + mAn − Ksp = [Bm+]n [An−]m
Solubility: concentration of the saturated solution of a poorly soluble salt; S
If the poorly soluble salt only is present in solution:
[Bm ]  nS [ A n ]  mS  K sp  [Bm ]n [ A n ]m  (nS )n (mS )m  nnmmS nm
K sp
S nm
nnmm

K sp
1:1 electrolyte:S  K sp 1:2 electrolyte: S  3
4
Precipitation equilibria
Solubility of CaSO4 in the presence of an excess of CaCl2

Ksp = 2.4 x 10−5 M2

Precipitation equilibria
Effect of the common ion on solubility
1:1 electrolyte: A− + B+ = AB Ksp = [A−][B+]

Ksp = 1.6 x 10−10 M2

Ksp = CB[A−] Ksp = CA[B+]

S = [A−] = Ksp/CB S = [B+] = Ksp/CA

Precipitation equilibria
1:2 electrolyte: A2− + 2B+ = AB2 Ksp = [A2−][B+]2

Ksp = 4.0 x 10−11 M3

Ksp = CB2 [A2−] Ksp = CA[B+]2

2 K sp [B  ] K sp
S  [A ]  S 
CB2 2 4C A
Precipitation equilibria
Effect of complex formation on solubility
For PbI2: Ksp = 7.9 x 10−9 M3 → S = 1.265x10−3 M
(without excess of common ion)
Precipitation equilibria
Effect of foreign ion (ionic strength)
Solubility of a BnAm salt increases:
a
K sp  aBnaAm   Bn [B]n  Am [A]m   Bn AmK sp
a
K sp
K sp  n m
 1
 
B A

- With increasing ionic strength the solubility of salts formed from

multivalent ions increases better than that of salts formed from
monovalent ions
- The solubility increasing effect of an electrolyte consisting of
multivalent ions is larger than that of electrolytes of monovalent
ions
Precipitation equilibria
Effect of pH
Solubility of a precipitate can be affected by pH even if it does not
contain H+ or OH− ions. Acid-base properties of the cation and anion
need to be considered.

example: PbCrO4 (sz) ⇌ Pb2+ + CrO42−

effect of decreasing the pH

CrO42− + H+ ⇌ HCrO4−
HCrO4− + H+ ⇌ H2CrO4

effect of increasing the pH

Pb2+ + 4OH− ⇌ [Pb(OH)4]2−

Conditional solubility product can also be defined which takes

into consideration the effect of the pH.
Precipitation equilibria
Complex formation effect of a foreign ion
AgCl + 2NH3 ⇌ [Ag(NH3)2]+ + Cl−

2PbI2 + Cd2+ ⇌ 2Pb2+ + [CdI4]2−

Solubility of PbI2 (S) in various solutions:

water: 1.2 x 10−3 M
0.5 M Ca(NO3)2 : 5.0 x 10−3 M
0.5 M Cd(NO3)2 : 4.0 x 10−2 M
Effect of the temperature
Considering the Le Chatelier – Braun principle taking into account heat of
solution.
Effect of the solvent
Electrolytes have limited solubility in apolar solvents: formation of a solid
phase (precipitate).
Precipitation equilibria
Effect of redox reactions
Hg2Cl2 + Cl2 = 2HgCl2

Dissolution of transition metal sulphides in oxidizing acids

Ag2S + conc. HNO3
HgS + aqua regia

MS + 2H+ ⇌ M2+ + H2S(g)

owing to very little Ksp values these sulphides are not soluble in acids

oxidizing acids convert sulphide to elementary sulphur or sulphate

ion
Argentometric titrations
Analytical application of precipitation equilibria
qualitative analysis: identification of ions
quantitative analysis: gravimetry, precipitation titrations
The most often used precipitation method is argentometry.
Titrant: aqueous solution of AgNO3 (primary standard).
Titration curves:
before the equiv. point:
[Ag+] = Ksp/((1 − α)CI)

at the equiv. point:

[Ag+] = (Ksp)0.5

after the equiv. point:

[Ag+] = (α − 1)CI

α: titration degree
Argentometric titrations
Effect of Ksp of AgX on the shape of the titration curves for various halogenides
Argentometric titrations
Titration of a mixture

ΔU ≈ p[Ag+]

a: titration of 40 cm3 0.0502 M KI + 0.0500 M KCl with 0.0845 M AgNO3

b: titration of 20 cm3 0.1002 M KI with 0.0845 M AgNO3
Argentometric titrations
End-point detection:

a) Coagulation of the precipitate (Gay – Lussac)

b) Mohr method: with another precipitation agent

Formation of a coloured precipitate with the other ion should start at the
equivalence point. E.g. CrO42− forms red coloured precipitate with silver ions
when precipitation with halogenides is complete:
Ksp(AgCl) = 1.82 x 10−10 → [Ag+]eq = 1.35 x 10−5 M
[CrO42−] = Ksp(Ag2CrO4)/([Ag+]eq)2 = 1.1 x 10−10/(1.35 x 10−5 )2 = 6.0 x 10−3 M

c) Volhard method: with a complexing agent

Determination of Cl-: excess of known Ag+ is added and the excess of Ag+
is titrated with thiocyanate; AgSCN is formed. Excess of SCN- can be
detected with Fe3+ as the red coloured complex is formed in the
equivalence point.
Argentometric titrations
End-point detection:
d) Fajans method: with adsorption
indicators

Reasons of colour change:

polarization
precipitation
change of pK