V.

SOLUBILITY EQUILIBRIA &

PRECIPITIMETRIC METHODS

A. Solubility Equilibria
B. Factors Affecting Solubility
C. Argentometric Methods
 Solubility and Equilibria

maximum amount of SOLUTE

_______ that will
SOLVENT
dissolve in a given amount of ________
TEMPERATURE
at a specific _____________.

+ −
𝑨𝒈𝑪𝒍(𝒔) ⇌ 𝐴𝑔(𝑎𝑞) + 𝐶𝑙(𝑎𝑞) 𝒂𝒕 𝟐𝟓℃
𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 − = 1.82𝑥10−10
= 𝑠2 𝑠 = 1.35𝑥10−5 𝑀
 s and Ksp

Compound Ksp expression Cation Anion Ksp in terms of s

𝐴𝑔𝐶𝑙 [𝐴𝑔+ ] [𝐶𝑙− ] 𝑠 𝑠 𝐾𝑠𝑝 = 𝑠2

𝐴𝑔2 𝐶𝑂3 [𝐴𝑔+ ]2 [𝐶𝑂32− ] 2𝑠 𝑠 𝐾𝑠𝑝 = 4𝑠 3
𝑃𝑏𝐹2 [𝑃𝑏2+ ] [𝐹 − ]2 𝑠 2𝑠 𝐾𝑠𝑝 = 4𝑠 3
𝐴𝑙(𝑂𝐻)3 [𝐴𝑙3+ ] [𝑂𝐻− ]3 𝑠 3𝑠 𝐾𝑠𝑝 = 27𝑠 4
𝐶𝑎3 (𝑃𝑂4 )2 [𝐶𝑎2+ ]3 [𝑃𝑂43− ]2 3𝑠 2𝑠 𝐾𝑠𝑝 = 108𝑠 5
 Factors Affecting Solubility

Factor Example Ksp in terms of s

𝐾𝑠𝑝 = 𝑠 𝑠 + 0.01
Common ion effect AgCl in 0.01 M NaCl
= 𝑠 2 + 0.01𝑠
2
𝐾𝑠𝑝 = 𝑠 𝛼𝐹 2𝑠
Weak acid formation MgF2 at pH 2.00
= 𝛼 2 4𝑠 3

Complex ion formation AgCl in NH3 𝐾𝑠𝑝 = 𝛼𝐴𝑔 𝑠 2

RECALL:
Concept of equilibrium
 1. Common ion effect
+ −
𝑨𝒈𝑪𝒍(𝒔) ⇌ 𝐴𝑔(𝑎𝑞) + 𝐶𝑙(𝑎𝑞)

𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙− = 1.82𝑥10−10

in pure water: =𝑠∙𝑠 𝒔 = 𝟏. 𝟑𝟓𝒙𝟏𝟎−𝟓 𝑴

in 0.01 M NaCl: 𝐾𝑠𝑝 = 𝑠(𝑠 + 𝟎. 𝟎𝟏)

𝑠 2 + 𝟎. 𝟎𝟏s = 1.82𝑥10−10

a=1 b = 0.01 c = -1.82x10-10 𝒔 = 𝟏. 𝟖𝟐𝒙𝟏𝟎−𝟖 𝑴

↓ solubility
2. Effect of pH
 2. Effect of pH
2+ −
𝑴𝒈𝑭𝟐(𝒔) ⇌ 𝑀𝑔(𝑎𝑞) + 2𝐹(𝑎𝑞)

𝐾𝑠𝑝 = 𝑀𝑔2+ 𝐹 − 2
= 6.60𝑥10−9

at pH 7.00: = 𝑠 ∙ (2𝑠)2 = 4𝑠 3

3 𝐾𝑠𝑝
𝑠=
4

𝒔 = 𝟏. 𝟏𝟖𝒙𝟏𝟎−𝟑 𝑴
at pH 2.00:
RECALL:
STRONG acids/bases
2. Weak acid formation
Weak acids/bases 2+ −
𝑀𝑔𝐹2(𝑠) ⇌ 𝑀𝑔(𝑎𝑞) + 𝟐𝑭
2𝐹(𝑎𝑞)
(𝒂𝒒)

𝑯𝟑 𝑶+ = 𝟎. 𝟎𝟏 𝑴

at pH 2.00: 𝑯𝑭 𝐾𝑎 = 6.80𝑥10−4
Ka [F-] [F-]
0.0637 = = F- = =
[H+] + Ka CF- [HF] + [F-]

Ksp = [Mg2+] (F-CF-)2 s = [Mg+2]

3 𝐾𝑠𝑝 = s (F- 2s)2 2s = CF-
𝑠= = [HF] + [F-]
4𝜶𝟐𝑭 = 4s3 F-2

𝒔 = 𝟕. 𝟒𝟏𝒙𝟏𝟎−𝟑 𝑴 ↑ solubility
 3. Complex ion formation

+ − + +
𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝐴𝑔(𝑎𝑞) + 𝐶𝑙(𝑎𝑞) 𝐴𝑔(𝑎𝑞) + 2𝑁𝐻3 ⇌ 𝑨𝒈(𝑵𝑯𝟑 )𝟐 (𝒂𝒒)
RECALL:
Metal-ligand
3. Complex ion formation
equilibrium 𝐴𝑔𝐶𝑙(𝑠) ⇌ 𝑨𝒈+
(𝒂𝒒) + 𝐶𝑙 −
(𝑎𝑞)

𝑁𝐻3
𝑨𝒈(𝑵𝑯𝟑 )+
(𝒂𝒒) 𝐾𝑓1 = 2.04𝑥10 3

𝑁𝐻3
𝑨𝒈(𝑵𝑯𝟑 )𝟐 +
(𝒂𝒒) 𝐾𝑓2 = 8.13𝑥10 3

[Ag+] [Ag+]
Ag+ = CAg+
= [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+] 𝑠=
𝐾𝑠𝑝
𝜶𝑨𝒈
Ksp = [Ag+] [Cl-] s = CAg+
𝒔 = 𝟎. 𝟓𝟓 𝑴
= Ag+ CAg+ [Cl-] = Ag+ s2
↑ solubility
 Factors Affecting Solubility

Factor Example Effect on solubility

Common ion effect AgCl in 0.01 M NaCl decrease in solubility

Weak acid formation MgF2 at pH 2.00 INCREASE in solubility

Complex ion formation AgCl in NH3 INCREASE in solubility

 Argentometric Methods
Types of indicators:
1. Indicators that form colored soluble compounds
2. Indicators that form colored precipitate
3. Adsorption indicators

FeNH4(SO4)2 K2CrO4

Fe3+ + SCN- → FeSCN2+ CrO42- + Ag+ → Ag2CrO4 (s)

titrant titrant
 𝒎𝒐𝒍𝒔 𝑨𝒈+ = 𝒎𝒐𝒍𝒔 𝑺𝑪𝑵−
Jacob Volhard
 a German chemist
𝒎𝒐𝒍𝒔 𝑿− = 𝑴𝑽𝑨𝒈𝑵𝑶𝟑 − 𝑴𝑽𝑲𝑺𝑪𝑵
 Volhard Titration

before titration

at EP

after EP

Fe3+ + SCN- → FeSCN2+

Karl Friedrich Mohr 𝒎𝒐𝒍𝒔 𝑨𝒈+ = 𝒎𝒐𝒍𝒔 𝑿−
 a German chemist
 Mohr Titration

before titration

at EP

after EP

CrO42- + Ag+ → Ag2CrO4 (s)

 Fajans Titration
Cl- + Ag+ → AgCl (s)
analyte titrant

Before EP: AgCl (s) | Cl– | DCF –

Kazimierz Fajans (Cl– excess)
 a Polish chemist
- -
O O O

After EP : AgCl (s) | Ag+ | DCF –

-
C
l l-
C
C
OO- (Ag+ excess) adsorbed indicator

dichlorofluorescein
VI. REDOX EQUILIBRIA &
TITRIMETRIC METHODS
A. Redox Reactions
B. Equivalents in Redox Reactions
C. Permanganimetry
D. Iodometry
 Determining Normality

𝑵 = 𝑴𝒏
Normality = Molarity x number of H3O+ from acid
HCl 1N 1M 1
H2SO4 2N 1M 2

Normality = Molarity x number of e̶ lost or gained

KMnO4 5N 1M 5
Na2S2O3 1N 1M 1
 Permanganimetry

2𝑀𝑛𝑂4− + 5𝐻2 𝐶2 𝑂4 + 6𝐻3 𝑂+ ⇌ 2𝑀𝑛2+ + 10𝐶𝑂2 + 14𝐻2 𝑂

𝑴𝒏 𝑖𝑛 −
=7+ 𝟐+
𝑴𝒏𝑂4 𝑴𝒏 𝑖𝑛 𝑴𝒏 =2+

𝑔𝑎𝑖𝑛 𝑜𝑓 5𝑒 −

𝑵=𝑴∙𝟓

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Determining Equivalent Weight
𝑴𝑾
𝑬𝑾 =
𝒏
n EW
HCl 1 MW/1
H2SO4 2 MW/2

n EW
Na2C2O4 2 MW/2
K2Cr2O7 6 MW/6
Permanganimetry

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 Permanganimetry
2𝑀𝑛𝑂4− + 5𝐻2 𝐶2 𝑂4 + 6𝐻3 𝑂+ ⇌ 2𝑀𝑛2+ + 10𝐶𝑂2 + 14𝐻2 𝑂

𝑪 𝑖𝑛 𝐻2 𝑪𝟐 𝑂4 = 3 + 𝑪 𝑖𝑛 𝑪𝑂2 = 4 +
− −
1𝑒 2𝑒
𝑙𝑜𝑠𝑠 𝑜𝑓 →→ 𝑙𝑜𝑠𝑠 𝑜𝑓
𝐶 𝐻2 𝐶2 𝑂4
𝑴𝑾
𝒏=𝟐 𝑬𝑾 =
𝟐
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Iodometry

24
Iodometry

25