Program: PharmD

Course: Pharmaceutical Analytical Chemistry-1

Code: PMC 111

Lecture 10
Qualitative Analysis

Dr. Ahmed Sayed Saad 1

 Molar Solubility

The Molar Solubility

• It is the solubility in units of moles per liter (mol/L).

• The solubility can have different values in different kinds of solutions.

• For example, due to the common ion effect, the solubility of AgCl in pure water is different

from its solubility in NaCl solution, even though the solubility product constant is the same for

both solutions.

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 Solubility Equilibria and the Solubility Product Constant
Solubility Product Constant (Ksp)
It is the equilibrium constant for a chemical equation representing the dissolution of an ionic
compound.

• For CaF2, the expression of the solubility product constant is:

• The solubility product constant has only one value at a given temperature.
• The value of Ksp is a measure of the solubility of a compound.
• Ksp can be used to compare the solubility only in case of the same dissolution stoichiometry
(Salts having the same formula).
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 Relative Solubility
• We cannot generally use the Ksp values of two different
compounds to directly compare their relative solubilities.
o Ksp ➔ FeCO3 > Mg(OH)2
o Molar Solubility ➔ FeCO3 < Mg(OH)2
The direct comparison of Ksp values for different compounds can only be made if the compounds
have the same dissociation stoichiometry.
• Example:
• AB ➔ AgCl, AgI, KCl, CuS
• AB2 ➔ CuBr2, ZnCl2, PbI2, Mg(OH)2, CaF2
• A2B ➔ Na2CO3, Ag2S, K2SO4
Mg(OH)2 & CaF2 have the same dissociation stoichiometry
→ the Ksp values can be directly compared as a measure
of relative solubility.
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 The Effect of a Common Ion on Solubility
What is the solubility of CaF2 in a solution that is
0.100 M in NaF? How is the solubility of an ionic
compound affected when the
compound is dissolved in a
solution that already contains
one of its ions?

According to Le Châtelier’s principle, the presence of the F ion in solution → shift the equilibrium
to the left (compared to its position in pure water) ↓ CaF2 solubility.

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 Refresh

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 Q relative to Ksp

We can use Q to predict precipitation

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 Q relative to Ksp

At any point At equilibrium

___ Solution Additional Solid ___

𝑄 < 𝐾𝑠𝑝 Unsaturated dissolve

𝑄 = 𝐾𝑠𝑝 Saturated Precipitate

𝑄 > 𝐾𝑠𝑝 Supersaturated Precipitate

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 Solubility in acids
Stronger acids displaces weaker acids from their salts

𝐶𝑎 𝑪𝑯𝟑𝑪𝑶𝑶 𝟐 + 2 𝐻𝐶𝑙 → 𝐶𝑎𝑪𝒍𝟐 + 2𝐶𝐻3𝐶𝑂𝑂𝐻

Weaker acids can not displace stronger acids

𝐶𝑎𝑪𝒍𝟐 + 𝐶𝐻3𝐶𝑂𝑂𝐻 → 𝑁𝑜 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
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 Examples of strong and weak acids

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 Selective precipitation
• Upon addition of KOH to a solution containing equal concentrations of Mg2+ and Ca2+ ions →
Which one will precipitate first, and Why?
➢ Mg(OH)2 will precipitate first because it has lower Ksp (& Solubility).
➢ If we continue to add KOH → Ca(OH)2 will precipitate afterwards.

Mg(OH)2 Ca(OH)2
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 Refresh

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 Coordinate bond formation → Complex

Volumetric method involves reaction of metal with ligand to form complex → (weakly
dissociated stable compound )
Mn+ Contain Electron
: ligand
donating atom
Electron acceptor Electron donor

:
: :
Coordinate bond S,O,N

:
:
Lewis acid Lewis base

Complex formation is a type of acid base reaction according to lewis

concept.

where metal ion is lewis acid (electron acceptor) and ligand is lewis
base (electron donor)

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 :NH3
:NH3

H2O H2O

Cu2+
:NH3
H2O H2O

:NH3

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 Analytical Chemistry

I. Qualitative Analysis II. Quantitative Analysis

How much?
What?
- Detection
- Amount
- Identification
- Concentration
➢ We are going to deal with Qualitative
analysis of inorganic salts (e.g. NaCl).

Cation = Basic Radical Anion = Acid Radical

e.g. Na+ e.g. Cl-

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 I. Anions (Acid Radicals)
Anions are divided into six main groups:
1. Carbonates and Bicarbonates group
2. Sulfur group
3. Halides group
4. Cyanogen group
5. Phosphate group
6. Nitrogen group

Within each group we will discuss:

A. Group members
B. General Characters
C. Dry reactions
D. Wet reactions
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 1. Carbonates and Bicarbonates group
A. Group members

1. Carbonate (CO32-) 2. Bicarbonate (HCO3-)

B. General Characters
a. Parent Acid Carbonic acid (𝐻2 𝐶𝑂3 )
(1)It is a weak acid
(2)It is unstable (decompose spontaneously to form carbon
dioxide and water) 𝐻2 𝐶𝑂3 → 𝐶𝑂2 ↑ +𝐻2 𝑂
b. Solubility in water All are insoluble except
All are soluble
Na+, K+, Li+ and NH4+
c. Complexing agent  
d. Oxidizing agent  
e. Reducing agent  
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 C. Dry reactions
Dry Reactions = Solid + Dry heat or acid
a- Dry heat:
‫تفكك‬ ‫تصاعد‬
Decomposition + evolution of CO2 gas occur
Δ
𝑀(𝐻𝐶𝑂3 )2 𝑀𝐶𝑂3 + 𝐶𝑂2 ↑ +𝐻2 𝑂
Δ
𝑀𝐶𝑂3 𝑀𝑂 + 𝐶𝑂2 ↑

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 C. Dry reactions
b- Acid:
Effervescence due to the evolution of CO2 gas

Na2CO3 + 2HCl → CO2+ H2O + 2NaCl

NaHCO3 + HCl → CO2 + H2O + NaCl

The stronger acid HCl displaces the weaker acid H2CO3 in its salts.
(Displacement reaction)
Test for the evolving CO2 gas:
𝐶𝑂2 + 𝐻2 𝑂
𝐶𝑂2 𝑃𝑟𝑜𝑙𝑜𝑛𝑔𝑒𝑑 𝑝𝑎𝑠𝑠𝑎𝑔𝑒 𝑜𝑓 𝐶𝑂2
𝐶𝑎(𝑂𝐻)2 𝐶𝑎𝐶𝑂3 ↓ 𝐶𝑎(𝐻𝐶𝑂3 )2
Lime water White ppt Soluble
(turbidity appear) Turbidity disappears

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 D. Wet Reactions (salt solution + Reagent)
1. Reaction with AgNO3
For CO32-
CO32- + 2Ag+ → Ag2CO3  white ppt

1. The precipitate is soluble in HNO3 Why? The stronger mineral acids displace
the weaker parent acid H2CO3

Ag2CO3 + 2HNO3 → 2AgNO3 + CO2 + H2O

2. The precipitate is soluble in ammonia. Why? Due to the formation of soluble silver amine complex
[Ag(NH3)2]+

Ag2CO3+ 4NH3 → CO32- + 2[Ag(NH3)2]+ soluble silver amine complex.

For HCO3-, No ppt (Why???)

Because all Bicarbonates are soluble

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