TOPICS :

1. INTRODUCTION OF QUALITATIVE ANALYSIS : (Precipitation reaction,

Complexation reaction, Oxidation-reduction reaction)
2. EXPERIMENTAL TECHNIQUES OF QUALITATIVE ANALYSIS :
(Dry reaction of Cations, Wet reaction of Cation and Anions)
3. REACTIONS OF CATIONS AND ANIONS :( Classification Cations,
Anions, Reaction of Cations, Reaction of Anions)
4. SYSTEMATIC QUALITATIVE ANALYSIS OF CATIONS AND ANIONS :
(Separation of Cations into groups, Separation and Identification of the
Group I Cations, Separation and Identification of the Group II Cations,
Separation and Identification of the Group III Cations, Separation and
Identification of the Group IV Cations, Identification of Group V Cations.
Separation and Identification of Anions)
EVALUATION :
1. MIDLE EXAMINATION 30%
2. FINAL EXAMINATION 30%
3. TASK : Write paper, Individuals task 25%
4. CLASS PARTICIPATION : 5%
REFERENCES :
1. VOGEL’S, ARTHURS :1979. Textbook of Macro and Semimacro Qualitative
Inorganic Analysis. Fifth Edition. Longman, London, New York.
Qualitative analysis : Identification of a specific substance present
Quantitative analysis: Determination of the quantity of a substance present

Qualitative analysis: Recognition (pengenalan) of chemical species by means

reaction producing a precipitate, reaction producing a colour, reaction involving a
change of a physical parameter

Solubility equilibrium “ dissociation versus precipitation

• Equilibrium is dynamic
• AaBb(s) aA(aq) + bB(aq)

• Solubility Product Constant the degree to which the solid(solute) is

soluble in water, Ksp:
• Ksp = [A]a[B]b
 When Does a Precipitate Form?

When solutions containing soluble ionic compounds

are mixed, when do we predict a precipitate will form?

Qip is the ion product reaction quotient and is

based on initial conditions of the reaction
Precipitation should occur if Qip > Ksp
Precipitation cannot occur if Qip < Ksp
A solution is just saturated if Qip = Ksp
 THE REACTION QUOTIENT
 The reaction quotient (called ion product) may

be applied to solubility equilibria - determines

if a substance will precipitate from solution

Qsp < Ksp Forward process occurs

No precipitation occurs

Qsp = Ksp Solution is just saturated

Qsp > Ksp Reverse process occurs

 Ksp
• EX: Silver chromate
• Ag2CrO4(s) = 2Ag+ + CrO42-
• Ksp = [Ag+]2[CrO42-]

• EX: Ferrous Phosphate

• Fe3(PO4)2 = 3Fe2+ + 2PO43-
• Ksp = [Fe2+]3[PO43-]2
 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
The Solubility Product Constant, Ksp
Many ionic compounds are only slightly soluble in water: ex. Ag salts, sulfides

Equations are written to represent the equilibrium between the compound and the ions
present in a saturated aqueous solution
AgCl(s) Ag+(aq) + Cl–(aq)
[Ag  ][Cl  ]
Kc  but... K c [AgCl]  [Ag  ][Cl  ]
[AgCl]
Ksp = [Ag+][Cl–]
From stoichiometry, the ion ratio is 1:1, so [Ag+] = [Cl–],
both of which are unknown (x)

Ag+ Cl– Ag+ + Cl–

Ksp = x2 and [Ag+] = (Ksp)1/2
The larger the Ksp the larger the solubility of the compound.
(This comparison can be made when the ion ratios are equal).
Ex. Of the following, which is more soluble?
AgCl Ksp= 1.8x10-10
AgI Ksp= 8.3x10-17
Predicting Precipitation
• When solutions containing soluble ionic compounds are mixed,
when do we predict a precipitate will form?

Example:
50.00 mL of 0.00320 M Pb(NO3)2 is mixed with 50.00 mL of 0.111 M
NaCl. Will a precipitate form?

Look up Ksp of PbCl2 and write out solubility eq for PbCl2 in water

PbCl2(s)  Pb2+(aq) + 2 Cl-(aq) Ksp = 1.6 x10-5

Qip = [Pb2+][Cl-]2 = (0.0016)(0.0555)2 = 4.93x 10-6

Qip < Ksp thus, no precipitate formed

 PROBLEM 1:

If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M

CaCl2, will a precipitate form? (Ksp Ca(OH)2 = 8 x10-6)

The ions present in solution are Na+, OH-, Ca2+, Cl-.

Is Q > Ksp for Ca(OH)2?

[Ca2+]0 = 0.100 M [OH-]0 = 4.0 x 10-4 M

Q = [Ca2+]0[OH-]02 = 0.10 x (4.0 x 10-4)2 = 1.6 x 10-8

Ksp = [Ca2+][OH-]2 = 8.0 x 10-6

Q < Ksp No precipitate will form
Problem 2.
• If 15 mL of 0.024-M lead nitrate is mixed with 30 mL
• of 0.030-M potassium chromate - will a precipitate form?

• 25 mL of an 0.35 mM solution of barium nitrate is added to 40 mL of an 0.25 mM

solution of sodium sulfate. Will precipitation occur?
 Mixing Solutions - Will a Precipitate Form?
If 15 mL of 0.024-M lead nitrate is mixed with 30 mL
of 0.030-M potassium chromate - will a precipitate form?
Pb(NO3)2 (aq) + K2CrO4 (aq)  PbCrO4 (s) + 2 KNO3 (aq)
Pb(NO3)2 (aq) + K2CrO4 (aq)  PbCrO4 (s) + 2 KNO3 (aq)

Step 1: Is a sparingly soluble salt formed?

We can see that a double replacement reaction can
occur and produce PbCrO4. Since this salt has a
very small Ksp, it may precipitate from the mixture.
The solubility equilibrium is:
PbCrO4 (s)  Pb2+ (aq) + CrO42- (aq)

Ksp = 2 x 10-16 = [Pb2+][CrO42-]

If a precipitate forms, it means the solubility

equilibrium has shifted BACKWARDS.

This will happen only if Qsp > Ksp in our mixture.

Step 2: Find the concentrations of the ions that form the
sparingly soluble salt.
Since we are mixing two solutions in this example,
the concentrations of the Pb2+ and CrO42- will be
diluted. We have to do a dilution calculation!

Dilution: C1V1 = C2V2

C1V1 (0.024 M)(15 mL)
[Pb2+] =   0.0080 M Pb2
V2 (45 mL)

C1V1 (0.030 M)(20 mL) 2-

  0.020 M CrO 4
[CrO42-] = V2 (45 mL)
Step 3: Calculate Qsp for the mixture.

Qsp = [Pb2+][CrO42-] = (0.0080 M)(0.020 M)

Qsp = 1.6 x 10-4

Step 4: Compare Qsp to Ksp.

Since Qsp >> Ksp, a precipitate will form when

the two solutions are mixed!

Note: If Qsp = Ksp, the mixture is saturated

If Qsp < Ksp, the solution is unsaturated

Either way, no ppte will form!

• The solubility of ionic substances can be determined
from Ksp values
Problem 3.
• Find the solubility of silver sulfate given a Ksp for silver
sulfate of 1.2 x 10-5 at 25 oC.
• Write out equilibrium & set up equilibrium table

Ag2SO4(s)  2Ag+(aq) + SO42-(aq)

s 2s s
let s = solubility of silver sulfate
Ksp = [Ag+]2[SO42-] = (2s)2s = 4s3
5
1. 2 X 10
s3  0.014 M
4
 Factors Which Affect Solubility

• Important solution factors which may affect the solubility

of ionic substances in water

– Temperature - solubility is temperature dependent

– Common ions - the presence of common ions in
solution lowers solubility
– pH - solution pH can affect solubility if the anion of
the ionic solid (i.e., X) is the conjugate base of a
weak acid
– Complex ions - ammonia reacts with many metal
ions in solution through complexation reactions
SOLUBILITY GRAPH OF SALTS IN
WATER

SOLUTION AND SOLUBILITIES 20

 SOLUBILITY GRAPH OF GASES IN
WATER

Pressure has little effect on the solubility of liquids and solids. The solubility of gases is
strongly influenced by pressure. Gases dissolve more at high pressure.

SOLUTION AND SOLUBILITIES 21

 The Common Ion Effect on Solubility
The solubility of MgF2 in pure water is 2.6 x 10-4 mol/L.
What happens to the solubility if we dissolve the MgF2 in
a solution of NaF, instead of pure water?
Explaining the Common Ion Effect

The presence of a common ion in a solution will

lower the solubility of a salt.

• LeChatelier’s Principle:
The addition of the common ion will shift the
solubility equilibrium backwards. This means
that there is more solid salt in the solution and
therefore the solubility is lower!
 Example
• What is the solubility of strontium sulfate, SrSO4, in 0.15 M
sodium sulfate, Na2SO4? Ksp (SrSO4) = 2.5 x 10-7
The initial concentration of SO42- is 0.15 M,
SrSO4 (s) Sr2+ + SO42-
Starting 0 0.15
Change +x +x
Equilibrium x x + 0.15

Solve solubility product expression for x,

[Sr2+][SO42-] = Ksp
(x)(0.15 + x)  (x)(0.15)  2.5 x 10-7
x = 1.7 x 10-6 M And convert to g/L

1.7 x 10-6 mol 184 g

L
x 1 mol = 3.1 x 10-4 g/L
The common ion effect occurs when the ionic solid is dissolved in a
solution which already contains a common ion
For example, what is the solubility of PbCl2 in a 0.100 M
NaCl(aq) solution?
Chloride ion is common to both NaCl and PbCl2 and is
called the common ion

PbCl2  Pb2+(aq) + 2 Cl-(aq)

s s 2s (0.100 M)

Assume the [Cl-] remains constant at 0.100 M through the greatly

abundant chloride ion contributed by NaCl

1.2 X 10-5 = [Pb2+][0.100]2

s = [Pb2+] = 1.2 X 10-5/[0.100]2 = 1.2 x 10-3 M
 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.
 pH and Solubility
Solubility Reaction:
CuS(s) ↔ Cu2+(aq) + S2-(aq) Ksp= 8.5 x 10-45

Reaction of Sulfide with Acid:

S2-(aq) + H3O+(aq) ↔ HS-(aq) + H2O(l)
Kb = Kw/Ka = (1.0 x 10-14)/1.3 x 10-13 = 7.7 x 10-2

Since sulfide is basic, CuS will dissolve in

acidic solution.
 Example
• Determine which pH is better for removing lead from drinking water.
In a) pH = 7.00 or b) pH = 13.00. (Ksp Pb(OH)2 = 1.2 x 10-15

Pb(OH)2 (s) Pb2+ (aq) + 2OH- (aq)

Problem Solved:

pH = 7.00 = 14.00 – pOH or pOH = 7.00 So [OH-] = 1.0 x 10-7 M

Ksp = 1.2 x 10-15 = [Pb2+][1 x 10-7]2 Pb2+ = 0.12 M

pH = 13.00 = 14.00 – pOH or pOH = 1.00 So [OH-] = 0.10 M

Ksp = 1.2 x 10-15 = [Pb2+][0.1]2 Pb2+ = 1.2 x 10-13 M

Therefore,
Thus, Molar Solubility of Pb2+ = 0.12 M at pH = 7.00
Molar solubility of Pb2+ = 1.0 x 10-13 M at pH = 13.00

At higher pH, the solubility of Pb2+ decreases.

 Complexation Effects on Solubility

• The formation of soluble metal complexes increases the

solubility of sparingly soluble ionic solids
• An example is the reaction of silver ion with ammonia:
AgCl(s)  Ag+(aq) + Cl-(aq) Ksp = 1.8 x 10-10
Ag+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq) Kf = 2.0 x 107
Kc = KspX Kf = 3.6 x 10-3
Ag(NH3)2+ = complex ion
Ag+ = Lewis acid (electron pair acceptor)
NH3 = Lewis base (electron pair donor)

• The chemical processes are coupled, such that

AgCl(s) + 2 NH3(aq)  Ag(NH3)2+(aq) + Cl-(aq)


[Ag(NH 3 )2 ][Cl  ] 3
Kc   3.6  10
[NH 3 ] 2
The formation of complex ions
Ammonia will react with silver (I) ion:

Ag+ + NH3  Ag(NH3)+ K1 = 2.1 x 103

Ag(NH3)+ + NH3  Ag(NH3)2+ K2 = 8.2 x 103

Ag+ + 2NH3  Ag(NH3)2+ Kf = K1K2 = 1.7 x 107

Let’s examine some reactions:
Add these
AgCl (s)  Ag+ + Cl- Ksp two reactions

Ag+ + 2NH3  Ag(NH3)2+ Kf

AgCl (s) + 2NH3  Ag(NH3)2+ + Cl- KspKf

How is the solubility of AgCl (s) influenced?

According to Le Chatelier’s principle- the
solubility of AgCl (s) increases as the
(NH3) is increased.
 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
 This is a method which allows separation of

metal ions or anions based on solubility

e.g. Cl-, Br-, and I- can be separated by
selective precipitation with silver ions

Ksp AgCl  1.8 x 10-10

AgBr  3.3 x 10-13

AgI  1.5 x 10-16
 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.
 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.
 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)

Law of Mass Action
The mass action law
Example 1:
2.94 moles of I2 and 8.1 of H2 form at equilibrium at a constant
temperature 5.64 moles of HI. Calculate the equilibrium constant.

The reaction is: I2 + H2  2 HI and the constant k=cHI2/(cH2 cI2)

It is possible to draw up the following table:
Table H2 I2 HI
Initial moles 8.1 2.94 ---
Formed moles --- ---- 5.64
Used moles 2.82(5.64/2) 2.82 ----
At equilibrium 5.28 0.12 5.64
K = (5.64)2 / (5.28 x 0.12) = 50.2
Complex Ion Formation
A complex ion is a polyatomic cation or anion
consisting of a central metal atom or ion that has
other groups called ligands bonded to it

Common ligands

An example complex ion

Complex Ion Formation
The formation reaction of a complex ion is reversible,
and the equilibrium state in the reaction is described
through an equilibrium constant called a formation
constant, represented by the symbol Kf
Some Formation Constants
Complex Ion Formation and Solubilities

Even though AgCl is insoluble in water, it does

dissolve in aqueous ammonia to form the complex
ion [Ag(NH3)2]+
The Kc values are directly proportional to Ksp because Kf is
the same for each reaction
The source of Ag+ ions doesn’t matter ... AgCl, AgBr, AgI,
etc ... the complex ion is still Ag(NH3)2+

In this case, as Kc , Ksp 

In NH3, order of decreasing solubility is

AgCl > AgBr > AgI