D & f- Block Elements

General Trends in Properties of First Row

Elements
Metallic character.
Ionization Enthalpy
Oxidation states
Atomic & ionic radii
Colour
Catalytic properties
Magnetic properties
Formation of interstitial compounds
Alloy formation

Preparation of K2 Cr2 O7
Preparation of K2 Cr2 O7from Chromite ore
Step I: Concentration of Ore: Powdered
Chromite ore is concentrated by washing
with current of water in hydraulic classifier.

Step II: Roasting : Conversion of chromite

ore into sodium chromate:
Concentrated ore is mixed with sodium
carbonate & lime stone & roasted with
excess air in reverberatory furnace
4FeO.Cr2O3+ 8Na2CO3+ 7O2
2Fe2O3+8CO2+8Na2CrO4
Roasted mass is extracted with water.
sodium chromate goes in solution &
insoluble substances are separated by

Step III: Conversion of sodium chromate into

sodium dichromate:
2Na2CrO4 +H2SO4 -- Na2Cr2O7+ Na2
SO4+H2O
On concentration less soluble Na2SO4
crystallizes out. Crystals are separated by
filtration & concentrated solution of
sodium dichromate is obtained

Step IV: Conversion of sodium dichromate into

potassium dichromate:
Na2Cr2O7+ 2KCl---- K2Cr2O7+ 2NaCl
Concentrated solution of sodium dichromate is
treated with calculated amount of KCl. Double
decomposition reaction take place forming
K2Cr2O7 & NaCl.
Solution is concentrated & cooled. Less soluble
K2Cr2O7 separates as orange red crystals & NaCl
remains in solution

Properties of K2Cr2O7
Action of alkali
Oxidizing properties
Formation of chromyl
chloride

I)Action of alkali:
K2Cr2O7+ 2KOH------ K2CrO4+H2O
II) Oxidizing properties:
K2Cr2O7 is a good oxidizing agent in acidic
medium.
In this process K2Cr2O7 is reduced to
Chromic sulphate Cr2(SO4)3

Action on Ferrous sulphate

K2Cr2O7+ 6FeSO4+ 7 H2SO4 ------
K2SO4+ Cr2(SO4)3 +3Fe2(SO4)3+7H2O
Action on Potassium iodide
K2Cr2O7+ 6KI+ 7 H2SO4 ------
4K2SO4+ Cr2(SO4)3 +7H2O + 3I2

Action on Hydrogen sulphide

K2Cr2O7+ 4H2SO4 + 3H2S------
K2SO4+ Cr2(SO4)3 +7H2O+3S
Action on Sulphur dioxide
K2Cr2O7+ 3SO2+ H2SO4 ------
K2SO4+ Cr2(SO4)3 +H2O

Primary & secondary alcohols are oxidized to

Aldehydes & ketones respectively.
Aldehydes are further oxidized to
carboxylic acids.
CH3CH2OH + (O) -- CH3CHO + H2O
CH3CHO + (O) -- CH3COOH
CH3CHOH-CH3 + (O)--CH3COCH3 + H2O

Formation of Chromyl chloride

(CrO2Cl2)
K2Cr2O7+ 6H2SO4 + 4NaCl------
2KHSO4+ 4NaHSO4 +4CrO2Cl2
+3H2O

Structure of Chromate &

Dichromate ion
O
O

C
r
O

Uses of Potassium dichromate

As an oxidizing agent.
In the tanning of leather.
In dyeing.
In the manufacture of pigments & inks.
Used in the detection of chloride ion by
chromyl chloride test.

Preparation of KMnO4
KMnO4 is prepared from Pyrulosite
ore(MnO2) which is fused with alkali
metal hydroxide like KOH or K2CO3
and air or in presence of an oxidizing
agent like KNO3 or KClO3. A green
coloured K2MnO4 is obtained.

2MnO2+4KOH + O2 ---2K2MnO4 + 2H2O

2MnO2+2K2CO3 + O2 ---2K2MnO4 + 2CO2
MnO2+2KOH + KNO3 ---K2MnO4 + KNO2 +
H2O
3MnO2+6KOH + KClO3 --- 3K2MnO4 + KCl +
3H2O

The fused mass of K2MnO4 obtained is

treated with water & then converted into
KMnO4 either by oxidation or by
electrolysis.

a) By oxidation: Oxidation of K2MnO4 to KMnO4 is carried

out by H2SO4 by passing CO2 or Cl2 or O3 through the
solution.
3K2MnO4 + 2H2SO4 --- K2SO4+2KMnO4+2H2O+
MnO2
3K2MnO4+4CO2 + 2H2O --- 2KMnO4+MnO2 +KHCO3
2K2MnO4+ Cl2 --- 2KMnO4+ 2KCl
2K2MnO4+ H2O + O3 --- 2KMnO4+ 2KOH + O2

b)Electrolytic oxidation:
The manganate solution is electrolysd between iron
electrodes separated by diaphragm. The electrode
reactions are as follows:
At anode: MnO42- ----- MnO4- + egreen

purple

At cathode: 2H+ + 2e- ----- H2

The oxygen evolved at the anode converts manganate
into permanganate
2K2MnO4+ H2O + O ----- 2KMnO4+ 2KOH
The solution is filtered & evaporated to get deep purple
black crystals of KMnO4.

Properties:
i) It is a deep purple crystalline solid, moderately
soluble in water at room temperature.
ii) When heated to 473 K it decomposes giving
oxygen.
At red heat K2MnO4 further decomposes to
K2MnO3 and oxygen.
iii) With well cooled conc. Sulphuric acid KMnO 4
gives Mn2O7 which on warming decomposes to
MnO2
With warm conc. Sulphuric acid oxygen gas is
evolved.

Properties:
iv) When solid KMnO4 is heated in current of H2 gives
KOH , MnO and water vapours.
v) Oxidizing properties: It is a powerful oxidizing agent.
a) In neutral medium it oxidizes hot manganous sulphate
to manganese dioxide which is insoluble.
b) In alkaline medium it forms K2MnO4 which further
reduced to manganese dioxide.
c) In acidic medium it acts as oxidizing agent in
presence of dil sulphuric acid.

Structure of Manganate &

Permanganate

Uses of Potassium permanganate

As an disinfectant.
As oxidizing agent in the industry and
laboratory.
For detecting halides in qualitative analysis.
In volumetric analysis for estimation of ferrous
salts, oxalic acid etc.

f- Block Elements:
Lanthanoids:
i) The elements in which the last electron enters into
(n-2) f orbital are called as f- block elements.
ii) In all 28 elements from at. no. 58 to 71 and from 90 to
103 are called f-block elements.
iii) They are also called Inner Transition Elements
because of their periodic position and properties.
iv) There are two series of inner transition elements
Lanthanoids series (4f block elements ) and actinoids
series (5f block elements)

Lanthanoids series (4f block elements )

The elements of lanthanoid series are characterized
by the preferential filling of 4f orbital.
This series includes elements from Cerium(Z= 58) to
Lutetium (Z=71)
General Elec. Config.: [Xe] 4f1-14 , 5d0-1 , 6s2
Position :Lanthanoids belongs to 3 group and sixth
period.

Oxidation states: Common is +3

Chemical reactivity of Lanthanoids series :

1) Carbides: When lanthanoids are heated around 2500 0c
with carbon they form carbides having formulaes Ln3C,
LnC2, Ln2C3
2) Hydrides: The metals combine with hydrogen when
gently heated in the hydrogen gas.
3) Oxides: When burnt in oxygen they forms oxides with
formula Ln2O3
4) Reaction with nitrogen forms nitrides.
5) Reaction with mineral acids liberate hydrogen gas.
6) Reaction with water forms hydroxides and hydrogen gas.
7) Reaction with sulphur forms corresponding sulphides.

Lanthanoids Contraction & its consequences:

The gradual decrease in atomic & ionic radii or size of
lanthanoids with increase in the atomic number is
called lanthanoid contraction.
Effects:
a) Decrease in basicity.
b) Ionic radii of post lanthanoids.
Chemical Twins- Zr-Hf, Mo-W

Actinoids:
The elements of actinoid series are characterized by
the preferential filling of 5f orbital.
This series includes elements from Thorium(Z= 90)
to Lawrencium (Z=103)
General Elec. Config.: [Rn] 5f1-14 , 6d0-1 , 7s2
Position :Actinoids belongs to 3 group and seventh
period.

Oxidation states: Common is +3

Lanthanoids

Actinoids:

Electron enters 4f orbitals Electron enters 5f orbitals

3 group and sixth period.
3 group and seventh period.
Binding energy of 4f is
Binding energy of 4f is low
high
Only Promethium is
All members are radioactive
radioactive
Great tendency to form
Less tendency to form complexes
complexes
Hydroxides are less basic Hydroxides are more basic