D BLOCK ELEMENTS

Potassium Dichromate (K2Cr2O7)

Important chemical properties of K2Cr2O7:
1.

K2Cr2O7 is a powerful oxidizing agent. In acidic solution it takes up electrons from a reducing
agent and gets reduced to Cr3+.
Cr2O 72 + 14H+ + 6e
2Cr3+ + 7H2O

Some typical oxidation reactions are:

(i) Liberation of I2 from KI solution
Cr2O72 + 6I + 14H+
2Cr3+ + 7H2O + 3I2
(ii) Oxidation of Fe2+ to Fe3+:
2Cr3+ + 6Fe3+ + 7H2O
Cr2O 72 + 6Fe2+ + 14H+
(iii) Oxidation of SO 32 to SO 24
Cr2O 72 + 3SO 32 + 8H+
2Cr3+ + 3SO 24 + 4H2O
(iv) Oxidation of H2S to S and SO2 to sulphuric acid
Cr2O 72 + 3H2S + 8H+
2Cr3+ + 3S + 7H2O
2Cr3+ + H2O + 3SO 24
Cr2O 72 + 2H+ + 3SO2

2.

2K2CrO4 + H2O
K2Cr2O7 + 2KOH
orange red
yellow

2H2SO4
K2Cr2O7 + K2SO4 + H2O
Orange red

N. B:

In dichromate solution, the Cr2O 72 ions are in equilibrium with CrO 24 ions.
2CrO 24 + 2H+
Cr2O 72 + H2O

Orange red

yellow

In general, metal chromates are not precipitated in acidic medium because, chromate
dimerises to dichromates, which are soluble.
3.

Heating effect:
Strongheating

4K2Cr2O7
4K2CrO4 + 2Cr2O3 + 3O2
Structure:

_
O

Cr

Cr
O

_
O

Potassium Permanganate, KMnO4

The permanganate ion (MnO 4 ) is a strong oxidizing agent in solution. The course of the reaction
depends whether it is carried out in alkaline, neutral or acidic solution.
(A) In alkaline solution:
Alkali
2MnO2 + 2OH + 3[O]
2MnO 4 + H2O
Iodides are oxidized to iodates:
2MnO 4 + H2O + I
2MnO2 + 2OH + IO 3

(B) In neutral solution:

2MnO2 + 2OH + 3[O]
2MnO 4 + H2O
H2S is oxidized to S
2MnO2 + 3S + 2H2O + 2OH
2MnO 4 + 3H2S
Na2S2O3 is oxidized to Na2SO4 and S
2MnO2 + 3SO 24 + 3S + 2OH
2MnO 4 + 3S2O 32 + H2O
(C) In acidic solution:
2MnO 4 + 6H+
Mn2+ + 3H2O + 5[O]
2KMnO4 + 3H2SO4
K2SO4 + 2MnSO4 + 3H2O + 5[O]
2Mn2+ + 8H2O + 10Fe3+
2MnO 4 + 16H+ + 10Fe2+

2MnO 4 + 16H+ + 5C2O 24

2Mn2+ + 8H2O + 10CO2
2Mn2+ + 5SO 24 + 3H2O
2MnO 4 + 6H+ + 5SO 32

(nitrites
nitrates, arsenites
arsenates)
2Mn2+ + 8H2O + 5I2
2MnO 4 + 16H+ + 10I

Halogen hydracids
X2
2Mn2+ + 8H2O + 5X2
3MnO 4 + 16H+ + 10X

Heating effect:
240o C

2KMnO4
K2MnO4 + MnO2 + O2

IRON
FeO:

Non-stoichiometric, Fe0.95 O (metal deficient)

Basic oxide and dissolve readily in acids.
NaCl type crystal structure with some crystal lattice defect (O2 form CCP & Fe2+
occupy almost all of the octahedral voids).

Fe2O3: Non-stoichiometric, Fe1.95O3

Known in a number of modifications of which -Fe2O3 and Fe2O3are more
important. In -Fe2O3, the O2 have hcp arrangement and Fe3+ ions in two thirds of
the octahedral voids. -Fe2O3 is obtained by oxidizing Fe3O4. It has ccp
arrangement of O2 with Fe3+ ions randomly distributed in both the octahedral and
tetrahedral voids.
Fe3O4: Mixed oxide, can be written as FeO . Fe2O3.
Inverse spinel structure, O2 ions have ccp arrangement. All the Fe2+ ions are
present in octahedral voids whereas Fe3+ ions are half in octahedral voids and half
in tetrahedral voids created by the arrangement of oxide ions.
Ferrous Sulphate:
Known as green vitriol.

It is crystallized as FeSO4 . 7H2O.

o

300 C
high temperature
FeSO4.7H2O
2FeSO4
Fe2O3 + SO2 + SO3
-7H2 O

(green)

(white)

Fe2+ ion is a good reducing agent.

It reduces MnO 4 to Mn2+ and Cr2O 72 to Cr3+ in acidic medium.

It also reduces nitric acid to nitric oxide, Hg2+ to Hg and Sn4+ to Sn2+.

When NO2 gas is passed through the solution of FeSO4, it becomes black due to
the formation of FeSO4. NO.

Not a primary standard in volumetric analysis as it is susceptible to aerial

oxidation and dehydration.

Chlorides of Fe:
FeCl3 solid is almost black.

Sublimes at about 300oC, giving a dimeric gas.

Cl

Fe

Fe
Cl

Cl

Cl

Cl

Cl

(FeCl 3)2 dimer

anhydrous Salt is deliquescent and soluble in water, alcohol and ether.

Aqueous solution undergoes hydrolysis and is acidic towards litmus.

On hydrolysis, it does not give hydroxide, but gives a red-brown gelatinous

precipitate of the hydrous oxide Fe2O3(H2O)n.

Copper
Copper sulphate:
Crystallized as CuSO4 . 5H2O and known as blue vitriol.
o

100 C
350 C
strong heat

CuSO4 . H2O

CuO + SO3
CuSO4 . 5H2O

CuSO4
-4H2 O
720o C
-H2 O

blue

bluish white

white

With NH3, the Cu(OH)2 is first precipitated which dissolves in excess of ammonia
giving a complex, [Cu(NH3)4]SO4.
Cu(OH)2 + 2NH4OH + (NH4)2SO4
[Cu(NH3)SO4] + 4H2O

With KI, Cu2+ ion solution liberates I2

2Cu2+ + 4I
2CuI + I2

Halides of Cu: Cu(I) halides are partly covalent and have zinc blende structures with tetrahedrally
coordinated Cu+ ions.

In the vapour state, CuCl and CuBr are polymeric.

Cu(I) halides are insoluble in water. They dissolve in solutions containing an

excess of halide ions by forming soluble halide complexes such as [CuCl2],
[CuCl3]2 and [CuCl4]3. These and other Cu(I) complexes are tetrahedral in solid.

Cu(I) halides dissolve in strong HCl, HNO3 and aqueous solutions of NH3.

Cu(II) halides for ex: CuF2, CuCl2 and CuBr2 have distorted octahedral
arrangement with 4 bonds short and 2 bonds long.

CuCl absorbs CO gas forming CuCl . CO.

Zinc
Zinc Oxide (ZnO):
Obtained when ZnCO3, Zn(NO3)2 or Zn(OH)2 is strongly heated.

White powder, commonly known as philosphers wool.

Used as a white pigment in paint.

Also used in production of rubber, since it shortens the time taken for
vulcanization to occur.

is amphoteric, it dissolves in acids forming salts.

ZnCl2 + H2O
ZnO + 2HCl

It dissolves in alkali also forming zincates

ZnO + 2NaOH
Na2ZnO2 + H2O

White when cold, but turns yellow on heating and again returns to white on
cooling. The colour is due to defect in the solid structure.

Zinc Sulphate ZnSO4 . 7H2O

Known as white vitriol.

Prepared by the action of dilute H2SO4 on Zn, ZnO or ZnCO3.

Used to prepare Lithopone, a white pigment.

Above 70 C
Above 30 C
ZnSO4 . 6H2O
ZnSO4 .H2O
ZnSO4 . 7H2O
Below 70o C

above 280oC
o

800 C
ZnSO4
O2 + SO2 + ZnO

Halides:

Forms halides of the type, MX2.

Fluoride has higher m.pt. than the other halides

and not very soluble in water bz of their higher lattice energy.

In ZnF2, Zn2+ is octahedrally surrounded by Six F, ZnCl2, ZnBr2 and ZnI2 are
considered as closed packed arrays of halide ions with Zn2+ ions occupying one
quarter of the tetrahedral voids.

The chloride, bromide and iodide are hygroscopic and very soluble in water.

Zn(OH)2 + 2NH4Cl
ZnCl2 + 2NH4OH
[Zn(NH3)4]Cl2 + 4H2O.
Zn(OH)2 + 2NH4OH + 2NH4Cl