Formation of Coloured lons
When an electron from a lower energy d orbital is excited to higher Complementary Colours
ergy d orbital, the energy of excitation corresponds to the frequency
of light absorbed. This frequency absorbed generally lies in the visible Red Orange
region. The colour observed corresponds to the complementary colour
of light absorbed. Violet Yellow
The frequency of light that is absorbed is determined by Blue Green
(i) Nature of ligand
(ii) Size of metal ion
(iii) Oxidation state of metal
Colours of Some of the First Row (aquated) Transition Metal lons
Configuration Example Colour
3+
3d Sc colourless
3d Ti colourless
3d' Ti purple
3d blue
3d green
3 violet
3+
3g3 Cr violet
3¢ Mn* violet
2+
3d Cr blue
2+
3o Mn pink
3g Fe yellow
3df Fe green
34 2+
3d°,3d Co, Co blue pink
3d green
3d Cu2+ blue
2+
3g10 Zn colourless
complex
bond
for
some
orbitals
of
d
of Example
availability
compounds.
the
and
complex
charges
of
ionic (CuCI
number
high (Mn(H,0).J,
ions,
a
form
Compound
metal
[Cu(NH,),,
elements
the
of
Complex are
compounds/ions
sizetransition
(Fe(CN).
smaller
of formation,
Formation
to
Due
2.2 COMPOUNDS OF d-BLOCK ELEMENTS:
POTASSIUM PERMANGANATE (KMnO,) :
(a) Preparation
HIs prepared by fusing pyrolusite (MnO,) either with KOH or K,CO, in presence of atrncspheric
Oxygen or any other oxidising agent such as KNO,. The fused mass turns green with the forrmation of
3
potassium manganate, K,MnO,.
2Mn0, +4KOH + 0,’2K,MnO, ++2H,0
2MnO, + 2K,CO, +O, ’ 2K,MnO, + 2CO,
The fused mass is extracted with water and the solution is now treated with a current of chlorine or
0Z0ne or carbon dioxide to convert manganate into permanganate.
2K,MnO, + Cl, ’ 2KMnO, + 2KCI
2K MnO, + H,0 + O, ’2KMnO, +2KOH + 0,
3K_MnO, +2C0,’ 2KMnO, +MnO, ++2K,co,
(disproportionate in acidic medium)
Commercially it is prepared by fusion of MnO, with KOH followed by electrolytic oxidation of manganate.
Fused with KOH
MnO, ’ MnO,
MnO, (green) ’ MnO, (purple)
In the laboratory, a manganese(l) ion salt is oxidised by peroxodisulphate to pemanganate
2Mn' +55,0, + 8H,0’ 2MnO, + 10S0, + 16H
(b) Physical property : It is purple coloured crystaline compound. It ismoderately soluble in water at
room temnperature,
() Chemical property:
Effect of heating 2KMnO, Bl’ K,MnO, + MnO, + O,
On treatrment with concentrated H,SO, (KMnO, is taken in excess), it foms manganese
heptoxide
which decomposes explosively on heating.
KMnO, Cnc l, N0,-, Mn,0, (an explosive)
Potassium permanganate acts as an oxidising agent in weak alkaline, neutral or acidic
solutions.
acidified KMnO, (purple) Neutral or weak alkaline KMnO,
Br BrO,
H,S
2
SO, SO,?
S,0, SO,2
NO, NO,
Mn+2 MnO,
Fe*2 Fe+
C Cl, MnO,
Br Brz
H,C,0, CO,+H,0
S,0,2 S,o,?
Mn² (colourless)
oxidises HCl to CI,.
Note :- Hydrochloric acid is not used for acidification of KMnO, because KMnO,
(I) POTASSIUM DICHROMATE (K,Cr,0,) :
(a) Preparation : The chromite ore is fused with sodium carbonate in presence of alr.
4FeO. Cr,O, (chromite ore) + 8Na,CO, + 70, Fusion
8Na,CrO, + 2Fe,O, + 8C0,1
(residue)
The yellow solution of Na,CrO, is filtered and acidified with sulphuric acid to give a solution from
which orange sodium dichromate (Na,Cr,0,)can be crystallised.
2Na,CrO, + H,SO,’ Na,Cr,0, + Na,SO, + H,0
Sodium dichromate is more soluble than potassium dichromate so K,Cr,0, is prepared by treating
solution of Na,Cr,, with KCI.
Na,Cr,O, + 2KCI K,Cr,0, + 2NaCI
K,Cr,0, is preferred over Na,Cr,0, as a primary standard in volumetric analysis (titration) because
Na,Cr,0, is hygroscopic in nature but K,Cr,0, is not.
CrO,'Cr,0,?OH
Yellow Orange
(b) Physical property: It is orange-red coloured crystalline compound. It is moderately soluble in cold
water but freely soluble in hot water. It melts at 398°C.
(c) Chemical property :
Effect of heating: On strongly heating, it decomposes with liberating
oxygen.
2K,Cr,0, ’ 2K,CrO, +Cr,0, +
2
In acidic medium K,Cr,0, acts as an oxidising agent.
Acidified K,Cr,0, (Orange)
H,S S
SO, SO,2
NO, NO3
SO,2 SO,2
Sn+2 Snt4
Fe+2 Fe+3
Br Brz
C,H,OH CH,COOH
Cr+s
(Green)
1. Chromyl chloride test (used to identify ionic chlorides)
NaCl + K,Cr,0, + H,SO, ’ CrO,C1, (Red orange vapour)
NaOH solution
Na,CrO,(Yellow)
deep blue solution due to
2. Acidified K,Cr,0, solution reacts with H,0, in a etheral solution to give a
the formation of CrO,.
Cr,0, + 2H + 4H,0,’ 2Cr0, + 5H,0
