Preparation of KMnO4 from pyrolusite ore (MnO2) involves the following steps:
(i) Fusion of ore with alkali in presence of air : Pyrolusite ore is fused with alkali in the presence of air when potassium manganate is obtained as green mass.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
(green mass)
The green mass is dissolved in water to obtain aqueous solution of potassium manganate. The insoluble impurities of sand and other metal oxides are removed by filtration.
(ii) Oxidation of manganate into permanganate : The aqueous solution of K2MnO4 is oxidised electrolytically or by using ozone or Cl2 to obtain potassium permanganate. The process is carried out till green colour disappear and solution acquires distinct pink colour.
Potassium permanganate is crystallised out from the solution.
Oxidising Properties: It acts as a powerful oxidising agent in different media differently. In acidic medium, it oxidises iron(II) salts to iron(III) salts,
SO2 to H2SO4 and oxalic acid to CO2 and H2O.
(a) It oxidises iron(II) salt to iron(III) salts.
2MnO42–+ 16H++ 10Fe2+ → 2Mn2+ + 8H2O + 10Fe3+
(b) It oxidised sulphur dioxide to sulphuric acid.
2MnO4– + 5SO2 + 2H2O → 5SO42– + 2Mn2+ 4H+
(c) It oxidises oxalic acid to CO2 and H2O
2MnO4– + 16H+ + 5C2O42 → 2Mn2+ + 8H2O + 10CO2
For M2+/M and M3+/M2+ systems the E° values for some metals are as follows:
Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V
Mn2+/Mn – 1.2 V Mn3+/Mn2+ + 1.5 V
Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V
Use this data to comment upon
(a) The stability of Fe3+ in acid solution as compared to that of Cr3+ or Mn3+ and
(b) In case with which iron can be oxidised as compared to the similar process for either chromium or manganese metal
Predict which of the following will be coloured in aqueous solution? Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+. Give reason for each.
Compare the chemistry of actinides with that of the lanthanoids with special reference to:
(i) electronic configuration, (ii) atomic and ionic sizes, (iii) oxidation state (iv) chemical reactivity.
How would you account for the following:
(a) Of the d4 species, Cr2+ is strongly reducing while manganese(III) is strongly oxidising.
(b) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidized.
(c) The d1 configuration is very unstable in ions.