Oxides and Oxoanions of Metals
These oxides are generally formed by the reaction of metals with oxygen at high temperatures. All the
metals except scandium form MO oxides which are ionic. The highest oxidation number in the oxides,
coincides with the group number and is attained in Sc2O3 to Mn2O7 . Beyond group 7, no higher oxides
of iron above Fe2O3 are known.
In the case of Mn, Mn2O7 is a covalent green oil.
Even CrO3 and V2O5 have low melting points. In these higher oxides, the acidic character is
predominant.
Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7 .
V2O5 is, however, amphoteric though mainly acidic which reacts with alkalies as well as acids to give
VO4 3- and VO4 + respectively. The well characterised CrO is basic but Cr2O3 is amphoteric.
Potassium dichromate (K2Cr2O7 )
Preparation: From Chromite ore (FeCr2O4 )
• 4 FeCr2O4 + 8 Na2CO3+ 7O2 8 Na2CrO4+ 2 Fe2O3+ CO2 (chromite ore)
• 2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O • Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
• Orange crystals of K2Cr2O7 are obtained on crystallisation.
❖ Physical Properties:
•Orange-red coloured crystalline compound.
•Moderately soluble in cold water but freely soluble in hot water.
•It melts at 398°C.
• K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric estimation because Na2Cr2O7
is hygroscopic in nature but K2Cr2O7 is not.
Effect of pH on Potassium dichromate
• Cr2O7 2- + 2 OH- → 2 CrO4 2- + H2O (pH >7)
(Orange) (Yellow)
• 2 CrO4 + 2 H → Cr2O7 2- + H2O (pH <7)
2- +
(Yellow) (orange)
Oxidising nature of Potassium dichromate
Powerful oxidising agent in acidic medium (dil. H2SO4 )
Cr2O7 2- + 14H+ + 6e- → 2Cr3+ + 7H2O (E° = 1.33 V)
It shows following redox reactions;
• 6Fe2+ + Cr2O7 2- + 14 H+ → 6Fe3+ + 2Cr3+ + 7H2O
• 6I- + Cr2O7 2- + 14 H+ → 3I2 + 2Cr3+ + 7H2O
• 3Sn2+ + Cr2O7 2- + 14 H+ → 3Sn4+ + 2Cr3+ + 7H2O
• 3H2S + Cr2O7 2- + 14 H+ → 3S + 2Cr3+ + 7H2O
• Note: Oxidation state of Cr changes from +6 to +3
Uses Of Potassium Dichromate
• Used as a primary standard in volumetric analysis for the estimation of reducing agents such as oxalic
acid, ferrous ions, iodide ions, etc.
• For tanning of leather, calico printing, photography etc.
•As a cleansing agent for glass ware in the form of chromic acid.
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Potassium permanganate (KMnO4)
Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an oxidising
agent like KNO3. This produces the dark green K2MnO4 which disproportionates in a neutral or acidic
solution to give permanganate.
Preparation: From pyrolusite ore (MnO2)
• 2MnO2 + 4KOH + O2 → 2K2MnO4 (dark green) + 2H2O (K2MnO4 → 2K+ + MnO42- )
• 3MnO4 2- + 4H+ → 2MnO4- + 2H2O + MnO2
Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (Vl)
In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.
2Mn2+ + 5S2O82- + 8H2O → 2MnO4- + 10SO4 2- + 16H+
❖ Physical Properties:
•It is purple coloured crystalline compound which are isostructural with those of KClO4.
•Sparingly soluble in water at room temperature (6.4 g/100 g of water at 293 K), but when heated it
decomposes at 513 K.
•Effect of heating •2KMnO4 → K2MnO4 + MnO2 + O2
It has two physical properties of considerable interest: its intense colour and its weak temperature
dependent paramagnetism.
The π-bonding takes place by overlap of p orbitals of oxygen with d orbitals of manganese.
•Effect of pH
MnO4 – (OH-) = MnO42- (H+)
• Oxidising nature of potassium permanganate
• KMnO4 shows strong oxidising nature.
• It shows different oxidising nature in different medium.
❖ Acidic medium: MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O
❖ Neutral or faintly alkaline medium: MnO4 - + 2H2O + 3e- → MnO2 + 4OH-
❖ Strongly alkaline medium: MnO4- + e-→ MnO42-
Oxidising nature of KMnO4 • In acidic medium (presence of dil. H2SO4):
In acid solutions:
(a) Iodine is liberated from potassium iodide :
10I-+ 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5Fe2+ + MnO4- + 8H+ ——> Mn2+ + 4H2O + 5Fe3+
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42- + 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 10CO2
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Oxalic acid is oxidised to CO2 (This reaction is slow at room temperature, but is rapid at 60°C. Mn(II)
ions produced catalyse the reaction; thus the reaction is autocatalytic)
(d) Hydrogen sulphide is oxidised, sulphur being precipitated:
H2S —> 2H+ + S2-
5S2- + 2MnO4- + 16H+ ——> 2Mn2+ + 8H2O + 5S
(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:
5SO32-+ 2MnO4-+ 6H+ ——> 2Mn2+ + 3H2O + 5SO42-
(f) Nitrite is oxidised to nitrate:
5NO2- + 2MnO4- + 6H+ ——> 2Mn2+ + 5NO3- + 3H2O
(g) SO2 is oxidised to H2SO4
(SO2 + 2H2O → SO42- + 4H+ +2e-) x 5
(MnO4- + 8H+ + 5e- → Mn2+ + 4H2O) x 2
5SO2 + 2MnO4- + 2H2O → 5SO42- + 2Mn2+ + 4H+
Oxidising nature of KMnO4 In slightly alkaline & neutral medium :
In slightly alkaline medium KMnO4 is reduced to MnO2 (MnO4- to MnO2 )
(a) A notable reaction is the oxidation of iodide to iodate:
2 MnO4- + I- + H2O → 2 MnO2 + IO3- + 2 OH-
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8 MnO4-+ 3 S2O32- + H2O → 8 MnO2 + 6 SO42- + 2OH-
Point to be noted: Permanganometric titrations in the presence of HCl are unsatisfactory as HCl is
oxidised to chlorine by KMnO4
Uses of KMnO4
• Used as an oxidising agent in laboratory and industry.
• Alkaline potassium permanganate is called Baeyer's reagent. This reagent is used in organic chemistry
for testing unsaturation.
• KMnO4 is used in the manufacture of saccharin, benzoic acid, acetaldehyde,etc.
• KMnO4 is used as a reagent in qualitative analysis and as primary standard in quantitative analysis.
• KMnO4 is used as an antiseptic
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Note: KMnO4 (Mn7+) has d0 in Mn and
yet it is coloured because of charge
transfer from oxygen to metal atom.
