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GENERAL CHEMISTRY

STOICHIOMETRY

DISPROPORTIONATION

The reaction that involves simultaneous oxidation and reduction of atoms of same element from one oxidation state (OS) to two different oxidation states is known as disproportionation reaction.

disproportionation reaction

The minimum requirement for this reaction to occur is: the element undergoing disproportionation should exhibit minimum three different oxidation states.

Illustrations of disproportionation reaction

Dissociation of hydrogen peroxide

Dissociation of hydrogen peroxide is a disproportionation reaction. The oxygen atom in H2O2 is in -1 oxidation state. It is both oxidized to O2 (ox.st = 0) and reduced to H2O (ox.st = -2).

disproportionation of hydrogen peroxide

In above reaction, the relatively less stable peroxide disproportionate into relatively more stable compounds i.e. water and dioxygen.

Disproportionation of halogens (Cl2 ,Br2 , I2) in alkali

Except fluorine, halogens (Cl2 ,Br2 , I2) undergo disproportionation in alkaline medium.

They form halide and hypohalite in cold and dilute alkali.

disproportionation of chlorine in dilute alkali

Here, one chlorine atom is oxidized to +1 and second is reduced to -1 oxidation states.

Whereas, halide and halate are formed in hot and concentrated alkali.

disproportionation of chlorine in concentrated alkali

In this case, one chlorine atom loses 5 electrons and get oxidized to +5 state and five chlorine atoms are reduced to -1 state by accepting one electron each.

Disproportionation of phosphorus in alkali

Phosphorus disproportionates to phosphine and hypophosphite in alkaline medium. In this case, one P atom is reduced to -3 oxidation number (in PH3) and three P atoms get oxidized to +1 (in NaH2PO2).

disproportionation of phosphorus in alkali

Photolysis of Mercurous chloride, Hg2Cl2

Mercurous chloride undergoes disproportionation under UV light to give mercury and mercuric chloride. The Hg22+ ion is oxidized to Hg2+ and reduced to Hg.

disproportionation of mercurous chloride

Reaction of Nitrogen dioxide with water

Nitrogen dioxide, NO2 reacts with water to give nitric and nitrous acids (Ostwald process). It is a disproportionation reaction. The Nitrogen in NO2 is in +4 oxidation state. It is reduced to nitrous acid, HNO2 in which the OS of nitrogen is +3 and oxidized to nitric acid, HNO3 in which the OS of nitrogen is +5.

disproportionation of Nitrogen dioxide

 

 

 

 

 

 

Author: Aditya vardhan Vutturi