What is a disproportionation reaction?

Disproportionation is a type of redox reaction where the same element is both reduced and oxidized simultaneously. It can be described as a 'self-reduction / oxidation' reaction. 

 In this type of reaction, some atoms of an element are reduced while others are oxidized at the same time. The specific reaction that occurs often depends on conditions such as temperature.

Examples of reactions
  • In cold dilute aqueous NaOH, chlorine reacts with NaOH in a disproportionation reaction.
    \( \text{Cl}_2\text{(aq)} + 2\text{NaOH(aq)} \rightarrow \text{NaCl(aq)} + \text{NaClO(aq)} + \text{H}_2\text{O(l)} \)
  • One Cl atom is oxidised from 0 to +1. The other is reduced from 0 to -1. In other words:
    \( \text{Cl} + e^- \rightarrow \text{Cl}^- \)
    \( \text{Cl} \rightarrow \text{Cl}^+ + e^- \)
  • In hot concentrated aqueous NaOH, ClO3− (chlorate (V)) ions are produced instead of ClO- (hypochlorite). 
    \( 3\text{Cl}_2\text{(aq)} + 6\text{NaOH(aq)} \rightarrow 5\text{NaCl(aq)} + \text{NaClO}_3\text{(aq)} + 3\text{H}_2\text{O(l)} \)
  • 5 Cl atoms are reduced from 0 to -1. One Cl atom is oxidised from 0 to +5.
    \( 5\text{Cl} + e^- \rightarrow 5\text{Cl}^- \)
    \( \text{Cl} \rightarrow \text{Cl}^{5+} + 5e^- \)