Comproportionation

Comproportionation or synproportionation is a chemical reaction where two reactants, each containing the same element but with a different oxidation number, form a product in which the elements involved reach the same oxidation number. It is opposite to disproportionation.[1]

Frost diagrams

The tendency of two species to disproportionate or comproportionate can be determined by examining the Frost diagram of the oxidation states; if a species' value of ΔG/F is lower than the line joining the two oxidation numbers on either side of it, then it is more stable and if in a solution, these two species will undergo comproportionation.

Examples

  • In lead batteries, the spontaneous reaction is:
Pb + PbO2 + 2 H2SO4 → 2 PbSO4 + 2 H2O
  • The laboratory preparation of manganese dioxide involves comproportionation of Mn(II) and Mn(VII) reagents:
2 KMnO
4
+ 3 MnSO
4
+ 2 H
2
O
→ 5 MnO
2
+ K
2
SO
4
+ 2 H
2
SO
4
  • 15 Se + SeCl4 + 4 AlCl3 → 2 Se8[AlCl4]2
  • In the Claus Process, two gaseous compounds of sulfur comproportionate in the presence of a catalyst to give elemental sulfur:
2 H2S + SO2 → 3 S + 2 H2O
IO3 + 5 I + 6 H + → 3 I2 + 3 H2O
NH4+ + NO2 → N2 + 2H2O
  • In organotin chemistry, the mixed alkyl tin chlorides are produced by redistribution, a reaction called the Kocheshkov comproportionation:[2]
3 SnBu4 + SnCl4 → 4 SnBu3Cl

References

  1. Shriver, D. F.; Atkins, P. W.; Overton, T. L.; Rourke, J. P.; Weller, M. T.; Armstrong, F. A. “Inorganic Chemistry” W. H. Freeman, New York, 2006. ISBN 0-7167-4878-9.
  2. G. G. Graf (2005). "Tin, Tin Alloys, and Tin Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_049. ISBN 978-3527306732.
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