Comproportionation

Comproportionation or synproportionation is a chemical reaction where two reactants containing the same element but with different oxidation numbers, form a compound having an intermediate oxidation number. It is the opposite of 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.

A Frost diagram is another way of displaying the reduction potentials for the various oxidation states of a given element, X. It shows nE against the oxidation number N: here, E is the reduction potential for the X(N)/X(0) couple, and n is the number of electrons transferred in the conversion of X(N) to X(0)

Examples

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
2 FeCl3 + Fe → 3 FeCl2

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. Wildermuth, Egon; Stark, Hans; Friedrich, Gabriele; Ebenhöch, Franz Ludwig; Kühborth, Brigitte; Silver, Jack; Rituper, Rafael (2000). "Iron Compounds". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a14_591. ISBN 3527306730.
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