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
- 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
2O→ 5 MnO
2 + K
2SO
4 + 2 H
2SO
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
- In halogen chemistry:
- IO3− + 5 I− + 6 H + → 3 I2 + 3 H2O
- In anammox chemistry:
- NH4+ + NO2− → N2 + 2H2O
- Iron(III) chloride reacts with iron powder to form iron(II) chloride:[2]
- 2 FeCl3 + Fe → 3 FeCl2
References
- 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.
- 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.