Spinel group

The spinels are any of a class of minerals of general formulation A2+
B3+
2O2−
4 which crystallise in the cubic (isometric) crystal system, with the oxide anions arranged in a cubic close-packed lattice and the cations A and B occupying some or all of the octahedral and tetrahedral sites in the lattice. Although the charges of A and B in the prototypical spinel structure are +2 and +3, respectively, other combinations incorporating divalent, trivalent, or tetravalent cations, including magnesium, zinc, iron, manganese, aluminium, chromium, titanium, and silicon, are also possible. The anion is normally oxygen; when other chalcogenides constitute the anion sublattice the structure is referred to as a thiospinel.

A and B can also be the same metal with different valences, as is the case with magnetite, Fe3O4 (as Fe2+
Fe3+
2O2−
4), which is the most abundant member of the spinel group.[1] Spinels are grouped in series by the B cation.

Spinel group members

Members of the spinel group include:[2]

There are many more compounds with a spinel structure, e.g. the thiospinels and selenospinels, that can be synthesized in the lab or in some cases occur as minerals.

The heterogeneity of spinel group members varies based on composition with ferrous and magnesium based members varying greatly as in solid solution, which requires similarly sized cations. However, ferric and aluminium based spinels are almost entirely homogeneous due to their large size difference.[3]

The spinel structure

Crystal structure of spinel

Normal spinel structures are usually cubic close-packed oxides with two tetrahedral and one octahedral sites per formula unit. The tetrahedral spaces are smaller than the octahedral spaces. B3+ ions occupy half the octahedral holes, while A2+ ions occupy one-eighth of the tetrahedral holes. Mineral spinel MgAl2O4 has a normal spinel structure.

Inverse spinel structures have a different cation distribution in that all of the A cations and half of the B cations occupy octahedral sites, while the other half of the B cations occupy tetrahedral sites. An example of an inverse spinel is Fe3O4, if the Fe2+ (A2+) ions are d6 high-spin and the Fe3+ (B3+) ions are d5 high-spin.

In addition, there are intermediate cases where the cation distribution can be described as (A1−xBx)[A x⁄2B1− x⁄2]2O4, where parentheses () and brackets [] are used to denote tetrahedral and octahedral sites, respectively. The so-called inversion degree, x, adopts values between 0 (normal) and 1 (inverse), and is equal to  2⁄3 for a completely random cation distribution.

In order to explain the adoption of a particular cation distribution in a spinel structure, one must take into account the crystal field stabilization energies (CFSE) of the transition metals present. Some ions may have a distinct preference for the octahedral site depending on the d-electron count. If the A2+ ions have a strong preference for the octahedral site, they will displace half of the B3+ ions from the octahedral sites to tetrahedral sites. Similarly, if the B3+ ions have a low or zero octahedral site stabilization energy (OSSE), then they will occupy tetrahedral sites, leaving octahedral sites for the A2+ ions.

Burdett and co-workers proposed an alternative treatment of the problem of spinel inversion, using the relative sizes of the s and p atomic orbitals of the two types of atom to determine their site preferences.[4] This is because the dominant stabilizing interaction in the solids is not the crystal field stabilization energy generated by the interaction of the ligands with the d electrons, but the σ-type interactions between the metal cations and the oxide anions. This rationale can explain anomalies in the spinel structures that crystal-field theory cannot, such as the marked preference of Al3+ cations for octahedral sites or of Zn2+ for tetrahedral sites, which crystal field theory would predict neither has a site preference. Only in cases where this size-based approach indicates no preference for one structure over another do crystal field effects make any difference; in effect they are just a small perturbation that can sometimes affect the relative preferences, but which often do not.

See also

Taaffeite, which has the same empirical formula as a spinel, but the chemical formula is four times as large.

Musgravite, another and even rarer "multi-spinel".

Further reading

References

  1. ↑ Ernst, W. G. (1969). Earth Materials (Print ed.). Englewood Cliffs, NJ: Prentice-Hall. p. 58.
  2. ↑ Spinel group at Mindat
  3. ↑ Ernst, W. G. (1969). Earth Materials (Print ed.). Englewood Cliffs, NJ: Prentice-Hall. p. 59.
  4. ↑ J.K. Burdett, G.L. Price and S.L. Price (1982). "Role of the crystal-field theory in determining the structures of spinels". J. Am. Chem. Soc. 104: 92–95. doi:10.1021/ja00365a019.
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