Variable Oxidation States – The Intuition
Think of an atom as having a wallet with two compartments. In most elements, one compartment is much easier to open than the other — you can only take money from the shallow one, so the amount you can spend (the oxidation state) is fixed. For transition metals, both compartments are at nearly the same depth. You can reach into either, and you can take different combinations of notes from each. That is variable oxidation states in a nutshell.
Iron, for example, can lose two electrons to become Fe2+ or three to become Fe3+. Manganese can show +2, +3, +4, +6, and +7. This is not random — it follows a clear pattern rooted in energy.
The Precise Statement
Transition metals exhibit variable oxidation states because the (n−1)d and ns subshells have similar energies. Electrons can be removed from both subshells in different numbers, producing a range of stable positive oxidation states.
The key is similar energies. In main-group elements (like sodium or chlorine), the outermost ns and np electrons are far higher in energy than the inner core — you lose only the valence electrons, and the oxidation state is fixed. In transition metals, the (n−1)d orbital is not much lower than the ns orbital. Both are close enough that losing a few d electrons along with the s electrons costs comparable energy.
Why This Happens – The Energy Picture
For a transition metal like iron ([Ar]3d64s2), the 4s orbital is actually slightly lower in energy than the 3d when the atom is neutral. But once you start removing electrons, the energy ordering shifts. The first two electrons lost are from the 4s orbital (giving Fe2+). The next electron lost comes from the 3d orbital (giving Fe3+). Because the 3d and 4s are so close in energy, removing that third electron does not require a huge jump in energy — it is feasible.
The actual order of filling is 4s before 3d, but the order of removal is also 4s first. This is not a contradiction — it is a consequence of how orbital energies change as the nuclear charge increases.
The Pattern Across the Series
For the first transition series (Sc to Zn), the common oxidation states are:
| Element | Common oxidation states |
|---|
| Sc | +3 |
| Ti | +3, +4 |
| V | +2, +3, +4, +5 |
| Cr | +2, +3, +6 |
| Mn | +2, +3, +4, +6, +7 |
| Fe | +2, +3 |
| Co | +2, +3 |
| Ni | +2 |
| Cu | +1, +2 |
| Zn | +2 |
Notice the trend: the maximum oxidation state increases from Sc (+3) to Mn (+7), then decreases. The maximum possible oxidation state equals the total number of electrons in the (n−1)d and ns orbitals (the "group number" for many). Manganese, with 3d54s2, can lose all seven — giving MnO4− where Mn is +7. After manganese, the d orbitals become more stable (higher effective nuclear charge), and it becomes harder to remove all of them.
Stability and the Environment
Not all oxidation states are equally stable. The stability depends on:
- The medium: Cr3+ is stable in acidic solution, but Cr6+ (as chromate) is stable in alkaline medium.
- The ligand: Some oxidation states are stabilised by certain ligands (this is where coordination chemistry meets redox). …