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Worked Examples · Example 6.1

Q.Suggest a condition under which magnesium could reduce alumina.

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Step 1 – Recall what an Ellingham diagram shows

The Ellingham diagram plots ΔfG∘\Delta_fG^\circ (per mole of O2_2 consumed) against temperature for the formation of various metal oxides. A line that lies lower (more negative ΔfG∘\Delta_fG^\circ) represents an oxide that is thermodynamically more stable at that temperature.

Step 2 – Rule for who reduces whom

If metal A's oxide-formation line lies below metal B's line at a given temperature, then A has a greater affinity for oxygen than B at that temperature, and A metal can reduce B's oxide (A takes the oxygen from B, forming AO and freeing B):

BxOy+(suitable multiple of) A→A2O…+BB_xO_y + \text{(suitable multiple of) } A \rightarrow A_2O_{\ldots} + B

Step 3 – Apply to Mg and Al

On the standard Ellingham diagram, the Mg,MgO line and the Al,Al2_2O3_3 line cross at roughly 1623 K (about 1350°C):

  • Below ~1623 K: the Mg,MgO line is lower than the Al,Al2_2O3_3 line, so ΔfG∘\Delta_fG^\circ(MgO) < ΔfG∘\Delta_fG^\circ(Al2_2O3_3) (more negative). Mg is thermodynamically capable of reducing alumina:

3Mg+Al2O3→3MgO+2Al(ΔG∘<0 below 1623 K)3Mg + Al_2O_3 \rightarrow 3MgO + 2Al \qquad (\Delta G^\circ < 0 \text{ below } 1623\ K)

  • Above ~1623 K: the lines cross and the Al,Al2_2O3_3 line drops below the Mg,MgO line, so the reverse becomes favourable and Al can reduce MgO instead.

Step 4 – State the condition

So the condition to suggest is simply: carry out the reaction below the crossover temperature (~1623 K) on the Ellingham diagram, where Mg's oxide is more stable than aluminium's.

✓Final answer

Below about 1623 K (1350°C) — the temperature at which the Mg,MgO and Al,Al2_2O3_3 Ellingham lines intersect — Mg is thermodynamically able to reduce Al2O3Al_2O_3 to Al, since below this crossover ΔfG∘\Delta_fG^\circ(MgO) is more negative than ΔfG∘\Delta_fG^\circ(Al2_2O3_3).

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