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Exercises · 7.16

Q.Why does the following reaction occur ? XeO6 4–(aq) + 2F–(aq) + 6H+(aq) → XeO3(g) + F2(g) + 3H2O(l) What conclusion about the compound Na4XeO6 (of which XeO6 4– is a part) can be drawn from the reaction.

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The reaction occurs because XeOX6X4−\ce{XeO6^{4-}} is a powerful oxidising agent that oxidises FX−\ce{F^-} to FX2\ce{F2} while being reduced to XeOX3\ce{XeO3}. This reveals that NaX4XeOX6\ce{Na4XeO6} is thermodynamically unstable and decomposes readily in acidic conditions, acting as a strong oxidant.

Why the reaction proceeds: oxidation state and thermodynamic driving force

Xenon in XeOX6X4−\ce{XeO6^{4-}} sits in the +8 oxidation state, the highest known for xenon. This is an extraordinarily electron-deficient state for a noble gas. Even though xenon can form stable compounds (unlike lighter noble gases), the +8 state pushes the limits of stability. The species is desperate to gain electrons and drop to a lower, more comfortable oxidation state.

Fluoride ion, meanwhile, is normally very reluctant to be oxidised—fluorine is the most electronegative element and FX−\ce{F^-} holds its electrons tightly. Yet the oxidising power of XeOX6X4−\ce{XeO6^{4-}} is so extreme that it can rip electrons even from FX−\ce{F^-}, converting it to FX2\ce{F2} gas. This tells us immediately that we're dealing with one of the most powerful oxidising agents in chemistry.

Step-by-step analysis of the reaction

1. Identify the oxidation state changes

In XeOX6X4−\ce{XeO6^{4-}}, xenon has oxidation state +8 (oxygen is −2-2, so x+6(−2)=−4  ⟹  x=+8x + 6(-2) = -4 \implies x = +8).

In XeOX3\ce{XeO3}, xenon has oxidation state +6 (since x+3(−2)=0  ⟹  x=+6x + 3(-2) = 0 \implies x = +6).

Xenon is reduced from +8 to +6, gaining 2 electrons per xenon atom.

Fluoride FX−\ce{F^-} (oxidation state −1-1) is oxidised to FX2\ce{F2} (oxidation state 00), losing 1 electron per fluoride ion.

2. Write the half-reactions

Reduction half-reaction:

XeOX6X4−+6 HX++2 eX−→XeOX3+3 HX2O\ce{XeO6^{4-} + 6H^+ + 2e^- -> XeO3 + 3H2O}

Oxidation half-reaction:

2 FX−→FX2+2 eX−\ce{2F^- -> F2 + 2e^-}

The electrons balance perfectly: 2 electrons released by two fluoride ions are consumed by one XeOX6X4−\ce{XeO6^{4-}} ion.

3. Thermodynamic feasibility

Fluoride is oxidised only by reagents that out-oxidise the FX2/FX−\ce{F2/F^-} couple (E⊖=+2.87E^\ominus = +2.87 V) — the strongest common oxidant there is. That this reaction runs at all tells us perxenate in acid is one of the very few species that clears that bar. The reaction is driven by:

  • The instability of the +8 oxidation state of xenon
  • The acidic medium, which stabilises the products
  • The escape of gaseous products (XeOX3\ce{XeO3} and FX2\ce{F2}), shifting equilibrium forward
Watch out

Don't assume that because fluorine has the highest reduction potential, FX−\ce{F^-} can never be oxidised. In the presence of an exceptionally strong oxidiser like XeOX6X4−\ce{XeO6^{4-}}, even FX−\ce{F^-} can lose electrons.

4. Role of acid

The HX+\ce{H^+} ions are essential. They protonate the oxide ligands, allowing water molecules to leave and stabilising the lower oxide XeOX3\ce{XeO3}. Without acid, the reaction would not proceed efficiently.

Conclusions about NaX4XeOX6\ce{Na4XeO6}

From this reaction, we can draw several important conclusions about sodium perxenate: …

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