Explain why the reaction of nitrogen gas with oxygen gas to form nitrogen monoxide, N₂(g) + O₂(g) → 2NO(g), is non-spontaneous at standard conditions, yet becomes spontaneous at very high temperatures.

IB DP Chemistry Higher Level (2023 syllabus) — R1.4 Entropy and spontaneity (HL only) · Explain · 4 marks · View as Markdown

Written & reviewed by James Millett — Biology (Imperial College London), PGCE Science (University of Cambridge).

The standard enthalpy change for the reaction N₂(g) + O₂(g) → 2NO(g) is +180 kJ mol⁻¹. The standard entropy change for the same reaction is approximately +25 J K⁻¹ mol⁻¹.

Model answer (4 marks)

1. ΔG° = ΔH° – TΔS°.
2. ΔH° = +180 kJ mol⁻¹ is large and positive, so at 298 K ΔG° ≈ +180 kJ – 298 K×0.025 kJ K⁻¹ = +174 kJ, positive → non‑spontaneous.
3. ΔS° is +25 J K⁻¹ mol⁻¹ (≈+0.025 kJ K⁻¹ mol⁻¹) because two moles of gaseous reactants give two moles of gaseous products – a small increase in disorder.
4. As T rises, the TΔS term grows; when T > ΔH/ΔS (≈180 kJ ÷ 0.025 kJ K⁻¹ ≈ 7200 K) ΔG becomes negative, so the reaction becomes spontaneous at very high temperatures.

Examiner tips

  • Use the ΔG = ΔH – TΔS formula explicitly; show the sign of each term.
  • State the numerical values and the sign of ΔG at 298 K.
  • Explain how a positive ΔS makes the TΔS term favourable as T increases.
  • Mention the crossover temperature where ΔG changes sign.

Common mistakes

  • Saying the reaction is spontaneous at all temperatures; ignoring the large positive ΔH.
  • Confusing ΔS sign or giving the wrong magnitude; forgetting to convert J to kJ.
  • Not showing the calculation of ΔG at 298 K or the crossover temperature.

Mark scheme (4 marks)

  1. The reaction is non-spontaneous at standard conditions because ΔG is positive, arising from a large positive ΔH that outweighs the TΔS term at low temperatures.
  2. The entropy change is positive (small but positive) because two moles of reactant gases produce two moles of product gases — there is a slight increase in disorder/the number of accessible microstates.
  3. As temperature increases, the TΔS term increases in magnitude, because ΔS is positive; therefore ΔG = ΔH − TΔS decreases.
  4. Above a critical/crossover temperature (where T > ΔH/ΔS), ΔG becomes negative and the reaction is spontaneous.

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