A saturated aqueous solution of calcium fluoride, CaF₂, is in equilibrium with excess undissolved solid. Explain the effect on the position of equilibrium and on the value of Ksp when a small volume of concentrated hydrofluoric acid, HF(aq), is added to this system at constant temperature.

IB DP Chemistry Higher Level (2023 syllabus) — R2.3 How far? The extent of chemical change · Explain · 4 marks · View as Markdown

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

The dissolution equilibrium for calcium fluoride is: CaF₂(s) ⇌ Ca²⁺(aq) + 2F⁻(aq)

Model answer (4 marks)

Adding HF increases the concentration of F⁻ in solution (HF partially dissociates to give F⁻, or the common ion F⁻ is added). The higher [F⁻] raises the reaction quotient Qsp above Ksp, so the equilibrium shifts to the left – CaF₂(s) is favoured and dissolution is reduced. Consequently the solubility of CaF₂ decreases (common‑ion effect). The numerical value of Ksp does not change, because Ksp depends only on temperature and the temperature is held constant.

Examiner tips

  • Show the common‑ion effect by stating that added F⁻ raises Qsp and shifts equilibrium left.
  • Explain that Ksp is a constant at fixed temperature – it does not change with concentration changes.
  • Use the correct symbol Ksp and mention the solid phase is unchanged in the expression.
  • Keep the answer concise – 4 marks only.

Common mistakes

  • Confusing the effect on Ksp with a change in solubility – Ksp stays the same.
  • Failing to recognise that HF is a weak acid and only partially dissociates, yet still contributes F⁻.
  • Not stating that the shift is to the left (towards the solid) rather than to the right.

Mark scheme (4 marks)

  1. Adding HF(aq) increases the concentration of F⁻ ions in solution (since HF is a weak acid that partially dissociates, contributing F⁻, or equivalently the common ion F⁻ is added).
  2. The increased [F⁻] causes the reaction quotient Qsp to exceed Ksp, so the position of equilibrium shifts to the left (towards the solid / towards less dissolution).
  3. As the equilibrium shifts left, Ca²⁺ ions are removed from solution (and more solid CaF₂ is deposited), so the solubility / extent of dissolution of CaF₂ decreases (common ion effect).
  4. The value of Ksp remains unchanged because temperature is constant; Ksp depends only on temperature.

Key terms in this question

position of equilibrium

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