Explain why the standard electrode potential (E°) for the Fe³⁺/Fe²⁺ half-cell cannot be measured directly, and outline the procedure used to assign it a value.

IB DP Chemistry Higher Level (2023 syllabus) — R3.2 Electron transfer reactions · Explain · 4 marks · View as Markdown

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

Standard electrode potentials are measured relative to the standard hydrogen electrode (SHE), which is assigned a value of 0.00 V. The Fe³⁺/Fe²⁺ half-cell has a standard electrode potential of +0.77 V.

Model answer (4 marks)

Electrode potentials are relative values; a reference electrode is required for measurement.

A platinum electrode is immersed in a solution containing equal concentrations (1 mol dm⁻³) of Fe³⁺ and Fe²⁺ ions.

The half‑cell is connected to the standard hydrogen electrode (SHE) under standard conditions (298 K, 100 kPa) via a salt bridge and external circuit.

The measured cell voltage equals the standard potential of the Fe³⁺/Fe²⁺ half‑cell (+0.77 V) because E°(SHE)=0.00 V by definition; the positive sign indicates Fe³⁺/Fe²⁺ is the cathode (reduction occurs at this electrode).

Examiner tips

  • State that potentials are relative and a reference electrode is needed.
  • Describe the platinum electrode with 1 M Fe³⁺/Fe²⁺ solution.
  • Mention connection to SHE via salt bridge at 298 K, 100 kPa.
  • Explain that the measured voltage equals +0.77 V because SHE is 0.00 V.

Common mistakes

  • Claiming the Fe³⁺/Fe²⁺ potential can be measured alone without a reference.
  • Using a non‑inert electrode or unequal ion concentrations.
  • Ignoring the role of the salt bridge and standard conditions.

Mark scheme (4 marks)

  1. Electrode potentials are relative (not absolute) values, so a reference electrode is required for measurement.
  2. The Fe³⁺/Fe²⁺ half-cell uses a platinum (inert) electrode immersed in a solution containing equal concentrations (both 1 mol dm⁻³) of Fe³⁺ and Fe²⁺ ions.
  3. This half-cell is connected to the standard hydrogen electrode (SHE) under standard conditions (298 K, 100 kPa) via a salt bridge and external circuit.
  4. The measured cell voltage equals the E° of the Fe³⁺/Fe²⁺ half-cell (+0.77 V) because E°(SHE) = 0.00 V by definition; the positive sign indicates Fe³⁺/Fe²⁺ is the cathode (reduction occurs at this electrode).

Key terms in this question

standard electrode potential (E°)

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