Electrode Potentials and Cells
A half-cell's standard electrode potential E⦵ is measured against the standard hydrogen electrode (SHE, 0.00 V) at 298 K, 1 mol dm⁻³ and 100 kPa. Half-equations are written as reductions; the more positive E⦵, the stronger the oxidising agent (left side). . A reaction is feasible if (but may be slow, or conditions may be non-standard). Changing concentration shifts E (Nernst: ). . Fuel cells and batteries apply this.
Learning objectives
- Describe the SHE and how E⦵ is measured.
- Calculate E⦵cell and predict feasibility.
- Write cell diagrams.
- Explain the effect of concentration; use the Nernst equation.
Why can copper metal not displace hydrogen from dilute acid, while zinc can?
Core idea
Put zinc in copper sulfate and it just gets warm. Separate the two halves with a wire and a salt bridge, and the same reaction lights a bulb.
Each half-cell has a reduction potential measured against hydrogen. The more positive half-cell is reduced, the other is oxidised, and E⦵cell is the difference.
1. Building a cell
Electrons flow through the wire; ions flow through the salt bridge.
- More positive: goes forward (reduction).
- Less positive: goes backward (oxidation).
- Positive minus negative.
- Add the half-equations; electrons cancel.
Find E for Cu²⁺/Cu when [Cu²⁺] = 0.010 mol dm⁻³.
- Goal
- E in V.
- Strategy
- .
- Logarithm.
- Substitute.
Summary
- SHE = 0.00 V.
- E⦵cell = positive − negative.
- Positive E⦵cell → feasible.
- Nernst; ΔG = −nFE.
- Half-cell
- An element and its ions (or two ions) in equilibrium at an electrode.
- Salt bridge
- Allows ions to move between half-cells.
- Standard conditions
- 298 K, 100 kPa, 1.00 mol dm⁻³.
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