Electrode Potential - Clean Notes
MEASUREMENT OF ELECTRODE POTENTIAL
- The potential of an individual half-cell cannot be measured directly.
- Only the potential difference (emf) between two half-cells can be measured.
- To compare values, the Standard Hydrogen Electrode (SHE) is used as a reference
electrode.
- SHE is assigned a potential of 0 V at all temperatures.
STANDARD HYDROGEN ELECTRODE (SHE)
- Consists of a platinum electrode coated with platinum black.
- Dipped in 1 M H+ solution (usually HCl).
- Pure hydrogen gas at 1 bar is bubbled around the electrode.
- Electrode reaction: H+(aq) + e- ■ 1/2 H2(g).
- Can act as anode (oxidation: H2 → 2H+ + 2e-) or cathode (reduction: H+ + e- → 1/2 H2).
MEASUREMENT OF CELL emf
- At 298 K, a cell is constructed with SHE and another half-cell.
- The measured emf = Standard Electrode Potential (E°) of the other half-cell.
EXAMPLES
1. Copper Half-cell:
Pt|H2(g, 1 bar)|H+(aq, 1 M) || Cu2+(aq, 1 M)|Cu
Measured emf = +0.34 V.
Therefore, E°(Cu2+/Cu) = +0.34 V.
Positive value means Cu2+ ions are reduced more easily than H+.
2. Zinc Half-cell:
Pt|H2(g, 1 bar)|H+(aq, 1 M) || Zn2+(aq, 1 M)|Zn
Measured emf = -0.76 V.
Therefore, E°(Zn2+/Zn) = -0.76 V.
Negative value means H+ is reduced more easily than Zn2+ (so Zn oxidizes easily).
INTERPRETATION OF SIGN
- Positive E°: species is a strong oxidizing agent (reduced form stable).
- Negative E°: species is a strong reducing agent (oxidized form stable).
DANIELL CELL
- Left electrode (Anode): Zn → Zn2+ + 2e-.
- Right electrode (Cathode): Cu2+ + 2e- → Cu.
- Overall reaction: Zn + Cu2+ → Zn2+ + Cu.
- emf = 0.34 - (-0.76) = 1.10 V.
ROLE OF INERT ELECTRODES
- Used when ions or gases are involved but no solid metal electrode.
- Platinum or gold are common inert electrodes.
- They don’t react, only provide surface for electron transfer.
Examples:
- Hydrogen electrode: Pt(s)|H2(g)|H+(aq).
- Bromine electrode: Pt(s)|Br2(aq)|Br-(aq).
STANDARD ELECTRODE POTENTIALS AND SIGNIFICANCE
- E° > 0: reduced form of species more stable than hydrogen gas.
- E° < 0: hydrogen gas more stable than reduced form of the species.
- Fluorine has the highest E° → strongest oxidizing agent (reduces easily to F-).
- Lithium has the lowest E° → strongest reducing agent (Li oxidizes easily to Li+).
- As we go down the electrochemical series:
• E° decreases.
• Oxidizing power decreases.
• Reducing power increases.
KEY USES OF ELECTRODE POTENTIALS
- Predicting feasibility of redox reactions.
- Arranging elements in electrochemical series.
- Calculating emf of galvanic cells.
- Applications in equilibrium constants, solubility products, titrations, batteries, and
thermodynamics.
QUICK SUMMARY TABLE
Sign of E° | Meaning | Example
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Positive | Strong oxidizing agent, reduced form stable | Cu2+/Cu (+0.34 V)
Negative | Strong reducing agent, oxidized form stable | Zn2+/Zn (-0.76 V)
Highest E° | Strongest oxidizing agent | F2 → F-
Lowest E° | Strongest reducing agent | Li+ → Li