Calculate electrochemical cell potential, EMF, and Gibbs free energy. Use the Nernst equation for non-standard conditions.
Calculate cell potential under non-standard conditions using the Nernst equation:
Cell potential (Ecell), also known as electromotive force (EMF), is the measure of the potential difference between two half-cells in an electrochemical cell. It determines the direction of spontaneous redox reactions and the amount of electrical work the cell can perform.
Key Insight: A positive cell potential indicates a spontaneous reaction, while a negative value indicates a non-spontaneous reaction that would require energy input to occur.
Standard Cell Potential (E°cell): Measured under standard conditions (1 M concentrations, 1 atm pressure, 25°C). Calculated as E°cell = E°cathode - E°anode.
Non-Standard Cell Potential (Ecell): Calculated using the Nernst equation to account for non-standard conditions such as different concentrations or temperatures.
Equilibrium Cell Potential: The cell potential when the system is at equilibrium (Ecell = 0 V). At this point, the forward and reverse reaction rates are equal.
The Nernst equation relates the cell potential to the standard cell potential and the reaction quotient (Q):
Where:
| Half-Reaction | E° (V) | Reducing Power |
|---|---|---|
| Li⁺ + e⁻ → Li (s) | -3.04 | Strong |
| K⁺ + e⁻ → K (s) | -2.93 | Strong |
| Ca²⁺ + 2e⁻ → Ca (s) | -2.87 | Strong |
| Na⁺ + e⁻ → Na (s) | -2.71 | Strong |
| Mg²⁺ + 2e⁻ → Mg (s) | -2.37 | Strong |
| Al³⁺ + 3e⁻ → Al (s) | -1.66 | Moderate |
| Zn²⁺ + 2e⁻ → Zn (s) | -0.76 | Moderate |
| Fe²⁺ + 2e⁻ → Fe (s) | -0.44 | Weak |
| Pb²⁺ + 2e⁻ → Pb (s) | -0.13 | Weak |
| 2H⁺ + 2e⁻ → H₂ (g) | 0.00 | Reference |
| Cu²⁺ + 2e⁻ → Cu (s) | +0.34 | Weak |
| Ag⁺ + e⁻ → Ag (s) | +0.80 | Moderate |
| Au⁺ + e⁻ → Au (s) | +1.68 | Strong |
Cell potential is directly related to the Gibbs free energy change (ΔG) of the redox reaction:
Where:
A negative ΔG (positive Ecell) indicates a spontaneous reaction, while a positive ΔG (negative Ecell) indicates a non-spontaneous reaction.
Practical Application: Cell potential calculations are essential in designing batteries, fuel cells, and corrosion prevention systems. They help predict which metals will corrode when in contact and determine the voltage output of electrochemical cells.