Electrode and Cell Potential Summary

Key Concepts and Summary

The property of potential, E, is the energy associated with the separation/transfer of charge. In electrochemistry, the potentials of cells and half-cells are thermodynamic quantities that reflect the driving force or the spontaneity of their redox processes. The cell potential of an electrochemical cell is the difference between its cathode and anode. To permit easy sharing of half-cell potential data, the standard hydrogen electrode (SHE) is assigned a potential of exactly 0 V and used to define a single electrode potential for any given half-cell. The electrode potential of a half-cell, EX, is the cell potential of said half-cell acting as a cathode when connected to a SHE acting as an anode. When the half-cell is operating under standard state conditions, its potential is the standard electrode potential, E°X. Standard electrode potentials reflect the relative oxidizing strength of the half-reaction’s reactant, with stronger oxidants exhibiting larger (more positive) X values. Tabulations of standard electrode potentials may be used to compute standard cell potentials, cell, for many redox reactions. The arithmetic sign of a cell potential indicates the spontaneity of the cell reaction, with positive values for spontaneous reactions and negative values for nonspontaneous reactions (spontaneous in the reverse direction).

Key Equations

$E^°_{cell}=E^°_{cathode}-E^°_{anode}$








Write the balanced cell reaction for the cell schematic below, calculate the standard cell potential, and note whether the reaction is spontaneous under standard state conditions.

$Cu(s)$ │ $Cu^{2+}(aq)$ ║ $Au^{3+}(aq)$ │ $Au(s)$

Solution

$3Cu(s)+2Au^{3+}(aq)⟶3Cu^{2+}(aq)+2Au(s)$; +1.16 V; spontaneous

Determine the cell reaction and standard cell potential at 25 °C for a cell made from a cathode half-cell consisting of a silver electrode in 1 M silver nitrate solution and an anode half-cell consisting of a zinc electrode in 1 M zinc nitrate. Is the reaction spontaneous at standard conditions?

Determine the cell reaction and standard cell potential at 25 °C for a cell made from an anode half-cell containing a cadmium electrode in 1 M cadmium nitrate and an anode half-cell consisting of an aluminum electrode in 1 M aluminum nitrate solution. Is the reaction spontaneous at standard conditions?

Solution

$3Cd(s)+2Al^{3+}(aq)⟶3Cd^{2+}(aq)+2Al(s)$; -1.259 V; nonspontaneous

Write the balanced cell reaction for the cell schematic below, calculate the standard cell potential, and note whether the reaction is spontaneous under standard state conditions.

$Pt(s)$ │ $H_2(g)$ │ $H^+(aq)$ ║ $Br_2(aq)$, $Br^−(aq)$ │ $Pt(s)$