Electrochemical Cells Overview

Jul 30, 2025

Overview

This lecture explains the setup and functioning of electrochemical cells, details how to calculate cell potentials, and explores examples like lithium-ion and hydrogen fuel cells.

Electrochemical Cell Basics

  • An electrochemical cell consists of two different metals (electrodes) dipped in solutions containing their own ions.
  • A salt bridge (often filter paper soaked in potassium nitrate) completes the circuit by allowing ion flow between half-cells.
  • Electromotive force (emf) or cell voltage drives electron flow through the connecting wire.
  • The more reactive metal is oxidized (loses electrons) and the less reactive is reduced (gains electrons).
  • The setup can also use inert electrodes (e.g., platinum) with different ion solutions (e.g., Fe²⁺/Fe³⁺).

Half-Equations and Electrode Potentials

  • Both oxidation and reduction can occur at each electrode; reactions are reversible.
  • Write half-equations with the reduction reaction going forward (electrons on the left).
  • The more negative electrode potential indicates the metal will be oxidized.
  • Combine half-equations to form the overall redox reaction in the cell.
  • Electrode potentials are measured relative to the standard hydrogen electrode (SHE), which is defined as 0 volts.

Standard Conditions and Calculating emf

  • Standard conditions: solutions at 1 mol/dm³, temperature at 298 K, and pressure at 100 kPa (1 atm).
  • The cell emf is calculated as the difference between the electrode potentials of the two metals (subtract one from the other, accounting for sign).

Electrochemical Cell Notation

  • Shorthand notation: On the left, reduced form | oxidized form || oxidized form | reduced form on the right.
  • A double vertical line (||) represents the salt bridge.

Battery and Cell Examples

  • Lithium-ion batteries use a graphite and lithium cobalt oxide electrode with a lithium salt electrolyte.
  • Lithium is oxidized at one electrode; lithium ions travel and are reduced at the other, forming a complex ion.

Hydrogen Fuel Cells

  • Hydrogen fuel cells use hydrogen and oxygen gases at separate platinum electrodes with potassium hydroxide solution and an anion exchange membrane.
  • The membrane allows hydroxide ions (OH⁻) to travel and combine with hydrogen to form water (H₂O).
  • Electrons flow through the external circuit, creating usable current.
  • Main advantage: only water is produced, with no release of pollutants.

Key Terms & Definitions

  • Electromotive force (emf) — The voltage generated by an electrochemical cell.
  • Salt bridge — A device allowing ion flow to complete the electrochemical circuit.
  • Half-cell — One compartment of an electrochemical cell containing an electrode and ion solution.
  • Electrode potential — The voltage of a half-cell compared to the standard hydrogen electrode.
  • Redox reaction — A reaction involving simultaneous oxidation and reduction.

Action Items / Next Steps

  • Review the table of standard electrode potentials.
  • Practice writing half-equations and overall redox equations for given cell setups.