Understanding the NO₂/N₂O₄ Equilibrium System

Expert reviewed 22 November 2024 5 minute read


The dynamic equilibrium between nitrogen dioxide (NO₂) and dinitrogen tetroxide (N₂O₄) provides an excellent visual demonstration of how chemical systems respond to environmental changes. This reversible reaction is particularly important in the study of Le Chatelier's principle.

The Equilibrium System

The equilibrium reaction between nitrogen dioxide and dinitrogen tetroxide can be represented by:

2NO2(g)N2O4(g)ΔH=58 kJ mol12NO_2(g) \rightleftharpoons N_2O_4(g) \quad \Delta H = -58 \text{ kJ mol}^{-1}

This system is particularly useful for demonstration because:

  • NO₂ is brown in color
  • N₂O₄ is colorless
  • The reaction occurs readily at room temperature

Effects of Pressure and Volume Changes

When studying this equilibrium in a gas syringe, we can observe several key phenomena:

Increasing Pressure (Decreasing Volume)

  • When the syringe plunger is pushed in:
    • The volume decreases
    • Pressure increases
    • Concentration of both gases increases
    • The equilibrium shifts toward N₂O₄ formation
    • The brown color gradually fades

This shift occurs because:

  • The forward reaction produces fewer moles of gas (2 moles → 1 mole)
  • According to Le Chatelier's principle, the system reduces stress by favoring the reaction that produces fewer gas molecules

Decreasing Pressure (Increasing Volume)

When the syringe plunger is pulled out:

  • The volume increases
  • Pressure decreases
  • Concentration of both gases decreases
  • The equilibrium shifts toward NO₂ formation
  • The brown color intensifies

Temperature Effects

The reaction shows clear temperature dependence:

Heating the System

  • When heated in warm water:
    • The solution becomes browner
    • Equilibrium shifts toward NO₂ formation
    • The endothermic reverse reaction is favored

Cooling the System

  • When cooled in ice:
    • The solution becomes paler
    • Equilibrium shifts toward N₂O₄ formation
    • The exothermic forward reaction is favored

Summary

This equilibrium system demonstrates how:

  • Pressure changes affect systems with unequal moles of gaseous reactants and products
  • Temperature changes influence endothermic/exothermic reactions
  • Le Chatelier's principle predicts system behavior under changing conditions

Return to Module 5: Equilibrium and Acid Reactions