Equilibrium

The Equilibrium State

  • Reversible Reactions: All reactions can reverse under suitable conditions, reaching equilibrium.
  • Equilibrium Defined: At equilibrium, concentrations of products and reactants remain constant, as the rate of the forward reaction equals the rate of the reverse reaction:
    \text{rate}{\text{forward}} = \text{rate}{\text{reverse}}
  • Dynamic State: Chemical equilibrium is dynamic; reactions occur continuously, but no net change is observable at a macroscopic level.

The Equilibrium Constant

  • Considering a Reaction: For the reaction 2NO2(g) \rightleftharpoons 2NO(g) + O2(g)
    • At equilibrium:
      \text{rate}{\text{forward}} = \text{rate}{\text{reverse}}
  • Expression for K: The equilibrium constant (K) is derived from the concentrations of reactants and products:
    K = \frac{[NO]^2[O2]}{[NO2]^2}

K and the Extent of Reaction

  • Meaning of K: K reflects the ratio of product concentrations to reactant concentrations at equilibrium.
  • Small K value: Indicates the reaction yields little product, favoring reactants.
  • Large K value: Indicates the reaction produces predominantly products, favoring products.

The Reaction Quotient Q

  • Definition of Q: For the general reaction
    aA + bB \rightleftharpoons cC + dD
    Q = \frac{[C]^c[D]^d}{[A]^a[B]^b}
  • Equilibrium Comparison: At equilibrium,
    Q = K
  • Direction of Reaction: The value of Q indicates the direction the reaction must shift to reach equilibrium. If:
    • Q < K: Shift to products
    • Q > K: Shift to reactants
    • Q = K: System is at equilibrium.

Heterogeneous Equilibrium

  • Definition: Involves reactants and/or products in different phases.
  • Concentration Exclusion: Pure solids and liquids are not included in equilibrium expressions.
  • Example: For
    CaCO3(s) \rightleftharpoons CaO(s) + CO2(g)
    Q = [CO_2]

Sample Problems

Writing Reaction Quotients

  • Balanced Equations for Reaction Quotients:
    • (a) 4NO2(g) \rightleftharpoons 2N2O4(g) Qc = \frac{[N2O4]^2}{[NO_2]^4}
    • (b) 2Na(s) + 2H2O(l) \rightleftharpoons 2NaOH(aq) + H2(g)
      Qc = \frac{[NaOH]^2[H2]}{[Na]^2}
  • Note: Only species with changing concentrations are included in Q.

Determining Direction of Reaction

  • Example: For the reaction N2O4(g) \rightleftharpoons 2NO_2(g) at K = 0.21
    • If concentrations are [N2O4] = 0.12 M and [NO2] = 0.55 M:
    • Calculate Q and compare with K. If
      Q > K, reaction moves left.

Le Châtelier’s Principle

  • Principle Statement: When a system at equilibrium is disturbed, it shifts to counteract the disturbance.
  • Common Disturbances:
    • Change in concentration
    • Change in pressure (via volume change)
    • Change in temperature
  • Response:
    • Increase in reactants shifts right (to products)
    • Increase in products shifts left (to reactants)

The Effect of Concentration Changes

  • Increase in Reactants: Shifts equilibrium to right, increasing products.
  • Decrease in Reactants: Shifts equilibrium to left, increasing reactants.
  • Changes in Concentration Have No Effect on K: Only changes in temperature do.

The Effect of Pressure Changes

  • Pressure Increase: Shifts equilibrium toward fewer moles of gas.
  • Volume Increase: Shifts equilibrium toward more moles of gas.
  • Inert Gas Addition: No effect on equilibrium position if volume constant

The Effect of Temperature Changes

  • Temperature Increase: For exothermic reactions, K decreases; for endothermic, K increases.
  • Temperature Decrease: Opposite effects apply.

Catalysts and Equilibrium

  • Catalysts speed up both forward and reverse reactions equally.
  • Impact on Equilibrium: Catalysts do not alter the equilibrium position, only the time to reach it.

Solubility and Equilibrium

  • Saturated Solutions: At equilibrium with undissolved solute.
  • Ksp: The solubility product constant, indicating the solubility of slightly soluble compounds.
  • Common Ion Effect: Lowering solubility when a common ion is added.
  • Precipitation Prediction: Formed based on Qsp compared to Ksp.