Disturbing a system at equilibrium

Any disturbance to a system at equilibrium that results in a change in the magnitude of either Q or K results in a change in the equilibrium composition.

The magnitude of K changes with temperature. The direction of the change depends on the sign of ΔH for the reaction.
  • For exothermic reactionsH negative) have smaller K at higher temperatures. Thus reactants are present in relatively larger amounts when equilibrium is restored.
  • For endothermic reactionsH positive) have larger K at higher temperatures. Thus products are present in relatively larger amounts when equilibrium is restored.

Disturbances to an equilibrium system at constant temperature change the magnitude of Q, but NOT the magnitude of K. Examples are

  • changing the concentration of a component appearing in the Q expression
  • changing external pressure or total volume for some reactions involving gases

The direction in which reaction must occur to reestablish equilibrium depends on the relative magnitude of Q after the change has been applied and K.
  • If Q < K, reaction occurs in the forward direction until Q = K.
  • If Q > K, reaction occurs in the reverse direction until Q = K.