Chemical Equilibrium

Le Chatelier's principle

/ luh-SHAT-lee-ay /

Imagine a hammock with a person resting in the middle. Push down on one side and the whole hammock shifts to take up the slack, settling into a new balanced shape that partly absorbs your push. A chemical system at equilibrium behaves the same way. Le Chatelier's principle says that if you disturb a system at equilibrium, the system responds by shifting in the direction that partly opposes — and so relieves — the disturbance.

In practice the 'disturbances' are familiar: add more of a substance and the system consumes some of it; remove a substance and the system makes more of it; raise the pressure on a gas mixture and the equilibrium shifts toward the side with fewer gas molecules; heat the mixture and it shifts in the direction that absorbs heat (the endothermic direction). Each time, the equilibrium moves to a new position that softens the change you imposed.

It is a wonderfully handy rule of thumb, but treat it as a qualitative guide, not a law of nature. It predicts the direction of a shift, not the exact amount, and it can mislead in tricky cases — for example, adding an inert gas at constant volume changes nothing, even though the total pressure rises. The principle is really a shorthand for what the equilibrium constant and reaction quotient would tell you if you did the full calculation.

In the equilibrium N2 + 3H2 ⇌ 2NH3, four gas molecules on the left become two on the right. Squeeze the mixture into a smaller volume and the equilibrium shifts toward ammonia — the side with fewer gas molecules — because that partly relieves the rise in pressure.

Disturb an equilibrium and it shifts to soften the disturbance.

A subtle trap: adding an inert gas at constant volume raises total pressure but does not shift the equilibrium, because it changes neither the partial pressures nor the concentrations of the reacting species.

Also called
Le Chatelier–Braun principle勒夏特列原理勒沙特列原理