Chemical Equilibrium & SolubilityEquilibriumContent level: Core 22 min

Le Chatelier's Principle and System Shifts

What you'll be able to do: Predict the direction an equilibrium shifts when concentration, volume, pressure or temperature is changed, and say whether K changes.

Introduction

Industrial chemists do not accept the yield a reaction happens to give. They change the conditions to push it. Le Chatelier's principle is the reasoning behind those choices.

These are recommended, not required. You can start this lesson at any time.

Learning objectives

  • Predict shifts caused by concentration and volume changes
  • Explain why only temperature changes the value of K
  • Treat heat as a reactant or product to predict temperature effects
  • Identify changes that cause no shift at all

Lesson

The principle

If a system at equilibrium is disturbed, it shifts in the direction that partially counteracts the disturbance. Partially matters: the system never fully undoes the change, it only settles at a new position where Q has returned to K.

Concentration changes

Adding a reactant makes Q too small, so the system shifts right to consume it. Removing a product also lowers Q and shifts the system right. This is why continuously removing a product, for example condensing out water, drives a reaction to high yield.

Every concentration prediction can be checked by asking what happened to Q.

Volume and pressure

Compressing a gaseous system raises every partial pressure, and the system responds by shifting toward whichever side has fewer moles of gas. Expanding does the opposite. If both sides have equal moles of gas, changing the volume causes no shift at all.

Compression shifts toward fewer moles of gas

Inert gas at constant volume

Adding argon at constant volume raises the total pressure but leaves every partial pressure and every concentration unchanged. Q is untouched, so nothing shifts. This trips up more students than any other case.

Total pressure is not what matters. Partial pressures are.

Temperature and K

Write heat as a product for an exothermic reaction and as a reactant for an endothermic one, then treat a temperature change like adding or removing that term. Heating an exothermic reaction shifts it left and lowers K; cooling it shifts right and raises K. This is the only stress that changes the value of K.

A + B ⇌ C + heat (exothermic)

The Haber process

N + 3 H2 NH is exothermic with four moles of gas becoming two. High pressure and low temperature both favor ammonia, but low temperature makes the reaction unbearably slow, so industry compromises at about 450 C with a catalyst and very high pressure.

Key ideas

Definition
Le Chatelier's principle

A system at equilibrium shifts to partially relieve an applied stress.

Rule
Concentration

Adding a species shifts away from it; removing a species shifts toward it.

Rule
Compression

Reducing the volume shifts the equilibrium toward the side with fewer moles of gas.

Rule
Inert gas at constant volume

No partial pressure changes, so there is no shift.

Rule
Temperature

The only stress that changes the value of K.

Equation
Exothermic reaction with heat shown

reactants ⇌ products + heat

  • heat = treat as a product when ΔH is negative
Equation
Endothermic reaction with heat shown

reactants + heat ⇌ products

  • heat = treat as a reactant when ΔH is positive

Worked examples

Worked example 1

For N(g) + 3 H(g) ⇌ 2 NH(g), ΔH = -92 kJ. Predict the effect of (a) adding H, (b) decreasing the volume, (c) raising the temperature.

Try it first: For each change, decide whether Q rises, falls, or stays the same.

    0 of 3 steps revealed.

    Worked example 2

    Argon is added to the equilibrium NO(g) ⇌ 2 NO(g) at constant volume. What happens?

    Try it first: Ask whether any partial pressure in the Q expression changed.

      0 of 3 steps revealed.

      Worked example 3

      Cooling a flask of NO/NO turns the brown color pale. Is the forward reaction NO2 NO endothermic or exothermic?

      Try it first: Decide which species is brown and which way the system moved.

        0 of 3 steps revealed.

        Common mistakes

        Saying an equilibrium shift changes the value of K.

        Why it's wrong: Only temperature changes K; every other stress moves the system to a new position with the same K.

        Check instead: Ask whether the temperature changed.

        Predicting a shift when an inert gas is added at constant volume.

        Why it's wrong: No partial pressure in the expression changes, so Q is unchanged.

        Check instead: Test whether Q moved.

        Thinking adding a solid to a heterogeneous equilibrium shifts it.

        Why it's wrong: Pure solids do not appear in the expression.

        Check instead: Check whether the species is in the K expression at all.

        Claiming a catalyst increases equilibrium yield.

        Why it's wrong: It speeds both directions equally.

        Check instead: A catalyst changes only the time taken.

        Applying the moles-of-gas rule while counting aqueous or solid species.

        Why it's wrong: Volume changes act on gases.

        Check instead: Count only species labelled (g).

        Practice this skill

        No practice questions are available for this topic yet. You can still practice the whole unit.

        What you should now know

        Le Chatelier's principle states that a system at equilibrium responds to a stress by shifting in the direction that partly relieves it. Adding a species shifts the system away from that species and removing it shifts the system toward it. Compressing a gaseous system shifts it toward the side with fewer moles of gas, while adding an inert gas at constant volume changes nothing because no partial pressure changes. Temperature is the one stress that changes K itself: treat heat as a product for an exothermic reaction and as a reactant for an endothermic one. A catalyst changes neither K nor the position of equilibrium.

        • A system shifts to partially relieve an applied stress
        • Adding a species shifts away from it, removing shifts toward it
        • Compression shifts toward fewer moles of gas
        • Inert gas at constant volume causes no shift
        • Only temperature changes the value of K

        Sources and further reading

        This lesson is original Chem Help content. No external sources were adapted.