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Chapter 7 Equilibrium
7.1 Equilibrium

Equilibrium and the equilibrium constant

An equilibrium may occur in a closed system, where both the forward reaction and the
backward reaction are occurring (dynamic equilibrium) at the same rate.

In an equilibrium mixture, the proportion of reactants and products is referred as the

equilibrium position

The equilibrium constant of a reaction Kc has a fixed value at a specific temperature.

For a reaction aA + bB ⇌ cC + dD,

💡 Kc =
[C]ceqm [D]deqm
[A]aeqm [B ]beqm

Kc is large → equilbrium lies to the right

Kc is small → eq. lies to the left
Kc >> 0 → complete reaction
Kc << 0 → no reaction

Chapter 7 Equilibrium 1
 The magnitude of Kc determines the equilibrium position but not how fast the
reaction reaches its equilbrium position
′
1. For an inverse reaction cC + dD ⇌ aA + bB, Kc = 1/Kc
2. For a multiple of a reaction naA + nbB ⇌ ncC + ndD, Kcx = (Kc )n
3. For an addition of two reactions, Kc = Kc1 ×Kc2
The reaction quotient Q measures the relative amounts of reactants and products at a
given time (not at equilibrium)

💡 Q=
[C]c [D]d
[A]a [B ]b

If Q = Kc , reaction is at equilibrium
If Q > Kc , reaction proceeds to the left
If Q < Kc , reaction proceeds to the right

Le Chatlier’s Principle
The Le Chatlier’s Principle states that when a system at equilibrium is disrupted, it will
respond in a way that minimizes the effect of the change

Change in concentration: Kc unchanged. Equilibrium shifts to the side with fewer

compounds.

Change in pressure: Kc unchanged. If pressure increases, equilibrium shifts to the side

with fewer number of gas molecules. Vice versa.

Change in temperature: when temperature increases, Kc(endothermic) increases and

Kc(exothermic) decreases. When temperature increases, equilibrium lies to the right for
an endothermic reaction, and equilibrium lies to the left for an exothermic reaction. Vice
versa.

Adding catalyst: Kc unchanged. Equilbrium doesn’t shift, but the equilibrium position is
reached faster.

Industrial applications
The Haber process: N2 + 3H2 ⇌ 2NH3 , exothermic
The Contact process: 2SO2 + O2 ⇌ 2SO3 , exothermic

Chapter 7 Equilibrium 2
 17.1 The equilibrium law

Calculations involving the equilibrium constant

Always write the balanced equation, and then the expression for the equilibrium
constant.

Then, substitute concentration values into the expression, or set a variable. Changes in
concentrations to eq. are proportionate to the stiochiometry.

When Kc < 10−3 , [reactant]initial ≈ [reactant]equilibrium

Equilibrium, thermodynamics and kinetics

ΔGθ < 0 → reaction proceeds to the right
ΔGθ > 0 → reaction proceeds to the left
ΔGθ = 0 → reaction is at equilibrium (Gθproduct = Gθreactant )

💡 ΔGθ = −RT ln K

For a bimolecular reaction A + B ⇌ C + D with rate constant k for the forward reaction
and rate constant k’ for the backward reaction,

💡 Kc = k
k′

If k > k’ → reaction proceeds to the right

If k < k’ → reaction proceeds to the left

Chapter 7 Equilibrium 3