Equilibrium HL

(answers)
IB CHEMISTRY HL
17.1 The equilibrium law
Understandings:
• Le Châtelier’s principle for changes in concentration can be explained by the equilibrium law.

• The position of equilibrium corresponds to a maximum value of entropy and a minimum in the
value of the Gibbs free energy.

• The Gibbs free energy change of a reaction and the equilibrium constant can both be used to
measure the position of an equilibrium reaction and are related by the equation:

ΔG = -RT ln K
Applications and skills:
• Solution of homogeneous equilibrium problems using the expression for K.
• Relationship between ∆G and the equilibrium constant.
• Calculations using the equation:
ΔG = -RT ln K

• Relationship of ΔG to the position of equilibrium.

Guidance:
• The expression ΔG = -RT ln K is given in the data booklet in section 1.
• Students will not be expected to derive the expression.
• The use of quadratic equations will not be assessed.

Syllabus checklist

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with this this with this
Calculate the value of Kc for
homogeneous equilibria
Calculate equilibrium
concentration of reactants and
products using an ICE box
Use the equation ΔGo = - RT ln K
to calculate the change in Gibbs
free energy for a reaction.
Explain the relationship
between the change in Gibbs
free energy and the position of
equilibrium.

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Determining the value of Kc

The value of Kc can be determined in different ways, depending on what data you are
given.

Given the concentration of products and reactants at equilibrium

Calculate the Kc given the reaction:

H2(g) + CO2(g) ⇌ H2O(g) + CO(g) at 99°C
with the following equilibrium concentrations:
[H2] = 0.61 mol dm-3, [CO2] = 1.6 mol dm-3, [H2O] = 1.1 mol dm-3, [CO] = 1.4 mol dm-3
Write the expression for the Kc and plug in the equilibrium concentrations;

Kc = (1.1 × 1.4) ÷ (0.61 × 1.6) = 1.6

Given the initial concentration of one species and the equilibrium concentration of
another.

Before equilibrium is reached, a 1 dm3 flask contains 0.350 mol of SO3(g) at 832° C.
What is the Kc for the reaction at equilibrium if 0.093 mol of oxygen is present?
2SO3(g) ⇌ O2(g) + 2SO2(g)

Make an ICE box. ICE stands for Initial, Change, Equilibrium

2SO3(g) O2(g) 2SO2(g)

Initial (mol dm-3) 0.350 0 0

Change (mol dm-3) -2 × 0.093 +0.093 + 2 × 0.093

Equilibrium (mol 0.164 0.093 0.186

dm-3 )

Next, calculate the Kc value.

Kc = (0.093 × 0.1862) ÷ (0.1642) = 0.12

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Calculating the equilibrium concentrations given Kc and initial concentrations

The Kc for the following reaction is 6.78 at a certain temperature.

The initial concentrations of NO and SO3 were both 0.0300 mol dm-3.
Calculate the equilibrium concentration of each reactant.
SO3(g) + NO(g) ⇌ NO2(g) + SO2(g)

SO3(g) NO(g) NO2(g) SO2(g)

Initial (mol dm-3) 0.0300 0.0300 0 0
Change -x -x +x +x
(mol dm-3)
Equilibrium 0.0300 - x 0.0300 - x x x
(mol dm-3)

6.78 = (x 2) ÷ (0.0300 – x)2

take the square root of both sides.
2.60 = x ÷ (0.0300 – x)
Solve for x
x = 0.0217
[SO3] = 0.0300 – 0.0217 = 0.00830 mol dm-3
[NO] = 0.0300 – 0.0217 = 0.00830 mol dm-3
[NO2] = 0.0217 mol dm-3
[SO2] = 0.0217 mol dm-3

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Calculating equilibrium concentrations when Kc is very small

• In some chemical reactions, Kc is a small value, less than 1 × 10-3. In these

reactions, the forward reaction has barely proceeded, and the equilibrium mixture
consists of mostly reactants.
• The change in the initial concentration of reactants is almost zero and the
equilibrium concentrations of reactants are almost equal to their initial
concentrations.
Example:
The thermal decomposition of water has a Kc value of 7.3 × 10-18 at 1000 oC. If the initial
concentration of H2O is 0.10 mol dm-3, calculate the concentration of O2 at equilibrium.
2H2O (g) ⇌ 2H2 (g) + O2 (g)

2H2O(g) 2H2(g) O2(g)

Initial (mol dm-3) 0.10 0 0
Change (mol dm-3) -2 x +2 x -x
Equilibrium (mol dm-3) 0.10 – 2 x 2x x

Because value of Kc is so small, the equilibrium concentration of the H2O is the same as
the initial concentration.
Solve for x
x = 2.6 × 10-7
Equilibrium concentration of H2 = 2x = 5.2 × 10-7 mol dm-3

The assumption made in this previous question is that subtracting x from the initial
concentration will not make a difference within the precision used (to 2 significant
figures). In general, if the value of Kc is less than 1 × 10-3, this assumption can be made.

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ΔGo and equilibrium

• At the minimum value of Gibbs free energy, the reaction is at equilibrium.

• This corresponds to a maximum value of entropy.

A reaction at equilibrium has a minimum value of Gibbs free energy and a maximum
value of entropy.

• The following equation is given in section 1 of the data booklet and can be used to
show the relationship between the ΔGo and the equilibrium constant Kc.

The above equation can be arranged to give the following:

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Example:
1. Calculate the value of K at 298 K for a reaction given that ΔGo = -32.96 kJ mol-1

K = e -32960 ÷ (8.31 × 298)

K = e 13.3
K = 5.98 × 105
2. Calculate the ΔGo for a reaction given that the Kc is 45.6 at 761 K.

ΔGo = -8.31 × 761 × ln 45.6

ΔGo = -24.2 kJ mol-1

The table below shows the relationship between the ΔGo and the equilibrium constant K.
• The trend that can be seen from the table is that as the ΔGo becomes more
negative (more spontaneous), the value of the equilibrium constant increases.
• Conversely as the ΔGo becomes more positive (less spontaneous), the value of
the equilibrium constant K decreases.

Reaction (298 K) ΔGo (kJ mol-1) K

2SO3(g) ⇌ 2SO2(g) + O2(g) +141.7 1.4×10-25

H2O(l) ⇌ H+(aq) + OH-(aq) +79.9 1.0×10-14

N2(g) + 3H2(g) ⇌ 2NH3(g) -32.9 5.8×105

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) -211 1.4×1037

• For a reaction with a larger negative value for the ΔGo, the equilibrium position lies
to the right and the reaction almost goes to completion (as in the reaction of Zn
and Cu2+), and the equilibrium mixture will contain mostly products.
• For a reaction with a larger positive value for the ΔGo, the equilibrium position lies
to the left and the equilibrium mixture will contain mostly reactants (as in the
decomposition of SO3).

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