TEACHER COPY – WITH SUGGESTED SOLUTIONS

Anglo−Chinese School (Independent)

Year 5 (2022) IBDP Chemistry HL

TOPIC 7 EQUILIBRIUM

(IBDP syllabus Topic 7)

7.1 Equilibrium
- Essential Idea: Many reactions are reversible. These
reactions will reach a state of equilibrium when the
rates of the forward and reverse reaction are equal.
The position of equilibrium can be controlled by
changing the conditions.

(IBDP syllabus Topic 17)

17.1 The equilibrium law

- Essential Idea: The position of equilibrium can be
quantified by the equilibrium law. The equilibrium
constant for a particular reaction only depends on the
temperature.

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7.1 Equilibrium

Nature of science:

Obtaining evidence for scientific theories—isotopic labelling and its use in defining equilibrium. (1.8)
Common language across different disciplines—the term dynamic equilibrium is used in other
contexts, but not necessarily with the chemistry definition in mind. (5.5)

Understandings:

• A state of equilibrium is reached in a closed system when the rates of the forward and reverse
reactions are equal.
• The equilibrium law describes how the equilibrium constant (Kc) can be determined for a particular
chemical reaction.
• The magnitude of the equilibrium constant indicates the extent of a reaction at equilibrium and is
temperature dependent.
• The reaction quotient (Q) measures the relative amount of products and reactants present during
a reaction at a particular point in time. Q is the equilibrium expression with non-equilibrium
concentrations. The position of the equilibrium changes with changes in concentration, pressure,
and temperature.
• A catalyst has no effect on the position of equilibrium or the equilibrium constant.

Applications and skills:

• The characteristics of chemical and physical systems in a state of equilibrium.

• Deduction of the equilibrium constant expression (Kc) from an equation for a homogeneous
reaction.
• Determination of the relationship between different equilibrium constants (Kc) for the same
reaction at the same temperature.
• Application of Le Châtelier’s principle to predict the qualitative effects of changes of temperature,
pressure and concentration on the position of equilibrium and on the value of the equilibrium
constant.

Guidance:

• Physical and chemical systems should be covered.

• Relationship between Kc values for reactions that are multiples or inverses of one another should
be covered.
• Specific details of any industrial process are not required.

17.1 The equilibrium law

Nature of science:

Employing quantitative reasoning—experimentally determined rate expressions for forward and

backward reactions can be deduced directly from the stoichiometric
equations and allow Le Châtelier’s principle to be applied. (1.8, 1.9)

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, ∆G = –RT lnK

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 Applications and skills:

• Solution of homogeneous equilibrium problems using the expression for Kc.

• Relationship between ∆G and the equilibrium constant.
• Calculations using the equation ∆G = –RT lnK

Guidance:

• The expression ∆G = –RT lnK is given in the data booklet in section 1.

• Students will not be expected to derive the expression ∆G = –RT lnK.
• The use of quadratic equations will not be assessed.

7.1 Equilibrium

7.1.1 Reversible Chemical Reaction

• Consider the following example:

When heated strongly in the open, calcium carbonate decomposes to form calcium
oxide and carbon dioxide:

heat
CaCO3 (s) CaO (s) + CO2 (g)

As the carbon dioxide, CO2 escapes, it is impossible for the calcium oxide, CaO to be
converted back to calcium carbonate, CaCO3. We say that the above reaction is
irreversible. However, if calcium carbonate is heated in a closed evacuated container
(closed system), the following reverse reaction becomes possible.

CaO (s) + CO2 (g) CaCO3 (s)

In the closed system, both the forward and reverse reactions take place simultaneously,
the reaction is known as a reversible reaction. Reversible reactions are chemical
reactions that can take place in both directions and they are denoted by the use of a
double headed arrow, ⇌.

CaCO3 (s) ⇌ CaO (s) + CO2 (g)

• Reversible reactions have the following characteristics:

o Reversible reactions can only occur in a closed system, where there is no gain or
loss of chemicals to or from the surroundings.
o The reaction that proceeds from left to right is known as the forward reaction.
o The reaction that proceeds from right to left is known as the reverse reaction.
o At equilibrium, the rates of the forward and reverse reactions are equal.
o Equilibrium can be achieved from either direction: you can start with either
reactants or products.

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7.1.2 Dynamic Equilibrium

• In a reversible reaction, dynamic equilibrium is achieved when the rates of the forward
and reverse reaction are equal. At this stage, the concentration of all the reactants and
the products remain constant if the temperature is kept constant.

• Consider the following dynamic equilibrium:

H2 (g) + I2 (g) ⇌ 2HI (g)

• The dynamic nature of the equilibrium can be demonstrated by adding a small amount
of radioactive iodine (I2*) to the above reaction at a state of equilibrium. Measurements
will show that after some time, the mixture contains radioactive hydrogen iodide (HI*),
indicating that the reaction is still continuing. After a period of time, the forward reaction
rate becomes equal to the reverse reaction rate. A state of dynamic equilibrium is re–
established.

• At a microscopic (molecular) scale, reactions continue but both the forward and reverse
reaction rates are equal. At dynamic equilibrium, there is no change in macroscopic
properties such as colour and density of the reaction mixture.

(TOK: Refer to Pg 313 of chemistry course companion.)

7.1.3 Graph of Concentration vs Time and Rate vs Time

• Consider the decomposition of the colourless gas dinitrogen tetroxide (N2O4) to form
dark brown nitrogen dioxide (NO2) gas.

N2O4 (g) ⇌ 2NO2 (g)

Colourless Brown

• The reaction begins with an initial concentration of 0.0400 mol dm–3 of N2O4 and the
formation of NO2 is indicated by the appearance of a brown colour. The progress of the
reaction can be monitored by measuring the intensity of the brown colour with a
spectrophotometer.

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• According to the chemical equation, 2.0 mol of NO2 forms for each mole of N2O4 that
decomposes, so the concentration of N2O4 remaining at any time can be computed by
subtracting half the concentration of NO2 formed from the initial concentration of N2O4.
As time passes, the concentration of N2O4 decreases and the concentration of NO2
increases until both concentrations level off at constant equilibrium values.

• The concentrations of the reactants and products reach constant values, not because
the reactions stop, but because the rates of the forward and reverse reactions
become equal. A dynamic equilibrium is reached.

Dynamic equilibrium is reached:

Concentration
[NO2] increases as [N2O4], [NO2] remain constant
/ mol dm–3
[N2O4] decreases (but may not be the same)

N2O4

NO2

Time / s

Rate
/ mol dm–3 s–1 As N2O4 is consumed,
the rate of forward
reaction decreases.
Dynamic equilibrium is reached:
Rate of forward and reverse
Rate of forward reaction reactions are equal

Rate of reverse reaction

As NO2 is produced, the
rate of reverse reaction
increases.
Time / s

• Because reaction rates depend on concentrations, the rate of the forward reaction
decreases as the concentration of N2O4 decreases, while the rate of the reverse reaction
increases as the concentration of NO2 increases. Eventually, the decreasing rate of the
forward reaction and the increasing rate of the reverse reaction become equal.

Therefore, at dynamic equilibrium,

• Rate of forward reaction = Rate of reverse reaction
• The substances are still reacting together although the concentration of the
reactants and products remain constant.

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• Main features of the equilibrium state:

o Equilibrium is dynamic
 The reaction has not stopped but both forward and reverse reactions are still
occurring at the same rate.

o Equilibrium is achieved in a closed system

 A closed system has no exchange of matter with the surroundings, so
equilibrium is achieved where both reactants and products can react and
recombine with each other.

o The concentrations of reactants and products remain constant (but may not be the
same) at equilibrium
 They and being produced and destroyed at an equal rate.

o There is no change in macroscopic properties

 Macroscopic properties are observable properties such as colour and
density. These do not change as they depend on the concentrations of the
components of the mixture.

o Equilibrium can be reached from either direction

 The same equilibrium mixture will result under the same conditions, no
matter whether the reaction is started with all reactants, all products or a
mixture of both.

Example 1: Chemical System

• Consider the synthesis of ammonia in a closed container which has different

concentrations of nitrogen gas and hydrogen gas.

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

• The following two graphs show how the concentration of reactants and products change
until the time when equilibrium is reached. Equilibrium can be reached from either
direction.

(a) Forward reaction (b) Reverse reaction

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Example 2: Physical System

• Consider water in a closed flask at constant temperature, as shown in the diagram below.

• Fast moving water molecules at the surface may have enough kinetic energy to escape.
As the number of molecules in the vapour phase increases, the pressure of the water
vapour increases. As the water vapour becomes more concentrated, the rate of
condensation increases. Eventually, the rate of condensation equals the rate of
vaporisation when equilibrium is reached.

7.1.4 Activation Energy and Reversibility

• The reversibility of a reaction depends on the relative activation energies of the forward
and backward reactions.

• Irreversible reactions are those:

o which have a very high activation energy for the backward reaction (Eb >> Ef).
o in which only the forward reaction takes place.

Energy
Ef : activation energy for forward reaction
Eb : activation energy for reverse reaction
Ef

reactants Eb

products

Progress of reaction

• Reversible reactions are those:

o those with a smaller difference in their activation energies for the forward and
backward reactions.
o those in which both the forward and backward reactions can take place.

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• Case (i): Ef < Eb

Energy
Ef : activation energy for forward reaction
Eb : activation energy for reverse reaction

Ef Eb

reactants products

Progress of reaction

o At equilibrium, there is a higher concentration of products than reactants.

o The position of equilibrium lies to the right (products).

• Case (ii): Ef > Eb

Energy
Ef : activation energy for forward reaction
Eb : activation energy for reverse reaction

Ef Eb

products
reactants

Progress of reaction

o At equilibrium, there is a higher concentration of reactants than products.

o Position of equilibrium lies to the left (reactants).

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• Comparison of the Concentration vs Time Graphs for cases (i) and (ii):

o Case (i): Ef < Eb

Concentration
/ mol dm–3

Products

Reactants

Time / s
tequilibrium

o Case (ii): Ef > Eb

Concentration
/ mol dm–3

Reactants

Products

Time / s
tequilibrium

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Exercise 1

1. (a) What are the characteristics of a reversible reaction at dynamic equilibrium?

• Rate of the forward reaction is equal to the rate of the reverse reaction
• Forward and reverse reactions must be occurring
• Concentrations of reactants and products unchanged

(b) What condition(s) is / are necessary before dynamic equilibrium can be achieved?

• Temperature must be constant

• Closed system
• Equilibrium is dependent on rates of forward and backward reactions which
are temperature dependent

2. When the gases sulfur dioxide and oxygen are mixed in a 2:1 ratio by volume, the two
gases slowly react to form the sulfur trioxide according to the following equation.

2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

Sketch a graph showing how the rates of the forward and reverse reactions change from
the time the two gases are mixed to the time the reaction reaches equilibrium. Label the
graph clearly.

Rate
/ mol dm–3 s–1

Dynamic equilibrium is reached:

Rate of forward and reverse
Rate of forward reaction reactions are equal

Rate of reverse reaction

Time / s

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7.1.5 The Reaction Quotient (Q), Equilibrium Constant Expression and Equilibrium
constant (Kc)

• Homogenous chemical equilibria refer to systems where the reactants and products
are in the same physical states.

• Consider a reaction at equilibrium,

aA + bB ⇌ cC + dD

• where a, b, c, d are the coefficients in the balanced equation, the equilibrium constant
expression at a particular temperature is:

[C]c [D]d
Kc =
[A]a [B]b

o [ ] = concentration of the reactants or products at equilibrium in mol dm–3.

o Units of Kc = (mol dm–3)c+d–a–b

• If the chemical equation is written in the reverse direction, the new equilibrium constant
expression, Kc’ is the reciprocal of the original equilibrium constant expression, Kc.

1 [A]a [B]b
Kc‘ = =
Kc [C]c [D]d

• The value of the new equilibrium constant Kc’ is the reciprocal of the value of the original
equilibrium constant Kc.

• The expression for the reaction quotient, Q, looks like that used to calculate equilibrium
constant, Kc but Q can be calculated for any set of conditions, not just for equilibrium.

• The reaction quotient (Q) measures the relative amount of products and reactants
present during a reaction at a particular point in time. Q represents the expression
with non–equilibrium concentrations.

[C]c [D]d
Q=
[A]a [B]b

• Q can be used to determine which direction a reaction will shift to reach equilibrium.
o If Kc > Q, a reaction will proceed forward, converting reactants into products.
o If Kc < Q, the reaction will proceed in the reverse direction, converting products
into reactants.
o If Q = Kc, the system is at equilibrium.

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Example 3

Consider the neutralisation reaction between aqueous ammonia and dilute ethanoic acid. The
balanced chemical equation for the reaction is:

NH3 (aq) + CH3COOH (aq) ⇌ NH4+ (aq) + CH3COO– (aq)

Write the equilibrium constant expression for the reaction and state its units.

�NH4 + �[CH3 COO− ]

Kc =
[NH3 ][CH3 COOH]

No units.

Example 4

Consider the reaction between iron(III) ions and iodide ions in aqueous solution. The balanced
ionic equation is:

2Fe3+ (aq) + 3I– (aq) ⇌ 2Fe2+ (aq) + I3– (aq)

Write the equilibrium constant expression for the reaction and state its units.

2
�Fe2+ � [I3 − ]
Kc = 2
�Fe3+ � [I− ]3

Units of Kc = (mol dm–3)2+1–2–3 = (mol dm–3)–2 = mol–2 dm6

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Example 5

In the reaction:

CH3COOH (l) + C2H5OH (l) ⇌ CH3COOC2H5 (l) + H2O (l)

Write the equilibrium constant expression and state its units.

[CH3 COOC2 H5 ][H2 O]

Kc =
[CH3 COOH][C2 H5 OH]

No units.

Example 6

At a certain temperature the reaction,

CO (g) + Cl2 (g) ⇌ COCl2 (g)

has an equilibrium constant, Kc = 13.8.

If [CO]0 = 2.5 mol dm–3 ; [Cl2]0 = 1.2 mol dm–3 ; and [COCl2]0 = 5.0 mol dm–3, which direction
(forward or reverse) will reaction occur to reach equilibrium? (where [ ]0 represents the
concentration at time = 0 seconds)

[COCl2 ] 5.0
Q= = = 1.7
[CO][Cl2 ] (2.5)(1.2)

Since Q < Kc the reaction mixture is not an equilibrium mixture. The product concentrations
are too low and a net forward reaction will occur until Q = Kc.

Enrichment: Heterogeneous Equilibrium

An example of a heterogeneous equilibrium is the thermal decomposition of solid calcium

carbonate in a sealed vessel.

CaCO3 (s) ⇌ CaO (s) + CO2 (g)

Other examples of heterogeneous equilibrium include:

• H2 (g) + CO2 (g) ⇌ CO (g) + H2O (l)

• SnO2 (s) + 2CO (g) ⇌ Sn (s) + 2CO2 (g)
• NH3 (g) + HCl (g) ⇌ NH4Cl (s)

It has been found that for systems where a pure solid or liquid is in equilibrium with a gas:

• The position of equilibrium is independent of the amount of solid or liquid as long as

some is present and the temperature is kept constant

• Concentration terms for pure solids or liquids need not appear in the expression for
Kc. This is because the concentration of a pure solid or a pure liquid which is similar
to its density; which remains almost constant at any temperature.

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Exercise 2

Write the equilibrium constant expressions for the reactions below, stating their units.

1. Fe3+ (aq) + SCN– (aq) ⇌ [Fe(SCN)]2+ (aq)

�Fe(SCN)2+ �
Kc = − ; Units = mol–1 dm3
[Fe3+ ][SCN ]

2. N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

[NH3 ]2
Kc = ; Units = mol–2 dm6
[N2 ][H2 ]3

3. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

[SO3 ]2
Kc = ; Units = mol–1 dm3
[SO2 ]2 [O2 ]

4. 4NH3 (g) + 5O2 (g) ⇌ 4NO (g) + 6H2O (g)

[NO]4 [H2 O]6

Kc = ; Units = mol dm–3
[O2 ]5 [NH3 ]4

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7.1.6 Magnitude of Kc and the Position of Equilibrium

• The equilibrium constant, Kc, is essentially a measure of the extent of a reversible

reaction. If the value of Kc is much greater than 1 then the position of equilibrium lies to
the products side (or to the right) and the mixture contains mainly the products. An
example of this is the oxidation of zinc when it is added to a solution of copper(II) ions.

Zn (s) + Cu2+ (aq) ⇌ Zn2+ (aq) + Cu (s) Kc = 1 x 1037 at 298 K

For this reaction, it has almost gone to completion since Kc is extremely large.

• If the value of Kc is lesser than 1 then the position of equilibrium lies to the reactants side
(or to the left) and the mixture contains mainly the reactants. An example of this is the
dissociation of ethanoic acid in water.

CH3COOH (aq) ⇌ CH3COO– (aq) + H+ (aq) Kc = 1.8 x 10–5 mol dm–3 at 298 K

From the value of Kc, we can deduce that the acid is mainly in the undissociated
molecular form at 298 K and it is a weak acid.

• Relationship between Kc and the extent of a reversible reaction:

Reaction About equal Products

Reactants Reaction
hardly amounts of
predominate at predominate at virtually goes
products and
proceeds equilibrium equilibrium to completion
reactants
Kc < 10–10 Kc = 10–2 Kc = 100 = 1 Kc = 102 Kc > 1010

• The magnitude of Kc only shows the extent of the reaction. It does not indicate the
kinetics of the reaction; it does not give any information about the rates of conversion of
products into reactants. The value of Kc is only temperature dependent and is not
affected by:

o changes in the concentrations of the reactants or products,

o changes in the pressure of the system for gaseous reactants and products,
o the use of a catalyst.

• When the stoichiometric coefficient of a reaction has been multiplied by a factor, n, the
Kc is raised to the power of the factor (Kc)n, so if the reaction has been multiplied by 2,
Kc is squared.

Example:

Reaction 1: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

[NH3 ]2
The equilibrium constant for reaction 1, Kc1 =
[N2 ][H2 ]3

Reaction 2: 2N2 (g) + 6H2 (g) ⇌ 4NH3 (g)

2
[NH3 ]4 [NH3 ]2
The equilibrium constant for reaction 2, Kc2 = =� �
[N2 ]2 [H2 ]6 [N2 ][H2 ]3

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Example 7

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

The following concentrations were measured for an equilibrium mixture at 500 K:

[N2] = 3.0 x 10–2 mol dm–3 ; [H2] = 3.7 x 10–2 mol dm–3 ; [NH3] = 1.6 x 10–2 mol dm–3

Calculate the value of the equilibrium constant for the forward and backward reactions.

2
[NH3 ]2 �1.6 × 10−2 �
Kc = = = 1.7 x 102 mol–2 dm6
[N2 ][H2 ]3 −2 −2 3
[3.0 × 10 ]�3.7 × 10 �

[N2 ][H2 ]3 1 1
Kc’ = = = = 5.9 x 10–3 mol2 dm–6
[NH3 ] 2 Kc 1.7 × 102

• In summary, the manipulations of the value of Kc are as such:

Effect on equilibrium
Effect on Kc
expression
1
Inversing the reaction Inverts the expression
Kc
Multiply reaction coefficients Expression is raised
(Kc)n
by a factor of n to the power of n
Halving the reaction
Square roots the expression �Kc
coefficients

Adding together 2 reactions Multiplies the 2 expressions (Kc1) x (Kc2)

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7.2 The Position of Equilibrium

7.2.1 Le Châtelier’s Principle

Le Châtelier’s principle states that if a change is made to the conditions of a system at

dynamic equilibrium, then the position of equilibrium will shift to counteract the
change and establish a new equilibrium.

• At equilibrium, if the conditions such as the temperature, concentration and pressure of

a closed system are changed, it will cause the system to go into a state to
“re–equilibrate”. The system will be driven to restore the state of equilibrium by means
of changing the composition of the equilibrium mixture. Therefore, the initial composition
of the mixture will be different from the final composition of mixture after the state of
equilibrium is restored. (The composition of mixture refers to the relative amounts of
reactants and products present at equilibrium.)

• However, Le Châtelier’s principle is only a generalisation and it cannot be used to

explain why the position of equilibrium changes or calculate the exact amount of each
of the reactant or product. It is merely used as a prediction of what will happen and it
helps to describe qualitatively the position of equilibrium when the system’s new
dynamic equilibrium is restored.

• On the other hand, the equilibrium expression can be used to calculate quantitatively
the percentage composition of the products and reactants of systems in equilibrium.

7.2.2 Changes in Concentration and the Equilibrium Law

• Consider a reaction at equilibrium,

A+B⇌C+D

If some A is added to a reaction at If some A is removed from a reaction at

equilibrium equilibrium
• The forward reaction works to remove • The reverse reaction works to replace
excess A and position of equilibrium A and the position of equilibrium shifts
shifts from left to right. from right to left.

• A and B react to produce more C and • C and D react together to produce

D. more A and B.

• At the new equilibrium, there will be • At the new equilibrium, there will be
more C and D but less B compared to more B but less C and D compared to
the original equilibrium. the original equilibrium.

• Kc remains unchanged. • Kc remains unchanged.

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Example 8

In the Haber process,

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

[NH3 ]2
Kc =
[N2 ][H2 ]3

(a) When more nitrogen is added at constant volume, [N2] increases.

• Using the equilibrium law argument:

o H2 reacts with the added N2 to form NH3.

o [NH3] increases; [N2] is increased and [H2] is decreased since Kc is unchanged.
o The position of equilibrium shifts to the right (favouring products).

• Using the rate argument:

o Adding more N2 increases its concentration, which causes an increase in the rate
of forward reaction.
o This uses up N2 and H2, so the rate of the forward reaction slowly decreases.
o As more NH3 is formed; the rate of the reverse reaction increases.
o The decreasing rate of forward reaction and the increasing rate of backward
reaction finally become equal when a new equilibrium is re–established.

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(b) When some ammonia is removed, [NH3] decreases.

• Using the equilibrium law argument:

o N2 and H2 react to make up for the lost NH3.

o All concentrations of reactants and products decrease since Kc is unchanged.
o The position of equilibrium shifts to the right (favouring products).

• Using the rate argument:

o Removing NH3 decreases the rate of reverse reaction.

o The rate of forward reaction gradually decreases as the forward reaction uses up
N2 and H2.
o The forward rate slows, while the rate of the reverse reaction increases until they
are again equal when a new equilibrium is re–established.

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7.2.3 Changes in Pressure and the Equilibrium Law

• Consider a reaction at equilibrium,

4A (g) + 3B (g) ⇌ 2C (g) + D (g)

Pressure of a system in equilibrium is Pressure of a system in equilibrium is

increased decreased
• Increasing the reaction pressure will • Decreasing the reaction pressure will
cause the position of equilibrium to move cause the position of equilibrium to move
in the direction that results in a decrease in the direction that results in an
in the total number of moles of increase in the total number of moles
gaseous particles. of gaseous particles.

• The position of equilibrium shifts from left • The position of equilibrium shifts from
to right, A and B will react to form C and right to left and C and D will react to form
D. A and B.

• At the new equilibrium, there will be more • At the new equilibrium, there will be more
C and D but less A and B compared to A and B but less C and D compared to
the original equilibrium. the original equilibrium.

• Kc remains unchanged. • Kc remains unchanged.

Note: Pressure changes will only affect reactions in which the number of moles of gaseous
reactants is not equal to the number of moles of gaseous products.

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Example 9

Predict what will happen to the equilibrium concentrations when the pressure is increased in
the Haber process.

When the pressure is increased in the Haber process,

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

[NH3 ]2
Kc =
[N2 ][H2 ]3

By Le Châtelier’s principle, doubling the pressure doubles all the concentrations, the position
of equilibrium shifts to the right (products) to decrease the total number of moles of gases. Kc
remains unchanged.

Enrichment: Adding an inert gas – (noble gas or a gas that does not react with those
in the reaction).

• If an inert gas is added at constant volume to the equilibrium mixture, the total pressure
of the system will increase. However, all concentrations of the different components of
the reacting mixture will be unchanged. Hence there is no effect on the position of
equilibrium.

• If the gas is added such that the pressure is kept constant, then the total volume must
increase. Thus, the concentrations of reactants and products will be reduced. By Le
Châtelier’s principle, the system will respond by shifting the equation to the side that
has the greater number of gaseous molecules.

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7.2.4 Changes in Temperature and the Equilibrium Law

• Consider a reaction at equilibrium,

A+B⇌C+D , ∆H = +ve or –ve

Increase in reaction temperature Decrease in reaction temperature

• Heat energy is added to the • Heat energy is removed from the
equilibrium mixture. equilibrium mixture.

• The position of equilibrium shifts to • The position of equilibrium shifts to

favour the endothermic reaction to favour the exothermic reaction to
remove some heat energy. produce some heat energy.

• Kc changes. • Kc changes.

• Why Kc changes when temperature changes

• If we assume that the forward and backward reactions are first order in each of the
substances and reaction is elementary, then the rate expressions for the forward and
backward reactions are:

Forward rate = kf [A] [B] ; Reverse rate = kb [C] [D]

where kf and kb are the rate constants at a given temperature.

Hence the ratio of these rate constants must also be a constant.

At equilibrium,

Forward rate = Reverse rate

kf [A] [B] = kb [C] [D]

kf [C][D]
= = Kc
kb [A][B]

Therefore, Kc is temperature dependent only.

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Example 10

In the synthesis of ammonia,

N2 (g) + 3H2 (g) ⇌ 2NH3 (g), ∆H = –92.4 kJ mol–1

[NH3 ]2
Kc =
[N2 ][H2 ]3

• When there is an increase in temperature, it will favour the endothermic reaction as it

absorbs heat. Since the backward reaction is endothermic, NH3 will decompose into N2
and H2.

• The position of equilibrium will shift to the left and [NH3] decreases while [N2] and [H2]
increase.

• As there are more reactants than products at the new equilibrium, Kc will decrease.

• The rates of both forward and backward reactions will increase, however, the rate of
backward reaction increases more than the rate of forward reaction.

Enrichment Material

The effect of temperature on the solubility of solids in liquids can be explained with the help
of Le Châtelier’s Principle. If during the dissolving process, heat is absorbed, the solubility
increases with increase in temperature. Examples include ammonium chloride and sodium
nitrate. In contrast, substances, such as calcium chloride, release heat during dissolving.
The solubility of these substances decreases with increase in temperature. The dissolving
of gases in liquids is always exothermic and hence the solubility of gases in liquids
decreases with an increase in temperature. (This is one reason for chilling carbonated
drinks).

7.2.5 Effect of Catalysts on Position of Equilibrium

• A catalyst alters the rate of a chemical reaction without being used up in the reaction. In
a reversible reaction, it lowers the activation energies of both the forward and backward
reactions.

• Therefore, a catalyst will only change the rate of the reaction but not the position of
equilibrium as it increases the reaction rates of the forward and the backward reactions
by the same extent.

• Catalysts increases the rate constants of both the forward and backward reactions by
the same extent. Adding a catalyst will change the activation of a reaction. The rate
constant, k, will in turn be affected. This can be explained by using the Arrhenius
−Ea
equation, k = A𝑒𝑒 RT .

• Catalysts have no effect on the composition of an equilibrium mixture and Kc does not
change but equilibrium is reached in a shorter time.

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Exercise 3

1. H2O (g) + C (s) ⇌ CO (g) + H2 (g) ∆H = +131 kJ mol–1

At 1000 oC, the above reaction reaches equilibrium and 1 atmospheric pressure is used.

(a) What would be the effect on the concentrations of CO and H2 in the equilibrium mixture
if
(i) temperature increases to 1500 oC?

When the temperature is increased, the position of equilibrium shifts to the right
so as to remove excess heat by favouring the forward endothermic reaction.
Therefore, more CO and H2 will be formed.

(ii) pressure doubles to 2 atm?

When the pressure is increased, the position of equilibrium shifts to the left so as
to reduce the pressure by reducing the total number of molecules of gas.
Therefore less CO and H2 will be formed.

(b) If more carbon monoxide was added to the equilibrium mixture, how would this affect
the amount of H2O and H2 in the equilibrium mixture?

When more CO gas was added, the position of equilibrium shifts to the left so as to
remove some of the extra CO and thus more H2O will be produced in the equilibrium
mixture.

When more CO gas was added, the position of equilibrium shifts to the left so as to
remove some of the extra CO, which will react with some H2 and thus less H2 will be left
in the equilibrium.

2. Fe3+ (aq) + SCN– (aq) ⇌ [Fe(SCN)]2+ (aq)

blood–red complex

In which direction will the equilibrium for the above reaction shift to and hence the
predicted observation, when

(a) extra SCN– is added to the equilibrium mixture;

The position of equilibrium will shift to the right to decrease the [SCN–].

(b) some Fe3+ is removed from the equilibrium mixture.

The position of equilibrium will shift to the left to increase the [Fe3+].

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3. For the following reversible reactions, in which direction will the position of equilibrium
shift to if there is an increase in pressure?

(a) H2 (g) + Cl2 (g) ⇌ 2HCl (g)

There will be no change in position of equilibrium.

(b) 2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

The position of equilibrium will shift to the right.

(c) H2O (g) + C (s) ⇌ CO (g) + H2 (g)

The position of equilibrium will shift to the left.

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Summary – Changes of Conditions on Position of Equilibrium and Kc

Consider, aA + bB ⇌ cC + dD ∆H

Changes to
Equilibrium Equilibrium
conditions at Rate of reaction
position shifts constant, Kc
equilibrium
1 Concentration of A → right No change Increase
and/or B increased (forward reaction)

2 Concentration of C ← left No change Increase

and/or D increased (backward reaction)

3 Pressure is When A, B, C and No change Increase

increased D are gases

(Consider only → right,

moles of gaseous If (a + b) > (c + d)
products and
reactants) ← left,
If (a + b) < (c + d)

4 Temperature → right, Increase Faster for both

increased If ∆H > 0 forward and reverse
(endothermic) reactions

← left, Decrease
If ∆H < 0
(exothermic)

No effect No change
If ∆H = 0

5 Addition of catalyst No effect No change Both forward and

backward reactions
are speeded up
equally

Scan me to
view a video
on the Haber
Process and
its
applications

IBDP Chemistry HL/Equilibrium Page 26

7.2.6 Equilibrium in Industrial Processes

• Many important industrial processes are reversible reactions and the physical conditions
affect the position of equilibrium. Industrial manufacturers are concerned with finding the
optimum conditions to maximize the yield of the products. In addition, they must
consider the rate at which the products are being produced or whether it is economically
viable so that the time taken is significant.

The Haber Process

• Ammonia, NH3, is manufactured by the Haber process which was first patented in 1908.
It was a significant achievement as it meant that countries could manufacture artificial
fertilisers.

N2 (g) + 3H2 (g) ⇌ 2NH3 (g), ∆H = –92.4 kJ mol–1

• About 80% of the 140 million tons of ammonia produced each year is used to make
fertilisers and the rest used to make nitric acid, polymers such as nylon and other
chemicals.

• In the process, nitrogen and hydrogen gases are passed over a finely divided iron
catalyst. Only about 15 to 20% of the reactants are converted into ammonia, NH3, at
equilibrium.

Theoretical conditions Conditions chosen

High pressure gives a higher yield of NH3
but requires a higher cost for the Moderate pressure is used to keep the
expensive chamber to withstand the high cost and maintenance of equipment low.
pressure.
Low reaction temperature gives a higher Moderate temperature is used to speed
yield of NH3. However, low reaction up the reaction. Although the percentage
temperature slows down the rate of yield of ammonia at equilibrium is
reaction. reduced but the process is faster.
Use of catalyst increases the rate of
reaction and allows equilibrium to be
Catalyst of finely divided iron is used.
reached in a shorter time. Note – the
percentage yield of NH3 is not affected.

NOS – The Haber Process and Cause and Effect (refer to page 327 of Chemistry
Course Companion)

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Exercise 4

1. The equilibrium between nitrogen dioxide (dark brown) and dinitrogen tetroxide
(colourless) is represented by the following equation:

2NO2 (g) ⇌ N2O4 (g)

brown colourless

Given that ∆H is negative and Kc = 1 at 328 K

(a) Write the equilibrium constant expression, Kc.

[N2 O4 ]
Kc =
[NO2 ]2

(b) State and explain the effect of increasing temperature on the value of Kc.

Kc decreases;

Forward reaction is exothermic / ∆H is negative / position of equilibrium shifts to left

(c) State and explain the visible change that takes place as a result of a decrease in
pressure.

The mixture will get darker / darker brown than expected;

Equilibrium position shifts to the left / towards reactants (NO2) to favour an increase in
the number of (moles) molecules of gas.

(d) Two moles of NO2 and two moles of N2O4 were placed in an empty 1 dm3 container and
mixture reached equilibrium at 328 K. Predict, with reference to the value of Kc, whether
the equilibrium mixture would contain greater or lesser than two moles of NO2.

Equilibrium mixture contains less than 2 moles of NO2;

[N2 O4 ] 1
given values gives = , i.e. [NO2]2 is too much as Kc stated is 1 at 328 K
[NO2 ]2 2

forward reaction where NO2 converts to N2O4 is preferred.

(Explanation may include the reaction quotient, Q < Kc to predict)

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2. The following equilibrium is established at 1700 oC.

CO2 (g) + H2 (g) ⇌ H2O (g) + CO (g)

(a) Initially, only carbon dioxide gas and hydrogen gas is present, sketch the rate of reaction
against time for each reaction and explain the shape of the graph.

• the forward reaction

• the reverse reaction until shortly after equilibrium is established.

Rate
/ mol dm–3 s–1

Dynamic equilibrium is reached:

Rate of forward and reverse
Rate of forward reaction reactions are equal

Rate of reverse reaction

Time / s

forward reaction:
highest concentration, thus rate is fast at the beginning;
as reaction proceeds, concentrations decrease, so the rate slows

reverse reaction:
zero rate initially / at t = 0 (no products present);
rate increases as concentration of products increases;

dynamic equilibrium happens when rate of forward reaction = rate of backward reaction

(b) Kc for the reversible reaction is determined at two different temperatures. At 850 oC,
Kc = 1.1 whereas at 1700 oC, Kc = 4.9.

Explain whether the forward reaction is exothermic or endothermic.

Kc increases from 1.1 to 4.9 with (increasing) temperature;

When temperature increases, [H2O] and [CO] increases and [H2] and [CO2] decreases.
Hence, forward reaction is favoured / equilibrium position shifts to the right.

By Le Chatelier’s Principle, a increase in temperature favours the endothermic reaction

to absorb heat (to decrease temperature).

Hence forward reaction is endothermic.

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3. 2H2 (g) + CO (g) ⇌ CH3OH (g) ∆H = –92.5 kJ mol–1

Carbon monoxide and hydrogen gases are passed over a Zn / Cr2O3 catalyst at 300 oC
and 300 atm to manufacture methanol, CH3OH.

(a) In this reaction, what conditions of temperature and pressure are required to produce a
large amount of methanol in the equilibrium mixture?

A low temperature will shift the position of equilibrium to the right so as to produce more
methanol by favoring the forward exothermic reaction.

A high pressure will shift the position of equilibrium to the right so as to reduce the
increased pressure by favouring the product as there are lesser total number of moles
of gas molecules.

(b) 300 oC is a moderate temperature.

(i) State one advantage of using a very high temperature (i.e. over 1000 oC).

Rate of reaction is faster at 1000 oC than at 300 oC.

(ii) State one advantage of using a very low temperature (i.e. below 100 oC).

Higher yield of methanol at below 100 oC.

(iii) Explain the choice of using a moderate temperature

The reaction can be completed quickly without compromising on the product’s

yield.

(c) Explain the advantage of using excess hydrogen in the reaction.

This will ensure that the position of equilibrium shifts to the right giving a higher yield of
methanol.

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17.1 The Equilibrium Law

• The equilibrium expression for homogenous reaction can be used to calculate the value
for Kc. If the value of Kc is known, it can be used to calculate the concentration of a
product.

Example 11

Consider the following data from the synthesis of ammonia at 600 oC.

Trial [N2] / mol dm–3 [H2] / mol dm–3 [NH3] / mol dm–3
1 0.922 0.763 0.157
2 0.399 1.197 0.203
3 2.590 2.770 1.820

Calculate the Kc value for the three trials. What do you notice about the value of Kc?

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

[NH3 ]2
Kc =
[N2 ][H2 ]3

• The value of Kc is the same for all the trials, Kc is 0.0602 mol–2 dm6. The position of
equilibrium lies towards the reactants i.e. nitrogen and hydrogen.

Example 12

Two gases P2 and R2 react as follows:

P2 (g) + R2 (g) ⇌ 2PR (g)

A mixture containing 0.50 mol of P2 and 0.40 mol of R2 was placed in a closed vessel and
allowed to reach equilibrium. The graph below shows how the amount in moles of each gas
varies with time. Calculate the value of the equilibrium constant for the forward and reverse
reaction.

0.6 2
[PR]2 �V�
Kc = = 0.2 0.1 = 18 (no units)
[P2 ][R2 ] � �� �
V V

1 1
Kc’ = = = 0.0556 (no units)
Kc 18

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17.1.1 ICE Method

• Deduce the balanced chemical equation for the reaction.

• Arrange the data according to the ICE method.

o I: The initial concentration of the reactants and products.

o C: The change in concentration. This is the amount by which the concentration of

reactants decrease and the concentration of products increase. These changes
must be consistent with the stoichiometric ratios shown by the coefficients
in the balanced chemical equation.

o E: equilibrium concentration is the concentration of reactants and products when

equilibrium is established.

• Substitute the concentration at equilibrium into the equilibrium constant

expression and determine the value of the equilibrium constant.

Example 13

Nitrogen(IV) oxide NO2, dissociates to form nitrogen(II) oxide and oxygen.

2NO2 (g) ⇌ 2NO (g) + O2 (g)

The following graph shows the variation of concentration of NO2 until equilibrium is reached.

Calculate the equilibrium concentration of the products and comment whether Kc is greater or
lesser than 1.

2NO2 2NO O2
Initial 0.5 0 0
Change –0.4 +0.4 +0.2
Equilibrium 0.1 0.4 0.2

[O2 ][NO]2 [0.2][0.4]2

Kc = = = 3.2 mol dm–3
[NO2 ]2 [0.1]2

Kc is greater than 1.

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Example 14

When 1.0 mole each of CH3OH and CH3CO2H react together according to the equation,

CH3OH (l) + CH3CO2H (l) ⇌ CH3CO2CH3 (l) + H2O (l)

the equilibrium mixture contains 0.2 mol each of CH3CO2CH3 and H2O at room temperature.

(a) Calculate Kc at room temperature.

CH3OH (l) CH3CO2H (l) CH3CO2CH3 (l) H2O (l)

Initial 1.0 1.0 0 0
Change –0.2 –0.2 +0.2 +0.2
Equilibrium 0.8 0.8 0.2 0.2

0.2 0.2
� V �� V �
[CH3 CO2 CH3 ][H2 O]
Kc = = 0.8 0.8 = 0.0625 (no units)
[CH3 OH][CH3 CO2 H] � �� �
V V

(b) If 3.0 moles each of CH3OH and CH3CO2H were mixed together at room temperature,
how much CH3CO2CH3 will be produced at equilibrium?

CH3OH (l) CH3CO2H (l) CH3CO2CH3 (l) H2O (l)

Initial 3.0 3.0 0 0
Change –x –x +x +x
Equilibrium 3–x 3–x x x

Since concentration changes do not affect Kc,

x x
[CH3 CO2 CH3 ][H2 O] �V��V�
Kc = = = 0.0625
[CH3 OH][CH3 CO2 H] 3−x 3−x
� V �� V �

x = 0.6 mol

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Example 15

The equilibrium mixture in a 3.0 dm3 flask at 250 oC was found to be 1.00 mol of PCl5 (g);
2.00 mol of PCl3 (g) and 0.3 mol of Cl2 (g). Calculate the value of equilibrium constant, Kc, and
state its units.

PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)

Concentration of gases
(mol dm–3)
1.0
PCl5 = 0.33
3
2.0
PCl3 = 0.67
3
0.3
Cl2 = 0.10
3

[PCl5 ][Cl2 ] [0.67][0.10]

Kc = = = 0.203 mol dm–3
[PCl3 ] [0.33]

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17.1.2 Gibbs Free Energy

• The thermodynamic state function ΔG is a measure of reaction spontaneity.

• Relationship between ΔG and reaction spontaneity:

o ∆G < 0 (Reaction is spontaneous)

o ∆G > 0 (Reaction is not spontaneous)

o ∆G = 0 (Reaction mixture is at equilibrium)

• In reality, most reactions do not go to 100% completion; instead they reach a point of
equilibrium, where there is minimum value of free energy and a maximum value of
entropy.

• The Gibbs free energy is related to the reaction quotient by the following equation:

ΔG = ΔGθ + RT ln Q

where
ΔGθ is the free energy change under standard conditions
R represents the gas constant
T the absolute temperature in Kelvin.

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• At equilibrium ΔG = 0 and Q = Kc. Substituting into the equation given above,

0 = ΔGθ + RT ln Kc

ΔGθ = −RT ln Kc

• The relationship between Kc and ΔG obtained from this expression is summarised below.

ΔGθ ln Kc Kc
− + >1
+ − <1
0 0 1

• If ΔG is negative, Kc is greater than 1 and the products will be at a higher concentration

in the equilibrium mixture.

• Alternatively, if ΔG is positive, Kc will be less than 1 and the reactants will be at a higher
concentration in the equilibrium mixture.

Example 16

Use ΔGθ = −32.96 kJ mol–1, calculate the equilibrium constant, Kc for the following reaction at
25 oC:

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

ΔGθ = −RT ln Kc

𝜃𝜃
∆G
ln Kc = −
RT
Substituting the known value of ΔGθ, R, and T into this equation gives the following result:

(−32960)
ln Kc = − = 13.3
(8.31)(298)

Kc = e13.3 = 6.0 x 105

The equilibrium constant, Kc for this reaction at 25 oC is 6.0 x 105

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Example 17

Using the information given, calculate the standard Gibb's free energy formation of HI and the
equilibrium constant Kc for the reaction.

1 1
H2 (g) + I2 (g) ⇌ HI (g),
2 2
ΔHθreaction = 26.5 kJ mol–1 and ΔSθreaction = 83.18 J mol–1 K–1

ΔGθ
= ΔHθ – T ΔSθ
= 26.5 – (298 x 0.08318)
= +1.71 kJ mol–1

(+1710)
ln Kc = − = –0.6905
(8.31)(298)

Kc = e–0.6905 = 0.5

(TOK – Role of intuition in problem solving refer to page 334 of Chemistry Course Companion)

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Summary

• Dynamic equilibrium is a state in which the rates of the forward and reverse reactions
are equal and the concentrations of the reactants and products remain constant.

• The equilibrium constant, Kc, measures the extent of a reversible reaction. It is the ratio
of the equilibrium concentrations of products over the equilibrium concentrations of
reactants each raised to the power of their stoichiometric coefficients.

• Magnitude of Kc
o If the Kc value is large (Kc >> 1), the equilibrium lies to the right and the reaction
mixture contains mostly products.
o If the Kc value is small (Kc <<1), the equilibrium lies to the left and the reaction
mixture contains mostly reactants.
o If the Kc value is close to 1 (0.10 < Kc < 10), the mixture contains appreciable
amounts of both reactants and products.

• The value of Kc is only temperature dependent and is not affected by:

o changes in the concentrations of the reactants or products,
o changes in the pressure of the system for gaseous reactants and products,
o the use of a catalyst.

• The reaction quotient (Q) measures the relative amount of products and reactants
present during a reaction at a particular point in time.
o If Q > Kc, the reaction will proceed to the left. The ratio of products over reactants
is too large and the reaction will move toward equilibrium by forming more
reactants.
o If Q < Kc, the reaction will proceed to the right. The ratio of products over reactants
is too small and the reaction will move toward equilibrium by forming more
products.
o If Q = Kc, the reaction mixture is at equilibrium, so no shift occurs.

• Le Châtelier’s principle states that if a change is made to the conditions of a system at

dynamic equilibrium, then the position of equilibrium will shift to counteract the change
and establish a new equilibrium.

• The relationship between Kc and ΔG is summarised below.

ΔGθ ln Kc Kc
− + >1
+ − <1
0 0 1

IBDP Chemistry HL/Equilibrium Page 38

Enrichment: Experimental Determination of Equilibrium Constants

To determine the Kc for the Esterification reaction.

The following procedure details how the equilibrium constant, Kc, for the esterification reaction
can be determined:

C2H5OH (l) + CH3CO2H (l) ⇌ CH3CO2C2H5 (l) + H2O (l)

1 Known quantities of pure or glacial ethanoic acid, CH3CO2H and absolute or pure
ethanol, C2H5OH, are mixed together in a sealed flask of volume V dm3.

2 The flask is placed in a water bath for 20 hours to attain equilibrium. The temperature of
the water is maintained at a fixed temperature; eg 70 oC, using a thermostat.

3 A fixed volume sample is run into a flask containing ice and water. This is to slow down
the reaction before titration with aqueous NaOH. (The reaction between NaOH (aq) and
CH3CO2H would disturb the equilibrium.)

4 A pipette is used to withdraw a known volume of the equilibrium mixture.

5 The amount of CH3CO2H left unreacted in the mixture is determined by titration using
NaOH (aq) and phenolphthalein as an indicator.

6 The concentrations of the other substances in the equilibrium can be calculated.

7 These concentration values are substituted into the expression for Kc. A value for Kc
can then be evaluated.

IBDP Chemistry HL/Equilibrium Page 39