CHEMICAL EQUILIBRIUM

IS

DYNAMIC

COLLEN "COACH” MKHOMAZI

 TABLE OF CONTENTS

TOPIC PAGE(S)

1. ACKNOWLEDGEMENTS 2

2. FOREWORD 3

3. TOPIC OVERVIEW-(In accordance with CAPS) 4

4. PART 1:REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM 5-7

5. PART 2: THE EQUILIBRIUM CONSTANT (KC) 8-13

6. PART 3: FACTORS WHICH INFLUENCE CHEMICAL EQUILIBRIUM 14-26

7. PART 4: APPLICATIONS OF EQUILIBRIUM PRINCIPLES 27-29

8. IN- CLASS DISCUSSION QUESTIONS 30-33

9. PRACTICE EXERCISES 34-48

10. MARATHON PROBLEMS 49-65

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 ACKNOWLEDGMENTS

The author would like to thank the following people for their advice and
support in the development of this module:

Lindiwe Nkutha
Admin Assistant
Kutlwanong Centre for Maths Science and Technology

Kehumile Rachel Taunyane

Admin Assistant
Kutlwanong Centre for Maths Science and Technology

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 FOREWORD

This module is intended as a curriculum supplement for high school science

teachers who would like to introduce their learners to concepts in Dynamic
Chemical Equilibrium. Teachers are urged to use one, some, or all parts of
the module. Some teachers may wish to implement this module in its entirety
as a subject unit in a course. Others may wish to utilize only part of the
module, perhaps the practice exercises. Teachers are encouraged to
reproduce and use these materials in their classrooms and to contact the
author with any assessment, comments, or suggestions they may have.

This is one in a series of physical sciences modules developed and revised

during the Pedagogical Content Knowledge (PCK) Workshops I presented at
the different pronvinces/districts during 2012-'16.

This model offers, above all, an in-depth presentation of Chemical

Equilibrium.

This greater and more careful introduction to Chemical Equilibrium and

their application is of crucial pedagogic importance. Learners who do not
master this early material (and is not so easy for many of them) can become
discouraged and may never recover. Many new worked-out examples
throughout the text, some fairly simple for helping learners get started,
others more difficult than in previous modules (to show learners how to
attack complicated situations).

General exam problems (Marathon Problems) from past question papers,

ranked and arranged by situations (contexts) have been reworked for
increased clarity. All problems have been checked and rechecked by several
Physical Sciences teachers and subject advisors for reasonableness, clarity,
and accuracy.

Thanks

The revision of this module has depended to a great extent on the hundreds
of teachers who have attended the Pedagogical Content Workshops I have
presented and were kind enough to send me their comments and
suggestions for improvement. To all of them I owe a debt of thanks. I also
thank the subject advisors who read and checked the manuscript and
offered valuable suggestions, both for previous modules and for this new
edition.

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 TOPIC OVERVIEW

OBJECTIVES:

The objective of this module is to identify and characterize fundamental concepts of Dynamic
Chemical Equilibrium.

Chemical equilibrium and factors affecting equilibrium

• Explains what is meant by:

o Open and closed systems
o A reversible reaction
o Dynamic Chemical Equilibrium
• List the factors that influence the position of an equilibrium, i.e. pressure (gases only),
concentration and temperature.

Equilibrium Constant

• Explains how to write down an expression for the equilibrium constant (Kc).
• Write down an expression for the equilibrium constant having been given the equation for the
reaction.
• Lists the factors which influence the value of the equilibrium constant (Kc).
• Perform calculations based on Kc values.
• Explains the significance of high and low values of the equilibrium constant.

Application of Equilibrium Principles

• States Le Chatelier’s Principle.

• Uses Le Chatelier’s Principle to identify and explain the effects of changes of
pressure, temperature and concentration on the concentrations and amounts of
each substance in an equilibrium mixture.
• Explains the use of a catalyst and its influence on an equilibrium mixture.
• Explains how to interpret graphs of equilibrium.
• Apply the rate and equilibrium principles to important industrial applications
(Haber Process and the Contact Process).

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 PART 1

REVERSIBLE REACTIONS AND CHEMICAL EQUILIBRIUM

Reversible reactions

In reversible reaction, reactants bond to form products, and products react to form the original
reactants. Most chemical reactions are reversible.

How are reversible reactions represented?

A reversible reaction is a chemical reaction that can proceed in both the forward and reverse
directions. In other words, the reactants and products of one reaction may reverse roles

A double arrow which indicates that reactants react to form products, and that products react
to form reactants, is used to represent reversible reactions. The reversible reaction of ammonia
and hydrogen chloride can be represented as follows:

NH3(g) + HCl(g) ⇋ NH4Cl(s)

This equation shows that the ammonia and hydrogen chloride gases bond to form solid
ammonium chloride and that solid ammonium chloride can break up into ammonia and
hydrogen chloride.

HEAT OF REACTION(ΔH ) IN REVERSIBLE REACTIONS:

In a reversible reaction ΔH is written, e.g., as follows:

2AB2(g) A2B4 (g) (ΔH < 0)

OBSERVATIONS:

• As written, (ΔH) ALWAYS refers to the heat of reaction and for the FORWARD
reaction. In the example the forward reaction is exothermic.
• If the forward reaction is exorthermic then the reverse reaction is ALWAYS
endothermic. [Refer to Ep diagrams].

CONVERSELY, In the reaction:

A+B C+D (ΔH > 0)

• As written, the forward reaction is endothermic

• The reverse reaction is exothermic

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Open and Closed systems

An open system continuously interacts with its environment, while a closed system is isolated
from its surroundings. A closed system is one in which energy can enter or leave the system,
but matter cannot.

The reversible reaction NH3(g) + HCl(g) ⇋ NH4Cl(s) is possibleonly if none of the reactants
or products escape from the container. Such a system is known as a closed system.

The forward reaction can be observed by placing only an open bottle of hydrochloric acid near
an open bottle of ammonia. The solid ammonium chloride can be observed as a white cloud.
This reaction takes place in an open system. The ammonium chloride disappears into the air
as a fine white powder.

NH3(g) + HCl(g) → NH4Cl(s)

The heating of ammonium chloride produces the two gases. If it takes place in an open
container so that the two gases can escape, only the forward reaction, shown below, will take
place. The reaction takes place in an open system and the reverse reaction will not take place.

NH4Cl(s) → NH3(g) + HCl(g)

Note: A closed system does not necessarily mean that a container has to be closed. A reaction
where all the reactants and products are in the liquid phase is a closed system, even if it takes
place in an open container. No gases form and therefore no reactant or product will escape
from the system.

Approaching Equilibrium

• Chemical reactions in a closed system are reversible and do not run to completion.
• A chemical equilibrium is a dynamic equilibrium in which the rate of the forward
reaction is equal to the rate of the reverse reaction.

Decrease in rate of forward reaction as concentration

of reactants decreases
Rate of reaction

Equilibrium

Increase in rate of reverse reaction as concentration of

products increases

Time

Figure 1: A reversible reaction in a closed system eventually reaches equilibrium

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• The concentrations of the reactants and products remain constant(but not equal)once
a state of equilibrium has been reached. As equilibrium is established, the separate
concentrations of the reactants and the products reach steady values.

Concentration
of reactants
Concentrations reach steady values-
Concentration

equilibrium is established

Concentration
of products

O Time

• At equilibrium the concentrations of the reactants and products remain constant. It is a

dynamic equilibrium – the reaction does not stop. The forward and reverse reactions
still take place, but there is no change in the macroscopic properties of the reaction
mixture.

Example: Consider the following reaction that is at equilibrium:

A(g) + B(g) ⇋ C (g) + D(g)

The following statements are TRUE:

• [A], [B], [C] and [D] are constant at equilibrium.

• [A] x [B] is constant at equilibrium.
• [C] x [D] is constant at equilibrium.
• Rate of forward reaction = Rate of reverse reaction

The following statements are FALSE:

• [A] = [B] OR [C] = [D] at equilibrium.

• [B] =[C] OR [A] x [B] = [C] x [D] at equilibrium.

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 PART 2
THE EQUILIBRIUM CONSTANT (KC)
In the 19th century, scientists found that the relationship of products to reactants for a specific
equilibrium reaction is always the same at a specific temperature. Scientists formulated the
law of mass action in 1864:
The Law of Mass Action:For the general equilibrium equation,

jA + kB⇋lC + mD

the relationship between reactants and products at equilibrium can be expressed as follows:

[C ]l [ D] m
Kc = and is known as the equilibrium constant(Kc)expression.
[ A] j [ B] k

• Kc has only a value and no unit.

• If the balanced equation for a chemical reaction is known, the equilibrium constant
expression for the reaction can be written.
• Kc is obtained by the substitution of equilibrium concentrations from products and
reactants in the equilibrium constant expression. Square brackets are used to indicate
equilibrium concentrations.
• An equilibrium position is defined by a particular set of concentrations (equilibrium
concentrations) that satisfies the equilibrium expressions. The specific equilibrium
position attained by a system depends on the initial concentrations.
• An equilibrium position never depends on the amount of pure solids or pure liquids,
and therefore, these substances are not included in the expression for Kc.
• Kc is independent of the reaction mechanism. Only the specific reaction and the
temperature can influence the value of Kc. Kc is therefore always given for a specific
reaction at a specific temperature.
• For each reaction system at a given temperature, there is only one value for the
equilibrium constant but an infinite number of possible equilibrium positions.
• The equilibrium constant for solubility equilibrium is called the solubility product Ksp.
• The “common ion effect” is a disruption of solubility equilibrium by the addition of a
common ion.
• The equilibrium constant that indicates the degree of ionisation of an acid is called the
ionisation constant, Ka.
• The equilibrium constant that indicates the degree of ionisation of water is known as
the ionic product of water, Kw.
• In industrial processes conflicting influences of equilibrium constant and reaction rate
may require consideration, to ensure that reactions are economically viable ( and cost
effective).

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The meaning of equilibrium constants (KC)

For any equilibrium Kc is the relationship of the equilibrium concentration of the products to
[products]
the equilibrium concentrations of the reactants: Kc =
[reactants]
Kc = 1:

The equilibrium concentrations of products are equal to those of the reactants.

• A high Kc (Kc> 1) value therefore means that the concentration of the products is
very high in comparison to that of the reactants. The reaction therefore favours
product formation. We say that the equilibrium lies to the right or the equilibrium
favours the formation of products.

• A low Kc (Kc< 1) value means that the concentration of the products is very low
in comparison to that of the reactants. The reaction therefore does not favour
product formation. We say that the equilibrium lies to the left or the equilibrium
favours the formation of reactants.

What is the significance of the actual Kc value?

If Kc is greater than 1 it means that at equilibrium, there are no more products present than
reactants and vice versa.

A very important thing to note is that only a change in temperature has the ability to
change the Kc value.

• If you would like to increase the Kc value, then do something to the temperature that
favours the forward reaction. Then the equilibrium will shift to the right and the Kc
value will increase

• If you would like to decrease the Kc value, then do something to the temperature that
favours the reverse reaction. Then the equilibrium will shift to the left and the K c
value will decrease.

Example1:

In the following equilibrium reaction, what would have to be done to temperature in order
to decrease Kc?
CO2(g) + H2(g) ⇄ H2O(g) + CO(g) (H = +150 kJ)

You would need to favour the reverse reaction. This would decrease the concentration of
the products and increase the concentration of the reactants, and as a result decrease K c.
The reverse reaction is exothermic and is favoured by a decrease in temperature,
thereforetemperature must be decreased.

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 Example 2:

Consider the following equilibrium reaction:

C(s) + CO2(g) ⇄ 2CO(g) (H > 0)

At 300 K the equilibrium constant is 12. Explain what happens to Kc if the temperature
increased to 600K.

Increasing temperature would favour the endothermic reaction. In this case it will be the
forward reaction that is favoured. The concentration of the products will increase and the
concentration of the reactants will decrease. As a result, Kc will increase.

Calculations with equilibrium constants

If the equilibrium concentrations of reactants and products are known, Kc can be calculated
directly from the equilibrium constant expression, as illustrated in Example 1.

Example 1

A mixture of nitrogen and hydrogen reaches equilibrium in a closed container at a specific

temperature according to the following balanced equation:

N2(g) + 3 H2(g) ⇋ 2 NH3(g)

The analysis of the equilibrium mixture produced the following equilibrium constants for
reactants and products: [N2] = 1 mol·dm-3;[H2] = 2 mol·dm-3;[NH3] = 2 mol·dm-3.

Calculate Kc at this temperature.

Solution:

[ NH 3 ] 2 (2) 2
Kc = = = 0,5
[ N 2 ][H 2 ]3 (1)(2) 3

Example 2 below, shows a case where Kc and equilibrium concentrations of some of the
reactants and products are known.

The equilibrium concentration of the unknown reactant or product can then be calculated from
the given data.

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 Example 2

The equilibrium constant for the reaction:

SO2(g) + NO2(g) ⇋ NO(g) + SO3(g)

is 4 at a certain temperature.

The equilibrium concentrations of the reactants and products are as follows:

[SO2] = 0,2 mol·dm-3; [NO2] = 0,1 mol·dm-3; [NO] = 0,4 mol·dm-3.

Calculate the equilibrium concentration of SO3 (g).

Solution:

[ NO][SO 3 ] (0,4)[SO 3 ]
Kc = 4=  [SO3] = 0,2mol·dm-3
[SO 2 ][ NO 2 ] (0,2)(0,1)

The equilibrium concentrations of reactants and products are often unknown. If only one of
the products/reactants’ equilibrium concentration is known, the equilibrium concentrations of
the other one can be determined from the stoichiometry of the reaction. The following steps
are followed in such a case:

• Draw a table with a column for each reactant and product in the reaction equation.
Write the reaction equation at the top of the table with reactants and products above the
appropriate columns.
• Indicate the stoichiometry of the reaction in the first row under each reactant and
product.
• Indicate the initial concentrations in the second row under the appropriate reactants and
products.
• Leave the third row open for the changes that take place during the reaction. i.e. the
reactants that reacted and the products that formed.
• Write the given equilibrium concentrators in the fourth row.
• Calculate the change in concentration for reactants and products of which both the
equilibrium and initial concentrations are known.
• Use the stoichiometry of the reaction to calculate the changes for the other reactants
and products.
• Now calculate the equilibrium concentrations from the initial concentration and the
change in concentration.

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Example 3 below, illustrates the use of these steps in problem-solving.

Example 3

1 mol·dm-3H2(g) and 2 mol·dm-3 I2(g) were initially mixed in a closed container.

The reaction was allowed to reach equilibrium at 448 °C according to the following
balanced equation:

H2(g) + I2(g) ⇋ 2 HI(g)

When the equilibrium mixture was analysed it showed that the equilibriumconcentration of
HI is 1,80 mol·dm-3. Calculate Kc at 448 °C.

Solution:

Write all the given values in the table:

H2(g) + I2(g) ⇋ 2 HI(g)
Stoichiometry 1 1 2
Initial concentration
1 2 0
(mol·dm-3)
Change in concentration (reagent
and product) (mol·dm-3)
Equilibrium concentration
1,80
mol·dm-3

Now calculate the change in concentration of HI – both the initial and equilibrium
concentrations are known. Use stoichiometry to calculate the change in concentration of H 2
and I2. Then determine the equilibrium concentrations of H2 and I2 by subtraction.

H2(g) + I2(g) ⇋ 2 HI(g)

Stoichiometry 1 1 2
Initial concentration
1 2 0
(mol·dm-3)
Change in concentration (reagent
- 0,90 - 0,90 + 1,80
and product) (mol·dm-3)
Equilibrium concentration
0,1 1,1 1,80
mol·dm-3

Note: Reactants react and become less – as a result the change in reactants is subtracted from
the initial concentration. Products form and increase – as a result the change in product
is added to the initial concentration.

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 [HI] 2 (1,80 ) 2
Kc = = = 29, 45
[H 2 ][I 2 ] (0,1 )(1,1)

Predicting the direction of a reaction

Kc values can be used to predict whether a forward or reverse reaction will take place. The
given concentrations of reactants and products are substituted into the equation constant
expression. These given concentrations are not necessarily equilibrium concentrations and as
a result the answer cannot be equated with Kc. The answer that is obtained in this manner is
called the reaction quotient, Q.

By comparing the value obtained for Q with the value for Kc the direction in which the reaction
will take place can be determined.

** Q = Kc: The system is already in equilibrium.

**Q > Kc: The concentration of the products is too large and that of the reactants too small.
As a result products will react to form reactants, i.e. the equilibrium will shift to the
left.

**Q < Kc: The concentration of products is too small and that of reactants too big. As a result
reactants will react to form products, i.e. the equilibrium will shift to the right.

Key: ** (Enrichment) Not Examinable

Example 4
The Kc for the preparation of NH3 from N2 and H2 is 0,105 at 472 °C.

N2(g) + 3 H2(g) ⇋ 2 NH3(g)

It was found that 2 mol NH3, 2 mol H2 and 1 mol N2were in a 1 dm3 container at472 °C.
Determine whether the reaction is in equilibrium. If not, how will the reaction mixture
react to reach equilibrium?

Solutions:

[ NH 3 ] 2 (2) 2
Q= = = 0,5  Kc – the system is not in equilibrium.
[ N 2 ][H 2 ]3 (1)(2) 3

Q > Kc: NH3 will therefore decompose to form more N2 and H2until equilibrium
is reached. The reaction will therefore take place from right to left.

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 PART 3

FACTORS WHICH INFLUENCE CHEMICAL EQUILIBRIUM

The position of a chemical equilibrium is of great industrial importance. An equilibrium that

lies far to the right indicates high production. An equilibrium that lies far to the left indicates
low production. Industries try to manipulate conditions under which reactions take place in
such a way that the maximum production can be obtained.
Factors which influence equilibrium
The position of the equilibrium, i.e. the number of reactants and products that are present at
equilibrium, is determined by the following factors:
• Concentration
• Temperature
• Pressure (for gases)

Catalysts and chemical equilibrium

• A catalyst has no influence on the equilibrium position.

• The concentration of products will be the same with or without a catalyst.
• Equilibrium may well be reached faster if a catalyst is present, but
• The rates of both the reverse and the forward reactions are increased.

Le Chatelier’s Principle

In 1884 the French chemist, Henri Louis Le Chatelier (1850 – 1936), suggested a principle
according to which the influence of concentration, temperature and pressure on an equilibrium
system can be determined.

Le Chatelier’s Principle allows us to predict qualitatively the effects of changes in

concentration, pressure, and temperature on a system at equilibrium.

Le Chatelier’s Principlestatesthat:

When a closed system in equilibrium is subjected to a change (in temperature, pressure or

concentration) the system will re-establish the equilibrium by opposing the effect of change.

NB: Although a change in temperature, concentration or total pressure will affect the
equilibrium position, only temperature will affect the equilibrium constant .

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USEFUL GUIDELINES WHEN APPLYING LE CHATELIER’S PRINCIPLE

EQULILIBRIUM SYSTEMS tend to compensate for the effects of perturbing influences.

• If the concentration of a solute reactant is increased, the equilibrium position shifts to

use up the added reactants by producing more product. Thus favouring the forward
reaction in the direction of products.
• If the concentration of a solute reactant is decreased, the equilibrium position shifts to
replace the removed reactants by producing more reactants. Thus favouring the reverse
reaction in the direction of reactants.
• If the concentration of a solute product is increased, the equilibrium position shifts to
use up the added products by producing more reactants. Thus favouring the reverse
reaction in the direction of reactants.
• If the concentration of a solute product is decreased, the equilibrium position shifts to
replace the removed products by producing more products. Thus favouring the forward
reaction in the direction of products.
• If the pressure on an equilibrium system is increased, then the equilibrium position
shifts to reduce the pressure. This can be done by favouring the reaction that produces the
least number of gas molecules.
• If the pressure on an equilibrium system is decreased, then the equilibrium position
shifts to increase the pressure. This can be done by favouring the reaction that produces
the most number of gas molecules.
• If the volume of a gaseous equilibrium system is reduced (equivalent to an increase in
pressure) then the equilibrium position shifts to increase the volume (equivalent to a
decrease in pressure).
• If the volume of a gaseous equilibrium system is increased (equivalent to an decrease
in pressure) then the equilibrium position shifts to decrease the volume (equivalent to an
increase in pressure).
• If the temperature of a forward ENDOTHERMIC equilibrium system is increased, the
equilibrium position shifts to use up the heat by producing more products. A decrease in
temperature favours the exothermic reaction in the direction of reactants.
• If the temperature of a forward EXOTHERMIC equilibrium system isincreased, the
equilibrium position shifts to use up the heat by producing more reactants. A decrease in
temperature favours the exothermic reaction in the direction of products.
• Catalyst added: No change in Equilibrium. Equilibrium is only reached much sooner/
faster.

Note: In an equilibrium involving gases, the addition of another gas that is not part of
reaction taking place does not disturb the reaction.

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Application of Le Chatelier’s Principle

When Le Chatelier’s Principle is used to predict the influence of a disturbance on an existing

equilibrium, the following steps must be followed:

• Identify the disturbance

• Indicate the action of the system on the disturbance.
• Indicate how the system will oppose the disturbance.
• Indicate what the result of the action will be on the system.

The three examples (below)that are included at each of the factors which influence
equilibrium, illustrate the application of these steps.

A. Influence of concentration on equilibrium

According to Le Chatelier’s principle the system will oppose an increase in

concentration by favouring the reaction which will decrease the concentration. In the
same manner a decrease in concentration will be opposed by favouring the reaction
which will increase the concentration.

Example 1

A learner prepares separate solutions of iron(III)chloride and potassium thiocyanate by

dissolving 1 g of each substance in 100 cm3 of water in two separate beakers. The learner then
mixes equal amounts of each of the two solutions in two separate test tubes, A and B, and
dilutes the mixture in each of the test tubes until the mixture takes on a light yellow colour.

The equilibrium in the two test tubes can be represented by the following equation:

Fe3+(aq) + CNS-(aq) ⇋ [Fe(CNS)]2+(aq)

Yellow(Colourless) Red

The learner now adds a few potassium thiocyanate crystals to the content of test tube A and
shakes the test tube. The learner also adds a few iron(III)chloride crystals to the content of test
tube B and shakes the test tube.
KCNS crystals FeCl3 crystals

Light yellow Light yellow

solution solution

A B

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Using Le Chatelier’s principle, predict and explain the colour change that the learner ought to
observe in each of the test tubes.

Solution:

Test tube A: Solution turns red

• The addition of KCNS crystals increases the concentration of the CNS- ions.
• According to Le Chatelier’s principle the system will attempt to decrease the
concentration of the CNS- ions.
• The forward reaction is favoured.
• As a result more [Fe(CNS)]2+ forms and the solution turns red.

Test tube B: Solution turns red

• The addition of FeCl3 crystals increases the concentration of the Fe 3+ ions.
• According to Le Chatelier’s principle the system will attempt to decrease the
concentration of the Fe3+ ions.
• The forward reaction is favoured.
• As a result more [Fe(CNS)]2+ forms and the solution turns red.

B. Influence of temperature on equilibrium

An increase in temperature will favour an endothermic reaction which makes use of the
heat. A decrease in temperature will favour an exothermic reaction which releases heat.

Example 2
The following reaction reaches equilibrium in a closed container at a specific temperature.
The gas in the container has a light yellow colour.

2 NO2(g) ⇋ N2O4(g) ΔH < 0

Reddish-brown Colourless

(a) What will be observed if the temperature is increased? Explain your answer in terms
of Le Chatelier’s Principle.
(b) What will be observed if the temperature is decreased?
Explain your answer in terms of Le Chatelier’s Principle.

Solution:
(a) The gas will become darker or reddish-brown/dark brown.
• The increase in temperature is the disturbing factor.
• The system will attempt to decrease the temperature.
• The reverse endothermic reaction which uses heat will be favoured.
• More NO2(g) forms and the gas in the container turns reddish-brown/becomes
darker.
(b) The gas will become lighter.
• The decrease in temperature is the disturbing factor.
• The system will attempt to increase the temperature.
• The forward exothermic reaction which releases heat will be favoured.
• More N2O4(g) forms and the gas in the container becomes lighter.

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C. Influence of pressure on equilibrium

• Pressure will influence equilibrium reactions only where gases are involved.
• An increase in pressure (decrease in volume) will be opposed by an equilibrium
shift which decreases the number of gas molecules.
• A decrease in pressure (increase in volume) will be opposed by an equilibrium shift
which increases the number of gas molecules.
• A reaction where there is no change in the number of gas molecules will not be
influenced by a change in pressure. An example of such a reaction is

H2(g) + I2(g) ⇋2 HI(g).

• Note that the number of mol of gas on the left-hand side is equal to the number of
mol of gas on the right-hand side of the equation.

Example 3
The following reaction reaches equilibrium in a closed container at a specific temperature. The
gas in the container has a light yellow colour.

2 NO2(g) ⇋ N2O4(g) ΔH < 0

Reddish-brown Colourless

(a) What will be observed if the pressure on the system is increased by decreasing
the volume? The temperature stays constant. Explain your answer by applying
of Le Chatelier’s principle.
(b) What will be observed if the pressure on the system is decreased by increasing
the volume? The temperature stays constant. Explain your answer by applying
Le Chatelier’s principle
Solution:
(a) The gas in the container will become lighter.
• The increase in pressure (decrease in volume) is the disturbing factor.
• The system will attempt to decrease the pressure.
• The forward reaction (from 2 mol gas to 1 mol gas) will be favoured.
• More N2O4(g) forms and the gas in the container becomes lighter.
(Note: With a sudden increase in pressure the gas will probably first become darker because
molecules are compressed more. After equilibrium has been reached the gas will take
on a lighter colour.)

(b) The gas in the container will become darker.

• The decrease in pressure (increase in volume) is the disturbing factor.
• The system will attempt to increase the pressure.
• The reverse reaction (from 1 mol gas to 2 mol gas) will be favoured.
• More NO2(g) forms and the gas in the container becomes darker.

(Note: With a sudden decrease in pressure the gas will probably first become
lighter because molecules are less compressed. After equilibrium has been reached
the gas will take on a darker colour.)

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 CHANGING THE FACTORS THAT AFFECT A STATE OF DYNAMIC CHEMICAL
EQUILIBRIUM AND PREDICTING THE EFFECTS:

Consider the following reaction that is at equilibrium in a closed container:

2NO2(g) N2O4 (g) (ΔH < 0)

Factor Change of Effect on reaction Reaction Change in Change in Change

Factor rate favoured the amount the amount in Kc
of products of reactants
Temperature Increase in Both forward and Reverse Amount of Amount of Decreses
Temperature reveverse reaction reaction product reactants
rates increase BUT (N2O4) (NO2)
rate of reverse decreases increases
reaction is faster
Decrease in Both forward and Forward Amount of Amount of Increases
temperature reveverse reaction reactio product reactants
rates decrease BUT (N2O4) (NO2)
rate of forward increases decreases
reaction is faster
BUT takes
long time to
do so
Concentration Increase in Overall reaction rate Forward Amount of Amount of Remains
concentration increases BUT rate reaction product reactants the same
of a reactant of forward reaction (N2O4) (NO2)
[NO2] is faster increases decreases
Increase in Overall reaction rate Reverse Amount of Amount of Remains
concentration increases BUT rate reaction product reactants the same
of aproduct of reverse reaction (N2O4) (NO2)
[N2O4] is faster decreases increases
Decrease in Overall reaction rate Reverse Amount of Amount of Remains
concentration decreases BUT rate reaction product reactants the same
of a reactant of reverse reaction (N2O4) (NO2)
[NO2] is faster decreases increases
Decrease in Overall reaction rate Forward Amount of Amount of Remains
concentration decreases BUT rate reaction product reactants the same
of a product of forward reaction (N2O4) (NO2)
[N2O4] is faster increases decreases
Pressure Increase in Both forward and Forward Amount of Amount of Remains
pressure by reveverse reaction reaction product reactants the same
decreasing rates increase BUT (N2O4) (NO2)
volume of gas rate of forward increases decreases
in container reaction is faster
Decrease in Both forward and Reverse Amount of Amount of Remains
pressure by reveverse reaction reaction product reactants the same
increasing rates decrease BUT (N2O4) (NO2)
volume of gas rate of reverse decresaes Increases
in container reaction is faster
Catalyst Adding a Both forward and None are Remains the Remains the Remains
Catalyst reveverse reaction favoured same same the same
rates increase equally

19 | P a g e
Concentration-Time and Reaction Rate –Time Graphs in an Equilibrium Situation

In a concentration/ no. of moles versus time graph in an equilibrium system, each substance
in the container is represented by its own line on the graph and the amount of that substance
present at any time can be seen and read off the graph. When the system is in equilibrium the
lines representing the amount of substances present areparallel, indicating that the
concentrations of the substances present remains constant.

However, in a reaction rate versus time graph in an equilibrium system, there are only two
lines on the graph – one representing the forward reaction and one representing the reverse
reaction. When the system is in equilibrium the lines representing the rates of reaction meet
one another, indicating that the rate of the forward reaction equals the rate of the reverse
reaction.
Imagine that the following equilibrium exists: A2(g) + 3B2(g) ⇌ 2AB3(g) (H <0)
Let us change some variables and see how the graphs change under different conditions:

1. Change in concentration

(a) More A2 is added to the container

The system will try and use A2 that has

[B2] been added. The forward reaction will be
favoured and equilibrium will shift to the
Concentration

right. As a result, the [A2] will decrease,

the [B2] will decrease and the [AB3] will
[AB3] increase.

[A2]

time

Forward
Reaction

Increasing the concentration of

Reverse
Reaction A2increases the rate of both reactions.
But increasing the concentration of A2
favours the forward reaction, so the
forward reaction will speed up more than
Reaction rate

the reverse reaction.

time
20 | P a g e
(b) AB3 is removed from the container

The system will try and replace the AB3 that

[B2]
has been removed. The forward reaction will
Concentration

be favoured and equilibrium will shift to the

right. As a result, the [A2] will decrease, the
[AB3] [B2] will decrease and the [AB3] will
increase.

[A2]

time

Forward Decreasing the concentration of

Reaction
AB3decreases the rate of both reactions.
Reverse
But decreasing the concentration of AB3
Reaction rate

Reaction favours the forward reaction, so that the

forward reaction will slow down less
than the reverse reaction.

time

21 | P a g e
2. Change in temperature

(a) Temperature is increased

Increasing the temperature favours the

[B2] endothermic reaction, which in this case
is the reverse reaction.The reverse
reaction will be favoured and equilibrium
Concentration

will shift to the left. As a result, the [A2]

[AB3] will increase, the [B2] will increase and
the [AB3] will decrease.
[A2]

time

Forward
Reaction
Increasing the temperature increases the
Reverse
Reaction
rate of both reactions. But because the
reverse reaction is favoured, the reverse
reaction will speed up more than the
Reaction rate

forward reaction.

time

22 | P a g e
(b) Temperature is decreased

Decreasing temperaute favours the

exothermic reaction, which in this case is
[B2] the forward reaction. The forward
reaction will be favoured and equilibrium
Concentration

will shift to the right. As a result, the

[AB3] [A2] will decrease and the [B2] will
decrease and the [AB3] will increase.

[A2]

time

Forward
Reaction

Decreasing the temperature decreases the

Reverse
Reaction rate of both reactions. But because the
forward reaction is favoured, the forward
reaction will slow down less than the
Reaction rate

reverse reaction.

time

23 | P a g e
3. Change in pressure

(a) Pressure is increased

Increasing the pressure will favour the

[B2] reaction that proceeds towards the least
Concentration

number of moles, which in this case is

the forward reaction and equilibrium will
[AB3] shift to the right. As a result, the [A2] will
decrease, the [B2] will decrease and the
[AB3] will increase
[A2]

time

Forward
Increasing the pressure increases the rate
Reaction of both reactions. But because the
forward reaction is favoured, the forward
Reverse
Reaction reaction will speed up more than the
reverse reaction
Reaction rate

time

24 | P a g e
(b) Pressure is decreased

Decreasing the pressure will favour the

[B2] reaction that proceeds towards the most
number of moles, which in this case is
Concentration

the reverse reaction and equilibrium will

shift to the left. As a result, the [A2] will
[AB3] increase and the [B2]will increase and the
[AB3] will decrease.
[A2]

time

Forward
Reaction
Decreasing the pressure decreases the
Reverse
rate of both reactions. But because the
reaction reverse reaction is favoured, the reverse
reaction will slow down less than the
Reaction rate

forward reaction.

time

25 | P a g e
4. Adding a catalyst

Adding a catalyst does not affect

equilibrium therefore does not affect the
[B2] concentration of the individual
substances.
Concntration

[AB3]

[A2]

time

Forward
Reaction

Reverse
Reaction

Adding a catalyst increases the rate of

Reaction rate

both reactions equally.

time

26 | P a g e
 PART 4

APPLICATIONS OF EQUILIBRIUM PRINCIPLES TO INDUSTRIAL PROCESSES

1. Haber Process

The Haber Process is the name given to the industrial preparation of ammonia (NH3).

During this process, nitrogen (N2) bonds directly with hydrogen (H2) to form ammonia (NH3)
according to the following reaction:

N2(g) + 3 H2(g) ⇋ 2 NH3(g) H = - 92kJ·mol-1

Conditions for the preparation of ammonia

The reaction between hydrogen and nitrogen is reversible. Initially when the concentrations of
H2 and N2 are still high, the rate of the forward reaction will be the fastest. As the ammonia
forms, the reverse reaction will take place until equilibrium is reached.

a) Influence of concentration:

According to Le Chatelier’s Principle a rise in the concentration of reactants favours the yield
of ammonia. The ratio between hydrogen and nitrogen in the reaction container is monitored
and is kept at 3: 1. This ensures that there are always reactants to react and that the space is
not wasted by too much of one reactant. The constant removal of NH3 as it is produced ensures
that the forward reaction is permanently favoured, increasing the yield of NH3.

b) Influence of temperature:

The reaction between H2 and N2 is exothermic. A low temperature is thus advantageous for
the production of ammonia.

N2(g)+ 3 H2(g)⇋2 NH3(g) H = - 92kJ·mol-1

However, very low temperatures are disadvantageous for the rate at which ammonia is
produced. At higher temperatures the production of ammonia is faster but the yield is lower.
400 – 450 °C is the best temperature where both yield and rateare such that the process is
financially beneficial.

27 | P a g e
c) Influence of pressure:

According to the balanced, reaction 4 mol gas reacts to deliver 2 mol gas. High pressure is
thus advantageous for the yield of ammonia.

N2(g)+ 3 H2(g)⇋2 NH3(g)

High pressure is also advantageous for the rate at which ammonia forms. The gas molecules
are closer to each other at high pressure and more effective collisions will take place, which
will lead to reactions. High pressure will thus ensure a larger yield at a faster rate.

The cost of an ammonia plant which is able to resist extremes of pressure is very expensive.
In order to ensure that the yield and rate of production are as high as possible at the lowest
possible cost, a pressure of 200 atmosphere is used.

d) Catalyst:

A fine iron catalyst, or a mixture of iron and iron oxide, is used to accelerate the rate of
ammonia formation. The catalyst increases the rate at which the whole reaction proceeds.

NB: All these conditions produce an ammonia yield of approximately 15%.

This yield is the best after rate, yield and cost are taken into consideration.

2. Contact Process

The Contact Process is the name given to the industrial process for the formation of Sulphuric
acid (H2SO4).

The contact process can be divided into three steps:

o Preparation of sulphur dioxide (SO2)

o Conversion of sulphur dioxide to sulphur trioxide (SO3) in the presence of a
catalyst.
o Conversion of sulphur trioxide to sulphuric acid (H2SO4)

The conversion of sulphur dioxide to sulphur trioxide (SO3) in the presence of a catalyst can
be understood in terms of equilibrium principles.

28 | P a g e
Conversion of sulphur dioxide to sulphur trioxide

After purification and cooling the sulphur dioxide reaches the converter where, in the presence
of vanadium pentoxide (V2O5) as catalyst, it is converted to sulphur trioxide. This reaction is
reversible and the formation of sulphur trioxide is exothermic.

2 SO2(g) + O2(g) ⇋ 2 SO3(g) H = - 196 kJ·mol-1

Sulphur dioxide and oxygen are mixed in equal amounts in the reaction container. According
to the balanced equation this means that there is excess oxygen present. The yield of sulphur
trioxide is affected by the concentration of reactants, pressure and temperature.

a) Influence of concentration:

According to Le Chatelier’sPrinciple an increase in concentration of the reactants will increase

the production of sulphur trioxide. This is accomplished inexpensively by keeping the oxygen
concentration high. A 1:1 ratio of reactants produces the best yield of sulphur dioxide.

b) Influence of temperature:

The forward reaction is exothermic and is favoured by decreasing the temperature. For the
maximum yield, is the temperature must be as low as possible. However, too low a temperature
unfavourable for the rate at which sulphur trioxide is prepared. Manufacturers must thus find a
balance between yield and rate. The result is that the reaction is carried out at 400 – 450 °C.
Although the yield is lower, the product is obtained at a faster rate.

c) Influence of pressure:

According to the balanced equation 3 mol gas reacts to produce 2 mol gas. According to Le
Chatelier’s Principle a high pressure will be favourable for the yield of sulphur trioxide. An
increase in pressure will also increase the reaction rate. For economic reasons, the process is
carried out at a pressure close to atmospheric pressure. At this pressure the conversion is
already approximately 99% and a further increase is not worth the expense.

d) Catalyst:

Vanadium Pentoxide (V2O5) is used as the catalyst.The catalyst increases the rate at which
sulphur trioxide is prepared. It has no effect on the yield of sulphur trioxide – only the rate at
which it is produced.

29 | P a g e
 IN-CLASS DISCUSSION QUESTIONS

CHEMICAL EQUILIBRIUM

IS

DYNAMIC EQUILIBRIUM

PREPARED BY: COLLEN "COACH" MKHOMAZI

30 | P a g e
IN- CLASS DISCUSSION QUESTIONS

These questions are designed to be considered by groups of learners in class. Often these
questions work well for introducing a particular concept/topic in class.

Dynamic Chemical Equilibrium – In-Class Discussion Questions

1. What are the conditions necessary for equilibrium?

2. What is a forward reaction versus a reverse reaction?

3. Why does the forward reaction rate decrease as equilibrium is approached ?:

4. What are the characteristics of equilibrium?

5. Define equilibrium.

6. Define the word dynamic and explain its relevance to the concept of equilibrium.

7. Why does the reverse reaction rate increase as equilibrium is approached?

As a reaction is approaching equilibrium describe how the following change. Explain

what causes each change.
8. Reactant concentration.

9. Products concentration.

10. Forward reaction rate.

11. Reverse reaction rate.

12. What is equal at equilibrium?

13. What is constant at equilibrium?

31 | P a g e
14. Sketch each graph to show how concentrations change as equilibrium is approached

[Reactant] [Product] Overall Rate

15. Label each graph with the correct description.

 The forward and reverse rates as equilibrium is approached

 The overall rate as equilibrium is approached

C. The reactant and product concentrations as equilibrium is approached (two

graphs)

32 | P a g e
16. Consider an equilibrium mixture of four chemicals/substances (A, B, C, and D, all
gases) reacting in a closed flask according to the equation:

A+B ⇋ C+D

a. You add more A to the flask. How does the concentration of each chemical
compare to its original concentration after equilibrium is re-established? Justify
your answer.

b. You have the original set-up at equilibrium, and add more D to the flask. How
does the concentration of each chemical compare to its original concentration after
equilibrium is re-established? Justify your answer.

17. Given the reaction, A(g) + B(g) ⇋ C (g) + D (g), consider the following
situations:

i. You have 1.3 M of A and 0,8M of B initially.

ii. You have 1.3 M of A and 0,8Mof B and 0,2 M of C initially.
iii. You have 2.0 M of A and 0,8M of B initially.

Order the preceding situations in terms of increasing equilibrium concentration of D.

Explain your order. Then give the order in terms of increasing equilibrium
concentration of B and explain.

18. How will the equilibrium position of a gas-phase reaction be affected by changing the
volume of the reaction vessel? Are there reactions that will not have their equilibria
shifted by a change in volume? Explain.

19. Consider the reaction, A (g) + B(g) ⇋ C (g) + D (g).

A friend asks the following: ‘I know we have been told that if a mixture of
chemicals/substances A, B, C, and D, is at equilibrium and more of A is added, more
C and D will form. But how can more C and D form if we do not add more B?”

What do you tell your friend?

20. For the reaction, H2 (g) + I2(g) ⇋ 2HI (g), consider two possibilities:

a. You mix 0,5 mol of each reactant, allow the system to come to equilibrium, and
then add another mole of H2 and allow the system to reach equilibrium again, or
b. You mix 1,5 mol H2 and 0,5 mol I2 and allow the system to reach equilibrium.

Will the final equilibrium mixture be different for the two procedures? Explain your
answer.

33 | P a g e
 PRACTICE EXERCISES
(IN THIS QUESTIONS SIMILAR EXERCISES ARE PAIRED)

34 | P a g e
Practice Exercise 1
1.1 Characterize a system at chemical equilibrium with respect to each of the following:

a. The rates of the forward and reverse reactions

b. The overall composition of the reaction mixture

1.2 Distinguish between the terms equilibrium constant and equilibrium position.

1.3 There is only one value of the equilibrium constant for a particular system at a

particular temperature, but there is an infinite number of equilibrium positions.

Explain.

1.4 The magnitude of the equilibrium constant is related to the tendency of a reaction to

occur. Explain.
1.5 Write the equilibrium expressions (Kc) for each of the following gas-phase reactions:
a. N2 (g) + O2 (g) ⇄ 2 NO (g)

b. 2 N2 (g) + 6 H2 (g) ⇄ 4 NH3 (g)

c. 2 SiH4 (g) + 2 Cl2 (g) ⇄ SiCl4 (g) + 2 H2 (g)

d. 2 PBr3 (g) + 3 Cl2 (g) ⇄ 2PCl3 (g) + 3 Br2 (g)

1.6 In which direction will the position of the equilibrium

2HI (g) ⇄ H2 (g) + I2 (g)

in each of the following cases?

a. H2(g) is added

b. I2(g) is removed
c. HI(g) is removed

d. Some Ar(g) is added

e. The volume of the container is doubled.

f. The temperature is decreased ( the forward reaction is exothermic).

35 | P a g e
Practice Exercise 2: LeChatelier’s Principle
Describe the changes that occur after each stress/disturbance is applied to the equilibrium
mixture.

N2(g) + 3H2 (g)⇄ 2NH3(g) ∆H = - 92 KJ

Reaction
Favoured Shifts to the
Stress [N2] [H2] [NH3] Forward or
Reverse Reactants or
Product

1. [N2] is increased

2. [H2] is increased

3. [NH3] is increased

4. Temp is increased
5. [N2] is decreased

6. [H2] is decreased

7. [NH3] is decreased

8. Temp is decreased

9. A catalyst is added

36 | P a g e
 N2O4(g) ⇄ 2NO2(g) H = + 92 KJ

Reaction Favoured Shifts to Favour the

Stress [N2O4] [NO2] Forward or Reverse Reactants or
Products

1. [N2O4] is increased

2. [NO2] is increased

3. Temp is increased

4. [N2O4] is decreased

5. [H2] is decreased

6. [NO2] is decreased

7. Temp is decreased

4HCl (g) + O2 (g)⇄ 2H2O(g) + 2Cl2 (g) + 98 KJ

Reaction Favoured Shifts to

Favour the
Stress [O2] [H2O] [HCl] Forward or Reverse Reactants
or Products

1. [HCl] is increased
2. [H2O] is increased
3. [O2] is increased
4. Temp is increased
5. [H2O] is decreased
6. [HCl] is decreased
7. [O2] is decreased
8. Temp is decreased
9. A catalyst is added

37 | P a g e
CaCO3 (s) + 170 KJ ⇄ CaO (s) + CO2 (g)

Note : Adding solids or liquids and removing solids or liquids does not shift the equilibrium.
This is because you cannot change the concentration of a pure liquid or solid as they are
100% pure. It is only a concentration change that will change the no of collisions and hence
shift the equilibrium.

Reaction Favoured Shifts to Favor the

Stress [CO2] Forward or Reverse Reactants or
Products

1. CaCO3 is added

2. CaO is added

3. CO2 is added

4. Temp is decreased

5. A catalyst is added

6. [CO2] is decreased

7. Temp is increased

8. CaO is removed

38 | P a g e
Practice Exercise 3: Applying Le Châtelier's Principle
The oxidation of ammonia is a reversible exothermic reaction that proceeds as follows:
4 NH3 (g) + 5 O2 (g) ⇄ 4 NO (g) + 6 H2O (g)

For each situation described in the table, indicate an increase or decrease in overall
concentration from before to after a new equilibrium has been established.

Component Stress Equilibrium Concentrations

NH3] [O2] [NO] [H2O]

NH3 addition

removal

O2 addition

removal

NO addition
removal
H2O addition
removal

[NH3] [O2] [NO] [H2O]

Increase in temperature

Decrease in temperature
Increase in pressure

Decrease in pressure

Addition of a catalyst

An Inert gas is added

39 | P a g e
Practice Exercise 4: Applying Le Châtelier's Principle
1. The chromate and dichromate ions set up an equilibrium system as follows:

energy+ 2 CrO4 2-(aq) + 2 H+(aq) ⇄ Cr2O7 2-(aq) + H2O (l)

yellow orange

Describe how the above equilibrium will shift after each stress below:

Shift
(Reaction favoured) color change
+
Increase in [H ]
Increase in [CrO4 2-]
Increase in [Cr2O7 2-]
Decrease in [H+]
Decrease in [CrO4 2-]
Increase in temperature
Decrease in temperature
Add HCl (aq)
Add NaOH

2. The copper (II) ion and copper (II) hydroxide complex exist in equilibrium as follows:

Cu(OH)2 (aq) + 4 H2O (l) ⇄ Cu(H2O)4 2+(aq) + 2 OH-(aq) + 215 kJ

violet light blue

Describe how the above equilibrium will shift after each stress below:

Shift
(Reaction favoured) color change
Increase in [Cu(H2O)4 2+]
Add NaOH
Increase in [Cu(OH)2]
Decrease in [Cu(H2O)4 2+]
Decrease in [Cu(OH)2]
Increase temperature
Decrease temperature
Add KCl (aq)
Add HCl (aq)

40 | P a g e
3. Consider the equilibrium that follows:

4 HCl (g) + 2 O2 (g) ⇄2 H2O (l) + 2 Cl2(g) + 98 kJ

(clear) (yellow)

Describe how the above equilibrium will shift after each stress below:

Shift
(Reaction favoured) color change
Increase in temperature
Increase [HCl]
Decrease in [Cl2]
Decrease temperature
Add Ne at constant volume

4. Consider the equilibrium that follows:

Cu+(aq) + Cl-(aq) ⇄CuCl (s) ΔH = + 98 kJ

(green)

Describe how the above equilibrium will shift after each stress below:
Cu+ is green
Shift
(Reaction favoured) color change
Increase in temperature
Increase [HCl]
Add NaCl
Decrease temperature
Add NaOH (aq)

(check your solubility table for a possible reaction)

Add CuCl(s)
Add AgNO3(aq)

(check your solubility table for a possible reaction)

Add CuNO3(aq)
Add Cu(NO3)2(aq)

41 | P a g e
Practice Exercise 5: Graphing and LeChatelier’s Principle
Consider the following equilibrium system.
I2(g) + Cl2(g)⇄ 2 ICl (g) + energy

Label the graph that best represents each of the following stresses and shift.

 adding I2(g)

B increasing the temperature

C increasing the volume

D removing Cl2(g)

I2
I2

ICI
ICI

I2 I2

ICI CI2

42 | P a g e
Practice Exercise 6: Maximizing Yield

1. N2O4(g) + 59 KJ ⇄ 2 NO2(g)

Describe four ways of increasing the yield of for the reaction above.

Describe three ways to increase the rate of the above reaction.

2. 2SO3(g)⇄ 2SO2(g) + O2(g) + 215 KJ

Describe four ways of increasing the yield of for the reaction above.

Describe three ways to increase the rate of the above reaction.

3. H2O(g) ⇄ H2O(l) H = -150 KJ

Describe three ways of increasing the yield of for the reaction above.

Describe four ways to increase the rate of the above reaction.

4. In the Haber reaction: 3H2(g) + N2(g)⇌ 2NH3(g) + energy

Explain why each condition is used in the process to make ammonia.

A High pressure of 50 MP

The presence of Ur or Os

Condensing NH3 to a liquid

A relatively high temperature 500 oC

43 | P a g e
Practice Exercise 7: The EquilibriumConstant (Kc)
1. What can be deduced from the following:
1.1 A large value for the equilibrium contant ( Kc>1)
1.2 A small value for the equilibrium contant ( Kc<1)
1.3 A value for the equilibrium contant where Kc=1
2. The equilibrium constant for three different reactions are given at certain temperatures:
A. Kc = 1,8 X 10-15 B. Kc = 1,8 X 10-1 C. Kc = 1,8 X 108

Which of the above reactions represents

2.1 a large product to reactant ratio
2.2 a small product to reactant ratio
3. Which factor ONLY will influence the equilibrium contant ( K c)
4. Write expressions for the equilibrium constant (KC) for the following reactions;

Reaction Equilibrium Expression

4.1. 2 SO2 (g) + O2 (g) ⇄ 2 SO3 (g) + energy

4. 2. C (s) + CO2 (g) + energy ⇄ 2 CO (g)

4.3. N2O4 (g) ⇄ 2 NO2 (g)

4.4. CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g)

4.5. 2 NOBr (g) ⇄ 2 NO (g) + Br2 (g)

4.6. 3 Fe (s) + 4 H2O (g) ⇄ Fe3O4 (s) + 4

H2 (g)
4.7. H2 (g) + I2 (g)⇄ 2 HI (g)

4.8. CaCO3 (s) ⇄ CaO (s) + CO2 (g)

4.9. N2 (g) + 3 H2 (g) ⇄ 2 NH3 (g)

4.10. Cu+(aq) + Cl-(aq) ⇄CuCl (sΔH = + 98 kJ

44 | P a g e
Practice Exercise 8: Equilibrium Calculations
1. SO3(g) + H2O(g) ⇄ H2SO4(l)

At equilibrium [SO3] = 0.400M [H2O] = 0.480M [H2SO4] = 0.600M

Calculate the value of the equilibrium constant.

2. At equilibrium at 100oC, a 2.0L flask contains:

0.075 mol of PCl5 0.050 mol of H2O 0.750 mol of HCl 0.500 mol of POCl3
Calculate the Kc for the reaction:
PCl5 (s) + H2O (g) ⇄ 2HCl (g) + POCl3 (g)

3. Kc = 798 at 25oC for the reaction: 2SO2 (g) + O2 (g) ⇄ 2SO3 (g).
In a particular mixture at equilibrium, [SO2] = 4.20 M and [SO3] =11.0M.
Calculate the equilibrium [O2] in this mixture at 25oC.

4. Consider the following equilibrium:

2SO2 (g) + O2 (g) ⇄ 2SO3 (g)

0.600 moles of SO2 and 0.600 moles of O2 are present in a 4.00 L flask at equilibrium
at 100oC. If the Kc = 680.0, calculate the SO3 concentration at 100oC.

5. Consider the following equilibrium: 2 NO2(g) ⇄ N2O4(g)

2.00 moles of NO2 and1.60 moles of N2O4 are present in a 4.00 L flask at equilibrium
at 20oC. Calculate the Kc at 20oC.

6. 2 SO3(g) ⇄ 2 SO2(g) + O2(g)

4.00 moles of SO2 and 5.00 moles O2 are present in a 2.00 L container at 100oC and
are at equilibrium. Calculate the equilibrium concentration of SO3 and the number of
moles SO3 present if the Kc = 1.47 x 10-3.

7. If at equilibrium [H2] = 0.200M and [I2] = 0.200M and Kc = 55.6 at 250oC, calculate
the equilibrium concentration of HI.
H2 (g) + I2 (g) ⇄ 2HI (g)

8. 1.60 moles CO, 1.60 moles H2O, 4.00 moles CO2, 4.00 moles H2 are found in an 8.00
L container at 690oC at equilibrium. CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g)
Calculate the value of the equilibrium constant.

45 | P a g e
Practice Exercise 9: Additional Equilibrium Calculations
Solve each problem and show all of your work.

1. At equilibrium, a 5.0L flask contains:

0.75 mol of PCl5 0.50 mol of H2O 7.50 mol of HCl 5.00 mol of POCl3
Calculate the Kc for the reaction: PCl5 (s) + H2O (g)⇄ 2HCl (g) + POCl3 (g)

2. Kc = 798 for the reaction: 2SO2 (g) + O2(g)⇄ 2SO3(g).

In a particular mixture at equilibrium, [SO2]= 4.20 M and [SO3]=11.0 M.

Calculate the equilibrium [O2] in this mixture.

3. Consider the following equilibrium: 2SO2 (g) + O2 (g) ⇄ 2SO3 (g)

When 0.600 moles of SO2 and 0.600 moles of O2 are placed into a 1.00 litre container
and allowed to reach equilibrium, the equilibrium [SO3] is to be 0.250 M. Calculate
the Kc value.

4. Consider the following equilibrium: 2 NO2(g) ⇄ N2O4(g)

2.00 moles of NO2 are placed in a 1.00 L flask and allowed to react. At equilibrium
1.80 moles NO2 are present. Calculate the Kc.

5. 2 SO2(g) + O2(g) ⇄ 2 SO3(g)

4.00 moles of SO2 and 5.00 moles O2 are placed in a 2.00 L container at 200oC and
allowed to reach equilibrium. If the equilibrium concentration of O 2 is 2.00 M,
calculate the Kc value.

6. If the initial [H2] = 0.200 M, [I2] = 0.200 M and Kc = 55.6 at 250oC

Calculate the equilibrium concentrations of all molecules.
H2 (g) + I2 (g) ⇄ 2HI (g)

7. 1.60 moles CO and 1.60 moles H2O are placed in a 2.00 L container at 690 oC
(Kc = 10.0). CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g)

Calculate all equilibrium concentrations.

8. SO3(g) + NO(g) ⇄ NO2(g) + SO2(g)

o
Kc = 0.800 at 100 C. If 4.00 moles of each reactant are placed in a 2.00L container,
calculate all equilibrium concentrations at 100 oC.

46 | P a g e
9. Consider the following equilibrium system: 2NO2(g)⇌ N2O4

Two sets of equilibrium data are listed for the same temperature.

Container 1 2.00 L 0.12 moles NO2 0.16 moles N2O4

Container 2 5.00 L 0.26 moles NO2 ? moles N2O4

Determine the number of moles N2O4 in the second container.

Get a Kc from the first container and use it for the second container.
Calculate the value of the equilibrium constant.

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 MARATHON PROBLEMS

CHEMICAL EQUILIBRIUM

IS

DYNAMIC EQUILIBRIUM

48 | P a g e
MARATHON PROBLEMS

These problems are designed to incorporate several concepts and techniques into one situation. Marathon
Problems can be used in class by groups of learners to help facilitate problem-solving skills.

QUESTION 1

Carbon monoxide is heated in water vapour in a 2 dm 3 container and the following

homogeneous, dynamicequilibrium is established at 300 K according to the equation below.

CO(g) + H2O(g) ⇌ CO2(g) + H2(g)

1.1 Explain the terms

1.1.1 Homogeneous (2)

1.1.2 Dynamic and (2)
1.1.3 Equilibrium. (2)

The value of Kc for this reaction is 25 at 300 K

1.2 Explain the significance of this value for an industrial chemist. (2)

At a certain stage of the reaction the mixture is analysed and the following amounts
of substances are found in the container of volume 2 dm 3:

1,6 moles CO; 1,6 moles H2O; 6 moles CO2; and 6 moles H2

From this point, the reaction is allowed to reach equilibrium at 300 K

1.3 Calculate the equilibrium concentration of CO2. (6)

The sketch graph below shows how the value of Kc for this reaction changes with
temperature.

Kc

Temperature

1.4 Use this graph to deduce whether the reaction is exothermic or endothermic.
Explain the answer. (4)
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QUESTION 2

When a number of moles of X2(g) and Y2(g) are placed in an empty, closed 2 dm3 container
at 8000 C, a reaction takes place an eventually reaches equilibrium according to the following
equation:

X2(g) + 3Y2 (g) ⇌2XY3(g)

At equilibrium there is 0,4 mol.dm-3 of Y2 and XY3 present.

You are also given the following information for the reaction:

Temperature 0 C Kc
400 0,8
600 2,5
800 4,0

2.1 Calculate the initial number of moles of X2 and Y2placed in the container. (9)
2.2 Is the forward reaction endothermic or exothermic? (1)
2.3 Explain your answer to QUESTION 2.2. (2)
2.4 What effect will adding more Y2 (g) at 8000 C have on the following?

Answer only INCREASE, DECREASE OR STAY THE SAME.

2.4.1 The rate of the reverse reaction. (1)

2.4.2 Concentration of X2(g) (1)
2.5 Which ONE of the following gases XY3 or X2would be present in a higher
concentration in the equilibrium mixture at 4000C? (1)

2.6 Explain your answer to QUESTION 2.5. (2)

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QUESTION 3

A hypothetical reaction, taking place in a closed 1 dm 3 container has reached equilibrium.

The reaction is represented by the equation below.

2A (g) + 3B(g) ⇌ 2C(g) ; H < 0

This equilibrium is considered dynamic.

3.1 Explain the term dynamic equilibrium. (2)

3.2 Give a reason why the forward reaction is exothermic. (1)
3.3 State what change must be made to the system to increase the yield of C.

Use your knowledge of Le Chatelier’s Principle to explain the answer. (4)

Initially, 2 moles of A(g) and 4 moles of B(g) were present in the container. The temperature
was maintained at 1500 C, and at equilibrium it was found that 2, 41 x 1023 molecules of A(g)
were present.

3.4 Calculate the value of the equilibrium constant (Kc) at 1500 C. (8)
3.5 The pressure on the system is decreased by increasing the volume of the reaction
vessel
at the same temperature. How will this change affect the value of Kc?

Write down only INCREASES, DECREASES or REMAIN THE SAME. (1)

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QUESTION 4

4.1 In a research laboratory, a mixture of SO2 gas and O2 gas was placed into a closed
container at 300 C with a small amount of V2O5. This corresponds to the second step
of the Contact Process and SO3 is formed.At certain times, various changes in the
physical conditions applicable to the reaction or to the chemicals themselves were
made. A graph of reaction rate versus time was constructed.

4.1.1 Explain what is meant by the term dynamic equilibrium. (2)

4.1.2 Write down a balanced chemical equation for the reaction represented by:

(a) The dotted line. (2)

(b) The solid line. (2)

4.1.3 At t = 20 s, there was a change in pressure. State whether this change was an

INCREASE or DECREASE in pressure. Give a reason for the answer. (3)

4.1.4 What other change in reaction conditions occurred at t = 40 s? (1)

4.2 0, 5 mole hydrogen gas and 0, 5 mole oxygen gas are sealed in 200 cm3container at
a temperature of 1180 C. The following chemical equilibrium is established after a
certain time.
2H2(g) + O2(g) ⇌ 2H2O(g)  H = -484KJ

Analysis of the equilibrium mixture shows that the mass of oxygen in the
container is 9,6 g. Calculate the equilibrium constant for the reaction at this
temperature. (7)
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QUESTION 5

In 1912, the German chemist Frizt Haber produced ammonia gas by direct combination of
nitrogen gas and hydrogen gas using an iron catalyst. The reaction is as follows:

N2(g) + 3H2(g) ⇌ 2NH3(g)  H = -92Kj

This reaction became known as the Haber Process.

In a small scale plant, used to investigate this reaction, 0,35 ,mol of N 2 and 0, 70 mol of H2
were added to a sealed reaction vessel of volume 2 dm3 and allowed to react until dynamic
chemical equilibrium was reached at 4500C.

Every 10 s, a sensor inside the reaction vessel was able to record the amounts of reactants and
product present and the results are given.

5.1 Explain what is meant by the term dynamic chemical equilibrium (3)

5.2 You are provided with a partially completed graph representing some of the
data given on the table. You are required to complete the graph by doing the
following:

53 | P a g e
Amount of reactant/product (mol) Equilibrium Graph for the Haber Process at 4500C

Time (seconds)

5.2.1 Insert the scale on each axis, used to plot the graphs shown. (2)
5.2.2 Label the lines on the graph representing the amount of N2 and the amount of H2 (2)
5.2.3 Using the data from the table, plot amount of product (NH3)versus time (s)
on the same axes. (4)
Use the now completed graph to answer the following questions:
5.3 Give the independent variable? Explain your answer. (3)
5.4 How long does it take for the reaction to reach equilibrium? Explain (2)
5.5 Do any reactions occur during the time interval t = 70 s and t = 80 s? Explain (3)
5.6 Explain what is represented on the graph at t = 50 s? (2)
0
5.7 Calculate the equilibrium constant (Kc) for the reaction at 450 C (4)
When t = 80 s, the sealed container is heated causing a rapid rise in temperature.
Equilibrium is re-established after additional 20s and maintained for a further 40 s.

5.8 Show the effect of an increase in temperature on the amounts of N2, H2 and NH3 for
the time 80 to 140 s by completing the lines on the graph for this period. (HINT:
You will be given credit for showing the relative changes of amount of N 2, H2 and
NH3). (6)
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QUESTION 6

The catalytic oxidation of ammonia is represented by the equation below:

4NH3(g) + 5O2(g) ⇌4NO(g) + 6H2O(g)

2,0 mol of ammonia gas and 1,0 mol of oxygen gas are placed in a 2,0 dm 3 container at
1 000 kPa and allowed to reach equilibrium at 1 000 °C. At this temperature and pressure
the amount of water vapour present is 0,6 mol.

6.1 Calculate the value of the equilibrium constant at this temperature. (8)

6.2 Briefly explain the significance of the value obtained in QUESTION 6.1. (1)

6.3 What effect will the addition of a platinum catalyst have on the yield of NO (g) at
the given temperature?

Write down only INCREASE, DECREASE or REMAIN THE SAME. (1)

6.4 The pressure on the system is decreased by increasing the volume.

Use Le Chatelier’s principle to explain how this change affects the yield of NO(g). (3)

6.5 It is found that at a temperature of 500 °C the value of the equilibrium

constant is greater than the value calculated in QUESTION 6.1.

What is the sign of ΔH for the reaction mentioned above?

6.6 Explain your answer to QUESTION 6.5. (4)

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QUESTION 7

Methanol vapour (CH3OH) is sealed in a closed container and reaches equilibrium at a

temperature of 400 K according to the following equation:

CH3OH(g) ⇌ CO(g) + 2H2(g)

After 8 minutes, the temperature is increased to 500 K. The graph shows the change in
reaction rate over 12 minutes.
Reaction rate

0 4 8 10 12
Time in minutes

7.1 Write down the balanced equation for the reaction represented by the broken line. (2)

7.2 Is the reaction represented by the solid line exothermic or endothermic? (1)

7.3 Explain your answer to question 7.2 by referring to the graph (3)

7.4 What is represented by the horizontal section of the graph between the
10th and the 12th minutes? (1)

7.5 How would the value of the equilibrium constant for the system at 400 K compare
with that for the system at 500 K? (1)
[8]

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QUESTION 8

Gasses X and Y are pumped into a 2dm3 container. When the container is sealed 4 moles
of gas X and 4 moles of gas Y are present. The following equilibrium is established:

2X(g) + 3Y(g) → X2Y3(g)

The graph below shows the number of moles of gas X and gas X2Y3 present from the
time the container is sealed.

4
Number of moles

X (g)
3

1
X2 y3 (g)
0, 5

0 30 70 100
Time(s)

8.1 How many moles of gas X2Y3 are formed by the time the reaction reaches
equilibrium at t =30 s? (1)
8.2 Calculate the value of the equilibrium constant at t = 50 s (6)
8.3 At t = 70 s the temperature is increased. Is the forward reaction endothermic
or exothermic? (1)
8.4 Explain your answer to Question 8.3 by applying Le Chatelier's Principle . (3)
8.5 How will this increase in temperature affect the value of the equilibrium constant? (1)

[12]

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QUESTION 9

The following equation represents a reaction in equilibrium

2CrO42- (aq) + 2H+ (aq) ⇌ Cr2O72- (aq) + H2O (l)
Yellow Orange

9.1 Define chemical equilibrium. (2)

9.2 Is this an example of an open or closed system? (1)

9.3 A few drops of nitric acid (HNO3) is added to the mixture.

9.3.1 What will the colour of the solution be?

Write only ORANGE or YELLOW. (1)

9.3.2 Give a reason for this observation. (2)

9.4 Write down the expression of the equilibrium constant (Kc) for this
reaction. (2)

9.5 Will the addition of water have any influence on the value of the
equilibrium constant . (1)

9.6 What colour will the solution be after a few pellets of sodium hydroxide (NaOH)
is added to the solution?

Write only ORANGE or YELLOW. (1)

9.7 Use Le Chatelier’s Principle and explain the answer to Question 9.6. (3)

[13]

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QUESTION 10

Consider the equilibrium in a saturated solution of sodium chloride as shown by the

equation below:

NaCl(s) ⇌ Na+ (aq) + Cl- (aq); H > 0

10.1 Is the forward reaction exothermic or endothermic? (1)

10.2 At 25 OC, the solubility of sodium chloride is 35,9 g per 100cm3 water.
Calculate the equilibrium constant for the system. (6)
10.3 What change to the reaction conditions will increase the value of KC for this
reaction? Give an explanation for the answer. (4)
10.4 At the same temperature, the equilibrium constant of a saturated solution of
silver chloride (AgCl) is 1,8 x 10-10. Is silver chloride more soluble or less soluble
than sodium chloride at 25 OC? (1)

[12]

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QUESTION 11

11.1 Ntombi listens to a radio advertisement. Its about a fizzy drink. “When you open
the can …it goes…ssssccchhhh…!”

Given the following equilibrium: CO2(aq)⇄CO2(g)

Explain why it goes ssssccchhhh…when the can is opened, by using

Le Chatelier’s Principle and the solubility of carbon dioxide in water. (4)

11.2 In the second step of the Contact process, Sulphur dioxide reacts with oxygen
to give Sulphur trioxide.

2SO2g) + O2(g) ⇄2 SO3 (g)

• Initially 10 moles of Sulphur dioxide and 4 moles of oxygen were put in the
container.
• The volume of the container is 2 dm3
• The equilibrium concentration of oxygen is 0, 25 mol.dm -3

Complete the following table. Redraw the table in your answer book and do the
calculations in the table. (12)

SO2 O2 SO3
Mole ratio
Number of moles initially 10 4 0
Number of moles used 0
Number of moles at equilibrium
Equilibrium concentration 0, 25 mol.dm-3

11.3 By using the information in the table, calculate the equilibrium constant for the
Reaction (5)
[21]

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QUESTION 12

The preparation of methanol from CO (g) and H2(g) is an example of a homogeneous

equilibrium. The equation for the reaction is:

CO (g) + 2H2 (g)  CH3OH (g) ∆H > 0

Initially CO (G) and H2 (g) are placed in a closed container at 3000 C. The graph below
shows the change in the number of moles of reactants and products as the reaction is allowed
to reach equilibrium at 3000C in a 2 dm3 container.

12.1 Is the forward reaction exothermic or endothermic? Give a reason for the
answer. (2)

12.2 Give a reason why the above reaction is referred to as a homogeneous

equilibrium. (1)
12.3 Calculate the value of the equilibrium constant for the above reaction
at 3000C. (7)
12.4 The volume of the container is now decreased to 1 dm3 while the temperature
is kept constant. How will this change influence the following?

Write down only INCREASES, DECREASES or REMAINS THE SAME.

12.4.1 The concentration of CH3OH (g) after the equilibrium is re-established. (1)

12.4.2 Explain your answer to QUESTION 12.4.1 (1)

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QUESTION 13

Scientists prepare an ester in a laboratory.They first weigh 15 g of ethanoic acid and 11, 5 g
of ethanol. They carefully place the acid and alcohol into a conical flask and then add a few
drops of concentrated sulphuric acid to the mixture.

The equilibrium reaction is represented by the equation below.

CH3COOH + C2H5OH ↔ CH3COO2H5 + H2O

At equilibrium the mixture contained 3 g of ethanoic acid.

13.1 State Le Chatelier’s principle. (2)

13.2 Write down the expression for the equilibrium constant, Kc, for this reaction. (2)
(Use all the reactants and products in the expression)
13.3 Calculate the value of the equilibrium constant, Kc. (8)
13.4 What mass of water will be present in the equilibrium mixture? (2)
13.5 Use your knowledge of Le Chatelier’s principle to briefly explain how
the removal of water affects the yield of the ester. (2)
13.6 What is the role of the few drops of concentrated sulphuric acid? (1)
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QUESTION 14

The following equation represents a hypothetical reaction that reaches equilibrium in

a 2 dm3 closed container at 500 °C after 8 minutes.

2AB3(g) ⇌ 2AB2(g) + B2(g) ΔH < 0

Graph of amount of gas versus time

10

8
Amount of gas (mol)

AB2(g)
6

AB3(g)
4
B2(g)

0
0 4 8 12 16 20 24 28 32
Time (minutes)
14.1 At 16 minutes, one of the conditions affecting the equilibrium is changed at
constant volume and a new equilibrium is thereafter established.

Calculate the Kc value at the new equilibrium. (8)

14.2 Which condition, CONCENTRATION or TEMPERATURE was changed? (2)

14.3 Was the condition identified in QUESTION 14.2 INCREASED or DECREASED?(1)

14.4 Use Le Chatelier's principle to explain the answer to QUESTION 14.3. (3)
14.5How does the equilibrium constant, Kc, between t = 8 minutes and t = 16 minutes
compare to that between t = 24 minutes and t = 32 minutes? Write down only
GREATER THAN, SMALLER THAN or EQUAL TO. (1)

14.6 How will the Kc value be affected if the volume of the container, is decreased
from 2 dm3 to 1 dm3 after 32 minutes, while keeping the temperature constant. (1)
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QUESTION 15

Twelve (12) moles of SO3(g) is sealed in an empty 2 dm3 container at 700 K. It decomposes
into SO2(g) and O2(g) and equilibrium is reached at 700 K according to the following
balanced equation:
2SO3(g) ⇌ 2SO2(g) + O2(g) H > 0

6.1 Define the term reversible reaction. (2)

6.2 If 5,0 moles of O2(g) are present at equilibrium, calculate the equilibrium
constant, Kc, for this reaction at 700 K. (7)
6.3 The graph below shows the changes in the rate of the reaction over
7 minutes from the time that the 12 moles of SO3(g) were sealed in the container.
Rate of reaction

0 2 4 5 7
Time (minutes)

15.3.1 Write down the balanced equation for the reaction that is
represented by the broken line. (1)
15.3.2 Give a reason for the decrease in reaction rate represented
by the solid line between t = 0 minutes and t = 2 minutes. (1)
15.3.3 State the change that was made to the equilibrium mixture at
t = 4 minutes. Fully explain how you arrived at the answer. (4)

15.3.4 How does the value of the equilibrium constant (Kc) for the reaction
at t = 5 minutes compare to that at t = 2 minutes?
Write down GREATER THAN, SMALLER THAN or EQUAL TO. (1)

15.3. Explain the answer to QUESTION 15.3.4. (2)

[18]

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