Equilibrium SL

IB CHEMISTRY SL
7.1 Equilibrium
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 amounts 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.

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Syllabus checklist

Objective I am confident I need to review I need help

with this this with this
Outline the features of
physical and chemical
equilibrium
Write expressions for the
equilibrium constant Kc for a
reaction
Calculate the value of the
equilibrium constant Kc
Outline the difference
between the equilibrium
constant Kc and the reaction
quotient Q
Determine, when given the
values of Q and Kc, in which
direction the reaction will
proceed.
Outline how the value of Kc
changes when changes are
made to the reaction at
constant temperature.
Apply Le Chatelier’s principle
to predict the changes in the
position of equilibrium for
changes in concentration,
temperature and pressure.
Outline the effect of a catalyst
on the position of equilibrium.

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Physical equilibrium
• Physical equilibrium involves a change of state.
• The flask below is a closed system (matter cannot escape).
• The rate of evaporation is equal to the rate of condensation (liquid level is constant).
• The system is at equilibrium.
• Note that in physical equilibrium, there is no chemical change occurring.

On a macroscopic level, there is no change in the level of the liquid.

However, the processes of evaporation and condensation are still
occurring; the liquid is evaporating and condensing at the same rate.
Therefore, we say the system is at dynamic equilibrium.
What will happen if the stopper is removed from the top of the flask?
Will the system reach equilibrium? Why/why not?

• The equation below represents the physical process occurring in the flask.

• The ⇌ sign is used to show that the system is at equilibrium.

Exercises:
1. Bromine (Br2) is a brown liquid that evaporates easily at room temperature. A sample of
bromine is placed in a sealed flask. Write an equation to show the system is at
equilibrium.

2. What can you say about the rates of evaporation and condensation when the system is at
equilibrium?

3. What other macroscopic properties would tell you the system is at equilibrium?

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Chemical equilibrium
• Unlike physical equilibrium, which only involves a change of state, chemical equilibrium
involves a chemical reaction.

• In the forward reaction, hydrogen iodide (HI) decomposes to form hydrogen (H2) and
iodine (I2)
• In the reverse reaction, H2 and I2 react to form HI.

At equilibrium, the rate of the forward reaction is equal to the

rate of the reverse reaction.

Important points about a reaction at equilibrium:

1. Equilibrium is dynamic; the reaction has not stopped and both forward and reverse
reactions are still happening (at the same rate).
2. Equilibrium is achieved in a closed system.
3. The concentrations of reactants and products at equilibrium are constant (NOT EQUAL).
4. At equilibrium, there is no change in macroscopic properties such as colour.
5. Equilibrium can be reached from either direction (from reactants to products or from
products to reactants).

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Equilibrium can be reached in either direction, as shown in the graphs below.

When the lines in the graphs are parallel, the reaction is at equilibrium. The concentrations of
reactants and products are constant at equilibrium, not equal.

Exercise:
1. Ammonia (NH3) is made in the reaction of N2 and H2. The reaction reaches equilibrium.
Write an equation for the forward reaction (with all species in the gaseous state).

2. What can you say about the rates of the forward and reverse reactions at equilibrium?

3. Are the concentrations of reactants and products equal at equilibrium? Explain your
answer.

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Equilibrium constant Kc
• Kc is calculated using equilibrium concentrations of reactants and products.
• The products go in the numerator and the reactants in the dominator.
• The concentrations are raised to the powers of the coefficients in the balanced equation.

• The equilibrium constant Kc has a fixed value for a reaction at a specific temperature (it is
temperature dependent).

Example: The following reaction is carried out at 440oC.

Write the expression for the Kc

Exercises:

1) Write expressions for the equilibrium constant Kc for the following reactions:
a) CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)
b) CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g)
c) CH3OH(g) ⇌ CO(g) + 2H2(g)
d) 2SO2(g) + O2(g) ⇌ 2SO3(g)
e) N2(g) + 3H2(g) ⇌ 2NH3(g)

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Calculating the value of the equilibrium constant Kc
Calculate the equilibrium constant, Kc, for the reaction shown, if 0.0954 mol of CO2, 0.0454 mol
of H2, 0.0046 mol of CO, and 0.0046 mol of H2O vapor were present in a 1.00 dm3 reaction vessel
at equilibrium (at 440oC).

Species Equilibrium concentrations (mol dm-3)

CO2 0.0954 / 1.00 = 0.0954

H2 0.0454 / 1.00 = 0.0454

CO 0.0046 / 1.00 = 0.0046

H2O 0.0046 / 1.00 = 0.0046

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Magnitude of Kc and extent of reaction
• The position of equilibrium of a reaction can lie to the left or to the right.
• If a reaction mixture at equilibrium contains mostly reactants, we say the equilibrium
position lies to the left.
• If a reaction mixture at equilibrium contains mostly products, we say the equilibrium
position lies to the right.
• A high value of Kc means at equilibrium, there are a higher concentration of products
than reactants (the equilibrium position lies to the right).
• A low value of Kc means at equilibrium, there are a higher concentration of reactants
than products (the equilibrium position lies to the left).

Reaction Kc value (at 298 K) Equilibrium position

CaCO3(s) → CaO(s) + CO2(g) 1.9 × 10-23 Lies to the left (forward reaction hardly
proceeds)
2H2(g) + O2(g) → 2H2O(g) 3.2 × 1081 Lies to the right (goes to completion)

N2O4(g) ⇌ 2NO2(g) 4.61 × 10-3 Lies to the left – reaction mixture contains
mostly reactants
N2(g) + 3H2(g) ⇌ 2NH3(g) 640 Lies to the right – reaction mixture
contains mostly products

Exercises:
1. Which is present in greater concentrations if the equilibrium position lies to the left,
reactants or products?

2. Which is present in greater concentrations if the equilibrium position lies to the right,
reactants or products?

3. A reaction has a Kc of 2. What can be said about the equilibrium position and the
concentration of reactants and products at equilibrium?

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 4. A reaction has a Kc of 1.8 × 10-5. What can be said about the equilibrium position and the
concentration of reactants and products at equilibrium?

5. The table below shows equilibrium concentrations of reactants and products for the
following reaction at 2130 oC
N2(g) + O2(g) ⇌ 2NO(g)
Equilibrium concentrations (mol dm-3)
N2(g) 0.81
O2(g) 0.75
NO(g) 0.030

From the above data, calculate the equilibrium constant Kc. Comment on the magnitude
of Kc with respect to the composition of the reaction mixture at equilibrium.

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Manipulating Kc for different reaction equations

Effect on equilibrium
expression Effect on Kc
Reversing the reaction
Doubling the reaction
coefficients
Halving the reaction
coefficients
Adding together 2 reactions

Example:

The equilibrium constant, Kc, for the following reaction is 0.04.

2HI(g) ⇌ H2 (g) + I2 (g)

What would be the value of the equilibrium constant for the following reaction at the same
temperature?

½H2(g) + ½I2(g) ⇌ HI (g)

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Reaction quotient Q
• The reaction quotient Q measures the relative amounts of reactants and products at a
point in time.
• It is expressed with non-equilibrium concentrations.

• At equilibrium, the concentrations of A, B, C and D are constant, and the reaction

quotient is known as Kc

Exercise: Outline the difference between the reaction quotient Q and the equilibrium constant
Kc

Q, Kc and direction of reaction

• Let’s start with a quick explanation of what is meant by the following terms:
• Reaction proceeds to the right – the reaction proceeds to the products side (more
products will be produced).
• Reaction proceeds to the left – the reaction proceeds to the reactants side (more
reactants will be produced).

Relationship between reaction quotient Q and Kc

• When the value of Q is equal to the value of the Kc the reaction is at equilibrium.
• What happens if the value of Q is lower or higher than the value of Kc?
• If the value of Q is lower than the value of Kc, the reaction will proceed to the right to
increase the value of Q.
• If the value of Q is higher than the value of Kc, the reaction will proceed to the left to
lower the value of Q.

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Example 1:

Calculate the value of Q when the concentration of HI is 0.100 mol dm-3 and the concentrations
of H2 and I2 are both 0.0500 mol dm-3

Based on your calculation, predict in which direction the reaction will proceed and explain your
answer.

Example 2:

Calculate the value of Q when the concentration of HI is 0.300 mol dm-3 and the concentration of
H2 is 0.0250 mol dm-3 and the concentration of I2 is 0.0350 mol dm-3

Based on your calculation, predict in which direction the reaction will proceed and explain your
answer.

Summary:

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Exercises:
1) The table below show non-equilibrium concentrations of reactions and products for the
following reaction at 527oC. The value of Kc for this reaction at 527 oC is 5.10.

CO(g) + H2O(g) ⇌ H2(g) + CO2(g)

Concentration at time t (mol dm-3)

CO(g) 0.15
H2O(g) 0.25
H2(g) 0.42
CO2(g) 0.37

From the above data, calculate the reaction quotient Q and predict in which direction the
reaction will proceed.

2) The table below shows non-equilibrium concentrations of reactions and products for the
following reaction at 1000oC. The value of Kc for this reaction at 1000oC is 1.00 × 10-13

2HF(g) ⇌ H2(g) + F2(g)

Concentration at time t (mol dm-3)

HF(g) 23.0
H2(g) 0.540
F2(g) 0.380

From the above data, calculate the reaction quotient Q and predict in which direction the
reaction will proceed.

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Le Chatelier’s principle

‘When a system at equilibrium is subjected to a change, the system will respond to

minimize the effect of the change.’

Changes in concentration
• If changes are made to the concentration of the reactants or products or the pressure of
the system, then the position of equilibrium will shift to keep the value of Kc the same.

The following questions refer to the graph below.

• From t=0 to t=10 min, the reaction is at equilibrium.
• At t=10 min, hydrogen gas, H2, is added to the system.
• What effect does this have on the equilibrium position and the concentrations of I 2 and
HI?
• What happens at t=15 min?

Example 1
Predict the effect of adding extra H2(g) to the equilibrium mixture below:

In which direction will the position of equilibrium shift and what is the effect on the value of Kc?

Example 2
Predict the effect of adding HI(g) to the equilibrium mixture above:

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Changes in pressure (gaseous reactions)
The pressure of a system can be changed by:
• Adding or removing a reactant or product
• Changing the volume of the reaction vessel
• Boyle’s law: pressure and volume are inversely proportional (at constant temperature).
• Changes in pressure only have an effect on the equilibrium position when there are
different amounts of gaseous molecules in the reactants and products.

• The direction to which the equilibrium shifts in gaseous reactions depends on the
number of moles of gas in the reactants and products.

Example 1:
Predict the direction in which the equilibrium will shift when pressure is increased. State and
explain the effect on the value of Kc.

Example 2:
Predict the direction in which the equilibrium will shift when pressure is decreased. State and
explain the effect on the value of Kc

Exercise: Consider the following reaction:

CO(g) + 2H2(g) ⇌ CH3OH(g)
Explain the effects on the position of equilibrium on the above reaction when:
a) The pressure is increased.

b) The pressure is decreased.

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Changes in temperature
• Important point about a change in temperature:

A change in temperature will change the value of Kc

• If the temperature of the reaction changes, the value of Kc will also change.

Predict the direction in which the equilibrium will shift when the temperature is increased in the
above reaction and explain your answer.

Predict the direction in which the equilibrium will shift in the above reaction when the
temperature is decreased and explain your answer.

The effect of temperature on the value of Kc

• For an exothermic reaction, increasing the temperature shifts the equilibrium to the left
(reactants side) and decreases the value of Kc
• For an endothermic reaction, increasing the temperature shifts the equilibrium to the
right (products side) and increases the value of Kc

Exercises:
Predict and explain the effect of decreasing the temperature on each of the following reactions
at equilibrium and the effect on the value of Kc.
a X2(g) + AB3(g) ⇌ 2BX(g) + AB(g) H = –50 kJ mol–1

b 2SO3(g) ⇌ 2SO2(g) + O2(g) H = –200 kJ mol–1

c N2O5(g) + NO(g) ⇌ 3NO2(g) H = +51 kJ mol–1

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Catalysts and equilibrium
• A catalyst increases the rate of the forward and reverse reactions by the same amount.
• Catalysts do not change the position of equilibrium or the value of Kc
• Catalysts allow equilibrium to be reached more quickly.

Exercise:
Many reversible reactions in industry use a catalyst. State and explain the effect of a catalyst on
the position of equilibrium and on the value of Kc.

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