Chemical equilibrium notes 2021

CHEMICAL EQUILIBRIUM

1 The concept of equilibrium

In grade 10 and 11 you worked with calculations on stoichiometric reactions. These
reactions all went to completion. There are, however, chemical reactions that do not
reach completion. They reach a point of equilibrium, at which nothing more seems to
happen.
What is necessary for a reaction to be able to reach chemical equilibrium?
It must take place in a closed system:

A closed system (in chemistry) is one in which

mass conserved inside the system but energy can
enter or leave the system freely.

An open system is one in which both energy and matter can be exchanged between
the system and the surroundings.
The reaction must be reversible:

A reversible reaction is one in which

products can be converted back into
reactants.

Once a chemical reaction satisfies these two requirements it may reach chemical
equilibrium. Such an equilibrium is said to be dynamic because the reactions
continue to occur at equilibrium. The reactions don’t stop.

Dynamic chemical equilibrium refers to a point in a

reversible reaction at which the forward and reverse
reactions are taking place at the same rate.

N.B. When a system reaches equilibrium the concentrations of products and

reactants remain constant.
When a system reaches equilibrium, there may be more products than reactants or
vice versa. In order to get an idea of which side the equilibrium lies on, we make use
of an equilibrium constant (Kc).

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Chemical equilibrium notes 2021

2 The equilibrium constant (Kc)

Reminder: the symbol [ ] means concentration in

mol·dm–3.

If we consider a general reaction:

aA(g) + bB(g) ⇌ cC(g) + dD(g)

(where a, b, c and d represent coefficients in front of chemical symbols/formulae),

rhen the general expression for Kc is:
[𝐂]𝐜 [𝐃]𝐝
𝐊 𝐜 = [𝐀]𝐚 [𝐁]𝐛

N.B the expression is always in the form: products/reactants

Example
Write down the equilibrium constant expression for the reaction:

N2(g) + 3H2(g) ⇌ 2NH3(g)

Solution
[NH3 ]2
K c = [N 2
2 ][H2 ]

The concentrations in the above expression are the equilibrium concentrations of

each substance.
Example
The following reaction reaches equilibrium at a temperature of 200 °C.

2SO2(g) + O2(g) ⇌ 2SO3(g)

when equilibrium is reached, the concentrations are:

[SO2] = 0,4 mol·dm–3

[O2] = 0,2 mol·dm–3

[SO3] = 0,5 mol.·dm–3

Calculate the value of Kc at 200 °C

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Chemical equilibrium notes 2021

Solution
[SO3 ]2
kc =
[SO3 ]2 [O2 ]
0,52
=
0.42 × 0,2
= 7,81
Note that the units of Kc, vary with the powers to which each term is raised. Unless
the question specifically asks for units, they can be left out. Note that the
concentrations of substances that are either pure solid (s) or pure liquid (l) are left
out of equilibrium constant expressions.
N.B. Temperature is the only factor that can affect the value of k2.
3 Le Chatelier’s principle
Once chemical equilibrium has been reached in a particular system, the position of
equilibrium can be affected by changing the external conditions. The conditions that
can be changed are concentration, temperature and pressure.
We can predict how the position of equilibrium is affected by changing conditions by
making use of Le Chatelier’s principle.

Le Chatelier’s principle states: When an external

stress is applied to a system in dynamic chemical
equilibrium, the equilibrium point will change in such
a way as to counteract the stress.

Changes in concentration
Consider the following chemical reaction, which has reached dynamic chemical
equilibrium:

2A(g) + 3 B(g) ⇌ A2B3(g)

The reaction is taking place in a sealed, rigid container. Some A(g) is now injected
into the container. What effect will this have on the position of equilibrium?
Explanation in terms of Le Chatelier’s principle:
The stress is an increase in the concentration of A. The reaction that counteracts the
stress is the reaction that uses up A. In this case it is the forward reaction. Mote
product will be formed, as the forward reaction is favoured.

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Chemical equilibrium notes 2021

Explanation in terms of reaction rates:

In terms of reaction rates, we can explain what happens by explaining that the rate of
the forward reaction increases initially so more products will be formed. This is
because the concentration of one of the reactants, (A), is increased. However, as the
added substance A gets used up, the rate of the forward reaction begins to
decrease. As more product is formed, the rate of the reverse reaction gradually
increases and eventually the two rates will be the same again and a new equilibrium
point is reached.
N.B. 1 When equilibrium is re-established, there will be less substance B
present in the container, than in the previous equilibrium. There will be
more A2B3 present than previously and there will more A present than
previously because A has been added and it doesn’t all get used up.

N.B. 2 Changes in concentration do not affect the value of Kc.

Changes in temperature
To be able to predict what will happen when the temperature changes, we need to
know which reaction is exothermic/endothermic. Forward or reverse. Consider the
following chemical reaction that has reached equilibrium:
N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH = –92 kJ
The information given by ΔH tells us that the forward reaction is exothermic. The
temperature is now increased. What effect will this have on the position of
equilibrium?
Explanation in terms of Le Chatelier’s principle:
The increase in temperature is a stress. The reaction that relieves the stress is the
reaction which absorbs energy, i.e. the endothermic reaction. This is the reverse
reaction, in this case. More reactants will be formed as the reverse reaction is
favoured.
Explanation in terms of reaction rates:
As the temperature increases, the rates of both the forward and reverse reactions
increase, but the rate of the endothermic reaction increases more. Here, as
explained before, it is the reverse rate that increases more initially, so more reactants
will be formed. Products are used up as a result and their concentration decreases,
so the rate of the reverse reaction will gradually decrease. As more reactants are
formed, their concentrations increase, so the rate of the forward reaction will
gradually increase until both rates are the same once again.
N.B. 1 When equilibrium is re-established, there will be less NH3 present in
the container, than in the previous equilibrium. There will be more N2
present than previously and there will more H2 present than
previously.
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Chemical equilibrium notes 2021

N.B. 2 Changes in temperature have an effect on the value of Kc.

N.B. 3 An increase in temperature favours the endothermic reaction and a
decrease in temperature favours the exothermic reaction.

Changes in pressure
Once again consider the reaction:
N2(g) + 3H2(g) ⇌ 2NH3(g)
To predict what happens when the pressure is changed, we need to count the
number of moles of each substance (gases only) on the reactants side and on the
products side. An increase in pressure favours the reaction that produces fewer
molecules.
The pressure on the above system is increased. What effect will this have on the
quantities of each substance present at equilibrium?
Explanation in terms of Le Chatelier’s principle:
The increase in pressure is a stress. In order to relieve the stress, the reaction that
produces fewer molecules will be favoured. This is the forward reaction (4 mol on
LHS and 2 mol on RHS). More products will be formed.
Explanation in terms of reaction rates:
An increase in pressure leads to a decrease in volume. A decrease in volume leads
to an increase in concentration (c is inversely proportional to V). Hence the rates of
both reactions are increased, but the rate of the reaction which produces fewer
molecules is increased more. So, the rate of the forward reaction increases more
than the reverse rate and more products will form. As more products are formed,
the rate of the reverse reaction will accordingly increase and the rate of the forward
reaction will decrease until the rates are equal and equilibrium is re-established.
N.B. 1 When equilibrium is established once more, there will be more NH3
present than previously and there will be less H2 and N2 present than
at the previous point of equilibrium.

N.B. 2 Changes in pressure have no effect on the value of Kc.

Addition of a catalyst

The addition of a catalyst to a system at equilibrium will have no effect, as a catalyst

speeds up the rates of the forward and reverse reactions to the same extent.

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Chemical equilibrium notes 2021

4 Equilibrium graphs

Graphs for chemical reactions reaching equilibrium, changing conditions, and then
returning to equilibrium again can be one 3 types:

• Amount vs time
• Concentration vs time
• Rate vs time

Amount vs time

The graph relates to the reaction represented by the equation:

A2(g) + B2(g) ⇌ 2AB(g) ΔH < 0

When the lines are parallel, it

means the system is at
equilibrium.

Equilibrium is established
again

[https://intl.siyavula.com/read/science/grade-12/chemical-equilibrium/images/3b33f0d4fafa54876792ed56e1cfc88a.png]

The positions where the graphs start A change in the equilibrium

on the vertical axis indicates the conditions has occurred at 10
number of moles of each present at minutes.
the start.

Whatever change occurred favoured the forward reaction because the number of
moles of product has increased and the number of moles of reactants has
decreased.
Let’s eliminate causes of the change. It cannot be a change in pressure because
there are equal numbers of gas moles on both sides.
It cannot be a change in the number of moles (concentration) of any substance
because there is no sudden change (vertical line) in the number of moles of any
substance.
It must be a change in temperature. The forward reaction is exothermic, which is
favoured by a decrease in temperature.

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Concentration vs time

The interpretation of this type of graph is the same as for amount vs time graphs. The
graph below is for the reaction:

N2(g) + 3H2(g) ⇌ 2NH3(g) ΔH < 0

The change at t2 is an increase in At t3, there could only have been a
pressure. As the pressure increases, an increase in temperature, which
the volume decreases, so all the favours the reverse reaction.
concentrations increase.

Equilibrium This change indicates an

increase in the
concentration of N2.

Rate vs time

Equilibrium

The rate of the reverse reaction is usually zero to start.

[https://intl.siyavula.com/read/science/grade-12/chemical-equilibrium/images/e1e80a85b7f13aec4c21f59575faa12d.png]

The change here could have been caused by either an

increase in pressure or an increase in temperature as
these both cause an increase in both rates. However, the
rate of the reaction that produces fewer moles and the
endothermic reaction are favoured more than their
opposites.

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Chemical equilibrium notes 2021

5 Summary of rates and equilibrium

Change in Effect on rate Effect on equilibrium

Temperature Changes both Affects rate of endothermic
reaction more
Pressure Changes both Affects the reaction that produces
fewer moles more
Concentration Increases rate of reaction of Affects only the reaction of which
the side on which the concentration of reactants
concentration is changed (forward or reverse) is increased

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