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2021

EDEXCEL AS LEVEL CHEMISTRY ☺

Unit 2: Reversible Reactions and Dynamic Equilibrium

Dynamic Equilibrium

A reaction in dynamic equilibrium:

• is undergoing no net change, so the concentration of each substance is constant

• is one in which the forward reaction (conventionally written from left to right) is happening
at the same rate as the reverse reaction

• Both forward and backward reactions are continuously occuring.

Two conditions must be met for dynamic equilibrium to be established:

1. the reaction must be reversible.

2. the reaction mixture must be in a closed container.

Effect of changes in conditions on equilibrium composition

When a reaction mixture reaches a position of equilibrium, the composition of the equilibrium
mixture will not alter as long as the conditions remain the same.

However, if we change a condition then the composition may change. This is often referred to as
‘changing the position of equilibrium’ and we refer to the position being moved to the right, to the
left or not changed.

e.g. If acid is added to a yellow solution containing chromate (VI) ions, CrO2 − , the solution turns
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orange. This is because of an increase in the amount of dichromate (VI) ions, Cr2O2 −.
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 CrO2 − (aq) + 2H+ (aq) Cr2O2 − (aq) + H2O (l)
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The equilibrium position moves to right when the acid (H+) is added. If sufficient alkali is added to
the orange solution, it will turn yellow as the amount of CrO2 − ions increases and exceeds the
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2−
amount of Cr2O ions. The equilibrium position moves to the left when alkali (OH-) is added.
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Four factors that may affect the position of equilibrium of a reaction mixture.

These are:

1. concentration of a component
2. pressure of the system
3. temperature of the system
4. addition of a catalyst

Effect of a change in concentration

If we increase the concentration of one of the reactants in a system in equilibrium, the rate of the
forward reaction will increase and more products will form. As the concentration of the products
increases, the rate of the backward reaction increases and eventually a new equilibrium is
established. The equilibrium position has moved to right, with slightly more product being present
than at the original position of equilibrium.

If concentration of one of the reactants is decreased, the position of equilibrium moves to the left.

Similar changes that occur if the concentration of the product is increased or decreased.

Concentration of reactants Concentration of products Change in position of

equilibrium

Increased To the right

Decreased To the left

Increased To the left

Decreased To the right

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Effect of a change in pressure

The effect of pressure only applies to reversible reactions involving gases. At a given temperature,
the pressure of a gaseous mixture depends only on the number of gas molecules in a given volume.

Number of moles reactants Number of moles of products Change in position of

equilibrium when the
pressure is increased

More Fewer To the right

Fewer More To the left

Same Same No change

The reverse changes are true for a decrease in pressure.

The effect of pressure changes using different amounts of nitrogen and hydrogen to form ammonia:

The equation for the reaction is:

N2 (g) + 3H2 (g) 2NH3 (g)

Increasing the total equilibrium pressure moves the equilibrium composition towards the side with
the smaller number of moles. In this case, the amount of ammonia would increase. A similar
argument can be put forward for a decrease in pressure, which would move the equilibrium
composition towards the reactants.
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Effect of a change in temperature

The change in position of equilibrium will depend on whether the forward reaction is exothermic or
endothermic.

Temperature change Thermicity of forward reaction Change in position of equilibrium

Increased Exothermic To the left

Decreased Exothermic To the right

Increased Endothermic To the right

Decreased Endothermic To the left

Effect of the addition of a catalyst

The position of equilibrium is not altered as rate will be the same for both reactions when a catalyst
is added.

The advantage of adding the a catalyst at the beginning of the reaction is that it will reduce the time
required to establish equilibrium.

Limitations of making qualitative predictions

There are occasions when it is impossible to predict the direction of change, or indeed when the
prediction turns out to be incorrect.

For example, if an equilibrium mixture of brown NO2 gas and colourless N2NO4 gas in a closed
container is placed into a beaker of hot water at room temperature, both the remperature and the
pressure of the gaseous mixture will rise.

The equation for the reaction is:

2NO2 (g) N2O4 (g) ΔH= - 58 kJmol-1

brown gas colourless gas

The forward reaction is exothermic so we would predict that an increase in temperature would shift
the equilibrium to left.

However, since there are fewer moles of gas on the right-hand side of the equation, we would
predict that an increase in pressure would shift the equilibrium to the right.

We do not know which shift is greater so we cannot make a prediction about equilibrium position.
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In practice, the mixture becomes darker in colour, so the temperature effect must be greater than
the pressure effect. This is because the equilibrium must have shifted to the left to produce more
brown NO2 (g).

Applying the principles of reaction rates and reversibility to industrial processes

In order to maximise profits, the major problems chemists face are to convert the reactants into
products as quickly as possible and as completely as possible.

The Haber process

Ammonia is manufactured in industry from nitrogen and hydrogen:

N2 (g) + 3H2 (g) 2NH3 (g) ΔH= -92 kJmol-1

If the reaction mixture were to reach equilibrium, the maximum yield of ammonia would be
obtained by using a low temperature and a high pressure.

The conditions used in Haber process:

- 450 oC of temperature
- 250 atm of pressure
- iron as a catalyst

Then the yield of ammonia would be just above 30%. In practice, the yield is approximately 15% as
the reaction mixture does not remain in the reaction chamber long enough for equilibrium to be
established.
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Why are conditions of 450oC and 250 atm used?

- The reaction betwee nitrogen and hydrogen is slow at room temperature. This is mainly because
of the very strong nitrogen to nitrogen triple bond producing a high activation energy for the
reaction.
- This reaction is slow in the absence of catalyst. Iron is used as catalyst in the industrial process
because other metals are very expensive to be used in the industrial process.
- The catalyst does not function very efficiently at low temperatures, so a relatively high
temperature is necessary. However, a very high temperature would be uneconomical.
- High temperatures might also decrease the yield since the forward reaction is exothermic and the
increase in rate of backward reaction will be greater than the increase in the rate of the forward
reaction.
- For the pressure, the higher the pressure, the larger the energy costs of compressing the gases.
The lower the pressure, the lower the yield.

The Contact Process

Sulfuric acid is manufactured by the Contact process.

SO2 (g) + ½ O2 (g) SO3 (g) ΔH= -96 kJmol-1

- The forward reaction is exothermic, so a low temperature would favour a high yield of SO3 (g).
- The catalyst, vanadium (V) oxide, would not be very effective at low temperatures so a
moderately high temperature of 450oC is used.
- The pressure in the Contact process is about 2 atm. This is high enough to maintain a constant
flow of gases through the reaction chamber. Pressure higher than this is unnecessary since the
yield is already very high.

The mechanism for the reaction is:

SO2 (g) + V2O5 (s) SO3 + V2O4 (s)

V2O4 (s) + ½ O2 (g) V2O5 (s)

Vanadium changes its oxidation state during the reaction but it then converts back to its original
oxidation state at the end.
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Subject Teacher: Guney Benli