IGCSE Revision guide: Chemistry

10 Reversible reactions and equilibrium

Extended i The experiment was repeated. Two pieces of magnesium ribbon were added to
100 cm3 of 1.0 mol / dm3 hydrochloric acid. Sketch this graph on the same grid
and label it X.
ii The experiment was repeated using one piece of magnesium ribbon and
100cm3 of 1.0 mol / dm3 hydrochloric acid. Describe how the shape of this The big picture
graph would differ from the one given on the grid. • Some reactions are reversible: they can go backwards as well as forwards.
b Reaction rate increases when concentration or temperature is increased. • In a closed container, these reactions do not complete. They reach a state of
Using the idea of reacting particles, explain why; equilibrium, with a mixture of reactants and products present.
i increasing concentration increases reaction rate, • But we usually want to obtain as much product as possible.
ii increasing temperature increases reaction rate. • There are steps we can take to change the equilibrium, and obtain more product.
c The rate of a photochemical reaction is affected by light. A reaction, in plants,
between carbon dioxide and water is photochemical.
i Name the two products of this reaction.
ii This reaction will only occur in the presence of light and another chemical.
Name this chemical.
10.1 What are reversible reactions?
Adapted from Cambridge IGCSE Chemistry 0620 Paper 3 Q7 November 2006
Many reactions are reversible – they can go backwards again.
Alternative to practical
1 Magnesium reacts with dilute sulfuric acid to form hydrogen gas. 50 Reversible reactions Equations
The speed of the reaction was investigated using the apparatus below. • produce products, like all reactions do reactants → products
40 We call this step the forward reaction.

total volume of gas / cm3

dilute
sulfuric • go backwards too reactants ← products
acid We call this step the backward reaction.
30
• may have both forward and backward reactions reactants → products and
measuring going on at the same time, in the container reactants ← products
cylinder 20
• so are shown by a special symbol reactants ⇋ products

10
Example 1: two forms of copper(II) sulfate

water magnesium 0 Hydrated copper(II) sulfate Anhydrous copper(II) sulfate

0 2 4 6 8 10 12
3 Chemical formula CuSO4 5H2O CuSO4
In an experiment 50 cm of dilute sulfuric acid was added to a large piece of Time / minutes
magnesium. A student measured the total volume of gas produced at 2 minute Appearance blue solid white solid
intervals.
When you heat hydrated copper(II) CuSO4 . 5H2O (s) → CuSO4 (s) + 5H2O (l)
Time / minutes sulfate, the colour changes from blue to
0 2 4 6 8 10 12 This is the forward reaction.
white, and steam comes off.
It is an endothermic reaction: you must put heat energy in.
0 10 25 25 35 40 40
Water level in If you add water to anhydrous copper(II) CuSO4 . 5H2O (s) ← CuSO4 (s) + 5H2O (l)
5 15 30 30 40 45 45
measuring cylinder sulfate, the colour changes from white
10 20 35 35 45 50 50 This is the backward reaction.
to blue, and the solid gets hot.
It is an exothermic reaction: energy is given out.
a Plot the student’s results on the grid. Use the points to draw a smooth line graph.
The equation uses the special symbol, to CuSO4 . 5H2O (s) ⇋ CuSO4 (s) + 5H2O (l)
b i At which time does the result appear to be inaccurate? show that it is a reversible reaction.
ii Use the graph to deduce what the correct volume should be at this time. This is the overall equation for the reaction.
Adapted from Cambridge IGCSE Chemistry 0620 Paper 6 Q6 November 2007
Note
2 Is manganese(IV) oxide a catalyst? • Hydrated copper(II) sulfate is also called copper(II) sulfate-5-water.
A catalyst is a substance that speeds up a chemical reaction and remains unchanged. • The water in copper(II) sulfate-5-water is called water of crystallisation
Hydrogen peroxide, H2O2 breaks down to form oxygen. This reaction is very slow
without a catalyst. A test for water
Describe an experiment to show that manganese(IV) oxide is a catalyst for this reaction.
Since white anhydrous copper(II) sulfate turns blue when water is added, it can be used to test for water.
You are provided with the following items:
• Add a few drops of the unknown liquid to anhydrous copper(II) sulfate.
hydrogen peroxide solution, manganese(IV) oxide, distilled water, measuring cylinder,
• If the compound turns blue, there is water in the liquid.
balance, beaker, ltration apparatus, splints, Bunsen burner.
• If the liquid also boils at 100 °C, and freezes at 0 °C, it is pure water.
Adapted from Cambridge IGCSE Chemistry 0620 Paper 6 Q8 June 2004

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IGCSE Revision guide: Chemistry Reversible reactions, and equilibrium 10

Example 2: the reaction between nitrogen and hydrogen Shifting the equilibrium

Extended
Nitrogen and hydrogen react together to form ammonia – but the reaction is reversible: Here again is the equation for making ammonia:
N2 (g) + 3H2 (g) ⇋ 2NH3 (g)
Forward reaction N2 (g) + 3H2 (g) → 2NH3 (g)
H H H Exothermic reaction: energy is given out. By changing conditions, we can shift the equilibrium for the reaction. (Shift means move.)
H H Remember
N H
N N H If the forward reaction H H H
H HH H N N
HH
H N N N
HH
H N
H
N N
HH
N
HH is exothermic, the backward H N H H HH N
N reaction is endothermic ... HH H H H H
H H H H H H H H H
N H H H H N H H H H N H
and vice versa. H H HH HH N HH N H
H H N H H H H H
Backward reaction N2 (g) + 3H2 (g) ← 2NH3 (g) N H H H H N H H H
N N H H HH
H N N H N H N
N H N H N N
H
H H H Endothermic reaction: energy is taken in. HH N N H H N
H N H HH H H H H H H H HH H HH
N N HH N H H N H HH
H H N H H N H N N H N
H H H H H H H H H H H H
HH H H
N
H H Look at this equilibrium mixture, for By changing conditions, we can obtain Or with different conditions, we can
the reaction. As you would expect, more ammonia. We have shifted the reduce the amount of ammonia. We
Overall equation N2 (g) + 3H2 (g) ⇋ 2NH3 (g) it contains nitrogen, hydrogen, and equilibrium to the right (or towards have shifted the equilibrium to the left
ammonia. the product, in the equation). (towards the reactants, in the equation).

Quick check for 10.1 (Answers on page 166) Conditions that can be changed
1 What is a reversible reaction? This table shows conditions that can be changed, for reversible reactions, and the result.
2 How can you tell from a chemical equation whether a reaction is reversible
or not? The change How the equilibrium shifts
3 What would you observe, if you heated copper(II) sulfate-5-water gently? Increase the pressure Equilibrium shifts to favour the side of the equation
4 How would you reverse the reaction you described in question 3? (for reactions involving gases) with fewer gas molecules (that is, with a lower
5 Hydrated cobalt(II) chloride has the formula CoCl2 .6H2O. It reacts similarly to volume of gas).
hydrated copper(II) sulfate when it is heated gently, and the reaction is
Reduce the pressure Equilibrium shifts to favour the side of the equation
reversible. Write the overall equation for it. Note
(for reactions involving gases) with more gas molecules (a higher volume of gas).
Increasing the temperature
Increase the temperature Equilibrium shifts to favour the endothermic reaction.
shifts equilibrium – AND
(any reaction)
speeds up both the forward
10.2 Reversible reactions and equilibrium Reduce the temperature
(any reaction)
Equilibrium shifts to favour the exothermic reaction. and backward reactions.

Add a catalyst Both the forward and backward reactions speed up –

What is equilibrium?
Extended

(any reaction) and by the same amount.

In a closed system (where no reactants or products can escape) a reversible reaction will So there is no shift in the equilibrium, but the
reach a state of dynamic equilibrium, where: reaction reaches equilibrium faster.
• the forward and backward reactions are taking place at exactly the same rate
• the amounts of reactants and products present do not change. Why does equilibrium shift?
When a reaction has reached equilibrium, and you change the temperature or pressure,
For example, look at the reaction for making ammonia: N2 (g) + 3H2 (g) ⇋ 2NH3 (g) it acts to oppose the change.
H HH H Remember
N H H N For example, in the reaction for making ammonia: In making ammonia from
H H
H N N H H H H H
H H H N N
H N H N H N H N nitrogen and hydrogen,
HH H exothermic
H H H H H H HH N2 (g) + 3H2 (g) (g) the forward reaction
N H H N N H 3
H H N H H endothermic
N H H N N H N H H HH
4 molecules 2 molecules
is exothermic.
H H H N
H H H H N H H HH HH
H N N H
H N H N H
H H HH H H H • If you increase the pressure, you in effect push more molecules into a smaller space.
So more ammonia forms, to reduce the number of molecules in that space – and
The reaction has reached dynamic … because every time nitrogen … other ammonia molecules break
therefore reduce the pressure. (Four molecules become two.)
equilibrium. So the amount of and hydrogen molecules react to down to give nitrogen and hydrogen
ammonia present will not increase … give ammonia molecules … molecules. • But if you increase the temperature, more ammonia breaks down, to absorb the extra
heat energy you have added. (The backward reaction is endothermic.)
The word dynamic means that reactions are still going on, all the time, in the container. The reaction mixture then reaches a new state of equilibrium, with different proportions of
We usually shorten dynamic equilibrium to just equilibrium nitrogen, hydrogen, and ammonia in the mix.

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IGCSE Revision guide: Chemistry Reversible reactions, and equilibrium 10

Extended Shifting the equlibrium for ammonia: a summary

This summarises how changing the conditions affects the amount of ammonia obtained: Questions on Section 10
The reactions exothermic Answers for these questions are on page 167
N2(g) + 3H2 (g) 2NH3 (g)
endothermic
4 molecules 2 molecules
Extended curriculum

Extended
Increase the Increasing the pressure will give more ammonia, since there are fewer molecules on the right. 1 Ammonia is made from nitrogen and hydrogen. The energy change in the reaction
pressure Equilibrium shifts to the right. is – 92 kJ/mole. The reaction is reversible, and reaches equilibrium.
a Write the equation for the reaction.
Reduce the Reducing the temperature will give more ammonia, since the forward reaction is exothermic.
temperature Equilibrium shifts to the right. b Is the forward reaction endothermic, or exothermic? How can you tell?
c Explain why the yield of ammonia:
Add a catalyst No change in the amount of ammonia obtained. i rises if you increase the pressure
(iron) The catalyst does not shift equilibrium. But it allows the reaction to reach equilibrium faster.
ii falls if you increase the temperature
d What effect does increasing: i the pressure ii the temperature
The chosen conditions for making ammonia have on the rate at which ammonia is made?
Ammonia is a very important compound. (For example, it is used in making nitric acid, and e Why is the reaction carried out at 450°C rather than at a lower temperature?
fertilisers.) So we want a high yield: we want to shift the equilibrium as far to the right as
we can. The table above shows that the best conditions for manufacturing ammonia are: 2 The colourless gas carbonyl chloride, COCl2, decomposes on heating to form carbon
• high pressure monoxide and chlorine. The equation for the reaction is:
• low temperature
COCl2 (g) ⇋ CO (g) + Cl2 (g)
• iron catalyst. Make the link to …
a i Explain why the yield of the products is affected by a change in pressure.
But the lower the temperature, the slower the reaction. A slow reaction is not desirable
the Haber process for making
ammonia, on page 132. ii Which will improve the yield: an increase in pressure, or a decrease?
in industry, since time is money. So a compromise temperature is chosen. b i How will the concentration of carbonyl chloride change as the temperature
is increased?
Changing concentration in equilibrium reactions ii Explain why the forward reaction must be the endothermic one.
Equilibrium can also be shifted in reversible reactions involving solutions:
reactants ⇋ products 3 The dichromate and chromate ions, Cr2O72 – and CrO42 –, exist in equilibrium like this:
Cr2O72 – (aq) + H2O (l) ⇋ 2CrO42 – (aq) + 2H+(aq)
You can shift the equilibrium by changing the concentration of a reactant or product
orange yellow
in the reaction mixture. Each time, the system acts to oppose the change:
a What would you see if you added dilute acid to a solution containing
Change made to the mixture Result chromate ions?
b How would you reverse the change?
Add more reactant Equilibrium shifts to the right. More product is produced.
c Explain why adding hydroxide ions shifts the equilibrium.
Remove some reactant Equilibrium shifts to the left. More product breaks down to form reactants.
Add more product Equilibrium shifts to the left. More product breaks down to form reactants.
4 Hydrogen and bromine react reversibly:
Remove some product Equilibrium shifts to the right. More product is produced. H2 (g) + Br2 (g) ⇋ 2HBr (g)
a Which of these will favour the formation of more hydrogen bromide?
For example, iodine reacts reversibly with dilute sodium hydroxide solution:
i adding more hydrogen
I2 (aq) + 2OH (aq) ⇋ I (aq) + IO (aq) + H2O (l) ii removing bromine
red-brown colourless colourless iii removing the hydrogen bromide as it forms.
b Increasing the pressure will have no effect on the amount of product. Explain why.
If you add more sodium hydroxide, the equilibrium moves to the right, and the solution c However, the pressure is likely to be increased, when the above reaction
goes colourless. But if you add dilute acid, its hydrogen ions react with hydroxide ions is carried out in industry. Suggest a reason for this.
to form water. So the equilibrium shifts to the left, and the solution turns red-brown.
Alternative to practical
Quick check for 10.2 (Answers on page 167)
1 Hydrated copper sulfate crystals, CuSO4.5H2O were heated in the apparatus to
the right.
1 A reaction reached equilibrium. Explain what this term means.
a Indicate on the diagram using arrows
2 Give three ways in which equilibrium can be shifted.
i where the copper sulfate crystals are placed,
3 In a reversible reaction, raising the temperature lowered the yield of product.
ii where heat is applied.
What does this tell you about the reaction? ice
b What is the purpose of the ice?
4 Why does a catalyst not shift equilibrium?
c The crystals changed colour from .................. to ..................
5 In the reaction 2SO2 (g) + O2 (g) ⇋ 2SO3 (g), the forward reaction is
Adapted from Cambridge IGCSE Chemistry 0620 Paper 6 Q1 November 2007
exothermic. How would you increase the yield of the product?

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