7 Chemical reactions

FOCUS POINTS
★ How does the rate of a reaction vary?
★ Why is the rate of a chemical reaction important?
★ What is a reversible reaction?

In this chapter we will look at how we are able to alter the rate at which chemical reactions occur.
Industry needs to produce chemical products in the shortest possible time, so they are made
efficiently and increase profits. We know that all chemical reactions go faster when heated to a
higher temperature, for example an egg cooks faster at higher temperatures, but why does this
happen?
Industry also wants to make more product from a reaction. In any chemical reaction, reactants will
make products eventually, so how can there be more product? We will introduce the fact that not
all reactions simply produce products from reactants: some reactions are reversible and once the
product has been formed, it may break down to produce reactants again.
By the end of this chapter you should be able to fully explain how the rates of chemical reactions can
be altered and how reversible reactions can be manipulated to produce products efficiently.

7.1 Reactions
A physical change does not result in the formation Figure 7.1 shows some slow and fast reactions.
of a new substance. It simply alters the state of the The two photographs at the top show examples
substance involved. For example, when ice melts to of slow reactions. The ripening of apples takes
form water it is a physical change because the water place over a number of weeks, and the making and
has not changed: only its state has changed from maturing of cheese may take months. The burning
a solid to a liquid. This is also the case if we boil of solid fuels, such as coal, can be said to involve
water to produce steam. chemical reactions taking place at a medium speed
A chemical change, however, results in the or rate. A fast reaction is an explosion (bottom
formation of something new. An everyday example right), where the chemicals inside explosives, such
of this is frying an egg. The chemicals in the fried as TNT, react very rapidly in reactions which are over
egg have undergone chemical reactions forming new in seconds or fractions of seconds.
substances, and the fried egg cannot be changed As new techniques have been developed, the
back into the egg you started with. This is the processes used within the chemical industry have
main difference between a physical and chemical become more complex. Therefore, chemists and
change. chemical engineers have increasingly looked for ways
In a physical change, it is possible to reverse to control the rates at which chemical reactions
the change, and the change can be temporary. For take place. In doing so, they have discovered that
example, the water from melted ice can be frozen there are five main ways in which you can alter the
again to form ice. In a chemical change this cannot rate of a chemical reaction. These ideas are not only
happen. For all chemical reactions, a chemical incredibly useful to industry but can also be applied
change occurs and this is a permanent change. to reactions in the school laboratory.

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 7.2 Factors that affect the rate of a reaction

▲ Figure 7.1  Some slow (ripening fruit and cheese making), medium (coal fire) and fast (explosion) reactions

7.2 Factors that affect the collision results in the formation of products.
This minimum amount of energy is known as the
rate of a reaction activation energy, Ea (Figure 7.2). Collisions which
result in the formation of products are known as
The five main ways to alter the rate of a chemical successful collisions.
reaction are:
» changing the concentration of solutions
» changing the pressure of gases Activation
» changing the surface area of solids energy
» changing the temperature
Energy

Enthalpy
» adding or removing a catalyst including enzymes. Reactants change
of reaction
Collision theory Products
For a chemical reaction to occur, reactant particles 0
Progress of reaction
need to collide with one another. For products to be
formed, the collision has to have a certain minimum ▲ Figure 7.2 Reaction profile diagram showing activation
amount of energy associated with it, and not every energy

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 7 Chemical reactions

Surface area mixture is measured at regular intervals. The total

loss in mass is calculated for each reading of the
Limestone (calcium carbonate, CaCO3) is a substance balance, and this is plotted against time. Some
which can be used to neutralise soil acidity. sample results from experiments of this kind have
Powdered limestone is used as it neutralises the been plotted in Figure 7.5.
acidity faster than if lumps of limestone are used. The reaction between hydrochloric acid and
Why do you think this is the case? limestone is generally at its fastest in the first
In the laboratory, the reaction between acid and minute. This is indicated by the slopes of the curves
limestone in the form of lumps or powder can be during this time. The steeper the slope, the faster
observed in a simple test-tube experiment. Figure 7.3 the rate of reaction. You can see from the two curves
shows the reaction between dilute hydrochloric acid in Figure 7.5 that the rate of reaction is greater with
and limestone in lump and powdered form. the powdered limestone than the lump form.
hydrochloric +  calcium   → calcium + carbon +  water
  acid    carbonate    chloride   dioxide
2HCl(aq)     +   CaCO3(s)  → CaCl2(aq) + CO2(g) + H2O(l)

▲ Figure 7.3 The powdered limestone (left) reacts faster

with the acid than the limestone in the form of lumps

The rates at which the two reactions occur can be

found by measuring either:
» the volume of the carbon dioxide gas which is
produced
» the loss in mass of the reaction mixture with time.
These two methods are generally used for measuring
the rate of reaction for processes involving the
formation of a gas as one of the products.
The apparatus shown in Figure 7.4 is used to
measure the loss in mass of the reaction mixture.
The mass of the conical flask plus the reaction ▲ Figure 7.4  After 60 seconds the mass has fallen by 1.24 g

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 7.2 Factors that affect the rate of a reaction

If the surface area of a reactant is increased, The surface area has been increased by powdering the
more particles are exposed to the other reactant, limestone (Figure 7.6). The acid particles now have an
so the rate of a chemical reaction can be raised by increased amount of surface of limestone with which
increasing the surface area of a solid reactant. to collide. The products of a reaction are formed
when collisions occur between reactant particles.
2
Powdered
limestone
Loss in mass/g

Powder
Cut up Cut up
Lumps of
1
limestone

etc.

▲ Figure 7.6 A powder has a larger surface area

0
1 2 3 4 5 6 7
Time/min

▲ Figure 7.5  Sample results for the limestone/acid

experiment

Practical skills

Experiment to show the effect of surface

area on reaction rate b How can you tell this from the graph?
5 What other factors must be kept constant
Safety during this experiment to show the effect of
l Eye protection must be worn. surface area on the rate of reaction?
6 Can you think of any sources of errors with
A student took a lump of limestone (calcium the method used?
carbonate) and reacted it with an excess of dilute
hydrochloric acid in a conical flask which had a A lump of Smaller fragments
delivery tube attached. The gas produced was Time/s limestone of limestone
collected in an inverted burette filled with water.
Volume of CO2/cm3 Volume of CO2/cm3
The experiment was repeated using smaller
fragments of limestone of the same mass. The table 0 0 0
on the right gives the results of the experiments. 10 12 25
1 Draw the apparatus which could be used in 20 25 42
the experiment above.
30 36 53
2 Plot a graph of volume of carbon dioxide
collected (y-axis) against time (x-axis) for both 40 46 62
experiments. Use the same axes. 50 54 66
3 a Which of the experiments is the fastest? 60 61 68
b How can you tell this from the graph? 70 65 68
c Use ideas about particles to explain
80 68 68
your answer.
4 a After how many seconds was the 90 68 68
experiment using the single lump of 100 68 68
limestone complete?

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 7 Chemical reactions

An increase in the surface area of a solid reactant Flour Mills Plant in Kingston, Jamaica, killing three
results in an increase in the number of collisions, workers, as a result of fine dust exploding.
and this results in an increase in the number of
successful collisions. Therefore, the increase in
surface area of the limestone increases the rate of
reaction.
In certain industries the large surface area
of fine powders and dusts can be a problem. For
example, there is a risk of explosion in flourmills
and mines, where the large surface area of the flour
or coal dust can – and has – resulted in explosions
through a reaction with oxygen gas in the air
when a spark has been created by machinery or the
workforce (Figure 7.7). On 26 September 1988, two ▲ Figure 7.7  The dust created by this cement plant is a
silos containing wheat exploded at the Jamaica potential hazard

Test yourself
1 What apparatus would you use to measure the Time/ 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
rate of reaction of limestone with dilute hydrochloric min
acid by measuring the volume of carbon dioxide
produced? Total 0 15 24 28 31 33 35 35 35 35 35
volume
2 The following results were obtained from an of CO2
experiment of the type you were asked to design gas/cm3
in question 1.
a Plot a graph of the total volume of CO2 against time.
b At which point is the rate of reaction fastest?
c What volume of CO2 was produced after 1 minute 15 seconds?
d How long did it take to produce 30 cm3 of CO2?

Concentration concentrations of sodium thiosulfate or hydrochloric

acid. If considering carrying out this practical,
A yellow precipitate is produced in the reaction teachers should take care as SO2 is released, which
between sodium thiosulfate and hydrochloric acid. can cause breathing issues, especially for asthmatics.
 sodium + hydrochloric →  sodium + sulfur + sulfur  +  water
thiosulfate       acid       chloride          dioxide
Na2S2O3(aq) +   2HCl(aq)  → 2NaCl(aq) + S(s) +  SO2(g)  +  H2O(l)

The rate of this reaction can be followed by

recording the time taken for a given amount of
the yellow sulfur to be precipitated. This can be
done by placing a conical flask containing the
reaction mixture on to a cross on a piece of paper
(Figure 7.8). As the precipitate of sulfur forms,
the cross is obscured and finally disappears from
view. The time taken for this to occur is a measure
of the rate of this reaction. To obtain sufficient
information about the effect of changing the
concentration of the reactants, several experiments
of this type must be carried out, using different ▲ Figure 7.8 The precipitate of sulfur obscures the cross

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 7.2 Factors that affect the rate of a reaction

Some sample results of experiments of this kind particles. The more often the particles collide, the
have been plotted in Figure 7.9. You can see from greater the chance they have of having sufficient
the graph that when the most concentrated sodium energy to overcome the activation energy of the
thiosulfate solution was used, the reaction was at reaction, and so it is more likely that a successful
its fastest. This is shown by the shortest time taken collision occurs. This means that the rate of a
for the cross to be obscured. chemical reaction will increase if the concentration
of reactants is increased, because there are more
120
particles per unit volume.
Time for cross to disappear/s

100

80 Pressure of gases
60 In reactions involving only gases, an increase in the
overall pressure at which the reaction is carried out
40
increases the rate of the reaction. The increase in
20 pressure results in the gas particles being pushed
0 closer together, increasing the number of particles
0.01 0.015 0.02 0.025 0.03 per unit volume. This means that they collide more
Concentration of sodium thiosulfate/mol/dm3 frequently and so the rate of reaction increases.
▲ Figure 7.9 Sample data for the sodium thiosulfate/
acid experiment at different concentrations of sodium Temperature
thiosulfate
Why do you think food is stored in a refrigerator?
From the data shown in Figure 7.9 it is possible to The reason is that the rate of decay of food is slower
produce a different graph which directly shows the at lower temperatures. This is a general feature of
rate of the reaction against concentration rather the majority of chemical processes.
than the time taken for the reaction to occur The reaction between sodium thiosulfate and
against concentration. To do this, the times can be hydrochloric acid can be used to study the effect
converted to a rate using: of temperature on the rate of a reaction. Figure 7.11
1 shows some sample results of experiments with
rate = sodium thiosulfate and hydrochloric acid (at
reaction time (s) fixed concentrations) carried out at different
This would give the graph shown in Figure 7.10. temperatures. You can see from the graph
0.035 that the rate of the reaction is fastest at high
0.03
temperatures.
Rate of reaction/s–1

0.025 140

0.02 120
Time for cross to disappear/s

0.015
100
0.01
80
0.005
0 60
0.01 0.015 0.02 0.025 0.03
40
Concentration of sodium thiosulfate/mol/dm3
20
▲ Figure 7.10 Graph to show the rate of reaction against
concentration 0
10 20 30 40 50 60
The products of a reaction are formed as a result of Temperature/ ºC
the collisions between reactant particles. In a more
concentrated solution there are more particles, which ▲ Figure 7.11 Sample data for the sodium thiosulfate/acid
experiment at different temperatures
leads to more frequent collisions between reactant

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 7 Chemical reactions

As the temperature increases, the reactant 180

1 g MnO2
particles increase their kinetic energy. Some of 160

Volume of oxygen/cm3
140
the particles will have an energy greater than the 0.5 g MnO2
120
activation energy, Ea, and they move faster. The 100
faster movement results in more frequent collisions 80
between the particles. Some of the extra collisions 60
that result from the temperature increase will be 40
successful collisions. This causes the reaction rate 20
to increase. 0
0 50 100 150 200 250 300 350
Time/s
Test yourself ▲ Figure 7.12 Sample data for differing amounts of MnO2
catalyst
3 Explain why potatoes cooked in oil cook faster than
those cooked in water. it is said to have been ‘poisoned’. Therefore, the
4 Devise an experiment to study the effect of
temperature on the reaction between magnesium
gaseous reactants must be pure.
and hydrochloric acid. Chemists have found that:
5 Explain why food cooks faster in a pressure cooker.
» a small amount of catalyst will produce a large
amount of chemical change
» catalysts remain unchanged chemically after a
Catalysts reaction has taken place, but they can change
Over 90% of industrial processes use catalysts. A physically. For example, a finer manganese(IV)
catalyst is a substance which can alter the rate of oxide powder is left behind after the
a reaction without being chemically changed itself. decomposition of hydrogen peroxide
In the laboratory, the effect of a catalyst can be » catalysts are specific to a particular chemical
observed using the decomposition of hydrogen reaction.
peroxide as an example.
Some examples of chemical processes and the
hydrogen peroxide → wáter  + oxygen
catalysts used are shown in Table 7.1.
2H2O2(aq) → 2H2O(l) + O2(g)
▼ Table 7.1  Examples of catalysts
The rate of decomposition at room temperature
is very slow. There are substances that can speed Process Catalyst
up this reaction, one being manganese(IV) oxide. Haber process – for the manufacture of Iron
When black manganese(IV) oxide powder is added ammonia
to hydrogen peroxide solution, oxygen is produced Contact process – for the manufacture of Vanadium(V)
rapidly. The rate at which this occurs can be seen by sulfuric acid oxide
measuring the volume of oxygen gas produced with
Oxidation of ammonia to give nitric acid Platinum
time.
Hydrogenation of unsaturated oils to form Nickel
Some results from experiments of this type
fats in the manufacture of margarines
have been plotted in Figure 7.12. At the end of the
reaction, the manganese(IV) oxide can be filtered A catalyst increases the rate of a chemical reaction
off and used again. The reaction can proceed even by providing an alternative reaction path which
faster by increasing the amount and surface area has a lower activation energy, Ea. A catalyst does
of the catalyst. This is because the activity of a not increase the number of collisions between
catalyst involves its surface. Note that, in gaseous the reactant particles but it causes more of the
reactions, if dirt or impurities are present on the collisions to become successful collisions, so
surface of the catalyst, it will not act as efficiently; increasing the rate of the reaction.
If the activation energy is lowered by using a
catalyst then, on collision, more particles will go on to
produce products at a given temperature (Figure 7.13).

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 7.3 Enzymes

Without
catalyst
7.3 Enzymes
Enzymes are protein molecules produced in living
cells. They are catalysts which speed up hundreds
With
catalyst Activation
of different chemical reactions taking place inside
energy living cells. These biological catalysts are very
Energy

Reactants specific in that each chemical reaction has a

Enthalpy different enzyme catalyst.
change
of reaction
Products
Test yourself
7 When using biological washing powders what
0 Progress of reaction factors have to be taken into consideration?
8 Enzymes in yeast are used in the fermentation
▲ Figure 7.13 A reaction pathway diagram showing of glucose. Why, when the temperature is raised
activation energy, with and without a catalyst to 45°C, is very little ethanol actually produced
compared with the amount formed at room
Key definition temperature?
A catalyst is a substance which alters the rate of a
chemical reaction and is unchanged at the end of the Rate of reaction is very important in the chemical
reaction. It increases the rate of a chemical reaction by industry. There are, however, many other factors
providing an alternative reaction path which has a lower
activation energy, Ea.
which the industry needs to take into account as
they manufacture chemicals such as safety and cost.
In the next section we will look at the industrial
Test yourself manufacture of a very important chemical called
ammonia.
6 Using a catalysed reaction of your choice, devise
an experiment to follow the progress of the
reaction and determine how effective the catalyst is.

Going further

There are literally hundreds of different kinds of

enzyme. Enzymes all have an active site. The active site
is a particular shape and locks into a corresponding
shape in a reactant molecule. When this has happened,
the enzyme can work to break up the reactant
(Figure 7.14).
For example, hydrogen peroxide is produced within our
bodies. However, it is extremely damaging and must be
decomposed very rapidly. Catalase is the enzyme which
converts hydrogen peroxide into harmless water and
oxygen within our livers:

hydrogen peroxide catalase

 → water + oxygen
2H 2O2(aq) catalase
 → 2H 2O(l) + O2(g)

Although many chemical catalysts can work under ▲ Figure 7.14 The enzyme molecules (red, pink, green
various conditions of temperature and pressure, as well and blue) lock on exactly to a particular reactant
as alkalinity or acidity, biological catalysts operate only molecule (yellow). Once the enzyme is locked on, the
under very particular conditions. For example, they reactant molecule breaks up into pieces

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 7 Chemical reactions

operate over a very narrow temperature range and, if the There have been problems associated with the early
temperature becomes too high, they become inoperative. biological washing powders. Some customers suffered
from skin rashes, because they were allergic to the
At temperatures above about 45°C, they denature. This enzymes. Manufacturers usually place warnings on the
means that the specific shape of the active site of the packets to indicate that the powder contains enzymes
enzyme molecule changes due to the breaking of bonds. which may cause skin rashes, and also advise that extra
This means that the reactant molecules are no longer rinsing is required.
able to fit into the active site.
Other industrial processes also make use of enzymes.
A huge multimillion-dollar industry has grown up
● In the manufacture of baby foods, enzymes called
around the use of enzymes to produce new materials.
proteases are used to ‘pre-digest’ the protein part of
Biological washing powders (Figure 7.15) contain
the baby food.
enzymes to break down stains such as sweat, blood and
● In the production of yoghurt, enzymes are added to
egg, and they do this at the relatively low temperature of
partially digest milk protein, allowing it to be more
40°C. This reduces energy costs, because the washing
easily absorbed by the body.
water does not need to be heated as much.
● In cheese making, enzymes are added to coagulate
milk and to separate it into solids (curds) and liquid
(whey).
In industry, enzymes are used to bring about reactions
at normal temperatures and pressures that would
otherwise require expensive conditions and equipment.
Successful processes using enzymes need to ensure
that:
● the enzyme is able to function for long periods of
time by optimising the environment
● the enzyme is kept in place by trapping it on
the surface of an inert solid (some processes
immobilise the enzymes when the process is
complete)
● continuous processes occur rather than batch
processes.

▲ Figure 7.15 These biological washing powders contain

enzymes

7.4 Reversible reactions and Some of these reactions produce important

industrial chemicals, such as ammonia and sulfuric
equilibrium acid. We will look at the industrial production of
ammonia later in this chapter but first let us look at
Most chemical reactions simply change reactants
some simpler examples of reversible reactions.
into products. For example, carbon reacts with
Copper(II) sulfate is available in two different
oxygen to produce carbon dioxide, but the carbon
forms: hydrated copper(II) sulfate, which is a blue
dioxide produced does not easily change back to give
solid, and anhydrous copper(II) sulfate which is a
carbon and oxygen again. There are, however, some
white solid. If hydrated copper(II) sulfate is heated,
chemical reactions which are reversible. These are
water is removed and the colour changes from blue
reactions in which reactants form products which
to white, as anhydrous copper(II) sulfate is formed.
can then react further to produce more reactants,
If water is then added to the white solid, it changes
which reverse the process and produce the original
back to a blue colour as the hydrated copper(II)
reactants. The resulting mixture may contain
sulfate is re-formed (Figure 7.16).
reactants and products, and their proportions can
be changed by altering the reaction conditions.

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 7.5 Ammonia – an important nitrogen-containing chemical

7.5 Ammonia – an important

nitrogen-containing
chemical
Nitrogen from the air is used to manufacture
ammonia, a very important bulk chemical. A bulk
chemical is one that is used in large quantities,
across a range of uses. The major process used for
making ammonia is the Haber process. This process
was developed by the German scientist Fritz Haber
in 1913. He was awarded a Nobel Prize in 1918 for
his work. The process involves reacting nitrogen and
hydrogen. Ammonia has many uses including the
manufacture of explosives, nitric acid and fertilisers
such as ammonium nitrate.

▲ Figure 7.16  Anhydrous copper(II) sulfate changes from Obtaining nitrogen

white to blue when water is added to it
The nitrogen needed in the Haber process is
This is an example of a reversible reaction: obtained from the atmosphere by fractional
distillation of liquid air (Chapter 12, p. 220).
hydrated copper(II)  anhydrous copper(II) + water
      sulfate              sulfate
Obtaining hydrogen
blue solid      white solid The hydrogen needed in the Haber process is
We can show this reaction as being reversible by obtained from the reaction between methane and
using the  symbol. steam.
methane + steam  hydrogen + carbon monoxide
Key definition
 CH4(g)  + H2O(g)  3H2(g) + CO(g)
Some chemical reactions are reversible as shown by the
 symbol. This means the reaction can go both ways. This process is known as steam re-forming and is
reversible.
Another example is cobalt(II) chloride, which is In any reversible reaction, the reaction shown
a blue solid in its anhydrous form and pink in its going from left to right in the equation is known as
hydrated form. Adding water to anhydrous cobalt(II) the forward reaction. The reaction shown going from
chloride changes the colour from blue to a pink right to left in the equation is known as the reverse
solid as it produces hydrated cobalt(II) chloride. reaction. Special conditions are employed to ensure
If hydrated cobalt(II) chloride is heated the colour that the reaction proceeds as the forward reaction
changes from pink back to blue. (to the right in the equation), producing hydrogen
and carbon monoxide. The process is carried out at
anhydrous cobalt(II) + water  hydrated cobalt(II) a temperature of 750°C, at a pressure of 3000 kPa
      chloride                    chloride (30 atmospheres) with a catalyst of nickel. These
    blue solid                   pink solid conditions enable the maximum amount of hydrogen
to be produced at an economic cost.
You will learn more about copper(II) sulfate in The carbon monoxide produced is then allowed
Chapter 8, p. 119. Both examples shown above can to reduce some of the unreacted steam to produce
be used as a chemical test for the presence of water. more hydrogen gas.
In summary, heating a hydrated compound
 carbon +  steam    hydrogen + carbon dioxide
will remove the water and form the anhydrous
monoxide
compound. Adding some water to an anhydrous
compound will produce the hydrated compound.   CO(g)  + H2O(g)   H2(g) + CO2(g)
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 7 Chemical reactions

Other ways of producing hydrogen for the Haber chemical equilibrium. Because the processes
process do exist, usually using hydrocarbons, but continue to happen, the equilibrium is said to be
steam re-forming is the most commonly used method. dynamic. A reversible reaction, in a closed system,
is at equilibrium when the rate of the forward and
Key definition reverse reactions are equal and the concentrations
The source of hydrogen used in the Haber process is of the reactants and products remain constant. The
methane, and nitrogen gas is obtained from the air. conditions used ensure that the ammonia is made
economically. Figure 7.17 shows how the percentage
of ammonia produced varies with the use of different
Making ammonia temperatures and pressures.
In the Haber process, nitrogen and hydrogen in
the correct proportions (1 : 3) are pressurised to Key definition
approximately 20 000 kPa (200 atmospheres) and A reversible reaction in a closed system is at equilibrium
passed over a catalyst of freshly produced, finely when the rate of the forward reaction is equal to the rate of
divided iron at a temperature of 450°C. The reaction the reverse reaction, and the concentrations of reactants
in the Haber process is: and products are no longer changing.

nitrogen + hydrogen  ammonia

60
 N2(g)  + 3H2(g)     2NH3(g); ΔH = −92 kJ/mol 350 C
The reaction is exothermic. % yield of ammonia at equilibrium
50

Key definition
40
The equation for the production of ammonia in the Haber
450 C
process is N2 + 3H2  2NH3.
The typical conditions used in the Haber process are 30
450°C, 20 000 kPa and an iron catalyst.
550 C
The industrial conditions employed ensure that 20
sufficient ammonia is produced at a fast enough
rate. Under these conditions, the gas mixture 10
leaving the reaction vessel contains about
15% ammonia, which is removed by cooling and
condensing it as a liquid. The unreacted nitrogen 0
100 000 200 000 300 000 400 000
and hydrogen are re-circulated into the reaction Pressure/kPa
vessel to react together once more to produce
▲ Figure 7.17 Yields from the Haber process
further quantities of ammonia.
Equilibrium You will notice from Figure 7.17 that the higher the
pressure and the lower the temperature used, the
The 15% of ammonia produced does not seem a great more ammonia is produced. In fact, the position of
deal. The reason for this is the reversible nature equilibrium is affected by each of the following:
of the reaction. Once the ammonia is made from
nitrogen and hydrogen, it decomposes to produce » changing temperature
nitrogen and hydrogen. There comes a point when » changing pressure
the rate at which the nitrogen and hydrogen react » changing concentration
to produce ammonia is equal to the rate at which » using a catalyst.
the ammonia decomposes. The concentrations of Relationships such as these were initially observed
nitrogen, hydrogen and ammonia in the reaction by Henri Le Chatelier, a French scientist, in 1888
vessel do not change, provided that the reaction (Figure 7.18). He noticed that if the pressure was
vessel is a closed system: one in which none of the increased in reactions involving gases, the reaction
gases can enter or leave. This situation is called which produced the fewest molecules of gas was

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 7.5 Ammonia – an important nitrogen-containing chemical

favoured. If you look at the reaction for the Haber

process you will see that, going from left to right,
the number of molecules of gas goes from four
to two. This is why the Haber process is carried
out at high pressures. We say that the position of
equilibrium has been moved to the right by using
the higher pressure. Le Chatelier also noticed that
reactions which were exothermic produced more
products if the temperature was low. Using a lower
temperature favours the exothermic process. In
the Haber process this would move the position
of equilibrium to the right. Indeed, if the Haber
process is carried out at room temperature, you
get a higher percentage of ammonia. However, in
practice the rate of the reaction is lowered too
much and the ammonia is not produced quickly
enough for the process to be economical. An
optimum temperature is used to produce enough
ammonia at an acceptable rate.
A catalyst is used in almost all industrial
processes to produce the product more quickly,
and in the Haber process an iron catalyst is used.
The catalyst increases the rate of both the forward
and reverse reactions to the same extent, so the
position is not affected: its use simply means the ▲ Figure 7.18 Henri Le Chatelier (1850–1936)
product is produced more quickly.
The concentration of nitrogen is often increased
as this will also favour the forward reaction, Test yourself
increasing the yield of ammonia. 9 What problems do the builders of a chemical plant
It should be noted, however, that the high designed to produce ammonia have to consider
pressure used is very expensive and is a major when they start to build such a plant?
10 What problems are associated with building a
safety concern so alternative, less expensive routes
plant which uses such high pressures as those
involving biotechnology are currently being sought. required in the Haber process?
Worldwide, in excess of 175 million tonnes of
ammonia are produced by the Haber process
each year.

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 7 Chemical reactions

7.6 Industrial manufacture optimum temperature which produces sufficient

sulfur trioxide at an economical rate.
of sulfuric acid – the Since the reaction from left to right is also
accompanied by a decrease in the number of
Contact process molecules of gas, it will be favoured by a high
Sulfuric acid is probably the most important pressure. In reality, the process is run at 200 kPa
industrial chemical, and the quantity of it produced (2 atmospheres) of pressure. Under these conditions,
by a country has been linked with the economic about 96% of the sulfur dioxide and oxygen are
stability of the country. Many million tonnes of converted into sulfur trioxide. The energy produced
sulfuric acid are produced worldwide each year. It is by this reaction is used to heat the incoming gases,
used mainly as the raw material for the production thereby saving money.
of substances such as detergents, paints, fertilisers The sulfur trioxide produced can be reacted with
and organic compounds including plastics. water to produce sulfuric acid.
The process by which sulfuric acid is produced is sulfur trioxide + water → sulfuric acid
known as the Contact process.
The process has the following stages. SO3(g)   + H2O(l) → H2SO4(l)
Sulfur dioxide is first produced by burning sulfur
with an excess of oxygen in the air. Key definition
sulfur + oxygen → sulfur dioxide The equation for the production of sulfur trioxide in the
Contact process is 2SO2 + O2  2SO3
S(s)   +  O2(g)  →   SO2(g) The typical conditions used in the Contact process are
450°C, 200 kPa and vanadium(V) oxide catalyst.
The sulfur dioxide can also be obtained by
roasting sulfide ores such as zinc sulfide in air. Burning sulfur or sulfide ores in air is the source of
The sulfur dioxide and oxygen gases are then sulfur dioxide and air is the source of oxygen in the
Contact process.
heated to a temperature of approximately 450°C
and fed into a reaction vessel, where they are
passed over a catalyst of vanadium(V) oxide (V2O5).
This catalyses the reaction between sulfur dioxide Test yourself
and oxygen to produce sulfur trioxide (sulfur(VI) 11 Produce a flow diagram to show the different
oxide, SO3). processes which occur during the production
of sulfuric acid by the Contact process.
sulfur dioxide + oxygen  sulfur trioxide Write balanced chemical equations showing
the processes which occur at the different
2SO2(g) +    O2(g)      2SO3(g); stages, giving the essential raw materials and
conditions used.
ΔH = −197 kJ/mol 12 Both the following reactions are reversible:
This reaction is reversible and so the ideas (i) X 2(g) + O2(g)  2XO(g)
(ii) 2XO(g) + O2(g)  2XO2(g)
of Le Chatelier described on p. 106 can be used Suggest a reason why an increase in pressure:
to increase the proportion of sulfur trioxide in a does not favour reaction (i)
the equilibrium mixture. The forward reaction b increases the amount of XO2 produced in
is exothermic and so would be favoured by low reaction (ii).
temperatures. The temperature of 450°C is an

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