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9.4 Chemical monitoring and management: 2. maximise
production
| Syllabus reference (October 2002
version) |
2. Chemical processes in industry require
monitoring and management to maximise production |
Students learn to:
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Students:
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Extract from Chemistry Stage 6 Syllabus (Amended October
2002). © Board of Studies, NSW.
[Edit: 24Jun08]
Prior learning:Preliminary modules
8.2 (8.2.2) 8.3 (8.3.2,
8.3.5), 8.5 (8.5.5)
and HSC modules 9.2 (9.2.1),
9.3 (9.3.2, 9.3.4).
Background: There are some chemical
reactions that have played a very important part in world
history and human activity, allowing the development of
industries and societies. The production of ammonia is one such
example.
gather and
process
information from secondary sources to describe the
conditions under which Haber developed the industrial
synthesis of ammonia and evaluate its
significance at that time in world history
The significance of Fritz Haber’s work
World context: Nitrogen compounds were
essential for the production of fertilisers and explosives.
Much of the fertiliser originated in Chile, a long way from
the industrial centres of Europe. It was known that the
atmosphere contains large quantities of diatomic nitrogen. It
would be advantageous to convert this readily available gas
to usable compounds for agriculture and industry, cheaply and
on a large scale.
Haber’s contribution: Fritz Haber
had studied under Robert Bunsen, in Germany, and was
interested in the effect of heat on the chemistry of gases.
In the early 1900s, Haber reacted nitrogen with hydrogen,
using an iron catalyst, to form ammonia. Ammonia can be
readily converted to a range of valuable products. In 1908 he
had improved the reaction and in 1911 he was rewarded with a
directorship at a German institute. Carl Bosch developed the
chemical engineering necessary for the large-scale
production of ammonia by the Haber-Bosch process.
Significance: Germany used the process to
make explosives in World War I after the British cut off
supplies of nitrate from Chile. This lengthened the war.

identify and
describe the
industrial uses of ammonia
- Ammonia is used to make solid and liquid fertilisers,
explosives, nitric acid, sodium carbonate, some
pharmaceuticals and household cleaners. It is also used as a
refrigerant.
- To make solid fertilizer industrially, ammonia, which is
a weak base, is reacted with sulfuric acid to form ammonium
sulfate fertiliser and with nitric acid to form ammonium
nitrate fertiliser.

identify that
ammonia can be synthesised from its component gases,
nitrogen and hydrogen.
- Under pressure and heat, nitrogen and hydrogen react in
the ratio of 1 volume of nitrogen to 3 volumes of hydrogen to
produce 2 volumes of ammonia.


describe that
synthesis of ammonia occurs as a reversible reaction that
will reach equilibrium
- The synthesis of ammonia occurs as a reversible reaction.
This means that ammonia is formed from nitrogen and hydrogen
(the forward reaction) and once some ammonia is produced,
some nitrogen and hydrogen are formed from the ammonia (the
reverse reaction). When nitrogen and hydrogen are initially
added to a reaction vessel, the reaction is slow. Equilibrium
is reached when the rate of the forward reaction is the same
as the rate of the reverse reaction.
- To ensure that sufficient ammonia is produced, conditions
need to be established that shift the equilibrium position to
the right.


explain that
the use of a catalyst will lower the reaction temperature
required and identify the
catalyst(s) used in the Haber process
- With the use of catalyst, the activation energy for the
reaction is lowered. A finely ground iron catalyst, with
large surface area, is used in the Haber process. The gaseous
nitrogen and hydrogen molecules are adsorbed on to the solid
catalyst surface and rearrange forming the ammonia molecules.
By lowering the activation energy, a catalyst enables a more
rapid reaction at lower temperatures.

identify the
reaction of hydrogen with nitrogen as
exothermic

explain why
the rate of reaction is increased by higher
temperatures
- As the temperature rises, the particles move more quickly
and have higher kinetic energy. This increases the frequency
of collisions between particles that can react and also
increases the amount of energy available for the reaction.
Most of the increased rate of reaction comes from more of the
colliding particles exceeding the activation energy needed
for the reaction to occur. The increased frequency of
collisions is less important in increasing the rate of
reaction. The rate of both the forward and reverse reactions
is increased.

explain why
the yield of product in the Haber process is reduced at
higher temperatures using Le Chatelier's
principle
- The forward reaction in which ammonia is formed is
exothermic. Le Chatelier's principle states that if a
system in equilibrium is disturbed, the system will adjust
itself to minimise the disturbance. In this case, Le
Chatelier's principle indicates that with high
temperature providing more heat, the reverse reaction is
favoured and the decomposition of ammonia occurs.
Another way to view it
If the reaction is written like that following, heat
is like a product.

As temperature, and therefore the heat available increases,
the equilibrium position shifts to the left and the yield of
ammonia is reduced.

analyse the
impact of increased pressure on the system involved in the
Haber process
- In accordance with Le Chatelier's principle,
increasing the pressure favours the production of ammonia
because two molecules of gaseous ammonia occupy a smaller
volume than the four molecules of gaseous reactants.
- High pressure also increases the reaction rate because
the gas molecules are closer and at higher concentrations.
However, high-pressure equipment is expensive and requires
considerable energy to operate.
- To achieve an economic yield of about 30%, a pressure of
35 000 kPa (35 MPa or 345 atm) is used.

explain why
the Haber process is based on a delicate balancing act
involving reaction energy, reaction rate and
equilibrium
- As the temperature is increased more energy is available
to exceed the reaction activation energy and thus the
reaction rate between nitrogen and hydrogen to form ammonia
increases. However increasing temperature favours
decomposition of the ammonia product. A compromise
temperature providing a satisfactory reaction rate and
satisfactory yield of ammonia is selected.
- To achieve an economic yield of about 30%, the
temperature is raised to 525°C and pressure
of 35 000 kPa (35 MPa or 345 atm) is used.
Increasing yield
Liquefying and removing the ammonia as it is produced also
increase the yield of ammonia.

explain why
monitoring of the reaction vessel used in the Haber process
is crucial and discuss the monitoring
required
- The raw materials must be monitored to ensure they are
clean. Any carbon dioxide detected must be removed. It is
often separated and diverted to use for the production of
urea at a nearby fertiliser manufacturing plant. Any oxygen
present could cause an explosion with the
hydrogen.
- A chemical engineer or technician monitoring the reaction
vessel needs to ensure that the appropriate temperature and
pressure conditions are maintained, within an acceptable
range, so that about 30% yield is achieved.
- The quality of the catalyst surface needs to be monitored
to ensure good adsorption of the nitrogen and hydrogen gases.
The system must be kept free of contaminants to ensure
maximum surface of the catalyst is available for adsorption
of nitrogen and hydrogen.
- Temperature needs to be monitored, as too high a
temperature can permanently damage the catalyst.
Haber
process for ammonia synthesis
by Jayant M Modak, Department of Chemical
Engineering
Indian Institute of Science, Bangalore 560012, India, printed in Resonance,
2002
