Chemical Monitoring and Management

identify and describe the

Ammonia is used industrially as a feedstock (raw material from which a
industrial uses of ammonia substance or industrial process is derived) mainly for:
fertilisers (derived from urea and ammonium and nitrates) to grow plants
where soils may be deficient in nitrogen compounds. 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.
explosives (derived from nitric acid) such as TNT, nitroglycerine and
nitrocellulose in order to destroy
plastics (nylon and acrylic) for general everyday use such as clothing,
containers and fibres
Other uses include cyanides (gold extraction), sulfonamides (antibiotics), aniline
derivatives (dyes) and cationic detergents.
identify that ammonia can
H2(g) + 3N2(g)
2NH3(g) H = -92kJ/mol
be synthesised from its
The industrial production of ammonium, known as the Haber Process, allows
component gases, nitrogen the production of ammonia from its constituent elements.
and hydrogen
The synthesis of ammonia is a reversible reaction. Drawing on from previous
knowledge, all reversible reactions in a closed reaction system will reach
describe that synthesis of
equilibrium after a time, when the forward and backward reaction rates are
ammonia occurs as a
reversible reaction that will equal. At standard conditions the equilibrium lies well to the left, and very little
ammonia is present in the reaction mixture. The conditions in the Haber
reach equilibrium
Process, however, make it viable commercially.
identify the reaction of
The forward reaction is exothermic as H is negative. This means that the
hydrogen with nitrogen as
substances involved lose energy as part of the reaction, which is given out as
exothermic
heat. For each mole of hydrogen and 3 moles of nitrogen used to produce 2
moles of ammonia, 92kJ of energy is released.
explain why the rate of
Recall from previous studies how kinetic factors affect the rates of reaction,
reaction is increased by
particularly temperature and pressure (for gaseous systems like the Haber
higher temperatures
Process). It is important in industry to have a high rate of production due to
economic considerations. The kinetic theory of gases predicts that the rate of a
explain why the yield of
reaction increases when more successful collisions occur in the shortest time.
product in the Haber
High temperatures favour an increase in reaction rate as the molecules have
process is reduced at
higher temperatures using higher kinetic energy and can overcome the activation energy barrier. As such,
the rate of reaction of the Haber Process is increased by higher temperatures.
Le Chateliers principle
However the yield from the Haber Process is adversely affected by increased
temperatures. The forward reaction is exothermic and as both reactions reach
equilibrium after a time, Le Chateliers Principle comes into effect. The
equilibrium shifts to oppose the change. Thus, if the temperature is increased
the equilibrium position shifts to counteract the change, by reducing the latent
heat by favouring the endothermic reaction. As such, the backwards reaction is
preferred and yield is reduced.
explain that the use of a
Recall from previous studies that a catalyst suitable for a reaction will lower the
catalyst will lower the
activation energy required for a reaction, by providing an alternative pathway for
reaction temperature
the reaction to proceed.
required and identify the
catalyst(s) used in the
Haber process

Note that, in a reversible reaction, the catalyst speeds both forward and
backward reaction rates equally such that the equilibrium position is not
changed, not affecting yields. However, the time taken to reach this equilibrium

analyse the impact of

increased pressure on the
system involved in the
Haber process

position is less as reaction rates are faster. As such, the temperature required to
attain a high reaction rate is less, allowing the equilibrium to favour the products
and hence increase profit, whereas using a temperature to attain an equivalent
rate of reaction would reduce in a much lower yield.
The catalyst used in the Haber Process is a mix of metals and oxides.
Magnetite (Fe3O4) is fused with potassium, aluminium and calcium oxides (K2O,
Al2O3, CaO) such that the magnetite is reduced to porous iron. It becomes finely
ground, with large surface area, to increase the available surface of reaction.
The gaseous nitrogen and hydrogen molecules are adsorbed on to the solid
catalyst surface and rearrange forming the ammonia molecules.
Pressure is beneficial to both wants in the Haber Process. High gas pressure
favours the frequency of successful molecular collisions. Essentially, the same
number of molecules is in a smaller space, thus having a higher concentration.

Recall that kinetically the rate of reaction is given by the concentration.

For example, for the Haber Process:
Thus, the forward rate of reaction is increased by increasing pressure. The
backward reaction similarly increases, but to a lesser extent.
Pressure is also important in shifting the equilibrium position of the mixture. The
equilibrium shifts in order to counteract the change that caused it (Le Chateliers
principle). By increasing the pressure we shift the equilibrium in favour of the
reaction which produces less moles of gas. This is the forward reaction,
favouring the production of ammonia. Thus, by increasing pressure we increase
the amount of ammonia in the equilibrium mixture.
Pressure (atm)
100
300
600
1000
Yield (% v/v)
25
47
66
80
explain why the Haber
process is based on a
delicate balancing act
involving reaction energy,
reaction rate and
equilibrium

In The Haber process we aim to maximise yield and reaction rate, and minimise
cost in order to gain maximum profit. However, some of these concerns naturally
conflict with one another. A delicate balance between all these conditions are
required to achieve the most profitable yield for the least cost.
Cost
Reaction Rate
Yield
Pressure
Low Pressure
High Pressure
High Pressure
Temperature
Low Temperature
High Temperature
Low Temperature
Thus compromise conditions are required, which balance energy, reaction rate
and equilibrium (yield). The set of conditions which are commonly used vary, but
there are typical ranges. However, the higher the reaction rate and the higher
the yield the cost is offset more.
Reactants: N2 and H2 are kept in the ratio 1:3 in order to maximise yield per
either reactant, irregardless of Le Chateliers principle as excess amounts of
one reaction leads to more product but less efficiency.
Pressure: 15-35 MPa (usually from 20 to 25MPa). Although equilibrium factors
suggests that pressure should be as high as possible, economic and safety
factors prevent this, to ensure the reaction vessel has a longer lifetime.
Temperature: from 400o to 550o C. Equilibrium and kinetic factors are in conflict,
as discussed above. This is the main compromise condition, and it is chosen to
have a decent rate of reaction while retaining reasonable yield.
Catalyst: Iron oxide (magnetite, Fe3O4), fused with other metal oxides
(potassium, aluminium, calcium). The porous catalyst has a high surface area in
order to provide a large surface for the reaction to occur upon. Obviously this
increases the rate of reaction.
The ammonia yield is around 15 to 20% each cycle. After each cycle ammonia
is liquefied under pressure (while N2 and H2 remain gaseous) and is removed

explain why monitoring of

the reaction vessel used in
the Haber process is
crucial and discuss the
monitoring required

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

from the equilibrium. This shifts the reaction to the products further when the N2
and H2 are re-injected into the reaction chamber. After 5 to 6 cycles about 98%
of the reactants are converted into ammonia.
Industrial chemists and chemical engineers employed in the manufacturing of
ammonia need to perform a range of monitoring activities to ensure quality
control. These include:
Continuous monitoring of the high pressure reaction vessel, ensuring that the
production of ammonia occurs under safe conditions (i.e. pressure not too
high) and yield is not compromised (i.e. pressure is too low). Pressure data
from various sensors is monitored electronically.
Monitoring of temperature, to ensure that it stays in the optimum range. If the
temperature is too high then ammonia yield is reduced. Temperature data is
similarly measured and monitored centrally from various temperature
sensors.
Monitoring the furnaces which produce the hydrogen and nitrogen
feedstocks, which must be made in the correct ratios and kept free from
contamination. Carbon oxide sensors send information about the gas stream
to a central monitoring computer.
Monitoring the catalyst, as the particle size needs to be monitored to ensure it
has a high surface area. The catalyst lasts about 5-10 years.
Monitoring the ammonia liquefaction process during each cycle to ensure
optimal yield.
Research chemists in the ammonia industry continue to identify new catalyst
and production line efficiencies. As most ammonia is used in the fertiliser
industry and the manufacture of explosives, there is an ever-increasing demand
for this product.
The Haber process was created at a crucial time. At the beginning of the
twentieth century, there was a shortage of naturally occurring nitrogen sources,
especially ammonia and nitrates. With world populations growing, the demand
for food increased, putting pressure on natural nitrate sources such as manure.
The demand for nitrogen compounds for making nitric acid in the chemical
industry grew around the same time, as Germany was about to enter WWI. Nitric
acid was used to make explosives such as TNT and dynamite, amongst others,
to fuel the war. Natural reserves of nitrates such as Peruvian guano, obtained
from sea-bird droppings, and Chilean sodium nitrate dwindled. Germany was
highly dependant on overseas supplies of nitrate salts for agriculture and
manufacture of explosives. The allied blockade of Chilean saltpetre did not even
nearly meet the very high demand for ammonium nitrate, used for explosives.
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.
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. In 1914, Carl Bosch developed the chemical engineering necessary for
the large-scale production of ammonia by the Haber-Bosch process.
The industrial synthesis of ammonia facilitated the manufacture of fertilisers for
continued food production, and nitric acid, an essential component in the
manufacture of explosives and other ammunition. It has been suggested that
without this process, Germany would almost certainly have run out of explosives
and fertiliser for food by 1916, thereby ending the war.
The Haber process now produces 100 million tons of nitrogen fertilizer per year,
mostly in the form of anhydrous ammonia, ammonium nitrate, and urea. That
fertilizer is responsible for sustaining one-third of the Earth's population, as well
as various deleterious environmental consequences.