Industrial chemistry

The Haber Process &

The Ostwald Process

Kazem.R.Abdollah (Asiaban)

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 The Haber Process
• In the early 1900’s a German chemist called
Fritz Haber came up with his chemical process
to make ammonia using the “free” very
unreactive Nitrogen from the air. (N2 is 80% of
atmosphere)

Fritz Haber, 1918

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• The Haber process combines nitrogen from
the air with hydrogen derived mainly from
natural gas (methane) into ammonia. The
reaction is reversible and the production of
ammonia is exothermic.
• Nitrogen + Hydrogen Ammonia

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 Raw Materials
• N2 (g) is taken from the air via a process of
fractional distillation.
• H2 (g) comes from natural gas, CH4 (g)
• CH4 (g) + H2O (g) 3H2 (g) + CO (g)
• The carbon monoxide then reacts with more
steam:
• CO (g) + H2O (g) H2 (g) + CO2 (g)
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 scheme for the Haber process

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 The temperature
Equilibrium considerations
• You need to shift the position of the equilibrium as far as
possible to the right in order to produce the maximum
possible amount of ammonia in the equilibrium mixture.

• The forward reaction (the production of ammonia) is

exothermic.
• According to Le Chatelier's Principle, this will be favoured if
you lower the temperature. However, 400 - 450°C isn't a low
temperature!

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 The compromise
• The lower the temperature you use, the slower the reaction
becomes. A manufacturer is trying to produce as much
ammonia as possible per day. It makes no sense to try to
achieve an equilibrium mixture which contains a very high
proportion of ammonia if it takes several years for the
reaction to reach that equilibrium.
• 400 - 450°C is a compromise temperature producing a
reasonably high proportion of ammonia in the equilibrium
mixture (even if it is only 15%), but in a very short time.

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 The pressure
• According to Le Chatelier's Principle, if you increase the
pressure the system will respond by favouring the reaction
which produces fewer molecules. That will cause the pressure
to fall again.
• Increasing the pressure brings the molecules closer together.
In this particular instance, it will increase their chances of
hitting and sticking to the surface of the catalyst where they
can react. The higher the pressure the better in terms of the
rate of a gas reaction.

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 Economic considerations
• Very high pressures are very expensive to
produce on two counts.
• You have to build extremely strong pipes and containment
vessels to withstand the very high pressure. That increases
your capital costs when the plant is built.
• High pressures cost a lot to produce and maintain. That
means that the running costs of your plant are very high.

• 200 atmospheres is a compromise pressure chosen on

economic grounds.

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 The catalyst
• The catalyst has no effect whatsoever on the position of the
equilibrium. Adding a catalyst doesn't produce any greater
percentage of ammonia in the equilibrium mixture. Its only
function is to speed up the reaction.
• The catalyst ensures that the reaction is fast enough for a
dynamic equilibrium to be set up within the very short time
that the gases are actually in the reactor.
• The catalyst is actually slightly more complicated than pure
iron. It has potassium hydroxide added to it as a promoter - a
substance that increases its efficiency.

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 Ostwald process
• The Ostwald process is a chemical process for
making nitric acid (HNO3).
• Wilhelm Ostwald developed the process, and
he patented it in 1902.

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 Description
• Ammonia is converted to nitric acid in 2 stages.

• It is oxidized (in a sense "burnt") by heating with oxygen in the

presence of a catalyst such as platinum with 10% rhodium, to
form nitric oxide and water.

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 Stage 1
• This step is strongly exothermic, making it a useful
heat source once initiated:

• 4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g) (ΔH = −905.2 kJ)

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 Stage 2
• Stage two encompasses two reactions and is carried out in an
absorption apparatus containing water. Initially nitric oxide is
oxidized again to yield nitrogen dioxide: This gas is then readily
absorbed by the water, yielding the desired product (nitric acid,
albeit in a dilute form), while reducing a portion of it back to
nitric oxide:

2 NO (g) + O2 (g) → 2 NO2 (g) (ΔH = −114 kJ/mol)

3 NO2 (g) + H2O (l) → 2 HNO3 (aq) + NO (g) (ΔH = −117 kJ/mol)

• Alternatively, if the last step is carried out in air:

• 4 NO2 (g) + O2 (g) + 2 H2O (l) → 4 HNO3 (aq)
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• The NO is recycled, and the acid is concentrated to
the required strength by distillation.

• Typical conditions for the first stage, which contribute to an

overall yield of about 98%, are:
• pressure between 4 and 10 atmospheres (approx. 400-1010
kPa or 60-145 psig) and
• Temperature is about 500 K (approx. 217 °C or 422.6 °F.).

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