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The manufacture of ammonia: the Haber

process
The Haber process, in which ammonia is synthesised from
nitrogen and hydrogen, is one of the most important chemical
processes to have had an impact on human civilisation. The
growth of plants depends on the availability of a source of
nitrogen in the soil in a form that the plants can use.
Useable forms of nitrogen include soluble ammonium and
nitrate salts and urea. N2 in the atmosphere needs to be
converted into compounds that plants can use to promote
growth. This process, called nitrogen fixation, is carried out in
nature by nitrogen-fixing bacteria.
In earlier times, crop rotation was an essential part of
regenerating soil with adequate levels of inorganic nitrogen to
support the growth of most crops. However, as populations
increased, greater quantities of food were required and the use
of nitrogenous fertilisers became essential. At the beginning of
the twentieth century, the main supply of fertilisers came from
natural deposits of saltpetre (potassium nitrate) and guano (bird
droppings that have accumulated over thousands of years).
During the early years of the twentieth century, the worldwide
demand for nitrogen-based fertilisers was far greater than
available supplies.

Fritz Haber
In 1912, Fritz Haber, a German chemist, developed a process
for the synthesis of ammonia from nitrogen and hydrogen. So
important was this process that it undoubtedly had a significant
influence on world history. At the time of the First World War,
Germany was highly dependent on overseas supplies of nitrate
for agriculture and the manufacture of explosives. The naval
blockade of Germany by allied forces blocked this supply route
for nitrate and other important materials required for the war
effort. The Haber synthesis of ammonia facilitated the
manufacture of fertilisers for continued food production, and
nitric acid, an essential component in the production of

explosives and other ammunition. Carl Bosch assisted in taking


Habers process from laboratory production to full-scale
industrial production.
In fact, the synthesis of ammonia is a classic example of the
influence of society upon chemistry and of the impact of
chemistry on human life.

Uses of Ammonia
Ammonia ranks second to sulphuric acid in terms of quantity
produced worldwide per year. It is used to make:
Fertilisers (sulfate of ammonia, ammonium nitrate, urea)
Fibres and plastics (rayon, acrylics, nylon)
Nitric acid, which in turn is used to make fertiliser, dyes,
fibres and plastics and explosives such as ammonium
nitrate, TNT, (trinitrotoluene) and nitroglycerine
Household cleaners
Detergents (non ionic ones)

INDUSTRIAL SYNTHESIS OF AMMONIA


The synthesis of ammonia uses the simple exothermic reaction:
N2(g) + 3H2(g)

2NH3(g)

H = -92kJ/mol

This is an equilibrium reaction which at ordinary pressures and


temperatures lies well to the left.

EQUILIBRIUM CONSIDERATIONS
Le Chateliers principle shows how to maximise the conversion
of nitrogen and hydrogen to ammonia.
1. If the pressure on a reaction system is increased, the
equilibrium moves in the direction which tends to reduce
the pressure.

Look at the reaction


N2(g) + 3H2(g)
4 moles of gas

2NH3(g)
2 moles of gas

If the pressure is increased then the reaction moves to the


right.
2. If the temperature is lowered, the equilibrium will move in
the direction which tends to increase temperature.
This reaction is exothermic, so if temperature is lowered it
will move towards the right.
On equilibrium considerations alone the reaction should be
conducted at high pressure and low temperature.

RATE CONSIDERATIONS
Another consideration is how long it will take to reach
equilibrium, that is, the rate of reaction.
As for most reactions, the rate decreases as temperature
decreases.
If we lower the temperature in order to produce more ammonia,
we make the reaction very slow and so it takes a very long time
to reach equilibrium.
The rate of reaction can be increased by using a suitable
catalyst. Iron is a good catalyst for this reaction but while it
speeds it up it is still to slow at room temperature.
Remember catalysts speed up reactions they do not affect the
position of the equilibrium as they speed up both the forward
and reverse reactions.
Hence have these situations:

Low temperatures produces a high yield but it takes a very


long time (weeks to months) even with a catalyst
High temperatures causes equilibrium to be reached
quickly but the yield is extremely low

COMPROMISE
A moderate temperature produces a moderate yield moderately
quickly.
Typical conditions for the industrial process, called the Haber
Process are:
A temperature of about 700 K (or about 400C) and
A total pressure of about 2.5 x 104 kPa (250 times
standard atmosphere)
Catalyst is magnetite Fe3O4 with its surface layer reduced
to free iron
With a reactant mixture having H2 and N2 in the ratio of 3:1,
these conditions give an equilibrium conversion to ammonia of
about 45%.

THE

HABER PROCESS

Reactants pass through the catalytic reactor,


The mixture is cooled to condense out the ammonia
formed
Unreacted gases are fed back into the catalyst chamber
along with incoming fresh reactants
None of the reactant mixture is wasted
Energy must be managed to prevent catalyst overheating
Heat released in reaction is used to partially heat
reactants ( saves energy and costs)

THE SOURCE OF REACTANTS

Nitrogen can be obtained from the atmosphere so hydrogen is


the difficult or expensive reactant to obtain.
Industrially, hydrogen is generally produced by reacting
methane or some other hydrocarbon with steam in the
presence of a nickel catalyst at a temperature of about 750C:
CH4 (g) + H20 (g)

CO (g) + 3H2 (g) H = +206 kJ/mol

Carbon monoxide poisons the iron catalyst and must be


removed.
CO (g)

H2O (g)

CO2 (g)

H2 (g)

Which has an added advantage of producing more hydrogen.


The catalyst used is either Fe3O4 at 500C or Cu at 250C
There must not be any oxygen in the gas mixture as it is
explosive with hydrogen under the conditions used.
Methane is used to remove oxygen from air (normal
combustion to CO2 and steam)
The only unwanted gas in the mixture is carbon dioxide. This is
removed by reaction with a base.
Use of a 3:1 mixture of hydrogen and nitrogen is the most
efficient way to make ammonia.

MONITORING
Because many different conditions must be maintained for
efficient and safe operation of the Haber process, monitoring is
essential. The conditions that need to be monitored include:
Temperature and total pressure in the reaction vessel
to keep within the optimum range

Prevent damage to catalyst


Ratio of H2 to N2 in the incoming gas stream to prevent
build up of one reactant
Concentrations of O2, CO, CO2 and sulfur compounds
explosions, contamination of catalyst
Concentrations of methane and argon lower efficiency of
conversion
Purity of product ammonia no contamination.