The Haber Process: Extended Response

Overview
 Developed by German chemists Fritz Haber and Carl Bosch- beginning of the twentieth century
 Full name of the process is the Haber-Bosch Process
 Joint effort between German university and a German industry
 While the reaction between nitrogen gas and hydrogen gas to produce ammonia gas had been
known for many years, the yields were very small and the reaction slow
 Manufacturing of ammonia from nitrogen and hydrogen
 Nitrogen is obtained from the air
 Hydrogen derived from natural gas (methane)
 Exothermic reaction

What is believed to be Haber’s motivation for developing an economic process for the manufacture of
ammonia? Explain
 Developed in the lead up to WW1, nations e.g. Germany used to import nitrates they needed for
fertilisers and explosives from South America
 Growing world populations were placing strain on this natural source
 Furthermore, in Germany growing militancy was promoting calls for more explosives creating
further demand for natural nitrate resources
 Germany also understood that any war that it might have with England would (at least initially)
result in the blockade of critical war materials abroad.
 The most important of these resources was guano, manure from seagulls that roosted along the
coast of Chile. This guano was rich in nitrates and was the basis of the German manufacture of
explosives. The problem was that it had to be shipped by the tanker-load across the Atlantic and
past patrolling British warships.

A simplified schematic diagram for the process starting with hydrogen and nitrogen. Your diagram should
include reaction conditions such as temperature, pressure, presence of catalyst, phase of reagents and
reagent origin

1 volume of nitrogen to 3 volumes of hydrogen

At each pass of gasses through the reactor only approximately 15% is
converted to ammonia, by continual recycling the overall conversion is
~98%

When the gases leave the reactor they are hot and at a very high
pressure. Ammonia is easily liquefied under pressure as long as it isn't
too hot, and so the temperature of the mixture is lowered enough for the
ammonia to turn to a liquid. The nitrogen and hydrogen remain as gases
even under these high pressures, and can be recycled.
Discuss the significance of conditions used in the Haber process in terms of ammonia yield, reaction rate
and economic considerations. Consider the conditions of temperature, pressure and the use of a catalyst.
 Proportions of nitrogen and hydrogen- Avogadro’s Law says that equal volumes of gases of the
same temperature and pressure contain equal numbers of molecules. This means that the gases
are going into the reactor in the ratio of 1 molecule of nitrogen to 3 molecules of hydrogen- this is
determined by the equation (what balances the equation). The importance of keeping to these
proportions is so that there isn’t excess of one reactant passing through the reactor which can’t
react because there’s nothing for them to react with- wasting reactor space => uneconomical

 Temperature- To get maximum yield we want the equilibrium position to be as far left as
possible. Being an exothermic reaction, temperature needs to be decreased to increase the
amount of ammonia produced. This is described by La Chateliers Principle, lowering the
temperature will cause the system to partially counteract the change by favouring the forward
reaction (the side that produces more heat).

When the temperature is lowered the reaction rate of both reactions first decrease, however
endothermic reactions are more sensitive to changes in heat and the reduction will impact the
reverse reaction rate more- the number of successful reactions of products breaking back to
reactants decreases. There are now more reactants available. However, we must be mindful not
to decrease the temperature too much as to slow the reaction rate down significantly.
Economically, it makes no sense to try to achieve an equilibrium mixture which contains a high
proportion of ammonia if it’s going to take a long time to even reach that equilibrium- You need
the gases to reach equilibrium within the short time they will be in contact with the catalyst in
the reactor. High temperatures also increase energy costs

In order to get as much ammonia as possible we can compromise at a temperature between 400-
450C producing a reasonably high proportion of ammonia even though it’s only about 10-20% it
produces that in a short time.

 Pressure- There are 4 gas molecules on the left hand side and only 2 on the right hand side. As
described by Le Chatelier’s Principle- increasing the pressure will favour formation of the
products. Increasing the pressure means the concentration of all the gases have increases, since
there are 4 molecules in total of the reactants they have a higher chance of successful collisions
and so more increasing the forward reaction rate. The reverse rate only has 2 molecules and will
happen a lot slower and so the formation of the ammonia gas will be favoured.

However, as the reaction counteracts the increase in pressure, the 2 molecules produced causes
the pressure to fall again so we need as high of a pressure as possible to get the most ammonia
yield.

Increasing the pressure brings the molecules closer together- increasing their chance of hitting
and sticking to the surface of the catalyst where they can react, the higher pressure the better in
terms of the reaction rate.

Very high pressures are very expensive to produce as you need extremely strong pipes and
containment vessels to withstand the very high pressure (which increases your capital costs
when the plant is built). High pressures cost a lot to produce and maintain which also means the
costs of running the plant is very high.

The compromise is 200 atm-atmospheres (atmospheric pressure), chosen mostly on economic

grounds. If the pressure used is too high the costs of generating exceeds the price received for the
ammonia produced.
  Catalyst- The catalyst has no effect whatsoever on the position of the equilibrium it doesn’t
produce a greater yield of ammonia but however it speeds up the reaction. In the absence of a
catalyst the reaction is so slow that virtually no reaction happens in sensible time. 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 used in the Haber process is magnetite (iron catalyst) (Fe3O4) fused with smaller
amounts of agents consisting of other metal oxides. The catalyst is ground finely such that it has a
large surface area of about 50 m2 g-1, and the magnetite is reduced to iron. The large surface area
allows gaseous molecules to rapidly absorb and react. The use of the catalyst allows the reaction
rate to remain high despite moderate temperatures. Iron is also a cheap catalyst and catalysts
aren’t used up in the reaction

Catalyst in use

Additionally, removing ammonia as it’s formed means equilibrium is never reached and so the rate never
goes down

When a chemical is manufactured, the optimum conditions used are the ones that give the lowest cost.
These conditions are not necessarily the ones that give the fastest reaction or highest percentage yield.

For example:
 the rate of reaction must be high enough to make enough product each day
 the percentage yield must be high enough to make enough product each day.

Note that a low percentage yield could be accepted if unreacted started materials can be recycled (as they
are in the Haber process)
Show your understanding of the principles of green chemistry (Ref chem book pg 160-161) by choosing
one aspect of the Haber process that is in line with the principles of green chemistry and one that is not.
You will need to briefly justify your answer.

Atom Economy- Synthetic methods should be designed to maximise the incorporation of all materials
used in the process into the final products.

In a world of limited resources, we need to make the most of what we have. The idea of yield and yield
efficiency is very important in helping us minimise the resources we use, but it is not the whole story. If
we want to reduce waste, we have to look at the reaction itself to see how much useful product is
produced compared to the total mass of atoms used. This is called the atom economy.

The Haber process abides within this principle as it has almost a 100% atom economy. At the end of the
process, when the gases emerge from the iron catalyst reaction chamber, the gas mixture is cooled under
high pressure, when only the ammonia liquefies and is so can be removed, tapped off from the cooled
compression chamber and stored in cylinders for use e.g. making fertilisers. Because the reaction is
reversible, not all the nitrogen and hydrogen atoms are converted to ammonia. Any unreacted nitrogen
and hydrogen (which is not in a liquefied state as only the ammonia liquefies) molecules, is recycled back
through the reactor chamber for further passes over the catalyst, very little is wasted! And almost
complete conversion is achieved.

Designing for energy efficiency- Energy requirements of chemical processes should be recognised for
their environmental and economic impacts and should be minimised. If possible synthetic methods
should be conducted at ambient temperature and pressure (that of their natural surroundings).

Even though compromises are reached to maximise the yield of ammonia these don’t necessarily take
into account environmental factors and their impacts. The Haber process is conducted between 400-
450C which is not a low temperature as well as a 200atm pressure used which is 200 times the normal
pressure. While compromises are made, they are generally with economic efficiency in mind as opposed
to in line with ‘green chemistry principles’.

Additionally, the preparation of the hydrogen causes the harmful carbon monoxide to be released and the
hydrogen is made from methane, a non-renewable fossil fuel resource. This is a finite resource, though
the nitrogen comes in abundance from the air and would never run out!

~Less hazardous chemical syntheses: Wherever practicable synthetic methods should be designed too
use and generate substances that posses little or no toxicity to human health and the environment.

A method of consideration could be electrolysis: An electric current splits water into hydrogen and
oxygen. If the electricity is from renewable sources, such as solar or wind, the resulting hydrogen will be
considered renewable as well, and have numerous emissions benefits. Because renewable electricity may
be available when it is not needed on the grid, power-to-hydrogen projects are taking off. These projects
use excess renewable electricity when it’s available and make hydrogen through electrolysis. These
renewable projects would have the potential to become even more economical if the hydrogen was sold
to the fuel cell electric vehicle market.