Case Study: The Haber Process:

Ammonia for Food and Bombs 7.4

In the late nineteenth century, rapid population growth in Europe and North America
began to outstrip the food supply. Research was showing that the addition of nitrogen-
based fertilizers such as sodium nitrate, NaNO3(s), and ammonium nitrate, NH3NO3(s),
significantly increased crop yield to help ease the worldwide food shortage. However,
there was initially not sufficient fertilizer to meet the growing demand. Guano (bird
droppings), a traditional fertilizer from Peru, and sodium nitrate supplies from Chile
would soon be exhausted, not least because those raw materials were also being used to
produce explosives.
An alternative source of ammonia or nitrate had to be found.
In 1909, a leading German chemical company, Badische Anilin und Soda Fabrik (BASF),
started to investigate the possibility of producing ammonia from atmospheric nitrogen,
N2(g). Little did they know that one year earlier, Fritz Haber, a professor at a technical
college in Karlsruhe, Germany, had discovered a method for doing just that (Figure 1).
Haber realized, after much experimentation, that nitrogen gas and hydrogen gas form
Figure 1
an equilibrium mixture with ammonia. The optimum conditions include a closed con- Fritz Haber (1868–1934) discovered a
tainer, a suitable catalyst (such as iron oxide), a temperature of 600°C, and a pressure of method for converting atmospheric
30 MPa. nitrogen into ammonia at a technical
college in Karlsruhe, Germany. He
Fe2O3(s) was awarded the Nobel Prize in
N2(g)  3 H2(g) e 2 NH3(g) H°  92 kJ Chemistry in 1918 for discovering the
process that now bears his name.
This method is now called the Haber process, in honour of its discoverer. BASF bought
the rights to the Haber process and with the help of Carl Bosch, BASF’s chief chemical
engineer, built a giant industrial plant capable of producing 10 000 t of ammonia per year.
N2(g) and H2(g) added
Today, ammonia is in sixth position in a ranking of chemicals produced worldwide, to system
with over 80 billion kilograms produced each year.

Practice

N2(g) and H2(g) recycled back into system

Understanding Concepts
1. Suggest five factors that could affect the production of ammonia in the Haber
process. Explain the effect of each factor, using rate theory. reaction
chamber 500˚C,
Making Connections
30–60 MPa,
2. Create a concept map starting with “Haber process” and including at least two end iron(III) oxide
uses of the product of this process. catalyst

The Temperature Puzzle

The reaction of nitrogen and hydrogen at low temperatures is so slow that the process
becomes uneconomical. Adding heat increases the rate of the reaction (Figure 2), which
is important in any continuous industrial process. However, in this reaction, the higher
the temperature, the lower the yield of ammonia. The relationship between percentage
NH3(g) removed
yield and temperature is shown in Figure 3.
from system

Figure 2
Schematic of conditions for the
Haber process

NEL Chemical Systems in Equilibrium 461

 Ammonium Yield at Various Conditions
of Temperature and Pressure
100
Percentage Yield (%)
Haber had to balance the rate of the reaction (increased by higher temperatures)
against the equilibrium of the reaction (pushed to the right by lower temperatures). He
discovered that using an iron oxide catalyst eliminates the need for excessively high tem-
peratures, allowing the equilibrium position to move quickly to the right at lower tem-
peratures. An industrial plant using a modification of the Haber process might operate

100 MPa at a temperature of about 500°C and a pressure of 50 MPa. After a suitable length of
80 time under these conditions, the yield of ammonia is about 40%.
30 MPa
Today, the Haber process and modifications of it are used to produce large quantities
60
of ammonia, which is used as a fertilizer (Figure 4). As a fertilizer, ammonia dissolves
in moisture present in the soil and, if the soil is slightly acidic, it is converted into the
40
10 MPa ammonium ion. The ammonium ion enters the nitrogen cycle, where it is converted to
20 nitrate ions by soil bacteria. Nitrate ions are absorbed by the roots of plants and used in
1 MPa the synthesis of proteins, chlorophyll, and nucleic acids. Without a source of nitrogen,
plants do not grow, but produce yellow leaves and die prematurely.
300 400 500 600 Ammonia is also used to make explosives.
Temperature ( ˚C)

Figure 3 Practice
Understanding Concepts
3. Why is a low temperature, which gives a higher percentage yield of ammonia, not
used in the Haber process?
4. What role does iron oxide play in the Haber process?

Making Connections
5. (a) Ammonia, produced by the Haber process, can be oxidized to nitric acid, the raw
material used in the manufacture of explosives. Perform library or Internet research
to determine the most common types of explosives produced with nitric acid.
(b) Draw structural formulas for the three most common nitogen-based explosives.
What are the specific uses of each?
(c) Write the chemical equation that describes a nitroglycerine explosion. Why is this
reaction explosive?
(d) What is gun cotton? What are its uses? How is it made?
Figure 4
Ammonia fertilizer can be added GO www.science.nelson.com
directly to the soil.

Section 7.4 Questions

Making Connections (b) Conduct library and/or Internet research to learn how
1. You have been hired as an efficiency consultant by a plant modern ammonia production facilities obtain pure
that produces ammonia by the Haber process. hydrogen and nitrogen for the process.
(a) Using equilibrium principles only, what advice would
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you give the company regarding the best environ-
mental conditions for optimal ammonia production?
3. To be used by growing plants, elemental nitrogen must first
(b) In what ways might the theoretically ideal conditions
be converted into another form (such as ammonia) in a
suggested in your answer to (a) be less than ideal,
natural process called nitrogen fixation. The Haber process
practically, for the company?
is synthetic nitrogen fixation.
(c) What additional advice could you give the company to
(a) How do bacteria fix nitrogen naturally?
help reduce the costs associated with your answer to
(b) Currently, which of the two processes, synthetic and
(a)?
natural, fixes the most nitrogen?
2. The Haber process requires nitrogen and hydrogen as (c) What problems have arisen from the dramatic increase
reactants. in nitrogen fixation in the last century? Pick one of
(a) Suggest reasonable sources for each of these ele- these problems and suggest some remedies.
ments.
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462 Chapter 7 NEL