TODAYS LECTURE
INTRODUCTION TO INDUSTRIAL CHEMISTRY
The Haber-Bosch Process
Annual production of ammonia
Ammonia ranks second, to sulfuric acid, as the
chemical with the largest tonnage
World 140 million tonnes
Europe 16 million tonnes
North America 15 million tonnes
US 8 million tonnes
Asia 74 million tonnes
Russia 12.5 million tonnes1
Middle East 13 million tonnes
Data from: Federal State Statistics Service: Russian Federation 2011
INTRODUCTION
Ammonia is made in the Haber process
The raw materials are nitrogen (from the air)
and hydrogen (from natural gas)
The conditions needed are; high temperatures
(about 600-700K) high pressures (200 atm).
iron is used as catalyst
N2(g) + 3H2(g) 2NH3(g)
HABER
Reversible Reactions
The Haber process is a REVERSIBLE reaction
N2(g) + 3H2(g) 2NH3(g) rxnH0=92 kJ/mol
nitrogen + hydrogen ammonia
A reversible reaction is one where the products of the
reaction can themselves react to produce the original
reactants.
Thermodynamic data(at 298 K)
N2(g) + 3H2(g) 2NH3(g)
N2(g) 3H2(g) 2NH3(g)
fH0(kJ mol-1) 0 0 2 -46.11 -92.11
S0(JK-1mol-1) 191.61 3 130.684 2192.45 -198.76
fG0(kJ mol-1) 0 0 2 -16.45 -32.90
Cp(JK-1mol-1) 29.125 3 28.824 2 35.06
0 = 92.11 kJ mol1 0
= exp( )
0 = 198.8 J K 1 mol1 32.90 1000
= exp( )
8.314 298
0 = 32.90 kJ mol1 = 5.85 105
Reversible Reactions
Factors that can affect a reversible reaction
include:
Changing pressure(or volume, concentration)
Changing temperature
Effect of Pressure
Effect of Pressure
Effect of pressure
On the left hand side there are 4 moles of gas, whilst on the right
hand side there are 2 moles
Any increase in pressure will favour the forward reaction to produce
more ammonia.
This is because the forward reaction will tend to decrease the
pressure in the system.
For High Yield
In the Haber process the pressure is set as
high as possible to give the best % yield.
High pressure containers are VERY expensive.
It could be possible to carry out the reaction
at 1000 atmospheres but this would not be
economical (it would cost more than the
product is worth).
The typical pressure used is 200 to 350
atmospheres.
Equilibrium Data T (C) Keq
300 4.34E-03
T (K) 1/T(1/K) ln(Keq)
573 0.00175 -5.43988
400 1.64E-04 673 0.00149 -8.71564
450 4.51E-05 723 0.00138 -10.0066
500 1.45E-05 773 0.00129 -11.1414
550 5.38E-06 823 0.00122 -12.1328
600 2.25E-06 873 0.00115 -13.0046
0
= 12618
0 = 12618
= 104906 1
= 104.9 1
Improving the yield of ammonia in the Haber
process
rxnH0=92 kJ/mol. LOW temperature!
BUT.
Reactions is slower at lower temperatures!
In operating the Haber process you have to
decide what is more important, the higher
YIELD you can get at lower temperatures or
the higher RATE at higher temperatures.
Improving the yield of ammonia in the
Haber process
In order to get ammonia produced at a
quicker RATE the reaction is carried out at a
high temperature (450oC).
It is better to get just a 10% yield in 20
seconds (at a high temperature) than a 20% in
60 seconds (at a lower temperature)
Equilibrium
Low temperature
High temperature
Carl Bosch
It took over 6500
experiments at different
temperatures and
pressures carried out by
the German Carl Bosch to
work all this lot out.
He got a Nobel Prize for it
in 1931!
(Haber got his Nobel Prize
in 1918)
Other ways of increasing the yield in the
Haber process
Removing the ammonia from the system also
pushes the reaction to the right so more
ammonia is produced to replace it.
Making Fertilizers
Ammonia (alkaline) and nitric acid react
together in a neutralization reaction
The fertilizer ammonium nitrate is produced
