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Nitrogen

The lack of reactivity


We know that nitrogen is an unreactive gas because it is mixed with reactive oxygen
in Earths atmosphere and reacts very little. The reason for this lack of reactivity
is the very strong NN bond in the molecule. The two nitrogen atoms share three
electron pairs, which form a triple covalent bond, and each atom retains a lone pair
of electrons. This is shown in Figure 12.1. The bond energy for nitrogen is 946 kJ mol 1
compared with the bond energy in fluorine, F2, which is 158 kJ mol1.
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NN
Figure 12.1 Structure of nitrogen

Although nitrogen is unreactive, it does react under the right conditions. For example,
burning magnesium reacts with the nitrogen in air to form magnesium nitride:
3Mg(s) N2(g) Mg3N2(s)
At high temperatures nitrogen will react with oxygen to form oxides of nitrogen, for
example:
N2(g) O2(g) 2NO(g)
In car engines (and in thunderstorms) nitrogen combines with oxygen to produce a
mixture of oxides of nitrogen often referred to as NOx.
Nitrogen also reacts with hydrogen to form ammonia:
N2(g) 3H2(g) 2NH3(g)
This is the basic reaction in the Haber process for the manufacture of ammonia. This
is covered in Chapter 7 and in more detail later in this section.
Finally, the roots of some plants of the pea and bean family have nodules that
contain bacteria able to fix nitrogen chemically. The bacteria convert the nitrogen
into ammonium ions, which the plants can use to make proteins.

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Ammonia
Ammonia, NH3, is an alkaline gas. You might expect it to have a trigonal planar
shape, but it is pyramidal with a lone pair of electrons occupying the apex, as is
shown in Figure 12.2.

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H
N
H
H 107
Figure 12.2 Structure of ammonia

Remember that the lone pair takes up more space than a pair of bonding electrons.
In the case of ammonia this reduces the H N H bond angles to about 107. The
high electronegativity (3.0) of nitrogen means that ammonia can form hydrogen
bonds, and as a result it is very soluble in water.
Ammonia is also a base, accepting a proton to form the ammonium ion, NH 4:
NH3(g) H(aq) NH4(aq)
This ion is tetrahedral, the proton forming a coordinate (dative) bond with the
nitrogen atom using the lone pair (Figure 12.3).
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H
H

N
H
H

Figure 12.3 Structure of the ammonium ion

In the laboratory, ammonia is easily displaced from ammonium compounds by


warming with a strong base such as sodium hydroxide:
NH4(aq) OH(aq) NH3(g) H2O(l)

The Haber process


We have already looked at some aspects of the Haber process in Chapters 7 and 8.
You may wonder why you have to study this manufacturing process. Ammonia is
one of the most important bulk chemicals manufactured, mainly because of its use
in the production of fertilisers. In 2008, more than 150 million tonnes of ammonia
were produced worldwide.
The original Haber process was developed almost 100 years ago and still forms the
basis of ammonia production, although the pressures and temperatures have been
refined to give maximum production at an optimum price. Most recent research
has focused on improving the iron catalyst. Both osmium and ruthenium are more
effective as catalysts, but both are more expensive than iron. Therefore, the catalyst
used depends on the market price of ammonia.

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For the examination you need to be able to state the essential operating conditions
for an ammonia plant (Figure 12.4), and to interpret these in terms of reaction
kinetics and the position of equilibrium.
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Compressor
N2(g) 3H2(g)
Condenser
Catalyst
Reactor
(400 C, 200 atm)
NH3(l)
storage
Unreacted
N2(g) and H2(g)
Figure 12.4 The Haber process

The set of conditions chosen are a compromise:


pressure around 20 000 kPa (or 200 atm)
temperature around 670 K
catalyst iron (which has a lifetime of around 5 years)
As well as its use in fertiliser manufacture (mainly as the sulfate or nitrate), ammonia
can be oxidised using a platinum catalyst to form nitrogen monoxide:
4NH3(g) 5O2(g) 4NO(g) 6H2O(l) Ho 909 kJ mol1
This exothermic reaction is the starting point for the manufacture of nitric acid.
The hot gas is cooled, reacted with more oxygen to form nitrogen dioxide, and then
dissolved in water to form nitric acid:
2NO(g) O2(g) 2NO2(g)
2NO2(g) N2O4(g)
3N2O4(g) 2H2O(l) 4HNO3(aq)

Nitrogen compounds and pollution


Nitrates
Nitrogen compounds, particularly nitrates, are used to make fertilisers. These have
had significant benefits in increasing crop yields around the world. However, if

excessive amounts of fertilisers are used they can get washed into streams and
rivers. This can have two effects:

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12 Nitrogen and sulfur
The nitrates can get into drinking water supplies, from which they are difficult
to remove. They can affect the ability of babies under 6 months to carry oxygen
in the bloodstream.
They can increase the growth of aquatic vegetation, which then decays reducing
oxygen levels in streams and rivers, and affecting other forms of aquatic life.

Nitrogen oxides
The combustion of motor fuels produces temperatures high enough to form oxides
of nitrogen, NOx, in exhaust gases. These gases in air at street level are known to
contribute to respiratory problems. They also have a pollution effect in the upper
atmosphere where they catalyse the oxidation of sulfur dioxide. The main source
of sulfur dioxide in the atmosphere is the combustion of fuels (mainly coal and oil)
that contain sulfur or its compounds. Some of the sulfur dioxide is removed from the
waste gases emitted by major users of these fuels, such as power stations.
The exact mechanism is uncertain, but the following is a possibility:
2NO2(g) H2O(g) HNO2(l) HNO3(l)
SO2(aq) HNO3(l) NOHSO4(l)
NOHSO4(l) HNO2(l) H2SO4(l) NO2(g) NO(g)
SO2(aq) 2HNO2(l) H2SO4(l) 2NO(g)
The other form of atmospheric pollution caused by nitrogen oxides is the formation
of ozone, O3, in the presence of unburnt hydrocarbons from vehicles. Ozone formed
at street level can cause respiratory problems. However, once nitrogen oxides escape
into the upper atmosphere they cause the reverse problem, removing ozone and
reducing the ability of ozone to protect the Earths surface from harmful ultraviolet
radiation.
The emission of nitrogen oxides from vehicles has been greatly reduced since the
introduction of catalytic converters. These also reduce the emission of carbon
monoxide and unburnt hydrocarbons (see also Chapter 8).
2NO
x(g) xO2(g) N2(g)
2CO(g) O2(g) 2CO2(g)
C
nH2n2(g) [(3n 1)/2]O2(g) nCO2(g) (n 1)H2O(g)

Sulfur
The Contact process
Sulfuric acid is an extremely important industrial chemical that is used in the
production of a huge range of manufactured goods. Figure 12.5 shows some of the
major uses of sulfuric acid. In 2008, world production of sulfuric acid was more than
200 million tonnes.

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Uses of sulfuric acid
Petroleum
refining
20%
Fertiliser
manufacture
30%

Chemicals
including
(NH4)2SO4
16%
Pickling
steel 10.6%
Storage
batteries
10.2%
Pigments, textiles 4.6%
Explosives 2.7%
Other uses 5.9%
Figure 12.5 Uses of sulfuric acid

For the examination you need to be able to state the essential operating conditions
for the manufacture of sulfuric acid by the Contact process (Figure 12.6), and to
interpret these in terms of reaction kinetics and the position of equilibrium.
Sulfur
burner
SO2 SO3
converter
Absorption
tower
Oleum
storage for
dilution to
H2SO4
S(l) Exhaust
stack
Air
SO2 inlet Air inlet
Concentrated
sulfuric acid
Cooling SO2 recycled
Cooling
Cooling
Figure 12.6 The Contact process

The conditions chosen are a compromise:


pressure around 100200 kPa (or 12 atm)
temperature around 700 K
catalyst vanadium(V) oxide (although some plants now use ruthenium which
is more expensive)

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Sulfur dioxide
Acid rain
We have already seen that the combustion of sulfur-containing fuels releases sulfur
dioxide into the atmosphere, and that in the presence of oxides of nitrogen, this can
be converted into sulfuric acid. This decreases the pH of rain. Acid rain can harm
plants and animals directly, and indirectly by making lakes acidic. It also releases
toxic metals such as aluminium from soils, and below pH 4.5 no fish are likely to
survive. This has further effects up the food chain. Acid rain also increases the
erosion of limestone-based buildings and statues. The production and some effects
of acid rain are shown in Figure 12.7.
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Acid rain
Power stations,
industries and vehicles
release gases into

the atmosphere
Sulfur dioxide and nitrogen oxides
Oxidation in clouds produces
sulfuric acid and nitric acid
Acid polluted air
blown by the wind
Water droplets
become polluted
Wet deposition acid rain
Trees and
vegetation affected
Soils polluted and acid rain
leaches aluminium from soils
Rivers and lakes polluted
affecting water life
Figure 12.7 Acid rain

Food preservation
Although sulfur dioxide is a pollutant that causes widespread damage to the environment, it also
has beneficial uses, particularly as a preservative for foodstuffs. It
has the advantage of being a reducing agent (preventing spoilage by oxidation) and
has anti-microbial properties. It is used in the preservation of fruit products (such
as dried fruits and juices) and in winemaking. It can be a problem for people who
suffer from asthma.