13 - Nitrogen and Sulfur

2021-23 Curriculum
AS/A2 - Chemistry
13 - Nitrogen & Sulfur

01 – Learning Outcomes
1 – Nitrogen Gas 2 - Ammonia 3 - Ammonium 4 - Oxides 5 – Sulfuric Acid 6 - Questions
You should be able to:

 describe and explain:
– the lack of reactivity of nitrogen gas
– the basicity of ammonia (also see Chapter 8, page 130), and the
formation and structure of the ammonium ion
– the displacement of ammonia from its salts
 state the industrial importance of ammonia and nitrogen compounds derived
from ammonia
 state and explain:
– the environmental consequences of the uncontrolled use of nitrate
fertilisers
– the natural and man-made occurrences of oxides of nitrogen and their
catalytic removal from the exhaust gases of internal combustion
engines
– why atmospheric oxides of nitrogen are pollutants, including their
catalytic role in the oxidation of atmospheric sulfur dioxide (see also
Chapter 9, page 144)
 describe the formation of sulfur dioxide gas from sulfur-contaminated fossil
fuel, its role in the formation of acid rain and how acid rain affects the
environment.
Introduction
The Group 15 element nitrogen makes up nearly four-fifths of
the atmosphere on Earth. Nitrogen is a vital element in
many of the processes of life, but as a pure gas it is
unreactive. For this reason, nitrogen gas helps to prevent
explosions when crude oil is pumped into or out of
super-tankers, when the volatile
fuel vapours can mix with oxygen
from the air.
Figure 13.1 a Nitrogen gas is used in the

hold of oil tankers above the crude oil as
it is pumped ashore. This unreactive gas
helps to prevent the chance of an
explosive mixture of crude oil vapour and
air forming inside the tanker.
Introduction
Sulfur is a Group 16 element that is mined for the
production of sulfuric(VI) acid, one of the most
important industrial chemicals, used in the manufacture
of paints, dyes, plastics and fibres.
Figure 13.1 b Sulfur can be mined
from underground deposits by
pumping down super-heated water to
melt the sulfur (it melts at about 115
°C). The molten sulfur is then forced to
the surface under pressure and
allowed to solidify back into a brittle,
yellow solid. The ‘crown-shaped’ sulfur
molecules, S8, can pack together in
regular patterns, forming crystals.
01 – Nitrogen Gas
Nitrogen gas
► Nitrogen is in Group 15 of the Periodic Table. It is a
nonmetallic element that makes up about 78% of the
Earth’s atmosphere.
► It exists as diatomic molecules, N 2. Nitrogen gas is the
unreactive gas in air that dilutes the effects of the

reactive gas, oxygen.
► To understand the lack of reactivity of nitrogen gas, we
have to look at the bonding within its
molecules.
► The electronic configuration of a
nitrogen atom is 1s22s22p3. Its atoms
need to gain three electrons to achieve
the noble gas configuration of neon.
01 – Nitrogen Gas
Nitrogen gas
► Nitrogen atoms do this by forming a triple covalent
bond between
two atoms
(see Figure
13.2).
Figure 13.2 The bonding in a nitrogen molecule, N2.

► The triple covalent bond is very strong; its bond energy
is almost 1000 kJ mol−1. It is difficult to break and so
nitrogen gas will only react under extreme conditions.
► For example, the nitrogen and oxygen in the air react
together during thunderstorms.
01 – Nitrogen Gas
Nitrogen gas
► Lightning provides the
activation energy needed
for this reaction to occur
(Figure 13.3):
N2(g) + O2(g) → 2NO(g)
nitrogen(II) oxide
► The nitrogen(II) oxide Figure 13.3 Nitrogen
formed is further oxidised oxides are formed when
by oxygen in the air to give lightning strikes.
nitrogen(IV) oxide, NO2.
2NO(g) + O2(g) → 2NO2(g)
nitrogen(IV) oxide
01 – Nitrogen Gas
Nitrogen gas
► Nitrogen(IV) oxide dissolves in water droplets
and forms nitric acid, which falls to earth in
rain. This is a vital part of the natural nitrogen
cycle:
2NO2(g) + H2O(l) + O2(g) → 2HNO3(aq)
nitric acid
► In this way, nitrogen gets into the soil in a

soluble form that plants can absorb. They
use the nitrate ions, NO3−, to make the
proteins essential for growth.
02 – Ammonia and Ammonium Compounds
Ammonia and ammonium compounds

► Ammonia is a very important compound of nitrogen. It
is an alkaline gas whose formula is NH3.
► In industry it is made on a large scale in the Haber
process (for details of the process see Chapter 8,
page YY).

► The bonding in ammonia is shown in Figure 13.4. You
learned why the presence of a lone pair of electrons on
the nitrogen atom causes ammonia molecules to have
a pyramidal shape on page 56.
► You have also learnt that nitrogen’s lone pair can be
donated to an H+ ion from an acid, forming a co-ordinate
(or dative) covalent
bond (see page 53).
Figure 13.4 A dot-and-
cross diagram showing
the covalent bonding in
an ammonia molecule
and its pyramidal shape.

► You have also learnt that nitrogen’s lone pair can be
donated to an H+ ion from an acid, forming a co-
ordinate (or dative) covalent bond (see page 53).
► Ammonia is acting as a base in this reaction
(because it is accepting an H+ ion):
NH3(aq) + H+(aq) → NH4+(aq)
ammonium ion
► Ammonium compounds are very important

fertilisers. Nitrogen is removed from the soil as
nitrates are absorbed through the roots when plants
are growing.

► When crops are harvested by farmers the nitrogen is not
replaced, as the plants do not die naturally and rot back
into the soil. So farmers use ammonium compounds to
replace this nitrogen in the soil.
► Common ammonium salts used in fertilisers include
ammonium chloride, NH4Cl, ammonium nitrate, NH4NO3,
ammonium phosphate, (NH4)3PO4, and ammonium sulfate,
(NH4)2SO4.
► If we heat an ammonium salt
with a base, the ammonium
ion produces ammonia gas.
► We use this reaction to
prepare ammonia gas in the
laboratory.

► Ammonium chloride and calcium hydroxide, both in the
solid state, are
usually mixed
then heated (see
the apparatus in
Figure 13.5).
Figure 13.5 Preparing ammonia gas from an ammonium

salt, NH4Cl, and a base, Ca(OH)2.

► This reaction is used as the basis of the test for
ammonium ions. If an unknown compound contains
NH4+ ions it will give off ammonia when heated with a
base. The ammonia given off is the only common
alkaline gas. It turns red litmus blue.
Questions
1. a. Explain the lack of reactivity of nitrogen gas.
b. Write a balanced chemical equation, including state
symbols, for the reaction of ammonia solution with
dilute nitric acid.
c. Write a balanced chemical equation, including state
symbols, for the reaction of solid ammonium sulfate
with solid sodium hydroxide.
03 – Uses of Ammonia and Ammonium Compounds
Uses of ammonia and ammonium compounds

► Farmers harvest crops to provide the world with food.
Each year millions of tonnes of fertilisers are spread
onto fields to replace the nitrogen and other plant
nutrients lost from the soil.
► About 85% of the millions of tonnes of ammonia
produced each year in the Haber process are used to
make fertilisers.
► A relatively small amount of ammonia
itself is used as fertiliser, mainly in
the USA. This is injected into the soil.
► However, the vast majority of
ammonia is reacted with acids to
make solid ammonium salts.

► The major nitrogen-based fertiliser is ammonium nitrate,
NH4NO3. This is manufactured from ammonia and nitric
acid:
NH3(aq) + HNO3(aq) → NH4NO3(aq)
► The ammonium nitrate solution is heated to evaporate off
the water and melt the solid. The molten solid is then
sprayed into a tower with air blown into it. This solidifies the
ammonium nitrate into pellets,
which makes it convenient for
farmers to spread from tractors
(Figure 13.6).
Figure 13.6 Ammonium nitrate is

spread as pellets onto the soil.

► Ammonium sulfate, (NH4)2SO4, and ammonium
phosphate, (NH4)3PO4, are other ammonium salts

used in fertilisers.
► The nitric acid used to make ammonium nitrate is
itself made from ammonia in another chemical
process. Fertiliser factories making ammonium
nitrate often have three plants side by side, making:
 ammonia in the Haber process
 nitric acid from ammonia
 ammonium nitrate from
nitric acid and ammonia.

► Concentrated nitric acid has other important
uses. It is used to make many types of
explosive, such as trinitrotoluene (TNT).
► About 10% of ammonium nitrate
is used to make explosives.
Nitric acid is also needed in
the manufacture of
detergents, paints,
pigments, dyes and
nylon.
Questions
2. a. Ammonia is made in industry using the
Haber process. Write the balanced
equation to show the synthesis of ammonia
from its elements, including the catalyst
used.
b. Write a balanced equation, including state
symbols, for the formation of ammonium
sulfate fertiliser from ammonia solution.
c. Work out the percentage of nitrogen in
ammonium nitrate fertiliser.
(Ar values: N = 14.0, H = 1.0, O = 16.0)
Environmental problems caused by nitrogen compounds -

Nitrate fertilisers
► In order to work, nitrogen-based fertilisers, mainly
ammonium nitrate and potassium nitrate (KNO3), must be
soluble in water. This has created an environmental problem.
► The nitrates can be washed, or leached, out of the soil by
rain into groundwater. These can then find their way into
rivers and lakes. Once in the rivers and lakes, the nitrates
promote the growth of the water
plants, which can ‘strangle’ a river.
Figure 13.7 Fertilisers leached

from farmland have caused
eutrophication in this river.
Environmental problems caused by nitrogen

compounds - Nitrate fertilisers
► But the biggest problem is the growth of algae (a simple
water plant) on the surface, causing eutrophication
(Figure 13.7).
 A bloom of algae can spread across the surface,
blocking out the light for other plant life in the water.
 When the plants and algae die, bacteria in the water
feed on them, decomposing the plant material.
 The bacteria multiply rapidly with so much food
available, using up the dissolved oxygen in the water.
 Fish extract dissolved oxygen from water, taken in
through their gills. Without this dissolved oxygen they
die, affecting the whole ecosystem.
Nitrate fertilisers
► This isn’t the only problem with fertilisers being leached
from the soil. Nitrates have also been detected in our
drinking water, especially in agricultural areas.
► People are worried that nitrates in drinking water cause
‘blue baby’ syndrome (when a newborn baby’s blood is
starved of oxygen), as well as stomach cancer.
► But others argue that links between nitrates and diseases
have not been proven and that recommended nitrate
levels are set unrealistically low.
► Farmers can help limit the amount of nitrates in water
courses by adding the most economical amounts of
fertilisers at the right time of year. This will minimise the
leaching of excess fertiliser from the soil and into our
rivers and lakes.
Environmental problems caused by nitrogen compounds

- Nitrogen oxides in the atmosphere
► At the start of this chapter we saw how unreactive nitrogen
gas is. However, in the extreme conditions in a
thunderstorm, lightning can trigger the reaction between
nitrogen and oxygen to form gaseous nitrogen oxides –
nitrogen(II) oxide, NO and nitrogen(IV) oxide, NO 2.
► A similar oxidation of nitrogen takes place inside a car
engine. In the engine’s cylinders a mixture of air (mainly
nitrogen plus oxygen) and fuel is compressed and ignited
by a spark.
► Under these conditions (high pressure and high
temperature) nitrogen forms nitrogen oxides. These are
released into the atmosphere in the car’s exhaust fumes.

► Nitrogen oxides are pollutants. They cause acid rain and
photochemical smog. Nitrogen oxides also catalyse the
oxidation of sulfur dioxide gas, SO2, in the atmosphere
during the formation of acid rain.
► The sulfur trioxide, SO3, gas that is produced by this
oxidation reacts with rainwater, forming sulfuric acid. The

reactions below show the catalytic activity of the nitrogen
oxides:
SO2(g) + NO2(g) → SO3(g) + NO(g)
► Then NO2 is regenerated as NO reacts with oxygen in the
air:
NO(g) + O2(g) → NO2(g)

► This NO2 molecule can then go on to oxidise another
sulfur dioxide molecule, at the same time producing an

NO molecule to make another NO2 molecule. this will
oxidise another sulfur dioxide molecule, and so on.
Therefore NO2 catalyses the oxidation of SO2.
► Nowadays, car exhaust systems are fitted with catalytic
converters to help reduce the pollutants from motor
vehicles (see page 205).
► The reaction on the surface of the hot catalyst (e.g.
platinum) reduces the nitrogen oxides to harmless
nitrogen gas, which is released from the vehicle’s exhaust
pipe.
2CO(g) + 2NO(g) 2CO2(g) + N2(g)
Questions
3. a. Why is ammonia so important in providing
enough food to feed the world?
b. Give one environmental problem and one
possible health problem associated with nitrate
fertilisers.
c. Explain how nitrogen oxides are involved in the
formation of atmospheric sulfur trioxide (SO3).
d. The following reaction takes place in a car’s
catalytic converter once it is warmed up:
2CO(g) + 2NO(g) → 2CO2(g) + N2(g)
Use oxidation numbers to explain which species
is reduced and which is oxidised in the reaction.
04 – Sulfur and its oxides
Sulfur and its oxides

► We have just seen how sulfur dioxide in the atmosphere
can be oxidised by nitrogen(IV) oxide to form sulfur(VI)
oxide (also known as sulfur trioxide). This reacts with
water to form sulfuric acid, which is the main cause of acid
rain.
SO3(g) + H2O(l) → H2SO4(aq)
► The sulfur dioxide is formed when we burn fossil fuels,
especially coal. Crude oil, natural gas
and coal have sulfur compounds
present in them as impurities.
► When the fossil fuels (or fuels
extracted from them, such as petrol
or diesel) are burnt, the sulfur
impurities get oxidised to sulfur dioxide.

► There are also large volumes of sulfur dioxide
released naturally from volcanic activity.
► Acid rain has harmful effects on:
 plants (especially trees)
 rivers, streams and lakes (and
the fish and other animals in
these habitats)
 buildings, statues (Figure
13.8) and metal structures.
Figure 13.8 This limestone carving has

been chemically weathered by acid rain.

► The acid rain leaches (washes out) nutrients from the
soil, and so prevents the healthy growth of plants. Not
only that, the acid rain can attack the waxy layer on
leaves. This increases water loss and makes the plant
more susceptible to disease and pests.
► Trees that grow at high altitudes are especially
vulnerable, as they are often in contact with the tiny
droplets of water (sulfuric acid solution) in clouds.
► Acid rain falling into streams,
rivers and lakes will lower the
pH of the water. Many aquatic
animals are very sensitive to
changes in pH.

► Many insect larvae cannot survive even slight
increases in acidity. Other animals higher up the food
chain may be more resistant, but their numbers will
decrease as their food source dies off.
► In our cities, the acid rain attacks buildings and
statues, especially those made from carbonate rock.
The most common of these is limestone, containing
calcium carbonate.
► The main metal used in
construction, iron in the
form of steel, is also
corroded by acid rain.

► Chemists have found ways to reduce sulfur dioxide
emissions from fossil fuels. They now produce ‘low-
sulfur’ versions of petrol and diesel.
► In power stations that burn fossil fuels, the sulfur is
removed from the fuel before burning.
► Alternatively sulfur dioxide can be removed from the
waste gases before they are released to the
atmosphere through tall chimneys.
Questions
4. a. Write a balanced equation, including state symbols,
showing the formation of sulfuric acid from
atmospheric sulfur trioxide, SO3.
b. List three consequences of acid rain.
04 – Sulfuric Acid
Sulfuric acid
► Sulfuric(VI) acid, H2SO4, is one of the most important
manufactured chemicals. It has been said that the

amount of sulfuric acid used by a country is one of
the best indicators of how well developed it is.
► The chemical industry makes
sulfuric acid in the Contact
process (page 129). The raw
materials needed are sulfur, air
and water.
► Sulfur can be mined from
underground (see Figure 13.1b
at the start of this chapter).
04 – Sulfuric Acid
Sulfuric acid
► Poland and the USA export sulfur around the world.
The sulfur extracted from the impurities in fossil
fuels can also be used in the Contact process.
► Like nitric acid, sulfuric acid is used to manufacture
fertilisers, detergents, paints,
pigments, dyes and synthetic
fibres.
► It is also used to make various
chemicals and plastics, as well
as being used in car batteries,
tanning leather and cleaning
metal surfaces (‘pickling’).
05 – Summary
 Nitrogen, N2, is a very unreactive gas because of the high

bond energy of the N≡N triple bond.
 Ammonia, NH3, is a common compound of nitrogen. An
ammonia molecule can act as a base, accepting an H+ ion
to form an ammonium ion, NH4+.
 Ammonia is manufactured in the Haber process (see
page 129):
 Most ammonia is used to make ammonium salts in

neutralisation reactions with different acids. The salts,
such as ammonium nitrate, NH4NO3, are used as
fertilisers,
 Excess fertiliser can be leached out of soils into rivers and
05 – Summary
 Nitrogen oxides are formed naturally during lightning

strikes, when nitrogen gas is oxidised. These gaseous
oxides are also formed in internal combustion engines
and become pollutants in the atmosphere, contributing
to acid rain.
 Sulfur can be mined as the element and is used as a
raw material for manufacturing sulfuric acid in the
Contact process (see page 129).
 Sulfur dioxide is the main cause of acid rain. Its
oxidation to sulfur trioxide is catalysed by oxides of
nitrogen.
 Acid rain causes the death of aquatic wildlife in rivers
and lakes, kills trees and damages buildings and other
structures.
05 – End of Chapter Questions
1. Ammonia is made in the Haber process.

a. What is the formula of ammonia?
[1]
b. Write a balanced equation for the formation of ammonia
from nitrogen and hydrogen in the Haber process.
[1]
c. Give three uses of ammonia.
[3]
d. Give the formulae of the following ammonium salts:
i. ammonium chloride
? [1]
2. The reaction 2SO2(g) + O2(g) → 2SO3(g) reaches

dynamic equilibrium. The forward reaction is
exothermic. The reaction is catalysed by ?
vanadium(V) oxide, V2O5. You are given a vessel
containing all three gases at equilibrium.
a. What will happen to the position of equilibrium if:
i. you add more oxygen to the vessel?
[1]
ii. you remove some sulfur trioxide from the
vessel? [1]
iii. the pressure in the vessel is lowered?
[1]
iv. more V2O5 is added?
b. i. Give three uses of sulfuric acid.

[3]
ii. Why is it important that as little sulfur
dioxide as possible is released into
the atmosphere when sulfuric acid is
manufactured?
[1] ?
iii. Explain, including a balanced
equation, how sulfur dioxide enters
the atmosphere from a coal-fired

13 - Nitrogen and Sulfur

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2021-23 Curriculum

13 - Nitrogen & Sulfur

You should be able to:

Figure 13.1 a Nitrogen gas is used in the

unreactive gas in air that dilutes the effects of the

Figure 13.2 The bonding in a nitrogen molecule, N2.

► In this way, nitrogen gets into the soil in a

Ammonia and ammonium compounds

Ammonia and ammonium compounds

Ammonia and ammonium compounds

► Ammonium compounds are very important

Ammonia and ammonium compounds

Ammonia and ammonium compounds

Figure 13.5 Preparing ammonia gas from an ammonium

Ammonia and ammonium compounds

Uses of ammonia and ammonium compounds

Uses of ammonia and ammonium compounds

Figure 13.6 Ammonium nitrate is

Uses of ammonia and ammonium compounds

phosphate, (NH4)3PO4, are other ammonium salts

Uses of ammonia and ammonium compounds

Environmental problems caused by nitrogen compounds -

Figure 13.7 Fertilisers leached

Environmental problems caused by nitrogen

Environmental problems caused by nitrogen compounds

Environmental problems caused by nitrogen compounds

oxidation reacts with rainwater, forming sulfuric acid. The

Environmental problems caused by nitrogen compounds

sulfur dioxide molecule, at the same time producing an

Sulfur and its oxides

Sulfur and its oxides

Figure 13.8 This limestone carving has

Sulfur and its oxides

Sulfur and its oxides

Sulfur and its oxides

manufactured chemicals. It has been said that the

 Nitrogen, N2, is a very unreactive gas because of the high

 Most ammonia is used to make ammonium salts in

 Nitrogen oxides are formed naturally during lightning

1. Ammonia is made in the Haber process.

2. The reaction 2SO2(g) + O2(g) → 2SO3(g) reaches

b. i. Give three uses of sulfuric acid.

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