NIS Chem section 12.

1B

Nitrogen and Sulfur

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 NIS Chem section 12.1B

Vocabulary
• Diatomic, Reversible, Yield
• Fertiliser, eutrophication, environment,
enriched, nutrients, marine habitats, algal
blooms

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 NIS Chem section 12.1B

Nitrogen

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Learning Objectives
• understand the bonding and be able to explain the unreactivity of
nitrogen
• be able to draw and explain the shape of the ammonia molecule
• know and understand the chemistry of ammonia as a gas and in
aqueous solution
• know the industrial manufacture of ammonia and be able to
understand it as an equilibrium process
• know and understand the environmental impact of oxides of
nitrogen in the atmosphere and nitrates in soils and water supplies
• be able to evaluate ways of minimising these environmental
impacts

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 NIS Chem section 12.1B

Nitrogen

 Nitrogen is a diatomic molecule and the structure is as

follows:

 It is under normal conditions unreactive. Why?

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 NIS Chem section 12.1B

Ammonia
 Ammonia (NH3) is a gas at room temperature and has a
structure as follows:

 It is a polar molecule and has a higher boiling point than

would be expected. Why?

 Ammonia can act as a base. How and why?

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 NIS Chem section 12.1B

Ammonia
 In an aqueous solution NH3 will act as a base, as shown
below:

 Ammonia can be formed in the lab by heating a mixture

of ammonium chloride and calcium hydroxide:


2NH4Cl (s) + Ca(OH)2 (s) 2NH3 (g) + CaCl2 (s) + 2H2O(l) 7
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 NIS Chem section 12.1B

Manufacture of ammonia
 The Haber Process combines nitrogen from the air with
hydrogen (from natural gas methane and steam) into
ammonia. The reaction is reversible and the production
of ammonia is exothermic.

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 NIS Chem section 12.1B

Haber Process
 A flow scheme for the Haber Process looks like this:

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Haber Process
 What will the effect of temperature be?

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 NIS Chem section 12.1B

Temperature
 Lower temperatures will shift the equilibrium
to the right and cause higher yields of
Ammonia.

 However, there is a problem with lower

temperatures. What is it?

 The rate of a reaction can be lowered by

lowering the temperature.

 Therefore the chemists involved use a higher

temperature between 400 and 450 C
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 NIS Chem section 12.1B

Haber Process
 Higher pressure will have a positive affect
on the yield of Ammonia. How?

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 NIS Chem section 12.1B

Pressure
 The pressures used industrially are 2500
kPa to 30,000 kPa (often 20,000 kPa).
Anything higher is too costly and unsafe.

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 NIS Chem section 12.1B

Haber Process
 What will the effect of a catalyst be?

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 NIS Chem section 12.1B

Catalyst
 The yield will not be affected but the forward and
reverse reaction rates will be higher.

 Therefore, the yield will be accomplished quicker.

 The following is a summary of the conditions:

P = 20,000 kPa
T = 400 – 450 C
Catalyst: Iron

 The yield under these conditions is about 30%

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Uses of Ammonia
 About 80% of the ammonia produced by industry is used
in agriculture as fertilizer. Ammonium, NH4+ , compounds
are very important as fertilizers as they replace the
nitrogen removed from the soil during the harvesting
process.

 Common ammonium salts used for this are NH4Cl,

NH4NO3 and (NH4)2SO4.

 Ammonia is also used as a refrigerant gas, for

purification of water supplies, and in the manufacture of
plastics, explosives, textiles, pesticides, dyes and other
chemicals.

TASK: Name the above mentioned salts 17

 NIS Chem section 12.1B

NPK fertilisers

• Contain water soluble compounds containing N/P/K

18% of mass = N atoms
24% of mass = P atoms • Help crops grow (increases crop yield)
12% of mass = K atoms • Different formulations for different crops
 NIS Chem section 12.1B

NPK fertilisers
• Compounds in NPK fertilisers are salts
• Some of these salts are mined (e.g. KCl, K2SO4)
• Most are made by reacting acids with bases
 NIS Chem section 12.1B

NPK fertilisers
 NIS Chem section 12.1B

Reactions of Nitrogen
N2 + O2 →
Li + N2 →
NH4Cl + Ca(OH)2 →
NH3 + HCl →
NH3 + HNO3 →
NH3 + H2SO4 →
NH3 + H3PO4 →
Cu + HNO3 →
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 NIS Chem section 12.1B

Reactions of Nitrogen

 Lightning provides the activation energy required for the

following reaction:

N2(g) + O2 (g) 2 NO (g)

 NO is further oxidized by oxygen in the air to NO2:

2NO(g) + O2 (g) 2 NO2 (g)

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 NIS Chem section 12.1B

Reactions of Nitrogen

 NO2 then dissolves in water droplets and the resulting

mixture falls to the earth:

2NO2(g) + H2O (l) + ½ O2 (g) 2 HNO3 (aq)

 This is a vital part of the nitrogen cycle as the NO3- is

used by plants to synthesize proteins.

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 NIS Chem section 12.1B

Nitrogen
 Nitrogen oxides are pollutants and are made by
industrial processes and exhaust fumes from vehicles.

 NO2 will catalyze the formation of SO2 into SO3 as

follows

NO2(g) + SO2 (g) SO3 (g) + NO (g)

 Catalytic converters in cars will reduce the amount of NO

and CO pollution as follows:

NO(g) + CO (g) 2 CO2 (g) + N2 (g)

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 NIS Chem section 12.1B

Eutrophication
Fertilisers are often used in farming, sometimes these
fertilisers run-off into nearby water causing an increase in
nutrient levels.

Eutrophication is when the environment becomes

enriched with nutrients. This can be a problem in marine
habitats such as lakes as it can cause algal blooms.

This is the beginning of a harmful process (eutrophication)

NIS Chem section 12.1B

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 NIS Chem section 12.1B

Steps of Eutrophication
1. Fertilisers run-off into nearby water causing
an increase in nutrient levels.
2. This causes phytoplankton to grow and
reproduce more rapidly, resulting in
algal blooms.
3. The algae may use up all the oxygen in the
water. This results in the death of many
aquatic organisms, which need the oxygen in
the water to live.

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 NIS Chem section 12.1B

4. The bloom of algae may also block sunlight

from photosynthetic marine plants under the
water surface.
5. Some algae even produce toxins that are
harmful to higher forms of life. This can
cause problems along the food chain and
affect any animal that feeds on them.

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NIS Chem section 12.1B

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 NIS Chem section 12.1B

Sulfur

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Learning Objectives
• know the occurrence of sulfur
• understand the structure and allotropy of sulfur
• know the sources of sulfur dioxide in the atmosphere and
understand its consequences, including the formation and effects of
acid rain
• understand the need for food preservatives and know the use of
sulfur dioxide for this purpose
• understand the role of sulfuric acid as an acid and as an oxidising
agent
• recall at least one process for the manufacture of sulfuric acid in
terms of an equilibrium process and know its major uses as an
industrial chemical
• understand the environmental impact of sulfuric acid manufacture

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 NIS Chem section 12.1B

Sulfur
• Occurrence:
– Native sulfur in volcanoes
– In ores like pyrites, galena as sulfides, sulfates

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 NIS Chem section 12.1B

Sulfur
Structure and allotropy
• Rhombic (α) sulfur: Yellow solid consisting
of S8 rings. The thermodynamically stable
form at ordinary temperatures
• Monoclinic (β): Yellow crystalline solid,
consisting of S8 rings. Only stable above
95.6oC, it reverts to α-sulfur at room
temperature
• Plastic: amorphous
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NIS Chem section 12.1B

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Range of sulphur compounds

Chemical formulae Oxidation state

S2-, H2S -2
S8 0
SCl2, S2O32- +2
SO2, SO32-, H2SO3 +4
SO3, SO42-, H2SO4 +6
 NIS Chem section 12.1B

Sulfur
 SO2 is used to preserve many forms of food including
dried fruits and vegetables and sausages.

 The lower pH that it causes by reacting with water to

form H2SO3(aq) inhibits the growth of bacteria and yeast.

 SO2 also stops the oxidation of fats to prevent the over-

ripening of fruits after they have been picked.

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Sulfuric acid

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Sulfuric Acid – The Contact Process

Stage 1

 Sulfur is burned in an excess of air:

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 NIS Chem section 12.1B

Sulfuric Acid – The Contact Process

Stage 2
 This is a reversible reaction, and the formation of the
sulphur trioxide is exothermic.

 What pressures and temperatures would be favored?

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 NIS Chem section 12.1B

 High pressures should give a better yield,

however due to the already high yield of
97% it would not make sense to increase
the pressure much past 100 to 200 kPa.

 Again lower temperatures should give a

better yield, however kinetic
considerations have to be looked at. (as in
the Haber process)

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Sulfuric Acid – The Contact Process

Stage 2

 The temperature used is 450 C.

 The catalyst used for stage 2 is V2O5 and again does not
increase the yield of SO3, but speeds up the process.

Stage 3

 The final stage involves reacting the SO3 with water to

form H2SO4 as follows:
SO3 (g) + H2O (l) H2SO4 (aq)

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Sulfuric Acid – The Contact Process

Stage 3

 However, the sulfuric acid formed from reacting pure

water with SO3 is difficult to condense.

 Therefore, the SO3 is reacted with the water in a solution

of concentrated sulfuric acid.

 The concentrated sulfuric acid goes from 98% to 99.5%.

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Sulfuric Acid – The Contact Process

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 NIS Chem section 12.1B

Chemical properties of H2SO4

• Dilute H2SO4, a typical acid

– Zn + H2SO4  ZnSO4 + H2
– 2NaOH + H2SO4  Na2SO4 + H2O
– CuO + H2SO4  CuSO4 + H2O
– MgCO3 + H2SO4  MgSO4 + H2O + CO2
– 2NaHCO3 + H2SO4  Na2SO4 + H2O + CO2
 NIS Chem section 12.1B

Chemical properties of H2SO4

• Concentrated H2SO4
– As an oxidizing agent
• Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
• C + 2H2SO4  CO2 + 2SO2 + 2H2O
– As a dehydrating agent
– Reaction with HX
• 2HBr + H2SO4  Br2 + SO2 + 2H2O
• 8HI + 2H2SO4  4I2 + H2S + 4H2O
 NIS Chem section 12.1B

Uses of sulphuric(VI) acid

• Manufacture of detergents, dyestuffs,

polymers, fibres, paints, fertilizers
 NIS Chem section 12.1B

Sulfur and Environment

 When SO3 is formed it can react with in rain to create the major
problem of acid rain:
SO3 (g) + H2O (l) H2SO4 (aq)
 The SO2 is one of the many by-products of fossil fuel burning (eg.,
coal, gasoline and diesel)

 Acid rain causes many problems with living organisms by lowering

the pH of lakes and rivers.

 This acid rain can also cause major problems in attacking buildings
and statues. Limestone (calcium carbonate) structures will react
with the sulfuric acid. Also, iron building frames will be corroded.

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 NIS Chem section 12.1B

• Chemists have found ways to reduce the

sulfur content in fossil fuels in order to
solve this problem.
• Also, the SO2 can be captured using
chemical processes so it is not released
into the atmosphere.

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 NIS Chem section 12.1B

CaCO3(s) + SO2(g) → CaSO3(s) + CO2(g)

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