1

NITROGEN AND ITS COMPOUNDS

Nitrogen
Occurrence of nitrogen
 Nitrogen is the most abundant gas in the atmosphere, occupying about 78 percent
by volume.
 Also nitrogen exists in minerals such as sodium nitrate.
 It is found in living things in form of proteins.
Laboratory preparation of Nitrogen
a) From air
Experiment: laboratory preparation of nitrogen from air

water

Sodium hydroxide

 When water is run into the reservoir of air in the apparatus, air is pushed through
the apparatus.
 When air reaches the bottle containing sodium hydroxide solution (or potassium
hydroxide solution), carbon dioxide is absorbed from the air.
2NaOH(aq) + CO2(g) → Na2CO3(aq) + H2O(l)
 Oxygen is removed from the air when the air is passed over heated copper.
2Cu(s) + O2(g) → 2CuO(s)
 After leaving the heated copper, nitrogen is collected over water
 or may be dried by passing the gas through a U-tube containing glass beads
wetted with concentrated sulphuric acid to dry it and then collected in a syringe.
 Nitrogen cannot be collected by downward displacement of air since it is slightly
less dense than air.

 Nitrogen formed by this method is not pure. It contains several impurities, mainly
the noble gases as well as unreacted oxygen. The noble gases cannot be
removed by any chemical means.

 Commercially nitrogen is manufactured through fractional distillation of liquid air.

b) From ammonium nitrite
A mixture of ammonium chloride solution and sodium nitrite solution is heated in a
round bottomed flask fitted with a safety valve
NH4Cl (aq)+ NaNO2(aq) →NH4NO2(aq)+NaCl(aq)
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Test for nitrogen

Under ordinary conditions, nitrogen is inert (unreactive). This is because nitrogen is
composed of diatomic molecules, the atoms of which are held together very strongly by
three covalent bonds. Only when sufficient energy is supplied to break these bonds does
nitrogen react. Because of being inert, it has no simple positive test. It can only be
identified by its negative response to the following tests for other common gases.
1. Nitrogen extinguishes a burning splint and the gas does not burn. This distinguishes it
from other gases that support burining like oxygen and dinitrogen oxide or any
combustible gas such as hydrogen, carbon monoxide, hyrodgen sulphide.
2. Nitrogen has no smell. This distinguishes it from gases such as sulphur dioxide,
ammonia hydrogen chloride.
3. Nitrogen has no action on lime-water. This distinguishes it from carbon dioxide.

Properties of nitrogen
1. Nitrogen is a colourless and tasteless gas
2. It is slightly soluble in water under ordinary conditions.
3. It is slightly less dense than air.
Chemical properties
4. Nitrogen and hydrogen combine at high temperatures and pressure in the presence
of a catalyst to form ammonia.
N2(g) + 3H2(g) ⇌ 2NH3(g)
5. Nitrogen reacts only with the reactive metals (magnesium and calcium). When these
metals are heated strongly, they burn in nitrogen forming the corresponding nitride,
which is white in colour.
3Mg(s) + N2(g) → Mg3N2(s)
3Ca(s) + N2(g) → Ca3N2(s)
The heat produced by the burning magnesium ribbon or calcium is strong enough to
break the triple bond in the nitrogen molecule forming free nitrogen atoms. The free
atoms very reactive and combine with these metals to form a nitride. If a burning
wooden splint is placed in a jar of nitrogen, it gets extinguished. This is because the
heat is produces is not sufficient to break the triple bond between the nitrogen atoms.

The nitride dissolves in water to form the corresponding hydroxide and ammonia.
Mg3N2(s) + 6H2O(l) → 3Mg(OH)2(aq) + 2NH3(g)
Ca3(s) + 6H2O2(l) → 3Ca(OH)2(aq) + 2NH3(g)

6. In thunderstorms, a small amount of nitrogen reacts with the oxygen in the air to
form nitrogen monoxide and nitrogen dioxide.
N2(g) + O2(g) → 2NO(g)
2NO(g) + O2(g) → 2NO2(g)
The electrical discharge in a thunderstorm provides sufficient energy for this
reaction to occur.

Uses of nitrogen
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1. Used in the Haber process for the manufacture of ammonia.

N2(g) + 3H2(g) ⇌ 2NH3(g)
2. It is used in food packaging, for example in crisp packets, to keep the food fresh
and in this case to prevent the crisps being compressed.
3. Liquid nitrogen is used as a refrigerant.
4. Because of its unreactive nature, nitrogen is used as an inert atmosphere for
some processes and chemical reactions. For example, empty oil tankers are filled
with nitrogen to prevent fires.

2.2. NITROGEN MONOXIDE (NITROGEN(II) OXIDE

Experiment: laboratory preparation of nitrogen monoxide

 The experiment is set up as shown in figure above.

 Copper is covered with water and concentrated nitric acid added, about equal in
volume to the water.
 Vigorous effervescence occurs and brown fumes dissolve in water over which
nitrogen monoxide (main product) is collected as a colourless gas.
 A green solution of Copper(II) nitrate is left in the flask.
3Cu(s) + 8HNO3(aq) → 3Cu(NO3)2(aq) + 4H2O(l) + 2NO(g)

 Nitrogen dioxide (the brown fumes) is produced partly by the action of the acid
upon the copper and partly by the oxidation of the main product (nitrogen
monoxide) by the oxygen of the air in the flask.
Cu(s) + 4HNO3(l) → Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
2NO(g) + O2(g) → 2NO2(g)

Tests for nitrogen monoxide

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 Exposure to air
Remove the cover from gas-jar of nitrogen monoxide. Brown fumes are at once
produced due to oxidation of the gas by oxygen of the air to nitrogen dioxide.
2NO(g) + O2(g) → 2NO2(g)
 Action on iron(II) sulphate: A solution of iron(II) sulphate is poured into a gas-jar
containing nitrogen monoxide, a dark brown or black colouration is observed
due to formation of nitroso-iron(II) sulphate.
FeSO4(aq) + NO(g) → FeSO4.NO(aq)

Properties of nitrogen monoxide

 It is colourless and almost insoluble in water
 It is slightly denser than air
 It is neutral to litmus
 It supports the combustion of those burning materials whose flames are hot
enough to decompose it and so liberate free oxygen with which the material may
combine. The gas extinguishes a splint, candle, sulphur and glowing charcoal, but
the gas supports the combustion of strongly burning phosphorus or magnesium.
P4(s) + 10NO(g) → 2P2O5(s) + 5N2(g)
2Mg(s) + 2NO(g) → 2MgO(s) + N2(g)

NITROGEN(IV) OXIDE (NITROGEN DIOXIDE)

Experiment: Laboratory preparation of nitrogen dioxide

 The experiment is set up as shown above.

 When lead(II) nitrate is heated, it makes a cracking sound giving off a brown gas
(nitrogen dioxide) and oxygen.
 Nitrogen dioxide is liquefied in the freezing mixture and collected in the U-tube as
green liquid.
 The oxygen passes on as gas and is either allowed to escapes or it is collected
over water.
2Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g)
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 Lead (II) nitrate is the most suitable to use because it crystallizes without water of
crystallization which is found in crystals of most nitrates and which would interfere
with the preparation.
 Nitrogen dioxide may also be prepared by the action of concentrated nitric acid on
copper turnings. The gas is collected by downward delivery in a gas-jar when
required dry, or is collected over water.
Cu(s) + 4HNO3(1) → Cu(NO3)2(aq) + 2NO2(g) + 2H2O(1)

Properties of nitrogen dioxide

 It is a brown gas
 It has a pungent, irritating smell and it is a poisonous gas.
 It is soluble in water forming a pale blue solution containing nitric acid and nitrous
acid.
2NO2(g) + H2O(l) → HNO3(aq) + HNO2(aq)
 Nitrogen dioxide neutralizes alkalis forming a mixture of their corresponding
nitrates and nitrates. In this case nitrogen dioxide acts as an acid.
2NaOH(aq) + 2NO2(g) → NaNO3(aq) + NaNO2(aq) + H2O(1)
2KOH(aq) + 2NO2(g) → KNO3(aq) + KNO2(aq) + H2O(1)
 Nitrogen dioxide does not burn, but supports combustion of substances whose
flames are hot enough to decompose it and so liberate free oxygen with which the
substance may combine. It supports the combustion of carbon, sulphur,
phosphorus and magnesium.
2C(s) + 2NO2(g) → 2CO2(g) + N2(g)
2S(s) + 2NO2(g) → 2SO2(g) + N2(g)
2P4(s) +10NO2(g) → 2P4O10(s) + 5N2(g)
4Mg(s) + 2NO2(g) → 4MgO(s) _ N2(g)
 Nitrogen dioxide oxidizes red hot metals and is itself reduced to nitrogen.
4Cu(s) + 2NO2(g) → 4CuO(s) + N2(g)
4Zn(s) + 2NO2(g) → 4ZnO(s) + N2(g)
 When nitrogen dioxide is heated at temperatures above 150 0C, it dissociates to give
nitrogen monoxide and oxygen. The brown colour of nitrogen dioxide fades to give a
colourless gas which is the mixture of nitrogen monoxide and oxygen.

Ammonia
Laboratory preparation of ammonia
The apparatus is set up as shown below
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A mixture of calcium hydroxide and ammonium chloride is first thoroughly ground

and then placed in the flask which is slanted to prevent water produced flowing
backwards into the hot flask and causing it to crack. The mixture is then heated,
producing ammonia which is collected by downward displacement of air since it is
less dense than air. The gas is dried by calcium oxide, and not sulphuric acid or
calcium chloride because it reacts with them.
Ca(OH)2(s) + 2NH4CI(s) → CaCl2(s) + 2H2O(1) + 2NH3(g)

 Instead of calcium hydroxide, sodium hydroxide or potassium hydroxide solution may

be used, in which case the flask would be placed in the vertical position and heated.
NaOH(aq) + NH4Cl(s) → NaCl(aq) + H2O(1) + NH3(g)
KOH(aq) + NH4Cl(s) → KCl(aq) + H2O(1)+NH3(g)
 Ammonium sulphate may be used instead of ammonium chloride.
Ca(OH)2(s) + (NH4)2SO4(s) → CaSO4(s) + 2H2O(1) + 2NH3(g)

 The usual drying agents such as concentrated sulphuric acid and anhydrous
calcium chloride are not used because ammonia reacts with them to form
ammonium sulphate and tetraamine calcium chloride respectively.
2NH3(g) + H2SO4(1) → (NH4)2SO4(s)
CaCl2(s) + 4NH3(g) → CaCl2.4NH3(s)
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Industrial preparation of ammonia (Haber process)

 Dry nitrogen and hydrogen in the ratio of one to three respectively, are passed
over a catalyst of iron with some traces of aluminium oxide present.
 The reaction occurs at the surface of the catalyst; therefore, the catalyst should be
finely divided to increase the surface area over which the reaction occurs.
 Aluminium oxide improves the performance of the catalyst by making it more
porous thus providing a higher surface area for the reaction. The temperature is
between 4500C.
 The temperature is between 4500C - 5000C.
 The gases are under a pressure of 250 atmospheres to 500 atmospheres.
Ammonia is produced.
N2(g) + 3H2(g) ⇌ 2NH3(g)
 Ammonia is removed from the mixture of gases by cooling the mixture with a
freezing mixture. It is only ammonia that liquefies and can be removed from the
mixture unreacted nitrogen and hydrogen are recycled.

 Nitrogen used in this process is obtained by fractional distillation of liquid air and
hydrogen is obtained from natural gas or electrolysis of brine.

Tests for ammonia

 The gas has a characteristic chocking smell.
 It turns damp red litmus paper blue and
 forms white fumes with concentrated hydrochloric acid or hydrogen chloride.

Properties of ammonia
 It is a colorless gas with a choking smell.
 It is less dense than air and thus collected by upward delivery.
 It an alkaline gas and therefore turns red litmus blue. It is the only common
alkaline gas.

1. Solubility of ammonia in water

It is very soluble in water to give an alkaline solution. The great solubility of ammonia
is due to the reaction of the gas with water. Ammonia is a base and removes protons

NH3(g) + H2O(1) ⇌ NH4+(aq) + OH-(aq)

from water to produce ammonium ions and hydroxide ions.
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The solution is only weakly alkaline because of the reversible nature of this reaction,
which results in a relatively low concentration of hydroxide ions. Ammonia gas
dissolved in water is usually known as aqueous ammonia.
Fountain experiment: To demonstrate the high solubility of ammonia gas in water

 This experiment is done to demonstrate the high solubility of ammonia gas in

water.
 A large round thick walled flask is filled with ammonia gas.
 It is then fitted with two glass tubes C and D with clips on tube D opened to allow
in a few drops of water and then closed. These are shaken with ammonia to
dissolve it.
 If the red litmus solution is added to water in the trough, water in the flask will turn
to blue indicating that it is an alkaline gas which dissolved in water.
 The clip on tube C is opened. Water runs up the tube and spreads at the end of
the tube forming a fountain.

 The few drops of water, which entered through tube D, dissolved all the ammonia
gas in the flask so that a partial vacuum was created in the flask. When the clip on
tube C was opened, atmospheric pressure pushed the water up the tube forming
a fountain.

2. Action of ammonia on copper(II) oxide.

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 When a stream of dry ammonia is passed over very strongly heated copper(II)
oxide as shown in figure above, a colourless liquid (water) forms in the U-tube.
 The black oxide turns brown and a colourless gas collects in the jar over water.
Ammonia reduces the Copper(II) oxide to copper and itself oxidized to nitrogen.
3CuO(s) + 2NH3(g) → 2Cu(s) + 3H2O(l) + N2(g)
 Here ammonia behaves as a reducing agent. A similar reaction takes place with
oxides of lead and iron.
3PbO(s) + 2NH3(g) → 3Pb(s) + 3H2O(l)+N2(g)
Fe2O3(s)+2NH3(g) → 2Fe(s) + 3H2O(l)+N2(g)
 This experiment can also be used to demonstrate that ammonia contain nitrogen.
3. Combustion of ammonia Ammonia is a good reducing agent, which means that it can
be easily oxidized. Ammonia burns with a green/yellow flame, in an atmosphere of air
slightly enriched by oxygen forming nitrogen and water.
4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(i)
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The figure above shows how ammonia is burnt. The role of the glass wool is to distribute
oxygen evenly throughout the gas vessel. In presence of catalyst, ammonia is oxidized
to nitrogen monoxide.
The figure above shows the setup of the experiment. A hot platinum or copper wire
which acts as a catalyst is suspended in a beaker of concentrated ammonia and oxygen
is bubbled through the solution. The metal catalyst remains red-hot because the reaction
is exothermic. Brown fumes of nitrogen dioxide, which are formed due to oxidation of
nitrogen monoxide, are observed.
4NH3(g) + 5O2(g) → 2NO(g) + 6H2O(l)
then 2NO(g) + O2(g) → 2NO2(g)
The fumes later turn white due to formation of ammonium nitrate.
4NO2(g)+O2(g)+2H2O(g) → 4HNO3(g)
NH3(g) + HNO3(g) → NH4NO3(s)
4. Reaction with hydrogen chloride
Ammonia reacts with hydrogen chloride to form white fumes, which turn to a hite solid of
ammonium chloride on standing.
NH3(g) + HCl(g) → NH4Cl(s)

5. Reaction with chlorine

Ammonia burns spontaneously in chlorine forming a mist of hydrogen chloride.
2NH3(g) + 3Cl2(g) → N2(g) + 6HCl(g)
In excess ammonia, dense white fumes of ammonium chloride are formed. Hydrogen
chloride formed reacts with excess ammonia to form the white fumes, which later settle
to a white solid.
2NH3(g) + 3Cl2(g) → 4NO(g) + 6HCl(g)
Then HCl(g) + NH3(g) → NH4Cl(s)
This can be represented by one equation.
3Cl2(g) + 8NH3(g) → N2(g) + 6NH4Cl(s)

Uses of ammonia
1. Ammonia solution is used in laundry work to remove temporary hardness
2. Ammonia is used to manufacture ammonium sulphate and ammonium nitrate used
as fertilizers.
3. It is used in manufacture of nitric acid.
4. It is used in production of nylon.
5. It can be used as a refrigerant because it evaporates readily, removing heat from
surroundings as it does so. It can also be easily liquefied by compression.

AMMONIA SOLUTION
Experiment: Preparation of ammonia solution
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 It can be prepared by dissolving ammonia in water using the setup shown in the
figure above.
 The filter funnel is used in passing ammonia into water in order to prevent the
‘sucking back’ of water from the beaker into the reaction flask.
 Ammonia is so soluble in water that, in the process of dissolving, too much of it
could dissolve at one time creating a low gaseous pressure in the reaction flask
as well as in the delivery tube by the atmospheric pressure outside.
 The funnel is arranged with its rim only just immersed in order to ensure that when
water is sucked into funnel, contact with the water is broken and the water falls
back into the beaker rather than being sucked back along the delivery tube.

AMMONIUM SALTS
Nitrogenous fertilizers
 Fertilizers supply crops with inorganic elements required for their growth.
 Such elements include nitrogen, phosphorus, potassium and calcium. Nitrogen is
one of the most important elements required for the growth of plants.
 However, the plants are not able to take in nitrogen as an element. They obtain it
in the form of nitrates.
 Ammonium salts also supply plants with nitrogen since they are converted by soil
bacteria to nitrates.
 Nitrogenous fertilizers supply nitrogen together with various other elements to
plants. Majority of them are ammonium salts. They include ammonium sulphate
(AS), ammonium nitrate (AN), di-ammonium phosphate (DAP), calcium
ammonium nitrate (CAN) and ammonium sulphate nitrate (ASN).

 In the laboratory, ammonium salts are made by reaction of the appropriate acid
with ammonia. For example, ammonium sulphate is made by neutralizing
sulphuric acid with ammonia.
2NH3(g) + H2SO4(aq) → (NH4)2SO4(aq)
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 In industry, ammonium sulphate is not made using sulphuric acid, as the later is
very expensive. Instead, it is made by reacting ammonium carbonate with calcium
sulphate. Ammonium carbonate is first prepared by saturating ammonia solution
with carbon dioxide.
2NH3(g) + CO2(g) → H2O(l) → (NH4)2CO3(aq)

 Solid calcium sulphate is added and the mixture is stirred forming ammonium
sulphate solution and a precipitate ofcalcium carbonate.
(NH4)2CO3(aq) + CaSO4(g) → (NH4)2SO4(aq) + CaCO3(s)

 Calcium carbonate is removed by filtration and solid ammonium sulphate is

obtained by crystallization.

Effect of heat on ammonium salts

 Ammonium chloride sublimes when heated. The cause of this sublimation is that
ammonium chloride dissociates on heating to ammonia and hydrogen chloride,
which recombine on cooling.
NH4Cl(s) ⇌ NH3(g) + HCl(g)

 Also ammonium carbonate sublimes.

(NH4)2CO3(s) ⇌ 2NH3(g) + CO2(g) + H2O(g)

 Ammonium sulphate decomposes on heating into ammonia and sulphuric acid.

Although the reaction is similar to that of ammonium chloride no sublimation
occurs because sulphuric acid is less volatile than ammonia. The ammonia gas
escapes before sulphuric acid volatiles such that the two cannot recombine.
(NH4)SO4(s) → 2NH3(g) + N2SO4(g)

 Ammonium nitrate is decomposed to nitrogen(I) oxide (dinitrogen oxide) and

water.
NH4NO3(s) → N2O(g) + 2H2O(g)
 Dinitrogen oxide is a colourless gas. It is fairly soluble in water and neutral to
litmus. It is denser than air and a glowing splint is relit when lowered into a gas-jar
containing dinitrogen oxide. The heat decomposes dinitrogen oxide into oxygen
and nitrogen. It is oxygen that relights the glowing splint.
2N2O(g) → 2N2(g) + O2(g)
 Caution: Ammonium nitrate should not be heated in the laboratory because it
explodes on strong heating.
 Ammonium nitrite decomposes to nitrogen and water
NH4NO2(s) → N2(g) + 2H2O(g)

Test for ammonium salts

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 When ammonium salts are heated with an alkali, a colourless gas (ammonia)
which has pungent choking smell and turns wet red litmus paper blue is given off.
NH4+ (aq) + OH-(aq) → NH3(g) + 2H2O(g)

Reactions of ammonia solution and sodium hydroxide solution

 Ammonia solution nuetralises acids forming a salt and water only.
2NH4OH(aq) + H2SO4(aq) → (NH4)2SO4(aq) + 2H2O(1)

 Ammonia solution precipitates metal hydroxides from solutions containing the

metal ions. When a few drops of ammonia solution are added to a solution of
copper(II) ions, a blue precipitate is formed.
Cu2+ (aq) + 2OH-(aq) → Cu(OH)2(s)

 When excess aqueous ammonia is added to the blue precipitate, the precipitate
dissolves to form a deep blue solution containing complex tetraamine copper(II)
ions.
Cu(OH)2(s) + 4NH3(aq) → [Cu(NH3)4]2+ aq) + 2OH-(aq)
(

 A solution of zinc ions forms a white precipitate with a few drops of aqueous
ammonia. The precipitate dissolves in excess ammonia solution to form a
colourless solution containing a complex called tetraaminezinc ions.
Zn2+ aq) + 2OH-(aq) → Zn(OH)2(s)
(

Zn(OH)2(s) + 4NH3(aq) → [Zn(NH3)4]2+(aq) + 2OH-(aq)

 Iron(II), iron(III), lead(II) and aluminium ions form precipitates of the hydroxides
with aqueous ammonia which are insoluble in excess ammonia solution.
Fe2+(aq) +2OH-(aq) → Fe(OH)2(s)
(green)
Fe (aq) + 3OH (aq) → Fe(OH)3(s)
3+ -

(brown)
Pb (aq) +2OH-(aq) → Pb(OH)2(s)
2+

white)
Al (aq) +3OH (aq) → Al(OH)3(s)
3+ -

(white)
 A solution of aluminium, zinc and lead(II) ions reacts with sodium hydroxide
solution to form a white precipitate that is soluble in excess sodium hydroxide
solution to form a colourless solution.
Al3+ aq) + 3OH-(aq) → Al(OH)3(s)
(
 14

(OH)3(s) + OH-(aq) → Al(OH)4-(aq)

(aluminate ion)
Zn2+ aq) + 2OH-(aq) → Zn(OH)2(s)
(

Zn(OH)2(s) + 2OH-(aq) → Zn(OH)42-(aq)

zincate ion)
Pb (aq) + 2OH (aq) → Pb(OH)2(s)
2+ -

Pb(OH)2(s) + 2OH-(aq)→ Pb(OH)42-(aq)

(plumbate ion)

 Iron(II) and iron(III) ions in solution, react with sodium hydroxide solution to give a
green and brown precipitate respectively, insoluble in excess sodium hydroxide
solution.
Fe2+(aq) + 2OH-(aq) → Fe(OH)2(s)
Fe3+(aq) + 3OH-(aq) → Fe(OH)3(s)
 Magnesium and calcium ions in solution react with sodium hydroxide solution to
give a white precipitate insoluble in excess sodium hydroxide solution.
Ca2+(aq) +2OH-(aq) → Ca(OH)2(s)
Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)

NITRIC ACID
Experiment: Laboratory preparation of nitric acid
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 When a mixture of potassium nitrate and concentrated sulphuric acid is heated

gently, potassium nitrate gradually dissolves and effervescence occurs giving off
nitric acid which is condensed in another flask placed in a sink and cooled by tap
water as shown in the figure above.
KNO3(s) + H2SO4(l) →KHSO4(s) + KNO3(g)
 Brown fumes of nitrogen dioxide are produced during heating because of thermal
decomposition of nitric acid.
4HNO3(g) → 2H2O(l) +4NO2(g)+O2(g)
 The experiment must be carried out in an all-glass apparatus because nitric acid
vapour attacks rubber and cork.

Industrial preparation of nitric acid

 Nitric acid is manufactured by the catalytic oxidation of ammonia.
 Ammonia and excess air are passed over a heated platinum catalyst at about
8000C, forming nitrogen monoxide. The reaction is exothermic.
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(i)
 Nitrogen monoxide is cooled and reacts with oxygen from excess air to produce
brown fumes of nitrogen dioxide.
2NO(g) +O2(g) → 2NO2(g)
 Nitrogen dioxide together with excess air is dissolved in hot water to form nitric
acid.
2H2O(i)+4NO2(g)+O2(g) → 4NHO3(aq)

Uses of nitric acid

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1. In the manufacture of fertilizers such as ammonium nitrate. It is manufactured by

reacting ammonia gas and nitric acid.
NH3(g) + HNO3(aq) → NH4NO3(aq)
2. Used for the manufacture of dyes and explosives.
3. Used in manufacture of drugs

Properties of nitric acid

It behaves chemically in two ways.
1. It is a strong acid.
2. It is a powerful oxidizing agent

1. Nitric acid acting as a strong acid

Nitric acid is a very strong acid, being almost completely ionized in dilute solution with
the production of the hydrogen ion and the nitrate ion.
HNO3(aq) ⇌ H+(aq) + NO3-(aq)
This ionization confers on it the usual acidic properties, modified to some extent by the
powerful oxidizing action of the acid.
(a) It liberates carbon dioxide from carbonates and hydrogen carbonate
CuCO3(s) + 2HNO3(aq) → Cu(NO3)2(aq) + H2O(1) + CO2(g)
NaHCO3(s) + HNO3(aq) → NaNO3(aq) +H2O(1) + CO2(g)
(b) It reacts with oxides and alkalis to form salt and water only.
CuO(s) +2HNO3(aq) → Cu(NO3)(aq) +H2O(l) + CO2(g)
NaOH(aq) + HNO3(aq)
(c) Hydrogen is liberated when very dilute acid is added to magnesium.
Mg(s) +2HNO3(aq) → Mg(NO3)2(aq)+H2(g)
(d) Magnesium is the only metal that liberates hydrogen with nitric acid and only when
the acid is very dilute. Other metals are oxidized by the acid to the corresponding
nitrates.

2. Nitric acid as an oxidizing agent

(a) When concentrated nitric acid is added to a green solution of iron (II) sulphate and
warmed, it oxidizes it to a yellow or brown solution of iron(III) sulphate.
Fe2+(aq) → Fe3+(aq) + e-
(b) Concentrated nitric acid reacts with copper giving off nitrogen dioxide.
4HNO3(aq) + Cu(s) → Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
If the acid is 50% concentrated (equal volume of water as the volume of acid),
nitrogen monoxide is formed.
3Cu(s) + 8HNO3 (aq) +4H2O+2NO (g)
(c) Reaction with non – metal
(i) Concentrated nitric acid reacts with sulphur to give brown fumes of nitrogen dioxide.
S(S) + 6HNO3 (aq) →H2SO4 (aq) +2H2O ll) + 6NO2 (g)
(ii) When a piece of red-hot charcoal is put into concentrated nitric acid, it continues to
burn and brown fumes are formed.
C(s) + 4HNO3(aq) → CO2(g) +4NO2(g) + 2H2O(l)
(iii) When red phosphorus is gently heated with moderately dilute nitric acid, brown fumes
are formed.
 17

P(s) + 2.5HNO3(aq) → H3PO4(aq) + H2O(l) +2.5 NO2(g)

(d) Other oxidation reactions

When hydrogen sulphide is passed through moderately dilute nitric acid, a pale yellow
precipitate of sulphur is formed. Hydrogen sulphide is oxidized to sulphur and nitric acid
is reduced to nitrogen monoxide. With concentrated nitric acid, nitrogen dioxide is
formed.
3H2S(g) + 2HNO3(aq) → 3S(s) + 2NO(g) + 4H2O(l)
H2S(g) + 2HNO3(l) → S(s) + 2NO2(g) + 2H2O(l)

Nitrates
Nitrates of potassium and sodium when heated melt to a colourless liquid and then
slowly decompose to give a pale yellow nitric and a colourless gas which rekindles (re-
lights) a glowing splint.
2NaNO3(s) → 2NaNO2(l) + O2(g)
2KNO3(s) → 2KNO2(l) + O2(g)

Lead(II) nitrate makes a cracking sound when heated. The sound is due to the fact that
inside the crystals splits them when it expands due to heating. A brown mixture of
nitrogen dioxide and oxygen is given off. Lead(II) oxide (residue) is brown when hot and
when cold.
2Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g)
Most metallic nitrates decompose to a metal oxide, nitrogen dioxide (brown fumes)
oxygen gas which relights a glowing splint.
2Ca(NO3)2(s) → 2CaO(s) + 4NO2(g) + O2(g)
(white) (white)

2Mg(NO3)2(s) → 2MgO(s) + 4NO2(g) + O2(g)

(white) (white)

2Zn(NO3)2(s) → 2ZnO(s) + 4NO2(g) + O2(g)

(white)

2Cu(NO3)2(s) → 2CuO(s) + 4NO2(g) + O2(g)

(green) (black)

Zinc oxide is yellow when hot and white when cold. Zinc nitrate and copper(II) nitrate are
hydrated and when heated do not produce a cracking sound. They melt first and dissolve
in their water of crystallization forming a solution. The solution then evaporated and
when most of the water has evaporated, decomposition starts. Mercury(II) nitrate and
silver nitrate decompose to the metal, nitrogen dioxide and oxygen.
Hg(NO3)2(s) → Hg(l) + 2NO2(g) + O2(g)
2AgNO3(s) → 2Ag(s) + 2NO2(g) + O2(g)

Test for nitrates

1. Brown ring test:
 18

To a solution of nitrate in test-tube, an equal volume of freshly prepared iron(II) sulphate

solution is added. The test-tube is held in a slanting position and very carefully
concentrated sulphuric acid is poured down the sides of the test-tube. Concentrated
sulphuric acid is denser than the solution and therefore sinks to the bottom. A brown ring
form where the two layers meet as shown in the figure below

The formula of the brown ring is FeSO4.NO. Concentrated sulphuric acid reacts with
nitrate ions to give nitric acid.
H+(aq) + NO3-(aq) → HNO3(aq)
Nitric acid formed then oxidizes iron (II) to iron(III) and itself reduced to nitrogen
monoxide.
Fe2+(aq) → Fe3+ (aq) +e-
4HNO3(aq) → 2H2O(1) + 4NO(g) +3O2(g)
Nitrogen monoxide combines with the remaining iron(II) sulphate to form the dark brown
compound, nitroso-iron(II) sulphate.
FeSO4(aq) + NO(g) → FeSO4.NO(aq)
The ring disappears if the solution is shaken. This is because when concentrated
sulphuric acid and water mix, a lot of heat is evolved which decomposes the compound.
FeSO4.NO(aq) → FeSO4(aq) + NO(g)

2. Using hot concentrated sulphuric acid

A solid nitrate is gently heated with concentrated sulphuric acid in a test-tube forming
nitric acid. The top part of the tube is heated to decompose nitric acid forming brown
fumes of nitrogen dioxide.
4HNO3(g) → 2H2O(l) + 4NO2(g) + O2(g)
3. Copper and concentrate sulphuric acid
Mix a solid nitrate with copper and heat gently with concentrated sulphuric acid. Nitric
acid formed reacts with copper forming brown fumes of nitrogen dioxide.
Cu(s) + 4HNO3(l) → Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)
 19

3. CHLORINE AND ITS COMPOUNDS

Chlorine
Chlorine is element number 17 in the periodic table of elements. It belongs to group VII,
the halogens. Chlorine comes from the Greek word chloros, meaning green.

Experiment: laboratory preparation of chlorine

(a) By oxidation of concentrated hydrochloric acid with manganese(IV) oxide
The experiment is set up as shown in figure 3.1. Concentrated hydrochloric acid is
poured into a flask containing managanese(IV) oxide and the flask shaken well. The
mixture is heated and chlorine gas formed is passed through a bottle shaken well. The
mixture is heated and chlorine gas formed is passed through a bottle containing water to
dissolve any fumes of hydrogen chloride, which are produced from concentrated
hydrochloric acid. It is then dried by passing it through concentrated hydrochloric acid. it
is then dried by passing it through concentrated sulphuric acid and collected in a gas-jar
by downward delivery because it is denser than air.
MnO2(s) + 4HCl(1) → MnCl2(aq) + 2H2O(1) +Cl2(g)
(b) By oxidation of concentrated hydrochloric acid with potassium permanganate.
Solid potassium permanganate is placed in a flask and concentrated hydrochloric acid
dropped on to it from a tap funnel as shown in figure 3.2. Green/yellow gas is produced
which is collected over brine.
2KMnO4(s) + 16HCl(1) → 2KCl(aq) +2MNCl2(aq) + 8H2O(1) + 5Cl2(g)
The experiment need not be conducted in a fume-chamber, if the gas is collected brine.

(c) Preparation of chlorine from bleaching powder

Dilute nitric acid or hydrochloric acid can be used together with bleaching powder. The
experiment is set up as shown in figure 3.2.
CaOCl2(s) + 2HNO3(aq) → Ca(NO3)2(aq) + H2O(1) +Cl2(g)
CaOCl2(s) + 2HCl(aq) → CaCl2(aq) + H2O(1) +Cl2(g)

Industrial manufacturer of chlorine

Chlorine is produced commercially by the electrolysis of sodium chloride solution (brine)
using a carbon anode and a mercury cathode. Sodium is deposited at the catholic and
chlorine has liberated at the anode.
Na+(aq) + e- → Na(s)
Reaction at anode:
2Cl-(aq) → Cl2(g) + 2e-
Sodium ion is discharged because it requires less energy than the discharge of hydrogen
ions in case a mercury cathode is used.

Properties of chlorine
Chlorine bleaches damp blue and red litmus paper. Blue litmus paper is bleached after
turning red. It is a greenish yellow gas with a chocking irritating smell. It is fairly soluble in
water.
 20

1. Reaction with phosphorus

When a piece of yellow phosphorus is lowered in a gas-jar full of chlorine, it burns
spontaneously (without application of heat) giving off white fumes of phosphorus
trichloride (phosphorus(III) chloride) and phosphorus pentachloride (phosphorus(V)
chloride).
P4(s) + 6Cl(g) → 4PCl3(s)
P4(s)+10Cl2(g) → 4PCl5(s)

2. Affinity for hydrogen

Chlorine readily combines with substances, which contain hydrogen. When a piece of
filter paper is dipped in warm turperntine (C 10H16) and then dropped in a gas-jar full of
chlorine, there is a red flash accompanied by a violent reaction and a black cloud of
solid particles of carbon is formed. Chlorine combines with hydrogen in turpentine
leaving the black carbon behind.
C10H16(1) + 8Cl2(g) → 10C(s) + 16HCl(g)

3. Reaction with hydrogen

When a jet of burning hydrogen is lowered into a gas-jar full of chlorine, hydrogen
continues to burn with a white flame and clouds of steamy fumes of hydrogen
chloride are formed (figure 3.3.) The greenish yellow colour of chlorine gradually
disappears.
H2(g) + Cl2(g) → 2HCl(g)

4. Reaction with hydrogen sulphate

Chlorine reacts with hydrogen sulphide forming a yellow particles of sulphur and
white fumes of hydrogen chloride.
H2S(g) _ Cl2(g) → 2HCl(g) + S(s)

5. Action of chrlorine on iron

A stream of dry chlorine gas is passed over a coil of iron wire as shown in figure
3.4.On heating the iron wire, it glows and continues to burn without further application
of the flame. It reacts with chlorine to form brown fumes of iron(III) chloride which
condense in a bottle placed at the end of the combustion tube as black crystals.
2Fe(s) + 3Cl2(g) → 2FeCl3(s)
A tube containing the drying agent, anhydrous calcium chloride, is connected to the
bottle to prevent water from the atmosphere from entering the bottle as this would be
absorbed by iron(III) chloride which is very deliquescent. Excess chlorine, which is
poisonous, escapes into the fume chamber.

The formation of iron(III) chloride and not iron(II) chloride shows that chlorine is an
oxidizing agent. Iron(II) chloride is immediately oxidized by chlorine to iron(III)
chloride.

Sodium chloride can be prepared in similar way.

2Na(s) + Cl2(g) → 2NaCl(s)
 21

Iron(II) chloride (white solid) is made in the same way, using dry hydrogen chloride
instead of chlorine.
2HCl(g) + Fe(s) → FeCl2(s) + H2(g)
Sodium, potassium, calcium and magnesium burn in chlorine forming white fumes of
the chloride which settle to a white solid.

Note: When iron(III) chloride crystals are dissolved in water they give a deep yellow
solution from which yellow crystals of hydrated iron(III) chloride may be obtained by
evaporation to the point of crystallization.

6. Reaction with a dutch metal

When a thin strip of Dutch metal (alloy of copper and zinc, mainly copper) is placed in
a gas-jar full of chlorine, it burns spontaneously with a green flame (due to the
copper) to form copper(II) chloride and a little of zinc chloride.
Cu(s) + Cl2(g) → CuCl2(s)
Zn(s) + Cl2(g) → ZnCl2(s)

7. Action of chlorine on iron(II) chloride solution

When a stream of chlorine is bubbled through a pale green solution of iron(II)
chloride, the colour of the solution changes to yellow. Chlorine oxidizes the iron(II)
ions to iron(III) ions.
2FeCl2(aq) + Cl2(g) → 2FeCl3(aq)
Or 2Fe2+(aq) + Cl2(g) → 2Fe3+(aq) + 2Cl-(aq)

8. Reaction with alkalis

(i) Cold dilute alkalis
When chlorine gas is bubbled through cold aqueous alkalis, the hypochlorite and
the chloride of the metal are formed.
Cl2(g) + 2NaOH(aq) → NaOCl(aq) + H2O(1)
Cl2(g) + 2KOH(aq) → KOCl(aq) + KCl(aq) + H2O(1)
(ii) Hot concentrated alkalis
When chlorine is passed into hot concentrated alkalis, a mixture of the chlorate
and the chloride is formed.
6KOH(aq) + 3Cl2(g) → KCl3(aq) + 3H2O(1)
6NaOH(aq)+ 3Cl2(g) → NaClO3(aq) + 5NaCl(aq)+3H2O(1)
Or 6OH-(aq) + 3Cl2(g) → ClO3-(aq) + 5Cl-(aq) + 3H2O(1)

(iii)
9. Bleaching action of chlorine
Chlorine reacts with water forming hypochlorous acid and hydrochloric acid.
CI2 (g) + H2O (1) → HCI (aq) + HOCI (aq)
Hypochlorous acid is a very reactive compound and readily gives up its oxygen to the
dye, to form a colorless compound, that is, the dye is oxidized to a colorless
compound.
Dye + HOCI (aq) → HCI (aq) + (dye + O)
Colourless
 22

Dry litmus paper is not bleached by chlorine because there is no formation of

hypochlorous acid. Sodium hypochlorite and potassium hypochlorite have a
bleaching effect.

10. Effect of sunlight on Chlorine water.

Chlorine gas is passed into distilled water for sometime until the water becomes yellow –
green in colour. When an inverter tube containing this chlorine water is exposed to
sunlight, a colourless gas (oxygen) which re- lights a glowing splint is formed.
2CI(g) + 2H2O(1)→ 4HCI(aq) +O2(g) (overall equation)
This occurs in two stages.
i. Formation of hypochlorous acid and hydrochloric acid as a result of reaction between
water and chlorine.
H2O(1) +CI2(g) → HOCI(aq) + HCI(aq)
ii. Decomposition of hypochlorous acid to liberate oxygen.
2HOCI(aq)→2HCI(aq) + O2(g)

11. Displacement reactions of chlorine.

Chlorine is higher in the reactivity series than bromine and therefore can displace them
from solutions of their salt in water. This is because chlorine is more reactive than
bromine and iodine due to the fact that, the incoming electron is more strongly attracted
into the outer energy level of the smaller atom. The attraction force on the electron will
be greater for chlorine than for bromine and iodine, since the outer energy level of
chlorine is closer to the nucleus. As one goes down the group, the extra electron is
further away from the nucleus. It will, therefore, be attracted less strongly thus the
reactivity of the halogens decreases down the group.

Order of reactivity of halogens

F Flourine – most reactive
CI Chlorine
Br Bromine
I Iodine – least reactive.

When chlorine gas is bubbled into a solution of potassium bromide in water, the colorless
solution immediately turns red due to formation of bromine water.
2KBr(aq) + CI2(g) →2KCI(aq) + Br2(aq)

Chlorine displaces iodine from potassium iodine solution forming a dark brown solution
due to formation of iodine.
2KI(aq) + CI2(g)→2KCI(aq) + I2(aq)
 23

Bromine can displace iodine from iodides but cannot displace chlorine from chlorides.
Therefore on addition of a few drops of bromine to a solution of potassium iodide in
water, the solution becomes brown due to the formation of iodine.
2KI(aq) + Br2(I) → 2KBr(aq) + I2(aq)

3.2 Hydrogen chloride

Concentrated sulphuric acid is added to sodium chloride in the flask . effervescence
occurs and misty fumes of a gas are formed. The gas is passed through a bottle
containing concentrated sulphuric acid to dry it and collected by upward displacement of
air since the gas is denser than air.
H2SO4(s) + NaCl(s) → NaHSO4(aq) + HCL(g)
Sodium sulphate is not formed because it requires higher temperature than is provided in
this experiment. Sodium chloride is the one most commonly used because it is cheap
and readily.

Test for hydrogen chloride

It produces a white precipitate of silver chloride with silver nitrate solution.
AgNO3(aq) + HCl(g) → AgCl(s) + HNO3(aq)
It also produces dense white fumes of ammonium chloride with ammonia
NH3(g) + HCl(g) → NH4Cl(g)

Properties of hydrogen chloride

1. It is a white funning gas with a choking smell.
2. It turns damp blue litmus paper red.
3. It is very soluble in water. This can be shown by the fountain experiment.
4. It liberates hydrogen from certain metals. All metals above copper in the reactivity
series react with hydrogen chloride to form hydrogen and the corresponding chloride.
Fe(s) +2HCl(g) → FeCl2(s) + H2(g)
Mg(s) + 2HCl(g) → MgCl2(s) + H2(g)
 24

3.3 HYDROCHLORIC ACID

Experiment: Preparation of hydrochloric acid
It can be prepared by dissolving chloride gas in water using the setup shown in figure
3.7. The filter funnel is used in passing hydrogen chloride into water in order to prevent
the ‘sucking back’ of water from the beaker into a reaction flask. Hydrogen chloride is so
soluble in water that, in the process of dissolving, too much of it could dissolve at one
time creating a low gaseous pressure in the reaction flask as well as in the delivery tube
by the atmospheric pressure outside. The funnel is arranged with its rim only just
immersed in the water in order to ensure that when water is sucked into the funnel,
contact with the water is broken and the water falls back in the beaker rather than being
sucked back along the delivery tube.

Properties of hydrochloric acid

1. It turns blue litmus paper acid
2. It reacts with metals producing hydrogen gas. It reacts with metals above
hydrogen in the activity series.
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
3. It liberates carbon dioxide from carbonates and hydrogencarbonates.
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(1) + CO2(g)
NaHCO3(s) + HCl(aq) → NaCl(aq) + H2O(1) + CO2(g)
4. It reacts with alkalis and basic oxides producing salt and water only.
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(1)
CuO(s) + 2HCl(aq) → CuCl2(aq) + H2O(1)
5. Concentrated hydrochloric acid reacts with oxidizing agents such as potassium
permanganate liberating chloride gas.
2KMn4(s) + 16HCl(1) → 2KCl(aq) + 2MnCl2(aq) + 8H2O(1) + 5Cl2(g)

Uses of hydrochloric acid

1. It is used in removal (de-scaling) of rust iron before it is galvanized. It is also used
in cleaning metals before they are electroplated.
2. It is used in manufacture of plastics such as polychloroethene.
 25

Properties of hydrogen chloride in methylbenzene

Dry hydrogen chloride is a covalent compound and therefore it dissolves in organic
solvents such as methylbenzene. In the solution, the dissolved hydrogen chloride does
not ionize and remains in the molecular state because methylbenzene is not a proton
(H+) acceptor. Therefore the solution contains no ions and does not conduct electricity.
Water, however is a proton acceptor and in dilute solution, hydrogen chloride is fully
ionized.
HCl(g) + H2O(1) → H3O+(aq) + Cl-(aq)
These ions are responsible for conducting electricity in the solution. The oxonium ion
liberates hydrogen with the more electropositive metals and carbon dioxide with
carnonates and hydrogencarbonates.
Mg(s) + 2H3O+(aq) → Mg2+(aq) + 2H2O(aq) + H2(g)
CO32-(aq) + 2H3O+(aq) → 3H2O(1) + CO2(g)
HCO3-(aq) + H3O+(aq) → 2H2O(1) + CO2(g)
Thus these properties are not shown by hydrogen chloride in methylbenzene, that is, the
solution does not contain hydrogen or oxonium ions responsible for acidic characteristics
and the solution contains no ions which carry an electric current.

Testing for soluble chlorides

To the solution of the suspected chloride in water, add dilute nitric acid followed by silver
nitrate solution. A white precipitate of silver chloride will be observed.
Ag+(aq) + Cl -(aq) → AgCl(s)
To the white precipitate add ammonia solution. The precipitate dissolves to forma
colourless solution.
AgCl(s) + 2NH3(aq) → Ag(NH3)2+(aq) + Cl-(aq)
Nitric acid prevents the precipitation of other insoluble silver salts such as silver
carbonate. The only common insoluble chlorides are lead(II) chloride and silver chloride.
Lead(II) chloride is soluble in hot water.

SULPHUR AND ITS COMPOUNDS

Sulphur
Occurrence
Sulphur occurs as free sulphur and as hydrogen sulphide in petroleum gases

Extraction of sulphur by the Frasch sulphur pump

A hole about 30cm in diameter is dug into the soil and the hole in lined with an iron pipe.
A sulphur pump is sunk into the iron pipe. It consists of three concentric tubes (figure
4.1). in the outermost tube, superheated water at 170 0C and at a pressure of 10
atmospheres, to keep it in a liquid form, is sent down to the beds of sulphur. The sulphur
melts and flows into the reservoir at the base of the pump. Hot compressed air under a
pressure or about 15 atmospheres is sent down through the innermost tube. It pushes
the molten sulphur and water up through the middle tube and its collected in containers.
Water is evaporated off and almost 99% pure sulphur is obtained.

Extraction of sulphur from natural gas

 26

Natural gases obtained during the refining of petroleum contain hydrogen sulphide which
is absorbed by special solvents. The gas is removed from the solvent and a small portion
of the gas is burnt in air to form sulphur dioxide.
2H2S(g) + 3O2(g) → 2H2O(1) + 2SO2(g)

The remaining portion of the gas is left to react with the sulphur dioxide to formsulphur
and water. The water is evaporate off.
2H2S(g) + SO2(g) → 3S(s) + 2H2O(1)

Uses of sulphur
1. Used in manufacture of sulphuric acid
2. Used to dust vines to prevent the growth of fungi.
3. Used in making calcium hydrogensulphite which is used as a bleaching agent of
wood pulp in manufacture of paper.
4. It si adde to rubber to make it hard (vulcanisation of rubber)
5. Used in manufacture of carbon disulphide which is used to ill weevils
6. Used in making ointments for treatment of skin diseases such as ringworm.

Properties of sulphur
It is a yellow non-metal. It is insoluble in water. It is a poor conductor of heat and
electricity.

1. Action of ehat on sulphur (In absence of air)

When a yellow solid of sulphur is heated, it melts at about 113 0C to a clear amber
liquid which flows easily like water. Sulphur contains small rings of atoms, S 8.the
liquid flows with ease because the rings have been seperated. On further heating at
about 1600C, the sulphur becomes brown and viscous. It flows slowly because the
small rings of 8 atoms break and longer chains are formed. These chains twist
together and do not flow readily colour and mobile again (less viscous). The chains
break and become shorter which can flow more readily. Sulphur boils at 444 0C and
forms a brown vapour. On cold surfaces, the vapour condenses directly into a yellow
sublimate.

2. Combustion of sulphur (in plantiful supply of air)

When burning sulphur is plunged into a gas-jar of air, the sulphur burns with a blue
flame leaving a misty gas. The mist is due to traces of sulphur trioxide formed
smultaneously with sulphur dioxide.
S(s) + O2(g) → SO2(g)

3. Reaction with metals and non-metals

The mixture of iron filings and sulphur when heated glows giving a black solid of
iron(II) sulphide.
Fe(s) + S(s) → Cu2S(s)
A hot copper foil glows in sulphur vapour forming a black solid, copper(I) sulphide.
2Cu(s) + S(s) → Cu2S(s)
 27

Carbon combines directly with sulphur to form a liquid, carbon disulphide. Very high
temperatures are required for this reaction to occur.
C(s) + 2S(s) → CS2(1)

4. Action of acids on sulphur

Dilute acids do not act upon sulphur. It is oxidised by hot concentrated sulphuric acid
with formation of sulphur dioxide.
S(s) + 2H2SO4(1) → 3SO2(g) + 2H2O(1)
Sulphur is oxidised by hot concentrated nitric acid to sulphuric acid. bromine is added
to speed up the rate of reaction.
S(s) + 6HNO3(1) → H2SO4(aq) + 6NO2(g) + 2H2O(1)

Allotropes of sulphur
Sulphur has five allotropes; monoclinic sulphur, rhombic sulphur, amorphous sulphur,
plastic sulphur and colloidal sulphur.

Experiment: Preparation of rhombic sulphur (alpha-sulphur)

Dissolve some powdered sulphur in carbon disulphide in a boiling tube. Place it in a
beaker after extinguishing all flames in the area around. Filter the solution into
another dry beaker and lace a piece of clean filter paper on top of the beaker. Pierce
some small holes in the filter paper and place the set up near a window for a day to
allow the carbon disulphide to evaporate. Large rhombic cryastals o sulphur will form
having a shape shown in figure 4.2.

Experiment: Preparation of monoclinic sulphur (Beta-sulphur)

Place some powdered sulphur in an evaporating dish. Carefully heat it until it melts.
Stir and gradully add more sulphr until the crucible is full of molten sulphur. Stop
heating and allow it to cool. A crust will form on the surface of sulphur. Carefully
pierce through the crust and immediately pour off the liquid sulphur inside. Cut away
the crust by cutting around the edge of the crucible with a knife. Small needle shaped
crystals will be seen inside the evaporating dish as shwon in figure 4.2.
Transition temperature
This is the temperature at which a change from one form of sulphur to another form
takes place. It is 960C. rhombic sulphur is stable below 96 0C. above this temperature,
it slowly chnages to the monoclinic form.

Differences between rhombic and monoclinic sulphur

Rhombic sulphur consists of relatively large yellow, transulcent, octahedral cryatals
with a meting point of 1140C and density of 2.08g/cm3. Monoclinic sulphur consists of
needle shaped, pale-yellow transparent crystals with a melting point of 119 0C and
density of 1.98g/cm3. Crystals of rhombic sulphur are stable below 96 0C while
monoclinic sulphur is stable above this temperature.

Amorphus sulphur
 28

Amorphous sulphur is formed by oxidation of hydrogen sulphide by air. When a

saturated solution of hydrogen sulphide is left exposed to air for about two days. An
almost white powder of amorphous sulphur is formed.
2H2S(aq) + O2(g) → 2S(s) + 2H2O(1)

Plastic sulphur
When boiling sulphur is quickly cooled by pouring into cold water, a yellow/brown
elastic solid called plastic sulphur is formed.

Colloidal sulphur
When dilute hydrochloric acid is added to dilute sosium thiosulphate, a yellow
suspension of colloidal sulphur if formed.
Na2S2O3(aq) + 2HCl(aq) → 2NaCl(aq) + H2O(1) + S(s) + SO2(g)

Sulphur dioxide
Experiment: Laboratory preparation of sulphur dioxide
Hot concentrated sulphuric acid reacts with copper turnings giving off sulphur dioxide.
The gas is dried by passing it through a bottle containing concentrated sulphuric acid
and collected in a gas-jar by upward displacement of air since it is denser than air, as
shown in figure 4.3.
Cu(s) + 2H2SO4(1) → CuSO4(aq) + 2H2O(1) + SO2(g)
Instead of using copper turnings, it is also ossible to prepare the gas by using sodium
sulphiric and dilute sulphuric acid.
Na2SO2(aq) + H2SO4(aq) → Na2SO4(aq) + H2O(1) + SO2(g)
Sulphur dioxide is very soluble in water and therefore heating reduces its solubility in
the water formed in the flask. Since sulphur dioxide is very soluble in water, it cannot
be collected over water.

Properties of sulphur dioxide

1. It is a colourless gas with an irritating smell.
2. It turns damp blue litmus paper red because it is acidic gas.
SO2(g) + H2O(1) → H2SO3(aq)
3. It is very soluble in water and its solubility in water can be shown by the fountain
experiment.
4. It is more dense than air.
5. It is a powerful reducing agent.
(a) When sulphur dioxide is bubbled through a solution of iron(III) salt for sometime,
iron(III) ions are reduced to iron(II) ions where the colour of the solution changes
from brown to pale green.
(b) When sulphur dioxide is dissolved in water, it forms sulphurous acid which is a
bleaching agent. Sulphurous acid takes up oxygen from the dye to form sulphuric
acid. The removal of oxygen from a dye converts the dye to a colourless
compound. This is essentailly a different reaction from that of most bleaching
agents, which oxidise the dye to a colourless compound.
(c) Sulphur dioxide reduces concentrated nitric acid to nitrogen dioxide, the sulphur
dioxide being oxidised to sulphuric acid.
 29

SO2(g)+2HNO3(1) → H2SO4(1)+2NO2(g)
(d) Sulphuric dioxide reduces yellow acidified potassium dichromate solution to green
chronium(III) sulphate and itself oxidised to sulphuric acid. this is a characteristic
test for sulphur dioxide.
3SO2(g)+Cr2O72-(aq) +2H+(aq) → 3SO42-(aq) +2Cr3+(aq) + H2O(1)

6. Sulphur dioxide acts as an oxidising agent when it reacts with a more powerful
reducing agent than itself.
(a) Sulphur dioxide reacts with hydrogen sulphide to form a yellow deposit of sulphur.
Sulphue dioxide oxidises hydrogen sulphide to water by supplying oxygen and
itself reduced to sulphur.
2H2S(g) + SO2(g) → 2H2O(1) + 3S(s)
(b) Burning magnesium continues to burn in sulphur dioxide for sometime forming a
white powder of magnesium oxide and sulphur.
2Mg(s) + SO2(g) → 2MgO(s) + S(s)

Uses of sulphur dioxide

1. It is used for the manufacture of sulphuric acid
2. It is used as a bleaching agent in paper industry
3. It is used as a preservative of some liquids such as orange juice where it reacts
with oxygen and prevents oxidation of the liquid.
4. It is used for fumigation of houses since it is poisonous and kills micro organisms.

Sulphur trioxide
Experiment: Preparation of sulphur trioxide
It is prepared by pasing a mixture of dry sulphur dioxide and dry air over heated
vanadium(V) oxide (or latinised asbestos) at a temperature of 450-500 0C as shown in
figure 4.4.. sulphur trioxide is seen as dense white fumes which are solidified in a
freezing mixture of ice and dsodium chloride.
2SO2(g) + O2(g) → 2SO3(g)

SULPHURIC ACID
Sulphuric acid is dilbastic mineral acid.

Industrial manaufacture of sulphuric acid by the contact process

Sulphur is burnt in air to produce sulphur dioxide
S(s) + O2(g) → SO(g)
Sulphur dioxide may contain some impurities such as arsenic compounds which may
‘poison the catalyst’, that is, make the catalyst ineffective. Therefore sulphur dioxide is
cleaned to remove the impurities then it is dried. Then sulphur dioxide is mixed with air
and passed along heated pipes containin pellets of vanadium pentoxide (V 2O5) at a
temperature of 4500C-5000C under a pressure of 200 atmospheres. Sulphur trioxide is
formed.
2SO2(g) + O2(g) → 2SO3(g)
 30

It is the close contact of the reacting gases with vanadium pentoxide which gives the
contact process its name. sulphur trioxide formed is dissolved in concentrated sulphuric
acid to produce a fuming liquid called oleum.
SO3(g) + H2SO4(1) → H2S2O7(1)
The oleum is diluted with a known amount of water to give concentrated sulphuric acid.
H2S2O7(1) + H2O(1) → 2H2SO4(aq)
The whole process is summarised in figure 4.5
Sulphur
Sulphur SO2 Cleaners
Air burner and driers
Air
Catalyst
Oleum SO3 chamber
Sulphuric Dilution Absorption
acid chamber chamber

Fug 4.5. A summary of the contact process for the preparation of sulphuric acid

Sulphur trioxide is not dissolved in water directly because the reaction is too exothermic
leading to the boiling of the sulphuric acid produced and therefore produces a spray of
sulphuric acid which would affect the workers in the factory.

Properties of sulphuric acid

Concentrated sulphuric acid is a colourless liquid, which does not show any acidic
properties unless water is present. A great deal of heat is produced when concentrated
sulphuric acid is diluted with water. It is therefore advisable to add the acid to water
rather than water to acid because the first droplets of water vaporize quickly to steam
and spit out droplets of concentrated acid.

1. Sulphuric acid behaves as a strong acid in dilute concentration.

(a) Metals displace hydrogen from sulphuric acid.
Mg(s)+H2SO4(aq) → MgSO4(aq) + H2(g)

(b) It reacts with bases to form salt and water only.

ZnO(s)+H2SO4(aq) → ZnSO4(aq)+H2O(1)
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(1)

(c) It reacts with carbonates and hydrogencarbonates liberating carbon dioxide.

Na2CO3(s) + H2SO4(aq) → Na2SO4(aq) + H2O(1) + CO2(g)
2NaHCO3(s) + H2SO4(aq) → Na2SO4(aq) + 2H2O(1) + 2CO2(g)

2. When concentrated and hot, it acts as an oxidizing agent to both metals and non-
metals and it is reduced to sulphur dioxide. It accepts electrons or supplies oxygen in
its reaction.
(a) It oxidizes copper to Copper(II) sulphate. Reaction with zinc and iron produces
similar results.
Cu(s)+2H2SO4(1) → CuSO4(aq) + 2H2O(1) + SO2(g)
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(b) It oxidizes sulphur and carbon to their oxides.

2S(s) + 2H2SO4(1) → 2H2O(1) +3SO2(g)
C(s) + 2H2SO4(1) → CO2(g) + 2SO2(g) + 2H2O(1)
(c) It oxidizes hydrogen sulphide to sulphur forming a yellow deposit.
H2S(g) + H2SO4(1) → S(s) 2H2O(1) + SO2(g)

3. It is a dehydrating agent. Sulphuric acid has a very affinity for water and can remove
it from substances including air, that is, it is hygroscopic. It can be used as a drying
agent for most gases.
(a) When concentrated sulhuric acid is poured onto sugar (sucrose) in a beaker, the
sugar turns yellow then brown and finally a black spongy mass of charcoal rises
filling the beaker. Steam is given off and the whole mass becomes very hot. The
acid takes out the elements of water from sugar leaving a black mass of carbon.
C12H22O11(s) → 12C(s) +11H2O(1)
Similar reactions take place when other carbohydrates are used.
C6H12O6(s) → 6C(s) +6H2O(1)
(glucose)

(b) When concentrated sulphuric acid is added to blue crystals of copper(II) sulphate
(hydrated) and warmed, they change to a white solid of anhydrous copper(II)
sulphate as water of crystallization is removed by concentrated sulphuric acid.
CuSO4.5H2O(s) → CuSO4(s) + 5H2O(1)
(c) Other substances which are dehydrated by concentrated sulphuric acid include
ethanol, methanoic acid and oxalic acid.
C2H5OH(1) → C2H4(g) + H2O(1)
Ethanol Ethane

HCOOH(1) → CO(g) + H2O(1)

Methanoic acid

H2C2O4(s) → CO(g) + CO2(g) + H2O(1)

Oxalic acid

Uses of sulphuric acid

1. It is used in car batteries and accumulators as an electrolyte
2. It is used in manufacture of fertilizers such as ammonium sulphate
3. Used in extraction of metals and also cleaning them prior to plating
4. Used in manufacture of paints

SULPHATES
Action of heat on sulphates
When a blue solid of hydrated Copper(II) sulphate is heated, water vapor is given off as
water of crystalisation is lost, giving a white solid. On further heating, it decomposes to
form white fumes of sulphur trioxide and a black residue of Copper(II) oxide.
 32

CuSO45H2O(s) → CuSO4(s) +5H2O(1)

CuSO4(s) → CuO(s) + SO3(g)
Overall equation: CuSO4.5H2O(s) → CuO(s) + 5H2O(1) + SO3(g)

Hydrated iorn(II) sulphate (green) loses its water of crystallisation when heated. On
further heating, it decomposes to give white fumes of sulphur trioxide together with
sulphur dioxide and a reddich brown solid of iron(III) oxide.
FeSO4.7H2O(s) → FeSO4(s) +7H2O(1)
2FeSO4(s) → Fe2O3(s) + SO3(g) + SO2(g)
Overall equation: 2FeSO4.7H2O(s) → Fe2O3(s) + 14H2O(1) + SO3(g) + SO2(g)

Testing for soluble sulphate (SO42-)

To the solution of the suspected suplhate in water, add dilute hydrocholoric acid followed
by barium chloride solution (barium nitrate solution and dilute nitric acid can be used). A
white precipiate of barium sulphate which is insoluble in the acid indicates the presnece
of a sulphate ion.
BaCl2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaCl(aq)
Ba(NO3)2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaNO3(aq)
Or Ba2+(aq) + SO42-(aq) → BaSO4(s)

Carbonate ions (CO32-) and sulphite ions (SO32-) are precipitated as barium arbonate and
barium sulhite respectively, if carbonate and sulphite ions are present in solution.
Ba2+(aq) + CO32- + CO32-(aq) → BaCO3(s)
Ba2+(aq) + SO32-(aq) → BaSO3(s)

The purpose of adding dilute nitric acid hydrochloric acid is to remove the carbonate ions
and the sulphite ions if they are present in solution.
2H+(aq) SO32-(aq) → H2O(1) + SO2(g)
2H+(aq) + CO32-(aq) → H2O(1) + CO2(g)

The sulphate ions (SO42-) remain in solution because they do not react with dilute
hydrochloric acid or nitric acid. also lead(II) nitrate solution forms a white precipitate of
lead(II) sulphate with a sulphate.
Pb2+(aq) + SO42-(aq) → PbSO4(s)

HYRDOGEN SULPHIDE
Experiment: Laboatory preparation of hydrogen sulphide
As the acid reaches the iron(II) sulphide, effervescence begins and hydrogen sulhide is
collected over warm water because it is quite solule in cold water (figure 4.6)
FeS(s) + 2HCl(aq) → FeCl2(aq) + H2S(g)
Dilute sulphuric acid may be used
FeS(s) + H2SO4(aq) → FeSO4(aq) + H2S(g)
To prepare hydrogen sulphide from sulphur, iron(II) sulphide is first prepared by heating
a mixture of iron and sulphur.
Fe(s) + S(s) → FeS(s)
 33

Hydrogen sulphide can be dried by using anhydrous calcium chloride. Concentrated

sulphuric acid is not used to dry the gas because it reacts with hydrogen sulphide
forming a yellow precipitate of sulphur.
H2SO4(1) 3H2S(g) → 4H2O(1) + 4S(s)

Testing for hydrogen sulphate

A strip of filter paper is soaked in Lead(II) ethanoate solution and dropped into a gas-jar
of hydrogen sulphide. The paper turns black. This colour change is caused by
precipitation of black Lead(II) sulphide.
(CH3COO)2Pb(aq) +H2S(g) → 2CH3COOH(aq) + PbS(s)

PROPERTIES OF HYDROGEN SULPHIDE

Physical properties
1. The gas is colorless and has a repulsive smell similar to that of a rotten egg. It is in
fact given off from rotting eggs and also from decaying cabbages both of which
contain sulphur.
2. It is also fairly soluble in water forming a weak acidic solution.
3. It is denser than air.
4. The gas is extremely poisonous.

Chemical properties
1. Hydrogen sulphide is a powerful reducing agent
It reduces oxidizing agents and itself oxidized to sulphur which appears as a pale yellow
precipitate.
a) Hydrogen sulphide reduces iron (III) chloride to iron (II) chloride. When hydrogen
sulphide is passed through iron (III) chloride solution (yellow), a yellow precipitate of
sulphur appears. On filtering, a green solution of iron (II) chloride appears as the
filtrate.
2FeCI3 (aq) +H2S (g → 2FeCI2 (aq) + 2HCI (aq) +S(s)
b) Hydrogen sulphide reacts with concentrated nitric acid to form brown fumes of
nitrogen dioxide and a yellow deposit of sulphur. Also the mixture becomes hot. The
hydrogen sulphide reduces the nitric acid to nitrogen dioxide.
2HNO3 (I) + H2S (g) → 2H2O (1) + 2NO2 (g) + S(s)

2. Combustion of Hydrogen sulphide

a) With a plentiful supply of air
Hydrogen sulhide burns with a blue flame forming water and sulphur dioxide.
2HsS (g) +3O2 → 2H2O (1) + 2SO2 (g)

b) With a limited supply of air

When hydrogen sulphide is burnt in a limited supply of air, a yellow deposit of
sulphur is formed. The oxygen supply cannot oxidize the gas completely and
therefore free sulphur is deposited.
 34

2HsS(g) + O2(g) → 2S(S) + 2H2O(1)

3. Reaction with salts of metals

Hydrogen sulphide can precipitate insoluble sulphide of copper and lead only by
reacting with solutions o their salts. A dark brown precipitate of copper (II) sulphide
and a black precipitate of lead (II) sulphide are formed.
CuSO4(aq) + H2S(g) → CuS(S) + H2SO4(aq)
Pb(NO3)2(aq) + H2S(g) → PbS(s) + 2HNO3(aq)