DIVINE WISDOM INTERNATIONAL SCHOOL

CHEMISTRY NOTE OF LESSON FOR SS II STUDENTS

REDEEMER TERM 2024/2025 ACADEMIC SESSION.

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SCHEME OF WORK

Week 1 - 3: Chlorine and its compounds

Week 4 - 5: Nitrogen and its compounds ( N2, NH3, N2O and NO )

Week 6 : Mid Term Test

Week 7: Nitrogen and its compounds 2 ( NO2 and HNO3 )

Week 8-10: Sulphur and its compounds

Week 11 : Revision

Week 12 : Examination

WEEK ONE: CHLORINE AND ITS COMPOUNDS

Chlorine is the most important element of the family of the most reactive non – metals called the Halogens
(Group 7 elements).

Chlorine was first discovered by Scheele in 1774. Because of its reactivity it does not occur free in nature
but in the combined form mostly as chlorides e. g NaCl in the sea and salt deposits. Its exist as a diatomic
gas.

Laboratory preparation of chlorine gas

Chlorine is usually prepared in the laboratory by the action of oxidizing agents ( such as MnO 2 or KMnO4 )
on concentrated hydrochloric acid HCl:

I. Action of Manganese (IV) oxide on concentrated hydrochloric acid when heated.

MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) + Cl2(g)
Ionically: Mn4+(aq) + 4H+(aq) + Cl-(aq) → Mn2+(aq) + 2H2O(l) + Cl2(g).
II. Action of Potassium tetraoxomanganate (vii) on concentrated hydrochloric acid.
2KMO4(aq) + 16HCl(aq) → MnCl2(aq) + 2KCl(aq) + 8H2O(l) + 5Cl2(g)
Ionically:

III. Alternately, Chlorine can also be prepared by heating common salt NaCl with manganese (IV)
oxide MnO2 in the presence of concentrated H2SO4.
2NaCl(s) + MnO2(aq) + 2H2SO4(aq) → Na2SO4(aq) + MnSO4(aq) + 2H2O(l) + Cl2(g)
Ionically:
2Cl-(s) + Mn2+(aq) + 4H+(aq) → Mn2+(aq) + 2H2O(l) + Cl-

DIAGRAM ( Leave 6 – 8 lines)

 The apparatus set up has two wash bottles: the 1st contains water to dissolve fumes of HCl gas while
the 2nd contains conc. H2SO4 as a drying agent for chlorine gas. Dry chlorine gas is then collected
by the downward delivery method or upward displacement of air (being denser than air)

INDUSTRIAL PREPARATION OF CHLORINE

Chlorine is manufactured industrially by the electrolysis of brine and the chloride of molten sodium,
magnesium or calcium. The chlorine is then liquefied and stored under pressure in steel cylinders.

PHYSICAL PROPERTIES OF CHLORINE

1. Chlorine is a greenish – yellow gas with an unpleasant choking smell

2. It is moderately soluble in water
3. It is denser than air about 2.5 times.
4. It can be liquefied under a pressure of about 6 atmospheres.
5. It is poisonous as little quantity of it in the air can cause damage to the mucous lining the
lungs.

CHEMICAL PROPERTIES OF CHLORINE

1. Displacement of other halogen members

Chlorine can displace less reactive halogens from solutions of their acids or salts. An exception is
Fluorine which is above chlorine in the activity series.
Cl2(g) + 2NaBr(aq) → 2NaCl(aq) + Br2(l)
Cl2(g) + 2HI(aq) → HCl(aq) + I2(s)
2. Direct combination with metals and non – metals
(a) Direct combination of chlorine with metals Chlorine directly combines with metals when
heated to form metallic chloride. Where a metal forms more than one chloride, the higher
chloride is formed due to the strong oxidizing power of chlorine.

2Na(s) + Cl2(g) → 2NaCl(s)

Zn(s) + Cl2(g) → ZnCl2(s)
2Fe(s) + 3Cl2(g) → 2FeCl3(s)
(b) Direct combination of chlorine with non – metals
With the exception of noble gases, oxygen, nitrogen and carbon, all other non – metals burn in chlorine to
form non – metallic chloride.
Hydrogen and chlorine combine in the presence of bright sunlight, although the reaction is slow in diffused
light,
H2(g) + Cl2(g) → 2HCl(g)
2P(s) + 3Cl2(g) → 2PCl3(g)
2P(s) + 5Cl2(g) → 2PCl5(g)

3. Affinity of chlorine for hydrogen

Chlorine attracts chlorine from hydrocarbons, ammonia, hydrogen sulphide and water to form hydrogen
chloride.

a) A piece of filter paper soaked in turpentine (hydrocarbon, C 10H16) introduced into a container of
chlorine catches fire, forming soot (black carbon deposit) and misty fumes of hydrogen chloride.
C10H16(l) + 8Cl2(g) → 10C(s) + 16HCl(g)
 b) In the presence of ultraviolet ray of the bright sunlight, chlorine undergoes substitution reaction
with saturated hydrocarbon like methane to produce a chlorinated compound like chloromethane in
addition to hydrogen chloride.
CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g)
c) Chlorine removes hydrogen from ammonia resulting to the formation of hydrogen chloride while
the ammonia is oxidized to form nitrogen.
2NH3(g) + 3Cl2(g) → N2(g) + 6HCl(g). The hydrogen chloride combines with excess ammonia to
form dense white fumes of ammonium chloride.
HCl(g) + NH3(g) → NH4Cl(s).
d) When chlorine and hydrogen sulphide are mixed, a yellow deposite of sulphure and misty fumes of
hydrogen chloride are formed.
H2S(g) + Cl2(g) → 2HCl(g) + S(s)
e) Chlorine dissolves in water to form oxochorate (I) acid (known as chlorine water) and hydrochloric
acid. Cl2(g) + H2O(l) → HOCl(l) + HCl(aq)
The chlorine water decomposes in the presence of sunlight to liberate oxygen and form hydrogen
chloride.
HOCl(aq) → 2HCl(aq) + O2(g)

4. Reaction of chlorine as an oxidizing agent

Chlorine is a powerful oxidizing agent because of its ability to remove hydrogen and its readiness to accept
electrons from the reducing agent to form chloride ion, Cl -. Chlorine’s behavior as an oxidizing agent can
be shown when it reacts with iron (II) salts, trioxosulphate (IV) ion,

a) Reaction of chlorine as an oxidizing agent with iron (II) salts

Chlorine oxidizes a solution of green iron (II) chloride to yellow iron (III) chloride.
2FeCl2(aq) + Cl2(g) → 2FeCl3(aq)
Ionically:
2Fe2+(aq) + Cl2(g) → 2Fe3+(aq) + 2Cl-(aq)
b) Reaction of chlorine as an oxidizing agent with trioxosulphate (IV) ion,
When bubbled through a freshly prepared solution of trioxosulphate (IV) ion, acid, H 2SO3, chlorine
oxidizes the trioxosulphate (IV) ion, to traoxosulphate (VI) ion, .
H2SO3(aq) + H2O(l) + Cl2(g) → H2SO4(aq) + 2HCl(aq)
Ionically:

5. Reaction of chlorine as a bleaching agent

Chlorine is a common bleaching agent. It bleaches most dyes and ink in the presence of water, except those
containing carbon, e.g. printer’s ink. Chlorine reacts with water to form oxochlorate (I) acid which is
unstable, it decomposes to release oxygen that oxidizes the dye into a colourless compound.

HOCl(l) → HCl(aq) + [O]

Coloured dye + [O] → Colourless [Dye + O]

6. Reaction of chlorine with alkalis

a) Chlorine reacts with hot concentrated alkalis to form trioxochlorate (V), metallic chloride and
water.
3Cl2(g) + 6NaOH(aq) → NaClO3(aq) + 5NaCl(aq) + 3H2O(l)
 b) Chlorine reacts with cold concentrated alkalis to produce a pale yellowish mixture of the
oxochlorate (I), chloride of metal and water.
Cl2(g) + 2NaOH(aq) → NaOCl(aq) + NaCl(aq) + H2O(l)

Bleaching powder is produced by bubbling chlorine through freshly prepared solution of slaked
lime.
Cl2(g) + 2Ca(OH)2(aq) → Ca(OCl)2.H2O(s) [Bleaching powder].

TESTS FOR CHLORINE

Chlorine is a greenish – yellow gas with an irritating smell. Its presence can be confirmed as it:

a) Turns starch iodide paper blue as it displaces iodine from potassium iodide.
2KI(aq) + Cl2(g) → 2KCl(aq) + I2(s);
b) Turns damp blue litmus paper pink and then bleaches it.

USES OF CHLORINE

1. It is used as a germicide due to its powerful oxidizing nature and hence, it is used for the treatment
of water for domestic and industrial use and also in the treatment of sewages.
2. Chlorine is used as a bleaching agent for cotton, linen, and wood – pulp.
3. Chlorine is used in producing other chemical substances such as organic solvents like
trichloromethane, CHCl3, tetrachloromethane , conc. HCl etc.
4. Insecticide such as D.D.T is produced with chlorine.
5. Widely used plastic such as polychloroethene also called polyvinyl chloride (PVC) is manufactured
from chlorine and ethane.
6. Potassium trioxochlorate (V) used in making matches and fireworks is made with chlorine.
7. Sodium trioxochlorate (V), a herbicide is made from chlorine.
8. Bleaching agents such as bleaching powder and sodium oxochlorate (I) used in dye works and
laundries is made with chlorine.
9. Domestic antiseptics like acidified sodium oxochlorate (I) solution is a made with chlorine.

HYDROGEN CHLORIDE HCl

Hydrogen chloride exists as a gas at standard temperature and pressure. When it is dissolved in water, it
forms hydrochloric acid. Pure hydrogen chloride was first prepared in 1772 by Priestly who called it marine
acid gas as it was made from sea salt.

Hydrogen chloride occurs in traces in the air and as industrial by – product.

Laboratory preparation of hydrogen chloride HCl

Hydrogen chloride is prepared by the action of hot concentrated tetraoxosulphate (VI) acid on any soluble
chloride like sodium chloride. It is a displacement reaction , H2SO4 , a stronger acid displaces a weaker acid
HCl from its salt. Initially, NaHSO4 is formed at low temperature.

NaCl(s) + H2SO4(aq) → NaHSO4(aq) + HCl(g)

Later, at higher temperatures, the reaction goes to completion, forming sodium tetraoxosulphate (VI) and
more hydrogen chloride.

NaHSO4(aq) + NaCl(s) → Na2SO4(aq) + HCl(g)

The overall reaction equation can be represented as follow:

NaCl(s) + H2SO4(aq) → Na2SO4(aq) + HCl(g)

DIAGRAM ( Leave 6 – 8 lines)

HCl gas can be dried using conc. H2SO4 in a wash bottle and then collected by the downward delivery
method being denser than air.

PHYSICAL PROPERTIES OF HYDROGEN CHLORIDE

1. Pure hydrogen chloride is a colourless gas with a sharp, irritating smell.

2. It turns damp blue litmus paper red
3. It is denser than air
4. It is very soluble in water, forming an aqueous solution of hydrochloric acid ( it is useful in the
fountain experiment)
5. It forms misty fumes in moist air as it dissolves in the moisture to form tiny droplets of hydrochloric
acid.
6. Dry hydrogen chloride readily dissolves in non – polar solvents like chloroform and toluene due to
its covalent molecular nature. It also ionizes in water to form chloride ion and oxonium ion.
7. Hydrogen chloride neither burns nor supports combustion and hence, it extinguishes a burning
splinter.

Chemical properties of Hydrogen Chloride \ Hydrochloric acid HCl

1. Direct combination of hydrogen chloride with ammonia

When a gas jar of hydrogen chloride is inverted into the gas jar of ammonia, a dense white fumes of
ammonium chloride are formed. HCl(g) + NH3(g) → NH4Cl

2. Reaction of hydrogen chloride as an acid

Hydrogen chloride dissolves in water to form aqueous solution of hydrochloric acid which exhibit
the three primary chemical properties of acids such as:
a) Reaction with reactive metals to liberate H2 gas
b) Reaction with base / alkalis to form salt and water only.
c) Reaction with trioxocarbonate (IV) salts CO32- to liberate CO2 gas
a. Reaction of hydrochloric acid with reactive metals
Zn(s) + 2HCl(g) → ZnCl2(s) + H2(g)
Fe(s) + HCl(g) → FeCl2(s) + H2(g).
b. Reaction of hydrochloric acid with bases/alkalis [neutralization]
HCl(aq) + ZnO(s) → ZnCl2(aq) + H2O(l).
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
c. Reaction of hydrochloric acid with trioxocarbonate (iv) and hydrogen
trioxocarbonate (iv) to liberate CO2 gas
2HCl(aq) + K2CO3(s) → 2KCl(aq) + CO2(g) + H2O(l)
HCl(aq) + KHCO3(s) → KCl(aq) + CO2(g) + H2O(l)
3. Action of heat on hydrochloric acid

When concentrated hydrochloric acid is heated, it boils to liberate hydrogen chloride fumes, making
the solution more dilute. When dilute hydrochloric acid is heated, water is lost, making the residual
solution more concentrated. In both cases, the solutions will boil until they contain about 20.24%
 hydrochloric acid. This solution is known as a constant boiling mixture or an azeotropic mixture
because any further heating will not affect its concentration.

4. Reaction of hydrochloric acid as a precipitating agent

When hydrochloric acid is added to Silver trioxonitrate (V) or lead (II) trioxonitrate (V) solution, a
white precipitate of silver or Lead (II) chloride is formed.
AgNO3(aq) + HCl(aq) → AgCl(s) + HNO3(aq).
Pb(NO3)2(aq) + 2HCl(aq) → PbCl2(s) + 2HNO3(aq)
5. Reaction of hydrochloric acid with strong oxidizing agent
Concentrated hydrochloric acid is easily oxidized by strong oxidizing agents like potassium
tetraoxomanganate (VI) to liberate chlorine gas.

Tests for hydrogen chloride

I. Hydrogen chloride is a colourless gas with an irritating smell, fumes in moist air and turns
damp blue litmus paper red.
II. If a glass rod dipped in ammonia solution is placed at the mouth of gas jar containing the
unknown gas, the appearance of dense white fumes of ammonium chloride confirms that
the unknown gas is hydrogen chloride.
HCl(g) + NH3(l) → NH4Cl(aq)
III. If a few drop of silver trioxonitrate (V) or lead (II) trioxonitrate (V) solution is added to a
gas jar containing hydrogen chloride and shake, the appearance of a white precipitate of
silver chloride or lead (II) chloride confirms the unknown gas to be hydrogen chloride.

Uses of hydrogen chloride

1. It is used in synthesis of chloro - ethane used in making plastic.

2. It is used in making gelatin and glue from the tendons of animals and in production of glucose from
starch.
3. It is also used in making textiles and dyes.
4. It is used in removing oxides from metals prior to electroplating. This process known as picking is
useful in steel industry.
5. It is used in testing, analysis and preparation of other chemicals in the laboratory.

CHLORIDES
Chlorides are normal salts formed when metallic ions replace the hydrogen ions in hydrochloric acid.
Chlorides are soluble in water, except: CuCl,, Hg2Cl2 and AgCl.
Lead (II) chloride, PbCl2, is insoluble in cold water but dissolves gradually when warmed.
TEST FOR SOLUBLE CHLORIDES
Acidify the test solution with excess dilute trioxonitrate (V) acid (to prevent the precipitation of other salts)
and then add a few drops of silver trioxonitrate (V). A white precipitate of silver chloride, which dissolves
in aqueous ammonia indicates the presence of a chloride ion Cl -
Ag+(aq) + Cl-(aq) → AgCl(s) +

NITROGEN AND ITS COMPOUNDS

NITROGEN GAS N2
Nitrogen occurs chiefly as a free element in the air, making up about 78% by volume of the atmosphere.
Free nitrogen in the air is important because it dilutes the oxygen to the point where combustion,
respiration and oxidation of metals are reasonably slow. In the combined form, nitrogen occurs abundantly
in the earth’s crust as trioxonitrate (V) of sodium, calcium and ammonium. Combined nitrogen is also
found in organic matter such as proteins, urea and the vitamin B compounds.
Laboratory preparation of nitrogen gas N2
 I. From air - Since nitrogen makes up a large percentage of air, it can be obtained from free air by
removing the other constituents such as carbon (IV) oxide and oxygen CO 2 and O2 gas can be
removed by passing air through caustic soda and heated copper turnings respectively.
2NaOH + CO2 → Na2CO3 + H2O
2Cu + O2 → 2CuO
However, the nitrogen obtained in this way contains about 1% by volume of rare gases and
impurities and so, it is denser than a pure nitrogen gas.
II. Thermal decomposition of ammonium dioxonitrate (iii)
Pure nitrogen is usually obtained by the thermal decomposition of ammonium dioxonitrate (III), NH 4NO2.
The dioxonitrate (III), however, is not heated directly as the reaction may get out of control and explosion
may occur. This is because ammonium dioxonitrate (III) is unstable and decomposes exothermically. A
mixture of sodium dioxonitrate (III) and ammonium chloride in the ratio 7:5 is heated to yield ammonium
dioxonitrate (III) which in turn decomposes to produce nitrogen and steam.
a) NaNO2(aq) + NH4Cl(aq) → NH4NO2(aq) + NaCl(aq).
b) NH4NO2(aq) → N2(g) + 2H2O(l)

DIAGRAM ( Leave 6 – 8 lines)

Nitrogen gas is collected over water as it is slightly lighter than air.

Industrial preparation of nitrogen

Industrially, nitrogen is prepared by fractional distillation of liquid air. Air, from which carbon (IV) oxide
has been removed, is liquefied by subjecting it to successive compression and cooling processes. Upon
distillation, nitrogen gas is evolved first at (at s.p) and is separated from oxygen which boils at (at s.p).
Nitrogen is stored in steel cylinder and sold as liquid nitrogen or as the compressed gas.

Physical properties of nitrogen gas

1. Nitrogen is a colourless, odourless and tasteless gas.
2. Pure nitrogen is slightly lighter than air.
3. It is only slightly soluble in water.
4. The melting point of nitrogen is and its boiling point is
Note: The low temperature melting and boiling points of nitrogen is due to the presence of van der
Waal’s force that exist between the nitrogen molecules in the solid and liquid states.
Chemical properties of nitrogen gas
Nitrogen gas occur as a diatomic molecule with triple covalent bonds between its atoms. This accounts for
the unreactive nature of nitrogen gas at ordinary temperature. However at high temp and pressure, nitrogen
readily reacts with metals and non-metals.
1. Reaction of nitrogen with metals: Nitrogen combines directly with very electropositive metals
like magnesium, calcium, aluminium and iron to form nitrides on heating
3Mg(s) + N2(g) → Mg3N2(s) ( it hydrolyzed in water to form ammonia)
Mg3N2(s) + 6H2O(l) → 3Mg(OH)2(s) + 2NH3(g)
2Al + 3N2 → 2AlN
2. Reaction of nitrogen with non – metals:
a) Nitrogen combines reversibly with hydrogen to produce ammonia.
N2(g) + 3H2(g) 2NH3(g)
b) It combines directly with oxygen at a very high temperature of about or in the presence of a
high voltage electric spark to form small amount of nitrogen (II) oxide. In nature, this
reaction occurs in the atmosphere when lightning flashes. N2(g) + O2(g) → 2NO(g)

Uses of nitrogen
1. Nitrogen is used in the industrial manufacture of ammonia, cyanide and carbamide (an important
fertilizer)
2. Liquid fertilizer is used as cooling agent.
3. Due to its inert nature, nitrogen is used:
i) As a carrier gas in gas chromatography;
 ii) In providing an inert atmosphere for certain industrial process involving easily oxidizable
chemicals, e.g. in making electric components such as transistors and in the annealing of
metals
iii) As a preservative to prevent rancidity (due to oxidation of fats) in packaged foods.

AMMONIA GAS NH3

Ammonia is a hydride of nitrogen. It is a very important chemical in industry. In nature, ammonia is
produced when nitrogenous matter decays in the absence of air. The decomposition may be brought about
by heat or putrefying bacteria. As a result, small traces of ammonia may be present in the air. However,
because of its great solubility in water, it rapidly dissolves in rain water and finds its way into the soil
where it may be converted into other compounds.

Laboratory preparation of ammonia gas

In the laboratory, ammonia is prepared by heating any ammonium salt with non – volatile base. Usually,
ammonium chloride and calcium hydroxide (slaked lime) are used. Calcium hydroxide is chosen because it
is cheaper and not deliquescent like caustic soda NaOH.

Since both the reactants are solids, they should be thoroughly ground to provide the maximum surface area
for reaction.
Ca(OH)2(g) + 2NH4Cl(s) → CaCl2(s) + 2H2O(l) + 2NH3(g)
The usual drying agents such as concentrated tetraoxosulphate (VI) acid and fused calcium chloride cannot
be used to dry ammonia since they react with ammonia. The drying agent is quicklime. Ammonia is
collected by upward delivery after passing it through quick lime . The reacting particles of ammonium
chloride and slacked lime are grounded and placed in a round bottom conical flask. The flask is usually
bent to prevent water formed from sucking back so that it would not cause crack to the flask.

DIAGRAM ( Leave 6 – 8 lines)

Industrial preparation of ammonia gas

Ammonia is manufactured from nitrogen and hydrogen by the Haber process. Since the direct combination
between nitrogen and hydrogen is reversible, special conditions of reaction are necessary for the optimum
yield of ammonia. Basically, the process involves mixing nitrogen and hydrogen in the volume ratio of 1:3
and passing the mixture over finely divided iron catalyst at the temperature of about and a pressure of
about 200 atmosphere.
The yield of ammonia is about 1.5% under the above condition of temperature, pressure and suitable
catalyst. The ammonia gas is thereafter liquefied by cooling and the unused gases are recirculated over the
catalyst for further production of ammonia.
N2(g) + 3H2(g) 2NH3(g) + Heat

Physical properties of ammonia

1. Ammonia is a colourless gas with a characteristic chocking/pungent smell.
2. In large quantity, ammonia is poisonous because of its effect on respiratory muscles.
3. It is an alkaline gas as it turns moist red litmus paper blue.
4. It is less denser than air.
5. It liquefy at . and boils at which is relatively high due to the presence of hydrogen bond connecting
several ammonia molecules.
6. Ammonia is a very soluble gas and this is due to its readiness to form hydrogen bond with water
molecules and form aqueous ammonia, NH3.H2O.
7. Aqueous ammonia ionizes slightly to produce ammonium, and hydroxide, OH- ion.
8. On warming, aqueous ammonia decomposes readily to liberate ammonia gas.

Chemical properties of ammonia gas

 1. Reaction of ammonia with oxygen: Ammonia does not burn in air, but readily burns in oxygen
with a greenish – yellow flame to form water vapour and nitrogen. 4NH 3(g) + 3O2(g) → 6H2O(g) +
N2(g)
2. Ammonia as a reducing agent: Ammonia reacts as a reducing agent:

a) Reaction of ammonia as a reducing agent with copper (ii) oxide: Ammonia is not a
strong reducing agent. However, it reduces heated copper (II) oxide to copper while itself is
oxidized to water and nitrogen.
3CuO + 2NH3(g) → 3Cu(s) + 3H2O(l) + N2(g)
b) Reaction of ammonia as a reducing agent with chlorine: In excess, ammonia first
reduces chlorine to produce hydrogen chloride and nitrogen after which the hydrogen
chloride reacts with the excess ammonia to produce dense white fumes of ammonium
chloride.
2NH3(g) + 3Cl2(g) → 3HCl(g) + N2(g)
6NH3(g) + 6HCl(g) → 6NH4Cl(s)
3. Reaction of ammonia with carbon (iv) oxide
Ammonia reacts with carbon (IV) oxide at and high pressure of 150 atmosphere to produce urea, an
important organic compound in urine.
2NH3(g) + CO2(g) → (NH2)2CO(s) + H2O(l)
4. Reaction of ammonia as a base: Ammonia reacts with an acid to form ammonium salt.
NH3(g) + H2SO4(aq) → (NH4)2SO2(s)
5. REaction of ammonia as a precipitating agents: Aqueous ammonia precipitates the insoluble
hydroxides of metals from solutions of their salts.
a) Pb2+(aq) + 2NH3(aq) + 2H2O(l) → Pb(OH)2(s) [White precipitate]
b) Zn2+(aq) + 2NH3(aq) + 2H2O(l) → Zn(OH)2(s) [White precipitate]
c) Fe3+(aq) + 3NH3(aq) + 2H2O(l) → Fe(OH)3(s) [Reddish - brown precipitate]
d) Cu2+(aq) + 3NH3(aq) + 2H2O(l) → Cu(OH)2(s) [Blue precipitate]
Some metallic hydroxides like copper (II) and zinc hydroxide will dissolve in excess ammonia solution to
form complex ions.
Zn(OH)2(aq) + 4NH3(aq) → 2OH-(aq) + (aq) [Colourless]
Cu(OH)2(aq) + 4NH3(aq) → 2OH-(aq) + (aq) [Dark blue]

Tests for Ammonia

a) Ammonia is a colourless gas with choking smell
b) Hold a damp red litmus paper into the jar containing an unknown gas, if the gas is ammonia, it turns
damp red litmus paper blue.
c) Dip a glass rod in concentrated hydrochloric acid and then insert it in the gas jar containing the
unknown gas. White fumes of ammonium chloride are formed.
Uses of Ammonia
1. Aqueous ammonia is used in softening temporarily hard water.
2. Aqueous ammonia is used in laundries as a solvent for removing grease and oil stains.
3. Liquid ammonia is used as a refrigerant.
4. Ammonia is used in the manufacture of HNO3 and Na2CO3 by solvay process.
5. It is used in making fertilizers.

AMMONIUM SALTS NH4+

Ammonium salts are electrovalent compounds which contain ammonium ion, as the cation. They are
mostly prepared by dissolving ammonia or aqueous ammonia in the appropriate acid. The ammonium salt
is then separated by crystallization and not by evaporation as they easily decompose by dry heating.
NH3(g) + HCl(aq) → NH.4Cl(aq).
Properties of ammonium salts
1. All common ammonium salts are white crystalline solids which are soluble in water.
2. They are strong electrolytes as they ionize completely in water.
3. Ammonium chloride sublimes when heated and it dissociates to form ammonia and hydrogen
chloride which recombine on cooling. NH.4Cl(s) NH3(g) + HCl(g)
4. Ammonium tetraoxosulphate (VI) decomposes on heating to liberate ammonia and tetraoxosulphate
(VI) acid. (NH4)2SO4(s) → 2NH3(g) + H2SO4(aq)
 5. Ammonium dioxonitrate (III) decomposes on heating to produce nitrogen and water. NH 4NO2(s) →
N2(g) + 2H2O(l).
6. Ammonium trioxonitrate (V) decomposes on heating to nitrogen (I) oxide and water. NH 4NO3(s) →
N2O(g) + 2H2O(l)
7. Ammonium trioxocarbonate (IV) is an unstable compound. It decomposes very readily to yield
ammonia, carbon (IV) oxide and water. (NH4)2CO3(s) → 2NH3(g) + CO2(g) + H2O(l).
8. All ammonium salts liberate ammonia when heated with bases or alkalis. (s) + OH-(aq) → NH3(g) +
H2O(l).
Test for ammonium salts
Heat some of the unknown salt with sodium hydroxide solution. If the salt is an ammonium salt, a
colourless gas with pungent smell which turns red litmus paper red evolves. The gas is ammonia from
ammonium ion.

NITROGEN (I) OXIDE N2O

Nitrogen (I) is the first oxide of nitrogen identified and it was discovered by Priestley. It is known as
laughing gas as it causes uncontrollable fits of laughter when inhaled.
Laboratory preparation of nitrogen (i) oxide
Nitrogen (I) oxide is liberated by the thermal decomposition of ammonium trioxonitrate (V).The direct
heating is dangerous as the reaction, which is endothermic, may become uncontrollable and explosive. The
gas is therefore prepared by heating any mixture of salts which will yield ammonium trioxonitrate (V).
Usually, a finely ground mixture of potassium trioxonitrate (V) and ammonium chloride is uded. It is
gently heated and the nitrogen (I) oxide gas formed is collected over warm water as the gas is fairly soluble
in cold water.
KNO3(s) + NH4Cl(s) → KCl(s) + NH4NO3(s)
NH4NO3(s) → 2H2O(g) + N2O(g)
Physical properties of nitrogen (i) oxide
1. It is a colourless gas with a faint, pleasant but sticky smell and a sweetish taste.
2. It is fairly soluble in cold water.
3. It is 1.5 times denser than air.
4. It is neutral to litmus paper.
Chemical properties of nitrogen (i) oxide
1. Action of heat: Nitrogen (I) oxide does not burn in air. It decomposes rapidly at red heat () into its
component elements, nitrogen and oxygen. It rekindles a brightly glowing splinter but extinguishes
a feebly glowing one which is not hot enough to decompose the gas to liberate oxygen. 2N 2O(g) →
2N2(g) + O2(g).
nitrogen (I) oxide supports the combustion of substances which is hot enough to decompose it to
yield nitrogen. S(s) + 2N2O(g) → SO2(g) + N2(g);
Mg(s) + N2O(g) → MgO(g) + N2(g).
2. Reduction by heated metals: Nitrogen (I) oxide is reduced to nitrogen when it passes over heated
copper or iron. Cu(s) + N2O(g) → N2(g) + CuO(s).
TEST FOR NITROGEN (I) OXIDE
Insert a brightly glowing splinter into a test tube containing the unknown gas. If the splinter is rekindled,
the gas is either nitrogen (I) oxide or oxygen. Nitrogen (I) oxide rekindles a brightly glowing splinter and
then releases reddish – brown fumes of nitrogen (IV).

Uses of nitrogen (i) oxide

1. Nitrogen (I) oxide is used as mild anaesthetic for minor surgical operations
2. Nitrogen (I) oxide is usually administered with about 20% oxygen, which is required to keep the
patient alive and some traces of carbon (IV) oxide, which is required to maintain breathing.

NITROGEN (II) OXIDE NO

Nitrogen (II) oxide, NO. was discovered by Cavendish in 1770 as one of the products formed on passing an
electric spark through air. It is always difficult to obtain the gas in the pure state because of its great affinity
for oxygen. It readily reacts with oxygen even at ordinary conditions to form nitrogen (IV) oxide.
Laboratory preparation of nitrogen (ii) oxide
Nitrogen (II) oxide can be prepared by the action of trioxonitrate (V) acid on most metals. Usually, 50%
acid solution and copper turnings are used.
3Cu(s) + 8HNO3(aq) → 3Cu(NO3)2(aq) + 4H2O(l) + 2NO(g).

The gas is collected over water.

Physical properties of nitrogen (ii) oxide

1. Nitrogen (II) oxide is a colourless, poisonous gas.
2. It is almost insoluble in water.
3. It is slightly denser than air.
4. It is neutral to litmus paper.
Chemical properties of nitrogen (ii) oxide
1. Reaction with oxygen: Nitrogen (II) oxide combines readily with oxygen at room temperature to
yield brown fumes of nitrogen (IV) oxide. 2NO(g) + O2(g) → 2NO2(g).
2. Action of heat on nitrogen (ii) oxide: Nitrogen (II) oxide decomposes into equal volumes of
nitrogen and oxygen only at high temperature of about 2NO(g) → N 2(g) + O2(g). It only supports
the combustion of strongly burning substances. For example, burning phosphorus, lead and
magnesium will continue to burin in nitrogen (II) oxide, forming nitrogen and their oxides but a
burning splinter and burning sulphur will be extinguished by the gas. 2Mg(s) + 2NO(g) →
2MgO(s) + N2(g).
3. Reduction by hot metals: Nitrogen (II) oxide reacts with heated metals, which reduce it to
nitrogen. 2Cu(g) + 2NO(g) → 2MgO(s) + N2(g).
4. Reaction as a reducing: It is a weak reducing agent. Thus, it decolourizes acidified potassium
tetraoxomanganate (VII) very slowly. .

Tests for nitrogen (ii) oxide

a) On exposure to air: Remove the stopper of the test – tube containing the unknown gas. If the gas
turns reddish – brown on exposure to air, then it is probably nitrogen (II) oxide.
b) With iron (II) tetraoxosulphate (VI): Pour a solution of iron (II) tetraoxosulphate (VI) which has
acidified with a little dilute tetraoxosulphate (VI) acid, into a test – tube containing the unknown
gas. If the solution turns dark brown, then the gas is nitrogen (II) oxide. This is due to the formation
of dark brown addition compound. FeSO4(aq) + NO(g) FeSO4.NO(aq).

MID – TERM TEST

NITROGEN (IV) OXIDE NO2,

Nitrogen (IV) oxide, NO2, is the reddish – brown gas given off when the trioxonitrate (V) of heavy metals
are heated.
Laboratory preparation of NO2,
The trioxonitrate (V) of heavy metals decompose on heating to yield nitrogen (IV) oxide as one of the
products. The most suitable trioxonitrate (V) for the preparation of nitrogen (IV) oxide is lead (II)
trioxonitrate (V) because its crystals do not contain water of crystallization which would interfere with the
preparation. The gases formed are passed through a u – tube immersed in a freezing mixture. The nitrogen
(IV) oxide becomes liquefied in the u – tube as a green liquid (yellow if pure), while oxygen escapes as a
gas. The residue of lead (II) oxide left behind in the boiling tube is reddish – brown when hot, but turns
yellow on cooling.
2Pb(NO3)2(s) → 2PbO(s) + O2(g) + 4NO2(g) .

DIAGRAM ( Leave 6 – 8 lines)

Physical properties of NO2 gas

 1. Nitrogen (IV) oxide is a reddish – brown gas.
2. It has an irritating smell and it is poisonous.
3. It turns damp blue litmus paper red and dissolves in water to form acidic solution.
4. It is easily liquefied into a yellow liquid at .
5. It is much heavier than air and can be poured downwardly.

Chemical properties of NO2 gas

1. Action of heat on NO2 gas : Nitrogen (IV) oxide can exist in two molecular forms. At low
temperature, it exists mainly as pale yellow dinitrogen (IV) oxide, N2O4 and at high temperature as
the reddish – brown nitrogen (IV) oxide, NO2. Further heating to temperature above , the
dissociation results to the formation of colourless nitrogen (II) oxide. On cooling, the reverse of the
process occurs.
N2O4(g) 2NO2(g) + O2(g)
Nitrogen (IV) oxide does not burn in air like other two oxides of nitrogen, but it supports the
combustion of any burning substance which is hot enough to decompose it into oxygen and
nitrogen. 2NO2 → N2(g) + O2(g). It does not rekindle a glowing splinter but will allow a vigorous
burning splinter or burning sulphur, carbon, Phosphorus or magnesium to continue to burn in it.
2C(s) + 2NO2(g) → 2CO2(g) + N2(g) and
4Mg(s) + 2NO2(g) → 4MgO(g) + N2(g).
2. Reduction of nitrogen (iv) oxide by reducing agents: Like the other two oxides of nitrogen,
nitrogen (IV) oxide is reduced to nitrogen by heated copper or iron.
4Cu(s) + 2NO2(g) → 4CuO(s) + N2(g). It is also reduced to nitrogen (II) oxide by hydrogen
sulphide and carbon (II) oxide. H2S(g) + NO2(g) → H2O(l) + NO(g) + S(s) and CO(g) + NO 2(g) →
CO2(g) + NO(g)

3. Reaction of nitrogen (iv) oxide with water: Nitrogen (IV) oxide dissolves in water to form a
mixture of dioxonitrate (III) acid and trioxonitrate (V) acid (Mixed acid anhydride). 2NO 2(g) +
H2O(l) → HNO3(aq) + HNO2(aq). The dioxonitrate (III) acid decomposes at room temperature to
form nitrogen (II) oxide and more trioxonitrate (V) acid.
4. Reaction of nitrogen (iv) oxide with alkalis: Nitrogen (IV) oxide reacts with alkalis to yield a
corresponding mixture of dioxonitrate (III) acid and trioxonitrate (V) salts. 2KOH(aq) + 2NO 2(g) →
KNO3(aq) + KNO2(aq) + H2O(l).
TRIOXONITRATE (V) ACID HNO3
Trioxonitrate (V) acid, HNO3, was first prepared by Glauber, in 1658, from tetraoxosulphate (VI) acid and
potassium trioxonitrate (V). The early alchemists used the acid for separating gold from silver. Due to its
corrosive action on many metals, it was previously known as aqua fortis, meaning strong water.
Laboratory preparation of trioxonitrate (v) acid
Trioxonitrate (V) acid can be displaced from any trioxonitrate (V) by concentrated tetraoxosulphate (V)
acid which is a less volatile but stronger acid.
KNO3(s) + H2SO4(aq) → KHSO4(aq) + HNO3(g).
The reacting substances are strongly heated in a retort flask in a sand bath. Trioxonitrate (V) acid fumes
produced, which distils over and is collected in a receiving flask which is cooled under a running tap where
it cools and condenses as a yellow liquid (it is colourless when pure). An all glass apparatus are used to
avoid the attack of non – glass apparatus by hytdrogen tetraoxosulphate (VI) formed.

DIAGRAM ( Leave 6 – 8 lines)

Industrial preparation of trioxonitrate (v) acid HNO3

Trioxonitrate (IV) acid is prepared in the industry by the catalytic oxidation of ammonia. The ammonia
reacts with excess air, in the presence of platinum – Rhodium catalyst at , to produce nitrogen (II) oxide
and steam. 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g). The reaction is exothermic. Once started, the heat
released maintains the catalyst at the required temperature. The nitrogen (II) oxide formed is cooled and
mixed with excess air to produce nitrogen (IV) oxide. 2NO(g) + O 2(g) → 2NO2(g). In the presence of more
air, the nitrogen (IV) oxide is then dissolved in a spray of hot water to yield a trioxonitrate (V) acid solution
of up to 50% centration. In modern plants, nitrogen (IV) oxide is absorbed to obtain more concentrated
solution of the acid.

Physical properties of trioxonitrate (v) HNO3

1. Trioxonitrate (V) acid is a fuming liquid with a sharp chocking smell. Although it is colourless
when pure but it turns yellow after a while due to the decomposition of some of the acid to yield
nitrogen (IV) oxide.
2. The density of the pure acid is 1.5g cm-3.
3. Pure trioxonitrate (V) acid is miscible with water in all proportions and forms a certain boiling
mixture with it at . This mixture containing about 68% of the acid is the ordinary concentrated
trioxonitrate (V) acid found in the laboratory. 98% trioxonitrate (V) acid is called fuming
trioxonitrate (V) acid.
4. The pure acid is very corrosive.
5. The dilute acid turns blue litmus paper red.

Chemical properties of trioxonitrate (v) acid

1. As an acid: Trioxonitrate (V) acid undergoes the following acidic properties chemically:
a. Reaction with base or alkali (Neutralization reaction)
HNO3 + NaOH NaNO3 + H2O
b. Reaction with trioxocarconate (IV) to liberate CO2 gas
HNO3 + CaCO3 Ca(NO3)2 + H2O + CO2
c. Reaction with electropositive metals to liberate H2 gas – very dilute cold HNO3 react with
Magnesium to liberate hydrogen gas. With other metals however, the hydrogen produced is
further oxidized to water
Mg + 2HNO3 Mg(NO3)2 + H2

2. As an oxidizing agent:
(a) Trioxonitraye (v) acid is a strong oxidizing agent and the oxidizing power of trioxonitrate
(v) acid depends on its concentration. In concentrated form, it oxidizes certain metal to
trioxonitrate (v) while the acid is reduced to nitrogen (iv) oxide and in moderately
concentrated form it is reduced to nitrogen (ii) oxide.
Cu + 4HNO3 Cu(NO3)2 + 2H2O + 2NO2 ( moderately conc. Acid)
3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO ( with conc. Acid)
Lead, mercury and silver react in similar way to copper with the metal
Magnesium, zinc and iron only react with dilute trioxonitrate (v) acid .
(b) With non-metals: Hot concentrated tetraoxosulphate (vi) acid oxidizes non-metals to their
oxides, which may dissolve in water to for the corresponding acids.
C + 4HNO3 CO2 + 2H2O + 4NO2
S + 6HNO3 H2SO4 + 2H2O + 6NO2
 P + 5HNO3 H3PO4 + H2O + 5NO2
3. Decomposition - HNO3 decomposes slowly at room temp when expose to sunlight and rapidly
when heated to yield reddish – brown NO2
4HNO3 2H2O + 4NO2 + O2
Uses of trioxonitrate (v) acid
1. It is an important raw material for the manufacture of many useful trioxonitrate (v) salts and
organic nitro-compounds such as those used for making dyes. Explosives, fertilizers and drugs.
2. It is used for making of nylon and terylene.
3. It is useful oxidizing agent for many purposes in the laboratory.

SULPHUR AND ITS COMPOUNDS

Sulphur has been known for its medical value and its germicidal effect since 1000 B.C. However, its
chemical nature remained unknown until 1787 when Lavoisier recognized it as an element.
Sulphur makes up about 0.1% of the earth’s crust. It occurs freely as deposits in U.S.A., Poland, Japan,
New Zealand and Sicily. It is also found in combined state as sulphides and as the tetraoxosulphate (VI).
Sulphur is also present in some proteins.
Extraction of sulphur

Sulphur is mostly extracted from underground deposits which may be more than 200 m below the surface
of earth. Extraction of sulphur from these deposits is based on the Frasch process. A hole of about 30 cm in
diameter is drilled through the soil layers to the sulphur bed. A sulphur pump made up of three concentric
steel pipes is then driven down the hole. Super – heated water at about and 10 atm pressure is forced
through the outermost tube to the sulphure bed to melt the sulphur whose melting point is . Hot compressed
air at a pressure of 15 atm is then blown down the innermost tube to force the molten up through the middle
tube. The moulten sulphur is continuously pumped into a receptacle at the surface where it is allowed to
solidify in large tanks. The sulphur obtained is about 99.5% pure.

Allotropes of sulphur

The main allotropes of sulphur are:

i. Rhombic sulphur ()
ii. Monoclinic or prismatic sulphur () and
iii. Amorphous sulphur ().

Rhombic sulphur

Free sulphur exists as rhombic sulphur in nature stable at temperature below . Crystals of rhombic sulphur
are bright yellow and octahedral. They are made up of S 8 molecule consists of a ring of eight atoms. The
melting point and the density of rhombic sulphur respectively is and .

Rhombic sulphur is prepared by allowing a saturated solution of sulphur in carbon (IV) sulphide to
evaporate slowly. Octahedral crystals will gradually be deposited.

Monoclinic sulphur
Monoclinic sulphur is the only stable sulphur allotrope at temperatures between and . Its melting point and
density respectively is and The colour of monoclinic sulphur is amber The crystals are long, thin and
needle – shaped and consists of S8 molecules. At room temperature, they slowly revert to rhombic sulphur
crystals.

Monoclinic sulphur is less dense than rhombic sulphur. This is because S8 molecules are more tightly
packed in rhombic sulphur than monoclinic sulphur.

Monoclinic sulphur is obtained by cooling molten sulphur after heating to a high temperature.

The temperature of at which Rhombic sulphure and Mononclinic sulphur change to each other’s allotropic
form is known transition temperature.
Amorphus sulphur
Amorphus sulphur has no regular crystalline shape. It is prepared as a pale yellow, almost white deposit
when hydrogen sulphide is bubbled through water for a long time and the saturated solution is exposed to
air. H2S(g) + O2(g) → 2H2O(l) + 2S(s). It is also deposited by the action of dilute hydrochloric acid on a
trioxothiosulphate (VI) solution. NaS2O3(aq) + 2HCl(aq) → H2O(l) + SO2(g) + Cl2(g) + S(s).
Plastic sulphur
Plastic sulphur is a super – cooled form of sulphur. If yellow sulphur is heated and poured into cold water,
it will roll up into yellow ribbon which looks like a plastic material. It is soft and elastic and will never
dissolve in carbon (IV) sulphide. Plastic sulphur is generally not considered as a true allotrope of sulphur
because it is unstable and reverts to rhombic sulphur on standing.
Physical properties of sulphur
1. Sulphur is a yellow solid. It exists in two forms – amorphous and crystalline.
2. It is insoluble in water but dissolves in carbon (IV) sulphide and methyl benzene (Toluene).
3. Sulphur is not a good conductor of heat and electricity, being a non – metal.
4. Sulphur’s density depends on its allotropic form.
5. It has a melting point of and a boiling point of .
Action of heat on sulphur
The crystalline structure of sulphur exists as S8 molecules , when heated in a limited supply of air, it melts
at the temperature between into an amber – coloured liquid. The colour darkens as the temperature
increases. At about , the liquid becomes very dark and starts to turn viscous, reaching its maximum
viscosity at . On further heating, it begins to flow again and boils to give off a light brown sulphur vapour
at its boiling point of . When this vapour is condensed on a cold surface, a fine powder, which forms a
floral pattern is obtained.

Chemical properties of sulphur

1. Direct combination of sulphur with other elements - Sulphur directly combines with metals and non –
metals.
a. Direct combination of sulphur with metals - When heated, sulphur combines with metals to
form sulphides. Reactive metals like sodium and potassium readily combine with sulphure without
heating, provided the metals and the sulphur are both in finely divided form.
Fe(s) + S(s) →FeS(s).
b. Direct combination of sulphur with non – metals - Sulphur readily reacts with non – metals like
oxygen, hydrogen, carbon, phosphorus, chlorine and fluorine.
With oxygen - When sulphur is heated in a plentiful supply of air, it burns with a bright blue flame
to form sulphur (IV) oxide and small amount of sulphur (VI) oxide. S(s) + O 2(g) → SO2(g).
With hydrogen - At high temperature, sulphur combines slowly with hydrogen to form hydrogen
sulphide. The reaction is more rapid, if hydrogen is bubbled through boiling sulphur. H 2(g) + S(s)
→ H2S(g).
 With carbon - Sulphur combines with coke in an electric furnace to form a colourless liquid
known as carbon (IV) sulphide, which vapourizes readily, forming poisonous and highly
flammable fumes. C(s) + S(s) → CS2(l).
2. Action of oxidizing acids on sulphur - Sulphur is readily oxidized when warmed with concentrated
tetraoxosulphate (VI) acid to form sulphur (IV) oxide. The acid itself is reduced to sulphur (IV) oxide.

2H2SO4(aq) + S(s) → 2H2O(l) + 3SO2(g)

When warmed with concentrated trioxonitrate (V) acid, using bromine as a catalyst, sulphur is oxidized
to tetraoxosulphate (IV) acid. 6HNO3(aq) + S(s) → 2H2SO4(aq) + 6NO2(g) + 2H2O(l).

Uses of sulphur

1. Sulphur is used to produce sulphur (IV) oxide for the manufacture of tetraoxosulphate (VI) acid through
contact process.
2. Sulphur is used in the vulganization of rubber.
3. Sulphur and some of its products are used as fungicides and insecticides for spraying crops.
4. Sulphur is used manufacture the bleaching agent used in the pulp and paper industry. It is also used for the
production of carbon (IV) sulphide, skin ointments and dyes and as sulphides in manufacturing matches,
fireworks and gun powder.

HYDROGEN SULPHIDE GAS ( H2S)

Hydrogen sulphide is a colourless acid gas with rotten egg smell. It is found in volcanic gases, suphur spring, coal
gas and gases found during decay of organic matter containing sulphur.

Laboratory Preparation of hydrogen sulphide

Hydrogen sulphide is prepared both in the laboratory and industrially by the action of dilute acid on metallic sulphide
like iron (II) sulphide.
2HCl(aq) + FeS(s) → FeCl2(aq) + H2S(g).
H2SO4(aq) + FeS(s) → FeSO4(aq) + H2S(g).
The gas is easily liquefied and may be purchased in this form in steel cylinders.

KIPP’S APPARATUS

Kipp’s apparatus allows a gas to be supplied anytime it is required i.e for intermittent gas supply. The apparatus
consists of three chambers, A, B and C. The solid reagent is packed in B while A and C contain the liquid reagent.
The apparatus is used to produce frequently used gases like hydrogen sulphide and carbon (IV) oxide.

Physical properties of hydrogen sulphide

1. Hydrogen sulphide is a colourless gas with a repulsive smell like that of rotten egg.
2. It is very poisonous.
3. It is about 1.18 times denser than air.
4. It moderately soluble in water.
5. It turns moist red litmus paper red

Chemical properties of hydrogen sulphide

I. As an acid - Hydrogen sulphide ionizes in water to form a weak dibasic acid which exhibits typical acidic
properties. When it is bubbled through an alkali, a normal salt and water is formed. 2NaOH(aq) + H 2S(g)
→ Na2S(s) + 2H2O(l)

However, in excess, it react to form the salt. NaOH(aq) + H 2S(g) → NaHS(s) + 2H2O(l).
 II. As a precipitating agent - Many metals from insoluble sulphides which are usually coloured. When
hydrogen sulphide is bubbled through solutions of salts of such metals, the coloured sulphides are
precipitated. This reaction is used in quantitative analysis, to identify the metal ions present in unknown
substance.

Pb(NO3)2(aq) + H2S(g) → 2 HNO3(aq) + PbS(s) [black precipitate].

III. Reaction of hydrogen sulphide with oxygen

Hydrogen sulphide does not support combustion but it burns in a plentiful supply of air with a bright blue flame to
produce sulphur (IV) oxide. 2H2S(g) + 3O2(g) → 2H2O(l) + SO2(g). If the supply of oxygen is limited, a deposit of
sulphur may form. 2H2S(g) + O2(g) → 2H2O(l) + 2S(s).

IV. As a reducing agent

Hydrogen sulphide is a strong reducing agent. It acts as a reducing agent with tetraoxomanganate (VII) KMnO 4,
Heptaoxodichromate (VI) K2Cr2O7, halogens, iron (III) chloride, sulphur (IV) oxide, strong oxidizing agents.

a) Reaction of hydrogen sulphide as a reducing agent with tetraoxomanganate (vii): When hydrogen
sulphide is bubbled through a solution of acidified potassium tetraoxomanganate (VII), the purple colour of
the salt is decolorized.
2KMnO4(aq) + 3H2SO4(aq) + 5H2S(g) → K2SO4(aq) + 2MnSO4(aq) + 8H2O(l) + 5S(s)
b) Reaction of hydrogen sulphide as a reducing agent with heptaoxodichroate (vi): When hydrogen
sulphide is bubbled through a solution of acidified potassium heptaoxodichromate (VI), the solution changes
from orange to green. Sulphur is also deposited at the same time. K 2Cr2O7(aq) + 4H2SO4(aq) + 3H2S(g) →
K2SO4(aq) + Cr2(SO4)3(aq) + 7H2O(l) + 3S(s).
Ionically,

c) Reaction of hydrogen sulphide as a reducing agent with halogens: Hydrogen sulphide is oxidized by the
halogens to sulphur. Moisture must be present for the reactions to occur.
Cl2(g) + H2S(g) → 2HCl(g) + S(s)
d) Reaction of hydrogen sulphide as a reducing agent with iron (iii) chloride: Hydrogen sulphide reduces a
green solution of iron (III) chloride to a green solution of iron (II) chloride. The hydrogen sulphide itself is
oxidized to sulphur and hydrogen chloride.
2FeCl3(aq) + H2S(g) → 2FeCl2(aq) + 2HCl(aq) + S(s).
Ionically,
e) Reaction of hydrogen sulphide as a reducing agent with sulphur (iv) oxidE: Hydrogen sulphide is a
stronger reducing agent than sulphur (IV) oxide. It reduces sulphur (IV) oxide to sulphur in the presence of
moisture. SO2(g) + 2H2S(g) → 2H2O(l) + 3S(s).
f) Reaction of hydrogen sulphide as a reducing agent with oxidizing acids: Hydrogen sulphide is readily
oxidized by the oxidizing acids to sulphur. Since concentrated trioxonitrate (V) acid is a very strong
oxidizing agent, it oxidizes the sulphide to tetraoxosulphate (VI) acid to certain extent.
H2SO4(aq) + H2S(g) → 2H2O(l) + SO2(g) + S(s)
2HNO3(aq) + H2S(g) → 2H2O(l) + 2NO2(g) + S(s)
8HNO3(aq) + H2S(g) → 4H2O(l) + 8NO2(g) + H2SO4(aq).

Test for hydrogen sulphide

A gas with a repulsive smell, like that of rotten eggs, is probably hydrogen sulphide. This is confirmed by doing the
following test:

With Lead (II) trioxonitrate (V): Moisten a piece of filter paper with lead (II) trioxonitrate (V) solution and drop it
into a gas jar of the unknown gas. If the gas is hydrogen sulphide, the paper turns black due to the formation of black
lead (II) sulphide. Lead (II) ethanoate too gives the same reaction.

Pb(NO3)2(aq) + H2S(g) → PbS(s) + 2HNO3(aq)

Pb(CH3COO)2(aq) + H2S(g) → PbS(s) + 2CH3COOH(aq)

Uses of hydrogen sulphide

Hydrogen sulphide is used in the analysis of ores and metals. It is possible to separate groups of metals from one
another because their sulphides have different solubilities in acids and alkalis. The presence of a certain metal is
often indicated by the colour of its sulphide.

SULPHUR (IV) OXIDE SO2

Sulphur (IV) oxide is usually present in volcanic gases and in the waters of certain sulphur springs. The presence of
substantial amount of sulphur (IV) oxide in the atmosphere is one of the major causes of acid rain.

Preparation of sulphur (iv) oxide

Sulphur (IV) oxide is produced industrially by burning sulphur or metallic sulphides in air or oxygen. The gas is
usually sold in the liquid form under pressure.

S(s) + O2(g) → SO2(g) and Na2S(s) + O2(g) → 2Na(s) + SO2(g).

In the laboratory, it is readily generated by heating sodium or potassium trioxosulphate (IV) with tetraoxosulphate
acid or hydrochloric acid.

Na2SO3(aq) + 2HCl(aq) → 2NaCl(aq) + H2O(l) + SO2(g)

Sulphur (IV) oxide is also obtained by heating concentrated tetraoxosulphate (IV) acid with copper.
Cu(s) + 2H2SO4(aq) → CuSO4(aq) + 2H2O(l) + SO2(g).
Physical properties of sulphur (iv) oxide

1. Sulphur (IV) oxide is a colourless and poisonous gas with a very irritating smell like that of burning matches.
2. It is very soluble in water.
3. It is denser than air.
4. It can easily be liquefied under pressure at room temperature.

Chemical properties of sulphur (iv) oxide

1. As an Acid: The gas reacts with alkalis to form a normal salt, i.e. a trioxosulphate (IV) and water only.
2NaOH(aq) + SO2(g) → Na2SO3(aq) + H2O(l). In the presence of excess of the gas, the acid salt,
hydrogentrioxosulphate (IV) is formed. NaOH(aq) + SO2(g) → NaHSO3(aq).
2. As a reducing agent: Sulphur (IV) oxide is a strong reducing agent, in the presence of water. This is due to
the formation of the trioxosulphate (IV) ion, , which redily donates electron an oxidizing agent. It acts a
reducing agent:
i. With Tetraoxomanganate (VII): Sulphur (IV) oxide decolourizes an acidified potassium
tetraoxomanganate (VII) solution by reducing it to manganese (II) tetraoxosulphate (VI). At the same time,
sulphur (IV) oxide is itself is oxidized to tetraoxosulphate (VI) acid.
2KMnO4(aq) + 5SO2(g) + 2H2O(l) → K2SO4(aq) + 2MnSO4(aq) + H2SO4(aq)
Ionically, .

ii. With heptaoxodichromate (VI): Sulphur (IV) oxide changes the colour of acidified potassium
heptaoxodichromate (VI) solution from orange to green by reducing it to chromium (III) tetraoxosulphate
(VI). K2Cr2O7(aq) + 3SO2(g) + H2SO4(aq) → K2SO4(aq) + Cr2(SO4)3(aq) + H2O(l).
Ionically,
.
iii. With iron (III) chloride: Sulphur (IV) oxide reduces brown iron (III) chloride to green iron (II) chloride
solution while it is itself oxidized to tetraoxosulphate (VI) acid. 2FeCl 3(aq) + SO2(g) + 2H2O(l) →
2FeCl2(aq) + H2SO4(aq) + 2HCl(aq). Ionically, .
iv. With trioxonitrate (V) acid: Sulphur (IV) oxide reduces concentrated trioxonitrate (V) acid to liberate
reddish – brown nitrogen (IV) oxide. 2HNO 3(aq) + SO2(g) → H2SO4(aq) + NO2(g). Ionically, .
v. With the halogens: Sulphur (IV) oxide reduces the coloured solutions of chlorine, bromine and iodine to
colourless solutions of their hydrogen compounds. .
 3. As a bleaching agent: A solution of sulphur (IV) oxide in water bleaches both natural and artificial dyes.
Sulphur (IV) oxide is a good bleaching agent because of its reducing powers. In the presence of water, it
dissolves to form trioxosulphate (IV) acid which then donates electrons to the dye and becomes oxidized to
tetraoxosulphate (VI) acid. In the process, the dye is reduced to a colourless compound. H 2SO3(aq) + Dye(aq)
→H2SO4(aq) + Bleached dye (aq).
.
4. Direct combination reactions of sulphur (iv) oxide:
i. With certain metallic oxides: When Lead (IV) oxide is heated and lowered into a gas jar of sulphur
(IV) oxide, the two compounds combine to form white deposits of Lead (II) tetraoxosulphate (IV).
PbO2(s) + SO2(g) → PbSO4(s).
ii. With oxygen: In the presence of a catalyst, sulphur (IV) oxide combines reversibly with oxygen to
form sulphur (VI) oxide. The forward reaction is exothermic reaction. .
iii. As an Oxidizing agent: Sulphur (IV) oxide can act as an oxidizing agent in the presence of a
stronger reducing agent. E. g it oxidizes hydrogen sulphide to sulphur in the presence of moisture.
2H2S(g) + SO2(g) → 2H2O(l) + 3S(s). At , it also oxidizes carbon while itself being reduced to
sulphur. C(s) + SO2(g) → CO2(g) + S(s).

Tests for sulphur (iv) oxide

Sulphur (IV) oxide may be recognized by its irritating smell and confirmed by these tests:

i. Bleaching action: Place some moist coloured flowers into a jar of the unknown gas. If the flowers are
bleached, the presence of sulphur (IV) oxide can be suspect. Confirm this by testing for its reducing effect on
oxidizing agents.
ii. Action on oxidizing agents: Bubble the unknown gas through solutions of either acidified potassium
heptaxodichromate (VI) or potassium tetraoxomanganate (VII). If the unknown gas is sulphur (IV) oxide, the
acidified potassium heptaoxodichromate (VI) solution will change from orange to green colour while the
purple colour of potassium tetraoxomanganate (VII) solution will become colourless. . It does not produce a
yellow precipitate of sulphur unlike H2S.

USES OF SULPHUR (IV) OXIDE

1. The most important use of sulphur (IV) oxide is in the making of tetraoxosulphate (VI) acid.
2. It is used as a germicide and fumigant and often used to destroy termites.
3. It used as a bleaching agent for straw, sponges , silk, wool and other fabrics which could be damaged by
chlorine. It is also used in making calcium hydrogen tetraoxosulphate (IV), a bleaching agent for bleaching
wood pulp and artificial silk.
4. Liquid sulphur (IV) oxide is sometimes used as a refrigerant because of its easy liquefaction and high latent
heat of vapourization.
5. The gas is sometimes used as a preservative in some liquids like orange juice. It kills bacteria and bacteria
and fungi and prevents the oxidation the liquid by reacting with the oxygen. It is used in preserving fruits and
grains.

SULPHUR (VI) OXIDES SO3

It exists as volatile white needle – like crystals at normal temperature..

Preparation of sulphur (vi) oxide

In the laboratory, It can be prepared by the catalytic oxidation of SO 2 a mixture of sulphur (IV) oxide and oxygen is
first dried by passing it through concentrated tetraoxosulphate (VI) acid. Then the gaseous mixture is passed over a
strongly heated catalyst .like platinized asbestos or vanadium (V) oxide A temperature of are all required . The
sulphur (VI) oxide formed is seen as dense white fumes. It solidifies when cooled in a freezing mixture of ice and
salt.

Properties of sulphur (vi) oxide

At room temperatuture, sulphur (VI) oxide exists as volatile white needle – like crystals. It has a low boiling point of
and hence readily vapourizes on gentle heating.

It is an acidic oxide. It reacts exothermically with water to form tetraoxosulphate (VI) acid and neutralizes bases
tetraoxosulphate (VI). It is known as tetaoxosulphate (VI) acid anhydride.

. It also dissolves in concentrated tetraoxosulphate (VI) acid to form Oleum, a fuming tetraoxosulphate (VI) acid. .

TETRAOXOSULPHATE (VI) ACID H2SO4

Tetraoxosulphate (IV) acid, H2SO4, is one of the heavy chemicals used in the laboratory and almost every
manufacturing process make use of this acid directly at some stage.

Industrial preparation of H2SO4

Most of the world’s supply of tetraoxosulphate (IV) acid is now manufactured by contact process. The main reaction
in this process is the catalytic combination of sulphur (IV) oxide and oxygen.

Sulphur (IV) oxide is obtained by burning sulphur in dry air or by roasting sulphur ores.

The sulphur (VI) oxide is then mixed with excess air and passed through an electric chamber to remove impurities
and dust which might poison the catalyst. The gaseous mixture is then passed through concentrated tetraoxosulphate
(VI) acid to be dried before it is delivered to the reaction chamber or contact tower. In this chamber, the sulphur (IV)
oxide combines with oxygen in the presence of pellets of the catalyst, vanadium (V) oxide to yield sulphur (VI)
oxide.

The process is operated at atmospheric pressure and a temperature of about , with an excess of air or oxygen to
ensure that all the sulphur (IV) oxide has reacted. About 98% of the possible yield of sulphur (VI) oxide is obtained.

The sulphur (VI) oxide is cooled and passed into an absorption tower where it dissolves in concentrated
tetraoxosulphate (VI) acid to produce a very thick liquid called oleum.

SO3(g) + H2SO4(aq) → H2S2O7(aq). The oxide is not dissolved directly in water because the heat evolved during the
process would cause the acid solution to boil, producing a mist of acid droplets which would spread throughout the
factory.

The oleum is then diluted with appropriate amount of water to produce the 98% tetraoxosulphate (IV) acid used in
the laboratory and other desired condition. H2S2O7(aq) + H2O(l) → 2H2SO4(aq).

S + O2 → SO2 → SO3 → H2S2O7 → 2H2SO4

Oleum

O2 Concentr Water
(Excess ated
air) H2SO4

Physical properties OF H2SO4

1. Concentrated tetraoxosulphate (VI) acid often called the oil of vitriol is a colourless, viscous liquid with a
density of 1.84 g cm-3.
2. It is corrosive and cause severe burns if it comes into contact with the skin.
3. Concentrated tetraoxosulphate (VI) acid has a great affinity for water, evolving a large amount of heat as it
dissolves. It is hygroscopic in nature.

Chemical properties OF H2SO4

1. As an acid: Dilute H2SO4 is a strong dibasic acid which ionizes in two stages.:
 H2SO4 2H+ + SO4 2-, H2SO4 H+ + HSO4 2-,
It is a typical acid as shown by its reactions with metals, bases and trioxocarbonate (IV).
i. With Metals: Dilute tetraoxosulphate (VI) acid reacts with metals which are above hydrogen in the
electrochemical series to liberate hydrogen.
H2SO4(aq) + Zn(s) → ZnSO4(aq) + H2(g).
ii. With bases: Dilute tetraoxosulphate (VI) acid reacts with bases or alkalis to form salts and water.
H2SO4(aq) + Mg(s) → MgSO4(aq) + H2O(l). Since it is a dibasic acid, it forms two series of salts,
which are normal salts e.g. H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O(l) and acidic salt (with
limited supply of bases/alkalis)
. H2SO4(aq) + NaOH(aq) → NaHSO4(aq) + H2O(l).
iii. With trioxocarbonate (IV): Dilute tetraoxosulphate (VI) acid reacts with trioxocarbonate (IV) to
liberate CO2 gas
. H2SO4(aq) + CuCO3(aq) → CuSO4(aq) + CO2(g) + H2O(l).
2. As an oxidizing agent: Hot concentrated tetraoxosulphate (VI) acid exhibits oxidizing properties by
accepting electrons from reducing agents. The acid itself is is usually reduced to trioxosulphate (IV) acid or
sulphur (IV) oxide. In these reactions, the oxidation number of sulphur decrease from +6 to +4. It acts as
oxidizing agent with metals, non – metals and hydrogen sulphide.

i. With metals: The concentrated acid oxidizes metals to produce the corresponding metallic tetraoxosulphate
(VI) and sulphur (IV) oxide. In these reactions, the metals supply the electrons and become oxidized to
metallic ion. Zn(s) + 2H2SO4(aq) → ZnSO4(aq) + 2H2O(l) + SO2(g).
ii. With Non – Metals: The concentrated acid oxidizes non – metals to produce their corresponding oxides and
sulphur (IV) oxide. For example, when powdered carbon is heated with the concentrated acid, CO 2 gas is
formed. C(s) + 2H2SO4(aq) → CO2(g) + 2H2O(l) + 2SO2(g).
iii. With hydrogen sulphide: Tetraoxosulpte (VI) acid oxidizes hydrogen sulphide to sulphur. The reaction
takes place readily when hydrogen sulphide is bubbled into hot or cold concentrated tetraoxosulphate (VI)
acid. H2S(g) + H2SO4(aq) → SO2(g) + 2H2O(l) + S(s).
3. As a dehydrating agent: Concentrated tetraoxosulphate (VI) acid is able to remove the element hydrogen
and oxygen in the form of water from compounds like sugar, ethanol, methanoic acid.
4. Displacement of other acids from their salts: Concentrated H2SO4 is able to displace volatile acids from
their corresponding salts.

Uses of tetraoxosulphate (vi) acid

1. It is used in making fertilizers
2. It is used in making pigments for painting and dying
3. It is used in making cellulose film, natural and artificial fabrics and plastics.
4. The acid is used to clean or pickle metals before electroplating or enameling.
5. It is used as a dehydrating agent in the nitration of compounds used for making explosives
6. It is used as an electrolyte in lead accumulator and batteries and in the refining of metals by electrolysis.
7. In the refining of petroleum, the acid is used to remove waxes, gummany dark – coloured compounds.
8. It is used a drying agent for many gases except alkaline gases like ammonia and reducing gases like
hydrogen sulphide.

Test for Teyraoxosulphate (vi) salt SO4 2-

With a solution of barium chloride BaCl2 followed by dilute HCl, SO4 2- gives a white
precipitate which is insoluble in excess acid