CHLORINE AND ITS COMPOUNDS

 Chlorine is a non-metallic element

 It belongs to group VII of the periodic table(halogens)
 Its atomic number is 17 and electronic configuration of 2. 8. 7
 It is a molecular substance made up of diatomic molecules
 It is highly reactive and thus does not exist naturally as chlorine but in combined
states like chlorides of potassium, sodium and magnesium

Laboratory preparation of chlorine gas

 Chlorine is prepared in the laboratory by the reaction of concentrated
hydrochloric acid with an oxidising agent. The oxidising agents usually used
include; Potassium manganate (VII), manganese (IV) oxide or lead (IV) oxide.
 Heating is not required when using potassium manganate (VII) because it is a
strong oxidising agent. The reactions are shown below;

2KMnO4(s) + 16HCl(aq) → 2KCl(aq) + 2MnCl2(aq) + 8H2O(l) + 5Cl2(g)

MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) + Cl2(g)
PbO2(s) + 4HCl(aq) → PbCl2(s) + Cl2(g) + 2H2O(l)

Diagram KLB Pg

 Concentrated hydrochloric acid acts as a reducing agent and itself oxidised to

water and chlorine.
 The gas is passed through water to remove the more soluble hydrogen chloride
gas formed when the hydrochloric acid decomposes on heating.
 It’s then passed through concentrated sulphuric (VI) acid to be dried. Dry
chlorine is collected by downward delivery (upward displacement of air) because
it is denser than air.
 The purpose of the blue litmus paper in the experiment is to indicate when the
gas jar is full of chlorine. When the gas jar is full, it turns red before being
decolourised.
 Chlorine is not collected over water because it is soluble in water.
 Chlorine gas is poisonous and the reaction should be performed in the fume
chamber or in the open air.

Physical properties of chlorine

i) Chlorine is a pale green gas at room temperature.
ii) It has an unpleasant choking and irritating smell
iii) It is denser than air – reason why it is collected by downward delivery.
iv) It is fairly soluble in water. At 0ºC, 1 volume of water dissolves 3volumes of the
gas.

Chemical properties of chlorine

Reaction with water
Chlorine reacts with water forming both chloric (I) acid (hypochlorous acid) and
hydrochloric acid. The solution is pale yellow is commonly known as chlorine water.

Cl2(g) + H2O(l) → HOCl(aq) + HCl(aq)

Chlorine & its compounds 1

Moist blue litmus paper placed in a gas jar full of chlorine first turns red and then
decolorized (bleached). Coloured petals are decolorized too. The chloric (I) acid is
unstable. It gives up its oxygen atom when exposed to sunlight. The pale yellow
solution consequently loses colour.

HOCl(aq) sunlight HCl(aq) + [O]

(pale yellow) (colourless)

When mixed with dyes, the free oxygen atom released by chloric (I) acid readily
combines with the dyes to form colourless matter.

Dye + HOCl(aq) → HCl(aq) + colourless matter.

The overall equation is:

Cl2(g) + H2O(l) + Dye → [Dye + O] + 2HCl(aq)

(coloured) (colourless)

Chlorine thus bleaches by oxidation. Bleaching by oxidation is permanent.

Reaction with hot elements

 Hot magnesium continues to burn in chlorine forming a white solid, magnesium
chloride.
Mg(s) + Cl2(g) → MgCl2(s)
Magnesium continues to burn because the heat produced sustains the
reaction.
 Hot iron glows producing black crystals of iron (III) chloride.
2Fe(s) + 3Cl2(g) → 2FeCl3(s)

 The glow continues for a long time because the reaction between iron and
chlorine is exothermic. The iron (III) chloride sublimes and is thus collected as a
sublimate in the cooler parts of the apparatus.
 Anhydrous calcium chloride prevents entry of moisture to the set-up. Calcium
oxide may also be used to replace calcium chloride because it reacts with the
acidic chlorine gas to form a salt, thus preventing air pollution.
 Where a metal has more than one oxidation state, the chloride of the metal with
the higher oxidation number is formed. For instance iron (III) chloride is formed
instead of iron (II) chloride.

Chlorine & its compounds 2

 When a piece of warm red phosphorous is lowered into a gas jar of chlorine, a
vigorous reaction takes place producing white fumes of phosphorous (III)
chloride and phosphorous (V) chloride mixture.
P4(s) + 6Cl2(g) → 4PCl3(s)
P4(s) + 10Cl2(g) → 4PCl5(s)

 Chlorine and hydrogen do not react at room temperature. However when a jet of
burning hydrogen is lowered in to the gas jar of chlorine gas, they react
explosively to form hydrogen chloride.

Oxidising properties of chlorine

 When barium nitrate is added to an acidified solution of sodium sulphite through
which chlorine has been bubbled, a white precipitate is formed.
 The white precipitate confirms the presence of sulphate ions. Chlorine is a strong
oxidizing agent and oxidizes the sulphite to sulphate ions.
Na2SO3(aq) + Cl2(g) + H2O(l) → 2HCl(aq) + Na2SO4(aq) or ionically;
Cl2(g) + SO32-(aq) + H2O(l) → 2H+(aq) + 2Cl-(aq) + SO42-(aq)

 Barium ions combine with the sulphate ions to form insoluble barium sulphate.
Ba2+(aq) + SO42-(aq) → BaSO4(s)

 The solution is acidified before barium nitrate solution is added to rule out
precipitation of barium sulphite or barium carbonate.
 When lead (II) nitrate is added to the solution formed by bubbling chlorine in
sodium sulphite solution, a white precipitate is formed. The white precipitate
does not dissolve on warming hence confirming presence of sulphate ions.
Pb2+(aq) + SO42-(aq) → PbSO4(s)

 Any precipitate of lead (II) chloride formed dissolves when the mixture is
warmed but recrystallises on cooling. This test confirms that the white
precipitate is lead (II) chloride.
 Chlorine reacts with ammonia to form white fumes of ammonia chloride.
8NH3(g) + 3Cl2(g) → 6NH4Cl(s) + N2(g)

 When chlorine is mixed with moist hydrogen sulphide gas, yellow deposit of
sulphur is seen in the gas jar. Chlorine oxidizes sulphide ions in the hydrogen
sulphide to yellow sulphur.
H2S(g) + Cl2(g) → S(s) + 2HCl(g)

Reaction with alkaline solutions

 The product formed when chlorine reacts with alkalis depends on the
temperature and concentration of the alkali.
 Chlorine reacts with cold dilute sodium hydroxide or potassium hydroxide
forming a pale-yellow solution of chlorite (I) and the chlorides of the respective
metals.
Cl2(g) + 2NaOH(aq) → NaOCl(aq) + NaCl(aq) + H2O(l)
Cl2(g) + 2KOH(aq) → KOCl(aq) + KCl(aq) + H2O(l)

 With hot concentrated sodium hydroxide or potassium hydroxide, the respective

metal chlorate (V) and chlorides are formed.

Chlorine & its compounds 3

 6NaOH(aq) + 3Cl2(g) → NaClO3(aq) + 5NaCl(aq) + 3H2O(l)
6KOH(aq) + 3Cl2(g) → KClO3(aq) + 5KCl(aq) + 3H2O(l)

 A similar reaction takes place when chlorine is bubbled through solutions of

calcium hydroxide.
2Ca(OH)2(aq) + 2Cl2(g) → CaCl2(aq) + Ca(OCl)2(aq) + 2H2O(l)
 Calcium hypochlorite, Ca(OCl)2, is commonly referred to as bleaching powder.

Reaction with bromides and iodides

 When chlorine gas is bubbled through a solution containing bromide ions, the
colorless solution turns orange. Chlorine has a higher tendency to gain electrons
than bromine. It thus readily oxidizes bromide ions to bromine.
Cl2(g) + 2KBr(aq) → 2KCl(aq) + Br2(aq) or ionically;
Cl2(g) + 2Br-(aq) → 2Cl-(aq) + Br2(aq)

 Similarly, if bubbled through a solution containing iodides ions, the colorless

solution turns brown. Chlorine oxidizes iodide ions to iodine which in the
presence of iodide ions is a red-brown solution.
Cl2(g) + 2KI(aq) → 2KCl(aq) + I2(aq) or ionically;
Cl2(g) + 2I-(aq) → 2Cl-(aq) + I2(aq)
These are displacement reactions.

Tests for chlorides

When concentrated sulphuric (VI) acid is added to sodium chloride crystals, white
fumes are produced. The fumes turn moist blue litmus red. The white fumes are
hydrogen chloride.
NaCl(s) + H2SO4(l) → NaHSO4(aq) + HCl(g)

 The less volatile sulphuric (VI) acid displaces the more volatile hydrochloric acid
from its salts.
 To confirm the presence of hydrogen chloride, a glass rod dipped in ammonia
solution is held over the mouth of the gas jar as the gas is liberated. Formation
of dense white fumes of ammonium chloride confirms the presence of hydrogen
chloride hence chloride ions in the solid substance.
 Presence of chloride ions in a solution can be tested with the lead (II) nitrate
solution. A white precipitate of lead (II) chloride is formed.
Pb(NO3)2(aq) + 2HCl(aq) → PbCl2(s) + 2HNO3(aq)

 When warmed, the lead (II) chloride precipitate dissolves in the solution. It
however it recrystallises on cooling.

Uses of chlorine and its compounds

i) Manufacture of hydrochloric acid
ii) Manufacture of bleaching agents such as calcium hypochlorite and sodium
chlorate (I) used in the cotton and paper industries.
iii) Chlorine is used in the treatment of drinking water and in sewage plants.
iv) Manufacture of chloroform, an anesthetic.

Chlorine & its compounds 4

v) Manufacture of solvents such as trichloroethane and some chloroflourocarbons.
CFCs, commonly referred to as ‘freons’ are used as refrigerants in fridges and air
conditions units due to their low boiling points. Also used as aerosol propellants
vi) Compounds of chlorine are used in the manufacture of plastics such as polyvinyl
chloride.
vii) Manufacture of germicides, fungicides and pesticides such as DDT.

Hydrogen chloride
 Hydrogen chloride is a compound of hydrogen and chlorine.
 It is a molecular substance which exists as a gas at room temperature.
 It dissolves in water to produce hydrogen ions(H +) and chloride ions (Cl-)

Laboratory preparation
 Hydrogen chloride is prepared by reacting rock salt (solid sodium chloride) with
concentrated sulphuric (VI) acid.
NaCl(s) + H2SO4(l) → NaHSO4(aq) + HCl(g)

KLB Pg 232 fig 6.3 (b)

 Effervescence occurs in the cold and the volatile hydrogen chloride is displaced.
A larger supply of the gas can be obtained by heating.
 The gas is dried using concentrated sulphuric (VI) acid
 The gas is collected by downward delivery because it is denser than air. It is not
collected by over water it is very soluble in water.

Physical properties
i) It is a colourless gas with a sharp pungent smell
ii) It is denser than air.
iii) It has a melting point of -114°C and boiling point of -85° C.
iv) It turns moist blue litmus red.
v) It is very soluble in water. When a gas full of hydrogen is inverted in a trough of
water, the water rises rapidly in the gas jar. At 0° C, 1 volume of water dissolves
about 500 volumes of the gas.
 The high solubility in water can be demonstrated by the fountain experiment.
Dry hydrogen chloride gas is collected in a round bottomed flask and apparatus
is set up as shown:

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 The clip is opened and water let into the tube until it just reaches the top of the
tube. The tube is opened again after a while and observations made.
 When a drop of water gets into the flask, it dissolves a lot of the hydrogen
chloride gas in the flask creating a partial vacuum. When the clip is opened
again, the water is forced into the flask by the atmospheric pressure leading to
formation of a fountain.
 The solution turns red when it reaches inside the flask indicating the acidic
nature of hydrogen chloride gas.

Preparation of aqueous hydrogen chloride

This is done by replacing the gas jar with a large beaker filled with distilled water to
about three-quarters its capacity. A filter funnel is fitted at the end of the delivery
tube and the apparatus arranged as shown below;

NB: The funnel is used when dissolving the gas instead of a delivery tube to prevent
the water from ‘sucking back’ into the flask by providing a large surface area for
absorption of hydrogen chloride.
Chemical properties of hydrogen chloride
 Hydrogen chloride turns litmus paper red, indicating that the gas is acidic. In
aqueous solution, it dissociates into hydrogen and chloride ions

Chlorine & its compounds 6

 HCl(g) water H+(aq) + Cl-(aq)

 When hydrogen gas is blown over the mouth of a gas jar full of ammonia gas,
dense white fumes of ammonia chloride are formed.
NH3(g) + HCl(g) → NH4Cl(s)
This serves as the confirmatory test of hydrogen chloride gas.

 An aqueous solution of hydrogen chloride gas forms a white precipitate with

silver nitrate. The precipitate, silver chloride is insoluble on warming.
Ag+(aq) + Cl-(aq) → AgCl(s)

 A white precipitate is formed when lead (II) nitrate is added to aqueous solution
of hydrogen chloride gas. The precipitate dissolves on warming. This confirms
that Cl- ions are present in the solution.
Pb2+(aq) + 2Cl-(aq) → PbCl2(s)

 All metals above hydrogen in the reactivity series react with hydrochloric acid to
liberate hydrogen gas.
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

 Copper metal is below hydrogen in the reactivity series and thus does not react
with hydrogen chloride solution.
 Hydrogen chloride solution reacts with carbonates and hydrogen carbonates to
liberate carbon (IV) oxide gas.
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)
NaHCO3(s) + HCl(aq) → NaCl(aq) + H2O(l) + CO2(g)

 Hydrogen chloride solution reacts with bases/alkalis; neutralisation reaction

takes place.
NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
Zn(OH)2(s) + 2HCl(aq) → ZnCl2(aq) + 2H2O(l)

NB: In methylbenzene, hydrogen chloride gas dissolves but does not ionise. It exists
in molecules. It does not show acidic properties.

Large scale manufacture of hydrochloric acid

 The raw materials in this process are hydrogen and chlorine.
 Hydrogen used is obtained from cracking long-chain alkanes in crude oil or from
electrolysis of brine
 Chlorine is obtained from electrolysis of fused sodium chloride or brine
 Hydrogen and chlorine are combined directly by burning to produce hydrogen
chloride gas.
H2(g) + Cl2(g) → 2HCl(g)

 The mixture reacts explosively when heated and thus to control the reaction, a
small amount of hydrogen gas through a jet is allowed to burn in excess chlorine
as shown below;

Chlorine & its compounds 7

 The hydrogen chloride gas formed is dissolved in water over glass beads. The
beads increase surface area over which the gas dissolves in water.
HCl(g) H2O(l) HCl(aq)

 Commercially prepared hydrochloric acid is sold at a purity of about 35%.

Uses of hydrochloric acid

1. Manufacturing photographic materials e.g. silver chloride
2. Manufacturing dyes, drugs and paints
3. Water treatment(chlorination)
4. Treatment of sewage
5. To clean metal surfaces before electroplating(de-scaling)
6. To neutralize bases where purity is required in industries

Chlorine & its compounds 8