Page 1 of 11 THE HALOGENS

THE HALOGENS
The halogens are the group VII elements of the periodic table. These elements are called halogens because
they combine directly with most metals to form salts. The name halogen literally means salt former. The
halogens are all non-metals.

The halogens family is made up of the following elements which exist as diatomic molecules at room
temperature.

HALOGEN SYMBOL MOLECULE ATOMIC NUMBER ELECTRONIC CONFIGURATION

Fluorine F F2 9 2:7
Chlorine Cl Cl2 17 2:8:7
Bromine Br Br2 35 2:8:18:7
Iodine I I2 53 2:8:18:18:7
Astatine At

PROPERTIES OF THE HALOGENS

a) Physical properties: Some physical properties of the halogens are summarized in the table below.

HALOGEN STATE COLOUR MELTING POINT BOILING POINT

Fluorine Gas Pale yellow -220 -188
Chlorine Gas Greenish-yellow -101 -34
Bromine Liquid Reddish-brown -7 58
Iodine Solid Shiny-black 144 183
Astatine solid

SOME TRENDS IN THE PHYSICAL PROPERTIES OF THE HALOGENS

As you go down the group from fluorine to iodine:

- Their melting and boiling points increase due to an increase in the strength of the van der waal’s forces
between their molecules.
- Their colours become darker.
- Atomic size increases.
- The elements become more “condensed” in form i.e. fluorine and chlorine are gases; iodine is a liquid;
iodine and astatine are solids.

b) Chemical properties: The halogens are the most chemically reactive non-metals. They do not therefore
occur free in nature due to their high reactivity. Their chemical reactivity decreases down the group in the
order: 𝐅𝟐 > 𝐂𝐥𝟐 > 𝐁𝐫𝟐 > 𝐈𝟐 . This is due to a decrease in electronegativity as a result of an increase in
atomic size from fluorine to iodine. Fluorine, at the top of the group is therefore the most reactive non-
metal.

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Remark: The halogens have similar chemical properties because they all:
- Have seven valence electrons.
- Gain one electrons to attain the octet structure, thus forming an ionic bond. Hence they each have a
valency of 1.
- Share a pair of electrons with a similar or dissimilar atom to attain the octet structure, thus forming a
single covalent bond.

NOTE: The chemistry of Astatine is not studied in secondary schools because it is radioactive and has been
synthesized only in tiny amounts.

CHLORINE

Chlorine is too reactive and hence does not occur free in nature. It is usually found in the combined state
mainly as chlorides, the most abundant of which is sodium chloride (common salt). The sodium chloride is
found dissolved in sea water and in the earth’s crust as rock salt. The rock salt is a mixture of sand and sodium
chloride.

LABORATORY PREPARATION OF CHLORINE

Chlorine can be prepared in the laboratory in the following ways:

- By the oxidation of concentrated hydrochloric acid with manganese (IV) oxide.

Heat
4HCl(aq) + MnO2 (s) → MnCl2 (aq) + 2H2 O(l) + Cl2 (g)
- By the oxidation of concentrated hydrochloric with acidified potassium permanganate. This method is very
convenient because the reaction occurs readily without heating.
Heat
16HCl(aq) + 2KMnO4 (s) → 2KCl(s) + 2MnCl2 (aq) + 8H2 O(l) + 5Cl2 (g)
- By heating a mixture of solid sodium chloride, concentrated sulphuric acid and manganese (IV) oxide.
2NaCl(s) + 2H2 SO4 (aq) + MnO2 (s) → Na2 SO4 (aq) + MnSO4 (aq) + 2H2 O(l) + Cl2 (g)
This reaction takes place in two stages:
 On heating, concentrated sulphuric acid reacts with sodium chloride liberating hydrogen chloride gas.
2NaCl(s) + H2 SO4 (aq) → Na2 SO4 (aq) + 2HCl(g)
 The hydrogen chloride is then oxidized by manganese (IV) oxide in the presence of sulphuric acid, to
give chlorine gas.
2HCl(g) + H2 SO4 (aq) + MnO2 (s) → MnSO4 (aq) + 2H2 O(l) + Cl2 (g)

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AN EXPERIMENT TO PREPARE CHLORINE IN THE LABORATORY BY THE OXIDATION OF CONCENTRATED

HYDROCHLORIC ACID WITH MANGANESE (IV) OXIDE

Apparatus: Some manganese (IV) oxide is placed in a round-bottomed flask and the following apparatus is set
up in a fume cupboard because chlorine gas is poisonous.

Procedure:
- Concentrated hydrochloric acid is added to manganese (IV) oxide by means of a thistle funnel and the
mixture is heated gently.
- On heating, effervescence is observed as chlorine gas is evolved. A small amount of misty fumes of
hydrogen chloride (an impurity) is also evolved from the concentrated acid.
Heat
4HCl(aq) + MnO2 (s) → MnCl2 (aq) + 2H2 O(l) + Cl2 (g)
- The mixture of gases first passed through water to remove the hydrogen chloride impurity which is very
soluble in water.
- The pure chlorine gas is then passed through concentrated sulphuric acid to dry it.
- The dry gas is then collected by downward delivery because chlorine is denser than air.

INDUSTRIAL PREPARATION OF CHLORINE

Chlorine is prepared industrially by the electrolysis brine (concentrated sodium chloride solution).

PROPERTIES OF CHLORINE

a) Physical properties:
- Chlorine is a greenish-yellow gas with a characteristic pungent, choking smell.
- It is denser than air.
- It is moderately soluble in water.
- It is a poisonous gas and hence should be handled in a fume cupboard.
- At room temperature and under a pressure of about 7atm it liquefies.

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b) Chemical properties:
- Reactions with metals: Metals combine readily with chlorine especially when heated to form the
corresponding chlorides, e.g.
2Na(s) + Cl2 (g) → 2NaCl(s)
2Al(s) + 3Cl2 (g) → 2AlCl3 (s)
Where a metal can form more than one chloride, the higher chloride is formed when the metal reacts with
chlorine gas, e.g. iron reacts with chorine to form iron (III) chloride and with copper to form copper (II)
chloride.
2Fe(s) + 3Cl2 (g) → 2FeCl3 (s)
Cu(s) + Cl2 (g) → CuCl2 (s)
- Reactions with non-metals: With the exception of oxygen, nitrogen and carbon, all the other non-metals
burn in chlorine gas to produce the corresponding chlorides, e.g.
 With hydrogen: Hydrogen and chlorine react explosively in bright sunlight or when heated forming
misty fumes of hydrogen chloride.
H2 (g) + Cl2 (g) → 2HCl(g)
This reaction is slower in diffused light.
 With phosphorus: Phosphorus burns spontaneously in a limited supply of chlorine to form phosphorus
(III) chloride or phosphorus trichloride. In excess chlorine, phosphorus (V) chloride or phosphorus
pentachloride is formed.
P4 (s) + 6 Cl
⏟2 (g) → 4PCl3 (g)
𝐋𝐢𝐦𝐢𝐭𝐞𝐝

P4 (s) + 10 Cl
⏟2 (g) → 4PCl5 (g)
𝐄𝐱𝐜𝐞𝐬𝐬

 With sulphur: Burning sulphur continues to burn in chlorine and a yellow liquid called disulphur
choride is formed.
2S(s) + Cl2 (g) → S2 Cl2 (l)
- Reactions with hydrides: Chlorine has a high affinity for hydrogen and thus readily removes hydrogen
from hydrides i.e. it oxidizes the hydrides, e.g.
⏟ 3 (g) + 3Cl2 (g) →
2 NH N2 (g) + 6HCl(g)
𝐀𝐦𝐦𝐨𝐧𝐢𝐚

H
⏟2 S(g) + 3Cl2 (g) → S(s) + 2HCl(g)
𝐇𝐲𝐝𝐫𝐨𝐠𝐞𝐧 𝐬𝐮𝐥𝐩𝐡𝐢𝐝𝐞

CH4 (g) + Cl2 (g) →

⏟ CH3 Cl(g) + HCl(g)
𝐌𝐞𝐭𝐡𝐚𝐧𝐞

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- Displacement reactions: Chlorine displaces bromine and iodine from aqueous solutions of their
compounds i.e. when chlorine gas is bubbled through an aqueous solution of hydrogen bromide and its
salts, the greenish-yellow colour of chlorine disappears and reddish-brown liquid (bromine) is formed, e.g.
⏟2 (g)
Cl + 2KBr(aq) → 2HCl(aq) + Br
⏟ 2 (l)
𝐆𝐫𝐞𝐞𝐧𝐢𝐬𝐡−𝐲𝐞𝐥𝐥𝐨𝐰 𝐑𝐞𝐝𝐝𝐢𝐬𝐡−𝐛𝐫𝐨𝐰𝐧

When chlorine gas is passed through an aqueous solution of Hydrogen iodide and its salts, the greenish-
yellow colour of chlorine gradually disappears and a black solid (iodine) is deposited.
⏟2 (g)
Cl + 2HI(aq) → 2HCl(aq) + I⏟
2 (l)
𝐆𝐫𝐞𝐞𝐧𝐢𝐬𝐡−𝐲𝐞𝐥𝐥𝐨𝐰 𝐁𝐥𝐚𝐜𝐤

Remark: Generally, any halogen displaces all the other halogens below it in the group from aqueous
solutions of their compounds, e.g.
⏟2 (g)
Br + 2NaI(aq) → 2NaCl(aq) + I⏟
2 (l)
𝐑𝐞𝐝𝐝𝐢𝐬𝐡−𝐛𝐫𝐨𝐰𝐧 𝐁𝐥𝐚𝐜𝐤

- As an oxidizing agent: Chlorine is a powerful oxidizing agent because of its ability to remove hydrogen
readily from substances and its readiness to gain an electron. As an example, chlorine oxidizes a solution of
green iron (II) chloride to yellow iron (III) chloride.
FeCl2 (aq) + Cl2 (g) →
2⏟ FeCl3 (aq)
2⏟
𝐆𝐫𝐞𝐞𝐧 𝐘𝐞𝐥𝐥𝐨𝐰

- As a bleaching agent: When dissolved in water, chlorine acts as a bleaching agent for most dyes and non-
carbon containing inks. The solution of chlorine in water, called chlorine water, contains hydrochloric acid
and hypochlorous acid.
Cl2 (g) + H2 O(l) → HCl(aq)
⏟ + HOCl(aq)
⏟
𝐇𝐲𝐝𝐫𝐨𝐜𝐡𝐥𝐨𝐫𝐢𝐜 𝐚𝐜𝐢𝐝 𝐇𝐲𝐩𝐨𝐜𝐡𝐥𝐨𝐫𝐨𝐮𝐬 𝐚𝐜𝐢𝐝

The hypochlorous acid is responsible for the bleaching action of chlorine water. This is because it
decomposes readily releasing oxygen which oxidizes a coloured dye converting it into a colourless
substance.
HOCl(aq) + dye
⏟ → HCl(aq) + (dye
⏟ + O)
𝐂𝐨𝐥𝐨𝐮𝐫𝐞𝐝 𝐂𝐨𝐥𝐨𝐮𝐫𝐥𝐞𝐬𝐬

Whenever chlorine water bleaches, hydrochloric acid is formed, hence the article that has been bleached
must be thoroughly washed otherwise it will be attacked by the free hydrochloric acid formed. Chlorine is
generally used to bleach cotton, linen and many plant fibres.
Chlorine bleaches by oxidization unlike sulphur dioxide which bleaches by reduction.
Remark: chlorine water will give off oxygen in sunlight because the hypochlorous acid in it slowly
decomposes releasing oxygen gas.
Sunlight
2HOCl(aq) → 2HCl(aq) + O2 (g)
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- Reactions with alkalis: Chlorine reacts with cold dilute alkalis to form a mixture of the corresponding
chlorides and hypochlorites, e.g.
2NaOH(aq)
⏟ + Cl2 (g) → NaOCl(aq)
⏟ + NaCl(aq) + H2 O(l)
𝐂𝐨𝐥𝐝 & 𝐝𝐢𝐥𝐮𝐭𝐞 𝐒𝐨𝐝𝐢𝐮𝐦 𝐡𝐲𝐩𝐨𝐜𝐡𝐥𝐨𝐫𝐢𝐭𝐞

- With hot concentrated alkalis, a mixture of the corresponding chlorides and chlorates is formed, e.g.
6NaOH(aq)
⏟ + 3Cl2 (g) → NaClO3 (aq) + 5NaCl(aq) + H2 O(l)
⏟
𝐇𝐨𝐭 & 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐞𝐝 𝐒𝐨𝐝𝐢𝐮𝐦 𝐜𝐡𝐥𝐨𝐫𝐚𝐭𝐞

Note: Sodium hypochlorite is commonly used as a bleaching agent called camel water (eau de javel).

ASSIGNMENT
When excess ammonia is reacted with chlorine gas, white fumes of a certain substance are formed. Identify
the substance and write chemical equations to show how the substance is formed.

ANSWER
The substance is ammonium chloride
2𝑁𝐻3 (𝑔) + 3𝐶𝑙2 (𝑔) → 𝑁2 (𝑔) + 6𝐻𝐶𝑙(𝑔)
⏟ 3 (𝑔) + 𝐻𝐶𝑙(𝑔) →
𝑁𝐻 𝑁𝐻4 𝐶𝑙(𝑠)
𝑬𝒙𝒄𝒆𝒔𝒔

THE TEST FOR CHLORINE

An unknown gas that turns damp blue litmus paper red and then bleaches it is chlorine.

USES OF CHLORINE

- It is used in sterilizing water, a process called chlorination of water, for domestic use. It is also used in
sterilizing swimming pools.
- It is used as a bleaching agent for cotton, linen and wood-pulp as well as in the manufacture of bleaching
powder (CaOCl. H2 O).
- It is used to make pesticides, disinfectants and antiseptics.
- It is used to make plastics e.g. PVC that is useful for making plastic pipes, windows etc.
- It is used in the manufacture solvents such as CCl4 and dry-cleaning agents.

HYDROGEN CHLORIDE

Hydrogen chloride exists as a gas at room temperature and pressure. It occurs in traces in the air as a pollutant
emitted by industries. It is the only acidic gas that does not contain oxygen.

LABORATORY PREPARATION

Hydrogen chloride is prepared in the laboratory by the action of hot concentrated sulphuric acid on any
soluble chloride, e.g. sodium chloride.

The following apparatus is set up.

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Procedure:
- Concentrated sulphuric acid is added gently to the sodium chloride in the flask. Effervescence is observed
and misty fumes of hydrogen chloride gas are observed.
NaCl(s) + H2 SO4 (aq) → NaHSO4 (aq) + HCl(g)
- The gas is passed through concentrated sulphuric acid to dry it and the dry gas is then collected by
downward delivery because chlorine is denser than air.

PROPERTIES OF HYDROGEN CHLORIDE

a) Physical properties:
- Pure hydrogen chloride is a colourless gas with a pungent irritating smell.
- It turns damp blue litmus paper red.
- It is denser than air.
- It forms misty fumes in moist air (it is a fuming gas). This is because it dissolves in the moisture forming a
mist of tiny droplets of hydrochloric acid.
- Dry hydrogen chloride readily dissolves in non-polar solvents like chloroform; toluene etc. to form non-
acidic solutions because HCl does not ionize in such solvents.
b) Chemical properties:
- Reactions with metals: Hydrogen chloride reacts with many metals especially when heated to form their
respective chlorides, e.g.
Zn(s) + 2HCl(g) → ZnCl2 (s) + H2 (g)
If the metal can form more than one chloride, only the lower chloride is formed, e.g.
Fe(s) + 2HCl(g) → FeCl2 (s) + H2 (g)

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- Reaction with ammonia: Hydrogen chloride gas combines directly with ammonia gas to form dense white
fumes of ammonium chloride.
NH3 (g) + HCl(g) → NH4 Cl(s)

TESTS FOR HYDROGEN CHLORIDE

- With ammonia: It produces dense white fumes of ammonium chloride with ammonia gas.
- With silver nitrate solution: If a glass rod dipped into silver nitrate solution that has been acidified with
nitric acid, is lowered into a gas jar containing hydrogen chloride, a white precipitate of silver chloride is
formed.

HYDROCHLORIC ACID

Hydrochloric acid is obtained when hydrogen chloride gas is dissolved in water. Thus hydrochloric acid is
aqueous hydrogen chloride.
Water
HCl(g) → H − (aq) + Cl− (aq)

To dissolve hydrogen chloride gas in water, an inverted filter funnel is attached to the delivery tube and then
inserted in water such that its rim is just below the water surface. This inverted filter funnel prevents water
from sucking back into the reacting flask and also provides a larger surface area over which the gas dissolves.

PROPERTIES OF HYDROCHLORIC ACID

a) Physical properties: Hydrochloric acid has all the physical properties of a strong acid.
b) Chemical properties:
- Reactions with metals: Metals above hydrogen in the reactivity series will liberate hydrogen gas from the
acid e.g.
Zn(s) + 2HCl(aq) → ZnCl2 (aq) + H2 (g)

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- Reactions with bases: It reacts with bases i.e. metal oxides and alkalis to form salts (chlorides) and water
only, e.g.
CaO(s) + 2HCl(aq) → CaCl2 (aq) + H2 O(l)
NaOH(aq) + HCl(aq) → NaCl(aq) + H2 O(l)
- Reactions with carbonates: It reacts with carbonates and hydrogen carbonates to form salts (chlorides),
water and carbon dioxide, e.g.
2HCl(aq) + Na2 CO3 (s) → 2NaCl(aq) + H2 O(l) + CO2 (g)
HCl(aq) + NaHCO3 (s) → NaCl(aq) + H2 O(l) + CO2 (g)
- As a precipitating agent: When hydrochloric acid is added to silver nitrate or lead (II) nitrate solution, a
white precipitate of silver chloride or lead (II) chloride is formed respectively.
AgNO3 (aq) + HCl(aq) → AgCl(s)
⏟ + HNO3 (aq)
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭

Pb(NO3 )2 (aq) + 2HCl(aq) → PbCl2 (s) + 2HNO3 (aq)

⏟
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭

USES OF HYDROCHLORIC ACID

- It is used in pickling metals i.e. removing oxides from their surfaces, prior to electroplating.
- It is used in the laboratory for chemical analysis and testing as well as in the preparation of other
compounds.
- It is used in the manufacture of glue from the tendons of animals and in the production of glucose from
starch.

HALIDES

Halides are; fluorides, chlorides, bromides and iodides which contain the fluoride ion (𝐹 − ), chloride ion (𝐶𝑙 − ),
bromide (𝐵𝑟 − ) and the iodide ion (𝐼 − ) respectively.

CHLORIDES

Chlorides are the salts of hydrochloric acid. They are made up of metallic ions or the ammonium ion combined
with the chloride ion.

All metallic chlorides are soluble in water except: silver chloride (𝐴𝑔𝐶𝑙), copper (I) chloride (𝐶𝑢𝐶𝑙) and
mercury (I) chloride (𝐻𝑔2 𝐶𝑙2). Lead (II) chloride (𝑃𝑏𝐶𝑙2 ) is insoluble in cold water but dissolves gradually in hot
water.

PREPARATION OF METALLIC CHLORIDES

The method used to prepare any given chloride of a metal depends on the position of the metal in the
reactivity series and the nature of the chloride.

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1) By neutralization: The chloride of the highly reactive metals such as K, Na, Ca are prepared by neutralizing
dilute hydrochloric acid with the corresponding alkalis e.g.
NaOH(aq) + HCl(aq) → NaCl(aq) + H2 O(l)
2) By the action of hydrogen chloride or hydrochloric acid on metals: The chlorides of Mg and Zn can be
prepared by this method. i.e.
Mg(s) + 2HCl(aq) → MgCl2 (aq) + H2 (g)
Zn(s) + 2HCl(aq) → ZnCl2 (aq) + H2 (g)
3) By the action of dilute hydrochloric acid on metal oxides or metal carbonates: The chlorides of the highly
reactive metals such as K, Na and Ca can be prepared by reacting dilute hydrochloric acid with their oxides
or carbonates, e.g.
2HCl(aq) + K 2 CO3 (aq) → 2KCl(aq) + H2 O(l) + CO2 (g)
2HCl(aq) + CaO(s) → CaCl2 (aq) + H2 O(l)
4) By direct combination of metals and chlorine: This is done by passing pure dry chlorine gas over the
heated metal, e.g.
2Fe(s) + 3Cl2 (g) → 2FeCl3 (s)
2Al(s) + 3Cl2 (g) → 2AlCl3 (s)
5) By double decomposition: This is the method used to prepare insoluble chlorides such as silver chloride
and lead (II) chloride.
AgNO3 (aq) + NaCl(aq) → AgCl(s) + NaNO3 (aq)
Pb(NO3 )2 (aq) + 2KCl(aq) → PbCl2 (s) + 2KNO3 (aq)

THE TESTS FOR HALIDE IONS (𝐅 − , 𝐂𝐥− , 𝐁𝐫 − , 𝐈− )

A. Using acidified silver nitrate solution: Acidify the test solution with excess dilute nitric acid and then add a
few drops of aqueous silver nitrate. After making observations, excess aqueous ammonia is added:
- If the solution contains chloride ions, a white precipitate of silver chloride, which is soluble in aqueous
ammonia, would be formed.
Ag − (aq) + Cl− (aq) → AgCl(s)
⏟
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭

- If the solution contains bromide ions, a pale-yellow or cream precipitate of silver bromide, which is slightly
soluble in aqueous ammonia, would be formed.
Ag − (aq) + Br − (aq) → AgBr(s)
⏟
𝐏𝐚𝐥𝐞−𝐲𝐞𝐥𝐥𝐨𝐰 𝐨𝐫 𝐜𝐫𝐞𝐚𝐦 𝐩𝐩𝐭

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- If the solution contains iodide ions, a yellow precipitate of silver iodide, which is insoluble in aqueous
ammonia, would be formed.
Ag − (aq) + I − (aq) → AgI(s)
⏟
𝐘𝐞𝐥𝐥𝐨𝐰 𝐩𝐩𝐭

B. Using concentrated sulphuric acid: A sample of the unknown solid is heated with a little concentrated
sulphuric acid:
- If a chloride is present; misty fumes of pungent smelling hydrogen chloride gas which turns moist blue
litmus red, is evolved.
Cl− (s) + H2 SO4 (aq) → HCl(g)
⏟ + HSO4 − (aq)
𝐌𝐢𝐬𝐭𝐲 𝐟𝐮𝐦𝐞𝐬

- If a bromide is present, misty fumes of hydrogen bromide and a reddish-brown vapour of bromine are
evolved.
Br − (s) + H2 SO4 (aq) → HBr(g)
⏟ + HSO4 − (aq)
𝐌𝐢𝐬𝐭𝐲 𝐟𝐮𝐦𝐞𝐬

The concentrated sulphuric acid then oxidizes some of the hydrogen bromide to bromine.
2HBr(g) + H2 SO4 (aq) → ⏟2 (g)
Br + 2H2 O(l) + SO2 (g)
Reddish−brown

- If an iodide is present, a pungent purple vapour of iodine is evolved and a shiny black (iodine) is deposited.
I − (s) + H2 SO4 (aq) → HI(g) + HSO4 − (aq)
Concentrated sulphuric acid then oxidizes the hydrogen iodide to iodine vapour which eventually solidifies
forming shiny black iodine solid.
2HI(g) + H2 SO4 (aq) → 2 (g)
I⏟ + 2H2 O(l) + SO2 (g)
𝐏𝐮𝐫𝐥𝐞 𝐯𝐚𝐩𝐨𝐮𝐫
Deposition
I2 (g) → 2 (s)
I⏟
𝐒𝐡𝐢𝐧𝐲−𝐛𝐥𝐚𝐜𝐤

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