Halogens

HALOGENS

Halogens (salt formers) are found in group VII of the periodic table. They are the most
reactive non-metals. They have seven valence electrons, they exist as diatomic molecules,
and they are coloured and ionizes to form univalent negative ions. They form electrovalent
compounds with metals. In the group are chlorine, fluorine, bromine, iodine and astatine.

ELECTRONIC CONFIGURATION OF HALOGENS

The electronic configurations of the halogens are shown below:

Fluorine = 9: 1s2 2s2 2p5

Chlorine = 17: 1s2 2s2 2p6 3s2 3p5

Bromine = 35: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5

Iodine = 53: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5

PHYSICAL PROPERTIES OF THE HALOGENS

1. They are usually univalent, and easily accept one electron from
other atoms to form ionic compounds (especially from metals e.g.
Na & K). They also share electrons with themselves or with non-
metals to form covalent compounds.
2. They exist in their natural states as non-polar diatomic molecules.
 3. Fluorine and chlorine are gases, bromine is a liquid and iodine is a
solid.
4. The halogens are coloured, with a typical penetrating odour. The
colours deepen down the group. Fluorine is pale-yellow, chlorine is
greenish-yellow, bromine is red and iodine is violet.
5. They are volatile substances. Their volatility decreases down the
group.
6. All the halogens except fluorine, dissolve to some extent in water,
fluorine reacts with water to give oxygen and hydrogen fluoride.

CHEMICAL PROPERTIES OF THE HALOGENS

The halogens are very reactive elements. Their reactivity decreases down the group. Fluorine
is the most reactive halogen. They are also strongly electronegative. Their Electronegativity
decreases down the group.

1. As oxidizing agents: Halogens are strong oxidizing agents. They

do so by accepting electrons and forming halide ions especially in
the reaction with metals. The oxidizing power decreases down a
group.
2. Reaction with metals: Halogens react with metals to form ionic
compounds. 2Na(s) + F2(g) → 2NaF(s)
3. Reaction with hydrogen: Fluorine explodes with hydrogen even in
the dark, chlorine reacts slowly in the dark but explodes in bright
sunlight, bromine reacts with hydrogen in the presence of a
platinum catalyst; while iodine reacts partially with hydrogen on
heating. Example

H2(g) + Cl2(g) → 2HCl(g)

Stability of the hydrogen halides decreases down the group. Hydrogen fluoride is a liquid
with a boiling point of 19OC. The other hydrogen halides are gases.

4. Reaction with water: Fluorine reacts vigorously with water to give off
oxygen gas. Chlorine reacts very slowly with water to give a mixture
of hydrochloric acid and oxochlorate (I) acid which later decomposes
to give hydrochloric acid and oxygen gas. The oxygen gas given off
by the oxochlorate (I) acid is responsible for the bleaching action of
moist chlorine gas and chlorine water.

H2O(g) + Cl2(g) → HCl(aq) + HOCl(aq)

CHLORINE

Chlorine is the most important element in the halogen family. It does not occur as a free
element in nature because it is too reactive. It is usually found in combined state as chlorides.
LABORATORY PREPARATION OF CHLORINE

1. By the oxidation of concentrated HCl with strong oxidizing agent

such as MnO2 or KMnO4

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

2. By heating concentrated H2SO4 with a mixture of NaCl and MnO2

2NaCl(s) + MnO2(s) + 2H2SO4(aq) → Na2SO4(aq) + MnSO4(aq) + H2O(l) + Cl2(g)

INDUSTRIAL PREPARATION

Chlorine is manufactured industrially by the electrolysis of brine and molten NaCl, MgCl 2 or
CaCl2.

PHYSICAL PROPERTIES

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

2. It is a poisonous gas.
3. It is about 2.5 times denser than air.
4. It can be liquefied under a pressure of about 6atm.
5. It is moderately soluble in water.

CHEMICAL PROPERTIES

1. It is very reactive and tends to attain stability by forming an

electrovalent compound with metals and a single covalent bond
compound with non-metals.

2Na(s) + Cl2(g) → 2NaCl(s)

Cl2(g) + H2(g) → 2HCl(g)

2. It displaces other halogens from solution of their acids and salts

 Cl2(g) + NaI(aq) → 2NaCl(aq) + I2(g)

3. It combines directly with other elements except oxygen, nitrogen

carbon and the noble gases; to form chlorides

Ca(s) + Cl2(g) → CaCl2(s)

4. It has a very strong affinity for hydrogen; it removes hydrogen from

its compounds.

C10H12(l) + 8Cl2(g) → 10C(s) + 16HCl(g)

5. It is a powerful oxidizing agent: it oxidizes green Fe 2+ to yellow Fe3+

2FeCl2(aq) + Cl2 →2FeCl3(aq)

6. It has a bleaching action: in the presence of water, chlorine bleaches

most dyes and inks except printer’s ink. The bleaching action of
chlorine is due to its ability to react with water to form oxochlorate
(I) acid which decomposes to release oxygen which oxidizes the dye
to form a colourless compound.

H2O(l) + Cl2(g) → HCl(aq) + HOCl(aq)

HOCl(aq) → HCl(aq) + [O]

Dye + [O] → [Dye + O]

Coloured . Colourless

7. It reacts with hot concentrated NaOH solution to give a mixture of

trioxochlorate (V) and chloride of the metal.

6NaOH + 3Cl2(g) → NaClO3(aq) + NaCl(aq) + H2O(l)

. Sodium trioxochlorate (V)

With cold dilute solution of NaOH, a pale yellowish mixture of oxochlorate (I) and chloride
of the metal is formed.

2NaOH(aq) + Cl2(g) → NaOCl(aq) + NaCl(aq) + H2O(l)

8. It reacts with slaked lime solutions to produce bleaching powder

Ca(OH)2(aq) + Cl2(g) → CaOCl2.H2O(s)

Bleaching powder

TEST FOR CHLORINE

 1. It turns damped blue litmus paper pink and then bleaches it. It is an
acidic gas.
2. It turns damped starch-iodide dark blue. Chlorine turns starch-iodide
paper blue because it displaces iodine from the iodide. The iodine
liberated then turns the starch blue.

USES OF CHLORINE

1. It is a powerful germicide [due to its oxidizing nature].

2. It is used as a bleaching agent for cotton, wool, pulp etc.
3. It is used in the manufacture of polyvinyl chloride (PVC) and
synthetic rubber.
4. It is used in the manufacture of organic compound e.g. CHCl 3, CCl
5. It is used in producing KClO3, for making matches and fireworks.
6. It is used for making NaClO3, a weed killer.
7. It is used for making domestic antiseptics e.g. acidified NaClO
solution.

COMPOUNDS OF CHLORINE

HYDROGEN CHLORIDE

Hydrogen chloride (marine-acid gas) exists as a gas at room temperature. It dissolves in water
to form hydrochloric acid. It occurs in traces in the air as an industrial by-product and is
considered as air pollutant, but it can be easily washed down as acid rain since it is very
soluble in water.

LABORATORY PREPARATION
The gas is prepared by the action of hot concentrated H2SO4 on any soluble chloride.
Example 2NaCl(s) + H2SO4(aq) → Na2SO4(aq) + 2HCl(g)

Note: NaHSO4 is first formed at a lower temperature and later at higher temperature HCl gas
is formed. The gas is dried by passing it through concentrated H2SO4 in another flask and
collected.

INDUSTRIAL PREPARATION

Pure HCl gas can be produced in large scale by direct combination of hydrogen and chloride
gas obtained from the electrolysis of brine.

H2(g) + Cl2(g) → 2HCl(g)

PHYSICAL PROPERTIES

1. Pure HCl gas is colourless and has a sharp irritating smell

2. It turns damp blue litmus paper red
3. It is about 1.25times denser than air
4. It is very soluble in water, forming aqueous HCl acid
5. It is readily dissolved in non-polar solvents like chloroform and
toluene, but the solution does not conduct electricity and has no
acidic properties because hydrogen chloride which is a covalent
molecule does not ionize when it dissolve in non-polar solvents. But
it dissolves in water and ionizes. The ions formed in aqueous
solution are responsible for the acidic property and conductivity of
its aqueous solution.
6. It forms misty fumes in moist air because it dissolves in the moisture
to form tiny droplets of HCl acid.
7. It does not support combustion.

CHEMICAL PROPERTIES

1. It combines directly with NH3 and produces white fumes of

ammonium chloride

HCl(g) + NH3(g) → NH4Cl(s)

2. It reacts with various heated metals to form their respective chloride

and hydrogen

Zn(s) + 2HCl(g) → ZnCl2(s) + H2(g)

TEST FOR HYDROGEN CHLORIDE

1. A gas rod that has been dipped in ammonia solution is brought near
the gas jar containing the unknown gas, if there are dense white
fumes on the glass rod, then the gas is hydrogen chloride gas.
 2. Few drops of silver trioxonitrate (V) is added to the gas jar
containing the unknown gas and shaken. If white precipitate of silver
chloride is observed, then the gas is hydrogen chloride gas.

CHLORIDES

Chlorides are normal salts formed when metallic ion replace the hydrogen ion in hydrochloric
acid. Chlorides are prepared by neutralization reaction. Chlorides are soluble in water with
the exception of few.

Soluble chlorides Insoluble chlorides

NaCl, NH4Cl, KCl CuCl2, AgCl, PbCl2

CaCl2 etc

PROPERTIES

1. Chlorides are not decomposed by heat. They can only be recovered

from solution by evaporation to dryness or sometimes by
crystallization.
2. They react with hot concentrated tetraoxosulphate (VI) acid to
produce hydrogen chloride gas.

2NaCl(s) + H2SO4(aq) → Na2SO4(aq) + 2HCl(g)

3. On heating a chloride with concentrated tetraoxosulphate (VI) in the

presence of a strong oxidizing agent, chlorine is produced.

ZnCl2(s) + KMnO4(s) + 2H2SO4(aq) → ZnSO4(aq) + K2SO4(aq) +

2MnO2(aq) + 2H2O(l) + Cl2(g)

TEST FOR CHLORIDES

The test solution is acidified with dilute trioxonitrate (V) acid to prevent precipitation of other
salts. Few drops of AgNO3(aq) is then added to the acidified solution in a test tube, a white
precipitate of AgCl which readily dissolves in excess NH3(aq) solution indicates the presence
of chloride.