Halogens

The halogens are the collective name given to the elements in group VII of the Periodic Table which
include fluorine, chlorine, bromine, iodine and astatine. Astatine is radioactive element. All these
elements are most commonly found in the -1 oxidation state.
Melting and boiling points
The melting and boiling points of the halogens increase steadily down the group. This is due to the
increase in strength of the Van Der Waal’s forces between the molecules, which results from the
increasing number of electrons in the molecule and the increasing surface area of the molecule.
Electronic Configuration
The followowing are the electronic configuration of halogens; fluorine 2,7, chlorine 2,8,7 Bromine
2,8,18,7, Iodine 2,8,28,18,7 and Astatine 2,8,18,32,18,7 respectively
Chemical tests
1. Chlorine – Turns damp litmus red, and then bleaches it.
2. Bromine – Bromine also turns damp litmus red and bleaches it but slower. When sodium
hydroxide is added, bromine loses its colour.
3. Iodine – When starch solution is added, a blue/black colour forms
Physical properties
1. Poor conductors of heat and electricity
2. Low melting point and boiling point.Melting point and boiling point increases (going down the
group) – molecular size increases / forces of attraction between molecules
3. Colour: F2 (pale yellow gas), Cl2 (greenish-yellow gas), Br2 (reddish-brown liquid), I2 (purplish-
black solid) and At2 (black solid – rarest naturally occurring element and extremely radioactive)
4. Low density (Density of element increases (going down the group) – increase in atomic mass)
Chemical properties
1. Oxidation – reduction behaviour
The halogens can act as oxidising agents by gaining electrons to form halide ions.
X2 + 2e– → 2X–
The oxidising ability decreases down the group with fluorine being the strongest oxidising agent. 2.
2. Reaction with water
F2 oxidises H2O to O2 gas in a very exothermic reaction
2F2(g) + 2H2O(l) → O2(g) + 4HF(g)
Cl2 dissolves in H2O and some hydrolysis occurs. A yellow solution of ‘chlorine water’ is formed which
is a mixture of two acids. No O2 is evolved.
Cl2(g) + H2O(l) → HCl(aq) + HOCl(aq)
Br is only slightly soluble in H2O and there is less hydrolysis.
Br2(l) + H2O(l) → HBr(aq) + HOBr(aq)
I2 is virtually insoluble in H2O. It is however soluble in KI solution due to the formation of the triiodide
anion.
I2(s) + I–(aq) → I3–(aq)
Note: All halogens are more soluble in non-polar solvents such as CCl4. Cl2 gives a colourless solution.
Br2 a red solution and I2 a violet one.
3. Displacement reactions
If a more reactive halogen is placed into a solution containing a less reactive halide a displacement
reaction is seen.
For example: Cl2(g) + KI(aq) → KCl(aq) + I2(s)
F2 will displace Cl– Br– I–
4. Reaction with alkali ( NaOH solution)
This reaction depends on the conditions:
Cold NaOH solution.
2NaOH(aq) + Cl2(g) → NaCl(aq) + NaClO(aq) + H2O(l)
Hot NaOH solution.
6 NaOH(aq) + Cl2(g) → 5 NaCl(aq) + NaClO3(aq) + 3H2O(l)

Chlorine
Chlorine is a greenish yellow gas which combines directly with nearly all elements. Chlorine mainly
occurs as rock salt (NaCl) Carnallite, (KCl, MgCl2.6H2O) and calcium chloride. (CaCl2). Chlorine is very
reactive and is not found free in nature as Cl2 gas. It is most found as common salt NaCl.
Industrial Preparation of Chlorine
Chlorine is extracted from the purified molten ore of sodium chloride by use of electrolysis in the Down’s
Cell. During this process sodium chloride is decomposed into sodium and chlorine. The Na ions are
attracted to the iron cathode, and deposit as sodium metal, whilst the chlorine ions move towards the
graphite anode to form chlorine gas. This gas bubbles up under the steel hood above the anode and is
collected.
2NaCl + 2H2O ———————> 2Na + Cl2
USE 10 TO 15 LINES FOR DIAGRAM
Laboratory Preparation of Chlorine
From concentrated hydrochloric acid by oxidation

Chlorine can be prepared by removing the hydrogen from hydrochloric acid using an oxidizing agent such
as potassium permanganate or potassium dichromate can be used.
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2
Note: No heating is required in when potassium permanganate is used as an oxidizing agent in the above
method of preparing chlorine.
USE 15 LINES FOR DIAGRAM AND EQUATION OF Cl FROM MnO2
Test for Chlorine
It is a greenish-yellow gas which turns damp blue litmus red and then bleaches it.
Physical Properties
1. It is a pale yellow-green gas which is denser than air
2. It has a choking smell, and even in small quantities
3. It is poisonous to people and animals
4. This made it suitable for use in chemical warfare during World War I
Chemical Properties
1. It combines with metals and non metals to form chlorides.
2. it decomposes water forming HCl and HClO (hypochlorous acid) which is unstable and
decomposes giving nascent oxygen which is responsible for oxidizing and bleaching action of
chlorine.
Cl2 + H2O ——> HCl + HClO;
HClO —> HCl + [O]
Coloured matter + O —> Colourless matter.( permanent)
 it cannot be used for bleaching delicate articles such as straw, silk, wool etc. which are damaged
by it.
3. Cl2 oxidizes Br– and I– ions to Br2 and I2 respectively.
Cl2 + 2X– ——> 2Cl– + X2 (X = Br or I).
4. It combines with alkalis forming hypochlorite and chlorate salts in cold and hot conditions
respectively.
2NaOH (dil.) + Cl2 ————> NaCl + NaClO + H2O (Cold condition)
2NaOH (conc.) + 3Cl2 ————> 5NaCl + NaClO3 + 3H2O (Hot condition)
5. Reactions where a halogen is simultaneously reduced to X– ion and is oxidized to either
hypohalite (XO–) or halate (XO–3) ion is are called disproportionation reaction.
6. With slaked lime, Cl2 gives bleaching powder (CaOCl2)

Ca(OH)2 + Cl2 ———> CaOCl2 + H2O

7. With ammonia, Cl2 reacts as follows
8NH3 (excess) + 3Cl2 ———> 6 NH4Cl + N2
NH3 + 3Cl2(excess) ———> NCl3 + 3HCl
Uses
Chlorine is a major industrial chemical and it is used in:
1. The extraction of metals such as titanium
2. The manufacture of plastics, such as PVC and solvents, such as trichloroethane
3. The production of drugs, dry-cleaning fluids, weedkillers, pesticides and bleaches
4. The purification of water
Hydrogen Chloride
Hydrogen chloride was discovered in 1648. It occurs in free state in volcanic gases and in gastric juices of
mammals. It was first prepared in 1648 by scientist called Johann Rudolf Glauber using rock salt and
concentrated sulphuric acid. In 1772, Joseph Priestley was able to obtain it in pure form.
Industrial Preparation of Hydrogen Chloride
Hydrogen can be burnt in chlorine.
H2(g) + Cl2(g) —–> 2HCl(g)
The product can then be used to prepare hydrochloric acid. This is done by passing hydrogen chloride gas
through an absorption tower where it is dissolved in water. HCl(g)—-> HCl(aq)
Laboratory Preparation
In the laboratory, hydrogen chloride may be prepared by reacting sodium chloride with concentrated
tetraoxosulphate (VI) acid. It is a reversible reaction, but as the hydrogen chloride gas is removed, the
equilibrium shifts to the right
USE 14 LINES FOR DIAGRAM
NaCl(s) + H2SO4(l) —-> NaHSO4(s) + HCl(g)
Physical properties
1. It is a colourless gas with a pungent smell and a slightly sour taste
2. It does not support combustion but extinguishes a glowing splint
3. acid which turns both litmus and pH paper red.
4. It is very soluble in water
5. Liquefies at 10⁰ C, boils at –83⁰C and Freezes at –113⁰ C
Chemical properties
1. It forms dense white fumes of ammonium chloride when it reacts with ammonia.
NH3(g) + HCl(g) —-> NH4Cl(g)
2. It reacts with metals producing salt and hydrogen,
Mg(s) + 2HCl(aq) MgCl2(s) + H2(g)
3. It will react with bases to form a salt (metal chloride) and water.
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
4. It will react with copper (II) oxide forming copper (II) chloride and water.
CuO(s) + 2HCl(aq) CuCl2(aq) + H2O(l)
5. It will react with carbonates forming a salt, water and carbon dioxide. CaCO3(s) + 2HCl(aq)
CaCl2(aq) + H2O(l) + CO2(g)
Uses of hydrochloric acid
It is used in the:
1. Production of vinyl chloride, the monomer for PVC
2. Preparation of metal surface before electroplating or galvanizing
3. Manufacture of drugs where acidic conditions may be required
4. Manufacture chlorine and some other chlorides.
5. Saturated solution of zinc chloride in dilute hydrochloric acid is used to clean metallic surfaces
before plating or soldering.