Halogens

The four non-metals, fluorine,

chlorine, bromine and iodine make
up a family of related elements. The
first member, fluorine is so reactive that
it cannot be isolated and therefore its
properties have no use in a school
laboratory. The properties of the
halogens have already been covered in
the topic periodic table.

As a group:

 all have the ability to form ionic salts with metals

 all are coloured

 all are poisonous and corrosive

 the reactivity decreases down the group (atomic size increases)

 are rarely found isolated since they are very reactive.

Complete the following table using the picture above.

Name of element Chlorine Iodine Bromine

State

Colour

Chemical properties

Oxidizing agents

Halogens are electron acceptors or oxidizing agents- chlorine, being the

smaller atom( of the commonly used halogens) is a stronger electron
acceptor thus a stronger oxidizing agent than bromine or iodine.

Bonding

Halogens can form both ionic (NaCl) and covalent (HCl, I 2) bonds.
 Displacement reactions

F (most reactive)

Cl

Br
(least reactive)
I

Each halogen can oxidize the ions of the halogen below it to the atoms:

E.g. Cl2 + 2NaBr → 2NaCl + Br2

Electron Acceptor
Oxidized because it lost electrons

This shows that chlorine is a very good electron acceptor. It causes the
bromide ions (Br-) to lose electrons (and hence be oxidized) and become
bromine atoms which join up to form bromine molecules, Br 2. The more
reactive the halogen is, the better an oxidizing agent it is.

Br2 + 2KI → 2KBr + I2

Cl2 + 2KI → 2KCl + I2

Note:

Bromine will NOT displace chlorine

Iodine will NOT displace bromine or chlorine

These reactions are accompanied by colour changes as shown in the table

below. Fumes/ vapors are produced at high temperatures while cloured
solutions are produced at room temperature.

Halide Halogen that will Colour changes

displace it

Chloride(Cl- F2 only Colourless →green fumes or yellow

) green solution
 Chlorine gas

Bromide(Br- Cl2, F2 Colourless → orange brown vapour or

) reddish brown solution

Bromine

Iodide (I-) Br2, Cl2, F2 Colourless → purple fumes or dark

brown solution or black solid deposits

Iodine

Reaction with silver nitrate (test for halide ions)

The suspected halide is dissolved in distilled water

A little amount of nitric acid is added ( to prevent formation of other

precipitates)

Silver nitrate (AgNO3) solution is added

The precipitation that forms is divided into 2 parts

o Ammonia solution is added to the first part

o The second part is exposed to light

Results

Halide ion Colour of ppt + Ppt + NH3 In light turns

AgNO3 solution violet than black
…..
Chloride White (AgCl) Dissolves Quickly
Bromide Pale Dissolves in Slower
yellow(AgBr) conc soln
Iodide Yellow (AgI) insoluble Slow

Reaction with hydrogen

All the halogens react with hydrogen, the reaction becoming less vigorous
going down the group.

Fluorine and hydrogen → explosive even in the dark ( to produce

HF)

Chlorine and hydrogen → slowly in daylight( to produce HCl)

Bromine and hydrogen → slowly in sunlight ( to produce HBr)

Iodine and hydrogen → has to be heated; reaction still slow ( to

produce HI)

The hydrogen halides (HCl, HI etc) that are produced are gases at room
temperature, very soluble in water to produce strong acids.

Chlorine
Occurs naturally as sodium chloride or rock salt. It is a pale green gas
which dissolves in water producing an acidic mixture.

Lab preparation of Chlorine

Chlorine gas is prepared by the oxidation of HCl using manganese (IV)

oxide, MnO2, or potassium permanganate, KMnO4.

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

In short : 2HCl + [O] → H2O + Cl2

The reaction is done in a fume cupboard (choking smell, very

poisonous).

Chlorine is denser than air, so downward delivery is used

Fumes of HCl are removed by passing through water

To dry chlorine gas, it is passed through a second bottle containing

conc H2SO4.

No heat is required if KMnO4 is used.

Chlorine produced may be collected over brine to decrease the

danger caused by the poisonous fumes.

Manufacture of chlorine

In industry, chlorine is manufactured by:

1. Electrolysis of molten NaCl

2. Electrolysis of brine.

Uses of chlorine

1. Sterilizing drinking water

 2. Sterilizing swimming pool water

3. To make PVC

4. Production of bleaches

5. As a fluid solvent( in correction fluid)

6. In the manufacture of HCl

Test for chlorine

Chlorine is a greenish yellow gas that rapidly bleaches damp litmus paper.

The bleaching action of chlorine

Chlorine is slightly soluble in water. The solution is known as chlorine

water and is a colourless solution with a tinge of green. Chlorine water is a
mixture of two acids: hydrochloric acid and hypochlorous acid.

Chlorine + water hydrochloric acid + hypochlorous acid

Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

Hypochlorous acid is an oxidizing agent- it gives oxygen to other

substances. If chlorine water is added to any dye, the dyed object is
bleached. This occurs as follows:

Dye + HOCl → HCl + (dye + O)

Since HCl is produced, the object must be rinsed well so that it is not
attacked by the acid. Commercial bleaches are not simply chlorine water
but also contain: sodium or calcium hypochlorite which releases the
bleaching action of chlorine when dissolved in water. These bleaches are
alkaline while chlorine water is acidic.

Chemical properties of chlorine

Chlorine burns with a small, red sooty flame.

1. Reaction with water

Very soluble in water to form chlorine water which contains a mixture of

hydrochloric and hypochlorous acids therefore it is acidic. Hypochlorous
acid (HOCl) easily decomposes in sunlight to produce HCl and oxygen.
 2. Combines with other elements

Chlorine is a very reactive non-metal and it combines with other elements

easily.

a. + Hydrogen: Cl2 + H2 → 2HCl

A mixture of hydrogen and chlorine is explosive if exposed to sunlight( or

sunlight ( or any uv light). Chlorine reacts with all metals including gold.

b. + aluminum: 2Al + 3Cl2 →2AlCl3

If aluminum is heated in a steam of dry chlorine, white of aluminum

chloride are produced.

c. + iron: 2Fe + 3Cl2 →2FeCl3 ( passing over heated iron)

FeCl3 is dark brown and very deliquescent; it easily turns into FeCl 3. 6H2O
which is yellow.

3. As an oxidizing agent

Chlorine gains electrons and this makes it an oxidizing agent. It accepts

electrons quite readily and this makes it a strong oxidizing agent.

Eg.a. +H2S:

H2S(g) + Cl2(g) → 2HCl(g) +S(s)

Cl2 is a stronger oxidizing agent than H 2S

Eg.b. + FeCl2:

2FeCl2 + Cl2 → 2FeCl3

Pale green brownish yellow

In this reaction, chlorine atoms in the Cl 2 molecule gain electrons from the
Fe2+ ions which turn into Fe3+ ions in the process. The chlorine atoms
change into Cl- ions (forming part of the FeCl3).

4. Reaction with alkali

a. With dilute, cold alkali solution → pale yellow solution containing the
chloride + hypochlorite
 Cl2 + NaOH → NaOCl + NaCl + H2O

b. with hot, conc alkali solution: → chlorate + chloride

6KOH + 3Cl2 → KClO3 + 5KCl + 3H2O

Hydrogen chloride

Properties of hydrogen chloride

Hydrogen chloride is:

A colourless gas

Has a chocking smell

Is denser than air

Produces fumes in moist air

Lab. Preparation of Hydrogen Chloride

Hydrogen chloride is prepared by adding concentrated sulfuric acid to

sodium (or calcium chloride.

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

There is effervescence and misty fumes of HCl are observed. Conc sulfuric
acid is used to dry the gas produced and collection is by downward
delivery (since HCl is denser than air).To prepare hydrochloric acid a
solution of the gas in water is made by means of a funnel arrangement as
used in the preparation of ammonia solution (and other very soluble
gases)For properties of acid and preparation of chlorides from acid, see
Acids and Alkalis.

Test for hydrogen chloride

 Turns moist blue litmus red

Produces white precipitate with silver nitrate ( or nitric acid)

Produces dense white fumes with ammonia

Hydrochloric acid

Hydrochloric acid is a typical strong acid and behaves like any other acid.
It is used to make:

To make PVC

For preparing metal surfaces for electroplating

In the manufacture of dyes and drugs

Work sheet - Displacement

1. A student wanted to investigate the reactions of halogens with

solutions of their salts. The student obtained the following results.

Potassium Potassium Potassium No of

chloride bromide iodide reactions
taking place
Chlorine No reaction The solution The solution
water turned turned into a
orange grey colour

Bromine No reaction No reaction The solution

water turned into a
grey colour
Iodine No reaction No reaction No reaction
solution

a) Count the number of reactions seen in each row and write the results
in your table – the halogen that produces the most reactions is the
most reactive of the three.
b) Write the names of the halogens in order of reactivity, from the most
reactive to the least.
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c) Explain this trend in reactivity.
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d) What results might you get if fluorine water and potassium fluoride
were in the experiment too?
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e) Write symbol equations for each of the reactions seen in the
experiment.
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