The Halogens

The Halogens
Properties of the halogens
• The halogens are the elements in group 7 of the periodic table.

• They all have seven electrons in their outer shells and form negative ions with a -1
charge.
• Since they gain an electron to achieve a full outer shell, halogens are reduced in redox
reactions.
• They all have an outer shell electron configuration of s2 p5.
• In their neutral state, they exist as diatomic molecules (two atoms covalently bonded
together)
As you go down the group, their melting and boiling point increases — so the elements at
the top of the group (fluorine and chlorine) exist as gases at room temperature, whereas
bromine is a liquid and the elements at the bottom (iodine, astatine) are solids.
Melting and boiling points increase down the group because:
• The number of electrons increases, so they form stronger London forces with other
molecules.
• The stronger London forces need more energy to overcome.

Reactivity
As you go down the group, the reactivity of halogens

decreases.
This is because:
• The outer electrons are further away from the

nucleus, so the attraction between the nucleus and
outer electron shell decreases.
• There is more electron shielding, which further

decreases the nuclear charge.
• This makes it harder to grab hold of an additional

electron and place it in the outermost shell, resulting in a reduction in reactivity
from fluorine to iodine.
You can work out the order of halogen reactivity by carrying out a displacement reaction,
since a more reactive halogen will be able to replace a less reactive halogen in a compound
but not vice versa.
• For any element in group 7, it will be able to displace any halogen that is beneath
it in the periodic table.
• For example, if you mix bromine water with potassium iodide, we’d expect the
bromine to displace iodine because it is more reactive. We end up with iodine and
potassium bromide. Bromine water is yellowy orange, so we will observe a colour
change from yellow/orange to colourless.
But no reaction takes place if you mix bromine water with potassium chloride. Bromine is
beneath chlorine in group 7, so it is less reactive and unable to replace it in the compound.
The reaction mixture will remain a yellow/orange colour.
To make the colour changes of halogen displacement reactions easier to see, we can add
an organic solvent (e.g., hexane) to the reaction mixture. The halogen that is present will
dissolve in the organic solvent, settling out
as a distinct layer above the aqueous
solution. Here’s what colour each halogen
will appear as in organic solvent:
• Chlorine – pale yellow green
• Bromine – orange
• Iodine – purple
Test for halide ions
To test for halide ions, add dilute nitric acid and silver nitrate. Nitric acid removes any
impurities that might obscure the result. Silver nitrate then reacts with any halide ions to
form coloured silver halide precipitates.
• Silver chloride is a white precipitate
• Silver bromide is a cream precipitate
• Silver iodide is a pale yellow precipitate
The issue with this test is that the colours of the precipitates are subjective. To confirm our
result, we can carry out an additional test involving ammonia solution.
The three precipitates have different solubilities in aqueous ammonia:
• Silver chloride dissolves in dilute ammonia solution
• Silver bromide will only dissolve in concentrated ammonia solution
• Silver iodide will not dissolve in dilute or concentrated ammonia solution (it is
insoluble)
Disproportionation reactions
Disproportionation is when the same element is simultaneously oxidised and reduced.
For example, in the manufacture of bleach, chlorine gas is mixed with cold, dilute aqueous
sodium hydroxide. Sodium hypochlorite (NaClO), or bleach, is formed, along with sodium
chloride and water.
Assigning oxidation numbers to the reactants and products, we can see that chlorine is
being both oxidised and reduced.
• Cl goes from 0 in Cl2 to +1 in NaClO therefore it is being oxidised
• Cl goes from 0 in Cl2 to -1 in NaCl therefore it is being reduced
Since oxidation and reduction are happening to the same element in the same
reaction, disproportionation is taking place.
Uses of chlorine
• Used in bleach — a useful household disinfectant.

• Added to water to make it safe to drink — chlorine kills microorganisms and prevents
diseases such as cholera and typhoid.
• The equation below shows what happens when chlorine is added to water. This is
another example of a disproportionation reaction.
Toxicity
• Chlorine gas is toxic and can irritate the respiratory system if inhaled.
• Liquid chlorine can burn the skin and irritate the eyes, causing serious injuries.
• When chlorine reacts with hydrocarbons, it forms chlorinated hydrocarbons which
can cause cancer if they make their way into the human body (they are
carcinogenic).

The Halogens

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The Halogens

Properties of the halogens

• The halogens are the elements in group 7 of the periodic table.

Melting and boiling points increase down the group because:

• The stronger London forces need more energy to overcome.

As you go down the group, the reactivity of halogens

• The outer electrons are further away from the

• There is more electron shielding, which further

• This makes it harder to grab hold of an additional

• Chlorine – pale yellow green

Test for halide ions

• Silver bromide is a cream precipitate

• Silver iodide is a pale yellow precipitate

The three precipitates have different solubilities in aqueous ammonia:

• Silver chloride dissolves in dilute ammonia solution

• Silver bromide will only dissolve in concentrated ammonia solution

Disproportionation is when the same element is simultaneously oxidised and reduced.

• Cl goes from 0 in Cl2 to -1 in NaCl therefore it is being reduced

• Used in bleach — a useful household disinfectant.

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