The Halogens

The elements in Group 17* (the halogens) all exist as diatomic molecules, containing a
single covalent bond. They are all non-metals.
* the convention is to number all groups across the periodic table, including the groups of d-block
elements. We did not do this at GCSE as it was convenient to have the group number equalling the
number of outer-shell electrons, and therefore refer to the halogens as Group 7.

Physical properties

F2

Cl2

Br2

I2

Down the group:

- the melting and boiling points increase (gas liquid solid at room temp.)
- the colour becomes more intense
The trend in boiling points (-188C, -34.6C, 58.8C, 184C) and melting points is explained
in terms of the increasing strength of the intermolecular forces which hold the halogen
molecules to one another. There are no polar bonds (same atom so same electronegativity
at each end of the bond) and no prospect of hydrogen bonding, so instantaneous dipoleinduced dipole (London forces) are the only intermolecular forces present. These increase
with the number of electrons present in the molecule.
Note: Iodine is unusual because it SUBLIMES when it is heated (goes straight from solid to vapour without
going through a liquid state).

On the basis of the observed properties we can predict the physical properties of fluorine
(too reactive for use in school labs) and astatine (radioactive and decays very quickly, so
very low abundance):
Fluorine is a very pale coloured gas at room temperature
Astatine is a black solid at room temperature
Chemical properties
The halogens all form halide ions (F-, Cl-, Br- and I-) by gaining an electron to become
isoelectronic with noble gases.
e.g.

Cl2 + 2e- 2Cl-

The gain of an electron is reduction, so the halogens are oxidising agents, themselves
being reduced and causing the substances they react with to be oxidised.
Halide ions are colourless.

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Trend in reactivity
The ease with which the halogens can attract an electron to become a halide determines
their reactivity: The reactivity decreases down the group with fluorine being the most and
iodine the least reactive halogen.
Down the group reactivity decreases because:
The atomic radius increases as more shells are filled the smaller the halogen atom is,
the closer it's (positively charged) nucleus can get to other atoms to attract an electron
from them. Fluorine will be able to get closer than any other halogen.

Shielding increases the more filled shells there are between a halogen atom's nucleus
and other atoms, the less its nucleus will be able to attract an electron from them.
Fluorine has fewest filled shells surrounding the nucleus.

Nuclear charge increases due to the increasing number of protons in the nucleus, but
the two factors above outweigh this, so the electron to be attracted experience less
attraction.

Oxidising Power
Since the halogens get less reactive down the group, they are less effective at oxidising
other substances, and hence their oxidising power decreases down the group.
Reactions of Group 7
i) Displacements
These displacement reactions demonstrate the decreasing reactivity down Group 17. A
more reactive halogen atom can remove an electron from a halide ion of a less reactive
halogen. In doing this, the more reactive halogen is reduced to a halide ion, and the halide
ion is oxidised to a halogen, so these are also redox reactions.
We can represent the set of such reactions using ionic equations:
chloride ions
bromide ions
iodide ions

chlorine
No reaction
Cl2 + 2Br - 2Cl- + Br2
Cl2 + 2I- 2Cl- + I2

bromine
No reaction
No reaction
Br2 + 2I- 2Br- + I2

iodine
No reaction
No reaction
No reaction

In practice we can do these reactions using iodine solution, bromine water (bromine
solution) and chlorine water or chlorine gas, reacting these halogens with sodium or
potassium halide solutions. In each case we need to observe the colour of the halogen that
is initially present, then note the colour of the halogen present after the halide ions have
been mixed, to determine if a reaction has taken place. There is no contribution to the
colour from the halide ions, as these are colourless.
It can be difficult to tell the colour of aqueous bromine from the colour of dilute aqueous
iodine, so the solution can be shaken with a layer of an inert organic liquid such as
cyclohexane, in which the halogens are very soluble.

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Halogen
Chlorine, Cl2
Bromine, Br2
Iodine, I2

In aqueous solution
Colourless
Yellow orange
Orange red/brown

In organic layer
Colourless
Orange
Purple

Reactions with chlorine

Chlorine undergoes displacements reactions with bromide ions, forming bromine in the
solution, along with chloride ions:
Full:
Ionic:

2 KBr(aq) + Cl2(aq) 2 KCl(aq) + Br2(aq)

2 Br-(aq) + Cl2(aq) 2 Cl-(aq) + Br2(aq)
-1
0
-1
0
reduction
oxidation

Observations: yellow - orange colour appears in the colourless solution. If shaken with an
organic layer, this turns orange.
Chlorine also undergoes displacements reactions with iodide ions, forming iodine in the
solution, along with chloride ions:
Full:
Ionic :

2 KI(aq) + Cl2(aq) 2 KI
+ Br2(aq)
2I (aq) + Cl2(aq) 2 Cl (aq) + I2(aq)
-1
0
-1
0
reduction
oxidation

Observations: orange/red/brown colour appears in the colourless solution (colour depends

on the amount of iodine released into solution). If shaken with an organic layer, this turns
purple.
Reactions with bromine
Bromine undergoes a displacement reactions with iodide ions forming iodine in the solution
along with bromide ions, but does not react with choride ions.
Full:
Ionic :

2 NaI(aq) + Br2(aq) 2 NaBr(aq) + I2(aq)

2 I-(aq) + Br2(aq) 2 Br-(aq) + I2(aq)
-1
0
-1
0
reduction
oxidation

Observations: The bromine water is initially orange. After mixing the bromine water and
colourless iodide ions, the colour deepens becoming orange/red/brown. The presence of
iodine can be seen by shaking with an organic layer, which will turn purple.

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On the basis of these reactions we can predict that fluorine will displace chlorine from
chloride ion solutions, bromine from bromide ions, and iodine from iodide ions. None of the
other halogens will be able to displace fluorine from a solution containing fluoride ions.
ii) Reaction of halide ions with silver ions
Aqueous halide ions react with aqueous silver ions to form precipitates of insoluble silver
halides, which have characteristic colours. These are not redox reactions.
Typically silver nitrate solution is used as a source of aqueous silver ions, and any soluble
halides can be used e.g. sodium or potassium halide solutions.
The ionic equations for the reactions taking place are:
Ag+(aq) + Cl-(aq) AgCl(s)

white precipitate

Ag+(aq) + Br-(aq) AgBr(s)

cream precipitate

Ag+(aq) + I-(aq) AgI(s)

yellow precipitate

The silver bromide precipitate is light-sensitive, and soon darkens to a grey colour. This is
the basis of photographic film and papers.
iii) Disproportionation reactions
An interesting effect is seen when halogens reacts with water, or with cold dilute sodium
hydroxide, known as disproportionation.
Definition:

Disproportionation is a reaction in which the same element is simultaneously

oxidised and reduced.

Reaction of chlorine with water

Chlorine reacts with the water to form two acids in solution:
hydrochloric acid
Cl2(g) + H2O(l) HCl(aq)
reduction +1 -1
0
oxidation

chloric acid
+

HClO(aq)
+1 +1 -2

Both HCl and HClO split up in aqueous solution to produce H+ ions, turning indicators such
as blue litmus red, however the ClO-(aq) ion is also a powerful oxidizing agent, so shortly
after the indicator paper becomes bleached to a white colour.
Reaction of chlorine with cold dilute sodium hydroxide
This is the reaction used commercially to produce bleach. Bleach is an aqueous solution of
sodium chloride and sodium chlorate(I). The reaction is:

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Cl2(g) + 2 NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)

0
-1
+1
The bleaching action occurs because the ClO- ion is a powerful oxidizing agent, reacting
with dyes to oxidize them, and itself becoming reduced to Cl- ions.
Similar disproportionation reactions happen with the other halogens, and with other alkalis,
such as potassium hydroxide.
Water treatment with chlorine
Chlorine began to be used as a disinfectant for dinking water treatment over 100 years ago.
Harmful bacteria are killed by the chloric acid and chlorate(I) ions rather than by chlorine
itself, making the water safe to drink or swim in. The use of chlorine has both risks and
benefits, and there are also ethical considerations: not everyone agrees with not having a
choice over having our water chlorinated.
Risks
Chlorine gas is toxic in large concentrations, and a respiratory irritant in lower
concentrations.
Chlorine in drinking water can react with organic hydrocarbons such as methane
from decaying vegetation, forming chlorinated hydrocarbons which may be
carcinogenic.
Benefits
Risk to health from chlorinated hydrocarbons is far less than the risk to health from
diseases such as typhoid and cholera.
Some chlorine persists in the water preventing re-infection after treatment.

Alternatives to chlorine
Ozone, O3, is also a powerful oxidizing agent and can be added to water to kill
microorganisms. It is expensive to produce, however, and does not last for long in
the water.
Ultraviolet light can also be used to kill microorganisms by damaging their DNA, but
it is ineffective in cloudy water and like O3 does not stop the water becoming infected
subsequently to treatment.

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