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What are the halogens?
The halogens are the elements in Group 7 of the
periodic table.

The name halogen comes from the Greek

words for salt-making.

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Physical properties of halogens

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Trends in boiling point
Halogen molecules increase in size down the group. This
leads to greater van der Waals forces between molecules,
increasing the energy needed to separate the molecules
and therefore higher melting and boiling points.

van der
Waals forces

fluorine iodine
atomic radius = 42 × 10-12 m atomic radius = 115 × 10-12 m
boiling point = -118 °C boiling point = 184 °C
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Trends in electronegativity
Electronegativity of the halogens decreases down the group
due to an increase in atomic radius.

Increased nuclear charge has no significant effect because

there are more electron shells and more shielding. Iodine
atoms therefore attract electron density in a covalent bond
less strongly than fluorine.

fluorine iodine
atomic radius = 42 × 10-12 m atomic radius = 115 × 10-12 m
electronegativity = 4.0 electronegativity = 2.5

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Astatine
The name astatine comes from the Greek word for unstable.

Astatine exists in nature in only very tiny

amounts. It is estimated that only 30 grams of
astatine exist on Earth at any one time. This is
because it is radioactive, and its most stable
isotope (210At) has a half-life of only 8 hours.

It was first made artificially in 1940, by bombarding 209Bi with

a-radiation. What do you predict for these properties of
astatine?
 colour
 state at room temperature
 electronegativity.

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Halogens: true or false?

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Reactions of the halogens
Halogens react with metals such as sodium and iron:

halogen + sodium ® sodium halide

They also react with non-metals such as hydrogen:

halogen + hydrogen ® hydrogen halide

They also take part in displacement reactions with halide

ions, such as the reaction that is used to make bromine from
potassium bromide in seawater:

potassium potassium
chlorine + ® bromine +
bromide chloride

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Reaction with iron

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Reactions with hydrogen
The halogens react with hydrogen gas to product hydrogen
halides. For example:

Cl2(g) + H2(g) ® 2HCl(g)

 Chlorine and hydrogen explode in bright sunlight but

react slowly in the dark.

 Bromine and hydrogen react slowly on heating with

a platinum catalyst.

 Iodine combines partially and very slowly with

hydrogen, even on heating.

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Redox reactions of halogens

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What is the reactivity of the halogens?
The reactions of the halogens with iron and hydrogen show
that their reactivity decreases down the group.
Halogen Reaction with iron Reaction with
wool hydrogen
chlorine Iron wool burns and Explodes in
glows brightly. sunlight, reacts
slowly in the dark.
bromine Iron wool glows but less Reacts slowly on
brightly than with chlorine. heating with catalyst.
iodine Iron wool has a very Reacts partially
slight glow. and very slowly.
How do you think fluorine and astatine would react with
iron wool and hydrogen?

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Electron structure and reactivity

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Halogen displacement reactions

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Halogen displacement reactions

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Halogen displacement reactions
Halogen displacement reactions are redox reactions.

Cl2 + 2KBr ® 2KCl + Br2

To look at the transfer of electrons in this reaction, the

following two half equations can be written:

Cl2 + 2e-  2Cl- 2Br-  Br2 + 2e-

What has been oxidized and what has been reduced?

 Chlorine has gained electrons, so it is reduced to Cl- ions.
 Bromide ions have lost electrons, so they have been
oxidized to bromine.

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Oxidizing ability of halogens
In displacement reactions between
halogens and halides, the halogen

increasing oxidizing ability

acts as an oxidizing agent. fluorine
This means that the halogen:

 oxidizes the halide ion to the chlorine

halogen

 gains electrons
bromine
 is reduced to form the halide ion.

What is the order of oxidizing

ability of the halogens?
iodine
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Oxidizing ability of halogens

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Chlorine and disproportionation

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Reaction of chlorine with water
Chlorine is used to purify water supplies
because it is toxic to bacteria, some of
which can cause disease. Adding it to
water supplies is therefore beneficial for the
population.

However, chlorine is also toxic to humans,

so there are risks associated with gas leaks
during the chlorination process. There is
also a risk of the formation of chlorinated
hydrocarbons, which are also toxic.

Chlorination of drinking water raises questions about individual

freedom because it makes it difficult for individuals to opt out.

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Bleach and the chlorate(I) ion
Household bleach commonly contains the chlorate(I) ion,
ClO-, in the form of sodium chlorate(I), NaOCl.

The chlorate(I) ion behaves as an oxidizing agent. It oxidizes

the organic compounds in food stains, bacteria and dyes.

ClO- + H2O + 2e- ® Cl- + 2OH-

How many electrons are needed to balance this equation?

Has the chlorine been oxidized or reduced in the reaction?

The chlorine has been reduced because it has gained

electrons. Its oxidation state has decreased from +1 in
ClO- to –1 in Cl-.

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Redox reactions of chlorate ions

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Halides
When halogens react with metals, they form compounds
called halides. Many naturally-occurring halides have
industrial, household and medical applications.
Halide Formula Uses
caesium chloride CsCl Extraction and
separation of DNA
sodium NaAlF6 Electrolysis of
hexafluoroaluminate aluminium oxide
titanium(IV) chloride TiCl4 Extraction of titanium
lithium iodide LiI Electrolyte in batteries
potassium bromide KBr Epilepsy treatment in
animals

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Identifying halide ions
Halides can be identified by their reaction with acidified
silver nitrate solution to form silver halide precipitates.

potassium silver potassium silver

+ ® +
nitrate nitrate chloride
chloride

KCl(aq) + AgNO3(aq) ® KNO3(aq)

+ AgCl(s)

Silver chloride has a low solubility

in water, so it forms a white
precipitate: the positive result in
the test for chloride ions.

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Identifying halide ions

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Identifying halide ions

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Uses of halides in photography
Silver halides are used in photography.
Photographic film coated with a silver halide is exposed to
light, causing the halide to decompose to form silver. This
appears as a black precipitate on the photographic film.

Ag+ + e- ® Ag

light
silver
mask
precipitate
paper
coated in white paper
silver halide under mask

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William Fox Talbot
William Fox Talbot (1800–1877) was a British scientist and
mathematician. He was one of the key figures in the
development of the use of silver halides in photography.

A French scientist called Louis Daguerre developed the

use of silver halides on copper plates. These were effective
at producing prints, but could only be used once.

Fox Talbot adapted the process by

removing any unreacted silver
halide by washing with sodium
thiosulfate solution. This meant that
the print could be used repeatedly
in the way that photographic
negatives can be today.

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Hydrogen halides
The hydrogen
Hydrogen halide Boiling point (°C)
halides are
colourless gases HF 20
at room
temperature. HCl -85
HBr -67
HI -35

Hydrogen fluoride has an

unexpectedly high boiling point
compared to the other
hydrogen halides. This is due to
hydrogen bonding between the
H–F molecules.
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Halides as reducing agents
A substance that donates electrons

increasing reducing ability

in a reaction (i.e. is oxidized) is a
reducing agent because it fluoride
reduces the other reactant.

The larger the halide ion, the easier

it is for it to donate electrons and
chloride
therefore the more reactive it is.

This is because its outermost

electrons are further from the
attraction of the nucleus and more bromide
shielded from it by other electrons.
The attraction for the outermost
electrons is therefore weaker.
iodide
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Halides: true or false?

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Sodium halides and sulfuric acid
The sodium halides react with concentrated sulfuric acid.

During this reaction two things can

happen to the sulfuric acid. It can

 be reduced

 act as an acid.

The reactions of sodium halides with concentrated sulfuric

acid demonstrate the relative strengths of the halide ions
as reducing agents.

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Sodium halides and sulfuric acid

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Sodium halides and sulfuric acid

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Oxidation states

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Sodium halides and sulfuric acid

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Glossary

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What’s the keyword?

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