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.
What are the general properties of the halogens?
All the halogens are:
 non-metals and so do not conduct electricity
 brittle and crumbly when solid
 poisonous and smelly.

They become darker in colour down the group:

is pale yellow

is green-yellow

is red-brown

is blue-black.
What is the physical state of the halogens?
The melting and boiling points of the halogens increase
down the group, as the molecules become bigger.
Halogen Relative Melting Boiling State
size point (°C) point (°C)
-220 -118 gas

-101 -34 gas

-7 59 liquid

114 184 solid

What is the state of each halogen at room temperature?

Melting and boiling points of halogens
Halogen vapours
Bromine and iodine are not gaseous, but have low boiling
points. This means that they produce vapour at relatively
low temperature. They are volatile.

Bromine produces some When iodine is heated gently, it

red-brown vapour, seen changes directly from a solid to a
here above the liquid gas without first becoming a liquid.
bromine in the jar. This is called sublimation.
True or false?
Physical properties of halogens
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
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
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

-radiation. What do you predict for these properties of
astatine?
 colour
 state at room temperature
 electronegativity.
Halogens: true or false?
Halogen vapours
Bromine and iodine are not gaseous, but have low boiling
points. This means that they produce vapour at relatively
low temperature. They are volatile.

Bromine produces some When iodine is heated gently, it

red-brown vapour, seen changes directly from a solid to a
here above the liquid gas without first becoming a liquid.
bromine in the jar. This is called sublimation.
True or false?
How do the halogens react with metals?
The reactivity of halogens means that they readily react with
most metals.
Halogens need to gain electrons for a full electron shell and
metals need to lose electrons for a full electron shell.
This means that halogens and metals react to form ionic
compounds.
These are metal halides, which are a type of salt.

nickel (II) chloride copper (II) chloride

What are halides?
When halogens react with another substance, they become
negative ions, as they are gaining an extra electron.
When this happens, they are called halides.
The name of each of the halogens changes slightly once
it has reacted – instead of ending with ‘–ine’, they end
with ‘-ide’.

Halogen reaction Halide

(F) fluoride (F-)

(Cl) chloride (Cl-)

(Br) bromide (Br-)

(I) iodide (I-)

Halogens reacting with iron wool
What is the order of reactivity?
What is the reactivity of the halogens?
The iron wool experiment shows that the reactivity of
halogens decreases as you go down the group.
decrease in reactivity

Halogen Reaction with iron wool

Iron wool burns and glows brightly.

Iron wool glows but less brightly than
with chlorine.
Iron wool has a very slight glow.

Astatine is the halogen that appears directly below iodine in

the periodic table.
How do you think astatine would react with iron wool?
Equations of halogens and iron
When a halogen reacts with iron it forms an iron halide:
halogen + iron  iron (III) halide
The word and chemical equations for the reaction between
chlorine and iron are:
iron (III)
chlorine + iron 
chloride
3Cl2 (g) + 2Fe (s)  2FeCl3 (s)
What would the equation be for the reaction that forms
iron (III) bromide?
iron (III)
bromine + iron 
bromide
3Br2 (g) + 2Fe (s)  2FeBr3 (s)
How does electron structure affect reactivity?

The reactivity of alkali metals decreases going down the

group. What is the reason for this?
 The atoms of each element get
F
larger going down the group.
 This means that the outer shell gets

decrease in reactivity
further away from the nucleus and
is shielded by more electron shells. Cl
 The further the outer shell is from
the positive attraction of the
nucleus, the harder it is to attract
another electron to complete the
outer shell. Br
 This is why the reactivity of the
halogens decreases going down
group 7.
How do the halogens react with non-metals?

Halogens also react with non-metals.

For example, halogens react with hydrogen to create
hydrogen halides.

H + Cl  H Cl

hydrogen chlorine hydrogen chloride

Unlike their reactions with metals, halogens share electrons

with non-metals, and so react to form covalent compounds.
All hydrogen halides are gases. They dissolve easily in
water and become strong acids.
Displacement of halogens
If a halogen is added to a solution of a compound containing a
less reactive halogen, it will react with the compound and form
a new one.
This is called displacement.

sodium sodium
fluorine + chloride

fluoride
+ chlorine

F2 (aq) + 2NaCl (aq)  2NaF (aq) + Cl2 (aq)

A more reactive halogen will always displace a less reactive

halide from its compounds in solution.
Displacement of halogens
Why will a halogen always displace a less reactive halogen?
Displacement theory
If a metal halide is mixed with a more reactive halogen,
the extra electron will be transferred from the less reactive
to the more reactive halogen.
--
+
sodium chlorine
chloride
Na Cl

-
fluorine
fluoride F
Displacement reactions of halogens
Displacement reactions: summary
The reactions between solutions of halogens and metal
halides (salts) can be summarised in a table:

salt (aq) potassium potassium potassium

halogen chloride bromide iodide

chlorine 2KCl + Br2 2KCl + I2

bromine no reaction 2KBr + I2

iodine no reaction no reaction

Is there a displacement reaction?
Reactions of halogens: summary
What are the uses of halogens?
How many everyday uses of halogens can you see below?
What are the uses of halogens?
What are the uses of halogens?
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
Reaction with iron
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.
Redox reactions of halogens
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?
Electron structure and reactivity
Halogen displacement reactions
Halogen displacement reactions
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.
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
Oxidizing ability of halogens
Chlorine and disproportionation
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.
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-.
Redox reactions of chlorate ions
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
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.
Identifying halide ions
Identifying halide ions
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
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.
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.
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
Halides: true or false?
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.
Sodium halides and sulfuric acid
Sodium halides and sulfuric acid
Oxidation states
Sodium halides and sulfuric acid
Glossary
What’s the keyword?
Multiple-choice quiz