3.2.3.

GROUP 7 – THE
HALOGENS
 3.2.3.1/3.2 – TRENDS IN PROPERTIES +
USES OF CHLORINE AND CHLORATE(I)
By the end of this lesson you should be able to:
understand and explain the trend in:
electronegativity + ionisation energy of Group 7 elements;
boiling point of the halogens in terms of their structure and bonding;
oxidising ability of the halogens down the group (including displacement reactions);
reducing ability of halide ions (including reactions of solid sodium halides with conc. H 2SO4).

know how acidified silver nitrate is used to identify and distinguish between halide ions;
recognise and state the trend in solubility of silver halides in ammonia;
know the uses of chlorine and chlorate(I).
THE HALOGENS – WHAT DO YOU
REMEMBER?!
FROM GCSE: Chlorine
(green gas)
 Group 7

 Non-metals
Bromine
(red-brown
 Diatomic molecules (F2, Cl2, Br2, I2 and At2)
liquid)

The word “halogen” means “salt former”  Iodine

they react with metals to form salts e.g. NaCl (black solid)
 TRENDS – WHAT ARE THEY?!
Atomic Melting Boiling
Halogen Electronegativity
Radius (nm) Point (K) Point (K)
Fluorine 4.0 0.071 53 85

Chlorine 3.0 0.099 172 238

Bromine 2.8 0.114 266 332

Iodine 2.5 0.133 387 457

 ATOMIC RADIUS
160
F
140
Atomic radius (pm)
120 Cl

100 Br
80

60 I

40

20 At

0
fluorine chlorine bromine iodine
 more electron shells + more shielding = less attraction between nucleus and outer electrons
 so bigger atoms.
 1 IONISATION ENERGY
ST

1800
1600
Ionisation energy (kJ/mol)
1400
1200
1000
800
600
400
200
0
F Cl Br I At

 more electron shells + more shielding (atoms get larger)

 therefore weaker attraction from nucleus to electron in outer shell
 WEIRD FLUORINE
Melting Boiling Point
Halogen Electronegativity Atomic Radius (nm)
Point (K) (K)
Fluorine 4.0 0.071 53 85
Chlorine 3.0 0.099 172 238
Bromine 2.8 0.114 266 332
Iodine 2.5 0.133 387 457

 F-F bond is unexpectedly weak compared to other diatomic bonds. This is

because repulsion

 …the small size of fluorine means non-bonding

electrons (lone pairs) are (too) close together
 they repel each other (weaker bond).
 ELECTRONEGATIVITY –
YOU KNOW THIS ONE TOO!!
Atomic Radius Melting Point
Halogen Electronegativity Boiling Point (K)
(nm) (K)
Fluorine 4.0 0.071 53 85
Chlorine 3.0 0.099 172 238
Bromine 2.8 0.114 266 332
Iodine 2.5 0.133 387 457

 Shared electrons get further from the nucleus since atoms get larger down the group;
Electronegativity
 More  measure
shielding by inner shells; of the ability of an atom to attract electrons in a covalent
bond to itself.
 These 2 factors are more important than the increasing nuclear charge = down the group the
attraction
Depends onof the nucleusbetween
a balance towardsnuclear
pair of charge
shared and
electrons in covalent
distance bondto
from nucleus decreases (lower
the bonding
electronegativity).
electrons.
 MELTING AND BOILING
POINTS Atomic Radius Melting Point
Halogen Electronegativity Boiling Point (K)
(nm) (K)
Fluorine 4.0 0.071 53 85
Chlorine 3.0 0.099 172 238
Bromine 2.8 0.114 266 332
Iodine 2.5 0.133 387 457
 All halogen molecules non-polar (only VdW forces between them);
 Larger atoms have more electrons = make larger molecules;
 Larger molecules down the group;
 Van der Waals forces between molecules get stronger;
 More energy needed to separate them = higher melting and boiling points = trend is
shown in the physical states down the group (gas to solid).
 VISUALISING IT…
400

300

200
Temperature (°C)

100
melting point (°C)
boiling point (°C)
0
fluorine chlorine bromine iodine astatine
-100

-200

-300

bigger molecules  more van der Waals’ forces  higher mpt/bpt

 3.2.3.1/3.2 – TRENDS IN PROPERTIES +
USES OF CHLORINE AND CHLORATE(I)
By the end of this lesson you should be able to:
understand and explain the trend in:
electronegativity + ionisation energy of Group 7 elements;
boiling point of the halogens in terms of their structure and bonding;
oxidising ability of the halogens down the group (including displacement reactions);
reducing ability of halide ions (including reactions of solid sodium halides with conc. H 2SO4).

know how acidified silver nitrate is used to identify and distinguish between halide ions;
recognise and state the trend in solubility of silver halides in ammonia;
know the uses of chlorine and chlorate(I).
 REACTIONS OF THE
HALOGENS – WITH METALS
Halogens react with metals such as sodium and iron:
halogen + sodium  sodium halide

Chemical equation:
E.g. sodium + bromine  sodium bromide
2Na + Br2  2NaBr

Halogens also react with non-metals such as hydrogen.

 REACTIONS OF HALOGENS
– WITH HYDROGEN
The halogens react with hydrogen gas to product hydrogen halides.

 Chlorine and hydrogen explode in bright sunlight but react slowly in the dark.
Cl2(g) + H2(g)  2HCl(g)
 Bromine and hydrogen react slowly on heating with a platinum catalyst.
Br2(g) + H2(g)  2HBr(g)
 Iodine combines partially and very slowly with hydrogen, even on heating.
I2(g) + H2(g)  2HI(g)
 REACTIVITY OF THE HALOGENS?
Halogen Reaction with iron wool Reaction with hydrogen

Iron wool burns and glows Explodes in sunlight, reacts

chlorine
brightly. slowly in the dark.

Iron wool glows but less brightly Reacts slowly on heating with
bromine
than with chlorine. catalyst.

iodine Iron wool has a very slight glow. Reacts partially and very
slowly.

How would fluorine and astatine react with iron wool and hydrogen?
The reactions of the halogens with iron and hydrogen show that their reactivity decreases
down the group.
 MORE TRENDS – OXIDISING
POWER
 halogens are oxidising agents (remember what this means?);
 they need one electron to complete their octet;
 the oxidising power (ability to receive electrons) decreases down the group. Why is that?

Down a group…
… the nuclear charge increases which should attract electrons more BUT
this is offset by • INCREASED SHIELDING
• INCREASING ATOMIC RADIUS
So,
The oxidising ability of the halogens decreases as we go down the group.
DISPLACEMENT REACTIONS…
WHAT?!?
This decrease in reactivity of the halogens down the group is well demonstrated using Displacement
Reactions.

In general, a halogen will displace (take the place of) the ion of less reactive
halogens (halogens below it in the periodic table).

Fluorine Chlorine Bromine Iodine

Increasing oxidising power / reactivity

 DISPLACEMENT REACTIONS
A solution of the halogen is added to a solution of a halide (salts formed from halogens).

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE.

e.g. chlorine + sodium bromide → bromine + sodium chloride

Cl2(aq) + 2NaBr(aq) → Br2(aq) + 2NaCl(aq)

ionic equation: Cl2(aq) + 2Br-(aq) → Br2(aq) + 2Cl-(aq)

chlorine + sodium iodide → iodine + sodium chloride

bromine + sodium iodide → iodine + sodium bromide

BUT bromide + sodium chloride X

→ chlorine + sodium bromide WHY?

(Bromine is below chlorine in the Group so is less reactive)

 MORE DISPLACEMENT
REACTIONS
Chlorine will displace Bromine:
0 -1 0 -1
Cl2 (aq) + 2NaBr (aq) → Br2 (aq) + 2NaCl (aq)

Ionically:

Cl2 (aq) + 2Na+ (aq) + 2Br-  Br2 (aq) + 2Na+ (aq) + 2Cl- (aq)
Sodium ions are just spectator ions (can be excluded).
Chlorine is acting as an oxidising agent.
 REACTIONS OF HALIDES
Oxidising agent – takes electrons from another species.

Reducing agent – gives electrons to another species.

Halide Ionic radius REDUCING AGENTS

ion (nm)
F- 0.133 Halide ions lose electrons and become halogen molecules.
Cl- 0.180
Larger ions lose electrons more easily
Br- 0.195
I- 0.215
→ electrons are further from nucleus and shielded.

Increasing reducing power

 REDUCTION…REMEMBER?
What is reduction? Reduction is the gain of electrons.

What happens when a Halide is used as a reducing agent?

When a halide ion reduces another substance, the halide itself is oxidised to a
halogen.

Give the half equation for the reaction.

2 X– → X2 + 2 e–
 REDUCTION POWER OF
HALIDES Halide salts and H2SO4 reaction.
Copy this table into your book and fill it in. Use your knowledge and the videos on the next slide to help you:

Halide Products Observation Reaction type Equation

Cl-

Br-

I-
 REDUCTION POWER OF
HALIDES
These experiments compare how well the halides reduce H2SO4 in order to
compare the reducing power of the halide ions.
Some of the products are very toxic – hence the video clips!

NaCl + sulfuric acid

NaBr + sulfuric acid Watch the clips and complete the

OBSERVATIONS column in the
NaI + sulfuric acid previous table.
 WHAT DID YOU SEE?!
Halide Products Observation Reaction type Equation

HCl
Cl -
Steamy fumes
NaHSO4
HBr Steamy fumes
NaHSO4
Br- SO2 Colourless gas
H2O
Br2 Orange fumes

HI Steamy fumes
NaHSO4
I- H2S Eggy gas
H2O
I2 Grey solid
 REACTIONS THAT
OCCURRED
Formation of hydrogen halides:

NaX + H2SO4 → NaHSO4 + HX

X- + H2SO4 → HSO4- + HX

e.g. NaCl + H2SO4 → NaHSO4 + HCl

Complete the final two columns of the table.

 Reaction
Halide Products Observation Equation
type

HCl
Cl- Steamy fumes Acid-base NaCl + H2SO4 → NaHSO4 + HCl
NaHSO4

HBr
Br- Steamy fumes Acid-base NaBr + H2SO4 → NaHSO4 + HBr
NaHSO4

HI
I- Steamy fumes Acid-base NaI + H2SO4 → NaHSO4 + HI
NaHSO4
 POWERFUL?!
Bromide and Iodide ions are strong enough reducing agents to reduce sulfuric acid
(that’s why you see more happening there).
Bromide: -1 +6 +4 0
2H+ + 2Br- + H2SO4 → SO2 + 2H2O + Br2
Can you work out the
oxidation states?
 Sulfuric acid is reduced to sulphur dioxide so

 Oxidation state of sulfur is reduced from +6 to +4 (sulfur is reduced)

 Oxidation state of bromine increases from -1 to 0 (bromine is oxisided)

 Halide Products Observation Reaction type Equation

HCl
Cl -
Steamy fumes Acid-base NaCl + H2SO4 → NaHSO4 + HCl
NaHSO4

HBr Steamy fumes

NaHSO4 NaBr + H2SO4 → NaHSO4 + HBr
SO2 Acid-base;
Br- Choking fumes
then redox
H2O 2H+ + 2Br- + H2SO4 → SO2 + 2H2O + Br2
Br2 Brown fumes

HI Steamy fumes
NaHSO4 NaI + H2SO4 → NaHSO4 + HI
SO2 Acid-base;
I- Choking fumes
then redox
H2O 2H+ + 2I- + H2SO4 → SO2 + 2H2O + I2
I2 Purple fumes
 EVEN MORE POWERFUL??!
Iodide ions are even stronger reducing agents.
Sulphuric acid is reduced even further (+6 → -2) so that sulphur dioxide, sulphur and
hydrogen sulphide are all formed.
E.g.

-1 +6 -2 0
8H+ + 8I- + H2SO4 → H2S + 4H2O + 4I2

 During the reduction from +6 to -2, sulphur passes through oxidation state zero so
some solid yellow sulphur can also be seen.
 Reaction
Halide Products Observation Equation
type

HCl
Cl- Steamy fumes Acid-base NaCl + H2SO4 → NaHSO4 + HCl
NaHSO4

HBr Steamy fumes

NaHSO4 NaBr + H2SO4 → NaHSO4 + HBr
SO2 Acid-base;
Br- Choking fumes
then redox
H2O 2H+ + 2Br- + H2SO4 → SO2 + 2H2O + Br2
Br2 Brown fumes

HI Steamy fumes
NaHSO4 NaI + H2SO4 → NaHSO4 + HI
H2S Eggy gas
H2O Acid-base; 2H+ + 2I- + H2SO4 → SO2 + 2H2O + I2
I-
then redox
I2 Purple fumes
S 6H+ + 6I- + SO2 → H2S + 3H2O + 3I2
SO2 Choking fumes
REDUCING POWER TREND

Cl– does not reduce H2SO4

Br– reduces H2SO4 to SO2, from S(+6) to S(+4)

I– reduces H2SO4 to H2S, from S(+6) to S(-2)

 USING SILVER NITRATE TO
IDENTIFY METAL HALIDES
All metal halides (except fluorides) react with silver ions to form a precipitate of the
insoluble silver halide:

Cl- (aq) + Ag+ (aq) → AgCl (s)

Watch the video and make notes.

Testing for halide ions using silver nitrate and ammonia solution from www.ChemistryTuition.Net (youtu
be.com)
Fill in the table in page 8 of your booklet.
 3.2.3.1/3.2 – TRENDS IN PROPERTIES +
USES OF CHLORINE AND CHLORATE(I)
By the end of this lesson you should be able to:
understand and explain the trend in:
electronegativity + ionisation energy of Group 7 elements;
boiling point of the halogens in terms of their structure and bonding;
oxidising ability of the halogens down the group (including displacement reactions);
reducing ability of halide ions (including reactions of solid sodium halides with conc. H 2SO4).

know how acidified silver nitrate is used to identify and distinguish between halide ions;
recognise and state the trend in solubility of silver halides in ammonia;
know the uses of chlorine and chlorate(I).
 USES OF CHLORINE AND CHLORATE(I) –
REACTION OF Cl2 AND WATER
A reversible reaction occurs to form chloric acid and hydrochloric acid:

0 +1 -1
Cl2 (g) + H2O (l) ⇌ HClO (aq) + HCl (aq)

Oxidation number of one Cl atom increases;

Oxidation number of the other Cl atom decreases.
Remember what this reaction is called?
This is a disproportionation.

This is the reaction that takes place when water is purified for drinking and in swimming pools
Chloric acid is an oxidising agent that kills bacteria by oxidation.
USES OF CHLORINE AND CHLORATE(I)
– REACTION OF Cl2 AND WATER (CONT.)
Changing the conditions slightly, by carrying out this reaction in sunlight, alters the
reaction also:

2Cl2(g) + 2H2O(l) → 4HCl(aq) + O2(g)

This is why pools need frequent “topping-up” / adding of chlorine – it is rapidly lost
and needs to be replenished.
 ALTERNATIVE TO
CHLORINATION
We can also add solid sodium (or calcium) chlorate:

NaClO(s) + H2O(l) ⇌ Na+(aq) + OH-(aq) + HClO(aq)

Sodium chlorate dissolves in water to give the Chloric acid.

In alkali conditions the equilibrium shifts to the left and removes HClO.
Pools must be kept slightly acidic using this method to prevent the reverse reaction
from occurring.
 REACTION OF Cl2 WITH
ALKALI
Reactants Conditions Products
Chlorine NaOH must be Sodium chlorate
cold & dilute Sodium Chloride
Sodium hydroxide
Water
0 +1 -1
Cl2(g) + 2NaOH(aq) → NaClO(aq) + NaCl(aq) + H2O(l)

This is another disproportionation reaction – have you worked it out?

Sodium chlorate is an oxidising agent and active ingredient in bleach!
 TASK
1. Write word and chemical symbol equations for the following:

a) Bromine and water.

b) Iodine and water in sunlight.
c) Bromine and sodium hydroxide.

2. Research how drinking water is treated by water companies.

Create a PowerPoint to explain it to others.

The links below might help:

http://www.southernwater.co.uk/at-home/your-water/about-your-water/drinking-water-quality/

http://www.south-staffs-water.co.uk/your_home/how_your_water_is_treated.asp
THE THING YOU LIKE THE
MOST LEFT TO DO!!