AN INTRODUCTION TO

THE HALOGENS
Group 17 (7)

KNOCKHARDY PUBLISHING
2015
SPECIFICATIONS
 KNOCKHARDY PUBLISHING

HALOGENS (Group 17)

INTRODUCTION
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 THE HALOGENS
CONTENTS
• Trends in appearance
• Trends in electronic configuration
• Trends in in Atomic and Ionic radius
• Trends in Electronegativity
• Trends in oxidation power
• Displacement reactions
• Other reactions

• Testing for halides – AgNO3

• Testing for halides - concentrated H2SO4

• Volumetric analysis of chlorate(I) in bleach

 GROUP PROPERTIES

GENERAL • non-metals
• exist as separate diatomic molecules… eg Cl2
• all have the electronic configuration ... ns2 np5

TRENDS • appearance
• boiling point
• electronic configuration
• electronegativity
• atomic size
• ionic size
• oxidising power
 GROUP TRENDS
APPEARANCE

F2 Cl2 Br2 I2
Colour Yellow Green Red/brown Grey
State (at RTP) GAS GAS LIQUID SOLID

BOILING POINT

F2 Cl2 Br2 I2
Boiling point / °C - 188 - 34 58 183

INCREASES down Group

• increased size makes the induced dipole-dipole interactions* increase

• more energy is required to separate the molecules

* also known as London (or dispersion) Forces

 GROUP TRENDS
ELECTRONIC CONFIGURATION

F Cl Br I
Atomic Number 9 17 35 53
Old 2,7 2,8,7 2,8,18,7 2,8,18,18,7
New … 2s2 2p5 …3s2 3p5 … 4s2 4p5 … 5s2 5p5

• electrons go into shells further from the nucleus

 GROUP TRENDS
ATOMIC & IONIC RADIUS

F Cl Br I
Atomic radius / nm 0.064 0.099 0.111 0.128

F¯ Cl¯ Br¯ I¯
Ionic radius / nm 0.136 0.181 0.195 0.216

ATOMIC RADIUS INCREASES down Group

IONIC RADIUS INCREASES down Group

• the greater the atomic number the more electrons there are
these go into shells increasingly further from the nucleus

• ions are larger than atoms - the added electron repels the
others so radius gets larger
 GROUP TRENDS
ELECTRONEGATIVITY

F Cl Br I
Electronegativity 4.0 3.5 2.8 2.5

DECREASES down Group

• the increasing nuclear charge due to the greater number of protons

should attract electrons more, but there is an ...

an increasing number of shells;

 more shielding and less pull on electrons

an increasing atomic radius

 attraction drops off as distance increases
 GROUP TRENDS
OXIDISING POWER

• halogens are oxidising agents

• they need one electron to complete their octet
• the oxidising power gets weaker down the group
 GROUP TRENDS
OXIDISING POWER

• halogens are oxidising agents

• they need one electron to complete their octet
• the oxidising power gets weaker down the group

• the trend can be explained by considering the nucleus’s attraction

for the incoming electron which is affected by the...

• increasing nuclear charge which should attract electrons more

but this is offset by • INCREASED SHIELDING

• INCREASING ATOMIC RADIUS
 GROUP TRENDS
OXIDISING POWER

• halogens are oxidising agents

• they need one electron to complete their octet
• the oxidising power gets weaker down the group

• the trend can be explained by considering the nucleus’s attraction

for the incoming electron which is affected by the...

• increasing nuclear charge which should attract electrons more

but this is offset by • INCREASED SHIELDING

• INCREASING ATOMIC RADIUS

This is demonstrated by reacting the halogens with other halide ions.

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...
 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE

e.g. CHLORINE + SODIUM BROMIDE BROMINE + SODIUM CHLORIDE

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

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)

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

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)

Cl2(aq) + 2Br¯(aq) ——> Br2(aq) + 2Cl¯(aq)

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE

e.g. CHLORINE + SODIUM BROMIDE BROMINE + SODIUM CHLORIDE

CHLORINE + SODIUM IODIDE IODINE + SODIUM CHLORIDE

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE

e.g. CHLORINE + SODIUM BROMIDE BROMINE + SODIUM CHLORIDE

CHLORINE + SODIUM IODIDE IODINE + SODIUM CHLORIDE

BROMINE + SODIUM IODIDE IODINE + SODIUM BROMIDE

 HALOGENS - DISPLACEMENT REACTIONS

THE DECREASE IN REACTIVITY DOWN THE GROUP IS DEMONSTRATED

USING DISPLACEMENT REACTIONS...

A SOLUTION OF THE HALOGEN IS ADDED TO A SOLUTION OF A HALIDE

HALIDES ARE SALTS FORMED FROM HALOGENS (see next slide for examples)

A MORE REACTIVE HALOGEN WILL DISPLACE A LESS REACTIVE ONE

e.g. CHLORINE + SODIUM BROMIDE BROMINE + SODIUM CHLORIDE

CHLORINE + SODIUM IODIDE IODINE + SODIUM CHLORIDE

BROMINE + SODIUM IODIDE IODINE + SODIUM BROMIDE

BUT BROMINE + SODIUM CHLORIDE CHLORINE + SODIUM BROMIDE

(Bromine is below chlorine in the Group so is less reactive)
 GROUP TRENDS
OXIDISING POWER

Chlorine oxidises bromide ions to bromine

Cl2 + 2Br¯ ——> Br2 + 2Cl¯

Chlorine oxidises iodide ions to iodine

Cl2 + 2I¯ ——> I2 + 2Cl¯

Bromine oxidises iodide ions to iodine

Br2 + 2I¯ ——> I2 + 2Br¯

 HALOGENS - DISPLACEMENT REACTIONS
DISPLACEMENT REACTIONS - EXPERIMENT

SODIUM CHLORIDE SODIUM BROMIDE SODIUM IODIDE

CHLORINE

BROMINE
 HALOGENS - DISPLACEMENT REACTIONS
DISPLACEMENT REACTIONS - EXPERIMENT

SODIUM CHLORIDE SODIUM BROMIDE SODIUM IODIDE

Solution stays Solution goes from Solution goes from

CHLORINE colourless colourless to orange- colourless to orange-
yellow red
NO REACTION BROMINE FORMED IODINE FORMED

Solution goes from Solution goes from Solution goes from

BROMINE colourless to orange- colourless to orange- colourless to red
yellow yellow IODINE FORMED
NO REACTION NO REACTION
 OTHER REACTIONS OF CHLORINE

Water Halogens react with decreasing vigour down the group as

their oxidising power decreases

Litmus will be turned red then decolourised in chlorine water

Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)

strong acid bleaches by oxidation
 OTHER REACTIONS OF CHLORINE

Water Halogens react with decreasing vigour down the group as

their oxidising power decreases

Litmus will be turned red then decolourised in chlorine water

0 -1 +1
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
strong acid bleaches by oxidation
 OTHER REACTIONS OF CHLORINE

Water Halogens react with decreasing vigour down the group as

their oxidising power decreases

Litmus will be turned red then decolourised in chlorine water

0 -1 +1
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
strong acid bleaches by oxidation

This is an example of DISPROPORTIONATION …

‘simultaneous oxidation and reduction of a species’
 OTHER REACTIONS OF CHLORINE

Water Halogens react with decreasing vigour down the group as

their oxidising power decreases

Litmus will be turned red then decolourised in chlorine water

0 -1 +1
Cl2(g) + H2O(l) HCl(aq) + HOCl(aq)
strong acid bleaches by oxidation

This is an example of DISPROPORTIONATION …

‘simultaneous oxidation and reduction of a species’

Alkalis Chlorine reacts with cold, aqueous sodium hydroxide.

2NaOH(aq) + Cl2(g) —> NaCl(aq) + NaOCl(aq) + H2O(l)

 TESTING FOR HALIDES – AgNO3

• make a solution of the halide

• acidify with dilute nitric acid – this prevents the precipitation of other salts

• add a few drops of silver nitrate solution

• treat any precipitate with dilute ammonia solution

• if a precipitate still exists, add concentrated ammonia solution

 TESTING FOR HALIDES – AgNO3

CHLORIDE white ppt of AgCl soluble in dilute ammonia

BROMIDE cream ppt of AgBr insoluble in dilute ammonia

but soluble in conc.

IODIDE yellow ppt of AgI insoluble in dilute and

conc. ammonia solution
 TESTING FOR HALIDES – AgNO3

CHLORIDE white ppt of AgCl soluble in dilute ammonia

BROMIDE cream ppt of AgBr insoluble in dilute ammonia

but soluble in conc.

IODIDE yellow ppt of AgI insoluble in dilute and

conc. ammonia solution

halides precipitate as follows Ag+(aq) + X¯(aq) ——> Ag+X¯(s)

when they dissolve in ammonia a colourless diammine complex is

formed [Ag(NH3)2]+(aq)
 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

PLACE A SOLUTION OF THE HALIDE IN A TEST TUBE

 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD SOME DILUTE NITRIC ACID

 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD SILVER NITRATE SOLUTION

WHITE PRECIPITATE OF SILVER CHLORIDE AgCl

CREAM PRECIPITATE OF SILVER BROMIDE AgBr
YELLOW PRECIPITATE OF SILVER IODIDE AgI
 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD DILUTE AMMONIA SOLUTION

WHITE PRECIPITATE OF SILVER CHLORIDE - SOLUBLE

CREAM PRECIPITATE OF SILVER BROMIDE - INSOLUBLE
YELLOW PRECIPITATE OF SILVER IODIDE - INSOLUBLE
 TESTING FOR HALIDES – AgNO3

CHLORIDE BROMIDE IODIDE

ADD CONCENTRATED AMMONIA SOLUTION

WHITE PRECIPITATE OF SILVER CHLORIDE - SOLUBLE

CREAM PRECIPITATE OF SILVER BROMIDE - SOLUBLE
YELLOW PRECIPITATE OF SILVER IODIDE - INSOLUBLE
 TESTING FOR HALIDES – Conc. H2SO4

• an alternative test for halides

• add concentrated sulphuric acid carefully to a solid halide

• H2SO4 displaces the weaker acids HCl, HBr, and HI from their salts

• as they become more powerful reducing agents down the group

they can react further by reducing the sulphuric acid to lower
oxidation states of sulphur
 TESTING FOR HALIDES – Conc. H2SO4

Summary

Halide Observation(s) Product O.S. Reaction type

NaCl misty fumes HCl -1 Displacement of Cl¯

NaBr misty fumes HBr -1 Displacement of Br¯

brown vapour Br2 0 Oxidation of Br¯
colourless gas SO2 +4 Reduction of H2SO4

NaI misty fumes HI -1 Displacement of I¯

purple vapour I2 0 Oxidation of I¯
colourless gas SO2 +4 Reduction of H2SO4
yellow solid S 0 Reduction of H2SO4
bad egg smell H2S -2 Reduction of H2SO4
 HYDROGEN HALIDES - PROPERTIES

Boiling points At room temp. and pressure HCl, HBr, HI are

colourless gases, HF a colourless liquid.

b. pts ... HF 20°C HCl -85°C HBr -69°C HI -35°C

HF value is higher than expected due to hydrogen bonding

 HYDROGEN HALIDES - PROPERTIES

Boiling points At room temp. and pressure HCl, HBr, HI are

colourless gases, HF a colourless liquid.

b. pts ... HF 20°C HCl -85°C HBr -69°C HI -35°C

HF value is higher than expected due to hydrogen bonding

Reducing
ability Increases down the group as bond strength decreases

bond energy H-F 568 H-Cl 432 H-Br 366 H-I 298
/ kJ mol-1
 HYDROGEN HALIDES - PREPARATION

Direct
combination Hydrogen halides can be made by direct combination

H2(g) + X2(g) ——> 2HX(g)

• fluorine combines explosively, even in the dark

• chlorine combines explosively when heated or in sunlight
• bromine is fast at 200°C with a catalyst
• iodine reaction is reversible.
 HYDROGEN HALIDES - PREPARATION

Direct
combination Hydrogen halides can be made by direct combination

H2(g) + X2(g) ——> 2HX(g)

• fluorine combines explosively, even in the dark

• chlorine combines explosively when heated or in sunlight
• bromine is fast at 200°C with a catalyst
• iodine reaction is reversible.

Displacement Chlorides are made by displacing the acid from its salt

NaCl(s) + conc. H2SO4(l) ——> NaHSO4(s) + HCl(g)

 HYDROGEN HALIDES - PREPARATION

Direct
combination Hydrogen halides can be made by direct combination

H2(g) + X2(g) ——> 2HX(g)

• fluorine combines explosively, even in the dark

• chlorine combines explosively when heated or in sunlight
• bromine is fast at 200°C with a catalyst
• iodine reaction is reversible.

Displacement Chlorides are made by displacing the acid from its salt

NaCl(s) + conc. H2SO4(l) ——> NaHSO4(s) + HCl(g)

HBr and HI are not made this way as they are more powerful
reducing agents and are oxidised by sulphuric acid to the halogen

2HBr(g) + conc. H2SO4(l) ——> 2H2O(l) + SO2(g) + Br2(g)

 HALOGENS & HALIDES - USES

Chlorine, Cl2 • water purification

• bleach
• solvents
• polymers - poly(chloroethene) or PVC
• CFC’s

Fluorine, F2 • CFC’s
• polymers - PTFE poly(tetrafluoroethene) as used in...
non-stick frying pans, electrical insulation,
waterproof clothing

Fluoride, F¯ • helps prevent tooth decay

- tin fluoride is added to toothpaste
- sodium fluoride is added to water supplies

Hydrogen
fluoride, HF • used to etch glass

Silver
bromide, AgBr • used in photographic film
 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Oxidation state +1 -1
 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Analysis (1) Add excess potassium iodide;

the chlorate oxidises the iodide ions to iodine

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

2I¯ ——> I2 + 2e¯

 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Analysis (1) Add excess potassium iodide;

the chlorate oxidises the iodide ions to iodine

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

2I¯ ——> I2 + 2e¯

overall ClO¯ + 2H+ + 2I¯ ——> I2 + Cl¯ + H 2O

moles of I2 produced = original moles of OCl¯ -- (i)

 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Analysis (2) Titrate the iodine produced with sodium thiosulphate

using starch as the indicator near the end point

2S2O32- ——> S4O62- + 2e¯

I2 + 2e¯ ——> 2I¯

 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Analysis (2) Titrate the iodine produced with sodium thiosulphate

using starch as the indicator near the end point

2S2O32- ——> S4O62- + 2e¯

I2 + 2e¯ ——> 2I¯

overall I2 + 2S2O32- ——> S4O62- + 2I¯

 VOLUMETRIC ANALYSIS OF CHLORATE(I)

Introduction Chlorate(I) ions are oxidising agents

In acid solution they end up as chloride ions

ClO¯ + 2H+ + 2e¯ ——> Cl¯ + H2O

Analysis (2) Titrate the iodine produced with sodium thiosulphate

using starch as the indicator near the end point

2S2O32- ——> S4O62- + 2e¯

I2 + 2e¯ ——> 2I¯

overall I2 + 2S2O32- ——> S4O62- + 2I¯

moles of I2 = ½ x moles of S2O32- -- (ii)

from (i) and (ii) original moles of OCl¯ = ½ x moles of S2O32-

AN INTRODUCTION TO

THE HALOGENS
Group 17 (7)
THE END

©2015 JONATHAN HOPTON & KNOCKHARDY PUBLISHING