Department of Chemistry

2022 – 2023
Grade : AS Level

UNIT 12: GROUP 17

Educator: Ms. Saira

 Unit 12: GROUP 17
Sub unit 12.1: Properties of Elements and their Uses
OBJECTIVES
a) Explain and interpret the colours and the trend in volatility of the elements in terms of
van der Waals’ forces

b) Explain the the relative reactivity of the elements as oxidising agents, reactions of the
elements with hydrogen, relative thermal stabilities of the hydrides .

c) Discuss the reactions of halide ions

d) Explain the reactions of chlorine in terms of changes of oxidation number in a

disproportionation reaction

e) Summarise the use of chlorine in water purification and industrial importance and
environmental significance of the halogens and their compounds.
GLOSSARY
Dispersion forces/London Forces – Van der Waal’s forces is a temporary
attractive force that results when the electrons in two adjacent atoms occupy
positions that make the atoms form temporary dipoles. ... Dispersion forces are
present between any two molecules (even polar molecules) when they are almost
touching.

Thermal Stability – It refers to the heat resistance of the material, the

deformation ability of the object under the influence of temperature, the
smaller the deformation, the higher the stability.
Or Thermal stability reflects the difficulty of chemical reactions in some
conditions.
INTRODUCTION
Periodicity
The Group 17 Elements – Halogens
Group VII elements(also called the 'halogens') are p-block elements with a
characteristic outer shell configuration of ns2np5.
They exist as non-metals and as separate diatomic molecules… eg Cl2
 General Properties Of Group 17 Elements:
Bromine is a dark red liquid but forms reddish-brown gas.
ii. Iodine is a black solid but forms a purple vapour on gentle heating.
iii. The trend is the halogens get darker going down the Group.
iv. Iodine is insoluble in water but it dissolves in potassium iodide, KI solution
due to the formation of I3− ion.
v. In organic solvents, halogens exist as free molecules, X2.
General Properties Of Group 17 Elements:
General Properties Of Group 17 Elements:
CORE TOPIC – 1
Group Trends
Melting Point and Boiling Point

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
Melting Point and Boiling Point
 Atomic & Ionic Radius

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
Electronegativity

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

Fluorine is the most electronegative element, and is assigned an

electronegativity of 4.0 on the Pauling scale.
Oxidising Power
• halogens are oxidising agents
• they need one electron to complete their octet
• the oxidising power DECREASES 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.
Bond Enthalpy
Excluding fluorine, the bond enthalpy of halogens
DECREASES down the Group.
This is because going down the Group,
the distance between the nucleus and bonding pair
of electrons increases.
The bonding electrons are less attracted and as a
result, the covalent bond gets weaker.
Less energy is required to break the bond.

The bond enthalpy is exceptionally low because F2 is a

very small molecule with six lone pairs of electrons. The
repulsion created between these electrons reduces the
energy needed to break the covalent bond.
 CORE TOPIC – 2
Chemical Properties
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.
A more reactive halogen will displace a less reactive one.
Example:Chlorine + sodium bromide → bromine + sodium chloride

Similarly :
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)
Halogens - Displacement Reactions

The colours of the halogen molecules

in solution are difficult to identify
positively in these displacement
reactions. However, the halogens
dissolve well in cyclohexane (which is
Dissolved iodine is purple in this upper
immiscible in water, forming two
organic layer, bromine is orange and
separate layers).
chlorine is very pale green.
Halogens - Displacement Reactions
Reactions Of Chlorine

Chlorine undergoes disproportionation when it reacts with alkali. In this reaction,

chlorine is simultaneously oxidised and reduced.
Reactions Of Chlorine – hot and cold alkali
In cold alkali(150C), the reaction is as follow:
Cl2(aq) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l)
The ionic equation is:
Cl2(aq) + 2OH−(aq) → Cl−(aq) + ClO−(aq) + H2O(l)

In hot alkali(700C), the reaction is as follow:

3Cl2(aq) + 6NaOH(aq) → 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
The ionic equation is:
3Cl2(aq) + 6OH−(aq) → 5Cl−(aq) + ClO3−(aq) + 3H2O(l)

This reaction is the result of disproportionation of chlorate(I) ions in the

presence of heat
3ClO−(aq) → 2Cl−(aq) + ClO3−(aq)
Bromine and iodine react in a similar manner. However, the bromate(I) and
Other Reactions Of Halogens
Reaction with aqueous sodium thiosulfate, Na2S2O3

Chlorine and bromine can oxidise sodium thiosulfate, Na2S2O3 to sodium

sulfate, Na2SO4. The oxidation number of sulphur changes from +2 to +6.

4Cl2 + S2O32− + 5H2O → 2SO42− + 10H+ + 8Cl−

4Br2 + S2O32− + 5H2O → 2SO42− + 10H+ + 8Cl−

2However, iodine can only oxidise sodium thiosulfate to sodium tetrathionate,
Na2S4O6. The oxidation number of sulfur changes from +2 to +2.5.

I2 + 2S2O32− → S4O62− + 2I−

Other Reactions Of Halogens
Reaction with aqueous iron(II) ions, Fe2+
Chlorine and bromine would oxidise Fe2+ to Fe3+ but not iodine.
Cl2 + 2Fe2+ → 2Cl− + 2Fe3+

Br2 + 2Fe2+ → 2Br− + 2Fe3+

Reaction with iron, Fe
i. When chlorine gas is passed over hot iron, iron(III) chloride is formed.
Cl2 + Fe → FeCl3 ; rapid and vigorous reaction
ii. When bromine vapour is passed over hot iron, iron(III) chloride is formed.
Br2 + Fe → FeBr3 ; less rapid and vigorous reaction
iii. When iodine vapour is passed over hot iron, iron(II) chloride is formed.
I2 + Fe → FeI2 ; even less vigorous
Halogens As Oxidising Agent
Halogens are powerful oxidising agents. However, the oxidising ability
DECREASES down the Group. Therefore, F2 is the most powerful oxidising agent
while I2 is the weakest.
This is reflected in their ability to oxidise other halide ions, as follow:
CORE TOPIC – 2
Halides
Hydrogen Halides - Properties
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)

Thermal Stability Of Hydrogen Halides, HX
The thermal stability of the hydrogen
halides, HX DECREASES down the Group.
This is because the size of the atom
increases and so the strength of the H-X
bond decreases.
In other words, the hydrogen halides
become less stable on heating going down
the Group.
i. Hydrogen iodide decomposes easily on
heating, thick purple fumes of I2 are
observed. When hydrogen halides decompose, X−
ions are oxidised. The ease of oxidation
ii. Hydrogen bromide decomposes slightly,
down the Group indicates the increase
little orange-brown of Br2 is observed. in reducing ability of X− ion. Hence, I− is
iii. Hydrogen chloride and fluoride are stable the strongest reducing agent while F− is
on heating. the weakest.
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

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
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 – 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
Testing For Halides – conc. H2SO4
Uses
Chlorine is used in the chlorination of water to kill bacteria. The chlorine
undergoes disproportionation.
Cl2(aq) + H2O(l) → HCl(aq) + HClO(aq)
Chloric(I) acid, HClO produced decomposes slowly to produce reactive oxygen
atoms that kill bacteria in water.
HClO → HCl + [O]

Bleach is an equal mixture of sodium chloride, NaCl and sodium chlorate(I),

NaClO.
Cl2(aq) + 2NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l)
Sodium chlorate(I) is a powerful oxidising agent and bleaches dye and other
coloured molecules by oxidising them.
Uses
Chlorofluorocarbons(CFCs) are widely used as refrigerants, propellants and
aerosols. They are also used as solvents for dry cleaning and generating foamed
plastics like expanded polystyrene or polyurethane foam.
Unfortunately, CFCs are largely responsible for destroying the ozone layer, hence
are now being replaced by less environmentally harmful compounds.

Plastic PVC (Polychloroethene Or Polyvinyl Chloride) are made from halogen

compounds.

Poly(chloroethene) is used to make a wide range of things including guttering,

plastic windows, electrical cable insulation, sheet materials for flooring and other
uses, footwear, clothing, and so on.

Bromine and Iodine are often used in the manufacture of dyes and drugs.
SUMMARY
Full Summary including exam style Questions
https://youtu.be/oDvQvu_xfAw
https://youtu.be/yW_C10cEzMk
Learning Resources
Group 17 Elements
https://www.chemguide.co.uk/inorganic/group7/properties.html

http://www.chembook.co.uk/chap16.htm#chap16