NSSCAS

Chemistry
Theme 3
Topic 3.4 Group 17
 Topic 3.4 Group 17
3.4.1 Physical properties of the group 17 elements
3.4.2 The chemical properties of the elements and
their hydrides
3.4.3 Some reactions of the halide ions
3.4.4 The reactions of chlorine with aqueous
sodium hydroxide
3.4.5 Some important uses of halogens and of
halogen compounds
 3.4.1 Physical properties of the group 17
elements
• describe the colours of chlorine, bromine and
iodine:
– as vapours
– at room temperature and pressure
– in solution
• describe the trend in state of chlorine, bromine
and iodine at room temperature and pressure
• interpret the volatility of the elements in terms of
intermolecular forces
Electron configuration of group 17 elements
Group VII
elements (also
called the
'halogens') are p-
block elements
with a
characteristic
outer shell
configuration of
ns²np⁵.
Variation in atomic radius of halogens

• The atomic radius of halogens increases going down the

Group.
• This is because going down the Group, each succeeding
element has one more shell of electrons. The distance
between nucleus and outer electrons are progressively
further.
 Variation in electronegativity of halogens
• The electronegativity of halogens
decreases down the Group. This is
because going down the Group, the
distance between the nucleus and
bonding electrons increases. Therefore
the electrons are attracted less strongly
by the nucleus.
• Fluorine is the most electronegative
element, and is assigned an
electronegativity of 4.0 on the Pauling
scale. In other words, the oxidising
power(and reactivity) decreases down
the Group.
 some common properties of group 17
elements
colour and colour as boiling solubility in solubility in
state at r.t.p vapour point / water organic
solvent
F2 pale yellow pale yellow -188 - -
gas gas

Cl2 yellow-green yellow-green -34 moderately yellow solution

gas gas soluble

Br2 dark-red liquid reddish- 59 slightly soluble orange brown

brown gas solution

I2 shiny dark purple 184 insoluble violet / purple

grey solid vapour solution
Their colours deepen as you move down the group in
different states at room temperature and pressure
halogen appearance melting point boiling (oc)
(oc)

fluorine pale yellow - 219 - 188

gas

chlorine yellow-green - 101 - 34

gas

bromine dark red -7 59

liquid
iodine shiny dark 114 184
grey solid

astatine black 302 380

 The volatility of the halogens

Looking at the boiling points on previous slide
indicate the volatility of each halogen.

Halogens with boiling points below zero degrees
(fluorine and chlorine) have high volatility

Halogens with boiling points above zero (bromine,
iodine, astatine) degrees have low volatility

The volatility of halogens decreases down the Group.

This is because going down the Group, the number of
electrons in the halogen molecules increases. More
temporary dipoles can be set up and the strength of van
der Waal's forces increases. Hence the boiling point
increases and the halogens become less volatile.

The reason is the weak intermolecular forces
between the molecules, which is weak Van der
Waals forces acting between the simple
diatomic molecules.

As we move down the group, the molecules
contain more electrons and intermolecular
forces between the molecules increase down
the group

A greater number of electrons in a molecule
means that there is a greater chance of
instantaneous dipoles and induced dipoles
forming. Therefore, fluorine is the most volatile
halogen and astatine is the least volatile.
 3.4.2 The chemical properties of the elements and their hydrides

• describe the relative reactivity of the

elements as oxidising agents
• describe and explain the reactions of the
elements with hydrogen
• describe and explain the relative thermal
stabilities of the hydrides
• interpret these relative stabilities in terms of
bond energies
 The halogens as oxidising
ability

All the halogens are oxidising agents;

Their oxidising ability (power) decreases along their
reactivity (i.e. moving down the group)

Halogens have high electron affinity (they gain electrons
easily)

Fluorine is the most powerful oxidising agent

A halogen can oxidise the halide ion below it on the Periodic
Table, fluorine is excluded in this argument because it is too
powerful as an oxidising agent and will oxidise water into
oxygen. If chlorine is able to displace bromide ion from its
aqueous solution, this indicates that chlorine has a higher
tendency to be reduced and to accept electrons to form ions.
 Halogens oxidise other halide ions
(displacement reactions)
chlorine, bromine, iodide,
reaction with bleaches quickly bleaches quickly bleaches
coloured very slowly
dyes

reaction with no reaction no reaction no reaction

chlorides

reaction with Cl2 + 2NaBr => Br2 + 2NaCl no reaction no reaction

bromides (Cl displaces Br)

reaction with Cl2 + 2NaI => I2 + 2NaCl Br2 + 2NaI => I2 + 2NaBr no reaction
iodides (Cl displaces I) (Br displaces I)
 Reactions with hydrogen
 All halogens react with hydrogen gas to form hydrides, HX.
 H2 + X2 → 2HX ; where X = A halogen
H2(g)+ F2(g) → 2HF(g); explosive reaction under all
temperatures
H2(g)+ Cl2(g) → 2HCl(g); explosive reaction under sunlight
H2(g)+ Br2(g) → 2HBr(g); slow reaction on heating
H2(g)+ I2(g) ⇌ 2HI(g) ; an equilibrium mixture is obtained.
The reactivity of halogens towards hydrogen gas decreases
down the Group due to the decrease in oxidising ability of
the halogens.
Thermal stability of hydrogen halides
• 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.
Hydrogen iodide decomposes easily on heating, thick purple
fumes of I are observed.
2

Hydrogen bromide decomposes slightly, little orange-brown of

Br is observed.
2

• Hydrogen chloride and fluoride are stable on heating.

• When hydrogen halides decompose, X⁻ ions are oxidised.
• The ease of oxidation down the Group indicates the increase
in reducing ability of X⁻ ion. Hence, I⁻ is the strongest
reducing agent while F⁻ is the weakest.
 The role of bond energies

The bonds that form between the halogen atoms and
hydrogen, called hydrogen halides, are greater
between hydrogen and chlorine than between
hydrogen and bromine.

To break the bonds between the halogen atoms and
hydrogen require more heat for the stronger bonds if
hydrogen halides reacting with another species.

So, the hydrogen halides of the upper halogens are
relatively more stable than those of the lower halogens
 Variation in bond enthalpy of halogens
• Excluding fluorine, the bond enthalpy of halogens
decreases down the Group.
• This is because going down the Group, the atomic
radius 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 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.
Bond energies of the H-halogen
bonds
Hydrogen – Bond energy
halogen bond (kJ )

H-Cl 428
H-Br 362
H-I 295
Bond energies of the H-halogen bonds
 3.4.3 Some reactions of the halide ions

• describe and explain the reactions of halide

ions with:
– aqueous silver ions followed by aqueous ammonia
– concentrated sulfuric acid
 How to test for halide ions –
reaction with silver ion, Ag⁺

Step 1: Place a small amount of the aqueous halide solution in
a test tube

Step 2: Add the same amount of dilute nitric acid

Step 3: Add a small amount of silver nitrate solution

If one of the three halide ions is present in the solution, a
precipitate of specific colour will form:

chloride – pale, milky white ppt

bromide – pale, milky cream ppt

iodide – pale, milky yellow ppt

The reason for adding dilute nitric acid i.e. acidified condition is
that nitric acid removes any other ions that may give a ppt. In
effect, it removes any chance of creating a false positive test.
halide ions ppts
 It’s used as a confirmatory test as cream and
white precipitate may be hard to distinguish
colour reaction with (aq)
AgCl white ppt AgCl(s) + 2NH3(aq) → [Ag(NH3)2]+(aq) + Cl-(aq)
is diamine silver (I) ion
(precipitate readily dissolves in ammonia (aq) to give a
colourless solution)

AgBr cream ppt AgBr(s) + 2NH3(aq)→ [Ag(NH3)2]+(aq) + Br-(aq)

is diamine silver (I) ion (ppt is almost unchanged using dilute
ammonia solution, but precipitate only dissolves in
concentrated ammonia solution

AgI yellow ppt precipitate insoluble in ammonia (aq)

 Reactions of halide ions with
concentrated sulfuric acid

All the halide ions react with sulfuric acid to give
highly poisonous, but distinguishable gases.

The reactions must take place in a fume hood.

Chlorides react readily with sulfuric acid to form
pure white fumes of hydrochloric acid:
 NaCl(s) + H2SO4(l) ==> NaHSO4(s) + HCl(g)

The same reaction does not work well for
bromides and iodides, because concentrated
sulfuric acid oxidises and decomposes the gas
product.
 When halides(NaX) are reacted with concentrated
sulfuric acid, the following happens:
reaction with concentrated observations

Cl- NaCl + H2SO4 → NaHSO4 + HCl Only steamy fumes of HCl (g) produced.
steamy fumes

Br- NaBr + H2SO4 → NaHSO4 + HBr Orange-brown fumes (of and HBr)
2HBr + H2SO4 → Br2 + SO2 + 2H2O obtained.
Some of the HBr produced is oxidised
by concentrated H2SO4 to Br2.

I- NaI + H2SO4 → NaHSO4 + HI Purple vapour of HI(g) obtained. HI

2HI + H2SO4 → I2 + H2S + H2O produced is oxidised by concentrated
H2SO4 to I2
• The ease of oxidation of halide ions increases
from Cl⁻ to I⁻ because the tendency to be
oxidised (the reducing power) increases.
• The HBr and HI produced are oxidised to and
respectively while the HCl produced is not. (HI
is oxidised readily while HBr is not)
• To prepare HI or HBr, phosphoric acid, is used
instead because all halides react to give the
corresponding hydrides.
• 2NaX + H3PO4 → 2HX + Na2HPO4; where X = is a
halogen
3.4.4 The reactions of chlorine with aqueous sodium hydroxide

• describe, in terms of changes of oxidation

number, the disproportionation reaction of
chlorine with cold and with hot aqueous
sodium hydroxide
• describe the effects on equilibrium of changes
in pH to the reactions of chlorine with sodium
hydroxide
The reaction of chlorine with hot and cold alkali
(disproportionation reaction)
• Chlorine undergoes disproportionation when it reacts
with alkali. In this reaction, chlorine is simultaneously
oxidised and reduced.
• In cold alkali(below 20oC), the reaction is as follow:
• Cl2(g) + 2NaOH(aq) → NaCl(aq) + NaClO(aq) + H2O(l).
• The ionic equation is: Cl2(g) + 2OH⁻(aq) → Cl⁻(aq) +
ClO⁻(aq) + H2O(l)
• In cold alkali, the oxidation number of chlorine
changes from 0 in to -1 in Cl⁻(reduction) and +1 in
ClO⁻(oxidation).
The reaction of chlorine with hot and cold
alkali (disproportionation reaction)
• In hot alkali(above 65oC), the reaction is as follow:
• 3Cl2(aq) + 6NaOH(aq) → 5NaCl(aq) + NaClO(aq) + 3H 2O(l)
• The ionic equation is: 3Cl-(aq) + 6OH⁻(aq) → 5Cl⁻(aq) + ClO-(aq) +
3H2O(l)
• In hot alkali, the oxidation number of chlorine changes from 0 in
to -1 in Cl⁻(reduction) and +5 in (oxidation).
• This reaction is the result of disproportionation of chlorate(I) ions
in the presence of heat. 3ClO⁻(aq) → 2Cl⁻(aq) + ClO -
• Bromine and iodine react in a similar manner. However, the
bromate(I) and iodate(I) ions formed disproportionate readily at
all temperatures.
 changes in pH and reactions
of chlorine

As chlorine reacts with aqueous sodium hydroxide, a
percentage of the chlorine molecules also react (and
disproportionate) with water from both aqueous sodium
hydroxide and the product formed in the reaction;

The reaction forms hydrochloric acid and hypochlorous
acid;
 Cl2(aq) + H2O(l) ==> HCl (aq) + HClO(aq)

Under alkaline conditions, the hypochlorous acid easily
dissociates to form a hypochlorite ion
 HClO(aq) + OH– (aq) ==> ClO– (aq) + H2O(l)

Chlorine, hypochlorous and hypochlorite
exist together in equilibrium;

But equilibrium is shifted depending on the
overall pH of the solution:
 Cl2(g) + H2O(l) <==> HClO(aq) + OCl – (aq)

low pH High pH
3.4.5 Some important uses of halogens and of halogen compounds

• explain the use of chlorine in water treatment

• state the industrial importance and
environmental significance of the halogens
and their compounds (e.g. for bleaches, PVC,
halogenated hydrocarbons as solvents,
refrigerants and in aerosols, see section 4.3.2)
• relate the importance of these reactions to
the use of chlorine as a bleach and the
treatment of water in Namibia
 uses of halogens
• Chlorine is used in the chlorination of water to kill
bacteria.
• The chlorine undergoes disproportionation.
• (aq) + O(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. Sodium chlorate(I) is a
powerful oxidising agent and bleaches dye and other
coloured molecules by oxidising them.
 uses of halogens …
• Halogens are also used in chlorofluorocarbons(CFCs).
• 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. In the high atmosphere, the
carbon-chlorine bonds break to give chlorine free
radicals and these radicals destroy the ozone.
• CFCs are now being replaced by less environmentally
harmful compounds.
 uses of halogens …
• Plastic PVC(poly(chloroethene) or polyvinyl chloride)
are made from halogen compounds.
• Poly(chloroethene) is made through polymerisation of
organic molecules, the organic molecule is
chloroethene, CH2CHCl. These organic molecules join
together repeatedly to form the polymer.
• 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.
 Water Treatment

Water is disinfected by treating it with chlorine after it
has been filtered;

Chlorine kills micro-organisms, bacteria and viruses that
may be present;

It removes any colour, taste or odour residue that may
still be present

Fluorine is very expensive so it would be an ideal gas to
use.

Disproportionation reactions that chlorine undergoes in
water play an important role in its application as both a
bleach and as a water treatment chemical.

Hypochlorite ion in both cases is the active ingredient.
 Uses of halogens

Bleach is a mixture of sodium chloride and sodium chlorate

Industrially, bleach is produced by reacting aqueous chlorine and
sodium hydroxide;
 Cl2(g) + 2NaOH(aq) ==> NaCl(aq) + NaClO(aq) + H 2O(l)

Chlorate ion is an active ingredient in bleach

It is a powerful oxidising agent because of its oxygen atom.

It is this oxygen atom that removes stains and dyes (from coloured
materials)

Bleaches are also used to bleach paper pulp and textiles industrially

Chlorine-based bleaches are used in household cleaning products
because of their ability to kill bacteria.
 PVC – Poly Vinyl Chloride

PVC is a very common type of plastic that is used
in construction, electronics, health care and in the
car manufacturing industry.

It is produced by combining chlorine (from the
electrolysis of salt water) and ethylene (from
crude oil) to produce ethylene dichloride.

Under high temperature, ethylene dichloride
forms a monomer called vinyl chloride.

These monomers are polymerised to form poly
vinyl chloride resin
 Solvents

Carbon tetrachloride and chloroform are
examples of halogenated hydrocarbons which
are popular choices for industrial solvents;

They are relatively non-flammable (unlike
paraffin or petrol) and fats and oils dissolve
easily in them;

Some countries have banned the use of solvents
in applications such as dry cleaning because
they are linked to liver damage with prolonged
exposure.
 Refrigerants and aerosols

Halogenated hydrocarbons in particular was used in these applications:
CFCs (chlorofluorocarbons)

CFCs were banned globally from use because of the destruction of the
Earth’s protective ozone layer and replacement refrigerants and aerosols
were developed to replace the CFCs:

A much safer

But effective group of halogenated hydrocarbons called the
hydrochlorofluorocarbons (HCFCs);

CFCs have chlorine atoms replacing all the hydrogen atoms in the organic
compound, HCFCs have one or more hydrogen atoms on each carbon atom.

This makes them less environmentally harmful, but not 100% safe.

Because they were only meant to be a temporary solution

HCFCs use will be phased out completely by 2030 globally.

Hydrofluorocarbons (HFCs) are currently investigating by the scientists as
effective replacement as they should pose no threat to the ozone layer

Question:

State whether trends down the group in
each of the following properties are the
same or different when group 2 and group
17 are compared:

a. electronegativity

b. reactivity

c. melting point

d. ionisation energy
End of Topic Activity
 Assessment

Question Paper 2 questions

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