GROUP 17

HALOGENS
BY,
CHIA YEN
KEVIN LAI
SUGANRAAJ
WEI HONG
MELISSA TEH
 GENERAL PROPERTIES
•Non-metallic elements  fluorine, chlorine,
bromine, iodine and astatine.
•Diatomic molecules , X 2 , with a single covalent
bond.
•As the proton number increases down the
group:
- melting point increases
- ionisation energy decreases
- electronegativity decreases
•The strength of van der Waals forces of
attraction increases, F2 < Cl 2 < Br2 < I 2
•All halogens except iodine are slightly soluble in
water to give coloured solutions.
•Halogens dissolve in organic solvents to form
coloured solutions.
Halogen Colour in CCl4 solution
Cl Colourless
Br Reddish brown
I Purple

•Have valence electronic configuration of ns2np5 .

•Oxidising agents.
Element Chlorine(Cl) Bromine(Br) Iodine (I)
Proton number (Z) 17 35 53
Valence electron configuration 3s2 3p5 4s2 4p5 5s2 5p5

Relative atomic mass 35.5 79.9 127.0

State at room temperature Gas Liquid Solid
Colour Greenish Reddish brown Dark purple
yellow
Boiling point / 0 C -35 59 184
Covalent radius/ nm 0.099 0.114 0.133
Ionic radius/nm 0.181 0.196 0.216
Electronegativity 3.2 3.0 2.7
Electron affinity/ kJ mol-1 -348 -325 -295
Ionisation energy/kJ mol-1 1250 1141 1009
Standard electrode potential/V +1.36 +1.07 +0.54
( X2 + 2e  2X- )
 Atomic radius/ionic radius
Element Chlorine(Cl) Bromine(Br) Iodine (I)
Covalent radius/ nm 0.099 0.114 0.133
Ionic radius/nm 0.181 0.196 0.216

• Down Group 17, the nuclear

charge and the screening
effect increases.
• However, the increase in
the screening effect is larger
than the increase in the
nuclear charge, causing a
decrease in the effective
nuclear charge.
Atomic radius Ionic radius
 Electronegativity
Element Chlorine(Cl) Bromine(Br) Iodine (I)
Electronegativity 3.2 3.0 2.7

• Is the measure of the

relative strength of atoms
to attract electrons in a
covalent bond to which
they are bonded.
• The smaller the size of the
atom or/and the higher
the nuclear charge, the
stronger is the attraction
for the electrons in a Proton number
covalent bond
The Colour Intensity Of Group 17
Elements
The Volatility Of Group 17 Elements
• Decreases down the group.
• The higher the melting point or boiling point,
the stronger the intermolecular forces of
attraction.
• The van der Waals forces of attraction
between the halogen molecules increase as
the molecular size of the molecules increases.
 The Relative Reactivity Of The Elements As
Oxidising Agents
• An oxidising agent is an electron acceptor
• X2 (aq) + 2e-  2X – (aq)
Cl2 (aq) + 2e- 2Cl- (aq) Eθ = + 1.36 V
Br2 (aq) + 2e- 2Br -(aq) Eθ = + 1.07 V

I2 (aq) + 2e- 2I- (aq) Eθ = + 0.54 V

• The more positive the Eθ value, the stronger the
element acts as an oxidising agent.
• The smaller is the atomic radius, the stronger the
element act as an oxidising agent. F2 < Cl 2 < Br2 < I
2
 • The reactivity of halogens as oxidising agents can be
shown by the following reactions
Cl2 (aq) + 2Br – (aq) 2Cl– (aq) + Br2 (aq) Eθ = + 0.27V
Cl2 (aq) + 2I – (aq) 2Cl– (aq) + I2 (aq) Eθ = + 0.82V

Br2(aq) + 2I – (aq) 2Br –(aq) + I2 (aq) Eθ = + 0.27V

2Fe2+(aq) + I2 (aq) 2Fe3+(aq) + 2I – (aq) Eθ = - 0.23V

2Fe2+(aq) + Cl2 (aq) 2Fe3+(aq) + 2Cl– (aq) Eθ = + 0.59V

2Fe2+(aq) + Br2 (aq) 2Fe3+(aq) + 2Br– (aq) Eθ = + 0.30V
 Reactions Of Chlorine, Bromine And
Iodine With Hydrogen
• Hydrogen halides  hydrides of halogens
• H2 (g) + X2 2HX (g) , where X = F, Cl, Br, and I.
• The order of reactivity decreases down the group.
Eg: a) Fluorine explodes with hydrogen at low
temperature and in the dark to form hydrogen
fluoride.
H2 (g) + F2 (g) 2HF (g)
b) At room temperature, a mixture of chlorine and
hydrogen will explode if exposed to sunlight or
ultraviolet light.
H2 (g) + Cl2 (g) 2HCl(g)
c) Bromine reacts with hydrogen only at a high
temperature of 200 oC and in the presence of
platinum catalyst to form hydrogen bromide.
H2 (g) + Br2 (g) Pt 2HBr(g)
200 oC

d) At 400 oC and in the prensence of platinum

catalyst, iodine and hydrogen react slowly to form
hydrogen iodide.
Pt
H2 (g) + I 2 (g) 2HI(g)
400oC
 Thermal Stability Of The Hydrogen
Halides
• when heated , 2H−X (g) H2 (g) + X 2 (g)

2000 oC
• 2HCl (g) H2 (g) + Cl2 (g)

600 oC
• 2HBr (g) H2 (g) + Br2 (g)

200 oC
• 2Hl (g) H2 (g) + l2 (g)
On descending Group 17, the atomic size of the halogens
increases, and hence the H-X bond length increases.
H-F < H-Cl < H-Br < H-I
Bond length increases

The longer the bond length, the weaker the H-X bond and
hence the more easily the bond can be broken.
BOND LENGTH(nm)
H-Cl H-Br H-I
0.127 0.141 0.161
BOND ENERGY( kJ mol-1 )
H-Cl H-Br H-I
432 366 298
Reactions Of Chlorine, Bromine And Iodine
With Metal
• Halogens react with every metal in the
Periodic Table forming halides.
• examples:
2Na (s) + Cl 2  2NaCl (s)
Mg (s) + Cl 2  MgCl2 (s)
Fe (s) + Cl 2  FeCl2 (s)
• In the above reaction, reactivity of the
halogen decreases down the group.
Reactions Of The Halides Ions With
Aqueous Silver Ions
• Chloride ions react with aqueous silver nitrate
to produce a white precipitate of silver chloride.
Ag+ (aq) + Cl – (aq)  AgCl (s)
• Silver chloride turns violet in sunlight.
• The white precipitate of silver chloride
dissolves readily in dilute ammonia solution to
form a colourless solution of silver complex.
AgCl (s) + 2NH3 (aq)  [Ag(NH3)2]+ (aq) + Cl- (aq)
silver complex
• Bromide ions react with aqueous silver nitrate
to form a cream precipitate of silver bromide.
Ag+ (aq) + Br – (aq)  AgBr (s)

• The cream coloured silver bromide is insoluble

in dilute ammonia solution but dissolves in
concentrated ammonia solution
AgBr (s) + 2NH3 (aq)  [Ag(NH3)2]+ (aq) + Br-(aq)
• Iodide ions react with aqueous silver nitrate
to form a yellow precipitate of silver iodide.
Ag+ (aq) + I – (aq)  AgI (s)

• The yellow precipitate of silver iodide is

insoluble in both dilute ammonia solution
ammonia solution and concentrated ammonia
solution.
 Reaction Of Halogens With Alkali
• Chlorine reacts with cold dilute sodium hydroxide to give
a mixture of sodium chloride and sodium chlorate(I).
o
Cl2 (g) + 2NaOH (aq) 15 C
NaCl (aq) + NaClO(aq) + H2O(l)

0 -1 +1

• In the above reaction, chlorine undergoes

disproportionation to -1 in Cl- and +1 in ClO- .
• Heat ClO- from NaClO, it will undergoes
disproportionation to ClO3- and Cl- .

3ClO- (aq) ∆ 2Cl- (aq) + ClO3- (aq)

3 NaClO (aq) ∆ 2NaCl(aq) + NaClO3 (aq)

+1 -1 +5
• Reaction of chlorine with hot concentrated sodium
hydroxide.
o
70 C
3Cl2(aq) + 6NaOH(aq) ∆ 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
 Reactions Of Halides Ions With
Concentrated Sulphuric Acid
X– (aq) + H2SO4 (l)  HX (g) + HSO4 –(aq)
• In these reactions, concentrated sulphuric acid acts as a
strong acid to displace the acid, HX, from its salt.
• When solid halides are heated with concentrated
sulphuric acid, white fumes of hydrogen halides are
liberated.
• NaCl (s) + H2SO4 (aq) NaHSO4(aq) + HCl(g)
• NaBr(s) + H2SO4 (aq) NaHSO4(aq) + HBr(g)
• KI (s) + H3PO4 (aq) KHSO4 (aq) + HI(g)
• Concentrated sulphuric acid is also an oxidising agent.
• Thus, it will further oxidise
~ HBr  Bromine ( reddish brown vapour)
~ HI  Iodine (a violet vapour)
~ HCl  Because concentrated sulphuric acid is not
strong enough to oxidise HCl.
To oxidise HCl to chlorine, a stronger oxidising agent such as
manganese (IV) oxide is used in the presence of concentrated
sulphuric acid.

4NaCl(s)+4H2SO4(aq)+MnO2(s) ∆
Cl2(g)+MnCl2(aq)+4NaHSO4(aq)+2H2O(l)
• Concentrated sulphuric acid is also an oxidising agent and
will further oxidise HBr and HI to Br2 (g) and I2(g)
respectively.
• NaBr(s)+ H2SO4(aq) NaHSO4(aq)+ HBr(g)
• 2HBr(g) + H2SO4(aq)Br2(g)+2H2O(l)+SO2(g)
• 2Br-(s) + 3H2SO4(aq)2HSO4-(s)+Br2 (g)+SO2(g)+2H2O(l)

• NaI(s) + H2SO4(aq) NaHSO4(aq) + HI(g)

FURTHER
• 2HI(g) +H 2SO4(aq) I 2(g)+ 2H 2O(l)+ SO 2(g) OXIDATION
• 8HI(g) +H2SO4(aq) 4I2(g)+ 4H2O(l)+ H2S(g)
Overall reaction:
• 2I-(s)+ 3H2SO4(aq)2HSO4-(aq)+I2(g)+SO2(g) +2H2O(l)
•Or, 8I-(s)+ 9H2SO4(aq)8HSO4-(aq)+H2S(g) +4I2(g) +4H2O(l)
 Cl - < Br - < I -
• Ease of oxidation of halide ions.
• Reducing power of halide ions.

To Obtain Just HBr And HI

A non-oxidising acid such as excess concentrated phoshoric(v)
acid is used together with heat.

• KBr(s)+H3PO4(aq) ∆ KH2PO4(aq)+HBr(g)
• KI(s)+ H3PO4(aq) ∆ KH2PO4(aq)+HI(g)
 OXOACIDS OF CHLORINE

The important oxidations states of chlorine are

-1,+1,+3,+5, and +7
•The oxo-acids are:
a. HOCI : chloric(I) acid
b. HCIO2 : chloric(III) acid
c. HCIO3 : chloric(V) acid

d. HCIO4 : chloric(VII) acid

• All the oxo-acids dissociate in water:
a. HOCI (aq) H+ (aq) + CIO - (aq)
b. HOCI2 (aq) H+ (aq) + CIO2- (aq)
c. HOCI3 (aq) H+ (aq) + CIO3- (aq)
d. HOCI4 (aq) H+ (aq) + CIO4- (aq)
• The acid dissociation constant, Ka
ACID Ka /mol dm -3
HCIO 1.0×10⁻6
HCIO2 1.0×10⁻2
HCIO3 1.0×10
HCIO4 1.0×1010
 As oxygen is more electronegative than chlorine, the O-H
bond in the oxo-acids are weakened by the –I inductive effect
(electron-withdrawing effect) of the oxygen atoms which are
bonded to the chlorine atoms as shown below.
a. HCIO : H-O-CI
b. HCIO2 : H-O-CI O

O
c. HCIO3 : H-O-CI O
O
d. HCIO4 : H-O-CI O
O
HCIO < HCIO2 < HCIO3 < HCIO4
INDUCTIVE EFFECT INCREASES
 PREPARATION OF HALOGENS
THE MERCURY CATHODE CELL
Chlorine is produce by the electrolysis of
brine(concentrated aqueous sodium chloride)
using mercury as cathode and graphite as anode.
The sodium produced at the cathode combines with mercury
to form unreactive sodium amalgam. The amalgam is directed
into another steel tank where it reacts with water to produce
sodium hydroxide and hydrogen gas.

2Na/Hg(l) + 2H2O (l) 2NaOH(aq)+ H2(g) +2Hg(l)

• The mercury is recycled.

• Sodium hydroxide can be obtained by evaporating the
solution.
• The disadvantage of this method is in the disposal of used
mercury. Indiscriminate disposal will lead to mercury
poisoning of human, animals and fishes.
 OTHER METHODS OF PREPARATION:

a. Heating a chloride with MnO2 and concentrated H2SO4.

2NaCl+3 H2SO4 +MnO2MnSO4+2NaHSO4+2H2O+Cl2

b. Action of acidified aqueous potassium manganate(VII) on

a chloride.
- - + 2+
10Cl + 2MnO + 16H  5Cl2 + 2Mn + H2O
4
•
BROMINE AND IODINE

Both bromine and iodine exist in large quantities in the sea

water. Bromine is prepared commercially from sea water.
The sea water is treated with chlorine gas which oxidises
bromide ions to bromine.
- -
Cl2(g) + 2Br (aq)  Br2(l)+ 2Cl (aq)

Certain marine plants, such as seaweeds, absorb and

-
concentrate iodine ions(I ) selectively. Iodine is obtained in
small quantities from such plants.
 USES OF HALOGENS AND THEIR
COMPOUNDS
CHLORINE
•used in the extraction of bromine from seaweed
•used in the sterilising water supplies for home and industrial
use, for swimming pools.
CI2 (g) + H2O (l)  HCI (aq) + HOCI(aq)
The OCI- ion which is formed kills bacteria by oxidising life-
sustaining compounds within them.
• used as bleaching agent in the paper and fabric industry.
• used as antiseptics and disinfectants
eg: TCP( trichlorophenol)
Dettol (4-chloro-3,5-dimethylphenol)
Compounds of chlorine include:
•Trichloromethane and tetrachloromethane are used as
organic solvents.
•Chloroethene is the monomer for PVC.
•Sodium chloride is used as table salt.
•D.D.T (dichlorodiphenyltrichloroethane) is used as
insecticide.
•Sodium chlorate(V), NaClO3 is a weed killer.
•Sodium chlorate(I) ,NaCIO ,and calcium chlorate(I), Ca(OCI)2,
is used as household bleach.
•Freons (e.g. CCI2F2 , CFCI3 ) are used as refrigerants or as
propellants in aerosol cans.
BROMINE
• 1,2- dibromoethane, BrCH2CH2Br, is added to leaded petrol
to remove the lead oxide sticking to the piston surface.
•Silver bromide is used in the manufacturing of photographic
film and photochromic lenses.
•Used in the manufacture of dyes and drugs.

IODINE
•A 50%( by mass) solution of iodine in ethanol (known as
tincture) is used as an antiseptic.
•Silver iodide is used in photographic film and in ‘cloud
seeding’
 BLACK-AND-WHITE PHOTOGRAPHY
•Silver chloride and silver bromide slowly turn purple and
finally dark grey when exposed to sunlight because of the
following photochemical decomposition.
AgCl (s) sunlight Ag(s) + ½ Cl2 (g)
AgBr (s) sunlight Ag(s) + ½ Br2(g)
• the use of silver halides in black-and-white photography
depends on this photosensitive nature of silver salts.
• Black-and-white photographic film is a clear, cellulose strip
coated with grains of silver bromide.
• When the film is exposed, the light coming from the
subject passes through the lens of the camera and strikes
the film. The silver bromide that was exposed gets
activated: AgBr (s) sunlight AgBr *(s)
•The exposed film is then treated with aqueous hydroquinone
(a reducing agent), where the activated silver bromide is
preferentially reduces to metallic silver.

2AgBr(s)*+C6H6O2(aq)2Ag(s)+2HBr(aq)+C6H4O2(aq)

•The film is then immersed in an aqueous solution of

thiosulphate (‘hypo’) where the unreactive silver bromide is
removed:
AgBr(s)+2S2O32-(aq)[Ag(S2O3) 2 ]3- (aq)+Br- (aq)
•The resulting film is now a ‘negative’.

•Where light shines through the ‘negative’ onto a piece of

photographic paper, the dark areas containing precipitate or
metallic silver that are opaque to light on the negative appear
white on the photography paper while the white areas- the
unactivated areas on the negative will appear dark.

•A print of the photograph is obtained.

THANK
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