Group 17

( Halogens )

Chlorine , bromine , iodine

General characteristics
1. All have 7 electrons in valence shell
Readily accepts 1 electron
2. Outermost electronic configuration :
ns2 np5
3. Reactive non metals
Exists as diatomic molecules
 4. States at room temperature :
a. Cl2 : green/yellow gas b.p increases
Br2 : reddish brown/red/ Less volatile
orange liquid Volatility decreases
I2 : black solid
 b. trend in volatility :
Halogens are non polar molecules
Weak VDW forces exist between molecules
Down the group, no of electrons increases
Strength of VDW increases
Boiling point increases ( less volatile )
Volatility decreases
Halogens as oxidising agents
1. Cl2 Br2 I2
Decreasing oxidising
power
Halogens are readily reduced
X2 + 2e 2X-
Functions as oxidising agents
From Cl2 I2 , size of X2 increases
Accepts e less readily , less readily reduced
Oxidising power decreases
 2. Difference in oxidising power explains
their displacement reactions
Eg. Cl2 + 2I- 2Cl- + I2
Cl2 can oxidise I- to I2 ( Cl2 stronger
oxidising agent )
Chlorine displaces iodine
But I2 cannot oxidise Cl-
Chemical reactions
Reactions of halogens
1. With alkali : product depends on temp
a. cold dilute alkali ( temp 150 C )
Eg Cl2 + 2OH- Cl- + ClO- + H2O
chlorate (I) ion
0 -1 +1
reduced
Disproportionation
oxidised reaction
 b. hot concentrated alkali ( temp 700C )
Eg 3Cl2 + 6OH- 5Cl- + ClO3- + H2O
chlorate (V) ion
0 -1 +5
reduced

Disproportionation
oxidised
reaction
 Notes :
i)Products ( ClO- and ClO3- ) called oxoanions (
anions containing oxygen )
ii)Chlorine required can be formed by :
4HCl + MnO2 Cl2 + MnCl2 + 2H2O
conc
Similar reactions shown by bromine and iodine
eg BrO3- , bromate (V) and IO3- , iodate (V) ion
 2. With hydrogen hydrogen halides / halogen
hydrides
a. prepared by direct combination :
H2 (g) + X2 (g) 2HX (g)
b. solutions of HX (g) in water produces acidic
solutions :
HX + H2O H3O+ + X-
H-X bond broken acidic
 Acidity of solution : HCl HBr HI

Acidity increases
Size of halogen atom increases
HX bond length increases
HX bond strength decreases
H-X bond breaks more readily to form H3O+
Acidity increases
 From Data booklet :
Bond Bond energy/kJmol-1
H-Cl 432 Bond energy decreases
Bond more readily
H-Br 366 broken
H-I 298 Acidity increases
 c. i) thermal stability of HX decreases down the
group:
2H-X H2 + X2 ( H-X bond broken )
Size of halogen atom increases
H-Cl HX bond length increases
H-Br HX bond strength decreases
H-I HX bond more readily broken (decomposes)
Thermal stability decreases
 ii)Observations :
HCl : stable to heat
HBr : produces red brown fumes ( Br2 )
HI : decomposes readily on contact with a
hot glass rod (provides activation energy)
to form purple vapour ( I2 ) + black solid
Reactions of halide ions (X-)
1. Reaction with AgNO3(aq) followed by
aqueous NH3 :
a)Used as a test for halide ions
Ag+ (aq) + X- (aq) AgX (s )
i)White ppt soluble in aq NH3 forming colourless
solution: Cl-
ii)Cream ppt sparingly soluble in dilute NH3 but
soluble in concentrated NH3 : Br-
 iii) Yellow ppt insoluble in dilute or concentrated
ammonia : I-
b) Difference in solubility in NH3:
AgCl and AgBr dissolves due to complex ion
formation
Eg: Ag+ (aq) + Cl- (aq) AgCl (s) Equilibrium
Add aqueous NH3 : the ammonia acts as a
ligand and forms a complex ion with Ag+
 Equation :
Ag+(aq) + 2NH3 (aq) [Ag(NH3)2]+ (aq)
complex ion
Complex ion : H3N Ag+ NH3
Formation of the complex ion causes [Ag+] in
equilibrium to decrease
Equilibrium shifts left
Observation : AgCl (s) dissolves
 Or : AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ Cl- (aq)
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ Br- (aq)

Add an excess of H+(aq)/acid ,

precipitate reappears
 2. Reaction with concentrated H2SO4 :
a. concentrated H2SO4 + solid ionic halides
HX ( hydrogen halides )
H2SO4(l) + 2X- (s) 2HX (g) + SO42- (s)
acid
Eg H2SO4 + 2NaCl(s) 2HCl + Na2SO4
No further reaction occurs
Alternative method to prepare HCl only
 b. However , conc H2SO4 is also an oxidising agent
powerful enough to oxidise HBr Br2
and HI I2.
But it is not powerful enough to oxidise HCl Cl2
i) with bromide ions :
Br- is oxidised to Br2 while SO42- is reduced to SO2
Eg H2SO4 + 2NaBr(s) 2HBr + Na2SO4
2HBr + H2SO4 Br2 + 2H2O + SO2 (*)
 ii) with iodide ions :
red
I oxidised to I2 , SO4 SO2 S H2S
- 2-

Eg 2HI + H2SO4 I2 + 2H2O + SO2

8HI + H2SO4 4I2 + 4H2O + H2S
Note : Product usually contaminated by
sulphur or sulphur compounds ( eg SO2
and H2S )
 c. Observations :
i) Cl- : only steamy/white fumes of HCl

ii) Br- : Br2 (g) and HBr (g)

red brown fumes steamy/white fumes
 iii) I- : I2 (g) and HI (g)
purple vapour steamy/white fumes
main product : I2 (g) + black solid
Other observations: yellow solid (S),
stinking gas (H2S)
HI most readily oxidised
 Notes :
(1) comparing ease of oxidation of HX
HCl HBr HI
Ease of oxidation
increases

HX is more readily oxidised

reducing power of HX increases
 (2) Concentrated H2SO4 is a stronger oxidising
agent than iodine / bromine but weaker than
chlorine
(3) Concentrated H3PO4 is a weaker oxidising
agent than concentrated H2SO4 or iodine
therefore not able to form iodine from reaction
with an ionic iodide
(4) Role of concentrated H2SO4

Compound As a strong acid As an oxidising

agent
Chloride

Bromide

Iodide
Use of halogens and their
compounds
1. Chlorine :
a. in water purification : household and
swimming pool
Cl2 + H2O HCl + HClO
hypochlorous acid
(oxidising agent)
Acidic solutions formed kills bacteria or
microorganisms
 b. manufacture of
bleach for textile and paper industry eg
NaClO,
degreasing solvent eg CH3CCl3 ,
CFCs
polymers eg pvc
 2. Bromine :
a. fire extinguisher/flame retardants (*) eg
CH2ClBr
b. petrol additive : eg C2H4Br2
c. photographic film : eg AgBr
 3. Iodine :
a. dissolved in alcohol , used as mild antiseptic
for cuts and scratches
b. used in photographic film eg AgI