CHEMISTRY-

INORGANIC
GROUP 17=Cl, Br, I
VOLATILITY & COLOUR INTENSITY OF Cl2,
BR2, & I2.

Volatility of Cl2, Br2, I2

Group 17 r called Halogen, non metal, exist as
diatomic molecules.
 The melting point of Group 17.
I2 > Br2 > Cl2 > F2
 The boiling point of Group 17

I2 > Br > Cl2 > F2

At RTP, Cl= gas Br= liquid I= solid

In vapour state, Cl =brown I=purple
RELATIVE REACTIVITY OF THE ELEMENTS AS
OXIDISING AGENTS
I. All e G17 r oxidising agent bcoz they tend 2
accept e- 2 form halide ion.
X2 + 2eˉ ->2Xˉ
II.Oxidising power of e G17 decrease on going
down e group.
Cl2 > Br2 > I2
III.The relative oxidising powers of e halogens
is explained in terms of their atomic radii.
The atomic radius of e G17 increase in :
F2 < Cl2 < Br2 < I2
 F is e strongest ox ag bcoz its atom has e
smallest size. F – greatest ability to
gain an e-
III. Cl is a stronger ox ag than Br & I.
IV. The 1 electron affinity of an element is e
enthalpy change 4 e reaction
Cl(g) + eˉ -> Clˉ Cl > Br > I
V. The relative oxidising power of G17 can also b
compared in terms of e enthalpy changes 4 e
reaction
½ X2 + eˉ -> Xˉ(aq) H
VI. 3 factor affect e value of H:
 Enthalpy of atomisation ( H1)
 Electron affinity ( H2 )
 Enthalpy change of hydration ( H3 )
Energy level diagram for e conversion of X2 to Xˉ

X (g) + eˉ

H1 H2

½ X2

Xˉ(g)
H
H3

Xˉ(aq)
VII. The enthalpy changes ( H total) 4 e formation
of halide ions bcome < exothermic on descending
e group .
VIII. The oxidising power decreases in:
Cl2 > Br2 > I2
 The reactivity of halogens as oxidising
agents.
 Fluorine oxidises H2O -> O2 at room condition.
2F2 (g) + 2H2O (l) -> 4HF (aq) + O2 (g)
Cl, Br, & I x oxidise H2O -> O2. Cl react with
H2O 2 give a mixture of acids,hydrochloric acid
& chloric(I) acid (HCIO).
 oxidation
0 -1 +1

Cl2 (g) + H2O (l) <-> HCl (aq) + HOCl (aq)

reduction

This is a disproportionation reaction :

->Cl is simultaneously oxidised & redused
during e reaction. -
>Chloric (I) acid is unstable & decomposes 2
give hydrochloric acid & O2.

2HCIO (aq) -> 2HCl (aq) + O2 (g)

 ->Br reacts with H2O in a similar way 2 produce
hydrobromic acid (HBr) & bromic (I) acid (HOBr).
Br2 (g) + H2O (l) <-> HBr (aq) + HOBr (aq)

 Chlorine oxidises bromide ions 2 bromine & iodide

ions 2 iodine.
Cl2 (aq) + 2Br- (aq) -> 2Cl(aq) + Br2(aq)
Cl2(aq) + 2I-(aq) -> 2Cl(aq) + I2(aq)
-This are displacement reactions. The presence
 - Aqueous solution of Br & I r yellow
(dilute solution) or brown (concentrate
solution).
- Br will dissolve in in organic solvents ->
brown red solution.
- I -> purple solution.
 Bromine oxidise iodide ions 2 iodine.
Br2(aq) + 2Cl(aq) -> 2Br-(aq) + I2(aq)
-Br cannot oxidise e chloride ion bcoz it
is a weaker oxidising agent than Cl.
 I2 is e weakest oxidising agent, hence it
cannot oxidise chloride ions (Cl-) or bromide
 I2 does not oxidise iron (II) ions.
2Fe2+ (aq) + I2(aq) -> 2Fe3+ (aq) + 2I- (aq)
E= -0.23V
- The ‘-’ value of E show e reaction is not
feasible. Both Cl & Br can oxidise iron (II)
ions (Fe2+) to ion (III) ions (Fe3+).
2Fe2+(aq) + Cl2 (aq) -> 2Fe3+ (aq) + 2Cl-(aq)
 REACTON OF Cl2 , Br2 , & I2
WITH HYDROGEN

Thermal stability of hydrogen halides

I. Halogens react directly with hydrogen to
form hydrogen halides or hydrides of
halogens.
H2(g) + X2(g) <-> 2HX(g)
X= F, Cl, Br, & I.
- All hydrogen halides r colourless, acidic
gases & dissolve in water readily.
II. Reaction between Fl & hydrogen take place
very rapidly. Fl explodes with hydrogen at
low temperature & in dark to form
hydrogen fluoride.
H2(g) + F2(g) -> 2HF(g)
III. At room temperature, a mixture of Cl & H
will explode if exposed to sunlight or uv.
H2(g) + Cl2 <-> 2HCl(g)
-a jet of H can burn safely in Cl to form
HCl2(g). This method used in industry 4 e large
scale production of hydrogen chloride.
IV. Br react with H only at e high temp of 200°C
& in e presence of a platinum catayst. Hidrogen
bromide is formed.
H2(g) + Br2 Pt
2HBr(g)
200

V. I & H react slowly & partially to form hydrogen iodide.

H2(g) + I2 Pt
2HI
400OC
Halogen react with hidrogen:
- form hydrogen halides
- e reactivity decrease on descending e group
- e reaction bcome less vigorous
- e reaction rates bcome slower
THERMAL STABILITY OF HYDROGEN
HALIDES
 hydrogen fluoride n hydrogen chloride r
very stable when heat.
 At 2000°C, hydrogen chloride dissociates
only slightlyto form hydrogen n chlorine.
 Hydrogen bromide decomposed at 600°C
-> H & brown Br vapour.
 Hydrogen iodide decomposed -> H &
violet fumes of I at low temp (200°C)
 The stability of hydrogen halides towards
thermal decomposition decrease with increasing
relative molecular mass.
HF > HCl > HBr > HI
 The relative stability of hydrogen halides can
b explain in terms of bond length & bond
strength.
 On descending G17 e atomic size of e halogens
increase, e H-X bond length increases.
HF < HCl < HBr <HI
bond length increase
 The decomposition of hydrogen halides
involves breaking e H-X bonds. E longer e bond
length e weaker e bond n easy e bond broken.
 The stability of hydrogen halides towards
thermal decomposition decrease in e order
HF > HCl > HBr > HI
- this is due 2 e progressive decreasein e
H-X bond enery n e progressive decrease (less
exthermic) in e enthalpy of formation.
- e enthalpy of formation for HI is
endothermic.
 REACTION OF HALIDE IONS
 REACTION OF HALIDE IONS WITH AQUEOUS SILVER IONS
 SOLUBILITY OF SILVER HALIDES IN AMMONIA SOLUTION
 REACTIONS OF HALIDES ION WITH CONCENTRATE
SULPHURIC ACID
 PREPARATION OF HYDROGEN HALIDES
REACTION OF HALIDE IONS WITH AQUEOUS SILVER IONS

i. F- x produce a precipitate when they react

with silver nitrate solution bcoz silver fluoride
is soluble in H2O.
ii. Chloride ions react with aqueous silver nitrate
to produce a white precipate of silver chloride.
Ag+(aq) + Cl-(aq) -> AgCl(s)
silver chloride turns violet in sunlight.
iii. Bromide ions react with aqueous silver nitrate to form
a creamprecipitate of silver bromide.
Ag +(aq) + Br-(aq) -> AgBr(s)
iv. Iodide ions react with aquoues silver nitrate to form a
yellow precipitate of silver iodide.
Ag+ (aq) + I- (aq) -> AgI(s)
SOLUBILITY OF SILVER HALIDES IN AMMONIA SOLUTION

 The reaction between halide ions & of silver nitrate

solution followed by ammonia solution can be used
as a test to confirm e presence of halide ions.
 The white precipitate of silver chloride dissolve
readily in dilute ammonia solution to form e
colourless solution of silver complex.
AgCl(s) + 2NH3 (aq) -> [Ag(NH3)2]+(aq) + Cl-(aq)
 The cream coloured silver brimide is insoluble in
dilute ammonia solution, but dissolve in
concentrate ammonia solution.
AgCl(s) + 2NH3 (aq) ->[Ag(NH3)2]+ (aq)
 The yellow precipitate of silver iodide is
insoluble in both dilute ammonia solution &
concentrate ammonia solution.
 The solubility of silver halides in ammonia can
b explained in terms of silver halides.
The solubility of silver halides in water
decrease in e following order.
AgCl > AgBr > AgI
 The concentration of silver halides in H2o is
extremely low, & is not sufficient to react with
ammonia solution.
 REACTION OF HALIDES IONS WITH
CONCENTRATED SULPHURIC ACID

When concentrated sulphuric acid is added to a

solid halide & e mixture heated strongly, white
fumes of hydrogen halides r produced initially.
X- (s) + H2SO4 (l) -> HX (g) + HSO4-(aq) -
concentrate sulphuric acid acts as a stronger
acid & displace a weaker acid (HX) fr its salt.
When solid sodium chloride is heated with
concentrate sulphuric acid, hydrogen chloride gas
is produced.
NaCl(s) + H2SO4(l) -> NaHSO4(s) + HCl(g)
- used to prepare hydrochloric acid in lab.
 Concentrate sulphuric acid aiso act as an oxidising
agent. It is not powerful enough to oxidise
hydrogen chloride to chlorine, but it is powerful
enough to oxidise HBr(colourless) to Br2 (brown red
vapour) & HI (colourless) to I2 (violet vapour).
The reaction between esolid sodium bromide &
concentrate sulphuric acid produce bromine &
sulphur dioxide gases.
When solid sodium iodide is heated with
concentrate sulphuric acid, more complicated
reaction take place to produce a mixture of gases,
which include HI,I2, SO2 & H2S(hydrogen sulphide)
 The reaction of concentrated sulphuric acid
with solid ionic halides show e ease of oxidation of
halide ions increase in e order
Cl- < Br- < I-
As e ionic radius of e halide ion increase fr Cl-
to I-, it becomes easier to remove an electron fr e
halide ion. E reducing power of e halide ion
increase in e following order.
Weak reducing Cl- < Br- < I- strong reducing
Preparation of HYDROGEN HALIDES
Hydrogen halides prepared in lab by heating solid
sodium chloride with concentrate sulphuric acid. HCl gas
produce dissolved in H2O to form HCl.
HBr & HI x prepared by e reaction between concent
sulphuric & e respective halides, NaBr & NaBr.
- HBr & HI prepared by hydrolysis of phosphorus
tribromide & phosphorus triiodide respectively.

- PBr3(l) + 3H2O(l) -> H3PO3(aq) + 3HBr(g)

- PI3 (l) + 3H2O(l) -> H3PO3(aq) + 3HI (g)
The H3PO3 produce in e above reaction is x an oxidising
agent & x oxidise hydrogen bromide & hydrogen iodide.
REACTION OF CHLORINE WITH
AQUEOUS SODIUM HYDROXIDE
REACTION OF CHLORINE WITH
COLD, DILUTE SODIUM
HYDROXIDE
Chlorine gas passed into cold, dilute sodium hydroxide
solution :
- sodium chloride, sodium chlorate(I) & H2O
Cl2 (g) + 2NaOH(aq) 15°C
NaCl (aq) + H2O (l) + NaCIO (aq)…(1)
Disproportionaton reaction-chlorine oxidise to e chlorate
(I) ion (CIO-) & reduce to e chloride ion (Cl-)
0 -1 +1
Cl2 (g) + 20H- (aq) -> Cl- (aq) + H2O (l) + CIO-(aq)
 REACTION OF CHLORINE WITH HOT,
CONCENTRATED SODIUM HYDROXIDE
Chlorine reacts with hot, NaOH to produce NaCl,
NaClO3(V) & H2O. 3Cl2(g)
+ 6NaOH (aq) 5NaCl (aq) + 3H2O (l) +
NaClO3(aq)…(2) Sodium chlorate Sodium
chlorate (V) is used as a weedkiller.
Sodium chlorate (V) can also be obtained by
heating sodium chlorate (I) solution. 3NaClO
(aq) -> 2NaCl (aq) + NaClO3 (aq) …(3)
Reaction (1), (2), (3) r all disproportionation
reactiions. In (3), NaClO is reduced 2 NaCl &
oxidise 2+1NaClO3. -1 +5
IMPORTANT USES OF
HALOGENS & HALOGEN
COMPOUND
AS ANTISEPTICS
AS BLEACHING AGENTS
FOR PURIFYING WATER
IN BLACK-AND –WHITE