GROUP 17

Colors and trend in volatility

F2 Cl2 Br2 I2
Colour Yellow Green Red/brown Grey
State (at rtp) GAS GAS LIQUID SOLID

BOILING POINT

F2 Cl2 Br2 I2
Boiling point / °C - 188 - 34 58 183

• total number of electrons increase down the group makes the induced
dipole forces stronger going down the group, boiling point INCREASES
down the group. (more E to separate molecules)
 Trends in bond strength of
halogen molecules
• Covalent bond in the halogen molecules
getting weaker down the group because
size of halogen atoms increase due to
more shells of electrons descending the
group.
 OXIDISING POWER (Cl2>Br2>I2)

Chlorine oxidises bromide ions to bromine

Cl2 + 2Br¯ ——> Br2 + 2Cl¯

Chlorine oxidises iodide ions to iodine

Cl2 + 2I¯ ——> I2 + 2Cl¯

Bromine oxidises iodide ions to iodine

Br2 + 2I¯ ——> I2 + 2Br¯

 Relative reactivity of elements in Group VII as oxidsing
agents

SODIUM CHLORIDE SODIUM BROMIDE SODIUM IODIDE

Solution stays yellowish brown reddish brown

CHLORINE colourless solution form solution with black
BROMINE FORMED deposit of Iodine solid
NO REACTION form

Brown colour solution Brown solution of

BROMINE reddish brown
of bromine remain bromine remain
solution with black
unchange unchange
deposit of Iodine solid
NO REACTION NO REACTION form
Elements Reaction with H2 form hydride
Fluorine Explodes with hydrogen under all conditions
H2(g) + F2 (g) → 2 HF (g)
Chlorine Hydrogen burns in chlorine; H2 and Cl2
explodes in the presence of light
H2 (g) + Cl2 (g) → 2 HCl (g)
Bromine Reacts with hydrogen when heated to 200°C
the presence of platinum catalyst
H2 (g) + Br2 (l) → 2 HBr (g)
Iodine No reaction unless strongly heated
-Reaction is incomplete and equilibrium is
obtained
H2 (g) + I2 (s) ↔ 2 HI (g)
 Thermal stability of Hydrogen Halide
- As the size of the halogens increases down the
group, the H-X bond becomes longer and weaker
and so, is easily broken.
Hydrogen Halide Bond energy
HF 562
HCl 431
HBr 366
HI 299

- Hence, thermal stability of the hydrides decreases

down the group due to the decrease in strength of
the H-X bond as the size of the halogen increases.
Thermal stability : HF > HCl > HBr > HI
 Reaction of AgX with Aqueous
Ammonia ( No need)
Colour Reaction with NH3 (aq)
+ -
AgCl White AgCl(s) + 2NH3(aq) → [Ag(NH3)2] + Cl
ppt. silver (I) diammine ion
(Ppt. readily dissolves in NH3(aq) to give a
colourless solution, recall QA test for halide)
+ -
AgBr Cream AgBr(s) + 2NH3(aq) → [Ag(NH3)2] + Br
ppt. silver (I) diammine ion
(Ppt. only dissolves in concentrated NH3 solution)

AgI Yellow Ppt. insoluble in NH3(aq)

ppt.
 Reactions of halide ions with concentrated H2SO4

• add concentrated sulphuric acid carefully to a solid halide

salt (NaCl/NaBr/NaI)

• H2SO4 displaces the HCl, HBr, and HI from their salts

NaCl(s) + conc. H2SO4(l) ——> NaHSO4(s) +HCl(g)

HCl not oxidized to Cl2 because Cl- is a weak reducing agent, it

cannot reduced sulphuric acid or Cl2 is a stronger oxidizing
agent than H2SO4, H2SO4 cannot oxidized Cl2.
NaBr + H2SO4
 Halide as reducing agent

• Strength as reducing agent: I->Br->Cl-

 Reaction of Halide Ions with Conc.
H2SO4 (Summary)
Reaction with
conc. H2SO4
-
Cl NaCl + H2SO4 → HCl + NaHSO4
-
Br NaBr + H2SO4 → HBr + NaHSO4
2HBr + H2SO4 → Br2 + SO2 + 2H2O
-
I NaI + H2SO4 → HI + NaHSO4
2HI + H2SO4 → I2 + SO2 + 2H2O
6HI + H2SO4 → 3I2 + S + 4H2O
8HI + H2SO4 → 4I2+ H2S + 4H2O
Observation
•Only steamy fumes of HCl(g)
produced.
•Brown fumes (Br2) obtained.
•Some of the HBr produced is
oxidised to Br2 by the conc.
H2SO4
•Purple vapour of I2(g) or black solid I2(s)
obtained.
•HI produced is oxidised by conc. H2SO4
to I2
•Yellow solid of sulphur and rotten egg
smell of H2S as observation in additional to
the above
 Reactions of Cl2 with NaOH
• Cl2 react with cold NaOH at 15 & 70 °C to
form NaCl, NaClO and NaClO3
respectively
• 2OH- + Cl2 ---→ Cl- + ClO- + H2O
• 6OH- + Cl2 ---→ 5Cl- + ClO3- + 3H2O
• Cl2 disproportionate because it is oxidised
and reduced at the same time
 Cl2 in water purification
• Cl2 is added to water as disinfectant
• Cl2 react with water:
• Cl2 + H2O ----→ HCl + HClO
• HClO is not stable and can be further
decompose:
• HClO --→ HCl + ½ O2
• HOCl and OCl- can kill bacteria