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Inorganic Chem - Halogens
Inorganic Chem - Halogens
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The longer the bond length, the weaker the H-X bond and
hence the more easily the bond can be broken.
BOND LENGTH(nm)
÷ ÷ ÷
0.127 0.141 0.161
BOND ENERGY( kJ mol-1 )
÷ ÷ ÷
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 G 2NaCl (s)
Mg (s) + Cl 2 G MgCl2 (s)
Fe (s) + Cl 2 G 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 ʹ (aq) G 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) G ´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 ʹ (aq) G agBr (s)
0 -1 +1
+1 -1 +5
Reaction of chlorine with hot concentrated sodium
hydroxide.
o
70 C
3Cl2(aq) + 6NaOH(aq) ѐ 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
Reactions Of Halides Ions With
Concentrated Sulphuric acid
ʹ (aq) + H2SO4 (l) G HX (g) + HSO4 ʹ(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)G NaHSO4(aq) + HCl(g)
NaBr(s) + H2SO4 (aq)G NaHSO4(aq) + HBr(g)
dI (s) + H3PO4 (aq)G dHSO4 (aq) + HI(g)
Concentrated sulphuric acid is also an oxidising agent.
Thus, it will further oxidise
~ HBr G Bromine ( reddish brown vapour)
~ HI G Iodine (a violet vapour)
~ HCl G 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) ѐ
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) GNaHSO4(aq)+ HBr(g)
2HBr(g) + H2SO4(aq)GBr2(g)+2H2O(l)+SO2(g)
2Br-(s) + 3H2SO4(aq)G2HSO4-(s)+Br2 (g)+SO2(g)+2H2O(l)
dBr(s)+H3PO4(aq) ѐ dH2PO4(aq)+HBr(g)
dI(s)+ H3PO4(aq) ѐ dH2PO4(aq)+HI(g)
OXOaCIDS OF CHLORINE
a
HCIO 1.0×10Ё6
HCIO2 1.0×10Ё2
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 U
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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
seeding͛
BLaCd-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)G2ag(s)+2HBr(aq)+C6H4O2(aq)