General characteristics of halogen
1. Electronic configuration
-Seven electrons in their valence shell
2. Oxidation state
-Chlorine, Bromine and iodine (O.S.-1 to
+7)
-Fluorine (O.S. -1) due to no d-orbitals
3. Atomic and ionic radii
-Increases with increase in atomic number from top to bottom
4. Ionization potential
-Very high value of IP
-Decreases with increasing atomic number
5. Electronegativity
-Fluorine is the most electronegative among all halogen
-Decreases with increasing atomic number
6. Oxidizing power
-Strong oxidizing agent
X2 + 2e- 2X-
-Oxidizing power decreases with increasing atomic number
7. Bond dissociation energy
-Decreases as Cl-Cl > Br-Br > F-F > I-I
-Fluorine has lower bond dissociation energy than chlorine and
bromine
8. Reactivity
-Decreases with increasing atomic number
-F2 > Cl2 > Br2 > I2
9. Colour and state
Halogen Colour State
F2 Light yellow Gas
Cl2 Yellowish Gas
Br2 Reddish brown Liquid
I2 Purple black Solid
Comparative study on preparation of halogens
1. General methods of preparation
a. By electrolytic oxidation of halides:
KF K+ + F-
HF H+ + F-
At cathode,
2H+ + 2e- H2 (g)
At anode,
2F- F2 (g) + 2e-
Similarly,
electrolysis
2NaCl (fused) 2Na+ + Cl2
2NaCl (aq.) electrolysis 2NaOH + Cl2 + H2
b. By chemical oxidation of halides:
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 3Cl2 + 7H2O
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O
2. Laboratory preparation of chlorine, bromine and
iodine:
Chlorine
NaCl + H2SO4 NaHSO4 + HCl ] x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HCl + [O] Cl2 + H2O
2NaCl + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + Cl2 + 2H2O
Bromine
NaBr + H2SO4 NaHSO4 + HBr ] x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HBr + [O] Br2 + H2O
2NaBr + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + Br2 + 2H2O
Iodine
KI + H2SO4 KHSO4 + HI ] x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HI + [O] I2 + H2O
2KI + 3H2SO4 + MnO2 2KHSO4 + MnSO4 + I2 + 2H2O
Preparation from metallic halide with conc. Sulphuric
acid
Bromine
KBr + conc. H2SO4 KHSO4 + HBr
2HBr + conc H2SO4 Br2 + SO2 + 2H2O
Iodine
KI + conc. H2SO4 KHSO4 + HI
2HI + conc H2SO4 I2 + SO2 + 2H2O
Chemical properties of halogens
1. With water:
2H2O + 2F2 4HF + O2 Fluorine being strong oxidizing agent,
3H2O + 3F2 6HF + O3 oxidises water to O2 and O3
H2O + Cl2 Cl2.H2O Chlorine, bromine and iodine dissolve in
water to some extent forming pale green,
H2O + Cl2 HCl + HOCl orange red and pale brown solution
respectively. Chlorine water contains
2. With caustic alkali: hydrated chlorine, Cl- and OCl-
2NaOH + 2F2 2NaF + H2O + OF2 (used as rocket fuel)
(dil)
4NaOH + 2F2 4NaF + 2H2O + O2
(conc)
H2O + Cl2 HCl + HOCl
NaOH + HCl NaCl + H2O
NaOH + HOCl NaOCl + H2O
2NaOH + Cl2 NaCl + H2O + NaOCl (used as household bleach)
(dil and cold) Sodium hypochlorite
(This reaction is disproportionation reaction as chlorine is oxidized as well as
reduced.)
2NaOH + Cl2 NaCl + NaOCl + 2H2O ] X 3
3NaOCl 80°C NaClO3 + 2NaCl
6NaOH + 3Cl2 5NaCl + 3H2O + NaClO3 (used as weedicide)
(hot and conc)
Sodium chlorate
0°C
2NaOH + Br2 NaBr + NaBrO + H2O
(dil and cold) Sodium
hypobromite
Above
6NaOH
(hot and conc)
+ 3Br2 50°C 5NaBr + NaBrO3 + 3H2O
Sodium bromate
2NaOH + I2 NaI + NaIO + H2O
NaIO + H2O HIO + NaOH
NaOH + I2 NaI + HIO
(dil and cold) Hypoiodous acid
6NaOH + 3I2 5NaI + NaIO3 + 3H2O
(hot and conc) Sodium iodate
3. Oxidizing nature of halogens
F2>Cl2>Br2>I2
a. Displacement reaction
2NaBr + Cl2 2NaCl + Br2
2KI + Cl2 2KCl + I2
2KI + Br2 2KBr + I2
b. With hydrogen sulphide
H2O + Cl2 HCl + HOCl
HOCl HCl + O
H2S + O H2O + S
H2S + Cl2 2HCl + S
c. With Sulphur dioxide
H2O + Cl2 HCl + HOCl
HOCl HCl + O
SO2 + O + H2O H2SO4
SO2 + 2H2O + Cl2 2HCl + H2SO4
d. With sodium sulphite
H2O + Cl2 HCl + HOCl
HOCl HCl + O
Na2SO3 + O Na2SO4
Na2SO3 + H2O + Cl2 2HCl + Na2SO4
e. With sodium arsenite
H2O + Cl2 HCl + HOCl
HOCl HCl + O
Na2AsO3 + O Na2AsO4
Na2AsO3 + H2O + Cl2 2HCl + Na2AsO4
f. With sodium nitrite
H2O + Cl2 HCl + HOCl
HOCl HCl + O
NaNO2 + O NaNO3
NaNO2 + H2O + Cl2 2HCl + NaNO3
g. With sodium thiosulphate
H2O + Cl2 HCl + HOCl
HOCl HCl + O
Na2S2O3 + O Na2SO4 + S
Na2S2O3 + H2O + Cl2 Na2SO4 + 2HCl + S
Similarly,
Na2S2O3 + H2O + Br2 Na2SO4 + 2HBr + S
But,
2Na2S2O3 + I2 Na2S4O6 (Sodium tetrationate) + 2NaI
This reaction is used in iodometric titration.
4. With hydrogen
H2 + F2 -250°C,
dark
2HF
H2 + Cl2 sunlight 2HCl
H2 + Br2 400°C 2HBr
H2 + I2 400°C, Pt 2HI
5. With non-metals
P4 + 6Cl2 4PCl3
P4 + 10Cl2 4PCl5
SO2 + Cl2 sunlight SO2Cl2
CO + Cl2 COCl2
Phosgene
6. Bleaching action
H2O Cl2 HCl + HOCl
HClO HCl + O
Coloured substance + O Colourless substance
Chlorine bleaches the colouring materials (textiles, wood, pulp,
paper, etc) into colourless by oxidation which is permanent.
Uses of halogen
1.Uses of chlorine
a) To prepare organic compounds like PVC, methyl chloride, ethyl
chloride, chloroform, chlorobenzene, BHC, DDT etc
b) For bleaching textile, wood, pulp and paper
c) As disinfectant in drinking water and swimming pool water
H2O + Cl2 HCl + HOCl
HClO HCl + O
Microorganism + O Sterilization
2. Uses of bromine
a) To prepare 1,2-dibromoethane which is added in petrol to remove lead
b) To prepare organic derivatives like methyl bromide, ethyl bromide,
dibromochloropropane which are used as pesticides
c) KBr is used as sedative and in treating epilepsy
d) For unsaturation test in organic compounds as bromine water test
e) To prepare several bromine derivatives of organic compounds like bromoform,
ethylene bromide, methyl bromide etc
3. Uses of iodine
a) To prepare organic compounds like iodoform, methyl iodide, etc
b) AgI is used to prepare photographic film, seeding of clouds for artificial rain
c) As antiseptic (tincture of iodine)
Test for halogens
Test Chlorine Bromine Iodine
State Yellowish gas Pungent smelling Purple black solid at room
reddish brown liquid temperature and violet vapour
on heating
Action towards starch Turns starch iodide Turns starch iodide Turns moist starch iodide paper
iodide paper paper blue paper blue blue
Action to litmus Bleaches litmus
paper and indigo blue paper and indigo
solution
Action with sodium Oxidizes sodium Oxidizes sodium Colour of iodine is discharged
thiosulphate thiosulphate thiosulphate solution
solution
Hydrogen halides
Comparative study on preparation of halogen acids
1. By the reaction of conc. sulphuric acid and metal halide:
NaCl + H2SO4(conc.) NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl
NaBr + H3PO4 NaH2PO4 + HBr
NaI + H3PO4 NaH2PO4 + HI
2. Laboratory preparation of hydrogen bromide (HBr)
P4 + 6Br2 + 12H2O 4H3PO3 + 12HBr
Drying of HBr
-By passing HBr through anhydrous CaCl2 or
anhydrous P2O5
-CaO and Conc. H2SO4 cannot be used
3. Laboratory preparation of hydrogen iodine (HI)
P4 + 6I2 + 12H2O 4H3PO3 + 12HI
Drying of HI
-By passing HI through anhydrous CaCl2 or
anhydrous P2O5
-CaO and Conc. H2SO4 cannot be used
Physical properties of halogen acids
-Colourless gas with pungent odour and produce steamy fume in moist
air
-Boiling point in the order HCl < HBr < HI < HF
-Covalent gas molecules
-Turns moist blue litmus paper into red
Chemical properties of halogen acids
1. Acidic nature
-Aqueous solutions are called hydrohalic acids or halogen acids
HCl + H2O H3O+ + Cl-
-Strong acid
-Strength of halogen acid is in the order: HI > HBr > HCl > HF
➢ Reaction with base
HCl + NaOH NaCl + H2O
2HCl + Na2O 2NaCl + H2O
2HCl + Na2CO3 2NaCl + CO2 + H2O
➢ Reaction with metals
2HCl + 2Na 2NaCl + H2
2HCl + Zn ZnCl2 + H2
2HCl + Mg MgCl2 + H2
➢ Turns blue litmus to red, phenolphthalein from pink to colourless and methyl
orange from yellow to orange
2. Reducing nature
➢ Reducing power is in the order HI > HBr > HCl > HF
➢ HCl reduces MnO2, K2Cr2O7 and KMnO4
➢ MnO2 + 2HCl MnCl2 + H2O + O
2HCl + O Cl2 + H2O
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
➢ 2KMnO4 K2O + 2MnO + 5O
K2O + 2HCl 2KCl + H2O
MnO + 2HCl MnCl2 + H2O ] X 2
2HCl + O Cl2 + H2O ] X 5
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8 H2O
➢HBr and HI can reduce even conc. H2SO4 but HCl cannot
as it is weaker reducing agent
H2SO4 H2O + SO2 + [O]
2HBr + [O] H2O + Br2
2HBr + H2SO4 2H2O + SO2 + Br2
➢HI is more powerful reducing agent hence reduces copper
sulphate too
CuSO4 + 2HI CuI2 + H2SO4 ]X2
2CuI2 Cu2I2 + I2
2CuSO4 + 4HI Cu2I2 + I2 + H2SO4
Uses of hydrogen halides
➢HCl is used for pickling metals during galvanization
➢Also used to prepare metal chlorides, to prepare aqua regia
and as laboratory reagent
➢HBr is used to prepare AgBr which is used in photography
➢Also used for bromination of organic compounds
