Halogens: ( Greek words Halo = sea salt and Genes = producer)

 Halogens are the elements of group VIIA or 17 of modern periodic table. It includes the
elements like F(9), Cl (17), Br (35), I (53), and At(85).
 They are P-block elements and hence are placed at the right of the periodic tablejust before
the noble gas gases.
 Among them Fluorine is the representative element of this group.
 The general electronic configuration into their valance shell is ns2np5. As they have short of
one electron to complete their octet they are highly reactive in nature.
 Chlorine gas (bertholite) is a toxic gas bromine is liquid iodine exist as solid at room
temperature but Astatine is radioactive.
General characteristics of halogens:
1. Electronic configurationThe general electronic configuration into their valance shell is
ns2np5. As they have short of one electron to complete their octet they are highly reactive
in nature.
2.Oxidation state: Due to having 7 electrons into their valence shell they have common
oxidation state -1. Flurine always exist in -1 oxdn state except in OF2 where it has +1 oxdn state.
However other halogens commonly show variable oxidation states.
Elements Oxidation
Fluorine -1
Chlorine -1. +1, +3, +4, +5, +6 +7
Bromine -1. +1, +3, +4, +5, +6
Iodine -1. +1, +3, +6 +7
3. Atomicity:
 All halogens exist as diatomic molecules. This is because of having short of one electron to
complete their octet. E.g. F2, Cl2 ,Br2, I2
4. Physical State :
 As mentioned above they exist as diatomic molecules and are held together by very week
Vander Waal’s forces. The strength of this Force increases with increasing size of atoms. So
F2 and Cl2 exist as gas at room temperature, Br2 is volatile liquid and I2 exist as volatile
solid.
5. Melting point and boiling point:
M.p and B.p. of halogens increases with increasing atomic size this is again because of
increasing magnitude of Vander Waal’s forces fro fluorine to iodine.
F2< Cl2 < Br2 < I2
Increasing order of M.P. and B.P.
6.Colour:
All the halogens are coloured F2(Pale yellow), Cl2(Greenish yellow), Br2(reddish brown) and
I2 (Purple black)
7. Atomic radii: Halogens have smallest atomic size in their respective periods. However
atomic size goes on increasing from Fluorine to Iodine.
8. Formation of Ionic compounds:
 Halogens have short of only one electron to complete their octet so they have strong
tendency to gain electron form electropositive elements resulting the formation of ionic
compounds. Like NaCl ,KCl , NaBr. KF , KI etc.
9. Ionization Energy:
 Halogens are the smallest elements in their respective groups so their ionization energy
highest in their respective group and go on decreasing from F to I.
10. Electron affinity:
 Halogens have short of only on electron to attain the configuration of inert gases so they
have strong desire to gain electron due to this they have very high value of electron affinity
which goes on decreasing down the group however the electron affinity of Cl is higher than
fluorine due to having extremely small size of fluorine. Cl > F > Br > I
11.Electronegativity:
 Due do small atomic size and high nuclear charge each halogen has highest
electronegativity in its period. Fluorine has highest value of electronegativity i.e 4. The
electronegativity goes on decreasing down the group due increasing atomic size.
F > Cl > Br > I
12.Non metallic character:
 Due to having high value of ionization energy and electronegativity they are non metallic in
nature however this character goes on decreasing down the group. So, F2 > Cl2 > Br2 > I2.
13. Oxidizing agent:
 As halogens have strong tendency to gain electron they are oxidizing agents. This property
goes on decreasing down the group. So, F2 > Cl2 > Br2 > I2.
Comparative study of preparation of halogens:
 In principle all halogens can be prepared by the oxidation of their corresponding halides
either electrolytically or chemically using oxidizing agents stronger than halogens.
2X- X2 + 2e- (where X =F, Cl, Br or I)
1. Preparation of halogens by electrolytic oxidation of respective halides:
 Fluorine is the strongest oxidizing agent and hence no other chemical oxidizing agents can
oxidize HF or KF or NaF into F2. Therefore , it can only be prepared by electrolytic method .
HF H + + F-
KF K+ + F -
2 H+ + 2e- H2 (g) (at cathode)
2F- 2F + 2e-
2F F2(g) (at anode)
 Even the electrolysis of HF or NaF could not be successfully used for the isolation of fluorine
because of the following.
i. F2 being highly reactive non metals reacts with all metals including Pt and glass. So
apparatus used for its preparation can’t be made from these materials.
ii. HF Is extremely volatile (B.P.= 19oC) fairly low temp . Should be maintained.
iii. Anhydrous HF can’t be use as it is a poor conductor.
iv. Aq.HF is good conductor but its electrolysis gives O2 and O3.
2H2O + F2 4HF + O2
3H2O + 3F2 6HF + O3
Similarly electrolysis of fused or aqueous NaCl gives Cl2.
NaCl(Fused) electrolysis 2Na + Cl2
NaCl(aq.) electrolysis 2NaOH + H2 +Cl2
2. By the chemical oxidation of halides. Fluorine can’t be prepared by the chemical oxidation
of fluoride because fluorine is the most powerful oxidizing agent. Cl2 , Br2 and I2 can be
prepared by the oxidation of respective halides with strong oxidizing agent like MnO2 ,KMnO4
and K2Cr2O7. MnO2 + 2HX MnX2 + H2O + [O]
2HX + [O] H2O + X2
MnO2 + 4HX MnX2 + 2H2O + X2 (Where, X = Cl ,Br, I)
Similarly, Chlorine can be prepared by the oxidation of HCl by K2Cr2O7 or KMnO4.
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 +7H2O +3 Cl2
2KMNO4 +16 HCl 2KCl +2MnCl2 +8H2O +5Cl2
Laboratory Method of preparation of Cl2,Br2 and I2:
Cl2 .Br2 and I2 can be prepared by a common general method of preparation. In this method
a mixture of metal halide ,conc,H2SO4 and MnO2 is heated while doing so hydrogen halide first
formed which on oxidation by [O] contributed by MnO2 liberate respective halogens.
Rxn: MX + H2SO4 MHSO4 + HX]x2 [where M = Metal like Na or K]
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HX + [O] H2O + X2
2MX + 3H2SO4 + MnO2 2MHSO4 + MnSO4 + 2H2O+ X2 (where X = Cl ,Br, I)
Lab preparation of Chlorine:
Principle : In the lab chlorine gas can be prepared by heating a mixture of NaCl and conc.
H2SO4 with MnO2. The HCl first formed oxidized by MnO2 liberating Cl2 gas.
NaCl + H2SO4 NaHSO4 + HCl]x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HCl + [O] H2O + Cl2
2NaCl + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + 2H2O+ Cl2
 Conc.H2SO4
• The apparatus used for the prn of Cl2 gas consist of
MnO2 + a R.B. flask fitted with a thistle funnel and a delivery
NaCl tube .A Mixture of NaCl and MnO2 is taken in to the
x flask and Conc H2SO4 is dropped through the thistle
funnel and the flask Is heated while heating the flask
rxn takes place giving Cl2 gas which passed through
the delivery tube and collect at the gas jar by the
upward displacement of air as shown in the figure.

 The Cl2 gas thus prepared can be purified first

passing through water which removes acids and
then into conc. H2SO4 to remove moisture i.e.
Vap of H2SO4 to make it dry.

Fig: Lab Prn of Chlorine

Lab preparation of Bromine:
Principle : In the lab chlorine gas can be prepared by heating a mixture of NaBr and conc. H2SO4 with MnO2.
The HBr first formed oxidized by MnO2 liberatingBr2 gas.
NaBr + H2SO4 NaHSO4 + HBr]x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HBr + [O] H2O + Br2
2NaBr + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + 2H2O+ Br2
 NaBr+ MnO2 +  The apparatus used for the lab prn of Br2 consist of a
Conc. H2SO4
glass retort which is connected with a receiver floated
Glass retort Liq.Br2
over water. A mix. of NaBr, MnO2 and Conc. H2SO4 is
taken into the retort and then heated ,where reaction
takes place giving vapour of Br2 which is then condensed
and liq. Br2 is collected at the receiver as shown in the
figure.

Lab preparation of Iodine:

Principle : In the lab chlorine gas can be prepared by heating a mixture of NaI and conc. H2SO4 with MnO2.
The HI first formed oxidized by MnO2 liberating I2 gas.
NaI + H2SO4 NaHSO4 + HI]x2
MnO2 + H2SO4 MnSO4 + H2O + [O]
2HI + [O] H2O + I2
2NaI + 3H2SO4 + MnO2 2NaHSO4 + MnSO4 + 2H2O+ I2
Chemical properties of Halogens:
Properties Chlorine Bromine Iodine
hµ
1. Action Cl2 + H2O 4HCl + O2 Similar No rxn
with
water
2. Action Cl2 + NaOH(Cold) NaCl + NaClO + H2O Similar I2 + NaOH NaI + HOI
with Cl2 + NaOH(Hot) NaCl + NaClO3 + H2O Similar Similar
alkali Cl2 + Ca(OH)2 (cold) CaCl2 + Ca(ClO)2 +H2O ‘’ ‘’
3. With Cl2 + Ca(OH)2 (hot) CaCl2 + Ca(ClO3)2 +H2O ‘’ ‘’
NH3 NH3 + Cl2 (insuff) N2 + NH4Cl NH3 + Br2 (insuff) N2 + NH4Br NH3 + I2 NI3.NH3 + NH4I
NH3 + Cl2 (excess) NCl3 + NH4Cl NH3 +Br2 (excess) NBr3.6NH3+NH4Br
4. Bleach Moist Cl2 has Strong bleaching action Mild bleaching agent No bleaching action
ing Cl2 +H2O 2HCl + [O]
action coloured Flower+[O] Colourless flower
5oxidizing Similar Similar
a)WithH2S Cl2 + H2S HCl + S Similar Similar
b) FeSO4 Cl2 +H2SO4 + FeSO4 Fe2(SO4)3 + HCl Similar Similar
c) SO2 Cl2 + SO2 + H2O H2SO4 + HCl Similar Similar
d)KNO2 Cl2 + KNO2 +H2O KNO3 + HCl Similar Similar
e)Na2S2O3 Cl2 + Na2S2O3+H2O Na2SO4 + HCl + S Similar Na2S2O3+ I2 Na2S4O6 +NaI
hµ
6.With SO2 Cl2 + SO2 SO2Cl2 (sulphuryal chloride) No rxn No rxn
& CO Cl2 + CO hµ COCl2 (phosgene )
Bleaching Action of Chlorine:
Bleaching is the process of conversion of vegetable colouring matter into colourles product.
Chlorine is a strong bleaching agent . Its bleaching action is due to oxidation reaction.
Bleaching action of chlorine due to oxidation.
 Moist chlorine acts as a bleaching agent . Its bleaching action is because in presence of
moisture it gives nascent oxygen which is utilized to oxidized the vegetable colouring
matter into colourless oxidized product.
Cl2 + H2O 2HCl + [O]
Vegetable closuring matter + [O] colourless oxidized product
 The colourless product thus obtained may not regain its original colour .So bleaching
action of chlorine is a permanent change.
 Chlorine being a strong bleaching agent used to bleach rigid article like wood. paper ,textile
etc.
 Uses of Halogens:
Chlorine
1. Used for sterilizing drinking
water.
2. Used for bleaching paper, pulp &
textile.
3. Used for the manufacture of
insecticides like DDT,BHC etc.
4. Used for the manufacture of vinyl
chloride which in turn is used for
the manufacture PVC .
5. Used for the manufacture of
poisonous gases like phosgene,
mustard gas,tear gas etc.
6. Used for the manufacture of
CCl4,Chloroform,bleaching
powder.
7. Used for the extraction of gold
and platinum.
8. Liquid chlorine is used as solvent
for rubber
Bromine
1.As germicide and disinfectant.
2.Used for the manufacture of dyes
and drugs and tear gas.
3. Metal bromides of Na, K, Ca and Sr
are used in medicine as nerve
sedatives.
4. Used to prepare AgBr which intern
use in photography i.e. for the
manufacture of photographic films
and papers.
5.Use for the manufacture
ethylenedibromide which is used in
petrol as antiknocking agent.
6. Used as oxidizing agent in
laboratories
7. used for the detection of double
or triple bonds in unsaturated
compounds.
Iodine
1.Is is as antiseptic under the name
tincture of iodine which is a mixture
if iodine and alcohol.
2.Used for the preparation of
iodoform which is an antiseptic and
iodex which is an analgesic and
antiseptic.
3.AgI is used in photography similar
to AgBr
4. It is used to control goitre mixing
it into water or table salt.
 Test for Cl2, Br2 and I2
Chlorine
1. Greenish yellow pungent gas
2. Turns starch iodide paper blue
3. Bleaches moist red flower
Bromine
1.Dark red pungent liquid
2.Turns starch iodide paper blue
3.Br2 water decolourize the blue litmus
Iodine
1.Dark violet slight pungent solid
2.Turns moist starch paper blue.
3.It dissolve in CHCl3 and CCl4 giving
violet colour solution.

Halogen Acids or hydrogen Halides [HCl, HBr, HI]:

Comparative study of the preparation of Halo acids:
1.By the direct combination of Hydrogen and Halogen:
a. H2 + Cl2 h µ 2HCl

b. H2 + Br2 HBr
C. H2 + I2 Δ Hot tube
HI (I2 is in vapour form)
2. From alkali metal halides:
a. NaCl + Conc.H2SO4 NaHSO4 + HCl (This is also used as lab preparation of HCl)
b. HBr and HI can’t be prepared similar
Δ to HCl it is because HBr and HI being stronger reducing agents react
immediately with conc. H2SO4 which is a strong oxidizing agent and get oxidized into Br2 and I2 respectively.
NaBr + H2 SO4 NaHSO4 + HBr]x2
H2SO4 H2O + SO2 + [O]
2HBr + [O] H2O + Br2
2NaBr + 2 H2SO4 2NaHSO4 + SO2 + 2H2O + Br2

NaI + H2 SO4 NaHSO4 + HI]x2

H2SO4 H2O + SO2 + [O]
2HI + [O] H2O + I2
2NaI + 2 H2SO4 2NaHSO4 + SO2 + 2H2O + I 2
 So HBr and HI can be prepared by heating alkali metal halides with H3PO4 but not Conc.
H2SO4.
Δ
NaBr + H3PO4 NaH2PO4 + HBr
NaI + H3PO4 Δ NaH2PO4 + HI
3.By the action of halogens with SO2 water.
X2 + SO2 +H2O H2SO4 + HX (where X = Cl, Br, I)
Laboratory method of preparation of HCl:
Principle : In the lab HCl gas can be prepared by heating NaCl with Conc. H2SO4.
NaCl + Conc. H2SO4 NaHSO4 + HCl
Drying : By passing over Conc.H2SO4
Laboratory method of preparation of HBr:
Principle : In the lab HBr gas can be prepared by the action of Br2 with moist red
phosphorus.
6Br2 + P4 4 PBr3
PBr3 + 3H2O H3PO3 +3HBr]x4
6Br2 + P4 + 12H2O 4H3PO3 + 12HBr
Drying : By passing over anhydrous CaCl2 or P2O5 but not conc.H2SO4 and CaO due to its
reaction with them ( HBr + H2SO4 H2O + SO2 + Br2) (CaO + HBr CaBr2 + H2O)
Laboratory method of preparation of HI:
Principle : In the lab HI gas can be prepared by the action of I2 with moist red phosphorus.
6I2 + P4 4 PI3
PI3 + 3H2O H3PO3 +3HI]x4
6I2 + P4 + 12H2O 4H3PO3 + 12HI
Drying : Same as in HBr
Properties HCl HBr HI

1.Acidic nature
a. Dry litmus No Change in the colour Similar Similar
b.Moist Litmus Blue litmus turns red Similar Similar
c. With Metals Zn + HCl ZnCl2 + H2 Similar Similar
d.With alkalis. NaOH + HCl NaCl + H2O Similar Similar
e. With NH3 NH3 + HCl NH4Cl (white fume) Similar NH3 + HI NH4I (dense white)
2.Reducing Reducing strength increases from HCl
strength to HI (HCl Mild HI Strong)
a.MnO2 MnO2 + HCl MnCl2 + H2O + Cl2 Similar Similar
b. PbO2 PbO2 + HCl PbCl2 + H2O + Cl2 Similar Similar
c.KMnO4 KMnO4 + HCl KCl+MnCl2+H2O+ Cl2 Similar ‘’
d.K2Cr2O7 K2Cr2O7+HCl KCl + CrCl3+H2O +Cl2 Similar ‘’
e. Conc H2SO4 No rxn HBr + H2SO4 H2O + SO2 + Br2 HI + H2SO4 H2o + So2 + I2
f. Conc H2SO4 + MnO2+ H2SO4 + HCl MnSO4 + H2O Similar but more vigorously Similar(More readily than HBr)
MnO2 Cl2 hµ Similar but more vigorously
g. Photo Oxdn Not oxidized HBr + O2 H2O + Br2 Similar
h.With CusO4 No rxn No rxn HI+CuSO4 Cu2I2 +I2 +H2SO4
Test For Halogen acids.
Test
1. Silver Nitrate Test:
About 2ml of original
solution of acid is taken in
a test tube few drops of
conc HNO3 is dropped ,boil
and cool. Few drops of
AgNO3 solution is added.
2. Chlorine Water Test:
About 1ml of aqueous
solution of acid is taken
with CCl4 and little
chlorine water.
H Cl-
White ppt.of AgCl is
obtained which readily
dissolved into NH4OH and
white ppt easily reappeared
with the addition of dil.
HNO3
Cl-+AgNO3 AgCl + NO3-
AgCl+NH4OH Ag(NH3)2Cl
Ag(NH3)2Cl +HNO3
AgCl + NH4NO3
No Change in the colour of
solution
HBr-
Pale yellow ppt.of AgBr is
obtained which is sparingly
soluble in NH4OH and ppt
easily reappeared with the
addition of dil. HNO3.
Br-+AgNO3 AgBr + NO3-
AgBr+NH4OH Ag(NH3)2Br
Ag(NH3)2Br +HNO3
AgBr + NH4NO3
Lower layer of CCl4 becomes
brown
Cl2 +HBr HCl + Br2
CCl4 + Br2 Absorb Brown
HI-
Yellow ppt of AgI
obtained which is
insoluble in NH4OH.
I-+AgNO3 AgI + NO3-
AgI+NH4OH No Rxn
Lower layer of CCl4
becomes violet
Cl2 +HI HCl + I2
CCl4 + I2 absorb violet
Uses Of HCl ,HBr and HI
HCl HBr
1.As important lab reagent 1. As a lab reagent.
2. For the preparation of 2. As a reducing agent
aquaregoia 3. As medicine as a sleeping
3. Used in medicine with HNo3 dose.
4.For the manufacture of 4. As brominating agent
chlorides and Cl2 gas. 5. In the preparation of
5.Used in textile tanning and bromides.
dyeing industries.
HI
1. Preparation of iodides and
Iodine.
2. As a reducing agent.
3. Iodides are used in
medicine ,photography
and lab.