OXYGEN FA MILY

1. OXYGEN (O 2 )

Preparation

(a) From oxides

(i) By thermal decomposition of the oxides

3MnO 2  Mn3O4 + O2

3Pb 3O 4  6PbO + O2

2BaO 2  2BaO + O 2
450 º C
2HgO   2Hg + O2
350 ºC
2Ag 2 O   4Ag + O2
(ii) By the action of water on sodium peroxide (Oxone)
2Na2O2 + 2H2O  4NaOH + O2
(iii) By the action of conc. H2SO4 on MnO2

2MnO2 + 2H2SO4  2MnSO4 + 2H2O + O2

(b) From salts
(i) Alkali metal nitrates on heating give out oxygen
2NaNO3  2NaNO 2 + O 2
2KNO3  2KNO2 + O2
(ii) KClO3, K2Cr2O7 and KMnO4 decompose at high temperatures evolving oxygen.
400 º C
2KClO3   2KCl + 3O2
400 º C
4K2Cr2O7   4K2CrO4 + 2Cr2O3 + 3O 2
250 º C
2KMnO4   K2MnO4 + MnO2 + O2
(iii) By heating KMnO4 or K2Cr2O7 with concentrated H2SO4.
4KMnO4 + 6H2SO4  2K2SO 4 + 4MnSO4 + 6H2O + 5O2
2K2Cr2O7 + 8H2SO4  2K2SO4 + 2Cr2(SO4)3 + 8H2O + 3O2
(iv) By adding H2O2 to acidified KMnO4 solution.
2KMnO4 + 3H2SO 4 + 5H2O2  K2SO4 + 2MnSO4 + 8H2O + 5O2
(c) Laboratory method
In laboratory, oxygen is prepared by heating of a mixture of potassium chlorate and manganese dioxide
in 4 :1 ratio. (MnO2 used as a catalyst)
MnO 2
2KClO 3 

 2KCl  3O 2

Potassiumchlorate

(d) Electrolysis of water : Electrolysis of either acidified water using platinum electrodes or alkaline water
using nickel electrodes is made in an electrolytic cell for obtaining oxygen and hydrogen.



H 2 SO 4   2
 2H  SO 4
1
At cathode : 2H+ + 2e  H2 At anode : 2OH–  H2O + O + 2e
2 2
 Properties
It is non inflammable but a supporter of combustion.
Some typical reactions of dioxygen –

H2O(g)

2. OZONE (O 3 )

Preparation

(a) Unstable deep blue, diamagnetic gas, with fishy smell. Toxic enough (more toxic than KCN). It's intense
blue colour is due to the absorption of red light.

(b) Ozonised oxygen is separated by passing into spiral tube cooled by liquid air. Ozone condense at –
112.4ºC. [B.P. of O2 – 183ºC ; B.P. of liquid air is – 190ºC]

2F2 + 2H2O 4HF + O2

F2 + 3H2O 6HF + O3

Properties

(a) Oxidising property

It is one of best oxidising agent, in acid solution, its standard, reduction potential value is 2.07V.

O3 + 2H+ + 2e  O2 + H2O Eº = + 2.07 V

(i) Metal Sulphides to Sulphates.

MS + 4O3  MSO4 + 4O2 [M = Pb, Cu, Zn, Cd]

(ii) 2HX + O3 X2 + H2O + O2 [X= Cl, Br, I]

(iii) NaNO2 + O 3  NaNO3 + O 2

Na2SO3 + O3  Na2SO4 + O2

Na3AsO3 + O3  Na3AsO4 + O2

(iv) S + H2O + 3O3  H2SO4 + 3O2

2P + 3H2O + 5O3  2H3PO4 + 5O2

2As + 3H2O + 5O3  2H3AsO4 + 5O2

(v) Moist I2  HIO3 + 5O2

I2 + 5O3 + H2O  2HIO3 + 5O2

Dry I2  I4O9 (yellow)

2I2 + 9O3   I4O9 + 9O2

(vi) 2K2MnO4 + O3 + H2O  2KMnO4 + 2KOH +O2

2K4 [Fe(CN)6] + O3 + H2O  2K3 [Fe(CN)6] + 2KOH + O2

2FeSO4 + O3 + H2SO4  Fe2 (SO4)3 + O2 + H2O

(vii) 2KI (acidified) + O3 + 2HCl  I2 + 2KCI + H2O + O2

2KI(neutral)  O 3  2HCl  I2  2KOH  O 2 

 
KI  KOI  O estimated by this reaction.
KI  KOI  2HCl  2KCl  I2  H 2 O  3

I 2  2S 2 O 23   S 4 O 26   2I 

KI  3O 3  KIO 3  3O 2

alkaline 
KI  4O 3  KIO 4  4O 2

(viii) Hg loses its fluidity (tailing of Hg)

2Hg + O3  Hg2O + O2 Similarly

2Ag + O3  Ag 2 O + O2
Brown

(ix) BaO2 + O3  BaO + 2O2

H2O2 + O3  H2O + 2O2

Na2O2 + O3 + H2O  2NaOH + 2O2

(x) 2KOH + 5O3  2KO3 + 5O2 + H2O

Note: In all above reaction O3 gives up O2 but some reactions are there which consumes all O-atom.

 3SO2 + O3  3SO3

 3SnCl2 + 6HCl + O3  3SnCl4 + 3H2O

Absorbent

(a) Turpentine oil

(b) Oil of cinnamon

Uses

(a) Sterilizing water

(b) Detection of position of the double bond in the unsaturated compound.

3. HYDROGEN PEROXIDE (H 2 O 2 )

Preparation

ice cold water

(a) Na2O2 + H2O  2NaOH + H2O2

(b) BaO2 + H2SO4  BaSO4 + H2O2

Instead of H 2SO 4 , H 3PO 4 is added now-a-days because H 2SO 4 catalyses the decomposition of H 2O 2
whereas H3PO4 favours to restore it.

3BaO2 + 2H3PO4  Ba3(PO4)2 + 3H2O2

Ba3(PO4)2 + 3H2SO 4  3BaSO4 + 2H3PO4 (reused again)

(c) Electrolysis of 50% H2SO4 using high current density.

–
2H 2SO 4  +
 2H + 2HSO 4


–
At anode; 2HSO 4  H2S2O8 + 2e At cathode; 2H+ + 2e H2

H2S2O8 + 2H2O  2H 2SO 4 +H2O 2

O OH O
C2H5 Et Et
H 2 / Pd O2
(d)     + H2O2

O OH O
Properties

(a) Colourless, odourless liquid (B.P.152ºC)

(b) Acidic nature

H2O2 + 2NaOH  Na2O2 + H2O

H2O2 + Ba(OH)2  BaO2 + 2H2O

H2O2 + Na2CO3  Na2O2 + H2O + CO2

(c) Oxidising and reducing nature

H2O2 + 2H+ + 2e  2H2O [acidic medium]

H2O2 + 2e  2OH– [alkali medium]

Oxidising nature

PbS + 4H2O2  PbSO4 + 4H2O (Used in washing of oil painting)

NaNO2 + H2O2  NaNO3 + H2O

Na2SO3 + H2O2  Na2SO4 + H2O

Na3AsO3 + H2O2  Na3AsO4 + H2O

2KI + H2O2  2KOH + I2  X 2  H 2 O 2  2HX  O 2 X  Cl, Br. 

 
H2S + H2O2  S + 2H2O  Standered Reduction Poten tial order of Cl 2  Br2  H 2 O 2  I 2 
 H2SO4 + 2FeSO4 + H2O2  Fe2(SO4)3 + 2H2O

2K4 [Fe(CN)6] + H2O2 + H2SO4  2K3[Fe(CN)6] + K2SO4 + 2H2O

2[Cr(OH)4]– + 3H2O2 + 2OH–  2CrO 24  + 8 H2O

CrO 24  + 2H+ + 2H2O2   CrO5 (Blue) + 3H2O

4CrO5 + 12H+  4Cr+3 + 7O2 + 6H2O

Mn+2 + OH – + H 2O 2  MnO 2 + 2H 2O (This reaction can be utilised to detect NH 3)

Reducing nature

Ag2O + H2O2  2Ag + H2O +O2

O3 + H2O2  H2O + 2O2

MnO2 + H2O2 + H2SO4  MnSO4 + 2H2O + O2

PbO2 +H2O2  PbO+ H2O + O2

Pb3O4 + 4HNO3  2Pb(NO3) 2+PbO 2 + 2H2O

PbO2 + H2O2  PbO + H2O + O2

PbO + 2HNO3  Pb(NO3)2 + H2O

Pb3O4 + H2O2 + 6HNO3  3Pb(NO3)2 + 4H2O + O2

X2 + H2O2    2HX + O2 [X = Cl, Br]

2KMnO4 + 3H2O2   2KOH + 2MnO2 + 2H2O + 3O2

– –
2MnO 4 + 2OH   2MnO 24 – + H2O + O
–
2MnO 24 – + 2H2O   2MnO2 + 4OH + 2O
– –
2MnO 4 + H2O   2MnO2 + 2OH + 3O

2KMnO4 + 5H2O2 + 3H2SO4  2MnSO4 + K2SO4 + 5O2 + 8H2O

2[Fe(CN)6]3– + 2OH– + H2O2   2[Fe(CN)6]4– + 2H2O + O2

NaOCl + H2O2   NaCl + H2O + O2

NaIO4 + H2O2   NaIO3 + H2O + O2

Uses

(a) As a rocket propellant

NH2 . NH2 + 2H2O2    N2 + 4H2O [highly exothermic and large increase in volume]

(b) In detection of Cr+3, Ti+4 etc.

Ti(SO4)2 + H2O2 + 2H2O   H2TiO4 + 2H2SO4
Pertitanic acid
Yellow or orange
4. HYDROGEN SULPHIDE (H 2 S) SULPHUR ATED H YDROGEN
Preparation
By the action of dil. HCl or H2 SO 4on iron pyrites.
FeS + H2 SO4  FeSO4 +H2S 
Note : The gas is then dried over fused CaCl2 or P2O5. Conc. H2SO4 cannot be used for drying purpose
because H2S oxidize to sulphur.
Properties
It is a colourless gas having an offensive smell of rotten eggs.
(a) It burn in air with blue flame
2H2S + O2   2H2O + S
If the air supply is in excess
2H2S + 3O2   2H2O + 2SO3
(b) It is a mild acid.
H2S  H+ + SH–
SH–  H+ + S–2
(c) It act as a reducing agent. It reduces halogen into corresponding hydroacid.
H2S + X2  2HX + S
Te st s of H 2 S
(a) Unpleasant odour resembling that of rotten eggs.
(b) It turns lead acetate into paper black
(CH3 COO)2 Pb + H2 S   PbS + 2 CH3 COOH
Black
(c) It gives a violet colouration with a solution of sodium nitroprusside.
Structure of H 2 S
(a) Similar to structure of water molecule i.e. V– shaped structure with bond length (H–S) 1.35A° and
bond angle (H–S–H) is 92.5° ..
S
..
°

1.
A

35
35
1.

92.5°
A°

H H

Uses
(a) It is mainly employed in salt analysis for the detection of cation.
(b) Reducing agent for H 2SO 4, KMnO 4, K 2Cr 2O7, O3, H 2O 2, FeCl 3

5. SULPHUR DIOXIDE (SO 2 )

P re p a r a t i o n

Prepared by any of the following methods.

, conc.
(a) Cu + 2H 2 SO 4  CuSO 4 + SO 2+ 2H 2 O
(b) C + 2H 2SO 4   CO 2 + 2SO 2 +2H 2 O
(c) 4Fe S2 + 11O2  2Fe2 O3 + 8SO2
 Properties

(a) It has a pungent and suffocating odour.

(b) It acts as lewis base due to presence of a lone pair of electrons.

(c) Acidic nature

It dissolves in H2 O to give sulphurous acid, hence known as sulphurous anhydride.

SO2 + H2 O  H2SO3

Due to acidic nature, it can react with bases to give salts.

2NaOH + SO2   Na2 SO3 + H2 O

(d) Reducing nature

In the presence of moisture it can liberate nascent hydrogen or in presence of an oxidising agent it can
easily take an oxygen atom.
HNO3
H2SO4 + NO2

FeCl3 + H2O
H2SO4 + HCl + FeCl2
SO2
KMnO4 + H2SO4
K2SO4 + MnSO4 + HSO
2 4

K2Cr2O7 + H2SO4
K2SO4 + Cr2(SO4)3 + H2O

(e) Oxidising nature

SO 2 +2H 2 S  2H2 O+ 3S 

SO 2+2CO  2CO 2 +S 

(f) Bleaching nature

(i) Sulphur dioxide acts as bleaching agent in the presence of water, it is oxidised with the liberation of
nascent hydrogen which reduces the colouring matter to colourless.

SO 2+2H 2O  H 2SO 4+2 [H]

Colouring matter + 2[H]  Colourless compound.

(ii) Since the colourless (reduced) compound is reoxidised by air to coloured compound, bleaching by SO2
is temporary.

Note : Chlorine has permanent bleaching action, so reaction is not reversible.

6. SULPHURIC ACID H 2 SO 4 (OIL OF VITRIOL)

King of chemical (due to very great commericial importance)

Preparation

H2 SO4 is prepared by two methods

(a) Lead chamber process

The mixture containing SO2 , air & nitric oxide when treated with steam, sulphuric acid is formed.
 Stage I : 2NO(Catalyst) + O2  2NO2

Stage II : 2SO 2 + 2NO 2  2SO 3 +2NO

Stage III : SO3 + H2 O  H2 SO4

(b) Contact process

In this process SO2 is oxidised by air in the presence of catalyst (platinised asbestos).

Stage I : 
S + O2   SO2

Stage II : 2SO2 + O2 v 2o5

  2SO3
Stage III : SO3 + H2 SO4   H2 S2 O7 (oleum)

Stage IV : Sulphuric acid of any desired concentration can be obtained from oleum by
dilution with water

H2 S2 O7 + H2 O  2H2 SO4

Chemical properties

(a) As an oxidising agent

(i) H2SO4 gives oxygen on strong heating, hot conc.H2SO4 acts as an oxidising agent.

H2SO4  H2O + SO2 + [O]

(ii) Non metals oxidised to their oxides.

C + 2H2 SO4  CO2 + 2SO2 + 2H2 O

(iii) Dilute acid releases hydrogen with all metals except mercury, copper and noble metals.

H2SO4 + Zn  ZnSO4 + H2 

Hot conc. H2SO4 releases SO2 on reaction with metals.

Zn + 2H2SO4  ZnSO4 + 2H2O + SO2

(iv) Oxidation of compounds


2HX + H2 SO4  X2 + SO2 + 2H2O ( where X = Br or I)

(b) As a dehydrating agent

(i) Conc. H2 SO4 is a powerful dehydrating agent. Its corrosive action on skin is due to dehydration of skin
which then burns and produces itching sensation.

(ii) It's dehydrating property is due to strong affinity for water.

H SO
C12 H22 O11  
2

4
 12C + 11H2O
This is called as charring of sugar.
conc.H2SO 4
CH3 CH2 OH    CH2 = CH2 +H2 O
160 C

H 2 SO 4
HCOOH    CO + H2O
 COOH
Conc.H 2 SO 4
    CO + CO2 + H2O
COOH
Conc.H 2 SO 4
Chloro benzene + Chloral    D. D. T..
H O2

2 : 1

Uses

(a) In the manufacture of fertilisers like ammonium sulphate, calcium superphosphate etc.

(b) As a drying agent.

7. SODIUM THIOSULPHATE (Na 2 S 2 O 3 · 5H 2 O)

Preparation

boiling evaporation
(a) Na2SO 3 + S (powder)  Na2S 2O3  Na2S2O3.5H2O, monoclinic crystal

Na2CO3 + 2SO2 + H2O 2NaHSO3 + CO2

2NaHSO3 + Na2CO3 2Na2SO3 + H2O + CO2
Excess

roasting 2 SO
(b) Na2SO4 + 4C 4CO + Na2S  Na2S2O3 + S
Salt cake Coke

(c) 2Na2S + Na2CO 3 + 4SO2   3Na2S 2O3 + CO2

(d) 6NaOH + 4S  Na2S2O3 + 2Na2S + 3H2O

3Ca(OH)2 + 12 S  CaS2O3 + 2CaS5 + 3H2O

(e) Na2SO3 + Na2S + I2  Na2S2O3 + 2NaI

(f) 2Na2S + 2O2 + H2O  Na2S2O3 + 2NaOH

Properties


Na2S5 + 3Na2SO4
+
2H  H O + SO + S (White turbidity)
H2S2O3  2 2

I2 2–
S4O6 + 2I–
Cl2 + water 2–
Na2S2O3 SO4 + S + 2HCl
Br2 + water 2–
SO4 + S + 2HBr
– –
4Ol + 5OH –
2SO42–+ 4I + H2O
4Cl2 + 5H2O
Na2SO4 + 8HCl + H2SO4
Action of AgNO 3 : A white precipitate of silver thiosulphate is obtained by the action of AgNO3 which
changes to yellow, brown and finally black due to the formation of silver sulphide.

2AgNO 3 + Na2S 2O 3  Ag 2S 2O 3 + 2NONO 3

Ag2S2O 3 + H2O  Ag2S + H2SO 4

 Action of silver halides : Halides form complexes with sodium thiosulphate. Silver bromide forms
argento thiosulphate complex.

AgBr + 2Na2S2O3  Na3 [Ag(S2O3)2] + NaBr

Sodium argento thiosulphate
(Colourless)
This property is used in photography for fixing.
Action on copper sulphate : Cuprous thiosulphate is formed which dissolves in excess of sodium
thiosulphate to form a complex.

CuSO4 + Na2S2O3    CuS2O3 + Na2SO4

Cupric thiosulphate

2CuS2O3 + Na2S2O3    Cu2S2O3 + Na2S4O6

Cuprous thiosulphate

3Cu 2S 2O 3 + 2Na 2 S 2O 3  Na 4[Cu 6(S 2O 3) 5 ]

Sodium cupro thiosulphate
Uses
(a) As an antichlor to remove excess of chlorine from bleached fabrics.
(b) In photography as a fixing agent in the name of hypo.
(c) In the extraction of silver and gold.
(d) As a reagent in iodometric and iodometric titrations for the estimation of iodine CusO4, K2Cr2O7, KMnO4,
Na 3AsO 3 etc.
(e) Sodium hyposulphite (Na2S2O4) is used for reducing indigo or other vat dyes.
 HALOGEN FA MILY
1. FLUORINE (F 2 )

Preparation

Moissan's method
Electrolyte is a [KHF2 (1 part) and anhydrous H2F2 (5 parts)]. 1 : 5 mixture of KHF2 and anhydrous H2F2. The
reaction taking place in this method are :
2KHF2  2KF + H2F2
–
H2F2 2H+ + 2F
–
at anode ; 2F  F2 + 2e– at cathode ; 2H+ + 2e–  H2
2NaF + H2F2  2NaHF2
Physical properties
(a) Fluorine is a pale yellow gas which condenses to a clear yellow liquid having a density of 1.108 and B.P
is –187.7ºC. At – 223ºC it freezes to a pale yellow solid and at –252ºC the solid becomes colourless.
(b) It is a pungent smelling and poisonous gas but less poisonous than HF gas.
(c) It attacks organic matter and hence should be handled carefully.
Chemical Proper t ie s
(a) Reaction with water : Reaction is vigorous even in the dark giving O2 and O3
2F2 + 2H2O  4HF + O2
3F2 + 3H2O  6HF + O3
(b) Reaction with hydrogen : F2 combines with H2 explosively even in the dark, forming HF.
F2 + H2 2HF
(c) Action on alkalies : Unlike Cl2, Br2 and I2, F2 reacts with dil. alkalies (2% solution) and forms NaF and
OF2 (not NaFO). With conc. alkalies F2 gives NaF and O2 (not NaFO3).
2F2 + 2NaOH (2% solution)  2NaF + OF2 + H2O
2F2 + 4NaOH (conc. solution)  4NaF + O2 + 2H2O
(d) Oxidising property : Since F 2 has the largest positive value of standard reduction electrode potential
for the reduction reaction.
–
F2(g) + aq + e–  2F
F2 is the strongest oxidising agent among all the halogens. Maximum oxidising power of F2 is confirmed
by the following reactions –
(i) Action of F 2 on halides : F 2 can liberate halogen from the aqueous solution of all the three halides
(generally sodium or potassium halides) while other halogens connot do so.
F2 + 2KX  2KF + X2 (X = Cl, Br, I)
–
In the above reaction X is oxidised to X2.
(ii) Action of F2 on H2O : F2 oxidises (decomposes) H2O to O2 and O3
2H2O (l) + 2F2(g)  4HF(aq) + O2(g)
3H2O (l) + 3F2(g)  6HF(aq) + O3(g)
 (e) Action on NH3 : F2 reacts with NH3 to give N2 and some NF3

3F2 + 2NH3  N2 + 6HF

3F2 + NH3  NF3 + 3HF

(f) Action on H2 S: H2S burns in an atmosphere of F2, forming SF6 and HF

H2S + 4F2  SF6 + 2HF

Uses : F2 is used as an insecticide.

2. CHLORINE (Cl 2 )

Preparation

(a) From HCl : HCl is most important chemical to prepare chlorine and HCl reacts with a number of
oxidising agents to liberate Cl2.

2HCl + [O]  Cl2 + H2O

MnO2 + 4HCl  MnCl2 + 2H2O + Cl2 

Pb3O4 + 8HCl   3PbCl2 + 4H2O + Cl2 

2KMnO4 + 16HCl   2KCl + 2MnCl2 + 8H2O + 5Cl2 

K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2 

NaOCl + 2HCl  NaCl + H2O + Cl2 

O3 + 2HCl  O2 + H2O + Cl2 

(b) From bleaching powder : Bleaching powder liberates Cl2 when treated with mineral acid or CO2.

CaOCl2 + 2HCl  CaCl2 + H2O + Cl2

CaOCl2 + H2SO4  CaSO4 + H2O + Cl2

CaOCl2 + CO2  CaCO3 + Cl2

(c) From chlorides : Cl2 may also be obtained by decomposing metal chlorides by MnO2/H2SO 4

2NaCl + MnO2 + 3H2SO4  2NaHSO4 + MnSO4 + 2H2O + Cl2

(d) Laboratory method : In laboratory, Cl2 is prepared by action of HCl on MnO2 or KMnO4 or K2Cr2O7

(i) From MnO 2

MnO2 + 4HCl  MnCl2 + 2H2O + Cl2

(ii) From K 2 Cr 2 O 7 or KMnO 4

2KMnO4 + 16HCl  2KCl + 2MnCl2 + 8H2O + 5Cl2

K2Cr2O7 + 14 HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2

(iii) Preparation of pure Cl 2 : Cl2 of high purity may be obtained by decomposing platinic chloride (PtCl4)
or gold chloride (AuCl3)
580ºC
PtCl4   Pt + 2Cl2
300ºC
2AuCl 3   2Au + 3Cl 2
(iv) Manufacturing
Weldon's process : This method involves the heating of pyrolusite (a mineral of Mn, contain MnO2) with
conc. HCl.
MnO2 + 4HCl  2H2O + MnCl2 + Cl2
MnCl2 thus obtained is also used for production of Cl2 by following process.
MnCl2 + Ca(OH)2  Mn(OH)2 + CaCl2
2Mn(OH)2 + O2 (air)  2MnO2 + 2H2O
MnO2 + Ca(OH)2  CaMnO3  + H2O
Calcium mangnite
CaMnO3 + 6HCl  CaCl2 + MnCl2 + Cl2  + 3H2O
Deacon's process : In this method, HCl is oxidised by air in the presence of CuCl2 catalyst
CuCl2/450ºC
4HCl + O 2  2H 2O + 2Cl 2
The probable mechanism of the reaction is as
2CuCl2  Cl2 + 2CuCl
4CuCl + O2  2(CuO · CuCl2)
CuO · CuCl 2 + 2HCl  2CuCl2 + H 2O
Thus Cl2 is formed continuously by oxidation of HCl.
By electrolysis of brine : Concentrated aqueous solution of NaCl is known as brine and on electrolysis
of brine, Cl2 is liberated at anode.
NaCl Na+ + Cl– Ions present
H2O H+ + OH– in brine
at cathode 2H+ + 2e–  H2 ( D.P. H  < D.P.. N a  )
–
at anode 2Cl  Cl2 ( D.P. C l – < D.P.. O H –)
No te : For electrolysis Nelson Cell or Solvay –Kellner cell are used.
By electrolysis of molten NaCl : Electrolysis of molten NaCl gives Cl 2 at anode and Na metal at
cathode. This method of extraction of Na is known as Down's process. Down's cell is composed of:

 Anode : Steel rod

 Cathode : Graphite

 Electrolyte : Mixture of molten NaCl, and NaF

 Temperature : 600ºC

Following reactions take place in the cell

–
at cathode ; Na+ + e–  Na at anode ; 2Cl  Cl2 + 2e–
Nitrosyl chloride process : Common salt (NaCl) is treated with concentrated nitric acid, when a mixture
of chlorine and nitrosyl chloride is evolved.
3NaCl + 4HNO3  3NaNO3 + NOCl(g) + Cl2 + 2H2O
The gaseous mixture formed is also oxidised with oxygen.
2NOCl(g) + O2  2NO2 + Cl2
The gaseous mixture is liquefied which on distillation gives Cl2
Physical Properties
(a) It is yellow green, pungent smelling, toxic gas. It has toxic effect on lungs, throat and nose.
(b) It gives chlorine water when passed through water which is strong oxidation. If passed through ice cold
water, crystals of Cl2·8H 2O are obtained.
(c) On liquifaction it gives yellow liquid (B.P. – 34.6ºC). Its f.p. is –101.1ºC.
(d) It is heavier ( ~2.4 times) than air..
Chemical proper t ie s
hv
(a) Reaction with Hydrogen : H2 + Cl2  2HCl
It reacts with ammonia under two conditions.
(i) When ammonia in excess
8NH3 + 3Cl2  N2 + 6NH4Cl
(ii) When chlorine in excess
NH3 + 3Cl2  NCl3 + 3HCl
(b) Reaction with metals
2Na + Cl2  2NaCl
2Fe + 3Cl2  2FeCl3
2Al + 3Cl2  2AlCl3
Zn + Cl2  ZnCl2
Cu + Cl2  CuCl2
Mg + Cl2  MgCl2
(c) Reaction with non metals
2S + Cl2  S2Cl2
2P + 3Cl2  2PCl3
2B + 3Cl2  2BCl3
(d) Oxidising and bleaching nature
Cl2 + H2O  HCl + HClO
HClO HCl + O
___________________________________
Cl2 + H2O 2HCl + O
Coloured matter + (O)  Colourless matter
The bleaching action is permanent.
(i) Ferrous chloride or ferrous sulphate containing dilute H2SO4,is oxidised to ferric chloride or ferric sulphate
respectively.
2FeCl2 + Cl2  2FeCl3
2FeSO4 + H2SO 4 + Cl2  Fe 2(SO4) 3 + 2HCl
(ii) Sulphites are oxidised to sulphates.
Na2SO3 + H2O + Cl2  NaSO4 + 2HCl
 (iii) Moist sulphur dioxide is oxidised to H2SO4
SO2 + 2H2O + Cl2  H2SO4 + 2HCl
(iv) Sulphur is precipitated from sodium thiosulphate.
Na2S2O3 + H2O + Cl2  Na2SO4 + 2HCl + S
(v) Cl2 oxidises I2 to HIO3.
5Cl2 + I2 + 6H2O  10HCl + 2HIO3
(e) Action of alkalies : When passed into cold dilute solution of alkalies, it forms chloride and hypochlorites.
2 NaOH + Cl2  NaCl + NaClO + H2O
2Ca(OH)2 + 2Cl2  CaCl2 + Ca(ClO)2 + 2H2O
However with hot concentrated alkali solutions it forms chlorates.
6NaOH + 3Cl2  5NaCl + NaClO3 + 3H2O
6Ca(OH)2 + 6Cl2  5CaCl2 + Ca(ClO3)2 + 6H2O
(f) Addition reactions : Chlorine forms addition compounds with SO2, CO and unsaturated hydrocarbons.
SO2 + Cl2  SO2Cl2
Sulphuryl chloride

CO + Cl2 COCl2
Carbonyl chloride (phosgene)

C2H4 + Cl2 C2H4Cl2

Ethylene chloride

3. OXIDES OF CHLORINE

+1 +4 +6 +7
Cl2O ClO2 Cl2O6 Cl2O7
(Brownish yellow) (Pale yellow) (liq dark red Colourless solid
Solid yellow)

Dichloro oxide (Cl 2 O)

Preparation : Cl2 does not combine directly to produce its oxides but indirect method are there.
2Cl2 + 2HgO(s)   HgO.HgCl2 + Cl2O (Brownish yellow gas)
dry in cooled tube Basic Hg (II) chloride

Condensed to orange liquid

P rop e r t i e s
(a) It dissolves in water
Cl2O + H2O  2HClO
(b) Explodes violently with NH 3
3Cl2O + 10NH 3  2N 2 + 6NH 4Cl + 3H 2O
(c) It is oxidising agent
Cl2O + 2HCl  2Cl2 + H2O
(d) Structures. O S

Cl 110º Cl Cl 102º Cl

Chlorine dioxide (ClO 2 )

Preparation
(a) 3KClO3 + 3H2SO4 3KHSO4 + HClO4 + 2ClO2  + H2O
(powder) conc. pale yellow gas
60ºC
(b) 2HClO 3 + H 2C 2O4  2H 2O + 2ClO 2 + 2CO 2
90ºC
(c) 2AgClO3 + Cl2  2AgCl + 2ClO2 + O 2 [By this reaction pure ClO2 obtained]

P rop e r t i e s

(a) ClO2 dissolves in water producting dark green solution which decomposes in presence of light.
ClO2  ClO + O
2ClO + H2O  HCl + HClO3
(b) But in alkali gives a mixture of chlorite and chlorate. It is a powerful oxidising and bleaching agent.
2ClO2 + 2NaOH  NaClO2 + NaClO3 + H2O
2ClO 2 + 2NaOH + H 2 O 2  2NaClO 2 + O 2 + 2H 2 O
(c) ClO2 does not dimerise because odd electron undergoes delocalisation (in its own vaccant 3d-orbital)
Cl2O4 (Cl.ClO4) is not the dimer of ClO2. Actually it is Cl-perchlorate.
CsClO4 + ClOSO 2F  Cs(SO 3)F + ClOClO 3

Dichlorine Hexoxide (Cl 2O 6 )

P re p a r a t i o n
0ºC
2ClO2 + 2O3  Cl2O6 + 2O2

Cl 2O 6 2ClO 3 (monomer is paramagnetic)

P rop e r t i e s
Cl2O6 + H 2O  HClO3 + HClO4
Cl 2O 6 + NaOH  NaClO 3 + NaClO 4 + H 2O
Cl2O6 + HF  ClO2F + HClO4
–
Cl2O 6 + NO2  ClO2 + [NO2]+ [ClO4]

Str ucture s
O O O O O
+ –
O Cl—Cl O Cl Cl ClO2 ClO4
O O O O O

liq  dark red

Solid  Yellow
 Clorine Heptoxide (Cl 2 O 7 )
It is the anhydride of HClO4 and perpared from it by the reaction of P2O5
Preparation
2HClO4 + P2O5   2HPO3 + Cl2O7
Properties : It is colourless liquid which is explosive in nature.
Cl2O7 + H2O  2HClO4 (perchloric acid)
Structure

O O

O 3 C l– O– C lO 3 Cl 119ºC Cl
O O
O
O O
4. BROMINE (Br 2 )

(a) From Brine water : Contains 65 ppm of Br –

–
Cl2 + 2Br–  2Cl + Br2 (Br2 is volatile in nature)
Hence it is collected by
(i) Removal of Br2 vapour by steam of air.
(ii) Absorbing it into Na 2CO 3 Solution
– –
Br2 + 6OH  Br– + BrO 3 +3H2O
Then acidified to get pure Br2
–
5Br– + BrO 3 + 6H+  3Br2 + 3H2O

5. IODINE (I 2 )
– –
Chille salt petre contains traces of NaIO3 which is reduced to I by NaHSO3, then oxidation of I– to I2 by IO3 .
– –
2IO3 + 6 HSO 3  2I– + 6SO 24 – + 6H+
+
– 6H
5I– + IO3  3I2 + 3H2O

6. HALOGEN ACIDS

Preparation
All the halogens combine directly with hydrogen to form halogen acids but their reactivity decreases progressively
from fluorine to iodine.

H2 + X2    2HX (X=F, Cl,Br or I)

Pt / asbestos
H2 (g) + Br2 (g)    2 HBr
A mixture of calcium fluoride (fluorite of fluorospar) and sodium chloride with concentrated sulphuric acid.

CaF2 (s) + H2 SO4 (aq)   CaSO4 (s) + 2HF (g)

2NaCl(s) + H2 SO4 (aq)  Na2 SO4 (s) + 2HCl (g)

H2 SO 4 is not satisfactory for the preparation of HBr and HI because the HBr or HI formed are oxidised by
H2SO4 and the product is contaminated with the respective halogen. This difficulty can be overcome by using
a non-oxidizing acid such as H3 PO4 .
 2NaI + H2 SO4   Na2 SO4 + 2HI

2HI + H2 SO4  2H2 O + SO2 + I2

Physical properties

(a) Except HF (due to presence of H-bond) all hydrogen halides are gases

(b) These can be liquified.

(c) Covalent character : The bonds between H & X have some degree of polarity in the following order.

HF > HCl > HBr > HI

(d) Thermal stability : Thermal stability of the hydrides decreases from HF to Hl i.e. HF >HCl >HBr > Hl.
This is due to the reason that as the size of the halogen increases from F to l the bond dissociation energy
decreases.

(e) Boiling point or volatility

(i) Because of high electronegativity, H–F forms strong H–bonds.

(ii) As a result, it exists as an associated molecule,(HF)n and hence is a liquid at room temperature while all
other halogen acids are gases.

(iii) However, after a sudden drop in boiling point from HF to HCl, the boiling points of other hydrides
gradually increases from HCl to Hl because of increase in size of the halogen from Cl to l.

(iv) In other words volatility decreases in the order. HCl >HBr>Hl>HF.

Chemical proper t ie s

(a) Acidic Strengt h

(i) In gaseous state these are covalent but in aqueous solutions they ionise and act as acids.

(ii) The relative strength increases from HF to Hl according to their dissociation constant Ka.

(iii) The acidic strength of halogen decreases from Hl > HBr > HCl > HF.

(iv) This is due to the reason that as the size of halogen increases, H–X bond becomes weaker and hence
breaks easily to split off a proton.

(b) Reducing property

(i) The reducing nature increases from HF to Hl as the stability decreases from HF to Hl.

(ii) HF does not show reducing nature. It can not be oxidised even by strong oxidizing agents.

(c) Action of ammonia

NH 3 + HX  NH4 X (Where X = Cl,Br,l)

White fumes

(d) Action of halogens

Chlorine is liberated from HCl only by fluorine Br2 is liberated from HBr by Cl2 and F2 only (not by l2).

2HCl + F2  HF+Cl2

2Hl + Br2  2HBr + l2

 Abnormal Properties of HF

(a) Liquid at room temperature due to H bonding.

(b) Most thermal stable then other halogen hydrides.
(c) It is weak acid but is extremely stable. It is not oxidised by strong oxidising agents. On the other hand all
other halogen acid is oxidised.
(d) HF form two type of salt (NaHF2 , Na2F2 )
(e) This acid attacks on silica of glass & formation of following compounds.

SiO2 + 2H2F2  SiF4 + 2H2O

Na2 SiO3 + 6HF   Na2SiF6 +3H2O

CaSiO3 +6HF   CaSiF6 + 3H2 O

SiO2 + 4HF  SiF4 + 2H2 O

SiF4 + 2HF  H2 SiF6

7. OXY ACID OF HALOGEN FA MILY

Name of the Oxidation state Oxoacids Structure Stability Acidic

acids and of the halogen strength
their salts in the acid Cl Br I

Hypohalous
Hypohalite +1 HClO HBrO HlO H–O–X Decreases Increases

Halous,
+3 HClO2 H–O–XO Decreases Increases
Halites
Halic, O
Halates +5 HClO3 HBrO3 HlO3  Decreases Increases
H–O–XO
Perhalic, O
Perhalates 
+7 HClO4 HBrO4 HlO4 HO–XO Decreases Increases

O

Acidity order : HOX < HXO2 < HXO3 < HXO4

Oxidising power : HOX > HXO2 > HXO3 > HXO4
Thermal stability : HOX < HXO2 < HXO3 < HXO4
(a) Fluoric (I) acid (HOF) : it is obtained when F2 is passed over ice at 273 K.

273 K
F2 + H 2 O HOF + HF
It is colourless unstable gas which decomposes to HF and O2. It is strong oxidising agent and oxidises
H2 O to H 2O 2 .
(b) Hypochlorous acid or chloric (I) acid (HOCl) : It can be prepared by following reactions.
2HgO + 2Cl2 + H2O  Hg 2OCl2 + 2HOCl
2CaOCl2 + H2O + CO2  CaCl2 + CaCO3 + 2HOCl
 It is stable only in solution whose dilute solution is colourless while concentrated solution is yellow. It
decomposes as
2HOCl  2HCl + O2
weak acid and with Mg it evolves H2
Mg + 2HClO  Mg(ClO)2 + H2
It is powerful bleaching and oxidising agent due to evolution of nascent oxygen.
HOCl HCl + [O]
(c) Chlorous acid or chloric (III) acid (HClO 2) : It is also known in aqueous solution and can be prepared
by following reactions.
Ba(OH)2 + H2O2 + 2ClO2  Ba(ClO2)2 + 2H2O + O2
Ba(ClO2)2 + H2SO4   BaSO4 + 2HClO2
It fresh solution is colourless but soon it turns yellow due to formation of ClO2
5HClO2  4ClO2 + HCl + 2H2O
It shows disproportionation reaction as
2HClO2  HClO + HClO3
It liberates I2 from KI.
4KI + HClO2 + 2H2O  4KOH + HCl + 2I2
Its shape is angular with sp3 hybridised Cl-atom.
Cl
110º
O O—

(d) Chloric acid (HClO 3 ) : It is stable in aquous solution only. It is prepared by action of conc. H2SO4 on
barium chlorate.
6Ba(OH)2 + 6Cl2  Ba(ClO3)2 + 5BaCl2 + 6H2O
Ba(ClO3)2 + H2SO4  BaSO4 + 2HClO3
It is colourless pungent smelling liquid. It is stable in dark but decomposes in light. It acts as both oxidising
and bleaching agent. Chlorate ion is pyramidal in geometry and central Cl-atom is sp3 hybridised.

Cl
–
O O
O
(e) Perchloric acid (HClO4) : It most stable among oxoacids of chlorine. It is prepared by following reaction.
Ba(ClO4)2 + H2SO4  2 HClO4 + BaSO4
In anhydrous form, it can be prepared by distillation of mixture of KClO4 and 96-97% of H2SO4.

90-160ºC
KClO4 + H2SO4 Low
 
pressure  HClO4 + KHSO4

Anhydrous HClO4 is colourless oily liquid which turns dark on standing. If fumes is moist air.
It is amongst strongest protonic acids known.

HClO4 H+ + ClO4
 It is strong oxidising agent and explodes when comes in contact of organic matter. It dissolves most of the
metals.
Zn + 2HClO4  Zn(ClO4)2 + H2

In ClO 4 , central Cl-atom is sp3 hybridised and so its structure is tetrahedral.
–
O

Cl
O O
O

8. INTER HALOGEN

Types AX AX3 AX5 AX7

ClF ClF 3 ClF 5 IF 7
BrF BrF 3 BrF 5
BrCl (ICl 3 ) 2 IF 5
ICI IF 3 (unstable)
IBr
IF (unstable)

P rop e r t i e s

(i) BrF5 + 3H2O HBrO3 + 5HF

(ii) IF5 + 3H2O HIO3 + 5HF
(iii) IF7 + H2O IOF5 + 2HF less

4H2O HIO4 + 7HF Parallel reaction

(iv) CIF is highly reactive and as a fluorinating agent.
6CIF + 2Al  2AlF3 + 3Cl2
6CIF + U  UF6 + 3Cl2
6CIF + S  SF6 + 3Cl2
CIF + SF4  SF5 Cl
One pecularity with ICl

Cl CO2H
ICl vap.
CO2H is chlorination (I)
OH
OH ICl in I CO2H
Nitrobenzene is Iodination (II)
OH
In IIndcase, the attacking species is I+ which has been supported by the formation of I+ in fused state as follows:
3ICl  [I2Cl]+ + [ICl2]–
ICl3 does not exist but its dimer exist.
2ICl3 I2Cl6
 Structure :
Cl Cl Cl
I I (Bright yellow solid)
Cl Cl Cl

(v) I2Cl6 : liquid has appreciable electrical conductivity like other interhalogens.
+ –
I2Cl6 [ICl2] + [ICl4]
+ –
BrF3 [BrF2] + [BrF4]
+ –
IF5 [IF4] + [IF6]
+ –
3ICl [I2Cl] + [ICl2]

Characteristics

 5lF  lF5 + 2I2 [The overall system gains B.E. by 250 kJ/mol]
 There are never more than two halogens in a molecule.
 Bonds are essentially covalent and B.P. increases as the E.N. difference increases.
 AX5 & AX7 type formed by large atoms like Br & I to accommodate more atoms around it.
 The interhalogens are generally more reactive than the halogens (except F2) due to weaker A–X
bonds compared to X–X bonds.
ICl + H2O  HCl + HOI

9. P O LY H A L I D E S
Preparat ion a nd proper t ie s

(a) KI + I2  KI3

+ –
(b) ICl + KCl  K [ICl2]
+ –
(c) ICl3 + KCl  K [ICl4]
+ –
(d) IF5 + CsF  Cs [IF6]
+ –
(e) ICl + KBr  K [BrICl]


(f) Rb[ICl2]  RbCl + ICl [not RbI + Cl 2 ]
No te : Here the products on heating depends on the lattice energy of the product halide. The lattice energy of
alkali halide with smaller halogen is highest since the interatomic distance is least.

Str uc tu re
–
I5 – –
I7 – –
I8 –2
I
I –I ----I I –I -----I
I –I I
–

I I I I –I I
I
–

I I
–

Ex. [N(CH 3 ) 4 ] + I7 , Cs 2 I 8

 Only F3 not known [due to absence of d-orbital] [i.e. Cs2 I3 – I2 – I3]

 I 3 , Br3 , Cl 3 are known Cl 3 compounds are very less.

–
 Stability order : I 3  Br3  Cl 3 : depends upon the donating ability of X .
10. PSEUDO HALOGEN

There are univalent ion consisting of two or more atoms of which at least one is N, that have properties similar
to those of the halide ions. Ex.
(a) Na-salts are soluble in water but Ag-salts are insolubler in water.
(b) H-compounds are acids like HX.
(c) Some anions can be oxidised to give molecules X2.
Anions Acids Dimer
CN – HCN (CN) 2
SCN – HSCN (thiocyanic acid) (SCN) 2
SeCN – (SeCN) 2
OCN – HOCN (cyanic acid)
NCN 2– (Bivalent) H 2NCN (cyanamide)
ONC – HONC (Fulminic acid)
N 3 HN3 (Hydrazoic acid)
CN shows maximum similarites with Cl–, Br–, I–
(d) forms HCN
(e) forms (CN)2
(f) AgCN, Pb(CN)2, are insoluble
(g) Interpseudo halogen compounds ClCN, BrCN, ICN can be formed.
(h) AgCN is insoluble in H2O but soluble in NH3
(i) forms large number of complex Ex. [Cu(CN)4]3– & [CuCl4]–3
[Co(CN)6]–3 & [CoCl6]–3
 NOBEL GASES
1. INTRODUCTION
(a) The relative abundance in dry air by volume (ppm) of different noble gases is :
He Ne Ar Kr Xe Rn
5.24 18.18 93.40 1.14 0.09 traces
(b) The melting points (K) for different noble gases are given as under :
He Ne Ar Kr Xe Rn
– 24.6 83.3 115.9 161.3 202.0
(c) The boling point (K) for different noble gases are given as under :
He Ne Ar Kr Xe Rn
4.2 27.1 87.3 119.7 165.0 211

(d) The atomic radii (pm) for different noble gases are :

He Ne Ar Kr Xe Rn
93 112 154 167 190 –

(e) The vander wall's radii (pm) of differnet noble gases are given below :

He Ne Ar Kr Xe Rn
120 160 191 200 220 –

(f) The ionization energy values (kJ mol–1) for different noble gases are given below :

He Ne Ar Kr Xe Rn
2372 2080 1520 1351 1170 1037

(g) The enthalpies of vaporization, H vapoure (kJ mol–1) for noble gases are given below :

He Ne Ar Kr Xe Rn
0.08 1.74 6.52 9.05 12.65 8.1
Cp
(h) for noble gases is 1.67.
Cv

(i) The refractive index, dielectric constant and other physical properties of noble gases correspond to their
monoatomic nature.

(j) The most important source of noble gases is atmosphere in which they are present in following proportions
by volume and mass:
Element Percentage by volume Percentage by mass
He 0.0006 0.000037
Ne 0.0015 0.001
Ar 0.932 1.285
Kr 0.0001 0.00028
Xe 0.00001 0.00004
(k) Helium is present to the extent of 2% in natural gas found in the united states and Canada.

(l) Helium is also present in the minerals of radioactive elements uranium and thorium Ex. clevite, uranite,
thorianite, monazite, pichblende etc.

(m) The sixth member of the zero group was discovered in 1900 by Dorn as one of the disintegration
products of radium and was named radon or nitron.

(n) In Dewar's method, the separation of noble gases are summerized below :

Mixtue of noble gases (He, Ne, Ar, Kr, Xe)

in contact with coconut charcoal at 173 K

Unadsorbed adsorbed
(He, Ne) (Ar, Kr, Xe)
in contact with charcoal at 93 K in contact with another charcoal at
liquid air temperature.

Adsorbed Unadsorbed In the first charcoal Second charcoal

Ne He Kr, Xe. Temp. raised Ar
to 183 K

Evolved Kr Remained adsorbed Xe

1
(o) The viscosity of He is extermely low, about th of hydrogen gas.
100

(p) The thermal conductivity of He is very high about 800 times that of copper at room temperature

(q) The lifting power of He is 92% that of hydrogen.

(r) Helium is used for filing airships and balloons for meteorological abservations.

(s) Mixture of He with O2 under pressure is supplied to sea divers for respiration.

(t) Helium is used to provide inert atmosphere in the welding of metals or alloys that are easily oxidized.

(u) Helium (density 2) is lighter than that of air (density 14.4) and is used for inflating the tyres of big
aeroplanes.

(v) Neon is used to produce glow sign boards.

(w) Argon mixed with 26% N2 is used in gas filled electric lamps and in radio valves and tubes.

(x) Krypton and xenon have not been prepared in large quantities and have not been employed for a useful
purpose.

(y) Radon is used in radioactive research and in radiotherapy for the treatment of cancer.
2. Xe-COMPOUNDS

Xenon fluorides

400ºC, 1 atom
2 : 1 XeF2
600ºC, 7 atom
(a) Xe + F2 1 : 5 XeF4
300ºC, 60-70 atom
1 : 20 XeF6
(b) H2 reduces Xe-fluorides to Xe
XeF2 + H2  Xe + 2HF
– –
(c) Xe-fluorides oxidise Cl to Cl2 and I to I2
XeF2 + 2HCl  2HF + Xe + Cl2
XeF4 + 4Kl  4KF + Xe + 2I2
(d) Hydrolysis
XeF2 reacts slowly with water
XeF2 + 2H2O  2Xe + 4HF + O2
XeF4 and XeF6 react violently with water giving XeO3
3
3XeF4 + 6H2O  2Xe + XeO3 +12HF + O
2 2
XeF6 + 3H2O  XeO3 + 6HF

(explosive, white hygroscopic solid)
(e) SiO2 also converts XeF6 into XeOF4
2XeF6 + SiO2  SiF4 + 2XeOF4 Similarly
violet
XeO3 + XeOF4  2XeO2F2
XeO3 + 2XeF6  3XeOF4
(f) Xe-fluorides are also hydrolysed in alkaline medium
–
2XeF2 + 4OH–  2Xe + 4F + 2H2O + O2
–
XeF6 + 7OH–  HXeO 4 + 3H2O + 6F–
Xenate ion
– 4–
2HXeO 4 + 2OH–  XeO 6  + Xe + 2H2O + O2
(g) They are used as fluorinating agent
2SF4 + XeF4  2SF6 + Xe
Pt + XeF4  PtF4 + Xe
(h) Act as a fluoride donor
XeF2 + MF5  [XeF]+ [MF6]– (M = As, Sb, P)
–
XeF6 + BF3  [XeF5]+ [BF 4 ]
XeF6 + HF  [XeF5]+ [HF2]–
(i) Act as Fluoride aceptor also
XeF6 + RbF/CsF  Rb+/Cs+ [XeF7]–

2Cs+ [XeF7]–  XeF6 + Cs2[XeF8]
50°C
–
XeF4 + MF  M+ + XeF 5
(alkali metals fluoride)