CHALCOGENS

Oxygen
Preparation: Oxygen can be obtained in the laboratory by following methods:

(i) From Oxides: (a) By thermal decomposition of the oxides of metals which are in lower part of
electrochemical series.
2HgO 450
0
C
 2Hg + O2; 2AgO2 350

0
C
 4Ag + O2
(b) By the thermal decomposition of higher oxides.
3MnO2 Heat
 Mn3O4 + O2; 2Pb3O4 Heat
  6PbO + O2
2BaO2 Heat
 2BaO + O2

(c) By action of conc. H2SO4 on MnO2
2MnO2 + 2H2SO4  2MnSO4 + 2H2O + O2
(d) By action of water on sodium peroxide (oxone),
2Na2O2 + 2H2O  4NaOH + O2

(ii) From salts: (a) Alkali nitrates on heating evolve oxygen.

2NaNO3  2NaNO2 + O2 ; 2KNO3  2KNO2 + O2

(b) K2Cr2O7, KMnO4 and KClO3 decompose at high temperatures evolving oxygen.
4K2Cr2O7 400

0
C
 4K2CrO4 + 2Cr2O3 + 3O2
2KMnO4 250

0
C
 K2MnO4 + MnO2 + O2
2KClO3 400
0
C
 2KCl + 3O2
(c) By heating KMnO4 or K2Cr2O7 with concentrated H2SO4.
4KMnO4 + 6H2SO4  2K2SO4 + 4MnSO4 + 6H2O + 5O2
2K2Cr2O7 + 8H2S4  2K2SO4 + 2Cr2(SO4)3 + 8H2O + 3O2

(d) By adding H2O2 to acidified KMnO4 solution.

2KMnO4 + 3H2SO4(dil.)  K2SO4 + 4MnSO4 + 3H2O + 5[O]
[H2O2 + O  H2O + O2] x 5
––––––––––––––––––––––––––––––––––––––––––––––––––––––––
2KMnO4 + 3H2SO4 + 5H2O2  K2SO4 + 2MnSO4 + 8H2O + 5O2

4KClO3  3KClO4 + KCl

Potassium Potassium
chlorate perchlorate

KClO4 650
 C
 KCl + 2O2
0

Manufacture: Oxygen is obtained on commercial scale by following methods:

(a) By Brin’s process
(b) By electrolysis of water

Properties : Oxygen is a colourless, odourless and tasteless gas. It is little heavier than air and is slightly
soluble in water. this small amount of dissolved oxygen in water supports the respiration of fish and other
aquatic animals. It is soluble in alkaline pyrogallol. It exhibits allotropy. Its allotropic madofications is ozone
(O3). There are three isotopes of oxygen with mass numbers 16, 17 and 18 (O16, O17 and O18). O16 is the
main one with an abundance of nearly 99.8%.

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

Oxygen is not a combustible gas, but it is a strong supporter of combustion. It is very active element.
Structure: According to the M.O.T. structure of O2 molecule is as follows:
KK(2s)2*(2s)2(2px)2(2py)2(2pz)2*(2py)1*(2pz)1
Bond order in this case is ½(8 – 4) = 2

Properties:
Oxygen combines nearly with all other elements excepts inert gases, noble metals and halogens. The
binary compounds of oxygen with other elements are called oxides. However, the compounds of
oxygen and fluorine (OF2, O2F2) are not called as oxides but oxygen fluorides as fluorine is more
electronegative than oxygen.

Oxides may be prepared by burning of elements such as C, P, S, Na, K, Mg, etc. in air or oxygen
atmosphere.
C + O2  CO2 (Carbon burns with flush light)
S + O2  SO2 (Sulphur burns with blue light)
4Na + O2  2Na2O (Sodium burns with yellow light)
4K + O2  2K2O (Potassium burns with violet light)
2Mg + O2  2MgO (Magnesium burns with white light)
Peroxide: The oxides when treated with dilute acids form hydrogen peroxide. These oxides are considered
as derivatives of H2O2 and contain peroxo linkage in their molecule.
Examples: NaO2, K2O2, BaO2 etc.
Na2O2 + H2SO4 (dil.)  Na2SO4 + H2O2
BaO2 + H2SO4 (dil.)  BaSO4 + H2O2
Na2O2 can be written as Na–O–O–Na. The linkage –O–O– is called peroxo linkage.
Super oxides contain O2– ion. The superoxides known are KO2, RbO2 and CsO2. These react with water
to give hydrogen peroxide and oxygen.
2KO2 + 2H2O  2KOH + H2O2 + O2
OZONE
Laboratory preparation: Ozone is obtained by passing silent electric discharge through dry oxygen. It is
believed that some of the oxygen molecules dissociate and then atomic oxygen combines with oxygen
molecules to form ozone.
O2 Energy
 O + O
O2 + O  O3
3O2 2O3 – energy

The mixture obtained consists of 5–10% ozone by volume and the mixture is called ozonised oxygen. The
apparatus used for this purpose is known as ozoniser. The commnoly used ozonisers are:
(i) Siemen’s ozoniser; and (ii) Brodie’s ozoniser

Manufacture: For the manufacture of ozonised air Seimen and Halske’s ozoniser is employed.

Recovery of Pure Ozone from Ozonised Oxygen

The ozonised oxygen is passed through a spiral cooled by liquid air. Ozone condenses as its condensation
temperature is –112.40 C. The liquid ozone thus obtained may contain some dissolved oxygen. This liquid
is fractionally distilled to get pure ozone.

Some Reactions Forming Ozone

(i) Fluorine reacts with water at a very low temperature when mixture of ozonised oxygen is formed.
2 F2  2 H 2 O  4 HF  O 2 U
Vozonised oxygen
3F2  3H 2 O  6HF  O 3 W
0XYGEN FAMILY & NOBLE GAS [by AA SIR]
(ii) By action of ultraviolet rays, oxygen can be converted into ozone.
O2  UV
 O+O
O2 + O  O3
(iii) The electrolysis of acidified water with high current density and platinum anode yields ozone on the
anode. Nascent oxygen discharged at anode combines with molecular oxygen to form ozone.

Physical properties: (a) It is a pale blue gas with a charactersticstrong smell.

(b) It is slightly soluble in water but more soluble in turpentine oil, glacial acetic acid, or carbon tetrachloride.

Chemical properties:
(a) Decomposition: It is unstable and decomposes completely into oxygen at 3000C.
2O3 Heat  3O2 + 68kcal

MnO2, platinum black, silver, lead dioxide etc., decompose ozone at ordinary temperature, i.e., they catalyse
its decomposition.
(b) Oxidising nature: Due to the ease with which it can liberate nascent oxygen, it acts as a powerful
oxidising agent. The potential equation is:
O3  O2 + O
The oxidation potential in acid medium is +2.07 V.
O3 + 2H+ + 2e–  O2 + H2O E 0 = +2.07 V
2HCl + O3  H2O + Cl2 + O2
(ii) Acidified ferrous sulphate into ferric sulphate.
2FeSO4 + H2SO4 + O3  Fe2(SO4)3 + H2O + O2
(iii) It liberates iodine from neutral KI solution.
2KI + H2O + O3  2KOH + I2 + O2
(iv) Lead sulphide (black) is oxidised to lead sulphate (colourless).
PbS + 4O3  PbSO4 + 4O2
Similarly, CuS, ZnS and CdS are oxidised to CuSO4, ZnSO4 and CdSO4, respectively.
(v) It oxidises nitrites into nitrates, sulphites into sulphates, arsenites to arsenates, manganate to permanganate
and ferroxyanide to ferricyanide.
NaNO2 + O3  NaNO3 + O2
Na2SO3 + O3  Na2SO4 + O2
Na3AsO3 + O3  Na3AsO4 + O2
sodium arsenite sodium arsenate
2K2MnO4 + H2O + O3  2K3Fe(CN)6 + 2KOH + O2
Potassium Potassium
manganate permanganate
2K4Fe(CN)6 + H2O + O3  2K3Fe(CN)6 + 2KOH + O2
Potassium Potassium
ferrocyanide ferricyanide
(vi) Moist iodine is oxidised to iodic acid.
I2 + H2O + 5O3  2HIO3 + 5O2
Iodic acid
Similarly moist sulphur, phosphorus and arsenic are oxidised to their corresponding oxyacids.
S + H2O + 3O3  H2SO4 + 3O2
2P + 3H2O + 5O3  2H3PO4 + 5O2
2As + 3H2O + 5O3  2H3AsO4 + 5O2
(vii) H2S is oxidised to sulphur
H2S + O3  H2O + S + O2
(viii) Alkaline KI is oxidised to potassium iodate and periodate.
KI + 3O3  KIO3 + 3O2

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

 Potassium iodate
KI + 4O3  KIO4 + 4O2
Pot. periodate
(ix) Dry iodine is oxidised to yellow powder, I4O9
[O3  O2 + O] x 9
2I2 + 9O  I4O9 .
–––––––––––––––––––––––
2I2 + 9O3  I4O9 + 9O2
(x) Silver metal is blackened due to alternate oxidation of the metal and reduction of oxide.
2Ag + O3  Ag2O + O2
Ag2O + O3  2Ag + 2O2
(xi) Mercury in presence of ozone is oxidised to suboxide which dissolves in mercury. It starts sticking to
glass and loses mobility. Hence, mercury loses its meniscus in contact with ozone. This is termed as the
tailing of mercury.
2Hg + O3  Hg2O + O2

(xii) Ozone reacts with KOH and forms potassium ozonide, KO3, which is an orange coloured solid and
contains paramagnetic O3– ion.
2KOH + 5O3  3KO3 + 5O2 + H2O
In all above reactions, oxygen is evolved.
There are few reactions in which whole of the oxygen is used up in the process of oxidation.
1. Oxidises SO2 to SO3
3SO2 + O3  3SO3
2. Acidified stannous chloride is oxidised to stannic chloride.
3SnCl2 + 6HCl + O3  3SnCl4 + 4H2O

(c) Bleaching property: It is a good bleaching agent. The bleaching action is due to its oxidising action
on the organic matter.
coloured substance + O  Colourless
It bleaches oil, ivory, flour, starch, waxes, wood pulp, etc.

(d) Formation of ozonides: Ozone reacts with unstaurated organic compounds containing double bonds.
The products formed are known as ozonides. The ozonides break up when treated with water to form
carbonyl compounds. The process is called ozonolysis. H2O2 is evolved in most of the cases.

(e) Reaction withe peroxide: Reaction of ozone with peroxide results in their mutual reduction with the
liberation of oxygen.
BaO2 + O3  BaO + 2O2
H2O2 + O3  H2O + 2O2

Uses: (i) As a germicide and disinfectant for sterilizing water and improving the atmosphere of crowded
places like tube railways mines and cinema halls.
(ii) As a bleaching agent for oils, flour, ivory, wax and delicate fabrics.

Structure of Ozone:

The bond length is intermediate between that for a single bond (1.48Å as in H2O2) and for a double bond
(1.21Å as in O2). Ozone is, therefore, considered to be a resonance hybrid of the following two forms.

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

 Distinction between Ozone and Hydrogen Peroxide
Ozone Hydrogen peroxide
1. Pale blue gas with a strong rotten smell. Colourless and odourless syrupy liquid.
2. It does not decolourise acidified potassium It decolourises acidified potassium permanganate.
permanganate.
3. Mercury loses its meniseus in contact with No action on mercury.
ozone. It starts sticking to glass.
4. It turns an alcoholic solution of benzidine No action.
brown.
5. It turns an alcoholic solutionof tetramethyl No action.
base violet.
6. It turns starch-iodide paper blue in presence of ferous
It does not turn starch-iodide paper blue in
presnece of ferrous sulphate. sulphate.
7. Orange colour with titanium sulphate solution is
No action with titanium sulphate solution.
developed.
8. No action with acidified potassium Blue colour in ether layer when H2O2 is added to
dichromate in presence of ether. mixture containing potassium dichromate and
concentrated H2SO4 in presence of ether.

SULPHUR
Occurrence: It occurs in abundance in the combined state as:

(i) Sulphide ores, e.g., Zine blende (ZnS), galena (PbS), cinnabar (HgS), copper pyrites (CuFeS2) and
iron pyrites (FeS2).

(ii) Sulphate ores, e.g., Gypsum (CaSO4.2H2O), barytes (BaSO4), Epsom salt (MgSO47H2O) and celesite
(SrSO4).

(iii) H2S and SO2 in volcanic gases. H2S in spring waters, coal gas, sewage gas, etc.

(iv) Organic compounds of plant and animal origin, e.g., onion, garlic, mustard, eggs, proteins, hair, wool,
etc. contain organic sulphur compounds.

Extraction: (i) To extract underground sulphur, Frasch process is used. Three concentric pipes are sunk
deep into the ground. Super heated water at 170oC is forced down the outer pipe into sulphur which is
melted. Compressed air blown through inner pipe forces the sulphur as a liquid to the surface where it is
allowed to solidify. 99.5% pure sulphur is obtained by this process.

(ii) Sulphur as a byproduct:(a) From alkali waste of Leblanc’s process: The alkali waste (mainly
CaS) is suspended in water and carbon dioxide is circulated. Hydrogen sulphide is liberated which is burnt
in an insufficient supply of air.
CaS + H2O + CO2  CaCO3 + H2S
2H2S + O2  2H2O + 2S
(Air)

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

(b) From the spent oxides of the gas works: It contains ferric sulphide (Fe2S3). It is exposed to air for
a few days when sulphur is deposited.
2Fe2S3 + 3O2  2Fe2O3 + 6S

(c) From iron pyrites: Iron pyrites is a good source of sulphur. It is recovered when pyrite is distilled.
3FeS3 Distillation
 Fe3S4 + 2S
Pure sulphur is obtained by boiling impure sulphur at 444oC. The vapours of sulphur evolved are condensed
on the cold walls as a light yellow powder.

Allotropic forms: Sulphur exists in several allotropic forms, the important ones are described below:

1. Rhombic or octahedral or  sulphur: This is the common form of sulphur. It is pale yellow in colour..
It melts at 114.5oC. Its specific gravity is 2.06. It is insoluble in water but readily soluble in carbon disulphide.
It is a crystalline variety and consists of S8 structural units packed together into octahedral shape. This is
the stable variety at orginary temperature and all other forms gradually change into this form.

2. Monoclinic or prismatic or  sulphur: This form is formed by melting sulphur in a dish and cooling
till crust is formed. Two holes are made in the crust and liquid is poured out. On removing the crust, needle
shaped crystals of monoclinic sulphur are obtained.
This form of sulphur is stable above 95.6oC. The crystals are amber yellow in colour and have specific
gravity of 1.96. Crystals melt at 119oC. It is also soluble in carbon disulphide. Below 95.6oC, it changes
into rhombic form. Thus, 95.6oC is the transition temperature.

Rhombic Sulphur Monoclinic Sulphur

3. Plastic sulphur: This is obtained when boiling sulphur is poured into cold water. It is soft rubber like
mass which hardens on standing and gradually changes into rhombic sulphur. It is amberbrown in colour
and has specific gravity of 1.95. It is insoluble in CS2 and has no sharp melting point. It consists of a
completely random arrangement of chains of sulphur atoms.

Action of heat on sulphur: Orginary sulphur melts at 114oC to a pale yellow mobile liquid. On heating
further instead of becoming more mobile, it grows thicker. The colour changes to reddish brown and then
to almost black. At about 180OC. the viscosity increases so much that it cannot be poured out by inverting
the container. At about 200oC the viscosity begins to decrease and at its boiling point of 444oC, the liquid
is again mobile. No difinite explanation of these observations is known uptil now.

Uses: Sulphur is used:

(i) In the manufacture of SO2, H2SO4, CS2, matches, gun powder, fire works. etc.
(ii) for vulcanising rubber and in the manufacture of sulphur dyes.

COMPOUNDS OF SULPHUR
Hydrogen Sulphide or Sulphuretted Hydrogen (H2S)
Laboratory preparation: Hydrogen sulphide is obtained in the laboratory by the action of dilute sulphuric
acid on ferrous sulphide.
FeS + H2SO4  FeSO4 + H2S
As the gas is required intermittently in the laboratory, it is prepared in the well known Kipp’s apparatus.
The gas obtained is always impure as it is contaminated with hydrogen. Pure hydrogen sulphide can be
prepared by the action of pure HCl on antimony sulphide.
Sb2S3 + 6HCl  2SbCl3 + 3H2S

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

Physical properties: (a) It is a colourless gas with unpleasant odour of rotten eggs.
(b) It is slightly heavier than air and moderatory soluble in cold water. The solubility decreases in hot water.
(c) It is poisonous in nature. It produces headache when inhaled in small quantities but may cause death
when inhaled for a long time.
(d) It can be easily liquefied by pressure. The boiling point is about –60 0C. It freezes to a transparent solid
at –85.60C.

Chemical properties: (a) Combustibility: The gas burns with a blue flame in oxygen on air forming
sulphur dioxide and water.
2H2S + 3O2  2H2O + 2SO2
In restricted supply of oxygen, sulphur is formed due to incomplete combustion.
2H2S + O2  2H2O + 2S
(b) Thermal decomposition: The gas is not so stable as water. It decomposes on heating. The decomposition
starts at 3100C and completes at 17000C.
H2S  H2 + S
(c) Reducing nature: Hydrogen sulphide acts as a strong reducing agent as it decomposes evolving
hydrogen. The following are the important examples of its reducing action:
(i) It reduces halogens into corresponding hydracids.
H2S + X2  2HX + S (X2 = F2, Cl2, Br2 or I2)
(ii) It reduces ferric chloride to ferrous chloride.
2FeCl3 + H2S  2FeCl2 + 2HCl + S
(iii) Sulphur dioxide is reduced to sulphur in presence of moisture.
SO2 + 2H2S  3S + 2H2O
The occurrence of sulphur in volcanic regions is attributed due to the above reaction as both gases are
present in volcanic gases.
(iv) H2O2 is reduced to water.
H2O2 + H2S  2H2O + S
(v) O3 is reduced to O2.
H2S + O3  H2O + S + O2
(vi) HNO3 is reduced to NO2.
2HNO3 + H2S  2NO2 + S + 2H2O
(vii) H2SO4 is reduced into SO2
H2SO4 + H2S  2H2O + SO2 + S
(viii) Acidified KMnO4 is decolourised
2KMnO4 + 3H2SO4 + 5H2S  K2SO4 + 2MnSO4 + 8H2O + 5S
(ix) Acidified K2Cr2O7 is reduced forming green chromic sulphate.
K2Cr2O7 + 4H2SO4 + 3H2S  K2SO4 + Cr2(SO4)3 + 7H2O + 3S

(d) Acidic nature: The aqueous solution of H2S acts as a weak dibasic acid. It ionises as follows:
H 2S H+ + HS– 2H+ + S–

It forms two series of salts, hydrosulphides and sulphides.

NaOH + H2S  NaHS + H 2O
Sodium hydro
sulphide
2NaOH + H2S  Na2S + 2H2O
Sodium sulphide

(e) Reaction with metals and metal oxides: H2S reacts with metals and metal oxides to form
corresponding sulphides.
2Na + H2S  Na2S + H2

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

 Cu + H2S  CuS + H2
2Ag + H2S  Ag2S + H2
Pb + H2S  PbS + H2
CaO + H2S Heat
 CaS + H2O

ZnO + H2S Heat
 ZnS + H2O

(f) Action on salts: Hydrogen sulphides reacts with salts of various metals forming corresponding sulphides.
The metal sulphides can be divided into three groups.

1. Sulphides precipitated in acidic medium: These are sulphides of Hg, Ag, Pb, Cu, Bi, Cd, As, Sb and
Sn.
CuSO4 + H2S  CuS + H2SO4
Pb(CH3COO)2 + H2S  PbS + 2CH3COOH
CdSO4 + H2S  CdS + H2SO4

U
HgS, CuS, PbS  Black
| Inso lub le in yellow
Bi S  Brown V
Yellow |
2 3
ammonium sulphide
CdS  W
SnS , As S  Yellow U
Sb S
2 2 3

 Orange V
| So lub le in yellow
 Chocolate |
2 3
ammonium sulphide
SnS W
2. Sulphides precipitated in alkaline medium: These are the sulphides of Zn, Co, Ni, Mn and Fe.
MnCl2 + H2S  MnS + 2HCl
Ni(NO3)2 + H2S  NiS + 2HNO3
ZnSO4 + H2S  ZnS + H2SO4
CoS, NiS; Black, ZnS; White, MnS; Flesh coloured

3. Sulphides which are precipitated neither in acidic nor in alkaline medium: These are the sulphides
of Cr, Al, Mg, Ba, Sr, Ca, K and Na.
(g) Formation of polysulphides: Polysulphides of metals are obtained by passing H2S through their
hydroxides.
Ca(OH)2 + H2S  CaS + 2H2O
CaS + 4H2S  CaS3 + 4H2
On passing excess of H2S through ammonium sulphide, yellow ammonium sulphide is formed.
2NH4OH + H2S (NH4)2S + 2H2O
(NH4)2S + xH2S  (NH4)2Sx+1 + xH2
Ammonium
polysulphide

Structure of H2S: The shape of the H2S molecule is similar to that of the water molecule, i.e., Vshaped
structure with bond length (H–S) 1.35Å and bond angle (H–S–H) 92.50.

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

Oxides of Sulphur
Sulphur forms a number of oxides. These are:
(i) Sulphur suboxide, S2O (colourless gas)
(ii) Sulphur monoxide, SO (colourless gas)
(iii) Sulphur sesquioxide, S2O3 (green crystalline solid)
(iv) Sulphur dioxide, SO2 (colourless gas)
(v) Sulphur trioxide, SO3 (volatile liquid)
(vi) Sulphur heptoxide, S2O7 (liquid)
(vii) Sulphur tetroxide, SO4 (white solid)
Out of these, sulphur dioxide and sulphur trioxide are common and important and described here.

1. Sulphur dioxide, SO2

The following reactions can be used for the preparation of sulphur dioxide.
(a) By burning sulphur in air or oxygen.
S + O2  SO2
(b) By heating sulphur with concentrated sulphuric acid
S + 2H2SO4 Heat 2H2O + 3SO2
(c) By heating copper or silver with concentrated sulphuric acid.
Cu + 2H2SO4  CuSO4 + 2H2O + SO2
2Ag + 2H2SO4  Ag2SO4 + 2H2O + SO2
(d) By reacting sodium sulphite or sodium hydrosulphite with dil. HCl
Na2SO3 + 2HCl  2NaCl + H2O + SO2
NaHSO3 + HCl  NaCl + H2O + SO2
(e) By roasting of sulphides
2ZnS + 3O2  2ZnO + 2SO2
4FeS2 + HO2 2Fe2O3 + 8SO2
The reactions b, c and d can be used for the preparation of SO2 in the laboratory while the reactions (a)
and (e) are used in industry to obtain SO2.
In places where gypsum or anhydride are found in abundance, sulphur dioxide can be obtained on a large
scale by heating gypsum or anhydride with carbon at about 10000C.
2CaSO4 + C  2CaO + 2SO2 + CO2

Physical properties : (a) It is a colourless gas with a pungent, suffocating odour.

(b) It is highly soluble in water.

Chemical properties: (a) It neither burns nor it helps in burning. However, burning magnesium and potassium
continue to brun in its atmosphere.
3Mg + SO2  2MgO + MgS
4K + 3SO2  K2SO3 + K2S2O3
(b) Thermal decomposition: It decomposes at 12000C producing sulphur trioxide and sulphur.
3SO2  2SO3 + S
(c) Acidic nature: It is an acidic oxide. It dissolves in water forming sulphurous acid.
SO2 + H2O  H2SO3 (Sulphurous acid)
The gas is, therefore, known as sulphurous anhydride. It combines with basic oxides and forms sulphites.
BaO + SO2  BaSO3
(d) Addition reactions: (i) It combines directly with halogens to form sulphuryl halides.
SO2 + Cl2  SO2Cl2 (sulphuryl chloride)
(ii) It combines directly with oxygen in presence of a catalyst (platinised asbestos)
2SO2 + O2 2SO3

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

(iii) It directly combines with lead dioxide to form lead sulphate
PbO2 + SO2  PbSO4
(e) Reducing nature: The aqueous solution of SO2 acts as a reducing agent as sulphurous acid changes
into aulphuric acid giving nascent hydrogen.
H2O + SO2  H2SO3
H2SO3 + H2O  H2SO4 + 2H
Examples: (i) It reduces halogens to their respective hydracids.
SO2 + 2H2O + Cl2  H2SO4 + 2HCl
(ii) Acidified KMnO4 is reduced, i.e., it is decolourised
2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO4 + 2H2SO4
(iii) Acidified K2Cr2O7 is turned green due to formation of chromic sulphate
K2Cr2O7 + 3SO2 + 2H2SO4  K2SO4 + Cr2(SO4)3 + H2O
(green)
(iv) Ferric sulphate is reduced to ferrous sulphate
Fe2(SO4)3 + SO2 + 2H2O  2FeSO4 + 2H2SO4
(v) It reduces acidified iodates to iodine
2KIO3 + 5S2 + 4H2O  K2SO4 + 4H2SO4 + I2
(f) Oxidising nature: It also acts as an oxidising agent particularly when treated with stronger reducing
agents.
(i) It oxidises H2S into S
2H2S + SO2  2H2O + 3S
(ii) Metals are oxidised by SO2
3Mg + SO2  2MgO + MgS
4K + 3SO2  K2SO3 + K2S2O3
3Fe + SO2  2FeO + FeS
(iii) CO is oxidised to CO2 by SO2
2CO + SO2  2CO2 + S
(iv) At 10000C, it oxidises hydrogen into water.
SO2 + 2H2  2H2O + S
(v) Stannous and mercurous salts are oxidised in presence of excess of HCl.
2SnCl2 + SO2 + 4HCl  2SnCl4 + 2H2O + S
2Hg2Cl2 + SO2 + 4HCl  4HgCl2 + 2H2O + S
(g) Bleaching action: SO2 in presence of moisture acts as a bleaching agent. This is due tothe reducing
nature of SO2.
SO2 + 2H2O  H2SO4 + 2H
Coloured matter + H  Coloureless matter
The bleaching is temporary. The bleached matter when exposed to air regains its colour due to oxidation.

Uses: (i) As a refrigent in the form of liquid SO2.

(ii) It is used as an antichlor for removing chlorine from a fabric after bleaching.

2. Sulphur Trioxide, SO3

Preparation: Sulphur trioxide is obtained:
(i) by dehydrating sulphuric acid with excess of phosphorus pentoxide.
6H2SO4 + P4O10  4H3PO4 + 6SO3
(ii) by heating ferric sulphate strongly
Fe2(SO4)3  Fe2O3 + 3SO3
(iii) by oxidation of SO2 with oxygen in presence of a catalyst (commercial method)
2SO2 + O2 2SO3

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

Both SO2 and O2 should be completely dry. The mixture is passed over platinised asbestos at 400 0C, when
SO3 is formed.

Properties: (i) SO3 exists in three allotropic forms:

(a) SO3. It is chemically active form. It forms long transparent ice like crystals. The melting point of this
form is 170C.
(b) SO3. It is dimeric (S2O6). It forms needle like silky white crystals. t melts at 32.50C. Above 500C,
it changes to form.
(c) SO3. It is like –form and obtained by completely drying –SO3. It melts at 62.20C under 2
atmospheric pressure.
(ii) SO3 is an acidic oxide. It dissolves in water forming sulphuric acid with evolution of heat.
SO3 + H2O  H2SO4 + heat
It reacts with basic oxides forming sulphates
CaO + SO3  CaSO4
Na2O + SO3  Na2SO4
(iii) It dissolves in concentrated sulphuric acid forming oleum (fuming sulphuric acid)
H2SO4 + SO3  H2S2O7
(iv) It dissociates on heating at 10000C into SO2 and O2
2SO3 1000

0
C
 2SO2 + O2
(v) It combines with concentrated hydrochloric acid and forms chlorosulphonic acid, a derivative of
sulphuric acid.
SO3 + HCl  SO2·(OH)Cl
Chlorosulphonic acid
(vi) SO3 acts as an oxidisng agent.

Examples: 2SO3 + S 100


0
C
 3SO2
5SO3 + 2P  5SO2 + P2O5
SO3 + PCl5  POCl3 + SO2 + Cl2
Phosphoryl
chloride
SO3 + 2HBr  H2O + Br2 + SO2

Uses: (i) In the manufacture of sulphuric acid and oleum.

(ii) It is used as a drying agent for gases.

Oxyacids of Sulphur: Oxyacids with S–S links are called thioacids. Acids having sulphur in lower oxidation
state belong to ous series while those having sulphur in higher oxidation state belong to ic series. For
example:
Sulphurous acid (H2SO3) O.N. sulphur, +4
Sulphuric acid (H2SO4) O.N. sulphur, +6
The following are main oxyacids of sulphur:

1. Sulphurous acid series :

(i) Sulphurous acid, H2SO3
(ii) Thiosulphurous acid, H2S2O2
(iii) Hyposulphurous acid, H2S2O4
(iv) Pyrosulphurous acid, H2S2O5

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

2. Sulphuric acid series :
(i) Sulphuric acid, H2SO4
(ii) Thiosulphuric acid, H2S2O3
(iii) Pyrosulphuric acid, H2S2O7

3. Thionic acid series :

(i) Dithionic acid, H2S2O6
(ii) Polythionic acid, H2SnO6 (n = 3, 4, 5, 6)

4. Peroxy acid series :

(i) Peroxy monosulphuric acid, H2SO5 (Caro’s acid)
(ii) Peroxy disulphuric acid, H2S2O8 (Marshall’s acid)

Only two oxyacids (sulphurous acid and sulphuric acid are described below)

3. Sulphurous acid, H2SO4

This acid is known only in solution. The solution is obtained by dissolving sulphur dioxide in water.
SO2 + H2O  H2SO3
The solution gives a smell of sulphur dioxide which is evolved completely on heating. It is, thus, believed
that the acid is present in equilibrium with the free gas.
H2SO3 H2O + SO2

Properties: It is a strong dibasic acid. It ionises in two stages.

H2SO3 H+ + HSO3– 2H+ + SO3– –
It thus forms two series of salts. The salts are known as bisulphites (e.g. NaHSO3) and sulphites (e.g.
Na2SO3). The salts are fairly stable.
Like SO2, it acts as a reducing agent and shows bleaching properties. These properties have been described
under sulphur dioxide.
The acid also acts as an oxidising agent particularly when treated with strong reducing agents.

(i) The preparation of sulphurous acid by the action of H2O on thionyl chloride.

(ii) The molecule of sulphurous acid readily takes up oxygen or sulphur atom. This can be explained if
symmetrical formula is accepted.

4. Sulphuric Acid (oil of vitriol) H2SO4

In ancientdays, it was called oil of vitriol as it was prepared by distilling ferrous sulphate (Green Vitriol).
2FeSO4·7H2O Heat  Fe2O3 + H2SO4 + SO2 + 13H2O

(Green vitriol) (oil of vitriol)
Native sulphur is the starting material for the preparation of sulphuric acid. Sulphur is burnt and easily

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

converted into sulphur dioxide. The conversion of sulphur dioxide into sulphur trioxide is a matter of difficulty.
It requires either a catalyst or a strong oxidising agent. The trioxide dissolves in water to form sulphuric
acid. The whole process may be summarised as:
S  SO2  SO3  H2SO4
For the oxidation of sulphur dioxide into sulphur trioxide, the following reactions may be used:
(i) By atmospheric oxygen in presence of a catalyst, V2O5, at 4000C.
2SO2 + O2 400
  2SO
V2 O 5
0
C 3

SO3 + H2O  H2SO4

(ii) By Cl2 or Br2 in presence of moisture.
SO2 + 2H2O + Cl2  H2SO4 + 2HCl
SO2 + 2H2O + Br2  H2SO4 + 2HBr
(iii) By H2O2 SO2 + O3  H2SO4
(iv) By ozone (O3) 3SO2 + O3  3SO3
SO2 + H2O  H2SO4
(v) By conc. HNO3 SO2 + 2HNO3  H2SO4 + 2NO2

Manufacture: Sulphuric acid is manufactured these days by the following two processes:
(a) Lead chamber process (b) Contact process
Lead chamber process
Principle: The mixture containing sulphur dioxide, air and nitric oxide when treated with steam, sulphuric
acid is formed.
2SO2 + O2 + 2H2O + [NO]  2H2SO4 + [NO]
(Air) catalyst catalyst
Nitric oxide acts as a catalyst in this reaction.
Contact process
Principle: This process involves the oxidation of sulphur dioxide by air in the presence of a catalyst.

2SO2 + O2 2SO3
Sulphur trioxideis dissolved in 98% sulphuric acid when oleum is formed.
H2SO4 + SO3  H2S2O7(Oleum)
Sulphuric acid of any desired concentration can be obtained from oleum by dilution with water.
H2S2O7 + H2O  2H2SO4
The oxidation of sulphur dioxide is reversible and exothermic.
2SO2 + O2 2SO3 + 46.98 kcal
Comparison between the Lead Chamber and Contact Process
Lead chamber process Contact process

1. Catalyst used is a gasnitric oxide 1. Catalyst used is a solid vanadium pentoxide or

platinum asbestos.
2. Acid obtained is impure 2. Acid obtained is pure.
3. Acid obtained is 80% 3. Oleum is obtained. Sulphuric acid of any
concentration can be obtained from oleum.
4. Methods of concentration of the acid are 4. Furhter concentration is not necessary.
troublesome.
5. It is not necessary to purify the gases 5. It is absolutely necessary to purify the gases as
impurities acts as poison to catalyst.
6. It is a cheaper method. 6. It is a costlier method. The cost had been reduced
by the use of V2O5 in place of platinum.

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

Physical properties: (a) It is a colourless syrupy liquid. It contains 98.3% sulphuric acid. Its specific
gravity is 1.84 at 150C.
(b) It fumes strongly in moist air and is highly corrosive in nature.
(c) It is highly soluble in water. Various hydrates such as H2SO4·H2O, H2SO4·2H2O, H2SO4·4H2O, are
known. Heat is evolved when dissolved in water, usually bumping occurs. Water should not be added to
concentrated sulphuric acid for dilution but concentrated sulphuric acid should be added slowly to
cold water with constant stirring. Due to its great affinity for water, it is used as a dehydrating substance.
(e) It is a conductor of heat and electricity.

Chemical properties: (a) Dissociation: At 4440C, the vapours of sulphuric acid dissociate into steam
and sulphur trioxide,
H2SO4 H2O + SO3
(b) Acidic nature: Dilute sulphuric acid is a strong dibasic acid. It ionises as:
H2SO4 H+ + HSO4– 2H+ + SO42–
(i) It forms two series of salts with bases.
NaOH + H2SO4  NaHSO4 + H2O;
sodium
bisulphate
2NaOH + H2SO4  Na2SO4 + H 2O
sodium
sulphate
(ii) It decomposes carbonates and bicarbonates into carbon dioxide.
Na2CO3 + H2SO4  Na2SO4 + H2O + CO2
NaHCO3 + H2SO4  NaHSO4 + H2O + CO2
(iii) It reacts with electropositive metals evolving hydrogen.
Zn + H2SO4  ZnSO4 + H2
Fe + H2SO4  FeSO4 + H2
(iv) It displaces more volatile acids from their metal salts.
2NaCl + H2SO4  Na2SO4 + 2HCl
Ca3(PO4)2 + 3H2SO4  3CaSO4 + 2H3PO4
CaC2O4 + H2SO4  CaSO4 + H2C2O2
Calcium oxalate oxalic acid
FeS + H2SO4  FeSO4 + H2S
2CH3COONa + H2SO4  Na2SO4 + 2CH3C + OH
2NaNO3 + H2SO4  Na2SO4 + 2HNO
CaF2 + H2SO4  CaSO4 + 2HF
2NaNO2 + H2SO4  Na2SO4 + 2HNO2

NO + NO2 + H2O
(c) Oxidising nature: It acts as a strong oxidising agent. The potential equation is:
H2SO4  H2O + SO2 + O
(Hot conc.)
or 2H2SO4 + 2e–  SO42– + 2H2O + SO2
(i) Nonmetals such as carbon and sulphur are oxidised to their oxides.
C + 2H2SO4  CO2 + 2SO2 + 2H2O
S + 2H2SO4  3SO2 + 2H2O
Phosphorus is oxidised to orthophosphoric acid

(ii) Metals like copper, silver, mercury, etc., are first oxidised by conc. H2SO4 and then the oxides combine
with acid to form corresponding sulphates.
H2SO4  H2O + SO2 + O
Cu + O  CuO

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

 CuO + H2SO4  CuSO4 + 2H2O
––––––––––––––––––––––––––––––––––––
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
––––––––––––––––––––––––––––––––––––
2Ag + 2H2SO4  Ag2SO4 + SO2 + 2H2O
Hg + 2H2SO4  HgSO4 + SO2 + 2H2O

(iii) Iodine is liberated from KI (HI is oxidised to I2)

2KI + 2H2SO4  K2SO4 + SO2 + I2 + 2H2O
Similarly, bromine is liberated from KBr (HBr is oxidised to Br2).
2KBr + 2H2SO4  K2SO4 + SO2 + Br2 + 2H2O

(iv) In presence of Hg as a catalyst, naphthalene is oxidised to phthalic acid.

C10H8 + 9H2SO4  C8H6O4 + 10H2O + 9SO2 + 2CO2
Phthalic acid

(d) Dehydrating nature: As sulphuric acid has great affinity for water, it acts as a powerful dehydrating
agent. Its corrosive action on skin is also due to dehydration of skin. It absorbs water from organic
compounds.
C12H22O11 H  12 C
2 SO 4

( 11 H 2 O )
Cane sugar

C6H12O6 (   6 C
H 2SO 4
6 H O) 2

Glucose

(COOH)2 (   CO + CO
H 2SO 4
H O) 2 2

Oxalic Acid

HCOOH (   CO
H 2SO 4
H O) 2

Formic acid

2C2H5OH (   C H OC H
H 2SO 4
H O) 2 5 22 5

Ethyl alcohol Ether

Cloth, wood, starch, paper, etc., are all charred in concentrated sulphuric acid.

(e) Miscellaneous reactions: (i) Sulphonation: Aromatic compounds react with sulphuric acid forming
sulphonic acid.
C6H6 + H2SO4  C6H5SO3H + H2O
Benzene Benzene
Sulphonic acid
(ii) Action of PCl5: The molecule of sulphuric acid contains two hydroxyl groups. One or both the hydroxyl
groups can be replaced by chlorine when treated with PCl5.

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

(iii) On heating potassium ferrocyanide with concentrated sulphuric acid, carbon monoxide is evolved.
K4Fe(CN)6 + 6H2SO4 + 6H2O  2K2SO4 + FeSO4 + 3(NH4)2SO4 + 6CO
(iv) On heating potassium chlorate with concentrated sulphuric acid, carbon dioxide is evolved with explosion
3KClO3 + 3H2SO4  3KHSO4 + HClO4 + 2ClO2 + H2O
(v) Sulphuric acid reacts with barium and lead salts to form insoluble sulphates. These sulphates are even
insoluble in conc. HCl and conc. HNO3.
BaCl2 + H2SO4  BaSO4 + 2HCl
Pb(NO3)2 + H2SO4  PbSO4 + 2HNO3
(vi) H2SO4 absorbs sulphur trioxide forming oleum or fuming sulphuric acid.
H2SO4 + SO3  H2S2O7
Oleum
(vii) H2SO4 when treated with phosphorus pentoxide loses water and forms sulphur trioxide.
H2SO4 + P2O5  2HPO3 + SO3

XENON FLUORIDES
XePtF6 was first real compound of any of the noble gases. In a short time three fluorides of xenon, XeF2,
XeF4 and XeF6 had been obtained as white crystalline solids.

Xenon difluoride,
Preapation of XeF2:
Xenone fluoride is formed by heating a mixture of xenon and fluorine in molecular ratio 1 : 2 at 400oC in a nickel
tube.
Xe + F2 XeF2
Dioxygen fluride reacts with Xe at about 118oC to give XeF2
Xe + O2F2 118 
o
C
 XeF2 + O2 
In presence of mercury arc light, Xe and fluorine combine
Xe + F2 XeF2
Properties:
It is a colourless, crystalline solid (m. pt. 140oC)
It is decomposed by hydrogen and water.
XeF2 + H2  Xe + H2F2
2XeF2 + 2H2O  2Xe + 2H2F2 + O2
It is acts as a strong oxidising agent.
XeF2 + I2 BF 
3 2IF + Xe
XeF2 + 2HCl  Xe + H2F2 + Cl2
XeF2 dissolved in HF but do not react with HF.XeF2 forms addition compound with Lewis acids by itself acting
as Lewis base, e.g.,
Lewis base + Lewis acid  Adduct
XeF2 + 2SbF5  XeF2.2SbF5
or
[XeF]+[Sb2F11]
XeF2 + IF5  [XeF]+[IF6]

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

XeF2 undergoes hydrolysis in aqueous alkaline solution, e.g.,
2XeF2 + 4OH  2Xe + 4F + 2H2O + O2
Lastly, XeF2 acts as fluorinating agent also.
+ XeF2  + HF + Xe
2NO + XeF2  2NOF + Xe
2NO2 + XeF2  Xe + 2NO2F

Note: Vessels of monel metal (alloy of nickel) are used to store XeF2.

Xenon tetrafluoride, XeF4

Perparation: It is formed by heating a mixture of xenon and fluorine in the molecular ratio 1 : 10 at 400oC in a
nickel tube.
o

Xe + 2F2   XeF4
400 C
Ni

It is never synthesized in pure because its formation is accompanied with the formation of XeF2 and XeF6.

properties: It is a colourless, crystalline solid (m. Pt. 107oC). It undergoes sublimation. It is reduced by hydrogen,
mercury and boron trichloride.
XeF4 + 2H2  Xe + 2H2F2
XeF4 + 2Hg  Xe + 2Hg F2
3XeF4 + 4BCl3  4BF3 + 3Xe + 6Cl2
It forms a highly explosive solid, xenon trioxide (XeO3) when treated with water.
2XeF4 + 3H2O  Xe + XeO3 + 3H2F2 +F2
It is soluble in fluoro acetic acid (CF3COOH). When it is heated with excess of Xe it changes to XeF2.
XeF4 + Xe (excess) warm   2XeF2
It undergoes addition reaction like XeF2, forming adducts
XeF4 + SbF5  [XeF3]+[SbF6]
Lewis base Lewis acid Adduct

Other Lewis acids like PF5, AsF5, SbF5, NbF5, RuF5, OsF5 also undergo similar addtion reactions.
Like XeF2, tetrafluoride also acts as fluorinating agent, e.g.,
XeF4 + Pt  Xe + PtF4
4NO + XeF4  Xe + 4NOF
4NO2 + XeF4  Xe + 4NO2F

Xenon hexafluoride, XeF6

Preparations: It is formed by heating xenon and fluorine in molecular ratio 1 : 20 under pressure in a nickel
tube.
o

Xe + 3F2 50
 XeF6
300 C
atm .

Properties: It is a colourless crystalline solid (m. Pt. 49.5oC).

It is reduced by H2, HCl and NH3.
XeF6 + 3H2  Xe + 3H2F2 + 3Cl2
XeF6 + 8NH3  Xe + 6NH4F + N2
The hydrolysis of XeF6 with water yields new compounds.
XeF6 + H2O  XeOF4 + H2F2

0XYGEN FAMILY & NOBLE GAS [by AA SIR]

 XeOF4 + H2O  XeO2F2 + H2F2
XeO2F2 + H2O  XeO3 + H2F2
Like other xenon fluorides, XeF6 is also stored in nickel alloy (monel metal vessel). It cannot be stored in glass
vessel because silica in glass reacts with XeF6.
2XeF6 + 3SiO2  2SiF4 + 2XeO3
XeF6 dissolved in HF according to the following reaction
XeF6 + HF  [XeF5]+[HF2]
XeF6 undergoes thermal decomposition
XeF6  XeF2 + XeF4 + 3F2
Like XeF2 and XeF4, XeF6 also acts as fluorinating agent. XeF6 has strongest fluorinating tendancey. XeF6
udnergoes addition reactions with Lewis acids, e.g,
XeF6 + AsF5  [XeF5]+ [AsF6]+
XeF6 + BF3  [XeF5]+[BF4]
XeF6 + NaF  NaXeF7
2NOF + XeF6  [NO]22+ [XeF8]2
Hexafluoride undergoes hydrolysis in strongly alkaline medium.
2XeF6 + 16OH  8H2O + 12F + XeO64 + Xe + O2
*****

0XYGEN FAMILY & NOBLE GAS [by AA SIR]