PREPARATION &

PROPERTIES OF COMPOUNDS

Oxide, peroxides, hydroxide; bicarbonates, chlorides and sulphates of sodium,

potassium, magnesium and calcium; Boron : boric acid and borax; Aluminium : alumina,
aluminium chloride and alums; Carbon : oxides and oxyacids, Silicon : Silicones,
silicates and silicon carbide; Nitrogen : Oxides, oxyacids and ammonia; Phosphorous :
Phosphoxyacids (phosphorus acid, phosphoric acid) and phsophine; Oxygen : ozone and
hydrogen peroxides hydrogen sulphide, oxides, sulphurous acid, sulphuric acid and
sodium thiosulphate; Halogens : oxides and oxyacids of chlorine, bleaching power;
Xenon fluorides; Fertilizers : (NPK type) .

CONTENTS INTRODUCTION
 Sodium In this chapter, we will deal with
 Potassium preparation and properties of compounds
 Magnesium which contain elements of s–block and p–
block, s–block contains alkali metal and
 Calcium
alkaline earth metal . p–block contains
 Boron
aluminium family, carbon family, nitrogen
 Aluminium family, oxygen family, halogens and noble
 Carbon gases.
 Silicon
 Nitrogen
 Phosphorus
 Oxygen
 Sulphur
 Halogen
 Xenon fluorides
 Fertilizers
 Chemistry : Preparation & Properties of Compounds

1. SODIUM
1. Sodium Monoxide (Na2O)
Preparation: It is obtained by burning sodium at 180°C in a limited supply of air or oxygen
and distilling off the excess of Na in vaccum or by heating Na2O2 (sodium
peroxide), nitrate (NaNO3) with sodium.
2Na  12 O 2 
 Na 2O
Na 2 O 2  2Na 
 2Na 2O
2NaNO3  10Na 
 6Na 2O  N 2
Properties: 1. It reacts with water violently forming NaOH.
Na 2 O  H 2 O 
 2NaOH
2. On heating above 400°C, it disproportionates to give peroxide and metallic
sodium.
400 C
2Na 2O   Na 2O2 2Na
3. It reacts with liquid ammonia forming sodamide and NaOH.
Na 2 O  NH 3 
 NaOH  NaNH 2

2. Sodium Peroxide (Na2O2)

Preparation: It is formed by heating the sodium metal in excess air or oxygen. The air should
be moisture free and the temperature required is 300°C.
2Na  O 2 
 Na 2O 2
Properties: i) It is a yellow substance but turns white on exposure to moist air due to the
formation of NaOH and Na2CO3.
ii) Action of water.
2Na 2O 2  2H 2O (warm) 
 4NaOH  O 2
iii) Action of acids.
cold
Na 2 O 2  H 2SO 4  Na 2SO 4  H 2O 2
hot
2Na 2 O 2  2H 2SO 4   2Na 2SO 4  2H 2O  O 2
iv) Oxidising action. It is a powerful oxidizing agent and oxidizes chromic
compounds to chromates, manganous salts to manganates, SO2 to SO3 or
sulphites, and sulphides to sulphates. For example,
[Na 2 O 2  H 2 O 
 2NaOH  O]  5

Cr2 (SO 4 )3  10NaOH  5O   3Na 2SO 4  2Na 2CrO4  O 2 5H 2O

Cr2 (SO4 )3  5Na 2 O2 
 3Na 2SO 4  2Na 2CrO 4  O 2
v) Reducing action. It reduces potassium permanganate, a stronger
oxidising agent.
Na 2 O 2  H 2SO 4 
 H 2O 2  Na 2SO 4
Chemistry : Preparation & Properties of Compounds

2KMnO 4  3H 2SO4  5H 2 O 2   K 2SO 4  2MnSO 4  8H 2O  5O 2

vi) It combines with CO to form Na 2 CO3
Na 2 O 2  CO 
 Na 2 CO3

3. Sodium Hydroxide (Caustic Soda), NaOH

Preparation: Sodium hydroxide is commonly called caustic soda because of its corrosive
action on animal and vegetable tissues. Large quantity of sodium hydroxide is
now a days, prepared by electrolytic process. There are two electrolytic methods
commonly used for preparing sodium hydroxide.

a) Castener Kellner cell:

NaCl(aq) Na   Cl –
At cathode (mercury) : 2Na   2e – 
 2Na
Na  Hg 
 NaHg (sodium amalgam)
At anode (graphite): 2Cl – 
 Cl2  2e –
Sodium amalgam is removed from the cell. It is then decomposed in a
separate cell by water giving NaOH, hydrogen and mercury. Mercury is
recirculated to the cell.
b) Nelson cell (or Diaphragm cell)
NaCl (aq) Na   Cl –
H2O H   OH –
At cathode (perforated steel) : 2H   2e – 
 H2
At anode (carbon rod) : 2Cl – 
 Cl2  2e –
Note: This cell is used for the industrial production of Cl2. As well as this cell can be used for production
of Na2 CO3, for which CO2 is mixed with steam.

Properties: i) NaOH is stable towards heat but is reduced to metal when heated with carbon
2NaOH + 2C  2Na +2CO + H2

ii) FeCl3 + 3NaOH  Fe(OH)3 + 3NaCl

NH4Cl + NaOH  NaCl + NH3 (pungent smell) + H2O
HgCl2 + 2NaOH  HgO (yellow powder) + 2NaCl + H2O
excess
Zn(OH)2  + 2NaOH   Na2ZnO2 + 2H2O
excess
Al2O3  + 2NaOH   2NaAlO2 + H2O
SiO2 + 2NaOH  Na2SiO3 + H2 O
P4 + 3 NaOH +3H2O  PH3 + 3NaH2PO2
2Al + 2 NaOH + 2H2 O  3H2 + 2NaAlO2

4. Sodium Carbonate: Na2CO3: It exists in various forms, namely anhydrous sodium

carbonate Na2CO3 (soda-ash); monohydrate, Na2CO3.H2 O (crystal carbonate); hepthydrate, Na-
 Chemistry : Preparation & Properties of Compounds

2CO3. 7H2O and decahydrate, Na2 CO3. 10H2O (washing soda or sal soda). It occurs in the form of
reh and sajji matti in U.P. and Bihar.

Manufacture: (Solvay or ammonia soda process). In this process, brine (NaCl), ammonia and
carbon dioxide are the raw materials. The chemical reactions involved are as
below.
30 C
NH 4 HCO3  NaCl   NaHCO3   NH 4 Cl
Sod. bicarbonate

250 C
2NaHCO3 
 Na 2CO3  H 2 O  CO 2
Sod. bicarbonate (used again)

2NH 4Cl  Ca(OH)2 

 CaCl2  2H 2O  2NH 3
Amm. chloride Slaked lime (used again)

Note: Solvay process can not be used for the production of K2CO3, since KHCO3 has much greater
solubility than NaHCO3. So, KHCO3 cannot be precipitated.

Properties: i) Sodium carbonate crystallizes from water as decahydrate. It is a white solid

which efflorescence on exposure to dry air forming the monohydrate.
dry
Na 2 CO3 .10H 2O 
air
 Na 2CO 3 . H 2O  9H 2O
On heating, the monohydrate changes to anhydrous salt (m.p. 853°C) which
does not decompose on further heating even to redness.
ii) It is soluble in water with considerable evolution of heat. The resulting
solution is alkaline due to hydrolysis.
Na CO  2H 2 O
2 3 H 2CO3  2NaOH
Sod. carbonate ( weak acid) (Strong alkali)

iii) It is readily decomposed by acids with the evolution of CO2 gas.

iv) It reacts with metal salts to form insoluble normal or basic carbonate.
CaCl2 Na 2CO3 
 CaCO3   2NaCl
2MgCl 2  2Na 2 CO 3  H 2O 
 MgCO 3. Mg(OH) 2   4NaCl  CO 2
Carbonates of metals like Al, Fe, Sn, etc. when formed are immediately
hydrolysed to hydroxides.
3H 2 O
Fe2 (SO 4 )3  3Na 2 CO3 
 Fe 2 (CO 3 )3   2Fe(OH)3  3CO 2
v) When CO2 gas is passed through aqueous solution of sodium carbonate,
sodium bicarbonate is formed.
Na 2CO3  H 2O  CO 2 
 2NaHCO3
Sod. bicarbonate

5. Sodium sulphate (Glauber’s salt): Na2SO4. 10H2O

Preparation: i) The anhydrous sodium sulphate (salt cake) is obtained as a by-product in the
manufacture of hydrochloric acid.
ii) Salt cake is also produced during the manufacture of sodium carbonate when
NaCl is heated with H2SO4.
Chemistry : Preparation & Properties of Compounds

2NaCl  H 2SO 4 
 Na 2SO 4  2HCl
iii) Salt cake is now-a-days manufactured by heating NaCl with sod. bisulphate
(nitre cake). Nitre cake is obtained by the action of H2SO4 on sodium nitrate
(Chile saltpeter).
NaNO  H 2SO4 
3  NaHSO4  HNO3
Chile saltpetre Nitre cake

NaCl  NaHSO 4 
 Na 2SO 4  HCl 
Nitre cake Salt cake

Properties: i) The decahydrate sodium sulphate effloresces in dry air forming the anhydrous
salt. It is crystalline solid, soluble in water.
ii) When treated with lead, barium or strontium salts, it forms the corresponding
insoluble sulphate, e.g.
Pb(NO3 )2  Na 2SO 4 
 PbSO 4   2NaNO3
iii) When a solution having equivalent quantity of anhydrous Na2SO4 and conc.
H2SO4 is cooled, prismatic crystals of sodium bisulphate (sodium hydrogen
sulphate, NaHSO4) are formed.
Na 2SO 4  H 2SO 4 
 2NaHSO 4
iv) When heated with carbon it is reduced to sodium sulphide
Na 2SO 4  4C 
 Na 2S  4CO
6. Sodium Chloride (NaCl)
Preparation: It is also called common salt occurs abundantly in nature as rock salt or halite.
The most abundant source is sea-water where sodium chloride occurs to the
extent of 2.6 – 2.9 percent. The sea water is exposed to the sun and air in large
shallow pits. The gradual evaporation of water lead to the crystallization of the
salt. The purification is done by dissolving the salt in minimum volume of water
and filtering, if necessary, to remove insoluble impurities. The solution is then
saturated with a current of dry hydrogen chloride whereby crystals of pure
sodium chloride separate out.
Properties: i) NaCl is a colourless crystalline salt, almost insoluble in alcohol and highly
soluble in water.
ii) It gives rise to HCl when heated with conc. H2SO4 and Cl2, with MnO2 plus
H2SO4.
NaCl + H2SO4  NaHSO4 + HCl
NaHSO4 + NaCl  Na2SO4 + HCl
2NaCl + MnO2 + 2H2 SO4  MnSO4 + Na2SO4+ 2H2O + Cl2 
 Chemistry : Preparation & Properties of Compounds

Illustration 1: Give reason for decreasing order of conductivity of following

Cs+  Rb+  K+  Na+  Li+
Solution: Ions are hydrated in solution. Since Li is very small it is heavily hydrated. This make
the radius of the hydrated ions large and hence it move only slowly (although Li+ is
very small) and the radius of hydrated Cs+ ion is smaller than the radius of hydrated
Li+.

2. POTASSIUM
1. Potassium Oxides: Three oxides are known : (i) potassium mono-oxide (potassium oxide),
K2O; (ii) dioxide (tetroxide or superoxide), KO2 or K2O4; and (iii) sesquioxide, K2O3.
180 C
Preparation: a) 4K(excess)  O2 
reduced pressure
 2K 2O
Pot. monoxide
heat
2KOH  2K  2K 2O  H 2
2KNO3  10K 
 6K 2O  N 2
burning
b) K  O 2 (excess)   KO 2
Pot. dioxide

2KOH  O 3 
 2KO 2  H 2O
3O
c) 4K (dissolved in liq. NH3 ) 
2
2K 2 O3
Pot. sesquioxide

Properties: Potassium monoxide is a white hygroscopic solid while dioxide is a chrome yellow
powder. The important chemical property of oxides is their hydrolysis to form
KOH.
K 2 O  H 2 O 
 2KOH
2KO 2  2H 2 O 
 2KOH  H 2O 2  O 2
2. Potassium hydroxide (Caustic Potash), KOH
Preparation: It may be prepared like that of NaOH, i.e., by the electrolysis of KCl solution and
by the action of lime on potassium carbonate. It may also be obtained by the
action of baryta, Ba(OH)2 on potassium sulphate.
K 2SO 4  Ba(OH)2 
 BaSO 4   2KOH
Properties: Its properties are similar to those of sodium hydroxide. However, it is a stronger
alkali and more soluble in alcohol and is therefore, used in organic reactions
instead of caustic soda. Moreover, it is a better absorber of CO2 than NaOH
because potassium carbonate is more soluble and does not separate out. Its
aqueous solution is known as potash lye.
3. Potassium carbonate (K2CO3): It is also known as pearl ash.
Preparation: It is made by passing CO2 into a conc. solution of the chloride, containing
hydrated mangesium carbonate in suspension at 20C when an insoluble
potassium hydrogen magnesium carbonate is precipitated.
2KCl + 3(MgCO3.3H2O) + CO2  2(MgCO3.KHCO34H2O) + MgCl2
Chemistry : Preparation & Properties of Compounds

The precipitate is separated by filtration, and then decomposed either by heating

with water under pressure at 140C or by the action of magnesium oxide below
20C.
2(MgCO3 KHCO3 4H2O)  2MgCO3 + K2CO3 + 9H2O + CO2
2(MgCO3KHCO34H2 O) + MgO  3(MgCO3.3H2O) + K2CO3
Properties: i) It is white, deliquescent solid
ii) K2CO3 resembles Na2CO3 in properties, but is more alkaline and more
soluble than Na2CO3.
4. Potassium Bicarbonate (KHCO3)
Preparation: It is prepared by passing CO2 through a cold saturated solution of potassium
carbonate.
K 2 CO3  H 2 O  CO 2 
 2KHCO 3
Properties: It resembles sodium bicarbonate in all respects except that it is more soluble in water.
It is used in medicine and in baking powders.
5. Potassium Sulphate (K2SO4)
Preparation: i) By treating KCl or KOH with H2SO4
2KCl  H 2SO 4 
 K 2SO4  2HCl
2KOH  H 2SO 4 
 K 2SO 4  2H 2O
ii) By treating naturally occurring mineral, schonite (K2SO4. MgSO4. 6H2 O)
with sylvine (KCl).
K 2SO 4 .MgSO4 .6H 2 O  2KCl 
 2K 2SO4  MgCl2  6H 2O
Properties: i) It is a white crystalline (m.p. 1050°C) solid, not very soluble in water.
ii) Unlike sodium sulphate, its crystals do not contain water of crystallisation.
iii) When heated with carbon, it is reduced to potassium sulphide.
iv) It forms a series of double salts with the sulphates of trivalent metals, e.g.
potash alum, K2SO4 . Al2 (SO4)3. 24H2O.
6. Potassium Chloride (KCl)
Preparation: KCl is prepared from fused carnallite. Nearly pure KCl separates from the melt,
leaving fused MgCl2 behind.
KCl . MgCl2 . 6H 2O 
 KCl  MgCl2 . 6H 2O
Properties: It is a colourless cubic crystal soluble in water. Its solubility increases almost linearly
with temperature.

Illustration 2: Explain the stability of oxides of alkali metals.

Solution: Li forms only oxide, Na forms oxide and peroxides and remaining all alkali metal
form oxides, peroxides and super oxides.
Li + O2  2Li2O
( Oxide )

4Na + O2  2Na2O
( Oxide )
 Chemistry : Preparation & Properties of Compounds

2Na + O2  Na 2O 2
( Peroxide )

K + O2  KO 2
(superoxides)

Peroxide [–O–O–]2 has no unpaired electron therefore, it is diamagnetic. On the

other hand super oxide [O2]– has an unpaired electron therefore it is paramagnetic
super oxides are stronger oxidizing agent than peroxides Stability of the peroxides
and super oxides increases as the metal ions become large. Peroxide and super oxide
are larger in size. If both ions are similar in size, then coordination number will be
high and thus gives a high lattice energy.

KO2 is used in space capsules, breathing masks because it both produces dioxygen
and remove carbon dioxide.

4KO2 + 2CO2  2K2CO3 + 3O2

4KO2 + 4CO2 + 2H2O  4KHCO3 + 3O2

3. MAGNESIUM
1. Magnesium Oxides (MgO)
Preparation: It is prepared by burning Mg in air, by heating hydroxide, nitrate, sulphate or
carbonate. Oxide prepared by heating magnesite (MgCO3) is called calcined
magnesia.
2Mg(NO3 ) 2 
 2MgO  4NO 2  O 2

2MgSO 4 
 2MgO  2SO 2  O 2
Properties: i) Magnesium oxide is a light white powder, which is highly infusible (m.p.
2800°C), and only slightly soluble in water.
ii) It is a basic oxide and hence reacts with acids to form salts.
MgO  2HCl 
 MgCl 2  H 2O
iii) It is reduced by carbon at very high temperature to form magnesium carbide.
MgO  3C 
 MgC 2  CO
iv) It dissolves in aqueous solution of magnesium chloride or bromide forming
basic salts such as MgCl2 . 9Mg(OH)2 . 5H2O.

2. Magnesium Hydroxide (Mg(OH)2)

Preparation: It is obtained by adding caustic soda solution to a solution of magnesium sulphate
or chloride.
MgSO4 + 2NaOH  Na2SO4 + Mg(OH)2
Properties: i) It is converted into its oxide on heating.
Mg(OH)2  MgO + H2 O
Chemistry : Preparation & Properties of Compounds

ii) It dissolves in NH4Cl solution easily.

Mg(OH)2 + 2NH4Cl  MgCl2 + 2NH4OH

3. Magnesium Carbonate, (MgCO3): It occurs in nature as magnesite, MgCO3 and dolomite,

MgCO3.CaCO3.
Preparation: i) By adding sodium bicarbonate solution to a hot solution of magnesium salt.
MgSO 4  2NaHCO3 
 MgCO3   Na 2SO 4  H 2O  CO 2
In case Na2CO3 is used in place of NaHCO3, a basic carbonate is obtained.
2MgSO 4  2Na 2CO3  H 2O 
 MgCO3 .Mg(OH) 2  2Na 2SO 4  CO2
When CO2 gas is passed through the suspension of basic carbonate,
magnesium bicarbonate is formed which on heating forms MgCO3.
MgCO3 .Mg(OH) 2  3CO 2  H 2 O 
 2Mg(HCO 3 ) 2
heat
Mg(HCO 3 ) 2  MgCO3  H 2O  CO 2 
ii) Pure magnesium bicarbonate and hence carbonate can be prepared by passing
CO2 through suspension of magnesium oxide in water.
MgO  H 2 O  2CO 2 
 Mg(HCO 3 ) 2

Mg(HCO 3 ) 2  MgO 
 2MgCO 3  H 2O
Properties: i) Magnesium carbonate is a white powder, insoluble in water.
ii) It dissolves in acids forming salts.
MgCO3  2HCl 
 MgCl 2  H 2O  CO 2 
iii) Its aqueous solution also dissolves on passing a current of carbon dioxide
because of the formation of Mg(HCO3)2, a temporary hardness causing
substance.
MgCO3  H 2 O  CO 2 
 Mg(HCO) 3 ) 2
A solution of magnesium bicarbonate containing 12 gm. of the salt per 100
ml is known as fluid magnesia.
iv) It decomposes on heating to form magnesium oxide.
heat
MgCO3  MgO  CO 2
4. Magnesium Sulphate (MgSO4.7H2O) or Epsom salt: It occurs in nature as kieserite,
MgSO4.H2O; Epsom salt, MgSO4.7H2O; and kainite, KCl.MgSO4 . 3H2O. It is also found in some
mineral springs.
Preparation: i) From magnesite or dolomite.
MgCO3  H 2SO4 
 MgSO 4  H 2O  CO 2
Magnesite

MgCO 3 . CaCO 3  2H 2SO 4 

 MgSO 4  CaSO 4   2H 2O  2CO 2
Dolomite
 Chemistry : Preparation & Properties of Compounds

ii) From kieserite (Commerical method). By boiling kieserite in water and

cooling the resulting solution when crystals of Epsom salt separate out.
Properties: i) It is a colourless, efflorescent crystalline substance with bitter taste.
ii) It forms a number of hydrates.
iii) When heated to 150°C, it changes to monohydrate which on further heating
changes to anhydrous state at 200°C.
160 C 200 C
MgSO 4 .7H 2 O 
(–6H 2 O)
 MgSO4 .H 2O   MgSO 4  H 2O

On further heating, it decomposes to form MgO.

above 200 C
4MgSO 4  4MgO  2SO 2  2SO 3  O 2
iv) It is reduced by lamp black at 300°C
2MgSO 4  C 
 2MgO  2SO 2  CO 2
v) It forms double salts with alkali metal sulphates, e.g., K2SO4. MgSO4.6H2O.
5. Magnesium Chloride (MgCl2.8H2O)
Preparation: It is prepared in the laboratory by crystallizing a solution of the oxide, hydroxide
or carbonate in dilute hydrochloric acid.
MgO + 2HCl  MgCl2 + H2O
Properties: It is colourless, crystalline salt, deliquescent in nature and exceedingly soluble in
water.

4. CALCIUM
1. Calcium oxide (CaO) or Quick lime
Preparation: By heating lime stones at 804°C.
800 C
CaCO3 CaO  CO2
i) The reaction is reversible and thus in order to assure the complete
decomposition of CaCO3,CO2 formed must be swept away by a current
of air.
ii) Temperature should not be too high because at high temperature clay will
react with lime to form fusible silicates.
Properties: i) It is white amorphous powder, which emits intense white light (lime light), when
heated in the oxy-hydrogen flame.
ii) It reacts with strongly heated silica,forming easily fusible calcium silicate.
CaO + SiO2  CaSiO3
iii) CaO reacts with water evolving huge amount of heat and produce slaked
lime.
CaO + H2O  Ca(OH)2
2. Calcium Hydroxide (Slaked lime), [Ca(OH)2]
Preparation: i) By treating lime (quick lime) with water.
Chemistry : Preparation & Properties of Compounds

CaO  H 2 O 
 Ca(OH) 2
ii) By the action of caustic alkalies on a soluble calcium salt.
Properties: i) It is a white amorphous powder, only sparingly soluble in water. Its solubility
decreases with the increase in temperature.
ii) When dried and heated to redness, it loses a molecule of water and converted
into calciuim oxide (lime).
iii) Action of CO2: Lime water [Lime + H2O  Ca(OH) 2 ] is frequently used
for the detection of CO2 gas; CO2 gas turns lime water milky due to
formation of CaCO3.
Ca(OH) 2  CO 2 
 CaCO3   H 2 O
However, the precipitate disappears on prolonoged treatment with CO2
because of the conversion of CaCO3 (insoluble) to calcium bicarbonate
(soluble).
CaCO3  H 2O  CO 2 
 Ca(HCO3 ) 2
Inso lub le So lub le

3. Calcium Carbonate, (CaCO3): Calcium carbonate is found in nature as limestone, marble,

coral, ice land spar, calcite, chalk, dolomite, etc.
Preparation: It is prepared as a white powder, known as precipitated chalk by dissolving
marble or limestone in hydrochloric acid followed by precipitation with sod. or
ammonium carbonate.
CaCO3  2HCl 
 CaCl 2  H 2 O  CO 2
CaCl2  (NH 4 ) 2 CO 3 
 CaCO3  2NH 4 Cl
In the laboratory, it is prepared by passing CO2 through lime-water or by adding
sod. or ammo. carbonate solution to CaCl2.
Ca(OH) 2  CO 2 
 CaCO3   H 2 O
Properties: i) It is a white powder and exists in two crystallie forms: calcite and aragonite.
ii) It is insoluble in water but dissolves in the presence of CO2 due to the
formation of calcium bicarbonate.
CaCO3  H 2 O  CO 2 
 Ca(HCO 3 ) 2
4. Calcium Bicarbonate, (Ca(HCO3)2): It does not exists in solid state. However, its solution
can be prepared by passing CO2 gas through a suspension of calcium carbonate in water. On
warming, it decomposes to calcium carbonate along with the evolution of carbon dioxide gas.
5. Calcium Sulphate, (CaSO4): It occurs in nature as anhydrite (CaSO4) and gypsum (CaSO4.
2H2O).
Preparation: It may be prepared by adding dilue sulphuric acid or soluble sulphate (e.g.
Na2SO4 ) to the solution of a calcium salt.
CaCl2  H 2SO 4 
 CaSO 4  2HCl
Properties: i) It is a white crystalline solid. Like slaked lime, it is sparingly soluble in cold
water and its solubility decreases further with the increase in temperature.
 Chemistry : Preparation & Properties of Compounds

ii) It dissolves much more readily in dilute acids, even in acetic acid than in
water. It dissolves also in ammonium sulphate solution forming
CaSO4.(NH4 )SO4.H2O.
iii) Monoclinic crystals of gypsum when heated, first changes into orthorhombic
form without any loss of water. On further heating to 120°C, it loses three-
fourth of its water of crystallization and forms the hemihydrate,
(2CaSO4).H2O or CaSO 4 . 12 H 2 O which is commonly known as Plaster of
Paris.
120 C
CaSO 4 .2H 2O   CaSO 4 . 12 H 2O  1 12 H 2O
Plaster of Paris is a white powder which when mixed with water takes up the
water of crystallization again, thus converted back into the dehydrate and sets
to a hard mass with slight expansion. Setting takes about 10–15 minutes and
may be catalysed by the addition of common salt or delayed by the use of
alum or borax.
H2O hardening
CaSO 4 . 12 H 2 O 
setting
 CaSO 4 .2H 2O   CaSO4 .2H 2 O
Plaster of Paris Orthor hom bic Monoclinic (gypsum)

Plaster of pairs or gypsum when heated to about 200°C is converted into

anhydrous calcium sulphate. The anhydrous form (anhydrite) is known as
dead burnt because it does not set like Plaster of Paris when moistened with
water.
6. Calcium Chloride (CaCl2)
Preparation: It separates out as deliquescent crystals when a solution of lime or calcium
carbonate in HCl is evaporated.
CaCO3 + 2HCl  CaCl2 + H2CO3
But it separates out from the reaction mixture as CaCl26H2O. The anhydrous salt
is obtained on heating above 200C.
Properties: It is a colourless, deliquescent salt, highly soluble in water. The anhydrous salt is
an excellent drying agent.

Illustration 3: Thermal decomposition of a compound 'X' yields, a basic oxide ( Y ) and acidic
oxide( Z ) simultaneously. The acidic oxide(Z) can be absorbed by alkaline KOH.
What is X,Y,Z.

Solution: CaCO3  CaO  CO2

'X' Basic Acidic
(Y) (Z)
CO2 + 2KOH  K2CO3 +H2O

5. BORON
Preparation: Boron is obtained by the reduction of B2O3 with magnesium or sodium B2O3 is first
prepared by strongly heating H3BO3 which is obtained by the action of HCl or H2SO4 on a
concentrated solution of borax:
Chemistry : Preparation & Properties of Compounds

Na2B4O7 + 2HCl + 5H2O 

 4H3BO3 + 2NaCl
2H3BO3 
 B2O3 + 3H2O
B2O3 + 3Mg 
 2B + 3MgO
Pure crystalline boron may be obtained in small quantities by the reduction of BBr3 with
H2 on a heated metal filament at 1275-1475 K.
Properties: Physical
a) Small atomic size
b) low electro negativity and hard, absorbs neutron, steel grey in colour. Some
dissimilarities of boron with other elements of this group are :
i) Boron is a non-metals, while all other elements of this group are metals.
ii) Boron forms only covalent compounds, while other elements of this group form
both covalent and ionic compounds.
iii) Boron shows a maximum covalency of four, while other elements of this group
show a maximum valency of six, absorbs neutron, steel grey in colour. Its density
is 2.34 gm/cc.
Chemical
1. Crystalline Boron is not active. Amorphous Boron reacts.
700 C
4B 3O 2   2B2 O3
700 C
2B  N 2   2BN
2. These above reaction accompanies red flame.
BN  3H 2 O 
 H 3 BO3  NH 3
3. Action an alkalis and acids
2B  2NaOH  2H 2O 
 2NaBO 2  3H 2
oxidation
2B  3H 2SO 4   2H 3BO3  3SO 2
oxidation
2B  6HNO 3   H 3BO 3  6NO 2
4. Boron reacts with Mg and consequent hydrolysis gives diborane.
3Mg  2B 
 Mg3B2
3Ca  2B 
 Ca 3B2
Mg3B2  6HCl 
 3MgCl2  B2 H 6
B2 H 6  6H 2O 
 2H 3BO3  6H 2
5. Boron reduces silicon, CO2
3SiO2  4B 
 2B2O 3  3Si

3CO 2  4B 
 2B2 O3  3C
 Chemistry : Preparation & Properties of Compounds

1. Diborane (B2H6)
Preparation: Diborane can be prepared in almost quantitative yields by the reduction of boron
trifluoride etherate (BF3.OEt2) with lithium aluminium hydride (LiAlH4) or
sodium borohydride (NaBH4).
Et 2 O
4BF3 .OEt 2  3LiAlH 4   2B2 H 6  3LiAlF4  4Et 2 O
diglyme
4BF3 .OEt 2  3NaBH 4   2B2 H 6  3NaBF4  4Et 2O
where, diglyme is diethyleneglycol dimethyl ether, (MeOCH2CH2)2 O.
Diborane can also be prepared by treating NaBH4 with conc. H2SO4 or H3PO4:
2NaBH 4  H 2SO 4 
 B2 H 6  2H 2  Na 2SO 4

2NaBH 4  2H 3 PO 4 
 B2 H 6  2H 2  2NaH 2 PO 4
Properties: 1. Diborane is a colourless gas (b.p., 183K). It is rapidly decomposed by water
with the formation of H3BO3 and H2 :
B2 H 6  6H 2O 
 2H 3BO3  6H 2
2. Mixtures of diborane with air or oxygen inflame spontaneously produce large
amount of heat. Diborane has a higher heat of combustion per unit weight of
fuel than most other fuels. Therefore, it is used as a rocket fuel.
 B2 O3  3H 2O, H  –2165 kJ mol –1
B2 H 6  3O 2 
3. Pyrolysis of B2H6 in sealed vessels at temperatures above 375 K is an
exceedingly complex process producing a mixture of various boranes, e.g.,
B4H10, B5H9, B5H11, B6H10, B6 H12 and B10H14. By careful control of
temperature, pressure and reaction time, the yield of various intermediate
boranes can be optimised. For example, by storing B2H6 under pressure for
10 days, B4H10 is produced in 15% yield according to the following equation:
2B2 H 6 
 B4 H10  H 2
4. Diborane undergoes a facile addition reaction with alkenes and alkynes in
ether solvents at room temperature to form organoboranes:
6RCH = CH2 + B2H6 
 2B(CH2CH2R)3 (Hydroboration Reaction)
2. Boric Acid: Orthoboric acid H3BO3 commonly known as boric acid and metaboric acid HBO2,
are two well-known and important oxoacids of boron.
Chemistry : Preparation & Properties of Compounds

Preparation: On a large scale, H3BO3 is prepared by the action of HCl or H2SO4 on a

concentrated solution of borax:
Na 2 B4O7  2HCl  5H 2O 
 4H 3BO3  2NaCl
Properties: 1. Boric acid is a flaky, white crystalline solid.
2. It is moderately soluble in water.
3. Boric acid is a very weak monobasic acid (pK = 9.25), because it acts as an
electron pair acceptor (Lewis acid) from OH – rather than as a proton donor
(Arrhenius acid).
H 3 BO3  2H 2 O [B(OH) 4 ]–  H 3O 
4. On heating boric acid at 375 K, metaboric acid, HBO2 is formed. On further
heating above 500 K, B2O3 is formed:
375 K
H 3 BO3   HBO 2  H 2 O
500 K
2HBO 2   B2 O 3  H 2 O
In solution metaboric acid changes into orthoboric acid.
3. Borax (Sodium tetraborate decahydrate, Na2B4O7. 10H2O)
Preparation: It is obtained by extracting impure borax with water and concentrating the
solution until crystals of borax separate out.
Borax can also be prepared from the mineral colemanite by boiling it with
Na2CO3 solution :
Ca 2 B6O11  2Na 2CO3 
 Na 2 B4O 7  2NaBO2  2CaCO3 
Properties: 1. Borax is a white crystalline solid. It is hydrolysed by water to give an alkaline
solution:
Na 2 B4 O7  7H 2 O 4H3 BO3  2NaOH
2. On heating, borax loses water to become anhydrous. Anhydrous borax on
strong heating with NH4Cl gives boron nitride and boron trioxide:
Na 2 B4 O7  2NH 4Cl 
 2BN  B2O 3  2NaCl  4H 2O
3. On heating alone, it decomposes to form NaBO2 and B2O3
Na 2 B4O7 
 2NaBO 2  B2O3
4. Borax bead Test: The formation of coloured metaborates by transition
metal salts is used in borax bead test in qualitative analysis. The colour
depends on the oxidising or reducing flame of the bunsen burner.
A cupric salt forms blue cupric metaborate in the oxidising flame:
Na2B4O7 + CuO Cu(BO2)2 + 2NaBO2
In the reducing flame , (ie. in presence of carbon ) the coloured salt is
reduced to colourless cuprous metaborate:
 Chemistry : Preparation & Properties of Compounds

2Cu(BO2)2 + 2NaBO2 + C  2CuBO2 + Na2B4O7 + CO. and to metallic

copper and hence bead becomes dull red and opaque.
2Cu(BO2) + 4NaBO2 + 2C  2Cu + 2Na2B4O7 + 2CO
Colour of borax bead
Compounds of
Oxidising flame Reducing flame
Chromium Green Green
Manganese Amethyst Colourless
Iron Yellow(cold) Bottle green
Cobalt Deep blue Deep blue
Nickel Brownish(cold) Grey
Copper Green(hot),blue(cold) Colourless or red

6. ALUMINIUM
1. Aluminium oxide - Al2O3(Alumina)
Preparation: In the lab, it is prepared by igniting aluminium hydroxide, aluminium sulphate or
ammonium alum.
2Al(OH)3  Al2O3 + 3H2O
Al2(SO4)3  Al2O3 + 3SO3
(NH4)2SO4.Al2(SO4)3.24H2O  2NH3 + Al2O3 + 4SO3 + 25H2O
Properties: White crystalline powder and it is an amphoteric oxide.
Al2O3 + 6HCl  2AlCl3 + 3H2O
Al2O3 + 2NaOH  2NaAlO2 + H2O
2. Aluminium Chloride: AlCl3.6H2O
Preparation: It is prepared by the action of dil or conc. hydrochloric acid on aluminium
2Al + 6HCl  2AlCl3 + 3H2
i) Aluminium chloride exists as dimer (Al2Cl6) in inert solvent as well as in
vapour state.
ii) It is a white crystalline, hygroscopic solid and it fumes in moist air due to
hydrolysis.
AlCl3 + 3H2O Al (OH)3 + 3HCl
3. Alums: Alums are the double sulphates having general formula: X2SO4.M2(SO4)3.24H2O
X = monovalent cation such as Na+, K+, NH4 + etc.
M = trivalent cation such as Al3+, Cr3+, Fe3+ etc.
when alum contains aluminium as trivalent cation then it is named after monovalent cation.
e.g. K2SO4.Al2(SO4)3.24H2O potash alum
Na2SO4 .Al2(SO4)3.24H2O - Soda alum.
Chemistry : Preparation & Properties of Compounds

When trivalent cation is not aluminium then alum is named after both, monovalent as well as
trivalent cation.
(NH4)2SO4.Fe2(SO4)3.24H2O - ferric ammonium alum.
Illustration 4: Explain briefly why boron trichloride is a gas and aluminium trichloride is a
dimeric solid.
Solution: In BCl3 boron attains an octet of electrons by means of p – p bonding between B
and Cl atoms. Thus it exists as a monomeric gas. Due to the larger size of aluminium
in aluminium trichloride, efficient p – p bonding cannot take place between Al
and Cl atoms. Consequently, aluminium trichloride dimerises to attain an octet of
electrons around Al by forming a dative bond between Cl and Al atoms. Thus, it
exists as a solid.

7. CARBON
Allotropes of carbon: The phenomenon of the existence of an element in different forms, which
have different physical properties but similar chemical properties, is known as allotropy. such different
forms of an element are called its allotropes or allotropic forms.
The various allotropic forms of carbon can be broadly classified into two classes.
a) Crystalline form: Diamond and graphite are the two crystalline forms of carbon. Graphite is
thermodynamically more stable than diamond, thermodynamically, diamonds should get transformed
into graphite on their own. But it does not happen at least on our life time scale. This is because, this
conversion is not favoured by kinetic factors, i.e., the activation energy for this reaction is very high.
b) Amorphous form: Coal, Coke, Charcoal (or wood charcoal), animal charcoal (or bone black),
Lamp black, Carbon black, Gas carbon and Petroleum coke are the amorphous form of carbon.
Structure of Diamond: In diamond, the carbon atoms are arranged tetrahedrally (sp3 hybridisation of
C): each C atom is linked to its neighbours by four single covalent bonds. This leads to a three-
dimensional network of covalent bonds. It is because of this, that diamond is very hard and has high
melting and boiling points. Since, all the valence electrons of carbon are used up in forming the covalent
bonds, hence diamond does not conduct electricity.
Structure of Graphite: In graphite, the carbon atoms are arranged in regular hexagons in flat parallel
layers. Each carbon in these layers is bonded to three other by sp2 covalent bonds. This gives some double
bond character to graphite. Each layer is bonded to the adjacent layers by weak vander Waal’s forces. As
a result, each layer can slide over the other easily. It is because of this structure that graphite is soft and
slippery and can act as a lubricant. The presence of double bond character (the presence of delocalised π-
electrons) makes graphite a good conductor of electricity.
 Chemistry : Preparation & Properties of Compounds

1. Oxides: Carbon burnt in air forms two oxides, carbon monoxide, CO and Carbon dioxide CO2.
a) Carbon Monoxide (CO)
Preparation: i) By heating carbon in limited supply of oxygen.
1
C+ O2  CO.
2
ii) By heating oxides of heavy metals e.g. iron, zinc etc with carbon.
Fe2O3 + 3C  2Fe + 3CO
ZnO + C  Zn + CO
Two important industrial fuels water gas and producer gas contain carbon
along with hydrogen and nitrogen, Water gas is obtained by passing
steam over hot coke
C + H2O  CO  H 2
(water gas)

When air is passed over hot coke, producer gas is obtained.

2C + O2 + 4N2  2CO  4N 2
(producer gas)

Properties: i) It is powerful reducing agent and reduces many metal oxides to the
corresponding metals e.g.
Fe2O3 + 3CO  2Fe + 3CO2
CuO + CO  Cu + CO2
ii) It burns in air to give heat and carbon dioxide
1
CO + O2  CO2 + heat.
2
Tests: a) Burns with blue flame
b) A filter paper soaked in platinum or palladium chloride is turned pink,
green or black due to reduction of the chloride by carbon monoxide.
b) Carbon di-oxide (CO2):
Preparation: i) In the lab., it is prepared by the action of acids on carbonates.
CaCO3 + 2HCl  CaCl2 + H2O + CO2
ii) By combustion of carbon
C + O2  CO2
Properties: i) It turns lime water milky and milkiness disappears when CO2 is passed in
excess
Ca(OH)2 + CO2  CaCO3  + H2O
CaCO3 + H2O + CO2  Ca(HCO3)2
ii) Solid carbon dioxide or dry ice is obtained by cooling CO2 under
pressure. It passes to the solid state straight form gaseous state without
liquefying (hence dry ice).
Chemistry : Preparation & Properties of Compounds

iii) A burning candle is put out but burning magnesium continues burning in
the gas jar.
2. Carbides: Carbon combines with more electropositive elements than itself when heated to high
temperature to form carbides. Carbides are of mainly three types.
i) Salt like Carbides: These are the ionic salts containing either C22- (acetylide ion) or C4-
(methanide ion)e.g. CaC2 , Al4 C3, Be2 C.
ii) Covalent Carbides: These are the carbides of non-metals such as silicon and boron. In
such carbides, the atoms of two elements are bonded to each other through covalent bonds.
SiC is also known as Carborundum.
iii) Interstitial Carbides: They are formed by transition elements and consist of metallic
lattices with carbon atoms in the interstices. e.g. tungsten carbide WC, vanadium carbide VC.

8. SILICON
Extraction: Commercial form of silicon is obtained by reduction of SiO2 with C or CaC2 in an electric
furnace. High purity silicon is obtained either from SiCl4 or from SiHCl3. These volatile
compounds are purified by exhaustive fractional distillation and then reduced with very
pure Zn or Mg. The resulting spongy Si is melted, grown into cylindrical single crystal
and then purified by zone refining.
Properties: Silicon is obtained by the reduction of silica. It exists in two allotropic forms: (a)
amorphous and (b) crystalline. The amorphous variety is obtained by heating dry
powdered silica with magnesium.
SiO2  2Mg 
 Si  2MgO
1. The crystalline variety is obtained by heating a finely powdered sand or quartz with
carbon and in electric furnace a small amount of iron is added to prevent the
formation of carborundum (SiC).
SiO2  2C 
 Si  2CO
2. Amorphous silicon is chemically more reactive than crystalline silicon. Amorphous
silicon is brownish powder. It burns brilliantly in oxygen and ignites spontaneously in
fluorine.
Si  O 2 
 SiO 2
Si  2F2 
 SiF4
3. It decomposes steam at red heat. It dissolves in the mixture of HNO3 and HCl.
However, it dissolves readily in alkaline medium.
Si  2H 2 O 
 SiO 2
Si  2F2 
 SiF4
4. It combines with certain metals forming silicides
2Mg  Si 
 Mg 2Si
 Chemistry : Preparation & Properties of Compounds

5. When amorphous silicon is strongly heated, it fuses and on cooling solidifies to the
crystalline form. It is very hard crystallie silicon, does not burn in oxygen but it
readily combines with fluorine. It dissolves in mixture of HNO3 and HF. When fused
with alkali, it gives a silicate.
Na 2 CO3  Si 
 Na 2SiO 3  C
1. Silicones: Silicones are a group of organo silicon polymers. Unlike SiCl4 which on complete
hydrolysis gives SiO2, alkyl substituted chlorosilanes on hydrolysis do not give the expected
silicon compound analogous to ketone but get hydrolysed to long chain polymers or silicones.
While the hydrolysis of trialkylmonochlorosilane yields hexalkyldisiloxane, the
alkyldichlorosilane gives straight chain polymers with active hydroxyl groups at each end of the
chain and trichlorosilane gives complex cross-linked polymers. The chain size is limited by the
size of alkyl group and the amount of cross-linking is regulated by the relative amounts of di- and
tri-methylchlorosilanes
R R R
H3C O O O
R R R
Si Si CH3 R R
O
Si O Si O Si O Si Si
O O O
R O O R
R R R Si
CH3
Linear silicone polymer H3C O O O R R
R R R Cyclic silicone
Cross linked silicone polymer

2. Silicates: Silicates are regarded as the salts of silicic acid, H4SiO4. All the silicates are
comprised of SiO4 units. These units have a tetrahedral structure formed as a result of sp3
hybridistion.
Silicon atom has its complete octet but each oxygen atom is still short of one O
electron to complete its octet. They can complete their octet by taking up 4
electrons from a metal, getting converted to an anion [SiO4]4–. O Si O

O
The [SiO4]4– tetrahedral can be represented in three ways
O

O O O

Si
O
O O
O
O O
4–
Representations of SiO tetrahedra 4
In some silicates, the oxygen atoms of SiO4 units tend to complete their octet by sharing electrons
with other silicon atoms, the oxygen atoms, thus, form bridges of the type Si—O—Si to other
silicon atoms. The number of such bridges can vary from one to four. This leads to the formation
of complex silicates. Any oxygen which fails to pick up electrons from the other silicon atom is
Chemistry : Preparation & Properties of Compounds

not able to complete its octet. The resulting silicate chains are, therefore, negatively charged
anions. The metal cations generally present in silicate minerals are Li+, Na+, K+, Ca2+, Al3+, etc.
Depending upon the way these SiO4 units are linked, silicates of different structure and
complexity are obtained. Some representative types are:

(a) pyrosillicate (b) cyclic silicate (c) chain silicate

(d) sheet silicate

3. Silicon Carbide or (Carborundum)

Preparation: SiC is made commercially by reducing silicon with carbon in an electric
resistance furnace.

SiO2 + 3C  SiC + 2CO

Properties: It is extremely hard and is very difficultly fusible (does not decompose below
2200o C)

It resists most chemical reagents but is oxidised by fused NaOH in contact with
air.

SiC + 4NaOH + 2O2 Na2CO3 + Na2SiO3 + 2H2O

In SiC, carbon and silicon atoms are alternate and are each surrounded
tetrahedrally. It is widely used as an abrasive for grinding, cutting and polishing.

Illustration 5: If you had a mixture of CO and CO2, how would you find out relative proportion of
the two gases in the mixture?

Solution: Method I: Mixture of CO and CO2 is run into Ca(OH)2 solution. CO2 is absorbed by
Ca(OH)2 and thus residual volume will be that of CO.
 Chemistry : Preparation & Properties of Compounds

Ca(OH)2 + CO2  CaCO3 + H2O

Method II: Mixture of CO and CO2 is passed over heated charcoal.

CO2 + C  2CO

Increase in volume will be due to CO2. By measuring total volume after passing over
heated charcoal, composition of mixture of CO and CO2 can be determined.

9. NITROGEN

Preparation: 1. NH 4 NO 2   N 2  2H 2 O
Since ammonium nitrite is very unstable, it cannot be kept as such. Hence nitrogen is
usually prepared by heating a mixture of ammonium chloride and sodium nitrite.


NH 4 Cl  NaNO 2   NH 4 NO 2  NaCl

NH 4 NO 2   N 2  2H 2 O

2. By heating ammonium dichromate: Ammonium dichromate on heating decomposes

to give nitrogen gas.

(NH 4 ) 2 Cr2 O 7   N 2  4H 2O  Cr2O 3

2NH3  3CuO   N 2 (g)  3Cu  3H 2 O
NH 2 CONH 2  2HNO 2 
 2N 2  CO 2  3H 2O
NaNO2  HCl 
 NaCl  HNO 2
NH 2 CONH 2  2HNO 2 
 3H 2O  CO 2  2N 2
Fixation of Atomspheric nitrogen in cyanamide fertilizer (The cyanamide process)
Nitrogen is also fixed as calcium cyanamide on heating it with calcium carbide at 1000°C
in an electric furnace.
electric furnace
CaC 2  N 2   CaCN 2 C
calcium carbide calcium cyanamide

The mixture of calcium cyanamide and carbon (trade name nitrolim) is an important
fertilizer.
Calcium cyanamide may also be used as a source of ammonia. The ammonia so produced
can be converted into useful fertilizers. Calcium cyanamide is decomposed by water to
give ammonia.
CaCN 2  3H 2 O 
 CaCO3  2NH 3
2NH3  H 2SO4 
 (NH 4 ) 2 SO4
2NH3  H 2SO 4 
 (NH 4 ) 2 SO 4
P2 O5  6NH 3  3H 2O 
 2(NH 4 ) 3 PO 4
Chemistry : Preparation & Properties of Compounds

CaCl 2  8NH 2 
 CaCl2 .8NH 3

1. Oxides of Nitrogen
Formula Name Colour Remarks
N2O Nitrous oxides Colourless Rather unreactive
NO Nitric oxide Colourless Moderately reactive
N2O3 Dinitrogen trioxide Dark blue Extensively dissociated as gas
NO2 Nitrogen dioxide Brown Moderately reactive
Extensively dissociated to NO2 as gas
N2O4 Dinitrogen tetroxide Colourless
and partly as liquid
N2O5 Dnitrogen pentoxide Colourless unstable as gas; ionic solid
Not well characterized and quite
NO3, N2O6
unstable

Preparation: 1. N2O is obtained genrally by heating NH4 NO3:

NH 4 NO3 
 N 2 O  2H 2 O
N2O is also known as laughing gas because it induces laughter mixed with
N2. It is used as an anesthetic by dentists
2. NO is best prepared by the reduction of 8M HNO3 with reducing agents like
Cu or by reduction of nitrous acid or nitrites by Fe2+ of I– ions:
3Cu  8HNO3 
 2Cu(NO 3 ) 2  2NO  4H 2O

2NaNO 2  2FeSO 4  3H 2SO 4 


2NaHSO 4  Fe 2 (SO 4 )3  2NO  2H 2O

2NaNO 2  2NaI  4H 2SO 4 

 4NaHSO 4  2NO I 2  2H 2O
NO is formed as an intermediate in the manufacture of nitric acid by
oxidation of NH3.
3. N2O3 is obtained as an intense blue liquid or a pale blue solid on cooling an
equimolar mixture of NO and NO2:
NO  NO 2 
 N 2 O3
On warming, its colour fades due to its dissociation into these two oxides.
4. NO2 can be prepared by reduction of conc. HNO3 with Cu or by heating
heavy metal nitrates:
Cu  4HNO3 
 Cu(NO3 )2  2NO2  2H 2O
2Pb(NO 3 ) 2 
 2PbO  4NO 2  O 2
5. N2O5 is an anhydride of HNO3. It is best prepared by dehydrating HNO3 with
P4O10 at low temperatures:
250 K
4HNO3  P4O10   2N 2O5  4HPO3
 Chemistry : Preparation & Properties of Compounds

Properties: Oxides of nitrogen are all oxidizing agents. N2O even support the combustion of
S and P. NO which is thermally more stable, supports the combustion of Mg and
P but not of S. Sulphur flame is not hot enough to decompose it N2O and NO are
neutral, while the other oxides are acidic.
Liquid N2O4 undergoes self-ionisation to form NO+ and NO3– ions and therefore,
it has been extensively studied as a non-aqueous solvent. Solid N2 O5 exists in the
ionic form, NO 2 NO 3– . In the gaseous form, the discrete N2O5 molecules have a
N—O—N bond angle close to 180°.
2. Oxyacids: The most important oxo-acid of nitrogen is nitric acid HNO3
Preparation: i) In the lab, it is prepared by heating NaNO3 or KNO3 with conc. sulphuric
acid in a glass retort.
NaNO3 + H2SO4  NaHSO4 + HNO3
ii) It is manufactured by the catalytic oxidation of ammonia and the process is
known as Ostwald process
4NH3 + 5O2 Pt

/ Rh
 4NO + 6H2O

2NO + O2 1120K
 2NO2
3NO2 + H2O  2HNO3 + NO.
Properties: i) In aqueous solution, nitric acid is a strong acid and dissociates to give
hydronium and nitrate ions.
HNO3 + H2O H3O+ + NO3-
ii) Action on metals: Conc. nitric acid is a strong oxidising agent and attacks
most metals except noble metals such as gold and platinum. The product of
reduction depend upon the concentration of the acid, temp and the nature of
the material undergoing oxidation. With dilute nitric acid the principle
product is nitric oxide NO and with conc. nitric acid, the principle product is
N(IV) oxides
3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O
(dilute)
Cu + 4HNO3  Cu(NO3)2 + 2NO2 + 2H2O
Zinc, which is a more powerful reducing agent than copper, reacts with dilute
nitric acid to give ammonium nitrate.
4Zn + 10HNO3  4Zn(NO3)2 + NH4NO3 + 3H2O
Nitric acid also oxidises non - metals and their compounds. Iodine is oxidised to
iodic acid, carbon to carbon dioxide, sulphur to H2SO3 and H2SO4 and
phosphorus to phosphoric acid. Nitric acid is reduced to nitrogen dioxide (NO2)
I2 + 10HNO3  2HIO3 + 10NO2 + 4H2O
C + 4HNO3  CO2 + 2H2O + 4NO2
1/8 S8 + 6HNO3  H2SO4 + 6NO2 + 2H2O
P4 + 20HNO3  4H3 PO4 + 20NO2 + 4H2O
3. Ammonia (NH3)
Preparation: 1. By heating ammonium salt with a base, e.g. slaked lime (lab. method).
2NH 4 Cl  Ca(OH) 2 
 CaCl2  2H 2O  2NH 3 
The gas so formed is dried with quick lime, CaO.
Chemistry : Preparation & Properties of Compounds

2. By the action of water on nitrides of Ca, Mg and Al

Ca 3 N 2  6H 2 O 
 3Ca(OH) 2  2NH 3
AlN  3H 2 O 
 Al(OH)3  NH 3
3. Cyanamide process (commercial method).
800 – 1000 C
CaO  3C   CaC 2  CO 
CaC2  N 2 
 CaCN 2  C
Cal. cyanamide

Nitro lim
3 atm.
CaCN 2  3H 2 O (steam)   CaCO 3  2NH 3
4. By Haber’s process (from air). Commerical method.
N 2  3H 2 2NH 3
Conditions: Catalyst : Fe + Mo; temperature 450°C; Pressure 200–250 atm.
Properties: i) Basic nature: Its aq. solution is basic in nature and turns red litmus blue.
NH 3  H 2 O NH 4  OH –
ii) Reaction with halogens:
Chlorine : 8NH 3  3Cl 2 
 6NH 4Cl  N 2
Excess of chlorine : NH 3  3Cl2 
 NCl3  3HCl
Bromine : 8NH 3  3Br2 
 6NH 4 Br  N 2
Excess of bromine : NH 3  3Br2 
 NBr3  3HBr
Iodine : 2NH3  3l2 
 NH 3 Nl3  3Hl
Nitrogen
tri iodide ammonate

NH 3.Nl3 explodes in dry state

8NH 3 .Nl3 
 6NH 4l  9l 2  6N 2
iii) Complex formation: Due to the presence of lone pair of electrons on
nitrogen, it acts as Lewis-base. Thus it forms co-ordinate linkage with metal
ions and these ammonia compounds find use in qualitative analysis.
Ag   NH 3 
[Ag(NH 3 ) 2 ]

Cu 2   4NH 3 
[Cu(NH 3 ) 4 ]2 

Cd 2   4NH 3 
[Cd(NH 3 ) 4 ]2 
iv) Precipitation of heavy metals ions from the aq. solution of their salts:
Heavy metal ions like Fe3+, Al3+, Cr3+ etc. are precipitated from their aqueous
salt solution.
FeCl3  3NH 4OH 
 Fe(OH)3  3NH 4Cl
Brown ppt.
 Chemistry : Preparation & Properties of Compounds

AlCl3  3NH 4 OH 
 Al(OH)3  3NH 4Cl
White ppt.

CrCl3  3NH 4 OH 
 Cr(OH) 3  3NH 4Cl
Green ppt.

Liquid Ammonia as a Non-aqueous Solvent

Liquid ammonia functions as a good solvent for many substances and many types of reactions. In this
behaviour, it resembles water as a solvent. Both are self-ionising, the difference being in the lower degree
of ionization of ammonia:

2NH3 NH 4 NH 2–
2H 2 O H3 O  OH –
All those substances which dissolve in liquid ammonia to give NH 4 ions are acids and those which give
amide ions, NH 2– , are bases. Thus, NH4Cl, NH4NO3 are acids and NaNH2 is a base in liquid ammonia.
Acid-base neutralisation reaction in liquid ammonia, thus, can be a reaction giving a salt and the solvent.
NH 4 Cl NH 4  Cl –
NaNH 2 Na   NH 2–
NH 3
NH 4Cl  NaNH 2   NaCl  2NH 3
H2O
HCl  NaOH   NaCl  H 2O
Similarly,
NH3
2NH 4Cl  PbNH   PbCl 2  3NH3
lead imide
NH 3
3NH 4Cl  AlN   AlCl3  4NH 3
Alu min ium nitride

Thus, we see that imides like PbNH, and nitrides such as AlN, also function as bases in liquid ammonia.
Liquid ammonia is a basic solvent because it can easily accept a proton.

10. PHOSPHORUS
Extraction: It is a very reactive element, so it does not occur free in nature. Different ores are:
Phosphorite : Ca3 (PO4)2
Chlorapatite: 3Ca3 (PO4)2 . CaCl2
Phosphorous is obtained by heating bone ash or phosphorite rock Ca3(PO4)2 with sand
(SiO2) and coke (c) in an electric furnance at about 1770 K. The reactions are as the
following:
2Ca 3 (PO 4 ) 2  6SiO2 
 P4 O10  6CaSiO 3

P4 O10  10C 
P4 (v)  10CO

Properties: i) Reaction with oxygen: Yellow phosphorus readily catches fire in air giving dense
white fumes of phosphorus pentaoxide. Red phosphorus combines with oxygen only
on heating. Both of them form either phosphorus trioxide or phosphorus pentaoxide.
Chemistry : Preparation & Properties of Compounds

heat
P4  3O 2  2P O
2 3
red phosphorous phosphorus trioxide

heat
P4  5O2  2P O
2 5
red phosphorus phosphorus pentoxide

ii) Reaction with chlorine: Phosphorus reacts with chlorine gas to form tri and
pentachlorides. Yellow phosphorus reacts violently at room temperature, whereas red
phosphorus reacts on heating only.
P4  6Cl 2 
 4PCl 3
phosphorus trichloride

P4  10Cl 2 
 4PCl 5
phosphorus pentachloride

iii) Reaction with alkalies (sodium/potassium hydroxide): Yellow phosphorus

dissolves in caustic soda on boiling under an inert atmosphere liberating phosphine.
boil
4P  3NaOH  3H 2O  PH 3 (g)  3NaH 2 PO2
yellow phosphorus phosphine sodium hypophosphite

iv) Reaction with nitric acid

Phosphorus gets oxidized by nitric acid to phosphoric acid.
P4  20HNO3 
 4H3PO4  20NO 2  4H 2O
phosphoric acid

v) With metals
Phosphorus reacts with metals forming phosphides. For example
6Mg  P4 
 2Mg P 3 2
magnesium phosphide

Allotropes: Phosphorus exists in the following five different allotropic forms.

i) White (yellow) phosphorus is extremely reactive.
ii) Below 800°C, its vapor density corresponds to the formula P4. Above 1700°C, it
exists as P2.
iii) Due to is low ignition temperature (~30°C), it undergoes P
oxidation in the presence of air which slowly raises its
temperature and after a few moments it catches fire
spontaneously. Due to this reason, it is stored under
water. P P

Red Phosphorus: Red phosphorus is stable allotrope at room temperature. Red

phosphorus is formed by heating white phosphorus in the absence of air at about 250°C. It
is not poisonous. It is safe to handle because it does not burn spontaneously at room
temperature.
 Chemistry : Preparation & Properties of Compounds

P P

P P P P

P P
Structure of red phosphorus

1. Oxides: Two important oxides of phosphorus are :

1. Phosphorus trioxide - P4O6, also called phosphorous oxide or phosphorus (III) oxide

2. Phosphorus pentoxide - P4O10, also called as phosphoric oxide or phosphorus (V) oxide

a) Phosphorus trioxide (P4O6):

Preparation: Prepared by burning white phosphorus in limited supply of air

P4 + 3O2  P4O6

Properties: i) On heating in air, it forms phosphorus (V) oxide

P4 O6 + 2O2  P4 O10

ii) Reacts with water as follows :

P4 O6 + 6H2 O (cold)  4H3 PO3

Phosphorous acid

P4 O6 + 6H2 O (hot)  3H3PO4 + PH3

Chemistry : Preparation & Properties of Compounds

b) Phosphorus Pentoxide (P4O10)

Preparation: Prepared by burning white phosphorus in excess of air or oxygen
P4 + 502  P4O10
Properties: i) Because of its great affinity for water, it acts as a dehydrating agent.
2HNO3 + P4O10  2N2O5 + 4HPO3
2H2SO4 + P4O10  2SO3 + 4HPO3
ii) Reacts with water as follows:
P4 O10 + 2H2O (cold)  4HPO3
P4 O10 + 6H2O (hot)  4H3PO4
Structure of P4O6 & P4O10
P O

O 127° O 143 pm
O P

P
P O 102° O
O 123°
100° O 160 pm
P P
O 166 pm O P
O
O O
P
O O

2. Oxoacids of Phosphorus : Phosphorus forms two series of oxoacids, the phosphoric and
the phosphorous acids. The oxidation state of phosphorus is +5 in phosphoric acids whereas it is
+3 in phosphorous acids.
Oxoacids of phosphorus and their properties

Acid Nature Preparation Anion Remarks

–
H 3 PO 2 or crystalline white P4 + alkali H 2 PO 2 strongly reducing,
H 2 P(OH)O white solid hypophosphite monobasic pK ~ 2
Hypophosphorus
H 3 PO3 or deliquescent P4O6 or PCl3 + H2 O H 2 PO3– , HPO32– reducing, but slow,
HPO(OH) 2 colourless phosphite dibasic pK1 ~ 2
Orthophosphorus solid pK 2 ~ 6
H4P2O3 white solid PCl3 + H3PO3 H 2 P2 O52 – reducing, dibasic
Pyrophosphorus pyrophosphite
H4P2O6 white solid red P + alkali P2 O 64 – hypophosphate not reducing or
Hypophosphoric oxidizing, tetrabasic
pK1 ~ 2
H3PO4 white solid P4O10 + H2O H 2 PO4– , HPO 42– , not oxidizing, tribasic
Orthophosphoric 3–
PO , phosphate
4

H4P2O7 colourless heat phosphates or P2 O 74 – pyrophosphate tetrabasic pK1 ~ 2

Pyrophosphoric solid phosphoric acid
HPO3 deliquescent heat H3PO4 to 600 K
Metaphosphoric solid
 Chemistry : Preparation & Properties of Compounds

A large number of condensed phosphoric acids or their salts are known which have rings or chains of PO4
tetrahedrally linked through P-O-P linkages, e.g., di or pyrophosphoric acid, H4P2O7 and triphosphoric
acid, H5P3O10.
O O O O O

HO P O P OH HO P O P O P OH

OH OH OH OH OH
Diphosphoric acid Triphosphoric acid

Sodium salt of triphosphoric acid, Na5P3O10, forms stable chelate complexes with alkaline earth metal
cations. It is, therefore, used in water softerning. What is known as metaphosphoric acid and given the
empirical formula HPO3 is in fact a mixture of cyclo-polyphosphoric acids containing —P—O—P—O—
linkages. Two important cyclo-polyphosphoric acids are cyclotriphosphoric acid, H3P3O9 and cyclo-
tetraphosphoric acid, H4P4O12.
O O

HO O HO P O P OH
P
O O O O
O O
P P HO P O P OH
O OH
HO
O O
cyclo-triphosphoric acid Cyclo-tetraphosphoric acid
3. Phosphine, PH3: Phosphine, PH3, is the most stable hydride of phosphorus. It is intermediate
in thermal stability between ammonia and arsine.
Preparation 1. Hydrolysis of metal phosphides such as AlP or Ca3P2:
Ca 3 P2  6H 2 O 
 2PH 3  3Ca(OH) 2
2. Pyrolysis of phosphorous acid at 480 – 485 K:
4H 3 PO3 
 PH 3  3H 3 PO 4
3. Alkaline hydrolysis of phosphonium iodide:
PH 4 I  KOH 
 PH 3  KI  H 2O
4. Alkaline hydrolysis of white phosphorus (industrial process):
P4  3KOH  3H 2 O 
 PH 3  3KH 2 PO 2
Phosphine is a colourless, extremely poisonous gas having a faint garlic
odour. As the P–H bond is not polar enough to form P–H----P or P-H----O
bonds, unlike ammonia, phosphine is not associated in the liquid state and is
much less soluble in water. In contrast to the basic nature of solutions of
ammonia in water, aqueous solutions of phosphine are neutral, which is due
to the much weaker tendency of PH3 to protonate in water. However, it does
react with HI to form phosphonium iodide:
PH3  HI 
 PH 4 I
Pure phosphine ignites in air at about 435 K, but when contaminated with
traces of P2H4 it is spontaneously inflammable:
Chemistry : Preparation & Properties of Compounds

PH3  2O 2 
 H3 PO 4
Illustration 6 : Explain briefly why the hydrolysis of NCl3 and PCl3 yield different types of
products.
Solution: In the hydrolysis of PCl3 , a four coordinate intermediate is formed, it hydrolyses
forming H 3 PO3 . Due to the non-availability of d-orbitals, nitrogen cannot form this
intermediate so the hydrolysis of NCl3 takes place by a different mechanism. In this
mechanism, water attacks the chlorine atom of NCl3 resulting in the formation of
NH 3 and hypochlorous acid.

11. OXYGEN
Extraction: Oxygen is separated from air on a large scale by the fractional distillation of liquid air. It
is obtained as a by-product along with hydrogen during electrolysis of water for the
manufacture of heavy water. Ordinary water, H2O, electrolyses faster with the result that
residual water is richer in D2 O. In laboratory, O2 can be prepared by thermal
decomposition of KClO3 in presence of MnO2 as a catalyst:
heat
2KClO3 
MnO 2 catalyst
 2KCl  3O 2
Properties: 1. Acidic oxides
SO 2  H 2 O 
 H 2SO3
SO3  H 2O 
 H 2SO 4
2. Basic oxides
CaO  H 2O 
 Ca(OH) 2
3. Amphoteric oxides: Amphoteric oxides are the metallic oxides which show both
basic as well as acidic properties. When they react with an acid, they produces salt
and water, thus, showing basic properties. While reacting with alkalies to form salt
and water they show acidic properties, e.g.,
ZnO  2HCl 
 ZnCl2  H 2 O (basic nature)

ZnO  2NaOH 
 Na 2 ZnO 2  H 2O (acidic nature)

Al2 O3  2NaOH 
 2NaAlO 2  H 2O (acidic nature)
4. Basic oxides
Fe3O4  8HCl 
 2FeCl3  FeCl2  4H 2 O
 Chemistry : Preparation & Properties of Compounds

1. Ozone (O3)

Preparation: It is prepared by passing a silent electric discharge through dry, pure and cold
oxygen in special type of apparatus called ozoniser.

3O2 2O3 {H   68 Kcal}

Properties: i) It is pale-blue gas (b.p. –111°C) with a characteristic fishy smell. It

condenses at –120°C as a dark blue liquid. It is poisonous gas; Ozone is a
dangerous gas because of its destructive action on body tissues and being
explosive. Ozone is heavier than air and slightly soluble in water. It turns
starch iodide paper blue.

ii) Decomposition. Ozonised oxygen decomposes slowly, while pure ozone

decomposes with an explosive violence.

2O3 
 3O 2

iii) Oxidation reactions. Since ozone can easily lose oxygen atom (nascent
oxygen), it acts as a powerful oxidising agent than the molecular oxygen.

O3 
 O2  [O]

O3  H 2O  2e – 
 2OH –  O2
(neutral medium)

O3  2H   2e – 
 H 2O  O 2

a) Oxidation of lead sulphide (black) to lead sulphate (white)

O3 
 O2  [O]  4

PbS  4[O] 
 PbSO4
PbS  4O3  PbSO 4  4O 2

b) H 2S  O 3 
 H 2O  S  O 2

c) 2KI  H 2 O  O 3 
 2KOH  I 2  O 2

Note that KI is not oxidized to iodine by ozone in presence of FeSO4

d) 2HBr  O 3 
 H 2 O  Br2  O 2

e) KNO2  O3 
 KNO3  O 2

f) 2FeSO 4  H 2SO4  O3 
 Fe 2 (SO4 )3  H 2O  O 2
g) 2K 4 [Fe(CN) 6 ]  H 2O  O3 
 2 K 3[Fe(CN) 6 ]  2KOH  O2
Pot. ferrocyanide Pot. ferricyanide
Chemistry : Preparation & Properties of Compounds

h) 2K 2 MnO4  H 2 O  O3 
 2KMnO 4  2KOH  O2
Pot. manganate Pot. permanganate

i) 2Ag  O3 
 Ag 2O  O 2
Silver oxide may be reduced back to Ag by O3.
Ag 2 O  O3 
 2Ag  2O2
j) 3SO2  O3 
 3SO3
3SnCl2  6HCl  O 3 
 3SnCl 4  3H 2O
iv) Reducing reactions. Ozone reduces certain peroxides.
a) H 2 O2  O3 
 H 2 O  2O 2
b) BaO 2  O 3 
 BaO  2O 2
c) Ag 2 O  O3 
 2Ag  2O2
v) Addition to olefins and acetylenes to form ozonides which are decomposed
by zinc dust and water to form carbonyl compounds (ozonolysis).
O
H2 C CH2
H 2 C  CH 2  O3 
 
 CH 2 O  CH 2O  H 2O 2
O O
Ethylene ozonide Formaldehyde (2 moles)

2. Hydrogen Peroxide (H2O2)

Preparation i) Lab Method: It is prepared by the action of cold, dilute sulphuric acid on
sodium or barium peroxide
Na2O2 (s) + H2SO4(aq)  H2O2(aq) + Na2SO4(s)
BaO2 .8H2O + H2SO4(aq)  H2O2 (aq) + BaSO4(s)
Anhydrous barium oxide is not used because the precipitated BaSO4 forms a
protective layer on the unreacted barium peroxide and thus prevents its
further participation in the reaction. However it can be overcome by using
phosphoric acid.
ii) By Electrolysis: It can also be prepared by the hydrolysis of
peroxydisulphuric acid which is obtained by the electrolytic oxidation of
sulphuric acid
Electrolysis
2H2SO4(aq)  H2S2O8 (aq) + H2(g)
2H 2O
H2S2O8(aq)  2H2 SO4(aq) + H2O2(aq)
iii) By the auto-oxidation of 2-ethyl anthraquinol. The net reaction is a catalytic
union of H2 and O2 to yield hydrogen peroxide.
O2 (air )
2-ethyl anthraquinol H 2 (Pd)
oxidised product + H2O2
 Chemistry : Preparation & Properties of Compounds

Properties: i) Unstable liquid, decomposes to give water and dioxygen and the reaction is slow
in the absence of catalyst. It is catalysed by certain metal ions, metal powders
and metal oxides.

2H2O2 (l)  2H2O (l) + O2 (g)

ii) It acts as oxidant as well as reductant in both acid and alkaline medium. On
the whole, hydrogen peroxide is a very powerful oxidising agent and poor
reducing agent. Some typical oxidation and reduction reaction of hydrogen
peroxide are as follows :

(A) As oxidising agent

In acidic medium : H2O2 + 2H+ + 2e-  2H2O

i) PbS  4H 2O 2 
 PbSO4  4H 2O
Lead sulphide Lead sulphate

ii) 2KI  H 2 O 2 
 2KOH  I 2

or 2KI  H 2SO4  H 2O2 

 K 2SO 4  2H 2 O  I2

iii) 2K 4 [Fe(CN) 6 ]  H 2 O2 
 2K 3[Fe(CN) 6 ] 2KOH
Pot. ferrocyanide Pot. ferricyanide

iv) K 2Cr2 O7  H 2SO 4  4H 2O 2 

 K 2SO 4  2CrO 5  5H 2O
Pot.dichromate Chromium peroxide
( blue)

In basic medium : H2O2 + OH- + 2e-  3OH—

Pyrogallol
i) 2HCHO  H 2O 2   2HCOOH  H 2
Formaldehyde Formic acid

(B) As reducing agent

In acidic medium : H2O2  2H+ + O2 + 2e-

i) 2KMnO4  3H 2SO 4  5H 2O 2 
 K 2SO4  2MnSO 4  8H 2O  5O 2
ii) K 2 Cr2O7  4H 2SO 4  3H 2O2 
 K 2SO4  Cr2 (SO 4 )3  7H 2 O  3O2
iii) O3  H 2O 2 
 H 2O  2O 2

In basic medium: H2O2 + 2OH-  2H2O + O2 + 2e-

i) 2Fe2+ + H2O2 + 2H+  2Fe3+ + 2H2O
ii) 2MnO4- + 5H2O2 + 6H+  2Mn2+ + 8H2O + 5O2
iii) Mn2+ + H2O2  Mn+4 + 2OH-
Chemistry : Preparation & Properties of Compounds

iv) 2Fe3+ + H2O2 + 2OH-  2Fe2+ + 2H2O + O2

The oxidising property of hydrogen peroxide is put to use in the restoration of
old paintings, where the original white lead paint has been converted to black
PbS by the H2S in the atmosphere. Hydrogen peroxide oxidises the black PbS
into white PbSO4.
PbS(s) + 4H2O2 (aq)  PbSO 4 (s) + 4H2O
black white
Tests: a) It liberates iodine from potassium iodide in presence of ferrous sulphate
b) Acidified solution of dichromate ion forms a deep blue colour with H2O2 due
to the formation of CrO5. , The blue colour fades away gradually due to
decomposition of CrO5 into Cr3+ ions and oxygen
Cr2O72- + 4H2O2 + 2H+  2CrO5 +5H2O
c) With a solution of titanium oxide in conc.H2SO4, it gives orange colour due
to the formation of pertitanic acid.
Ti4+ + H2O2 + 2H2O  H 2TiO 4 + 4H+
pertitanic acid

12. SULPHUR
Extraction: The most important method for the extraction of sulphur from native deposits is the
Frasch Process. It consists of boring a hole from the ground surface to the sulphur bearing
calcite deposit and lowering three concentric pipes to the ore bed. Superheated water, 438
K, is forced down the outer pipe into the ore bed where it melts the sulphur. Compressed
hot air is pumped down through the innermost pipe when a frothy mixture of molten
sulphur, water and air is forced to the surface through the middle pipe. As it comes out
from the well, sulphur has a purity of 99.5–99.9% and virtually does not contains As, Se
or Te.

Properties: Sulphur displays allotropy to a remarkable degree, existing both in a variety of different
molecular and physical forms. The molecular species, viz., S2, S4, S6 and S8 are in
equilibrium in gaseous sulphur, their proportions varying with the temperature. The
commonest and the most stable allotrop of sulphur at room temperature is known as
rhombic sulphur or α-sulphur, S . In rhombic sulpur, S8 rings are arranged in a way that
gives a rhombic crystal structure. AT 369 K, rhombic sulphur gets converted into
monoclinic sulphur or β-sulphur, S . In monoclinic sulphur, S8 rings are arranged in a
monoclinic structure. It is stable between 369 and 392 K. AT 392 K it melts to produce a
liquid containing S8 molecules, S. At about 433 K the S8 rings open up and join together
into long spiral-chain molecules resulting in a thick viscous liquid  -sulphur, S. Liquid
sulphur boils at 718 K to give gaseous sulphur containing S8 molecules, which dissociate
to S6, S4, S2 and finally to sulphur atoms at 2273 K. If liquid sulphur at 463 K is poured
into cold water, plastic sulphur or -sulphur is formed. The allotropy of sulphur as a
function of temperature is summarized as follows:
 Chemistry : Preparation & Properties of Compounds

Cold water
  S
369 K 392 K 433 K 718 K
S   S   S   S   S8 (g) 
 S6
1273 K 2273 K

 S4   S2  S

1. Hydrogen Sulphide (H2S)

Preparation: H2S is prepared in the laboratory by treating FeS with dilue HCl in Kipp’s
apparatus.
Properties: 1. Hydrogen sulphide is the only thermodynamically stable sulphide. It is a foul
smelling and poisonous gas
2. In aqueous solution H2S is a weak acid. At 293 K, it dissociates as
H 2S (aq) H  (aq)  SH – (aq); pKa1  6.88  0.02

SH – (aq) H  (aq)  S2– (aq); pKa 2  14.15  0.05

2. Oxides
a) Sulphur dioxide (SO2)
Preparation: It is formed by burning sulphur in air or roasting metal sulphides in the
presence of air
S8 + 8O2  8 SO2
4FeS2 + 11O2  2Fe2O3 + 8SO2
Properties : 1. As reducing agent
i) Action on halogens :
SO2 + Cl2 +2H2O  H2SO4 + 2HCl
ii) Action on FeCl3 :
2FeCl3 + SO2 + 2H2O  H2SO4 + 2FeCl2 + 2HCl
2. Reaction with acidified KMnO4 :
2KMnO4 + 5SO2 + 2H2O  K2SO4 + 2MnSO4 + 2H2SO4
3. Reaction with acidified K2Cr2O7 :
K2Cr2O7 + 3SO2 + H2SO4  K2SO4 + Cr2(SO4)3 + H2O
4. Oxidising property
i) 2H2S + SO2  2H2 O + S
ii) SO2 + 2Mg  2MgO + S
b) Sulphur trioxide (SO3)
Preparation: i) By catalytic oxidation of sulphur dioxide
V2O5 , 700K
2SO2(g) + O2(g) 2SO3(g)
ii) By dehydration of H2SO4
H2SO4 P
2 O5
 SO3 + H2O.
heat
Chemistry : Preparation & Properties of Compounds

3. Sulphurous Acid (H2SO3): Sulphurous acid, H2SO3, is known only in solution. It exists
mainly as a hydrate of sulphur dioxide, SO2. 7H2O. Two series of salts, the bisulphites, containing
HSO3– , and sulphites containing SO32– ions are well known.
Properties: 1. It owes its reducing nature to the ease with which it can get oxidized to
sulphuric acid. It reduces I2 to HI, KMnO4 to MnSO4 and K2Cr2 O7 to Cr2
(SO4)3:
H 2SO3  H 2 O  I 2 
 H 2SO 4  2HI
2KMnO 4  5SO 2  2H 2O 
 K 2SO 4  2MnSO 4  2H 2SO 4
K 2Cr2O7  3SO 2  H 2SO4 
 K 2SO 4  Cr2 (SO 4 )3  H 2O
2. In the presence of strong reducing agents like H2S,it can behave as an
oxidising agent.
2H 2S  H 2SO3 
 3H 2O  3S
4. Sulphuric acid or Oil of Vitriol (H2SO4)
Preparation: Contact process - Sulphur trioxide from the catalytic chamber is passed through
sulphuric acid to obtain oleum, H2S2O7. Dilution of oleum with water gives
H2SO4 of the desired concentration.
SO3 + H2SO4  H2S2O7
H2S2O7 + H2O  2H2SO4
Properties: Chemical reactions of sulphuric acid are as a result of the following characteristics :
a) Low volatility
b) Strong acidic character
c) Strong affinity to water
d) Ability to act as an oxidising agent.
i) Low volatility of sulphuric acid is put to use in the manufacture of more
volatile acids from their salts.
2MX + H2SO4  2HX + M2 SO4.
- - -
(X = F , Cl , NO3 )
ii) Conc. sulphuric acid is a strong dehydrating agent. Many wet gases can be
dried by passage through a sulphuric acid bubbler provided the gases do not
react with the acid. Sulphuric acid removes water from organic compounds as
shown by its charring action on carbohydrates.
C12H22O11 + 11H2SO4  12C + 11H2SO4 + 11H2O.
iii) Hot conc. sulphuric acid is a moderately strong oxidising agent. In this
respect, it is intermediate between phosphoric and nitric acids. Both metals
and non-metals are oxidised by conc. sulphuric acid, which is reduced to SO2.
C + H2SO4  CO2 + 2SO2 + 2H2O
Cu + 2H2SO4  CuSO4 + SO2 + 2H2O
5. Thiosulphuric Acid (H2S2O3): It has never been isolated but its salts are well known which
contain the thiosulphate ion, S2 O 32– . The best known thiosulphate is the sodium salt, Na2S2O3.
5H2O.
 Chemistry : Preparation & Properties of Compounds

Preparation: It is obtained by boiling a solution of sodium sulphite with sulphur followed by

filtration and crystalliastion.
Na 2SO3  S 
 Na 2S2O 3
Properties: 1. Sodium thiosulphate is a colourless, crystalline solid highly soluble in water and
commercially known as hypo. The thiosulphate ion is unstable in the
presence of acids breaking to give H2O, SO2 and S.
Na 2S2 O3  2HCl 
 2NaCl  SO 2  S  H 2 O
2. It functions as a reducing agent, reducing chlorine to chloride. This reaction
is utilized for removing excess chlorine from bleached fabrics.
Na 2S2 O3  4Cl2  5H 2 O 
 2NaHSO 4  8HCl
3. The milder oxidising agents iodine behaves rather differently giving sodium
tetrathionate instead of Na2 SO4, though it is also converted into iodide.
Na 2S2 O3  I 2 
 2NaI  Na 2S4O 6
sodium tetrathionate

This reaction is used in iodometric titrations for determination of copper.

4. Sodium thiosulphate is used in photography for `fixing’ the negative. It
removes the unreacted light sensitive silver bromide from photographic plates
to avoid further reaction of light.
AgBr  2Na 2S2 O3 
 Na 3 [Ag(S2 O 3 ) 2 ]  NaBr
Illustration 7: Why is SO3 not dissolved in water directly during the preparation of sulphuric
acid?
Solution: In the preparation of H 2SO4 , SO3 is not dissolved directly in H 2 O as it -reacts
violently with water forming a dense white fog of dilute sulphuric acid.

13. HALOGENS
a) Fluorine
Extraction: Fluorine the only practicable method of preparing fluorine gas is Moissan’s
original procedure based on the electrolysis of KF dissolved in anhydrous HF.
He electrolysed a cooled solution of KF in anhydrous liquid HF at 250 K using
platinum-iridium electrodes sealed with fluorspar caps in a platinum U-tube. In
this reaction, the actual electrolyte is KF while HF acts as an ionizing solvent, F2
is evolved at the anode and H2 at the cathode as indicated below:
KF K   F–

At the anode
F – 
Fe
F  F 
 F2

At the cathode
K   e 
K
2K  2HF 
 2KF  H 2 
Chemistry : Preparation & Properties of Compounds

Moisson’s original method has been modified. In place of the expensive Pt/Ir
alloy, cells made of copper, steel or Monel metal, which is a nickel-copper alloy,
have been used. Anode is a carbon rod impregnated with copper to render it inert
and cathode is made of steel or copper. A mixture of KF and HF in the molar
ratio of 1 : 1 or 1 : 2 is used as electrolyte.
Properties of Fluorine: Pale greenish yellow gas, which is highly poisonous and having pungent
odour. It is heavier than air. Electronegativity value is 4.0 (Pauling’s scale).
Chemical: 3H 2 O  3F2 
 6HF  O 3 
2H 2O  2F2 
 4HF  O2 
2Al  3F2 
 2AlF3
Copper does not appreciably react with F2 at this temperature because of CuF2
layer formation on it.
NaOH  2F2 
NaF  O 2  2H 2O

2NaOH  2F2 
 F2 O  2NaF  H 2O

I 2  5F2 
 2IF5

3F2  4HBr 
 4HF  Br2  2BrF

3F2  4HI 
 4HF  I 2  2IF

SiO2  2F2 
 SiF4  O 2
Strongest oxidising behaviour of F2
KClO3  F2  H 2 O 
 2HF  KClO 4

K 2 CO3  F2  H 2 O 
 2HF  K 2CO 4

K 2SO4  F2 
 K 2S2O8  2KF
b) Chlorine: Electrolysis of molten sodium chloride gives chlorine and sodium. It is also produced
by the electrolysis of aqueous HCl.
Properties of Cl2: Greenish yellow gas having a choking and irritating smell, 2.5 times heavier
than air, liquefied to a yellow liquid by compressing it at 15°C. Electronegativity is 3.0 (Pauling’s
scale).
Chemical: Arsenic catches fire in Cl2 but P burns.
2As  3Cl2 
 2As Cl3
2Sb  3Cl2 
 2SbCl3
2P  3Cl2 
 2PCl3
2P  5Cl 2 
 2PCl5
c) Bromine: Bromine is made on an industrial scale by reaction of bromides with chlorine. A
mixture of air and chlorine is blown through an aqueous solution of a bromide at a pH of 3.5.
Chlorine displaces bromine and air blows it out of the solution.
Properties of Br2: Dark red, dense, heavy liquid at ordinary temperature, boils at 59°C, and the
vapours attack skin, eyes, nose, throat.
 Chemistry : Preparation & Properties of Compounds

Chemical properties and Oxidising properties

Br2  H 2S 
 2HBr  S
Na 2SO3  Br2  H 2 O 
 Na 2SO 4  8HBr  H 2SO 4
HI  Br2 
 HBr  I2
6FeSO 4  3Br2 
 Fe2 (SO 4 )3  2FeBr3
8NH 3 3Br2 
 6NH 4 Br  N 2
KNO2  Br2  H 2 O 
 2HBr  KNO 3
Change of red colour of Br2 takes place when C2 H2 or C2H4 (unsaturtaed compounds) are reacted
with
C 2 H 4  Br2 (red) 
 C 2 H 4 Br2 (colourless)
Reducing properties:
Br2  3F2 
 2BrF3
Br2  5F2 
 2BrF5
Br2  Cl 2 
 2BrCl
d) Iodine: Iodine can also be prepared similarly by the oxidation of iodides by chlorine. Iodine is
also prepared by treating brine with AgNO3 to precipitate AgI.
AgNO3
I – (brine)  Fe
 AgI    Ag   FeI 2
Cl2
FeI 2  FeCl2  I 2
2Ag  4HNO3 
 3AgNO3  NO  2H 2 O

Compounds of Halogens
1. Hydrohalic Acids (HX): Aqueous solutions of hydrogen halides are called hydrohalic acids,
viz., hydrofluoric, hydrochloric, hydrobromic and hydriodic acid. Hydrohalic acids form constant
boiling point mixtures with water. The aqueous solutions of acids ionize as follows:
 H 3O (aq)  X – (aq)
HX(aq)  H 2 O 
Their acid strength follows the order HI > HBr > HCl > HF.
Of these the most marked change is in the enthalpy of dissociation of H-X bond, which decreases
in the order HF > HCl > HBr > HI and the enthalpy of hydration of X – , which decreases from
F –  Cl –  Br –  I – . The total enthalpy change becomes more negative, i.e., the reaction
 H  (aq)  X – (aq)
HX(aq) 
becomes more exothermic from HF to HI. As expected, acid strength varies in the reverse order,
HI being the strongest acid and HF the weakest acid.
2. Oxides
Fluorides Oxides
Comp Oxidation Chlorine O.N Bromine O.N Iodine O.N
ound number Compound Compound Compound
(O.N)
Chemistry : Preparation & Properties of Compounds

OF2 –1 Cl2O +1 Br2O +1

O2F2 –1 ClO2 +4 BrO2 +4
I2O5 +5
Cl2O6 +6 BrO3 +6
Cl2O7 +7
Preparation: 1. Oxygen difluoride is prepared by passing fluorine into a 2% NaOH solutions.
2F2  2NaOH 
 2NaF  H 2O  OF2
It is a stable colourless gas. It reacts vigorously with metals, sulphur,
phosphorous and halogens and gives fluorides dioxides. It reacts with bases
to give F – ion and free oxygen.
2. Cl2O and Br2O are prepared by heating freshly precipitated mercuric oxide
with the halogen gas:
573 K
2X 2  2HgO   HgX 2 . HgO  X 2O, where X = Cl or Br
3. Chlorine dioxide (ClO2) is also prepared by the following reactions:
2NaClO3  SO 2  H 2SO 4 
 2ClO 2  2NaHSO 4
4. It is also obtained by treating silver chlorate with dry chlorine at
363 K:
2AgClO3  Cl 2 
 2AgCl  2ClO 2  O 2
Properties: 1. Chlorine dioxide is a gas at normal temperature, b.p. 284 K. It is a powerful
oxidising and chlorinating agent. It reacts with alkalies to form chlorites and
chlorates:
2ClO2  2NaOH 
 NaClO2  NaClO3  H 2O

2. Iodine pentoxide (I2O5) is prepared by dehydration of iodic acid at

513 K:
513 K
2HIO3 
H2O
 I 2 O5  H 2 O

It is a white solid which decomposes to iodine and oxygen above 573 K. I2O5
is a good oxidising agent, it oxidizes H2S to sulphur and HCl to chlorine.

3. A combination of kinetic and thermodynamic factors leads to the generally

decreasing order of stability F > Cl > Br. The higher oxides tend to be more
stable than the lower. Except for that of iodine all oxides tend to be explosive.
chlorine oxides, Cl2 O and ClO2 are used as bleaching agents and as
germicides.

3. Oxyacids of Chlorine: Different oxyacids of chlorine are:

Formula Name Corresponding Salt

HOCl Hypochlorous acid Hypochlorites
HClO2 Chlorous acid Chlorites
 Chemistry : Preparation & Properties of Compounds

HClO3 Chloric acid Chlorates

HClO4 Perchloric acid Perchlorates

Acidic Character: Acidic at character of the same halogen increases with increase in oxidation
number of the halogen:
HClO4 > HClO3 > HClO2 > HOCl
Reason: It is because the release of H+ ion in each case would result in the formation of
ClO4– , ClO3– , ClO2– and ClO – ions. Now more is the number of oxygen atoms
in the ion greater is the dispersal of the negative charge and hence more is the
stability of resulting ion. Since a more stable ion would be formed relatively with
more ease, therefore, the ease of formation of ions would be
ClO4–  ClO3–  ClO 2–  ClO –
Preparation: HOCl: Ca(OCl) 2  2HNO 3 
 Ca(NO 3 ) 2  2HOCl
H 2 O2
2HgO  H 2O  2Cl2 HgO. HgCl   2HOCl 2
(insoluble basic mercury chloride)

HClO2: BaO 2  2ClO 2 

 Ba(ClO 2 ) 2 (liquid)  O 2
Ba(ClO2 ) 2  H 2SO 4 (dil.) 
 BaSO 4   2HClO 2
HClO3: 6Ba(OH) 2  6Cl2 
 5BaCl 2  Ba(ClO 3 ) 2  6H 2O
Ba(ClO3 ) 2  H 2SO 4 (dil.) 
 BaSO 4   2HClO 3
HClO4: KClO 4  H 2SO 4 
 KHSO 4  HClO 4
2HClO3 
 HClO 4  2ClO 2  H 2 O

4. Bleaching Powder (Ca(OCl)2: The exact chemical composition of bleaching powder is not
yet known but it behaves as if it contains calcium hypochlorite Ca(OCl)2 and basic calcium
chloride, CaCl2.Ca(OH)2H2O.
Preparation: It is prepared by passing chlorine over slaked lime
3Ca(OH)2  2Cl2 
 Ca(OCl)2  CaCl2 .Ca(OH)2 .H 2 O  H 2O

Bleaching powder

Properties: i) Reaction with Dilute Acids: With dilute acids, it gives chlorine which is known
as available chlorine.
CaOCl2  2HCl 
 CaCl 2  H 2O  Cl2 
CaOCl2  H 2SO 4 
 CaSO 4  H 2O  Cl2 

ii) When treated with water it decomposes into calcium chloride and calcium
hypochlorite

2CaOCl 2  H 2 O 
 CaCl 2  Ca(OCl) 2 H 2 O

iii) Bleaching powder reacts with CO2 (atmospheric) and gives chlorine which
accounts for its oxidising and bleaching actions.
Chemistry : Preparation & Properties of Compounds

CaOCl2  CO 2 
 CaCO 3  Cl 2 

iv) Action of heat: On heating bleaching powder gives a mixture of chlorate and
chloride

6CaOCl2   Ca(ClO 3 ) 2  5CaCl2

Illustration 8: The solutions of the salts of hypohalous acids are alkaline, explain why?
Solution: The salts of hypohalous acids undergo hydrolysis in water as shown below:
NaOX  H 2O Na   OH –  HOX
The hypohalous acids are fairly weak acids and remain largely undissociated in
solution. As the solution contains OH – , it becomes alkaline in nature.

14. XENON FLUORIDES

Structures and Bonding: XeF2 is a linear molecule F – Xe – F. Valence bond representation of
XeF2 may be explained, if one of the 5p electrons is promoted to the 5d orbital.

5s 5p 5d F
Xe in ground state

Xe

Xe in excited state


 F
sp 3 d

One 5s, three 5p and one 5d atomic orbitals hybridise to give five sp3d hybridized orbitals. The two
orbitals, which are singly occupied are used by two fluorine atoms to form bonds with xenon and the rest
of the three are occupied by the lone pairs as shown.
1. Xenon Tetrafluoride (XeF4)
400 C, 5 – 6atm.
Preparation: Xe  2F2   XeF4
Properties : It reacts violently with water
3XeF4  6H 2 O 
 2Xe  XeO 3  12HF  3/ 2 O 2
2. Xenon hexafluoride, (XeF6)
–130 C
Preparation XeF4  O 2 F2   XeF6  O2 (g)
Properties: It is white solid, which sublimes at room temperature, it melts at 49.5°C to give
yellow liquid.
2XeF6  3SiO 2 
 3SiF4  2XeO3
XeF6  3H 2 O 
 XeO 3  6HF

2XeF6   XeF2  XeF4  3F2
Hybrdization, Shape and Structure
 Chemistry : Preparation & Properties of Compounds

Among the three known fluorides (XeF2, XeF4 and XeF6), xenon tetrafluoride is the most important;
while among oxides xenon trioxide is more important that the tetroxide.

Xenon tetrafluoride was the first xenon fluoride to be prepared by Classen, Selig and Malm in 1962. The
shape of XeF4 is square planar. It is formed by sp3d2 hybridization. Xenon difluoride is liner involving
sp3d hybridization while XeF6 has distorted pentagonal bibyramidal shape involving sp3d3 hybridisation.
These fluorides are prepared by the interaction of xenon and fluorine.

Summary of Stable Compounds of Xe

Oxidation No. of lone pair(s) of
Compound Hybridisation Shape
state of Xe electrons
XeF2 +2 sp3 d 3 Linear
XeF4 +4 sp3d2 2 Square planar
XeF6 +6 sp3d3 1 Distorted pentagonal
bipyramidal
XeOF2 +4 sp3 d 2 T-shaped
XeO2 F2 +6 sp3 d 1 Distorted trigonal
bipyramidal
XeOF4 +6 sp3d2 1 Square pyramidal
XeO3 +6 sp3 1 Pyramidal

Molecular structure of Xenon Compounds

F F
F F
180°
F F
F Xe F Xe Xe

F F
F F
XeF2 XeF4 XeF6
(Xe atom in 1st excited state) (Xe atom in 2nd excited state) (Xe atom in 3rd excited state)

F F

Xe
Xe
F Xe F

F F O O
O
O O O
XeOF4 XeOF2 XeO3
(Xe atom in 3rd excited state) (Xe in 1st excited state) (Xe in 1st excited state)
Chemistry : Preparation & Properties of Compounds

15. FERTILIZERS
Substances which increase the fertility of soils are known as fertilizers. They are classified into three
categories:
i) Nitrogeneous fertilizers: These are fertilizers which mainly supply nitrogen to the plants.
e.g ammonium sulphate, ammonium nitrate, calcium ammonium nitrate, calcium cyanamide and
urea

ii) Phosphatic fertilizers: They supply phosphorus to the plants. e.g. superphosphate of lime
Ca(H2PO4)2

iii) Mixed fertilizers: Fertilizers containing more than one element, namely nitrogen, phosphorus
and potassium. They contain a mixture of ammonium salt, ammonium phosphate, superphosphate
and potassium salt. It is known as NPK fertilizers
Phosphatic fertilizers such as superphosphate of lime is obtained from phosphatic rocks by
treatment with conc. sulphuric acid. In this way, insoluble phosphate rock is rendered soluble in
water for use as a source of this essential plant nutrient.
Ca3(PO4)2 + 2H2SO4 + 5H2O  Ca(H2PO4)2 H2O + 2CaSO4. 2H2O.
soluble

Treatment of phosphate rock with phosphoric acid leads to the formation of triple superphosphate
which is free from calcium sulphate and hence contains a greater percentage of phosphorus.

Ca5(PO4)3F + 7H3PO4 + 5H2O  5Ca(H2PO4)2.H2O + HF