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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), sodium nitrate (NaNO3) with sodium.

2Na + 12 O 2 
→ Na 2 O
Na 2 O 2 + 2Na 
→ 2Na 2 O
2NaNO3 + 10Na 
→ 6Na 2 O + N 2

Properties: 1. It is a white amorphous substance.

2. It reacts with water violently forming NaOH.

Na 2 O + H 2 O 
→ 2NaOH

3. On heating above 400°C, it disproportionates to give peroxide and

metallic sodium.
400° C
2Na 2 O  → Na 2 O 2 +2Na

4. 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 2 O 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 2 O 2 + 2H 2 O (warm) 
→ 4NaOH + O 2

iii) Action of acids.

Na 2 O 2 + H 2SO 4 →
cold
Na 2SO 4 + H 2 O 2

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2Na 2 O 2 + 2H 2SO 4 
hot
→ 2Na 2SO 4 + 2H 2 O + O 2

iv) Oxidizing action. It is a powerful oxidizing agent and oxidizes

chromic compounds to chromates, manganous salts to manganates,
SO2 to SO3 or sulphates, 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 2 CrO 4 + O 2 +5H 2 O
Cr2 (SO 4 )3 + 5Na 2 O 2 
→ 3Na 2SO 4 + 2Na 2 CrO 4 + O 2

v) Reducing action. It reduces potassium permanganate, a stronger

oxidising agent.

Na 2 O 2 + H 2SO 4 
→ H 2 O 2 + Na 2SO 4
2KMnO 4 + 3H 2SO 4 + 5H 2 O 2 
→ K 2SO 4 + 2MnSO 4 + 8H 2 O + 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 – 
→ Cl 2 + 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 –
H 2O H + + OH –
At cathode (perforated steel) : 2H + + 2e – 
→ H2
At anode (carbon rod) : 2Cl – 
→ Cl 2 + 2e –
Note: This cell is used for the industrial production of Cl2. As well as this cell can be used for production
of Na2CO3, for which CO2 is mixed with steam.

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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
Zn(OH)2 ↓ + 2NaOH  excess
→ Na2ZnO2 + 2H2O
Al2O3 ↓ + 2NaOH 
excess
→ 2NaAlO2 + H2O
SiO2 + 2NaOH → Na2SiO3 + H2O
P4 + 3 NaOH +3H2O → PH3 + 3NaH2PO2
2Al + 2 NaOH + 2H2O → 3H2 + 2NaAlO2

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

carbonate Na2CO3 (soda-ash); monohydrate, Na2CO3.H2O (crystal carbonate);
heptahydrate, Na2CO3. 7H2O and decahydrate, Na2CO3. 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.
NH 3 + CO 2 + H 2 O → NH 4 HCO3
30° C
NH 4 HCO3 + NaCl  → NaHCO3 ↓ + NH 4 Cl
Sod. bicarbonate
250° C
2NaHCO3 
→ Na 2 CO3 + H 2 O + CO 2
Sod. bicarbonate (used again )

2NH 4 Cl + Ca(OH) 2 
→ CaCl2 + 2H 2 O + 2NH3
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.

Na 2 CO3 .10H 2 O 
dry
air
→ Na 2 CO3 . H 2 O + 9H 2 O

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 2 CO3 + 2NaOH
Sod. carbonate (weak acid) (Strong alkali)

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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 2 CO3 
→ CaCO3 ↓ + 2NaCl
2MgCl2 + 2Na 2 CO3 + H 2 O 
→ MgCO3 . Mg(OH) 2 ↓ + 4NaCl + CO 2

Carbonates of metals like Al, Fe, Sn, etc. when formed are
immediately hydrolysed to hydroxides.

Fe2 (SO 4 )3 + 3Na 2 CO3 

→ Fe 2 (CO3 )3 
3H 2 O
→ 2Fe(OH)3 + 3CO 2

v) When CO2 gas is passed through aqueous solution of sodium

carbonate, sodium bicarbonate is formed.

Na 2 CO3 + H 2 O + 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.

2NaCl + H 2SO 4 
→ Na 2SO4 + 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 → NaHSO 4 + HNO3
Chile saltpetre Nitre cake

NaCl + NaHSO4 
→ 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 2SO4 
→ PbSO 4 ↓ + 2NaNO3

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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 + 2H2SO4 → MnSO4 + Na2SO4+ 2H2O + Cl2 ↑

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 moves only slowly
(although Li+ is very small) and the radius of hydrated Cs+ ion is smaller than
the radius of hydrated Li+.

BRAIN TEASER 1:
Fire extinguisher contains NaHCO3 and the compound (X). What is the compound (X).
Explain.

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.

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180° C
Preparation: a) 4K(excess) + O 2 
reduced pressure
→ 2K 2 O
Pot. monoxide

2KOH + 2K → 2K 2 O + H 2
heat

2KNO3 + 10K 
→ 6K 2 O + N 2
b) K + O2 (excess) 
burning
→ KO 2
Pot. dioxide

2KOH + O3 
→ 2KO2 + H 2 O

c) 4K (dissolved in liq. NH3) →

3O 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
2KO2 + 2H 2 O 
→ 2KOH + H 2 O2 + O2

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 
→ BaSO4 ↓ + 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 magnesium 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

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⋅4H2O) + MgO → 3(MgCO3.3H2O) + K2CO3

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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 
→ 2KHCO3

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 2SO4 
→ K 2SO 4 + 2H 2 O

ii) By treating naturally occurring mineral, schonite (K2SO4. MgSO4.

6H2O) with sylvine (KCl).

K 2SO 4 .MgSO 4 .6H 2 O + 2KCl 

→ 2K 2SO4 + MgCl2 + 6H 2 O

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 . MgCl 2 . 6H 2 O 
→ KCl + MgCl 2 . 6H 2 O

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.

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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 → 2Na 2O
( Oxide )

2Na + O2 → Na2O2
(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. It is same, 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

BRAIN TEASER 2:
Identify A, B, C, D, E, F, G

K2Cr2O7  → (A)  → (B)

KOH 3 2 Pb(CH COO)
CH3COOH
NH4Cl

(C) →
∆
(D) + (E)
(gas) (green)

Al, ∆

(F) (metal) + (G) oxide

Magnesium
1. Magnesium Oxide (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 + 4NO2 + O2

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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 2 O

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 + H2O

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 2 O + CO2

In case Na2CO3 is used in place of NaHCO3, a basic carbonate is

obtained.

2MgSO 4 + 2Na 2 CO3 + H 2 O 

→ MgCO3 .Mg(OH) 2 + 2Na 2SO4 + CO 2

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(HCO3 ) 2

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Mg(HCO3 )2 →
heat
MgCO3 + H 2 O + CO2 ↑

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(HCO3 ) 2
Mg(HCO3 ) 2 + MgO 
→ 2MgCO3 + H 2 O

Properties: i) Magnesium carbonate is a white powder, insoluble in water.

ii) It dissolves in acids forming salts.
MgCO3 + 2HCl 
→ MgCl2 + H 2 O + 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.

MgCO3 →
heat
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 2SO 4 
→ MgSO4 + H 2 O + CO 2
Magnesite

MgCO3 . CaCO3 + 2H 2SO 4 

→ MgSO 4 + CaSO 4 ↓ + 2H 2 O + 2CO 2
Dolomite

ii) From kieserite (Commercial method). By boiling kieserite in water

and cooling the resulting solution when crystals or 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.

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160° C 200° C
MgSO 4 .7H 2 O 
(–6H 2 O)
→ MgSO 4 .H 2 O  → MgSO 4 + H 2 O
On further heating, it decomposes to form MgO.
above 200° C
4MgSO 4 → 4MgO + 2SO 2 + 2SO3 + 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.

Calcium
1. Calcium oxide (CaO) or Quick lime
Preparation: By heating lime stones at 804°C.
800° C
CaCO3 CaO + CO 2
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]

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Preparation: i) By treating lime (quick lime) with water.

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 calcium 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 prolonged treatment with CO2

because of the conversion of CaCO3 (insoluble) to calcium bicarbonate
(soluble).

CaCO3 + H 2 O + 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 
→ CaCl2 + H 2 O + CO 2
CaCl2 + (NH 4 ) 2 CO3 
→ 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 crystalline 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(HCO3 ) 2

4. Calcium Bicarbonate, (Ca(HCO3)2): It does not exist in solid state. However, its
solution can be prepared by passing CO2 gas through a suspension of calcium carbonate

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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 anhydride (CaSO4) and gypsum

(CaSO4. 2H2O).

Preparation: It may be prepared by adding dilute 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.
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
CaSO4 .2H 2 O  → CaSO4 . 12 H 2 O + 1 12 H 2 O

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.

CaSO 4 . 12 H 2 O 
H 2O
setting
→ CaSO4 .2H 2 O 
hardening
→ CaSO4 .2H 2 O
Plaster of Paris Orthor hom bic Monoclinic (gypsum)

Plaster of paris 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.

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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 + CO 2

'X' Basic Acidic
(Y) (Z)
CO2 + 2KOH → K2CO3 +H2O

BRAIN TEASER 3:
Ca(HCO3)2 and Ca(OH)2 can’t be stored in the same vessel – Explain

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:

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 electronegativity and hard, absorbs neutron, steel grey in colour. Some
dissimilarities of boron with other elements of this group are :

i) Boron is a non-metal 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 +3O2  → 2B2 O3

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700° C
2B + N 2  → 2BN

2. These above reaction accompanies red flame.

BN + 3H 2 O  → H3 BO3 + NH 3

3. Action in alkalis and acids

2B + 2NaOH + 2H 2 O 
→ 2NaBO 2 + 3H 2

2B + 3H 2 O 
→ B2 O3 + 3H 2

2B + 3H 2SO 4 
oxidation
→ 2H3 BO3 + 3SO 2

2B + 6HNO3 
oxidation
→ H3 BO3 + 6NO 2

4. Boron reacts with Mg and consequent hydrolysis gives diborane.

3Mg + 2B 
→ Mg 3 B2

3Ca + 2B 
→ Ca 3 B2

Mg 3 B2 + 6HCl 
→ 3MgCl2 + B2 H 6

B2 H 6 + 6H 2 O 
→ 2H 3 BO3 + 6H 2

5. Boron reduces silica and CO2

3SiO 2 + 4B 
→ 2B2 O3 + 3Si
3CO 2 + 4B 
→ 2B2 O3 + 3C

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).

4BF3 .OEt 2 + 3LiAlH 4 

Et 2 O
→ 2B2 H 6 + 3LiAlF4 + 4Et 2 O
4BF3 .OEt 2 + 3NaBH 4 
diglyme
→ 2B2 H 6 + 3NaBF4 + 4Et 2 O
where, diglyme is diethyleneglycol dimethyl ether, (MeOCH2CH2)2O.

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 PO4

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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 2 O 
→ 2H 3 BO3 + 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 H 6 + 3O 2 
→ B2 O3 + 3H 2 O, ∆H = –2165 kJ mol –1

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, B6H12 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.

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

concentrated solution of borax:

Na 2 B4 O7 + 2HCl + 5H 2 O 
→ 4H3 BO3 + 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 +

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4. On heating boric acid at 375 K, metaboric acid, HBO2 is formed. On

further heating above 500 K, B2O3 is formed:

H 3 BO3 
375 K
→ HBO 2 + H 2 O

2HBO 2 
500 K
→ 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 B6 O11 + 2Na 2 CO3 

→ Na 2 B4 O 7 + 2NaBO 2 + 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 O 7 + 2NH 4 Cl 
→ 2BN + B2 O3 + 2NaCl + 4H 2 O

3. On heating alone, it decomposes to form NaBO2 and B2O3

Na 2 B4 O 7 
→ 2NaBO 2 + B2 O3

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:

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
Compounds of Colour of borax bead

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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

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.

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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 pπ – pπ bonding

between B and Cl atoms. Thus it exists as a monomeric gas. Due to the larger
size of aluminium in aluminium trichloride, efficient pπ – pπ 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.

BRAIN TEASER 4:
Boron and aluminium both are in the same group. Yet AlCl3 shows anomalous
molecular weight while BCl3 doesn’t – why?

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

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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.

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

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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 from gaseous state
without liquefying (hence dry ice).

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, Al4C3, Be2C.

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.

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.

SiO 2 + 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).
SiO 2 + 2C  → Si + 2CO

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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  → SiO2
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

5. When amorphous silicon is strongly heated, it fuses and on cooling solidifies

to the crystalline form. It is very hard crystalline 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 2SiO3 + 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.

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Silicon atom has its complete octet but each oxygen atom is still short of O
one 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
4–
The [SiO4] 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 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)

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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.
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.

BRAIN TEASER 5:
(SiH3)3N is planar while (CH3)3N is pyramidal – Explain.

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

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2. By heating ammonium dichromate: Ammonium dichromate on heating

decomposes to give nitrogen gas.
∆
(NH 4 ) 2 Cr2 O7  → N 2 + 4H 2 O + Cr2 O3
∆
2NH3 + 3CuO  → N 2 (g) + 3Cu + 3H 2 O
NH 2 CONH 2 + 2HNO 2 
→ 2N 2 + CO 2 + 3H 2 O
NaNO 2 + HCl 
→ NaCl + HNO 2
NH 2 CONH 2 + 2HNO 2 
→ 3H 2 O + CO 2 + 2N 2

Fixation of atmospheric 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.

CaC 2 + N 2 
electric furnace
→ 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 + 2NH3
2NH3 + H 2SO 4 
→ (NH 4 ) 2 SO 4
2NH3 + H 2SO 4 
→ (NH 4 ) 2 SO 4
P2 O5 + 6NH3 + 3H 2 O 
→ 2(NH 4 )3 PO4
CaCl2 + 8NH 2 
→ CaCl2 .8NH3

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
N2O4 Dinitrogen tetroxide Colourless
gas and partly as liquid
N2O5 Dinitrogen pentoxide Colourless unstable as gas; ionic solid
NO3, N2O6 Not well characterized and quite

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unstable

Preparation: 1. N2O is obtained generally by heating NH4NO3:

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 HNO3 with reducing agents

like Cu or by reduction of nitrous acid or nitrites by Fe2+ of
I– ions:
3Cu + 8HNO3 
→ 2Cu(NO3 ) 2 + 2NO + 4H 2 O

2NaNO 2 + 2FeSO 4 + 3H 2SO 4 

→
2NaHSO4 + Fe 2 (SO 4 )3 + 2NO + 2H 2 O
2NaNO 2 + 2NaI + 4H 2SO 4 
→ 4NaHSO 4 + 2NO +I 2 + 2H 2 O

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 + 2NO 2 + 2H 2 O
2Pb(NO3 )2 
→ 2PbO + 4NO2 + O 2

5. N2O5 is an anhydride of HNO3. It is best prepared by dehydrating

HNO3 with P4O10 at low temperatures:
4HNO3 + P4 O10 
250 K
→ 2N 2 O5 + 4HPO3

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.

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Liquid N2O4 undergoes self-ionisation to form NO+ and NO3– ions and
therefore, it has been extensively studied as a non-aqueous solvent. Solid
N2O5 exists in the ionic form, NO +2 NO3– . 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
1120K
2NO + O2  → 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
oxidized 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 → 4H3PO4 + 20NO2 + 4H2O

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3. Ammonia (NH3)

Preparation: 1. By heating ammonium salt with a base, e.g. slaked lime (lab. method).
2NH 4 Cl + Ca(OH) 2  → CaCl 2 + 2H 2 O + 2NH3 ↑
The gas so formed is dried with quick lime, CaO.

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 + NH3

3. Cyanamide process (commercial method).

800 – 1000° C
CaO + 3C  → CaC2 + CO ↑
CaC2 + N 2 
→ CaCN 2 + C
Cal. cyanamide
14243
Nitro lim

CaCN 2 + 3H 2 O (steam) 

3 atm.
→ CaCO3 + 2NH 3

4. By Haber’s process (from air). Commerical method.

N 2 + 3H 2 2NH3

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 4 Cl + 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 + 3l 2 
→ NH 3 Nl3 + 3Hl
Nitrogen
tri iodide ammonate

NH 3 .Nl3 explodes in dry state

8NH 3 .Nl3 
→ 6NH 4 l + 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

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metal ions and these ammonia compounds find use in qualitative

analysis.

Ag + + NH3 
→[Ag(NH 3 ) 2 ]+
Cu 2+ + 4NH 3 
→[Cu(NH3 )4 ]2 +
Cd 2 + + 4NH3 
→[Cd(NH3 )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 4 OH 
→ Fe(OH)3 + 3NH 4 Cl
Brown ppt.

AlCl3 + 3NH 4 OH 
→ Al(OH)3 + 3NH 4 Cl
White ppt.

CrCl3 + 3NH 4 OH 
→ Cr(OH)3 + 3NH 4 Cl
Green ppt.

Liquid Ammonia as a Non-aqueous Solvent

Liquid ammonia functions as a good solvent for many substances and many types of relations. 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 H3O+ + 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 4 Cl + NaNH 2 
NH 3
→ NaCl + 2NH 3
HCl + NaOH 
H 2O
→ NaCl + H 2 O

Similarly,

2NH 4 Cl + PbNH 

NH3
→ PbCl2 + 3NH3
lead imide

3NH 4 Cl + AlN 

NH3
→ AlCl3 + 4NH 3
Alu min ium nitride

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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.

Phosphorous
Extraction: It is a very reactive element, so it does not occur free in nature. Different ores are:

Phosphorite : Ca3 (PO4)2

Fhrorapatite : 3Ca3(PO4)2 CaF2
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 + 6SiO 2 

→ P4 O10 + 6CaSiO3
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.

P4 + 3O 2 →
heat
2P O
2 3
red phosphorous phosphorus trioxide

P4 + 5O 2 →
heat
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 + 10Cl2 
→ 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.
4P + 3NaOH + 3H 2 O →boil
PH3 (g) + 3NaH 2 PO 2
yellow phosphorus phosphine sodium hypophosphite

iv) Reaction with nitric acid

Phosphorus gets oxidized by nitric acid to phosphoric acid.
P4 + 20HNO3  → 4H3 PO 4 + 20NO 2 + 4H 2 O
phosphoric acid

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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.
P
iii) Due to is low ignition temperature (~30°C), it undergoes
oxidation in the presence of air which slowly raises its
temperature and after a few moments it catches fire
P P
spontaneously. Due to this reason, it is stored under water.

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.
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) Phosphorous 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

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P4O6 + 2O2 → P4O10

ii) Reacts with water as follows :

P4O6 + 6H2O (cold) → 4H3PO3

Phosphorous acid

P4O6 + 6H2O (hot) → 3H3PO4 + PH3

b) Phosphorous 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:

P4O10 + 2H2O (cold) → 4HPO3

P4O10 + 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 Phosphours: 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
Hypophosphorous

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H 3 PO3 or deliquescent P4O6 or PCl3 + H2O H 2 PO3– , HPO32– reducing, but slow,
HPO(OH) 2 colourless phosphite dibasic pK1 ~ 2
Orthophosphorous solid pK 2 ~ 6
2–
H 4P 2O 3 white solid PCl3 + H3PO3 H 2 P2 O 5 reducing, dibasic
Pyrophosphorous pyrophosphite
H 4P 2O 6 white solid red P + alkali P2 O64 – hypophosphate not reducing or
Hypophosphoric oxidizing, tetrabasic
pK1 ~ 2
H3PO4 white solid P4O10 + H2O H 2 PO 4– , HPO 2–
4 , not oxidizing, tribasic
Orthophosphoric 3–
PO , phosphate
4

H 4P 2O 7 colourless heat phosphates or P2 O74 – pyrophosphate tetrabasic pK1 ~ 2

Pyrophosphoric solid phosphoric acid
HPO3 deliquescent heat H3PO4 to 600 K
Metaphosphoric solid

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 softening. 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:

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Ca 3 P2 + 6H 2 O 
→ 2PH3 + 3Ca(OH)2

2. Pyrolysis of phosphorous acid at 480 – 485 K:

4H3 PO3 
→ PH3 + 3H 3 PO 4

3. Alkaline hydrolysis of phosphonium iodide:

PH 4 I + KOH 
→ PH3 + KI + H 2 O

4. Alkaline hydrolysis of white phosphorus (industrial process):

P4 + 3KOH + 3H 2 O 
→ PH 3 + 3KH 2 PO2

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:

PH 3 + HI 
→ PH 4 I

Pure phosphine ignites in air at about 435 K, but when contaminated

with traces of P2H4 it is spontaneously inflammable:

PH 3 + 2O 2 
→ H 3 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 NH3 and hypochlorous acid.

BRAIN TEASER 6:
Why are the oxides of nitrogen so different from those of phosphours?

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

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for the manufacture of heavy water. Ordinary water, H2O, electrolyses faster with
the result that residual water is richer in D2O. In laboratory, O2 can be prepared by
thermal decomposition of KClO3 in presence of MnO2 as a catalyst:

2KClO3 
heat
MnO2 catalyst
→ 2KCl + 3O2

Properties: 1. Acidic oxides

SO2 + H 2 O 
→ H 2SO3
SO3 + H 2 O 
→ H 2SO4

2. Basic oxides
CaO + H 2 O 
→ 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 
→ ZnCl 2 + H 2 O (basic nature)

ZnO + 2NaOH 
→ Na 2 ZnO 2 + H 2 O (acidic nature)

Al 2 O3 + 2NaOH 
→ 2NaAlO 2 + H 2 O (acidic nature)

4. Basic oxides

Fe3O 4 + 8HCl 
→ 2FeCl3 + FeCl 2 + 4H 2 O

Oxidising property

Ozone acts as a powerful oxidizing agent due to the reaction,

O2 
→ O 2 + [O]

4O3 + PbS 
→ 4O 2 + PbSO 4

O3 + 2Kl + H 2 O 
→ 2KOH + O2 + I 2

2HCl + O3 
→ O 2 + H 2 O + Cl2

O3 + 2K 4 [Fe(CN)6 ] + H 2 O 
→ 2K 3 [Fe(CN)6 ] + 2KOH + O2

Reducing property
H 2 O 2 + O3 
→ H 2 O + 2O 2
BaO2 + O3 
→ BaO + 2O2

1. Ozone (O3)

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

3O 2 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 2 O + 2e – 
→ 2OH – + O 2
(neutral medium)

O3 + 2H + + 2e – 
→ H 2O + O2

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

O3 
→ O 2 + [O] × 4
PbS + 4[O] 
→ PbSO 4
PbS + 4O3 → PbSO 4 + 4O2
b) H 2S + O3 
→ H 2O + S + O2
c) 2KI + H 2 O + O3 
→ 2KOH + I 2 + O 2

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

d) 2HBr + O3 
→ H 2 O + Br2 + O 2
e) KNO 2 + O3 
→ KNO3 + O2
f) 2FeSO 4 + H 2SO 4 + O3 
→ Fe 2 (SO4 )3 + H 2 O + O 2
g) 2K 4 [Fe(CN)6 ] + H 2 O + O3 
→ 2 K 3 [Fe(CN)6 ] + 2KOH + O 2
Pot. ferrocyanide Pot. ferricyanide

h) 2K 2 MnO 4 + H 2 O + O3 
→ 2KMnO 4 + 2KOH + O 2
Pot. manganate Pot. permanganate

i) 2Ag + O3 
→ Ag 2 O + O 2

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Silver oxide may be reduced back to Ag by O3.

Ag 2 O + O3 → 2Ag + 2O 2
j) 3SO 2 + O3 
→ 3SO3
3SnCl 2 + 6HCl + O3 
→ 3SnCl 4 + 3H 2 O

iv) Reducing reactions. Ozone reduces certain peroxides.

→ 2H + + 2O 2
a) H 2 O + O3 
b) H 2 O 2 + O3 
→ H 2 O + 2O 2
c) BaO2 + O3 
→ BaO + 2O2
d) Ag 2 O + O3 
→ 2Ag + 2O 2

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 2 O + H 2 O 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)

2H2O
H2S2O8(aq) → 2H2SO4(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.

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O 2 (air)
2-ethyl anthraquinol H 2 (Pd)
oxidised product + H2O2

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 
→ PbSO 4 + 4H 2 O
Lead sulphide Lead sulphate

ii) 2KI + H 2O 2 
→ 2KOH + I2

or 2KI + H 2SO 4 + H 2 O 2 
→ K 2SO 4 + 2H 2 O + I 2

iii) 2K 4 [Fe(CN)6 ] + H 2O 2 
→ 2K 3[Fe(CN)6 ]+ 2KOH
Pot. ferrocyanide Pot. ferricyanide

iv) K 2 Cr2 O 7 + H 2SO 4 + 4H 2 O 2 

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

In basic medium : H2O2 + OH- + 2e- → 3OH—

i) 2HCHO + H 2O 2 
Pyrogallol
→ 2HCOOH + H 2
Formaldehyde Formic acid

(B) As reducing agent

In acidic medium : H2O2 → 2H+ + O2 + 2e-

i) 2KMnO 4 + 3H 2SO 4 + 5H 2 O 2 
→ K 2SO 4 + 2MnSO 4 + 8H 2 O + 5O 2

ii) K 2 Cr2 O7 + 4H 2SO 4 + 3H 2 O 2 

→ K 2SO 4 + Cr2 (SO 4 )3 + 7H 2O + 3O 2

iii) O3 + H 2O 2 
→ H 2 O + 2O 2

In basic medium: H2O2 + 2OH- → 2H2O + O2 + 2e-

i) 2Fe2+ + H2O2 + 2H+ → 2Fe3+ + 2H2O

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ii) 2MnO4- + 5H2O2 + 6H+ → 2Mn2+ + 8H2O + 5O2

iii) Mn2+ + H2O2 → Mn+4 + 2OH-
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 2 TiO 4 + 4H+

pertitanic acid

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 common and the most stable allotrope of sulphur at room
temperature is known as rhombic sulphur or α-sulphur, Sα . 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, Sβ . In

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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, Sλ. At about 433 K the S8 rings open up and join together into long
spiral-chain molecules resulting in a thick viscous liquid µ -sulphur, Sµ. 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 γ-sulphur is formed. The
allotropy of sulphur as a function of temperature is summarized as follows:


Cold water
→ Sγ
Sα 
369 K
→ Sβ 
392 K
→ Sλ 
433 K
→ Sµ 
718 K
→ S8 (g) 
→ S6

→ S4 
1273 K
→ S2 
2273 K
→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

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3. Reaction with acidified K2Cr2O7 :

K2Cr2O7 + 3SO2 + H2SO4 → K2SO4 + Cr2(SO4)3 + H2O

4. Oxidising property
i) 2H2S + SO2 → 2H2O + 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

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 K2Cr2O7 to
Cr2 (SO4)3:
H 2SO3 + H 2 O + I 2 → H 2SO 4 + 2HI
2KMnO 4 + 5SO 2 + 2H 2 O 
→ K 2SO 4 + 2MnSO 4 + 2H 2SO 4
K 2 Cr2 O 7 + 3SO 2 + H 2SO 4 
→ K 2SO 4 + Cr2 (SO 4 )3 + H 2 O

2. In the presence of strong reducing agents like H2S,it can behave as an

oxidizing agent.
2H 2S + H 2SO3 
→ 3H 2 O + 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 oxidizing agent.

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i) Low volatility of sulphuric acid is put to use in the manufacture of

more volatile acids from their salts.
2MX + H2SO4 → 2HX + M2SO4.
(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 oxidizing 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 O32– . The best known thiosulphate is the
sodium salt, Na2S2O3. 5H2O.

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

followed by filtration and crystalliastion.
Na 2SO3 + S 
→ Na 2S2 O3

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 oxidizing agents like iodine behaves rather differently

giving sodium tetrathionate instead of Na2SO4, though it is also
converted into iodide.
Na 2S2 O3 + I2 → 2NaI + Na 2S4 O6
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.

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AgBr + 2Na 2S2 O3 

→ Na 3 [Ag(S2 O3 )2 ] + NaBr

Illustration 7: Why is SO3 not dissolved in water directly during the preparation of
sulphuric acid?

Solution: In the preparation of H 2SO 4 , SO3 is not dissolved directly in H 2 O as it -reacts

violently with water forming a dense white fog of dilute sulphuric acid.

BRAIN TEASER 7:
Why is the contact process preferred over lead chamber process for the preparation of
H2SO4?

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 ↑

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 + O3 ↑
2H 2 O + 2F2 
→ 4HF + O 2 ↑
2Al + 3F2 
→ 2AlF3

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Copper does not appreciably react with F2 at this temperature because of

CuF2 layer formation on it.
NaOH + 2F2  →NaF + O 2 + 2H 2 O
2NaOH + 2F2 
→ F2 O + 2NaF + H 2 O
I 2 + 5F2 
→ 2IF5
3F2 + 4HBr 
→ 4HF + Br2 + 2BrF
3F2 + 4HI 
→ 4HF + I 2 + 2IF
SiO 2 + 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 2 CO 4
K 2SO 4 + F2 
→ K 2S2 O8 + 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 + 3Cl 2 
→ 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.

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 + I 2
6FeSO 4 + 3Br2 
→ Fe2 (SO 4 )3 + 2FeBr3
8NH 3 +3Br2 
→ 6NH 4 Br + N 2

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KNO 2 + Br2 + H 2 O 
→ 2HBr + KNO3

Change of red colour of Br2 takes place when C2H2 or C2H4 (unsaturtaed compounds) are
reacted with
C2 H 4 + Br2 (red) 
→ C2 H 4 Br2 (colourless)

Reducing properties:
Br2 + 3F2 
→ 2BrF3
Br2 + 5F2 
→ 2BrF5
Br2 + Cl2 
→ 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.

I – (brine) 
AgNO3
→ AgI ↓ 
Fe
→ Ag ↓ + FeI2
FeI2 →
Cl 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)
OF2 –1 Cl2O +1 Br2O +1 I2O5 +5

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O2F2 –1 ClO2 +4 BrO2 +4

Cl2O6 +6 BrO3 +6
Cl2O7 +7

Preparation: 1. Oxygen difluoride is prepared by passing fluorine into a 2% NaOH

solutions.

2F2 + 2NaOH 
→ 2NaF + H 2 O + 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:

2X 2 + 2HgO 
573 K
→ HgX 2 . HgO + X 2 O, 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 + Cl2 
→ 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:

2ClO 2 + 2NaOH 
→ NaClO 2 + NaClO3 + H 2 O

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

513 K:

2HIO3 
513 K
H 2O
→ I 2 O5 + H 2 O

It is a white solid which decomposes to iodine and oxygen above

573K. 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 I > Cl > Br. The higher oxides
tend to be more stable than the lower. Except for that of iodine all

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oxides tend to be explosive. chlorine oxides, Cl2O 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
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 ClO 4– , ClO3– , ClO 2– 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

ClO 4– > ClO3– > ClO 2– > ClO –

Preparation: HOCl: Ca(OCl) 2 + 2HNO3 

→ Ca(NO3 )2 + 2HOCl
2HgO + H 2 O + 2Cl 2 HgO. HgCl ↓ + 2HOCl
H 2 O2
2
(insoluble basic mercury chloride)

HClO2: BaO 2 + 2ClO 2 

→ Ba(ClO 2 )2 (liquid) + O 2
Ba(ClO 2 )2 + H 2SO 4 (dil.) 
→ BaSO 4 ↓ + 2HClO 2

HClO3: 6Ba(OH) 2 + 6Cl2 

→ 5BaCl2 + Ba(ClO3 ) 2 + 6H 2 O
Ba(ClO3 ) 2 + H 2SO 4 (dil.) 
→ BaSO 4 ↓ + 2HClO3

HClO4: KClO 4 + H 2SO 4 

→ KHSO 4 + HClO 4

2HClO3 
→ HClO 4 + 2ClO 2 + H 2 O

4. Bleaching Powder [CaOCl2]: 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

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3Ca(OH) 2 + 2Cl 2 
→ Ca(OCl) 2 + CaCl 2 .Ca(OH) 2 .H 2 O + H 2 O
14444444244444443
Bleaching powder

Properties: i) Reaction with Dilute Acids: With dilute acids, it gives chlorine which
is known as available chlorine.

CaOCl 2 + 2HCl 
→ CaCl2 + H 2 O + Cl2 ↑

CaOCl2 + H 2SO 4 
→ CaSO 4 + H 2 O + Cl2 ↑

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

2CaOCl 2 + H 2 O 
→ CaCl2 + Ca(OCl) 2 +H 2 O

iii) Bleaching powder reacts with CO2 (atmospheric) and gives chlorine
which accounts for its oxidising and bleaching actions.

CaOCl 2 + CO 2 
→ CaCO3 + Cl2 ↑

iv) Action of heat: On heating bleaching powder gives a mixture of

chlorate and chloride
∆
6CaOCl2  → Ca(ClO3 )2 + 5CaCl 2

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 2 O 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.

BRAIN TEASER 8:
HF cannot be stored in glass container - Explain.

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.

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5s 5p 5d F
Xe in ground state

Xe

Xe in excited state
1444
424444
3 F
sp3 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 + XeO3 + 12HF + 3 / 2 O 2

2. Xenon hexafluoride, (XeF6)

–130° C
Preparation XeF4 + O 2 F2  → XeF6 + O 2 (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 
→ XeO3 + 6HF
∆
2XeF6  → XeF2 + XeF4 + 3F2

Hybrdization, Shape and Structure

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
3
XeF2 +2 sp d 3 Linear
XeF4 +4 sp3d2 2 Square planar
3 3
XeF6 +6 sp d 1 Distorted pentagonal
bipyramidal
XeOF2 +4 sp3d 2 T-shaped
XeO2F2 +6 sp3d 1 Distorted trigonal
bipyramidal
XeOF4 +6 sp3d2 1 Square pyramidal

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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 3rd excited state) (Xe in 3rd excited state)

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.

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

Answer To Brain Teasers

1. X : H+ (like CH3CO2H)
2. A : K2CrO4 B : PbCrO4
C : (NH4)2Cr2O7 D : N2
E : Cr2O3 F : Cr
G : Al2O3
3. Ca(HCO3)2 behaves as an acid with Ca(OH)2.
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + H2O
Hence neutralization takes place.

4. AlCl3 lacks back bonding as in BCl3 because of increase in size of aluminium.

Aluminium metal atoms complete their octet by coordinate bond formed by chlorine atom
between two Al atoms hence AlCl3 exists as dimer hence, shows anomalous mol. wt.
5. In case of (CH3)3N, lone pair on N and three covalent bonds with CH3 groups results in
sp3 hybridisation but lone-pair bond pair repulsion causes distortion hence gives
pyramidal structure.

N
H3C CH3
CH3
But in case (SiH3)3N, lone pair on the nitrogen is transferred to the empty d-orbitals of
silicon (pπ -dπ overlap) thereby causing planarity of unit.
6. Nitrogen forms weak N—O bonds and strong N=O bonds with oxygen. Its oxides exist as
monomeric gaseous species. On the other hand, phosphorus forms strong P—O bonds and
weak P = O bonds, its oxides exist as dimeric species.
7. The contact process is preferred over lead chamber process for two reason.
a) Contact process gives pure H 2SO 4 while chamber acid has got impurities of arsenic
and lead.
b) Sulphuric acid of any concentration can be obtained by contact process while the acid
obtained from lead chamber process is quite dilute (60—78%).
8. HF attacks glass, other halogen acids do not. Glass is silicates of sodium and calcium and
are converted into complex fluorides:
Na2SiO3 + 6HF → Na2SiF6 + 3H2O
CaSiO3 + 6HF → CaSiF6 + 3H2O
Hence HF can’t be stored in a glass vessel. Instead, it is stored in a wax-vessel which
does not react with HF. This unique property of HF of attacking glass is used for making
permanent marking on glass-wares.

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Solved Problems
Objective

Problem 1: Crude common salt is hygroscopic because of impurities of

(a) CaSO4 and MgSO4 (b) CaCl2 and MgCl2
(c) CaBr2 and MgBr2 (d) Ca(HCO3)2 and Mg(HCO3)2

Solution: (b)

Problem 2: The metal (s) soluble in aqua regia is (are)

(a) Pt (b) Au
(c) Ag (d) Cu.

Solution: (a), (b), (c), (d)

Problem 3: When CO is heated with NaOH under pressure, we get,

(a) Sodium benzoate (b) Sodium acetate
(c) Sodium formate (d) Sodium oxalate

Solution: (c)

Problem 4: Which is deliquescent?

(a) MgCl2 (b) NaOH
(c) CaCl2 (d) All

Solution: Because MgCl2, NaOH and CaCl2 all absorbs water from the atmospheric
moisture.
∴ (d)

Problem 5: Ammonium salts are oxidised in the oil to nitrites by

(a) Denitrifying bacteria (b) Nitrifying bacteria
(c) Ammonifying bacteria (d) Nitrosifying bacteria

Solution: (b)

Problem 6: Carbon dioxide is used for extinguishing fire because

(a) it has a relatively high critical temperature
(b) in solid state, it is called dry ice
(c) it is neither combustible nor a supporter of combustion
(d) it is a colourless gas

Solution: (c)

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Problem 7: Non combustible hydride is

(a) NH3 (b) PH3
(c) AsH3 (d) SbH3
Solution: (a)
Problem 8: Acid rain may cause
(a) rusting easier (b) stone cancer in Taj Mahal
(c) non – fertility of soil (d) all are correct

Solution: (d)

Problem 9: Decomposition of H2O2 is slowed down by addition of

(a) Alcohol (b) MnO2
(c) Alkali (d) Pt.

Solution: (a)

Problem 10: Red lead on reaction with dil. HNO3 form

(a) PbO (b) PbO2
(c) PbO + Pb(NO3)2 (d) PbO2 + Pb(NO3)2

Solution: Pb3O4 + 4HNO3 → 2Pb(NO3)2 + PbO2 + 2H2O

∴ (d)

Subjective
Problem 1: A student suggested that calcium should be made if calcium oxide is reacted
with aluminium powder. Was the student correct?
∆G °f (CaO) = –604.2 kJ mol –1 , ∆G °f (Al 2 O3 ) = –15824 kJ mol –1

Solution: A given reaction is spontaneous if ∆G °f is negative.

3CaO + 2Al 
→ Al2 O3 + 3Ca
∆G °f = ∆G °f (Al 2 O3 ) – 3∆G °f (CaO)
= –1582.4 – 3 (–604.2) = –1582.4 + 1812.6
= +230.2 kJ mol–1
The positive sign tells that the reaction cannot occur under standard
conditions.

Problem 2: Beryllium gives a compound X with the following percentage composition:

Be–6.1%; N–37.8%, Cl–48%, H–8.1%. Molecular weight of (X) is
148 g mol–1 and that of Be is 9 g mol–1.
i) What is the molecular formula of the compound.
ii) In aqueous solution, 1 mol of the compound reacts with 2 mol of AgNO3
giving white ppt. What is structural formula of (X)?

Solution: Atom Atomic weight (A) % %/A Simplest ratio

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Be 9 6.1 0.68 1

N 14 37.8 2.70 4

Cl 35.5 48.0 1.35 2

H 1 8.1 8.10 12

i) Molecular formula is BeN4Cl2H12.

ii) Since 1 mol of X reacts with 2 mol of AgNO3, hence two Cl are outside
the complex. Since there are four N and twelve H, this indicates four NH3
molecules attached to Be. This gives structural formula as
[Be(NH 3 )4 ]Cl2

Problem 3: Al and Ga are trivalent in their compounds but in case of Tl, monovalent
compounds are the most stable. Why?

Solution: It is due to `inert pair’ effect due to which stability of +3 state decreases and
that of +1 state increases while going down the group (in this case Group 13).
Al3+ > Ga 3+ > In 3+ > Tl3+
(most stable)

Al + < Ga + < In + < Tl +

(most stable)

Problem 4: a) Explain briefly the difference between the two center electron pair bond
and a three center electron pair bond.
b) Compare NaBH4 and LiAlH4 as reducing agents.
c) Which of the above two would you use in the following conversions:
i) R—CH=CH—CHO  → R—CH=CH—CH2OH
ii) R—CH2—COOEt  → R—CH2—CH2OH

Solution: a) In a two center electron pair bond, a pair of electrons binds two atoms,
whereas in a three center electron pair bond a pair of electrons binds three
atoms together.
b) LiAlH4 is a more versatile reducing agent than NaBH4; it reduces as many
as sixty functional groups in organic chemistry. On the other hand, NaBH4
is more selective. For example, NaBH4 reduces >C=O group in aldehyde
and ketones to alcohols, but functional groups such as >C=C<, —COOH
and —NO2 are not normally attacked.
c) i) NaBH4 ii) LiAlH4

Problem 5: Explain the following

a) Al2 (SO4)3 is used as a mordant in textile industry
b) AlCl3.6H2O on heating never produces anhydrous AlCl3.
c) AlCl3 in water shows acidity
d) Why red colour Rousin’s salt [Fe(NO)2S]2 is diamagnetic. How do you
account for the phenomenon..

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Solution: a) Al 2 (SO 4 )3 + H 2 O  → 2Al(OH)3 + 3H 2SO 4

Because of this hydrolysis of aq. Al2(SO4)3 the fibres when dipped in aq.
Al2(SO4)3 solution, Al(OH)3 forms on the surface of the fibres. Dye then
combine with Al(OH)3 to form an insoluble lake which is fast in washing.
The process of formation of metallic hydroxides on the fibres before
dyeing is known as mordnating.
∆
b) 2(AlCl3 .6H 2 O)  → Al 2 O3 + 6HCl + 9H 2 O
Because of hydrolysis of AlCl3 it never produces anhydrous AlCl3.
c) AlCl3 + 6H 2O [Al(H 2O)6 ]+3 + 3Cl –
[Al(H 2O)6 ]+3 [Al(H 2 O)5 OH]+2 + H +
because of H+ generation in aq. solution AlCl3 shows acidity.
ON S NO

d) Fe Fe

ON S NO
There is Fe – Fe bond in the molecule

Problem 6: Glass made of SiO2 is attacked by HF with the formation of SiF62– anion. The
analogous CF62– does not exist.

Solution: Silicon has 3d-orbitals and can use octahedral sp3d2-hybrid orbitals to bond to
six F – ions. Carbon lacks 2d-orbital (2d does not exist) and with just 2s and
2p valence orbitals, carbon can form maximum of only four bonds.

Problem 7: What happens when

a) FeSO4 reacts with K2Cr2O7/H+ and then K4[Fe(CN)6] is added.
b) FeSO4 is strongly heated.

Solution: a) 6FeSO4 + K2Cr2O7 + 7H2SO4 → 3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + 7H2O

4Fe3+ + 3K4[Fe(CN)6] → Fe4[Fe(CN)6]3 + 12K+
b) 2FeSO4 →Δ
Fe2O3 + SO2 + SO3

Problem 8: Comment on each of the following observations:

a) When an aqueous solution of potassium cyanide is added to aluminium
sulphate, Al(OH)3 is precipitated.
b) The carbide Mg2C3 liberated propyne ((CH3C ≡ CH) on treatment with
water.
c) Magnesium silicide reacts with ammonium bromide in liquid ammonia to
form silane.
d) SiMe2 Me
Me2 Si Si

SiMe2 H

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Is hydrolysed by aqueous alkali at the same rate as the corresponding

Si – D compound.

Solution: a) Aqueous solution of KCN is alkaline due to hydrolysis of CN – ion.

CN – + N 2 O → HCN + OH –
weak acid
–
OH formed causes precipitation of Al2 (SO4)3 as Al(OH)3
Al3+ + 3OH – 
→ Al(OH)3 ↓
→ 2Mg 2+ + C34–
b) Mg 2 C3 
C34– ion is decomposed by H2O giving CH 3C ≡ CH
C3– — C ≡ C – + 4H 2 O 
→ CH 3 — C ≡ CH + 4OH –
2Mg 2+ + 4OH – 
→ 2Mg(OH) 2
Net: Mg 2C3 + 4H 2O  → 2Mg(OH)2 + CH 3 — C ≡ CH
c) Solutions of NH4Br (in general ammonium halide) in NH3 may be used as
acids and SiH4 (silane) is formed when NH4Br in NH3 reacts with Mg2Si
(magnesium silicide)
Mg 2Si + 4NH 4 Br  → SiH 4 + 2MgBr2 + 4NH 3
magnesium silicide silane

d) Si—H or Si—D bond is not broken in rate determing step, it is probable

that there is attack of OH – on Si.

Problem 9: Compound (A)

i) On strong heating gives two oxides of sulphur
ii) On adding aqueous NaOH solution to its aqueous solution, a dirty green
ppt is obtained which starts turning brown on exposure to air. Identify (A)
and give chemical equations involved.
∆
Solution: 2FeSO 4  → Fe 2 O3 + SO 2 + SO3
(A)

FeSO 4 + 2NaOH 
→ Fe(OH) 2 + Na 2SO 4
Fe(OH) 2 →
(O)
Fe(OH)3

Problem 10: Silver nitrate gives a white precipitate with aqueous sodium thiosulphate; the
precipitate dissolves in excess of thiosulphate. If the precipitate is heated with
water it turns black, and the supernatant liquid then gives a white precipitate
with acidified barium nitrate solution.

Solution: When sodium thiosulphate (Na2S2O3) solution is added to silver nitrate

(AgNO3) solution, there is a white precipitate due to the formation of silver
thiosulphate (Ag2S2O3); these precipitate dissolve in excess of sodium
thiosulphate due to the formation of the complex [Ag(S2O3)2]3–
2AgNO3 + Na 2S2 O3  → Ag 2S2 O3 ↓ + 2NaNO3
silver thiosulphate
(white precipitate)

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Ag 2S2 O3 + 3Na 2S2 O3 

→ 2Na 3 [Ag(S2 O3 )2 ]
sodium argentothiosulphate

If the precipitate of Ag2S2O3 is heated, there is disproportionation giving black

precipitate of Ag2S and soluble H2SO4 which remains in the upper
(supernatant) layer which gives white precipitate (of BaSO4) with Ba(NO3)2
solution.
Ag 2S2 O3 + H 2 O  → AgS ↓ + H 2SO 4
white precipitate black precipitate

H 2SO 4 + Ba(NO3 )2 
→ BaSO 4 ↓ + 2HNO3
white precipitate

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KVPY
1. The solubility of the hydroxide of Be, Mg, Ba and Ca in water follows the order (2007)
(A) Be > Mg > Ca > Ba (B) Mg > Be > Ca > Ba
(C) Ca > Ba > Mg > Be (D) Ba > Ca > Mg > Be

2. The pair of atoms having the same number of neutrons is (2013)

(A) 126 C,12
24
Mg (B) 23 19
11Na,9 F (C) 23 24
11Na,12 Mg (D) 23
11 Na,39
19 K

No solution

3. Acetic acid reacts with sodium metal at room temperature to produce (2013)
(A) CO2 (B) H2 (C) H2O (D) CO
4. Li metal is a better reducing agent than Na metal because (2008)
(A) The ionization enthalpy of Li is lower that of Na
(B) The hydration enthalpy of Li is lower than that of Na
(C) The ionization enthalpy of Li is higher than that of Na
(D) The hydration enthalpy of Li is higher than that of Na

5. The numbers of lone pairs of electrons in XeF2 and XeF4 respectively, are- (2008)
(A) 3 and 3 (B) 2 and 3 (C) 2 and 2 (D) 3 and 2

6. When chlorine gas is passed through an aqueous solution of KBr, the solution turns orange brown
due to the formation of (2011)
(A) KCI (B) HCl (C) HBr (D) Br2

7. Methyl chloride reacts with X at high temperature in the presence of a catalyst Y to give Me2SiCl2 as
one of the product. The compound can also be formed by reaction of silicon tetrachloride with an
organometallic reagent, Z. X, Y, and Z respectively, are (2008)
(A) Si, Cu, MeMgBr (B) SiO2, Cu, Me2Zn (C) Si, Ni, MeMgBr (D) SiO2, Fe,
Me2Zn

8. The number of P–H bond(s) in H3PO2, H3PO3, and H3PO4, respectively, is (2011)
(A) 2, 0, 1 (B) 1, 1, 1 (C) 2, 0, 0 (D) 2, 1, 0

9. The Lewis acid strength of BF3, BCl3 and BBr3 follows the order. (2008)
(A) BBr3 > BCl3 > BF3 (B) BF3 > BCl3 > BBr3
(C) BCl3 > BBr3 > BF3 (D) BCl3 > BF3 > BBr3

Answer Key :
1:D 2:C 3:B 4:D

5:D 6:D 7:A 8:D

9:A

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Assignments
SECTION – I Single Choice Questions

1. The species that does not contain peroxide ion is

(a) PbO2 (b) H2O2
(c) SrO2 (d) BaO2

2. Butter of tin is
(a) (NH4)2SnCl6 (b) SnCl2 + Sn(OH)2
(c) SnCl4. 5H2O (d) H2SnCl4

3. Which compound gives O2 on moderate heating?

(a) CuO (b) HgO
(c) ZnO (d) Al2O3

4. When orthoboric acid is heated strongly, it gives

(a) B2O3 (b) H2B4O7
(c) HBO2 (d) B

5. When conc. H2SO4 is added to dry KNO3, brown fumes are evolved. These fumes are of
(a) SO2 (b) SO3
(c) N2O (d) NO2

6. Pyrene (a fire extinguisher)is

(a) SiCl4 (b) CCl4
(c) GeCl4 (d) SbCl5

7. A gas which burns with blue flame is

(a) CO (b) O2
(c) N2 (d) CO2

8. In Holmes signals the compound used is

(a) Ca 3 P2 + CaC 2 (b) CaC2
(c) Ca3P2 (d) CaCN2 + Ca3P2

9. Which of the following on heating give O2 gas?

(a) Lead nitrate (b) Potassium chlorate
(c) Manganese dioxide (d) All the above

10. A kettle which becomes furred – up in use has a deposit inside it which is composed
mainly of
(a) Calcium carbonate (b) Magnesium bicarbonate
(c) Magnesium sulphate (d) Sodium sulphate

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11. The anhydride of nitrous acid is

(a) N2O3 (b) NO
(c) N2O (d) N2O4

12. A mixture of hydrazine and H2O2 is

(a) antiseptic (b) rocket fuel
(c) germicide (d) insecticide
13. Hydrolysis of one mole of peroxy disulphuric acid produces
(a) two moles of sulphuric acid
(b) two moles of peroxy monosulphuric acid
(c) one mole of sulphuric acid and one mole of peroxy mono sulphuric acid
(d) one mole of sulphuric acid, one mole of peroxy mono sulphuric acid and one mole of
H2O2 .

14. The blue colour mineral lapis lazull which is used as a semi precious stone is a mineral of
the following class
(a) Sodium alumino silicate (b) Zinc cobaltate
(c) Basic copper carbonate (d) Prussian blue.

15. The following compounds have been arranged in the order of increasing thermal
stabilities. Identify the correct order.
K2CO3(I), MgCO3 (II), CaCO3 (III), BeCO3 (IV)
(a) I < II < III < IV (b) IV < II < III < I
(c) IV < II < I < III (d) II < IV < IIII < I
16. A solution of Na2SO4 in water is electrolysed using inert electrodes. The products at the
cathode and anode are respectively.
(a) H2O2 (b) O2, H2
(c) O2, Na (d) O2, SO2
17. Of the following acids
I: hypo phosphorous acid II: hydrofluoric acid
III: oxalic acid IV: glycine
(a) I, II are monobasic, III dibasic acid and IV amphoteric
(b) II monobasic, I, III dibasic acid, IV amphoteric
(c) I monobasic, II, III dibasic, IV amphoteric
(d) I, II, III diabasic, IV amphoteric

18. The material used in the solar cells contains.

(a) Cs (b) Si
(c) Sn (d) Ti
19. The products formed when a solution of CuSO4 is added to conc. solution of KI are
(a) I2 + Cu+2 (b) CuI2
(c) I2 + Cu (d) Cu2I2

20. When iodine reacts with NaF, NaBr and NaCl:

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(a) It gives mixture of F2, Cl2 and Br2 (b) It gives chlorine
(c) It gives bromine (d) None of the above
21. The metal that is extracted from sea water is:
(a) Mg (b) Be
(c) Ca (d) Sr
22. Ordinary blackboard chalk is made of :
(a) limestone (b) gypsum
(c) fluorspar (d) calcium phosphate

23. The most electropositive amongst the alkaline earth metals is:
(a) Be (b) Mg
(c) Ca (d) Ba

24. Which of the following is most acidic ?

(a) Na2O (b) MgO
(c) Al2O3 (d) CaO

25. Al2O3 formation from aluminium and oxygen involves evoluation of a large quantity of
heat, which makes aluminium use in:
(a) deoxidiser (b) confectionary
(c) indoor photography (d) thermite welding

SECTION – II May be more than one choice

1. In the electrolysis of alumina, cryolite is added to:

(a) lower the melting point of a alumina (b) increase the electrical conductivity
(c) minimize the anode effect (d) remove impurities from alumina

2. Nitrogen (I) oxide is produced by :

(a) thermal decomposition of ammonium nitrate
(b) disproportionation of N2O4
(c) thermal decomposition of ammonium nitrite
(d) interaction of hydroxylamine and nitrous acid.

3. The compounds used as refrigerant are

(a) NH3 (b) CCl4
(c) CF4 (d) CF2Cl2 (e) CH2F2

4. The major role of fluorspar (CaF2), which is added in small quantities in the electrolytic
reduction of alumina dissolved in fused cryolite (Na3AlF6), is
(a) as a catalyst
(b) to make the fused mixture very conducting
(c) to lower the temperature of the melt
(d) to decrease the rate of oxidation of carbon at the anode.

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5. When zeolite, which is hydrated sodium aluminium silicate, is treated with hard water,
the sodium ions are exchanged with
(a) H+ ions (b) Ca+2 ions
(c) SO4–2 ions (d) Mg+2 ions

6. Sodium nitrate decomposes above 8000C to give

(a) N2 (b) O2
(c) NO2 (d) Na2O
7. White phosphorus (P4) has
(a) six P-P single bonds (b) four P-P single bonds
(c) four lone pairs of electrons (d) PPP angle of 600
8. Ammonia, on reaction with hypochlorite anion, can form
(a) NO (b) NH4Cl
(c) N2H4 (d) HNO2
9. The pairs of compound which cannot exist together in aqueous solution are
(a) NaH2PO4 and Na2HPO4 (b) Na2CO3 and NaHCO3
(c) NaOH and NaH2PO4 (d) NaHCO3 and NaOH
10. Highly pure dilute solution of sodium in liquid ammonia :
(a) shows blue colour (b) exhibits electrical conductivity
(c) produces sodium amide (d) produces hydrogen gas
11. Alkali metals are characterized by:
(a) good conductor of heat and electricity (b) high oxidation potentials
(c) high melting points (d) solubility in liquid ammonia

12. Li has following abnormal behaviour in its group:

(a) Lithium carbonate decomposes into its oxide on heating, unlike other elements
(b) LiCl is covalent in nature
(c) Li3N is stable compound
(d) LiCl is poor conductor of electricity in molten state

13. Select wrong statements about alkali metals :

(a) all form (M NH2) amide (b) all form super oxides (M O2)
(c) all form ionic hydrides (M H) (d) all form nitrides

14. Which among the following compounds are paramagnetic

(a) KO2 (b) K2O2
(c) K2O (d) NO2

15. Nitrate of which of the following elements are converted to their oxides on heating ?
(a) Li (b) Na
(c) K (d) Mg

16. Orthoboric acid (H3BO3) and metaboric acid (HBO2) differ in respect of :
(a) basicity (b) structure
(c) melting point (d) oxidation

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17. Select the correct statements about diborane :

(a) B2H6 has three centred bound
(b) each boron atom lies in sp3 hybrid state
(c) Hb . . . . . B . . . . . .Hb bond angle is 1220
(d) All hydrogens in B2H6 lie in the same plane
18. Stability of monovalent and trivalent cations of Ga, In, Tl lie in following squence:
(a) Ga3+ < In3+ > Tl3+ (b) Ga3+ > In3+ > Tl3+
+ + +
(c) Tl > In > Ga (d) Ga3+ > In+ > Tl+
19. Which of the following are true about silicones ?
(a) they are formed by hydrolysis of R2SiCl2
(b) they are polymer, made up of R2SiO2 units
(c) they are made up of SiO44 − units
(d) they are macromolecules

20. Which among the following statements are correct ?

(a) Aqua dag and oil dag are made up of graphite
(b) Graphite reacts with conc. HNO3 to form mellitic acid C6(COOH)6
(c) C3O2 is also toxic like CO
(d) Zircon, ZrSiO4 is a gemstone

21 Select the correct statements about oxygen molecule :

(a) It is paramagnetic (b) its bond order is two
(c) In liquid state it is blue coloured (d) It has two unqaired electrons

22. Sulphuric acid can be used as :

(a) hygroscopic agent (b) oxidizing agent
(c) sulphonating agent (d) efflorescent

23. Sodium sulphate is soluble in water but barium sulphate is sparingly soluble because :
(a) the hydration energy of Na2SO4 is more that its lattice energy
(b) the lattice energy of BaSO4 is more than its hydration energy
(c) the lattice energy has no role to play in solubility
(d) the lattice energy of Na2SO4 is more than its hydration energy
24. Mg and Zn has following resemblance :
(a) MgO and ZnO are amphoteric
(b) MgCO3, ZnCO3 both on heating give corresponding oxide
(c) both are used as electrodes
(d) both are used to prevent corrosion
25. Be and Al have following resemblance due to diagonal relationship :
(a) have nearly equal electronegativity (b) form amphoteric oxides
(c) have same charge / radius ratio (d) both form dimeric halides

SECTION – III Comprehension Type Questions

Write-up I

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The thermal stability of the salts of the s-block elements is dependent upon three main
factors. Firstly, the greater the charge of the ions involved, the stronger the interionic
attraction and the more stable the salt. Also, the smaller the ions become in terms of their
ionic radii the closer they approach each other in the lattice area of comparable size, the
crystal lattice is arranged in a more uniform fashion and thus possess greater thermal
stability. There is one another factor that affects thermal stability. The larger the anions in
the crystal become, for example CO32− , unless the cation is of comparable size, the anions
decompose on heating to give smaller anions such as O2–. This point is especially
important when considering the thermal stability of the carbonates, nitrates and
hydroxides of the s-block elements.

An unknown s-block salt was uncovered at the landing of a meteor. When converted to its
hydroxide, it was found that the Kb of salt was 1.0 × 10−6. It did not decompose to the
oxide. The metal obtained exhibited the typical properties of most s-block metals :-
ductile, malleable, luster, good electrical and thermal conductivity and a high reactivity.
The original salt obtained from the meteor possessed a complex formula and the metal
itself had a high molecular weight.

1. Which groups of the periodic table comprise the s-block elements ?

(a) Groups I, II and III (b) Groups I and II
(c) Groups II and III (d) Groups I and II

2. Given that the CO2− anion is approximately the same size as the early Group I cations,
3
what would occur if Na2CO3 were heated ?
(a) It would decompose to yield Na2 (b) It would decompose to yield Na2CO2
(c) It would decompose to yield NaOH (d) No decomposition would occur

3. Comparing calcium oxide and magnesium oxide, which of the two would be more stable?
(a) Magnesium oxide would be more stable because the magnesium cation is smaller
(b) Magnesium oxide would be more stable because magnesium has a lower atomic mass
than calcium
(c) Calcium oxide would be more stable because the calcium cation is smaller than the
magnesium cation
(d) Calcium oxide would be more stable because calcium has a greater atomic
mass than magnesium

4. (
The nitrates of the Group I elements decompose not to the oxide but to the nitrite NO 2
−
)
−
although O2− is smaller than NO2 . Why ?
(a) Because only doubly charged anions like CO2− decompose to the oxide
3
(b) Because the double charge on the oxygen would make the salt less stable than
a singly charged nitrite anion
(c) Because the nitrite anion contains two oxygen atoms while the oxide anion
contains only one

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(d) Because the nitrite anion is probably about the same size as the Group I
cations

5. When s-block carbonates decompose, a gas is obtained which is heavier than air and does
not support a lighted splint. What gas is it ?
(a) O2 (b) CO
(c) CO2 (d) CO3

6. What would be the pH of a 1.0 M solution of the unknown salt hydroxide given that the
metal is monovalent ?
(a) 11 (b) 8.0
(c) 75 (d) 13.0
7. Li2O is often considered to be covalent in nature because of the unusually high electro-
negativity of lithium. Which of the following would be a plausible Lewis dot structure for
the compound.
• • • •

(a) Li − Li − O
• •
(b) Li − O− Li
• •

• •

(c) Li = O = Li (d) Li − O− Li
• •

Write-up II
In all the oxyacids of phosphorus, each phosphorus atom is in sp3 hybrid state, i.e., it is
tetrahedrally bonded to neighbouring four atoms. All these acids contain P - OH bonds,
the hydrogen atom of which are ionisable imparting acidic nature to the compound. The
ous acids (oxidation state of P = +1 or +3) also have P - H bonds in which hydrogens are
not ionisable (P and hydrogen have nearly same electronegativity). The presence of P − H
group in these acids imparts reducing properties. The structure of the various acids are
drawn below (note that the tetrahedral shape of phosphorus is not shown only for
convenience of representation).
O O O

OH P H HO P OH HO P P OH

H H OH OH
(A) Hypophosphorous acid (B) Phosphorous acid (C) Hypophosphoric acid

O O O O

HO P OH HO P O HO P O P OH

H H OH OH
(D) Phosphoric acid (E) Metaphosphirc acid (F) Pyrophosphric acid
(Orthophosphoric) acid

8. In which of the above structures, the oxidation state of P is +5.

(a) D & E (b) F & E
(c) C,D & E (d) D,E & F

9. Among the above acids, the acids having basicity 4 are :

(a) A & E (b) C & D
(c) C & F (d) D & F

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10. There is very little difference in acid strength in the series H3PO4, H3PO3 and H3PO2
because
(a) phosphorus in these acids exists in different oxidation states
(b) the hydrogen in these acids are not all bonded to phosphorus
(c) phosphorus is not a highly electronegative element
(d) phosphorus oxides are less basic
11. Which of the acids show reducing properties?
(a) A & C (b) A & B
(c) A, B & E (d) A only
12. Although metaphosphoric acid is written as a monomer, it exists as a polymer, (HPO3)n. The
number of P − O − P bonds in cyclic tri-metaphosphoric acid is
(a) zero (b) two
(c) three (d) four
13. Metaphosphoric acid (E) can be prepared by heating
(a) D & F (b) C & F
(c) C & D (d) B,C & F

Write-up III
Several features of sulfuric acid are given below:
Preparation of Sulfuric Acid: Sulfuric acid is commonly prepared by the combustion of
elemental sulfur to sulfur dioxide, followed by the catalytic oxidation of sulfur dioxide to
sulfur trioxide. Sulfur trioxide is then absorbed into a 98% aqueous solution of H2SO4 , and
water is added to maintain a 98% concentration. SO3 reacts with the water in the aqueous solution
according to Reaction-1.
SO3(g) + H2O ——> H2SO4(l); Reaction-1
Properties: Concentrated sulfuric acid is 98% H2SO4 and 2% water by mass. It has a density of
1.84 g/mL and a boiling point of 338° C. Preparation of other Acids: HC1 (g) and HNO3 (l) may
be prepared by the reaction between sulfuric acid and the sodium salt of the corresponding
conjugate base (C\~ or NOJ, respectively).
Formation of SO2: Sulfuric acid forms SO2 gas when it reacts with several compounds. For
example, I2 and SO2 are formed when 12 reacts with concentrated H2SO4; Br2 and SO2 are formed
when Br2 reacts with concentrated H2SO4. Cu+ and SO2 are formed in hot solutions of Cu(s) in
H2SO4. This last reaction is unusual, because most metals react with solution of H2SO4 to form
hydrogen gas and a metal sulfate.

14. When sulfuring acid reacts with copper, how does the oxidation of number of the sulfur
change ?
(a) From + 4 to + 6 (b) From + 6 to + 4
(c) From + 6 to + 8 (d) From + 8 to + 6

15. The apparatus shown below can be used to prepare HNO3 (boiling point = 86°C).

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The yield of HNO3 collected in the tube can be maximized by maintaining the
temperatures of the flask and tube, respectively, at
(a) 0°C and 100°C (b) 100°C and 0°C
(c) 350°C and 150°C (d) 350°C and 100°C

16. Which of the following is the balanced equation describing the combustion of element
sulfur ?
(a) 2H 2S + 3O2 → 2SO 2 + 2H 2O (b) H 2S + 2O 2 → SO3 + H 2O
(c) 2SO3  → 2S + 3O 2 (d) S + O 2  → SO 2
17. In the second step of preparing H2SO4 from elemental sulfur (the catalytic oxidation of
SO2), which strategy is most likely to increase the yield of SO3 formed ?
(a) Reducing the reaction temperature
(b) Reducing the reaction pressure
(c) Removing SO3 from the reaction mixture
(d) Removing O2 from the reaction mixture

18. Which of the following expressions can be used to determine the number of moles of
water in 1 mL. Of concentrated H2SO4 ?

(a)
(1.84 )( 0.98 ) + (1.84 )( 0.02 ) (b)
(1.84 )( 0.2 )
98 18 18
(c)
(1.84 )( 0.98 ) (d)
(1.84 )( 0.98 )(18.0 )
18 98.0

19. If H2(g) is formed from the reaction of Fe(s) with dilute H2SO4 (aq), which species acts as
the reducing agent ?
(a) Fe (b) FeSO4
2−
(c) SO4 (d) H 3O+

20. Which of the following species has the smallest concentration in 98% H 2SO 4 ?
(a) SO24− (b) H 2SO 4
+
(c) H 3O (d) HSO−4

SECTION – IV Subjective Questions

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LEVEL – I

1. BaO2 is a peroxide but PbO2 is not a peroxide why?

2. Why sodium thiosulphate is used in photography?

3. What happens when (NH4)2 Cr2O7 is heated?

4. Is there any coloured oxide of Nitrogen?

5 PCl5 exists but NCl5 does not. Explain.

6. MnO4–2 disproportionates to MnO2 and MnO4– in alkaline medium. Explain by reactions.

7. Explain how do you account for high b.p. and high viscosity of sulphuric acid.

8. Fluorine does not show positive oxidation state. Why?

9. When a blue litmus is dipped into a solution of hypo chlorous acid, it first turns red and
then later gets decolourised. Why?

10. Xe cannot form XeF3 , XeF5 type of compound. Why?

11. Calcium burns in nitrogen to produce a white powder which dissolves in sufficient water
to produce a gas (A) and an alkaline solution. The solution on exposure to air produces a
thin solid layer of (B) on the surface. Identify the compound (A) and (B).

12. You have been given AlCl3 and ZnCl2 solution. To each NaOH and NH4OH are added in
excess. What happens?

13. A mixture of Al(OH)3 and Fe(OH)3 are given to you. How would you separate it?

14. Explain briefly: Why hydrazine is unstable?

15. Anhydrous AlCl3 cannot be prepared by heating hydrated AlCl3.6H2O – why?

LEVEL – II
1. CO2 is gas but SiO2 is Solid – Explain.
2. Complete the following reactions:
a) Cl2 + S–2 →
b) SiO2 + HF (excess) →

3. Statues coated with white lead on long exposure to atmosphere turns black and the
original colour can be restored in treatment with H2O2 why?

4. When SnCl2 solution is added excess into a solution of HgCl2 , a white ppt is turning
grey. Why?

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5. a) Write one reaction each showing oxidizing and reducing properties of HNO2.
b) Describe briefly the manufacture of nitric acid.
6. In the following, find out A, B, C, D and E. Write down the reactions also.
i) A black mineral (A) on treatment with dilute NaCN solution in presence of air gives a
clear solution of (B) and (C).
ii) The solution of (B) on reaction with Zn gives precipitate of a metal (D).
iii) (D) is dissolved in dil. HNO3 and the resulting solution gives a white ppt. (E) with dil.
HCl.
iv) (E) on fusion with Na2CO3 gives (D).
v) (E) dissolves in aqueous solution of NH3 giving a colourless solution of (F).
7. Why hydrated barium peroxide is used in the preparation of H2O2 instead of the
anhydrous variety?
8. Boric acid can be estimated by titration with standard alkali solutions, in the presence of
glycerol using phenolphthalein as an indicator. What is the function of glycerol in this
titration?
9. Complete the following by identifying (A) to (H)
100° C 230° C 800° C
i) CuSO 4 ⋅ 5H 2 O  →(A)  →(B)  →(C) + (D) C
ii) AgNO3 
Red heat
→(E) + (F) + O 2
740° C
iii Na 2 B4 O7  →(G) + (H)

10. Borazine is isoelectronic with benzene but it is much more reactive than benzene. Explain
briefly why this is so and what will be the nature of reagent attacking the borazine
molecule.

11. The gas liberated on heating a mixture of two salts with NaOH gives a reddish brown
precipitate with an alkaline solution of K2Hgl4. The aqueous solution of the mixture on
treatment with BaCl2 gives a white precipitate which is sparingly soluble in concentrated
HCl. On heating the mixture with K2Cr2O7 and conc. H2SO4, red vapours (A) are
produced. The aqueous solution of the mixture gives a deep blue colouration (B) with
K3Fe(CN)6] solution. Identify the radicals in the given mixture and write the balanced
equations for the formation of (A) and (B).

12. An organic solid (A) on heating gives a green residue (B), a colourless gas (C) and water
vapours. The dry gas (C) passing over heated Mg gave a white solid (D). (D) on reaction
with water give a gas (E) which formed dense white fumes with HCl. Identify (A) to (E)
and give the reactions involved.

13. What mass of H2SO4 could be produced in the process given below if 1.00 kg of FeS2 is
used? The unbalanced equations for the process are:
FeS2 (s) + O2 (g) 
→ Fe 2 O3 (s) + SO 2 (g)
SO2 (g) + O 2 (g) 
→ SO3 (g)
SO3 (g) + H 2SO4 (l) 
→ H 2S 2 O 7 ( l )

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H 2S2 O7 (l) + H 2 O(l) 

→ H 2SO 4 (aq)
(Fe = 56, S = 32)

14. Colourless salt (A)  → (B) gas

NaOH, ∆

↓ CaCl2- solution
White ppt. (C)
(B) gives white fumes with HCl.
(C) decolourises acidified KMnO4.
What is (A), (B) and (C)? Explain reactions
15. The action of concentrated sulphurous acid on urea (NH2CONH2) results in the
production of a white crystalline solid X of formula H3NO3S. This is a monobasic acid.
On treatment with sodium nitrate and dilute hydrochloric acid at 0°C it liberates 1 mol of
N2 per mol of X, and on addition of aqueous barium chloride the resulting solution yields
1 mol of BaSO4 per mol of X taken. Deduce the structure of X.

LEVEL – III (Judge yourself at JEE level)

1. When a white crystalline compound X is heated with K2Cr2O7 and concentrated H2SO4, a
reddish brown gas A is evolved. On passing A into caustic soda solution, a yellow
coloured solution of B is obtained. Neutralizing the solution of B with acetic acid and on
subsequent addition of lead acetate, a yellow precipitate C is obtained. When X is heated
with NaOH solution, a colourless gas is evolved and on passing this gas into K2HgI4
solution, a reddish brown precipitate D is formed. Identify A, B, C, D and X. Write the
equations of reaction involved. [IITJEE, 2002]
2. How is boron obtained from borax? Give chemical equations with reaction conditions.
Write the structure of B2H6 and its reaction with HCl. [IITJEE, 2002]
3. Compound (X) on reduction with LiAlH4 gives a hydride (Y) containing 21.72%
hydrogen along with other products. The compound (Y) reacts with air explosively
resulting in boron trioxide. Identify (X) and (Y). Give balanced reactions involved in the
formation of (Y) and its reaction with air. Draw the structure of (Y). [IITJEE, 2001]

4. Starting with SiCl4, prepare the following in steps not exceeding the number given in
parentheses (give reactions only):
i) Silicon (1)
ii) Linear silicone containing methyl groups only (4)
iii) Na2SiO3(3) [IITJEE, 2001]
5. A white solid is either Na2O or Na2O2. A piece of red litmus paper turns white when it is
dipped into a freshly made aqueous solution of the white solid.
i) Identify the substance and explain with balanced equation.
ii) Explain what would happen to the red litmus if the white solid were the other
compound. [IITJEE, 1999]
6. Give reasons for the following in one or two sentences only.
i) BeCl2 can be easily hydrolysed.
ii) CrO3 is an acid anhydride. [IITJEE, 1999]

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7. a) In the following equation:

A + 2B + H 2 O  → C + 2D
(A = HNO 2 , B = H 2SO3 , C = NH 2 OH)
Identify D. Draw the structures of A, B, C and D.
b) In the contact process for industrial manufacture of sulphuric acid, some amount of
sulphuirc acid is used as a starting material. Explain briefly. What is the catalyst used
in the oxidation of SO2? [IITJEE, 1999]

8. a) Complete and balance the following chemical equations:

i) P4 O10 + PCl5 
→
ii) SnCl4 + C 2 H 5 Cl + Na 
→
b) Work out the following using chemical equations:
i) In moist air, copper corrodes to produce a green layer on the surface
ii) Chlorination of calcium hydroxide produces bleaching power. [IITJEE, 1998]

9. a) Write balanced equations for the following:

i) Phosphorus is treated with concentrated nitric acid.
ii) Oxidation of hydrogen peroxide with potassium permanganate in acidic medium.
iii) Manufacture of phosphoric acid from phosphorus.
iv) Reaction of aluminium with aqueous sodium hydroxide.
v) Reaction of zinc with dilute nitric acid.
b) Element A burns in nitrogen to give an ionic compound B. Compound B reacts with
water to give C and D. A solutions of C becomes `milky’ on bubbling carbon dioxide.
Identify A, B, C and D. [IITJEE, 1997]

10. i) Gradual addition of Kl solution to Bi(NO3)3 solution initially produces a dark brown
precipitate which dissolves in excess of KI to give a clear yellow solution. Write
chemical equations for the above reactions.
ii) A colourless inorganic salt (A) decomposes completely at about 250°C to give only
two products (B) and (C), leaving no residue. The oxide (C) is a liquid at room
temperature and neutral to moist litmus paper while the gas (B) is a neutral oxide.
White phosphorus burns in excess of (B) to produce a strong white dehydrating agent.
Write balanced equations for the reactions involved in the above process.

Answers to Assignments
SECTION - I

1. (a) 6. (b) 11. (a) 16. (a) 21. (a)

2. (c) 7. (a) 12. (d) 17. (a) 22. (b)
3. (b) 8. (a) 13. (c) 18. (b) 23. (d)
4. (a) 9. (d) 14. (a) 19. (d) 24. (c)
5. (d) 10. (a) 15. (b) 20. (d) 25. (d)

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SECTION - II

1. (a), (b) 8. (c) 15. (a), (d) 22. (a), (b), (c

2. (a), (d) 9. (c), (d) 16. (a), (b), (c) 23. (a), (b)
3. (a), (d) 10. (a), (b) 17. (a), (b), (c) 24., (b), (c), (d)
4. (b), (c) 11. (a), (b), (d) 18. (b), (c) 25. (a), (b), (c), (d)
5. (b), (d) 12. (a), (b), (c) 19. (a), (b), (d)
6. (a), (b), (d) 13. (b), (d) 20. (a), (b), (d)
7. (a), (c), (d) 14. (a), (d) 21. (a), (b), (c), (d)

SECTION - III

1. (d) 6. (a) 11. (b) 16. (d)

2. (d) 7. (b) 12. (c) 17. (c)
3. (a) 8. (d) 13. (a) 18. (b)
4. (d) 9. (c) 14. (a) 19. (a)
5. (c) 10. (b) 15. (b) 20. (a)

SECTION - IV

LEVEL – I
1. Metallic oxides which on treatment with dilute acids produce hydrogen peroxide are
called peroxides. All peroxides contain a peroxide ion (O2)2– having the structure [– O –
O –]. PbO2 does not contain a peroxide ion (O2)2− and it can not be called as peroxides.

2. It can remove the undecomposed AgBr as soluble silver thiosulphate complex.

2Na2S2O3 + AgBr →Na3 [Ag(S2O3)2 ] + NaBr

3. (NH4)2Cr2O7 → N2 + Cr2O3 + 4H2O

4. The known oxides of N are N2O , NO,NO2 , N2O3 , N2O4 and N2O5 . Among these NO2 is
brown gas and N2O3 is blue coloured liquid.

5. Nitrogen does not possess 2d - subshell and it cannot excite its 2s paired electron to get
unpaired whereas phosphorus does so on account of availability of 3d - subshell.

6. 3MnO4–2 + 2H2O → MnO2 + 2MnO4– + 4OH–

7. The high boiling point and viscosity of sulphuric acid are due to the presence of hydrogen
bonding which binds a number of simple molecules into clusters.

8. It is the most electronegative element. So, whenever it is bonded with any other atom, the
bond pair is shifted towards F only.

9. HClO is an acid, thus turns blue litmus into red. HClO is an oxidizing agent also and the
nascent oxygen given by HClO bleaches the red litmus
Red litmus + O  → colour less.

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10. The electronic configuration of Xe is 5s2 5p6. So, all the electrons are paired up and when
it is excited, then either 2, or 4 or 6 etc. electrons will be unpaired .There is no scope to
get odd number of unpaired electrons in its outer most shell. For this reason it cannot
form XeF3 or XeF5 type of compound.

11. A = NH3 B = CaCO3

12. AlCl3 

NaOH
→ Al(OH)3 
excess
→ NaAlO2
white ppt. NaOH ppt. dissolved

AlCl3 →
NH 4 OH
Al(OH)3 
excess
→ ppt. not dissolved
white ppt. NH 4 OH

ZnCl2 
NaOH
→ Zn(OH)2 
excess
→ Na 2 ZnO 2
white ppt. NaOH ppt. dissolved

ZnCl2 → Zn(OH)2 

NH 4 OH excess
→ ppt. not dissolved
white ppt. NH 4 OH

13. It can be easily separated by the use of conc. NaOH solution which react only with
Al(OH)3 and forms soluble sodium aluminate. Fe(OH)3 will remain in the residue.
Al(OH)3 + NaOH → NaAlO2 +2H2O

14. In hydrazine, there is N—N single bond with a lone pair on each nitrogen. Due to the
small size of nitrogen, there is considerable repulsion between these nonbonding
electrons, thus weakening the N—N single bond. This makes hydrazine unstable.

15. Hydrolysis of AlCl3 takes place forming Al2O3

2AlCl3 + 3H 2 O → Al 2 O 3 + 6HCl

LEVEL – II

1. Carbon and silicon have four valence electrons. We might expect carbon and silicon to
form oxides with similar properties. In CO2 the ability of C and O atoms to form π bonds
through the side-wise overlap of their 2p orbitals is strong. The result is strong C – to –O
double bonds and a very stable triatomic molecule.
O=C=O
Silicon, being in third period, would have to use 3p orbtials to form double bonds with
oxygen.The side-wise overlap of these orbitals with the 2p orbitals of oxygen is too
limited for π bond formation. From an energy stand point, a stronger bonding
arrangement results if the Si atoms form four single bonds with O atoms (bond energy:
464 kJ/mol) rather than two double bonds (bond energy: 640 kJ/mol) since each O atom
must be simultaneously bonded to two Si atoms, the result is a network of
–– Si –– O –– Si –– bonds and thus a hard (giant) solid.

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O O

O O S O S O

O Si O O O

O O S O S O

O O

2. a) Cl2 + S–2 → 2Cl– + S

b) SiO2 + 6HF → H2[SiF6] + 2H2O

3. On long exposure to atmosphere, white lead is converted into black PbS due to the action
of H2S present in the atmosphere. As a result statues turn black.
PbO2 + 2H2S → PbS + 2H2O
On treatment of these blackened statues with H2O2, the black PbS gets oxidised to white
PbSO4 and the colour is restored
PbS + 4H2O2 → PbSO4 + 4H2O

4. When SnCl2 solution is added to HgCl2 solution, initially white ppt, of Hg2Cl2 is formed
which further reacts with SnCl2 forming metallic grey Hg.
2HgCl2 + SnCl2 → SnCl4 + Hg2Cl2 (white)
Hg2Cl2 + SnCl2 → SnCl4 + 2Hg (grey)

5. a) i) 2KI+ 2HNO 2 + 2HCl 

→ 2KCl + 2NO +2H 2 O + I 2
ii) 2KMnO 4 + 5HNO 2 + 6HCl  → 2MnCl2 + 5HNO 3 + 2KCl + 3H 2 O
b) Nitric acid is manufactured by Ostwald process. Ammonia is first oxidized to NO by
air in the presence of a Pt—Rh catalyst. NO is then mixed with more air to convert in
to NO2 which is dissolved in water to give HNO3.

6. (A) Ag2S (a black mineral) (B) Na[Ag(CN)2]

(C) Na2S (D) Ag
(E) AgCl (F) Ag(NH3)2Cl
The reaction are
1. Ag 2S + 4NaCN  → 2Na[Ag(CN) 2 ] + Na 2S
2. 2Na[Ag(CN) 2 ] + Zn 
→ Na 2 [Zn(CN) 4 ] + 2Ag
3. 3Ag + 4HNO 3 
→ 3AgNO 3 + NO + 2H 2 O
4. AgNO 3 →
HCl
AgCl + HNO 3
5. 4AgCl + 2Na 2 CO3 
→ 4Ag + 4NaCl + 2CO 2 + O 2
6. AgCl + 2NH 3 
→ Ag(NH 3 ) 2 Cl

7. If anhydrous barium peroxide is used in the preparation, the barium sulphate, thus
obtained forms an insoluble protective coating on the surface of solid barium peroxide.
This prevents the further reaction of the acid, i.e., causing the reaction to stop. If,
however, hydrated barium peroxide (in the form of this paste) is used, the water causes to

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dislodge the insoluble BaSO4 from the surface of BaO2. BaSO4 thus settles at the bottom
of the reaction vessel and the reaction continues without any difficulty.

8. As explained above, boric acid is a weak monobasic acid. On addition of glycerol to boric
acid, a chelate complex is formed due to which the strength of boric acid increases by a
factor of 10 4 . Thus, in the presence of glycerol, boric acid can be used as a primary
standard using phenolphthalein as indicator.
100° C 230° C
9. i) CuSO 4 ⋅ 5H 2 O  → CuSO 4 ⋅ H 2 O  → CuSO 4
(A) (B)
800° C
CuSO 4 
→ CuO + SO3
(B) (C) (D)

ii) 2AgNO3 

→ 2Ag + 2NO2 + O 2
Red heat

(E) (F)
740° C
iii) Na 2 B4 O7 
→ NaBO2 + B2 O3
(G ) (H)

10. In benzene, the π electrons are completely delocalised over all the carbon atoms whereas
in borazine these are only partially delocalised. Due to the difference in electro
negativities of B and N atoms, there is a drift in the electron density in both σ- and π-B-N
bonds. The drift in B-N-σ-bond is from B to N and it outweighs the drift in B-N π- bond
which is from N to B. Thus, nitrogen acquires a net negative charge whereas boron
acquires a net positive charge. This results in a nucleophilic attack on boron in borazine.

11. i) The gas which is liberated on heating the mixture with NaOH gives red ppt. with
K2Hgl4 so gas is NH3 and mixture contains NH +4 ion.
ii) Mixture on heating with K 2 Cr2 O7 and H 2SO 4 gives red vapours of CrO 2 Cl2 so
mixture contains Cl – ions.
iii) Aqueous solution of mixture gives blue colour with K 3 [Fe(CN)6 ] and thus, it
contains Fe +2 ion.
iv) Thus mixtures has NH +4 , Fe +2 ,SO 4–2 , Cl –
Reaction:
i) NH +4 + NaOH  → NH 3 + Na + + H 2 O
ii) SO4–2 + BaCl2 
→ BaSO 4 ↓ + 2Cl –
white crystalline ppt.

iii) 4Cl + K 2 Cr2 O7 + 3H 2SO 4 

–
→ CrO2 Cl2 + K 2SO 4 + 3H 2 O +2SO 4–2
(Red) (A)
+2
→ Fe[Fe(CN)6 ]2 + 6K +
iv) 3Fe + 2K 3 [Fe(CN)6 ] 
(B) Blue

12. A = (NH4)2Cr2O7 B = Cr2O3

C = N2 D = Mg3N2
E = NH3

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13. Sulphuric acid contains one sulphur atom per molecule, and each FeS2 molecule gives
two atoms of sulphur. Thus,
FeS2  → 2SO 2 → 2SO 3  → H 2S2 O 7  → 2H 2SO 4
Thus, 1 mol of FeS2 gives = 2 mol H2SO4 = = 2 × 98g H 2SO 4
1000
Hence, 1.00 kg FeS2 = 1000 g FeS2 = mol FeS2
120
1000 2 × 98 × 1000
H 2SO 4 from mol FeS2 = g = 1.63 kg H2SO4
120 120

14. A = (NH4)2C2O4 B = NH3

C = CaC2O4

15 NH2CONH2 (urea) reacts with conc. H2SO3 forming X(H3NO3S) X contains one
ionization H (since X is a monobasic acid). Thus.
O H O
H2N + S O 
→ NH 2 — SO3 H + NH 3 + CO
X
NH2 H O
urea sulfurous acid
X contains free —NH2 as well as free —SO3H. (NaNO2 + HCl) converts free —NH2 into
free —OH group liberating N2.

NaNO 2 + HCl 
→ HNO 2 + NaCl
NH 2 — SO3 H + HNO 2 
→ N 2 ↑+ H 2 O + H 2SO 4
1 mol X 1 mol X 1 mol

H 2SO 4 + BaCl2 
→ BaSO 4 + 2HCl
1 mol 1 mol

Thus X is NH2 – SO3H (amino sulphonic acid), 1 mol of which liberated 1 mol of N2OH
reaction with (NaNO2 + HCl) at 0°C and in turns resulting solution gives 1 mol of BaSO4
on reaction with BaCl2.

LEVEL – III

1. The given reactions are as follows:

X + K 2Cr2 O7 + H 2SO 4  ∆
→ Gas
(white) (conc.) (reddish brown )

A + NaOH 
→ B
(yellow coloured solution)

B + CH 3COOH + Pb(CH 3COO) 2 

→ C
(yellow precipitate)

X +NaOH 
∆
→ Colourless gas →
K 2 HgI 4
D
(reddish brown precipitate)

The above reactions indicate that the compound X contains Cl – and NH +4 ions, hence the
compound is NH4Cl.
The reactions shown above are as follows:

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[Type text]

4Cl – + K 2 Cr2 O 7 + 6H 2SO 4 

→ 2 CrO 2 Cl2 + 2KHSO 4 + 4HSO 4– + 3H 2 O
(from NH 4 Cl) (Gas A)

CrO 2 Cl 2 + 4NaOH 
→ Na 2 CrO 4 + 2NaCl + 2H 2 O
yellow solution

Na 2 CrO 4 + (CH 3COO) 2 Pb 

→ PbCrO 4 + 2CH 3COONa
( yellow ppt.)
+
NH 4 + NaOH 
∆
→ NH 3 + Na + + H 2 O
(from NH 4 Cl) (gas)
+
NH 3 + 2HgI +H 2 O 
→ H2 N I + 7I + 3H
2– –
4 O
Hg Hg
(reddish brown precipitate)

2. Na 2 B4 O 7 .10H 2 O →
acid
H 3 BO3 
red heat
→ B2 O3 
Mg, high
temperature
→ 2B + 3MgO
B2 H 6 + HCl 
→ B2 H 3Cl + H 2
97Å
H 1.33Å H
H
122° B B 122°
1.19Å H
H H
1.77Å

3. Compound `X’ 

LiAlH 4
→ `Y’ [which contains 21.72% hydrogen and other products]
Compound `Y’ + O2 (air)  → B 2O3

Therefore compound `Y’ is hydride of boron and it is obtained by the reduction of `X’
with LiAlH4. Hence, X is BCl3.
Thus, 4BCl3 + LiAlH 4  → 3AlCl3 + 3LiCl + 2B2 H 6
`X ' 144244 3 `Y ' (diborane)
Other compound

Now,
Mol. wt. of compound Y (B2H6) = 21.76 + 6 = 27.76
6
∴ % of H in Y (B2H6) = ×100 = 21.72 % (Given)
27.76
B2 H 6 + 3O 2 (air) 
→ B2O3 + 3H 2 O + heat
`Y'

Structure of Y (B2H6)
In this case, two electrons of a B-H bond are involved in formation of three center bond
(Banana bond) these two bonds are represented by dotted lines in figure, in which one lies
above and second lies below to the main plane.
97Å
H 1.33Å H
H
122° B B 122°
1.19Å H
H H
1.77Å

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4. i) SiCl4 + 2Mg 
→ Si + 2MgCl2
ii) Step (i) 3 SiCl4 + 4Al  
—AlCl3
→ 3Si
∆
Step (ii) Si + Cu  → Cu — Si
Step (iii) Cu —Si + 2CH 3Cl 
→ (CH 3 ) 2 SiCl 2 + Cu
Step (iv)
H3C Cl H—O—H H3C OH

Si + 
–2HCl
→ Si

H3C Cl H—O—H H3C OH

Dimethyl silianediol
(Linear silicone)
CH3 CH3 CH3 CH3

∆
H O Si O H + HO Si O H 
–2H O
→ H O Si O Si O H
2

CH3 CH3 CH3 CH3

th
This polymerization continues on 60 ends to give linear silicone.

iii) Step (i) SiCl4 + 4H 2 O 

→ Si(OH) 4
Step (ii) Si(OH) 4 
→ SiO 2 + 2H 2 O
1500° C
Step (iii) SiO 2 + Na 2 CO 3  → Na 2SiO 3 + CO 2

5. i) The substance is Na2O2. When Na2O2 is dissolved in water, it forms NaOH with
H2 O2 .
Na 2 O 2 + 2H 2 O 
→ 2NaOH + H 2 O 2
Since, H 2 O 2 → H 2O + O
Therefore, H2O2 turns colour of red litmus paper into white due to its bleaching action
which is due to its oxidizing character.
ii) Other compound = Na2O
Na 2 O + H 2 O  → 2NaOH
NaOH solution turns colour of red litmus paper into blue due to its stronger alkaline
character.

6. i) Be = 1s 2 2s 2 2p1x 2p0y 2pz0

BeCl2 is hydrolysed due to high polarizing power and presence of vacant p-orbitals in
Be-atom.
ii) H 2 Cr2 O 4 
Dehydration
→ CrO 3 + H 2 O
Chromic acid
Therefore, CrO3 is acid anhydride of H2Cr2O4.
7. a) Given that,

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A + 2B + H 2 O 
→ C + 2D
Here A = HNO2, B = H2SO3, C = NH2OH
∴ HNO 2 + 2H 2SO3 +H 2 O 
→ NH 2 OH + 2H 2SO 4
(A) (B) (C) (D)

Therefore `D’ is H2SO4.

Structure of A : H – O – N = O
Structure of B:
S
O O
H O H
Structure of C:
H

N O H

H
Structure of D:
O

S
O O
O
H H

b) In SO3 + H 2 O → H 2SO 4 reaction, H2SO4 is obtained in misty form and reaction is
highly exothermic. By adding H2SO4 the above reaction is prevented.
H 2SO 4 + SO 3 
→ H 2S2 O 7 (oleum)
H 2S2 O 7 + H 2 O 
→ 2H 2SO 4
The catalyst used is V2O5 for the oxidation of SO2 into SO3.

8. a) i) P4 O10 + 6PCl5 
→ 10POCl3
ii) SnCl4 + 2C 2 H 5Cl + 2Na 
→ Na 2SnCl6 + C 4 H10
b) i) 2Cu + H 2 O + CO 2 + O 2 
→ CuCO 3 . Cu(OH) 2
ii) 3Ca (OH) 2 + 2Cl 2 
→ CaOCl 2 + CaCl2 2H 2 O . Ca(OH) 2

9. a) i) P4 + 20HNO 3 
→ 4H 3 PO 4 + 20NO 2 + 4H 2 O
ii) 2KMnO 4 + 5H 2 O 2 + 3H 2SO 4 
→ K 2SO 4 +2MnSO 4 + 8H 2 O + 5O 2
iii) P4 + 20HNO 3 
→ 4H 3 PO 4 + 4H 2 O + 2ONO 2
iv) 2Al + 2NaOH + 6H 2 O 
→ 2NaAlO 2 + 2H 2 O + 3H 2 O
v) 4Zn + 10HNO 3 
→ 4Zn(NO 3 ) 2 + N 2 O + 5H 2 O
b) 3Mg + N 2 
→ Mg3 N 2
`A' `B'

Mg 3 N 2 + 6H 2O 
→ 3Mg(OH)2 + 2NH3
`B' `C' `D'

10. i) Gradual addition of KI solution to Bi(NO3)3 solution, initially dark brown precipitates
of I2 are obtained which are dissolved in excess KI and give clear yellow colour

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solution due to formation of KI3. In Bi(NO3)3, Bi3+ ions hydrolysed and to give free
H+ ion in solution
Bi3+ + H 2O Bi(OH) 22+ + H +
The liberated H+ ion along with NO 3– ion of Bi(NO3)2 oxidises I – to I2
2NO3– + 8H + + 6I – 
→ 3I 2 + 4H 2 O + 2NO
This I2 (dark brown ppt.) dissolves in excess KI and to give KI3
KI(aq) + I 2(s) 
→ KI3
Yellow colour solution

ii) Given that

250° C
A  → B + C
Colourless iorganic salt Natural oxide Liq. oxide netural
to moist litmus paper

P + B  → Strong white dehydrating agent phosphorus

If `A’ is taken to be NH4NO3
NH 4 NO3(s)  → N 2 O + 2H 2 O
`A ' `B' `C'

P4 + 10N 2 O → P4 O10 + 10N 2

Thus, P4O10 is strong dehydrating agent.

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