CHAPTER # 4 CHEMISTRY Class – XII

P-BLOCK ELEMENTS
INTRODUCTION:
The general electronic configuration of p-block elements is ns2 np1-6. Except for Helium, all the other elements
in this block follow this configuration.
First group: group IIIA called as Boron family
Second group: group IVA called as Carbon family.
Third group: group VA called as Nitrogen family.
Fourth group: group VIA called as Oxygen family
Fifth group: group VIIA called as Halogens family.
Sixth group: zero group is called as Inert or Noble gasses group.
There are 30 elements in six sub groups of p-block. Out of which 10 are metals and 20 are non-metals.
Among these elements one is liquid, 9 are gases and 20 are solids.

TREND PROPERTIES OF P-BLOCK ELEMENTS:

1. ATOMIC RADII:
The distance from the center of nucleus to the outer most shell of an atom is called atomic radius.
Atomic radius increases from top to bottom in all groups. This is due to the increase in the number of
shells as we go down in each group.
The atomic radii decrease from left to right in a periodic table due to increase in nuclear charge.

2. IONIC RADII:
Some elements of p-block normally form anions and other form cations. Actions are positive ions and
anions are negative ions. A cation is smaller than neutral parent atom while an anion is larger than the
neutral parent atom.
Ionic radius increase down the group like atomic radius.

3. ELECTRONEGATIVITY:
The relative tendency of an atom to attract the shared pair of electrons to itself is called electronegativity.
p-block elements are generally electronegative elements. Electronegativity decreases from top to bottom
in each group. This is due to the increase in atomic radii.
Electronegativity ∞ 1/ atomic radius

4. IONIZATION POTENTIAL:
The amount of energy required to remove the outermost electron from a gaseous atom is called ionization
potential
Ionization potential ∞ 1/ atomic radius
p-block elements have high ionization potential. Ionization potential decreases down the group from top
to bottom as the atomic size and shielding (screening) effect increases down the group.

5. ELECTROPOSITIVITY OR METALLIC CHARACTER:

The tendency of an atom to give out electrons is known as electro positivity.
Electropositivity and the metallic character increase with increasing atomic size. The metallic character is
related to the ionization potential and electron population. It increases with the decrease in both the ionization
potential and the electron population.
 ELECTRON POPULATION
For a particular group the total number of electron present in the outer most shell of atom out of the total
number of electron that can be accommodated in that shell.
For example: boron and aluminium both belongs to IIIA group and the electron population of both the
elements is given below:
B = atomic number 5 = 1s2, 2s2, 2p1 (outer most shell is L the ration of electron is 3:8)
Al = atomic number 13=1s2, 2s2, 2p6, 3s2,3p1 (outer most shell is M the ration of electron is 3:18)
It means that the electron population of aluminium is less than boron

6. MELTING AND BOILING POINTS:

p-Block of elements includes solids, liquids and gases, so they show no regular change in melting point
and boiling point along the periods or groups. We can explain the trends in the melting and boiling points on
the basis of a number of factors such as:
i. Atomic sizes
ii. Intermolecular forces
iii. Interatomic forces
iv. Structure or state of elements
Melting and boiling points decrease in IV A group, increase from VA to VIIA. Down the group
the melting and boiling point increases

ALUMINIUM:
Aluminium is the third most abundant element in the Earth’s crust. Aluminium does not occur free in nature.
The important ores of aluminium are given below.

1. OXIDES ORES:
i. Bauxite (Al2O3, nH2O)
ii. Corundum (Al2O3)
iii. Gibbisite (Al2O3 . 3H2O)
iv. Diaspore (Al2O3 . H2O)
2. SILICATE ORES:
i. Kaolin (Al2O3 . 2SiO2 . 2H2O)
ii. Potash felspar (K2O . Al2O3 . 6SiO2)
3. FLOURIDE ORE:
Cryolite (Na3 AlF6)
4. SULPHATE ORE:
Alunite (K2SO4 . Al2 (SO4)3 . 4Al (OH)3

EXTRACTION OF ALUMINIUM:
Aluminium is extracted from its ore bauxite by electrolysis. The extraction is carried out in two steps.
1. Purification of bauxite to alumina.
2. Electrolysis of alumina to 99% aluminium.

1. PURIFICATION OF BAUXITE:
Bauxite usually contain oxides of iron (Fe2O3) and silica (SiO2) as chief impurities. These impurities make
the metal brittle and liable to corrosion. The bauxite ore may be purified by any one of the following methods
depending upon the nature of impurities present in it.

a. Hall’s Method:
This method is used when main impurities are Fe2 O3 and SiO2. In this method finely powdered bauxite
is fused with sodium carbonate. Bauxite reacts with sodium carbonate to form soluble sodium aluminate.
While the impurities remain unaffected and removed away by washing and filtration.
Al2O3 . nH2O + Na2CO3 2NaAlO2 + CO2 + nH2O
 When sodium Aluminate is heated upto 50-60oC in the presence of carbon dioxide and water,
aluminium hydroxide is obtained in the form of precipitates. These precipitates are filtered, washed and
ignited at about 1500oC to get pure alumina (Al2O3).
2NaAlO2 + 3H2O + CO2 2Al(OH)3 + Na2CO3
heat
2Al(OH)3 Al2O3 + 3H2O
o
1500 C
b. Baeyer’s Method:
This method is used when Fe2O3 is present in excess as an impurity. In this method finely
powdered bauxite is heated with 45% caustic soda to form sodium aluminate.
Al2O3 . nH2O + 2NaOH 2NaAlO2 + 2(n) H2O
It is then washed and filtered to obtain pure sodium aluminate. The sodium aluminate is heated upto 50-
o
60 C in the presence of carbon dioxide and water, aluminium hydroxide is obtained in the form of precipitates.
These precipitates are filtered, washed and ignited at about 1200oC to get pure alumina (Al2O3).
2NaAlO2 + 3H2O + CO2 2Al(OH)3 + Na2CO3
2Al(OH)3 Al2O3 + 3H2O
1500oC
c. Serpek’s Method:
This method is used to purify bauxite when silica is the major impurity. In this method finely powdered
bauxite is mixed with carbon and heated up to about 1800oC with nitrogen to give aluminium nitride and silica
is reduced to silicon.
Al2O3 . nH2O + 3C + N2 2AlN + 3CO + nH2O
SiO2 + 2C Si + 2CO

Then, aluminium nitride is hydrolyzed with hot water to produce precipitates of aluminium hydroxide
which is filtered, washed, dried and ignited to obtain pure alumina.
AlN + 3H2O Al(OH)3 + NH3 
heat
2Al(OH)3 Al2O3 + 3H2O

ELECTROLYSIS OF ALUMINA
The electrolysis is carried out in a steel tank lined with carbon (graphite). The carbon lining serves as
cathode, where as carbon rods hanging in the molten mass.
The purified bauxite i.e. alumina is dissolved in molten cryolite Na3AlF6 and fluorspar. Cryolite lowers the
melting point of alumina i.e. about 950 o C and fluorspar increases the fluidity of the metal so that the liberated
aluminium may sink at the bottom of electrolytic cell. When electric current is passed through this mixture,
as a result of electrolytic reduction, aluminium metal is obtained at cathode in molten state, from where it runs
out of the tank and solidified periodically.
O2 gas evolves at anode due to oxidation of O–2 ions and produce carbon dioxide gas by reacting with graphite.
The anodes are therefore consumed. The anodes are replaced when required.

2Al2O3 4Al+3 + 6O–2

4Al+3 + 12e– 4Al (at Cathode)
6O-2 3O2 + 12e- (at anode)
The Al thus obtained is 99% pure.
REFINING OF ALUMINIUM
The alumina obtained by the electrolysis is 99% pure and it can be further refined by Hoop’s electrolysis
method. This process consists of an iron tank having carbon lining at the bottom which acts as anode. The
cathode consists of carbon electrodes. The carbon tank has three layers, which differ in their specific gravity.
The bottom layer consists of alloy of impure aluminium having Cu and Si as anode. Middle layer consists of
a mixture of solution of Cryolite and barium fluoride. The top layer is pure molten aluminium which serves
as cathode. When electric current is passed, Al+3 from middle layer passed into upper layer, where it is reduced
to aluminium. Equal number of Al +3 ions are produced in the lower layer which migrate to the middle layer.
Pure aluminium is tapped off from time to time. In this process 99.9% pure aluminum is obtained.

Na3AlF6 3NaF + AlF3

AlF3 → Al+3 + 3F-

At the cathode:
Al+3 + 3e- → Al
At the anode:
Al → Al+3 + 3e-
Overall reaction:
Al+3 + Al → Al + Al+3

PHYSICAL PROPERTIES:
1. It is a bluish white metal with brilliant silvery lusture.
2. It is very good conductor of heat and electricity.
3. It is very light and cheap.
4. It is malleable and ductile.
5. It melts at 658oC and boils at 1800oC in the absence of air.
6. It is resistant to corrosion
7. Its density is about 2.7 gm/ml.
USES:
1. It is used in making household utensils.
2. It is used in making transmission wires.
3. Aluminium foil is used for wrapping chocolates, medicines, cigarettes and photographic films.
4. The mixture of aluminium powder and aluminium nitrate is known as ammonal which is used in explosive
bombs.
5. It is used in the preparation of some important alloy namely:
(i) Aluminium bronze: it contain 10% Al and 90% Cu. This alloy is light, tough, resistant to corrosion
and golden in color. It is used in the manufacture of imitation jewelry, coins and statues etc.
(ii) Dura lumen: it is composed of 95% Al, 4% Cu, 0.5% Mg and 0.5% Ni. This alloy is light, tough,
ductile, tensile and resistant to corrosion. It is used in making areophane etc.

CHEMICAL PROPERTIES:
1. ACTION OF AIR:
Dry air has no action on the metal but in moist air it forms a thin film of oxide on its surface. On heating
strongly in the presence of air it burns with a brilliant white light to form aluminium oxide.
4Al + 3O2 2Al2O3 ΔH= -798.18 Kcal/mol

2. ACTION OF NITROGEN:
On heating with nitrogen upto 700 oC it forms aluminium nitride.
heat
2Al + N2 2AlN

3. ACTION OF ACIDS:
a. It reacts with hydrochloric acid to form metal chloride and hydrogen gas.
2Al + 6HCl 2AlCl3 + 3H2
It reacts with dilute sulphuric acid to form metal sulphate and hydrogen
2Al + 3H2SO4 Al2(SO4)3 + 3H2

b. Conc. H2SO4 reacts with aluminium to give SO2 gas.

2Al + 6H2SO4 Al2(SO4)3 + 3SO2 + 6H2O

c. Nitric acid (dil or conc.) has no action on the metal because metal becomes passive due to the formation
of metal oxide layer.

4. ACTION WITH CARBON:

When aluminium is heated with carbon at 2000 oC aluminium carbide is formed.
4Al + 3C Al4C3

5. ACTION WITH HALOGENS:

On heating Al with halogens forms respective halides.
2Al + 3X2 2AlX3
2Al + 3Cl2 2AlCl3
Aluminium trichloride

6. ACTION WITH ALKALIES:

When Al is treated with hot alkalis it forms aluminates and hydrogen is released.
2Al + 2NaOH + 2H2O 2NaAlO2 + 2H2
(Sodium Aluminate)
7. AS REDUCING AGENT:
Due to its strong affinity for O2 it reduces many metal oxides.
Fe2O3 + 2Al 2Feo + Al2O3
The reaction where aluminium act as reducing agent are the exothermic reactions and great amount of energy
is released so that the temperature increase up to 3500 oC. Due to this reason the process is used for welding
purposes. The reduction of metal oxides involving aluminium as reducing agent is termed as thermite process.

ALUMS
The series of double sulphates of monovalent and trivalent metals containing 24 molecules of water of
crystallization are known as alum.
Alums are crystalline, isomorphous and soluble in water. They contain 24 molecules of water of
crystallization, which can be removed by heating, some of the example of alum are:
1. Potassium Alum K2SO4 • Al2(SO4)3 • 24H2O
2. Ammonium Alum (NH4)SO • Al2(SO4)3 • 24H2O
3. Potassium Chromium Alum K2SO4 • Cr2(SO4)3 • 24H2O
4. Ammonium Iron Alum (NH4)2 SO4 • Fe2(SO4)3 • 24H2O
POTASSIUM ALUM:
The potash alum is the common alum also known as phitkari. It can be prepared by mixing the hot solution of K2SO4
and Al2(SO4)3 containing the calculated amounts of these salts. The solution is then evaporated to saturation and allowed
to cool. On cooling crystals of potash alum are separated.
K2SO4 + Al2(SO4)3 + 24H2O K2SO4 • Al2(SO4) •24H2O
PROPERTIES:
1. Potash alum is a white crystalline solid with 24 molecules of water of crystallization.
2. It is soluble in water but insoluble in alcohol.
3. The aqueous solution of potash alum is acidic.
4. It melts at 92oC and at 200oC it loses its water of crystallization and becomes anhydrous, a white porous
mass called burnt alum or phul phitkari.
K2SO4 + Al2(SO4)3 • 24H2O K2O + Al2O3 + 4SO3 + 24H2O
USES:
Potash alum is used:
1. In dying and calico-printing.
2. In purification of drinking water.
3. In the coagulation of colloid substances.
4. In tanning of hides.
5. In sizing of paper.

NITRIC ACID (HNO3)

PREPARATION OF NITRIC ACID:
Nitric acid is manufactured industrially by the following method.

1. OSTWALD’S PROCESS:
This method was first introduced by a German chemist William Ostwald and therefore is known as
Ostwald’s process.
 PRINCIPLE:
This methods is based on the fact that in the presence of a suitable catalyst, ammonia can be oxidized by
the oxygen of the air to form nitric oxide, which on reaction with water in the presence of oxygen form nitric
acid.

MANUFACTURING PROCESS:
The manufacturing process involves the following steps.
i. Oxidation of ammonia to nitric oxide.
ii. Oxidation of nitric oxide to nitrogen peroxide.
iii. Absorption of nitrogen peroxide with water to form nitric acid.

i. Oxidation of Ammonia to Nitric Oxide:

A mixture of ammonia and air in the ratio of 1:8 respectively is forced to pass through a layer of
platinum gauze, heated to about 600oC and packed in a chamber called catalyst chamber. In the beginning the
platinum gauze is heated electrically in order to start the reaction, but once the rate of flow of the gases is
properly adjusted, the heat of reaction itself maintain the necessary temperature as the reaction is exothermic.

Under these conditions ammonia is oxidized to nitric oxide.

Pt 600 C
4NH3 + 502 4NO + 6H2O + Heat

ii. Oxidation of Nitric Oxide to Nitrogen Peroxide:

The nitric oxide formed, is rapidly cooled by passing it through a heat boiler. The temperature is
lowered to about 150-200oC. The cooled gas is then passed through a filter to recover any particles of catalyst.
The filtered, cooled gas is now introduced to an oxidizing tower, which consists of vertical shaped
cylinder, lined with acid proof bricks. The temperature is further lowered to 50oC. The nitric oxide gets
oxidized in this chamber to form nitrogen peroxide.
2NO + O2 2NO2 + Heat.

iii. Absorption of Nitrogen Peroxide in Water:

The nitrogen per oxide formed above, is forced into the absorption tower, which is made up of granite
and is packed with broken quartz. The water sprayed into the tower is sprinkled down. Nitrogen peroxide
combined with water to form a mixture of nitric acid and nitrous acid.
2NO2 + H2O HNO2 + HNO3
The nitrous acid decomposes into nitric acid and nitric oxide.
3HNO2 HNO3 + 2NO + H2O
The nitric oxide is reoxidized by the air present, and reabsorbed again to form further nitric acid.

CONCENTRATION OF NITRIC ACID:

The nitric acid obtained is dilute and is 68% concentrated. It is concentrated by distillation with concentrated
sulphuric acid. The nitric acid thus obtained is 98% pure.

STRUCTURE OF HNO3:
 PROPERTIES OF NITRIC ACID
PHYSICAL PROPERTIES:
i. Pure nitric acid is a colourless fuming liquid with choking smell and has sour taste.
ii. Ordinary nitric acid is 65% HNO3. Density of ordinary HNO3 is 1.4g/l.
iii concentrated nitric acid contain 98% HNO3 and density of conc.HNO3 is 1.5g/l.
iv. Its boiling point is 83oC and Freezing Point is –41.6oC.
v. Fuming HNO3 is reddish yellow in color due to the dissolved NO2.

CHEMICAL PEROPERTIES:
i. As A Strong Oxidizing Agent:
Nitric acid is one of the strongest oxidizing agents. The oxidizing properties of nitric acid is due to the
highest oxidation state of nitrogen i.e. +5 in HNO3 and during oxidation nitrogen changes from +5 oxidation
state to -3.

(a) Oxidizing Action of conc. Nitric Acid on Metals:

Cu + 4HNO3 Cu(NO3)2 + 2H2O + 2NO2
(Conc.)
(b) Oxidizing Action of dil. Nitric Acid on Metals:
3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO
(dil)
(c) Oxidizing Action of dil. Nitric Acid with more active Metals:
4Mg + 10HNO3 Mg(NO3)2 + N2O + 5H2O
(dil)
(d) Oxidizing Action of very dil. Nitric Acid with more active Metals:
4Zn + 10HNO3 4Zn(NO3)2 + 3H2O NH4NO3

(e) Oxidizing Action of Nitric Acid on Non-metals:

Hot concentration nitric acid oxides non-metal to their oxides or acids, and itself reduces to nitrogen
per oxides.
C + 4HNO3 2H2O2 + CO2 + 4NO2
S + 6HNO3 H2SO4 + 2H2O + 6NO2
P + 5HNO3 H3PO4 + 5NO2 + H2O
Si + 4HNO3 SiO2O + 4NO2 + 2H2O

ii. Nitration Reaction:

Concentrated nitric acid acts as a nitrating agent and replaces one or more hydrogen atoms from
organic compounds by nitro group (–NO2). When vapours of nitric acid and alkane are passed through copper
tube at 450 oC nitro alkane is formed.
CH4 + HNO3 Cu CH3– NO2 + H2O
450oC
iii. Neutralization Reaction (As an Acid):
Nitric acid neutralizes alkalies to form salt and water. It also decomposes carbonates and bicarbonates.
HNO3 + NaOH NaNO3 + H2O

iv. Formation of Aqua Regia:

A mixture containing 1 part by volume of conc. nitric acid and 3 parts by volume of conc. HCl is
called Aqua Regia. It can dissolve noble metals like ‘Gold’ due to the liberation of chlorine gas.
 HNO3 + 3HCl 2H2O + NOCl + 2Cl
Au + 3Cl Au Cl3
AuCl3 + HCl H[AuCl4] hydroauric chloride

IMPORTANCE OF HNO3:
i. It is used in the manufacture of artificial fibers, nitrates and explosive glyceryl trinitrate or (Nitro
Glycerine). It is an explosive. Dynamite is prepared by absorbing nitro Glycerine ion kieselguhr.
ii. It is used in the purification of Gold and Silver.
iii. It is used in laboratory as a reagent.

CHLORINE:
INDUSTRIAL PREPARATION OF CHLORINE GAS:
In the industry the chlorine gas can be prepared by the electrolysis of brine.
A number of methods can be used for this purpose, but following two methods are important.
1. Nelson’s cell method.
2. Castner Kellner method

NELSON CELL:
CONSTRUCTION AND WORKING OF THE CELL
The principal of this process is a porous diaphragm. It consist of a perforated steel tube lined inside with
asbestos. The tube act as the cathode and a graphite rod dipped in sodium chloride solution serves as anode.
The electrolyte consist of 10% sodium chloride solution. On passing the electric current chlorine is liberated
at the anode and is collected through an outlet. Sodium ions penetrate through the asbestos and reach the
cathode when hydrogen and hydroxide ions are formed by the reduction of water. Sodium ions combine with
hydroxyl ions to form NaOH which is collected in the outer tank while hydrogen is drawn off through the
outlet.
CHEMICAL PROPERTIES OF CHLORINE:
1. Oxidation reaction:
Chlorine can oxidizes many metals and non-metals to form respective products
Zn + Cl2 ZnCl2
2P + 5Cl2 2PCl5
2. Addition reaction:
Chlorine combines with some compounds to form additive products
CH2=CH2 + Cl2 C2H4Cl2
CO + Cl2 COCl2
SO2 + Cl2 SO2Cl2

3. Substitution reaction:
Chlorine can replaces one or more atoms from another compounds and forms respective chlorides
H2S + Cl2 2HCl + S
2KI + Cl2 2KCl + I2
CH4 + Cl2 CH3Cl + HCl

AUTO-OXIDATION AND REDUCTION REACTION:

Chlorine reacts with water to form hydrochloric acid and hypochlorous acid. In this reaction chlorine
undergoes oxidation as well as reduction. Therefore, this reaction is known as self-oxidation reduction
reaction or auto oxidation reduction reaction.
Cl2 + HO HCl + HOCl
Solution of chlorine in water is strong oxidizing agent and in this solution HOCl usually act as oxidizing
agent. This is because in HOCl chlorine has an oxidation number +1 and has strong attraction for electron.
BLEACHING ACTION OF CHLORINE:
Chlorine is used as a bleaching agent because the acqueous solution of chlorine is strong oxidizing agent.
When chlorine is dissolve in water then it forms nascent oxygen.
HOCl HCl + [O]
(NascentOxygen)
This Nascent Oxygen oxidizes the organic matter and thus the colour is bleached.
colouring matter + [O] Colourless matter

USES OF CHLORINE:
1. It is used as oxidizing agent, bleaching agent and for the purification of drinking water
2. It is used as disinfectant and germicide.
3. It is used in the preparation of different chemical compound like CCl4, CHCl3 etc.
4. It is used in the manufacturing of plastic.