PART-A

P-BLOCK ELEMENTS

(GROUP 13 AND 14)

PROMINENT SCIENTIST
Moissan, (Ferdinand Frederic) Henri (1852-1907)
Noble Laureate. French inorganic chemist, first isolated
fluorine; pioneer of high temperature chemistry. In 1886 he
successfully prepared fluorine gas by electrolysis of a solution of KF
in HF at -50°C in an apparatus made of platinum and calcium
fluoride. He was the first person to obtain boron in pure form and
prepared a range of metal hydrides. He also prepared synthetic
gems such as ruby and silicides, borides and carbides of metal as
well as metals such as molybdenum, tantalum, niobium, vanadium,
titanium, tungsten and uranium.

1. GENERAL GROUP INTRODUCTION

Elements of p-block have the valence shell electronic
configuration as ns2 np1-6. The properties of these elements are due
to their p-electrons. Elements in which distinguishing electron
enters p orbital are known as p-block elements. The only
exceptional element in this block is helium (atomic number 20 that
has the electronic configuration 1s2.

Position in periodic table

The p-block includes elements belonging to group 13 to 18.
The outermost electronic configuration varies from ns2 np1 to ns2
np6 fig.1.The p-block consists of metals, metalloids, non-metals and
noble gases. The p-block

Fig.1.Position of p-block elements in the periodic table

elements display a wide range of properties and diverse chemistry

depending on the group and period to which the element belongs.
These elements are placed after the transition elements and occupy
right hand side of the periodic table.

GENERAL ELECTRONIC CONFIGURATION

The general electronic configuration of elements is ns2 np1 to
ns2 np6, hence there are six families in the p-block elements.

Boron family : ns2np1

Carbon family : ns2np2

Nitrogen family : ns2np3

Oxygen family : ns2np4

Halogen family : ns2np5

Noble gases : ns2np6

The p-block consists of following elements:

 Table1.p-block elements

It is interesting to note that the nonmetals and metalloids exist only

in the p-block elements of the periodic table. The nonmetallic
character of elements decreases down the group. In fact the
heaviest element in each p-block group is the most metallic in
nature.

GROUP 13 ELEMENTS (The Boron family)

2. INTRODUCTION
In this family, boron is a typical-nonmetal. Aluminium is a
metal but exhibits many chemical similarities to boron; Gallium,
indium and thallium are metallic in character. (Electronic
configuration of group 13 is shown in Table 2).
Table 2. Electronic configuration of the elements of group 13
2.1 Electronic configuration
The outer electronic configuration of group 13 elements in
ns2np1. In this Boron and Aluminium have noble gas core. Gallium
and Indium have noble gas core plus 10 d electrons. Thallium has
noble gas core plus 14 f electrons plus 10 d electrons. It means this
group has electronic structure more complex than s-block elements.
This difference in electronic structure results into different
properties and chemistry of elements.

The maximum oxidation state shown by a p-block element is equal

to the total number of valence electrons (It is the sum of s and p-
electrons). The number of possible oxidation states increases
towards right of the periodic table. Group oxidation states and other
important oxidation states of p-block elements are shown in Table 3
along with general electronic configuration.

Table 3. General Electronic Configuration and Oxidation States of p-block Elements

3. OCCURRENCE
Boron does not occur in the free state in the nature. It is a
fairly rare element. It mainly occurs as borates, orthoboric acid
(H3BO3) and borax (Na2B4O7, 10H2O). The other source of boron is
Kernite with formula Na2B4O7, 4H2O. In India borax occurs in Puga
Valley (Ladakh) and Sambhar Lake (Rajasthan). The abundance of
boron in earth crust is less than 0.0001% by mass. Boron shows
two isotopic forms as 10B(19%) and 11B(81%).
Aluminium does not occur in the free state in the nature. After
oxygen (45.5%) and silicon (27.7%), it is the fourth most abundant
element (8.3% by mass) in the earth crust. Important minerals of
aluminium are bauxite, Al2O3, 2H2O, cryolite, Na3AlF6. In India it is
available in the form of Mica (KAl3Si3O10(OH)2) in Madhya Pradesh,
Orissa, Karnataka and Jammu. Gallium, indium and thallium are
less abundant elements in nature. Thallium is the highly toxic
element amongst the group 13 members.

4. VARIATION IN PROPERTIES
The atomic and physical properties are shown in
Table 4.

Table 4.Atomic and physical properties of group 13 elements

4.1 Atomic radii

On moving down the group, for each successive element one
extra shell of electrons to increase. But one can notice a deviation.
Atomic radius of Ga is less than that of Al (Atomic radius of Al is
143 pm while that of Ga is 135 pm.). This is because of variation in
the inner core of the electronic configuration (Table 4). Aluminium
has noble gas core but gallium has noble gas plus 10 d electrons
offer only poor screening effect for the outer electrons from the
increased nuclear charge is gallium. Boron has the smallest atomic
radius (88 pm).

Atomic radii of group 13 elements are lower than that of

alkaline earth elements of group 2 primarily due to greater nuclear
charge of group 13 elements than alkaline earth elements.
4.2 Ionization Enthalpy (IE or ΔH)
Ionization enthalpies also irregular trend (Table 4). From B to
Al as expected ionization enthalpy decreases but from Al to Tl, there
is only a marginal difference. In case of Ga there is 10d-electrons in
its inner electronic configuration which shield the nuclear charge
less effectively than the s and p-electrons and therefore, the outer
electron is held fairly strongly by the nucleus. As a result, IE,
increases slightly. In case of Indium, the number of d-electrons and
hence their screening effect remain the same as in Gallium but on
increase in atomic size as we move from Ga to In results in decrease
in IE1. The last element Tl, has 10 d-electrons and 14f-electrons in
its inner electronic configuration which would exert still smaller
shielding effect on the outer electrons in Tl and consequently, there
is a considerable increase in IE1.

Electronegativity
Down the group, electronegativity first decreases from B to Al
and then increases marginally (Refer Table 4[A]).This is due to
discrepancies in atomic size of elements.

Table 4[A]

4.3 Inert pair effect

In case of heavier elements, compounds formed with lower
oxidation states are more stable e.g. Thallium forms stable
univalent thallous compounds which are covalent. s-electrons of the
valence shell do not participate in bonding by remaining paired.
Energy required to unpair these ns2 electrons is higher. This
phenomenon of electrons remaining paried in the valence shell is
called inert pair effect. It is due to poor shielding of ns2 electrons of
valence shell by inner d and f electrons. It is reluctance of s-
electrons of the valence shell to take part in the bonding. It arises
due to poor or ineffective shielding of ns2 electrons of the valence
shell by the intervening d and f electrons. Inert pair effect increases
down a group and thus elements present in the lower part of the
group show lower oxidation states. In group 13 elements, inert pair
effect is more pronounced in Tl.

4.4 Oxidation States

The elements of group 13 have ns2 np1, as the outer most
electronic configuration. If only np1 electron takes part in bonding
the oxidation state is +1 and if all the electrons, i.e. ns2 np1 take
part in bonding the oxidation state is +3. Hence, the expected
oxidation states of these elements are +1 and +3. However, in the
formation of M3+ ion the energy required to remove three electrons
(ns2 np1) is very high. Hence, tendency to form trivalent cation is
less. (Refer Table 3)
Boron form compounds in +3 oxidation state as its ionic
radius is very small and it has high degree of hydration energy.
Aluminium is extremely stable in +3 oxidation state decreases and
that of +1 state increases from aluminium to thallium due to inert
pair effect. Thus, aluminium is invariably trivalent gallium and
indium are normally trivalent though some compounds with +1
oxidation state are reported. The characteristic feature of thallium
chemistry is stability of univalent state (thallous) then in the
trivalent state (thallic). Thallic salts act as strong oxidizing agents
because of greater stability of Tl+1 than that of Tl+3.

Lewis acids
In trivalent state, the number of electrons around the central atom
in a molecule of the compounds of these elements (for example of
BF3) will be only six. Such electron deficient molecules have
tendency to accept a pair of electrons to achieve stable electronic
configuration and thus behaves as Lewis acids. The tendency to
behave as Lewis acid decreases with increase of size down the
group. BCl3 acts as Lewis acid. It accepts a lone pair of electron
from ammonia to form BCl3.NH3 (fig. 2)
 Fig. 2

But in AlCl3, stability is due to formation of dimer. (Fig. 3)

Fig. 3

4.5 Physical properties

In group 13, Boron is non-metallic in nature. It is extremely
hard and black coloured solid. Due to very strong crystalline lattice,
boron has high melting point and high electrical conductivity. It is
interesting to note that gallium with unusually low melting
(303 K), can exist in liquid state during summer. Its high boiling
point (2676 K) makes it a useful material for measuring high
temperatures.

5. CHEMICAL REACTIVITY
i. Action of air (oxygen)
Boron is unreactive in crystalline form. Aluminium forms
a very thin oxide layer on the surface which protects the metal from
further attack (reaction). Amorphous boron and aluminium metal
on heating in air form B2O3 and Al2O3. With nitrogen (N2) at high
temperature they form nitrides.
∆
4E(s) + 3O2 (g) → 2E2O3 (s)
2E(s) + N2 → 2EN (g)

Where E = Element
One can find variation in the nature of oxides. B2O3 is acidic.
Aluminium and gallium oxides are amphoteric and those of indium
and thallium are basic in their properties.

ii. Reactivity towards halogens

Group 13 elements react with halogens to form trihalides
(except TlI3)
2E(s) + 3X2 (g) → 2EX3 (s)
Where X=F, Cl, Br, I and E=Group 13 element

iii. Reactivity towards water

Pure boron does react with water. Aluminium decomposes
boiling water evolving hydrogen.
2Al + 6H2O → 2Al (OH)3 + 3H2 ↑
Gallium and indium are not attacked by pure, cold or hot water.
Thallium is a little more reactive than gallium and forms an oxide
on the surface.

6. ANOMALOUS PROPERTIES OF FIRST ELEMENT

OF THE GROUP 13 (BORON)
Boron because of its i) small size (88 pm.) ii) higher
electronegativity (2.0) iii) higher value of ionization enthalpy (801 kJ
mol-1) differs from other members of group 13 elements.

Some of the points of difference are

i. Boron is a nonmetal while other members are metals.
ii. Boron shows allotropy while other members do not.
iii. Amongst the elements of group 13, boron has highest melting
and boiling point.
 iv. Boron forms only covalent compounds (Maximum covalence of
boron is 4) while other members form both ionic and covalent
compounds.
v. Oxides and hydroxides of boron are weakly acidic, of
aluminium are amphoteric while those of rest of the members
are weakly basic.
vi. Boron hydride is quite stable while hybrids of other elements
are less stable.
vii. Only boron combines with active metals such as Mg to form
borides while rest of the members do not.

∆
3Mg + 2B → Mg3B2
Magnesium Boride

7. PHYSICAL AND CHEMICAL PROPERTIES OF BORON

Physical properties
Boron is nonmetal. It is extremely strong and black
coloured solid. Crystalline boron is as hard as diamond and is non-
reactive. Amorphous boron is very reactive. It has strong crystalline
lattice. It metals at 2453 K while boils at 3923 K. boron is a poor
conductor of electricity. Its atomic radius is 88 pm while ionic
radius (M3+) is 27 pm. It shows +3 oxidation state. It has highest
ionization enthalpy in group 13.

Chemical properties
i. Action of Air
Crystalline boron is unreactive. Only amorphous boron shows
reactivity. It reacts with air only when heated at high temperature
giving B2O3 and form boron nitride (BN)
973 𝐾
4B + 3O2 → 2B2O3
973 𝐾
2B + N2 → 2BN
ii. Action of water
Pure boron does not react with water.

iii. Reaction with alkalies

Boron when fused with alkalies dissolves to give borates with
evolution of H2 gas.
𝑓𝑢𝑠𝑒
2B + 6NaOH → 2Na3BO3 + 3H2↑
Sodium orthoborate

iv. Reaction with nitrogen

When heated with nitrogen it forms nitride.
∆
2B + N2 → 2BN

v. Reaction with carbon

Boron when heated with carbon forms carbide.
∆
4B + C → B4C

vi. Reactivity towards halogens

Boron reacts with halogens to form trihalides.
2B(s) + 3X2 (g) → 2BX3
[Where X=F, Cl, Br, I]
All these trihalides acts as Lewis acids.

vii. Reaction with acids

Boron does not react with acids even at moderate temperature.
Water, steam and hydrochloric acid have no action on boron.
Oxidizing acids (HNO3, H2SO4) convert boron to boric acid
(H3BO3)
B + 3HNO3 → H3BO3 + 3NO2
2B + 3H2SO4 → 2H3BO3 + 3SO2

viii. Reducing action of boron

Boron is a powerful reducing agent and it reduces CO2 and
SiO2 to C and Si respectively.
4B + 3CO2 → 2B2O3 + 3C
4B + 3SiO2 → 2B2O3 + 3Si
8. IMPORTANT COMPOUNDS OF BORON
Some useful compounds of boron are borax, orthoboric acid
and diborani.

I. Borax
Properties
i. Its aqueous solution is alkaline due to hydrolysis
Na2B4O7 +
7H2O → 2NaOH + 4H3BO3
orthoboric acid
ii. On heating, borax loses water of crystallization and swells up
to form fluffy mass. On further heating it melts to give a clear
liquid which solidifies to a transparent glossy bead consisting
of sodium metaborate (NaBO2) and boric unhydride i.e.B2O3.

∆
Na2B4O7, 10H2O → Na2B4O7 → 2NaBO2 + B2O3
−10H2 𝑂
Borax bead.
The bead is commonly known as borax bead and is used to
detect coloured radicals under the name borax bead text. For
example, when borax is heated with CoO on a loop of platinum
wire, a blue coloured Co (BO2)2 bead is formed.
CoO + B2O3 → Co (BO2)2 (Blue bead)
iii. When heated with ethyl alcohol and concentrated H2SO4, it
gives volatile vapours of triethyl borate which burn with blue
edge flame.
Na2B4O7 + H2SO4 + 5H2O → Na2SO4 + 4H3BO3

H3BO3 + 3C2H5OH → B(OC2H5)3 + 3H2O

Triethyl borate
This reaction is used as a test for borate radical in qualitative
analysis.
Uses: Borax is used in,
i. In manufacture of optical and hard glasses.
ii. In making enamels and paints for earthen pots.
iii. As a mild antiseptic in the preparation of medicinal soaps and
as a food preservative.
 iv. As a flux for soldering and welding and
v. In the borax bead test.

II. Orthoboric acid (H3BO3)

Orthoboric acid is a white crystalline solid, with a soapy touch.
It is sparingly soluble in water but highly soluble in hot water.
It is obtained from borax by treating it with dil. HCl or dil.
H2SO4
Na2B4O7 + 2HCl + 5H2O → 2NaCl + 4H3BO3
It can also be obtained from the mineral colemanite by passing
SO2 through a mixture of powered mineral in boiling water.
Ca2B6O11 + 4SO2 + 11H2O → 2Ca (HSO3)2 + 6H3BO3
Colemanite

Properties
i. It is a weak monobasic acid, does not act as a proton donor
bot behaves as a Lewis acid. It accepts a pair of electrons from
OH − ion of H2O.
H3BO3 + H2O → [B(OH)4]− + H +
or B(OH)3 +
2HOH → [B(OH)4] + H3O
− +

ii. On heating orthoboric acid at 370K, it forms metaboric acid

HBO2 which on further gives boric oxide, B2O3
∆ ∆
H3BO3 → HBO2 → B2O3
iii. With NaOH it forms sodium metaborate H3BO3 +
NaOH → NaBO2 + 2H2O.

iv. With C2H5OH and conc. H2SO4, it gives triethylborate which

burns with green edged flame.
H3BO3 + C2H5OH → B(OC2H5)3 + 3H2O
conc.H2 SO4

It has planar structure in which planar BO33- units are joined

by the hydrogen bonds. It is shown in Fig.4
 Fig. 4 Boric acid (the dotted lines represent
hydrogen bonds)

Uses
Boric acid is used,

1) as a food preservative.

2) as a mild antiseptic for eyewash under the name boric lotion.

3) for the preparation of glazes and enamels in pottery.

III. Diborane, B2H6

It is the simplest boron hydride. It is prepared by treating
boron trifluoride with LiAlH4 in diethyl ether.
4BF3 + 3LiAlH4 → 2B2H6 + 3LiF + 3AlF3

In a laboratory the diborane is prepared by the oxidation of sodium

borohydride with iodine

2NaBH4 + I2 → B2H6 + 2NaI + H2

In industry it is prepared by the reaction of BF3 with sodium

hydride.
 450K
2BF3 + 6NaH → B2H6 + 6NaF

Properties
i) Diborane is colourless highly toxic gas. It has b.p. of 180
K.

ii) Diborane catches fire spontaneously when it is exposed to

atmospheric air. It burns in oxygen. The reaction is
exothermic releasing a large amount of energy.
B2H6 + 3O2 →
B2O3 + 3H2O ΔH = -1976 kJ mol-1.

iii) it is readily hydrolysed by water to form boric acid

B2H6 (g) + 6H2O(l) →
2B(OH)3 (aq) + 6H2 (g)

iv) With Lewis bases, diborane first undergoes cleavage to

form borane (BH3) which then react to form adducts.
B2H6 + 2NMe3 → 2BH3∙NMe3
B2H6 + 2CO → 2BH3∙CO

v) With ammonia an addition product B2H6∙2NH3 formulated

as, [BH2 (NH3)2]+ [BH4]- is formed which then decomposes
on heating at 473 K to give a volatile compound called
borazole.
473 K
3B2H6 + 6NH3 → 3[BH2 (NH3)2]+ [BH4]- → 2B3N3H6 + 12H2
Borazole (Borazine)

This compound is called Inorganic benzene in view of its ring

structure with alternate NH and BH groups. Borazole contains 3
double bonds and has 6𝜋 electron system which is similar to
benezene.
 Fig. 5 Borazine or Borazole

Many metal hydrides react with dilborane to form

tetrahydridoborate which contains [BH4] tetrahedral ion.
-

diethyl ether
2MH + B2H6 → 2M+ [BH4]-
(Where M = Li or Na)

Structure of B2H6:
X-ray diffraction has shown the following structure
6(a) of diborane. Here B atoms undergo sp3 hybridization. There are
four terminal B-H1 normal covalent bonds which are quite strong
(also called two center electron pair bond two center two electrons
bonds i.e. 2c-2e) and two bridge B⋯Hb⋯B which are different from
normal covalent bonds and are quite weak (also called three
centered electron pair bond or three center two electron bonds i.e.
3c-2e). Because of their resemblance to a banana these are also
called banana bonds shown in structure Fig.6 (b). In structure (a),
the four H1 and two B atoms lie in the same plane while one Hb lies
above and one below the plane. As there are 12 electrons (3e from
each B atom and le from each H atom) and 8 bonds in a B2H6
molecule, it is an electron deficient molecule. Here diborane
molecule has two electrons less than minimum required number,
thus, an electron deficient molecule. [Fig. 6(c)]

Fig. 6 (a) structure of B2H6

Fig. 6 (b) structure of B2H6 showing banana

 Fig. 6 (c) Bonding on diborane

Uses of boron
Boron being extremely hard refractory solid of high melting
point, low density and low electrical conductivity, finds many
applications of borax and boric acid is in the manufacture of heat
resistance glasses (e.g. Pyrex), glass wool and fiber glass. Borax is
used in flux for soldering of metals, for heat, scratch and stain
resistant glazed coating to earthenwares and as constituent of
medicinal soaps. An aqueous solution of orthoboric acid is generally
used as a mild antiseptic.
Boron fibers are used in making bullet proof vest and light
composite material for air craft. The boron -10 isotope has high
ability to absorb neutrons and therefore, metal borides are used as
a good adsorbent and as protective shields and control rods in
nuclear industry.

9. Uses of aluminium and aluminium compounds

Aluminium is a bright silvery white metal with high tensile
strength. It has high electrical and thermal conductivity. Aluminium
forms alloy with Cu, Mn, Mg, Fe, Ni, Co. Important alloys are shown
in Table 5.
 Table 5. Some alloys of aluminium

Aluminium is the chief constituent of silvery paints. Alums are used

in purification of water. It is also used in sizing of papers. It acts as
antiseptic to stop bleeding. It is quite used in dyeing and tanning of
leather. Alums have good application in calico printing in
dehydration, decolouration and chromatography. Al2(SO4)3 is used
for making fire proof clothes. Anhydrous AlCl3 is used as a catalyst
in Friedel-rafts reaction and as a mordent in dyeing.
The use of aluminium and its compounds for domestic purpose
is now reduced considerably because of their toxic nature.

10. REACTIONS WITH ACIDS AND ALKALIES

I. Reaction with acid
Aluminium dissolves in dil. or conc. HCl and dil. H2SO4
slowly liberating H2 gas while conc. H2SO4 gives SO2 gas.
Aluminium chloride forms octahedral ions [Al(H2O)6]3+ in aqueous
acidified solution.
2Al + 6HCl(dil.) + 12H2O → 2[Al(H2O)6]Cl3 + 3H2
Or simply
2Al (g) + 6HCl(aq) → 2Al (aq) 6Cl− (aq) + 3H2 (g)
3+

heat
2Al (g) + 6H2SO4 (conc.) → Al2(SO4)3 + 3SO2↑ + 6H2O

However, aluminium becomes passive when treated with

cone. HNO3. This is due to the formation of thin protective film of its
oxide (Al2O3) on the surface which protects it from further action.
II. Reaction with alkalies
Aluminium dissolves in NaOH or KOH to form meta-aluminate
with the evolution of H2 gas.

2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2 ↑

Thus Al reacts with both acid and base showing it amphoteric

nature.

11. GROUP 14-ELEMENTS

General introduction and occurrence: Carbon (C), silicon (Si),
germanium (Ge), tin (Sn) and lead (Pb) are the elements of group 14.
C and silicon are nonmetals. Ge is a metalloid where Pb and Sn are
metals. Carbon is seventeenth most abundant element by weight in
the earth crust and forms many compounds than any other
elements except hydrogen. It has two stable isotopes 12C(98.9%) and
13C(1.1%). Carbon is widely distributed in nature in free state as

well as in the combined form. In elemental form it is available in

coal, graphite, diamond. In combined form it is available as metal
carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air.
Carbon is versatile element in the worlds. Fats, carbohydrates
proteins, vitamins, etc. and fossil fuels such as petroleum, lignite,
are made up of carbon compounds carbon is the essential
constituent of all living organisms. Carbon has third isotopes as
14C. It is radioactive and used for radiocarbon dating.

Silicon is the second (27.7% by mass) most abundant element

in the earth crust. It is present in nature as silica (SiO2) and
silicates. It is a very important component of ceramics, glass and
cement.

Germanium exists only in traces. Tin occurs as SnO2

(cassiterite or tinstone) and lea as galena (PbS)

Ultra-pure germanium and silicon are used in making

transistors and semiconductor devices.
The important atomic and physical properties of the group 14
elements are shown in Table .6

Table.6 Atomic and physical properties of group 14 elements

11.1 Electronic configuration

The valence shell electronic configuration of these elements is
ns2np2. The inner core of the electronic configuration of elements in
this group differs. Here C and Si have inert gas core. Ge and Sn
have inert gas core plus 10d-electrons but Pb has inert gas core
plus 10d-electrons and 14f-electrons.

Variation of Properties
Here we are considering atomic radii, ionization enthalpy,
electronegativity and physical properties. Electronic configuration of
group 14 is shown in Table 7.
 Table 7. Electronic configuration of the elements of group 14

11.2 Atomic Radii (covalent radii)

Atomic radii of these elements regularly increase as we move down
the group primarily due to the addition of new energy shell at each
succeeding element. The increase in atomic radii from Si onwards is
however, small due to ineffective shielding of the valence electrons
by the intervening d- and f- electrons. Heavier elements have
completely filled d and f orbitals. (Refer Table.6)

11.3 Ionization enthalpy

The ionization enthalpy of group 14 element is higher than
corresponding elements of group 13 due to increased nuclear
charge. (Refer Table .6)

The influence of inner core electrons is visible. In general the

ionization enthalpy decreases down the group. Small decrease in
ΔH1 from Si to Ge to Sn and slight increase in ΔH1 from Sn to Pb is
the consequence of poor shielding effect of intervening d and f
orbitals and increase in size of atom.

11.4 Electronegativity
Due to small size, the elements of this group are slightly more
electronegative than the corresponding group 13 element. The
electronegativity decreases as we move down the group but not after
silicon. The electronegativity values for elements for Si to Pb are
almost the same. Carbon with electronegativity of 2.5 is the most
electronegative element of group 14. (Refer Table .6)

11.5 Oxidation states

The group 14 elements have four electrons in outer most shell. All
the elements show an oxidation state of +4. However, as we move
down the group from C to Pb, the stability of +4 oxidation state
decreases while that of +2 oxidation state increases due to inert pair
effect. Carbon also exhibits negative oxidation states. Since the sum
of first four ionization enthalpies is very high, compounds in +4
oxidation states are generally covalent in nature. In heavier
elements the tendency to show +2 oxidation state increases in the
order Ge < Sn < Pb. It is due to the inability of ns2 electrons of
valence shell to participate in bonding. Carbon and silicon mostly
show +4 oxidation state. Germanium forms stable compounds in +4
oxidation state and very few compounds in +2 state. Tin forms
divalent as well as tetravalent compound. Sn in +2 state is reducing
agent. Lead compounds are stable in +2 state. Lead in +4 oxidation
states acts as oxidizing agent (PbO2). Carbon shows maximum
covalence as four. Other elements, because of the presence of d
orbitals, show covalence more than 4. The compound of carbon,
CCI4 (tetra chloride) cannot be hydrolysed by water. Here carbon
cannot expand its co-ordination number beyond 4 due to the
absence of d orbitals. It never acts as electron pair donor or electron
accepter species. On the other hand SiD6-2, [Ge Cl6]2-, [Sn (OH)6]2-
species exists. It means covalence is more than four and central
atoms undergo sp3d2 hybridizations.

11.6 Physical properties

All the group 14 elements are solids. Carbon and silicon are non
metals, germanium is metalloid, where as tin and lead are soft
metals with low melting points. The m.p. and b.p. of group 14
elements are higher than those of corresponding elements of group
13. This is due to strong interacting binding forces in their solids as
well as in liquid states. Down the group, there is regular decrease in
m.p. and b.p. as the size of atoms increases and interatomic forces
of attraction decreases. Hence silicon is a hard while lead is soft
metal.
12. TRENDS IN CHEMICAL REACTIVITY
Trends in chemical reactivity can be studied through i)
reactivity towards oxygen ii) reactivity towards water, iii) reactivity
towards halogen.

i) Reactivity towards oxygen

All members when heated in oxygen forms oxides. There are
two types of oxides i.e. monoxide and dioxide of formula MO and
MO2 respectively.
Monoxides: Carbon forms CO,
Si forms SiO
Ge forms GeO
Sn forms SnO
Pb forms PbO

These oxides except SiO and GeO are quite stable. SiO exists
only at high temperature. Oxides in higher oxidation states of
elements are generally more acidic than those in lower oxidation
state. The dioxides CO2, SiO2 and GeO2 are acidic in nature. SnO2
and PbO2 are amphoteric in nature, CO is neutral. GeO is distinctly
acidic while SnO and PbO are amphoteric. Red form of PbO is called
litharge and yellow form is called massicot.
∆
E + O2 → EO2

ii) Reactivity towards water

Carbon, silicon and germanium are not affected by water. Tin
decomposes steam to form dioxide and hydrogen gas.
∆
Sn + 2H2O → SnO2 + 2H2↑

Lead is unaffected by water. Lead always forms protective oxide

film on surface.
iii) Reactivity towards halogen
These elements can form halides of formula MX2 and MX4
where X = F, Cl, Br, l. All other members except carbon react
directly with halogens under suitable conditions to form halides.
The stability of tetrahalides decreases as we move from C to Pb.
CCl4 > SiCl4 > GeCl4 > SnCl4 > PbCl4
Most of the MX4 compounds are covalent in nature. In these
halides, the central metal atom undergoes sp3 hybridization and
therefore molecule is tetrahedral in shape. SnF4 and PbF4 are ionic
in nature. It is found that, Pbl4 does not exist. In this case Pb-I
bond initially formed during the reaction does not release enough
energy to unpair 6s2 electrons and excite one of them to higher
orbital to have four unpaired electrons around lead atom. Heavier
elements Ge to Pb are able to form dihalides (MX2). Stability of
dihalides increases down the group. Considering thermal and
chemical stability GeX4 is more stable than GeX4 is more stable
than GeX2 where as PbX2 is more stable than PbX4.
The tetrahalides of carbon for example, carbon tetrachloride (CCl4)
can not be hydrolysed by water since it can not expand co-
ordination number beyond 4 due to the non availability of d-
orbitals. Other tetrachlorides are easily hydrolysed by water
because the central atom can accommodate the lone pair of
electrons from oxygen atom of water molecule in d orbital.
SiCl4 + 4H2O → Si(OH)4 + 4HCl
Mechanism is as shown below,
 SiCl4 undergoes hydrolysis by initially accepting lone pair of
electrons from water molecule in d-orbitals of Si and finally forms
silicic acid.

13. Anomalous behavior of carbon

Carbon differs from rest of the element of group 14. It is due to
its smaller size, higher electronegativity, higher ionization enthalpy
and non availability of d-orbitals. Some important points of
difference are
i. Because of smaller size and lowest atomic volume carbon is
the hardest element of group 14. It has highest melting point
and boiling point, has the highest ionization enthalpy and is
the most electronegative element of this group.
ii. Due to the absence of d orbitals, it has no tendency to form
complex ions. As a result, its maximum covalence remains 4.
iii. Carbon has strong tendency to form multiple bonds i.e.,
double bonds and triple bonds. For example, alkenes, alkynes,
etc. The most remarkable property of carbon is , however,
catenation by virtue of which it forms thousands of
compounds in which carbon is linked to other carbon atoms.

14. CATENATION
The property of self – linking of atoms of an element to form
straight or branched chains and rings of different sizes by covalent
bonds is called catenation. The tendency of an element to form a
chain depends upon the strength of the element* element bond.
Among the group of 14 elements, C-C bond strength (384 kJ mol-1)
is maximum, therefore, carbon shows maximum tendency for
catenation. Following table 11.8 provides needful information.
 Table 8

The values of bond enthalpy show that carbon has the

maximum tendency to form chains, silicon has much lesser
tendency to form chains, germanium has still lesser tendency while
Sn hardly has this tendency of catenation. The order of catenation
is C>>Si>Ge=Sn. Lead does not show catenation.
Carbon also has unique property to form P𝜋- P𝜋 multiple bonds
with it self and with other atoms of small size and high
electronegativity. For example, C = C, C+C, C=O, C=S. C=N. Heavier
elements do not form P𝜋- P𝜋 bonds because their atomic orbitals
are too large and diffused to have effective overlapping. Due to
property of catenation and P𝜋- P𝜋 bond formation, carbon is able to
show allotropic forms.

15. ALLOTROPES OF CARBON

Allotropy is the phenomenon in which an element exists in
different physical forms having different physical properties but
chemical properties are same or similar. The different physical
forms are the allotropic modification of the element. Among the
elements of Group 14, carbon, silicon and Sn (tin) have allotropic
modifications.
 Carbon has the largest number of allotropic modifications.
Some of them are crystalline while some others are amorphous and
they are classifies as follows.

Diamond
Diamond has three dimensional structure. Each carbon atom
is bonded to four other carbon atoms which occupy four corners of
a tetrahedron and each of these four carbon atoms are bonded to
four more carbon atoms. Such pattern is repeated in the entire
crystal lattice resulting in a giant molecule. Since the single unit of
diamond is a tetrahedron, it follows that carbon atoms have
undergone sp3 hybridization.

Each carbon atom is covalently bonded to four other carbon

atoms by the overlapping of half filled sp3 hybrid orbitals in the
crystal structure of diamond and it is difficult to rupture these
bonds. C-C bond length is 154 pm. Diamond has high melting point
(3873 K) and it is very hard. Diamond has very high density of 3.51
gm cm-3 due to three dimensional giant structure. Since all four
valence electrons of carbon are involved in bonding and there is no
free electron in the crystal structure of diamond. Diamond is a non-
conductor of electricity. Structure of diamond is shown if Fig .11.7.

Fig. 7 The structure of diamond

In diamond it is very difficult to break extended covalent

bonding and therefore, diamond is the hardest substance on the
earth. It is used as an abrasive for sharpening hard tools, in making
dyes and in the manufacture of tungsten filaments for electric light
bulbs. Diamond is used for cutting glass, making bores and fro rock
drilling.

Graphite
Graphite has a two dimensional sheet like structure and the
sheets may be considered as fused system of planar hexagonal ring.
In the planar hexagonal rings, each carbon atom, is bonded to three
other carbon atoms, structure of graphite is shown in (Fig. 8).
Hence it shown that carbon atoms have undergone sp2
hybridization.

Fig. 8 The structure of graphite

 Each carbon atom is covalently bonded to three other atoms by
the overlapping of half filled sp2 hybrid orbitals. Each carbon atom
in hexagonal ring undergoes sp2 hybridization and forms three
sigma bonds with three neighboring carbon atoms. Fourth electron
from a 𝜋 bond. The electrons are delocalized over the whole sheet.
Electrons are mobile and therefore, graphite conducts electricity
along the sheet. The various layers are held together by weak van
der Waals forces of atoms and the distance between two successive
layers is 340 pm while C-C bond length is 141.5 pm. Graphite
cleaves easily between the layers and therefore, it is very soft and
slippery. For this reason graphite is used as a dry lubricant in
machines running at high temperature, where oil cannot be used as
a lubricant.
Amorphous carbon exists as charcoal and lampblack. Heating wood
in closed iron vessel in absence of air known as destructive
distillation of wood. The black material, that is, left behind by the
destructive distillation of wood is wood charcoal. Similar treatment
of bones gives animal charcoal. Petroleum and benzene on heating
in in sufficient air give out smoke which can be collected in e form
of black powder known as lamp black. This is used in making
printing ink and shoe polishing material.

Fullerenes
A newly discovered allotrope of carbon is fullerene. In 1985, a
soccer ball shaped cluster of carbon atoms C60 was discovered and
it created lot of excitement in scientific community.
Fullerenes are made by heating of graphite in an electric arc in the
presence of inert gases such as helium or argon. In the this process
the sooty material formed by condensation of vaporized C n small
molecules consists of mainly C60 with smaller quantity of C70 and
traces of fullerenes consisting of even number of carbon atoms upto
350 or above.
Fullerenes are cage like molecules. C60molecule has a shape like
soccer ball and called Buckminster- fullerene.
It contains 20 six membered rings and 12 five membered rings. A
six membered ring is fused with six or five membered rings but a
five membered ring can only fuse with six membered rings. All the
carbon atoms they undergo sp2 hybridization and re equivalent.
 Each carbon atom forms three sigma bonds with three other
carbon atoms. The remaining electron at each carbon is delocalized
in molecular orbitals, which in turn give aromatic character to
molecule. This ball shaped molecule has 60 vertices and each one is
occupied by one carbon atom and it’s also contains both single and
double bonds with C-C distance of 143.5 pm and 138.3 pm
respectively (Fig.11.9).
Spherical fullerenes are called bucky balls and cylindrical ones
are known as carbon nanotubes or bucky tubes. Graphene is an
example of planer fullerene sheet. It has a single planar sheet of sp2
bonded carbon atoms that are densely packed in a honey comb
crystal lattice. It is infinitely large aromatic molecule. (C540
Fig.11.10)
Fullerenes being covalent are soluble in organic solvents. They
react with group 1 alkali metals, forming solids such as K35C60
which behave as super conductor below 18 K. Fullerenes have
many Nano technological applications.

Fig.9 The structure of C60, Buckminster-fullerene

Note that molecule has the shape of a soccer ball (Football).

It is important to know that graphite is
thermodynamically most stable allotrope of carbon. ∆fH of graphite
is taken as zero. ∆fH values of diamond and fullerene C60 are 1.90
and 38.1 kJ mol-1 respectively.

Fig.10 C540

16. PHYSICAL AND CHEMICAL PROPERTIES OF CARBON

Atomic number of carbon is 6. Its electronic configuration is ls2
2s2 2p2. Atomic mass is 12.01.
It has smallest atomic radius (77pm) in group 14. It shows
anomalous behavior. Carbon is non metal. It has two stable
isotopes 12C(98.99%) and 13C(1.1%). It forms allotropes in the form
of diamond, graphite which exist in crystalline forms. Carbon exists
in several micro crystalline forms which were originally regarded as
amorphous. These are coal, coke, charcoal, lamp black, etc. Carbon
shows important property of catenation. Carbohydrates, proteins,
vitamins, etc. are required for all living system. All these are made
up of carbon compounds. Carbon shows negative oxidation state as
-4. Maximum covalence of carbon is 4. In tetravalent the number of
electrons around central atom in molecule (example CCl4) is eight. It
is electron precise molecule and never acts as Lewis acid or Lewis
base.
Carbon when heated in oxygen forms carbon monoxide (CO) and
carbon dioxide (CO2). CO is neutral bu CO2 is acidic in nature.
Carbon is not affected by water. Carbon combines with halogens to
form both simple CF4, CCI4, CBr4, and CI4 and mixed halogen
CFCI3, CF2 CI2, CCI, Br etc. CCI4 is used as fire extinguisher under
the name pyrene. CF2CI2 is used as refrigerant under the name
Freon.
Carbon forms carbides. Compounds of carbon with elements of
lower or equal electronegativity are called carbides. Carbides have
extensive applications in industry. For example CaC2 is used to
prepare acetylene.

CaC2 + 2H2O → Ca(OH)2 + HC ≡CH

Silicon carbide is used as abrasive under the name

carborundum. Boron carbide is still harder than silicon carbide
used as shield against radioactive radiations.

16.1 Uses of Carbon

Graphite has many industrial applications. Graphite fibers
embedded in plastic material form high strength, light weight
composites. The composites are used in products such as fishing
rods, tennis rackets, air crafts and canoes. Graphite is a goods
conductor of electricity. So it is used as electrodes in batteries and
industrial electrolysis. Graphite crucibles are used in laboratories.
These crucibles are inert to dilute acids and alkalies. Activated
charcoal is used in adsorbing poisonous gases and also used in
water filters to remove organic matter. Carbon black is used as
black pigment in black ink and filler in automobile tyres. Coke is
used as fuel and it acts as a reducing agent in metallurgy. Diamond
is a precious stone and used in jewelry. Purity of diamond is
expressed in terms of carats (1 carat = 200mg).
17. IMPORTANT COMPUNDS OF CARBON: OXIDES OF
CARBON
Two important oxides of carbon are carbon monoxide and carbon
dioxide.

1) Carbon monoxide
i) Direct combination of carbon in limited supply of oxygen
or air gives carbon monoxide.
∆
2C(s) + O2(g) → 2CO(g)
ii) On small scale (laboratory method) pure carbon
monoxide is prepared by dehydration of formic acid with
concentrated sulphuric acid at 373K.(heating formic acid
with conc. H2SO4

H2SO4 at 373K
HCOOH→ CO (pure) + H2O

Heating oxalic acid with conc. H2SO4

H2SO4 −H2O
H2C2O4 → CO + CO2

iii) On commercial scale it is prepared by the passage of

steam over hot coke. The mixture of CO and H2 thus
produced is known as water gas or synthesis gas.

473−1273K
C(s) + H2O(g) → CO(g) + H2(g) water gas

iv) When air is used instead of steam, a mixtures of CO and

N2 is produced, which is called producer
1273K
2C(s) + O2(g) + 4N2(g) → 2CO(g) + 4N2(g)

Water gas and producer gas are very important industrial

fuels. Carbon monoxide in water gas or producer gas can
undergo further combustion forming carbon dioxide with
the liberation of heat.
Properties of carbon monoxide
It is colourless and odourless gas and almost insoluble in water. It
is a powerful reducing agent and reduces almost all the metal
oxides other than those of alkali and alkaline earth metals,
aluminium and few transition metals. CO is used in the extraction
of many metals from their oxides.
∆
Fe2O3(s) + 3CO → 2Fe(s) + 3CO2 (g)
∆
CuO (s) + CO (g) → Cu(s + CO2 (g)

ZnO (s) + CO (g) → Zn(s) + CO2 (g)

It is poisonous gas, burns with blue flame and when inhaled

produces suffocation and finally death. The poisoning effect of CO is
due to the fact that it combines with haemoglobin of blood to form
arboxyhemoglobin complex, which is about 300 times more stable
than oxygen haemoglobin complex. This prevents haemoglobin in
the red blood corpuscles from carrying oxygen round the body and
ultimately resulting in death

Hb + O2 → HbO2 (oxyhaemoglobin)

Hb + CO → COHb (carboxy haemoglobin)

(Hb =haemoglobin)

In CO molecule, both C and O are sp hybridized. One sp Hybrid

orbital of each C and O overlap to form one C-O 𝜎 bond while other
sp-orbital on each atom contains lone pair of electrons. The two
each unhybridized p-orbitals of each C and O form two p𝜋- p𝜋
bonds. Thus CO is a linear molecule is presented as C ≡O:

Because of the presence of the lone pairs of electrons, CO acts as

Lewis base thus combines with many metals such as Fe, Cr, and Ni
etc. Forming their respective metal carbonyls
Fe + 5Co → Fe (CO)5 Iron PentacarbonyI

Ni + 4Co → Ni (CO)4 NickeltetracarbonyI

2) Carbon dioxide
i) It is prepared by complete combustion of carbon and
carbon containing fuels in excess of air.
∆
C(s) + O2 → CO2(g)
∆
CH4(g) + 2O2 → CO2(g) + 2H2O(g)
ii) It is prepared in the laboratory by the action of dilute
HCI on calcium carbonate.
CaCO3(s) + 2HCI(aq) → CaCI2(aq)+ CO2(g) + H2O(l)
iii) On commercial scale, it is obtained by heating lime
stone.
1600K
CaCO3 → CaO + COH2
iv) It is a valuable by product in the manufacture of ethyl
alcohol by fermentation of glucose or fructose.
zymase
C6H12O6 → 2C2H5OH + 2CO2

Properties
It is colourless and odourless gas. Its low solubility in water makes
it of great biochemical and geo chemical importance.

With water if forms carbonic acid which is a dibasic acid and

dissociates in two steps

H2CO3(aq) + H2O(l) ⇌ HCO-3(aq) + H3O+(aq)

HCO-3(aq) + H2O(l) ⇌ CO2-3(aq) + H3O+(aq)

H2CO3/HCO3- buffer system helps to maintain pH of blood between

7.26 to 7.42
CO2 is acidic in nature, it combines with alkalies to form metal
carbonates.

In photosynthesis, CO2 is converted to glucose and O2.

chlorophyll & sunlight
6CO2 + 12H2O → C6H12O6 + 6H2O + 6O2

CO2 reacts with NH3 at 453K -473K under a pressure of 220

atmosphere to give urea as the final product.
453−473K
2NH3 + CO2→ [NH2COONH4] → NH2CONH2
ammonium carbonate Urea + H2O

By photosynthesis plants make food for themselves, animals and

human beings. In the recent years, the increase of combustion of
fossil fuels and decomposition of lime stone for cement production
seems to increase the CO2 content of the atmosphere. This may lead
to increase in greenhouse effect. This enhanced greenhouse effect
raises the temperature of the atmosphere which might have serious
consequences in the form of global warming and climate change.
Solid carbon dioxide is called dry ice since it does not wet the
surface and gets directly converted to gaseous state. Dry ice is used
as a coolant for preserving perishable articles in food industries and
for making cold baths in laboratory. Being heavy and non supporter
of combustion it is used as fire extinguisher. CO2 is a linear
molecule in which carbon atom is sp hybridized. Two sp hybridized
orbitals of carbon atom overlap with two p-orbitals of oxygen atom
to make two sigma bonds. Other two electrons of carbon atom are
involved in P𝜋 -P𝜋 bonding with two oxygen atoms. Both C-O bonds
are of equal bond length of 115 pm. It has no dipole moment.

Compounds of silicon
Silicon being second member of group 14, has a much larger size
(118pm) and lower electronegativity than that of carbon. As a result
silicon does not form double bond with silicon or oxygen. Thus Si-O
bond is much stronger than Si-Si and Si-H bonds. Silicon has
vacant 3d orbitals in its valence shell due to which it can extend its
covalence from four to five and six. Important compounds of silicon
are silicon dioxide, silicon tetrachloride, silicones, silicates and
zeolites.

Silicon dioxide, SiO2

Silicon dioxide is commonly known as silica. 95% of the earth’s
crust is made up of silica and silicates. Silicon dioxide occurs as
quartz, cristobalite and tridymite. All these are crystalline forms of
silica. SiO2 is covalent in nature. It has three dimensional network
solid in which each silicon atom is covalently bonded in a
tetrahedral manner to four oxygen atoms. Each oxygen atom in
turn is covalently bonded to another silicon atom. It is shown in Fig
11.11. Each corner is shared with another tetrahedron. The entire
crystal may be regarded as giant molecule in which eight membered
rings are formed with alternate silicon and oxygen atoms.

Fig. 11 Structure of SiO2

SiO2 in its normal form is non-reactive because of very high Si-

O bond enthalpy. It resists the attack by halogens, dihydrogen and
most of the acids and metals even at elevated temperatures.
However, it is attacked by HF and NaOH.

SiO2 + 4HF → SiF4 + 2H2O

SiO2 + 2NaOH → NaSiO3 + H2O

Quartz (one form of SiO2) is used as piezoelectric material.

Quartz can play important role in making accurate clocks, modern
radio and television broad castings and mobile radio
communications. Silica gel is the important compound of silica. It is
used as dehydrating agent and adsorbent in chromatography.
Kieselguhr and amorphous form of silica is used in filtration plants.

II) Silicon tetrachloride SiCl4

It is prepared by action of chlorine on silicon

Si + 2Cl2 → SiCl4

This tetrahalide is covalent in nature and possesses tetrahedral

geometry.

The tetra chloride of carbon i.e. CCl4 is not hydrolysed by water

but SiCl4 gets easily hydrolysed.

CCl4 + H2O → No reaction

SiCl4 + 4H4O → Si(OH)4 +4HCl

orthosilicic Acid

Explanation
The inability of CCI4 to undergo hydrolysis is due to the absence
of vacant d orbitals in the valence shell of carbon. Due to this,
carbon in CCI4 is unable to expand its co-ordination number more
than four. On the other hand, silicon atom possesses vacant 3d
orbitals in its valence shell and can utilize them for accommodating
electron pairs given by oxygen atom of water molecules. Thus SiCI4
can expand its octet i.e. can increase its co-ordination number,
beyond four. As a result, it readily undergoes hydrolysis.

The complex thus formed eliminates a molecule of HCI to form SiCI3

. OH. The process continues till all the remaining CI atoms are
replaced by-OH groups and ortho-silicic acid is obtained.

Silicones
Silicones are synthetic organosilicon compounds containing
repeated R2SiO units held by Si-O-Si linkage. Since the empirical
formula R2SiO (where R=CH3 or C6H5 group) is similar to that of
ketone (R2CO), hence the name silicones has been given to these
compounds.

The starting materials for manufacture of silicones are alkyl or

aryl substituted silicon chlorides RnSiCI(4-n), where R is alkyl or aryl
group. When methyl chloride (CH3CI) reacts with silicon in the
presence of copper as catalyst at a temperature 570K various types
of methyl substituted chlorosilanes of formula Me4SiCI3 Me2SiCI2,
Me3SiCI with small amount of Me4Si are formed. Hydrolysis of
dimethyl dichlorosilane, (CH3)2SiCl2 followed by condensation
polymerization gives straight chain polymers.

Short chain silicones are oily liquids, medium chain silicones

behave as viscous oils, jellies and greases and those with very long
chains behave as rubbery elastomers and resin.

Silicones being surrounded by non polar alkyl groups are water

repellent in nature. They have in general high thermal stability,
high dielectric strength and resistance to oxidation and chemicals.

Silicones are used to prepare water proof papers, wood, textiles,

lubricant at high and low temperatures, etc.

Formation of silicone is explained as under.

The chain length of the polymer can be controlled by adding
(CH3)3SiCl which blocks the end as shown below;
They are used as sealant, greases and electrical insulators. They
play important role in surgical and cosmetic implants. It is because
of biocompatibility of silicone.

Silicates
Rocks, clays, soils are made up of silicates of aluminium, iron,
magnesium and other metals. Some of the examples are feldspar,
mica, zeolites and asbestos.

Feldspar is NaAlSi3O8

Mica (Abrak) is naturally occurring aluminium silicate

[KH2Al3(SiO4)3] or KAL3Si3O10 (OH)2

All silicates are made up of SiO4-4 tetrahedral units in which

silicon is sp3 hybridized and is surrounded by four oxygen atoms.
The SiO4-4 tetrahedral can be linked together in several different
ways. Depending on the number of corners of SiO4 tetrahedral
shared various kinds of silicates, such as ortho, pyro, cyclic chain,
sheet and three dimensional silicates are formed. If all the four
corners are shared with other tetrahedral unites, three dimensional
network is formed. Negative charge on silicate structure is
neutralized by positively charged metal ions. Following Fig.12 (a)
and (b) show structural unit of SiO4-4

Fig. 12. Structure of SiO44- anion;

a) Tetrahedral structure b) representation

Zeolites
If aluminium atoms replace few silicon atoms in three
dimensional network of silicon dioxide overall structure known as
aluminosilicate is formed which acquires a negative charge. Cations
such as Na+, K+ or Ca++ balance the negative charge.

The name zeolite (Greek: zein-boiling, lithos-stone) means boiling

stone. The chemical formula of sodium zeolite may be represented
as,
 Na2O . Al2O3 . XSiO2 YH2O

Where x = 2 to 10 and y = 2 to 6

It is hydrated sodium alumino silicate. This compound is capable

of exchanging reversibly their sodium ions for hardness in water.
Such zeolites are known as permutits.

Zeolites are of two types :

i) Natural zeolites
ii) Synthetic zeolites.
Zeolites are widely used as catalysts in petrochemical
industries for cracking of hydrocarbons and isomerization, e.g.
ZSM-5(a type of zeolite) used to convert alcohol directly into
gasoline.
 PART -B

INTRODUCTION OF P BLOCK
In this section, we will study about the elements in P-block and their
properties. P block elements are shiny and usually a good conductor of
electricity and heat as they have a tendency to lose an electron. You will find
some amazing properties of elements in a P-block element like gallium. It’s a
metal that can melt in the palm of your hand. Silicon is also one of the most
important metalloids of the p-block group as it is an important component of
glass.

What P-block elements are?

P block elements are nothing but the element in which the last electron enters
the outermost p-subshell. P block elements consist of boron family, nitrogen
family, oxygen family, fluorine family and lastly the family of noble gases that
are neon family. P block starts from the 13th group and goes till 18th group in
the periodic table.
You must have seen that coal is used in villages to cook food. It is nothing but
a P-block element i.e. carbon. Diamonds are used for making beautiful
ornaments are also made up of carbon. Aluminium foil made up of aluminum
is also made up of p block element.
The general electronic configuration of p-block elements is ns2np1-6(except
He).Whereas the inner core electronic configuration may differ. Just because
of this difference the inner core, there are changes in both physical and
chemical properties of the elements.
The oxidation state of elements in p – block is maximum when it is equal to a
total number of valence electrons i.e. the sum of S and P electrons. One of the
most interesting facts about the p-block elements is that it contains both non-
metals and metalloids.
The first member of the p block elements differ with other elements in two
major respects:
 First is the size and each and every property which depend upon size. The
second difference applies only to the p-block element which arises from the
effects of d-orbitals in the valence shell of heavier elements.

p-block elements- An overview

As explained above, the last electron in the electronic configuration enters the
p-orbital of the p-block elements. Elements in Groups 13-18 of the Periodic
Table are called P-block elements. These include metals, metalloids, noble
gases and halogens. Some of the commonly known elements in the P-block
are:

1. Metals: Aluminium (Al), Boron (B), Tin (Sn).

2. Metalloids: Silicon (Si), Germanium (Ge)
3. Noble Gases: Helium (He), Neon (Ne), Argon (Ar).
4. Halogens: Fluorine (F), Chlorine (Cl), Bromine (Br).

Definition of p-Block
Elements having a place within the group 13 (i.e. group IIIA) to group 17 (i.e.
group VIIA) of the periodic table alongside the group 18 i.e. the zero
groupelements together frame the p-block of the periodic table.

Position of p-Block Elements in the Periodic Table

In the elements of p-block, the last electron enters the furthest p orbital. They
have 3 to 8 electrons in the peripheral shell. As we realize that the quantity of
p orbitals is three and, therefore, the most extreme number of electrons that
can be obliged in an arrangement of p orbitals is six. Consequently, there are
six groups of p-block elements in the periodic table numbering from 13 to
18.First group: group IIIA called as Boron groupSecond group: group IVA
called as Carbon group.Third group: group VA called as Nitrogen
group.Fourth group: group VIA called as Chalcogens.Fifth group: group
VIIA called as Halogens.Sixth group: zero group or group 18 called
as Inert or Noble gasses group.
 In the p-block, all the three sorts of elements are available, i.e.
the Metals, Non-Metals, and Metalloids.The crisscross line in the p-block
isolates every one of the elements that are metals from those that are non-
metals. Metals are found on the left of the line, and non-metals are those on
the right. Along the line, we discover the metalloids. Because of the nearness
of a wide range of elements, the p-block demonstrates a great deal of variety
in properties.

Group-13 Elements
 Group-13 elements belong to the first group of p-block elements and
include Boron (B), Aluminium (Al), Gallium (Ga), Indium (In) and Thallium (Tl).
 Boron is the only metalloid in the group while the rest of the elements are
metals. Gallium is liquid at temperatures over 30oC.
 They contain three electrons in the outer most shell i.e. a filled s-orbital and one
electron in the p-orbital. (ns2np1)

General Physical and Chemical Properties

 Atomic Radius and density increases down the group with Thallium (Tl) having
the largest atomic radius and highest density. (**Atomic radius of gallium is less
than Aluminium due to poor shielding effect of d-orbital electrons.)
 First Ionization Energy decreases down the group. (except Thallium)
 Boiling Point decreases down the group.
 Electronegativity decreases from Boron to Aluminium, but then increases
marginally. This discrepancy is due to aberrant trends in atomic size.
 Sum of first three ionization enthalpies decreases considerably from boron to
aluminium, but then increases due to poor shielding effect of intervening d- and
f- orbital electrons.
 The relative stability of the +1 oxidation state increases from Aluminium to
Thallium.
 These are electron deficient elements, hence act as good Lewis acids. The
tendency to behave as Lewis acids decreases down the group.
 Oxide of boron is acidic, oxides of Aluminium and gallium are amphoteric, while
oxides of indium and thallium are basic in nature.
 Boron and Aluminium react at high temperatures with oxygen and nitrogen to
form oxides and nitrides respectively.
 Boron is nonreactive at moderate temperatures to acids and alkalis, whereas
Aluminium reacts with both acids and bases.

Uses
 Boron, in the form of borax (Na2B4O7.10H2O), is used in household cleaning
products, as a pH buffer for gel electrophoresis, as flux for soldering and in
laboratory tests for transition metals due to the characteristic colours of their
metaborates when exposed to flame.
 Orthoboric acid is used in the manufacture of fibreglass, LCD display screen glass
and as a dry lubricant for carom boards.
 Aluminium is used in the manufacture of aircraft bodies, food packaging
materials in the form of aluminium foil, pipes, tubes, coins and electrical wires
(due to high electrical conductivity).
 Lithium Aluminium Hydride (LiAlH4) and Sodium borohydride (NaBH4) are
potent reducing agents used in organic chemistry.

Group-14 Elements
 Group-14 elements include Carbon (C), Silicon (Si), Germanium (Ge), Tin (Sn) and
Lead (Pb).
 Carbon is a non-metal, silicon and germanium are metalloids, tin and lead are
metals.
 They contain four electrons in the outer most shell i.e. a filled s-orbital and two
electrons in the p-orbital. (ns2np2).

General Physical and Chemical Properties

 There is a considerable increase in covalent radius from carbon to silicon, but a
small increase from silicon to lead. This is due to poor shielding effect of
completely filled d and f orbitals.
 First ionization enthalpy is higher than the corresponding members of group 13.
Ionisation enthalpy generally decreases down the group. Discrepancies in the
trend are also due to poor shielding effect of d and f orbital electrons.
 Electronegativity from silicon to lead is almost same, but higher than the
corresponding group 13 members.
 Boiling point decreases down the group from silicon to lead.
 Melting and Boiling points are higher than the corresponding group 13
members.
 Tendency to show +2 oxidation state increases from germanium to lead.
Stability of +4 oxidation state decreases down the group.
 Lead is stable in +2 oxidation state and acts as an oxidising agent in +4 oxidation
state.
 Presence of d-orbital in elements apart from carbon increases their tendency to
form complexes by accepting electron pairs from donors.
 Two types of oxides are formed, on heating with oxygen- monoxides and
dioxides. Dioxides tend to be more acidic than monoxides.
 Acidic nature of dioxides decreases down the group; tin and lead dioxide is
amphoteric.
 Stability of dihalides increases down the group, whereas stability of tetrahalides
decreases down the group.
 Carbon has a unique property of forming long chains by linking with other
carbon atoms. This is called catenation. Tendency of catenation decreases down
the group (Lead does not show catenation.)
 Carbon also has unique ability to form pπ– pπ multiple bonds with itself and
with other atoms of small size and high electronegativity.
 Due to catenation and formation of pπ– pπ multiple bonds, allotropic forms of
carbon, namely graphite, diamond and fullerenes exist.

Uses
 Carbon, in form of graphite fibres, is used to make tennis racquets and
aircrafts. Graphite is used as an electrode in batteries.
 Activated charcoal is used in water purification and removal of poisonous
gases.
 Diamond is used in jewellery and in cutting equipment.
 Silicon is used in electronics and manufacture of cement.
 Germanium is used in synthesis of polyethylene terephthalate.
 Tin is used to make alloys and solder, used for making connections in
electrical circuits.
Lead is used in radiation shields.
Group-15 Elements

 Group-15 elements include Nitrogen (N), Phosphorous (P), Arsenic (As),

Antimony (Sb) and Bismuth (Bi).
 Nitrogen and Phosphorous are non-metals, arsenic and antimony are
metalloids while bismuth is a metal.
 They contain five electrons in the outer most shell i.e. a filled s-orbital and
three electrons in the p-orbital. (ns2np3). The p-orbital is half-filled,
making it more stable.

General Physical and Chemical Properties

  Covalent and ionic radii increase in size down the group. The lack of
regular trend is due to poor shielding effect of d and f orbitals.
 Ionisation enthalpy decreases down the group due to increase in atomic
size, and is higher than the corresponding group 15 members due to extra
stability of half-filled p orbitals.
 Electronegativity decreases down the group.
 Metallic character increases down the group.
 Boiling point increases up to arsenic and then decreases up to bismuth.
 Allotropy is seen in all elements except nitrogen.
 Stability of -3 and +5 oxidation state decreases down the group.
 Nitrogen can form multiple pπ– pπ bonds, whereas phosphorous and
arsenic can form dπ– pπ bonds.
 Oxides formed are of two types with different oxidation states of the
element – +3 and +5.
 Oxides of higher oxidation state are more acidic and acidic character of
these oxides decreases down the group.
 All elements react with metals and possess -3 oxidations states in their
respective compounds.

Uses
 Nitrogen is used as a coolant, to make fertilizers, plastics and explosives.
It is also used in cryopreservation, pharmaceuticals and X-ray detectors.
 Phosphorous is used in fertilizers along with nitrogen, in making matches
to light fires, softening hard water, and military applications like smoke
bombs.
 Arsenic is used in semiconductors in the form of gallium arsenide. Arsenic-
lead alloys are used to manufacture bullets.
 Antimony is used as a dopant in semiconductors.
 Bismuth is used as a catalyst to make acrylic fibres and in cosmetics.
 PART –C
MULTIPLE CHOICE QUESTIONS
1. When Cl2 gas reacts with hot and concentrated sodium
hydroxide solution, the oxidation number of chlorine
changes from
a) Zero to + 1 and zero to –3
b) Zero to + 1 and zero to –5
c) Zero to – 1 and zero to +3
d) Zero to – 1 and zero to +5

2. In which of the following compounds, nitrogen

exhibits highest oxidation state?
a) N3H
b) NH2OH
c) N2H4
d) NH3

3. Three reactions involving H2PO4- are given below

i. H3PO4 + H2O ® H3O+ + H2PO4-
ii. H2PO4- + H2O ® HPO42- + H3O+
iii. H2PO4- + OH- ® H3PO4 + O2-
In which of the above does H2PO4- act as an acid?
a) (i) only
b) (ii) only
c) (iii) only
d) (i) and (ii)
4. The correct order of increasing bond angles in the
following species is
a) Cl2O < ClO2 < ClO2-
b) ClO2- < Cl2O < ClO2
c) Cl2O < ClO2- < ClO2
d) ClO2 < Cl2O < ClO2-

5. The tendency of BF3, BCl3 and BBr3 to behave as

Lewis acid decreases in the sequence:
a) BCl3 > BF3 > BBr3
b) BF3 > BCl3 > BBr3
c) BBr3 > BF3 > BCl3
d) BBR3 > BCl3 > BF3

6. P4O10 is the anhydride of

a) H3PO2
b) H3PO3
c) H3PO4
d) H4P2O7

7. Which of the following statements regarding ozone

is not correct?
a) The oxygen-oxygen bond length in
ozone is identical with that of
molecular oxygen
b) The ozone is response hybrid of two
structures
c) The ozone molecule is angular in shape
 d) Ozone is used as a germicide
disinfectant for the purification of air.

8. Which of the following contains P - O - P bond?

a) Hypophosphorous acid
b) Phosphorous acid
c) Pyrophosphoric acid
d) Orthophosphoric acid

9. Which noble gas is most abundant in

atmosphere?
a) He
b) Ne
c) Ar
d) Kr

10. The reaction of P4 with X leads selectively to

P4O6. The X is
a) Dry O2
b) A mixture of O2 and N2
c) Moist O2
d) O2 in the presence of aqueous NaOH

11. Which of the following reactions of xenon

compounds is not feasible?
a) XeO3 + 6HF ® XeF6 + 3H2O
b) 3XeF4 + 6H2O ® 2Xe + XeO3 + 12HF
 +1.5O2
c) 2XeF2 + 2H2O ® 2Xe + 4HF + O2
d) XeF6 + RbF ® Rb [XeF7]

12. In which of the following arrangements, the

sequence is not strictly according to the property
written against it?

a) CO2 < SiO2 < SnO2 < PbO2 : Increasing

oxidizing power
b) HF < HCl < HBr < HI : Increasing acid
strength
c) NH3 < PH3 < AsH3 < SbH3 : Increasing
basic strength
d) B < C < O < N : Increasing first
ionization enthalpy

13. Among the following which is the strongest

oxidizing agent?

a) Br2
b) I2
c) Cl2
d) F2

14. The brown ring test for nitrates depends on

a) reduction of ferrous sulphate to iron
b) oxidation of nitric oxide to nitrogen
dioxide
c) the reduction of nitrate to nitric oxide
d) oxidising action of sulphuric acid

15. One mole of magnesium nitride on the reaction

with an excess of water gives:
a) one mole of ammonia
b) one mole of nitric acid
c) two moles of ammonia
d) two moles of nitric acid

16. Which of the following statements is not

valid for oxoacids of phosphorus?
a) All oxoacids contain tetrahedral four
coordinated phosphorus
b) All oxoacids contain at least one P = O
unit and one P – OH group
c) Orthophosphoric acid is used in the
manufacture of triple superphosphate
d) Hypophosphorous acid is a diprotic
acid

17. Sulphur trioxide can be obtained by which

of the following reaction
a) S + H2SO4
b) H2SO4 + PCl3
c) CaSO4 + C
d) Fe2 (SO4)3

18. Argon is used

a) To obtain low temperature
b) In high temperature welding
 c) In radio therapy for treatment of
cancer
d) In filling airships

19. The function of Fe(OH)3 in the contact

process is
a) to detect colloidal impurity
b) to remove moisture
c) to remove dust particles
d) to remove arsenic impurity

20. Of the following compounds the most acidic is

a) As2O3
b) P2O5
c) Sb2O3
d) Bi2O3

Answers:
1-d, 2-a, 3-b, 4-b, 5-d, 6-c, 7-a, 8-c, 9-c, 10-b, 11-a, 12-c,
13-d, 14-c, 15-c, 16-d, 17-d, 18-b, 19-d, 20-b.