Class XI Chemistry

Unit-11
THE p -BLOCK ELEMENTS
Topic:-
• General Introduction

Prepared by :-Vijay Kumar Sethi

 THE p -BLOCK ELEMENTS

• In p-block elements the last electron enters the outermost p orbital.

• The number of p orbitals is three and, therefore, the maximum number of electrons that can be
accommodated in a set of p orbitals is six.
• Consequently there are six groups of p–block elements in the periodic table numbering from 13
to 18.
• Boron, carbon, nitrogen, oxygen, fluorine and helium head the groups.
• Their valence shell electronic configuration is (except for He).
• The maximum oxidation state shown by a p-block element is equal to the total number of
valence electrons and this is called as group oxidation state.
• The oxidation state two unit less than the group oxidation state becomes progressively
more stable for the heavier elements in each group due to ‘inert pair effect’.
Inert pair effect:-
• Reluctance of the ns2 electron to participate in
bond formation of heavier members of p-block
elements.
• Energy required to unpair the ns2 electron is not
compensated in bond formation.
Metallic and Non-metallic Characters
• Metals, non-metals and metalloids are present
in the p-block of the periodic table.
• The non-metallic character of elements decreases down the group.
• In fact the heaviest element in each p-block group is the most metallic in nature.
• In general, non-metals have higher ionisation enthalpies and higher electronegativities
than the metals. Hence, in contrast to metals which readily form cations, non-metals
readily form anions
• The compounds formed by highly reactive non-metals with highly reactive metals are
generally ionic because of large differences in their electronegativities.
• On the other hand, compounds formed between non-metals themselves are largely
covalent in character because of small differences in their electronegativities.
• The non-metal oxides are acidic or neutral whereas metal oxides are basic in nature
First element differ in some respect from rest of the members in a group due to-
• Non-availability of d-orbitals
• Smaller size
• High charge to radius ratio
• High electronegativity
Some Important aspects regarding p-Block
Elements
1) The second period elements of p-groups starting from boron are restricted to a maximum
covalence of four (using 2s and three 2p orbitals).
2) In contrast, using d-orbitals the third period elements can expand their covalence above four.
• For example, while boron forms only [BF4]–, aluminium gives [AlF6]3– ion.
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Some Important aspects regarding p-Block
3)
Elements
The first member of a group differs from the heavier members in its ability to form
pπ - pπ multiple bonds to itself ( e.g., C=C, C≡C, N≡N) and to other second row
elements (e.g., C=O, C=N, C≡N, N=O).
4) The heavier elements do form π bonds but this involves d orbitals (dπ – pπ or dπ –dπ ).
5) However, the coordination number in species of heavier elements may be higher than
for the first element in the same oxidation state.
6) For example, in +5 oxidation state both N and P form oxoanions : (three-coordination
with π – bond involving one nitrogen p-orbital) and (four-coordination involving s, p
and d orbitals contributing to the π – bond).
MNEMONICS FOR The p-Block Elements
 Class XI Chemistry
Unit-11
THE p -BLOCK ELEMENTS
Topic:-
• Occurrence, Atomic and Physical
Properties of Group 13 Elements

Prepared by :-Vijay Kumar Sethi

 GROUP 13 ELEMENTS: THE BORON FAMILY
Metal/ Non-metal
Element Symbol Atomic
No.

Boron B 5 Typical non-metal

Aluminium Al 13 Metal but shows many

chemical similarities to boron

Gallium Ga 31 Metal

Indium In 49

Thallium Tl 81

Nihonium Nh 113
 Occurrence of Group 13 Elements
• Boron is a fairly rare element, mainly occurs as orthoboric acid, borax and kernite
• 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.
• There are two isotopic forms of boron 10B (19%) and 11B (81%).
• Aluminium is the most abundant metal and the third most abundant element in the earth’s crust
(8.3% by mass) after oxygen (45.5%) and Si (27.7%).
• Bauxite, and cryolite, are the important minerals of aluminium.
• In India it is found as mica in Madhya Pradesh, Karnataka, Orissa and Jammu.
• Gallium, indium and thallium are less abundant elements in nature
• Nihonium is a synthetically prepared radioactive element with half life period of 20 seconds
 The atomic properties of Group 13 Elements
Electronic Configuration-
The outer electronic configuration of these elements is ns2np1.

• boron and aluminium have noble gas core,

• gallium and indium have noble gas plus
• 10 d-electrons, and
• thallium and nihonium have noble gas plus
14 f-electrons plus 10 d-electrons cores.
 Continue…
The atomic properties of Group 13 Elements
Atomic Radii-
• In general on moving down the group, atomic radius is expected to increase due to
increase in number of shells.

• Atomic radius of Ga is less than that of Al ,because the presence of additional 10 d-

electrons offer only poor screening effect for the outer electrons which results in
increased nuclear charge in gallium. Consequently, the atomic radius of gallium (135
pm) is less than that of aluminium (143 pm).
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The atomic properties of Group 13 Elements
Ionization Enthalpy-

• The decrease from B to Al is due to increase in size.

• The ionisation enthalpy value of Ga is more than Al due to poor screening effect
of inner d- electrons
• The ionisation enthalpy value of Tl is more than In due to poor screening effect of
inner f- electrons
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The atomic properties of Group 13 Elements
Electronegativity-
• Down the group, electronegativity first decreases from B to Al and then increases
marginally .
• This is because of the discrepancies in atomic size of the elements
 Physical Properties of Group 13 Elements

1) Boron is non-metallic in nature. It is extremely hard and black coloured solid. It exists in
many allotropic forms. Due to very strong crystalline lattice, boron has unusually high
melting point.
2) Rest of the members are soft metals with low melting point and high electrical conductivity.
3) Gallium with unusually low melting point (303K), could exist in liquid state during
summer. Its high boiling point (2676 K) makes it a useful material for measuring high
temperatures.
4) Density of the elements increases down the group from boron to thallium.
 Class XI Chemistry
Unit-11
THE p -BLOCK ELEMENTS
Topic:-
• Chemical Properties of Group 13 Elements

Prepared by :-Vijay Kumar Sethi

 Oxidation state and trends in chemical reactivity

1) Due to small size of boron, the sum of its first three ionization enthalpies is very high.
Therefore it form s only covalent compounds.
2) The sum of the first three ionisation enthalpies of Al considerably decreases, and is
therefore able to form Al3+ ions. In fact, aluminium is a highly electropositive metal.
3) Due to inert pair effect in Ga, In and Tl, both +1 and +3 oxidation states are observed.
4) The relative stability of +1 oxidation state : Al<Ga<In<Tl.
5) In thallium +1 oxidation state is predominant whereas the +3 oxidation state is highly
oxidising in character.
6) The compounds in +1 oxidation state are more ionic than those in +3 oxidation state.
 Continue…
Oxidation state and trends in chemical reactivity
6) In trivalent state, the number of electrons around the central atom in a molecule of the
compounds of these elements (e.g., boron in ) will be only six. Such electron deficient
molecules have tendency to accept a pair of electrons to achieve stable electronic
configuration and thus, behave as Lewis acids.
7) The tendency to behave as Lewis acid decreases with the increase in the size down the group.
8) easily accepts a lone pair of electrons from ammonia to form .
 Continue…
Oxidation state and trends in chemical reactivity

• achieves stability by forming a dimer

• In trivalent state most of the compounds being covalent are hydrolysed in water.
• For example, the trichlorides on hyrolysis in water form tetrahedral species; the
hybridisation state of element M is .
• Aluminium chloride in acidified aqueous solution forms octahedral ion.
• In this complex ion, the 3d orbitals of Al are involved and the hybridisation state of Al
is sp3d2.
Problem 11.1
Standard electrode potential values, for is –1.66 V and that of is +1.26 V. Predict about
the formation of ion in solution and compare the electropositive character of the two
metals.
Solution
values for two half cell reactions suggest that aluminium has high tendency to make ,
whereas is not only unstable in solution but is a powerful oxidising agent also. Thus is
more stable in solution than . Aluminium being able to form
+3 ions easily, is more electropositive than thallium.
 Reactivity towards air
• Boron is unreactive in crystalline form.
• Aluminium forms a very thin oxide layer on the surface which protects the metal from
further attack.
• Amorphous boron and aluminium metal on heating in air form respectively.
• With dinitrogen at high temperature they form nitrides.
 Reactivity towards acids and alkalies
• Boron does not react with acids and alkalies even at moderate temperature;
• Aluminium dissolves in mineral acids and aqueous alkalies and thus shows amphoteric
character.
• Aluminium dissolves in dilute HCl and liberates dihydrogen.

• However, concentrated nitric acid renders aluminium passive by forming a protective

oxide layer on the surface.
• Aluminium also reacts with aqueous alkali and liberates dihydrogen.
 Reactivity towards halogens
• These elements react with halogens to form trihalides (except ).

Problem 11.2
White fumes appear around the bottle of anhydrous aluminium chloride. Give reason.
Solution
Anhydrous aluminium chloride is partially hydrolysed with atmospheric moisture to
liberate HCl gas. Moist HCl appears white in colour.
 IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF
BORON
• The tri-chlorides, bromides and iodides of all these elements being covalent in nature are
hydrolysed in water.
• Species like tetrahedral and octahedral , except in boron, exist in aqueous medium.
• The monomeric trihalides, being electron deficient, are strong Lewis acids.
• Boron trifluoride easily reacts with Lewis bases such as NH3 to complete octet around
boron.

• It is due to the absence of d orbitals that the maximum covalence of B is 4

 Continue…
IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF
• BORON
Since the d orbitals are available with Al and other elements, the maximum
covalence can be expected beyond 4.
• Most of the other metal halides (e.g., ) are dimerised through halogen bridging
(e.g., ).
• The metal species completes its octet by accepting electrons from halogen in these
halogen bridged molecules.
Problem 11.3
Boron is unable to form ion. Explain.
Solution
Due to non-availability of d orbitals, boron is unable to expand its octet. Therefore,
the maximum covalence of boron cannot exceed 4.
 Class XI Chemistry
Unit-11
THE p -BLOCK ELEMENTS
Topic:-
• Occurrence, atomic and Physical
Properties of Group 14 Elements

Prepared by :-Vijay Kumar Sethi

 GROUP 14 ELEMENTS: THE CARBON FAMILY
Metal/ Non-metal
Element Symbol Atomic
No.

Carbon C 6 Non-metal

Silicon Si 14 Non-metal

Germanium Ge 32 Metalloid

Tin Sn 50 Metal

Lead Pb 82 Metal

Flerovium Fl 114 Metal

 Occurrence of Group 14 Elements
1) Carbon is the seventeenth most abundant element by mass in the earth’s crust. It is widely
distributed in nature in free as well as in the combined state.
2) In elemental state it is available as coal, graphite and diamond; however, in combined state
it is present as metal carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air.
3) Carbon is the most versatile element in the world. It is an essential constituent of all living
organisms.
4) Naturally occurring carbon contains two stable isotopes : C -12and C-13
5) Third isotope, C -14 is also present. It is a radioactive isotope with half life 5770 years and
used for radiocarbon dating.
 Continue…
Occurrence of Group 14 Elements
6) Silicon is the second (27.7 % by mass) most abundant element on the earth’s crust and is
present in nature in the form of silica and silicates. Silicon is a very important component
of ceramics, glass and cement.
7) Germanium exists only in traces.
8) Tin occurs mainly as cassiterite, SnO2 and lead as galena, PbS.
9) Flerovium is synthetically prepared radioactive element
10)Ultrapure form of germanium and silicon are used to make transistors and semiconductor
devices
 The atomic properties of Group 14 Elements
Electronic Configuration-
• The valence shell electronic configuration of these elements is ns2np2.
 Continue…
The atomic properties of Group 14 Elements
Covalent Radius:-
• There is a considerable increase in covalent radius from C to Si, thereafter from Si to
Pb a small increase in radius is observed.
• This is due to the presence of completely filled d and f orbitals in heavier members
 Continue…
The atomic properties of Group 14 Elements
Ionization Enthalpy:-
• The first ionization enthalpy of group 14 members is higher than the corresponding members of
group 13.
• In general the ionization enthalpy decreases down the group.
• Small decrease in ΔiH from Si to Ge to Sn and slight increase in ΔiH from Sn to Pb is the
consequence of poor shielding effect of intervening d and f orbitals and increase in size of the
atom.
 Continue…
The atomic properties of Group 14 Elements

Electronegativity:-
• Due to small size, the elements of this group are slightly more electronegative than
group 13 elements.
• The electronegativity values for elements from Si to Pb are almost the same.
 Physical Properties of Group 14 Elements

1) All group 14 members are solids.

2) Carbon and silicon are non-metals, germanium is a metalloid, whereas tin and lead are
soft metals with low melting points.
3) Melting points and boiling points of group 14 elements are much higher than those of
corresponding elements of group 13.
 Class XI Chemistry
Unit-11
THE p -BLOCK ELEMENTS
Topic:-
Chemical Properties of Group 14 Elements

Prepared by :-Vijay Kumar Sethi

 Oxidation states and trends in chemical reactivity of Group 14 Elements
1) The common oxidation states exhibited by these elements are +4 and +2.
2) Carbon also exhibits negative oxidation states.
3) Since the sum of the first four ionization enthalpies is very high, compounds in +4 oxidation
state are generally covalent in nature.
4) In heavier members the tendency to show +2 oxidation state increases in the sequence
Ge<Sn<Pb. It is due to the inability of ns2 electrons of valence shell to participate in
bonding( Inert pair effect)
5) Carbon and silicon mostly show +4 oxidation state.
6) Ge forms stable compounds in +4 state and only few compounds in +2 state.
7) Tin forms compounds in both oxidation states (Sn in +2 state is a reducing agent).
 Continue…
Oxidation states and trends in chemical reactivity of Group 14 Elements
8) Lead compounds in +2 state are stable and in +4 state are strong oxidising agents.
9) In tetravalent state the number of electrons around the central atom in a molecule (e.g.,
carbon in ) is eight. Being electron precise molecules, they are normally not expected to act
as electron acceptor or electron donor species.
10) Although carbon cannot exceed its covalence more than 4, other elements of the group can
do so. It is because of the presence of d orbital in them.
11) Due to this, their halides undergo hydrolysis and have tendency to form complexes by
accepting electron pairs from donor species. For example, the species like, SiF 62–, [GeCl6]2–,

[Sn(OH)6]2– exist where the hybridisation of the central atom is .

 Reactivity towards oxygen
1) All members when heated in oxygen form oxides.
2) There are mainly two types of oxides, i.e., monoxide and dioxide of formula
respectively.
3) SiO only exists at high temperature.
4) Oxides in higher oxidation states of elements are generally more acidic than those in
lower oxidation states.
5) The dioxides— are acidic, whereas are amphoteric in nature.
6) Among monoxides, CO is neutral, GeO is distinctly acidic whereas SnO and PbO are
amphoteric.
Problem 11.5
Select the member(s) of group 14 that (i) forms the most acidic dioxide, (ii) is commonly
found in +2 oxidation state, (iii) used as semiconductor.
Solution
(i) carbon (ii) lead (iii) silicon and germanium
Reactivity towards water
1) Carbon, silicon and germanium are not affected by water.
2) Tin decomposes steam to form dioxide and dihydrogen gas.

3) Lead is unaffected by water, probably because of a protective oxide film formation.

 Reactivity towards halogen
1) These elements can form halides of formula (where X = F, Cl, Br, I).
2) Except carbon, all other members react directly with halogen under suitable condition to make
halides.
3) Most of the are covalent in nature. The central metal atom in these halides undergoes sp3
hybridisation and the molecule is tetrahedral in shape. Exceptions are , which are ionic in
nature.
4) does not exist because 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.
5) Heavier members Ge to Pb are able to make halides of formula
 Continue…
Reactivity towards halogen
6) Stability of dihalides increases down the group.
7) is more stable than , whereas is more than .
8) Except , 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

Hydrolysis can be understood by taking the example of . It undergoes hydrolysis by initially

accepting lone pair of electrons from water molecule in d orbitals of Si, finally leading to the
formation of as shown below :
Problem 11. 6
is known whereas not. Give possible reasons.
Solution
The main reasons are :
(i) six large chloride ions cannot be accommodated around due to limitation of its size.
(ii) interaction between lone pair of chloride ion and is not very strong .
 IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF
CARBON
1) Carbon differs from rest of the members of its group. It is due to its smaller size, higher
electronegativity, higher ionisation enthalpy and unavailability of d orbitals.
2) Carbon has maximum covalence to four whereas other members can expand their covalence due
to the presence of d orbitals in other members.
3) Carbon also has unique ability to form pπ– pπ multiple bonds with itself and with other atoms of
small size and high electronegativity . Few examples of multiple bonding are: C=C, C ≡ C, C =
O, C = S, and C ≡ N.
4) Heavier elements do not form pπ– pπ bonds because their atomic orbitals are too large and
diffuse to have effective overlapping.
 Continue…
IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF
CARBON
5) Carbon atoms have the tendency to link with one another through covalent bonds to form
chains and rings. This property is called catenation. This is because C—C bonds are very
strong.
6) Down the group the size increases and electronegativity decreases, and, thereby, tendency to
show catenation decreases.
7) The order of catenation is C > > Si > Ge ≈ Sn. Lead does not show catenation.
8) Due to property of catenation and pπ– pπ bond formation, carbon is able to show allotropic
forms.
 Class XI Chemistry
Unit-11
THE p -BLOCK ELEMENTS
Topic:-
• ALLOTROPES OF CARBON

Prepared by :-Vijay Kumar Sethi

 ALLOTROPY and AIIOTROPES
• Allotropy, the existence of a chemical element in two or more forms, which may differ in
the arrangement of atoms in crystalline solids or in the occurrence of molecules that contain
different numbers of atoms.
• Allotropes are different structural forms of the same element and can exhibit quite different
physical properties and chemical behaviours.
• Carbon exhibits many allotropic forms; both crystalline as well as amorphous.
 ALLOTROPES OF CARBON
1) Diamond and graphite are two well-known crystalline forms of carbon.
2) In 1985, third form of carbon known as fullerenes was discovered by [Link], [Link]
and [Link]. For this discovery they were awarded the Nobel Prize in 1996
3) Other forms of elemental carbon like carbon black, coke, and charcoal are all impure forms of
graphite or fullerenes.
4) Carbon black is obtained by burning hydrocarbons in a limited supply of air.
5) Charcoal and coke are obtained by heating wood or coal respectively at high temperatures in
the absence of air.
 Diamond

1) It has a crystalline lattice.

2) In diamond each carbon atom undergoes sp3 hybridisation
and linked to four other carbon atoms by using hybridised
orbitals in tetrahedral fashion.
3) The C–C bond length is 154 pm.
4) The structure extends in space and produces a rigid three
dimensional network of carbon atoms.
5) In this structure directional covalent bonds are present
throughout the lattice.
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Diamond
6) It is very difficult to break extended covalent bonding and, therefore, diamond is a hardest
substance on the earth.
7) It is used as an abrasive for sharpening hard tools, in making dies and in the manufacture of
tungsten filaments for electric light bulbs.

• An abrasive material is a hard, tough substance containing many sharp projection

cutting edges or points.
• It is used as a cutting tool to penetrate and cut away  material that is softer than itself. 

Die :-a device used for shaping metal

 Graphite
1) Graphite has layered structure .
2) Layers are held by van der Waals forces and distance
between two layers is 340 pm.
3) Each layer is composed of planar hexagonal rings of
carbon atoms.
4) C—C bond length within the layer is 141.5 pm.
5) Each carbon atom in hexagonal ring undergoes sp2
hybridisation and makes three sigma bonds with three
neighbouring carbon atoms. Fourth electron forms a π
bond.
 Continue…
Graphite
6) The electrons are delocalised over the whole sheet. Electrons are mobile and, therefore,
graphite conducts electricity along the sheet.
7) 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.
Problem 11.7
Diamond is covalent, yet it has high melting point. Why ?
Solution
Diamond has a three-dimensional network involving strong C—C bonds, which are very difficult
to break and, in turn has high melting point.
 Fullerenes
• Fullerenes are made by the heating of graphite in an electric arc in the presence of inert gases
such as helium or argon. The sooty material formed by condensation of vapourised small
molecules consists of mainly with smaller quantity of .
• Fullerenes are the only pure form of carbon because they have smooth structure without having
‘dangling’ bonds.
• In chemistry, a dangling bond is an unsatisfied valence on an immobilized atom.
• Fullerenes are cage like molecules. molecule has a shape like soccer ball and called
Buckminsterfullerene
• molecule got its name  Buckminsterfullerene after the American architect Buck minster Fuller
because its structure resembles the frame work of dome shaped halls designed by Fuller for
large industrial exhibition
 Continue…
Fullerenes
• It contains twenty six- membered rings and twelve
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.
• Spherical fullerenes are also called bucky balls in
short
 Continue…
Fullerenes
• All the carbon atoms are equal and they undergo hybridisation. Each carbon atom forms
three sigma bonds with other three carbon atoms. The remaining electron at each carbon is
delocalised 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 also contains both single and double bonds with C–C distances of 143.5 pm and 138.3 pm
respectively.