p-block elements

Position of p-block in periodic

table
 What are p-block elements?

p-block elements are the elements in which the

last electron enters ‘np’ orbital which include six
groups of elements i.e. group 13 to 18 boron
family, carbon family, pnicogens (Nitrogen
family), chalcogens (Oxygen family), halogens
and noble gases.
Note:
pnicogens: From ancient Greek πνίγειν, it means to choke
Chalcogens: from Greek word chalcos , meaning "ore formers," since they all are be found in copper ores
Halogens: From Greek, meaning “salt producer”, because a salt is formed in reactions involving these four
elements
 General electronic configuration &
oxidation state
Group 13 14 15 16 17 18
General ns2np6
electronic ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 (1s2 for
configuration He)
First member
B C N O F Ne
of the group
Group
Oxidation +3 +4 +5 +6 +7 +8
States
Other oxidation +4, +2, +5, + 3, +6, +4,
+1 +2, -4 +3, -3
states –2 +1, –1 +2
General electronic configuration &
oxidation state
• The maximum oxidation state shown by a p-block
element is equal to the total number of valence
electrons (i.e., the sum of the s- and p-electrons).
• Clearly, the number of possible oxidation states
increases towards the right of the periodic table.
• In addition to this so called group oxidation state, p-
block elements may show other oxidation states which
normally, but not necessarily, differ from the total
number of valence electrons by unit of two.
• In boron, carbon and nitrogen families the group
oxidation state is the most stable state for the lighter
elements in the group.
General electronic configuration &
oxidation state
• However, the oxidation state two unit less than the
group oxidation state becomes progressively more
stable for the heavier elements in each group.
• The occurrence of oxidation states two unit less than
the group oxidation states are sometime attributed to
the inert pair effect.
 General Characteristics
• As metals, non-metals and
metalloids exist only in p-
block of periodic table.
• The heaviest element in each
p-block group is mostly
metallic in nature.
• Non-metallic character
decreases down the group.
 General Characteristics
• Non metals have higher ionization enthalpy and
electronegativity than the metals. Hence metals form
cations, and non metals form anions.
• Compounds formed
between non-metals are
largely covalent in
nature because of small
differences in their
electronegativities.,
while the compounds
formed by highly
reactive non-metal and
metal are generally ionic
 General Characteristics
• The change of non-metallic to metallic
character can be best illustrated by the nature
of oxides they form
• The non-metal
oxides are acidic
or neutral
whereas metal
oxides are basic
in nature.
 General Characteristics
The first element of p-block elements differ…
•Size and all the properties of size: The lightest p-block
elements show the same kind of differences as the lightest s-
block element i.e. lithium and beryllium.
•Elements starting from boron are restricted to maximum
covalency of four (using 2s and three 2p orbitals).
•In contrast, the third period elements of p-groups with the
electronic configuration 3s23pn have the vacant 3d orbitals
lying between the 3p and the 4s levels of energy. Using
these d-orbitals the third period elements can expand their
covalence above four.
 General Characteristics
• For example, while boron forms only [BF4]–, aluminium gives
[AlF6]3– ion.

• The presence of these d-

orbitals influences the
chemistry of the heavier
elements in a number of other
ways. The combined effect of
size and availability of d
orbitals considerably
influences the ability of these
elements to form π bonds.
 General Characteristics
• 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).
•This type of π – bonding
is not particularly strong
for the heavier p-block
elements.
 General Characteristics
• The heavier elements do form π bonds but this
involves d orbitals (dπ – pπ or dπ –dπ ).

• As the d orbitals are of

higher energy than the p
orbitals, they contribute
less to the overall
stability of molecules
than does pπ – pπ
bonding of the second
row elements.
 General Characteristics
• However, the coordination number in species of heavier elements
may be higher than for the first element in the same oxidation state.

• For example, in +5 oxidation

state both N and P form
oxoanions : NO3– (three-
coordination with π – bond
involving one nitrogen p-orbital)
and PO43− (four-coordination
involving s, p and d orbitals
contributing to the π – bond)
Carbon family
 PRESENTATION OVERVIEW

 Group 14 – Elements of Carbon Family

 Atomic and physical properties
 Chemical Properties
 Anomalous behavior of carbon
 GROUP 14 ELEMENTS: THE CARBON FAMILY

Element Symbol Electron Configuration

Carbon C [He]2s22p2
Silicon Si [Ne]3s23p2
Germanium Ge [Ar]3d104s2 4p2
Tin Sn [Kr]4d105s2 5p2
Lead Pb [Xe]4f14 5d106s2
6p2
 Atomic and physical properties: Carbon Family
Property Elements
Carbon Silicon Germanium Tin Lead
Atomic number 6 14 32 50 82
Atomic mass(g/mol) 12.01 28.09 72.60 118.71 207.2
Electronic configuration [He]2s22p2 [Ne]3s23p2 [Ar]3d104s24p2 [Kr]4d105s25p2 [Xe]4f145d106s
2
6p2
Covalent radius/pm 77 118 122 140 146
Ionic radiusM4+/pm _ 40 53 69 78
Ionic radius M2+/pm _ _ 73 118 119
Ionization enthalpy/KJmol-1 1086 786 761 708 715
(∆iH)
Electronegativity 2.5 1.8 1.8 1.8 1.9
Density/g cm-3 3.51 2.34 5.32 7.26 11.34
Melting point/K 4373 1693 1218 505 600
Boiling point/K _ 3550 3123 2896 2024
Electrical resistivity/ohm cm 1014-1016 50 50 10-5 2 X 10-5

Physical state Non-metal Non-metal metalloid Soft metals Soft metals

 Some Physical properties
Allotrophy:
•Except Pb, all other elements in the group show allotrophy
•For e.g., Carbon exists in two allotrophic forms
– Crystralline – diamond & graphite
– Amorphous – coal, coke, charcoal etc.
•Silicon exists in two forms
– Crystalline & amorphous
•Germanium exists in two crystalline forms
•Tin exists in three allotrophic forms
– White tin, grey tin & Rhombic tin
 Chemical properties
Oxidation state:-
•The common oxidation states are +2 & +4
•C also exhibits -ve oxidation states.
•Since the sum of the first four ionization enthalpies is very high,
compounds in +4 oxidation state are generally covalent in nature.
•In heavier members the tendency to show +2 oxidation state
increases in the sequence Ge2+<Sn2+<Pb2+.
•It is due to the inability of ns2 electrons of valence shell to
participate in bonding (inert pair effect).
 Chemical properties (Cont…)
Oxidation state:-
•Carbon and silicon mostly show +4 oxidation state.
•Germanium forms stable compounds in +4 state and only few
compounds in +2 state and hence the compound of Ge2+ is
readily changed into Ge4+
•i.e., compounds of Ge2+ acts as strong reducing agent.
•Tin forms compounds in both oxidation states (Sn in +2 state is
a reducing agent).
•Lead compounds in +2 state are stable and in +4 state are
strong oxidising agents.
 Chemical properties (Cont…)
Negative oxidation state:-
•Since the electronegativities of these elements are low,
they do not have much tendency to form negative
ions.
•However, Carbon forms C4- & C2- ions in certain
compounds. For e.g., Be2C, Al4C3, Na2C, CaC etc.
 Chemical properties (Cont…)
Nature of M2+ & M4+ compounds:-
•It can be predicted by Fajan’s rule – “the smaller the cation, the
greater is the amount of covalent character in the compound”.
compound
•Since Sn4+ < Sn2+, the compound of Sn4+ are covalent in nature
while those of Sn2+ are ionic.
•Similarly, Pb4+ compounds are covalent and those of Sn2+ are
ionic.
•As we move down the group, the tendency of cations to form
ionic compounds increases.
 Chemical properties (Cont…)
Reactivity towards oxygen:-
•All members when heated with oxygen forms oxide.
•Group 14 elements form three types of oxides:-
MO(monoxide) MO2(Dioxide) M2O3(MO+MO2)(Mixed oxide)
•Expect silicon all other members form monoxides of the formula MO. (SiO only
exist in high temperature)
•Oxides in higher oxidation states of elements are generally more acidic than those
in lower oxidation states
•The dioxides — CO2, SiO2 and GeO2 are acidic, whereas SnO2 and PbO2 are
amphoteric in nature.
•Among monoxides, CO is neutral, GeO is distinctly acidic whereas SnO and PbO
are amphoteric.
Chemical properties (Cont…)
 Chemical properties (Cont…)
Reactivity towards halogen:-
•These elements can form halides of formula MX2 and MX4 (where X=F, Cl, Br, I).
•Except carbon, all other members react directly with halogen under suitable
condition to make halides.
•Most of the MX4 are covalent in nature.
•The central metal atom in these halides undergoes sp3 hybridisation and the
molecule is tetrahedral in shape.
•Exceptions are SnF4 and PbF4, which are ionic in nature.
•PbI4 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.
 Chemical properties (Cont…)
Reactivity towards halogen:-
•Thermal stability of tetrahalides decreases from CX4 to PBX4.
– CX4 > SiX4 > GeX4 > SnX4 > PbX4
•Thermal stability and volatility of the tetrahalide of the same
element decreases from F- to I-
– MF4 > MCl4 > MBr4 > MI4
•The fluorides of carbon are, therefore, the most stable and
inert.
 Chemical properties (Cont…)
Reactivity towards halogen:-
•Hydrolysis can be understood by taking the example of SiCl 4. It
undergoes hydrolysis by initially accepting lone pair of electrons from
water molecule in d orbitals of Si, finally leading to the formation of
Si(OH)4 as shown below :
 Chemical properties (Cont…)
Reactivity towards halogen:-
•Carbon has no d-orbitals in its valence shell and hence
is unable to accommodate the lone pair donated by the
donor oxygen atom of water molecule to form an
unstable intermediate compound. Thus, tetrahalides of
carbon are not hydrolysed.
•Heavier members Ge to Pb are able to make halides of
formula MX2.
•Stability of dihalides increases down the group.
 Chemical properties (Cont…)
Formation of acids:-
•All the elements give acids of H2MO3 type. E.g., carbonic acid
(H2CO3), silicic acid (H2SiO3), germanic acid (H2GeO3), metastannic
acid (H2SnO3), metaplumbic acid (H2PbO3).
•Sodium salts of these acids are stable.
•Carbon and silicon form acid of the (MOOH) 2 type as shown below:

•No such acids are formed by Ge, Sn & Pb.

Chemical properties (Cont…)
 Anomalous behavior of Carbon
• Carbon, due to its smaller size and higher electronegativity,
higher electronegativity, higher ionization energy and
unavailability of d-orbitals, differ from other members of its
group.
• In carbon, only s and p orbitals are available for bonding
and, therefore, it can accommodate only four pairs of
electrons around it.
• This would limit the maximum covalence to four whereas
other members can expand their covalence due to the
presence of d orbitals.
 Anomalous behavior of Carbon (Cont…)
Formation of multiple bonds - π bonding
•Carbon also has unique ability to form pπ– pπ multiple bonds with itself and with
other atoms of small size and high electronegativity.
•>C=C< ─C≡C─ >C=O >C=N ─C≡N >C=S
•Heavier elements do not form pπ– pπ bonds because their atomic orbitals are too
large and diffuse to have effective overlapping.
•However a few compounds containing multiple bonds have been isolated.
•Effect of pi bonding on the structure may be seen in graphite.
 Anomalous behavior of Carbon (Cont…)
Catenation:-
•The property of self linkage leading to the formation of long
chains and rings is termed catenation.
•Carbon has a greater tendency of self linking than other
elements.
•Down the group the size increases and electronegativity
decreases, and, thereby, tendency to show catenation decreases.
•Catenation tendency follows the order, C >> Si > Ge ≈ Sn
•Lead do not show catenation.
 Anomalous behavior of Carbon (Cont…)

Catenation:-
•Since, the M─M bond enthalpy decreases steadily from C to Sn.
Therefore, the catenation tendency also decreases down the group.

Bond C─C Si─Si Ge─Ge Sn─Sn

Bond energy
348 222 167 155
(KJmol-1)
•Due to property of catenation and pπ– pπ bond formation,
carbon is able to show allotropic forms.
 Allotropes of Carbon
• Carbon exhibits many allotropic forms; both crystalline as well as
amorphous.
• Diamond and graphite are two well-known crystalline forms of carbon.

• 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.
 Allotropes of Carbon (Cont…)

Diamond
•It has a crystalline lattice.
•In diamond each carbon atom undergoes sp3
hybridisation and linked to four other carbon
atoms by using hybridised orbitals in
tetrahedral fashion.
•The C–C bond length is 154 pm.
•The structure extends in space and produces a
rigid three dimensional network of carbon
atoms
 Allotropes of Carbon (Cont…)

Diamond
•It is very difficult to break extended covalent bonding and,
therefore, diamond is a 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.
 Allotropes of Carbon (Cont…)

Graphite
•It has layered structure.
•Layers are held by van der Waals forces and
distance between two layers is 340 pm.
•Each layer is composed of planar hexagonal
rings of carbon atoms.
•C–C bond length within layer is 141.5 pm.
 Allotropes of Carbon (Cont…)
Graphite
•Each Carbon atom in hexagonal rings undergoes sp 2 hybridization and
makes three sigma bonds with three neighbouring carbon atoms.
•Fourth electron forms a π bond.
•The electrons are delocalized over the whole sheet.
•Electrons are mobile and, therefore, graphite conducts electricity along the
sheet.
•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 lubricants
 Allotropes of Carbon (Cont…)

Fullerenes
•They 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 C n small
molecules consists of mainly C60 with smaller quantity of C70 and
traces of fullerenes consisting of even number of carbon atoms up to
350 or above.
•Fullerenes are the only pure form of carbon because they have
smooth structure without having ‘dangling’ bonds.
 Allotropes of Carbon (Cont…)
Fullerenes
•Fullerenes are cage like molecules.
•C60 molecule has a shape like soccer ball and called Buckminsterfullerene

• 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.
 Allotropes of Carbon (Cont…)
Fullerenes
•All the carbon atoms are equal and they undergo sp 2 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.
 Other compounds of Carbon

• Other forms of elemental carbon like carbon black, coke,

and charcoal are all impure forms of graphite or
fullerenes.
• Carbon black is obtained by burning hydrocarbons in a
limited supply of air.
• Charcoal and coke are obtained by heating wood or coal
respectively at high temperatures in the absence of air.
Other compounds of Carbon
Other compounds of Carbon
 Other compounds of Carbon

• 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.
• Carbon monoxide is a colourless, odourless and almost water
insoluble gas.
• It is a powerful reducing agent and reduces almost all metal
oxides other than those of the alkali and alkaline earth metals,
aluminium and a few transition metals.
Other compounds of Carbon
 Other compounds of Carbon

• The highly poisonous nature of CO arises because of its

ability to form a complex with haemoglobin, which is
about 300 times more stable than the oxygen-
haemoglobin complex.
• This prevents haemoglobin in the red blood corpuscles
from carrying oxygen round the body and ultimately
resulting in death.
Other compounds of Carbon
Other compounds of Carbon
Other compounds of Carbon
Other compounds of Carbon
 Other compounds of Carbon
Carbon dioxide
•This may lead to increase in green house effect and thus, raise
the temperature of the atmosphere which might have serious
consequences.
•Carbon dioxide can be obtained as a solid in the form of dry
ice by allowing the liquefied CO2 to expand rapidly.
•Dry ice is used as a refrigerant for ice-cream and frozen food.
•Gaseous CO2 is extensively used to carbonate soft drinks.
 Other compounds of Carbon
Carbon dioxide
•Being heavy and non-supporter of combustion it is used as fire
extinguisher.
•A substantial amount of CO2 is used to manufacture urea.
•In CO2 molecule carbon atom undergoes sp hybridisation. Two
sp hybridised orbitals of carbon atom overlap with two p
orbitals of oxygen atoms to make two sigma bonds while other
two electrons of carbon atom are involved in pπ– pπ bonding
with oxygen atom.
 Other compounds of Carbon
Carbon dioxide
•This results in its linear shape [with both C–O bonds of equal
length (115 pm)] with no dipole moment. The resonance
structures are shown below:

Resonance structures of carbon dioxide