P-block elements

General introduction:-
 In p-block elements the last electron enters the outermost p orbital.
 We know that 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.
 Hence 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 [Noble gas] ns2 np1-6(except
for He).
 P-block has metals, non-metals and metalloids.
 P-block elements show variable oxidation state. The maximum oxidation
state shown by a p-block element is either equal to number of valence
electrons or 8 minus number of valence electrons.
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’.
Group 13 elements – The Boron family
Physical properties:-

 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.

 Note that gallium has unusually low melting point (303K), can exist in liquid
state during summer. Its high boiling point (2676K) makes it a useful
material for measuring high temperatures.

 Density of the elements increases down the group from boron to thallium.
 Electronic configuration
 The outer electronic configuration of these elements is [Noble gas] ns 2 np 1
 Boron and aluminium have noble gas core, while gallium and indium have
noble gas plus 10 d-electrons, and thallium has noble gas plus 14 f- electrons
plus 10 d-electron cores.
 Thus, the electronic structures of these elements are more complex than for
the first two groups of elements discussed in unit 10.
 Atomic radii

 On moving down the group, for each successive member one extra shell of
electrons is added and, therefore, atomic radius is expected to increase.

 However, a deviation can be seen -> Atomic radius of Ga is less than that of
Al.

 The presence of additional 10 d-electrons offer only poor screening effect

for the outer electrons from the increased nuclear charge in gallium.

 Consequently, the atomic radius of gallium (135 pm) is less than that of
aluminium (143 pm).
 Ionisation enthalpy

 The ionisation enthalpy values as expected from the general trends do not
decrease smoothly down the group.

 The decrease from B to Al is associated with increase in size.

 The observed discontinuity in the ionisation enthalpy values between Al and

Ga, and between In and Tl are due to inability of d- and f-electrons ,which
have low screening effect, to compensate the increase in nuclear charge.
 Electronegativity

 Down the group,

electronegativity
first decreases from
B to Al and then
increases.
 This is because of
the discrepancies in
atomic size of the
elements.
 Chemical properties:-

 All compounds of 13th group elements in their +3 oxidation state are covalent
compounds and are electron deficient due to incomplete octet. These
compounds act as lewis acids.

Eg:
1. Reactivity towards air:
2. Reactivity towards acids:
3. Reactivity towards alkalies:
4. Reactivity towards halogens:
 Anomalous properties of boron
 Due to small size and absence of d-orbitals, the maximum covalency of
boron is 4 while the rest of the members show a covalency of 6.

 Due to small size and high ionisation enthalpy, boron is non-metallic while
the rest are metallic.

 BX3 on hydrolysis forms tetrahedral [B(OH)4]- while the rest form octahedral
[M(H2O)6]3+ .

 BX3 are monomeric while the rest are dimeric.

Eg: BCl3, Al2Cl6
 Halides of boron, BX3 are strong lewis acids as they are electron deficient
molecules due to incomplete octet. Boron trifluoride easily reacts with
lewis bases such as NH3 to complete octet.

 Boron does not decompose water or steam while other elements of the
family decompose steam.
Boron is sp3 hybridized
 Group 14 elements – The Carbon family
Occurrence-
• Carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) are the
members of group 14.
• 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.
• 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.
• Organic chemistry is devoted to carbon containing compounds.
• It is an essential constituent of all living organisms.
• Naturally occurring carbon contains two stable isotopes:12C and 13C.
• In addition to these, third isotope, 14C is also present. It is a radioactive
isotope with halflife 5770 years.
• 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.
• Germanium exists only in traces.
• Tin occurs mainly as cassiterite, SnO2 and lead as galena, PbS.
• Ultrapure form of germanium and silicon are used to make transistors
and semiconductor devices.
 Electronic configuration
The valence shell electronic configuration of these elements is [noble gas] ns 2 np2 .
The inner core of the electronic configuration of elements in this group also differs.
 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.
Ionization Enthalpy

• The first ionization enthalpy of group 14 members is higher than the

corresponding members of group 13.

• The influence of inner core electrons is visible here also. In general the
ionisation enthalpy decreases down the group.

• Small decrease in Δi H from Si to Ge to Sn and slight increase in Δi H from

Sn to Pb is the consequence of poor shielding effect of intervening d and
f orbitals and increase in size of the atom.
 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
• All group 14 members are solids. Carbon and silicon are non-metals,
germanium is a metalloid whereas tin and lead are soft metals with low
melting points.
• Melting points and boiling points of group 14 elements are much higher
than those of corresponding elements of group 13.
 Chemical Properties
• The group 14 elements have four electrons in outermost shell.
• The common oxidation states exhibited by these elements are +4 and +2.
• 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 Ge<Sn.
• 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. 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, SiF6 2–, [GeCl6] 2– , [Sn(OH)6] 2– exist where
the hybridisation of the central atom is sp 3d2 .
 1. Reactivity with oxygen
• All members when heated in oxygen form oxides.

• There are mainly two types of oxides, i.e., monoxide and dioxide of formula
MO and MO2 respectively.

• SiO only exists at 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
2. Reactivity towards water:

Carbon, silicon and germanium are not affected by water. Tin decomposes steam
to form dioxide and dihydrogen gas.

Lead is unaffected by water, probably because of a protective oxide film

formation.
3. 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 sp 3 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.
• Heavier members Ge to Pb are able to make halides of formula MX2.

• Stability of dihalides increases down the group.

• Considering the thermal and chemical stability, GeX4 is more stable than GeX2,
whereas PbX2 is more than PbX4. Except CCl4, 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 SiCl4. 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
Anomalous behavior of carbon