P-BLOCK

-BY THE APRON BOY

-In p-block elements the last electron enters the outermost p orbital.
-Their valence shell electronic configuration is ns2 np1-6 (except for He).
-The difference in inner core of elements greatly influences their physical properties.
-The maximum oxidation state shown by a p-block element is equal to the total number of valence
electrons.
-In boron, carbon and nitrogen families the group oxidation state is the most stable state for the
lighter elements in the group.
-The non-metals and metalloids exist only 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.
-The compounds formed by highly reactive non-metals with highly reactive metals are generally
ionic because of large differences in their electronegativities.
-The non-metal oxides are acidic or neutral whereas metal oxides are basic in nature.
-The first member of p-block differs from the remaining members of their corresponding group in
two major respects
-The second period elements of p-groups starting from boron are restricted to a maximum
covalence of four (using 2s and three 2p orbitals).

GROUP 13 ELEMENTS: THE BORON FAMILY

-Boron is a typical non-metal, aluminium is a metal but shows many chemical similarities to boron,
and gallium, indium, thallium and nihonium are almost exclusively metallic in character.
-Boron is a fairly rare element, mainly occurs as orthoboric acid, (H 3BO3 ), borax, Na2B4O7 ·10H2O,
and kernite, Na2B4O7 ·4H2O.
-[Rn] half life period 20 sec.

Electronic Configuration
-The outer electronic configuration of these elements is ns2np1.

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.
-Atomic radius of Ga is less than that of Al. This can be understood from the variation in the inner
core of the electronic configuration.

Ionization 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 marginally. This
is because of the discrepancies in atomic size of the elements

Physical Properties
-Boron is non-metallic in nature. It is extremely hard and black coloured solid.
-Due to very strong crystalline lattice, boron has unusually high melting point. Rest of the members
are soft metals with low melting point and high electrical conductivity.
-Density of the elements increases down the group from boron to thallium.

Chemical Properties
-down the group, due to poor shielding effect of intervening d and f orbitals, the increased
effective nuclear charge holds ns electrons tightly (responsible for inert pair effect) and thereby,
restricting their participation in bonding. As a result of this, only p-orbital electron may be involved
in bonding.
-In fact in Ga, In and Tl, both +1 and +3 oxidation states are observed
-The relative stability of +1 oxidation state progressively increases for heavier elements:
Al<Ga<In<Tl
-The compounds in +1 oxidation state, as expected from energy considerations, are more ionic than
those in +3 oxidation state.
-Such electron deficient molecules have tendency to accept a pair of electrons to achieve stable
electronic configuration and thus, behave as Lewis acids.
-The tendency to behave as Lewis acid decreases with the increase in the size down the group.
-BCl3 easily accepts a lone pair of electrons from ammonia to form BCl3 ⋅NH3 .
-In trivalent state most of the compounds being covalent are hydrolysed in water. For example, the
trichlorides on hyrolysis in water form tetrahedral [M(OH)4]-
(the hybridisation state of element M is sp3)

(i)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 B 2O3 and Al2O3 respectively. With
dinitrogen at high temperature they form nitrides.
-Boron trioxide is acidic and reacts with basic (metallic) oxides forming metal borates.
-Aluminium and gallium oxides are amphoteric and those of indium and thallium are basic in their
properties.

(ii) Reactivity towards acids and alkalies

-Boron does not react with acids and alkalies even at moderate temperature; but aluminium
dissolves in mineral acids and aqueous alkalies and thus shows amphoteric character.

(iii) Reactivity towards halogens

-These elements react with halogens to form trihalides (except TlI 3 ).

IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON- read from NCERT BOOK

Borax
-It is a white crystalline solid
-In fact it contains the tetranuclear units [B4O5(OH)4]-2 and correct formula; therefore, is Na2 [B4
O5 (OH)4 ].8H2O.
-Borax dissolves in water to give an alkaline solution.(READ REACTION FROM NCERT)
-On heating, borax first loses water molecules and swells up. On further heating it turns into a
transparent liquid, which solidifies into glass like material known as borax bead.

-The metaborates of many transition metals have characteristic colours and, therefore, borax bead
test can be used to identify them in the laboratory

Orthoboric acid
-white crystalline solid, with soapy touch.
-It can be prepared by acidifying an aqueous solution of borax.

-
-Layer structure in which planar BO3 units are joined by hydrogen bonds.
-Boric acid is a weak monobasic acid. It is not a protonic acid but acts as a Lewis acid by accepting
electrons from a hydroxyl ion.

-On heating, orthoboric acid above 370K forms metaboric acid, HBO2 which on further heating
yields boric oxide, B2O3.
-

Diborane
-It is prepared by treating boron trifluoride with LiAlH4 in diethyl ether.
-4BF3 + 3 LiAlH4 → 2B2H6 + 3LiF + 3AlF
-Boranes are readily hydrolysed by water to give boric acid.
(SEE ALL THE REACTIONS FROM NCERT)

GROUP 14 ELEMENTS: THE CARBON FAMILY

-Carbon is the seventeenth most abundant element by mass in the earth’s crust

Electronic Configuration
-The valence shell electronic configuration of these elements is ns2 np2

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.
-In general the ionisation enthalpy decreases down the group
-Small decrease in ∆iH from Si to Ge to Sn and slight increase in ∆iH 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
-The electronegativity values for elements from Si to Pb are almost the same.

Physical Properties
-All members of group14 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 common oxidation states exhibited by these elements are +4 and +2.
-Carbon also exhibits negative oxidation states
-In heavier members the tendency to show +2 oxidation state increases in the sequence Ge<Sn<Pb.
-Carbon and silicon mostly show +4 oxidation state. Germanium forms stable compounds in +4 state
and only few compounds in +2 state.
-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.

(i) Reactivity towards 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 MO 2
respectively.
-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.

(ii) 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.

(iii) Reactivity towards halogen

-These elements can form halides of formula MX2 and MX4 (where X = F, Cl, Br, I).
-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.
-Stability of dihalides increases down the group
-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 as shown below :

IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON

-In carbon, only s and p orbitals are available for bonding and, therefore, it can accommodate only
four pairs of electrons around it.
-Carbon also has unique ability to form pπ– pπ multiple bonds with itself and with other atoms of
small size and high electronegativity.
-Heavier elements do not form pπ– pπ bonds because their atomic orbitals are too large and diffuse
to have effective overlapping.
-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
-Down the group the size increases and electronegativity decreases, and, thereby, tendency to show
catenation decreases.
-This can be clearly seen from bond enthalpies values. The order of catenation is C > > Si > Ge ≈ Sn.
Lead does not show catenation
-Due to property of catenation and pπ– pπ bond formation, carbon is able to show allotropic forms.

ALLOTROPES OF CARBON-Read THEORY FROM NCERT

Oxides of Carbon
(1)Carbon Monoxide
-Direct oxidation of C in limited supply of oxygen or air yields carbon monoxide
-On small scale pure CO is prepared by dehydration of formic acid with concentrated H2SO4 at
373 K
-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.
-When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer
gas.
-Water gas and producer gas are very important industrial fuels.
-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
-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.

Carbon Dioxide
-It is prepared by complete combustion of carbon and carbon containing fuels in excess of air.
-In the laboratory it is conveniently prepared by the action of dilute HCl on calcium carbonate.
-It is a colourless and odourless gas. Its low solubility in water makes it of immense biochemical and
geo-chemical importance.
-Carbon dioxide, which is normally present to the extent of ~ 0.03 % by volume in the atmosphere,
is removed from it by the process known as photosynthesis.
(Read biological imp. From ncert)

COMPOUND OF Si – READ FRO NCERT NOT VERY IMP. AND TRY TO REMBER ALL THEORY
POINT AND DATA