Chapter - 11

p-Block
Elements

General outer Electronic configuration : ns2np1–6.

Inert Pair Effect:
 Reluctance of ns2 electrons of valence shell to participate in bond formation
is termed as inert pair effect.
 It arises due to poor or insufficient shielding of ns2 electrons by intervening
d- or f-electrons & hence increases down the group.
Causes of Anomalous Behaviour of First Element in groups of p-Block:
(i) Very small size
(ii) Unavailability of vacant d-orbital
(iii) Tendency to form pp – pp multiple bonds.
Group No-13 Elements: (B, Al, Ga, In, Tl, Nh)
 General Electronic Configuration: ns2 np1
 Atomic radius: B < Ga < Al < In <TI
rGa < rAl due to ineffective shielding of valence electrons by intervening 3d-
electrons in Ga.
 Ionization Enthalpies: : B > Tl > Ga > Al > In
 Electronegativity: B > Tl > In > Ga > Al
 Oxidation States: B (+3), Al (+3), Ga (+3, +1), In (+3, +1), Tl (+1, +3)
Tl (+1) is more stable than Tl (+3) due to inert pair effect.

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 Nature of Compounds: Compounds of group 13 elements are electron
deficient i.e. Lewis Acid and hence used as industrial catalyst e.g. BF3, AlCl3.
 Oxides: B2O3 Al2O3, Ga2O3 ln2O3 Tl2O
Acidic Amphoteric Basic Strongly Basic

 Halides: MX3 type, Electron deficient (Lewis acid), AICI3 exist as dimer
 Borax: Na2B4O7.10H2O. On heating it form transparent glassy bead
consisting of NaBO2 + B2O3.
 Boric acid: H3BO3, It acts as a Lewis acid by accepting electron pair from
OH– ions of water.
 Diborane: B2H6, Colourless & toxic gas, acts as Lewis acid due to having
electron deficient 3c-2e– bonds. Obtained by treating BF3 with LiAIH4 or
NaH, Also obtained by treating NaBH4 with l2.
 Borazine: B3N3H6, It is isostructural with benzene and hence known as inor-
ganic benzene. Prepared by heating B2H6 withNH3
Group -14 Elements: (C, Si, Ge, Sn, Pb,Fl)
 General Electronic Configuration: ns2 np2
 Atomic radius: C < Si < Ge < Sn < Pb
 lonisation Enthalpy: LiHx : C > Si > Ge > Sn < Pb
 Oxidation States: C (+4), Si (+4), Ge (+4, +2), Sn (+4, +2), Pb (+4, +2)
Pb (+2) is more stable than Pb (+4) due to inert pair effect.
 Oxides: Form di oxides (MO2) & mono oxides (MO).
PbO2 is powerfull oxidizing agent because Pb stabilizes in +2 oxidation state
due to inert pair effect. CO2 is gas while SiO2 is network solid because C has
ability to form pp — pp multiple bonds.
 Halides: Form tetra halides (MX4) & dihalides (MX2).
Tetra halides are more covalent due to greater polarizing power of cation.
CCI4 is not hydrolysed with water as C has no vacant d-orbital to accept
electron pair from water.

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 Catenation: C >> Si > Ge ≈ Sn >> Pb
 Allotrops of carbon: Diamond (sp3), Graphite (sp2), Fullerenes (sp2)
 Silicones: Silicones are synthetic organosilicon compounds containing
R2SiO repeating units. Silicones are water repellent, heat resistant, chemi-
cally inert, electrical insulators, resistant to oxidation.
 Silicates: Silicates are compounds in which anions are derived from
Si–o–si– tetrahedral units.
 Zeolites: Zeolites are 3D silicates in which some of the Si atoms are replaced
by Al3+ ions and negative charge is balanced by cations such as Na+, K+,
Ca2+ etc.
 ZSM-5 is used in petrochemical industries to convert methanol into petrol.
Group - 15 Elements: (N, P, As, Sb, Bi, Mc)
 General Electronic Configuration: ns2 np3
 Atomic radius: N < P < As < Sb < Bi
 lonisation Enthalpy: DiH1: N > P > As > Sb > Bi
 Oxidation States: N (+5, +3), P (+5,+3), As (+5, +3), Sb (+5,+3), Bi (+5,
+3) Bi (+3) is more stable than Bi (+5) due to inert pair effect.
 Oxides: Form trioxides (M2O3) & pentaoxides (M2O5).
 Halides: Form trihalides (MX3) & pentahalides (MX5).
Nitrogen does not form penta halides because it cannot extend its covalency
beyond four due to absence of vacant d-orbitals.
Pentahalides are more covalent than trihalides due to greater polarizing
power of cation.
 Hydrides: MH3 type, Lewis base, pyramidal structure
NH3 > PH3 > AsH3 > SbH3 > BiH3
(Basic character, Bond angle & Thermal Stability)
NH3 < PH3 < AsH3 < SbH3 < BiH3
(Reducing Character) PH3< AsH3< NH3< SbH3< BiH3 (Boiling point)

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 Oxides of Nitrogen: Nitrogen having ability to form pp – pp multiple bonds
can form oxides in all oxidation states from +1 to +5 i.e. N2O, NO,N2O3,
NO2,N2O4 & N2O5
 Dinitrogen (N2): Much less reactive due to high bond enthalpy of N≡N.
Prepared by heating (NH4)2Cr2O7 or a solution of NH4Cl + NaNO2.
 Ammonia (NH3): Pungent & irritating smell gas. It is prepared on commer-
cial scale by Haber's process. NH3 acts as Lewis base /Ligand / complexing
agent due to the presence of electron pair on N atom.
 Nitric acid (HNO3): It is very powerfull oxidizing agent because it readi-
ly gives nascent oxygen both in concentrated or dilute form. Concentrated
HNO3 oxidizes non-metals to their oxoacids and metals to their nitrates.
 Allotropes of Phosphorous: White (Most reactive due to angular strain),
Red & Black phosphorous.
 Phosphine (PH3): Poisonous gas with rotten fish smell, it is prepared by
heating white phosphorous with concentrated. NaOH in inert atmosphere of
CO2. Phosphine can also be prepared by dropping H2O or HCI on Ca3P2.
 Phosphorous trichloride (PCl3): Colourless liquid, fumes in moisture due
to the formation of HCI.
 Phosphorous pentachloride (PCl5): In gaseous state it is covalent (trigonal
bipyramid) but in solid state it is ionic i.e. [PCl4]+[PCl6]–.
 Oxoacids of Phosphorous:
(i) Hypophosphorous acid (H3PO2): Monobasic, reducing
(ii) Phosphorous acid (H3PO3): Dibasic/reducing
(iii) Phosphoric acid (H3PO4): Tribasic, Non-reducing
(iv) Hypophosphoric acid (H4P2O6): Tetrabasic, non-reducing a
(v) Pyrophosphoric acid (H4P2O7): Tetrabasic, non-reducing

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