p-block Elements (Group 13 and 14)

SHORT NOTES

Properties of Group 13 Elements Orthoboric Acid [H3BO3 or B(OH)3]

Property Remarks Monobasic Lewis acid
B(OH)3 + HOH → [B(OH)4] + H+
Atomic Radii B < Al > Ga < In < Tl
Properties
B(OH)3 Action of heat
Tetraboric
Ionisation Energy B > Al < Ga > In < Tl 100ºC 160ºC
H3BO3 H O HBO2 H2B4O7
2
metaboric
Electronegativity B > Al < Ga < In < Tl –H2O red hot

Oxidation state General oxidation states: +1, +3 B2O3

borontrioxide
Stability of +1 state increases down the Reaction with alcohol
group due to inert pair effect (Test of boric acid)
H3BO3 + 3C2H5OH B(OC2H5)3 + 3H2O
Metallic character Increases down the group Triethyl borate
green edged flame
Melting point Decreases up to Ga then increases Diborane, B2H6
Boiling point Decreases down the group Properties
(i) Diborane is a colourless, highly toxic gas with a boiling
Density Increases down the group point of 183 K.
(ii) Diborane catches fire spontaneously upon exposure to air.
Reactivity with air Reacts with air to form oxide (at (iii) Reaction with oxygen:
moderate temperature) and nitride (at B2H6 + 3O2 → B2O3 + 3H2O ; ∆cH = –1976 kJ mol–1
high temperature) (iv) Hydrolysis:
Crystalline boron unreactive, B2H6(g) + 6H2O(l) (Cold is enough) → 2B(OH)3(aq) + 6H2(g)
amorphous boron reacts. anh.
Aluminium forms oxide layer and does B2H6 + HCl (dry) AlCl B2H5Cl + H2
3

not react further. (v) Reaction with Lewis Bases

B2H3 + 2NMe3 → 2BH3.NMe3
Reactivity with acids Boron does not react. B2H6 + 2CO → 2BH3.CO
and alkalis Aluminium reacts with both acids and
alkalis to liberate hydrogen gas. (a) 3B2H6 + 6NH3 → 3[BH2(NH3)2]+[BH4]– Heat

Aluminium passive with conc. nitric unsymmetrical cleavage  2B3N3H6 + 12H2

acid. (vi) Reaction with ROH:
B2H6 + 6ROH → 2B(OR)3 + 6H2 (symmetrical cleavage)
Reactivity with Reacts with halogens to form trihalides Ht
H Hb
halogens (except triiodide of Thallium) t
B B
Nature of trioxides Boron-acidic, Al and Ga - amphoteric, Hb Ht
tH
In and Tl-Basic
Dimer due to formation of 3 centre-2e– bond inorganic benzene.

Alums [M2SO4.M2’(SO4)3.24H2O]
Alums are the double
Soda alum
salt of Type
Na2SO4.Al2(SO4)3.24H2O
[M2SO4. aq. solution acidic
M2'(SO4)3.24H2O] Potash alum Coagulant
example properties
K2SO4.Al2(SO4)3.24H2O Alum
Mordant for dyeing
M : Monovalent Cation: Ammonium alum
Na+, K+, Rb+, Cs+, NH4+ Tanning of leather
(NH4)2SO4.Al2(SO4)3.24H2O
M′ : Trivalent Cation:
Al3+, Fe3+ & Cr3+

1
Pseudo alums are double sulphates of a divalent and a trivalent Allotropes of Carbon
metals which crystallize with twenty four water molecules of
Diamond, Graphite and Fullerenes.
crystallization. For example:
(i) MnSO4. Al2(SO4)2.24H2O ™ In diamond, each carbon atom undergoes sp3 hybridisation
(ii) FeSO4.Al2(SO4)2.24H2O and is linked to four other carbon atoms by using hybridized
™ They are not isomorphous with true alums.
orbitals in tetrahedral manner. It is used as an abrasive for
sharpening hard tools in making dies (die casting) and
Properties of Group 14 Elements in the manufacture of tungsten filament for electric light
Property Remarks bulbs.
Covalent radii C < Si < Ge < Sn < Pb ™ In Graphite, each carbon atom in hexagonal ring undergoes
sp2 hybridisation and make three sigma bonds with three
Ionisation Enthalpy C > Si > Ge < Sn > Pb
neighboring carbon atoms. Fourth electron forms a π bond.
Elechongahvity C > Pb > Si ≈ Ge ≈ Sn The electrons are delocalised over the whole sheet. Electrons
Metallic character Increases down the Group are mobile and, therefore graphite conducts electricity along
the sheet.
Melting point General oxidation state: +4 and +2
Oxidation state Stability of +2 oxidation state increases ™ Fullerenes are made by the heating of graphite in an
down the group due to inert pair effect electrical arc in the presence of inert gases such as helium
Reactivity towards React with oxygen to form oxides or argon. All the carbon atoms are equal and they undergo
oxygen (mainly two types of oxides., monoxide sp2 hybridisation.
and dioxide)
Reactivity towards C, S, Ge and Pb do not react with water. Carbon Monoxide [CO]
Water Sn decomposes steam to form dioxide
and dihydrogen gas. Colorless odourless, tasteless, neutral, poisionous gas.
Sn + 2.H2O → SnO2 + 2H2
C=O
Reactivity of These element can form halides of Complexing agent
halogen formula MX2 and MX4 (where X = F,
Ni + 4CO ® [Ni(CO)4]
Cl, Br, I)
properties
Hence members Ge to Pb are able to CO Reducing agent
make halides of formula MX2 FeO + CO ® Fe + CO2
Anomalous Behavior of Carbon ZnO + CO ® Zn + CO2
Carbon atoms have the tendency to link with one another through Combustion
covalent bonds to form chains and rings. This property is called CO + ½O2 ® CO2
catenation. This is because C–C bonds are very strong. Down the blue flame
group, as size increases tendency to show catenation decreases.
Silicones (Organo Silicone Polymer)
Table: Catenation Property
™ Silicones are polymeric organosilicon compounds containing
Bond Bond enthalpy (kJ/mol–1)
Si–O–Si linkage. They have high thermal stability of Si–O–Si
C-C 348 chains and are also called high temperature polymers.
Si-Si 297
General formula: (R2SiO)n. Where R = –CH3, –C2H5, –C6H5
Ge-Ge 260
−2HC l ∆
Sn-Sn 240 (i) R2SiCl2 + 2H2O → R2Si(OH)2 → Linear
− H2 O

Silicones/Cyclic Silicones
Tendency
Down the to show HCl ∆
Size (ii) R3SiCl + H2O → R 3Si(OH) 2 → Dimer
group catenation − H2 O
Silicones
C >> Si > Ge ≈ Sn −3HCl ∆
Lead does not show catenation. (iii) RSiCl3 + 3H2O → RSi(OH)3 → Crossed
− H2 O
Fig.: Representation of catenation property Linked Silicones