P-Block Elements

13th-Group (ii) Bauxite, Al2O3.2H2O

™ Some important ores of Boron are given as under. (iii) Cryolite, Na3AlF6
(i) Boric acid, H3BO3 (iv) Feldspar, KAlSi3O8
(ii) Borax, Na2B4O7.10H2O BORAX Na2[B4O5(OH)4].8H2O
(iii) Colemanite, Ca2B6O11.5H2O OH
™ Some important minerals of aluminium are given as under.
B
(i) Corundum, Al2O3 O O
Na2 OH — B O B OH .8H2O
O O
B
OH

(i) Heating
∆ ∆
Na2B4O7.10H2O Na2B4O7 2NaBO2 + B2O3
Swells up Sodium Boric
metaborate anhydride

Orthoboric Acid [H3BO3 or B(OH)3]

Monobasic Lewis acid
B(OH)3 + H2O → [B(OH)–4] + H+
From Borax:
Na2B4O7 + H2SO4 + H2O MOP Properties
Na2SO4 + 4H3BO3 B(OH)3 Action of heat
Tetraboric
100ºC 160ºC
From Colemanite : H3BO3 H2O HBO2 H2B4O7
Ca2B6O11 + 4SO2 + 11H2O metaboric
–H2O red hot
2Ca(HSO3)2 + 6H3BO3
B2O3
borontrioxide
Reaction with alcohol
(Test of boric acid)
H3BO3 + 3C2H5OH B(OC2H5) + 3H2O
Triethyl borate
green edged flame
Properties
™ Boric acid is a weak monobasic acid
B(OH)3 + 2H2O ⇔ H3O⊕ + [B(OH)4]–
pKa = 9.25
 ™ It is difficult to titrate boric acid against NaOH solutions and the end point cannot be located correctly However, it can be successfully
titrated in the presence of polyhydroxy alcohols (e.g. Glycerol, mannitol, catechol or sugar). The presence of these compounds
greatly increase the acidity of boric acid.
OH O O –
H3O+
B(OH)3 + 2 B +2H2O

OH O O
Boron is complexed by these compounds. These complex ions cannot interact with H+ ions as boron atom has already acquired
it’s maximum covalency of four. Consequently, boric acid in presence of polyhydroxy alcohols can be titrated against NaOH to
a definite end point.

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

14th–Group Elements ™ CO2, SiO2, GeO2, GeO are acidic, PbO, PbO2 is SnO
1. The common oxidation exhibited by these elements are + 4 and SnO2 are amphoteric and CO neutral
and + 2. Carbon also exhibits negative oxidation states. ⇒ Among 14th group element only Sn reacts with
2. Tin forms compounds in both oxidation states (Sn in + 2 steam to produce H2 gas.
state is a reducing agent). ⇒ Tetrahalide of 14th group elements are covalent
except SnF4 and PbF4.
3. Lead compounds in + 2 state are stable and in +4 state are
strong oxidising agents. Stability of oxidation state.
⇒ C+4 → Pb+4 (Stability)
4. SiO only exists at high temperature.
⇒ C+2 → Pb+2 (Stability)
5. The dioxides – CO2, SiO2 and GeO2 are acidic, whereas SnO2
⇒ Pb+4 compounds are strong oxidizing agent.
and PbO2 are amphoteric in nature. Among monoxides, CO
is neutral, GeO is distinctly acidic whereas SnO and PbO are ⇒ PbI4 does not exist.
amphoteric. Oxide of Lead
6. Tin decomposes steam to form dioxide and dihydrogen gas. ™ Read lead (Pb3O4) is considered to be mixture of
7. All halide of 14th group are covalent. Exceptions are SnF4 lead monoxide and lead dioxide and it is written as
and PbF4, which are ionic in nature. (PbO2·2PbO).
8. Stability of dihalides increases down the group. ™ Lead dioxide (PbO2). It is a brown powder obtained by
9. The order of catenation is C > > Si > Ge ≈ Sn. Lead does not the treatment of red lead with HNO3.
show catenation. Pb3O4 + 4HNO3 → 2Pb(NO3)2 + 2H2O + PbO2
™ Catenation is the unique tendency of 14 group elements It is used as an active material of the positive plate
to form long chains of different sizes and shapes. The in storage cells and finds use in match industry as an
tendency to show catenation is directly related to oxidizing agent.
the strength of bond. The bond energies of 14 group
elements decrease as under:
Reaction of Lead Oxides
Catenation C–C Si–Si Ge–Ge Sn–Sn Pb–Pb Oxide ex NaOH HCl H2SO4 HNO3

Bond energy 348 222 167 155 – PbO Na2PbO2 PbCl2 PbSO4 Pb(NO3)2
(kJ mole–1)
This is the reason why carbon forms many chains, Si, a PbO2 Na2PbO3 PbCl2 + Cl2 PbSO4 + O2 Pb(NO3)2
few and Ge and Sn form practically no chains. Pb2O3 Na2PbO2 + NaPbO3 PbCl2 + Cl2 PbSO4 + O2 Pb(NO3)2 + PbO2
™ CO2 is a gas while SiO2 is a solid at room temperature.
Pb3O4 Na2PbO2 + Na2PbO3 PbCl2 + Cl2 PbSO4 + O2 Pb(NO3)2 + PbO2
™ SiO only exists at high temperature.

28 JEE (XI) Module-3 PW

Tin and Its Compound which finally turns to metallic mercury (dark grey or
™ Action of conc. HNO3 on tin black)
(a) Dilute HNO3           Hg2Cl2 + SnCl2 → 2Hg ↓ + SnCl4
Black
4Sn + 10HNO3
→ 4 Sn(NO3)2 + NH4NO3 + 3H2O
™ Mosaic gold (SnS2): Stannic sulphide exists in yellow
(b) Hot conc. HNO3
glistening scales which is used for decorative purposes
Sn + 4HNO3 → H2SnO3 + 4NO2 + H2O
under and the name mosaic gold. It is prepared by heating
Metastannic acid
mixture of tin fillings, sulphur and NH4Cl in a retort.
™ Action of conc. NaOH on tin Sn + 4NH4Cl → (NH4)2SnCl4 + H2 + 2NH3
(a) Sn + 2NaOH + H2O → Na2SnO3 + 2H2­↑
 2(NH4)2SnCl4 + 2S → SnS2 + (NH4)2SnCl6 + 2NH4Cl
SnCl2
Carbides
™ SnCl2·  2H2O on heating undergoes to form it’s basic
Binary compounds of carbon with other elements (except
chloride Sn(OH).Cl. The anhydrous salt, therefore, be
hydrogen) are known as carbides
obtained by heating the hydrated salt in the presence of
CARBIDES
HCl vapour.
™ Stannous chloride reduces mercuric chloride (HgCl2) to a
Ionic Carbide Covalent Carbide Interestial Carbides
white precipitate of mercurous chloride (Hg2Cl2)
C+ higher C + Non-metals C + transition metals
electropositive element (like B & Si)
2Hg2+ + 3Cl– + Sn2+ → Hg 2 Cl2 + Sn +4 (IA, IIA & Al)
Mercurous chloride
Eg. Be2 C, Mg2 C3, Al4C3, CaC2 Eg. B4C, SiC Eg. TiC,WC

P
W The p-Block Elements 29