p-Block Elements (B & C family)

Section (A), (B) & (C) : General facts about elements, Based on Periodic trends &
Based on Chemical Bonding
Introduction :
Group 13 to 18 of the periodic table of elements constitute the p–block. The p–block contains metals,
metalloids as well as non–metals.
Configuration ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6
He
B C N O F Ne
Al Si P S Cl Ar
Ga Ge As Se Br Kr
In Su Sb Te I Xe
Tl Pb Bi Po At Rn
Group Oxidation State +3 +4 +5 +6 +7 +8
Other Oxidation State +1 +2, –4 +3, –3 +4, +2, –2 +5, +3, +1, –1 +6, +4, +2
The p-block elements have general valence shell electronic configuration ns 2 np1–6.
The first member of each group from 13–17 of the p–block elements differ in many respects from the
other members of their respective groups because of small size, high electronegativity and absence of
d–orbitals.
The first member of a group also has greater ability to form p–p multiple bonds to itself (e.g. C=C,
CC, NN) and to element of second row (e.g C=O, C=N, CN, N=O) compared to the other members
of the same group.
The highest oxidation state of p–block element is equal to the group number –10. Moving down the
group, the oxidation state two less than the highest group oxidation state and becomes more stable in
groups 13 to 16 due to inert pair effect (reluctance of s-subshell electrons to participate in chemical
bonding)
Ge liquid expands when it forms the solid. This property is unique to Ga, Ge and Bi.

Catenation :
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 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 the property of catenation and p-p bonds formation, carbon is able to show allotropic forms.
Bond Bond enthalpy (kJ mol–1)
C—C 348
Si––Si 297
Ge—Ge 260
Sn—Sn 240

ANOMALOUS BEHAVIOUR OF CARBON :

Like first member of other groups, carbon also differs from rest of the members of its group. It is due to
its smaller size, higher electronegativity, higher ionisation enthalpy and unavailability of d orbitals.
Carbon accommodate only four pairs of electrons around it and thus this would limit the maximum
covalence to four whereas other members can expand their covalence due to the presence of d
orbitals, Carbon also has unique ability to form p-p multiple bonds with itself and with other atoms of
small size and high electronegativity. Few examples of multiple bonding are C=C, CC, C=O, C=S and
CN. Heavier elements do not form p-p bonds because their atomic orbital are too large and diffuse
to have effective overlapping.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 1
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON
The tri-chlorides, bromides and iodides of all these elements being covalent in nature are hydrolysed in
water. Species like tetrahedral [M(OH)4]– and octahedral [M(H2O)6]3+, except in boron, exist in aqueous
medium. It is due to the absence of d orbitals that the maximum covalence of boron is 4. Since the d-
orbitals are available with Al and other elements, the maximum covalence can be expected beyond 4.
GROUP 13 : BORON FAMILY & GROUP 14 : CARBON FAMILY
Occurrence :
Element Abundance Source Element Abundance Source
 Coal
 Natural gas
 oil
 Borax : (hydrocarbon)
Na2[B4O5(OH)4].8H2O  Natural
9 ppm  Colemnite : Graphite
B (Rare Ca2B6O11.5H2O C  Natural
180 ppm
(Boron) element)  Kernite : (Carbon) diamond
Na2[B4O5(OH)4].2H2O  Carbonates:
 Boric acid :  Calcite(CaCO3)
H3BO3  Magnesite
(MgCO3)
 Dolomite(MgC
O3.CaCO3]
83000 ppm
 Bauxite :
(Most
Al2O3.H2O–Al2O3.3H2O  Silica (sand &
abundant
Al  Aluminosilicate Si quartz) SiO2
metal, 272000 ppm
(Aluminium) rocks (feldspars, (Silicon)  Silicate
3rd most
mica) minerals
Abundant
element)  Cryolite : Na3AlF6
Ga Ge  Silver and Zinc
19 ppm  Ores of Al, Zn, Ge 1.5 ppm
(Gallium) (Germanium) ores, coal
In Sn  Cassiterite
0.24 ppm  ZnS & PbS ores 2.1 ppm
(Indium) (Tin) (SnO2)
Tl Pb
0.5 ppm  ZnS & PbS ores 13 ppm  Galena (PbS)
(Thallium) (Lead)

Allotropy :
Elements Allotropes Elements Allotropes
Crystalline Diamond,
5 crystalline forms :
hexagonal diamond
B -rhombohedral C
-graphite, -graphite
2 amorphous forms fullerenes
Amorphous - brown powder
Al No allotrope Si
Crystalline - greyish metallic
-Germanium
Ge
Ga No allotrope -Germanium
-Germanium
-tin (grey tin)
Sn
In No allotrope -tin (white tin)
13.2ºC
-Sn(diamond structure) -Sn(metallic)
Tl -Thallium -lead (Pb-I)
Pb
-Thallium -lead (Pb-II)

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 2
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Allotropy of carbon family
 Silicon is a very high melting-point solid with the same structure as diamond. The non-existence of
an allotrope with the graphite structure clearly shows the inability of silicon atoms to multiple bond with
themselves.
Allotropes of Carbon:
Diamond Graphite Fullerene

Structure

z
Hybridisation sp3 sp2 sp2
Density
3.51 2.22 1.65
(g/cm3)
Hf (KJ/mol) 1.9 0 38.1
Bond length 154 pm 141.5 pm 143.5 pm & 138.3 pm
 Crystalline lattice.  Layered structure  Cage like
 3-D network: each C-  Interlayer force-Vanderwaal’s forces molecules.
atoms is linked to four  Each carbon atom is linked to three  C60–Soccer ball
other C-atoms in other carbon atoms, fourth electron shape–Buck
tetrahedral manner. forms a  bond. minsterfullerene
 One of the hardest –  Good conductor along the sheet  20- six membered
next to boron nitride and semi-conductor perpendicular rings and 12- five
(only at certain to the sheet. membered rings.
conditions)  Inter layer distance 340 pm so  Six membered
 Uses: sharpening cleavage between layers is easy. ring is fused with
hard tools, cutter tools; Soft and slippery– lubricant at high six or five
as a gem. temperature. membered ring
 Natural graphite is found as a  Five membered
mixture with mica, quartz & ring is fused only
silicates. with six
3C+SiO2  
 SiC + 2CO  2500ºC
 membered ring.
C(graphite) + Si gas  Heating of
 Thermodynamically most stable graphite in an
among allotropes. electrical arc in
the presence of
Graphite  1600ºC
 synthetic diamond
50000–60000atm inert gases such
as helium or
argon can result
into fullerene

Ex-1. Thermodynamically graphite is more stable than diamond but diamond does not transform into graphite
on its own. Why?
Sol. This conversion is not favoured by kinetic factors (the activation energy for this is very high).

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 3
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
Atomic & 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. Rest of the
member are soft metals with low melting point and high electrical conductivity. Gallium with low melting
point (303 K), could exist in liquid state during summer. Its high boiling point (2676 K) makes it a useful
material for measuring high temperatures. Aluminium is a good conductor of heat and electricity. It is
malleable and ductile. Density of the elements increases down the group from boron to thallium.
Boron family:
Property B Al Ga In Tl
Character Metalloid Metallic Metallic Metallic Metallic
Atomic Number 5 13 31 49 81
Atomic Mass/g mol–1 10.81 26.98 69.72 114.82 204.38
[Xe] 4f14
Electronic configuration [He] 2s2 [Ne] 3s2 [Ar] 3d10 [Kr] 4d10
5d10
General electronic configuration=(ns2 np1) 2p1 3p1 4s24p1 5s2 5p1
6s26p1
Covalent Radius / pm 85 143 135 167 170
(B < Ga < Al < In < Tl) In Ga, poor shielding of 10 d-electrons

Ionic Radius X– / pm
27 53.5 62 80 88.5
(B < Al < Ga < In < Tl)

Ionization enthalpy iH1  801 577 579 558 589

(kJ mol–1)
(B > Al < Ga > In < Tl) iH2  2427 1816 1979 1820 1971
2877
iH3  3659 2744 2962 2704
Poor shielding of d-orbital and f-orbital in Ga & Tl respectively
Electronegativity 2.0 1.5 1.6 1.7 1.8
(B > Al < Ga < In < Tl)
Marginal increase after Al
Melting point / K 2453 933 303 430 576
Boiling point / K
3923 2740 2676 2353 1730
(B > Al > Ga > In > Tl)
Density/[g cm–3 ( at 293 K)
2.35 2.70 5.90 7.31 11.85
(B < Al < Ga < In < Tl)
+3 +3 +3, +1 +3, +1 +3, +1
+1 oxidation state arises due to inert pair effect.
Oxidation State
Stability of Oxidation state: +1: Ga < In < Tl
+3 : Al > Ga > In > Tl

Carbon family :
Property C Si Ge Sn Pb
Non Non
Character Metalloid Metallic Metallic
Metallic Metallic
Atomic Number 6 14 32 50 82
Atomic Mass/g mol–1 12.01 28.09 72.60 118.71 207.2
Electronic configuration [Xe] 4f14
[He] 2s2 [Ne] 3s2 [Ar] 3d10 4s2 [Kr] 4d10
5d10 6s2
General electronic configuration=(ns2 np2) 2p2 3p2 4p2 5s2 5p2
6p2

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 4
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
Covalent Radius / pm
77 118 122 140 146
(C < Si < Ge < Sn < Pb)
Ionic Radius M+4 / pm
– 40 53 69 78
(Si < Ge < Sn < Pb)

Ionization enthalpy iH1  801 577 579 558 589

(kJ mol–1)
(C > Si > Ge > Sn < Pb) iH2  2427 1816 1979 1820 1971
iH3  3659 2744 2962 2704 2877
Poor shielding f-orbital
Electronegativity
2.5 1.8 1.8 1.8 1.9
(C > Si  Ge  Sn  Pb)
Melting point / K 4373 1693 1218 505 600
Boiling point / K – 3550 3123 2896 2024
Density/[g cm–3 ( at 293 K)
3.51 2.34 5.32 7.26 11.34
(C (diamond) > Si < Ge < Sn < Pb)
+4 +4 +4, +2 +4, +2 +4, +2
+2 oxidation state arises due to inert pair effect.
Oxidation State
Stability of Oxidation state: +2: Ge < Sn < Pb
+4: Ge > Sn > Pb

The Elements
Preparation of elements :

BORON :
Source Process Comments
 low purity (95-98%) boron
(black)
 The product thus obtained
 Na2B4O7+2HCl+5H2O   4H3BO3+2NaCl
is boiled with HCl and
From Borax  filtered when Na2O or
 2H3BO3  B2O3 + 3H2O
(Na+)2B4O72- .10H2O MgO dissolves leaving
 B2O3+3Mg/Na 
High temp.
2B+3MgO/Na2O behind elemental boron. It
is thoroughly washed to
remove HCl and then
dried finally.
 2BX3+3H2 
red hot W
 2B(crystalline) + 6HX Problem in obtaining high
or Tantalum
purity boron:
(X = Cl or Br) 99.9% pure
From BX3  High melting point
 2BCI3 + 3Zn   3ZnCl2 + 2B
(2180ºC)
 2BI3 
red hot W
 2B + 3I2(Van Arkel method)  Liquid gets corroded
or Tantalum

From Diborane   Thermal decomposition of

 B2H6   2B(crystalline) + 3H2
(B2H6) diborane.
 By heating it with
From potassium  potassium metal.
 KBF4 + 3K   4KF + B
fluoroborate  It is then treated with dilute
(KBF4) HCl to remove KF and B is
then washed and dried.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 5
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
ALUMINIUM :
Method Process Comments
 The purified Al2O3 is mixed with
Na3AlF6 (cryolite) or CaF2
(fluorspar) which lowers the
melting point of the mixture and
brings conductivity. The fused
The electrolytic reactions are: matrix is electrolysed. Steel
cathode and graphite anode
Cathode : Al3+(melt) + 3e–   Al(l) are used. The graphite anode
Electrolytic 2–
Anode : C(s) + O (melt)  – is useful here for reduction to
 CO(g) + 2e
reduction 2–
C(s) + 2O (melt)   CO2 (g) + 4e
– the metal.
(Hall-Heroult The overall reaction may be taken as:  The electolysis of the molten
process) mass is carried out in an
2Al2O3 + 3C   4Al + 3CO2
electrolytic cell using carbon
electrodes. The oxygen
liberated at anode reacts with
the carbon of anode producing
CO and CO2. This way for
each kg of aluminium
Several other extraction processes will be studied in produced, about 0.5 kg of
detail in Metallurgy. carbon anode is burnt away.

CARBON :
Preparation of Process

Carbon black (soot) By incomplete combustion of hydrocarbon.


Graphite 3C + SiO2   SiC + 2CO 
2500ºC
 C (graphite) + Si gas
 Natural diamond can be extracted from mines.
Diamond  Synthetic diamond
1600ºC
Graphite 
50000  60000 atm
 synthetic diamond.

SILICON :
From Process Comments
SiO2 (excess) + 2C   Si (pure) + 2CO
Reducing SiO2 with high purity coke in an
SiO2 Si (pure) + 2Cl2  SiCl4
electric furnace
SiCl4 + 2Mg   Si (highly pure) + MgCl2
Sodium Reduction of Na2[SiF6] Zone refining is used to get ultra pure
Na2[SiF6] silicon from highly pure silicon, which can
Na2 [ SiF6] + 4Na  Si (ultra pure) + 6NaF
be used in semi-conductor industry.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 6
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Section (D) : Properties of Elements
Chemical Properties :
Reaction
Boron Family Carbon Family
with

E + O2  EO2

4E + 3O2  2E2O3 (diox ide
)
1 
E+ O2  EO
2 (m onoox ide)
O2 B2O3 – acidic CO2 – acidic CO – neutral
Al2O3 – amphoteric SiO2 – acidic SiO – unstable
Ga2O3 – amphoteric GeO2 – acidic GeO – acidic
In2O3 – basic SnO2 – amphoteric SnO – amphoteric
Tl2O3 – basic PbO2 – amphoteric PbO – amphoteric

2E + N2  2EN 1273 K
N2 EN + H2O 
E(OH)3 + NH3 2C(s)+O2(g)+4N2(g)  2CO(g)  4N2 (g)
(Produc er
gas )
E = B or Al
2E + 3X2  2EX3 ; (X=F, Cl, Br, I) E + 2X2  EX4 ; (X = F, Cl, Br, I)
BX3 – covalent  All members form MX4 ; Ge & Pb form MX2
(BI3 cannot be formed directly)  PbI4 does not exist
X2 – Ionic
(Halogen)
AlF3  Stability of EX4 decreases down the group
GaF3 – Ionic  Stability of EX2 increases down the group
InF3 – Ionic  Stability :
TlI3 – exist as Tl+I3– & T l I also forms GeX4 > GeX2 ; PbX2 > PbX4
B – does not react with water C(s) + H2O (steam) red
 CO(g)  H2 (g)
25ºC heat (water gas)
Al(OH)3
+H2O red
Al E(s) + H2O(steam) 
 EO2+H2;
(Si,Ge,Sn) heat
>480ºC
Al2O3  Pb is unafftected by water, probably
H2O +H2O
Ga because of a protective oxide layer.
Not attacked by cold & hot water  C, Si, Ge – not attacked by cold water.
unless oxygen is present.
In
Tl – oxidises in moist air & decomposes
steam at red heat.
+H2SO4 C
H3BO3 + SO2 +HCl
(Hot & Conc.)
Si No reaction
B dilute
+HNO3 Ge
H3BO3 + NO2 Sn dissolves in HCl (dil. & conc) but Pb in only
(Hot & Conc.)
(Boron reacts with only oxidising acids) dil.HCl.
HCl
PbCl2 + H2
+HCl (conc.) (coating)
AlCl3 + H2 Pb
(does not H2SO4
Al dissolve in) PbSO4 + H2
Acids +HNO3 (coating)
(Conc.)
Do not react
because it forms +HNO3
passive oxide layer.
(Hot & conc.)
Ga, In, T can also react with dilute mineral
acids. C (graphite) (Mellitic acid)
+HF/HNO3
Graphite oxide
(mixture)
Si + 6HF  H2SiF6 + 2H2
E + dil. HNO3 E(NO3)2
(Sn,Pb )

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 7
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
2B + 2NaOH + 2H2O   2NaBO2 + 3H2 C – unaffected by alkalies
2B + 6NaOH fused
 2Na3BO3 + 3H2 Si + 2NaOH + H2O   Na2SiO3 + 2H2

NaOH + H2O
NaAlO2.2H2O + H2
NaOH or
+ —
Na [Al(OH)4] 
Al E + NaOH   Na2EO3 + H2
(Sn,Pb ) or
NaOH
Na3AlO3 + H2 Na2 [E(OH)6 ]
(Al & Ga readily dissolves in alkalies).
In & Tl do not react with alkali.
3Mg +2B  Mg3B2 
2Mg +Si   Mg2Si (magnesium silicide)
Metal
3Ca +2B  Ca3B2
SiO2
B2O3 + Si

B
CO2
Reducing  B2O3 + C
Property MnO2
Al2O3 + Mn

Al
Cr2O3
 Al2O3 + Cr

Section (E) : Oxides, Hydroxides, Oxyacids, Borax

Oxides, oxy acids and hydroxide
Boron trioxide (B2O3) :
Preparation :

 Properties :
It is a acidic oxide and is anhydride of boric acid and it reacts with alkalies or bases to form borates.
3Na2O + B2O3   2Na3BO3 (sodium orthoborate).
It reacts with water slowly to form orthoboric acid.
H2O + B2O3   2HBO2 ; HBO2 + H2O   H3BO3
When heated with transition metal salts, it forms coloured compounds.

3B2O3 + Cr2(SO4)3   3SO3  + 2Cr(BO2)3(green)

2B2O3 + 2Cu(NO3)2  4NO2  + O2  + 2Cu(BO2)2 (blue)
It also shows weakly basic properties according to the following reaction.
B2O3 + P2O5 2BPO4
It reacts with hydrogen fluoride in presence of H2SO4 forming BF3 .
B2O3 + 6HF + 3H2SO4   2BF3 + 3H2SO4.H2O.

Boric acid (H3BO3) :

Preparation :
(i) It is precipitated by treating a concentrated solution of borax with sulphuric acid.
Na2B4O7 + H2SO4 + 5H2O   Na2SO4 + 4H3BO3 
(ii) From Colemanite: Powdered colemanite is suspended in water and excess SO 2 is passed through it.
On filtering and cooling the filtrate, white crystals of H3BO3 are obtained.
Ca2B6O11 + 4SO2 + 11H2O   2Ca(HSO3)2 + 6H3 BO3
 Properties:
It is a weak monobasic acid, soluble in water and in aqueous solution the boron atom completes its
octet by accepting OH– from water molecules:
B(OH)3(aq) + 2H2O() [B(OH)4]– (aq) + H3O+(aq). pK = 9.25.
It, therefore, functions as a Lewis acid and not as a proton donor like most acids.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 8
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Since B(OH)3 only partially reacts with water to form H3O+ and [B(OH)4]–, it behaves as a weak acid.
Thus H3BO3 cannot be titrated satisfactorily with NaOH as a sharp end point is not obtained. If certain
organic polyhydroxy compounds such as glycerol, mannitol or sugars are added to the titration mixture,
then B(OH)3 behaves as a strong monobasic acid and it can be now titrated with NaOH and the end
point is detected using phenolphthalein as indicator (pH = 8.3 - 10.0).
The added compound must be a cis-diol, to enhance the acid properties. The cis-diol forms very stable
complex with the [B(OH)4]–, thus removing it from solution. The reaction is reversible and thus removal
of one of the products shifts the equilibrium in the forward direction and thus all the B(OH) 3 reacts with
NaOH; in effect it acts as a strong acid in the presence of the cis-diol.
2B(OH)3 + 2NaOH 
 Na[B(OH)4] + NaBO2 + 2H2O

HB(OH)4 + 2 + H+ + 4H2O

Ethanol does not form similar complex but catechol, salicylic acids, mannitol form similar complexes.

When heated it first forms metaboric acid (HBO2) and then boron trioxide.

Orthoboric acid is greasy to touch less soluble in cold water but more soluble in hot water. In the solid
state, the B(OH)3 units are hydrogen bonded together in to two dimensional sheets with almost
hexagonal symmetry. The layered are quite a large distance apart (3.18 Å) and thus the crystal breaks
quite easily into very fine particles.

Figure : 1
 Polymeric metaborate species are formed at higher concentration, for example,
3B(OH)3 H3O+ + [B3O3(OH)4]– + H2O, pK = 6.84


 Boric acid dissolves in aqueous HF forming HBF4 (fluoroboric acid).
B(OH)3 + 4HF H3O+ + BF4–– + 2H2O


Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 9
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
 Test for Borate radical :
When boric acid is heated with ethyl alcohol, the evolved gas is burned forming a green edged flame.
H3BO3 + 3C2H5OH   B(OC2H5)3 + 3H2O
ethylborate (volatile)
 Uses :
(i) It is an antiseptic and its water solution is used as an eyewash.
(ii) It is also used in glass, enamel and pottery industry.

Ex-2. It has been observed that BF3 does not hydrolyses completely whereas BCl3 or BBr3 get easily
hydrolysed to form B(OH)3 and HX ? Explain.
Sol. The greater stability of B–F bond as compared to B–Cl and B–Br bonds is due to additional –bonding
in B–F bonds of BF3 molecules. The B–Cl and B–Br bonds are relatively weak and are easily cleaved
by water forming strong B–OH bonds instead of stable addition product (BF3.OH2) formed by BF3.

Borax (Na2B4O7.10H2O) :
 Preparation :
It is found in nature but can also be prepared by the following methods.
(i) From Colemanite.
When colemanite powder is heated with Na2CO3 solution, the following reaction occurs with the
precipitation of CaCO3.
Ca2B6O11 + 2Na2CO3   2CaCO3  + Na2B4O7 + 2NaBO2
The filtrate is cooled when white crystals of borax are precipitated. The mother liquor on treatment with
CO2 converts NaBO2 to Na2B4O7 which precipitates out on crystallization.
4NaBO2 + CO2   Na2B4O7 + Na2CO3
(ii) From orthoboric acid.
Borax is obtained by the action of Na2CO3 on orthoboric acid.
4H3BO3 + Na2CO3   Na2B4O7 + 6H2O + CO2



 Properties :
(i) Borax is a white powder, less soluble in cold water, more soluble in hot water.
(ii) Its aqueous solution is alkaline because of its hydrolysis to weak acid H 3BO3 and strong alkali NaOH.
Na2B4O7 + 7H2O   4H3BO3 + 2NaOH
(iii) Action of heat.
When borax powder is heated, it first swells due to loss of water in the form of steam but at 740oC it
becomes converted into colourless transparent borax bead.

Na2B4O7.10H2O   Na2B4O7 + 10 H2O
740ºC
Na2B4O7   2NaBO2 + B2O3 (borax bead)
(iv) Oxidation of boric acid or sodium metaborate with H2O2.

Na2B4O7   2NaBO2 + 2H2O2 + 6H2O   Na2 [(OH)2B (O—O)2B(OH)2].6H2O
Sodium per oxoborate is used as a brightner in washing powder. In very hot water (over 80ºC) the
peroxide linkages —O—O— break down to give H2O2.
(v) It is a useful primary standard for titrating against acids. One mole of it reacts with two moles of acid.
This is because when borax is dissolved in water both B(OH) 3 and [B(OH)4]– are formed, but only the
[B(OH)4]– reacts with HCl.
[B4O5(OH)4]2– + 5H2O 2B(OH)3 (weak acid) + 2[B(OH)4]– (salt)
2[B(OH)4]2– + 2H3O+   2B(OH)3 + 4H2O
On cooling, the white flakes of boric acid are obtained
 Borax is also used as a buffer since its aqueous solution contain equal amounts of weak acid and its
salt.
H O H SO
(vi) Na2[B4O5(OH)4] + 12HF  2
 [Na2O(BF3)4]   4BF3 + 2NaHSO4 + H2O
2 4

 Correct formula of borax is Na2[B4O5(OH)4] . 8H2O. It contains boron in both planar BO3 and tetrahedral
BO4 units. It contains five B—O—B linkages.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 10
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
 Borax-bead test :
Borax reacts with certain metal salts such as, Ni2+, Co2+, Cr3+, Cu2+, Mn2+ etc. to form coloured
metaborates. The colour of the metaborates can be used to identify the metallic ions (cations) in salts.

 2NaBO 2  B 2 O3 ; CuO + B2O3 
740ºC
Na2B4O7·10H2O  Na2B4O7   Cu(BO2)2 (blue bead)
10H2 O glassy mass

 Uses :
(i) In borax bead test. (ii) In purifying gold.
(iii) As flux during welding of metals. (iv) In production of glass.

 (A) 
(i) C H OH
Ex-.3 (a) Na2B4O7 + concentrated H2SO4 + H2O  2 5
(B)
(ii) ignite

(B) is identified by the characteristic colour of the flame. Identify (A) and (B).
(b) Complete the following reaction and identify the products formed.


Na2B4O7  (A)
 (B )

Sol. (a) Na2B4O7 + concentrated H2SO4 + 5H2O   Na2SO4 + 4H3BO3

H3BO3 + 3C2H5OH   B(OC2H5)3-volatile (burn with green edged flame) + 3H2O


(b) Na2B4O7   B2O3
 (NaBO 2 )

Aluminium Oxide (Al2O3) :

 It is also called alumina. It occurs in nature in the form of bauxite and corundum. It is also found in the
form of gems. Some important aluminium oxide gems are :
(A) Oriental Topaz-yellow (Fe3+), (B) Sapphire-blue (Fe2+ / 3+ / Ti4+),
(C) Ruby-red (Cr3+), (D) Oriental Emerald-green (Cr3+ / V3+)


 Preparation :
Pure Al2O3 is obtained by igniting Al2(SO4)3, Al(OH)3 or ammonium alum.
 
Al2(SO4)3   Al2O3 + 3SO3 ; 2Al(OH)3  Al2O3 + 3H2O

(NH4)2SO4.Al2(SO4)3.24H2O   2NH3 + Al2O3 + 4SO2  + 25H2O

 Properties :
It is a white amorphous powder insoluble in water but soluble in acids (forming eg., AlCl 3) as well as
alkalies (forming e.g., NaAlO2), Thus amphoteric in nature. It is a polar covalent compound. Exists in
two forms -Al2O3 or corundum and -Al2O3.
Addition of Cr2O3 or Fe2O3 makes alumina coloured.
-Al2O3 
 -Al2O3
1000ºC

 Uses :
(i) It is used for the extraction of aluminium.
(ii) It is used for making artificial gems.
(iii) It is used for the preparation of compounds of aluminium.
(iv) -Al2O3 is used in making furnace linings. It is a refractory material.
(v) It is used as a catalyst in organic reactions.
(vi) Corundum is extremely hard and is used as ‘Jewellers rouge’ to polish glass.
(vii) -Al2O3 dissolves in acids absorbs moisture and is used in chromatography.

Ex-4 What will happen if aluminium is heated with coke in an atmosphere of nitrogen ?

Sol. Al2O3 + N2 + 3C   2AlN + 3CO

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 11
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
Carbonmonoxide (CO) :
Preparation :
(i) It is formed together with CO2, when carbon or carbonaceous matter is oxidized by air or oxygen. It is
also produced when CO2 is reduced by red- hot carbon; this reaction is of importance in metal
extractions.
C(s) + CO2(g)   2CO(g)
(ii) In the laboratory it can be prepared by dehydrating methanoic acid with concentrated sulphuric acid.
373K
HCOOH (liq)   CO(g) + H2O
conc.H2SO4

(iii) If oxalic acid is dehydrated in the same way, CO 2 is formed as well.

conc. H2SO4 , 
H2C2O4   CO + CO2
–H2O

(iv) 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.
4731273K
C (s) + H2O (g)   CO (g) + H2(g) (water gas).
When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer gas.
1273K
2 C (s) + O2 (g) + 4 N2 (g)   2 CO (g) + 4 N2 (g) (Producer gas).
Water gas and producer gas are very important industrial fuels. Carbon monoxide in water gas or
producer gas can undergo further combustion forming carbon dioxide with the liberation of heat.
(v) CO2 + H2   CO + H2O

(vi) K4Fe(CN)6 + 6H2SO4 (concentrated) + 6H2O   2K2SO4 + FeSO4 + 3(NH4)2SO4 + 6CO
(vii) HCN + 2H2O   HCOOH + 2NH3 (absorbed by H2SO4)

HCOOH   2O + CO
H
(viii) Also obtained as by-product when carbon is used in reduction processes such as, of phosphite
rock to give phosphorus.
 Properties :
(i) Carbon monoxide is a colourless, odourless gas which burns in air with a blue flame, forming CO 2. It
is sparingly soluble in water and is a neutral oxide. CO is toxic, because it forms a complex with
haemoglobin in the blood and this complex is more stable than oxy-haemoglobin. This prevents the
haemoglobin in the red blood corpuscles from carrying oxygen round the body. This causes oxygen
deficiency, leading to unconsciousness and then death.
Hb—O2 + CO   Hb—CO + O2
Ordinary gas masks are no protection against the gas, since it is not readily adsorbed on active
charcoal. In the presence of air, a mixture of manganese (IV) oxide and copper(II) oxide catalytically
oxidizes it to CO2, and this mixed catalyst is used in the breathing apparatus worn by rescue teams in
mine disasters.
(ii) Carbon monoxide is a powerful reducing agent, being employed industrially in the extraction of iron
and nickel .
Fe2O3(s) + 3CO(g)   2Fe(s) + 2CO2(g) ; NiO(s) + CO(g)   Ni(s) + CO2(g)
(iii) It reacts with many transition metals, forming volatile carbonyls; the formation of nickel carbonyl
followed by its decomposition is the basis of the Mond’s process for obtaining very pure nickel .
28ºC 180ºC
Ni(s) + 4CO(g)   Ni(CO)4(liq)   Ni(s) + 4CO(g)
(iv) In addition to reacting with oxygen, carbon monoxide combines with sulphur to give carbonyl
sulphide and with chlorine in the presence of light to give carbonyl chloride (phosgene), used in the
production of polyurethane foam plastics. Phosgene is an exceedingly poisonous gas.
CO(g) + S(s)   COS(s) (carbonyl sulphide) ;
CO(g) + Cl2(g)   COCl2(g) (carbonyl chloride)
(v) Although carbon monoxide is not a true acid anhydride since it does not react with water to produce
an acid, it reacts under pressure with fused sodium hydroxide to give sodium methanoate :
dil. HCl
NaOH(liq) + CO(g)   HCOONa(s)   HCOOH(aq)

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 12
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
(vi) With hydrogen under pressure and in the presence of zinc oxide or chromium (III) oxide catalyst it
reacts to give methanol; this reaction is of industrial importance.
CO(g) + 2H2(g)   CH3OH(liq)
(vii) CO is readily absorbed by an ammonical solution of copper (I) chloride to give CuCl.CO.2H 2O. It
reduces an ammonical solution of silver nitrate to silver (black) and, in the absence of other gaseous
reducing agents, this serves as a test for the gas. It can be estimated by reaction with iodine pentoxide,
the iodine which is produced quantitatively being titrated with standard sodium thiosulphate solution.
5CO(g) + 2O5(s)  2(s) + 5CO2(g)
(viii) It reduces an aqueous PdCl2 solution to metallic Pd.

Carbon dioxide (CO2) :

 Preparation :
(i) In the laboratory it can be conveniently made by the action of dilute hydrochloric acid on marble
chips:
CO32-(aq) + 2H+(aq)   CO2(g) + H2O()

(ii) Industrially it is produced as a by-product during the manufacture of quicklime and in fermentation
processes:
CaCO3(s)   CaO(s) + CO2(g) ; C6H12O6(aq){glucose}   2C2H5OH(aq) + 2CO2(g)
 Properties :
(i) It is a colourless, odourless and heavy gas which dissolves in its own volume of water at ordinary
temperature and pressure. Like all gases, it dissolves much more readily in water when the pressure is
increased and this principle is used in the manufacture of soda water and fizzy drinks.
(ii) CO2 is easily liquefied (critical temperature = 31.1ºC) and a cylinder of the gas under pressure is a
convenient fire extinguisher. When the highly compressed gas is allowed to expand rapidly solid carbon
dioxide (‘dry ice’) is formed. Solid carbon dioxide sublimes at –78ºC and, since no massy liquid is
produced, it is a convenient means of producing low temperatures.
(iii) Carbon dioxide is the acid anhydride of carbonic acid, which is a weak dibasic acid and ionises in
two steps as follows :
H2CO3(aq) + H2O () HCO3– (aq) + H3O+ (aq)
HCO3– (aq) + H2O () CO32– (aq) + H3O+ (aq)
–
H2CO3 / HCO3 buffer system helps to maintain pH of blood between 7.26 to 7.42.
A solution of carbonic acid in water will slowly turn blue litmus red and when the solution is boiled, all
the CO2 is evolved.
(iv) Carbon dioxide readily reacts with alkalies forming the carbonate and, if CO 2 is in excess, the
hydrogen carbonate. This is the basis of the lime-water test for CO2 gas.
Ca(OH)2(aq) + CO2(g)  CaCO3(s) + H2O(liq); CaCO3(s) + H2O(liq) + CO2(g)  Ca(HCO3)2(aq)
The above reaction accounts for the formation of temporarily hard water.
(v) 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. It is the process by which green plants
convert atmospheric CO2 into carbohydrates such as glucose. The overall chemical change can be
expressed as:
hv
6 CO2 + 12 H2O  
 C6H12O6 + 6 O2 + 6 H2O
Chlorphyll
By this process plants make food for themselves as well as for animals and human beings. But the
increase in combustion of fossil fuels and decomposition of limestone for cement manufacture in recent
years seem to increase the CO2 content of the atmosphere. This may lead to increase in green house
effect and thus, raise the temperature of the atmosphere which might have serious consequences.
(vi) Gaseous CO2 is extensively used to carbonate soft drinks. Being heavy and non–supporter of
combustion it is used as fire extinguisher. A substantial amount of CO 2 is used to manufacture urea.
 Recovery of CO2 :
(a) Na2CO3 + CO2 + H2O 2NaHCO3
(b) Girbotol process : 2HOCH2CH2NH2 + CO2 + H2O (HOCH2CH2NH3)2CO3


Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 13
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)


Ex-5. H2C2O4   gas (A) + gas (B) + liquid (C)
oxalic acid
Gas (A) burns with blue flame and is oxidised to gas (B). Gas (B) turns lime water milky.
NH3 ,  NH3 , 
Gas (A) + Cl2   (D)   (E)   (B)
Identify (A) to (E) and explain reactions involved.

Sol. H2C2O4   CO + CO2 + H2O
NH3 ,  NH3 , 
CO + Cl2   COCl2   NH2CONH2   CO2


Carbon suboxide (C3O2) :

This is an evil-smelling gas and can be made by dehydrating propanedioic acid (malonic acid), of which
it is the anhydride, with phosphorus pentoxide :
3 CH2(COOH)2 + P4O10   3C3O2 + 4H3PO4
o
When heated to about 200 C, it decomposes into CO2 and C:
C3O2(g)   CO2(g) + 2C(s)
The molecule is thought to have a linear structure: O=C=C=C=O.

Silicon Dioxide (SiO2) :

Silicon dioxide, commonly known as silica, occurs in several crystallographic forms. Quartz, cristobalite
and tridymite are some of the crystalline forms of silica, and they are interconvertable at suitable
temperature. Silicon dioxide is a covalent, three-dimensional network solid in which each silicon atom is
covalently bonded in a tetrahedral manner to four oxygen atoms. Each oxygen atom in turn covalently
bonded to another silicon atoms. Each corner is shared with another tetrahedron. The entire crystal
may be considered as giant molecule in which eight membered rings are formed with alternates silicon
and oxygen atoms. Silica in its normal form is almost non-reactive because of very high Si–O bond
enthalpy. It resists the attack by halogens, dihydrogen and most of the acids and metals even at
elevated temperatures. However, it is attacked by HF and NaOH.
SiO2 + 2 NaOH   Na2SiO3 + H2O ; SiO2 + 4 HF   SiF4 + 2 H2O
Quartz is extensively used as a piezoelectric material; it has made possible to develop extremely
accurate clocks, modern radio and television broadcasting and mobile radio communications. Silica gel
used as a drying agent and as a support for chromatographic materials and catalysts. Kieselghur, an
amorphous form of silica is used in filtration plants.

Stannous Oxide (SnO) :

 Preparation :
By heating stannous hydroxide, Sn(OH)2, in absence of air.
Sn(OH)2  SnO + H2O
 Properties :
SnO is an amphoteric dark grey or black solid oxide, insoluble in water. It dissolves in acids to form
stannous salts.
SnO (basic) + 2H+  Sn2+ + H2O ;
SnO (acidic) + 4OH– + H2O  [Sn(OH)6]4– or SnO22– (stannite)
 Stannites are only known in aqueous solutions. Stannites absorb oxygen from air and are oxidised to
stannate which are stable in nature.
2 Na2SnO2 + O2  2 Na2SnO3


 Uses :
For the preparation of stannous chloride and stannous sulphate.

Stannic Oxide (SnO2) :

 Preparation :
By heating tin with concentrated HNO3.

Sn + 4HNO3   H2SnO3 + 4NO2 + H2O ; H2SnO3   H2O + SnO2

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 14
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
Properties :
(i) It is a white solid insoluble in water.
(ii) It is amphoteric in nature.
(iii) It dissolves in concentrated H2SO4 to form stannic sulphate.
SnO2 + 2H+   Sn+4 + 2H2O
(iv) It also dissolves in concentrated alkalies to form alkali metal stannate solution.
SnO2 + 6OH–   [Sn(OH)6]2– or SnO32– (stannate)

Litharge (PbO) :
PbO is prepared by heating Pb at 180oC. It is a volatile yellow organic solid.

2Pb + O2   2PbO
It is an amphoteric oxide and dissolves in acids as well as in alkalies.
It is used in rubber industry and in the manufacture of flint glasses, enamels, and storage batteries.

Lead Dioxide (PbO2) :

 Preparation :

(i) PbO + NaOCl   PbO2 (insoluble) + NaCl

(ii) Pb3O4 + 4HNO3 (dilute) 

 2Pb(NO3)2 + PbO2 + 2H2O

 Properties :
It is a chocolate/dark brown coloured insoluble solid.
(i) On heating at 440oC it gives the monoxide.
440ºC
2PbO2   2PbO + O2

(ii) PbO2 is an oxidising agent and reduced to PbO since stability of Pb(II) > Pb(IV) based on inert pair
effect.
(a) It oxidizes HCl to Cl2.
PbO2 + 4HCl   PbCl2 + 2H2O + Cl2
(b) It oxidises Mn salt to permanganic acid.
2MnSO4 + 5PbO2 + 6HNO3   2HMnO4 + 2PbSO4 + 3Pb(NO3)2 + 2H2O

(c) It reacts with SO2 at red heat to form lead sulphate.


PbO2 + SO2   PbSO4
(iii) It dissolves in concentrated NaOH solution.
PbO2 + 2OH– + 2H2O   [Pb(OH)6]2– (plumbate)
(iv) It reacts with concentrated HNO3 to evolve oxygen gas.
PbO2 + 2HNO3   Pb(NO3)2 + 1/2O2 + H2O
PbO2 + H2SO4   PbSO4 + 2H2O + O2

 Uses :
It is used in match industry for making ignition surface of match boxes, in the preparation of KMnO 4 and
in explosives.

Red Lead (Pb3O4) :

 Preparation :
It is prepared by heating PbO at 450oC for a long time.
450ºC
6PbO + O2   2Pb3O4

 Properties :
(i) It is a red powder insoluble in water but when heated with concentrated HNO 3 it gives a red
precipitate of PbO2.
Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 6H2O
(ii) When heated above 550oC, it decomposes into PbO.

Pb3O4   6PbO + O2

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 15
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
(iii) It oxidizes concentrated HCl to chlorine.
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2
(iv) When heated with concentrated H2SO4 it evolves oxygen.
2Pb3O4 + 6H2SO4  6PbSO4 + 6H2O + O2
 Uses :
It is used as an oxidizing agent, for making metal protecting paints like red oxide paint, for making
special lead cement and for making flint glass.

Section (F) : Hydrides

Compounds
Hydrides
Boranes
Binary compounds of B with H are called boron hydrides or boranes. These compounds form following
two types of series :
BnHn+4 - B2H6, B5H9, B6H10, B10H14
BnHn+6 - B4H10, B5H11, B6H12, B9H15
The chemistry of diborane has aroused considerable interest because of its usefulness in many
synthetic reactions and also because the elucidation of its structure helped to clarify the basic concepts
about the structure of electron deficient compounds.
 Preparation of Diborane (B2H6) :
ether
(i) 4BF3 + 3LiAlH4   2B2H6 + 3Li [AlF4]
silent electric
(ii) 2BCl3 + 6H2 (excess)   B2H6 + 6HCl
discharge
ether
(iii) 8BF3 + 6LiH  B2H6 + 6LiBF4
(iv) 2NaBH4 + 2 
ether
 B2H6 + 2Na + H2
ether
(v) 3NaBH4 + 4BF3  3NaBF4 + 2B2H6
450K
(vi) It can also be prepared by treating NaBH4 with concentrated H2SO4 or H3PO4.
2NaBH4 + H2SO4   B2H6 + 2H2 + Na2SO4 ; 2NaBH4 + 2H3PO4   B2H6 + 2H2 + 2NaH2PO4
453 K
(vii) 2BF3 + 6NaH   B2H6 + 6NaF (Industrial method)
750 atm
(viii) B2O3 + 3H2 + 2Al   B2H6 + Al2O3
150ºC

(ix) Mg3B2 + H3PO4 
 mixture of boranes mainly, B4H10  B2H6.

 Properties :
(i) B2H6 is colourless gas and highly reactive (boiling point 183 K).
(ii) Controlled pyrolysis of diborane leads to most of the higher boranes.
It catches fire spontaneously in air and explodes with O 2.Reaction with oxygen is extremely exothermic.
B2H6 + 3O2  B2O3 + 3H2O  H = – 2160 kJ mol–1
 Mixtures of diborane with air or oxygen inflame spontaneously producing large amount of heat.
Diborane has a higher heat of combustion per unit weight of fuel than most other fuels. It is
therefore used as a rocket fuel.
  At red-heat the boranes decomposes to boron and hydrogen.
(iii) Reaction with water is instantaneous.
B2H6 + 6H2O  2B(OH)3 + 6H2
Dibroane is also hydrolysed by weaker acids (e.g. alcohols) or aqueous alkali.
B2H6 + 6ROH  2B(OR)3 + 6H2
B2H6 + 2KOH + 2H2O  2KBO2 + 6H2
(iv) Reaction with HCl replaces a terminal H with Cl.
B2H6 + HCl  B2H5Cl + H2
(v) Reaction with chlorine gives the trichloride.
B2H6 + 6Cl2  2BCl3 + 6HCl
(vi) The electron deficient 3c-2e BHB bridges are sites of nucleophilic attack.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 16
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
  Small amines such as NH3, CH3NH2 and (CH3)2NH give unsymmetrical cleavage of diborane.
B2H6 + 2NH3  [H2B (NH3)2]+ + [BH4]–
  Large amines such as (CH3)3N and pyridine give symmetrical cleavage of diborane.
2(CH3)3N + B2H6  2H3B  N(CH3)3
  B2H6 + 2Me3P  2Me3PBH3
  200ºC, 20 atm
B2H6 + 2CO   2BH3CO (borane carbonyl)
  The boronium ion products [H2BL2]+, are tetrahedral and can undergo substitution by other
bases
[H2B(NH3)2]+ + 2PR3   [H2B(PR3)2]+ + 2NH3

  The reaction with ammonia depends on conditions.

 B2H6.2NH3 or [H2B(NH3)2]+ [BH4]– (ionic compound).
Excess NH3
B2H6 + NH3 
low temperature
Excess NH3
  (BN)x boron nitride.
higher temperature ( 200ºC)
Ratio 2NH3 : 1 B2H6
 
 B3N3H6 borazine.
higher temperature (200ºC)
Borazine is much more reactive than benzene. Borazine readily undergoes addition reactions which do
not occur with benzene. Borazine also decomposes slowly and may be hydrolysed to NH 3 and boric
acid at elevated temperature. If heated with water, B3N3H6 hydrolyses slowly.
B3N3H6 + 9H2O  3NH3 + 3H3BO3 + 3H2O
(vii) Reduction of diborane can be accomplished with sodium or with sodium borohydride.
  2B2H6 + 2Na  NaBH4 + NaB3H8
  B2H6 + NaBH4  NaB3H8 + H2.
  Reductions of diborane with NaBH4 can also lead to higher borane anions.
  2NaBH4 + 5B2H6  Na2B12H12
(viii) B2H6 + 2LiH  2LiBH4

Ex-6. Complete the following reactions and identify the products formed.
NaBH4
 (A)   (B)
140ºC
(a) BCl3 + NH4Cl 
C6H5Cl
17001800ºC
(b) BCl3 + H2 + Cfibre   product(s)
NaBH4
 B3N3H3Cl3   B3N3H6 (borazine)
140ºC
Sol. (a) 3BCl3 + 3NH4Cl 
C6H5Cl
17001800ºC
(b) 4BCl3 + 6H2 + Cfibre   B4C(fibre) + 12 HCl

Aluminium Hydride (AlH3) :

Aluminium hydride is obtained by interaction of LiAlH4 with100% H2SO4 in THF :
2LiAlH4 + H2SO4   2AlH3 + 2H2 + Li2SO4
The white hydride is thermally unstable. With donor ligands however, a range of molecular complexes
AlH3L & AlH3L2 are formed indicative of the lewis acidic behaviour of AlH3.
Hydrides of carbon :
Carbon forms a vast number of chain and ring compounds including :
 The alkanes (Paraffins) CnH2n+2  The alkenes (olefines) CnH2n
 The alkynes (acetylenes) CnH2n–2  Aromatic compounds
Silanes
SiH4 (monosilane)
160 ºC
(1) small scale preparation : SiO2 + LiAlH4   SiH4
(2) Hydrolysis of Magnesium silicide
Mg2Si + H2O  mixture of silanes
(3) Reduction of chlorosilanes by LiAlH4 to produce silane
(4) Photolysis of SiH4–H2 mixture can make higher silanes
(5) Among silanes only SiH4 & Si2H6 are indefinitely stable at 25°C.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 17
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Section (G) : Halides
Halides, Alums and Other metal salts :
Boron Halide :
Boron trihalides are strictly monomeric, trigonal planar molecules. This difference from aluminium is
attributed to back-donation from “nonbonding” electrons on halogen atoms into the “empty” p z orbital of
boron which lends some double bond character to B–X bonding (manifested by bond shortening) and
stabilizes the monomer.
Aluminium Chloride (AlCl3.6H2O) :
It is a colourless crystalline solid, soluble in water. It is covalent. Anhydrous AlCl 3 is a deliquescent
white solid.
 Preparation :
(i) By dissolving aluminium, Al2O3, or Al(OH)3 in dilute HCl :
2Al + 6HCl  2AlCl3 + 3H2 Al2O3 + 6HCl  2AlCl3 + 3H2O; Al(OH)3 + 3HCl  AlCl3 + 3H2O
The solution obtained is filtered and crystallized when the crystals of AlCl 3.6H2O are obtained.
(ii) Anhydrous AlCl3 is obtained by the action of Cl2 on heated aluminium.
(iii) By heating a mixture of Al2O3 and coke and passing chlorine over it.
Al2O3 + 3C + 3Cl2  2AlCl3 (anhydrous) + 3CO
 Properties :
(i) Action of heat : Hydrated salt when heated strongly is converted to Al 2O3.

2AlCl3.6H2O   Al2O3 + 6HCl + 3H2O
(ii) Action of moisture on anhydrous AlCl3: When exposed to air, anhydrous AlCl3 produces white
fumes of HCl.
AlCl3 + 3H2O Al(OH)3 + 3HCl
(iii) Action of NH3 : Anhydrous AlCl3 absorbs NH3 since the former is a Lewis acid.
AlCl3 + 6NH3  AlCl3.6NH3 (white solid)
(iv) Action of NaOH solution: When NaOH solution is added dropwise to an aqueous AlCl3 solution, a
gelatinous precipitate of Al(OH)3 is first formed which dissolves in excess of NaOH solution to give a
colourless solution of sodium meta-aluminate.
AlCl3 + 3NaOH  Al(OH)3 + 3NaCl; Al(OH)3 + NaOH  NaAlO2 + 2H2O
This reaction is important as a test to distinguish between an aluminium salt from salts of Mg, Ca, Sr,
and Ba. (When NaOH solution is added to their salt solutions, a white precipitate of hydroxide forms
which does not dissolve in excess of NaOH).
(v) Action of NH4OH solution: When NH4OH solution is added to a solution of AlCl 3, a white
precipitate of Al(OH)3 is formed which does not dissolve in excess of NH4OH.
AlCl3 + 3NH4OH  Al(OH)3(white gelatinous) + 3NH4Cl
This reaction is important as a test to distinguish an Al salt from a Zn salt. (With a Zn salt a white
precipitate of Zn(OH)2 is formed which dissolves in excess of NH4OH solution).
(vi) Hydrolysis with water: When AlCl3 is dissolved in water, it undergoes hydrolysis rapidly to
produce Al(OH)3 which is a weak base and HCl which is a strong acid. Hence the solution is acidic to
litmus.
[Al(H2O)6]3+ [Al(H2O)5OH]+2 + H+
The complex cation has a high tendency to get dimerised.
2[Al(H2O)5OH]2+  [(H2O)4 (H2O)4 ]+4 + 2H2O
(vii) 4LiH + AlCl3  LiAlH4 + 3LiCl
 Uses :
(i) As catalyst for cracking of petroleum.
(ii) As catalyst in Friedel-Crafts reactions.
(iii) For preparing aluminium compounds.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 18
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)

Ex-7. What happens when :

(write chemical equations only)
(a) Anhydrous AlCl3 is exposed to atmosphere.
(b) AlCl3 dissolves in aqueous sodium hydroxide (excess)

Sol. (a) AlCl3 + 3H2O  Al(OH)3 + 3HCl (HCl fumes in air).

(b) AlCl3 + 3NaOH  Al(OH)3+ 3NaCl
Al(OH)3 + OH–  [Al(OH)4]–
Ex-8. Anhydrous AlCl3 cannot be prepared by heating hydrated salt. Why ?
Sol. Gets hydrolysed forming Al2O3.

2AlCl3.6H2O   Al2O3 + 6HCl + 3H2O

Alums ; M2SO4. M2 (SO4)3. 24H2O or MM (SO4)2. 12H2O

Alums are transparent crystalline solids having the above general formula where M is almost any
univalent positive cation (except Li+ because this ion is too small to meet the structural requirements of
the crystal) and M’ is a trivalent positive cation (Al 3+, Ti3+, V3+, Cr3+, Fe3+, Mn3+, Co3+, Ga3+ etc.). Alums
contain the ions [M(H2O)6]+, [M’(H2O)6]3+ and SO42– in the ratio 1 : 1 : 2. Some important alums are :
(i) Potash alum K2SO4.Al2(SO4)3.24H2O (ii) Chrome alum K2SO4.Cr2(SO4)3.24H2O
(iii) Ferric alum K2SO4.Fe2(SO4)3.24H2O (iv) Ammonium alum (NH4)2SO4.Al2(SO4)3.24H2O
Alums are double salts which when dissolved in water produce metal ions (or ammonium ions) and the
sulphate ions.
 Preparation :
A mixture containing solutions of M2SO4 and M’2(SO4)3 in 1 : 1 molar ratio is fused & then the resulting
mass is dissolved into water. From the solution thus obtained, alums are crystallised.
 Uses :
(i) As a mordant in dye industry. The fabric which is to be dyed is dipped in a solution of the alum and
heated with steam. Al(OH)3 obtained as hydrolysis product of [Al(H2O)6]3+ deposits into the fibres and
then the dye is absorbed on Al(OH)3.
(ii) As a germicide for water purification
(iii) As a coagulating agent for precipitating colloidal impurities from water.

Ex-9. List the cations which are capable of replacing aluminium in alums ?
Sol. Cations of about the same size as that of Al3+ such as Ti3+, Cr+3, Mn+3, Fe3+ and Co3+ are capable of
replacing aluminium in alums.
Carbon Halides :
CF4 (Carbon tetrafluoride)
It is an extraordinarily stable compound.

 Lab preparation : SiC + F2   SiF4 + CF4
 No hydrolysis is possible.
CCl4 (Carbon tetrachloride)
Common solvent, fairly readily decomposed photo chemically.
 Although it is thermodynamically unstable with respect to hydrolysis, the observe of acceptor orbitals
carbon makes the attack very difficult.
CBr4 (Carbon tetrabromide)
Pale yellow solid at room temperature.
 Insoluble in water, soluble in non-polar solvent.
CI4 (Carbon tetraiodide)
Bright red, crystalline material.
 odor like that of iodine.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 19
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
p-Block Elements (B & C family)
Stannous Chloride (SnCl2·2H2O) :
 Preparation :
(i) Sn + 2HCl (concentrated)  SnCl2(aq) + H2
(ii) SnO + 2HCl  SnCl2(aq) + H2O
The solution on crystallization gives colourless crystals of SnCl 2·2H2O.
 Properties :
(i) It is a colourless solid soluble in water. It is soluble in alcohol and ether also.
(ii) It is a stronger reducing agent.
(a) Reaction with Hg2Cl2 solution: When SnCl2 solution is added to an aqueous solution of mercuric
chloride, a silky white precipitate of mercurous chloride, Hg2Cl2 is formed which turns black due to
further reduction of Hg2Cl2 to black mercury.
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4 ; Hg2Cl2 + SnCl2  2Hg + SnCl4
(b) It reduces ferric chloride, FeCl3 to ferrous chloride, FeCl2.
2FeCl3 + SnCl2  2FeCl2 + SnCl4
(c) It also reduces CuCl2 to CuCl (white).
(iii) SnCl2 partially hydrolyses in water forming the basic chloride, Sn(OH)Cl.
SnCl2 + H2O  Sn(OH)Cl (white) + HCl
As it produces a weak base and strong acid its aqueous solution is acidic. Its hydrolysis can be
prevented by adding concentrated HCl to it during the process of its preparation.
 Uses :
(i) In dye industry as a reducing agent.
(ii) For the test of mercuric salt.
(iii) For the preparation of other stannous compounds.
Stannic Chloride (SnCl4) :
 Preparation :
(i) By the action of Cl2 gas on heated Sn, Sn + 2Cl2  SnCl4
(ii) By the action of Cl2 on stannous chloride, SnCl2 + Cl2  SnCl4
 Properties :
(i) It is a colourless fuming liquid ; boiling point is 114ºC.
(ii) Action of moisture: It absorbs moisture and becomes converted into hydrated stannic chlorides,
SnCl4·3H2O, SnCl4·5H2O, SnCl4·6H2O and SnCl4·8H2O.SnCl4. 5 H2O is known as “butter of tin” or
“oxymercurate of tin”.
(iii) Hydrolysis with water : It hydrolyses in dilute solution but it is incomplete and can be repressed in
presence of halogen acid.
SnCl4 + 4H2O  Sn(OH)4 + 4HCl ; Sn(OH)4 + 4HCl  SnCl4 + 4H2O ;
SnCl4 + 2HCl  H2SnCl6 (stannic acid)
(v) In presence of ammonium chloride, it forms ammonium salt of H2SnCl6 (stannic acid).
SnCl4 + 2 NH4Cl  (NH4)2SnCl6
 Uses :
For the preparation of stannic compounds.

Lead Chloride (PbCl2) :

 Preparation:
Pb(OH)2·PbCO3 (basic lead carbonate) + 4HCl  2PbCl2 + CO2 + 3H2O
 Properties :
It is a white crystalline solid, insoluble in cold water but soluble in boiling water. It dissolves in
concentrated HCl forming a complex ion.
2 HCl + PbCl2 H2PbCl4 (chloroplumbous acid)
 Uses :
It is used for making pigments for paints.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 20
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Lead Tetrachloride (PbCl4) :
 Preparation :
It is prepared by the following methods:
(i) By dissolving PbO2 in cold concentrated HCl
PbO2 + 4HCl  PbCl4 + 2H2O
PbCl4 dissolves in excess of HCl to form a stable solution of H2PbCl6.
PbCl4 + 2HCl  H2PbCl6
 When NH4Cl is added to a solution of chloroplumbic acid, a yellow precipitate of ammonium
chloroplumbate is formed.
H2PbCl6 + 2NH4Cl  (NH4)2PbCl6 + 2HCl
 When crystals of ammonium chloroplumbate is added to ice cold concentrated H 2SO4, lead
tetrachloride is formed and separates as a yellow oily liquid.
(NH4)2PbCl6 + H2SO4   PbCl4 + (NH4)2SO4 + 2HCl
(ii) By the action of Cl2 on a solution of PbCl2 in concentrated HCl
PbCl2 + Cl2   PbCl4

 Properties :
(i) It is a yellow oily liquid which solidifies at –10oC and is soluble in organic solvents like ethanol and
benzene.
(ii) Rapid hydrolysis with water forms PbO2 precipitate
PbCl4 + 2H2O   PbO2 + 4HCl
 Uses :
It is used for making stannic compounds.

Carbonates (CO32–) and Bicarbonates (HCO3–)

Carbonic acid is a dibasic acids giving rise to two series of salts, carbonates (normal salts) and
bicarbonates (acid salts) due to successive removal of the replaceable hydrogens from H 2CO3.
H2CO3 + NaOH   NaHCO3 + H2O ; NaHCO3 + NaOH   Na2CO3 + H2O

 Preparation :
(i) With NaOH : 2NaOH + CO2   Na2CO3 ; Na2CO3 + H2O + CO2 
 2NaHCO3
(ii) By precipitation : BaCl2 + Na2CO3  BaCO3  + 2NaCl

SiCl4, Silicones, Silicates & Zeolites :

Silicones :
Silicones are synthetic organosilicon compounds having repeated R 2SiO units held by Si–O–Si
linkages. These compounds have the general formula (R2SiO)n where R = alkyl or aryl group.
The silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes and their
subsequent polymerisation. The alkyl or aryl substituted chlorosilanes are prepared by the following
reactions.
Cu
(a) RCl + Si   R3SiCl + R2SiCl2 + RSiCl3
300ºC

(b) RMgCl + SiCl4  RSiCl3 + MgCl2

2RMgCl + SiCl4  R2SiCl2 + 2MgCl2
3RMgCl + SiCl4  R3SiCl + 3MgCl2

After fractional distillation, the silane derivatives are hydrolysed and the ‘hydroxides’ immediately
condense by intermolecular elimination of water. The final product depends upon the number of
hydroxyl groups originally bonded to the silicon atom:

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 21
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)

In this manner several molecules may combine to form a long chain polymer whose both the ends will
be occupied by –OH groups. Such compounds are generally represented from the following formula.

The polymer chain depicted above is terminated by incorporating a small quantity of the
monochlorosilane derivative into the hydrolysis mixture.
 Silicones can be prepared from the following types of compounds only.
(i) R3SiCl (ii) R2SiCl2 (iii) RSiCl3
 Silicones from the hydrolysis of (CH3)3 SiCl
H2O
(CH3)3SiCl   (CH3)3Si(OH)

 Silicones from the hydrolysis of a mixture of (CH3)3 SiCl & (CH3)2 SiCl2
The dichloro derivative will form a long chain polymer as usual. But the growth of this polymer can be
blocked at any stage by the hydrolysis product of mono-chloro derivative.

 Silicones from the hydrolysis of trichloro derivative.

When a compound like CH3SiCl3 undergoes hydrolysis, a complex cross-linked polymer is obtained as
chain can grow in three places as

 The hydrocarbon layer along the silicon-oxygen chain makes silicones water-repellent.
 Silicones find a variety of applications because of their chemical inertness, water repelling nature,
heat resistance and good electrical insulation property.
Products having the physical properties of oils, rubbers and resins can be produced using silicones.
Silicone varnishes are such excellent insulators and so heat-resistance that insulating wiring with them
enabled motors to work over-loads that would have set fire to the insulation formerly used. Silicone
fluids are used as hydraulic systems of planes as they are thermally stable and their viscosity alters
very little with temperature. Silicone rubbers are used in placed of ordinary rubber as they retain their
elasticity at much lower temperature than ordinary rubber.

Ex-10. Complete the following reactions

ZnO  Cu
(a) CO + H2   .....................................
420670k, 300atm
(b) R3SiOH + OHSiR3 ......................... + ..............................
(c) Na2CO3 + Si  .......................... + ..............................
ZnO  Cu
Sol. (a) CO + 2H2   CH3OH
420670k, 300atm
(b) R3SiOH + OHSiR3  R3Si–O–SiR3 + H2O
(c) Na2CO3 + Si  Na2SiO3 + C

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 22
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Section (H) : Miscellaneous (Silicones, Silicates, Zeolites & Alums)
Silicates :
Binary compounds of silicon with oxygen are called silicates but they contain other metals also in their
structures.
(i) Since the electronegativity difference between O & Si is about 1.7, so Si–O bond can be considered
50% ionic & 50% covalent.
rSi4 
(ii) If we calculate the radius ratio then, = 0.29
rO2 
It suggests that the coordination number of silicon must be 4 and from VBT point of view we can say
that Si is sp3 hybridized. Therefore silicate structures must be based upon SiO 44– tetrahedral units.
(iii) SiO44– tetrahedral units may exist as discrete units or may polymerise into larger units by sharing
corners.
Classification of Silicates :
(A) Orthosilicates :
These contain discrete [SiO4]4– units i.e., there is no sharing of corners with one another as shown is
figure.

Figure : 2
e.g. Zircon (ZrSiO4), Forsterite of Olivine (Mg2SiO4), Willemite (Zn2SiO4)
(B) Pyrosilicate :
In these silicates two tetrahedral units are joined by sharing oxygen at one corner thereby giving
[Si2O7]6– units.

Figure : 3
e.g. Thorteveitite (Sc2Si2O7), Hemimorphite (Zn3(Si2O7) Zn(OH)2H2O)
  (–) charge will be present on the oxygen atoms which is bonded with one Si atom.
(C) Cyclic silicates :
If two oxygen atoms per tetrahedron are shared to form closed rings such that the structure with
general formula (SiO32–)n or (SiO3)n2n– is obtained, the silicates containing these anions are called cyclic
silicates. Si3O96– and Si6O1812– anions are the typical examples of cyclic silicates.
–
O

–
O
– – –
O O O
O O O
O – O –

–
O
O O O O

O– O– O– O
–

– – – –
O O O O O O O
O–

–
6–
O
Si3O9 Si6O1812–
Figure : 4 Figure : 5
Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 23
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
(D) Chain silicates :
Chain silicates may be further classified into simple chain & double chain compounds.
In case of simple chains two corners of each tetrahedron are shared & they form a long chain of
tetrahedron. Their general formula is also same as the cyclic silicates i.e. (SiO 3)n2n–

Figure : 6

Similarly, double chain silicates can be drawn in which two simple chains are joined together by shared
oxygen. Such compounds are also known as amphiboles. The asbestos mineral is a well known
example of double chain silicates. The anions of double chain silicates have general formula (Si4O11)n6n
O– O–

– –
O O
O O
O O O O O
O– O– O–

O O O

–
O O– O–
O O O O O O
O– O––

O– O–
Figure : 7
e.g., Synthetic silicates (Li2SiO3, Na2SiO3), Spondumene (LiAl(SiO3)2),
Enstatite (MgSiO3), Diopside (CaMg(SiO3)2 ), Tremolite (Ca2Mg5(Si4O11)2 (OH)2 ), etc.
(E) Two dimensional sheet silicates :
In such silicates, three oxygen atoms of each tetrahedral are shared with adjacent SiO 44– tetrahedrals.
Such sharing forms two dimension sheet structure with general formula (Si2O5)n2n–
e.g. Talc (Mg(Si2O5)2 Mg(OH)2 , Kaolin Al2(OH)4 (Si2O5)
(F) Three dimensional silicates :
These silicates involve all four oxygen atom in sharing with adjacent SiO 44– tetrahedral units.
e.g. Quartz, Tridymite, Crystobalite, Feldspar, Zeolite and Ultramarines.

Ex-11. Draw the structure of cyclic silicate containing Si6O1812– ion.

Sol.

Si6O1812–

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 24
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
Zeolites :
If aluminium atoms replace few silicon atoms in three-dimensional network of silicon dioxide, overall
structure known as aluminosilicate, acquires a negative charge. Cations such as Na +, K+ or Ca2+
balance the negative charge. Examples are feldspar and zeolites. Zeolites are widely used as a catalyst
in petrochemical industries for cracking of hydrocarbons and isomerisation, e.g., ZSM-5 (A type of
zeolite) used to convert alcohols directly into gasoline. Hydrated zeolites are used as ion exchangers in
softening of “hard” water.

Carborundum (SiC) :
 Preparation : electric furnace
SiO2 + 3C  SiC + 2CO
2000ºC
 Properties :
(i) It is a very hard substance (Hardness = 9.5 Moh)
(ii) On heating it does not melt rather decomposes into elements.
(iii) Not attacked by acids. However, it gives the following two reactions at high temperature.
 
SiC + 2NaOH + 2O2   Na2SiO3 + CO2 + H2O ; SiC + 4Cl2   SiCl4 + CCl4

  It has a diamond like structure in which each atom is sp 3 hybridized. Therefore, each atom is
tetrahedrally surrounded by 4 atoms of other type.

Ex-12. Write the chemical equations involved in the preparation of elemental boron from mineral colemanite.
Sol. Ca2B6O11 + 4SO2 + 11H2O   2Ca(HSO3)2 + 6H3BO3

2H3BO3  B2O3 + 3H2O ; B2O3 + 2Al   Al2O3 + 2B

Uses of boron :
(i) Boron is used in the construction of high impact-resistant steel and, since it absorbs neutrons, in
reactor rods for controlling atomic reactions.
(ii) Boron carbide is used as an abrasive.

Uses of Al :
It is extensively used :
(i) for manufacture of cooking and household utensils.
(ii) as aluminium plating for tanks, pipes, iron bars and other steel objects to prevent corrosion.
(iii) for manufacture of aluminium cables.
(iv) for making precision instruments, surgical apparatus, aircraft bodies, rail coaches, motorboats, car.
(v) Aluminates are important constituents of portland cement.

Uses of carbon : Graphite fibres embedded in plastic material form high strength, lightweight
composites. The composites are used in products such as tennis rackets, fishing rods, aircraft and
canoes. Being good conductor, graphite is used for electrodes in batteries and industrial electrolysis.
Crucibles made from graphite are inert to dilute acids and alkalies. Being highly porous and having
enormous surface area activated charcoal is used in adsorbing poisonous gases; also used in water
filters to remove organic contaminators and in air conditioning system to control odour. Carbon black is
used as black pigment in black ink and as filler in automobile tyres. Coke is used as a fuel and largely
as a reducing agent in metallurgy. Diamond is a precious stone and used in jewellery. It is measured in
carats (1 carat = 200 mg.).

Uses of silicon :
(i) Ultrapure form of germanium and silicon are used to make transistors and semiconductor devices.
(ii) Silicon is a very important component of ceramics, glass and cement.

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 25
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. Al and Ga are trivalent in their compounds but monovalent compounds are the most stable down the
13th group. Why ?
Sol. Down the group (13th), the stability of +3 state decreases and that of +1 state increases due to the
prominent "inert pair" effect.
Al3+ > Ga3+ > ln3+ > Tl3+
Most stable  least stable
Tl+ > ln+ > Ga+ > Al+
2. If you have a mixture of CO and CO2, how would you know about the relative proportions of the two
gases in the given mixture ?
Sol. (i) Pass mixture through the Ca(OH)2 solution; CO2 is absorbed by Ca(OH)2. The residual volume
will be that of CO
Ca(OH)2 + CO2  CaCO3 + H2O
(ii) Pass mixture through I2O5 ; CO reduces I2O5 to I2.
5CO + I2O5  I2 + 5CO2
I2 thus liberated is determined by titration with Na 2S2O3.
2Na2S2O3 + I2  2NaI + Na2S4O6
This is the quantitative method of estimation of CO.
3. What will happen if borontrifluoride is kept in moist air ?
(A) It will strongly fume. (B) It will partially hydrolyse.
(C) It will completely hydrolyse. (D) None of these
Ans. (A)
Sol. In moist air it strongly fume : but it is partially hydrolysed by excess of water.
4BF3 + 6H2O  3H3O+ + 3BF4– + B(OH)3
BF3 is a colourless gas.
4. What happens when : (write only chemical reactions)
(a) iodine is treated with SnCl2.
(b) carbondioxide is passed through a concentrated aqueous solution of sodium chloride saturated with
ammonia.
(c) red lead is treated with nitric acid.
(d) dilute nitric acid is slowly reacted with tin.
Sol. (a) 2SnCl2 + I2  2SnCl2I2  SnCl4 + SnI4
(b) NaCl + NH4OH + CO2  NaHCO3 + NH4Cl
(c) Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
(d) Sn + 10HNO3(dilute)  4Sn(NO3)2 + NH4NO3 + 3H2O
5. True / False
(a) BCl3 in aqueous solution exists as B3+ and Cl–.
(b) Pure crystalline boron is very unreactive and it is attacked only at high temperatures by strong
oxidising agents such as a mixture of hot concentrated H2SO4 and HNO3.
(c) AlX3 (X = Cl, Br) exists as dimer and retains dimer formula in non-polar solvents like ether, benzene
etc.
(d) Be2C is called acetylide because it reacts with water yielding ethyne.
(e) Pb3O4 a double oxide, is obtained by heating lead (II) oxide in air.
Ans. (a) False (b) True (c) True (d) False (e) True
Sol. (a) Statement is incorrect. BCl3 hydrolyses in aqueous solution to give boric acid. Because it has large
ionisation energies and to make the enthalpy of solution of BCl 3 negative, the enthalpy of hydration of
B3+ should be very high (~ 600 g kJ) which is unlikely for the small B3+ cation.
(b) 2B + 6HNO3 (aq.)  2H3BO3 (aq.) + 6NO2 (g)
(c) Statement is correct and its dimer structure is as follows. It acquires this structure for attaining an
octet of electrons. Dimer formula retains in non-polar solvent like ether, benzene

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 26
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
(d) Statement is incorrect as it is methanide because it gives methane on reaction with water.
Be2C + 4H2O  2Be(OH)2 + CH4

(e) 3PbO + O2   Pb3O4

6. Statement-1 : PbO2 is an oxidising agent and reduced to PbO.

 Statement-2 : Stability of Pb(II) > Pb(IV) on account of inert pair effect.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
Ans. (A)
Sol. Both are correct statements and statement-2 is the correct explanation of statement-1.
7. Write the chemical equations to represent the following reactions.
(a) The oxidation of HCl (aq) to Cl2 (g) by PbO2.
(b) The disproportionation of SnO to Sn and SnO2.
Sol. (a) PbO2 + 4HCl   PbCl2 + 2H2O + Cl2 (b) 2SnO   Sn + SnO2

8. What will happen if we take Si (CH3) Cl3 as a starting material for the preparation of commercial silicon
polymer ?
Sol. With Si(CH3)Cl3 the chain will grow in three places and we will get cross-linked silicon polymer as
shown below :
CH3 CH3
| |
— O — Si — O — Si — O —
| |
O O
| |
— O — Si — O — Si — O —
| |
CH3 CH3

9. Give three properties of diamond.

Sol. Diamond is very hard, high melting solid. It is an electrical insulator.
10. The silicate anion in the mineral kionite is a chain of three SiO 4 tetrahedra that share corners with
adjacent tetrahedra.The mineral also contains Ca2+ ions, Cu2+ ions, and water molecules in a 1:1:1
ratio.
(a) Give the formula and charge of the silicate anion.
(b) Given the complete formula for the mineral.
Sol. (a) The silicate anion has three SiO4 tetrahedra that share corners with adjacent tetrahedra thus silicate
is Si3O10, hence it can be represented as with charge as = 3 × 4n + 10 × (–2) = –8
8–
 O O O 
 | | | 
O — Si — O — Si — O — Si — O
 | | | 
 O O O 

(b) Ca2+, Cu2+ and H2O are in the ratio of 1 : 1 : 1 and to balance (–8) charge of silicate as ion, (+8)
charge is required thus there are two units each of Ca2+, Cu2+ and H2O thus, kinoite has formula
Ca2Cu2Si3O10.2H2O.

11. In what respect the reaction of N2 with (i) CaC2 (calcium carbide) & (ii) BaC2 (barium carbide) differ from
each other.
Sol. (i) CaC2 reacts with N2 to form calcium cyanamide.
1373K
CaC2(s) + N2(g)   CaCN2(s) + C(s)
Calcium cyanamide
(ii) BaC2 reacts with N2 to form barium cyanide
Heating
BaC2(s) + N2(g)   Ba(CN)2 (s)
Barium cyanide

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 27
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029
 p-Block Elements (B & C family)
12. Statement-1 : The thermal stability of hydrides of carbon family is in order :
CH4 > SiH4 > GeH4 > SnH4 > PbH4
 Statement-2 : E—H bond dissociation enthalpies of the hydrides of carbon family decrease down the
group with increasing atomic size.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
Ans. (A)
Sol. Both are correct statements and statement-2 is the correct explanation of statement-1. Down the group
the size of atom increases and thus bond length increases.
13. Which one of the following element does not dissolve in fused or aqueous alkalies?
(A) Boron (B) Silicon (C) Aluminium (D) None of these
Ans. (D)
Sol. Boron dissolved in fused alkalies according to the following reaction.
fused
2B + 6NaOH   2Na3BO3 + 3H2
Silicon and aluminium dissolved in both fused and aqueous alkalies.
14. What happens when CO2 (g) is passed through sodium meta borate solution ?
Sol. 4NaBO2 + CO2   Na2B4O7 + Na2CO3

15. Which of the following statement(s) is/are correct ?

(A) B2O3 and SiO2 are acidic in nature and are important constituents of glass.
(B) Borides and silicide are hydrolysed by water forming boranes and silanes respectively.
(C) Diborane on reaction with chlorine (g) forms B2H5Cl.
(D) SiO44– gets hydrolysed by acid or water and form Si2O76–.
Ans. (A), (B) and (D)
Sol. (A), (B) and (D) are correct statements but (C) is incorrect.
B2H6 + 6Cl2   2BCl3 + 6HCl
16. Match the following :
Column-I Column-II
(A) Boron (p) Forms acidic oxides.
(B) Carbon (q) Pure crystalline form is obtained by Van Arkel method.
(C) Tin (r) Exists in allotropic forms.
(D) Aluminium (s) Hydroxide is amphoteric in nature.
Ans. (A - p,q,r); (B - p,r) ; (C - r,s) ; (D - s)
Sol. (A) Exists in various allotropic forms and its oxide, B2O3 is acidic in nature.
red hot W
2BI3   2B + 3I2
Van Arkel method
 (B) Exists in various allotropic forms like diamond, graphite etc. and its oxide CO 2 is acidic in nature.
 (C) Exists in allotropic forms like grey tin (-Sn) and white tin (-Sn). Hydroxide is amphoteric in nature.
Sn(OH)4 + 2OH–   [Sn(OH)6]2–
Sn(OH)4 + 4H+   Sn4+ + 4H2O
 (D) Hydroxide is amphoteric in nature.
Al(OH)3 + OH–   [Al(OH)4]–
Al(OH)3 + 3H+   Al3+ + 3H2O

Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) - 324005
Website : www.resonance.ac.in | E-mail : contact@resonance.ac.in
ADVPBC - 28
Toll Free : 1800 258 5555 | CIN: U80302RJ2007PLC024029