P- BLOCK ELEMENTS

P- BLOCK ELEMENTS
GROUP 13 ELEMENTS
Physical Property
 Boron to indium show +3 oxidation state in their compounds while thallium show +1
oxidation state (due to inert pair effect) in their compounds. Relative stability of
M+ and M3+ ions may be given as:
B+ < Al+ < Ga+ < In+ < Tl+
B3+ > Al3+ > Ga3+ > In3+ > Tl3+

Chemical Properties
 Action of air:
4M + 3O2   2M2O3
Reaction occurs at high temperature. With Al, a protective oxide layer is formed which
makes it passive. Tl also forms Tl2O. Ga2O3, In2O3 also form.
 Action of Water:
2M + 3H2O   M2O3 + 3H2
Boron is not affected by water. It reacts with steam at red hot. Al decomposes cold water
if it is not passive by oxide layer formation. Ga and In are not attacked by cold or hot water
unless oxygen is present. Tl reacts with moist air to form TlOH.
 Action of nitrogen : 2M + N2   2MN
 Action of halogen : 2M + 3X2 
 2MN3

All the group 13 elements form trihalide except Tl. Tl from TlX. TlI reacts with I2 and form
TlI3 (Tl+ I3–)
 Action of acids : 2M + 6H+   2M + 3H2
3+

Boron is not affected by non-oxidizing acids like HCl and dilute H2SO4 while other elements
dissolve to form trivalent salts.
3Mg + 2B   Mg3B2
Mg3B2 + 6HCl   3MgCl2 + B2H6
The rest of the elements do not combine with metals. This shows that boron is a non-
metal and rest of the elements are metal.

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 P- BLOCK ELEMENTS

Important Compounds of Group 13 Elements

Boron is known to exist in two form (a) amorphous and (b) crystalline.
Amorphous boron is obtained by reduction of B2O3 with Na or K and Mg at high temperature
in a covered crucible.
Crystalline form is obtained by the reduction of B2O3 with Al-powder.
Crystalline boron is black and chemically inert in nature. It is very hard. Amorphous boron
is brown and chemically active. Boron is used as a deoxidiser in the casting of copper and
for making boron steel which are used as control rods in nuclear reactors.

 Hydrides
Boron forms a number of stable covalent hydrides called diboranes with general formula
BnHn+4 (Called nido boranes) and BnHn+6 called arachno boranes, less stable).
Aluminium forms a polymeric hydride called alane /alumane with general formula (AlH3)n.
Ga forms Ga2H6 and In forms (InH3)n. Tl does not form hydrides.

 Oxides and hydroxides

The members of boron family form oxides and hydroxides of the general formula M2O3 and
M(OH)3 respectively.
Oxides : B2O3 > Al2O3 > Ga2O3 > In2O3 > Tl2O3 (stability)
Hydroxides : B(OH)3 > Al(OH)3 > Ga(OH)3 > In(OH)3 > Tl(OH)3 (stability)
Nature : Acidic Amphoteric Amphoteric Basic Strongly Basic

 Halides :
BX3 is electron deficient so behaves as a Lewis acid.
BX3 +:NH3 
 [H3N   BX3]
Lewis acid Lewis base Adduct

Relative Lewis acid strength of boron halides are as follows:

Bl3 > BBr3 > BCl3 > BF3 (due to ppback bonding)
In BF3, each F has completely filled unutillised 2p orbitals while B has a vacant 2p-orbital.
Now since both of these orbitals belong to same energy level (2p) they can overlap
effectively as a result of which electrons of B resulting in the formation of an additional
ppbond. This type of bond formation of back as dative or back bonding. Formation of
back bonding between B and F in BF3 molecule as given below figure.

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 P- BLOCK ELEMENTS

Completely filled 2p-orbital of fluorine

Vecant 2p-orbital of boron

F F
+ –
F B F B

F F

As a result of back donation of electrons from F to B, the electron deficiency of B is reduced

and Lewis acid character is decreased. the tendency for the back bonding is maximum in
BF3 and decreases from BF3 to Bl3. Thus Bl3, BBr3 and BCl3 are stronger Lewis acids then
BF3.

Anomalous Behaviour of Boron :

Boron shows anomalous behaviour due to its small size, high nuclear charge, high
electronegativity and non-availability of d-orbitals.

IMPORTANT COMPOUNDS OF BORON

Boric acid (H3BO3)

 Preparation :
(a) From borax (Na2B4O7. 10H2O):
Boric acid can be prepared by adding a hot concentrated solution of borax to a calculated
quantity of conc. H2SO4. The solution on cooling gives crystals of boric acid, which can be
separated by filtration.
Na2B4O7 + H2SO4 + 5H2O  Na2SO4 + 4H3BO3 
(boric acid)

(b) From colemanite (Ca2B6O11.5H2O):

Ca2B6O11 + 4SO2 + 11H2O  2Ca(HSO3)2 + 6H3BO3 

 Properties :
(a) Action of heat:
o o
H3BO 3 
100 C
–H2 0
 HBO 2 
160 C
–H2 O
 H2B 4 O 7 
redhot
–H2 O
 B2O 3
boric acid meta boric acid tetra boric acid boron trioxide

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 P- BLOCK ELEMENTS

(b) Reaction with alcohol (test of boric acid):

H3BO3 + 3(C2H5OH)  B(OC2H5)3 + 3H2O
Triethyl borate (volatile)
Borax (Na2B4O7.10H2O) or Na2[B4O5(OH)4].8H2O

 Properties :
(i) Its solution is basic in nature due to hydrolysis.
Na2B4O7 + 7H2O  2NaOH + 4H 3BO 3
Strong base weak acid

Na2B4 O7 
o
740 C
 2NaBO2 +B2O3
(ii) Na2B4O7. 10H2O 

–10H 2 0 anhydrous  
(Swell up) (transparent glassy bead)

(iii) Borax bead test : Borax on strong heating forms B2O3 which forms coloured glassy bead
with coloured compounds of certain metals. It is called borax bead test.
Cr Mn
Colour of beads Green Fe Co Ni Cu
Pink Green Blue Brown Blue

eg. Cu(BO 2 )2
Blue bead

Dibrorane (B2H6)

 Preparation :
(i) 3Mg + 2B 
Δ H3PO4
Mg3B2  
Mixture of boranes  B2H6
diborane

o
(ii) B2O3 + 3H2 + 2Al 
150 C
pressure
B2 H 6 + Al2O3

(iii) 2BF3 + 6NaH 

180o C
 B2H6 + 6NaF

 Properties :
(i) Reaction with ammonia:

B2H6.2NH3 
low
 B2H6  NH3 
temperature
high
temperature
 (BN) n
(excess) Inorganic graphite
or Borazone

[BH2(NH3)2]+[BH4]–or B2H6 + NH3 

highTemperarure B3N3H6
 (borazine)
Ratio 1:2
(ii)Reaction with amine :
BH2 6 +2 Me3N  [N Me3 3  2BH3 ]
(Lewis acid) (Lewis base) adduct

– Borazine is known as inorganic benzene.

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 P- BLOCK ELEMENTS

Anhydrous AlCl3 is prepared by passing dry HCl or Cl2 gas over heated aluminium turnings
in absence of air. It is also obtained by passing Cl2 gas over heated mixture of Al2O3 and
coke. It is used as a catalyst in Friedel - Craft’s reaction. The molecule is an autocomplex
and is represented as:
Cl Cl Cl

Al Al

Cl Cl Cl
Anhydrous AlCl3 is a Lewis acid. Anhydrous form is covalent while hydrated AlCl3.6H2O is ionic.

ALUMS
Alums are the double sulphates of the type M2SO4. M2(SO4)3. 24H2O where M is a univalent
cation like Na+, K + and NH4+and M’ is a trivalent cation like Al3+, Fe3+ and Cr3+.

Potash alum K2SO4. Al2(SO4)3. 24H2O

Sodium Na2SO4. Al2(SO4)3. 24H2O
Ferric alum (Na4)2SO4. Fe2(SO4)3. 24H2O
Ammonium alum (NH4)Al(SO4)2. 12H2O
Chrome alum K2SO4. Cr2(SO4)3. 24H2O

Ultramarine is an artifical Lapis-Lazuli, a rare mineral (Na3Al3Si3S3O12) which has fine blue
colour. It is used in making blue paint.
Precious stones such as sapphire, ruby, topaz etc., are Al2O3 containing oxides of transition
metals.

(GROUP 14 ELEMENTS)
PHYSICAL PROPERTIES
Stability order
C+4 > Si+4 > Ge+4 > Sn+4 > Pb+4
C +2 < Si 2+ < Ge +2 < Sn 2+ < Pb 2+
(due to inert pair effect)
I.P. order
C > Si > Ge > Sn < Pb
(due to lanthanoid contraction)
Catenation C >> Si > Ge = Sn = Pb
Except lead, all other elements of this group show allotropy. Diamond, fullerene and graphite
are allotropes of carbon.

CHEMICAL PROPERTIES
Action of air:
(i) Monoxides : 2M + O2 
 2MO
CO,SiO, GeO, SnO, PbO
eg. unstable

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 P- BLOCK ELEMENTS

(ii) Dioxides : M + O2 
 MO2
Acidic Nature

 Action of water :
Si, Ge and Pb are unaffected by H2O.
Sn + 2H2O (steam)   SnO2 + 2H2O

 Action of acids : Non-oxidising acids do not attack C and Si, Ge is not attacked by dilute
HCl. When Ge is heated in a steam of HCl gas, germanium chloroform is formed.
Sn dissolves slowely in dilute HCl but readily in concentrated HCl.
Pb dissolves in conc. HCl forming chloroplumbous acid, but the reaction stops after sometime
due to deposition of PbCl2.

 Action of alkali : C is unaffected by cold alkali, Si reacts slowly with cold aqueous NaOH
and readily with hot NaOH forming silicate. Sn and Pb form stannate and plumbate
respectively on reaction with hot alkali.

Important compounds of group 14 elements :

 HYDRIDES : MH4 (General formula)
CH4 Methane On moving top to bottom
SiH4 Silane  Bond length increases
GeH4 Germane  Thermal Stability decreases
SnH4 stanane  Acidic nature increases
Pbh4 Plambane  reducing Nature incresaes

 Halides :
All the element forms covalent halides, MX4 (except PbBr4 and Pbl4) the thermal stability of
halide decreases as:

CX4 > SiX4 > GeX4 > SnX4 > PbX4.

MF4 > MCl4 > MBr4 > Ml4
The halides are readily hydrolysed by water (except CX4, due to absence of d-orbital). the
order of ease of hydrolysis is

SiCl4 > GeCl4 SnCl4 > PbCl4.

Degree of hydrolysis  covalent character.
 Carbides :
The binary compounds of carbon with elements other than hydrogen are called carbides.

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 Ionic carbides are formed by the most electropositive metals such as alkali and alkaline
earth metals and Al. both Be2C and Al4C3 are called methamides because they react with
H2O yielding methane.
Covalent carbides are formed by metalloids like Si and B. SiC (carborundum) has a diamond
like structure, hence it is called artificial diamond. B4C (Norbide) is hardest known artificial
substance.Interstitial carbides are formed by transition elements in which C-atoms occupy
tetrahedral holes in the close-packed metal atoms. W, Zr, Ti and Mo can form ideal intersitial
carbides.

 Silicones :
Silicones are polymeric organo-silicon compounds contaning Si-O-Si linkages. The name
silicon has been given from similarity of their empirical formula (R2SiO) with ketones (R2O)
Silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes and their
subsequent polymerisation.
Cu powder
2RCl+Si 570K
 R SiCl
2 2
dialkyldichloro silane

–HCl  2
H2O
R2SiCl2   R Si(OH)2  
–H2O


Silicones have good thermal, oxidative stability. These are excellent water repellants and
chemically inert substances. Liquid silicones are used as excellent lubricants.
Silicates: Silicates are metal derivatives of silicic acid [H4SiO4 or Si(OH)4]. Silicates are
made up of SiO44– tetrahedral units in which Si is sp3 hybridised and is surrounded by four
oxygen atoms.
All these elements combine with halogens forming corresponding halides.
Note: Boron and aluminium combine with nitrogen and carbon on heating to form nitride,
carbide respectively.
Types of Silicates :
(A) Orthosilicates :
4–
These contain discrete [SiO4] units i.e., there is no sharing of corners with one another
as shown is figure.

e.g. Zircon (ZrSiO4), Forsterite of Olivine (Mg2SiO4), Willemite (Zn2SiO4)

(B) Pyrosilicate :

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 In these silicates two tetrahedral units are joined by sharing oxygen at one corner thereby
giving [Si2O7]6– units.

e.g. Thorteveitite (Sc2Si2O7), Hemimorphite (Zn3(Si2O7) Zn(OH)2H2O)

(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.

–
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 12–
Si3O9 Si6O18

(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. (SiO3)n2n–

(E) Two dimensional sheet silicates :

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 In such silicates, three oxygen atoms of each tetrahedral are shared with adjacent SiO44–
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 SiO44– tetrahedral
units.
e.g. Quartz, Tridymite, Crystobalite, Feldspar, Zeolite and Ultramarines.

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