Chapter 1 Chemistry of P-block Elements

1.1 Group 13

1.1.1 Preparation and structure of diborane B2 H6

1. 8 BF3 + 6 LiH −−→ B2 H6 + 6 LiBF4
Δ
2. 2 BF3 + 6 NAH −−→ B2 H6 + 6 NAF
3. 4 BCl3 + 3 LiAlH4 −−→ 2 B2 H6 + 3 LiAlCl4

1.1.2 Structure :
1. Diborane B2 H6 and Ethane C2 H6 both are covalent compounds. Hence, it was proposed that the
structure of diborane was similar to Ethane. In Ethane 14 valence elections, but in diborane there are
only 12 electrons. Hence, diborane could not possess Ethane like structure.
H H H H

H C C HH B?B H

H H H H
2. Hydrogen bridge like structure proposed for diborane.

a. Raman and IR suggested two types of B – H bonds in diborane

b. On Methylation diborane gives teramethyl diborane indicating that two hydrogen atoms are differ-
ently linked.
Thus four hydrogen atoms are linked with two B atoms by normal covalent bonds. These lie in the
same plane.
c. Electron diffraction and X-ray studies indicates that two B atoms are linked through Hydrogen
atoms by bridge like structure. One H atom lies above the plane and second H atom lies below
the plane.
Thus the structure of diborane is
H H H

B B

H H H
d. Molecular orbital theory structure : In diborane B undergoes SP3 hybridisation. In this three SP3 hy-
brid orbitals are occupied by single electron and fourth SP3 is vacant.Half filled SP3 hybrid orbital
of one B atom, vacant SP3 hybrid orbital of another B together overlaps with half filled S orbital of
Hydrogen atom to form delocalized molecular orbitals, which contain two electrons three centre
bond.

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1.2. GROUP 14 CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS

This B – H – B,bridge three centre two electron bonds are also called Banana bonds or tau bond.

1.1.3 Borazole (or) Borazine (or) Inorganic Benzene (B3 N3 H6 )

120 ◦C
3 BH2 H6 + 6 NH3 −−−→ 2 B3 N3 H6 + 12 H3
Borazole structure is similar to Benzene. It is a planar molecule, in which B and N atom are Sp2 hy-
bridised. In borazole, n− bonding is dative , it forms by overlapping of empty P− orbitals of boron, with
filled P−orbitals of Nitrogen

1.2 Group 14

1.2.1 Preparation , properties and uses of Silicones

Silicones are orgonosilicon polymers containing Si – O – Silinkages. They may be linear, cyclic or cross
linked polymers.

CH3 Mgcl + SiCL4 −−→ CH3 SCl3 + Mgcl2

Methyl trichloro silane

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CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS 1.2. GROUP 14

2 CH3 Mgcl + SiCl4 −−→ (CH3 )2 SCL2 + 2 MGCL2

Dimethyl trichlorosilane
(a) Linear Silicones:
CH3 Cl CH3 OH
H2 O
Si −−→ Si

CH3 Cl CH3 OH
This polymerises to form linear silicone
CH3 CH3 CH3 CH3 CH3

O S O S O S O S O S

CH3 CH3 CH3 CH3 CH3

Liner Silicone

(b) Cyclic Silicones: These are formed when H2 O is eliminated from the terminal – OH groups.

(c) Cross linked Silicones : Hydrolysis of alkyl trichloro silane (CH3 Sicl3 ) undergoes polymerisation to
give cross linked silicones.
CH3 CH3

Cl Si Cl OH Si OH
+ H2 O

Cl OH
methyl trichlorosilane methyl silantriol
CH3 CH3 CH3

O Si O Si O Si

CH3 CH3
CH3 O CH3

O Si O Si O Si

CH3 CH3 CH3

1.2.2 Properties and uses of Silicones :
Silicones are intermediate between organic compounds and Sio2, thus they are oily and unreactive even
at high temp. They are durable and chemically inert. They are non-toxic. They possess good electrical
insulating power and water repellents. Hence, silicones are like fluids, greases, resins or rubbers.

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1.3. GROUP – 15 CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS

O CH3

CH3 Si O Si O
OH

O O
n CH3 Si OH

CH3 Si O Si CH3
OH

O O
Crossed linked silicone

1. Silicones are used to form water resistant coatings on glass, cloth, paper etc.,
2. Silicone resins are mixed with glass fibre for additional strength and used for coating electrical wires
to give water proof and high temperature insulation.
3. These are used for non-stick coatings for pans, used in paints and varnishes
4. Silicone fluids are water repellent and used as hydraulic fluids.
5. Also used in water proofing textiles, lubricants, as mould releasing agents, polishes, and antifarming
agents.

1.3 GROUP – 15

1.3.1 Preparation and structure of phosphonitrilic halides (PNCl2 )n where n = 3, 4

Phosphonitrilic compounds are the compounds of phosphorous and Nitrogen with a p−bond.

Ex:(PNCl2 )3 and (PNCl2 )4

Prepartion

1. Ammonolysis of

n PCl5 + n NH3 −−→ (PNCl2 )n + 3 n HCl

2. PCl5 is heated with NH4 Cl at 145◦ ˘160◦ c

n PCl5 + n NH4 Cl −−→ (PNCl2 )n + 4 n HCl

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CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS 1.4. GROUP 16

Structure :-
PhosphoNitrilic chlorides are having ring structures as in Benzene, but the reactivity of π˘ bond is dif-
ferent.
(PNCl2 )3 :-Trimer is having planar ring structure, ‘P’ undergoes SP3 hybridisation. The two chlorine
atoms in each pair is linked to ‘P’ lie in opposite side of the ring. According to M.O. theory, localized
σ bonds are formed throughout the ring due to overlap of SP3 hybrid orbitals of ‘P’ with SP2 hybrid or-
bitals of ‘N’. In addition, each ‘P’ atom has one electron in d−orbital and each N atom has one electron
in Pz orbital. These form delocalized π(d − p) extended over the whole ring.

(PNCl2 )4 :- The tetramer has puckered ring structure. In this ‘P’ and ‘N’ atoms are arranged alterna-
tively.

1.4 Group 16

1.4.1 Oxides and Oxyacids of Sulphur

Oxides:-
SO2 and SO3 SO2 : Sulphur dioxide has a planar triangular (V-shaped) involving SP2 hybridisation of ‘S’
atom,

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1.4. GROUP 16 CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS

In SO2 , each O ’ atom is joined to ‘S ’ by σ and π bonds

SO3 : SO3 is trigonal planar involving SP2 hybridisation of ‘S’atom

Oxyacids of Sulphur :

The oxy acids of sulpher and their structures are shown in the table

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CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS 1.4. GROUP 16

Acid formula S oxidation Structure

Number
Sulphoxylic acid H2 SO4 +2 HO – S – OH
OH

Sulphurous acid H2 SO3 +4 O S

OH
O

Pyrossulphurous H2 S2 O5 +4 OH S S OH
acid
O O
O

Sulphuric acid H2 SO4 +6 OH S OH

OH
S

Thiosulphuric acid H2 S2 O4 +6 OH S OH

OH
O O

Pyrosulphuric acid H2 S2 O7 +6 OH S O S OH

O O

Acid formula S oxidation Structure

Number
O O

Dithionic acid H2 S2 O6 +6 OH S S OH

O O
O O

Peroxy acid (Mar- H2 S2 O8 +6 OH S O O S OH

shall‘s acid)
O O
O

Peromonosul- H2 SO5 +6 H O S OH
phuric acid(Caro‘s
acid) O

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1.5. GROUP 17 CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS

1.5 Group 17

1.5.1 Pseudohalogens and structures of Interhalogen compounds

Pseudohalogens :-
Pseudohalides are the uninegative radicals, which shows properties similar to halide ions. Pseudohalo-
gens are the covalent dimers.
Ex: CN – ; SCN –
1. Cyanogen ((CN)2 ) It is prepared by the action of Copper on cyanide in aqueous solution.

2 C2+ + 4 CN− −−→ 2 CCN + (CN)2

a. It is a poisonous gas, thermally stable
b.

Cl2 + 2 NOH −−→ NCl+ NOCl+ H2 O

(CN)2 + 2 NOH −−→ NCN + H2 O

c. Cyanogen hydrolyses to give urea

H2 O
(CN)2 −−→ re NH2CONH2

d. Cyanide ion (CN – ) is a good ē donar and it forms 4 Co-ordinate complexes with Na+ , Pt2+ etc.,
e. Structure : N = C – C = N

2. Thiocyanogen (SCN)2 :-Bromine is passed through ethereal solution of Ag.thiocyanate to form thio-
cyanogen.
2 AgCNS + Br2 −−→ 2 AgBr + (SCN)2
It is a poisonous substance. Hydrolyse to give thiocyanic acid and hydro thiocyanic acid.

(SCN)2 + H2 O −−→ HSCN + HOSCN

It resembles halogens in addition reaction with alkenes.

CH2 = CH2 + Cl2 −−→ CH2 Cl + HOSCN

CH2 = CH2 + (SCN)2 −−→ CH2 (SCN)−CH2 (SCN)

Structure:
C N

S C N and S S

C N
S C N
Uses :-
a. Cyanogen is used as Poisonous gas in warfare and organic synthesis
b. Thiocyanogen is used as oxidant in titrations.

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CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS 1.5. GROUP 17

Interhalogen compounds :

The binary compounds formed by the combination of halogens among themselves are called ‘Interhalogen
compounds’.They are of four types namely Ax, Ax3 , Ax5 , and Ax7 . A is heavier halogen and has low elec-
tronegativity, and x is the halogen of higher E.N.

Ax : CF, BrF, Cl, Br

Ax3 : CF3 , BrF3 , Cl3
Ax5 : BrF5 , F5
Ax7 : F7

Structures:-
1. Ax Type: These are formed by sharing of one electron from each halogen.
Ex: CIF is formed by sharing of electrons between Cl and F . it is linear in shape.

Cl · F

2. Ax3 Type (CF3 : Chlorine in excited state undergoes SP3 hybridisation

images/gro-17-1.png

Three lone electrons of SP3 d hybrid orbitals shares with ‘P’ electrons of ‘F’ atoms. It should be trigo-
nal bipyramidal. Two equatorial positions are occupied by lone pair of electrons. Hence it is T-Shaped.

3. Ax5 Type (IF5 ) :- Iodine atom in second excited state undergoes SP3 d2 hybridisation.

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1.5. GROUP 17 CHAPTER 1. CHEMISTRY OF P-BLOCK ELEMENTS

Five SP3 d2 hybrid orbital electrons overlaps with p orbitals of 5 Fluorine atoms. One e pair is non
bonding. It is octahedral with slight distortion.

4. Ax7 Type ( IF7 ) :- Iodine atom in third in excited state undergoes SP3 d3 hybridisation. These overlaps
with ‘P’ orbitals of 7 Fluorine atoms, form IF7 . It is pentagonal bipyramidal.

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