CONTENTS

i Chemistry of P-block Elements

1 Chemistry of P-block Elements 5
1.1 Group 13 5
1.1.1 Preparation and structure of diborane
B2 H6 5
1.1.2 Structure : 5
1.1.3 Borazole (or) Borazine (or) Inorganic
Benzene (B3 N3 H6 ) 7
1.2 Group 14 7
1.2.1 Preparation , properties and uses of
Silicones 7
2 d-Block Elements 9
2.1 Transitional Elements 9
3 Test Chapter 15
3.1 A Section 15

ii Appendix
a Appendix Chapter 19
a.1 A Section 19

1
 Part I

C H E M I S T RY O F P - B L O C K E L E M E N T S
 1
C H E M I S T RY O F P - B L O C K E L E M E N T S

1.1 group 13

1.1.1 Preparation and structure of diborane B2 H6

1. 8 BF3 + 6 LiH −−→ B2 H6 + 6 LiBF4

∆
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 struc-
ture 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

5
6 chemistry of p-block elements

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 dib-
orane indicating that two hydrogen atoms are
differently 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
hybrid 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.
Diagram pending
Structure of Diborane
 1.2 group 14 7

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 hybridised. In
borazole, n− bonding is dative , it forms by overlapping
of empty P− orbitals of boron, with filled P−orbitals of
Nitrogen

Figure 1: Structure of Borazole

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 SICl3 + Mgcl2

| {z }
Methyl trichlorosilane

2 CH3 Mgcl + SiCl4 −−→ (CH3 )2 SICL2 + 2 MGCL2

| {z }
Dimethyl trichlorosilane
 2
D-BLOCK ELEMENTS

2.1 transitional elements

Transitional elements may be defined as those in which ele-

ments have partly filled d−subshells. In d−block elements,
the incomplete subshells are (n − 1)d subshells. These el-
ements are placed between S and P−block in the periodic
table. The elements of I IB group (Zn, Cd, Hg) have com-
pletely filled d-level, hence they are only d-block elements
but not transitional elements. The d−block consists of three
complete series involving the filling of 3d, 4d and 5d lev-
els and fourth row is incomplete consisting of only three
elements.

3d Series : Scandium to Zinc

4d Series : Yttrium to Cadmium
5d Series : La, Hf to Hg

1. Electronic Configuration:-The orbitals are filled in the

order of their increasing energy. Thus in 3d series, first
4S is filled, then the next electron goes to inner 3d.

Sc Ti V Cr Mn Fe Co Ni Cu Zn
At.No 21 22 23 24 25 26 27 28 29 30
E.C 3d1 4S2 3d2 4S2 3d3 4S 3d5 4S1 3d5 4S2 3d6 4S2 3d7 4S2 3d8 4S2 3d10 4S1 3d10 4S2

9
10 d-block elements

Cr and Cu possess anamalous configuration ie when

the orbitals are either filled or half filled they get extra
stability.

Cr : [ AR]3d4 4S2 but it is 3d8 4S1

Cu : [ AR]3d9 4S2 but it is 3d10 4S1

2. Oxidation states :Transition element exhibits different

types of oxidation states.
3d series

SC Ti V Cr Mn Fe Co Ni Cu Zn
3 2 2 1 1 2 2 2 1 2
3 3 2 2 3 3 3 2
4 4 3 3 4 4 4 3
5 4 5 5
5 5 6
6 6
7

The minimum oxidation state is +2, this is due to the

loss of ‘S’ electrons. These shows variable oxidation
states due to the loss of ns and (n − 1)d electrons. In
3d series Mn shows highest oxidation state (+7) in
K Mn04 . In 4d and 5d series Ruthenium and osmium
shows a highest oxidation state of +8(RuO4 , OsO4 ).
Stability :- Compounds are regarded as stable, if
they exist at room temp and are not oxidized by air,
hydrolysed by water. In 3d series, the elements are
stable when the configuration is 3d0 , 3d5 and 3d10 . Thus
Ti4+ (3d0 ) is more stable than Ti3+ (3d1 ); Mn2+ (3d5 ) is
more stable than Mn3+ (3d4 ); Fe3+ (3d5 ) is more stable
than Fe2+ (3d6 ).
 2.1 transitional elements 11

3. Magnetic Properties:- Electron is being –vely charged,

may be considered as small magnet. The magnetic
momentum of electron is due to its spin and orbital
motion. When a substance is kept in the magnetic field,
the induced magnetic field may act opposite to the
external magnetic field or it may add to the external
field. Thus compounds or atoms show diamagnetism,
paramagnetism, ferromagnetism.

4. Diamagnetism :- If the substance is repelled by the

magnetic field, it is said to be ‘diamagnetic’. Sub-
stances containing completely filled orbitals are dia-
magnetic.

5. Paramagnetism:- If the substance is attracted by the

magnetic field, it is called ‘Paramagnetic’. Substances
containing unpaired electrons are paramagnetic.

6. Ferromagnetism:Sometimes the substances will in-

crease the magnetic field strength by many times. It
is called ‘Ferromagnetic’. Substances like Fe, Co, Ni
shows Ferromagnetism Most of the transition metal

ions have unpaired d-electrons, thus they show param-

agnetism. SC3+ , Ti4+ , Zn2 +, Cu+ does not contain any
unpaired d−electron, hence they are diamagnetic. The
magnetic moment of an element depends on the no.
of unpaired electrons, and is calculated by the formula
12 d-block elements

p
µ = n(n + 2) Bohr magnetons, where n = no. of
unpaired electrons.

7. ccolor: The compounds of transition metals are coloured

either in the solid or solution state. The colour of the
ion is due to unpaired electrons. These unpaired elec-
trons of the ion absorb radiations of one particular
wavelength i.e., from white light and undergo transi-
tion from one orbital to another within the same d-
level. This transition transmits coloured light which is
complimentary to the absorbed light. Ex:Ti3+ is purple,
Cu2+ is blue, Ions having either empty or completely
filled d-level are colourless. Ex: SC3+ ,Cd2+ , Zn2+ ,Ti4+
are colourless.
In d − d transition, by the approach of –ve ion to
transition metal ion, the five degenerate d-orbitals
splits into two energy levels ie (i) dxy, dyz, dzx (t2 g) (ii)
dx2 − y2 , dz2 (eg).

In d − d transition, an electron passes from t2g to e g ,

and the energy difference is small, so light is absorbed
in the visible region, thus they show colour.
Ex: [Ti (H2 O)6 ]3+ , the lone electron is in t2g, when
light falls it is promoted to eg, hence it shows purple,
 2.1 transitional elements 13

because it absorbs green light and as complementary

shows purple. i.e, white light - Green light = Purple.
Pending

Figure 2: Caption

Ex: When light passes through [Cu(H2 O)6 ]2+ , the elec-
tron in t2g levels absorb red light, promotes to e g , and
exhibits blue. ie., white light – red light = Blue.
8. Catalytic Activity: Transition elements acts as good
catalysts. Eg:
a) Hydrogenation of oil is in the presence of Ni
b) Decomposition of H2 O2 by Mn NH3 is manufac-
tured by using Iron and Molybdenum
c) V2 O5 is used in the manufacture of H2 S04
The catalytic activity is due to the presence of vacant
(n-1)d orbitals, which accepts electrons from the reac-
tive molecules and the reactants get absorbed on the
surface of the metal. These also reduces the activation
energy to complete the reaction.
9. Complex forming ability:-Transition metals exhibit
strong tendency to form complexes with molecules
like CO, NH3 , H2 O and ions like F – , Cl – , CN – . Ions
of transition metal have small size, large charge and
suitable electronic configuration, hence they form com-
plexes easily.
In each transition series, the stability of complexes
increases with increase in atomic no. and in particular
oxidation state with decreasing size of atom. When
transition metal shows more than one oxidation state,
the higher valency forms more stable complexes.
14 d-block elements

Ex : [Ni(CO)4 ]; K4 [Fe(CN)6 ]; [Cr (NH3 )6 ]3+

 3
TEST CHAPTER

Lorem ipsum dolor sit amet, consectetuer adipiscing elit.

Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero,
nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristi-
que senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et
lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis
in, pretium quis, viverra ac, nunc. Praesent eget sem vel
leo ultrices bibendum. Aenean faucibus. Morbi dolor nulla,
malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi,
congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum.

3.1 a section

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Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero,
nonummy eget, consectetuer id, vulputate a, magna. Donec

15
16 test chapter

vehicula augue eu neque. Pellentesque habitant morbi tristi-

que senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et
lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis
in, pretium quis, viverra ac, nunc. Praesent eget sem vel
leo ultrices bibendum. Aenean faucibus. Morbi dolor nulla,
malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi,
congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum.
 Part II

APPENDIX
 A
APPENDIX CHAPTER

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Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero,
nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristi-
que senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et
lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis
in, pretium quis, viverra ac, nunc. Praesent eget sem vel
leo ultrices bibendum. Aenean faucibus. Morbi dolor nulla,
malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi,
congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum.

a.1 a section

Lorem ipsum dolor sit amet, consectetuer adipiscing elit.

Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero,
nonummy eget, consectetuer id, vulputate a, magna. Donec

19
20 appendix chapter

vehicula augue eu neque. Pellentesque habitant morbi tristi-

que senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et
lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis
in, pretium quis, viverra ac, nunc. Praesent eget sem vel
leo ultrices bibendum. Aenean faucibus. Morbi dolor nulla,
malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi,
congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum.