Velammal IIT Academy

Mogappair-Mel Ayanambakkam (Chennai)

XI IIT Chemistry-Chemical Bonding(Valence Bond Thoery-Hybridization) CW -3B
Hybridisation :
– Hypothetical concept Introduced by pauling and slater.
– Atomic orbitals of same atom combine to form new set of equivalent orbitals know as hybrid orbitals.
– This phenomenon is known hybridization.
– Process of Intermixing of the atomic orbitals of equal or slightly different energies in the formation of new
set of orbitals of equivalent energies and shape is known as hybridization.
Salient features of hybridisation : The main features of hybridisation are as under :
1. The number of hybrid orbitals is equal to the number of the atomic orbitals that get hybridised.
2. The hybridised orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. These hybrid orbitals are directed in space in some preferred direction to have minimum repulsion between
electron pairs and thus a stable arrangement is obtained. Therefore, the type of hybridisation indicates the
geometry of the molecules.
Important conditions for hybridisation :
(i) The orbitals present in the valence shell (and sometimes penultimate shell also) of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy.
(iii) Promotion of electron is not essential condition prior to hybridisation.
(iv) It is the orbital that undergo hybridization and not the electrons. For example, for orbitals of nitrogen atom
( 2s 2 2p1x 2p1y 2p1z ) belonging to valency shell when hybridize to form four hybrid orbitals , one of which
has two electrons (as before) and other three have one electron each. It is not necessary that only half filled
orbitals participate in hybridisation. In some cases, even filled orbitals of valence shell take part in
hybridisation.
Determination of hybridisation of an atom in a molecule or ion:
Steric number rule (given by Gillespie) :
Steric No. of an atom = number of atom bonded with that atom + number of lone pair(s) left on that atom.
Note : This rule is not applicable to molecules/ions which have odd e– (ClO2, NO, NO2 ), free radicals and
compounds like B2H6 which involve 3 centre 2e– bond (banana bond).

For example : O=C=O S.No. = 2 + 0 = 2

S.No. = 2 + 1 = 3

S.No. = 3 + 0 = 3

S.No. = 3 + 1 = 4

Steric number Types of Hybridisation Geometry Involving orbitals

2 sp Linear ns, npx / pz / py
2
3 sp Trigonal planar ns, npx , pz / py ,pz/px , py
3
4 sp Tetrahedral ns, npx , pz , py
3
5 sp d Trigonal bipyramidal ns, npx , pz , py d z2
3 2
6 sp d Octahedral ns, npx , pz , py d z2 d x2  y 2
3 3
7 sp d Pentagonal bipyramidal ns, npx , pz , py d z2 d x2  y 2 dxy

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sp hybridisation :
 This type of hybridisation involves the mixing of one s and one p orbital resulting in the formation of two
equivalent sp hybrid orbitals.
 Each sp hybrid orbitals has 50% s-character and 50% p-character. Such a molecule in which the
central atom is sp-hybridised and linked directly to two other central atoms possesses linear geometry. This
type of hybridisation is also known as diagonal hybridisation.
 The two sp hybrids point in the opposite direction along the Z-axis with projecting bigger positive lobes and
very small negative lobes, which provides more effective overlapping resulting in the formation of stronger
bonds.
Example of a molecule having sp hybridisation
BeCl2 : The ground state electronic configuration of Be is 1s2 2s2. In the excited state one of the 2s-
electrons is promoted to vacant 2p orbital to account for its divalency. One 2s and one 2p-orbitals get
hybridised to form two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite direction
forming an angle of 180°. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine axially
and form two Be-Cl sigma bonds.

Figure : (A) Formation of sp hybrids from s and p orbitals ; (B) Formation of the linear BeCl2 molecule.
Examples of sp hybridisation.
Species Important characteristic
H–C  N Linear, highly posionous, weak acid
H–C  C–H Linear,  bond planes are perpendicular
O=C=O Linear, both  bond are perpendicular to each other
H2C = C = CH2 Non planar both hydrogen are perpendicular to each other

N3– (azide ion) Iso electronic with CO2 and linear in shape. Both N–N bonds are similar

HgCl2
NO2+ (nitronium ion),
N2O

Hydrazoic acid

sp2 hybridisation :
(i) Mixing of one s and two p orbitals to form 3 equivalent sp2 hybridized orbitals.
For example, in BCl3 molecule, the ground state electronic configuration of central boron atom is 1s 2 2s2
2p1. In the excited state, one of the 2s electrons is promoted to vacant 2p orbital as a result boron has three
unpaired electrons.
These three orbitals (one 2s and two 2p) hybridise to form three sp2 hybrid orbitals. The three hybrid
orbitals so formed are oriented In a trigonal planar arrangement and overlap with 2p orbitals of chlorine to

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 form three B–Cl bonds.
Therefore, in BCl3, the geometry is trigonal planar with CI–B–Cl bond angle of 120°.

Figure : Formation of sp2 hybrids and the BCl3 molecule

Steric No. = 3 Geometry = Trigonal planar Ideal bond angle = 120°
Table-5

Molecule Structure Statements

SO3 All three S–O bonds are equivalent. out of 3p bond

one p-p other to are p-d.

O3 V shaped molecule. Both O–O bond length are equal.

CO3– –

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 NO2– Bond order of N–O bond is 1.5, planar molecule.

Note : In N2O5, N is sp2 hybridised but in solid, N2O5 exist

in NO2+ (N is sp hybridised) and NO3–
(N is sp2 hybridised) ions.

sp3 hybridisation :
 mixing of one s and three p orbitals to form 4 equivalent sp3 hybridized orbitals.
 4 sp3 orbitals are directed towards four corner of tetrahedron.
 This type of hybridisation can be explained by taking the example of CH4 molecule in which there is
mixing of one s-orbital and three p-orbitals of the valence shell to form four sp 3 hybrid orbital of equivalent
energies and shape.
 There is 25% s-character and 75% p-character in each sp3 hybrid orbital. The four sp3 hybrid orbitals
so formed are directed towards the four corners of the tetrahedron.
 The angle between sp3 hybrid orbital is 109.5° as shown in figure.

Figure

Ammonia

Water

Steric No. = 4 Geometry = tetrahedral Ideal bond angle = 109° 28

Table-6

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 Some other Examples of sp3 hybridisation
Cl Cl Cl Cl
(a)  BeCl2 (s) , Be Be Be
Cl Cl Cl Cl

(b)  BF4– ;

(c) Diamond, CCl4 , , all alkane ;

(d) SiCl4, Silicates etc.

Structure of SiO2

SiO2 is a covalent network solid like diamond

(e)  NH2– (amide ion)

V-shape

 NH2–NH2 (hydrazine)

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  NH2OH (hydroxylamine) lp-lp repulsion increases the N–O bond

length.

(f) P4 (White phosphorus)

 P4O6

The P – O bond lengths shows

that the bridging bonds on the
edges are 1.60 Å but the P = O
bonds on the corners are 1.43 Å
and this P = O is formed by pp – dp
back bonding. A full p-orbital on
the oxygen atom overlaps
 P4O10 sideway with an empty d-orbital
on the phosphorus atom. The
bond angle POP is 127º and there
is no P – P bonds.
Total L.P. = 20.
Total no. of p -d bonds = 4

– sp3
 Structures of silicate ion : [SiO4]4–  = Silicon ; O = Oxygen
– –

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  Structures of cyclic silicates : [Si3O9]6–

= Silicon ; O = Oxygen

 H2O2 H2O2(g)

 SOCl2 (Thionyl chloride) Trigonal pyramidal

 XeO4

 sp3 d hybridisation :
Steric number = 5 Geometry = trigonal bipyramidal

Table-7

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 Important points regarding sp3d -
(i) According to VSEPR theory lone pair will occupy equatorial (E) positions but not axial (a).

(ii) More electronegative atoms will prefer to occupy axial positions.

(iii) Since, double bonds occupy more space. Therefore, they will also prefer equatorial positions.

PCl5 (g)

PF5 (g)

+ –
PBr5 (g) PBr5 exist as (PBr4) Br in solid state.

PCl3 F2

PCl2 F3

SF4 SF4 molecule have T-shape geometry.

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 XeO2 F2 Both F atoms will be at equatorial position.

Cl F3 T -shape (It is planar molecule)

I 3–

XeF2

sp3d2 hybridization :
Steric number = 6 Geometry = octahedral
Table-8

Important : Since, octahedral is a symmetrical figure hence

(a) positions of a lone pair can be any where
(b) but if there are two lone pairs (max.) then these must be in the trans position.

SF6

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 [XeO6]4–

XeOF4 Molecule has square pyramidal geometry.

XeF4 Molecule has square plannar geometry.

sp3 d3 Hybridization :
Steric number = 7 Geometry = Pentagonal bi-pyramidal
Table-9

F 7 Bond angle = 72° & 90°

XeF6 (g)

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or

 XeF6(s)

 [XeF5] –


 I2Cl6

Note : The liquid has an appreciable electrical conductance due to self ionization.
2Cl6 [Cl2]+ (bent) + [Cl4]– (square planar)

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