Hybridization

In hybridization two or more than two atomic orbits having same energies or nearly same energies
combine to form two or more than two hybridized orbitals with same energy, same size and identical
shape.

 Is, 2s, can not mix

 2s, 2p can mix
 3s, 4d, 5s cannot mix
 On the basis of participation of atomic orbitals in hybridization, hybridized orbitals get their
names.
For e.g. If one s & one p orbitals undergo hybridization, they form two hybridized orbitals with
the name 'sp'.
Similarly, if one s and two p orbitals undergo hybridization then they form three hybridized
orbitals with the name 'sp2'

Atomic orbitals participating in hybridization No. of hybridized Shape of hybridized

orbitals produced orbitals
One s- + one 'p' Three sp hybridised
orbitals

One 's' + two ‘p' Three sp2 hybridised

orbitals

One s+ three p Three sp3 hybridised

orbitals

All hybridized orbitals have same energy with equal % of s, % of p & % of d character
sp hybridization 
 50 % 's' character, 50% 'p' character
sp2 hybridization 
 33.33% character, 66.66% 'p' character
sp3 hybridization   25% 's' character, 75% 'p' character
Note: -% s character  Electro negativity
With the increase in % s character the bulkiness of hybridized orbital increases where as with
increase in % p character it attains longitivity and thinness
 %'s' character  bulkiness of orbitals
% 'p' character  longitivity & thinness

Sp3 hybridised
sp hybridised Sp2 hybridised

 As the shape of orbital is spherical therefore, with increase in % 'e character bulkiness of
hybridized orbital also increases, where as, due to the increase in % 'p' character the longitivity
and thinness in hybridized orbital begins to develop because of thin and long shape of 'p' orbital.

 In sp hybridization %'s' character is more therefore, its size is big in comparative to sp 2 and sp3
hybridized orbitals. Hence sp hybridized orbitals experience more repulsion from each other and
due to this bond angle between two 'sp' hybridized orbitals is found to be maximum (180°)

Consider the following examples –

For the formation of two sigma bonds Be should have two unpaired electrons

CI atoms form two cy bonds by overlapping with these hybridized orbitals

Here Be – Cl bond is sp – p sigma bond

F atoms form three cy bonds by overlapping with these sp2 hybridized orbitals

Here B — F bonds are sp2 — p sigma bonds

Here, all C — H bonds are sp3 — s σ bonds

The concept of hybridization reduces the drawbacks of V.B.T. because it gives us the idea about bond
angle and shape. It gives the dear explanation why all C - H bonds of are identical.

In the same manner we can understand the geometries of PCI5, SF6 & IF7.

PCI5
Phosphorous wants to make 5 a bonds with 5 'CI' atoms, so it needs five hybridized orbitals. Thus,
it in volves mixing of five orbitals viz. one s, three p and one d orbital. 120°

SF6
For the formation of six σ bonds with six F atoms sulphur needs six hybridized orbitals thus, it
involves mixing of one s, three p and two d orbitals
IF7
Number Geometry Hybridization Bond Examples Orbitals involved
of bond angle in
pairs or hybridization
steric
number

2 Linear sp 180° BeCl2 s+ any 'p' orbital

3 Triangular sp2 120° BCl3, BF3 s+ any two p

planar orbitals

4 Tetrahedral sp3 109° CH4, CCl4, s+Px+Py+Pz

28' SiCl4

5 Trigonal sp3d 90°, PCl5 s+ all three p

Bipyramidal 120° orbitals + dz2

6 Octahedral sp3d2 90° SF6 s+ all three p

orbitals + dz2 +
dx2-y2

7 Pentagonal sp3d3 90°, IF7 s+ all three p

bipyramidal 72° orbitals + dz2 +
dx2-y2+d xy

Evaluation of hybridization:- To find hybridization of central atom either of the two ways can
be used.
Ist Method:-
(sigma bond pair) + (lone pair)+(-ve charge) = Hybridization
Examples:

Here bp & lp are bond pair & lone pair of electrons respectively
2nd Method: -Firstly, valence electrons of all atoms should be counted in the species. If
the sum of these valence electrons varies between 2 to 8 then it should be divided by 2 and
if sum varies from 9 to 56 then it should be divided by 8 and if sum is found to be greater
than 56 it should be divided by 18.
Sum of total valence electrons

The quotient so obtained is called steric number.

Examples :

By using both the methods (1st and 2nd) we can evaluate hybridization as well as lone pair
of electrons of the central atom.
For eg.

In PCl3, P can form 3 sigma bonds with three chlorine atoms

 σ bp + lp +(-ve charge) = steric number
3 + lp + 0 = 4
lp= 1
Thus, in PCl3, phosphorous possesses one lp of electrons.
Similarly in XeF2
Total valence electrons = 8+7x2=22

i.e 2+3 =5

steric number = 5 and hybridisation = sp3d

Xenon can form only two bonds with two 'F' atoms thus, in XeF2;
Xenon contains three lone pair of electrons.
σ bp + lp + (-ve charge) = steric number
2 + lp + 0 = 5
Lp = 3

Shapes of molecules/ions when central atom contains lone pair of

electrons
(1) While observing the shape of species, lone pair should not be considered, however, the
presence of lone pair may or may not influence the geometry of species but lone pair is not
the part of geometry.
For e.g.
If central atom does not have lone pair in sp2 hybridization, its shape is always
triangular planar but when central atom possesses one lone pair it attains bent shape

Trigonal planar Bent Linear

bp=3 bp=2 bp=1

lp=0 lp=1 lp=2

Similarly, if central atom of sp2 hybridization has two lp then it possesses linear shape.
(2) Sp3d hybridization holds trigonal bi pyramidal shape (TBP). It has two types of bond,
axial and equatorial as shown in figure.

Axial and equatorial bonds have different characteristics (See Bent's rule). Axial bonds are
longer and weaker than equatorial bonds. Due to this reason both axial bonds in PCI 5 break
while heating.

PCI5   Cl2 + PCI3
If lone pair is present in TBP geometry, then on the basis of repulsions in lp & bp, structure of
the species is decided.
Descending order of repulsion is :-
lp-lp lp-bp bp-bp
(more strong) (strong) (weak)
Only those repulsions are considered in which angle between electron pairs is less than or
equal to 90° rest of the repulsions are ignored.
For e.g. three geometries of CIF3, are possible

Repulsions
lp-lp =0 lp-lp =1 lp-lp =0
lp-bp = 6 lp-bp = 3 lp-bp = 4
bp-bp= 0 bp-bp= 2 bp-bp= 2

Among 1, 2 & 3, 3rd has minimum repulsions therefore 3rd shows the correct geometry of
CIF3.
Similarly for SF4

(Wrong) (correct)
Repulsions
lp-lp =0 lp-lp = 0
lp-bp = 3 lp-bp = 2
bp-bp= 3 bp-bp= 4

(3) Bent's rule (For sp3d hybridization)

This rule is applicable to understand TBP geometry According to this rule.
"More electronegative element prefers to stay at axial position
whereas lone pair prefers to stay at equatorial location.
For e.g.
Explanation: - We can split sp3d hybridized orbital in the following manner.

In TBP geometry two 'pd' orbitals are present on axial position; therefore % s character on
axial position is zero. This is why central atom has minimum electro negativity at axial
position. With the same reason electronegative element prefers to stay at axial location so
that the element attracts electrons of bond pair towards it.

Lone pair of electrons is always attracted towards the nucleus of one atom; therefore, they
like to stay where they feel close to nucleus. Since 's' orbital is closest to the nucleus, so
lone pair prefer to stay with those orbitals which have more %s character. This allows lone
pair of electrons to sit on equatorial location because at equatorial location (sp2) 33.33%'s'
character is present while at axial position % s character is zero.
 (correct) (Wrong)

Since axial bonds have more % p character comparative to equatorial bonds, therefore, axial
bonds are longer & less stable than equatorial bonds.
% p character  longitivity & thinness

By using Bent's rule various geometries in sp 3d hybridization can be predicted.

Example: - Discuss the shape of the following

(a) XeOF2 (b) SF4 (c) ICl2+
Solution:
(a) XeOF 2
Total valence electrons =8+6+14=28
 i.e. 3+2 =5 (sp3d)
'Xe' forms three sigma bonds, two with 'F' & one with 'O'
σ bp + lp +(-ve charge) = Steric number
3+ lp + 0 = 5,
Ip = 2
In TBP geometry lp prefers to stay at equatorial position hence XeOF 2, has T shape

Since in TBP geometry more electronegative element prefers to stay at axial position, thus,
F is placed at axial position while oxygen which is less electronegative than F, is placed at
equatorial position.

(b) SF4
Total valence electrons = 6+7×4 = 34

i.e.4+1=5 (sp3d)
σ bp + lp +(-ve charge) = Steric number
4 + lp + 0 = 5,
Ip = 1

Sea – Saw
(c) ICl2+
Total valence electrons = 7+7 × 2-1 (+ve charge) = 20
 i.e.2+2=4 (sp3)
σ bp + lp +(-ve charge) = Steric number
2 + lp + 0 = 4,
Ip = 2

Modified Bent's rule

XeF5- is the only species which exhibit pentagonal planar shape.
Total valence electrons = 8+7×5+1=44

i.e. 5+2=7 (sp3d3)

σ bp + lp +(-ve charge) = Steric number
5 + lp + 1 = 7,
Ip = 2

Experimentally it has been observed that XeF 5- has pentagonal planar shape. This geometry
of XeF5-, can not be explained by Bent's rule. To understand above concepts Bent's rule is
presented as follows

"The orbital occupying more space with respect to the central atom
will have more % s - character" In means lone pair and negative charge prefers to
stay in the orbital where % s character is more. Such orbitals are big in size because % s
character increases the bulkiness of hybridized orbitals. Hence these orbitals require more
space and like to stay where bond angle is more.

In TBP geometry bond angle between equatorial and axial bonds is 90° which is lesser than
the angle between two equatorial bonds i.e. 120°. Thus, lone pair stays with equatorial
bonds because here more space is available.

Similarly, in pentagonal bi pyramidal (sp3d3) geometry the bond angle between axial and
equatorial bonds is 90° whereas it is only 72° in between equatorial - equatorial bonds.

Thus, the bond angle between axial and equatorial bonds is more so lone pair and negative
charge stays at axial location as here more space is available.

Note:- (a) In sp3d2 hybridization lone pair can be placed anywhere because in octahedral
geometry all bond angles are 90°.
(b) XeF is the only exception of Bent's rule. Its shape is distorted octahedral

This can not be explained with the help of Bent's rule. The bond length of both axial Xe-F
bonds is different due to lp-bp repulsion. The upper Xe-F bond is long where as the lower
Xe-F bond is comparatively short.
Example: - Discuss the shape of XeO2F2 by the help of hybridization. How many pл - dл
bonds are present in it.
Solution:- Total valence electrons = 8+12+14=34

i.e. 4+1=5 (sp3d)

σ bp + lp +(-ve charge) = Steric number
4 + lp + 0 = 5,
Ip = 1
According to Bent's rule it should have Sea - Saw geometry.

Since 'O' is less electronegative than F hence, F is placed at axial position.

Xe 5s2 5p6 5d0

 Hence in XeO2F2 two pπ – dπ bons are present

Calculation of %s & % p character

The % s character and % p character can be calculated by using the following formula
Cosθ= s/(s-1) & Cos θ =(p-1)/p
Let us calculate %s character of axial bond is TBP geometry
For axial bond For axial bond
Since θ = 90° θ = 120°
Cos 90° =s/(s-1) Cos 120° =s/(s-1)
0 = s/ (s-1) -1/2 = s/ (s-1)
thus, thus,
s=0 i.e 0% character s=0.33 i.e 33% character

Example: - Calculate % s character in sp2 hybridized orbitals

Solution:-
θ= 120°
Cos 120° =s/(s-1)
s=0.33
i.e. 33%