UNIT 4.
CHEMICAL
BONDING &
MOLECULAR
STRUCTURE
(lecture 3)
Topics Covered
• Hybridization, Determination of hybridization,
Structure and bond angle of molecules/ions,
Valence Shell Electron Pair Repulsion (VSEPR)
theory.
Hybridization
The process of mixing of two or more atomic orbitals to
form same number of orbitals of equivalent energy is called
hybridization and the orbitals so formed during this process is
called hybrid orbitals. The number of hybrid orbitals so
formed is equal to the number of atomic orbitals mixed
together.
However Hybridization is not a physical reality but a
mathematical method to determine geometry of
molecules/ions.
• It is determined by using following formula:
1
No. of orbitals mixed = (V+M−C+A)
2
Where V= No. of valence electrons of central atom
M= No. of mono valent atoms (e.g. H, F, Cl, Br, I )
bonded with central atom
C= Cationic (+ve) charge
A = Anionic (-ve) charge
No. of Hybridization Structure Bond angle (in
orbitals absence of lone
mixed pair on central
atom)
2 sp Linear 180°
3 sp3 Triangular 120°
planar
4 sp3 Tetrahedral 109°28’
5 sp3d Trigonal 120° and 90°
bipyramidal
6 sp3d2 Octahedral 90°
7 sp3d3 Pentagonal 90° and 72°
bipyramidal
• Note: When central atom contain lone pair of electron, usually
bond angle becomes lesser than expected value.
• For e.g.,
CH4 NH3 H2O
No. of Bond 4 3 2
pair
No. of Lone 0 1 2
pair
Hybridization sp3 sp3 sp3
Bond angle 109°28’ 107.8° 104.5°
Note: (i)The d-orbitals used in different types of
hybridization:
sp3d : 𝑑𝑧 2
sp3d2 : 𝑑𝑥 2 −𝑦2 , 𝑑𝑧 2
sp3d3 : 𝑑𝑥𝑦 , 𝑑𝑦𝑧 , 𝑑𝑥𝑧
dsp2: 𝑑𝑥 2 −𝑦2
(ii) Greater the s-character of hybrid orbital, greater its
electronegativity.
Order of electronegativity : sp > sp2 >sp3
Determination of Shape, Structure (Geometry) &
Hybridization of molecules/ions
• With the help of hybridization and VSEPR theory, we can determine shape &
structure (Geometry) of molecules/ions. Some examples are:
(i) CH4
Here V=4, M=4, C=0, A=0
1 1
No. of orbitals mixed = (V+M−C+A) = (4+4−0+0)= 4
2 2
Hybridization: sp3, No. of bond pair: 4, No. of lone pair: 0
Shape & Structure: Tetrahedral
(ii) NH3
Here V=5, M=3, C=0, A=0
1
No. of orbitals mixed = (5+3−0+0) = 4
2
Hybridization: sp3, No. of bond pair: 3, No. of lone pair: 1
Structure: Tetrahedral, Shape: Pyramidal
(iii) H2O
Here V=6, M=2, C=0, A=0
1
No. of orbitals mixed = (6+2−0+0)= 4
2
Hybridization: sp3, No. of bond pair: 2, No. of lone pair: 2
Structure: Tetrahedral, Shape: Angular or Bent or V-shaped
(iv) NO2+
Here V=5, M=0, C=1, A=0
1
No. of orbitals mixed = (5+0−1+0)= 2
2
Hybridization: sp, No. of bond pair: 2, No. of lone pair: 0
Shape & Structure: Linear
(v) 𝑆𝑂42−
Here V=6, M=0, C=0, A=2
1
No. of orbitals mixed = (6+0−0+2)= 4
2
Hybridization: sp3, No. of bond pair: 4, No. of lone pair: 0
Shape & Structure: Tetrahedral
(vi) XeF4
Here V=8, M=4, C=0, A=0
1
No. of orbitals mixed = (8+4−0+0)= 6
2
Hybridization: sp3d2, No. of bond pair: 4, No. of lone pair: 2
Structure: Octahedral, Shape: Square planar
(vii) 𝐼3−
Here V=7, M=2, C=0, A=1
1
No. of orbitals mixed = (7+2−0+1)= 5
2
Hybridization: sp3d, No. of bond pair: 2, No. of lone pair: 3
Structure: Trigonal bipyramidal, Shape: Linear
(viii) BF3
Here V=3, M=3, C=0, A=0
1 1
No. of orbitals mixed = (V+M−C+A) = (3+3−0+0)= 3
2 2
Hybridization: sp2, No. of bond pair: 3, No. of lone pair: 0
Shape & Structure: Trigonal planar
(ix) PCl5
Here V=5, M=5, C=0, A=0
1
No. of orbitals mixed = (5+5−0+0)= 5
2
Hybridization: sp3, No. of bond pair: 5, No. of lone pair: 0
Shape & Structure: Trigonal bi pyramidal
(x) XeF6
Here V=8, M=6, C=0, A=0
1 1
No. of orbitals mixed = (V+M−C+A) = (8+6−0+0)= 7
2 2
Hybridization: sp3d3, No. of bond pair: 6, No. of lone pair: 1
Structure: Pentagonal bipyramidal, Shape: Distorted Octahedral
VSEPR (Valance shell electron pair repulsion)
Theory
This theory was given by Sidgwick and Powell (in 1940) and later modified
by Nyholm and Gillespi (in 1957).
The main points of this theory are as following:
1. All covalent molecules (polyatomic) that contain a central atom by which
other atoms gets bonded.
[Link] outermost shell of central atom electrons are present in pair, which may be
lone pair or bond pair or both.
3. Electron cloud of lone pair is much spread as compared to
electron cloud of bond pair because electrons of bond pair are
present between two positive charged nuclei.
4. The shape of a molecule depends upon valence shell electron pair
(bonded or non-bonded around the central atom).
5. Pairs of electrons in the valence shell repel one another since
electron clouds are negatively charged.
6. Electron pair tends to occupy such position in space to minimize
repulsion and thus maximize distance between them.
7. A single bond, double bond or triple bond is considered as a single bond
pair, because all of these bonds contain only one sigma bond.
8. The order of repulsion between various pair of electrons is as follows:
Bond pair- Bond pair < Bond pair – Lone pair < Lone pair – Lone pair
9. When central atoms belong to same group of periodic table and compounds
having similar empirical formula, bond angle decreases with increase in size of
central atom. It is mainly due to decrease in electronegativity with increase in
size of central atom.
For example:
Order of bond angle: NH3 >PH3 > AsH3 > SbH3 > BiH3
Here parental shape refers to structure (geometry) and
Molecular shape refers to shape or actual shape.
• PRESENTED BY
Dr. A. K. GAUTAM
[Link]. (Chem.), Ph.D.
CSIR-NET