CHM361

CHAPTER 1:

VALENCE BOND THEORY

 CONTENTS

1) Lewis Structure

2) Valence Shell Electron Pair Repulsion Theory (VSEPR)

3) Valence Bond Theory

4) Orbital Hybridization (sp, sp2, sp3, sp3d, sp3d2)

 LEARNING OUTCOMES

 Construct and sketch the geometry of molecules /polyatomic ions

based on :

 Lewis structure
 Valence Shell Electron Pair Repulsion Theory (VSEPR)
 Valence Bond Theory
 LEWIS STRUCTURE

 the symbol of the atom represents the nucleus and all

inner shell electrons.
 dots represent valence electrons:
 electrons in the outermost electron shell of an atom.
These electrons are used in forming chemical bonds
1A 2A 3A 4A 5A 6A 7A 8A
H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar
 DRAWING LEWIS STRUCTURE

1) Count the total no of VE of the molecule.

2) Draw the skeletal structure of the molecule.

3) Complete the duplet (H) and octet for all terminal atom.

3) Calculate number of electrons in the molecule. Each bond is counted as two electrons.

4) Excess VE are placed on the central atom.

5) If central metal atom do not achieved octet, make double/triple bond with terminal atom.

6) Calculate Formal charge.

 Valence Shell Electron Pair Repulsion
(VSEPR)

VSEPR - A pair of electrons on the CENTRAL ATOM occupies a

position in space as to minimize electron pair - electron pair repulsion.

The order of ep-ep repulsion:

lone pair - lone pair > lone pair – bonding pair > bonding pair - bonding pair

Theory that predict the shape of covalent molecule.

Focus on the central atom.

 Valence Shell Electron Pair
Repulsion (VSEPR)
 Predicting the shape depends on the electron domain.

 The electron domain geometry of an atom is dictated by the

number of electron domain attached to it directly.

 Electron domain:
 Sigma bond
 Lone pair

Only σ bond and lone pair contribute to the shape of

molecules.
ELECTRON 3D- STRUCTURE ELECTRON PAIR ANGLE
DOMAIN GEOMETRY

2 Linear 180°

3 Trigonal Planar 120°

4 Tetrahedral 109.5°

Trigonal-
5 120° & 90°
bipyramidal

6 Octahedral 90° & 180°

ELECTRON BONDING LONE PAIR MOLECULAR EXAMPLE
DOMAIN GEOMETRY

2 2 0
linear

3 0

Trigonal planar
3

2 1

bent
VSEPR
ELECTRON BONDING LONE PAIR MOLECULAR EXAMPLE
DOMAIN GEOMETRY

4 0

tetrahedral

3 1
4
Trigonal
pyramidal

2 2

bent
VSEPR
ELECTRON BONDING LONE MOLECULAR EXAMPLE
DOMAIN PAIR GEOMETRY

trigonal
5 0 PCl5
bipyramidal

seesaw CF4
4 1

3 2 T-shaped ClF3

2 3 linear XeF2
VSEPR
ELECTRON BONDING LONE MOLECULAR EXAMPLE
DOMAIN PAIR GEOMETRY

6 0 octahedral SF6

square
6 5 1 pyramidal BrF5

square
4 2 planar XeF4
VSEPR
 PREDICTING THE SHAPE

1) Draw a Lewis structure.

2) Count the electron domain.

3) Determine the electron pair geometry.

4) Determine the molecular geometry based on σ present.

 VALENCE BOND THEORY

Theory:

A covalent bond is formed when two neighboring atomic orbitals

overlap. The overlapping orbitals may only contain two electrons of
opposite spin.

The greater the orbital overlap, the stronger (more stable) the bond.

The theory arises from the concept of orbital.

ORBITALS

all s orbitals

all p orbitals

d orbitals
Overlapping of Overlapping of
s and p orbital two p orbital

1 σ bond 1 σ bond 1 σ bond

1 π bond 2 π bond
 σ BOND

σ bond is formed by the head-on overlapping of atomic orbitals

HEAD ON or END ON END

A bond where the line of electron density is concentrated symmetrically

along the line connecting the two atoms.
 π BOND

π bond is formed by sideways overlapping of p atomic orbitals

SIDE BY SIDE
 HYBRIDIZATION OF ATOMIC ORBITAL

 Hybridization- process of orbital mixing

 Hybrid orbitals- the new atomic orbitals

 σ Bond : unpair electron/ half full orbital ↑

 Lone pair : Paired electron/ full orbital ↑↓

 Double/ triple bond : remaining half full ↑

 sp HYBRIDIZATION

 One s orbital and one p orbital are mixed.

 Eg: BeH2

2 σ bond
Since there are 2 σ bond, thus it
needs 2 unpaired electrons

Be: ↑↓ promotion ↑ ↑
2s 2p 2s 2p
hybridization

↑ ↑
sp sp 2p
 sp HYBRIDIZATION

hybridization

1 s obital + 1 p orbital 2 sp orbital

linear
 sp2 HYBRIDIZATION

 One s & 2 p orbital are mixed.

 Eg: BCl3
3 σ bond

Since there are 3 σ bond, thus it

needs 3 unpaired electrons

B: ↑↓ ↑ promotion ↑ ↑ ↑
2s 2p 2s 2p
hybridization

↑ ↑ ↑
sp2 sp2 sp2 2p
 sp2 HYBRIDIZATION

hybridization

1 s obital + 2 p orbital 3 sp 2 orbital

trigonal planar
 sp3 HYBRIDIZATION

 One s & 3 p orbital are mixed.

 Eg: CH4 4 σ bond

Since there are 4 σ bond, thus it

needs 4 unpaired electrons

C: ↑↓ ↑ ↑ promotion ↑ ↑ ↑ ↑
2s 2p 2s 2p

hybridization

↑ ↑ ↑ ↑
sp3 sp3 sp3 sp3
 sp3 HYBRIDIZATION

hybridization

1 s obital + 3 p orbital 4 sp 3 orbital

tetrahedral
 sp3d HYBRIDIZATION

 One s, 3 p orbital & 1 d orbital are mixed. 5 σ bond

 Eg: PCl5 P: ↑↓ ↑ ↑ ↑
3s 3p
promotion
Since there are 5 σ bond, thus it needs 5
unpaired electrons

↑ ↑ ↑ ↑ ↑
3s 3p 3d 3d 3d 3d 3d

hybridization

↑ ↑ ↑ ↑ ↑
sp3d sp3d sp3d sp3d sp3d 3d 3d 3d 3d
sp3d HYBRIDIZATION

Trigonal bipyramidal
 sp3d2 HYBRIDIZATION

 One s, 3 p orbital & 2 d orbital are mixed. 6 σ bond

 Eg: SF6
S:16 ↑↓ ↑↓ ↑ ↑
3s 3p

Since there are 6 σ bond, thus it needs 6 promotion

unpaired electrons

↑ ↑ ↑ ↑ ↑ ↑
3s 3p 3d 3d 3d 3d 3d

hybridization

↑ ↑ ↑ ↑ ↑ ↑
sp3d2 sp3d2 sp3d2 sp3d2 sp3d2 sp3d2 3d 3d 3d
sp3d2 HYBRIDIZATION

octahedral
 LONE PAIR ELECTRON
 Eg: NH3
3 σ bond
1 lone pair

N: ↑↓ ↑ ↑ ↑
2s 2p

hybridization
lone pair σ bond σ bond σ bond

↑↓ ↑ ↑ ↑ Since there are 3 σ bond & 1 lone pair, thus it needs

3 unpaired electrons & 1 paired electron.
sp3 sp3 sp3 sp3
 LONE PAIR ELECTRON

 Eg: H2O
2 σ bond
2 lone pair

O: ↑↓ ↑↓ ↑ ↑
2s 2p

hybridization
lone pair lone pair σ bond σ bond
Since there are 2 σ bond & 2 lone pair, thus it needs
↑↓ ↑↓ ↑ ↑ 2 unpaired electrons & 2 paired electron.
sp3 sp3 sp3 sp3
 DOUBLE BOND

 Eg: C2H4
3 σ bond
1π bond

C: ↑↓ ↑ ↑
2s 2p
promotion Since there are 3 σ bond & 1 π bond, thus it needs 4
unpaired electrons.

↑ ↑ ↑ ↑
2s 2p

hybridization
σ bond σ bond σ bond π bond

↑ ↑ ↑ ↑
sp2 sp2 sp2 2p
 TRIPLE BOND

 Eg: C2H2
2 σ bond
2 π bond

C: ↑↓ ↑ ↑
2s 2p
Since there are 2 σ bond & 2 π bond, thus it needs 4
promotion unpaired electrons.

↑ ↑ ↑ ↑
2s 2p

hybridization
σ bond σ bond π bond π bond

↑ ↑ ↑ ↑
sp sp 2p 2p
SUMMARY

Electron Domain Hybridization Geometry

2 sp Linear
3 sp2 Trigonal planar
4 sp3 Tetrahedral
5 sp3d Trigonal
bipyramidal
6 sp3d2 octahedral