Chemical Bonding

VI:

Valence Bond
Theory
& Orbital
Hybridization
 Coordinate Covalent Bonds
• A co-ordinate bond (also called a dative
covalent bond) is a covalent bond in which
both electrons come from the same atom.

F H F H

F B + N H F B N H
••

F H F H
 Coordination Compounds
A coordination compound typically consists of a
complex ion and a counter ion.
A complex ion contains a central metal cation bonded to one
or more molecules or ions.

The molecules or ions that surround the

metal in a complex ion are called ligands.

A ligand has at least one unshared

pair of valence electrons
•• • ••
•O N ••
Cl
- C O
••

••
••
••

H ••
H H H H
 Bonding Theories
Valence Bond (VB) Theory

Molecular Orbital (MO) Theory

- MO theory no longer covered on AP Chem exam

 Valence Bond Theory
• e- in a molecule occupy orbitals of the
individual atoms
• Stable molecule form when P.E. of a system is
minimized
• Atomic orbitals overlap to form bonds
• To accommodate bonds, valence orbitals of
central atom combine or hybridize
A sigma bond (σ) forms as orbitals overlap

H 1s 1s H
H 1s H
Sigma bond (σ ) – electron density between the 2
 Hybridization – mixing of two or more atomic
orbitals to form a new set of hybrid orbitals.
1. Mix at least 2 nonequivalent atomic orbitals (e.g. s
and p). Hybrid orbitals have very different shape
from original atomic orbitals.
2. Number of hybrid orbitals is equal to number of
pure atomic orbitals used in the hybridization
process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid
orbitals 7
C+H

Carbon has only 2 unpaired

electrons, it should form only 2
bonds to hydrogen.
 Carbon actually
forms 4 bonds to
hydrogen.

How??
 Hybrid orbitals are energetically more
favorable
Carbon Hybridization

2p
2sp3

2s
Energy
 Carbon
Hybridizati
on
Energy

Four sigma bonds form

s + p + p + p = sp3
Formation of Covalent Bonds in CH4
 Valence Bond Theory and NH3

N – 1s22s22p3

3 H – 1s1
If the bonds form from overlap of 3 2p orbitals on nitrogen with
the 1s orbital on each hydrogen atom, what would the molecular
geometry of NH3 be?
If use the
3 2p orbitals
predict 90o

Actual H-N-H
bond angle is
107.3o
sp3-Hybridized N Atom in NH3

Predict correct
bond angle
H 2S

Need 2 bonding
orbitals on S to
bond with H.
sp3 Hybridization in H2S

σ bonds

Lone e- pairs
 Predicting Hybridization of the Central Atom
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the
number of atoms bonded to the central atom
( = STERIC NUMBER)
Steric # Hybridization Examples
2 sp BeCl2
3 sp2 BF3
4 sp3 CH4, NH3,
H2O
5 sp3d PCl5
Formation of sp Hybrid Orbitals

22
Formation of sp2 Hybrid Orbitals

24
 Hybridization for PCl5
1. Draw the Lewis structure of the molecule.

2. Determine Steric Number ( = # of hybrid orbitals)

Steric Number = 5
So 5 orbitals must hybridize
s+p+p+p+d=
sp3d
 sp3d Formation (in Phosphorus)
Carbon Hybridization

5 σ bonds can form

Carbon Hybridization sp3d2 Formation (in Sulfur)

6 σ bonds can form

 Pi Bonds (π )
• e- in unhybridized p orbitals overlap to
form π bonds
• e- density above and below plane of
nuclei of the bonding atoms
Ozone (O3)
 Bonding in Ethylene, C2H4

Sigma bond (σ ) – electron density between the 2 atoms

Pi bond (π ) – electron density above and below plane of nuclei

of the bonding atoms
35
 Sigma (σ ) and Pi Bonds (π )

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many σ and π bonds are in the acetic acid (vinegar) molecule CH3COOH?

H
O

σ bonds = 6 +1=7
H C C O H
π bonds = 1

H
36
How can we
explain the
bonding in
formaldehyde?
O
C
H H

Steric Number ?
3
 sp2
sp2 Hybridization of Carbon

π bond
How can we describe the
bonding
In acetylene?
sp Hybridization of Carbon

2 π bonds
45
Valence Bond Model for
Acetylene
If this slide does not work go to http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf Next
HW p. 442 # 20, 22, 25 -29