Ch.

9 Chemical Bonding and

Molecular Structure

Brady & Senese, 5th Ed

Index
9.1. Molecules are three-dimensional with shapes that are buil
t from five basic arrangements
9.2. Molecular shapes are predicted using the VSEPR model
9.3. Molecular symmetry affects the polarity of molecules
9.4. Valence bond theory explains bonding as an overlap of or
bitals
9.5. Hybrid orbitals are used to explain experimental molecul
ar geometries
9.6. Hybrid orbitals can be used to explain multiple bonds
9.7. Molecular orbital theory explains bonding as constructiv
e interference of atomic orbitals
9.8. Molecular orbital theory uses delocalized orbitals to desc
ribe molecules with resonance structure
Lima Bentuk Dasar Geometri Pasangan
Elektron
Domain Bentuk Dasar Molekul Geometri
Elektron
2 linear

3 trigonal planar

4 tetrahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic 3
arrangements
The Five Basic Electron Arrangements (Cont.)

Electron Domains Shape Electron Pair Geometry

5 Bipiramida trigonal

Memiliki posisi axial

dan equatorial

6 oktahedral

Memiliki posisi axial

dan equatorial

9.1 Molecules are three-dimensional with shapes that are built from five basic 4
arrangements
Learning Check:
Tentukan Geometri pasangan elektron untuk tiap
atom pusat

tetrahedral tetrahedral Trigonal

bipyramidal

9.1 Molecules are three-dimensional with shapes that are built from five basic 5
arrangements
Your Turn!

What is the electron pair geometry for C in CO2?

A. linear
B. planar triangular
C. tetrahedral
D. trigonal bipyramidal
E. octahedral

9.1 Molecules are three-dimensional with shapes that are built from five basic 6
arrangements
Bonding Domains And Non-bonding Domains

• Bonding domains are shared

between nuclei
• Non-bonding domains are not
shared between nuclei-they exert a
greater electrical field
• Repulsion leads non-bonding
domains to occupy larger space
• The basic shapes are distorted by
non-bonding domains to create the
molecular geometry

9.2 Molecular shapes are predicted using the VSEPR model 7

Trigonal Planar Molecular Geometries

Bonding Domains Non-bonding Molecular

Domains Geometry

3 0 trigonal planar

2 1 bent

9.2 Molecular shapes are predicted using the VSEPR model 8

Tetrahedral Molecular geometries

9.2 Molecular shapes are predicted using the VSEPR model 9

Trigonal Bipyramidal
• Equatorial (e)
positions are
substituted first
• This is because
the e,e bond
angles are 120°,
while a,e bond
angles are only
90°

9.2 Molecular shapes are predicted using the VSEPR model 10

Octahedral Geometries
• All bond angles
are 90°
• Axial positions
are substituted
first

9.2 Molecular shapes are predicted using the VSEPR model 11

Learning Check:
Identify the molecular geometry for each center

Trigonal Non-linear,
Linear
pyramidal bent

9.2 Molecular shapes are predicted using the VSEPR model 12

Your Turn!

Which require more space?

A. bond pairs
B. lone pairs
C. both are the same

9.2 Molecular shapes are predicted using the VSEPR model 13

Your Turn!

Which bond angles are closer in a trigonal

bipyramidal structure (a= axial; e=equatorial)?
A. a-a
B. a-e
C. e-e
D. they are all the same

9.2 Molecular shapes are predicted using the VSEPR model 14

Your Turn!

What is the molecular geometry of C in CH4?

A. Linear
B. Square planar
C. Square pyramidal
D. Tetrahedral
E. None of these

9.2 Molecular shapes are predicted using the VSEPR model 15

Polar Molecules Are Asymmetric
• To determine the polarity, draw the structure using
the proper molecular geometry
• Draw the bond dipoles
• If they cancel, the molecule is non-polar
• If the molecule has uneven dipole distribution, it is
polar

9.3 Molecular symmetry affects the polarity of molecules 16

Learning Check:

Polar or non-polar?

polar polar Non-polar

9.3 Molecular symmetry affects the polarity of molecules 17

Your Turn!

CH2ClCH2Cl (freon-150) is likely to be:

A. Polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules 18

Your Turn!

Benzoyl peroxide (used in common acne

medications) is likely to be:
A. polar
B. non-polar
C. cannot tell

9.3 Molecular symmetry affects the polarity of molecules 19

Teori Ikatan
• Terdapat tiga teori ikatan yang dapat menjelaskan
ikatan kovalen, yaitu:
1. Teori ikatan valensi (valence bond theory/VB)
2. Teori hibridisasi
3. Teori orbital molekul (molecular orbital
theory/MO)
1: Teori Ikatan Valensi (VB)

Teori ini menjelaskan bahwa pada suatu molekul,

ikatan kovalen terbentuk akibat tumpang tindih
(overlap) orbital-orbital valensi.
Contoh:
• Ikatan kovalen dalam H2 terbentuk karena orbital
valensi masing-masing atom saling overlap

1s 1s

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 21

• Ikatan pada HF merupakan overlap antara orbital s
pada atom H dan orbital 2p pada atom F.

1s 2s 2p
VB Theory dan H2S

• Asumsikan bahwa
elektron tak
berpasangan pada S
dan H langsung
membentuk ikatan.
• Ikatan H-S akan
terbentuk melalui
overlap antara orbital
s dan p
• Sudut ikatan 900

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 23

Your turn!

According to VB Theory:
Which type of overlap does not occur in BH3?
A. s-s
B. s-p
C. p-p
D. none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 24

Your turn!

According to VB Theory:
Which orbitals overlap in the formation of NH3?
A. s-s
B. s-p
C. p-p
D. none of these

9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 25

Kekurangan Teori VB:
• Mayoritas sudut ikatan hasil pengukuran
eksperimen tidak sesuai dengan hasil prediksi
teori VB
• Misalnya: C 1s22s22p2 and H 1s1
• Sudut ikatan hasil pengukuran eksperimen
pada metana (CH4) adalah 109.5° dan semua
sudutnya sama besar
• Orbital p memiliki sudut 900 satu sama
lainnya, tidak semua elektron valensi terdapat
pada orbital p
• Tidak dapat menjelaskan mengenai
pembentukan ikatan rangkap
9.4 Valence bond theory explains bonding as an overlap of atomic orbitals 26
2: Teori Hibridisasi
• Pada teori ini, terjadi penggabungan (hibridisasi)
orbital-orbital atom sehingga membentuk ikatan
yang sudutnya realistis
• Orbital baru hasil penggabungan orbital disebut
“orbital hibrida”
• Jumlah orbital hibrida yang dibutuhkan =
jumlah domain ikatan + jumlah domain
nonbonding (elektron bebas)

9.5 Hybrid orbitals are used to explain experimental molecular geometries 27

Bentuk Orbital Hibrida s & p sesuai dengan
Geometri VSEPR
Hybrid Atomic Electron
Orbitals Geometry
Used
sp3 s + px + py Tetrahedral,
+ pz bond angles
109.5˚
sp2 s + px + py Trigonal
planar, bond
angles 120 ˚
sp s + px Linear,
bond angles
180 ˚

9.5 Hybrid orbitals are used to explain experimental molecular geometries 28

Hybridization (sp3)

• 3. Now analyze the atomic orbital needs. You will need

to use one atomic orbital for every hybrid orbital .
• For C in CH4 we will need 4 hybrid orbitals.
• 2s↑ 2p ↑ _ ↑ ↑_
• Thus, we will need to use all valence level atomic
orbitals available to us.
• (2s↑ 2p ↑ _ ↑ _ ↑)
• S + p + p + p → 4 new equivalent “sp3” orbitals.
H

H
C
H H
9.5 Hybrid orbitals are used to explain experimental molecular geometries 29
s & p hybrid shapes

9.5 Hybrid orbitals are used to explain experimental molecular geometries 30

Your Turn!

In the compound CH3OH, what is the expected

hybridization on O?
A. sp
B. sp2
C. sp3
D. O does not hybridize

9.5 Hybrid orbitals are used to explain experimental molecular geometries 31

 Bonding Types
• Two types of bonds result from
orbital overlap:
• sigma (σ) bonds
 from head-on overlap
 lie along the bond axis
 account for the first bond
• pi (π) bonds
 from lateral overlap by adjacent p or
d orbitals
 pi bonds are perpendicular to bond
axis
 account for the second and third
bonds in a multiple bond

9.6 Hybrid orbitals can be used to describe multiple bonds 32

Pi Bonding

9.6 Hybrid orbitals can be used to describe multiple bonds 33

H−C≡C −H
• Each C has a
triple bond
and a single
bond
• Requires 2
hybrid
orbitals, sp
• unhybridized
p orbitals
used to form
the pi bond
9.6 Hybrid orbitals can be used to describe multiple bonds 34
Your Turn!

Consider a molecule of CH3CO2H:

How many pi bonds are there in the molecule?
A. 1
B. 2
C. 3
D. 4
E. There are none

9.6 Hybrid orbitals can be used to describe multiple bonds 35

3: Teori Orbital Molekul (MO)
• Merupakan modifikasi dari teori VB yang
memperhitungkan bahwa orbital-orbital yang mengalami
overlap mengalami interferensi (konstruktif dan destruktif)
• Orbital ikatan (bonding) mengalami stabilisasi sedangkan
orbital antiikatan (antibonding) mengalami destabilisasi.

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 36

orbitals
Diagram MO
• Show atomic energy level diagram for each atom
• Show molecular orbitals (bonding and antibonding*)
• 1 MO for each Atomic orbital.
• Show electron occupancy of the orbitals.

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 37

orbitals
Pengisian Diagram MO

1.  Elektron mengisi orbital dengan energi terendah

terlebih dahulu
2. Satu orbital molekul hanya dapat diisi
maksimum 2 elektron dengan spin berpasangan
3. Jika ada dua orbital molekul dengan energi yang
sama, pengisian elektron mengikuti aturan Hund
4. Orde ikatan = ½ (# e- bonding - # e-
antibonding)
5. Sifat magnet dapat ditentukan

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 38

orbitals
Diatomic MO diagrams differ by group
• A) I - V B) VI-VIIIA

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 39

orbitals
MO diagrams
Draw the expected MO diagram for:
• O2

• HB

• He2

Which are not likely to exist, and why?

9.7 Molecular orbital theory explains bonding as constructive interference of atomic 40

orbitals
Delocalized Electrons
• Lewis structures use resonance to explain that the
actual molecule appears to have several equivalent
bonds, rather than different possible structures
• MO theory shows the electrons being delocalized
in the structure

9.8 Molecular orbital theory uses delocalized orbitals to describe molecules with 41
resonance structures