Chapter 10 & 11:

Molecular Geometry

1. VSEPR Method
2. Polar Molecules and Dipole Moments
3. Valence Bond Theory: Hybridization of Atomic Orbitals
4. Multiple covalent bonds: Sigma and pi bonds

*Molecular Orbital Theory is not covered

 Molecular Geometry
The term molecular geometry = shape of molecules

Molecules occupy space in 3-D

Precise molecular geometry can only be determined by

experiment. However, we can try to predict the molecular
geometry of a molecule by applying VSPER method and
Valence Bond Theory

The VSEPR method uses the Lewis structure approach in

determining molecular geometry whereas the Valence Bond
Theory uses the Quantum Mechanical approach

SNSJ Chap10-11 2
 VSEPR Method
Valence-shell Electron-Pair Repulsion (VSEPR) is an
extension of the Lewis Dot Symbol and Lewis Structure

Based on the idea that pairs of valence e- in bonded atoms

repel one another

These mutual repulsions push e- pairs as far from one

another as possible

This max separation minimizes the energy of repulsion and

represents the lowest energy configuration of the
molecule (lowest potential energy)

SNSJ Chap10-11 3
 VSEPR Method
There are 2 types of molecule/compound:
a central atom with no lone pair e-
a central atom with 1 or more lone pair e-

To determine the Molecular geometry of a compound, you

must:
1. Draw its Lewis structure
2. Write the VSEPR notation based on its Lewis Structure
3. Lookup the structure in the Molecular Geometry Table

SNSJ Chap10-11 4
Figure 10.9 A summary of common molecular shapes with two to six electron
groups.

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Figure 10.2 Electron-group repulsions and molecular shapes.

trigonal planar

linear tetrahedral

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Figure 10.2 Electron-group repulsions and molecular shapes.

trigonal bipyramidal

octahedral

SNSJ Chap10-11 7
Figure 10.3 The single molecular shape of the linear electron-group
arrangement.

Examples:
CS2, HCN, BeF2

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Figure 10.4 The two molecular shapes of the trigonal planar electron group
arrangement.
Class

Shape

Examples:
SO3, BF3, NO3, CO32
Examples:
SO2, O3, PbCl2, SnBr2
SNSJ Chap10-11 9
 Factors Affecting Actual Bond Angles
Bond angles are consistent with theoretical angles when the
atoms attached to the central atom are the same and when all
electrons are bonding electrons of the same order.

Effect of Double Bonds 120o 122o

H larger EN H
120o C O 116o C O
Predicted or ideal H H
greater
electron actual
density
Effect of Nonbonding (Lone) Pairs

Lone pairs repel bonding pairs more strongly

Sn
than bonding pairs repel each other.
Cl Cl

95o
SNSJ Chap10-11 10
Figure 10.5 The three molecular shapes of the tetrahedral electron-group
arrangement.

Examples:
CH4, SiCl4,
SO42-, ClO4-

NH3
PF3 H2O

ClO3 OF2

H3O+ SCl2

SNSJ Chap10-11 11
Figure 10.6 Lewis structures and molecular shapes.

SNSJ Chap10-11 12
Figure 10.7 The four molecular shapes of the trigonal bipyramidal electron-
group arrangement.
SF4
XeO2F2
PF5
IF4+
AsF5
IO2F2-
SOF4

ClF3
XeF2
BrF3
I3-
IF2-

SNSJ Chap10-11 13
Figure 10.8 The three molecular shapes of the octahedral electron-group
arrangement.

SF6
IOF5

BrF5
XeF4
TeF5- ICl4-
XeOF4

SNSJ Chap10-11 14
Central Atom with one or more lone pair electrons

SNSJ Chap10-11 15
 Polar Molecules and Dipole Moments
The dipole moment of a molecule is the product of the
magnitude of the partial charge and the distance that
separates the centers of positive and negative charge
Recall that, polar covalent bonds are formed when two atoms
of different electronegativity (EN) form a bond
Partial charges exist in polar bonds. Polarity of bonds are
indicated by delta plus and minus or the cross-based arrow.
By predicting the dipole moment of a molecule, you can
predict if a molecule is polar or nonpolar
Generally, AXn molecules (where X is of the same type) are
nonpolar as the dipoles cancel each other

SNSJ Chap10-11 16
 Polar Molecules and Dipole Moments

Example of polar and nonpolar molecules

ENN = 3.0

ENH = 2.1

N N N
H H H H H H
H H H
molecular dipole

SNSJ Chap10-11 17
 Polar Molecules and Dipole Moments

CO2 is overall nonpolar because of equal e- sharing pointing away from

central atom, H2O is overall polar due to unequal e- sharing and
upward net dipole
SNSJ Chap10-11 18
 Polar Molecules and Dipole Moments

F
B F
1200
F

BF3 and CCl4 is overall nonpolar because all the dipoles cancel each
other, producing no net dipole (net dipole is zero)

SNSJ Chap10-11 19
Polar Molecules and Dipole Moments

CHCl3 is overall polar

SNSJ Chap10-11 20
Polar Molecules and Dipole Moments

SNSJ Chap10-11 21
Polar Molecules and Dipole Moments

SNSJ Chap10-11 22
 Polar Molecules and Dipole Moments

CHCl3 is overall polar

CH2Cl2 of the cis structure is polar, but the trans structure is nonpolar
SNSJ Chap10-11 23
 CHAPTER 11: Hybridization
Hybridization applies the Valence Bond Theory

Hybridization is just another method of determining the

molecular shape of compounds using quantum theory

Sometimes the VSEPR method cannot explain the discrepancy

between the experimental result and theoretical result.
Hybridization is better able to explain why this happen.

The lone pair electrons play a role in the polarity of a compound

and its reactivity (ability to pick up other atoms or ions) as you
will see in Chem II

SNSJ Chap10-11 24
 Hybridization
Summary of Hybridization:
Hybrid Geometric Orientation of Example
Orbitals a compound
sp Linear BeCl2
sp2 Trigonal planar BF3
sp3 Tetrahedral CH4
sp3d Trigonal bipyramidal PCl5
sp3d2 Octahedral SF6

We can specify the bonding type of an atom in that compound. E.g. the carbon
atom in methane has sp3 hybridization which corresponds to the tetrahedral
shape of methane. An sp3 hybrid represents an overlap of 1s orbital with 3 other
p orbitals.
SNSJ Chap10-11 25
Summary of Hybridization (from
textbook):

SNSJ Chap10-11 26
 Hybridization
Hybridization explains how the orbitals of covalent bonds overlap
in a molecule/compound

Each overlapping orbital will produce a NEW orbital or hybrid

These new orbitals are called sp, sp2, sp3, sp3d and sp3d2 for
which the molecular shape of the compound is linear, trigonal
planar, tetrahedral, trigonal bipyramidal and octahedral
respectively

Recall also that a linear molecule has 2 bonds, a trigonal planar

has 3 bonds, a tetrahedral has 4 bonds etc. Therefore, there must
be 2 sp hybrids for a linear molecule, 3 sp2 hybrids for trigonal
planar molecule and 4 sp3 hybrids for a tetrahedral molecule.

SNSJ Chap10-11 27
 Hybridization
VB Theory: A covalent bond forms when orbitals of 2 atoms
overlap & the overlap region (b/w the nuclei) is occupied by
a pair of e-

1. The e- pair must have opposing spins (Pauli Exclusion

Principle)

2. A maximum overlap of bonding orbitals is achieved. The

greater the overlap region, the stronger the bond. So, atoms
will align their valence orbitals until a maximum overlap is
achieved.

3. Linus Pauling: Valence orbitals in a molecule are different

from those in an isolated atom. The type of hybrid obtained
depends on the type of orbitals overlapped
SNSJ Chap10-11 28
 Figure 11.1 Orbital overlap and spin pairing in three diatomic
molecules.

Hydrogen, H2

Hydrogen fluoride, HF

Fluorine, F2

SNSJ Chap10-11 29
Figure 11.2 The sp hybrid orbitals in BeCl2

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Figure 11.3 The sp2 hybrid orbitals in BF3.

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Figure 11.4 The sp3 hybrid orbitals in CH4.

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Figure 11.5 The sp3 hybrid orbitals in NH3.

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Figure 11.5 continued The sp3 hybrid orbitals in H2O.

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Figure 11.6 The sp3d hybrid orbitals in PCl5.

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Figure 11.7 The sp3d2 hybrid orbitals in SF6.

SNSJ Chap10-11 36
 Multiple Covalent Bonds
The concept of hybridization also explains how a triple bond is
stronger than double and single bonds. Likewise in comparing
the strength of a triple bond and a double bond.

Single bond 1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma and 2 pi bonds

All single bonds are sigma bonds where the overlapping is

caused by end-to-end overlapping. A sigma bond is a linear
overlapping orbital.

SNSJ Chap10-11 37
 Multiple Covalent Bonds
Multiple bonds contain pi bonds where the overlapping is
caused by side-by-side overlapping. A pi bond consists of 2
parallel orbitals.

The overlapping region of a sigma bond occur at a maximum

overlap, making sigma bonds stronger than pi bonds.

On the other hand, a triple bond has the most overlapping

bonds and a single bond has the least overlapping bonds. This
makes a triple bond much stronger than a single bond.
Therefore, most difficult to break a triple bond.

The parallel overlapping (or shape) of the pi bonds cause

multiple bonds to have restricted rotation. In fact, rotation is
only possible by breaking the bonds.
SNSJ Chap10-11 38
Figure 11.10 The s and p bonds in ethylene (C2H4).

electron density

SNSJ Chap10-11 39
Figure 11.11 The s and p bonds in acetylene (C2H2).

SNSJ Chap10-11 40
 Conclusion
Different compounds can have different shapes based on the
number of lone pairs and bonding pairs on the central atom

VSEPR and Hybridization are 2 methods that can be used to

determine the shape of molecules.

Polarity of a molecule depends on the net dipole moment. A

nonpolar molecule occur when there is no net dipole, a polar
molecule occur when there is a net dipole.

The type of bond that exists between atoms would give

different physical and chemical properties

SNSJ Chap10-11 41