CHEM1907/8

Lecture 9. The Shapes of Molecules

The Shapes of Molecules

Learning Objectives

(Silberberg; 10.3)

Understand Valence Shell Electron Repulsion Theory

(VSEPR)

Draw geometries adopted by species with no

unpaired electrons

Draw geometries adopted by species with electrons

Orbital Hybridisation
(Silberberg; 11.1-11.2)

Learning Objectives

Understand the nature of the covalent bond (sigma and pi)

Understand orbital hybridisaiton

Linear
The number of electron groups is the number of bound atoms
and non-bonding electron pairs that are part of the molecule.
(1 pair of non-bonding electrons constitutes 1 electron group)

Total number of electron groups = 2

Total number of atoms (X) = 2
Total number of non-bonded electron
pairs (E) = 0
Symbol = AX2, where A is the central
atom

Tetrahedral I
Molecular Arrangement = Tetrahedral
Molecular Shape = Tetrahedral
Total number of electron groups = 4

Lecture Slides (28/03/03)

The Shapes of Molecules

Lewis structures show the type of bonding
(single, double, triple) and the distribution of
non-bonding electrons
Lewis structures do not model the
shapes of molecules
Valence Shell Electron Pair Repulsion (VSEPR)
theory is used to describe the
Shapes of Molecules
VSEPR. Each group of valence electrons around a
central atom is located as far away as possible from
the others in order to minimize repulsions

Trigonal Planar I

Total number of electron groups = 3

Total number of atoms (X) = 3

Molecular Arrangement = Trigonal Planar

Molecular Shape = Bent

Total number of non-bonded electron

pairs (E) = 0

Total number of electron groups = 3

Symbol = AX3, where A is the central

atom

Total number of non-bonded electron pairs (E) = 1

Tetrahedral II

Total number of atoms (X) = 2

Symbol = AX2E, where A is the central atom

Tetrahedral III

Molecular Arrangement = Tetrahedral

Molecular Shape = Trigonal Pyramidal
Total number of electron groups = 4

Total number of atoms (X) = 4

Total number of non-bonded
electron pairs (E) = 1

Molecular Arrangement = Tetrahedral

Molecular Shape = Bent
Total number of electron groups = 4
Total number of atoms (X) = 2

Symbol = AX3E, where

A is the central atom
Symbol = AX4, where A is the central atom

Trigonal Planar II

Molecular Arrangement = Trigonal Planar

Molecular Shape = Trigonal Planar

Total number of atoms (X) = 3

Total number of non-bonded

electron pairs (E) = 0

Valence Shell Electron Pair Repulsion (VSEPR)

Total number of non-bonded electron pairs (E) = 2

Symbol = AX2E2, where A is the central atom

AX4 Geometry - Tetrahedral

H

Methane

H
H

Using VSEPR Theory to Determine

Molecular Shape

109.50

CH4

Write the Lewis structure:

the Lewis structure from the molecular formula to see the
relative placement of atoms and the number of electron groups.

and name the molecular shape by counting bonding group

and non-bonding groups separately.

AX2 X-A-X = 180

BeCl2

Chemical bonds can be understood in terms of the interactions

between the orbitals of the atoms that comprise the molecule

trigonal planar
bent

3
3

3
2

0
1

AX3 X-A-X = 120

AX2E E-A-X > 120; X-A-X < 120

AlCl3
SO2

Types of Bonding

tetrahedral
trigonal pyramidal
bent

4
4
4

4
3
2

0
1
2

AX4 X-A-X = 109.5

AX3E E-A-X > 109.5; X-A-X < 109.5
AX2E2 E-A-X > 109.5; X-A-X < 109.5

CH4
NH3
H2O

Those involved in head-on atomic

orbital overlap to form
bonds (known a electrons)

Groups Atoms e pairs Symbol Angles () A-X-A; E-X-A

Example

But the molecular shapes of more complex molecules (eg

trigonal planar, tetrahedral), suggests that bonding in these
molecules cannot be explained by the overlap of spherical s
orbitals and dumb-bell-shaped perpendicular p orbitals.

z
y

H
1s

2s

2p

Linus Pauling proposed that the valence atomic orbitals in the

molecule are different from those in the isolated atoms.
The process of orbital mixing is called hybridization, and the
new atomic orbitals are called hybrid orbitals

1s

2s

H
H

C
H

2p

1s

sp (4)

2p

Methane-sp3 hybridisation

Carbon atoms must undergo hybridisation

in order to bond to other atoms

2s

How is carbon able to form tetrahedral complexes?

1s
x

The greater the orbital overlap, the stronger the bond

Ground state electron configuration of carbon, Z = 6

Hybridisation-sp3

NCl3 has a trigonal

pyramidal shape

Consider the formation of the bond in hydrogen fluoride, HF

Those which are not participating in bonding (known as

nonbonding electrons)

Orbital Hybridisation

..
..

Cl

A covalent bond forms when the orbitals of two atoms overlap

and are occupied by one pair of electrons (with opposing spins)

Those involved in a parallel

atomic orbital overlap to form
bonds (known a electrons)

In simple diatomic molecules, such as HF, the bond results from

the direct overlap of one s orbital (H) and one p orbital (F) from
the isolated atoms

..

The Formation of Covalent Bonds

Chemical Bonds

linear

Geometry

..
Cl
.. ..
Cl
..

Draw

The Shapes of Molecules

Draw and name the molecular shape:

..

For the tetrahedral arrangement, the ideal angle is 109.50. Since

there is one lone pair, the actual bond angle should be < 109.50

..

In the ammonium
ion (NH4+), all
angles are
the same

Predict the ideal bond angle from the electron-group

arrangement and the direction of any deviation caused by the
lone pairs or double bonds.

..

Ammonia (NH3) is a tetrahedral shape.

H
The electron pair increases the
(H)(N)(e-pair) angles (2) to > 109.5
and therefore, the (H)(N)(H) angles (2)
are < 109.5

Assign an electron-group arrangement by counting all electron

groups around the central atom, bonding plus nonbonding.

Cl

..
..

..

H
All molecules or ions with four electron groups around a
central atom adopt the tetrahedral arrangement
H
H
109.50
0
109.5
0
107.3
N
+ H+
H
N

.. .. ..
.. N Cl
..
Four electron groups around N,
Cl
(three bonding, and one non-bonding),
..
so the arrangement is tetrahedral
Assign the electron arrangement:

..

Write

Determine the molecular shape and ideal bond angles for NCl3

..

Predicting Molecular Shapes

1s

2s

1s

2p

sp (4)