Valence

Shell Planar
triangular
Electron Tetrahedral

Pair
Repulsion Trigonal
pyramidal

Theory Bent
Molecular Shape
VSEPR theory assumes that the shape of a
molecule is determined by the repulsion of
electron pairs.
 VSEPR Theory
• Based on Electron Dot (Lewis structures)

• Theory predicts shapes of compounds

• abbreviated VSEPR

• VSEPR (pronounced “vesper”) stands for

Valence Shell Electron Pair Repulsion

• VSEPR predicts shapes based on electron pairs

repelling (in bonds or by themselves)

• Electrons around central nucleus repel

each other. So, structures have atoms
maximally spread out
 VSEPR overview
• Each shape has a name
(you will have to know these)
• Names of Shapes:
• tetrahedral

• trigonal pyramidal

• Bent

• Linear

• trigonal planar
Models

Tetrahedral Triangular Planar Bent or V

Linear
Trigonal pyramidal
 Underlying principle
(see Shriver & Atkins)
• In the VSEPR model, electron
regions
of enhanced
pairs take up electron
positionsdensity
as far
take up
apart aspositions
possible.as far apart as
possible.
• EPs can be bonding pairs
(BPs) or lone pairs (LPs).
 How confident do you feel about
using VSEPR to determine shapes?
58%
1. It’s a doddle!

2. OK, but need to revise it a bit.

27%
3. Not too confident.
9%
4. I don’t remember much. 2% 4%

It’s a doddle!

Not too confident.

I don’t remember

I don’t remember this

OK, but need to
revise it a bit.
5. I don’t remember this at all!

much.

at all!
 Step-by-step
1. Write a Lewis dot structure for the molecule.
* A Lewis dot structure is like a dot-and-cross
* diagram that only uses dots.
e.g. methane
C – 4 valence electrons

All 4 valence electrons on

H – 1 valence electron C pair up with an electron
from an H atom, forming 4
bonds.
 Step-by-step
2. Count the number of atoms and lone pairs
around the central atom.
e.g.
4 atoms around carbon,
and no lone pairs.

4 regions of electron
density to distribute.
 Step-by-step
3. Work out how the regions of high electron
density will be arranged around the central
atom:
2 Regions – Linear
3 Regions – Trigonal planar
4 Regions – Tetrahedral
5 Regions – Trigonal bipyramidal
6 Regions – Octahedral
 Step-by-step
4. Draw the structure and label bond angles.

109.5º

Tetrahedral
 Step-by-step
4. Draw the structure and label bond angles.

109.5º

Tetrahedral
 Beryllium hydride

• Be – 2 valence electrons

• 2 bonds formed to H atoms

• Linear molecule

180º
 What is the shape of BF3 ?
1. Tetrahedral
2. Trigonal planar 0%6%

3. Linear
94%
4. V-shaped
5. Octahedral Tetrahedral Trigonal planar Linear
V-shaped Octahedral
 Boron trifluoride

• B – 3 valence electrons

• 3 bonds formed to F atoms

• Trigonal planar molecule

120º
 What is the shape of SF6 ?
1. Tetrahedral
2. Trigonal pyramidal 0%
3%
0%

3. Linear
97%
4. V-shaped
5. Octahedral Tetrahedral
Linear
Trigonal pyramidal
V-shaped
Octahedral
 Sulphur hexafluoride

• S – 6 valence electrons

• 6 bonds formed to F atoms

• Octahedral molecule

90º
What about lone pairs?
 Which statement is correct?
1. Repulsion due to bonding
pairs is greater than
repulsion due to lone pairs. 14%
5%
2. Repulsion due to bonding
pairs is the same as
81%
repulsion due to lone pairs.
3. Repulsion due to lone pairs
A B C
is greater than repulsion
due to bonding pairs.
 Step-by-step
1. Write a Lewis structure for the molecule.
e.g. water
O – 6 valence electrons

H – 1 valence electron 2 of oxygen’s 6 valence

electrons pair up with an
electron from an H atom,
forming 2 bonds. The
remaining valence electrons
make up 2 LPs.
 Step-by-step
2. Count the number of bonds and lone pairs
around the central atom.
e.g. Water

2 bonds and 2 LPs

4 regions of
electron density
to distribute
 Step-by-step
3. Work out how the electron regions will be
arranged around the central atom:
2 Regions – Linear
3 Regions – Trigonal planar
4 Regions – Tetrahedral
5 Regions – Trigonal bipyramidal
6 Regions – Octahedral
 Step-by-step
4. Deduce the shape of the molecule based on
the arrangement of atoms (not including LPs)
 Step-by-step
5. Draw the structure.

What about the bond angle?

 Methane, ammonia and water

4 bonds, 0 lone pairs

3 bonds, 1 lone pair
2 bonds, 2 lone
Tetrahedral Trigonal pyramidalBent (v-shape
Bond angle = 109.5º

This is the ideal tetrahedral an

What’s the bond angle in water?

A. 109.5º
B. 108º 7% 7%
C. 104.5º
86%

109.5º 108º 104.5º

 What’s the bond angle in
ammonia?
A. 109.5º
B. 108º
5% 8%
C. 104.5º

88%

109.5º 108º 104.5º

 Methane, ammonia and water

4 bonds, 0 lone pairs

3 bonds, 1 lone pair
2 bonds, 2 lone
Tetrahedral Trigonal pyramidalBent (v-shape
Bond angle = 109.5º
Bond angle = 108º
Bond angle = 1
One lone pair reduces the bond angle slightly
Two lone pairs reduce the bon
 Try another one yourself…
What is the shape of a XeF4 molecule?
• Lewis structure 
• Count e- regions around central atom  6
• How many lone pairs are there?  2
• Draw structure and label bond angles.
Press any button on your
handset when you have
completed the task.
 Xenon tetrafluoride
• Xe – 8 valence electrons

• 4 bonds formed to F atoms

• 4 electrons left = 2 LPs

• 6 regions  octahedral

• 4 regions are bonds 

Square planar molecule
 Xenon tetrafluoride
• Xe – 8 valence electrons

• 4 bonds formed to F atoms

• 4 electrons left = 2 LPs

• 6 regions  octahedral

• 4 regions are bonds 

Square planar molecule

Bond angle = 90º

 methane, CH4

Tetrahedral
109.5°

Bonds are all evenly spaced electrons

 .. ammonia

..
..

..
NH3
Trigonal
Pyramidal

Less repulsion between the bonding pairs of electrons

 .. ..
..

water, H2O

109.5° (109.5°) 109.5° (107°) 109.5° (104.5°)

.. ..
..
 Bent or V
2 unshared pairs of e’s at
top of O repel bonds and
force them to bend
Molecule Lewis Structure Number of SHAPE
electron pairs

CH4 4
Tetrahedral

Trigonal
NH3 4 Pyramidal

(3 shared
1 lone pair)
Molecule Lewis Structure Number of
electron pairs SHAPE

Bent or V
H 2O 4
(2 shared
2 lone pairs)

Linear

CO2 2
Molecule Lewis Structure Number of SHAPE
electron pairs

Linear
BeCl2 2

Trigonal
BF3 Planar
3
question: predict the shape of CO2 HCN CH4, NH3 SO2 PCl5,
SF6 and H2O by using VSEPR theory.
question: predict the shape of CO2 HCN CH4, NH3 SO2 PCl5,
SF6 and H2O by using VSEPR theory.
The nonbonding electron pairs are as important as bonding electron pairs in
determining the structure.

Nonbonding electrons take up more space in the valence shell than the bonding
electrons.

If one or more of the electron pairs are lone pairs, the distribution of electron
pair and the geometrical shape of the molecule must be different.

The bond angles decrease as the number of nonbonding electron pairs

increases

Repulsion strengths

lone pair -lone pair  lone pair e-bond pair  bond pair-bond pair
 Hybridization
• Look at the orbital
notation for the carbon
atom on the right.
• There appear to be only 2s 2p
two electrons available
for bonding with other
atoms. X
X
• However, one carbon X C X
will bond equally with
four hydrogens as in
methane, CH4.
 Hybridization of the carbon
atom
• The orbitals combine
an s orbital and three p
orbitals to form four
equal sp3 hybrid
orbitals. sp3 hybrid orbitals

• Each hybrid orbital can H

bond with a hydrogen X 0
atom. X X
H0 C 0 H
X 0

H
 Most molecular bonding
involves hybrid orbitals.
• Two equal bonds are • Five equal bonds are
formed by a s and a p formed by a s, 3p and a
orbital-2 sp hybrids d orbital-5 sp3d hybrids
• Three equal bonds are • Six equal bonds are
formed by a s and 2 p formed by a s, 3p and 2
orbitals-3 sp2 hybrids d orbitals-6 sp3d2
• Four equal bonds are hybrids
formed by a s and 3 p
orbitals-4 sp3 hybrids
Without VSEPR you want to
draw Methane, CH4 like this.
H
e- e-
e- e-
H e- C e-
H
e- e-

H
 However, this isn’t VSEPR.
• This looks good in 2
dimensions, all angles
are 90° but the H
molecule is 3D. e- e-

• The electron pairs e- - e-

C e- e- H
H e- e H
aren’t as far apart as
e- e-
possible.
• From the side we see H
that some are 180 °.
This doesn’t fit VSEPR.
The shape that allows the maximum
distribution of electron pairs in 3D is
the tetrahedron. All bond angles are
109.5°.
 Without VSEPR, this is the
way that you would draw the
water molecule. All angles
are equal and balanced.
e- e-

e- e-
H e- O e- H

e- e-
Due to the unequal repulsion of
the electrons the shape looks
more like this. Why?
H H
e- e-
e- e-

e- O e-
e- e-
 The angles aren’t all 109.5°, the
angle between the unshared pairs is
more than 109.5° and between the
shared pairs is only 104.5°.
Shared pairs push apart the least.
H H
e- e-
e- e-

e-
O e-
e- e-

Unshared pairs push apart

the most.
This figure shows the position of the
hydrogen atoms and the unshared
pairs in the water molecule. A
modified tetrahedral called “water
bent”.
 VSEPR Basic Shapes
• Linear shapes occur with 1 or 2 shared
pairs and sp hybrids.
• Trigonal planar shapes occur with sp2
hybrids.
• Tetrahedral shapes are based on sp3
hybrids.
• Trigonal bipyrimidals are based on sp3d
hybrids.
• Octahedrals are based on sp3d2 hybrids.
• All shapes are based upon these 5
 Organic molecules
• Often organic molecules (generally those
compounds containing carbon, hydrogen,
and sometimes oxygen) form multiple
bonds. These multiple bonds involve
more than one pair of e-. For V.S.E.P.R.,
count all multiple bonds as a single pair of
e-.
• When an organic compound has multiple
bonds it is called unsaturated. This means
that it doesn’t have the max. number of H
for the number of carbons.
  and  bonds
• All bonds contain a bond that occurs
directly between the nuclei involved. This
bond is a  bond.
• Multiple bonds also overlap above and out
to the side of  bonds. Bonds that occur
outside of a line drawn between the nuclei
are called  bonds.
• Double bonds have 1  and 1 . Triple
bonds have 1  and 2  bonds.
 Other bonds
• Conjugated systems occur when multiple
p orbitals overlap, as in benzene C6H6.
They are very stable.
• Coordinate covalent bonds are bonds
where both e- in the shared pair come
from one atom.
 Polar bond vs. Polar
molecule
• Every year students have trouble with the
difference between these two terms.
• Polar bonds refer to the difference in
electronegativities between two atoms.
Between 0.3 and about 1.7-polar bond.
• Polar molecules refer to the shape of a
molecule. If the partial charges aren’t
evenly distributed, it’s a polar molecule.
 Methane.
H δ+

C
H
δ+ H H δ+
 Molecular Orbitals
• When two atomic orbitals from different atoms
interact, two new molecular orbitals are
formed.
– Bonding molecular orbital- additive orbital, high
electron density between nuclei
– Antibonding molecular orbital- subtractive
orbital, low electron density between nuclei
(indicated by an *)
• Antibonding orbitals are higher energy than
bonding orbitals and therefore less stable.
• Bond order = ½ (e-bonding-e-antibonding)
Orbital Energy-Level Diagram
for the HF Molecule
The Electron Probability Distribution
in the Bonding Molecular Orbital of
the HF Molecule
The Sigma System for
Benzene
The Pi System for Benzene
 Valence bond theory
The covalent bonds are formed by overlap of atomic orbitals each of which
contains one electron of opposite spin.
The valence bond method predicts molecule
shapes from the shapes and orientation of the
atomic orbitals and their overlap regions when
two atoms approach.

In most cases the orbitals that overlap are

reconfigured orbitals, called hybrid orbitals,
having different shapes and orientations than
pure orbitals.

The process of hybridization corresponds to a

mathematical mixing of the valence-shell
atomic orbitals.
Bonding in Methane
 Valence Electron Pair Number of Hybrid
Geometry Orbitals Orbitals
Linear 2 sp
Trigonal Planar 3 sp2
Tetrahedral 4 sp3
Trigonal Bipyramidal 5 sp3d
Octahedral 6 sp3d2
question : find the hybridazation type and geometry of
CH4, PCl5, SF6. NH3 BeF2
Multiple Covalent Bonds
 Molecular Orbital Theory

A molecular orbital describes a region

of space in a molecule where electrons
are most likely to be found.

Molecular orbitals are formed by

combining atomic orbitals on different
atoms.
Combining Atomic Orbitals
 No. e- in bonding MOs - No. e- in antibonding MOs
Bond Order =
2
 Bonding in Metals

Electron sea model Band theory.

 12-7 Bonding in Metals

• Electron sea
model
 Bonding in Metals
Band theory.
Band Theory
Semiconductors
Photovoltaic Cells