The Bishops’ High School

Cape Chemistry Unit One

The Shapes and Bond Angles in Simple Molecules

The Valence Shell Electron Pair Repulsion Theory (VSEPR)

The VSEPR theory predicts the shapes and bond angles of simple covalent
molecules. A molecule’s shape is often an essential part of the explanation of its
properties. The shape of H2O molecule, for instance, is a factor in the water’s
ability to act as a good solvent for ionic compounds. In addition, the shape of
organic molecules affect their odours, their taste, their action as drugs, as well as
many of the reactions going on inside our bodies as we, think and work.

Different molecules have different shapes. The shape of a molecule is dictated by

number of Electron Pairs i.e. bonding pairs and lone pairs of electrons around a
central atom. This is because Electron Pairs repel each other. The VSEPR theory
focuses on the positions taken up by a given number of electron pairs in the
valence shell of the central atom of a molecule. This theory suggests that the
electron pairs around an atom repel each other and arrange themselves in a space
so as to minimize the repulsive forces. The molecule settles in a state where the
Electron Pairs are furthest apart from each other.

Different types of Electron Pairs have different repulsions. . There occur Lone
Pair Electrons (LP) and Bonding Pair Electrons (BP). The order of repulsion
between different combinations, in order of decreasing repulsion, and so
decreasing angle, is:

o LP - LP
o LP - BP
o BP – BP

Lone pair – lone pair repulsions are stronger than lone pair – bonding pair
repulsions.
Lone pair – bonding pair repulsions are stronger than bonding pair –
bonding pair repulsions.
Bonding pair – bonding pair repulsions are the least strong.

The strength of repulsion between electron pairs depends on the proximity of each
pair to the central atom. Lone pairs are closer to the central atom than bond pairs
since the lone pairs have no other nearby positive nucleus to pull them away from
the central atom. Bond pairs are attracted by a second nucleus and so they are
drawn further away from the central atom. The repulsion between electron pairs is
inversely proportional to the distance between them.

The presence of a lone pair in a molecule tends to push the other bond pairs closer
together. This will result in smaller bond angles in molecules containing a lone
pair.

Predicting the shape of simple molecules

 Common bond angles:

o 2 Electron Pairs on a single atom form 180° bond angles.
o 3 Electron Pairs on a single atom form 120° bond angles.
o 4 Electron Pairs on a single atom form 109.47° bond angles.
o 6 Electron Pairs on a single atom form 90° bond angles.
o 2 Lone Pairs and 2 Bonding Pairs on a single atom form a 104.5°
bond angle.
o 1 Lone Pair and 3 Bonding Pairs on a single atom form a 107° bond
angle.

Strategy

1. Write the Lewis structure.

2. Count the effective number of electron pairs around the central atom and predict

the arrangement of the atoms around each one.

3. Double bonds and triple bonds are treated as single electron pair.

Bond pair – Bond pair repulsion

Linear molecule

Two (2) Electron Pairs (bonding pairs) on a single atom form 180° bond angles.

Examples include BeCl2 and CO2

In CO2, a double bond acts as a single pair of shared electrons. Each carbon atom
has 4 bonding pairs which are equivalent.

Trigonal planar molecule

Three (3) Electron Pairs (bonding pairs) on a single atom form 120° bond
angles. Examples include BF3, SO3 and ethane.

Tetrahedral molecules

Four 4 Electron Pairs (bonding pairs) on a single atom form 109.5° bond angles.

Examples includes CH4, CHCl3 and POCl3

Trigonal bipyramidal molecules

Five (5) bonding pair around a central atom. The bond pairs arrange themselves to
form a trigonal bipyramidal shape. Three atoms form the trigonal plane with bond
angles of 120° while two atoms form the pyramid which is perpendicular to the
trigonal plane. Examples include PF5 and PCl5

Octahedral molecules

Six (6) Electron Pairs (bond pairs) on a single atom form 90° bond angles.
Examples include SF6 and SbCl6.
Effect of lone pairs on the shapes of molecules

Lone pair – bond pair repulsions

The presence of lone pairs influences the shapes of molecules. The number of bond
and lone pairs are used to predict a suitable structure for a molecule. Remember
that lone pairs repel bond pairs more strongly.

One lone pair – When a molecule has one lone pair with two bond pair, the three
pairs of electrons arrange themselves at maximum distance apart to form trigonal
planar molecule. However, the one lone pair will repel the two bond pairs closer
together and the molecule will be V- shaped or bent e.g SO2 and SnCl2.

One lone with three bond pairs form a tetrahedral shape, but the lone pair will
repel the three bond pairs closer together and the molecule will adopt a trigonal
pyramidal shape with bond angle les than 109.5. For example NH3 has abond angle
of 107°.
Two lone pairs with two bond pairs form a tetrahedral shape, but the lone pairs
will repel the two bond pairs closer together and the molecule will be V- shaped
with bond angle of 105°, e.g. H2O.

Two lone pairs with four bond pairs form a octahedral shape, but the lone pairs
will repel the four bond pairs closer together and the molecule will be square
planar with bond angle of 90°, e.g. XeF4
 Shapes of Simple Organic Compounds

Hybridisation of Orbitals

Hybridization is the process of mixing atomic orbitals. Carbon has the ability to
mix and rearrange the four orbitals in the outer shell. Carbon has the electronic
configuration 1s2 2s2 2p2 and can promote an electron from 2s orbital to the empty
2p orbital. Since both 2s and 2p subshells are half filled, the excited state is
relatively stable.

Two or more atomic orbitals can mix to create new orbitals of equal energy called
hybrid orbitals. If the s orbital and all three p orbitals mix, then four hybrid orbitals
of equal energy level are formed. The four unfilled C atomic orbitals can be
thought of as being mixed so that each has ½ s character and ¾ p character. These
mixed orbitals are called sp3 orbitals (sp3 hybridisation). For example, methane
and ethane.

Ethane Ethane

The 2s and all 2p orbitals in each carbon are mixed together to produce 4 identical
hybrid orbitals. These end- on overlap with the atomic orbitals in the other atoms
to give sigma bonds. Note that single bonds are sp3 hybridised orbitals and the
molecule of sp3 hybridised orbitals are tetrahedral in shape.

Hybridisation allows for greater overlap of atomic orbitals when a molecular

orbital is formed and also allows each bond to be the same. They are all sigma
bonds with equal repulsion between them. Sigma bonds are made from hybridized
orbitals while pi bonds are from left over orbitals. Therefore, we can say that a
sigma is the first bond made with any other atom and a pi bond is any second or
third bond made with any other atom.

sp2 hybridisation

If the s orbital and two p orbitals mix, then, three sp2 hybrid orbitals of equal
energy are formed. For example, ethane and benzene
Each carbon is sigma bonded to the other carbon and 2 hydrogen atoms. The 2s
and two of the 2p orbitals in each of the carbon atom are mixed together to give 3
identical hybrids. These over lap end-on to give three sigma bonds. The one
electron remaining in each of the unmixed pure p orbital of carbon overlap
sideways to form a pi bond above and below the plane of the sigma bond.

Note that double bonds are sp2 hybridised orbitals and the molecules trigonal
planar in shape.

The carbon atoms in benzene (C6H6) show sp2 hybridisation . Each atom forms
three sp2 hybrid orbitals and one unmixed pure p orbital. The hybrid orbitals
overlap with the carbon and hydrogen atoms to form a planar hexagonal ring of
sigma bonds.
The remaining six unmixed p orbitals are all paralle to one another, each containng
one electron. The p orbitals overlaps sideways at right angles to the planar
hexagonal; ring forming three pi bonds.

Since there are two equivalent choices for the arrangements of the single and
double bonds in the molecule, the structure called a resonance hybrid. The three pi
bonds are delocalized over the whole molecule i.e. the electrons are not in one
particular place but are in constant continual motion. Hence they form circular
rings of electron density above and below the plane of the molecule. Bear in mind,
that in generating resonance structures, only electrons, not nuclei, are moved.

However, it has been determined experimentally that all six bonds on the ring are identical. The natural
interpretation is that the three double bonds are distributed evenly around the ring, so that each bond
has a bond order of one and a half.
These valence structures are then called "resonance structures" or "canonical
structures", because individually they do not adequately represent the structure of
the real compound. As shown in the depiction below, the relationship between the
two structures is usually shown by a curved arrow, which depicts the flow of
electrons. Bear in mind, that in generating resonance structures, only electrons, not
nuclei, are moved. Either electrons in bonds (usually pi bonds) or on atoms may be
moved using the curved arrows.