MOLECULAR SHAPES

Chemistry Unit 1 D.Hines

When an atom forms a covalent bond with another atom, the electrons in the different bonds and
the non-bonding electrons in the outer shell all behave as negatively charged clouds and repel
each other. In order to minimize this repulsion, all the outer shell electrons spread out as far apart
in space as possible. The valence shell electron pair repulsion theory predicts the shapes and
bond angles of simple covalent molecules.

The VSEPR theory states that pairs of electrons in the outer shell of the atoms in a molecule
repel each other and move as far apart as possible to minimize repulsive forces in the molecule.

Molecular shapes and the angles between bonds can be predicted by the VSEPR theory
VSEPR = valence shell electron pair repulsion

VSEPR theory consists of some basic rules:

i) All -bonded electron pairs and all lone pairs arrange themselves as far apart in space as
is possible. -bonded electron pairs are excluded.
ii) Lone pairs repel more strongly than bonding pairs. Lone pair-lone pair > lone pair-bond
pair > bond pair-bond pair.
iii) The shapes of molecules are determined primarily by the number of bonding pairs and
lone pairs of electrons around a particular atom called the central atom.
iv) 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 molecule containing a lone pair.

These rules can be used to predict the shape of any covalent molecule or ion, and the angles
between the bonds.

a) 2 electron pairs
If there are two electron pairs on the central atom, the angle between the bonds is 180 o. No lone
pairs around central atom, equal repulsion.

Molecules which adopt this shape are said to be LINEAR.

E.g. BeCl2, CO2
b) three electron pairs
If there are three electron pairs on the central atom, the angle between the bonds is 120 o.

Molecules which adopt this shape are said to be TRIGONAL PLANAR.

E.g. BF3, AlCl3, CO32-, NO3-

 If one of these electron pairs is a lone pair in a molecule with two bond pairs, the bond
angle is slightly less than 120o due to the stronger repulsion from lone pairs, forcing them
closer together.

bond angle = 118o

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Molecules which adopt this shape are said to be NON-LINEAR, BENT OR V -SHAPE.
E.g. SO2, NO2-, SnCl2

c) Four electron pairs

If there are four bonded pairs on the central atom, the angle between the bonds is approx 109.5o.

Molecules which adopt this shape are said to be TETRAHEDRAL.

E.g. CH4, SiCl4, NH4+, SO42-

 If one of the electron pairs is a lone pair with 3 bond pairs, the bond angle is slightly less
than 109.5o, due to the extra lone pair repulsion which pushes the bonds closer together
(approx 107o).

Molecules which adopt this shape are said to be TRIGONAL PYRAMIDAL.

E.g. NH3, PCl3

 If two of the electron pairs are lone pairs with two bond pairs, the bond angle is also
slightly less than 109o, due to the extra lone pair repulsion (approx 104 o or 104.50).

Molecules which adopt this shape are said to be BENT.

E.g. H2O, OF2

d) Five electron pairs

If there are five bonded pairs on the central atom, the three bonds are in a plane at 120 o to each
other, the other 2 are at 90 o to the plane.

Molecules which adopt this shape are said to be TRIGONAL BYPRYMIDAL.

E.g. PF5, PCl5

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d) Six electron pairs

If there are six electron pairs on the central atom, the angle between the bonds is 90 o.

Molecules which adopt this shape are said to be OCTAHEDRAL.

E.g. SF6

 If there are 4 bonding pairs and 2 lone pairs, the bonded pairs are at 90 o in the plane and
the lone pairs at 180o. The angles are still exactly 90o because the lone pairs are opposite
each other so their repulsion cancels out.

Molecules which adopt this shape are said to be SQUARE PLANAR.

E.g. XeF4, ClF4-

SUMMARY OF MOLECULAR SHAPES

Valence Bonding Lone shape Bond

shell pairs pairs Angle (o)
electron
pairs
2 2 0 LINEAR 180

B A B
3 3 0 TRIGONAL PLANAR 120
B B
A

B
3 2 1 BENT 115 - 118
B
A

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 4 4 0 TETRAHEDRAL 109.5
B

A
B
B
B
4 3 1 TRIGONAL 107
PYRAMIDAL

A
B
B
B
4 2 2 BENT 104.5

A
B
B
5 5 0 TRIGONAL 90 and 120
BIPYRAMIDAL
B
B
B A
B
B
6 6 0 OCTAHEDRAL 90
B
B B
A
B B
B
6 4 2 SQUARE PLANAR 90

B B
A
B B
1. The bond angles of methane, ammonia and water are 109.50, 1070, and 104.50
respectively. Suggest an explanation for this variation in terms of repulsion between
electron pairs.
2. Use the VSEPR theory to deduce the shapes and bond angles of the following molecules:
a. PH3
b. F2O
c. SiH4
d. H2S
e. H3O+
f. NF3
g. CF4
h. SCl2
3. Give an account for the nitrogen trichloride molecule being pyramidal in shape but
aluminium chloride is trigonal planar in shape.

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 Shapes of simple organic compounds

Carbon has the ability to mix and arrange the four orbitals in the outer shell. This is called
hybridization. Carbon has the electronic configuration 1s2 2s2 2p2 and can promote an electron
from the 2s orbital to the empty 2p orbital. since both the 2s and the 2p sub-shells are half-filled,
the excited state is relatively stable.

Ground state

Excited state

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. This type of mixing is
called sp3 hybridization.
The sp3 hybrid orbitals look like half a p orbital and they arrange themselves in space as far apart
as possible.

sp3 orbital

This type of mixing occurs in the ethane molecules (C2H6). Each carbon is singly bonded to the
other carbon atom and 3 hydrogen atoms. The four identical four sp 3 hybrid orbitals overlap end-
on with the atomic orbitals in the other atoms to give sigma bonds.
Remember the hydrogen’s electron is in a 1s orbital – a spherical symmetric region of space
surrounding the nucleus. When a covalent bond is formed, the atomic orbitals merge to form a
new molecular orbital which contains the electron pair which creates the bond.

So just before bonding, that atoms look like this: This is after:

The shape of ethane around each carbon atom

The sp3 orbitals are arranged around each carbon atom to form a tetrahedral arrangement with an
angle of 109.50.

Hybridization in ethene
If the s orbital and two of the p orbitals mix, three sp 2 hybrid orbitals of equal energy level are
formed.

The three sp2 hybrid orbitals arrange themselves as far apart as possible which is at at 120 0 to
each other in a plane. The remaining p orbital is at right angles to them.

The two carbon atoms and four hydrogen atoms would look like this before they joined together:

Sp2 hybridization is the type of mixing that occurs in the ethene molecule (C 2H4). Each carbon is
sigma bonded to the other carbon atom and 2 hydrogen atoms. The three sp 2 identical hybrids
overlap end-on to give three sigma bonds.

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The one electron remaining in each of the unmixed pure p orbital of the carbon atoms overlap
sideways to form a pi bond above and below the plane of the sigma bonds.
The shape of ethene
There is no free rotation about a carbon-carbon double bond. Ethene is a planar molecule. The
sp2 orbitals are 1200 to each other.

The shape of the benzene molecule

Like ethene the carbon atoms show sp2 hybridization in benzene (C6H6). Each carbon atoms
forms three sp2 hybrid orbitals and one unmixed pure p orbital. The hybrid orbital overlap with
the carbon and hydrogen atoms to form a planar hexagonal ring of sigma bonds. The remaining
six unmixed p orbitals p orbitals are all parallel to one another, each containing one electron. The
p orbitals overlap 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 is called a resonance hybrid. The three pi bonds are delocalized over the
whole molecule, that is the electrons are not in one particular place but are in constant motion.
Hence they form circular rings of electron density above and below the plane of the molecule.
Benzene is a planar hexagon with bond angles of 120 0.
Questions
1. Carbon has the ability to mix to create new hybrid orbitals. Describe the shapes of the
following organic molecules in terms of their hybrid orbitals:
a. Ethane b. Ethene c. Benzene