Geometry of Molecules

Objectives:
1. Valence-Shell Electron-Pair Repulsion (VSEPR)
2. Prediction of geometry of molecules
3. Bond angles in molecules with lone pairs

1. Valence-Shell Electron-Pair Repulsion (VSEPR)

The valence shell is the outermost electron-occupied shell of an atom and
it holds the electrons that are usually involved in bonding.
Basis: electron pairs in the valence shell of an atom repel one another due
to same sign (negative) repulsion.
The correctly predicted geometry is the most stable geometry where
repulsion of electron pairs in valence shell of the central atom is a
minimal.

2. Prediction of Geometry of Molecules

3 steps to predict geometry of molecules:
a. Draw the Lewis structure of the molecule first.
b. Identify the central atom and count the number of electron pairs
attached to it.
c. Treat double and triple bonds as single bond when determining the
geometry.
Electron lone pairs of a molecule are electron pairs of a central atom
not involved in covalent bonding with another atom, i.e. they are non-
bonding electron pairs.
Central atoms with no electron lone pairs VS Central atoms with electron
lone pairs.
Without electron lone pairs With electron lone pairs
2 electron bonding pairs 4 electron pairs 3 bonding
molecule is linear pairs, 1 lone pair
bond angle of 180 molecule is trigonal pyramidal
e.g. BeCl2 bond angle of 107
e.g. NH3
3 electron bonding pairs 4 electron pairs 2 bonding
molecule is trigonal planar pairs, 2 lone pairs
bond angle of 120 molecule is bent or V-shaped
e.g. BCl3 bond angle of 104.5
e.g. H2O
4 electron bonding pairs molecular structure is defined
molecule is tetrahedral by the positions of atoms, not
bond angle of 109.5 electrons
e.g. CH4 differing repulsion of electron
pairs

3. Bond Angles in Molecules with Lone Pairs

Lone pairs are closer to the nucleus than bonding pairs and exert a
greater force of repulsion.
 Lone pair: lone pair > lone pair: bonding pair > bonding pair: bonding pair

Concept of Orbital Hybridisation

Objectives:
1. Molecular orbitals 4. sp3 methane
2. Electronic configuration of 5. sp2 ethene
carbon 6. sp ethyne
3. Hybridisation 7. Benzene
8.
1. Molecular orbitals
When atomic orbitals overlap, molecular orbitals are formed.
It describes a covalent bond that results from the overlap of two atomic
orbitals, each with one electron.
2 important types of molecular orbitals:
9. Sigma bond ( bond) 10. Pi bond ( bond)
formed by head-to-head overlap formed by overlap of parallel p
of atomic orbitals (s+s, p+p, s+p) orbitals at both lobes (side-on
11. overlap)
formed only after a sigma bond
is formed
electron density is concentrated two regions of electron density
between the two nuclei and is alongside the two nuclei (above
responsible for holding the and below the sigma orbital,
atoms together against the separated by a nodal plane a
mutual repulsion of the nuclei region with zero electron
density)
A pi bond is weaker than a sigma bond because the overlapping of
charge clouds is less than that in a sigma bond.
In covalent molecules, single bonds are sigma bonds, a double bond
consists of 1 sigma and 1 pi bond, a triple bond consists of 1 sigma and 2
pi bond.
Since covalent bonds are formed by overlapping of atomic orbitals, they
are directed in space due to the directional nature of p, d and f orbitals.
The electron pairs around the central atom dictate the shape of
molecule.
12.
2. Electronic configuration of carbon
Carbon atom in its ground state (1s22s22p2) has two unpaired electrons,
which only allows it to form 2 bonds.
To form 4 bonds, a 2s electron is promoted to a 2p orbital, creating 4
unpaired electrons (1s22s12p3), ready to form 4 bonds. (Carbon atom in its
excited state is achieved when the 2s electron gains excitation energy
and is promoted to 2p orbital.)
E.g. to achieve CH4, 4 equivalent C-H bonds have to be formed with
bond angles of 109.5.
13. However, the four bonds formed are from one 2s orbital and three 2p
orbitals. The s and p orbitals have different geometries and energies,
which will form non-equivalent bonds with hydrogen. In addition, bond
angles would be 90 rather than 109.5 (as the three p orbitals are
perpendicular to each other).
3. Hybridisation
Hybrid orbitals are formed by combination (hybridization) of atomic
orbitals from the same atom to form new orbitals of different shapes
and orientations.
Each hybrid orbitals will have the same energy level and shape but point
in different directions (towards the corners of the molecule).
14.
4. sp3 methane
In methane, each carbon atom is bonded to four other hydrogen atoms.
Hence, 4 hybrid orbitals are needed. The bond angle is 109.5.
One 2s electron is promoted to the 2p orbital to form 4 unpaired electrons.
One 2s orbital and three 2p orbitals mix to form four equivalent sp 3 hybrid
orbitals.
The four equivalent sp3 hybrid orbitals are directed towards the four
corners of a regular tetrahedron.
The four C-H bonds are all sigma bonds (head-to-head overlap)
formed with the overlapping of a sp3 orbital and a 1s orbital of
hydrogen.
15.
5. sp2 ethene
Each carbon atom is bonded to three other atoms: 2 hydrogen atoms and
1 carbon atom. Hence, only 3 hybrid orbitals are required for each carbon
atom. The bond angle is approximately 120.
One 2s electron is promoted to the 2p orbital.
Carbon atom undergoes sp2 hybridisation by mixing one 2s and two 2p
orbitals to form three sp2 hybrid orbitals.
One 2p orbital remains unhybridised.
The three sp2 hybrid orbitals lie in the same plane, 120 apart from one
another.
A C-C sigma bond is formed between the sp2 hybrid orbitals of
neighbouring carbon atoms.
Remaining two sp2 hybrid orbitals of each carbon atom form two
sigma bonds with two hydrogen atom.
Ethene is a planar molecule, with the unhybridised 2p orbitals
overlapping to form a pi bond with the electron densities above and
below the plane.
All atoms lie in the same plane so that the 2p orbitals that compromise the
pi bond can achieve a good overlap. If one CH 2 fragment twists with
respect to the other, the amount of overlapping of p orbitals will decrease
and the pi bond will be partially broken.
Since it requires energy to break a bond, the most stable arrangement of
the molecule is the one in which all six atoms lie in the same plane.
Hence, the pi bonds can introduce rigidity into the molecule.
Comparison between C=C and C-C bond:
16. C=C 17. C-C
Stronger bond Weaker bond
Shorter bond Longer bond
18. The shorter the bond length, the stronger the bond is.
19.
6. sp ethyne
Each carbon atom is bonded to two other atoms: one carbon atom and
one hydrogen atom. Hence, 2 hybrid orbitals are required for each carbon
atom. The bond angle is 180.
One 2s electron is promoted to 2p orbital.
Carbon atom undergoes sp hybridization by mixing one 2s orbital and one
2p orbital to form two sp hybrid orbitals.
Two 2p orbitals remain unhybridised.
One sp orbital form a sigma bond with hydrogen, while the other sp
orbital forms a sigma bond with the second carbon atom.
Two unhybridised 2p orbitals from each carbon atom overlap
sideways to form two pi bonds: each perpendicular to each other (one
above and below the line of the sigma bond, the other front and back).
These electrons in the sigma and pi bonds are located in the region
between the nuclei of the bonded atoms. They are known as localized
electrons.
20.
7. Benzene
The benzene has an alternating system of single and double bonds that is
known as a conjugated double bond system.
The benzene ring has 2 resonance structures.
Resonance is described as a condition occurring when more than 1
valid Lewis structure can be written for a particular molecule.
Resonance hybrid is the true representation of the benzene
structure.
Between each pair of adjacent carbon atoms is a sigma bond formed
by overlapping of sp2 hybrid orbitals.
Since sp2 bonds are coplanar, all the carbon atoms lie in the same plane
and form a regular hexagon.
Each carbon atom is bonded to 2 carbon atoms and 1 hydrogen atom at
120 bond angles.
Unhybridised 2p orbital are perpendicular to the hexagonal benzene plane.
Side-on overlap of 2p orbitals on adjacent carbon atoms gives rise to
pi bonds.
The 2p orbitals are able to overlap all round the ring and the six pi
electrons in the 2p orbitals cannot be regarded as located between any
two carbon atoms. They are free to move between all the six carbon atoms
in the ring. Hence, these electrons are delocalized.