SHAPES OF

COVALENT
MOLECULES
Valence Shell Electron Pair Repulsion (VSEPR) Theory

▪ In 1940, Sidgwick and powell put forward the VSEPR theory and
were able to account for the shapes of molecules.
▪ The shapes of molecules are determined by the number and
arrangement of electron pairs around each atom.
▪ There are two types of electron pairs :
➢ Bond pair (or shared pair) → electrons found in the covalent
bond
➢ Lone pair (or non-bonding pair) → electrons not involved in
covalent bonding
 (VSEPR) Theory

1. Electron pairs (lone and bond pairs) will arrange themselves as far apart as possible
so as to minimise repulsion and maximise stability.
2. A multiple bond (e.g. double or triple bond) can be considered like a single bond.
3. Electron pairs exert repulsion on one another in the following order
lone pair – lone pair > lone pair – bond pair > bond pair – bond pair
repulsion repulsion repulsion

Reason :
Bond pair is shared between the two atoms forming the bond. Hence it occupies a
larger volume, and has a lower negative charge density. Lone pair is localised on one
atom. Hence it occupies a smaller volume and has a higher negative charge density.
As a result, there will be greater repulsion between two lone pairs.
4. A central atom which is more electronegative will give rise to a larger electronic
repulsion between two bond pairs, hence larger bond angle between the bond pairs.
DETERMINING THE MOLECULAR SHAPES

1. Draw “dot-and-cross” diagram

2. Count the number of electron pairs around the central atom
3. Determine the arrangement of electron pairs around the
central atom
4. Count the number of bond pairs and lone pairs around the
central atom
5. The molecular shape is determined by the bond pairs.
 HYBRIDISATION
⸙ Orbitals of the same atom can overlap, mix and hybridise to form a new set of
orbitals. The hybrid orbitals formed take up distinctive shape and orientation,
depending on the number and type of atomic orbitals that have been mixed.
⸙ Hybridisation explains shape and bond length in molecule.
⸙ Two important principles :

1. The number of hybrid orbitals is the same as the number of atomic orbitals
mixed.

2. The hybrid orbitals are more directed from the central atom toward the
terminal atoms than the unhybridised atomic orbitals, leading to a better
orbital overlaps and a stronger bond between the central and terminal atoms.
 sp3 HYBRIDISATION
The mixing of one s and three p orbitals results in the formation of four sp3 hybrid orbitals. These point
towards the corners of a tetrahedron, for example in water, ammonia and methane.
Example : Formation of methane, CH4
 EXPLANATION
• The four orbitals of C (2s, 2px, 2py and 2pz) are mixed such that four
equivalent hybrid orbitals are formed.
• The four identical singly occupied sp3 orbitals overlap with the singly
occupied 1s orbitals of four hydrogen atoms to form four sigma bonds.
• All the four C - H bonds are sigma bonds, each with a bond energy of 410
kJmol-1 .
• The four sp3 hybrid orbitals are oriented tetrahedrally with a bond angle of
109.5o to minimise repulsion.
 sp2 HYBRIDISATION
• The mixing of an s and two p orbitals results in the formation of three identical sp2 hybrid orbitals.
These point towards the corners of an equilateral triangle (120o to each other)
PROBLEMS
1. What type of hybridization would you expect around the S atom in SF5- ?
a. sp3d b. sp c. sp3d2 d. sp3 e. sp2
2. Which of the following molecules is NOT linear in terms of its atom geometry?
a. I2 b. I3- c. CO2 d. H2O e. H2
3. Which atom geometry is associated with sp3d2 hybridization?
a. octahedral c. Trigonal planar e. Trigonal bipyramidal
b. linear d. Tetrahedral
4. Which of the following pairs have the same atomic geometry?
a. BF3 and NH3 c. NH3 and PF5 e. NH3 and PF5
b. Carbonate ion and BF3 d. PF5 and SF6
5. Which of the following is NOT trigonal planar?
a. Carbonate ion c. Nitrate ion e. Boron trichloride
b. Phosphorus trichloride d. Sulfur trioxide
PROBLEMS
6. What is the most likely bond angle for F-S-F in SF6?
a. 120 degrees b. 109.5 degrees c. 104.5 degrees d. 107.5 degrees e. 90 degrees
7. Molecule with a central atom exhibiting sp3d2 hybridization could have which of the following
atomic geometry/geometries?
a. Only octahedral d. Only octahedral and square planar
b. Only tetrahedral e. None of the above
c. Octahedral, square planar and square based pyramidal
8. In which of the following pairs are the two items NOT correctly related?
a. sp3 and 109.5 degrees d. sp2 and trigonal planar
b. linear and 180 degrees e. sp and 104.5 degrees
c. octahedral and six bonded pairs
PROBLEMS
9. Predict the electron-domain geometry and the molecular geometry for
a. SnCl3–
b. O3
c. SF4
d. IF5