MODULE 3

GEOMETRY OF MOLECULES
The shape of a molecule plays an important role in its reactivity. By noting the number of
bonding and lone electron pairs, the shape of the molecule will be easily predicted.

Molecular Shape
The overall shape of a molecule is described by two properties:
▪ Bond length – distance between the nuclei of the two bonded
atoms
▪ Bond angle – angle made by the lines joining the nuclei of the
bonding atoms

Valence Shell Electron Pair Repulsion (VSEPR)

This theory states that the best arrangement of a given number of shared and unshared
electrons is the one that minimizes the repulsions among them. To follow this theory, atoms tend to
move as far away as possible to be able to minimize the repulsion.

Electron-Group Geometry
The arrangement of atoms of a molecule in space.

Electron Groups

4 elec. groups An electron group is an atom or a lone pair of

electrons around the central atoms.
sp3
Electron group is equal to bonding atoms plus
lone pairs present around the central atom.
The number of electron group could help determine
the central atom’s hybridization.
 Basic Electron-Group Geometries
These are the geometries for two to six electron groups around a central atom:

number of e- groups arrangement geometry bond angles

The arrangement of electron groups about the central atom is called the electron-group
geometry. There are 5 common electron-group geometries.
 In contrast, molecular geometry is the arrangement of only the atoms in a molecule or ion.
Any nonbonding pairs are not part of the description of molecular geometry.

What Determines the Shape of a Molecule?

▪ Lone pair
▪ Multiple bond

Lone Pairs and Bond Angles
Lone pairs are physically larger than
atoms. Therefore, their repulsions are greater;
this tends to decrease bond angles in a
molecule.
Multiple Bonds and Bond Angles
Double and triple bonds place greater
electron density on one side of the central atom
than do single bonds. Therefore, they also
affect bond angles.

Geometries vs Shape
Within each geometry, there might be more than one shape.

In the VSEPR model, the molecule or polyatomic ion is given an AXmEn designation:

AXm En
A – central X – bonding atoms E – lone pairs m, n - integers

How to Predict the Molecular Geometry

Step 1: Draw the appropriate Lewis structure

Step 2: Determine the number of electron groups around the central atom, and identify each
as a bonding pair and a lone pair
Step 3: Determine the molecular geometry based on the code AXmEn
 1. Linear Geometry

number of e- group bonding lone

shape example
e- groups. geometry atoms pairs

AX2

In this geometry, linear is the only one molecular geometry. Note that if there are only two
atoms in the molecule, the molecule will be linear no matter what the geometry is.
2. Trigonal Planar Geometry
number of e- group bonding lone shape example
e- groups. geometry atoms pairs

AX3

AX2E1

3. Tetrahedral Geometry
number of e- group bonding lone
shape example
e- groups. geometry atoms pairs

AX4

AX3E1

AX2E2
 4. Trigonal Bipyramidal Geometry

number of e- group bonding lone

shape example
e- groups. geometry atoms pairs

AX5

AX4E1

AX3E2

AX2E3

5. Octahedral Geometry
number of e- group bonding lone
shape example
e- groups. geometry atoms pairs

AX6

AX5E1

AX4E2
EXAMPLES:

Total valence electrons: 26e-

NF3
Remaining valence electron: 0e-

Electron-group geometry: Tetrahedral

Type: AX3E

Shape: Trigonal Pyramidal

Total valence electrons: 32e-

CCl2F2
Remaining valence electron: 0e-

Electron-group geometry: Tetrahedral

Type: AX4

Shape: Tetrahedral

Larger Molecules
To predict molecular shapes when there is more than one central atom, we simply apply
VSEPR principles several times.
EXAMPLE: Acetone - (CH3)2CO

tetrahedral tetrahedral

trigonal planar
 Valence Bond Theory
Covalent bond is formed by the overlap of atomic orbitals. It states further that bonding
occurs through the overlap of the two half-filled orbitals of the bonding atoms.
This theory strengthens VSEPR principles by invoking directional properties of the orbitals.
Basic Principles of Valence Bond Theory:
▪ A covalent bond forms when the orbitals of two atoms overlap
▪ Atomic orbitals may mix to yield hybrid orbitals
▪ The overlap region, which is between nuclei, is occupied by a pair of
electrons spinning in opposite directions.

“Hybrid” orbitals arise from the “mixing” of appropriate atomic orbitals

Key Points:
▪ The number of hybrid orbitals obtained equals the number of atomic orbitals
mixed
▪ The type of hybrid orbitals obtained varies with the types of atomic orbitals
mixed
▪ The use of hybrid orbitals rationalizes the equivalence of bonds
Types of Hybrid Orbitals
sp sp2 sp3 sp3d sp3d2 ….

Polarity of Molecules
By adding the individual bond dipoles, one can determine the overall dipole moment for the
molecule.
Bond Polarity
Bond dipole moment – vector quantity (magnitude and direction). The polarity of bond is
sometimes indicated by an arrow pointing towards the more electronegative end of the bond.

If the dipole moment cancels each other out, then the overall dipole moment is zero. On the
other hand, if the dipole moments reinforce, there is an overall dipole moment.
Dipole Moment (μ)
Dipole moment is the product of the partial charge and the distance between them. It is the
measure of net molecular polarity. It is represented by the unit D.
 Predicting the Polarity of Molecules
Step 1: Determine the polarity of the bonds by getting the electronegativity difference of
the atoms present in the molecule
Step 2: Determine the polarity of molecule. If bonds making up a molecule are non-polar,
then the molecule is non-polar. On the other hand, if the bonds are polar, then the
molecule could either be polar or non-polar (depends on the direction of dipole
arrow).

EXAMPLES:
Carbon Dioxide
▪ C (EN=2.5) O (EN = 3.5)
▪ This bond is polar because the electronegativity difference is 1.0
▪ CO2 is linear

Since there is no net dipole moment, carbon dioxide is a non-polar molecule

Carbon Dioxide
▪ H (EN=2.1) O (EN = 3.5)
▪ This bond is polar because the electronegativity difference is 1.4
▪ H2O is linear

Since there is a dipole moment, water is a polar molecule