Molecular Geometry and Bonding Theories

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Miles Eckles April 5, 2011

Chem 101 A Chapter 9

Molecular Geometry and Bonding Theories

Molecular Shapes

 The overall shape of a molecule is determined by its bond angles.


 Valence Shell Electron Pair Repulsion (VSEPR) Model
o Takes all electron pairs (bonding and non-bonding) and finds the best
arrangement by minimizing repulsions between the pairs.
o Shapes revolving around the central atom

Electron Pair Geometries as a Function of Number of Electron Pairs


Electron pairs Arrangement Electron-pair Predicted bond
geometry angles
2 Linear 180˚
3 Trigonal planar 120˚
4 Tetrahedral 109.5˚
5 Trigonal 120˚
bipyramidal 90˚
6 octahedral 90˚
180˚

 # of bonds don’t matter


 5 and 6 electron pairs violate the octet rule
Predicting Molecular Geometry
1. Sketch Lewis structure.
2. Count number of electron pairs around central atom and arrange them to minimize
electron repulsions.
3. Describe molecular geometry in terms of angular arrangement of bonding pairs.
4. A multiple bond is counted as one bonding pair when predicting geometry.
 Nonbonding electrons still count as part of the group
Practice
 H2 O

o Bent
o 2 bonding p
o 2 non-bonding
o 4

 O3

o Bent
o 2 bonding p
o 1 non-bonding
o 3

 SnCl3

o Trigonal pyramidal
o 3 bonding p
o 1 non-bonding
o 4

Effect of Nonbonding electrons

 Consider the following:


 CH4 NH3 H2 O
o # L.P. 0 1 2
 Bond angle 109.5˚ 107˚ 104.5˚
 Nonbonding electron pairs exert greater repulsive forces on adjacent electron pairs and
tend to compress the angles between the bonding pairs.

Electron Pair Geometries and Molecular Shapes: 2—4 pairs

Electron Electron-pair Bonding Non- Molecular Example


pairs geometry pairs bonding geometry
pairs
2 Linear 2 0 linear CO2

3 Trigonal 3 0 Trigonal BF3


planar 1 Planar
2 NO2
bent
4 Tetrahedral 4 0 Tetrahedral CH4
3 1 Trigonal NH3
2 2 Pyramidal H 2O

bent
Effect of Multiple Bonds

 Multiple bonds contain a higher electronic-charge density than do single bonds.

 Thus, in general, electrons in multiple bonds exert a greater repulsive force on adjacent

electron pairs than do single bonds.

Molecules with Expanded Valence Shells

 Molecules with five or six electron pairs around the central atom display a variety of

molecular geometries.

 Central atom is from third period or beyond.


Five Electron Pairs on Central Atom

# Electron Bonding Non- Molecular Example


Electron pair pairs bonding geometry
pairs geometry pairs
5 Trigonal 5 0 Trigonal PCl5
bypyramid bypyrami
4 1 d SF4
3 2 seesaw ClF3
2 3 XeF2
T-shaped

linear

Six Electron Pairs on Central Atom

# Electron Bonding Non- Molecular Example


Electron pair pairs bonding geometry
pairs geometry pairs
6 Octahedral 6 0 Octahedra SF6
l
5 1 Squar BrF5
e
4 2 pyramidal XeF4

Square
planar
Molecules with more than one central atom
 In such cases, one can describe the geometry about each of the central atoms, rather

than the molecule as a whole.

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