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# Molecular Geometry and Chemical Bonding Theory

Chapter 10

## The valence-shell electron pair repulsion (VSEPR)

model predicts the shapes of molecules and ions by
assuming that the valence shell electron pairs are arranged
as far from one another as possible.

## To predict the relative positions of atoms around a given

atom using the VSEPR model, you first note the
arrangement of the electron pairs around that central
atom.

## The following rules and figures will help discern electron

pair arrangements.

## ♦ Determine how many electrons pairs are around the

central atom. Count a multiple bond as one pair.

## ♦ Arrange the electrons pairs are shown in Figure 10.3

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♦ 3-D geometries depend on number of e- pairs ( bond +
nonbonding) about the central atom

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2 pairs
Linear

3 pairs
Trigonal planar

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4 pairs
Tetrahedral

## Example: CH4 (draw Lewis structure)

Molecular Geometry:

4
5 pairs
Trigonal bipyramidal

PCl5

Lewis structure:

Molecular Geometry:

5
6 pairs
Octahedral

SF6

Lewis Structure:

Molecular Geometry:

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Role of non-bonding (lone) pairs:

## ♦ Electron pair – electron pair repulsions occur between

lone pairs and other lone pairs and with bonding pairs.

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Case I: AX2E

E = lone pair

Example: BH2-

Lewis Structure:

## Molecular Geometry: Bent

Bond Angles: Note that the E-B-H angle > 1200 and the
H-B-H angle < 1200. Any guesses as to why?

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Case II: AX3E Example NH3

Lewis structure:

Lewis structure:

## H-O-H angle = 104.90

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Case IV: AX4E Example: SF4

Lewis structure:

Lewis structure:

## Molecular geometry: T-Shape

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Case VI: AX2E3 Example: I3-

Lewis structure:

Lewis structure:

## Molecular geometry: Square Pyramidal

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Case VIII: AX4E2 Example: XeF4

Lewis structure:

Example CO2

Lewis structure:

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Example: HCN

Lewis structure

Lewis structure:

## Note the angles: O=C–H > 1200 > H–C–H

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Resonance forms and Molecular Geometry

## Note that the resonance forms always have the same

number of e- pairs around the central atom.

geometry.

Example: CO32-

## All are trigonal planar.

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Dipole Moment and Molecular Geometry

## • The dipole moment is a measure of the degree of

charge separation in a molecule.

## • We can view the polarity of individual bonds

within a molecule as vector quantities.

## • Thus, molecules that are perfectly symmetric have

a zero dipole moment. These molecules are
considered nonpolar. (see Table 10.1)

CO2: 0 dipole δ+
δ− O C O δ−

NH3: δ− δ−
:

N
H H
H
δ+ δ+
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Valence bond theory is an approximate theory
to explain the covalent bond from a quantum mechanical
view.

## According to this theory, a bond forms between two

atoms when the following conditions are met. (see
Figures 10.21)

than two.

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Basic Assumption

atomic orbitals.

Basic Tenets

## - Atomic orbitals with different n, and l quantum

numbers are mixed together form new orbitals of
degenerate energy.

## - Number of hybrid orbitals formed equals the number of

atomic orbitals combined.

## - Unhybridized atomic orbitals form may form both σ-

and π-bonding schemes.

## 2] pi (π) weaker – indirect overlap of orbitals.

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Types of hybridization schemes
Indicates Indicates number of
original atomic atomic orbitals used
in scheme

## sp, sp2, sp3, dsp3, d2sp3

The sp hybrid

^
Energy p __ __ __ p __ __
^ =hybridization=>
sp __ __
s __

+
s p sp1 sp2

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Example of sp hybridization scheme: BeH2

## - Hybridization of the Be atomic orbital

p ( )( )( ) p ( )( )
=hybridization=>
sp (↑ )(↑ )
s (↑↓)

electron pair.

## - To rationalize the contribution to bonding by these

electrons, hybridization takes place and two unpaired
electrons appear.

H + ↑ Be ↑ + H

↓↑ ↑↓

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Table 10.23

## Note how the hybrid orbitals relate to the VSEPR models.

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VSEPR hybridization

Linear, AX2 sp

AX3, AX2E

Tetrahedral sp3
AX4, AX3E, AX2E2

## Trigonal bipyramidal dsp3

AX5, AX4E, AX3E2, AX2E3

Octahedral d2sp3
AX6, AX5E, AX4E2

bonding schemes.

## - The Lewis structure of CO2 is

O=C=O

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- Consider that the central carbon atom has 4 bonds. We
should realize that the C atom should have four
unpaired electrons in order to accommodate 4 bonds.

## - C atom according to Hund’s rule:

C 2s(↑↓) 2p(↑ )( ↑ )( )

## - Now let’s consider the central C atom and it’s

hybridization scheme.

p (↑ )( ↑ )( ) p (↑ )( ↑ )
=hybridization=>
sp (↑ )(↑ )
s (↑↓)

## - We can see that there are 2 sp hybrid orbitals and 2

unhybridized p atomic orbitals on that central carbon
atom.

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Remember that:
- Hybrid orbitals form σ-bonding schemes.

bonding schemes.

s (↑↓)

## We see that there are two unpaired electrons already in

place on the oxygen atom for the formation of 2 covalent
bonds.

p orbitals on oxygen
↑↓
p2
p3

p1
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sp hybrids (shaded) and p orbitals on the C atom

p2

↓ sp2

sp1
↓ ↓

p1

## Now consider only the σ-bonding scheme:

↑↓ ↑↓

O–C–O

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Now consider the π-bonding scheme:

↓ ↑

The π-bonds are weaker since the orbital overlaps are not
as direct as with σ-bonds.

## In multiple bonding only one bond can be a sigma-bond

the rest must be pi-bonds.

## Example: C2H2 acetylene

One σ-bond

H–C≡C–H

Two π-bonds

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Let’s now consider H2, F2, and C2H4

## Note that both H2 and F2 do not require hybridization:

H: 1s (↑ )

F: 2s (↑↓) 2p(↑↓)(↑↓)(↑ )

## C2H4 ethylene requires π-bonding

2
H H
sp sp2
hybridization C=C hybridization

H H
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Hybridization scheme of the C atoms

p (↑ )( ↑ )( ) p (↑ )
=hybridization=>
sp2 (↑ )(↑ ) (↑ )
s (↑↓)

## Ethylene bonding scheme:

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Lone pairs and VBT

## Example H2O: H-O-H

VSEPR Molecular Geometry: Bent AX2E2
Two lone
VBT Hybridization on O atom: sp 3 pairs in sp3
hybrids

p (↑↓ )( ↑ )( ↑ ) p
=hybridization=>
sp2 (↑↓)(↑↓ )(↑ )(↑ )
s (↑↓)

Two unpaired
electrons
available for
bonding to H
atomic orbitals

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You can represent the bonding to the oxygen atom in H 2 O
as follows:

2p
sp3 sp3
lone O-H
2s pairs bonds
Energy

1s 1s 1s
O atom O atom O atom
(ground state) (hybridized state) (in H 2 O)

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As our last example for the course let’s consider the VBT
model for XeF4

## The Lewis structure helps us predict that the molecular

geometry is AX4E2 or square planar.

5d 5d

5p sp3d 2

5s

## Xe atom (ground state)

Xe atom (hybridized state)

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• This suggests that you use sp 3 d 2 hybrid orbitals
on xenon.

## The F atoms remain unhybridized and thus the following

applies to the XeF4 molecule.

5d

sp3d 2

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↑↓

↑↓
↑↓ ↑↓
↑↓

↑↓

Review:

## Lewis => VSEPR => VBT Model

Structure Model Hybridization Scheme

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