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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.

♦ Draw the Lewis structure

♦ 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

Figure 10.2: Arrangement of electron pairs about an atom.

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2 pairs
Linear

Example: BeH2 (draw Lewis structure)

3 pairs
Trigonal planar

Example: BF3 (draw Lewis structure)

3
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:

♦ Lone pairs are structurally significant.

♦ Electron pair – electron pair repulsions occur between


lone pairs and other lone pairs and with bonding pairs.

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Case I: AX2E

A = central atom X = terminal atom or ligand

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:

Molecular geometry: Trigonal Pyramidal

E-N-H > 109.50 H-N-H < 109.50

Case III: AX2E2 Example H2O

Lewis structure:

Molecular geometry: Bent

H-O-H angle = 104.90

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Case IV: AX4E Example: SF4

Lewis structure:

Molecular geometry: Seesaw

Case V: AX3E2 Example: ClF3

Lewis structure:

Molecular geometry: T-Shape

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Case VI: AX2E3 Example: I3-

Lewis structure:

Molecular geometry: Linear

Case VII: AX5E Example: BrF5

Lewis structure:

Molecular geometry: Square Pyramidal

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Case VIII: AX4E2 Example: XeF4

Lewis structure:

Molecular geometry: Square planar

Multiple Bonds and Molecular Geometry

Simple rule – count double and triple bonds as one e- pair

Example CO2

Lewis structure:

Molecular geometry: Linear

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Example: HCN

Lewis structure

Molecular geometry: linear

Example: H2CO formaldehyde

Lewis structure:

Molecular geometry: trigonal planar

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.

Each form will always have the same molecular


geometry.

Example: CO32-

Three Lewis structures:

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)

Two atomic orbitals “overlap”

The total number of electrons in both orbitals is no more


than two.

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Basic Assumption

Covalent Bonds form from the overlap of 2 half-filled


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.

- Hybrid orbitals form σ-bonding schemes.

- Unhybridized atomic orbitals form may form both σ-


and π-bonding schemes.

Types of Covalent Bonds

1] sigma (σ) stronger – direct overlap of orbitals.

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 (↑↓)

- We can see that the original atomic orbital has an


electron pair.

- To rationalize the contribution to bonding by these


electrons, hybridization takes place and two unpaired
electrons appear.

H + ↑ Be ↑ + H

↓↑ ↑↓

Note that the VSPER geometry for BeH2 is linear.


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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

Trigonal Planar sp2


AX3, AX2E

Tetrahedral sp3
AX4, AX3E, AX2E2

Trigonal bipyramidal dsp3


AX5, AX4E, AX3E2, AX2E3

Octahedral d2sp3
AX6, AX5E, AX4E2

CO2 VBT model

- This is an example of a molecule that requires σ, and π


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(↑ )( ↑ )( )

- We see that C has only 2 unpaired electrons.

- 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.

- Unhybridized atomic orbitals may form both σ- and π-


bonding schemes.

The oxygen atoms remain unhybridized.

p (↑↓ )(↑ )(↑ )

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

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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.

The hybridization scheme follows as:

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

lone pairs Xe-F bonds

Xe atom (in XeF4)

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↑↓

↑↓
↑↓ ↑↓
↑↓

↑↓

Review:

Lewis => VSEPR => VBT Model


Structure Model Hybridization Scheme

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