General Chemistry

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Transcript General Chemistry

Bonding and Molecular Structure

Chapter 10

Chapter 10 1

Covalent Bonding and Orbital Overlap

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Lewis structures and VSEPR do not explain how a

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bond forms.

VSEPR predicts the shape of a molecule, but it does

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not explain how the molecule is put together.

One method to explain bonding would be Valence Bond Theory:

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Bonds form when atomic orbitals on atoms overlap.

Two electrons are shared by the orbital overlap.

Chapter 10 2

Covalent Bonding and Orbital Overlap

Chapter 10 3

Hybrid Orbitals

sp Hybrid Orbitals

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Consider BeF 2 - Be has a 1s 2 2s 2 electron configuration.

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There is no unpaired electron available for bonding. We could promote and electron from the 2s orbital on Be to the 2p orbital to get two unpaired electrons for bonding.

The F-Be-F bond angle is 180

(VSEPR theory).

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BUT the geometry is still not explained .

Chapter 10 4

Hybrid Orbitals

sp Hybrid Orbitals

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We can solve the problem by allowing the 2s and one 2p orbital on Be to mix or form two hybrid orbitals (process called hybridization).

- The hybrid orbitals come from an s and a p orbital and is called sp hybrid orbital.

Chapter 10 5

Hybrid Orbitals

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sp Hybrid Orbitals The two sp hybrid orbitals are 180

apart.

Since only one of the Be 2p orbitals has been used in hybridization, there are two unhybridized p orbitals remaining on Be.

Chapter 10 6

Hybrid Orbitals

Hybrid Orbitals - Other hybrids can be formed by mixing additional p and/or d orbitals Chapter 10 7

Hybrid Orbitals

Chapter 10 8

Hybrid Orbitals

Chapter 10 9

Hybrid Orbitals

Summary To assign hybridization:

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draw a Lewis structure assign the electron pair geometry using VSEPR theory from the electron pair geometry, determine the hybridization Chapter 10 10

Multiple Bonds

-Bonds - electron density lies on the axis between the nuclei.

-Bonds - electron density lies above and below the plane of the nuclei.

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A double bond consists of one

-bond and one

-bond A triple bond has one

-bond and two

-bonds

-bonds come from unhybridized p orbitals.

Chapter 10 11

Multiple Bonds

Chapter 10 12

Multiple Bonds

Ethylene, C 2 H 4 Chapter 10 13

Multiple Bonds

Acetylene, C 2 H 2

Chapter 10 14

Molecular Orbitals

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Some aspects of bonding are not explained by Lewis

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structures, VSEPR theory and hybridization. For these molecules, we use Molecular Orbital Theory

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(MO theory).

Just as electrons in atoms are found in atomic orbitals, electrons in molecules are found in molecular orbitals.

Chapter 10 15

Molecular Orbitals

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The Hydrogen Molecule When two AOs overlap two MO’s form.

One molecular orbital has electron density between nuclei (

, bonding MO); One molecular orbital has little electron density between nuclei (

* , antibonding MO).

Chapter 10 16

Molecular Orbitals

The Hydrogen Molecule Chapter 10 17

Molecular Orbitals

The Hydrogen Molecule Chapter 10 18

Molecular Orbitals

The Hydrogen Molecule Chapter 10 19

Molecular Orbitals

The Hydrogen Molecule

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MO diagram shows the energies and orbitals in an MO diagram.

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The total number of electrons in all atoms are placed in the MO’s starting from lowest energy (

1s ) and ending when you run out of electrons.

Note that electrons in MO’s have opposite spins.

H 2 has two bonding electrons.

He 2 has two bonding electrons and two antibonding electrons.

Chapter 10 20

Molecular Orbitals

Bond Order Define Bond Order = ½( bonding electrons Bond order = 1 for single bond.

Bond order = 2 for double bond.

Bond order = 3 for triple bond.

antibonding electrons ).

Bond order for H 2 = ½( bonding electrons - antibonding electrons ) = ½(2 - 0) = 1.

Therefore, H 2 Bond order for He 2 has a single bond.

= ½( bonding electrons - antibonding electrons ) = ½(2 - 2) = 0. Therefore He 2 is not a stable molecule.

Chapter 10 21

Second-Row Diatomic Molecules

AO’s combine according to the following rules

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The number of MO’s equals the number of AO’s AO’s of similar energy combine As overlap increases, the energy of the MO decreases

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Pauli: each MO has at most two electrons Hund: for degenerate orbitals, each MO is first occupied singly.

Chapter 10 22

Second-Row Diatomic Molecules

Molecular Orbitals from 2p Atomic Orbitals

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There are two ways in which two p orbitals overlap

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end on so that the resulting MO has electron density on the axis between nuclei (

orbital) sideways so that the resulting MO has electron density above and below the axis between nuclei (

orbital).

The p-orbitals must give rise to 6 MO’s: one

and two

’s one

* and two

*’s The relative energies of these

and

orbitals can change.

Chapter 10 23

Second-Row Diatomic Molecules

Molecular Orbitals from 2p Atomic Orbitals Chapter 10 24

Second-Row Diatomic Molecules

Electron Configurations for B 2 through Ne 2 Chapter 10 25

Second-Row Diatomic Molecules

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Electron Configurations for B 2 For B 2 , C 2 and N 2 the

2p through Ne 2 orbital is higher in energy than the

2p .

For O 2 , F 2 than the

2p .

and Ne 2 the

2p orbital is lower in energy Chapter 10 26

Second-Row Diatomic Molecules

Electron Configurations for B 2 through Ne 2 Chapter 10 27

Second-Row Diatomic Molecules

Electron Configurations for B 2 through Ne 2 Chapter 10 28

Second-Row Diatomic Molecules

Electron Configurations and Molecular Properties Two types of magnetic behavior:

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Paramagnetism, unpaired electrons in molecule Diamagnetism, no unpaired electrons in molecule Chapter 10 29

Second-Row Diatomic Molecules

Electron Configurations and Molecular Properties Chapter 10 30

Homework

10, 12, 24, 47

Chapter 10 31