ChemCh8.3.ppt

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8.3 Bonding Theories >

Chapter 8

Covalent Bonding

8.1 Molecular Compounds

8.2 The Nature of Covalent Bonding

8.3 Bonding Theories

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The lines on a topographic map show you where

elevations change. In this lesson, you will learn how to interpret electron

CHEMISTRY & YOU

CHEMISTRY & YOU

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Molecular Orbitals

How are atomic and molecular

orbitals related?

Molecular Orbitals

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• The model you have been using for

covalent bonding assumes the orbitals are those of the individual atoms.

• There is a quantum mechanical model of bonding, however, that describes the

electrons in molecules using orbitals that exist only for groupings of atoms.

Molecular Orbitals

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• When two atoms combine, this model

assumes that their atomic orbitals overlap to produce molecular orbitals, or orbitals that apply to the entire molecule.

• In some ways, atomic orbitals and molecular orbitals are similar.

Molecular Orbitals

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Just as an atomic orbital belongs to a

particular atom, a molecular orbital

belongs to a molecule as a whole.

• A molecular orbital that can be occupied by two electrons of a covalent bond is called a

bonding orbital.

Molecular Orbitals

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When two atomic orbitals combine to form a

molecular orbital that is symmetrical around the axis connecting two atomic nuclei, a sigma

bond is formed.

• Its symbol is the Greek letter sigma (σ).

Molecular Orbitals Molecular Orbitals Sigma Bonds s atomic orbital s atomic orbital Bond axis Sigma-bonding molecular orbital

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In general, covalent bonding results from

an imbalance between the attractions and

repulsions of the nuclei and electrons

involved.

• The nuclei and electrons attract each other. • Nuclei repel other nuclei.

Molecular Orbitals

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• In a bonding molecular orbital of hydrogen, however, the attractions between the

hydrogen nuclei and the electrons are stronger than the repulsions.

• The balance of all the interactions between the hydrogen atoms is thus tipped in favor of

holding the atoms together.

• The result is a stable diatomic molecule of H₂.

Molecular Orbitals

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Atomic p orbitals can also overlap to form

molecular orbitals.

• A fluorine atom, for example, has a half-filled 2p orbital.

• When two fluorine atoms combine, the p

Molecular Orbitals

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• There is a high probability of finding a pair of electrons between the positively charged

nuclei of the two fluorines.

• The overlap of the 2p orbitals produces a

bonding molecular orbital that is symmetrical when viewed around the F—F bond axis

connecting the nuclei.

– Therefore, the F—F bond is a sigma bond.

Molecular Orbitals

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• In the sigma bond of the fluorine molecule, the p atomic orbitals overlap end to end.

• In some molecules, however, orbitals can overlap side to side.

Molecular Orbitals

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As shown here, the side-by-side overlap

of atomic p orbitals produces what are

called pi molecular orbitals.

Molecular Orbitals

p atomic orbital

Pi-bonding molecular orbital

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• In a pi bond (symbolized by the Greek letter ), the bonding electrons are most likely to be found in sausage-shaped regions above and below the bond axis of the bonded atoms.

• Because atomic orbitals in pi bonding overlap less than in sigma bonding, pi bonds tend to be weaker than sigma bonds.

Molecular Orbitals

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8.3 Bonding Theories > CHEMISTRYCHEMISTRY && YOUYOU

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Drawings can show molecular orbitals, which are the areas where bonding

electrons are most likely to be found.

CHEMISTRY & YOU

CHEMISTRY & YOU

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In molecules with sigma bonds,

where are the shared electrons

most likely to be found?

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VSEPR Theory

What do scientists use the VSEPR

theory for?

VSEPR Theory

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• Electron dot structures fail to reflect the three-dimensional shapes of molecules.

• The electron dot structure and structural

formula of methane (CH₄) show the molecule as if it were flat and merely two-dimensional.

VSEPR Theory

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• In reality, methane molecules are three-dimensional.

• The hydrogens in a methane molecule are at the four

corners of a geometric solid called a regular tetrahedron.

• In this arrangement, all of the H–C–H angles are 109.5°, the

tetrahedral angle.

VSEPR Theory

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In order to explain the

three-dimensional shape of molecules,

scientists use valence-shell

electron-pair repulsion theory (VSEPR theory).

• VSEPR theory states that the repulsion between electron pairs causes molecular shapes to adjust so that the

valence-VSEPR Theory

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• Unshared pairs of electrons are also important in

predicting the shapes of molecules.

• The nitrogen in ammonia (NH₃) is surrounded by four pairs of valence electrons.

• However, one of the

valence-electron pairs is an unshared pair.

VSEPR Theory

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• No bonding atom is vying for

these unshared electrons; thus, they are held closer to the

nitrogen than are the bonding pairs.

• The unshared pair strongly repels the bonding pairs, pushing them together.

• The measured H—N—H bond

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• In a water molecule, the two bonding pairs and the two

unshared pairs of electrons form a tetrahedral arrangement

around the central oxygen. • Thus, the water molecule is

planar (flat) but bent.

• With two unshared pairs

repelling the bonding pairs, the H—O

—

H bond angle is

compressed to about 105°.

VSEPR Theory

Unshared pairs

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• The carbon in a carbon dioxide molecule has no unshared electron pairs.

• The double bonds joining the oxygens to the carbon are farthest apart when the O=C=O bond angle is 180°.

– Thus, CO₂ is a linear molecule.

VSEPR Theory

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Here are some common molecular shapes.

VSEPR Theory

Linear Trigonal planar Bent Pyramidal

Tetrahedral Trigonal bipyramidal

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What causes valence-electron pairs

to stay as far apart as possible?

The repulsion between electron pairs due to their negative charges causes

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Hybrid Orbitals

In what ways is orbital hybridization

useful in describing molecules?

Hybrid Orbitals

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The VSEPR theory works well when accounting for molecular shapes, but it

does not help much in describing the types of bonds formed.

Hybrid Orbitals

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Orbital hybridization provides

information about both molecular

bonding and molecular shape.

• In hybridization, several atomic orbitals mix to form the same total number of

equivalent hybrid orbitals.

Hybrid Orbitals

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• Recall that the carbon atom’s outer

electron configuration is 2s22p2, but one of

the 2s electrons is promoted to a 2p orbital to give one 2s electron and three 2p

electrons.

• You might suspect that one bond in

methane would be different from the other three.

Hybrid Orbitals

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• In fact, all the bonds are identical.

• The one 2s orbital and three 2p orbitals of a carbon atom mix to form four sp3 hybrid

orbitals at the tetrahedral angle of 109.5°.

Hybrid Orbitals

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In methane, each of the four sp3 hybrid orbitals of

carbon overlaps with a 1s orbital of a hydrogen.

Hybrid Orbitals

Hybridization Involving Single Bonds

Atomic orbitals of two hydrogen

atoms

Hybrid orbitals of a carbon

atom

Sigma bond

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The sp

3

orbitals extend farther into space

than either s or p orbitals, allowing a great

deal of overlap with the hydrogen 1s

orbitals.

• The extent of overlap results in unusually

strong covalent bonds.

Hybrid Orbitals

Hybridization Involving Single Bonds

Sigma bond

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Ethene is a relatively simple molecule

that has one carbon-carbon double

bond and four carbon-hydrogen single

bonds.

Hybrid Orbitals

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• In ethene, sp2 hybrid orbitals form from the

combination of one 2s and two 2p atomic orbitals of carbon.

• As you can see in the figure on the next

slide, each hybrid orbital is separated from the other two by 120°.

Hybrid Orbitals

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8.3 Bonding Theories > Hybrid OrbitalsHybrid Orbitals

Hybridization Involving Double Bonds

Atomic orbital and hybrid orbitals of

a carbon atom Hybrid orbitals

of two hydrogen atoms

Hybrid orbitals of two hydrogen

atoms

Pi bond

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Hybridization Involving Double Bonds

Pi bond

Sigma bond

• In an ethene molecule, two sp2 hybrid orbitals of

each carbon form sigma-bonding molecular orbitals with the four available

hydrogen 1s orbitals.

• The third sp2 orbitals of each of the two carbons

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A third type of covalent bond is a triple

bond, which is found in ethyne (C

₂

H

₂

),

also called acetylene.

Hybrid Orbitals

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• Ethyne is a linear molecule.

• The best hybrid orbital description is

obtained if a 2s atomic orbital of carbon

mixes with only one of the three 2p atomic orbitals.

Hybrid Orbitals

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Hybridization Involving Triple Bonds

Atomic orbitals and hybrid orbitals of

a carbon atom Atomic orbital

of a hydrogen atom

Pi bond

Sigma bonds

Atomic orbital of a hydrogen

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Hybridization Involving Double Bonds

• In an ethyne

molecule, one sp

hybrid orbital from

each carbon overlaps with a 1s orbital of

hydrogen to form a sigma bond.

• The other sp hybrid orbital of each carbon

Pi bond

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How many hybridized orbitals form

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How many hybridized orbitals form

when one 2

s

orbital is hybridized with

three 2

p

orbitals?

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Just as an atomic orbital belongs to a particular atom, a molecular orbital

belongs to a molecule as a whole.

In order to explain the three-dimensional shape of molecules, scientists use the valence-shell electron-pair repulsion theory (VSEPR theory).

Orbital hybridization provides

information about both molecular bonding and molecular shape.

Key Concepts

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• molecular orbital: an orbital that applies to the entire molecule

• bonding orbital: a molecular orbital that can be occupied by two electrons of a covalent bond

• sigma bond ( bond): a bond formed when two atomic orbitals combine to form a molecular orbital that is symmetrical around the axis connecting the two atomic nuclei

• pi bond ( bond): a covalent bond in which the

Glossary Terms

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• tetrahedral angle: a bond angle of 109.5° that results when a central atom forms four bonds directed toward the center of a regular

tetrahedron

• VSEPR theory: valence-shell electron-pair

repulsion theory; because electron pairs repel, molecules adjust their shapes so that valence electron pairs are as far apart as possible

• hybridization: the mixing of several atomic orbitals to form the same total number of equivalent hybrid orbitals

ChemCh8.3.ppt

Molecular Orbitals

How are atomic and molecular

orbitals related?

Just as an atomic orbital belongs to a

particular atom, a molecular orbital

belongs to a molecule as a whole.

In general, covalent bonding results from

an imbalance between the attractions and

repulsions of the nuclei and electrons

involved.

Atomic p orbitals can also overlap to form

molecular orbitals.

As shown here, the side-by-side overlap

of atomic p orbitals produces what are

called pi molecular orbitals.

In molecules with sigma bonds,

where are the shared electrons

most likely to be found?

VSEPR Theory

What do scientists use the VSEPR

theory for?

In order to explain the

three-dimensional shape of molecules,

scientists use valence-shell

electron-pair repulsion theory (VSEPR theory).

—

Here are some common molecular shapes.

What causes valence-electron pairs

to stay as far apart as possible?

Hybrid Orbitals

In what ways is orbital hybridization

useful in describing molecules?

Orbital hybridization provides

information about both molecular

bonding and molecular shape.

Hybridization Involving Single Bonds

The sp

orbitals extend farther into space

than either s or p orbitals, allowing a great

deal of overlap with the hydrogen 1s

orbitals.

Hybridization Involving Single Bonds

Ethene is a relatively simple molecule

that has one carbon-carbon double

bond and four carbon-hydrogen single

bonds.

Hybridization Involving Double Bonds

Hybridization Involving Double Bonds

A third type of covalent bond is a triple

bond, which is found in ethyne (C

H

),

also called acetylene.

Hybridization Involving Triple Bonds

Hybridization Involving Double Bonds

How many hybridized orbitals form

How many hybridized orbitals form

when one 2

s

orbital is hybridized with

three 2

p

orbitals?

Shared electrons and the valence

electrons that are not shared affect

the shape of a molecular compound,

as the valence electrons stay as far

apart from each other as possible.

END OF 8.3