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General Chemistry, Chapter 7

Professor Thomas
Fall 2022
mthomas2@Oglethorpe.edu

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7.1 Molecular Geometry

Molecular shape can be predicted by using the valence-shell


electron-pair repulsion (VSEPR) model.

ABx

A is the central atom surrounded by x B atoms.


x can have integer values of 2 to 6.
TABLE 7.1 Examples of ABx Molecules and Polyatomic Ions
AB2 BeCl2 , SO 2 , H 2 O, NO2
AB3 BF3 , NH 3 , CIF3 , SO32
AB4 CCl 4 , NH 4 , SF4 , XeF4 ,ClO4
AB5 PCl5 , IF5 , SbF5 , BrF5
AB6 SF6 , UF6 , TiCl36
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The VSEPR Model 2

The basis of the VSEPR model is that electrons repel each other.

Electrons are found in various domains – bonds and lone pairs.

Electrons will arrange themselves to be as far apart as possible.

Arrangements minimize repulsive interactions.

2 electron domains 3 electron domains


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Linear Trigonal planar 6
The VSEPR Model 3

4 electron domains 5 electron domains


Tetrahedral Trigonal bipyramidal
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6 electron domains
Octahedral
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Electron-Domain Geometry and Molecular Geometry 1

The electron domain geometry is the arrangement of electron domains around the
central atom.
The molecular geometry is the arrangement of bonded atoms.
In an ABx molecule, a bond angle is the angle between two adjacent A–B bonds.

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Electron-Domain Geometry and Molecular Geometry 2

AB5 molecules contain two different bond angles between adjacent


bonds.
Axial positions; perpendicular
To the trigonal plane

Equatorial positions; three bonds


arranged in a trigonal plane.

Trigonal bipyramidal

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Electron-Domain Geometry and Molecular Geometry 3

When the central atom in an ABx molecule bears one or more


lone pairs, the electron-domain geometry and the molecular
geometry are no longer the same.

Electron-domain geometry: Molecular geometry:


trigonal planar bent
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Electron-Domain Geometry and Molecular Geometry 4

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Electron-Domain Geometry and Molecular Geometry 5

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Electron-Domain Geometry and Molecular Geometry 6

The steps to determine the electron-domain and molecular


geometries are as follows:
Step 1: Draw the Lewis structure of the molecule or polyatomic
ion.
Step 2: Count the number of electron domains on the central atom.
Step 3: Determine the electron-domain geometry by applying the
VSEPR model.
Step 4: Determine the molecular geometry by considering the
positions of the atoms only.

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Worked Example 7.1 1

Determine the shapes of (a) SO3 and (b) ICl 4 .

Strategy Use Lewis structures and the VSEPR model to determine first the
electron-domain geometry and then the molecular geometry (shape).
(a) The Lewis structure of SO3 is:

There are three electron domains on the central atom: one double bond and two single
bonds.
(b) The Lewis structure of ICl4 is:

There are six electron domains on the central atom in ICl4 :


four single bonds and two lone pairs.
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Worked Example 7.1 3

Think About It Compare these results with the information in


Figure 7.2 and Table 7.2. Make sure that you can draw Lewis
structures correctly. Without a correct Lewis structure, you will
be unable to determine the shape of a molecule.

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Deviation from Ideal Bond Angles
Some electron domains are better than others at repelling neighboring domains.
• Lone pairs take up more space than bonded pairs of electrons.
• Multiple bonds repel more strongly than single bonds.

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Geometry of Molecules with More Than One
Central Atom
The geometry of more complex molecules can be determined by
treating them as though they have multiple central atoms.

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Worked Example 7.2 1

Acetic acid, the substance that gives vinegar its characteristic smell and sour
taste, is sometimes used in combination with corticosteroids to treat certain
types of ear infections. Its Lewis structure is

Determine the molecular geometry about each of the central atoms, and determine
the approximate value of each of the bond angles in the molecule. Which if any of
the bond angles would you expect to be smaller than the ideal values?
Strategy The leftmost C atom is surrounded by four electron domains: one C−C
bond and three C−H bonds. The middle C atom is surrounded by three electron
domains: one C−C bond, one C−O bond, and one C=O bond. The O atom is
surrounded by four electron domains: one O−C bond, one O−H bond, and two
lone pairs.

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7.2 Molecular Geometry and Polarity 1

Molecular polarity is one of the most important consequences of


molecular geometry.
A diatomic molecule is polar when the electronegativities of the
two atoms are different.

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Molecular Geometry and Polarity 2

The polarity of a molecule made up of three or more atoms


depends on:
1. The polarity of the individual bonds.
2. The molecular geometry.
Carbon dioxide, CO2

The bonds in CO2 are polar but the molecule is nonpolar.

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Molecular Geometry and Polarity 3

The polarity of a molecule made up of three or more atoms


depends on:
1. The polarity of the individual bonds.
2. The molecular geometry.
Water, H2O

The bonds in H2O are polar and the molecule is polar.

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Molecular Geometry and Polarity 4

The polarity of a molecule made up of three or more atoms


depends on:
1. The polarity of the individual bonds.
2. The molecular geometry.
Boron trifluoride, BF3

The bonds in BF3 are polar but the molecule is nonpolar.

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Molecular Geometry and Polarity 5

The polarity of a molecule (3+ atoms) depends on:


1. The polarity of the individual bonds.
2. The molecular geometry.
The bonds in CCl4 are
polar but the molecule is
nonpolar.

The bonds in CHCl3 are


polar and the molecule is
polar.

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Worked Example 7.3 1

Determine whether PCl5 is polar.


Strategy Draw the Lewis structure, use the VSEPR model to determine its
molecular geometry, and then determine whether the individual bond dipoles
cancel.
(a) The Lewis structure of PCl5 is

With five identical electron domains around the central atom, the electron-domain
and molecular geometries are trigonal bipyramidal. The equatorial bond dipoles
will cancel one another, just as in the case of BF3, and the axial bond dipoles will
also cancel each other.
Solution PCl5 is nonpolar.
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Worked Example 7.3 2

Determine whether (b) H2CO (C double bonded to O) is polar.


Strategy Draw the Lewis structure, use the VSEPR model to determine its
molecular geometry, and then determine whether the individual bond dipoles
cancel.
(b) The Lewis structure of H2CO is

The bond dipoles, although symmetrically distributed around the C atom, are
not identical and therefore will not sum to zero.
Solution H2CO is polar.

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Worked Example 7.3 3

Think About It Make sure that your Lewis structures are correct
and that you count electron domains on the central atom
carefully. This will give you the correct electron-domain and
molecular geometries. Molecular polarity depends on both the
individual bond dipoles and the molecular geometries.

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7.3 Intermolecular Forces 1

Intermolecular forces are attractive forces between neighboring


molecules.
These forces are known collectively as van der Waals forces.

• The magnitude (and type) of


intermolecular forces can be
sufficient to hold the
molecules of a substance
together in a solid or liquid.
• Gases have no apparent
intermolecular forces.

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Dipole–Dipole Interactions 1

Dipole–dipole interactions are attractive forces that act between


polar molecules.

The magnitude of the attractive forces depends on the magnitude


of the dipole.
• Red is high electron density (δ−) and blue is low (δ+).

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Dipole–Dipole Interactions 2

TABLE 7.3 Dipole Moments and Boiling Points of Compounds


with Similar Molecular Masses
Compound Structural formula Dipole moment (D) Boiling point (℃)
Propane CH3CH2CH3 0.1 −42

Dimethyl ether CH3OCH3 1.3 −25

Methyl chloride CH3Cl 1.9 −24

Acetaldehyde CH3CHO 2.7 21

Acetonitrile CH3CN 2.9 82

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Hydrogen Bonding 1

Hydrogen bonding is a special type of dipole–dipole interaction.

Hydrogen bonding only occurs in molecules that contain H


bonded to a small, highly electronegative atom such as N, O, or F.

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Hydrogen Bonding 2

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Dispersion Forces

Dispersion forces or London dispersion forces result from the


Coulombic attractions between instantaneous dipoles of
nonpolar molecules.

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Intermolecular Forces 2

TABLE 7.4 Molar Masses, Boiling Points, and States of the


Halogens at Room Temperature
Molar mass Boiling point State
Molecule
(g/mol) (°C) (room temp.)
F2 38.0 −188 Gas
Cl2 70.9 −34 Gas
Br2 159.8 59 Liquid
I2 253.8 184 Solid

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Worked Example 7.4 1

What kind(s) of intermolecular forces exist in


(a) CCl4(l), (b) CH3COOH(l), (c) CH3COCH3(l), and (d) H2S(l).

Strategy Draw Lewis dot structures and apply VSEPR theory to determine
whether each molecule is polar or nonpolar. Nonpolar molecules exhibit
dispersion forces only. Polar molecules exhibit dipole-dipole interactions and
dispersion forces. Polar molecules with N–H , F–H, or O–H bonds exhibit
dipole-dipole interactions (including hydrogen bonding) and dispersion forces.

(a) (b) (c) (d)

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Ion–Dipole Interactions

Ion–dipole interactions are Coulombic attractions between ions (either


positive or negative) and polar molecules.

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7.4 Valence Bond Theory 1

According to valence bond theory, atoms share electrons when


atomic orbitals overlap.
1. A bond forms when single occupied atomic orbitals on two
atoms overlap.
2. The two electrons shared in the region of orbital overlap must
be of opposite spin.
3. Formation of a bond results in a lower potential energy for the
system.

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Valence Bond Theory 2

The H–H bond in H2 forms when the singly occupied 1s orbitals


of the two H atoms overlap:

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Valence Bond Theory 3

The F−F bond in F2 forms when the singly occupied 2p orbitals


of the two F atoms overlap:

Orbital diagram for F


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Valence Bond Theory 4

The H−F bond in HF forms when the singly occupied 1s orbital on the
H atom overlaps with the single occupied 2p orbital of the F atom:

TABLE 7.5 Bond Lengths and Bond Energies of H2, F2, and HF
Bond length (Å) Bond energy (kJ/mol)
H2 0.74 436.4
F2 1.42 150.6
HF 0.92 568.2
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Valence Bond Theory 5

• A covalent bond will form if the potential energy of the molecule


is lower than the combined potential energies of the isolated
atoms.

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Worked Example 7.5
Hydrogen selenide (H2Se) is a foul-smelling gas that can cause eye and
respiratory tract inflammation. The H−Se−H bond angle in H2Se is
approximately 92°. Use valence bond theory to describe the bonding in this
molecule.
Strategy The ground-state electron configuration of Se is [Ar]4s 2 3d 10 4 p 4 .

Its orbital diagram (showing only the 4p orbitals) is

Solution Two of the 4p orbitals are singly occupied and therefore available for
bonding. The bonds in H2Se form as the result of the overlap of a hydrogen 1s
orbital with each of these orbitals on the Se atom.
Think About It Because the 4p orbitals on the Se atom are all mutually
perpendicular, we should expect the angles between bonds formed by their
overlap to be approximately 90°.
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7.5 Hybridization of Atomic Orbitals 1

Hybridization or mixing of atomic orbitals can account for


observed bond angles in molecules that could not be described by
the direct overlap of atomic orbitals.

Actual bold angle is 180°.


Bold angle should be 90°.

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Hybridization of Atomic Orbitals 2

BeCl2

Lewis theory and VSEPR theory predict Cl−Be−Cl bond angle


of 180°.

2 electron domains
Linear molecular geometry

A ground state beryllium atom can not form two bonds; there are
no unpaired electrons.

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Hybridization of Atomic Orbitals 3

BeCl2

An excited state configuration for Be has two unpaired electrons


and can form to bonds.

The two bonds formed would not be equivalent.


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Hybridization of s and p Orbitals 1

BeCl2

Experimentally the bond in BeCl2 bonds is identical in length and


strength.
Mixing of one s orbital and one p orbital to yield two sp orbitals.

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Hybridization of s and p Orbitals 2

BeCl2

The 2s orbital and one of the 2p orbitals on Be combine to form


two sp hybrid orbitals.

Like any two electron domains, the hybrid orbitals on Be are 180° apart.
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Hybridization of s and p Orbitals 3

BeCl2

The hybrid orbitals on Be each overlap with a singly occupied 3p


orbital on a Cl atom.

The energy required to form an excited state Be atom is more than


compensated for by the energy given off when a bond forms.

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Hybridization of s and p Orbitals 4

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in BF3.

Step 1: Draw the Lewis structure:

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Hybridization of s and p Orbitals 5

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in BF3.
Step 2: Count the number of electron domains on the central
atom. This is the number of hybrid orbitals necessary to account
for the molecule’s geometry. (This is also the number of atomic
orbitals that must undergo hybridization.)

Three electron domains

Three hybrid orbitals required

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Hybridization of s and p Orbitals 6

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in BF3.
Step 3: Draw the ground-state orbital diagram for the central
atom.
Step 4: Maximize the number of unpaired valence electrons by
promotion.

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Hybridization of s and p Orbitals 7

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in BF3.
Step 5: Combine the necessary number of atomic orbitals to
generate the required number of hybrid orbitals.
Step 6: Place electrons in the hybrid orbitals, putting one electron
in each orbital before pairing any electrons.

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Hybridization of s and p Orbitals 8

Mixing of one s orbital and two p orbitals to yield three sp2 orbitals.

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Hybridization of s and p Orbitals 9

Hybrid orbitals on boron overlap with 2p orbitals on fluorine.

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Hybridization of s and p Orbitals 10

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in CH4.
Step 1: Draw the Lewis structure:

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Hybridization of s and p Orbitals 11

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in CH4.
Step 2: The number of electron domains on the central atom is
the number of hybrid orbitals necessary to account for the
molecule’s geometry.

Four electron domains


Four hybrid orbitals required

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Hybridization of s and p Orbitals 12

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in CH4.
Step 3: Draw the ground state orbital diagram for the central atom.
Step 4: Maximize the number of unpaired electrons by promotion.

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Hybridization of s and p Orbitals 13

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in CH4.
Step 5: Combine the necessary number of atomic orbitals to
generate the required number of hybrid orbitals.
Step 6: Place electrons in the hybrid orbitals, putting one electron
in each orbital before pairing any electrons.

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Hybridization of s and p Orbitals 14

Mixing of one s orbital and three p orbitals to yield four sp3 orbitals.

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Hybridization of s and p Orbitals 15

Hybrid orbitals on carbon overlap with 1s orbitals on hydrogen.

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Hybridization of s, p, and d Orbitals 1

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in PCl5.
Step 1: Draw the Lewis structure:

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Hybridization of s, p, and d Orbitals 2

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in PCl5.
Step 2: The number of electron domains on the central atom is
the number of hybrid orbitals necessary to account for the
molecule’s geometry.

Five electron domains


Five hybrid orbitals required

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Hybridization of s, p, and d Orbitals 3

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in PCl5.
Step 3: Draw the ground state orbital diagram for the central atom.
Step 4: Maximize the number of unpaired electrons by promotion.

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Hybridization of s, p, and d Orbitals 4

Determine the number and type of hybrid orbitals necessary to


rationalize the bonding in PCl5.
Step 5: Combine the necessary number of atomic orbitals to
generate the required number of hybrid orbitals.
Step 6: Place electrons in the hybrid orbitals, putting one electron
in each orbital before pairing any electrons.

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Hybridization of s, p, and d Orbitals 5

Hybrid orbitals on phosphorus overlap with 3p orbitals on chlorine.

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Hybridization of s, p, and d Orbitals 6

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Worked Example 7.6 1

Ammonia (NH3) is a trigonal pyramidal molecule with H−N−H bond


angles of about 107°. Describe the formation of three equivalent N−H
bonds, and explain the angle between them.
Strategy Starting with the Lewis structure, determine the number and
type of hybrid orbitals necessary to rationalize the bonding in NH3.

The ground state electron configuration of the N atom is [He]2s 2 2 p 3 .


Its valence orbital diagram is

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7.6 Hybridization in Molecules Containing
Multiple Bonds 1

Valence bond theory and hybridization can be used to describe


the bonding in molecules containing double and triple bonds.

Each carbon has three electron domains:


2 single bonds
1 double bond

Expect sp2 hybridization

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Hybridization in Molecules Containing Multiple
Bonds 2

Maximize unpaired electrons on carbon by promotion:

Hybridize the required number of atomic orbitals (one for each


electron domain on carbon)

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Hybridization in Molecules Containing Multiple
Bonds 3

Hybridization scheme for the carbon atoms in ethylene:

One unhybridized atomic 2p


orbital gives rise to multiple
bonds

Three equivalent sp2 hybrid orbitals


explain three bonds around carbon

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Hybridization in Molecules Containing Multiple
Bonds 4

A sigma (σ) bond forms when sp2 hybrid orbitals on the C atoms
overlap.
In a sigma bond, the shared electron density lies directly along
the internuclear axis.

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Hybridization in Molecules Containing Multiple
Bonds 5

The ethylene molecule contains five sigma bonds:


1 between the two carbon atoms (sp2 and sp2 overlap)
4 between the C and H atoms (sp2 and 1s overlap)

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Hybridization in Molecules Containing Multiple
Bonds 6

The remaining unhybridized p orbital is perpendicular to the plane


in which the atoms of the molecule lie.
The unhybridized p orbitals overlap in a sideways fashion to form
a pi (π) bond.

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Worked Example 7.7 1

Thalidomide (C13H10N2O4) is a sedative and antiemetic that was widely


prescribed during the 1950s, although not in the United States, for pregnant
women suffering from morning sickness. Its use was largely discontinued when
it was determined to be responsible for thousands of devastating birth defects.
Determine the number of carbon–carbon sigma bonds and the total number of pi
bonds in thalidomide.

Strategy Remember, a single bond is composed of a sigma bond, whereas a


double bond is usually composed of one sigma bond and one pi bond.
Solution Thalidomide contains 12 carbon–carbon sigma bonds and a total of
seven pi bonds (three in carbon–carbon double bonds and four in carbon–oxygen
double bonds.
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Worked Example 7.7 2

Think About It The Lewis structure given to thalidomide is one of two


possible resonance structures. Draw the other resonance structure, and
count sigma and pi bonds again. Make sure you get the same answer.

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Hybridization in Molecules Containing Multiple
Bonds 7

Sigma bonds exhibit free rotation around the bond axis.

All three Lewis structures represent the same molecule.

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Hybridization in Molecules Containing Multiple
Bonds 8

Pi bonds restrict free rotation around the bond axis.

There are two isomers of 1,2-dichloroethylene

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Hybridization in Molecules Containing Multiple
Bonds 9

The acetylene molecule is linear with sp hybridized carbons.

Promotion of an electron maximizes the number of unpaired


electrons:

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Hybridization in Molecules Containing Multiple
Bonds 10

The acetylene molecule is linear with sp hybridized carbons.


3 sigma bonds:
1 between the two carbon atoms (sp and sp)
2 between the C and H atoms (sp and 1s)
2 pi bonds
2 between the two carbon atoms (2p and 2p)

The 2s orbital and one of the 2p orbitals then mix to form two sp hybrid
orbitals:

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Hybridization in Molecules Containing Multiple
Bonds 11

The acetylene molecule is linear with sp hybridized carbons.

Two unhybridized atomic 2p orbitals


gives rise to 2 pi bonds

Two equivalent sp hybrid orbitals


gives rise to 2 sigma bonds

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Hybridization in Molecules Containing Multiple
Bonds 12

Formation of the C−C sigma bond in acetylene:


3 sigma bonds:
1 between the two carbon atoms (sp and sp)
2 between the C and H atoms (sp and 1s)

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Hybridization in Molecules Containing Multiple
Bonds 13

Formation of the C−C pi bond in acetylene:


2 pi bonds
2 between the two carbon atoms (2p and 2p)

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Worked Example 7.8 1

In addition to its use in aqueous solution as a preservative for laboratory


specimens, formaldehyde gas is used as an antibacterial fumigant. Use
hybridization to explain the bonding in formaldehyde (CH2O).
Strategy The Lewis structure of formaldehyde is

The C and O atoms each have three electron domains around them.
[Carbon has two single bonds (C−H) and a double bond (C=O); oxygen
has a double bond (O=C) and two lone pairs.]

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7.7 Molecular Orbital Theory 1

Lewis structures and valence bond theory fail to predict some important
properties of molecules.
Paramagnetism is a result of a molecule’s electron configuration.
Species that contain one or more unpaired electrons are paramagnetic.
Paramagnetic species are attracted to magnet fields.

The Lewis structure


for O2 shows no
unpaired electrons.
O2 exhibits
paramagnetism.

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Molecular Orbital Theory 2

Lewis structures and valence bond theory fail to predict some


important properties of molecules.
Species that contain paired electrons are diamagnetic.
Diamagnetic species are weakly repelled by magnetic fields.

The Lewis structure


for N2 shows no
unpaired electrons.
N2 exhibits
diamagnetism.

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Molecular Orbital Theory 3

Another bonding theory is needed to describe the paramagnetism of O2.


In molecular orbital theory, the atomic orbitals combine to form new
orbitals that are the “property” of the entire molecule.
The new orbitals are called molecular orbitals.
Molecular orbitals have characteristics similar to atomic and hybrid
orbitals:
• Specific shapes.
• Specific energies.
• Accommodate a maximum of 2 electrons each.
• Electron filling follows the Pauli exclusion principle.
• The number of molecular orbitals obtained equals the number of
orbitals combined.

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Bonding and Antibonding Molecular Orbitals 1

H2 is the simplest homonuclear diatomic molecule.

Valence bond theory:


• H2 forms when from the overlap of the 1s orbitals.

Molecular orbital theory:


• H2 forms when the 1s orbitals combine to give molecular
orbitals.
• Molecular orbitals result from the constructive and destructive
combination of atomic orbitals.

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Bonding and Antibonding Molecular Orbitals 2

Constructive combination of the two 1s orbitals gives rise to a


molecular orbital that lies along the internuclear axis.
Constructive combination increases the electron density between
the two nuclei.

This molecular orbital is referred to


as a bonding molecular orbital.
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Bonding and Antibonding Molecular Orbitals 3

Destructive combination of the two 1s orbitals gives rise to a molecular


orbital that lies along the internuclear axis, but does not lie between the
two nuclei.
Electron density in this molecular orbital pulls the two nuclei in opposite
directions.

This molecular orbital is referred to


as an antibonding molecular orbital.
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σ Molecular Orbitals 1

Molecular orbitals that lie along the internuclear axis are referred to as σ
molecular orbitals.
Examples:
σ1s bonding molecular orbital from the combination of two 1s orbitals.
σ*1s antibonding molecular orbital from the combination of two 1s
orbitals.
• The * distinguishes an antibonding molecular orbital from a bonding orbital.

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σ Molecular Orbitals 2

Molecular orbitals have specific energies.

Electrons in bonding molecular orbitals stabilize the molecule and


are lower in energy than the isolated atomic orbitals.

Electrons in antibonding molecular orbitals destabilize the


molecule and are higher in energy than the isolated atomic orbitals.

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Bond Order 1

The bond order indicates how stable a molecule is.

The higher the bond order, the more stable a molecule is.

N o . o f e  in b o n d in g o r b ita ls  N o . o f e  in a n tib o n d in g o r b ita ls


b o n d o rd er =
2

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Bond Order 2

H2

N o . o f e  in b o n d in g o rb ita ls  N o . o f e  in a n tib o n d in g o r b ita ls


b o n d o rd e r =
2

20 According to molecular orbital theory,


bond order  1 H2 is a stable molecule.
2

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Bond Order 3

He2

N o . o f e  in b o n d in g o rb ita ls  N o . o f e  in a n tib o n d in g o r b ita ls


b o n d o rd e r =
2

22 According to molecular orbital theory, He2


bond order  0 is NOT a stable molecule and does not exist.
2

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π Molecular Orbitals 1

p atomic orbitals also form molecular orbitals by both constructive and


destructive combination.
The orientations of px, py, and pz give rise to two different types of
molecular orbitals:
σ molecular orbitals – electron density along the internuclear axis

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π Molecular Orbitals 2

p atomic orbitals also form molecular orbitals by both constructive


and destructive combination.
π molecular orbitals – electron density above and below the
internuclear axis

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π Molecular Orbitals 3

Molecular orbitals resulting from the combination of p atomic


orbitals are higher than those resulting from the combination of s
atomic orbitals.

This order of orbital energies assumes


no mixing of s and p orbitals.

s orbitals only interact with s orbitals.

p orbitals only interact with p orbitals.

This is found in O2, F2, and Ne2.

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π Molecular Orbitals 4

Molecular orbitals resulting from the combination of p atomic


orbitals are higher than those resulting from the combination of s
atomic orbitals.

This order of orbital energies assumes


some mixing of s and p orbitals.
This arrangement of orbitals is found
in Li2, B2, C2, and N2.

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Molecular Orbital Diagrams 1

Filling molecular orbital diagrams follows the same rules as the


filling of atomic orbitals.
1. Lower energy orbitals fill first.
2. Each orbital can accommodate a maximum of two electrons
with opposite spin.
3. Hund’s rule is obeyed.

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Molecular Orbital Diagrams 2

Molecular orbital diagrams for second-period homonuclear


diatomic molecules.

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Worked Example 7.9 1

The superoxide ion (O 2  ) has been implicated in a number of degenerative


conditions, including aging and Alzheimer’s disease. Using molecular orbital
theory, determine whether (O 2  ) is paramagnetic or diamagnetic, and then
calculate its bond order.
Strategy Start with the molecular orbital diagram for O2 and add an electron to
the lowest-energy molecular orbital available.

Solution In this case, either of the two singly occupied π*2p


orbitals can accommodate an additional electron. This gives a
molecular orbital diagram in which there is one unpaired
electron, making (O 2  ) paramagnetic. The new diagram has six
electrons in bonding molecular orbitals and three in
antibonding molecular orbitals. We can ignore the electrons in
the σ2s and σ*2s orbitals because their contributions to the bond
order cancel each other. The bond order is (6  3) 2  1.5.
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Worked Example 7.9 2

Think About It Experiments confirm that the superoxide ion is


paramagnetic. Also, any time we add one or more electrons to an
antibonding molecular orbital, as we did in this problem, we
should expect the bond order to decrease. Electrons in
antibonding orbitals cause a bond to be less stable.

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7.8 Bonding Theories and Descriptions of Molecules
with Delocalized Bonding 1

Lewis Theory
Strength:
• Qualitative prediction of bond strength and bond length.
Weakness:
• Two-dimensional model, real molecules are three-dimensional.
• Fails to explain why bonds form.

Valence-Shell Electron-Pair Repulsion Model


Strength:
• Predict the shape of many molecules and polyatomic ions.
Weakness:
• Fails to explain why bonds form (based on Lewis theory).
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Bonding Theories and Descriptions of Molecules with
Delocalized Bonding 2

Valence Bond Theory


Strength:
• Covalent bonds form when atomic orbitals overlap.
Weakness:
• Fails to explain the bonding in many molecules.

Hybridization of Atomic Orbitals


Strength:
• An extension of valence bond theory. Using hybrid orbitals it is
possible to explain the bonding and geometry of more molecules.
Weakness:
• Fails to predict some important properties, such as magnetism.

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Bonding Theories and Descriptions of Molecules with
Delocalized Bonding 3

Molecular Orbital Theory


Strength:
• Accurately predict the magnetic and other properties of molecules.
Weakness:
• Complex.

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Bonding Theories and Descriptions of Molecules with
Delocalized Bonding 4

Some molecules are best described using a combination of


models.

Benzene, C6H6, is represented with two resonance structures:

The π bonds in benzene are delocalized—spread out over the


entire molecule.

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Bonding Theories and Descriptions of Molecules with
Delocalized Bonding 5

The π bonds in benzene are delocalized—spread out over the entire


molecule.

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Worked Example 7.10 1

It takes three resonance structures to represent the carbonate ion CO32 :

None of the three, though, is a completely accurate description. As with


benzene, the bonds that are shown in the Lewis structure as one double
and two single are actually three equivalent bonds. Use a combination
of valence bond theory and molecular orbital theory to explain the
bonding in CO32 .
Strategy The Lewis structure of the carbonate ion shows three electron
domains around the central C atom, so the carbon must be sp2
hybridized.

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