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Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals

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10.1

Valence shell electron pair repulsion (VSEPR) model:

Class

# of atoms bonded to central atom

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# lone pairs on central atom

Predict the geometry of the molecule from the electrostatic repulsions between the electron (bonding and nonbonding) pairs.
Arrangement of electron pairs Molecular Geometry

AB2

linear

linear
B B

10.1

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0 lone pairs on central atom Cl Be Cl 2 atoms bonded to central atom

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2 AB3

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2 3 0 0

Class

linear

linear trigonal planar

trigonal planar

10.1

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10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2 AB3 AB4

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2 3 0 0 0 4

Class

linear

linear trigonal planar tetrahedral

trigonal planar

tetrahedral

10.1

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10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2 AB3 AB4 AB5

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2 3 0 0 0 0 4 5

Class

linear

linear trigonal planar tetrahedral trigonal bipyramidal

trigonal planar

tetrahedral

trigonal bipyramidal

10.1

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10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2 AB3 AB4 AB5 AB6

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2 3 0 0 0 0 0 4 5 6

Class

linear

linear trigonal planar tetrahedral trigonal bipyramidal octahedral

trigonal planar

tetrahedral

trigonal bipyramidal octahedral

10.1

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10.1

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10.1

lone-pair vs. lone pair repulsion

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>
lone-pair vs. bonding pair repulsion

>

bonding-pair vs. bonding pair repulsion

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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3 0 1 2

Class

AB3 AB2E

trigonal planar trigonal planar

trigonal planar bent

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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4 0 1 3

Class

AB4 AB3E

tetrahedral tetrahedral

tetrahedral trigonal pyramidal

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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4 0 1 3 2 2

Class

AB4 AB3E AB2E2

tetrahedral tetrahedral

tetrahedral trigonal pyramidal bent O H H

tetrahedral

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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5 4 0 1

Class

AB5 AB4E

trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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5 4 3 0 1 2

Class

AB5 AB4E AB3E2

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped F F Cl F


10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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5 4 3 2 0 1 2 3

Class

AB5 AB4E AB3E2 AB2E3

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped linear I I I


10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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6 0 5 1

Class

AB6 AB5E

octahedral octahedral

octahedral square pyramidal F F F Br F F

10.1

VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

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6 0 5 1 4 2

Class

AB6 AB5E AB4E2

octahedral octahedral

octahedral square pyramidal square planar F Xe F F F

octahedral

10.1

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10.1

Predicting Molecular Geometry


1. Draw Lewis structure for molecule. 2. Count number of lone pairs on the central atom and number of atoms bonded to the central atom. 3. Use VSEPR to predict the geometry of the molecule. What are the molecular geometries of SO2 and SF4? O S O F AB4E distorted tetrahedron
10.1

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AB2E bent F S F

Dipole Moments and Polar Molecules

=Qxr

Q is the charge r is the distance between charges 1 D = 3.36 x 10-30 C m

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electron poor region electron rich region

10.2

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10.2

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10.2

Which of the following molecules have a dipole moment? H2O, CO2, SO2, and CH4

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H
O H

H dipole moment polar molecule

O dipole moment polar molecule


H C H H

no dipole moment nonpolar molecule

no dipole moment nonpolar molecule


10.2

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Does BF3 have a dipole moment?

10.2

Does CH2Cl2 have a dipole moment?

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10.2

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10.2

Chemistry In Action: Microwave Ovens

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How does Lewis theory explain the bonds in H2 and F2?

Sharing of two electrons between the two atoms.

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74 pm

Bond Dissociation Energy

Bond Length

Overlap Of 2 1s 2 2p

H2 F2

436.4 kJ/mole 150.6 kJ/mole

142 pm

Valence bond theory bonds are formed by sharing of e- from overlapping atomic orbitals.

10.3

Change in Potential Energy of Two Hydrogen Atoms as a Function of Their Distance of Separation

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10.3

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Change in electron density as two hydrogen atoms approach each other.

10.3

Valence Bond Theory and NH3 N 1s22s22p3 3 H 1s1

If the bonds form from overlap of 3 2p orbitals on nitrogen with the 1s orbital on each hydrogen atom, what would the molecular geometry of NH3 be? If use the 3 2p orbitals predict 900 Actual H-N-H bond angle is 107.30
10.4

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Hybridization mixing of two or more atomic orbitals to form a new set of hybrid orbitals.

2. Number of hybrid orbitals is equal to number of pure atomic orbitals used in the hybridization process. 3. Covalent bonds are formed by:

a. Overlap of hybrid orbitals with atomic orbitals b. Overlap of hybrid orbitals with other hybrid orbitals

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1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p). Hybrid orbitals have very different shape from original atomic orbitals.

10.4

Formation of sp3 Hybrid Orbitals

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10.4

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10.4

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Predict correct bond angle

10.4

Formation of sp Hybrid Orbitals

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10.4

Formation of sp2 Hybrid Orbitals

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10.4

How do I predict the hybridization of the central atom? 1. Draw the Lewis structure of the molecule.

# of Lone Pairs + # of Bonded Atoms 2 3 4 5 6

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Hybridization sp sp2 sp3 sp3d sp3d2

2. Count the number of lone pairs AND the number of atoms bonded to the central atom

Examples BeCl2 BF3

CH4, NH3, H2O PCl5 SF6


10.4

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10.4

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10.5

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10.5

Pi bond () electron density above and below plane of nuclei Sigma bond () electron density between the 2 atoms of the bonding atoms 10.5

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10.5

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10.5

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10.5

Describe the bonding in CH2O. H H C O

C 3 bonded atoms, 0 lone pairs C sp2

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10.5

Sigma () and Pi Bonds ()

Double bond Triple bond

How many and bonds are in the acetic acid (vinegar) molecule CH3COOH? H C H
10.5

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O
C O H

Single bond

1 sigma bond

1 sigma bond and 1 pi bond

1 sigma bond and 2 pi bonds

bonds = 6 + 1 = 7 bonds = 1

Experiments show O2 is paramagnetic

No unpaired e-

Should be diamagnetic

Molecular orbital theory bonds are formed from interaction of atomic orbitals to form molecular orbitals.
10.6

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O

Energy levels of bonding and antibonding molecular orbitals in hydrogen (H2).

A bonding molecular orbital has lower energy and greater stability than the atomic orbitals from which it was formed. An antibonding molecular orbital has higher energy and lower stability than the atomic orbitals from which it was formed. 10.6

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10.6

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10.6

Two Possible Interactions Between Two Equivalent p Orbitals

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10.6

Molecular Orbital (MO) Configurations

2. The more stable the bonding MO, the less stable the corresponding antibonding MO. 3. The filling of MOs proceeds from low to high energies. 4. Each MO can accommodate up to two electrons. 5. Use Hunds rule when adding electrons to MOs of the same energy. 6. The number of electrons in the MOs is equal to the sum of all the electrons on the bonding atoms.
10.7

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1. The number of molecular orbitals (MOs) formed is always equal to the number of atomic orbitals combined.

1 bond order = 2

bond order

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1

Number of electrons in bonding MOs

Number of electrons in antibonding MOs

0
10.7

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10.7

Delocalized molecular orbitals are not confined between two adjacent bonding atoms, but actually extend over three or more atoms.

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10.8

Electron density above and below the plane of the benzene molecule.

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10.8

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10.8

Chemistry In Action: Buckyball Anyone?

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