ITT CHNG CH 10 Chemical Bonding II

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

# 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

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

2 3 0 0
Class
linear
linear trigonal planar
trigonal planar
10.1
10.1
VSEPR
AB2 AB3 AB4

2 3 0 0 0 4
Class
linear
linear trigonal planar tetrahedral
trigonal planar
tetrahedral
10.1
10.1
VSEPR
AB2 AB3 AB4 AB5

2 3 0 0 0 0 4 5
Class
linear
linear trigonal planar tetrahedral trigonal bipyramidal
trigonal planar
tetrahedral
trigonal bipyramidal
10.1
10.1
VSEPR
AB2 AB3 AB4 AB5 AB6

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
10.1
10.1
lone-pair vs. lone pair repulsion

>
lone-pair vs. bonding pair repulsion
>
bonding-pair vs. bonding pair repulsion
VSEPR

3 0 1 2
Class
AB3 AB2E
trigonal planar trigonal planar
trigonal planar bent
10.1
VSEPR

4 0 1 3
Class
AB4 AB3E
tetrahedral tetrahedral
tetrahedral trigonal pyramidal
10.1
VSEPR

4 0 1 3 2 2
Class
AB4 AB3E AB2E2
tetrahedral tetrahedral
tetrahedral trigonal pyramidal bent O H H
tetrahedral
10.1
VSEPR

5 4 0 1
Class
AB5 AB4E
trigonal bipyramidal trigonal bipyramidal
trigonal bipyramidal distorted tetrahedron
10.1
VSEPR

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

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

6 0 5 1
Class
AB6 AB5E
octahedral octahedral
octahedral square pyramidal F F F Br F F
10.1
VSEPR

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
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

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

electron poor region electron rich region
10.2
10.2
10.2
Which of the following molecules have a dipole moment? H2O, CO2, SO2, and CH4

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
Does BF3 have a dipole moment?
10.2
Does CH2Cl2 have a dipole moment?
10.2
10.2
Chemistry In Action: Microwave Ovens
How does Lewis theory explain the bonds in H2 and F2?
Sharing of two electrons between the two atoms.

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
10.3
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
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
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
10.4
10.4

Predict correct bond angle
10.4
Formation of sp Hybrid Orbitals
10.4
Formation of sp2 Hybrid Orbitals
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

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
10.4
10.5
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
10.5
10.5
10.5
Describe the bonding in CH2O. H H C O
C 3 bonded atoms, 0 lone pairs C sp2
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

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

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
10.6
10.6
Two Possible Interactions Between Two Equivalent p Orbitals
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
1. The number of molecular orbitals (MOs) formed is always equal to the number of atomic orbitals combined.
1 bond order = 2
bond order

1
Number of electrons in bonding MOs
Number of electrons in antibonding MOs
0
10.7
10.7
Delocalized molecular orbitals are not confined between two adjacent bonding atoms, but actually extend over three or more atoms.
10.8
Electron density above and below the plane of the benzene molecule.
10.8
10.8
Chemistry In Action: Buckyball Anyone?

ITT CHNG CH 10 Chemical Bonding II

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ITT CHNG CH 10 Chemical Bonding II

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Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals

Pe U rso se n al W u IS se EL o Y nly !!! .

Pe U rso se n al W u IS se EL o Y nly !!! .

Valence shell electron pair repulsion (VSEPR) model:

# of atoms bonded to central atom

Pe U rso se n al W u IS se EL o Y nly !!! .

Pe U rso se n al W u IS se EL o Y nly !!! .

Pe U rso se n al W u IS se EL o Y nly !!! .

linear trigonal planar

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AB2 AB3 AB4

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linear trigonal planar tetrahedral

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AB2 AB3 AB4 AB5

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linear trigonal planar tetrahedral trigonal bipyramidal

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AB2 AB3 AB4 AB5 AB6

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linear trigonal planar tetrahedral trigonal bipyramidal octahedral

trigonal bipyramidal octahedral

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lone-pair vs. lone pair repulsion

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bonding-pair vs. bonding pair repulsion

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trigonal planar trigonal planar

trigonal planar bent

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tetrahedral trigonal pyramidal

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AB4 AB3E AB2E2

tetrahedral trigonal pyramidal bent O H H

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trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron

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AB5 AB4E AB3E2

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped F F Cl F

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AB5 AB4E AB3E2 AB2E3

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped linear I I I

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octahedral square pyramidal F F F Br F F

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AB6 AB5E AB4E2

octahedral square pyramidal square planar F Xe F F F

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Predicting Molecular Geometry

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Dipole Moments and Polar Molecules

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

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H dipole moment polar molecule

O dipole moment polar molecule

no dipole moment nonpolar molecule