Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals
Chapter 10
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Valence shell electron pair repulsion (VSEPR) model:
Predict the geometry of the molecule from the electrostatic repulsions between the electron (bonding and nonbonding) pairs.
# of atoms bonded to central atom # lone pairs on central atom
Class
Arrangement of electron pairs
Molecular Geometry
AB2
linear
B
linear
B
0 lone pairs on central atom Cl
Be
Cl
3
2 atoms bonded to central atom
VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB2
AB3
2
3
0
0
linear
trigonal planar
linear
trigonal planar
VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB2
AB3 AB4
2
3 4
0
0 0
linear
trigonal planar
linear
trigonal planar
tetrahedral
tetrahedral
VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB2
AB3 AB4 AB5
2
3 4 5
0
0 0 0
linear
trigonal planar
linear
trigonal planar
tetrahedral
trigonal bipyramidal
tetrahedral
trigonal bipyramidal
VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB2
AB3 AB4 AB5 AB6
2
3 4 5 6
0
0 0 0 0
linear
trigonal planar
linear
trigonal planar
tetrahedral
trigonal bipyramidal octahedral
tetrahedral
trigonal bipyramidal octahedral
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11
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lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding > > 13 repulsion pair repulsion pair repulsion
VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB3
AB2E
3
2
0
1
trigonal planar trigonal planar
trigonal planar
bent
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB4 AB3E
4 3
0 1
tetrahedral
tetrahedral
tetrahedral
trigonal pyramidal
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB4 AB3E AB2E2
4 3 2
0 1 2
tetrahedral tetrahedral tetrahedral
tetrahedral trigonal pyramidal bent
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB5
AB4E
5
4
0
1
trigonal bipyramidal
trigonal bipyramidal
trigonal bipyramidal
distorted tetrahedron
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB5
AB4E AB3E2
5
4 3
0
1 2
trigonal bipyramidal
trigonal bipyramidal trigonal bipyramidal
trigonal bipyramidal
distorted tetrahedron T-shaped
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VSEPR
Class
# of atoms bonded to central atom
# lone pairs on central atom
Arrangement of electron pairs
Molecular Geometry
AB5 AB4E AB3E2 AB2E3
5 4 3 2
0 1 2 3
trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal
trigonal bipyramidal distorted tetrahedron T-shaped linear
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB6 AB5E
6 5
0 1
octahedral
octahedral
octahedral
square pyramidal
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VSEPR
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry
Class
AB6 AB5E AB4E2
6 5 4
0 1 2
octahedral
octahedral octahedral
octahedral
square pyramidal square planar
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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 AB2E
bent O F
F S
F F
AB4E distorted tetrahedron
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Dipole Moments and Polar Molecules
electron rich region
electron poor region
H d+
F d-
m=Qxr
Q is the charge r is the distance between charges 1 D = 3.36 x 10-30 C m
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Behavior of Polar Molecules
field off
field on
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Bond moments and resultant dipole moments in NH3 and NF3.
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Which of the following molecules have a dipole moment? H2O, CO2, SO2, and CF4
O
dipole moment polar molecule
dipole moment polar molecule
F
F
no dipole moment nonpolar molecule
no dipole moment nonpolar molecule
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Does BF3 have a dipole moment?
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Does CH2Cl2 have a dipole moment?
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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.
Bond Enthalpy Bond Length 74 pm
Overlap Of 2 1s
2 2p
H2
436.4 kJ/mol
F2
150.6 kJ/mol
142 pm
Valence bond theory bonds are formed by sharing of e- from overlapping atomic orbitals.
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Change in Potential Energy of Two Hydrogen Atoms as a Function of Their Distance of Separation
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Change in electron density as two hydrogen atoms approach each other.
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Valence Bond Theory and NH3 N 1 s 22 s 22 p 3 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 90o Actual H-N-H bond angle is 107.3o
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Hybridization mixing of two or more atomic orbitals to form a new set of 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. 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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Formation of sp3 Hybrid Orbitals
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Formation of Covalent Bonds in CH4
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sp3-Hybridized N Atom in NH3
Predict correct bond angle
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Formation of sp Hybrid Orbitals
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Formation of sp2 Hybrid Orbitals
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How do I predict the hybridization of the central atom? 1. Draw the Lewis structure of the molecule. 2. Count the number of lone pairs AND the number of atoms bonded to the central atom # of Lone Pairs + # of Bonded Atoms
Hybridization
Examples
2 3 4
5 6
sp sp2 sp3
sp3d sp3d2
BeCl2 BF3 CH4, NH3, H2O
PCl5 SF6
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sp2 Hybridization of Carbon
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Unhybridized 2pz orbital (gray), which is perpendicular to the plane of the hybrid (green) orbitals.
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Bonding in Ethylene, C2H4
Sigma bond (s) electron density between the 2 atoms Pi bond (p) electron density above and below plane of nuclei of the bonding atoms 46
Another View of p Bonding in Ethylene, C2H4
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sp Hybridization of Carbon
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Bonding in Acetylene, C2H2
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Another View of the Bonding in Ethylene, C2H4
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Describe the bonding in CH2O. H H C O
C 3 bonded atoms, 0 lone pairs C sp2
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Sigma (s) and Pi Bonds (p)
Single bond Double bond Triple bond 1 sigma bond
1 sigma bond and 1 pi bond
1 sigma bond and 2 pi bonds
How many s and p bonds are in the acetic acid (vinegar) molecule CH3COOH? O s bonds = 6 + 1 = 7 p bonds = 1
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H H C H
Experiments show O2 is paramagnetic
No unpaired eShould be diamagnetic
Molecular orbital theory bonds are formed from interaction of atomic orbitals to form molecular orbitals.
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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 54 formed.
Constructive and Destructive Interference
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Two Possible Interactions Between Two Equivalent p Orbitals
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General molecular orbital energy level diagram for the second-period homonuclear diatomic molecules Li2, Be2, B2, C2, and N2.
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Molecular Orbital (MO) Configurations
1. The number of molecular orbitals (MOs) formed is always equal to the number of atomic orbitals combined. 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.
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1 bond order = 2
Number of electrons in bonding MOs
Number of electrons in antibonding MOs
bond order
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Delocalized molecular orbitals are not confined between two adjacent bonding atoms, but actually extend over three or more atoms. Example: Benzene, C6H6
Delocalized p orbitals
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Electron density above and below the plane of the benzene molecule.
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Bonding in the Carbonate Ion, CO32-
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Chemistry In Action: Buckyball Anyone?
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