Covalent Bonding: Molecular Geometry Hybridization of Atomic Orbitals Molecular Orbitals

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 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 tetrahedral trigonal bipyramidal octahedral 3

linear trigonal planar tetrahedral trigonal bipyramidal octahedral

VSEPR

linear

trigonal planar

tetrahedral

trigonal bipyramidal

octahedral

VSEPR
Cl Be Cl BF3 CH4

linear

trigonal planar

tetrahedral

trigonal bipyramidal

octahedral

PCl5

SF6

Effects of Lone Pairs

H H N H H H O H

lone-pair vs. lone pair repulsion

H C H

>

lone-pair vs. bonding pair repulsion

>

bonding-pair vs. bonding 6 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

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

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 O H H

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 F F Cl F

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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 AB2E3

5 4 3 2

0 1 2 3

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped linear I I

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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 F F F Br F F

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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 F Xe F F F

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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 16 F AB4E distorted tetrahedron

Dipole Moments and Polar Molecules

electron rich region

electron poor region

H +

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

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

H dipole moment polar molecule

O dipole moment polar molecule

H O C O H C H no dipole moment nonpolar molecule 19 H

no dipole moment nonpolar molecule

Does CH2Cl2 have a dipole moment?

20

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22

Chemistry In Action: Microwave Ovens

23

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

Sharing of two electrons between the two atoms.

Bond Dissociation Energy Bond Length 74 pm 142 pm Overlap Of 2 1s 2 2p

H2 F2

436.4 kJ/mole 150.6 kJ/mole

Valence bond theory bonds are formed by sharing of e- from overlapping atomic orbitals.
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Change in electron density as two hydrogen atoms approach each other.

26

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 27

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 28

Bonding in Methane

29

Fig. 10.7

Formation of sp3 Hybrid Orbitals

30

Formation of sp3 Hybrid Orbitals

31

Formation of a CH4 Molecule

32

Formation of a NH3 Molecule

33

Stylized Drawing of Valence Bond Theory

CH4

Predict correct bond angle

NH3

Sigma bond () electron density between the 2 atoms 34

Formation of sp2 Hybrid Orbitals

35

Formation of sp2 Hybrid Orbitals

36

Formation of sp2 Hybrid Orbitals

2pz orbital is perpendicular to the plane of hybridized 37 orbitals

sp2 Hybridization of a C atom

38

Bonding in Ethylene C2H4

H C H C H H

Sigma bond () electron density between the 2 39atoms

Bonding in Ethylene C2H4

Pi bond () electron density above and below plane of nuclei of the bonding atoms 40

Bonding in Ethylene C2H4

41

Formation of sp Hybrid Orbitals

42

Formation of sp Hybrid Orbitals

43

Formation of sp Hybrid Orbitals

44

Bonding in acetylene C2H2

45

How do I predict the hybridization of the central atom? Count the number of lone pairs AND the number of atoms bonded to the central atom # of Lone Pairs + # of Bonded Atoms 2 3 4 5 6

Hybridization sp sp2 sp3 sp3d sp3d2

Examples BeCl2 BF3 CH4, NH3, H2O PCl5 46 SF6

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Sigma ( ) and Pi Bonds ( )

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

O
C O H bonds = 6 + 1 = 7 bonds = 1 48

Drawback of Valence Bond Theory

Experiments show O2 is paramagnetic O O 49

No unpaired eShould be diamagnetic

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

An analogy between light waves and atomic wave functions

Amplitudes of wave functions added

Amplitudes of wave functions subtracted.

50

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. 51

Energy levels of bonding and antibonding molecular orbitals in boron (B2)

52

53

Second-Period Homonuclear Diatomic Molecules

54

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. 55

Bond Order
1 bond order = 2

Number of electrons in bonding MOs

Number of electrons in antibonding MOs

bond order

56

MO for 2nd Period Homonuclear Diatomic Molecules

MO theory predicts that O2 is paramagnetic! 57

Molecules with Resonance Structures

58

Delocalized Molecular Orbitals

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

59

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

60

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Acknowledgment
Some images, animation, and material have been taken from the following sources: Chemistry, Zumdahl, Steven S.; Zumdahl, Susan A.; Houghton Mifflin Co., 6th Ed., 2003; supplements for the instructor General Chemistry: The Essential Concepts, Chang, Raymon; McGraw-Hill Co. Inc., 4th Ed., 2005; supplements for the instructor Principles of General Chemistry, Silberberg, Martin; McGraw-Hill Co. Inc., 1st Ed., 2006; supplements for the instructor

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