Chemical Bonding II: Molecular Geometry and Hybridization of Atomic Orbitals

Chapter 10
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 The physical and chemical properties of a compound are very much determined by the size and shape of its molecules. Molecular geometry specifies the positions of the atoms in terms of bond lengths and bond angles. The 3-D structure depends on the nature of the central atom, the bonding electrons, and the lone pairs around it.

Molecular Geometry

Molecular Geometry, using Lewis Structures, the VSEPR (Valence-Shell Electron-Pair Repulsion) model and Valence Bond Theory. 1. Use Lewis structures and the VSEPR theory: bonding electrons and lone pairs (the valence electrons) are placed as far apart as possible. 2. Use Lewis structures and the VBT: Bonding electrons and lone pairs are accommodated in hybridized orbitals, as far apart as possible in three dimensional space

The VSEPR Model

Valence Shell Electron Pair Repulsion is a simple but effective model for predicting molecular geometry. The first assumption of VSEPR is:

A molecule adopts the geometry that minimizes the repulsive force among a given number of electron pairs.

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

linear
B

linear
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

Class

AB2 AB3

2 3

0 0

linear

linear

trigonal planar

trigonal planar

10.1

10.1

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

linear

trigonal planar
tetrahedral

trigonal planar
tetrahedral

10.1

10.1

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

linear

trigonal planar
tetrahedral trigonal bipyramidal

trigonal planar
tetrahedral trigonal bipyramidal

10.1

The Trigonal Bipyramid

There are two positions, axial and equatorial, and two bond angles: 90 and 120.

REMINDER: In AB5: More electronegative atoms are placed in the axial positions, (bond will be a bit longer), and lone pairs and double bonds in the equatorial position.

10.1

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

linear

trigonal planar
tetrahedral trigonal bipyramidal

trigonal planar
tetrahedral trigonal bipyramidal

octahedral

octahedral

10.1

10.1

Distortions from Ideal Geometry

Distortions in bond angles are influenced by (1) the lone pairs on the central atom and (2) the size of atoms,

Further assumptions of VSEPR: Nonbonding EP (electron pairs) exert a greater repulsive force than bonding EPs.

Multiple bonds exert a greater repulsive force than single bonds.

Example: H2O

H
104.5

lone-pair vs. lone pair repulsion

>

lone-pair vs. bonding pair repulsion

>

bonding-pair vs. bonding pair repulsion

VSEPR with lone pair electrons

# 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

10.1

VSEPR with lone pair electrons

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

AB4
AB3E

4
3

0
1

tetrahedral tetrahedral

tetrahedral trigonal pyramidal

10.1

VSEPR with lone pair electrons

# 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
bent O

AB2E2

tetrahedral

10.1

VSEPR with lone pair electrons

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

Class

AB5

trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron

AB4E

10.1

VSEPR with lone pair electrons

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

Class

AB5

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped F F Cl

AB4E
AB3E2

4
3

1
2

F
10.1

VSEPR with lone pair electrons

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

Class

AB5

trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal distorted tetrahedron T-shaped

AB4E
AB3E2

4
3

1
2

AB2E3

trigonal bipyramidal

linear
I I

10.1

VSEPR with lone pair electrons

# 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

10.1

VSEPR with lone pair electrons

# 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

octahedral

AB4E2

square pyramidal square planar

F F

Xe
F F

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. 4. Treat double bond & triple bond as if they were single bond. What are the molecular geometries of SO2 and SF4?

S
AB2E

O F

F
S F

AB4E

bent

distorted tetrahedron
10.1

Molecules With More than One Central Atom

The geometry around each central atom must be determined. H O Trigonal planar

HC2H3O2:

H C C O H
H
Tetrahedral

Molecular Dipole Moments

A molecule is polar if its centers of positive and negative charge are separated.

Polarity causes a neutral molecule to interact with ions or other dipoles. Dipoles in an electric field:

10.2

Molecular Dipole Moments

For polyatomic molecules, the dipole moment is the geometric sum of all bond dipole moments.

CO2 - Nonpolar

H2O - Polar

Dipole Moments and Polar Molecules

electron poor region

electron rich region

F d-

d+

m=Qxr
Q is the charge r is the distance between charges

1 D = 3.36 x 10-30 C m
10.2

10.2

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

dipole moment polar molecule

dipole moment polar molecule

H

C H

no dipole moment nonpolar molecule

no dipole moment nonpolar molecule

10.2

10.2

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

H2
F2

436.4 kJ/mole 150.6 kJ/mole

2 1s 2 2p

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

10.3

VALENCE BOND THEORY

The basic premise of this theory is that bonds are formed when atoms get close enough. In this case, atomic orbitals on the individual atoms will be able to overlap so that the three dimensional probability regions share a common volume.

Valence Bond Theory

Valence bond theory describes covalent bond in terms of the overlap of atomic orbitals.
H2:
1s 1s The simplest of these bonds involve the overlap of two "s" orbitals as in the example when two Hydrogen atoms get close enough to bond. The "s" orbitals overlap to form a "sigma" bond between the two "s" orbitals.

A second type of overlap is between two "p" orbitals to form a sigma bond () between two "p" orbitals. An example is the p-p overlap between two Fluorine atoms.

F2 :
2p 2p

A third type of sigma overlap is the overlap between an "s" orbital and a "p" orbital such as when a Hydrogen atom's "s" orbital overlaps with a "p" orbital of another atom like a Fluorine atom.

HF:
1s
2p

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 three 2p orbitals on Nitrogen with the 1s orbital on each hydrogen atom, what would the molecular geometry of NH3 be? If use the three 2p orbitals, we will predict 90 0 angle, Tshaped geometry. But actual H-N-H bond angle is 107.30 and the shape is trigonal pyramidal.
10.4

Hybrid Orbitals
Hybrid orbitals are mixtures of atomic orbitals with intermediate energy.

The number of s, p, and d orbitals in the mixture equals the number of hybrid orbitals.
s

p
sp sp

Hybridization mixing of two or more atomic orbitals to form a new set of hybrid orbitals.
1. Mix at least 2 non-equivalent 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

10.4

sp Hybrid Orbitals in BeF2

Linear geometry is achieved using two sp hybrid orbitals. Be atom:
s p p p

Promotion:
s p p p
sp

Hybridization:
sp sp p p

sp

Formation of sp Hybrid Orbitals

47

2 sp

Hybrid Orbitals in BF3

Trigonal planar geometry is achieved using three sp2 hybrid orbitals.

B atom:
Promotion: Hybridization:

sp2

sp2 sp2

sp2 sp2 sp2

Formation of sp2 Hybrid Orbitals

10.4

3 sp

Hybrid Orbitals in CH4

Tetrahedral geometry is achieved using four sp3 hybrid orbitals.

C atom:
s p p p p p p
sp3

Promotion:
s

Hybridization:
sp3 sp3 sp3 sp3

sp3 sp3 sp3

10.4

Formation of sp3 Hybrid Orbitals

52

Formation of Covalent Bonds in CH4

53

sp3d and sp3d2 Hybridization

Trigonal bipyramidal geometry is achieved using five sp3d hybrid orbitals. Octahedral geometry is achieved using six sp3d2 hybrid orbitals.

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

Hybridization sp

Examples BeCl2

3
4 5

sp2
sp3 sp3d

BF3
CH4, NH3, H2O PCl5

sp3d2

SF6
10.4

56

A (sigma) bond results from end-to-end overlap of orbitals. The maximum electron density lies along the bond.
Overlap of pz orbitals in O2:
Internuclear axis

Covalent Bond Formation

0.08

0.16

0.24

0.32 nm

Covalent Bond Formation

A p (pi) bond results from side-to-side overlap of p orbitals. The electron density is zero along the bond.

Overlap of py orbitals in O2:

 and p Bonding in C2H4

Diagram of bonding in C2H4:
p
H sp2 H

H H H C =C H Trigonal planar - sp2

C
sp2

sp2

H
p bond

bond

10.5

Unhybridized 2pz orbital (gray), which is perpendicular to the plane of the hybrid (green) orbitals.

61

Bonding in Ethylene, C2H4

Sigma bond () electron density between the 2 atoms

Pi bond (p) electron density above and below plane of nuclei of the bonding atoms 62

Another View of p Bonding in Ethylene, C2H4

63

 and p Bonding in C2H2

Diagram the bonding in HCCH
p

H C C H Linear - sp

sp p

sp

p bond A triple bond consists of a and two p bonds.

bond

10.5

Bonding in Acetylene, C2H2

66

10.5

Sigma () 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 and p bonds are in the acetic acid (vinegar) molecule CH3COOH?
O bonds = 6+ 1 = 7 p bonds = 1
10.5

H H
C H