Chemical Bonding II:

Molecular Geometry and

Hybridization of Atomic Orbitals

1
Chemical Bonding II

y Molecular Geometry (10.1)

y Dipole Moments (10.2)
y Valence Bond Theory (10.3)
y Hybridization of Atomic Orbitals (10.4)
y Hybridization in Molecules Containing
Double and Triple Bonds (10.5)
y Molecular Orbital Theory (10.6)
 ƒ Molecular Shape
Basic geometries

Chemical ƒ Polarity
VSEPR

Bonding II Electronegativity
Bond moments
Dipole moments
ƒ Valence Bond Theory
Bond energy and bond length
Atomic orbitals
Hybridization
Sigma and pi overlap
ƒ Molecular Orbital Theory
Atomic orbitals to molecular orbitals
Bonding and antibonding
Order of molecular orbitals
Stability of bonds
Bond order
10.1 Molecular Geometry
y Are molecules flat (2D)?
y If not, how do we determine the three
dimensional shape of molecules?
y How do lone pairs figure into the shape
of molecules?
y Does shape really matter?

Moving from bonding into structure

10.1 Molecular Geometry
y Consider the central atom (A):
What will affect the shape of the molecule?
◦ Number of bonded atoms (terminal atoms in
simpler molecules) (B)
x Regardless of multiple bonds
◦ Number of lone pairs

y We will first consider molecules with no lone

pairs on the central atoms
 10.1 Molecular Geometry
All of the molecules have no lone pairs on the central atom.
Only the number of terminal atoms affects the shape.

Table 10.1 p. 325

10.1 Molecular Geometry
Valence Shell Electron Pair Repulsion (VSEPR)
y Predicts the geometry of the molecule from the
electrostatic repulsions between the electron
(bonding and nonbonding) pairs

Lone pair – lone pair repulsion

>
Lone pair – bonded atom repulsion
>
Bonded atom – bonded atom repulsion
 10.1 Molecular Geometry
y Must consider (on the central
atom(A)):
◦ The number of terminal atoms (B)
VSEPR

◦ The number of lone pairs (E)

y The sum of these will give a similar (close) bond

angle to the geometries of the number of
electron groups from before

y For instance: O3 will have the general formula of

AB2E (3 electron groups) and close to a bond
angle (idealized) of 120o.
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3

4 0 Tetrahedral CH4
VSEPR

5 0 Trigonal PCl5
bipyramidal

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

5 0 Trigonal PCl5
bipyramidal

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3

5 0 Trigonal PCl5
bipyramidal

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal
5 1 See‐saw SF4
(distorted
tetrahedron)

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal
5 1 See‐saw SF4
(distorted
tetrahedron)
5 2 T‐shaped ICl3

6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal
5 1 See‐saw SF4
(distorted
tetrahedron)
5 2 T‐shaped ICl3
5 3 Linear I3–
6 0 Octahedral SF6
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal
5 1 See‐saw SF4
(distorted
tetrahedron)
5 2 T‐shaped ICl3
5 3 Linear I3–
6 0 Octahedral SF6
6 1 Square BrF5
pyramidal
 10.1 Molecular Geometry
Electron Groups # of lone pairs Shape Example
2 0 Linear CO2
3 0 Trigonal planar BH3
3 1 Bent O3
4 0 Tetrahedral CH4
VSEPR

4 1 Pyramidal NH3
4 2 Bent H2O
5 0 Trigonal PCl5
bipyramidal
5 1 See‐saw SF4
(distorted
tetrahedron)
5 2 T‐shaped ICl3
5 3 Linear I3–
6 0 Octahedral SF6
6 1 Square BrF5
pyramidal
6 2 Square planar XeF4
 Idealized bond angle of 120o

Idealized bond angle of 109.5o

VSEPR

Idealized bond angles of 90o

and 120o; linear molecule (with
3 lone pairs on the central
atom has a bond angle of 180o)

Idealized bond angle of 90o

Table 10.2 p. 331

 10.1 Molecular Geometry
VSEPR

Figure 10.1 p. 329

10.2 Dipole Moments
y Already discuss polar versus nonpolar
covalent bonds:
◦ electronegativity

Figure 9.5 p. 296

10.2 Dipole Moments

electron rich
electron poor
region
region

H F

δ+ δ−

μ=Qxr
Q is the charge
r is the distance between charges
1 D (Debye) = 3.36 x 10-30 C m
Figure 9.4 p. 296
10.2 Dipole Moments

Table 10.3 p. 336

10.2 Dipole Moments
y Already discuss polar versus nonpolar
covalent bonds:
◦ electronegativity
y How do these bonds overall contribute
to molecular polarity?
y Why does it matter if a molecule is polar
or nonpolar?
10.2 Dipole Moments

Margin figures p. 335 and 337

10.3 Valence Bond Theory
y How are single, double, and triple bonds
represented in Lewis dot structures?
y Are all single bonds represented the
same?
y Are all single bonds the same?
◦ same length
◦ same energy
10.3 Valence Bond Theory

Figure 10.4 p. 338

 10.3 Valence Bond Theory
How do we model the bonds in H2 and F2?

Bond Dissociation Bond

Energy Length Overlap Of
1s atomic
H2 436.4 kJ/mole 74 pm
orbitals
2p atomic
F2 150.6 kJ/mole 142 pm
orbitals

Valence bond theory – bonds are formed by sharing of

e- from overlapping atomic orbitals.
10.3 Valence Bond Theory

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

Figure 10.5 p. 339

10.4 Hybridization of Atomic
Orbitals
y In terms of atomic orbitals, how do bonds
form?
y How are these represented using atomic
orbitals?
y What are sigma bonds?
y What is hybridization?
◦ Mixing of atomic orbitals in an atom (usually a
central atom) to generate a set of hybrid orbitals
y How are hybrid atomic orbitals more
conducive to molecular shapes that are
observed?
10.4 Hybridization of Atomic
Orbitals

sp
Figures 10.9 and 10.10 p. 342
10.4 Hybridization of Atomic
Orbitals
y In terms of atomic orbitals, how do bonds
form?
y How are these represented using atomic
orbitals?
y What are sigma bonds?
y What is hybridization?
◦ Mixing of atomic orbitals in an atom (usually a
central atom) to generate a set of hybrid orbitals
y How are hybrid atomic orbitals more
conducive to molecular shapes that are
observed?
 10.4 Hybridization of Atomic
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 atomic orbitals with other atomic orbitals
(bonds in H2)
b.Overlap of hybrid orbitals with atomic orbitals
c.Overlap of hybrid orbitals with other hybrid orbitals
10.4 Hybridization of Atomic
Orbitals

sp2

Figures 10.11 and 10.12 p. 343

10.4 Hybridization of Atomic
Orbitals

sp3

Figures 10.6 -10.8 p. 340-341

10.5 Hybridization in molecules
containing double and triple bonds
y What are double and triple bonds?
y What are pi bonds?
y How do pi bonds fit into the model of
using hybridized atomic orbitals for sigma
bonding?
y Does this fit with the bond energies and
lengths we have?
10.5 Hybridization in molecules
containing double and triple bonds

C2H4

Figure 10.15, p. 346

 10.5 Hybridization in molecules
containing double and triple bonds
C 2H 4
 10.5 Hybridization in molecules
containing double and triple bonds
C 2H 4
10.5 Hybridization in molecules
containing double and triple bonds

C2H2

Figure 10.18 p. 347

 10.5 Hybridization in molecules
containing double and triple bonds
C 2H 2
 10.5 Hybridization in molecules
containing double and triple bonds
C 2H 2

Figure 10.18 p. 347

 What are the marked bond angles in formic acid (shown)?
a b a b
Chapter 10 – Practice

A. 90o 180o B. 120o 180o

C. 90o 109.5o D. 120o 109.5o

What is the Lewis dot structure for bromine pentafluoride?

What is the formal charge on bromine?

What are the oxidation states on: Br F

What is the bond angle in this molecule?

What is the geometry of this molecule?

This molecule contains POLAR / NONPOLAR bonds. (Circle one)

This molecule is POLAR / NONPOLAR. (Circle one)

Chapter 10 – Practice