Chapter 9: Molecular Geometry

and Bonding Theories

with examples from

Chapter 25: Organic Chemistry

Prepare for Recitation October 6th
ALEKS Objective 6 due October 4th
ANGEL Quiz 6, October 6th
Lecture 16: September 28th
Lecture 17: September 30th
Lecture 18: October 3rd
Read: Ch. 2.9, 9.4-9.6, 25.1
Additional Preparation:
BLB 9: 43,50,57; Packet 9: 8-17
BLB 25: 11,12,25

Exam 2
Monday, October 10, 2011, 6:30 PM
CH110 FA11 SAS

Chapter 9: Molecular Geometry

and Bonding Theories
with examples from

Chapter 25: Organic Chemistry

KEY QUESTIONS: THE BIG PICTURE
Are all covalent bonds the same?
What is the difference between a bond
and a bond?
What is a hybrid orbital?
Remember: structure affects function!
How is VSEPR theory used to predict
organic bond geometry?
How is valence bond theory used to
predict organic bond geometry?
Can the two be used to rationalize the
structure of organic molecules?
By the end of Todays Lecture you should know:
Valence Bond Theory (molecular orbitals)
Hybrid Orbitals

CH110 FA11 SAS

Atomic Orbitals Do NOT

Explain Everything
Consider CH4
How many -bonds?
How many -bonds?
Problem: VSEPR shape and atomic
orbital shape are not compatible!
H

C
H
H 109.5

1s2
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2s2

2p2
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Hybrid Orbitals in Methane

Step 1

C
1s2

2s2

2p2

electron promotion

C*
1s2

2s1

2p3

Electron promotion:
Requires _______
now have 4 ________ electrons on C
(* = excited state configuration)
CH110 FA11 SAS

Hybrid Orbitals in Methane

Step 2

The 4 (half-filled) atomic orbitals

mix to form a new set of (halffilled) orbitals with ____________
(= hybrid orbitals)

C atom hybridized
1s2

sp3

Hybridization:
the sp3 hybrid orbitals _____ each other,
and take on tetrahedral geometry (same
rules as VSEPR)
___________ energy required to hybridize
CH110 FA11 SAS

Hybrid Orbitals in Methane

Step 3

C H bonds are formed when

the 4 sp3 hybrid orbitals overlap
with the 1s orbitals of H atoms

Overlap Bonds
4 shared electron pairs
4 ______ bonds
H 1s1
Covalent, tetrahedral CH4
4 C sp3
How does this work?
promotion costs energy, but
resulting bond formation releases energy
overall process is __________
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Hybrid Orbitals in General

Three Steps:
1. Promotion (energy IN)
2. Hybridization
3. Bond formation (more energy OUT)
In CH4:
4 atomic orbitals:

promotion, hybridization
4 hybrid orbitals

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sp3 Hybrid Orbitals as Seen in C

4 degenerate sp3 orbitals.

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More Examples of sp3 Hybrid Orbitals

H
H: N : H
..

NH3

H
H 107

sp3 hybridization

___ sigma bonds, ___ pi bonds

1 lone pair in a sp3 hybrid orbital
:

H2O

H : O :H
:

H
H

104.5

sp3

___ sigma bonds, ___ pi bonds

2 lone pairs in sp3 hybrid orbitals
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Hybrid Orbitals in BF3

Consider BF3
F
Molecular shape:

F
B
F

B
1s2

2s2

2p1

promote & hybridize

1s2

sp2

Hybridization of one
2s and two 2p
orbitals gives three
trigonal planar sp2
orbitals and one
non-hybrid (empty)
2p orbital
perpendicular to the
plane of the sp2
orbitals.

2p

Non-hybridized

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sp2 Hybrid Orbitals as Seen in BF3

3 degenerate sp2 orbitals.

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Hybrid Orbitals in BeCl2

Consider BeCl2
Cl-Be-Cl molecular shape =

Be
1s2

2s2

2p
promote & hybridize

1s2

sp

2p
Not hybridized

2 sp orbitals formed
2 p orbitals not used
(these are perpendicular to hybrid orbitals)
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Hybrid Orbitals in PF5

Consider PF5
Electron Geometry:

F
P

Molecular shape:

P
[Ne]
3s2

3p3

promote & hybridize

[Ne]
sp3d

3d

Non-hybridized
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Hybrid Orbitals in SF6

Consider SF6
Electron Geometry:

F F
S

Molecular shape:

S
[Ne]
3s2

3p3

promote & hybridize

[Ne]
sp3d2

3d

Non-hybridized
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Lone Pairs: Hybrid Orbitals in ClF5

Consider ClF5
Electron Geometry:

F F
Cl

Molecular shape:
Cl
[Ne]
3s2

3p3

promote & hybridize

[Ne]
sp3d2

3d

Non-hybridized
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Double Bonds
H

Consider Ethylene

H
C=C

H
has 120o bond angles H
so, sp2 hybrid orbitals are involved
C
1s2

2s2

2p2
promote & hybridize

1s2

sp2

2p

Not hybridized

3 sigma bonds
Overlap of hybrid sp2
orbitals with 2 H 1 s
orbitals (2 C-H bonds)
and one carbon sp2
(C-C)

pi bond
Side-to-side overlap
of 2p orbitals from 2
carbons
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Triple Bonds
Consider Acetylene

H C C

has 180o bond angles

so, sp hybrid orbitals are involved
C
1s2

2s2

2p2
promote & hybridize

1s2

sp

2p

Not hybridized

2 sigma bonds
Overlap of hybrid sp
orbitals with H 1 s
orbital (C-H bond)
and one carbon sp
(C-C)

2 pi bonds
Side-to-side overlap
of 2p orbitals from 2
carbons
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Hybridization and VSEPR Shapes

Problem: Atomic orbitals (s, p, d, f) dont
have shapes consistent with bonding
shapes observed in molecules.
Solution:
Two atomic orbitals mix to form _____ hybrid orbitals

Three atomic orbitals mix to form _____ hybrid orbitals

Four atomic orbitals mix to form _____ hybrid orbitals

Five atomic orbitals mix to form _____ hybrid orbitals

Six atomic orbitals mix to form _____ hybrid orbitals

Use VSEPR to determine shape of hybrid

orbitals: the electron pairs will get as far from
each other as possible.
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Practice Problem
What are the hybridizations of the carbons
labeled 1 and 2 in the caffeine molecule
shown below?
H

H
H

C
H

H
1

N
C

N
C
H

N
2

A.
B.
C.
D.
E.

carbon 1
sp2
sp3d2
sp2
sp3
sp3

carbon 2
sp2
sp3
sp3
sp2
sp3

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Summary of Hybridization Types

# of epairs

Atomic
orbitals
used

Hybrid
type
formed

Hybrid
geometry

examples

s, p

two sp

Linear

BeF2
HgCl2

s, p, p

three sp2

Trigonal
planar

BF3
SO3

s, p, p, p

four sp3

Tetrahedral

CH4
NH3
H2O
NH4+

s, p, p, p, d

five sp3d

Trigonal
PF5
bipyramidal SF4
BrF3

s, p, p, p, d,
d

six sp3d2

Octahedral

CH110 FA11 SAS

SF6
ClF5
XeF4
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What You Should Know

Valence Bond Theory
What is valence bond theory and how is
it related to Lewiss notation?
According to VBT, when do covalent
bonds form?
According to VBT, what determines the
strength of a covalent bond?
What is a bond?
What is a bond? How is it different
from a bond?
Hybrid Orbitals
What is the difference between an
atomic orbital and a molecular orbital?
What is hybridization and what are the
steps associated with the process of
constructing a hybrid orbital diagram?
What mode of hybridization is
associated with each of the five
common electron domain geometries?
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