CHEM131 - Spring 14 -April 3

Lecture April 3
1
HW Chap. 10 - Due April 8
Quiz Chap. 10 - Due April 10
More Valence Bond Theory
Look and the gures in the text!
Summary Table 10.3
Next Exam April 10:
acid-base reactions, oxidation-reduction (Chap. 4)
Chap. 9 and 10
MO Theory Sec. 10.8
CHEM131 - Spring 14 -April 3
sp
2
Hybrids
2
CH
2
CO formaldehyde
O
C H
H
Determining the
geometry - count
the #! bonds and
the #lone pairs
about the atom
CHEM131 - Spring 14 -April 3
Review Multiple Bonds
3
CO
2
linear
sp hybrid
CO
3
2-
carbonate ion
trigonal planar
sp
2
hybrid
2 sigma bonds
3 sigma bonds
1 " bond
2 " bonds
leaves 2 p
orbitals free
central C is sp hybridized
central C is sp
2
hybridized
CHEM131 - Spring 14 -April 3
More Multiple Bonds
4
CH
2
Cl-CH
2
Cl CHCl=CHCl
OR
C-C rotates freely
rigid C=C
two distinct structures
cis trans
sp
3
sp
2
CHEM131 - Spring 14 -April 3
C
6
H
12
vs

C
6
H
6

5
cyclohexane
sp
3
exible - boat and
chair geometries
sp
2
rigid planar geometry
benzene
CHEM131 - Spring 14 -April 3
Resonance - Benzene
6
The ! bonds are
delocalized
O
3
ozone
O=O-O

O-O=O
2 ! and 1 "
See p. 445
CHEM131 - Spring 14 -April 3
Molecular Orbitals
7
We will start with the individual orbital shapes
Linear Combination of Atomic Orbitals (LCAO)
bonding - energy is
lower than the
individual orbitals
but have to end up
with the same energy
you started with so
something has to also
be higher
sum of
orbitals
di#erence
CHEM131 - Spring 14 -April 3
Complete Energy Diagram
8
!
1s
!*
1s
Figure p.435
CHEM131 - Spring 14 -April 3
9
Creating MO Bonds
1) Create the MO energy level diagram (given)
2) Fill in the number of valence electrons -
starting with the lowest energy and still
lling UNPAIRED rst
3) Find the BOND ORDER =
1/2 (# bonding electrons-#antibonding electrons)
From H
2
nd BO = 1/2(2) = 1
A BO = 0 means that no energetic advantage
to being bound
CHEM131 - Spring 14 -April 3
Another Example
10
BO = 1/2 (2-1) = 1/2
So conclude He
2
+
is bound and exists
But He
2
does NOT BO=0
CHEM131 - Spring 14 -April 3
The p Orbitals
11
p
x
orbital in the
! orientation
p
z
orbital in the
" orientation
CHEM131 - Spring 14 -April 3
MO Diagrams with p orbitals
12 10
"
2p
!
2p
"*
2p
"
2p
!
2p
order
inverted
!*
2p
!*
2p
"*
2p
order NOT
inverted
B
2
, C
2
, N
2
O
2
, F
2
, Ne
2
CHEM131 - Spring 14 -April 3
13 11
Paramagnetic
unshared
electrons
O
2
$% %$
$%
$%
$%$ $
$%$ $
%
% %
% %
$
$
$
BO=
1/2(6-2) = 2
Example with ps
CHEM131 - Spring 14 -April 3
Summary of 2s-2p MOs
14
Bond
energy
increases
with BO
Bond
length
decreases
with BO
1 2 3 2 1 0
Figure 10.15
CHEM131 - Spring 14 -April 3
Quiz of the Day
15
Give the number of ! and " bonds in the
following molecule. Give your answer with ,
between and NO spaces.
O
C
H
O
H
H
H
C
CH
3
-COOH
acetic acid
Answer: 7,1