ch10 PPT

Chapter 10: Theories of
Bonding and Structure

Chemistry: The Molecular Nature
of Matter, 6E

Jespersen/Brady/Hyslop
Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E 2
Molecular Structures
Molecules containing three or more atoms
may have many different shapes
Almost all are 3-dimensional
Shapes are made from five basic
geometrical structures
Shapes classified according to number of
electron domains they contain around
central atom
Simple model using the electron domain
concept
Two types of electron domains
Bonding domains
Electron pairs involved in bonds between two atoms
Nonbonding domains
Electron pairs associated with single atom
All electrons in single, double, or triple bond
considered to be in the same electron
domain
VSEPR Theory
Valence Shell Electron Pair Repulsion

VSEPR Theory
Simple theory for predicting shapes of
molecules
Fact:
Negative electrons repel each other very
strongly.
Result:
Electron pairs are arranged to be as far apart as
possible.
Minimizes repulsions
Result:
Electron pairs are arranged to have lowest
possible potential energy
VSEPR Theory
Assumes:
Bonds are shared pairs of electrons
Covalent bonds
Central atom will have 2, 3, 4, 5, or 6 pairs of
electrons in its valence shell.
Model includes central atoms with:
Incomplete octet
Complete octet
Extended octet
First look at cases where
All electron pairs around central atom
are bonding pairs
Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
6
Electron
Domains
Shape
Electron Pair
Geometry
2 linear
3 trigonal planar
4 tetrahedral
Five Basic Electron Domains
7
Electron
Domains
Shape
Electron Pair
Geometry
5
trigonal
bipyramidal
has equatorial
and axial
positions.
(cont.)
8
Electron
Domains
Shape
Electron Pair
Geometry
6
octahedral
All positions
are equivalent

(cont.)
9
Learning Check
Identify, for each of the following:
1. Number of electron domains
2. Electron pair geometry
N
H
H H
O
H
H
I
I I
Your Turn!
How many electron domains are there around
the central atom in SF
4
O? What is the electron
pair geometry for the compound?
A. 4, tetrahedron
B. 5, pentagon
C. 5, trigonal bipyramid
D. 4, square pyramid
E. 6, octahedron
10
VSEPR (cont)
What if one or more bonds are replaced by
lone pairs?
Lone pairs
Take up more space around central atom
Effect overall geometry
Must be counted as electron domains
What if there are one or more multiple
bonds?
Multiple bonds (double and triple)
For purposes of molecular geometry
Treat as single electron domain
Same as single bonds
Structures Based on Three
Electron Domains
Number of
Bonding
Domains

3

2
Number of
Nonbonding
Domains

0

1
Molecular Shape

Planar Triangular
(e.g. BCl
3
)
All bond angles 120

Nonlinear
Bent or V-shaped
(e.g. SO
2
)
Bond <120
Structure
13
Four Electron Domains
Number of
Bonding
Domains

4

3

2
Number of
Nonbonding
Domains

0

1

2
Molecular Shape

Tetrahedron
(e.g. CH
4
)
All bond angles 109.5

Trigonal pyramid
(e.g. NH
3
)
Bond angle
less than 109.5

Nonlinear, bent
(e.g. H
2
O)
Bond angle
less than109.5
Structure
14
Trigonal Bipyrimid
Two atoms in axial
position
90 to atoms in
equatorial plane
Three atoms in
equatorial position
120 bond angle to
atoms in axial
position
More room here
Substitute here first
90
120
Five Electron Domains
Number of
Bonding
Domains

5

4
Number of
Nonbonding
Domains

0

1
Molecular Shape

Trigonal bipyramid
(e.g. PF
5
)
Ax-eq bond angles 90
Eq-eq 120

Distorted
Tetrahedron, or
Seesaw
(e.g. SF
4
)
Ax-eq bond angles < 90
Structure
Where Do Lone Pairs Go?
Lone pair takes up more space
Goes in equatorial plane
Pushes bonding pairs out of way
Result: distorted tetrahedron
17
Five Electron Domains
Number of
Bonding
Domains

3

2
Number of
Nonbonding
Domains

2

3
Molecular Shape

T-shape
(e.g. ClF
3
)
Bond angles 90

Linear
(e.g. I
3
)
Bond angles 180
Structure
18
Bonding domains
More oval in shape
Electron density focused
between two positive
nuclei.
Nonbonding domains
More bell or balloon shaped
Take up more space
Electron density only has
positive nuclei at one end
Relative Sizes of Electron
Domains
Six Electron Domains
Number of
Bonding
Domains

6

5
Molecular Shape

Octahedron
(e.g. SF
6
)

Square Pyramid
(e.g. BrF
5
)
Structure Number of
Nonbonding
Domains

0

1
Structures Based on Six Electron
Domains
Number of
Bonding
Domains

4
Number of
Nonbonding
Domains

2
Molecular Shape

Square planar
(e.g. XeF
4
)
Structure
Steps Used to Determine Three
Dimensional Structures:

1. Draw Lewis Structure of Molecule
Don't need to compute formal charge
If several resonance structures exist, pick only
one

2. Count electron pair domains
Lone pairs and bond pairs around central atom
Multiple bonds count as one set (or one effective
pair)
3. Arrange electron pair domains to minimize
repulsions
Lone pairs
Require more space than bonding pairs
May slightly distort bond angles from those predicted.
In trigonal bipyramid lone pairs are equatorial
In octahedron lone pairs are axial

4. Name molecular structure by position of
atomsonly bonding electrons

22
Steps Used to Determine Three
Dimensional Structures (Cont.)

23
Learning Check
Identify for each of the following:
1. Number of bonding versus nonbonding
domains
2. Molecular geometry/molecular structure
N
H
H H
O
H
H
I
I I
Your Turn!
For the species, ICl
5
, how many bonding
domains exist?
A. 2
B. 3
C. 4
D. 5

24
Your Turn!
5,
how many non-bonding
domains exist?
A. 4
B. 3
C. 2
D. 1

25
Your Turn!
5
, what is the electron
domain geometry?
A. trigonal planar
B. tetrahedron
C. trigonal bipyramid
D. octahedron

26
Your Turn!
5
, what is the molecular
geometry?
A. trigonal bipyramid
B. trigonal planar
C. distorted tetrahedron
D. square pyramid

27
28
Polar Molecules
Have net dipole moment
Negative end
Positive end
Polar molecules attract
each other.
Positive end of polar
molecule attracted to
negative end of next
molecule.
Strength of this attraction
depends on molecule's
dipole moment
Dipole moment can be
determined experimentally
29
Polar Molecules
Polarity of molecule can
be predicted by taking
vector sum of bond
dipoles

Bond dipoles are usually
shown as crossed
arrows, where
arrowhead indicates
negative end
Molecular Shape and Molecular
Polarity
Many physical properties (melting and
boiling points) affected by molecular polarity
For molecule to be polar:
Must have polar bonds
Many molecules with polar bonds are
nonpolar
Possible because certain arrangements of bond
dipoles cancel
Why Nonpolar Molecules can
Have Polar Bonds
Reason depends on molecular shape
Diatomics: just consider two atoms
Calculate AEN

For molecules with more than two atoms,
must consider the combined effects of
all polar bonds
Polar Molecules are Asymmetric
To determine polarity of molecule:
1. Draw structure using proper molecular
geometry
2. Draw bond dipoles
3. If they cancel, molecule is non-polar
4. If molecule has uneven dipole
distribution, it is polar
1. Molecule is nonpolar if
All electron pairs around central atom are
bonding pairs and
All terminal groups (atoms) are same
The individual bond dipoles cancel

Molecular Polarity

Symmetrical molecules
Nonpolar because bond dipoles cancel
All five shapes are symmetrical when all
domains attached to them are composed of
identical atoms
Molecular Polarity
Cancellation of Bond Dipoles In
Symmetrical Trigonal Bipyramidal and
Octahedral Molecules
Trigonal Bipyramid
Molecular Polarity
2. Molecule is usually polar if
All atoms attached to central atom are NOT same
Or,
There are one or more lone pairs on central atom
Molecular Polarity
Water and ammonia both have non-bonding
domains
Bond dipoles do not cancel
Molecules are polar
Molecular Polarity
Following exceptions to rule 2 are nonpolar
Nonbonding domains (lone pairs) are
symmetrically placed around central atom
Your Turn!

Which of the following molecules is polar?
A. BClF
2

B. BF
3

C. NH
4
+

D. NO
3

E. C
2
H
2

39
Modern Atomic Theory of Bonding
Based on wave mechanics gave us
Electrons and shapes of orbitals
Four quantum numbers
Heisenberg uncertainty principle
Electron probabilities
Pauli Exclusion Principle
Valence Bond Theory

Individual atoms, each have their own
orbitals and orbitals overlap to form bonds
Extent of overlap of atomic orbitals is related
to bond strength
Molecular Orbital Theory
Views molecule as collection of positively
charged nuclei having a set of molecular
orbitals that are filled with electrons (similar
to filling atomic orbitals with electrons)
Doesn't worry about how atoms come
together to form molecule
Both Theories:

Try to explain structure of molecules,
strengths of chemical bonds, bond orders,
etc.
Can be extended and refined and often give
same results

Valence Bond Theory
Bond between two atoms formed when pair
of electrons with paired (opposite) spins is
shared by two overlapping atomic orbitals
43
Valence Bond Theory H
2

H
2
bonds form because 1s atomic valence
orbital from each H atom overlaps
44
Valence Bond Theory F
2

F
2
bonds form because atomic valence orbitals
overlap
Here 2p overlaps with 2p
Same for all halogens, but different np orbitals
45
Valence Bond Theory HF
HF involves overlaps between 1s orbital
on H and 2p orbital of F
1s 2p
Assume that
unpaired electrons
in S and H are
free to form
paired bond
We may assume
that HS bond
forms between s
and p orbital
Predicted 90 bond
angle is very close to
experimental value of
92.
Valence Bond Theory and H
2
S
Difficulties With
Valence Bond Theory
Example: CH
4
C 1s
2
2s
2
2p
2
and H 1s
1

In methane, CH
4

All four bonds are the same
Bond angles are all 109.5
Carbon atoms have
All paired electrons except two unpaired 2p
p orbitals are 90 apart
Atomic orbitals predict CH
2
with 90 angles
Hybridization
Mixing of atomic orbitals to allow formation
of bonds that have realistic bond angles.
Realistic description of bonds often requires
combining or blending two or more atomic
orbitals
Hybridization just rearranging of electron
probabilities
Why do it?
To get maximum possible overlap
Best (strongest) bond formed
Hybrid Orbitals

Blended orbitals result from hybridization
process
Hybrid orbitals have
New shapes
New directional properties
Each hybrid orbital combines properties of
parent atomic orbitals
New Names for These New
Orbitals?

Symbols for hybrid orbitals combine the
symbols of the orbitals used to form them
Use s + p form two sp hybrid orbitals
Use s + p + p form three sp
2
hybrid orbitals
One atomic orbital is used for each hybrid
orbital formed
Sum of exponents in hybrid orbital notation
must add up to number of atomic orbitals
used
Lets See How Hybridization
Works
Mixing or hybridizing
s and p orbital of
same atom results in
two sp hybrid orbitals
Two sp hybrid orbitals
point in opposite
directions
52
Using sp Hybrid Orbitals to Form Bonds
Now have two sp
hybrid orbitals
Oriented in correct
direction for bonding
180 bond angles
As VSEPR predicts and
Experiment verifies
Bonding =
Overlap of H 1s atomic
orbitals with sp hybrid
orbitals on Be
What Do We Know?
Experiment and VSEPR show that
BeH
2
(g) is linear
180 bond angle
For Be to form these bonds it must have
Two hybrid orbitals on Be must point in opposite
directions
Give correct bond angle
Each Be orbital must contain one electron
Each resulting bond with H contains only two
electrons
Each H supplies one electron
54
Hybrid Orbitals
Hybrid Atomic Orbitals Used Electron Geometry
sp s + p Linear
Bond angles 180
sp
2
s + p + p

Trigonal planar
Bond angles 120
sp
3
s + p

+ p + p

Tetrahedral
Bond angles 109.5
sp
3
d s + p

+ p + p + d

Trigonal Bipyramidal
Bond angles 90 and
120
sp
3
d
2
s + p

+ p + p + d + d

Octahedral
Bond angles 90
55
Bonding in BCl
3

Overlap of each half-
filled 3p orbital on Cl
with each half-filled
sp
2
hybrid on B
Forms three equivalent
bonds
Trigonal planar shape
120 bond angle
sp
2
2p
Bonding in CH
4
sp
3
Overlap of each half-
filled 1s orbital on H
with each half-filled
sp
3
hybrid on carbon
Forms four
equivalent bonds
Tetrahedral geometry
109.5 bond angle

Hybrid Orbitals
Two sp
hybrids

Three sp
2

hybrids

Four sp
3

hybrids
Linear
Planar
Triangular
Tetrahedral
All angles
120
All angles
109.5
Your Turn!
What is the hybridization of oxygen in OCl
2
?
A. sp
B. sp
3

C. sp
2

D. No hybridization

58
59
Conformations
CC single bond
has free rotation
around the CC
bond

Conformations
Different relative
orientations on
molecule upon
rotation

Multiple Conformations of Pentane
Expanded Octet Hybridization
Hybridization When Central Atom has
More Than Octet
If there are more than four equivalent bonds
on central atom, then must add d orbitals to
make hybrid orbitals
Why?
One s and three p orbitals means that four
equivalent orbitals is the most you can get
using s and p orbitals alone
Expanded Octet Hybridization
So, only atoms in third row of the periodic
table and below can exceed their octet
These are the only atoms that have empty d
orbitals of same n level as s and p that can be
used to form hybrid orbitals
One d orbital is added for each pair of
electrons in excess of standard octet
Expanded Octet Hybrid Orbitals
64
Hybridization in Molecules That
Have Lone Pair Electrons
CH
4
sp
3
tetrahedral geometry 109.5 bond
angle
NH
3
107 bond angle
H
2
O 104.5 bond
angle
Angles suggest that NH
3
and H
2
O both use sp
3

hybrid orbitals in bonding
Not all hybrid orbitals used for bonding e

Lone pairs can occupy hybrid orbitals
Lone pairs must always be counted to determine
geometry
Hybridization in Molecules That
Have Lone Pair Electrons NH
3

2s
2p
hybridize
sp
3
form bonds
lone
pair
bonding electrons
Hybridization in Molecules that
Have Lone Pair Electrons H
2
O
2s
2p
hybridize
sp
3
form bonds
lone
pairs
bonding
electrons
Your Turn!
For the species ClF
2
+
, determine the following:
1. electron domain geometry
2. molecular geometry
A. tetrahedron, trigonal planar
B. pentagon, tetrahedron
C. tetrahedron, bent
D. trigonal planar, bent
67
Your Turn!
For the species ClF
2
+
, determine the following:
1. hybridization around the central atom
2. polarity
A. sp
3
, polar
B. sp
3
, non-polar
C. sp
3
, polar
D. sp
2
, non-polar
68
Your Turn!

For the species XeF
4
O, determine the following:
1. electron domain geometry
2. molecular geometry
A. octahedral, square pyramidal
B. trigonal bipyramidal, distorted tetrahedral
C. square pyramidal, octahedral
D. trigonal bipyramidal, planar
69
Your Turn!

For the species XeF
4
O, determine the following:
1. hybridization around the central atom
2. the molecular polarity
A. sp
3
d , polar
B. sp
3
d
2
, polar
C. sp
3
d , nonpolar
D. sp
3
d
2
, nonpolar
70
Double and Triple Bonds
So where do extra electron pairs in multiple
bonds go?
Not in hybrid orbitals
Remember VSEPR, multiple bonds have no effect
on geometry
Why dont they effect geometry?

Two types of bond result from orbital overlap
Sigma (o) bond
Accounts for first bond
Pi (t) bond
Accounts for second and third bonds
Sigma (o) Bonds
Head on overlap of orbitals
Concentrate electron density concentrated most
heavily between nuclei of two atoms
Lie along imaginary line joining their nuclei
s + s
p + p
sp + sp
73
Pi (t) Bonds
Sideways overlap of unhybridized p orbitals
Electron density divided into two regions
Lie on opposite sides of imaginary line connecting
two atoms
Electron density above and below o bond.
No electron
density along o
bond axis
t bond consists
of both regions
Both regions =
one t bond
Pi (t) Bonds
Can never occur alone
Must have o bond
Can form from unhybridized p orbitals on
adjacent atoms after forming o bonds
t bonds allow atoms to form double and
triple bonds
75
Bonding in Ethene (C
2
H
4
)
Each carbon is
sp
2
hybridized (violet)
has one unhybridized p
orbital (red)
C=C double bond is
one o bond (sp
2
sp
2
)
one t bond (p

p)

pp

overlap forms
a CC t bond
76
Properties of t-Bonds
Cant rotate about
double bond
t bond must first
be broken before
rotation can occur

77
Bonding in Formaldehyde
C and O each
sp
2
hybridized
(violet)
Has one
unhybridized p
orbital (red)
C=O double
bond is
one o bond
(sp
2
sp
2
)
one t bond
(p p)
H
C
H
O
Unshared pairs of
electrons on
oxygen in sp
2

orbitals
sp
2
sp
2
overlap to form
CO o bond
Each carbon
is sp hybridized
(violet)
Has two unhybridized p
orbitals, p
x
and

p
y
(red)
CC triple bond
one o bond
sp

sp
two t bonds
p
x

p
x

p
y

p
y

Bonding in Ethyne (Acetylene)
C C H H
Bonding in N
2
Each nitrogen
sp hybridized (violet)
Has two unhybridized p
orbitals, p
x
and

p
y
(red)
NN triple bond
one o bond
sp

sp
two t bonds
p
x

p
x

p
y

p
y

Your Turn!
How many o and t bonds are there in
CH
2
CHCHCH
2
, and what is the hybridization
around the carbon atoms?
A. 7, 1, sp
B. 8, 2, sp
3

C. 9, 2, sp
2

D. 9, 3, sp
2

E. 8, 2, sp
80
Molecular Orbital Theory
1. Molecular orbitals are associated with entire
molecule as opposed to one atom
2. Allows us to accurately predict magnetic
properties of molecules
3. Energies of molecular orbitals determined
by combining electron waves of atomic
orbitals
82
Bonding Molecular Orbitals
Come from various combinations of atomic
orbital wave functions
For H
2
, two 1s wave functions, one from
each atom, combine to make two
molecular orbital wave functions

+
1s
A
+ 1s
B
Combined Bonding MO

Constructive interference of waves
Energy of bonding MO lower than atomic orbitals
83
o* Antibonding Molecular Orbitals
Number of atomic orbitals used must
equal number of molecular orbitals
Other possible combination of two 1s
orbitals: 1s
A
1s
B
+
Destructive interference of the 1s waves
Energy of the bonding molecular orbital is
higher than energy of parent atomic
orbitals
84
Summary of MO from 1s AO
Bonding molecular orbital
Electron density builds up between nuclei
Electrons in bonding MOs tend to stabilize molecule
Antibonding molecular orbital
Cancellation of electron waves reduces electron density
between nuclei
Electrons in antibonding MOs tend to destabilize molecule
85
MO Energy diagram for H
2

H
2
is very stable molecule
Rules for Filling MO Energy Diagrams
1. Electrons fill lowest-energy orbitals that are
available
Aufbau principle applies
2. No more than two electrons, with spin
paired, can occupy any orbital
Pauli exclusion principle applies
3. Electrons spread out as much as possible,
with spins unpaired, over orbitals of same
energy
Hunds rules apply
Bond Order
Measure of number of electron pairs shared
between two atoms

H
2
bond order = 1
A bond order of 1 corresponds to a single
bond

Bond order =
(number of bonding e
) (number of antibonding e
)
2 electrons/bond
MO Energy Diagram for He
2

Four electrons, so both o and o*
molecular orbitals are filled
Bond order

There is no net bonding
He
2
does not form
Bond order =
2 2
2
= 0
MO from 2p Orbital
MO Energy Diagrams for 2
nd
Row of
Periodic Table
Li
2
N
2

t
2p
Lower in energy
than o
2p
O
2
, F
2
and Higher o
2p

Lower in energy than
t
2p
Diatomic Molecules of Second Row
Elements
Second row
1s orbital smaller than 2s
For Li overlap of n = 2 orbitals will be much
more than 1s
Also 1s orbitals both completely filled
So both o and o* molecular orbitals formed
from these are filled
Therefore no net bonding
Can ignore 1s
Can focus on valence electrons and orbitals
2s
2
p
s
2s
s
2s
s
2pz
2px
,
2py
*
s
2pz
2px
,
2py
*
*
2
p
2s
*
92
MO Energy Diagram for Li
2

t
2p
Lower in Energy than o
2p
Li electron configuration = [He]2s
1

Bond order = (2 0)/2
= 1
Diamagnetic as
no unpaired spins
Li Li single bond
stable molecule
Li Li
Li
2

2s
2
p
s
2s
s
2s
s
2pz
2px
,
2py
*
s
2pz
2px
,
2py
*
*
2
p
2
s
*
93
MO Energy Diagram for Be
2

t
2p
2p
Be electron configuration = [He]2s
2

= 0
Be Be no net bond
does not form
Be
Be
Be
2

2s
2
p
s
2s
s
2s
s
2pz
2px
,
2py
*
s
2pz
2px
,
2py
*
*
2
p
2s
*
94
MO Energy Diagram for B
2

t
2p
2p
B electron configuration = [He]2s
2
2p
1

= 1
B B single bond
stable molecule
Paramagnetic as
2 unpaired spins
This is how we know that t
2p
is lower in energy than o
2p

B B B
2

MO Energy Diagram for C
2

t
2p
2p
C electron configuration = [He]2s
2
2p
2

= 2
C = C double bond
stable molecule
Diamagnetic as no
unpaired spins
C C C
2
2s
2
p
s
2s
s
2s
s
2pz
2px
,
2py
*
s
2pz
2px
,
2py
*
*
2
p
2s
*
MO Energy Diagram for N
2

t
2p
2p
N electron configuration = [He]2s
2
2p
3

= 3
NN triple bond
stable molecule
Diamagnetic as no
unpaired spins
N N N
2
2s
2
p
s
2s
s
2s
s
2pz
2px
,
2py
*
s
2pz
2px
,
2py
*
*
2
p
2s
*
MO Energy Diagram for O
2

o
2p
Lower in Energy than t
2p
O electron configuration = [He]2s
2
2p
4

= 2
O = O double bond
stable molecule
Paramagnetic as
2 unpaired spins
Lewis Structure Can't Tell us this!!
O O O
2
2s
2
p
s
2s
s
2s
s
2pz
*
s
2pz
*
2
p
2
s
2px
,
2py
2px
,
2py
* *
MO Energy Diagram for F
2

o
2p
2p
F electron configuration = [He]2s
2
2p
5

= 1
F F single bond
stable molecule
Diamagnetic as
no unpaired spins
F F
F
2
2s
2
p
s
2s
s
2s
s
2pz
*
s
2pz
*
2
p
2s
2px
,
2py
2px
,
2py
* *
MO Energy Diagram for Ne
2

o
2p
2p
Ne electron configuration = [He]2s
2
2p
6

= 0
Ne Ne no net bond
does not form
Ne Ne
Ne
2
2s
2
p
s
2s
s
2s
s
2pz
*
s
2pz
*
2
p
2
s
2px
,
2py
2px
,
2py
* *
What about Heteronuclear
Diatomic Molecules?
If Li through N t
2p
below o
2p

If O, F and higher atomic number, then
o
2p
below t
2p

Example
BC both are to left of N
so t
2p
below o
2p

OF both are to right of N
so o
2p
below t
2p

What about NF?
Each one away from O so average is O and o
2p

below t
2p

What is Bond order of NF and
BC?
t
2p
lower
o
2p
lower
BC NF
Number of valence e
= 3 + 4 = 7
Number of valence e
= 5 + 7 = 12
Bond Order = (5 2)/2 = 1.5
Bond Order = (8 4)/2 = 2
s
2s
s
2s
s
2pz
*
s
2pz
*
2px
,
2py
* *
2px
,
2py
s
2s
s
2s
s
2pz
*
s
2pz
*
2px
,
2py
* *
2px
,
2py
102
What is Bond Order of NO?
Tricky
N predicts t
2p
lower
O predicts o
2p
lower
Have to look at
experiment
Shows that o
2p
is
lower
o
2p
lower
Number of valence e
= 5 + 6 = 11
Bond Order = (8 3)/2 = 2.5
s
2s
s
2s
s
2pz
*
s
2pz
*
2px
,
2py
* *
2px
,
2py
103
What is Bond Order of NO
+
and
NO
?

Same diagram
Different number
of e

NO
+
has
11 1 = 10 valence e

Bond order
= (8 2)/2 = 3
NO
has
11 + 1 = 12 valence e

Bond order
= (8 4)/2 = 2
NO
+
NO

s
2s
s
2s
s
2pz
*
s
2pz
*
2px
,
2py
* *
2px
,
2py
s
2s
s
2s
s
2pz
*
s
2pz
*
2px
,
2py
* *
2px
,
2py
Compare Relative Stability of NO,
NO
+
and NO

Recall that as bond order increases,
bond length decreases, and bond
energy increases
Molecule
or ion
Bond
Order
Bond Length
(pm)
Bond Energy
(kJ/mol)
NO
+
3 106 1025
NO 2.5 115 630
NO

2 130 400
So NO
+
is most stable form
Highest bond order, shortest and strongest bond
Your Turn!
What is the bond order for each species, and
how many unpaired electrons are there in

A. 2, 2, 1; 2, 1, 1
B. 2, 1, 1; 1, 2, 1
C. 2, 1, 1; 2, 1, 1
D. 2, 1, 2; 1, 2, 1
E. 2, 2, 1; 2, 1, 1
105
2 2 2
O , O , and O ?
+
Your Turn!
Which of the following species is paramagnetic?
A. N
2

B. F
C.
D.
E.
106
2
2
O

2
2
O
+
2
2
N
+
VB Theory vs. MO Theory
Neither VB or MO theory is entirely correct
Neither explains all aspects of bonding
Each has its strengths and weaknesses
MO theory correctly predicts unpaired
electrons in O
2
while Lewis structures do not
MO theory is a difficult because even simple
molecules have complex energy level
diagrams
MO theory is a difficult because molecules
with three or more atoms require extensive
calculations

Successes of MO Theory
MO theory is particularly successful in
explaining paramagnetism of B
2
and O
2

One electron each in t
2px
and t
2py
(for B
2
)
One electron each in t*
2px
and t*
2py
(for O
2
)
Successes of VB Theory
Based on simple Lewis structures and related
geometric figures
Three dimensional structures based on
electron domains without massive calculations
Simple hybrid orbitals invoked where
experimental evidence shows the need
Integer bond orders are often correct

How Does MO Theory Deal with
Resonance Structures?
Formate anion, HCOO

C has three electron domains (all bonding
pairs) so
sp
2
hybridized; trigonal planar
Each O has three electron domains (one
bonding pair and two lone pairs)
so sp
2
hybridized; trigonal planar
Resonance Structures of Formate
Anion, HCOO
?
Have two resonance structures
Have lone pair on each O atom in unhybridized p
orbitals as well as empty p orbital on C
Lewis theory says
Lone pair on one O
Use lone pair of other O to form t (pi) bond
Must have two Lewis structures
Delocalized Molecular Orbitals
Bonding MO delocalized over all three atoms
This is also our resonance hybrid picture
This is the best view of what actually occurs and
can be obtained from both VB and MO theory
113
Benzene, In MO Terms
Six C atoms, each sp
2
hybridized (3 o bonds)
Each C also have one unhybridized p orbital (6 total)
So six t MOs, 3 bonding and three antibonding
So three t bonds
114
Benzene, In Valence Bond Terms
Can write benzene as two resonance structures
But actual structure is composite of these two
Electrons are delocalized
Have three pairs of electrons delocalized over six
C atoms
Extra stability is resonance energy
Functionally, resonance and delocalization
energy are the same thing
Your Turn!
Which of the following species exhibits
resonance ?

115

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Chapter 10: Theories of

Bonding and Structure

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