Chapter 10
Chemical
Bonding II
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Tro, Chemistry: A Molecular Approach 2
Structure Determines Properties!
properties of molecular substances depend on
the structure of the molecule
the structure includes many factors, including:
the skeletal arrangement of the atoms
the kind of bonding between the atoms
ionic, polar covalent, or covalent
the shape of the molecule
bonding theory should allow you to predict the
shapes of molecules
Tro, Chemistry: A Molecular Approach 3
Molecular Geometry
Molecules are 3-dimensional objects
We often describe the shape of a molecule
with terms that relate to geometric figures
These geometric figures have characteristic
corners that indicate the positions of the
surrounding atoms around a central atom in
the center of the geometric figure
The geometric figures also have characteristic
angles that we call bond angles
Tro, Chemistry: A Molecular Approach 4
Using Lewis Theory to Predict
Molecular Shapes
Lewis theory predicts there are regions of
electrons in an atom based on placing shared
pairs of valence electrons between bonding
nuclei and unshared valence electrons located
on single nuclei
this idea can then be extended to predict the
shapes of molecules by realizing these regions
are all negatively charged and should repel
Tro, Chemistry: A Molecular Approach 5
VSEPR Theory
electron groups around the central atom will be
most stable when they are as far apart as
possible we call this valence shell electron
pair repulsion theory
since electrons are negatively charged, they should
be most stable when they are separated as much as
possible
the resulting geometric arrangement will allow
us to predict the shapes and bond angles in the
molecule
Tro, Chemistry: A Molecular Approach 6
Tro, Chemistry: A Molecular Approach 7
Electron Groups
the Lewis structure predicts the arrangement of valence
electrons around the central atom(s)
each lone pair of electrons constitutes one electron group
on a central atom
each bond constitutes one electron group on a central
atom
regardless of whether it is single, double, or triple
O N O
there are 3 electron groups on N
1 lone pair
1 single bond
1 double bond
Tro, Chemistry: A Molecular Approach 8
Molecular Geometries
there are 5 basic arrangements of electron groups
around a central atom
based on a maximum of 6 bonding electron groups
though there may be more than 6 on very large atoms, it is very rare
each of these 5 basic arrangements results in 5 different
basic molecular shapes
in order for the molecular shape and bond angles to be a
perfect geometric figure, all the electron groups must be
bonds and all the bonds must be equivalent
for molecules that exhibit resonance, it doesnt matter
which resonance form you use the molecular
geometry will be the same
Tro, Chemistry: A Molecular Approach 9
Linear Geometry
when there are 2 electron groups around the central
atom, they will occupy positions opposite each other
around the central atom
this results in the molecule taking a linear geometry
the bond angle is 180
- - - -
-
-
-
-
- - - -
Cl Be Cl
-
-
-
-
- - - -
O C O
Tro, Chemistry: A Molecular Approach 10
Linear Geometry
Tro, Chemistry: A Molecular Approach 11
Trigonal Geometry
when there are 3 electron groups around the central
atom, they will occupy positions in the shape of a
triangle around the central atom
this results in the molecule taking a trigonal planar
geometry
the bond angle is 120
- -
-
-
-
-
- - - -
-
-
-
-
- - - -
F
F B F
Tro, Chemistry: A Molecular Approach 12
Trigonal Geometry
Tro, Chemistry: A Molecular Approach 13
Not Quite Perfect Geometry
Because the bonds are
not identical, the
observed angles are
slightly different from
ideal.
Tro, Chemistry: A Molecular Approach 14
Tro, Chemistry: A Molecular Approach 15
Tetrahedral Geometry
when there are 4 electron groups around the central
atom, they will occupy positions in the shape of a
tetrahedron around the central atom
this results in the molecule taking a tetrahedral
geometry
the bond angle is 109.5
- -
-
-
-
-
- - - -
-
-
-
-
- - - -
-
-
-
-
- -
F
F C F
F
Tro, Chemistry: A Molecular Approach 16
Tetrahedral Geometry
Tro, Chemistry: A Molecular Approach 17
Methane
Tro, Chemistry: A Molecular Approach 18
Trigonal Bipyramidal Geometry
when there are 5 electron groups around the central atom, they
will occupy positions in the shape of a two tetrahedra that are
base-to-base with the central atom in the center of the shared
bases
this results in the molecule taking a trigonal bipyramidal
geometry
the positions above and below the central atom are called the
axial positions
the positions in the same base plane as the central atom are
called the equatorial positions
the bond angle between equatorial positions is 120
the bond angle between axial and equatorial positions is 90
Tro, Chemistry: A Molecular Approach 19
Trigonal Bipyramid
Tro, Chemistry: A Molecular Approach 20
Trigonal Bipyramidal Geometry
P
Cl
Cl
Cl Cl
Cl
Tro, Chemistry: A Molecular Approach 21
Tro, Chemistry: A Molecular Approach 22
Octahedral Geometry
when there are 6 electron groups around the central
atom, they will occupy positions in the shape of two
square-base pyramids that are base-to-base with the
central atom in the center of the shared bases
this results in the molecule taking an octahedral
geometry
it is called octahedral because the geometric figure has 8
sides
all positions are equivalent
the bond angle is 90
Tro, Chemistry: A Molecular Approach 23
Octahedral Geometry
Tro, Chemistry: A Molecular Approach 24
Octahedral Geometry
S
F
F
F
F
F
F
Tro, Chemistry: A Molecular Approach 25
Tro, Chemistry: A Molecular Approach 26
The Effect of Lone Pairs
lone pair groups occupy more space on the central
atom
because their electron density is exclusively on the
central atom rather than shared like bonding electron
groups
relative sizes of repulsive force interactions is:
Lone Pair Lone Pair > Lone Pair Bonding Pair > Bonding Pair Bonding Pair
this effects the bond angles, making them smaller
than expected
Tro, Chemistry: A Molecular Approach 27
Effect of Lone Pairs
The bonding electrons are shared by two atoms,
so some of the negative charge is removed from
the central atom.
The nonbonding electrons are localized on the
central atom, so area of negative charge takes
more space.
Tro, Chemistry: A Molecular Approach 28
Derivative Shapes
the molecules shape will be one of basic
molecular geometries if all the electron groups
are bonds and all the bonds are equivalent
molecules with lone pairs or different kinds of
surrounding atoms will have distorted bond
angles and different bond lengths, but the shape
will be a derivative of one of the basic shapes
Tro, Chemistry: A Molecular Approach 29
Derivative of Trigonal Geometry
when there are 3 electron groups around the central
atom, and 1 of them is a lone pair, the resulting shape
of the molecule is called a trigonal planar - bent
shape
the bond angle is < 120
-
-
-
-
- - - - - -
O S O
-
-
-
-
- - - - - -
O S O
-
-
-
-
- - - - - -
O S O
Tro, Chemistry: A Molecular Approach 30
Derivatives of Tetrahedral Geometry
when there are 4 electron groups around the central
atom, and 1 is a lone pair, the result is called a
pyramidal shape
because it is a triangular-base pyramid with the central
atom at the apex
when there are 4 electron groups around the central
atom, and 2 are lone pairs, the result is called a
tetrahedral-bent shape
it is planar
it looks similar to the trigonal planar-bent shape, except the
angles are smaller
for both shapes, the bond angle is < 109.5
Tro, Chemistry: A Molecular Approach 31
Pyramidal Shape
Tro, Chemistry: A Molecular Approach 32
Bond Angle Distortion from Lone Pairs
Tro, Chemistry: A Molecular Approach 33
Tetrahedral-Bent Shape
Tro, Chemistry: A Molecular Approach 34
Pyramidal Shape
- -
-
-
-
-
- - - -
-
-
-
-
- - - - - -
F
F As F
Tro, Chemistry: A Molecular Approach 35
Bond Angle Distortion from Lone Pairs
Tro, Chemistry: A Molecular Approach 36
Tetrahedral-Bent Shape
1
O Cl O
(
(
(
(
- - - - - -
-
-
-
-
- - - - - -
Tro, Chemistry: A Molecular Approach 37
Derivatives of the
Trigonal Bipyramidal Geometry
when there are 5 electron groups around the central atom, and
some are lone pairs, they will occupy the equatorial positions
because there is more room
when there are 5 electron groups around the central atom, and
1 is a lone pair, the result is called see-saw shape
aka distorted tetrahedron
when there are 5 electron groups around the central atom, and
2 are lone pairs, the result is called T-shaped
when there are 5 electron groups around the central atom, and
3 are lone pairs, the result is called a linear shape
the bond angles between equatorial positions is < 120
the bond angles between axial and equatorial positions is < 90
linear = 180 axial-to-axial
Tro, Chemistry: A Molecular Approach 38
Replacing Atoms with Lone Pairs
in the Trigonal Bipyramid System
Tro, Chemistry: A Molecular Approach 39
See-Saw Shape
F S F
F
F
Tro, Chemistry: A Molecular Approach 40
T-Shape
Tro, Chemistry: A Molecular Approach 41
T-Shaped
F Cl F
F
Tro, Chemistry: A Molecular Approach 42
Linear Shape
Tro, Chemistry: A Molecular Approach 43
Derivatives of the
Octahedral Geometry
when there are 6 electron groups around the central
atom, and some are lone pairs, each even number lone
pair will take a position opposite the previous lone pair
when there are 6 electron groups around the central
atom, and 1 is a lone pair, the result is called a square
pyramid shape
the bond angles between axial and equatorial positions is < 90
when there are 6 electron groups around the central
atom, and 2 are lone pairs, the result is called a square
planar shape
the bond angles between equatorial positions is 90
Tro, Chemistry: A Molecular Approach 44
Square Pyramidal Shape
Br
F
F
F F
F
Tro, Chemistry: A Molecular Approach 45
Square Planar Shape
F Xe F
F
F
Tro, Chemistry: A Molecular Approach 46
Tro, Chemistry: A Molecular Approach 47
Predicting the Shapes
Around Central Atoms
1) Draw the Lewis Structure
2) Determine the Number of Electron Groups
around the Central Atom
3) Classify Each Electron Group as Bonding or
Lone pair, and Count each type
remember, multiple bonds count as 1 group
4) Use Table 10.1 to Determine the Shape and
Bond Angles
Tro, Chemistry: A Molecular Approach 48
Practice Predict the Molecular Geometry and
Bond Angles in SiF
5
-1
Tro, Chemistry: A Molecular Approach 49
Practice Predict the Molecular Geometry and
Bond Angles in SiF
5
Si = 4e
F
5
= 5(7e
) = 35e
() = 1e
total = 40e
5 Electron Groups on Si
5 Bonding Groups
0 Lone Pairs
Shape = Trigonal Bipyramid
Si
F
F
F F
F
-1
Bond Angles
F
eq
-Si-F
eq
= 120
F
eq
-Si-F
ax
= 90
Si Least Electronegative
Si Is Central Atom
Tro, Chemistry: A Molecular Approach 50
Practice Predict the Molecular Geometry and
Bond Angles in ClO
2
F
Tro, Chemistry: A Molecular Approach 51
Practice Predict the Molecular Geometry and
Bond Angles in ClO
2
F
Cl = 7e
O
2
= 2(6e
) = 12e
F = 7e
Total = 26e
4 Electron Groups on Cl
3 Bonding Groups
1 Lone Pair
Shape = Trigonal Pyramidal
Bond Angles
O-Cl-O < 109.5
O-Cl-F < 109.5
Cl Least Electronegative
Cl Is Central Atom
O Cl
O
F
Tro, Chemistry: A Molecular Approach 52
Representing 3-Dimensional Shapes on
a 2-Dimensional Surface
one of the problems with drawing molecules is trying
to show their dimensionality
by convention, the central atom is put in the plane of
the paper
put as many other atoms as possible in the same plane
and indicate with a straight line
for atoms in front of the plane, use a solid wedge
for atoms behind the plane, use a hashed wedge
Tro, Chemistry: A Molecular Approach 53
Tro, Chemistry: A Molecular Approach 54
SF
6
S
F
F
F
F F
F
S
F
F
F
F
F
F
Tro, Chemistry: A Molecular Approach 55
Multiple Central Atoms
many molecules have larger structures with many
interior atoms
we can think of them as having multiple central atoms
when this occurs, we describe the shape around each
central atom in sequence
H
|
H O C C H
|| |
O H
- -
- -
-
-
- -
shape around left C is tetrahedral
shape around center C is trigonal planar
shape around right O is tetrahedral-bent
Tro, Chemistry: A Molecular Approach 56
Describing the Geometry
of Methanol
Tro, Chemistry: A Molecular Approach 57
Describing the Geometry
of Glycine
Tro, Chemistry: A Molecular Approach 58
Practice Predict the Molecular Geometries in
H
3
BO
3
59
Practice Predict the Molecular Geometries in
H
3
BO
3
B = 3e
O
3
= 3(6e
) = 18e
H
3
= 3(1e
) = 3e
Total = 24e
3 Electron Groups on B
B has
3 Bonding Groups
0 Lone Pairs
Shape on B = Trigonal Planar
B Least Electronegative
B Is Central Atom
oxyacid, so H attached to O
O B
O
O H H
H
4 Electron Groups on O
O has
2 Bonding Groups
2 Lone Pairs
Shape on O = Tetrahedral Bent
Tro, Chemistry: A Molecular Approach 60
Polarity of Molecules
in order for a molecule to be polar it must
1) have polar bonds
electronegativity difference - theory
bond dipole moments - measured
2) have an unsymmetrical shape
vector addition
polarity affects the intermolecular forces of attraction
therefore boiling points and solubilities
like dissolves like
nonbonding pairs affect molecular polarity, strong
pull in its direction
Tro, Chemistry: A Molecular Approach 61
Molecule Polarity
The H-Cl bond is polar. The bonding
electrons are pulled toward the Cl end of the
molecule. The net result is a polar molecule.
Tro, Chemistry: A Molecular Approach 62
Vector Addition
Tro, Chemistry: A Molecular Approach 63
Tro, Chemistry: A Molecular Approach 64
Molecule Polarity
The O-C bond is polar. The bonding
electrons are pulled equally toward both O
ends of the molecule. The net result is a
nonpolar molecule.
Tro, Chemistry: A Molecular Approach 65
Molecule Polarity
The H-O bond is polar. The both sets of
bonding electrons are pulled toward the O
end of the molecule. The net result is a
polar molecule.
Tro, Chemistry: A Molecular Approach 66
Molecule Polarity
The H-N bond is polar. All the sets of
bonding electrons are pulled toward the N
end of the molecule. The net result is a
polar molecule.
Tro, Chemistry: A Molecular Approach 67
Molecular Polarity Affects
Solubility in Water
polar molecules are attracted to
other polar molecules
since water is a polar molecule,
other polar molecules dissolve
well in water
and ionic compounds as well
some molecules have both polar
and nonpolar parts
Tro, Chemistry: A Molecular Approach 68
A Soap Molecule
Sodium Stearate
Tro, Chemistry: A Molecular Approach 69
Practice - Decide Whether the Following Are Polar
O N Cl
O S
O
O
EN
O = 3.5
N = 3.0
Cl = 3.0
S = 2.5
Tro, Chemistry: A Molecular Approach 70
Practice - Decide Whether the Following Are Polar
polar
nonpolar
1) polar bonds, N-O
2) asymmetrical shape
1) polar bonds, all S-O
2) symmetrical shape
O N Cl
O S
O
O
Trigonal
Bent
Trigonal
Planar
Cl
N
O
3.0
3.0
3.5
O
O
O
S
3.5
3.5
3.5
2.5
Tro, Chemistry: A Molecular Approach 71
Problems with Lewis Theory
Lewis theory gives good first approximations of
the bond angles in molecules, but usually cannot
be used to get the actual angle
Lewis theory cannot write one correct structure
for many molecules where resonance is
important
Lewis theory often does not predict the correct
magnetic behavior of molecules
e.g., O
2
is paramagnetic, though the Lewis structure
predicts it is diamagnetic
Tro, Chemistry: A Molecular Approach 72
Valence Bond Theory
Linus Pauling and others applied the principles
of quantum mechanics to molecules
they reasoned that bonds between atoms would
arise when the orbitals on those atoms interacted
to make a bond
the kind of interaction depends on whether the
orbitals align along the axis between the nuclei,
or outside the axis
Tro, Chemistry: A Molecular Approach 73
Orbital Interaction
as two atoms approached, the partially filled or
empty valence atomic orbitals on the atoms
would interact to form molecular orbitals
the molecular orbitals would be more stable
than the separate atomic orbitals because they
would contain paired electrons shared by both
atoms
the interaction energy between atomic orbitals is
negative when the interacting atomic orbitals
contain a total of 2 electrons
Tro, Chemistry: A Molecular Approach 74
Orbital Diagram for the
Formation of H
2
S
+
H
1s
H-S bond
H
1s
S
3s 3p
H-S bond
Predicts Bond Angle = 90
Actual Bond Angle = 92
Tro, Chemistry: A Molecular Approach 75
Valence Bond Theory - Hybridization
one of the issues that arose was that the number of
partially filled or empty atomic orbital did not predict the
number of bonds or orientation of bonds
C = 2s
2
2p
x
1
2p
y
1
2p
z
0
would predict 2 or 3 bonds that
are 90 apart, rather than 4 bonds that are 109.5 apart
to adjust for these inconsistencies, it was
postulated that the valence atomic orbitals could
hybridize before bonding took place
one hybridization of C is to mix all the 2s and 2p
orbitals to get 4 orbitals that point at the corners of a
tetrahedron
Tro, Chemistry: A Molecular Approach 76
Unhybridized C Orbitals Predict the
Wrong Bonding & Geometry
Tro, Chemistry: A Molecular Approach 77
Valence Bond Theory
Main Concepts
1. the valence electrons in an atom reside in
the quantum mechanical atomic orbitals or
hybrid orbitals
2. a chemical bond results when these atomic
orbitals overlap and there is a total of 2
electrons in the new molecular orbital
a) the electrons must be spin paired
3. the shape of the molecule is determined by
the geometry of the overlapping orbitals
Tro, Chemistry: A Molecular Approach 78
Hybridization
some atoms hybridize their orbitals to maximize
bonding
hybridizing is mixing different types of orbitals to
make a new set of degenerate orbitals
sp, sp
2
, sp
3
, sp
3
d, sp
3
d
2
more bonds = more full orbitals = more stability
better explain observed shapes of molecules
same type of atom can have different
hybridization depending on the compound
C = sp, sp
2
, sp
3
Tro, Chemistry: A Molecular Approach 79
Hybrid Orbitals
H cannot hybridize!!
the number of standard atomic orbitals combined = the
number of hybrid orbitals formed
the number and type of standard atomic orbitals
combined determines the shape of the hybrid orbitals
the particular kind of hybridization that occurs is the
one that yields the lowest overall energy for the
molecule
in other words, you have to know the structure of the
molecule beforehand in order to predict the hybridization
Tro, Chemistry: A Molecular Approach 80
Orbital Diagrams with Hybridization
place electrons into hybrid and unhybridized
valence orbitals as if all the orbitals have equal
energy
when bonding, o bonds form between hybrid
orbitals and t bonds form between unhybridized
orbitals that are parallel
Tro, Chemistry: A Molecular Approach 81
Carbon Hybridizations
Unhybridized
2s
2p
|+ |
sp hybridized
2sp
| |
sp
2
hybridized
2p
sp
3
hybridized
|
|
|
2p
2sp
2
| | | |
2sp
3
| | | |
Tro, Chemistry: A Molecular Approach 82
sp
3
Hybridization
atom with 4 areas of electrons
tetrahedral geometry
109.5 angles between hybrid orbitals
atom uses hybrid orbitals for all bonds and
lone pairs
H C N H
H
H H
s
sp
3
s
sp
3
Tro, Chemistry: A Molecular Approach 83
sp
3
Hybridization of C
Tro, Chemistry: A Molecular Approach 84
Tro, Chemistry: A Molecular Approach 85
sp
3
Hybridized Atoms
Orbital Diagrams
Unhybridized atom
2s
2p
|+ |
sp
3
hybridized atom
2sp
3
| | | | |
C
2s
2p
|+ |
2sp
3
| | | |
N
|
|
|
Tro, Chemistry: A Molecular Approach 86
Methane Formation with sp
3
C
Tro, Chemistry: A Molecular Approach 87
Ammonia Formation with sp
3
N
Tro, Chemistry: A Molecular Approach 88
CH
3
NH
2
Orbital Diagram
| sp
3
C | | | | sp
3
N | | |+
| | | | |
1s H
o
o
o
o o o
1s H 1s H 1s H 1s H
Tro, Chemistry: A Molecular Approach 89
Practice - Draw the Orbital Diagram for
the sp
3
Hybridization of Each Atom
Unhybridized atom
3s
3p
|+ |
Cl
2s
2p
|+ |
O
| |+
|+ |+
Tro, Chemistry: A Molecular Approach 90
Practice - Draw the Orbital Diagram for
the sp
3
Hybridization of Each Atom
Unhybridized atom
3s
3p
|+ |
Cl
2s
2p
|+ |
O
| |+
sp
3
hybridized atom
3sp
3
|
2sp
3
| |
|
|
|+
|+ |+ |+ |+ |+
Tro, Chemistry: A Molecular Approach 91
Types of Bonds
a sigma (o) bond results when the bonding atomic
orbitals point along the axis connecting the two
bonding nuclei
either standard atomic orbitals or hybrids
s-to-s, p-to-p, hybrid-to-hybrid, s-to-hybrid, etc.
a pi (t) bond results when the bonding atomic
orbitals are parallel to each other and perpendicular
to the axis connecting the two bonding nuclei
between unhybridized parallel p orbitals
the interaction between parallel orbitals is not as
strong as between orbitals that point at each other;
therefore o bonds are stronger than t bonds
Tro, Chemistry: A Molecular Approach 92
Tro, Chemistry: A Molecular Approach 93
Tro, Chemistry: A Molecular Approach 94
Bond Rotation
because orbitals that form the o bond point
along the internuclear axis, rotation around that
bond does not require breaking the interaction
between the orbitals
but the orbitals that form the t bond interact
above and below the internuclear axis, so
rotation around the axis requires the breaking of
the interaction between the orbitals
Tro, Chemistry: A Molecular Approach 95
Tro, Chemistry: A Molecular Approach 96
Tro, Chemistry: A Molecular Approach 97
sp
2
atom with 3 areas of electrons
trigonal planar system
C = trigonal planar
N = trigonal bent
O = linear
120 bond angles
flat
atom uses hybrid orbitals for o bonds and lone
pairs, uses nonhybridized p orbital for t bond
H C O H
O
sp
2
s
sp
2
sp
3
s
Tro, Chemistry: A Molecular Approach 98
Tro, Chemistry: A Molecular Approach 99
+
sp
2
sp
2
t
o
Hybrid orbitals overlap to form o bond
Unhybridized p orbitals overlap to form t bond
Tro, Chemistry: A Molecular Approach 100
Tro, Chemistry: A Molecular Approach 101
sp
2
Hybridized Atoms
Orbital Diagrams
Unhybridized atom
2s
2p
|+ |
sp
2
hybridized atom
2sp
2
| | | | |
2p
C
3 o
1 t
2s
2p
|+ |
2sp
2
| | | |
2p
|
|
|
N
2 o
1 t
Tro, Chemistry: A Molecular Approach 102
CH
2
NH Orbital Diagram
| sp
2
C | |
| |
sp
2
N | | |+
| | |
1s H
o
o
o o
1s H 1s H
p C p N
t
Tro, Chemistry: A Molecular Approach 103
Practice - Draw the Orbital Diagram for
the sp
2
Hybridization of Each Atom. How many
o and t bonds would you expect each to form?
Unhybridized atom
2s
2p
|+ |
B
2s
2p
|+ |
O
| |+
Tro, Chemistry: A Molecular Approach 104
Practice - Draw the Orbital Diagram for
the sp
2
Hybridization of Each Atom. How many
o and t bonds would you expect each to form?
Unhybridized atom
2s
2p
|+ |
B
3 o
0 t
2s
2p
|+ |
O
1 o
1 t
| |+
sp
2
hybridized atom
2sp
2
| | |
2p
2sp
2
| |
2p
|
|
|+
Tro, Chemistry: A Molecular Approach 105
sp
atom with 2 areas of electrons
linear shape
180 bond angle
atom uses hybrid orbitals for o bonds or lone
pairs, uses nonhybridized p orbitals for t bonds
H C N
sp sp s
t
t
o
Tro, Chemistry: A Molecular Approach 106
Tro, Chemistry: A Molecular Approach 107
Tro, Chemistry: A Molecular Approach 108
sp Hybridized Atoms
Orbital Diagrams
Unhybridized atom
2s
2p
|+ |
sp hybridized atom
2sp
| | | | |
2p
C
2o
2t
2s
2p
|+ |
2sp
| | | |
2p
|
|
|
N
1o
2t
Tro, Chemistry: A Molecular Approach 109
HCN Orbital Diagram
| sp C |
| | |
sp N
|
| |+
|
1s H
o
o
p C p N
2t
Tro, Chemistry: A Molecular Approach 110
sp
3
d
atom with 5 areas of electrons
around it
trigonal bipyramid shape
See-Saw, T-Shape, Linear
120 & 90 bond angles
use empty d orbitals from
valence shell
d orbitals can be used to make
t bonds
I
F
F
O
O
O
-1
Tro, Chemistry: A Molecular Approach 111
Tro, Chemistry: A Molecular Approach 112
sp
3
d Hybridized Atoms
Orbital Diagrams
Unhybridized atom
3s
3p
|+ |
sp
3
d hybridized atom
3sp
3
d
| | | |
S
3s
3p
|+
|
3sp
3
d
| | | |
P
|
|
|+
3d
3d
|
|+ |
(non-hybridizing d orbitals not shown)
Tro, Chemistry: A Molecular Approach 113
sp
3
d
2
atom with 6 areas of electrons
around it
octahedral shape
Square Pyramid, Square Planar
90 bond angles
use empty d orbitals from
valence shell
d orbitals can be used to make
t bonds
Br
F
F
F
F
F
Tro, Chemistry: A Molecular Approach 114
Tro, Chemistry: A Molecular Approach 115
sp
3
d
2
Hybridized Atoms
Orbital Diagrams
Unhybridized atom sp
3
d
2
hybridized atom
S
3s 3p
3sp
3
d
2
3d
I
5s 5p
5d
5sp
3
d
2
(non-hybridizing d orbitals not shown)
Tro, Chemistry: A Molecular Approach 116
Tro, Chemistry: A Molecular Approach 117
Example - Predict the Hybridization of All
the Atoms in H
3
BO
3
O B
O
O H H
H
H = cant hybridize
B = 3 electron groups = sp
2
O = 4 electron groups = sp
3
Tro, Chemistry: A Molecular Approach 118
Practice - Predict the Hybridization and
Bonding Scheme of All the Atoms in NClO
O N Cl
Tro, Chemistry: A Molecular Approach 119
Practice - Predict the Hybridization and
Bonding Scheme of All the Atoms in NClO
O N Cl
N = 3 electron groups = sp
2
O = 3 electron groups = sp
2
Cl = 4 electron groups = sp
3
Tro, Chemistry: A Molecular Approach 120
Predicting Hybridization and
Bonding Scheme
1) Start by drawing the Lewis Structure
2) Use VSEPR Theory to predict the electron group
geometry around each central atom
3) Use Table 10.3 to select the hybridization scheme
that matches the electron group geometry
4) Sketch the atomic and hybrid orbitals on the atoms in
the molecule, showing overlap of the appropriate
orbitals
5) Label the bonds as o or t
Tro, Chemistry: A Molecular Approach 121
Ex 10.8 Predict the hybridization and
bonding scheme for CH
3
CHO
Draw the Lewis Structure
Predict the electron group
geometry around inside
atoms
C1 = 4 electron areas
C1= tetrahedral
C2 = 3 electron areas
C2 = trigonal planar
C
1
H
H
H
C
2
H
O
Tro, Chemistry: A Molecular Approach 122
Ex 10.8 Predict the hybridization and
bonding scheme for CH
3
CHO
Determine the hybridization
of the interior atoms
C1 = tetrahedral
C1 = sp
3
C2 = trigonal planar
C2 = sp
2
Sketch the molecule and
orbitals
C
1
H
H
H
C
2
H
O
Tro, Chemistry: A Molecular Approach 123
Ex 10.8 Predict the hybridization and
bonding scheme for CH
3
CHO
Label the bonds
C
1
H
H
H
C
2
H
O
Tro, Chemistry: A Molecular Approach 124
Problems with Valence Bond Theory
VB theory predicts many properties better than
Lewis Theory
bonding schemes, bond strengths, bond lengths,
bond rigidity
however, there are still many properties of
molecules it doesnt predict perfectly
magnetic behavior of O
2
Tro, Chemistry: A Molecular Approach 125
Molecular Orbital Theory
in MO theory, we apply Schrdingers wave equation
to the molecule to calculate a set of molecular orbitals
in practice, the equation solution is estimated
we start with good guesses from our experience as to what
the orbital should look like
then test and tweak the estimate until the energy of the orbital
is minimized
in this treatment, the electrons belong to the whole
molecule so the orbitals belong to the whole
molecule
unlike VB Theory where the atomic orbitals still exist in the
molecule
Tro, Chemistry: A Molecular Approach 126
LCAO
the simplest guess starts with the atomic orbitals
of the atoms adding together to make molecular
orbitals this is called the Linear Combination
of Atomic Orbitals method
weighted sum
because the orbitals are wave functions, the
waves can combine either constructively or
destructively
Tro, Chemistry: A Molecular Approach 127
Molecular Orbitals
when the wave functions combine constructively, the
resulting molecular orbital has less energy than the
original atomic orbitals it is called a Bonding
Molecular Orbital
o, t
most of the electron density between the nuclei
when the wave functions combine destructively, the
resulting molecular orbital has more energy than the
original atomic orbitals it is called a Antibonding
Molecular Orbital
o*, t*
most of the electron density outside the nuclei
nodes between nuclei
Tro, Chemistry: A Molecular Approach 128
Interaction of 1s Orbitals
Tro, Chemistry: A Molecular Approach 129
Molecular Orbital Theory
Electrons in bonding MOs are stabilizing
Lower energy than the atomic orbitals
Electrons in anti-bonding MOs are
destabilizing
Higher in energy than atomic orbitals
Electron density located outside the
internuclear axis
Electrons in anti-bonding orbitals cancel
stability gained by electrons in bonding orbitals
Tro, Chemistry: A Molecular Approach 130
MO and Properties
Bond Order = difference between number of
electrons in bonding and antibonding orbitals
only need to consider valence electrons
may be a fraction
higher bond order = stronger and shorter bonds
if bond order = 0, then bond is unstable compared
to individual atoms - no bond will form.
A substance will be paramagnetic if its MO
diagram has unpaired electrons
if all electrons paired it is diamagnetic
2
Elec. Antibond # - Elec. Bond #
Order Bond =
Tro, Chemistry: A Molecular Approach 131
1s 1s
o
-
o
Hydrogen
Atomic
Orbital
Hydrogen
Atomic
Orbital
Dihydrogen, H
2
Molecular
Orbitals
Since more electrons are in
bonding orbitals than are in antibonding orbitals,
net bonding interaction
Tro, Chemistry: A Molecular Approach 132
H
2
o* Antibonding MO
LUMO
o bonding MO
HOMO
Tro, Chemistry: A Molecular Approach 133
1s 1s
o
-
o
Helium
Atomic
Orbital
Helium
Atomic
Orbital
Dihelium, He
2
Molecular
Orbitals
Since there are as many electrons in
antibonding orbitals as in bonding orbitals,
there is no net bonding interaction
BO = (2-2) = 0
134
1s 1s
o
-
o
Lithium
Atomic
Orbitals
Lithium
Atomic
Orbitals
Dilithium, Li
2
Molecular
Orbitals
Since more electrons are in
bonding orbitals than are in antibonding
orbitals, net bonding interaction
2s 2s
o
-
o Any fill energy level will
generate filled bonding and
antibonding MOs;
therefore only need to
consider valence shell
BO = (4-2) = 1
Tro, Chemistry: A Molecular Approach 135
o bonding MO
HOMO
o- Antibonding MO
LUMO
Li
2
Tro, Chemistry: A Molecular Approach 136
Interaction of p Orbitals
Tro, Chemistry: A Molecular Approach 137
Interaction of p Orbitals
Tro, Chemistry: A Molecular Approach 139
O
2
dioxygen is paramagnetic
paramagnetic material have unpaired electrons
neither Lewis Theory nor Valence Bond Theory
predict this result
Tro, Chemistry: A Molecular Approach 140
O
2
as described by Lewis and VB theory
Tro, Chemistry: A Molecular Approach 141
Oxygen
Atomic
Orbitals
Oxygen
Atomic
Orbitals
2s 2s
2p 2p
o
-
o
o
-
o
t
-
t
Since more electrons are in
bonding orbitals than are in
antibonding orbitals, net bonding
interaction
Since there are unpaired
electrons in the
antibonding orbitals,
O
2
is paramagnetic
O
2
MOs
BO = ( 8 be 4 abe)
BO = 2
Tro, Chemistry: A Molecular Approach 142
O
2
t- Antibonding MO
HOMO
t Bonding MO
HOMO-1
o- Antibonding MO
LUMO+1
t- Antibonding MO
LUMO
Tro, Chemistry: A Molecular Approach 143
Draw a molecular orbital diagram of N
2
and
predict its bond order and magnetic properties
Tro, Chemistry: A Molecular Approach 144
Nitrogen
Atomic
Orbitals
Nitrogen
Atomic
Orbitals
2s 2s
2p 2p
o
-
o
o
-
o
t
-
t
Since there are no unpaired
electrons, N
2
is diamagnetic
N
2
MOs
BO = ( 8 be 2 abe)
BO = 3
Tro, Chemistry: A Molecular Approach 145
Heteronuclear Diatomic Molecules
the more electronegative atom has lower energy orbitals
when the combining atomic orbitals are identical and equal
energy, the weight of each atomic orbital in the molecular
orbital are equal
when the combining atomic orbitals are different kinds
and energies, the atomic orbital closest in energy to the
molecular orbital contributes more to the molecular orbital
lower energy atomic orbitals contribute more to the bonding MO
higher energy atomic orbitals contribute more to the
antibonding MO
nonbonding MOs remain localized on the atom donating
its atomic orbitals
Tro, Chemistry: A Molecular Approach 146
NO
Free-Radical
o
2s
Bonding MO
mainly Os 2s
atomic orbital
Tro, Chemistry: A Molecular Approach 147
HF
Tro, Chemistry: A Molecular Approach 148
Polyatomic Molecules
when many atoms are combined together, the
atomic orbitals of all the atoms are combined to
make a set of molecular orbitals which are
delocalized over the entire molecule
gives results that better match real molecule
properties than either Lewis or Valence Bond
theories
Tro, Chemistry: A Molecular Approach 149
Ozone, O
3
Delocalized
t bonding
orbital of O
3
