3.

5 Hybridization
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
3.5 Valence Bond Theory and
Hybridization of Atomic Orbital
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
2
Valence Bond Theory
Linus Pauling and others applied the principles of quantum
mechanics to molecules
They reasoned that bonds between atoms would occur 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
Orbital Interaction
As two atoms approached, the half-filled valence atomic orbitals
on each atom would interact to form molecular orbitals
molecular orbitals are regions of high probability of finding
the shared electrons in the molecule
The molecular orbitals would be more stable than the separate
atomic orbitals because they would contain paired electrons
shared by both atoms
Covalent bond between atoms occur when the atomic orbital of
one atom interacts or overlaps with the atomic orbital of another
atom
Overlapping of atomic orbitals can be either:
1.End-to-end (the shared electron density concentrates along the
axis joining the nuclei of the bonded atoms).
2.Sideway (the shared electron density concentrates on either
sides of the axis joining the nuclei of the bonded atoms).
Valence Bond Theory-Hybridization
Mixing of atomic orbitals to produce a new set of
orbitals called hybrid orbitals.
Reason for hybridization: Direct overlapping of
atomic orbitals may not be able to explain the
actual bond angle and shape
Hybridization can be used to predict the number of
bonds or the geometry of the bonds. Leading to the
expected molecular geometry (as predicted by the
VSEPR theory)

5
Hybridization mixing of two or more atomic
orbitals to form a new set of hybrid 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 hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals
Orbital Overlap and Spin Pairing in Three Diatomic
Molecules.
Hydrogen, H
2

Hydrogen fluoride, HF
Fluorine, F
2

Types of Bonds
A sigma () bond results when the interacting atomic orbitals point
along the axis connecting the two bonding nuclei (end-to-end
overlapping)
either standard atomic orbitals or hybrids
stos, ptop, hybridtohybrid, stohybrid, etc.

A pi () bond results when the bonding atomic orbitals are parallel
to each other and perpendicular to the axis connecting the two
bonding nuclei (side-way overlapping)
between unhybridized parallel p orbitals

The interaction between parallel orbitals is not as strong as
between orbitals that point at each other; therefore s bonds are
stronger than p bonds
Types of Bonds
9
Formation of sp
3
Hybrid Orbitals
10
Formation of Covalent Bonds in CH
4
11
Predict correct
bond angle
sp
3
-Hybridized N Atom in NH
3
12
Formation of sp
2
Hybrid Orbitals
13
Formation of sp Hybrid Orbitals
# of Lone Pairs
+
# of Bonded Atoms
Hybridization
Examples
2
3
4
5
6
sp
sp
2

sp
3

sp
3
d
sp
3
d
2

BeCl
2

BF
3

CH
4
,
NH
3
, H
2
O
PCl
5

How do I predict the hybridization of the central atom?
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the number of
atoms bonded to the central atom
SF
6

VSEPR
Model
AB
2

AB
3

AB
4

AB
5

AB
6

Geometry
Linear
Trigonal
planar
Tetra-
heydral
Trigonal
bypyramidal
Octaheydral
15
Unhybridized C Orbitals Predict the Wrong
Bonding & Geometry
Example of Carbon Hybridizations
Unhybridized
2s
2p

sp hybridized
2sp

sp
2
hybridized
2p
sp
3
hybridized



2p
2sp
2


2sp
3


19
sp Hybridization of Carbon
Unhybridized
electron
orbital for
bond
20
Bonding in Acetylene, C
2
H
2
21
Sigma (s) and Pi Bonds (p)
Single bond
1 sigma bond
Double bond
1 sigma bond and 1 pi bond
Triple bond 1 sigma bond and 2 pi bonds
sp Hybridization
Atom with two electron groups
linear shape
180 bond angle
Atom uses hybrid orbitals for bonds or lone pairs,
uses unhybridized p orbitals for bonds



sp Hybridized Atoms Orbital Diagrams
of HCN
Unhybridized atom
2s
2p

sp hybridized atom
2sp

2p
C
2
2
2s
2p

2sp

2p



N
1
2
HCN Orbital Diagram

Hybridized
sp-orbital C




1s H

unhybridized
p-orbital C

unhybridized
p-orbital N
Hybridized
sp-orbital N

2s
2p





Lone pair electrons
of s-orbital N
Overlap of
s-orbital C
with
s-orbital H
2p
Overlap of p-orbital C
with p-orbital N
2s
2p
2p
2p 2p
The sp hybrid orbitals in gaseous BeCl
2
.
atomic
orbitals
hybrid
orbitals
orbital box
diagrams
The sp hybrid orbitals in gaseous BeCl
2
(continued).
orbital box diagrams with
orbital contours
28
sp
2
Hybridization of Carbon
Unhybridized
electron
orbital for p
bond
29
Unhybridized 2p
z
orbital (gray), which is perpendicular
to the plane of the hybrid (green) orbitals.
30
Sigma bond (s) electron density between the 2 atoms
Pi bond (p) electron density above and below plane of nuclei
of the bonding atoms
Bonding in Ethylene, C
2
H
4
Atom with three electron
groups around it
trigonal planar system
C = trigonal planar
N = trigonal bent
O = linear
120 bond angles
flat
Atom uses hybrid orbitals for
s bonds and lone pairs, uses
nonhybridized p orbital for p
bond
sp
2
Hybridization
sp
2
Hybridized Atoms Orbital Diagrams
Unhybridized atom
2s
2p

sp
2
hybridized atom
2sp
2


2p
C
3
1
2s
2p

2sp
2


2p



N
2
1
CH
2
NH Orbital Diagram





1s H




1s H
1s H

C N
H
H H
Hybridized
sp
2
-orbital C
unhybridized
p-orbital C
unhybridized
p-orbital N
Hybridized
sp
2
-orbital N
2s 2s 2p 2p
2p 2p
Lone pair
electrons
of
s-orbital N
Overlap of
s-orbital C
with
s-orbital H
Overlap of
p-orbital C
with p-
orbital N
Overlap of
p-orbital C
with
s-orbital H



2p 2p
The sp
2
hybrid orbitals in BF
3
.
sp
3
Hybridization
Atom with four electron groups around it
tetrahedral geometry
109.5 angles between hybrid orbitals
Atom uses hybrid orbitals for all bonds and lone
pairs
Orbital Diagram of the sp
3
Hybridization
Unhybridized atom
2s
2p

sp
3
hybridized atom
2sp
3


C
2s
2p

2sp
3


N



Place electrons into
hybrid and unhybridized
valence orbitals as if all
the orbitals have equal
energy
Lone pairs generally
occupy hybrid orbitals
Methane : sp
3
hybridisation on atom C
Ammonia: sp
3
hybridisation on atom N


1s H




1s H 1s H 1s H 1s H
H C
H
H
N H
H

sp
3
Hybridization of CH
3
NH
2
Orbital Diagram
Hybridized
sp
3
-orbital C
Hybridized
sp
3
-orbital N
2s 2s 2p 2p
2p 2p 2p 2p
Lone pair
electrons
of
s-orbital N
sp
3
d Hybridization
Atom with five electron groups around it
trigonal bipyramid electron geometry
Seesaw, TShape, Linear
120 & 90 bond angles
Use empty d orbitals from valence shell
d orbitals can be used to make bonds
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)
sp
3
d Hybridization
sp
3
d Hybridization
sp
3
d
2
Hybridization
Atom with six electron groups
around it
octahedral electron geometry
Square Pyramid, Square Planar
90 bond angles
Use empty d orbitals from valence
shell to form hybrid
d orbitals can be used to make p
bonds
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)
Example 1
Determine the hybridization state of the central atom in each of
the following molecules:

(a) BeH
2

(b) AlI
3

(c) PF
3


Describe the hybridization process and determine the molecular
geometry in each case.
Example 1
Strategy The steps for determining the hybridization of the
central atom in a molecule are:




Solution
(a) The ground-state electron configuration of Be is 1s
2
2s
2
and
the Be atom has two valence electrons. The Lewis structure
of BeH
2
is
HBeH
Example 1
There are two bonding pairs around Be; therefore, the electron
pair arrangement is linear. We conclude that Be uses sp hybrid
orbitals in bonding with H, because sp orbitals have a linear
arrangement . The hybridization process can be imagined as
follows. First, we draw the orbital diagram for the ground state
of Be:




By promoting a 2s electron to the 2p orbital, we get the excited
state:
Example 1
The 2s and 2p orbitals then mix to form two hybrid orbitals:





The two BeH bonds are formed by the overlap of the Be sp
orbitals with the 1s orbitals of the H atoms. Thus, BeH
2
is a
linear molecule.
Example 1
(b) The ground-state electron configuration of Al is [Ne]3s
2
3p
1
.
Therefore, the Al atom has three valence electrons. The
Lewis structure of AlI
3
is



There are three pairs of electrons around Al; therefore,
the electron pair arrangement is trigonal planar. We
conclude that Al uses sp
2
hybrid orbitals in bonding with I
because sp
2
orbitals have a trigonal planar arrangement.
The orbital diagram of the ground-state Al atom is

Example 1
By promoting a 3s electron into the 3p orbital we obtain the
following excited state:



The 3s and two 3p orbitals then mix to form three sp
2
hybrid
orbitals:





The sp
2
hybrid orbitals overlap with the 5p orbitals of I to form
three covalent AlI bonds. We predict that the AlI
3
molecule is
trigonal planar and all the IAlI angles are 120.
Example 1
(c) The ground-state electron configuration of P is [Ne]3s
2
3p
3
.
Therefore, P atom has five valence electrons. The Lewis
structure of PF
3
is



There are four pairs of electrons around P; therefore, the
electron pair arrangement is tetrahedral. We conclude that P
uses sp
3
hybrid orbitals in bonding to F, because sp
3
orbitals
have a tetrahedral arrangement. The hybridization process can
be imagined to take place as follows. The orbital diagram of the
ground-state P atom is
Example 1
By mixing the 3s and 3p orbitals, we obtain four sp
3
hybrid
orbitals.




As in the case of NH
3
, one of the sp
3
hybrid orbitals is used to
accommodate the lone pair on P. The other three sp
3
hybrid
orbitals form covalent PF bonds with the 2p orbitals of F. We
predict the geometry of the molecule to be trigonal pyramidal;
the FF angle should be somewhat less than 109.5.
Example 2
Describe the hybridization state of phosphorus in phosphorus
pentabromide (PBr
5
).
Example 2
Strategy Follow the same procedure shown in Example 10.3.

Solution The ground-state electron configuration of P is
[Ne]3s
2
3p
3
. Therefore, the P atom has five valence electrons.
The Lewis structure of PBr
5
is





There are five pairs of electrons around P; therefore, the
electron pair arrangement is trigonal bipyramidal. We conclude
that P uses sp
3
d hybrid orbitals in bonding to Br, because sp
3
d
hybrid orbitals have a trigonal bipyramidal arrangement.
Example 2
The hybridization process can be imagined as follows. The
orbital diagram of the ground-state P atom is





Promoting a 3s electron into a 3d orbital results in the following
excited state:


Example 2
Mixing the one 3s, three 3p, and one 3d orbitals generates five
sp
3
d hybrid orbitals:





These hybrid orbitals overlap the 4p orbitals of Br to form five
covalent PBr bonds. Because there are no lone pairs on the P
atom, the geometry of PBr
5
is trigonal bipyramidal.

CHECKPOINT 10
What are the hybrid orbitals of carbon atoms in
the following molecules?


a) H
3
C-CH
3
b) H
3
C-CH=CH
2
Answer: a)sp
3

b)sp
3
, sp
2
, sp
2

62
3.6 Intermolecular Forces
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
63
Intermolecular Forces
Intermolecular forces (nonbonding forces) are attractive
forces between molecules.
Intramolecular forces (bonding forces) hold atoms together in
a molecule.
Intermolecular vs Intramolecular
Generally, intermolecular
forces are much weaker
than intramolecular forces.
Measure of intermolecular force
boiling point
melting point
DH
vap

DH
fus
DH
sub

These forces exist within each molecule.
They influence the chemical properties of the substance.
These forces exist between molecules.
They influence the physical properties of the substance.
To break this bond
you may need
thousand degrees
Celsius
To overcome
this forces you
just need to
boil the water
at 100
o
C
Intermolecular Attractions
vs. Intramolecular (Bonding)
Bonding forces are result of large charges (the charge
protons and electrons) interacting at very close distances.
Intermolecular forces are the result of smaller charge
interacting at greater distances
65
Intermolecular Forces
Forces that occur between molecules:
3.6.1 Dipole-dipole forces
3.6.2 Dispersion forces
3.6.3 Hydrogen bonding

66
Intermolecular Forces
3.6.1 Dipole-Dipole Forces
Attractive forces between polar molecules, that is,
between molecules that possess dipole moments.
The larger the dipole moment, the greater the force.
When polar molecules come closer to one another, their
partial charges act as tiny electric fields that orient and
give rise to dipole-dipole attraction. The positive end will
attracts the negative end of another.



67
Intermolecular Forces
3.6.1 Dipole-Dipole Forces
Figure 11.1 shows the molecules that have a permanent
dipole moment tend to align with opposite polarities in the
solid phase for maximum attraction interaction
Figure 11.1: Orientation of Polar Molecules in a Solid
68
Intermolecular Forces
3.6.2 Dispersion Forces
Attractive forces that arise as a result of temporary
dipoles induced in atoms or molecules
Its occur in all molecules
Is the weakest intermolecular forces
The dipole in the atom is said to be an induced dipole
because the separation of positive and negative charges
in the atom is due to the an ion or a polar molecule comes
closer.
69
Intermolecular Forces
3.6.2 Dispersion Forces
The attractive interaction between an ion and induced
dipole is called ion-induced dipole interaction
The attraction interaction between a polar molecule and
the induced dipole is called dipole-induced dipole
interaction
ion-induced dipole
interaction
dipole-induced
dipole interaction
70
Dipole moment also being induced depends on
polarizability
Polarizability is the ease in which the electron
distribution in the atom or molecule can be distorted
(becomes uneven distribution)
In a collection of He atoms(nonpolar), an instantaneous
dipole of one He atom can induce a dipole in each of its
nearest (Figure 11.5). Next, a different instantaneous
dipole can create temporary dipole in the surrounding He
atoms and its called dispersion forces.
3.6.2 Dispersion Forces
71
Figure 11.5: Example of interaction for He atoms(nonpolar gases).
Its shows an induced dipoles interacting with each other. Such
pattern exist only temporary, the new arrangement are formed in
the next instant.
3.6.2 Dispersion Forces
72
Intermolecular Forces
3.6.2 Dispersion Forces
Polarizability increases with:
greater number of electrons
more diffuse electron cloud
(electron cloud spread over
entire volume so electron are
not held tightly by nucleus)
Dispersion forces usually
increase with molar mass.
73
Intermolecular Forces
3.6.2 Dispersion Forces
The relative strength of the dispersion force depends on the
polarizability of the particle. Polarizability depends on the
number of electrons, which correlates closely with the molar
mass.
The molar mass increased when going down the groups VII
(halogen) and VIII (noble gas). Result in increasing dispersion
forces down the respective groups. Therefore, freezing and
boiling points increase down groups VII (halogen) and VIII
(noble gas).
Molar mass and trends in boiling point.
Dispersion forces are
stronger for more polarizable
particles.
Polarizability correlates
closely with molar mass
Boiling point increase with
increasing strenth of
dispersion forces

EXAMPLE 1
What type(s) of intermolecular forces exist between the
following pairs?

(a) HBr and H
2
S

(b) Cl
2
and CBr
4

(c) I
2
and

(d) NH
3
and C
6
H
6

EXAMPLE 1
Strategy Classify the species into three categories: polar
(possessing a dipole moment), and nonpolar. Keep in mind
that dispersion forces exist between all species.

Solution
(a) Both HBr and H
2
S are polar molecules. Therefore, the
intermolecular forces present are dipole-dipole forces, as
well as dispersion forces.

(b) Both Cl
2
and CBr
4
are nonpolar, so there are only dispersion
forces between these molecules.
EXAMPLE 1
(c) I
2
is a homonuclear diatomic molecule and therefore
nonpolar, so the forces between it and the ion are
ion-induced dipole forces and dispersion forces.


(d) NH
3
is polar, and C
6
H
6
is nonpolar. The forces are dipole-
induced dipole forces and dispersion forces.
79
Intermolecular Forces
3.6.3 Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction
between the hydrogen atom and an electronegative O, N, or F
atom. (N-H, O-H, or F-H) bond
Is the strongest intermolecular forces
A H

B A H

A
or
A & B are N, O, or F
80
Intermolecular Forces
Strength of Hydrogen Bond
The strength of the hydrogen bond decrease with decrease
in the electronegativity value of the atom bonded to the H
atom.
Since the electronegativity value of the 3 atoms decrease in
the order F>O>N, therefore, the strength of the hydrogen bond
also decreases in the order:

H-F H-F > H-O H-O >H-N H-N

81
Hydrogen Bond
HCOOH and water
82
Why is the hydrogen bond considered a special
dipole-dipole interaction?
Decreasing molar mass
Decreasing boiling point
83
Figure shows the effect of H bonding on the boiling points of
binary hydrides of groups 4A through 7A.
Group IV hydrides shows a gradual increase in boiling points
from CH
4
to SnH
4
, due to an increase in dipole-dipole force as
the molar mass of the molecules increases.
The first member in groups V, VI and VII form hydrides which
show a marked deviation from the trend. HF, H
2
O and NH
3

boils at an abnormally high temperature.
This is because these three hydrides can form hydrogen
bonds which are much stronger than the normal dipole-dipole
forces.

EXAMPLE 2
Which of the following can form hydrogen bonds with water?

CH
3
OCH
3

CH
4

F
2

HCOOH

Na
+

EXAMPLE 2
Strategy A species can form hydrogen bonds with water if it
contains one of the three electronegative elements (F, O, or N)
or it has a H atom bonded to one of these three elements.

Solution There are no electronegative elements (F, O, or N) in
either CH
4
or Na
+
. Therefore, only CH
3
OCH
3
, F
2
, and HCOOH
can form hydrogen bonds with water.
EXAMPLE 2
Check Note that HCOOH (formic acid) can form hydrogen
bonds with water in two different ways.
HCOOH forms hydrogen
bonds
with two H
2
O molecules.
EXAMPLE 3
PROBLEM: For each pair of substances, identify the key bonding
and/or intermolecular force(s), and predict which one of the
pair has the higher boiling point:
(a) MgCl
2
or PCl
3
(b) CH
3
NH
2
or CH
3
F (c) CH
3
OH or CH
3
CH
2
OH
(d) Hexane (CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
) or 2,2-dimethylbutane


PLAN:
We examine the formulas and structures for key differences
between the members of each pair: Are ions present? Are
molecules polar or nonpolar? Is N, O, or F bonded to H? Do
molecular compounds have different masses or shapes?
Predicting the Types of Intermolecular Forces
EXAMPLE 3
Remember that:
Bonding forces are stronger than nonbonding (intermolecular)
forces.
Hydrogen bonding is a strong type of dipole-dipole force.
Dispersion forces are decisive when the difference is molar mass
or molecular shape.
(a) MgCl
2
consists of Mg
2+
and Cl
-
ions held together by ionic bonding
forces; PCl
3
consists of polar molecules, so intermolecular dipole-
dipole forces are present. The ionic bonding forces in MgCl
2
are
stronger than the dipole-dipole forces in PCl
3
.
.

MgCl
2
has a higher boiling point than PCl
3
.
SOLUTION:
(b) CH
3
NH
2
and CH
3
F both consist of polar molecules of about the
same molar mass. CH
3
NH
2
has covalent N-H bonds, so it can form
H bonds between its molecules. CH
3
F contains a C-F bond but no
H-F bond, so dipole-dipole forces occur but not H bonds.
CH
3
NH
2
has a higher boiling point than CH
3
F.
(c) CH
3
OH and CH
3
CH
2
OH are both polar molecules and both contain
a covalent O-H bond. Both can therefore form H bonds.
CH
3
CH
2
OH has a higher boiling point than CH
3
OH.
CH
3
CH
2
OH has a larger molar mass than CH
3
OH and its
dispersion forces are therefore stronger.
(d) Hexane and 2,2-dimethylbutane are both nonpolar molecules and
therefore experience dispersion forces as their only intermolecular
force. They have equal molar masses but different molecular
shapes.
Cylindrical hexane molecules make more intermolecular contact
than the more compact 2,2-dimethylbutane molecules.
Hexane has a higher boiling point than 2,2-dimethylbutane.
92

Metallic bonding results from attraction of the metal cations
for the mobile, highly delocalized valence electrons.
In metal, bonding electron are delocalized over the entire crystal.
Metal atoms in the crystal can be imagined as an array of
positive ions immersed in the sea of delocalized valence electron
Cross Section of a Metallic Crystal
nucleus &
inner shell e
-

mobile sea
of e
-

3.7 Metallic Bonds
Properties of Metallic Bond
1. Conduct heat & electricity
The mobility of the delocalization electrons makes metals
good conductor of heat and electricity.

2. Malleable (can be flattened) and ductile (pulled into wires)
The metal structure are hold by the attractive forces and
the attractive forces should not break if positions of the
atom cores shift
because the mobility of the electrons allow the
attractions to be maintained


3.7 Metallic Bonds
94
3.7 Metallic Bonds
3. High melting and boiling point

In order to melt, some of the attractions holding the metallic
crystal together must be broken.
In order to boil, all the attractions holding the metallic crystal
together must be broken.
The attractions of the core atoms for the delocalized
electrons is strong because it involves full charges
thus metals generally have high melting points and
boiling points




3.7 Metallic Bonds
96
3.7 Metallic Bonds
4. The strength of the metallic bond

The strength of the metallic bond is inversely proportional to
the size of the ion and directly proportional to the number of
valence electron on the metal atom.
According to the period trend (atomic radii decrease across
a period but increase down the group), the melting and
boiling points of metals increases across a period but
decreases down a group.


3.7 Metallic Bonds
4. The strength of the metallic bond

Example:
Group 2A elements (alkaline earth metals) have higher
melting points than group 1A elements(alkali metals)
because of smaller size and the electron sea has twice as
many valence electron (2 valence electron) resulting in
stronger attractions among the metal ions.