Chapter 9

Lecture Presentation
Chapter 9
Molecular Geometry
and Bonding
Theories
James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
Molecular Shapes
• Lewis Structures show bonding and lone pairs, but
do not denote shape.
• However, we use Lewis Structures to help us
determine shapes.
• Here we see some common shapes for molecules
with two or three atoms connected to a central atom.
Molecular
Geometries
and Bonding
Theories
What Determines the
Shape of a Molecule?
• Simply put, electron pairs,
whether they be bonding
or nonbonding, repel each
other.
• By assuming the electron
pairs are placed as far as
possible from each other,
we can predict the shape
of the molecule.
This is the Molecular

Valence-Shell Electron-Pair Repulsion (VSEPR)
Geometries
and Bonding
model.
Theories
Electron Domains
• We can refer to the directions
to which electrons point as
electron domains (defines a
region in which the
electrons are most likely to
be found). This is true
whether there is one or more
electron pairs pointing in that
direction.
• The central atom in this
molecule, A, has four electron
domains. Molecular
Geometries
and Bonding
Theories
Valence-Shell Electron-Pair
Repulsion (VSEPR) Model
“The best arrangement of
a given number of
electron domains is the
one that minimizes the
repulsions among them.”
(The balloon analogy in
the figure to the left
demonstrates the
maximum distances,
which minimize Molecular
repulsions.) Geometries
and Bonding
Theories
Electron-Domain vs Molecular
Geometries
• The arrangement of electron domains about the

central atom of a molecule or ion is called its
electron-domain geometry
• The arrangement of only the atoms in a molecule

or ion is called molecular geometry
Molecular
Geometries
and Bonding
Theories
Electron-Domain Geometries
• The Table shows the
electron-domain
geometries for two
through six electron
domains around a
central atom.
• To determine the
electron-domain
geometry, count the
total number of lone
pairs, single, double,
and triple bonds on Molecular
the central atom. andGeometries
Bonding
Theories
Molecular Geometries
• Once you have determined the electron-domain

geometry, use the arrangement of the bonded atoms
to determine the molecular geometry.
• Tables 9.2 and 9.3 show the potential molecular
geometries. We will look at each electron domain Molecular
to see what molecular geometries are possible. Geometries
and Bonding
Theories
Linear Electron Domain
• In the linear domain, there is only one

molecular geometry: linear.
• NOTE: If there are only two atoms in the
molecule, the molecule will be linear no
matter what the electron domain is. Molecular
Geometries
and Bonding
Theories
Trigonal Planar Electron Domain
• There are two molecular geometries:

– trigonal planar, if all electron domains are
bonding, and
– bent, if one of the domains is a Molecular
Geometries
nonbonding pair. and Bonding
Theories
Nonbonding Pairs and Bond Angle
• Nonbonding pairs are physically
larger than bonding pairs.
• Therefore, their repulsions are
greater; this tends to compress
bond angles.
Molecular
Geometries
All have the same electron-domain geometry and Bonding
Theories
Multiple Bonds and Bond Angles
• Double and triple
bonds have larger
electron domains
than single bonds.
• They exert a greater
repulsive force than
single bonds, making
their bond angles
greater.
Molecular
Geometries
and Bonding
Theories
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 dashed wedge
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 13
Tetrahedral Electron Domain
• There are three molecular geometries:

– tetrahedral, if all are bonding pairs,
– trigonal pyramidal, if one is a nonbonding
pair, and Molecular
Geometries
– bent, if there are two nonbonding pairs. and Bonding
Theories
Sample Exercise 9.1 Using the VSEPR Model
Use the VSEPR model to predict the molecular geometry of (a)
O3, (b) SnCl3–.
Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
O3, (b) SnCl3–.
Solution
Analyze We are given the molecular formulas of a molecule and a polyatomic ion, both conforming to the general
formula ABn and both having a central atom from the p block of the periodic table. (Notice that for O 3, the A and B
atoms are all oxygen atoms.)
Plan To predict the molecular geometries, we draw their Lewis structures and count electron domains around the
central atom to get the electron-domain geometry. We then obtain the molecular geometry from the arrangement of
the domains that are due to bonds.
Solve
(a) We can draw two resonance structures for O 3:
Continued
Because of resonance, the bonds between the central O atom and the outer O atoms are of equal length. In both
resonance structures the central O atom is bonded to the two outer O atoms and has one nonbonding pair. Thus, there
are three electron domains about the central O atoms. (Remember that a double bond counts as a single electron
domain.) The arrangement of three electron domains is trigonal planar (Table 9.1). Two of the domains are from
bonds, and one is due to a nonbonding pair. So, the molecular geometry is bent with an ideal bond angle of 120°
(Table 9.2).
Continued
Comment As this example illustrates, when a molecule exhibits resonance, any one of the resonance structures can be
used to predict the molecular geometry.
(b) The Lewis structure for SnCl3– is
Continued
The central Sn atom is bonded to the three Cl atoms and has one nonbonding pair; thus, we have four electron
domains, meaning a tetrahedral electron-domain geometry (Table 9.1) with one vertex occupied by a nonbonding pair
of electrons. A tetrahedral electrondomain geometry with three bonding and one nonbonding domains leads to a
trigonal-pyramidal molecular geometry (Table 9.2).
Practice Exercise 2
Predict the electron-domain and molecular geometries for (a)

SeCl2, (b) CO32–.
Answer: (a) tetrahedral, bent; (b) trigonal planar
Continued
Practice Exercise 1
Consider the following AB3 molecules and ions: PCl3, SO3, AlCl3, SO32–, and CH3+. How many of these molecules and
ions do you predict to have a trigonal-planar molecular geometry?
(a) 1 (b) 2 (c) 3 (d) 4 (e) 5
SO3 , AlCl3 and CH3+
Expanding beyond the Octet Rule
• Remember that some elements can
break the octet rule and make more
than four bonds (or have more than four
electron domains).
• The result is two more possible electron
domains: five = trigonal bipyramidal;
six = octahedral (as was seen in the
slide on electron-domain geometries).
Molecular
Geometries
and Bonding
Theories
Trigonal Bipyramidal
Electron Domain
Octohedral Electron Domain
• There are two distinct positions in

this geometry:
– Axial
– Equatorial
• Lone pairs occupy equatorial Molecular
Geometries
positions (120o vs 90o). and Bonding
Theories
Trigonal Bipyramidal Electron Domain
• There are four
distinct molecular
geometries in this
domain:
– Trigonal
bipyramidal
– Seesaw
– T-shaped
– Linear
Molecular
Geometries
and Bonding
Theories
Octahedral Electron Domain
• All positions are
equivalent in the
octahedral domain.
• There are three
molecular
geometries:
– Octahedral
– Square pyramidal
– Square planar
Molecular
Geometries
and Bonding
Theories
Molecular
Geometries
and Bonding
Theories
Electron domain geometry
Molecular geometry
Molecular
Geometries
and Bonding
Theories
Sample Exercise 9.2 Molecular Geometries of Molecules with
Expanded Valence Shells
SF4, (b) IF5.
Solution
Analyze The molecules are of the ABn type with a central p-block atom.
Plan We first draw Lewis structures and then use the VSEPR model to determine the electron-domain geometry and
molecular geometry.
Solve
(a) The Lewis structure for SF4 is
Continued
The sulfur has five electron domains around it: four from the S—F bonds and one from the nonbonding pair. Each
domain points toward a vertex of a trigonal bipyramid. The domain from the nonbonding pair will point toward an
equatorial position. The four bonds point toward the remaining four positions, resulting in a molecular geometry that
is described as seesaw-shaped:
Continued
Comment The experimentally observed structure is shown on the right. We can infer that
the nonbonding electron domain occupies an equatorial position, as predicted. The axial
and equatorial S—F bonds are slightly bent away from the nonbonding domain, suggesting
that the bonding domains are “pushed” by the nonbonding domain, which exerts a greater
repulsion (Figure 9.7).
(b) The Lewis structure of IF5 is
Continued
The iodine has six electron domains around it, one of which is
nonbonding. The electron-domain geometry is therefore
octahedral, with one position occupied by the nonbonding pair, and
the molecular geometry is square pyramidal (Table 9.3):
Shapes of Larger Molecules
For larger molecules,
look at the geometry
about each atom
rather than the
molecule as a whole.
Molecular
Geometries
and Bonding
Theories
Describing the Geometry
of Methanol
Molecular
Geometries
and Bonding
Theories
© 2015 Pearson Education, Inc. 35
Describing the Geometry
of Glycine
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Sample Exercise 9.3 Predicting Bond Angles
Eyedrops for dry eyes usually contain a water-soluble polymer called poly(vinyl
alcohol), which is based on the unstable organic molecule vinyl alcohol:
Predict the approximate values for the H—O—C and O—C—C bond angles in vinyl
alcohol.
Solution
Analyze We are given a Lewis structure and asked to determine two bond angles.
Plan To predict a bond angle, we determine the number of electron domains surrounding the middle atom in the bond.
The ideal angle corresponds to the electron-domain geometry around the atom. The angle will be compressed
somewhat by nonbonding electrons or multiple bonds.
Solve In H—O—C, the O atom has four electron domains (two bonding, two nonbonding). The electron-domain
geometry around O is therefore tetrahedral, which gives an ideal angle of 109.5°. The H—O—C angle is compressed
somewhat by the nonbonding pairs, so we expect this angle to be slightly less than 109.5°.
To predict the O—C—C bond angle, we examine the middle atom in the angle. In the molecule, there are three
atoms bonded to this C atom and no nonbonding pairs, and so it has three electron domains about it. The predicted
electron-domain geometry is trigonal planar, resulting in an ideal bond angle of 120°. Because of the larger size of the
C C domain, the bond angle should be slightly greater than 120°.
Sample Exercise 9.3 Predicting Bond Angles
Continued
Practice Exercise 1
The atoms of the compound methylhydrazine, CH 6N2, which is used as a rocket propellant, are connected as follows
(note that lone pairs are not shown):
What do you predict for the ideal values of the C—N—N and H—N—H angles, respectively?
(a) 109.5 and 109.5° (b) 109.5° and 120° (c) 120° and 109.5° (d) 120° and 120° (e) None of the above
Practice Exercise 2
Predict the H—C—H and C—C—C bond angles in propyne:
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
Molecular
molecule. Geometries
and Bonding
Theories
Tro: Chemistry:
Polarity of Molecules
• 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
42
Vector Addition
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Predicting Polarity of Molecules
1. Draw the Lewis structure and

determine the molecular geometry
2. Determine whether the bonds in the
molecule are polar
a) if there are not polar bonds, the
molecule is nonpolar
3. Determine whether the polar bonds
add together to give a net dipole
moment Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Molecular Inc. Approach, 2/e
Example 10.5: Predict whether NH3 is a polar
molecule
1. Draw the Lewis

structure and
determine the
molecular geometry
a) eight valence electrons
b) three bonding + one
lone pair = trigonal
pyramidal molecular
geometry Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
molecule
2. Determine if the bonds

are polar
a) electronegativity
difference
ENN = 3.0
b) if the bonds are not ENH = 2.1
polar, we can stop here 3.0 − 2.1 = 0.9
and declare the therefore the
molecule will be bonds are
nonpolar polar covalent
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
molecule
3) Determine whether
the polar bonds
add together to
give a net dipole
moment
a) vector addition
b) generally, The H─N bond is polar. All
the sets of bonding
asymmetric shapes
electrons are pulled toward
result in the N end of the molecule.
uncompensated The net result is a polar
Molecular
polarities and a net molecule. Geometries
and Bonding
dipole moment Theories
Tro: Chemistry:
Comparison of the
Polarity of Two Molecules
A NONPOLAR molecule A POLAR molecule
Molecular
Geometries
and Bonding
Theories
Molecular
Geometries
and Bonding
Theories
Molecular
Geometries
and Bonding
Theories
Practice – Decide whether the following
molecules are polar
EN
O = 3.5
N = 3.0
Cl = 3.0
S = 2.5
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Practice – Decide whether the following
molecules Are polar
Trigonal
Bent Trigonal
Planar
2.5
1. polar bonds, N-O

2. asymmetrical shape 1. polar bonds, all S-O
2. symmetrical shape
polar
nonpolar Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Molecular Polarity Affects
Solubility in Water
• Polar molecules are attracted
to other polar molecules
• Because 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 Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Sample Exercise 9.4 Polarity of Molecules
Predict whether these molecules are polar or nonpolar: (a) BrCl,
(b) SO2, (c) SF6.
Solution
Analyze We are given three molecular formulas and asked to predict whether the molecules are polar.
Plan A molecule containing only two atoms is polar if the atoms differ in electronegativity. The polarity of a molecule
containing three or more atoms depends on both the molecular geometry and the individual bond polarities. Thus, we
must draw a Lewis structure for each molecule containing three or more atoms and determine its molecular geometry.
We then use electronegativity values to determine the direction of the bond dipoles. Finally, we see whether the bond
dipoles cancel to give a nonpolar molecule or reinforce each other to give a polar one.
Solve
(a) Chlorine is more electronegative than bromine. All diatomic molecules with polar bonds are polar molecules.
Consequently, BrCl is polar, with chlorine carrying the partial negative charge:
The measured dipole moment of BrCl is μ = 0.57 D.
Continued
(b) Because oxygen is more electronegative than sulfur, SO 2 has polar bonds. Three resonance forms can be written:
For each of these, the VSEPR model predicts a bent molecular geometry. Because the molecule is bent, the bond
dipoles do not cancel, and the molecule is polar:
Continued
(c) Fluorine is more electronegative than sulfur, so the bond dipoles point toward fluorine. For clarity, only one S—F
dipole is shown. The six S—F bonds are arranged octahedrally around the central sulfur:
Because the octahedral molecular geometry is symmetrical, the bond dipoles cancel, and the molecule is nonpolar,
meaning that μ = 0.
Continued
Practice Exercise 1
Consider an AB3 molecule in which A and B differ in electronegativity. You are told that the
molecule has an overall dipole moment of zero. Which of the following could be the
molecular geometry of the molecule? (a) Trigonal pyramidal (b) Trigonal planar (c) T-
shaped (d) Tetrahedral (e) More than one of the above
Practice Exercise 2
Determine whether the following molecules are polar or nonpolar: (a) SF4, (b) SiCl4.
non-polar
polar
VSEPR and Hybrid Orbitals
VSEPR provides a simple mean for predicting
molecular geometries but does not explain why
bonds exist between atoms
Valence-Bond Theory
• In Valence-Bond Theory,
electrons of two atoms begin
to occupy the same space.
• This is called “overlap” of
orbitals.
• The sharing of space
between two electrons of
opposite spin results in a
covalent bond.
Molecular
Geometries
and Bonding
Theories
Overlap and Bonding
• Increased overlap brings
the electrons and nuclei
closer together until a
balance is reached
between the like charge Bond
strength
repulsions and the
electron-nucleus
attraction.
• Atoms can’t get too close
because the internuclear Bond length
repulsions get too great. Molecular

Geometries
and Bonding
Theories
VSEPR and Hybrid Orbitals
• VSEPR predicts shapes of molecules very well.
• How does that fit with orbitals?
• Let’s use H2O as an example:
• If we draw the best Lewis structure to assign
VSEPR, it becomes bent.
• If we look at oxygen, its electron configuration
is 1s22s22p4. If it shares two electrons to fill its
valence shell, they should be in 2p.
• Wouldn’t that make the angle 90°?
Molecular
• Why is it 104.5°? Geometries
and Bonding
Theories
Valence Bond Theory – Hybridization
• One of the issues that arises is that the
number of partially filled or empty atomic
orbitals did not predict the number of
bonds or orientation of bonds
– C = 2s22px12py12pz0 would predict two or three
bonds that are 90° apart, rather than four 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
Molecular
orbitals to get four orbitals that point at the Geometries
and Bonding
corners of a tetrahedron Theories
Unhybridized C Orbitals Predict the
Wrong Bonding & Geometry
Tro: Chemistry: A Molecular Approach, 2/e 67 Copyright  2011 Pearson Education, Inc.
Hybrid Orbitals
• Atomic orbitals are mathematical functions
that come from the quantum mechanical
model for atomic structure
• Hybrid orbitals form by “mixing” of atomic
orbitals to create new orbitals of equal energy,
called degenerate orbitals.
• When two orbitals “mix” they create two
orbitals; when three orbitals mix, they create
three orbitals; etc.
• The process of mixing is called hybridization
Molecular
Geometries
and Bonding
Theories
Hybridization
• Some atoms hybridize their orbitals to
maximize bonding
• more bonds = more full orbitals = more stability
• Hybridizing is mixing different types of orbitals
in the valence shell to make a new set of
degenerate orbitals
 sp, sp2, sp3
 Same type of atom can have different types of
hybridization
 C = sp, sp2, sp3
Valence Bond Theory
Main Concepts
1. The valence electrons of the atoms in a molecule reside in
quantum-mechanical atomic orbitals. The orbitals can be the
standard s, p, d, and f orbitals, or they may be hybrid
combinations of s and p orbitals.
2. A chemical bond results when these atomic orbitals interact

and there is a total of two electrons in the new molecular
orbital. The greater the overlap, the stronger the covalent
bond
a) the electrons must be spin paired
3. The shape of the molecule is determined by the geometry of

the interacting orbitals
Hybrid Orbitals
• The number of standard atomic orbitals
combined = the number of hybrid orbitals formed
 combining a 2s with a 2p gives two 2sp hybrid
orbitals
 H cannot hybridize!!
its valence shell only has one orbital
• 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
Be—sp hybridization
• When we look at the orbital diagram for beryllium
(Be), we see that there are only paired electrons in
full sub-levels.
• Be makes electron deficient compounds with two
bonds for Be. Why? sp hybridization (mixing of one
s orbital and one p orbital)

sp Orbitals
• Mixing the s and p orbitals yields two degenerate
orbitals that are hybrids of the two orbitals.
– These sp hybrid orbitals have two lobes like a
p orbital.
– One of the lobes is larger and more rounded,
as is the s orbital.
Molecular
Geometries
and Bonding
Theories
Position of sp Orbitals
• These two degenerate orbitals would align
themselves 180 from each other.
• This is consistent with the observed geometry of
Be compounds (like BeF2) and VSEPR: linear.
• According to the valence-bond model, a linear
arrangement of electron domains implies sp
hybridization
Molecular
Geometries
and Bonding
Theories
Boron—Three Electron Domains
Gives sp Hybridization
2
Using a similar model for boron leads to three

degenerate sp2 orbitals.
Molecular
Geometries
and Bonding
Theories
Carbon: sp Hybridization
3
With carbon,
we get four
degenerate
sp3 orbitals.
Molecular
Geometries
and Bonding
Theories
sp3 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
Molecular
Geometries
and Bonding
Theories
Orbital Diagram of the
sp3 Hybridization of C
Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
Carbon Hybridizations
Unhybridized   
2s 2p
sp hybridized    
2sp 2p
sp2 hybridized    
2sp2 2p
sp3 hybridized    
2sp3
Hypervalent Molecules
• The elements which have more than an octet
• Valence-Bond model would use d orbitals to make
more than four bonds.
• This view works for period 3 and below or the ones
obeying octet such as PF3 or H2Se
• Theoretical studies suggest that the energy needed
would be too great for this (SF6).
• A more detailed bonding view is needed than we
will use in this course.
Molecular
Geometries
and Bonding
Theories
What Happens with Water?
• We started this discussion
with H2O and the angle
question: Why is it 104.5°
instead of 90°?
• Oxygen has two bonds and

two lone pairs—four
electron domains.
• The result is sp3

Molecular
hybridization! Geometries
and Bonding
Theories
Hybrid Orbital Summary
1) Draw the Lewis
structure.
2) Use VSEPR to
determine the
electron-domain
geometry.
3) Specify the hybrid
orbitals needed to
accommodate these
electron pairs. Molecular
Geometries
and Bonding
Theories
Sample Exercise 9.5 Describing the Hybridization of a Central Atom
Describe the orbital hybridization around the central atom in NH2–.
Solution
Analyze We are given the chemical formula for a polyatomic anion and asked to describe the type of hybrid orbitals
surrounding the central atom.
Plan To determine the central atom hybrid orbitals, we must know the electron-domain geometry around the atom.
Thus, we draw the Lewis structure to determine the number of electron domains around the central atom. The
hybridization conforms to the number and geometry of electron domains around the central atom as predicted by the
VSEPR model.
Solve The Lewis structure is
Continued
Because there are four electron domains around N, the electron-domain geometry is tetrahedral. The hybridization that
gives a tetrahedral electron-domain geometry is sp3 (Table 9.4). Two of the sp3 hybrid orbitals contain nonbonding
pairs of electrons, and the other two are used to make bonds with the hydrogen atoms.
Continued
Practice Exercise 1
For which of the following molecules or ions does the following description apply? “The bonding can be explained
using a set of sp2 hybrid orbitals on the central atom, with one of the hybrid orbitals holding a nonbonding pair of
electrons.”
(a) CO2 (b) H2S (c) O3 (d) CO32– (e) More than one of the above
Practice Exercise 2
Predict the electron-domain geometry and hybridization of the central atom in SO 32–.
Types of Bonds
• How does a double or triple bond form?
• It can’t, if we only use hybridized orbitals.
• However, if we use the orbitals which are not
hybridized, we can have a “side-ways” overlap.
• Two types of bonds:
– Sigma (σ) bond
– Pi (π) bond
• The interaction between parallel orbitals is not
as strong as between orbitals that point at
each other; therefore s bonds are stronger Molecular
than p bonds
Geometries
and Bonding
Theories
Types of Bonds
• A sigma (s) bond results when the interacting
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 (p) 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 s bonds are stronger than p bonds Geometries
Molecular
and Bonding
Theories
Sigma () and Pi () Bonds
• Sigma bonds are characterized by

– head-to-head overlap.
– cylindrical symmetry of electron density
about the internuclear axis.
• Pi bonds are characterized by
– side-to-side overlap.
– electron density above and below the Molecular
Geometries
internuclear axis. and Bonding
Theories
Bonding in Molecules
• Single bonds are always σ-bonds.
• Multiple bonds have one σ-bond, all other bonds are π-bonds.
• π bonds make weaker overlap therefore, are weaker than σ
bonds
• σ bonds can rotate freely,π introduce rigidity to molecules
• Only atoms having sp and sp2 hybridization can form π bonds
• Double and triple bonds are more common in molecules made
up of period 2 atoms, C, N, O
Molecular
Geometries
and Bonding
Theories
C2H4 -
ethylene • The three bond angles
around about each carbon
120o
• Each carbon uses sp2
hybrid orbitals to form σ
bonds
• 1 electron remains in the
unhybridized 2p(pee-pie)
orbital
• 10 electrons σ, 2 π
electrons
Molecular
Geometries
and Bonding
Theories
C2H4 -
ethylene • We can not experimentally
observe a π bond directly
• The structure of ethylene
provides evidence for it
• C-C bond in ethylene (1.34
Å) is much shorter than a C-
C single bond (1.54 Å)
• All six atoms in C2H4 lie in
the same plane, because π
bonds enforce planarity and
rigidity
Molecular
Geometries
and Bonding
Theories
C2H2 - acetylene
• Linear geometry suggests

that each carbon uses sp
hybrid orbitals to form σ
bonds with the other carbon
and H
• 2 unhybridized 2p orbitals
remain – 2 pπ

Do you expect diazine to be linear
Do you expect diazine to be planar?

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 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 s or p
Practice – Predict the hybridization of all
the atoms in H3BO3
H = can’t hybridize
B = 3 electron groups = sp2
O = 4 electron groups = sp3
Practice – Predict the hybridization and
bonding scheme of all the atoms in NClO
•• •• ••
•O N Cl ••
•
•• ↑↓
s:Osp2─Nsp2
↑↓
N = 3 electron groups = sp 2 O ↑↓ N
↑↓ s:Nsp2─Clp
↑↓
O = 3 electron groups = sp2
Cl = 4 electron groups = sp3 ↑↓ Cl
O N
p:Op─Np
Cl
Sample Exercise 9.6 Describing σ and Π Bonds in a Molecule
Formaldehyde has the Lewis structure
Describe how the bonds in formaldehyde are formed in terms of

overlaps of hybrid and unhybridized orbitals.
Solution
Analyze We are asked to describe the bonding in formaldehyde in terms of hybrid orbitals.
Plan Single bonds are bonds, and double bonds consist of one σ bond and one π bond. The ways in which these bonds
form can be deduced from the molecular geometry, which we predict using the VSEPR model.
Continued
Solve The C atom has three electron domains around it, which suggests a trigonal-planar geometry with bond angles
of about 120°. This geometry implies sp2 hybrid orbitals on C (Table 9.4). These hybrids are used to make the two C—
H and one C—O σ bonds to C. There remains an unhybridized 2p orbital (a pπ orbital) on carbon, perpendicular to the
plane of the three sp2 hybrids.
Continued
The O atom also has three electron domains around it, and so we assume it has sp2 hybridization as well. One of these
hybrid orbitals participates in the C—O σ bond, while the other two hold the two nonbonding electron pairs of the O
atom. Like the C atom, therefore, the O atom has a pπ orbital that is perpendicular to the plane of the molecule. The
two pπ orbitals overlap to form a C—O π bond (Figure 9.25).
Continued
Practice Exercise 1
We have just arrived at a bonding description for the formaldehyde molecule. Which of the following statements about
the molecule is or are true?
(i) Two of the electrons in the molecule are used to make the π bond in the molecule.
(ii) Six of the electrons in the molecule are used to make the σ bonds in the molecule.
(iii) The C—O bond length in formaldehyde should be shorter than that in methanol, H 3COH.
(a) Only one of the statements is true.

(b) Statements (i) and (ii) are true.
(c) Statements (i) and (iii) are true.
(d) Statements (ii) and (iii) are true.
(e) All three statements are true.
Practice Exercise 2
(a) Predict the bond angles around each carbon atom in acetonitrile:
(b) Describe the hybridization at each carbon atom, and (c) determine the number of σ and π bonds in the molecule.
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 doesn’t predict perfectly
 magnetic behavior of O2
 Describing excited states
• In addition, VB theory presumes the electrons
are localized in orbitals on the atoms in the
molecule – it doesn’t account for delocalization
Localized or Delocalized
Electrons
• Bonding electrons (σ or π) that are
specifically shared between two atoms
are called localized electrons.
• In many molecules, we can’t describe all
electrons that way (resonance); the other
electrons (shared by multiple atoms) are
called delocalized electrons.
Benzene -30 ve
The organic molecule benzene (C6H6) has six -bonds
and a p orbital on each C atom, which form delocalized
bonds using one electron from each p orbital.
30 ve = 24 ve to form -
bonds
6 occupy 6 pπ – smeared
out among all 6 C’s
Delocalization provides
rigidity
Sample Exercise 9.7 Delocalized Bonding
Describe the bonding in the nitrate ion, NO3–. Does this ion have
delocalized π bonds?
Solution
Analyze Given the chemical formula for a polyatomic anion, we are asked to describe the bonding and determine
whether the ion has delocalized π bonds.
Plan Our first step is to draw Lewis structures. Multiple resonance structures involving the placement of the double
bonds in different locations would suggest that the π component of the double bonds is delocalized.
Solve In Section 8.6 we saw that NO3– has three resonance structures:
Continued
In each structure, the electron-domain geometry at nitrogen is trigonal planar, which implies sp2 hybridization of the N
atom. It is helpful when considering delocalized π bonding to consider atoms with lone pairs that are bonded to the
central atom to be sp2 hybridized as well. Thus, we can envision that each of the O atoms in the anion has three sp2
hybrid orbitals in the plane of the ion. Each of the four atoms has an unhybridized pπ orbital oriented perpendicular to
the plane of the ion.
The NO3– ion has 24 valence electrons. We can first use the sp2 hybrid orbitals on the four atoms to construct the three
N—O σ bonds. That uses all of the sp2 hybrids on the N atom and one sp2 hybrid on each O atom. Each of the two
remaining sp2 hybrids on each O atom is used to hold a nonbonding pair of electrons. Thus, for any of the resonance
structures, we have the following arrangement in the plane of the ion:
Notice that we have accounted for a total of 18 electrons—six in the three N—O σ bonds, and 12 as nonbonding pairs
on the O atoms. The remaining six electrons will reside in the π system of the ion.
Continued
The four pπ orbitals—one on each of the four atoms — are used to
build the p system. For any one of the three resonance structures
shown, we might imagine a single localized N—O π bond formed by
the overlap of the pπ orbital on N and a pπ orbital on one of the O
atoms. The remaining two O atoms have nonbonding pairs in their pπ
orbitals. Thus, for each of the resonance structures, we have the
situation shown in Figure 9.28. Because each resonance structure
contributes equally to the observed structure of NO 3–, however, we
represent the π bonding as delocalized over the three N—O bonds, as
shown in the figure. We see that the NO3– ion has a six-electron π
system delocalized among the four atoms in the ion.
Practice Exercise 1
How many electrons are in the π system of the ozone
molecule, O3?
(a) 2 (b) 4 (c) 6 (d) 14 (e) 18
Practice Exercise 2
Which of these species have delocalized bonding: SO 2, SO3, SO32–,
H2CO, NH4+?
Molecular Orbital (MO) Theory
• Describe the electrons in molecules using specific wave
functions, each of which is called molecular orbital
• Wave properties are used to describe the energy

of the electrons in a molecule.
• Molecular orbitals have many characteristics like atomic

orbitals:
– maximum of two electrons per orbital
– Electrons in the same orbital have opposite spin.
– Definite energy of orbital
– Can visualize electron density by a contour diagram
Molecular
Geometries
and Bonding
Theories
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 Molecular
Geometries
and Bonding
Theories
Tro: Chemistry:
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
- s, p
– 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 an
Antibonding Molecular Orbital
- s*, p*
– most of the electron density outside the nuclei
Molecular
– nodes between nuclei Geometries
and Bonding
Theories
More on MO Theory
• They differ from atomic orbitals because they
represent the entire molecule, not a single atom.
• Whenever two atomic orbitals overlap, two
molecular orbitals are formed: one bonding, one
antibonding.
• Bonding orbitals are constructive combinations of
atomic orbitals.
• Antibonding orbitals are destructive combinations
of atomic orbitals. They have a new feature unseen
before: A nodal plane occurs where electron
density equals zero. Molecular
Geometries
and Bonding
Theories
Molecular
Geometries
and Bonding
Theories
Molecular Orbital (MO) Theory
Whenever there is direct
overlap of orbitals,
forming a bonding and an
antibonding orbital, they
are called sigma (σ)
molecular orbitals. The
antibonding orbital is
distinguished with an
asterisk as σ*. Here is an
example for the formation
of a hydrogen molecule
from two atoms. Molecular
Geometries
and Bonding
Theories
MO Diagram
• An energy-level diagram,
or MO diagram shows how
orbitals from atoms combine
to give the molecule.
• In H2 the two electrons go
into the bonding molecular
orbital (lower in energy).
• Bond order = ½(# of
bonding electrons – # of
antibonding electrons) =
½(2 – 0) = 1 bond Molecular
Geometries
and Bonding
Theories
Stability of a covalent bond is
related Bond Order
Bond order = ½(# of bonding– # of antibonding electrons)
Bond order greater than zero = stable molecule
Bond order = 1, single bond
Bond order = 2, double bond
Bond order = 3, triple bond
Higher the bond order, shorter the bond length, higher the bond
enthalphy Molecular
Geometries
and Bonding
Theories
Can He2 Form? Use MO Diagram
and Bond Order to Decide!
• Bond Order = ½(2 – 2)
= 0 bonds
• Therefore, He2 does
not exist.
Molecular
Geometries
and Bonding
Theories
Sample Exercise 9.8 Bond Order
What is the bond order of the He2+ ion? Would you expect this ion
to be stable relative to the separated He atom and He+ ion?
Solution
Analyze We will determine the bond order for the He 2+ ion and use it to predict whether the ion is stable.
Plan To determine the bond order, we must determine the number of electrons in the molecule and how these
electrons populate the available MOs. The valence electrons of He are in the 1s orbital, and the 1s orbitals combine to
give an MO diagram like that for H2 or He2 (Figure 9.33). If the bond order is greater than 0, we expect a bond to
exist, and the ion is stable.
Continued
Solve The energy-level diagram for the He 2+ ion is shown in Figure 9.34. This ion has three electrons. Two are placed
in the bonding orbital and the third in the antibonding orbital. Thus, the bond order is
Because the bond order is greater than 0, we predict the He 2+ ion to be stable relative to the separated He and He +.
Formation of He2+ in the gas phase has been demonstrated in laboratory experiments.
Continued
Practice Exercise 1
How many of the following molecules and ions have a bond order of
: H2, H2+, H2–, and He22+?
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4
Practice Exercise 2
What are the electron configuration and the bond order of the H2–
ion?
Period 2 Diatomic Molecules
• The number of MOs formed equals the number of
atomic orbitals combined.
• Atomic orbitals combine most effectively with other
atomic orbitals of similar energy.
• The effectiveness with which two atomic orbitals
combine is proportional to their overlap with one
another; that is, as the overlap increases, the bonding
MO is lowered in energy, and the antibonding MO is
raised in energy.
Period 2 Diatomic Molecules
• Each molecular orbital can accommodate, at most,
two electrons, with their spins paired (Pauli exclusion
principle).
• When MOs have the same energy, one electron enters
each orbital (with the same spin) before spin pairing
occurs (Hund's rule).
To participate in molecular
orbitals, atomic orbitals must
overlap in space
2s orbitals overlap more
effectively, resulting in higher
energy difference between
bonding and anti-bonding orbitals
Figure 9-32 p431

Lithium Dilithium, Li2 Lithium
Atomic Molecular Atomic
Orbitals Orbitals Orbitals
BO = ½(4-2) = 1
Any fill energy level will

Because more electrons are generate filled bonding
in bonding orbitals than are in and antibonding MO’s;
antibonding orbitals, there is a therefore only need to
net bonding interaction consider valence shell
1s orbitals almost contribute

nothing to bonding
What about Be2
• Rule: Core electrons usually do not contribute significantly to
bonding in molecules
• Be 1s22s2
What about Be2
• Rule: Core electrons usually do not
contribute significantly to bonding in Li2
molecules, Be 1s22s2
Be2
s and p Orbitals Can Interact
• For atoms with both s and p
orbitals, there are two types
of interactions:
• The s and the p orbitals that
face each other overlap in 
fashion.
• The other two sets of p
orbitals overlap in  fashion
( molecular orbitals).
• These are, again, direct and
“side-ways” overlap of
orbitals.
σ
σ*
π π*
MO Theory
• The resulting MO diagram:
– There are σ and σ*
orbitals from s and p
atomic orbitals.
– There are π and π*
orbitals from p atomic
orbitals.
– Since direct overlap is
stronger, the effect of
raising and lowering
energy is greater for σ
and σ*.
MO Theory
• For many-electron atoms,
the 2s atomic orbitals are
lower in energy than the 2p
atomic orbitals.
Consequently, both of the
molecular orbitals that
result from the 2s orbitals,
the bonding 2p and
antibonding , are lower in
energy than the lowest-
energy MO that is derived
from the 2p atomic orbitals.
MO Theory
• The overlap of the two 2pz orbitals is greater
than that of the two 2px or 2py orbitals. As a
result, the bonding σ 2p MO is lower in energy
than the π2p MOs, and the antibonding σ*2p MO
is higher in energy than the π*2p MOs.
• Both the 2p and molecular orbitals are doubly

degenerate; that is, there are two degenerate
molecular orbitals of each type.
s and p Orbital Interactions
• In some cases, s orbitals can interact wit the pz

orbitals more than the px and py orbitals.
• It raises the energy of the pz orbital and lowers the
energy of the s orbital.
• The px and py orbitals are degenerate orbitals.
Section 9.2
The Molecular Orbital Model
What about B, 1s2 2s2 2p1

Section 9.2
p432
Section 9.2
p433
Section 9.2
Figure 9-35 p433

Figure 9-37 p434
MO Diagrams for Diatomic
Molecules of 2 Period Elements
nd
Molecular
Geometries
and Bonding
Theories
MO Diagrams and Magnetism
• Diamagnetism is the result of all electrons in
every orbital being spin paired. These substances
are weakly repelled by a magnetic field.
• Paramagnetism is the result of the presence of
one or more unpaired electrons in an orbital,
attracted to the magnetic field.
• The more unpaired electrons, stonger the attaction
• Is oxygen (O2) paramagnetic or diamagnetic? Look
back at the MO diagram! It is paramagnetic.
Molecular
Geometries
and Bonding
Theories
Measuring Magnetism
Molecular
Geometries
and Bonding
Theories
Paramagnetism of Oxygen
• Lewis structures would
not predict that O2 is
paramagnetic.
• The MO diagram
clearly shows that O2
is paramagnetic.
• Both show a double
bond (bond order = 2).
Molecular
Geometries
and Bonding
Theories
Sample Exercise 9.9 Molecular Orbitals of a Period 2 Diatomic Ion
For the O2+ ion predict (a) number of unpaired electrons, (b) bond
order, (c) bond enthalpy and bond length.
Solution
Analyze Our task is to predict several properties of the cation O 2+.
Plan We will use the MO description of O2+ to determine the desired properties. We must first determine the number
of electrons in O2+ and then draw its MO energy diagram. The unpaired electrons are those without a partner of
opposite spin. The bond order is one-half the difference between the number of bonding and antibonding electrons.
After calculating the bond order, we can use Figure 9.43 to estimate the bond enthalpy and bond length.
Molecular
Geometries
and Bonding
Theories
Continued
Solve
(a) The O2+ ion has 11 valence electrons, one fewer than O 2. The electron removed from O2 to form O2+ is one of the
two unpaired π*2p electrons (see Figure 9.43). Therefore, O 2+ has one unpaired electron.
(b) The molecule has eight bonding electrons (the same as O 2) and three antibonding electrons (one fewer than O 2).
Thus, its bond order is
(c) The bond order of O2+ is between that for O2 (bond order 2) and N2 (bond order 3). Thus, the bond enthalpy and
bond length should be about midway between those for O 2 and N2, approximately 700 kJ ⁄ mol and 1.15 Å. (The
experimentally measured values are 625 kJ ⁄ mol and 1.123 Å.)
Molecular
Geometries
and Bonding
Theories
Continued
Practice Exercise 1
Place the following molecular ions in order from smallest to largest bond order: C 22+, N2–, O2–, and F2–.
(a) C22+ < N2– < O2– < F2–

(b) F2– < O2– < N2– < C22+
(c) O2– < C22 + < F2– < N2–
(d) C22+ < F2– < O2– < N2–
(e) F2– < C22+ < O2– < N2–
Practice Exercise 2
Predict the magnetic properties and bond orders of (a) the peroxide ion, O22–; (b) the acetylide ion, C22–.
Answers: (a) diamagnetic, 1; (b) diamagnetic, 3
Molecular
Geometries
and Bonding
Theories
Heteronuclear Diatomic Molecules
• Diatomic molecules can consist
of atoms from different elements.
• How does a MO diagram reflect
differences?
• The atomic orbitals have different
energy, so the interactions
change slightly.
• The more electronegative atom
has orbitals lower in energy, so
the bonding orbitals will more
resemble them in energy. Molecular
Geometries
and Bonding
Theories
Heteronuclear Diatomic Molecules & Ions
• When the combining atomic orbitals are
identical and equal energy, the contribution of
each atomic orbital to the molecular orbital is
equal
• When the combining atomic orbitals are
different types and energies, the atomic
orbital closest in energy to the molecular
orbital contributes more to the molecular
orbital
Heteronuclear Diatomic Molecules & Ions
• The more electronegative an atom is, the
lower in energy are its orbitals
• Lower energy atomic orbitals contribute
more to the bonding MOs
• Higher energy atomic orbitals contribute
more to the antibonding MOs
• Nonbonding MOs remain localized on the
atom donating its atomic orbitals
NO
a free radical
s2s Bonding MO BO = ½(6 be – 1 abe)

BO = 2.5
shows more
electron density
near O because
it is mostly O’s
2s atomic orbital
HF
READING ASSIGMENT
• READ :Closer look on page 417-418

• Chemistry put to work on page 423
Molecular
Geometries
and Bonding
Theories

Chapter 9

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Lecture Presentation

This is the Molecular

• The arrangement of electron domains about the

• The arrangement of only the atoms in a molecule

• Once you have determined the electron-domain

• In the linear domain, there is only one

• There are two molecular geometries:

• There are three molecular geometries:

(b) The Lewis structure for SnCl3– is

Predict the electron-domain and molecular geometries for (a)

SO3 , AlCl3 and CH3+

• There are two distinct positions in

(b) The Lewis structure of IF5 is

The H─Cl bond is polar. The bonding

1. Draw the Lewis structure and

1. Draw the Lewis

2. Determine if the bonds

1. polar bonds, N-O

The measured dipole moment of BrCl is μ = 0.57 D.

repulsions get too great. Molecular

2. A chemical bond results when these atomic orbitals interact

3. The shape of the molecule is determined by the geometry of

© 2015 Pearson Education, Inc.

Using a similar model for boron leads to three

• Oxygen has two bonds and

• The result is sp3

Solve The Lewis structure is

• A pi (p) bond results when the bonding atomic

• The interaction between parallel orbitals is not as

• Sigma bonds are characterized by

• Linear geometry suggests

© 2015 Pearson Education, Inc.

© 2015 Pearson Education, Inc.

Describe how the bonds in formaldehyde are formed in terms of

(a) Only one of the statements is true.

• Wave properties are used to describe the energy

• Molecular orbitals have many characteristics like atomic

• When the wave functions combine destructively,

Bond order greater than zero = stable molecule

Bond order = 1, single bond

Bond order = 2, double bond

Bond order = 3, triple bond

(a) 0 (b) 1 (c) 2 (d) 3 (e) 4

Figure 9-32 p431

Any fill energy level will

1s orbitals almost contribute

• Both the 2p and molecular orbitals are doubly

• In some cases, s orbitals can interact wit the pz

What about B, 1s2 2s2 2p1

Figure 9-35 p433

(a) C22+ < N2– < O2– < F2–

Answers: (a) diamagnetic, 1; (b) diamagnetic, 3

s2s Bonding MO BO = ½(6 be – 1 abe)

• READ :Closer look on page 417-418

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