Petrucci • Harwood • Herring • Madura

Ninth and

GENERAL
Tenth
Edition

CHEMISTRY
Principles and Modern Applications

Chapter 10: Chemical Bonding I:

Basic Concepts

Slide 1 General Chemistry: Chapter 10

 Contents
10-1 Lewis Theory: An Overview
10-2 Covalent Bonding: An Introduction
10-3 Polar Covalent Bonds
10-4 Writing Lewis Structures
10-5 Resonance
10-6 Exceptions to the Octet Rule
10-7 The Shapes of Molecules
10-8 Bond Order and Bond Lengths
10-9 Bond Energies

➢ Focus On Molecules in Space: Measuring Bond Lengths

Slide 2 General Chemistry: Chapter 10

 In this chapter, we will describe the interactions
between atoms called chemical bonds.

Most of the discussion centers on the Lewis

theory, which provides one of the simplest
methods of representing chemical bonding.

We will also explore another relatively simple

theory, one for predicting probable molecular
shapes.

Slide 3 General Chemistry: Chapter 10

 Throughout the chapter, we will try
to relate these theories to what is
known about molecular
structures from experimental
measurements.

Slide 4 General Chemistry: Chapter 10

 10-1 Lewis Theory: An Overview
1916 to 1919, G. N. Lewis and Irving Langmuir, and a
German, Walther Kossel, advanced an important proposal
about chemical bonding:

Something unique in the electron

configurations of noble gas atoms accounts
for their inertness, and atoms of other
elements combine with one another to
acquire electron configurations like those
of noble gas atoms.
The theory that grew out of this model has been most closely
associated with G. N. Lewis and is called the Lewis theory.
Some fundamental ideas of the theory:

 Valence e- play a fundamental

role in chemical bonding.
 e- transfer leads to
ionic bonds.
 Sharing of e- leads to covalent
bonds.
e- are transferred or shared to
give each atom a noble gas
configuration:
the octet.
Slide 6 General Chemistry: Chapter 10
 Lewis developed a special set of symbols
for his theory.

A Lewis symbol consists of a chemical symbol

to represent the nucleus and core (inner-shell)
electrons of an atom, together with dots placed
around the symbol to represent the
valence(outer-shell) electrons.

Slide 7 General Chemistry: Chapter 10

 Lewis Symbols

A chemical symbol represents the nucleus

and the core e-.
Dots around the symbol represent valence e-.
•
• Si •
•
•• •• •• •• ••
•N• • P• • As • • Sb • • Bi •
• • • • •

•• •• ••
• Al • • Se I • Ar

••
••
•
••

• • •• ••

Slide 8 General Chemistry: Chapter 10

 Electron Configurations and the Periodic Table

Slide 9 of 50 General Chemistry: Chapter 8

A Lewis structure
is a combination of Lewis symbols that represents
either the transfer or the sharing of electrons in a
chemical bond.

Slide 10 General Chemistry: Chapter 10

Slide 11 General Chemistry: Chapter 10
 . ..
.Mg. . Ge .
.
K. :Ne :
..

Slide 12 General Chemistry: Chapter 10

 - 2-
   
.Tl.
. .. ..
+
.Sn . : Br :
 ..  : S :
 .. 
.

Slide 13 General Chemistry: Chapter 10

EXAMPLE 10-2
Writing Lewis Structures of Ionic Compounds. Write Lewis
structures for the following compounds: (a) BaO; (b) MgCl2 ;
(c) aluminum oxide.

• •• 2+ •• 2-
BaO Ba• • O• Ba O

••
••
•• ••

Note the use of the “fishhook” arrow to denote a

single electron movement. A “double headed”
arrow means that two electrons move.

Slide 14 General Chemistry: Chapter 10

EXAMPLE 10-2
••
• Cl

••
• •• 2+ •• -
MgCl2 Mg • Mg 2 Cl

••
••
•• ••
• Cl

••
••

Slide 15 of 50 General Chemistry: Chapter 10

Na. - 1e- → Na  .Mg. - 2e- → Mg 
+ 2+

2- 3-
..
  .. .
  ..
. S . + 2e- → : S : . N . + 3e- → : N :
..  ..  ..  .. 
Lewis structure is
2- 3− 3−
     
Na  : S.. : Na  Mg Mg Mg
.. .. ..
+ + 2+ 2+ 2+

  : N :
..  : N :
.. 

Slide 17 General Chemistry: Chapter 10

 .Ca. - 2e- → Ca  .Ba. - 2e- → Ba 
2+ 2+

- 2-
..
  .. ..
  ..
: I . + 1e- → : I : . S . + 2e- → : S :
..  ..  ..  .. 
Lewis structure is
- - 2-
 ..  2+    .. 
: I.. : Ca  : I.. : Ba 
..
2+
: S.. :

Slide 18 General Chemistry: Chapter 10

 Electron Configurations and the Periodic Table

Slide 19 of 50 General Chemistry: Chapter 8

A chlorine atom shows a tendency to gain an electron, as
indicated by its electron affinity (-349 kJ/mol).

A hydrogen atom in the gaseous state does not give up an

electron to another nonmetal atom. Bonding
between a
hydrogen atom and a chlorine atom involves the
sharing of electrons, which leads to a covalent
bond.
 10-2 Covalent Bonding: An Introduction

Slide 21 General Chemistry: Chapter 10

Slide 22 General Chemistry: Chapter 10
 H
.. .. I
: Br Br : H C H
.. .. I
H

.. ..
H O Cl :
.. ..

Slide 23 General Chemistry: Chapter 10

 .. .. .. .. ..
:I N I: H N N H
.. I .. I I
I H H

H H
I I
H C C H
I I
H H
Slide 24 General Chemistry: Chapter 10
 Coordinate Covalent Bonds

A covalent bond in which a single atom contributes

both of the electrons to a shared pair is called a
coordinate covalent bond.
+
H H
•• -
H N H Cl H N H Cl

••
••

••
••
H H

Note the “double headed” arrow

showing that two electrons move.
Slide 25 General Chemistry: Chapter 10
 Multiple Covalent Bonds
Often, however, more than one pair of electrons must be
shared if an atom is to attain an octet. CO2 and N2 are two
molecules in which atoms share more than one pair of
electrons.

• • • • • •
O• •O O C O
••

• C•
••

••
••
•• • •• •• • ••

• • • •• ••
O C O O C O
••

••

•• • •• •• ••

Slide 26 General Chemistry: Chapter 10

 Multiple Covalent Bonds

• • • •
N• •N N N

••
••
••

••
• • • •

•
N N N N

••
••

••
• ••

The triple covalent bond in N2 is a very strong bond that is

difficult to break in a chemical reaction. The unusual strength of
this bond makes N2 (g) quite inert.
 Paramagnetism of Oxygen
Liquid oxygen is attracted into the
magnetic field of a large magnet.

Because of this there is some doubt

about the validity of structure

Slide 28 General Chemistry: Chapter 10

 As summary,

Ionic and covalent bonds are different: ionic

bonds involving a complete transfer of
electrons and covalent bonds involving an
equal sharing of electron pairs.

Most chemical bonds fall between the two

extremes of 100% ionic and 100% covalent.

Slide 29 General Chemistry: Chapter 10

 10-3 Polar Covalent Bonds and
Electrostatic Potential Maps
A covalent bond in which electrons are not
shared equally between two atoms is called
a polar covalent bond.

In which, electrons are displaced toward the

more nonmetallic element. This leads to a partial
negative charge on the more nonmetallic
element,

Slide 30 General Chemistry: Chapter 10

Slide 31 of 50 General Chemistry: Chapter 10
The computers has allowed chemists to develop
methods for displaying the electron distribution
within molecules.

This distribution is obtained, in principle, by

solving the Schrödinger equation for a molecule.

Although the solution can be obtained only by using

approximate methods, these methods provide an
electrostatic potential map, a way to visualize the
charge distribution within a molecule.
 The electrostatic potential at
any point on the charge
density surface of a
molecule is defined as the
change in energy that
occurs when a unit positive
charge is brought to this
point, starting from another
point that is infinitely far
removed from the molecule.

The electrostatic potential

FIGURE 10-4 Determination of the map gives information about
electrostatic potential map for the distribution of electron
ammonia charge within this surface.
Slide 33 General Chemistry: Chapter 10
For example, in a neutral molecule, if the potential
at a point is positive, it is likely that an atom at this
point carries a net positive charge.

An arbitrary rainbow color scheme is adopted in the display

of an electrostatic potential map.

• Red, the low-energy end of the spectrum, is

used for regions of the most negative
electrostatic potential,
• Blue is used to color regions of the most
positive electrostatic potential.
• Intermediate colors represent intermediate
values of the electrostatic potential.
 Thus, the potential increases from red
through yellow to blue, as seen in the
scale in the Figure.

For example,
the blue-green color surrounding the
hydrogen atoms in the figure suggests that
they carry a slight positive charge.

The nitrogen atom, being closest to the

red region, carries a net negative charge.

Slide 35 General Chemistry: Chapter 10

The electrostatic potential
maps for sodium chloride,
hydrogen chloride, and
chlorine.
The dark red and dark blue
on the electrostatic potential
map correspond to the
extremes of the electrostatic
potential, negative to
positive.

In the maps shown here the

range is to -250 to 750 kJ
mol-1.
• Cl2 has a uniform distribution of electron charge
density and uniform color distribution in the
electrostatic potential map.

• NaCl : non uniform distribution of electron charge

density. The sodium atom is in the blue extreme of
positive charge and the chlorine in the red extreme of
negative charge (an ionic bond), (80% ionic).

• HCl has an unsymmetrical distribution of electron

charge density (the gradation of color in the
electrostatic potential map). This depicts the polar
nature of the bond in HCl.
Electronegativity (EN)

describes an atom’s ability to compete for

electrons with other atoms to which it is
bonded.

As such, electronegativity is related to

• ionization energy (I)
• electron affinity (EA)

Slide 38 General Chemistry: Chapter 10

To see how they are related consider the reaction
between two hypothetical elements, A and B, which
could give the products A+B- or A-B+ .
An element with a high ionization energy and an
electron affinity that is large and negative, such as
fluorine, will have A large electronegativity

Slide 40 General Chemistry: Chapter 10

 Electronegativity
One widely used electronegativity scale

As a general rule, electronegativities decrease from top to bottom

in a group and increase from left to right in a period of elements
(L Pauling, 1901-1994).
 Percent Ionic Character
If for two atoms ΔEN is very small, the bond between them
is essentially covalent. If ΔEN is large, the bond is
essentially ionic. For intermediate values of ΔEN the bond is
described as polar covalent.

FIGURE 10-7
Percent ionic
character of a
chemical bond as
a function of
electronegativity
difference
So, electronegativity values give information on
the amount of polar character in a covalent bond
based on electronegativity difference.

For two atoms,

If ΔEN is very small, the bond between them is
essentially covalent (for nonmetal atoms).
.

If ΔEN is large, the bond is essentially ionic (for more

metallic and more nonmetallic elements)
For intermediate values of the bond is described as polar
covalent. (Figure 10-7).
Slide 44 of 50 General Chemistry: Chapter 10
The variation of bond polarity with electronegativity
using electrostatic potential maps,

The gradation of the charge on the H atom ranges from

quite positive in HCl to less positive in HBr and HI, (the
gradation of color on the H atom from dark blue to pale blue).

This trend of decreasing charge separation in these three

molecules corresponds to the decrease in electronegativity
of the halogen atoms from Cl to Br to I.
Electronegativities
H = 2.1 Br = 2.8 N = 3.0 O = 3.5 P = 2.1 Cl = 3.0
Bonds

H Br N H N O P Cl

EN values : 0.7 0.9 0.5 0.9

Therefore N - H bond is the most polar bond

Slide 46 General Chemistry: Chapter 10

Electronegativities
C = 2.5 S = 2.5 P = 2.1 O = 3.5 F = 4.0
Bonds

C S C P P O O F

EN values : 0.0 0.4 1.4 0.5

Therefore P - O bond is the most polar bond

Slide 47 General Chemistry: Chapter 10

Slide 48 General Chemistry: Chapter 10
 IBr IF

From the relative sizes of each ion it is evident that the one on
the right with small red end should be IF and
the one on the left should be IBr

Slide 49 General Chemistry: Chapter 10

Slide 50 of 50 General Chemistry: Chapter 10
 CH3OH
CH3SH

From the relative sizes of each atom it is evident that the one on
the left with small red end should be CH3OH and
the one on the right should be CH3SH

Slide 51 General Chemistry: Chapter 10

 10-4 Writing Lewis Structures

All the valence e- of atoms must appear.

Usually, all the electrons in a Lewis
structure are paired.
Usually, each atom requires an octet.
H only requires 2 e-.
Multiple bonds may be needed.
Readily formed by C, N, O, S, and P.

Slide 52 General Chemistry: Chapter 10

 Skeletal Structure

Identify central and terminal atoms.

H H
H C C O H
H H

Slide 53 General Chemistry: Chapter 10

 Skeletal Structure

Hydrogen atoms are always terminal atoms.

Central atoms are generally those with the
lowest electronegativity.
Carbon atoms are always central atoms.
Generally structures are compact and
symmetrical.

Slide 54 General Chemistry: Chapter 10

 Strategy for
Writing Lewis
Structures

Slide 55
Slide 56 General Chemistry: Chapter 10
Slide 57 of 50 General Chemistry: Chapter 10
C has 4 valence electronsand each S has 6 valence electrons
.. .. .. ..
4 + 2x6 = 16 ve - :S C S: S=C=S
.. .. .. ..
For HCN

1 + 4 + 5 = 10 ve - H C  N:

For COCl 2
:O:
.. II ..
4 + 6 + 2 x7 = 24 ve - : Cl C Cl :
.. ..

Slide 58 General Chemistry: Chapter 10

 For formic acid
:O:
II ..
H C O H
..

For acetaldehyde
H :O:
I II
H C C H
I
H

Slide 59 General Chemistry: Chapter 10

EXAMPLE10-7
Writing a Lewis Structure for a Polyatomic Ion. Write the
Lewis structure for the nitronium ion, NO2+.

Step 1: Total valence e- = 5 + 6 + 6 – 1 = 16 e-

Step 2: Identify the central and terminal atoms

Step 3: Plausible structure: O—N—O

•• ••
Step 4: Add e- to terminal atoms: O—N—O

••
••
•• ••

Slide 60 General Chemistry: Chapter 10

EXAMPLE 10-7

Step 5: Determine e- left over: 16 – 4 – 12 = 0

Step 6: Use multiple bonds to satisfy octets.

+
•• •• •• ••
O—N—O O=N=O
••
••

•• •• •• ••

Slide 61 General Chemistry: Chapter 10

 For NO +

:N  O:
For N 2 H 5+
H H
I I

H N N:
I I
H H
For O 2-

..
: O :2-
..
Slide 62 General Chemistry: Chapter 10
For BF4- For NH 3OH +
..
:F: H
.. I .. ..I
+
:F B − F: -
H N O H
.. I .. I
:F: H ..
..

For NCO -
.. .. .. .. -
:- N = C = O : : N- C  O + :
2-
: N  C-O :
.. ..

a b c
Slide 63 General Chemistry: Chapter 10
Slide 64 General Chemistry: Chapter 10
 Formal Charge

A formal charge (FC) is the charge assigned to

an atom in a molecule, assuming that electrons in
all chemical bonds are shared equally between
atoms, regardless of relative electronegativity.

When determining the best Lewis structure (or

predominant resonance structure) for a molecule,
the structure is chosen such that the formal charge
on each of the atoms is as close to zero as possible.

Slide 65 General Chemistry: Chapter 10

 1
FC = #valence e- - #lone pair e- - #bond pair e-
2

•• + ••
O=N=O
•• ••

1
FC(O) = 6 - 4 – (4) = 0
2
1
FC(N) = 5 - 0 – (8) = +1
2

Slide 66 General Chemistry: Chapter 10

 If an atom needs to donate more
electrons than normal in order for
everyone to get an octet, it will have
a positive formal charge.

If an atom donates fewer electrons than

normal and everyone still has an octet, it
must be getting extra electrons from
somewhere else. It will have a negative
formal charge.

Slide 67 General Chemistry: Chapter 10

 Alternative Lewis Structure

•• •• + + •• -
O—N—O O N O

••
••

••
••
•• •• ••

1
FC(O≡) = 6 - 2 – (6) = +1
2
1
FC(N) = 5 - 0 – (8) = +1
2
1
FC(O—) = 6 - 6 – (2) = -1
2

Slide 68 General Chemistry: Chapter 10

 General rules
• Sum of FC is the overall charge. The sum of the FC in a
Lewis structure must equal zero for a neutral molecule and must
equal the magnitude of the charge for a polyatomic ion.
 FC should be as small as possible.
 Negative FC usually on most electronegative elements.
 FC of same sign on adjacent atoms is unlikely.

+ + •• -
O≡N—O ••
••

••

Slide 69 General Chemistry: Chapter 10

EXAMPLE 10-8
Using the Formal Charge in Writing Lewis Structures. Write
the most plausible Lewis structure of nitrosyl chloride, NOCl,
one of the oxidizing agents present in aqua regia.

2+ 2- - 2+ - - +

Slide 70 General Chemistry: Chapter 10

 .. .. .. .. .. .. .. ..
: N − O − Cl : → : N − O− Cl : → : N = O− Cl :
.. .. .. .. − + ..

When we must choose among several lewis structures

with similar distributions of formal charges, the structure
with the negative formal charges on the more
electronegative atoms is preferable.

Slide 71 General Chemistry: Chapter 10

 Best structure has

• Most atoms with zero formal charge

• Lowest magnitude of formal charges

• If there is negative formal charge, it is

on the most electronegative atom.

Slide 72 of 50 General Chemistry: Chapter 10

Slide 73 General Chemistry: Chapter 10
 In other words
Using Formal Charges
to Identify viable
Resonance Structures

[Link] greater the number of covalent bonds,

the greater the stability since more atoms will
have complete octets.
[Link] structure with the least number of
formal charges is more stable.
[Link] structure with the least separation of
formal charge is more stable.

Slide 74 General Chemistry: Chapter 10

 In other words
Resonance Structures
[Link] most stable resonance
structure will have a full octet on
every atom.
[Link] most stable resonance
structure will have the smallest
possible number of charges.
[Link] most stable resonance
structure will have negative
charges on the most
electronegative atoms and
positive charges on the least
electronegative atoms.

Slide 75 General Chemistry: Chapter 10

 .. .. ..
H - N- C - N → H - N- C - N → → H - N- C - N :
I I I ..
H H H
a
.. .. .. ..  .. -
→ H - N- C- N : → H - N- C  N : → H-N = C = N
I I I ..
H H H
b c d
  .. 2-
H-N = N =C
I ..
H
Slide 76 General Chemistry: Chapter 10
 10-5 Resonance
•• ••+ •• - - •• ••+ ••
O O O O O O

••
••
•• •• •• ••

-½ •• ••+ •• -½
O
••
O O
••

Many Lewis structures may be written for a given structure..

Ozone has two good possibilities, but neither gives the correct
structure that has two equivalent O-O bonds.
Slide 77 General Chemistry: Chapter 10
Slide 78 General Chemistry: Chapter 10
Slide 79 General Chemistry: Chapter 10
The situation in which two or more plausible Lewis
structures contribute to the correct structure is called
resonance. The true structure is a resonance hybrid
of plausible contributing structures.

Acceptable contributing structures to a

resonance hybrid must all have the same
skeletal structure (the atomic positions
cannot change); they can differ only in
how electrons are distributed within the
structure.
Slide 80 General Chemistry: Chapter 10
Slide 81 General Chemistry: Chapter 10
A resonance hybrid is a compound, molecule, ion, or
radical exhibiting resonance and having a structure
represented in the written form as the average of two or
more structural formulas separated each from the next
by a double-headed arrow
 .. .. .. .. − .. .. .. .. ..
: O− S− O : → : O − S = O : (a) → : O = S− O : (b) -
.. .. ..   ..

.. − .. .. .. .. ..
:O −S = O:  : O = S− O : -
..   ..

.. .. ..
: O− S− O :

Slide 83 General Chemistry: Chapter 10

Slide 84 General Chemistry: Chapter 10
 10-6 Exceptions to the Octet Rule

Odd e- species.

•• ••
N=O

•
••

H
••
H—C—H O—H

•
••
•

Slide 85 General Chemistry: Chapter 10

 Exceptions to the Octet Rule

Incomplete octets.

•• •• ••

••
••
F F F

••
••

••
••

- +
B B B
-
F F + F F F F

The number of species with incomplete octets is limited to some

beryllium, boron, and aluminum compounds. Perhaps the best
examples are the boron hydrides. (Chapter 22).
 Exceptions to the Octet Rule
Expanded octets.
•• •• ••
F

••
••
Cl •• Cl
••

••
••
Cl F F
Cl
P P S
Cl Cl Cl Cl F F
F

••
••
••

There are a few Lewis structures that break the octet

rule by having 10 or even 12 valence electrons around
the central atom, creating an expanded valence shell.

Slide 87 General Chemistry: Chapter 10

 Molecules with expanded valence shells typically involve
nonmetal atoms of the third period and
beyond that are bonded to highly electronegative atoms.

Slide 88 General Chemistry: Chapter 10

 Expanded Valence Shell
Expanded valence shells have also been used to give a better
Lewis structure than strict adherence to the octet rule,

Slide 89 General Chemistry: Chapter 10

The argument for including the expanded valence-shell
structure is that it reduces formal charges.

Experimentally determined sulfur-to-oxygen bond lengths in SO42- and

H2SO42- are in agreement with this idea as follows.

Slide 90 General Chemistry: Chapter 10

 Experimental evidence appears to support using
an expanded valence shell in the Lewis
structure of sulfuric acid.

Slide 91 General Chemistry: Chapter 10

The problem with expanded valence-shell structures is, of
course,
to explain where the extra electrons go.
After the 3s and 3p subshells of the central atom fill to
capacity (eight electrons), extra electrons go into the empty
3d subshell.

If we assume that the energy difference between the 3p and

3d levels is not very large, the valence-shell expansion
scheme seems reasonable. But is this a valid assumption?

We will return to this topic, together with several other

unsettled issues, in Chapter 11.
 10-7 The Shapes of Molecules

Bond lengths are measured in the solid

phase by x-Ray diffraction or
approximated in the gas phase by
Slide 93 microwave spectroscopy.
The experimentally determined shape of the molecule is
not linear. The molecule is bent.

Does it really matter whether it is bent or linear? Yes.

• The bent shape accounts for the fact that

water is a liquid rather than a gas at room
temperature (Chapter 12)
• It also accounts for the ability of liquid water
to dissolve so many different substances
(Chapter 13).
 ➢ All diatomic molecules are linear.

➢ A triatomic molecule has two bonds and one bond

angle. If the bond angle is 180o the three atoms lie
on a straight line, and the molecule is linear.

➢ For any other bond angle, a triatomic molecule is

said to be angular, bent, or V-shaped.

➢ Some polyatomic molecules (more than three

atoms) have planar or even linear shapes.

Slide 95 General Chemistry: Chapter 10

 Terminology

 Bond length – distance between nuclei.

 Bond angle – angle between adjacent bonds.
 valence-shell electron-pair repulsion theory, VSEPR
Theory
Electron pairs repel each other whether they are bond pairs or
lone pairs. Electron pairs assume orientations about an atom to
minimize repulsions.
 Electron group geometry – distribution of e- pairs.
 Molecular geometry – distribution of nuclei.

Slide 96 General Chemistry: Chapter 10

 The shape of a molecule is established by
experiment or by a quantum mechanical
calculation confirmed by experiment.

The results of these experiments and

calculations are generally in good
agreement with the VSEPR.

In VSEPR theory, we focus on pairs of

electrons in the valence electron shell
of a central atom in a structure.
Slide 97 General Chemistry: Chapter 10
 Balloon Analogy
Balloon analogy to valence-
shell electron-pair repulsion.

When two elongated balloons

are twisted together, they
separate into four lobes. To
minimize interferences, the
lobes spread out into a
tetrahedral pattern.

(A regular tetrahedron has

four faces, each an equilateral
triangle.) General Chemistry: Chapter 10
Another aspect of VSEPR theory is a focus
not just on electron pairs but on electron
groups.

A group of electrons can be

 a pair, either a lone pair or a bond pair, or

 it can be a single unpaired electron on an atom
with an incomplete octet, as in NO.
 A group can also be a double or triple bond
between two atoms.

Slide 99 General Chemistry: Chapter 10

 Thus in the molecule,

the central C atom has two electron

groups in its valence shell.

Each of the double bonds with its

two electron pairs is treated as one
electron group.

Slide 100 General Chemistry: Chapter 10

Consider the methane molecule,

What orientation will the four electron

groups (bond pairs) assume?
The balloon analogy suggests that
electron-group repulsions will force the
groups as far apart as possible to the
corners of a tetrahedron having the C
atom at its center.

The VSEPR method predicts,

correctly, that is a tetrahedral molecule.

Slide 101 General Chemistry: Chapter 10

Representation of the
three-dimensional shape of
molecule on a sheet of
paper? Enclosed methane
molecule in a tetrahedron (red
lines).

We see that the C-H bonds point to

the vertices of the tetrahedron. Any
two of the C-H bonds define a
plane,

we choose two bonds (blue) to represent three-dimensional

lie in the plane of the page. structures of molecules
 The symbolism is based on
the following conventions:

• Ordinary lines to represent

bonds that lie in the plane of
the paper.
• Solid wedges to represent
bonds that point toward the
viewer, that is, in front of the
plane of the paper.
• Dashed wedges to represent
bonds that point away from the
viewer, that is, behind the
plane of the paper.

Slide 103 General Chemistry: Chapter 10

In NH3 and H2O the central atom is also surrounded
by four groups of electrons, but these molecules do
not have a tetrahedral shape.

VSEPR theory predicts the

distribution of electron groups,
and in these molecules, electron
groups are arranged
tetrahedrally about the central
atom. The shape of a molecule,
however, is determined by the
location of the atomic nuclei.
 To avoid confusion, we will call
the geometric distribution of
electron groups the electron-group
geometry

the geometric arrangement of the

atomic nuclei the actual
determinant of the molecular shape
the molecular geometry.

Slide 105 General Chemistry: Chapter 10

 In the NH3 molecule, only three of the electron
groups are bond pairs; the fourth is a lone pair.
Joining the N nucleus to the H nuclei by straight
lines outlines a pyramid with the N atom at the
apex and the three H atoms at the base; it is
called a trigonal pyramid.

We say that the electron-group geometry

is tetrahedral and the molecular
geometry is trigonal-pyramidal.

Slide 106 General Chemistry: Chapter 10

In the H2O molecule, two of the four
electron groups are bond pairs and two are
lone pairs. The molecular shape is obtained
by joining the two H nuclei to the O nucleus
with straight lines.

The electron-group geometry is

tetrahedral and the molecular
geometry is V-shaped, or bent.
 Methane, Ammonia and Water

Moleculer tetrahedral trigonal pyramidal bent Shape

Molecular geometries
Slide 108 General Chemistry: Chapter 10
 So, the symbol AX2E2 signifies
that
• two atoms or groups (X) are bonded to
the central atom (A).

• The central atom also has two lone pairs

of electrons (E).

• H2O is an example of a molecule of the

type.

Slide 109 General Chemistry: Chapter 10

 Molecular shapes based on tetrahedral electron-
group geometry of CH4 NH3 and H2O.

1. All three molecules have a tetrahedral arrangement of

electron groups around the central atom.

2. However, molecular shapes (or molecular geometries)

are established by focusing only on the positions of
the atoms.

Slide 110 General Chemistry: Chapter 10

 CH4, there are no lone pairs and the C atom
sits at the center of a tetrahedron; the molecular
shape is tetrahedral.

NH3, a lone pair on the N atom, the N atom is

the vertex in a pyramid having a triangular
base; the molecular shape is trigonal
pyramidal.

H2O, the O and H atoms form a V-shape and

the molecular shape is V-shaped or bent.

Slide 111 General Chemistry: Chapter 10

Possibilities for Electron-Group Distributions
The most common situations are those in which central atoms
have two, three, four, five, or six electron groups distributed
around them.

Electron-group geometries
• two electron groups:
linear
• three electron groups:
trigonal planar
• four electron groups:
tetrahedral
trigonal-planar (orange), tetrahedral (gray),
• five electron groups: trigonalbipyramidal (pink), and octahedral
trigonal bipyramidal (yellow).
• six electron groups:
octahedral
 Table 10.1 Molecular Geometry as a
Function of Electron Group Geometry

Slide 113 General Chemistry: Chapter 10

 Applying VSEPR Theory

 Draw a plausible Lewis structure.

 Determine the number of e- groups and identify
them as bond or lone pairs.
 Establish the e- group geometry.
 Determine the molecular geometry.
 Multiple bonds count as one group of electrons.
 More than one central atom can be handled
individually.

Slide 119 General Chemistry: Chapter 10

Slide 120 General Chemistry: Chapter 10
Slide 121 General Chemistry: Chapter 10
 .. .. ..
: Cl N − Cl :
.. I ..
: Cl :
..

There are four electron groups around the central N atom and
one of them is lone pair so the VSEPR notation is AX3E
Therefore it has:
Thetrahedral electron group geometry
Trigonal pyramidal molecular geometry

Slide 123 General Chemistry: Chapter 10

 ..
:O:
.. I ..
: Cl − P − Cl :
.. I ..
: Cl :
..

There are four electron groups around the central P atom and
all of them are bond pairs so the VSEPR notation is AX4
Therefore it has:
Thetrahedral electron group geometry
Thetrahedral molecular geometry
Slide 124 General Chemistry: Chapter 10
Slide 125 General Chemistry: Chapter 10
Slide 126 General Chemistry: Chapter 10
 .. ..
O=C=S
.. ..

There are two electron groups around the central C atom and all
of them are bond pairs so the VSEPR notation is AX2
Therefore it has:
Linear electron group geometry
Linear molecular geometry

Slide 127 General Chemistry: Chapter 10

 ..
: N  N−O:
..

There are two electron groups around the central N atom and
all of them are bond pairs so the VSEPR notation is AX2
Therefore it has:
Linear electron group geometry
Linear molecular geometry

Slide 128 General Chemistry: Chapter 10

Slide 129 General Chemistry: Chapter 10
Slide 130. General Chemistry: Chapter 10
 H
I ..
H − C − O− H
I ..
H
109.5o
109.5o

Slide 132 General Chemistry: Chapter 10

 120o
H H :O:
I I II ..
H − N − C − C − O− H
.. I ..
H

109.5o 109.5o

Slide 134 General Chemistry: Chapter 10

Slide 135 General Chemistry: Chapter 10
 Dipole Moments

An electrical
condenser (or
capacitor) consists of
a pair of electrodes
separated by a
medium that does not
conduct electricity.

When the field is off the molecules orient randomly. When the filed
is on, the molecules align with the field. The alignment can be
detected.
Slide 136
The HCl molecule is a polar
molecule.

The Cl atom is more electronegative.

Electrons are displaced toward the Cl
atom, (see the electrostatic potential
map).

Across-base arrow used points to the

atom that attracts electrons more
strongly.
Slide 138 General Chemistry: Chapter 10
 Molecular shapes and Dipole Moments
(a) The resultant of two of the bond
dipoles is shown as a red arrow, and
that of the other two, as a blue
arrow. The red and blue in opposite
directions and cancel. The molecule
is nonpolar. The balance of the
charge distribution in CCl4 is
clearly seen in the electrostatic
potential map.
(b) The individual bond dipoles do
combine to yield a resultant dipole
moment (red arrow) of 1.04 D. The
electrostatic potential map indicates
that the hydrogen atom has a partial
positive charge.
 The balance of
the charge
distribution in
CCl4 is clearly
seen in the
electrostatic
potential map.

The electrostatic
potential map
indicates that the
hydrogen atom
has a partial
positive charge.

Slide 140 General Chemistry: Chapter 10

 Bond Order and Bond Length

Bond Order
• Single bond, order = 1
• Double bond, order = 2
Bond Length
• Distance between two nuclei
Higher bond order
• Shorter bond
• Stronger bond

Slide 144 General Chemistry: Chapter 10

 For example, the measured length of the nitrogen-
to-nitrogen triple bond in NH2 is 109.8 pm,

whereas the nitrogen-to-nitrogen single bond in

hydrazine, H2N-NH2 is 147 pm.

Slide 145 General Chemistry: Chapter 10

The single covalent radius is one-half the distance between the
centers of identical atoms joined by a single covalent bond.

Thus, the single covalent radius of chlorine in Figure 9-9 (99

pm) is one-half the bond length given in Table 10.2, that is,
1/2x199 pm. So,

the length of the covalent bond between

two atoms can be approximated as the
sum of the covalent radii of the two
atoms.

Slide 146 General Chemistry: Chapter 10

Slide 147 General Chemistry: Chapter 10
Slide 148 General Chemistry: Chapter 10
 H
I ..
H − C − Br :
I ..
H
 −
 ..

: S
 .. − C  N :

Slide 150 General Chemistry: Chapter 10

 Bond Energies
Together with bond lengths, bond
energies can be used to assess the
suitability of a proposed Lewis
structure.

Bond energy, bond length, and

bond order are interrelated
properties in this sense: the
higher the bond order, the
shorter the bond between
two atoms and the greater
the bond energy.
Slide 152 General Chemistry: Chapter 10
 You can use bond energies in exactly the same
way you can use enthalpies of formation.

Enthalpy of formation is more accurately

known and bond energy is usually an
average, but it can be used effectively if
formation data is unavailable.

Slide 153 General Chemistry: Chapter 10

Energy is released when isolated atoms join to
form a covalent bond, and energy must be
absorbed to break apart covalently bonded
atoms.

Bond dissociation energy, D, is the quantity of energy

required to break one mole of covalent bonds in a
gaseous species. The SI units are kilojoules per mole of
bonds (kJ/mol).

We can think of bond-dissociation energy as an

enthalpy change or a heat of reaction,
for a diatomic molecule, there is only one
bond in the molecule.

The bond-dissociation energy of a

diatomic molecule can be expressed
rather precisely, as is that of H2 (g).

Slide 155 General Chemistry: Chapter 10

 For a polyatomic molecule, such as H2O the
situation is different (Fig. 10-16). The energy
needed to dissociate one mole of H atoms by
breaking one O-H bond per H2O molecule,

Slide 156 General Chemistry: Chapter 10

The two O-H bonds in H2O are identical; the bond
energy in H2O is the average of the two values listed
above: 463.4 kJ/mol.

The O-H bond energy in other molecules containing

the OH group will be somewhat different from that in
H-O-H.

For example, in methanol, CH3OH, the O-H

bond-dissociation energy, which we can
represent as CH3OH is 436.8 kJ/mol.
 The usual method of tabulating bond energies
(Table 10.3) is as averages.

An average bond energy is the average of bond-

dissociation energies for a number of different
species containing the particular bond.

Understandably, average bond energies

cannot be stated as precisely as specific
bond-dissociation energies.

Slide 158 General Chemistry: Chapter 10

EXAMPLE 10-15
Calculating an Enthalpy of Reaction from Bond Energies.
The reaction of methane (CH4) and chlorine produces a mixture
of products called chloromethanes. One of these is
monochloromethane, CH3Cl, used in the preparation of silicones.
Calculate H for the reaction.

ΔHrxn =  ΔH(product bonds) - ΔH(reactant bonds)

=  ΔH bonds formed -  ΔH bonds broken

= -770 kJ/mol – (657 kJ/mol) = -113 kJ/mol
.. .. .. . .. .. ..
.O− N = O + .O. → N=O + O=O
.. .. .. .. .. .. ..

Because a single bond (N-O) is broken and a double

bond (O=O) is forming, we expect that a double bond
to be stronger than a single bond.
So, we can say that the products will be more stable
than the reactants
Therefore this reaction would be exothermic
Slide 160
 .. .. .. .. .. ..
2 H − O− H + 2 : Cl− Cl : → 4 H − Cl : + O = O
.. .. .. .. .. ..

Bonds that are breaking

2 Cl-Cl + 4 H-O
=2 x 243 kJ/mol + 4 x 464 kJ/mol =2342 kJ/mol
Bonds that are forming
1 O=O + 4 H-Cl
=498 kJ/mol + 4 x 431 kJ/mol =2222 kJ/mol
H=1/2 x (2342 kJ/mol - 2222 kJ/mol ) = + 60 kJ/mol
Therefore the reaction is endothermic
Focus on Molecules in Space: Measuring
Bond Lengths

Slide 162 General Chemistry: Chapter 10

 End of Chapter Questions
•Testing your decisions:
–If you get an error or a nonsense result, then
climb back to an intersection where you KNOW
you were correct, and take another route.

a
b
c
d? e
e?!# f
Answer

Slide 163 General Chemistry: Chapter 10