Chemical Bonding

Chapter 3
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Chemical Bonding
3.0 Introduction
3.1 Lewis Structure
3.2 Ionic Bond
3.3 Covalent Bond
3.4 Molecular Geometry and VSEPR theory
3.5 Valence bonds theory and hybridizations
3.6 Intermolecular Forces
3.7 Metallic Bonding
2

Types of Chemical Bonding

Ionic bonding involves the transfer of electrons
and is usually observed when a metal bonds to a
nonmetal.
Covalent bonding involves the sharing of
electrons and is usually observed when a
nonmetal bonds to a nonmetal.
Metallic bonding involves electron pooling and
occurs when a metal bonds to another metal.
3

3.0 Introduction to Chemical Bonds

Ionic Bonds
When a metal atom loses electrons it becomes
a cation
metals relatively easy to remove electrons
from them
When a nonmetal atom gains electrons it
becomes an anion
Nonmetals are easier to add electrons to
these atoms
The oppositely charged ions are then attracted
to each other, resulting in an ionic bond

The Ionic Bond

Ionic bond: the electrostatic force that holds ions together in
an ionic compound.
Li+ F Li + F
1s22s1

LiF

1s22s22p5

Li+ + e-

Li
e- +
Li+ +

1s2 1s22s22p6
[He]
[Ne]

F -

F -

Li+ F -

3.0 Introduction to Chemical Bonds

Covalent Bonds
Covalent bond: chemical bond in which two
or more electrons are shared by two atoms.
Covalent compounds are compounds that
contain only covalent bonds.
In a covalent bond, each electron in a shared
pair is attracted to the nuclei of both atoms.
This attraction holds the two atoms together.

H + H H:H or H-H
6

Why should two atoms share electrons?

To complete the octet configuration of all elements attached.
F

7e-

F F

7e-

8e- 8e-

Lewis structure of F2

single covalent bond

lone pairs

lone pairs

single covalent bond

lone pairs

F F

lone pairs
7

Lewis structure of water

H

O +

single covalent bonds

H O H

or

2e- 8e- 2e-

Double bond two atoms share two pairs of electrons

O C O

or

double bonds

8e- 8e- 8e-

Triple bond two atoms share three pairs of electrons

N N
8e-8e-

or

triple bond
8

3.0 Introduction to Chemical Bonds

Metallic Bonds
The bonding of metals is quite different than other
bonding.
In a metal, the bonding electrons are delocalized
over the entire compound.
Metal atoms in a compound can be imagined as a
array of positive ions immersed in a sea of
delocalized valence electron.
The great cohesive force resulting from
delocalization is responsible for metals strength.
The mobility of the delocalized electron makes
metals good conductors of heat and electricity.

3.0 Introduction to Chemical Bonds

Three Models of Chemical Bonding.

11

Topic

3.1 Lewis Structure

G.N. Lewis (1875-1946)

3.1 Lewis Structure

Lewis Theory- using valence electrons to explain
bonding of atoms
Using Lewis Theory, we can draw models called
Lewis Structures or known as Electron-Dot
Structures.
Lewis structure represent the valence electrons of
main-group elements as dots surrounding the
symbol for the particular element.

13

3.1 Lewis Structure

Valence Electrons
Because chemical bonding involves the transfer
or sharing of electrons between two or more
atoms, valence electrons are most important in
bonding
Lewis theory focuses on the behavior of the
valence electrons

3.1 Lewis Structure

Determining the Number of Valence
Electrons in an Atom
The column number on the Periodic Table will tell you
how many valence electrons a main group atom has
Transition Elements all have two valence electrons. Why?

3.1 Lewis Structure

Lewis Electron-Dot Symbols
To draw the Lewis symbol for any main-group
element:
Note the A-group number, which gives the
number of valence electrons.
Place one dot at a time on each of the four sides
of the element symbol.
Keep adding dots, pairing them, until all are
used up.

Nitrogen, N, is in Group 5A, therefore has 5 valence electrons.

N or N or N or N

3.1 Lewis Structure

Lewis Electron-Dot Symbols for Elements
in Periods 2 and 3.

3.1 Lewis Structure

Example 1 Write the Lewis dot symbol for
phosphorous (P)
Phosphorous (P) is in group 5A, therefore it has
five valence electrons.

Lewis Dot Symbols for the Representative Elements &

Noble Gases

19

Writing Lewis Structures

1. Draw skeletal structure of compound showing
what atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e-. Add 1 for each
negative charge. Subtract 1 for each positive
charge.
3. Complete an octet for all atoms except hydrogen.
4. If structure contains too many electrons, form
double and triple bonds on central atom as
needed.
20

Example 1
Write the Lewis structure for nitrogen trifluoride (NF3) in which
all three F atoms are bonded to the N atom.

NF3 is a colorless, odorless, unreactive

gas.

Example 1
Solution We follow the preceding procedure for writing Lewis
structures.
Step 1:

The N atom is less electronegative than F, so the

skeletal structure of NF3 is

Step 2:

The outer-shell electron configurations of N and F

are 2s22p3 and 2s22p5, respectively. Thus, there are
5 + (3 7), or 26, valence electrons to account for in
NF3.

Example 1
Step 3:

We draw a single covalent bond between N and each

F, and complete the octets for the F atoms. We place
the remaining two electrons on N:

Because this structure satisfies the octet rule for all the atoms,
step 4 is not required.
Check Count the valence electrons in NF3 (in bonds and in
lone pairs). The result is 26, the same as the total number of
valence electrons on three F atoms (3 7 = 21) and one N
atom (5).

Example 2
Write the Lewis structure for nitric acid (HNO3) in which the
three O atoms are bonded to the central N atom and the
ionizable H atom is bonded to one of the O atoms.

HNO3 is a strong electrolyte.

Example 2
Solution We follow the procedure already outlined for writing
Lewis structures.
Step 1:

The skeletal structure of HNO3 is

Step 2:

The outer-shell electron configurations of N, O, and H

are 2s22p3, 2s22p4, and 1s1, respectively. Thus, there
are 5 + (3 6) + 1, or 24, valence electrons to
account for in HNO3.

Example 2
Step 3:

We draw a single covalent bond between N and each

of the three O atoms and between one O atom and
the H atom. Then we fill in electrons to comply with
the octet rule for the O atoms:

Step 4:

We see that this structure satisfies the octet rule for

all the O atoms but not for the N atom. The N atom
has only six electrons. Therefore, we move a lone
pair from one of the end O atoms to form another
bond with N.

Topic
3.2 Ionic Bond

3.2 Ionic Bond

Lewis Structures of Ions
Cations have Lewis symbols without valence
electrons
electrons lost in the cation formation

Anions have Lewis symbols with eight valence

electrons
electrons gained in the anion formation

Example:

3.2 Ionic Bond

The Octet Rule for Ionic Bonding
Metals form cations by losing enough electrons
until they get the same electron configuration as
the previous noble gas
Nonmetals form anions by gaining enough
electrons until they get the same electron
configuration as the next noble gas
The noble gas electron configurations are very
stable because they have 8 electrons (an octet) in
their outermost shells (except He)

3.2 Ionic Bond

Stable Electron Arrangements
and Ion Charge

3.2 Ionic Bond

Lewis Theory and Ionic Bonding
Lewis symbols can be used to represent the
transfer of electrons from metal atom to nonmetal
atom, resulting in ions that are attracted to each
other and therefore bond

3.2 Ionic Bond

Another Way to Depict Electron Transfer in
the Formation of Li+ and F-.
Electron configuration
Li 1s22s1 + F 1s22p5

Li+ 1s2 + F-

1s22s22p6

Orbital diagram
Li
+

1s

2s

Li+
2p

1s

2s

2p

1s

2s

2p

F-
1s

2s

2p

3.2 Ionic Bond

Predicting Ionic Formulas
Using Lewis Symbols
Electrons are transferred until the metal loses all
its valence electrons and the nonmetal has an
octet
Numbers of atoms are adjusted so the total
number of electrons lost balance up with number
of electrons gained
Lewis structure

Formula

Li2O

3.2 Ionic Bond

CHECKPOINT 1:
Depicting Ion Formation
Use partial orbital diagrams and Lewis symbols to
depict the formation of Na+ and O2 ions from the
atoms, and determine the formula of the compound
formed.
SOLUTION:

Na

2Na+

2O
+

Na

3.2 Ionic Bond

CHECKPOINT 2
Using Lewis theory to predict chemical formulas of ionic
compounds
Predict the formula of the compound that forms between
calcium and chlorine.
Ca
Cl

Cl

Ca

Ca2+
CaCl2

Draw the Lewis dot symbols

of the elements.

Transfer all the valence electrons

from the metal to the nonmetal,
adding more of each atom as you go,
until all electrons are lost from the
metal atoms and all
nonmetal atoms have eight electrons.

Cl

3.2 Ionic Bond

Periodic Trends in Lattice Energy
Lattice energy is the energy required to separate 1 mol of an
ionic solid into gaseous ions.
Lattice energy is a measure of the strength of the ionic bond.
Lattice energy is affected by ionic size and ionic charge.

As ionic size increases, lattice energy decreases. Lattice

energy therefore decreases down a group on the periodic
table.
As ionic charge increases, lattice energy increases.

3.2 Ionic Bond

Lattice Energy vs. Ion Size

3.2 Ionic Bond

Lattice Energy vs Ion Charge

Lattice Energy =
910 kJ/mol

Lattice Energy =
3414 kJ/mol

3.2 Ionic Bond

Example 3: Order the following ionic compounds in

order of increasing magnitude of lattice energy:
CaO, KBr, KCl, SrO
Ca2+& O2-,
K+ & Br,
K+ & Cl,
Sr2+ & O2

First examine the ion charges

and order by sum of the charges
(KBr, KCl) < (CaO, SrO)
Then examine the ion sizes of
each group and order by
radius; larger < smaller

(KBr, KCl) same cation,

Br > Cl (same Group)

(CaO, SrO) same anion,

Sr2+ > Ca2+ (same Group)
KBr
SrO < SrO)
CaO
KBr << KCl
KCl << (CaO,

3.2 Ionic Bond

Properties of Ionic Compounds
1. High melting and boiling point
Lewis theory predicts ionic compounds should have high
melting points and boiling points because breaking down
the crystal should require a lot of energy
the stronger the attraction (larger the lattice energy), the higher the
melting point

NaCl (s)

NaCl (liquid)
41

CHECKPOINT 3
Which ionic compound below has the highest
melting point?
KBr
KBr (734 C)

CaCl2

CaCl2 (772 C)

MgF2

MgF2 (1261 C)

3.2 Ionic Bond

Properties of Ionic Compounds
2. Hard and brittle crystalline solid
Lewis theory implies that the positions of the ions
in the crystal lattice are critical to the stability of
the structure
Lewis theory predicts that moving ions out of
position should therefore be difficult, and ionic
solids should be hard
hardness is measured by rubbing two materials
together and seeing which streaks or cuts the other
the harder material is the one that cuts or doesnt

3.2 Ionic Bond

Properties of Ionic Compounds
Lewis theory implies that if the ions are displaced
from their position in the crystal lattice, that repulsive
forces should occur
This predicts the crystal will become unstable and
break apart. Lewis theory predicts ionic solids will be
brittle.
Ionic solids are brittle. When struck they shatter.

-+ +- -+ +- -+ +- -+ +
- -+ +- -+ +- -+ +- -+ +- + - + - + - + - +
- + - + - + - + + +
-

3.2 Ionic Bond

Properties of Ionic Compounds
3. Good electrical conductor in liquid state

Lewis theory implies that, in the ionic solid, the ions

are locked in position and cannot move around
does not conduct electricity
Lewis theory implies that, in the liquid state or when
dissolved in water, the ions will have the ability to
move around
conduct electricity

4. Many ionic solids are soluble in water but not in

organic solvents

Example 4
Strategy We use electroneutrality as our guide in writing
formulas for ionic compounds, that is, the total positive charges
on the cations must be equal to the total negative charges
on the anions.
Solution The Lewis dot symbols of Al and O are

Because aluminum tends to form the cation (Al3+) and oxygen

the anion (O2) in ionic compounds, the transfer of electrons is
from Al to O. There are three valence electrons in each Al
atom; each O atom needs two electrons to form the O2 ion,
which is isoelectronic with neon.

Example 4
Thus, the simplest neutralizing ratio of Al3+ to O2 is 2:3; two
Al3+ ions have a total charge of +6, and three O2 ions have a
total charge of 6. So the empirical formula of aluminum oxide
is Al2O3, and the reaction is

Check Make sure that the number of valence electrons (24) is

the same on both sides of the equation. Are the subscripts in
Al2O3 reduced to the smallest possible whole numbers?

3.3 Covalent Bond

Lewis theory implies that another way atoms can
achieve an octet of valence electrons is to share
their valence electrons with other atoms
The shared electrons would then count toward
each atoms octet (Octet rule applied)
The sharing of valence electrons is called
covalent bonding

3.3 Covalent Bond

Bonding Pairs and Lone Pairs

Electrons that are shared by atoms are called

bonding pairs
Electrons that are not shared by atoms but
belong to a particular atom are called lone pairs
or nonbonding pairs

Bonding pairs

.
.
.
.
.
.
.. O .... S .. O ..
..

Lone pairs

3.3 Covalent Bond

Bonding Pairs and Lone Pairs
Generally, elements follow certain common
bonding patterns
The # of bonds = Group # or 8 Group #

C = 4 bonds & 0 lone pairs, N = 3 bonds & 1 lone pair,

O= 2 bonds & 2 lone pairs,
H and halogen = 1 bond,
Be = 2 bonds & 0 lone pairs,
B = 3 bonds & 0 lone pairs

3.3 Covalent Bond

Single Covalent Bonds

When two atoms share one pair of electrons it is

H only duet

F
F

H O
H

H O H

called a single covalent bond

One atom may use more than one single bond to
fulfill its octet

3.3 Covalent Bond

Double Covalent Bond
When two atoms share two pairs of electrons the
result is called a double covalent bond
four electrons

O
O

3.3 Covalent Bond

Triple Covalent Bond
When two atoms share three pairs of electrons the
result is called a triple covalent bond
six electrons

N
N

3.3 Covalent Bond

Lewis Structures
Lewis theory predicts that atoms will be most stable
when they have their octet of valence electrons.
It does not require that atoms have the same number
of lone pair electrons they had before bonding.
First use the octet rule

3.3 Covalent Bond

The Steps in Converting a Molecular
Formula into a Lewis Structure.
Molecular
Formula

Step 1

Atom
placement

Place atom with lowest

EN in center.
Step 2 Add A-group numbers.

Step 3
Sum of
valence e-

Draw single bonds, and

subtract 2e- for each bond.

Remaining
valence e-

Step 4

Lewis
structure

Give each atom

8e(2e- for H).

3.3 Covalent Bond

Writing Lewis Structures for NF3
Molecular
Formula

N has a lower EN than F, so N is placed in the center.

Atom
placement
Sum of
valence e-

Remaining
valence eLewis
structure

1 x N = 1 x 5 = 5e3 x F = 3 x 7 = 21 eTotal
= 28 e-

3.3 Covalent Bond

Writing Lewis Structures for Molecules
with One Central Atom
Example 4 : Write a Lewis structure for CCl2F2
Step 1: Carbon has the lowest EN and is the
central atom. The other atoms are
placed around it.
Step 2: [1 x C(4e-)] + [2 x F(7e-)] + [2 x
Cl(7e-)] = 32 valence eStep 3-4: Add single bonds, then give
each atom a full octet.

3.3 Covalent Bond

Writing Lewis Structures for Molecules with
More than One Central Atom
Example 5 :Write the Lewis structure for
methanol (molecular formula CH4O)
Step 1: Place the atoms relative to each
other. H can only form one bond, so C
and O must be central and adjacent
to each other.
Step 2: [1 x C(4e-)] + [1 x O(6e-)] + [4 x
H(1e-)] = 14 valence e-

Step 3-4: Add single bonds, then give

each atom (other than H) a full
octet.

3.3 Covalent Bond

Multiple Bonds
If there are not enough electrons for the central atom
to attain an octet, a multiple bond is present.
Step 5: If the central atom does not have a full octet,
change a lone pair on a surrounding atom into another
bonding pair to the central atom, thus forming a
multiple bond.

3.3 Covalent Bond

Writing Lewis Structures for Molecules with
Multiple Bonds
Example 6: Write Lewis structures for the
following: Ethylene (C2H4)
PLAN:

After following steps 1 to 4 we see that the central

atom does not have a full octet. We must therefore
add step 5, which involves changing a lone pair to a
bonding pair.

SOLUTION:
C2H4 has 2(4) + 4(1) = 12 valence e-. H can have only one bond per
atom.

3.3 Covalent Bond

Example 7: Write Lewis structure for HCN
Step 1: Place the atoms relative to each
other. H can only form one bond, so C
must be central and N adjacent to
carbon
H

Step 2: [1 x C(4e-)] + [1 x N(5e-)] + [1 x

H(1e-)] = 10 valence e-

Step 3-4: Add single bonds, then give

each atom (other than H) a full
octet.

H C N

3.3 Covalent Bond

Writing Resonance Structures
Example 8 : Write resonance structures for the nitrate ion, NO3
and find the bond order.

A resonance structure is one of two or more Lewis structures

for a single molecule that cannot be represented accurately by
only one Lewis structure.
SOLUTION:

Nitrate has [1 x N(5e-)] + [3 x O(6e-)] + 1e-] = 24 valence eAfter Steps 1-4:

3.3 Covalent Bond

Writing Resonance Structures
Step 5. Since N does not have a full octet, we change a
lone pair from O to a bonding pair to form a double bond.

3.3 Covalent Bond

Example 9: Writing Lewis structures of
molecules, HNO3
1. Write skeletal structure

H always terminal

in oxyacid, H outside attached to Os

make least electronegative atom

central

H O N O

N is central
not H

2. Count valence electrons

sum the valence electrons for each

atom
add one electron for each charge
subtract one electron for each + charge

N=5
H=1
O3 = 36 = 18
Total = 24 e

3.3 Covalent Bond

Example 9: Writing Lewis structures of
molecules, HNO3
3. Attach atom together with pairs of electrons, and
subtract from the total
dont forget, a line represents 2 electrons

..
..
..
..
..
..

..
O

..
..
H O.. N O..
..

Electrons
Start
24
Used
8
Left
16

Example 9: Writing Lewis structures of

molecules, HNO3
4. Complete octets, outside-in

H is already complete with 2

..
..

..
O

1 bond

..

..
..
H O.. N O
..

and re-count electrons

N=5
H=1
O3 = 36 = 18
Total = 24 e

Electrons
Start
24
Used
8
Left
16

Electrons
Start
16
Used
16
Left
0

..

Period 3 and below

follow common bonding patterns if

possible

..
..

..

6. If central atom does not have

octet, bring in electrons from
outside atoms to share

..
..

elements with d orbitals can

have more than eight electrons

..
..
H O.. N O
..
..
O
..
..
H O.. N O

..

5. If all octets complete, give

extra electrons to the central
atom

..

Example 9: Writing Lewis structures of

..
molecules, HNO3

..

..
..
H O.. N O
..

CHECKPOINT 4
Draw Lewis Structures of the Following
CO2

H3PO4

SeOF2

SO32

NO2

P2H4

CO2

16 e

H3PO4
32 e

SeOF2

SO32

26 e

26 e

NO2
18 e

P2H4
14 e

Two possible skeletal structures of formaldehyde (CH2O)

H

An atoms formal charge is the difference between the

number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge
on an atom in
a Lewis
structure

total number
of valence
electrons in
the free atom

total number
of nonbonding
electrons

1
2

total number
of bonding
electrons

The sum of the formal charges of the atoms in a molecule

or ion must equal the charge on the molecule or ion.
70

-1

+1

formal charge
on an atom in
a Lewis
structure

C 4 eO 6 e2H 2x1 e12 e-

2 single bonds (2x2) = 4

1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12

total number
total number
of valence
of nonbonding
electrons in electrons
the free atom

total number
of bonding
electrons

formal charge
= 4 - 2 - x 6 = -1
on C
formal charge
= 6 - 2 - x 6 = +1
on O

71

H
H

0
C

formal charge
on an atom in
a Lewis
structure

0
O

C 4 eO 6 e2H 2x1 e12 e-

2 single bonds (2x2) = 4

1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12

total number
total number
of valence
of nonbonding
electrons in electrons
the free atom

total number
of bonding
electrons

formal charge
= 4 - 0 - x 8 = 0
on C
formal charge
= 6 - 4 - x 4 = 0
on O

72

Example 10
Strategy The Lewis structure for the carbonate ion was
developed as below:

The formal charges on the atoms can be calculated using the

given procedure.
Solution We subtract the number of nonbonding electrons and
half of the bonding electrons from the valence electrons of each
atom.

Example 10
The C atom: The C atom has four valence electrons and there
are no nonbonding electrons on the atom in the
Lewis structure. The breaking of the double bond
and two single bonds results in the transfer of four
electrons to the C atom. Therefore, the formal
charge is 4 4 = 0.
The O atom in C=O: The O atom has six valence electrons and
there are four nonbonding electrons on
the atom. The breaking of the double
bond results in the transfer of two
electrons to the O atom. Here the formal
charge is 6 4 2 = 0.

Example 10
The O atom in CO: This atom has six nonbonding electrons
and the breaking of the single bond
transfers another electron to it.
Therefore, the formal charge is
6 6 1 = 1.
Thus, the Lewis structure for

with formal charges is

Check Note that the sum of the formal charges is 2, the same
as the charge on the carbonate ion.

Formal Charge and Lewis Structures

1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.

76

Example 11
Formaldehyde (CH2O), a liquid with a disagreeable odor,
traditionally has been used to preserve laboratory specimens.
Draw the most likely Lewis structure for the compound.

Example 11
Strategy A plausible Lewis structure should satisfy the octet
rule for all the elements, except H, and have the formal charges
(if any) distributed according to electronegativity guidelines.

Solution The two possible skeletal structures are

Example 11
First we draw the Lewis structures for each of these possibilities

To show the formal charges, we follow the procedure before. In

(a) the C atom has a total of five electrons (one lone pair plus
three electrons from the breaking of a single and a double
bond). Because C has four valence electrons, the formal
charge on the atom is 4 5 = 1. The O atom has a total of
five electrons (one lone pair and three electrons from the
breaking of a single and a double bond). Since O has six
valence electrons, the formal charge on the atom is 6 5 = +1.

Example 11
In (b) the C atom has a total of four electrons from the breaking
of two single bonds and a double bond, so its formal charge is
4 4 = 0. The O atom has a total of six electrons (two lone
pairs and two electrons from the breaking of the double bond).
Therefore, the formal charge on the atom is 6 6 = 0. Although
both structures satisfy the octet rule, (b) is the more likely
structure because it carries no formal charges.

Check In each case make sure that the total number of

valence electrons is 12. Can you suggest two other reasons
why (a) is less plausible?

CHECKPOINT 5
Assign formal charges
CO2

H3PO4

SeOF2

SO32

NO2

P2H4

CHECKPOINT 5 (answers)
CO2

H3PO4

all 0

P = +1
rest 0

SeOF2

SO32
S = +1

Se = +1

NO2

P2H4
all 0

3.3 Covalent Bond

Exceptions to Octet Rule
Some elements violate the octet rule
1. Incomplete octet
Be forms two bonds with no lone pairs in its compounds
B. Al forms three bonds with no lone pairs in its
compounds

2. Expanded octet
many elements may end up with more than eight valence
electrons in their structure if they can use their empty d
orbitals for bonding
3. Odd number electron species e.g., NO
- Will have one unpaired electron, free radical & very
reactive

3.3 Covalent Bond

Exceptions to Octet Rule
Molecules with Electron-Deficient Atoms
B and Be are
commonly electrondeficient.

Exceptions to the Octet Rule

The Incomplete Octet
BeH2

BF3

B 3e3F 3x7e24e-

Be 2e2H 2x1e4e-

Be

3 single bonds (3x2) = 6

9 lone pairs (9x2) = 18
Total = 24

F
85

3.3 Covalent Bond

Exceptions to Octet Rule
Odd-Electron Species

A molecule with an
odd number of
electrons is called a
free radical.

Expanded Valence Shells

An expanded valence shell is only possible for nonmetals

from Period 3 or higher because these elements have
available d orbitals.

Exceptions to the Octet Rule

Odd-Electron Molecules
NO

N 5eO 6e11e-

The Expanded Octet

(central atom with principal quantum number n > 2)

SF6

S 6e6F 42e48e-

S
F

6 single bonds (6x2) = 12

18 lone pairs (18x2) = 36
Total = 48
87

Example 13
Draw the Lewis structure for aluminum triiodide (AlI3).

AlI3 has a tendency to

dimerize or form two units as
Al2I6.

Example 13
Strategy We follow the procedures used in Examples 11 and
12 to draw the Lewis structure and calculate formal charges.
Solution The outer-shell electron configurations of Al and I are
3s23p1 and 5s25p5, respectively. The total number of valence
electrons is 3 + 3 7 or 24. Because Al is less electronegative
than I, it occupies a central position and forms three bonds with
the I atoms:

Note that there are no formal charges on the Al and I atoms.

Example 13
Check Although the octet rule is satisfied for the I atoms, there
are only six valence electrons around the Al atom.
Thus, AlI3 is an example of the incomplete octet.

Example 14
Draw the Lewis structure for phosphorus pentafluoride (PF5), in
which all five F atoms are bonded to the central P atom.

PF5 is a reactive
gaseous compound.

Example 14
Strategy Note that P is a third-period element. We follow the
procedures given in Examples 11 to draw the Lewis structure
and calculate formal charges.

Solution The outer-shell electron configurations for P and F

are 3s23p3 and 2s22p5, respectively, and so the total number of
valence electrons is 5 + (5 7), or 40.
Phosphorus, like sulfur, is a third-period element, and therefore
it can have an expanded octet.

Example 14
The Lewis structure of PF5 is

Note that there are no formal charges on the P and F atoms.

Check Although the octet rule is satisfied for the F atoms,

there are 10 valence electrons around the P atom, giving it an
expanded octet.

Example 15
Draw a Lewis structure for the sulfate ion
in which all
four O atoms are bonded to the central S atom.

Example 15
Strategy Note that S is a third-period element. We follow the
procedures given in Example 11 to draw the Lewis structure
and calculate formal charges.
Solution The outer-shell electron configurations of S and O
are 3s23p4 and 2s22p4, respectively.
Step 1: The skeletal structure of

is

Example 15
Step 2:

Both O and S are Group 6A elements and so have

six valence electrons each. Including the two
negative charges, we must therefore account for a
total of 6 + (4 6) + 2, or 32, valence electrons in

Step 3:

We draw a single covalent bond between all the

bonding atoms:

Example 15
Next we show formal charges on the S and O atoms:

Note that we can eliminate some of the formal charges for

by expanding the S atoms octet as follows:

Example 15

At this stage of learning, you should realize that both

representations are valid Lewis structures and you
should be able to draw both types of structures.
One helpful rule is that in trying to minimize formal
charges by expanding the central atoms octet, only
add enough double bonds to make the formal charge
on the central atom zero.

Example 15
Thus, the following structure would give formal charges on
S(2) and O(0) that are inconsistent with the electronegativities
of these elements and should therefore not be included to
represent the
ion.

Example 16
Draw a Lewis structure of the noble gas compound xenon
tetrafluoride (XeF4) in which all F atoms are bonded to the
central Xe atom.

Example 16
Strategy Note that Xe is a fifth-period element. We follow the
procedures in Example 11 for drawing the Lewis structure and
calculating formal charges.
Solution
Step 1: The skeletal structure of XeF4 is

Step 2:

The outer-shell electron configurations of Xe and F

are 5s25p6 and 2s22p5, respectively, and so the total
number of valence electrons is 8 + (4 7) or 36.

Example 16
Step 3:

We draw a single covalent bond between all the

bonding atoms. The octet rule is satisfied for the F
atoms, each of which has three lone pairs. The sum
of the lone pair electrons on the four F atoms (4 6)
and the four bonding pairs (4 2) is 32. Therefore,
the remaining four electrons are shown as two lone
pairs on the Xe atom:

We see that the Xe atom has an expanded octet.

There are no formal charges on the Xe and F atoms.

3.3 Covalent Bond

Determine Best Lewis Structures
Best Lewis structure have:
All atoms obey the octet rule
Zero or fewer formal charges
smaller formal charges
negative formal charge on the more
electronegative atom
Like charges on adjacent atoms are not
desirable
Sum of formal charges equal zero, or equal
the ionic charge for polyatomic ions

CHECKPOINT 6
Show the resonance forms of NCO- and
predict which resonance structure is the
most stable structure.

104

Answer:
NCO has 3 possible resonance forms:
N C

N C

N C

formal charges

2 0 +1
N C

1 0
N

0
O

0 1

N C

Forms B and C have negative formal charges on N and O; this

makes them more preferred than form A.
Form C has a negative charge on O which is the more
electronegative element, therefore C contributes the most to the
resonance hybrid.

3.3 Covalent Bond

Properties of Covalent Compounds

1)

Low melting points and boiling points

involves breaking the attractions between the molecules,
but not the bonds between the atoms
the covalent bonds are strong, but the attractions
between the molecules are generally weak
intermolecular forces

2)

Do not conduct electricity in the solid or liquid state

there are no charged particles (no ions) around to allow
the material to conduct

3.3 Covalent Bond

Properties of Covalent Compounds
3) Electronegativity
The ability of an atom to attract bonding electrons to itself is
called electronegativity
Increases across period (left to right) and
Decreases down group (top to bottom)
fluorine is the most electronegative element
francium is the least electronegative element
opposite of atomic size trend
The larger the difference in electronegativity, the more polar
the bond
negative end toward more electronegative atom

The Electronegativities of Common Elements

108

3.3 Covalent Bond

Polar Covalent Bonding
Covalent bonding between unlike atoms results in unequal
sharing of the electrons
The more electronegative atom pulls the shared electrons
closer to its side
one end of the bond has larger electron density than the
other
The result is a polar covalent bond
bond polarity
the end with the larger electron density gets a partial
negative charge ()
The other end that is electron deficient gets a partial
positive charge (+)

3.3 Covalent Bond

Polar Covalent Bonding

3.3 Covalent Bond

Bond Polarity

ENCl = 3.0
3.0 3.0 = 0
Pure Covalent

ENCl = 3.0
ENH = 2.1
E = 3.0 2.1
= 0.9
Polar Covalent

ENCl = 3.0
ENNa = 0.9
E = 3.0 0.9
= 2.1
Ionic

3.3 Covalent Bond

Bond Polarity

HF

EN = 2.1

EN = 4.0

d+ H
F d-

Classification of bonds by difference in electronegativity

Difference

Bond Type

Covalent

Ionic

0 < and <2

Polar Covalent

Increasing difference in electronegativity

Covalent

Polar Covalent

share e-

partial transfer of e-

Ionic
transfer e113

Example
Classify the following bonds as ionic, polar covalent, or
covalent:
(a) the bond in HCl
(b) The bond in KF
(c) the CC bond in H3CCH3

Excercise
Strategy We follow the 2.0 rule of electronegativity difference.
Solution
(a) The electronegativity difference between H and Cl is 0.9,
which is appreciable but not large enough (by the 2.0 rule)
to qualify HCl as an ionic compound. Therefore, the bond
between H and Cl is polar covalent.
(b) The electronegativity difference between K and F is 3.2,
which is well above the 2.0 mark; therefore, the bond
between K and F is ionic.
(c) The two C atoms are identical in every respectthey are
bonded to each other and each is bonded to three other H
atoms. Therefore, the bond between them is purely
covalent.

3.3 Covalent Bond

4) Covalent Bond Strength and Bond Length
In covalent bonding, the more electrons in two atoms share,
the stronger the bond
Bond strength is measured by how much energy needed
to break the bond
triple bonds are stronger than double bonds, and double
bonds are stronger than single bonds
The more electrons two atoms share, the shorter the bond
Bond length is determined by measuring the distance
between the nuclei of bonded atoms
In general, triple bonds are shorter than double bonds,
and double bonds are shorter than single bonds

3.3 Covalent Bond

Trends in Bond Strength
In general, the more electrons two atoms share,
the stronger the covalent bond
must be comparing bonds between like atoms
CC (837 kJ) > C=C (611 kJ) > CC (347 kJ)
CN (891 kJ) > C=N (615 kJ) > CN (305 kJ)

In general, the shorter the covalent bond, the

stronger the bond

must be comparing similar types of bonds

BrF (237 kJ) > BrCl (218 kJ) > BrBr (193 kJ)
bonds get weaker down the column
bonds get stronger across the period

3.3 Covalent Bond

Bond Lengths
The distance between the nuclei of
bonded atoms is called the bond
length
Because the actual bond length
depends on the other atoms around
the bond we often use the average
bond length
averaged for similar bonds from many
compounds

3.3 Covalent Bond

Bond Lengths

Covalent compounds

Ionic Compounds

usually gases, liquids, or low-melting usually very strong, so ionic

solids.
compounds are solids at room
temperature and have high melting
points.
insoluble in water, or if they do
dissolve, their aqueous solutions
generally do not conduct electricity,
because the compounds are
nonelectrolytes

Many ionic compounds are soluble

in water and the resulting aqueous
solutions conduct electricity,
because the compounds are strong
electrolytes.

Liquid or molten covalent

compounds do not conduct
electricity because no ions are
present.

Molten ionic compounds conduct

electricity because they contain
mobile cations and anions.
120

121

Chemical Bonding II:

Molecular Geometry and
Hybridization of Atomic
Orbitals
Copyright The McGraw-Hill Companies, Inc. Permission required for

122

Molecular Geometry
3-dimensional arrangement of atoms in a
molecules
Molecular geometry affects its physical and
chemical properties
We often describe the shape of a molecule
with terms that relate to geometric figures
The geometric figures also have
characteristic angles that we call bond
angles

Using Lewis Theory to

Predict
Molecular Shapes
In general, bond lengths and bond
angles are determined by
experiment
By knowing the number of electrons
surrounding a central atoms (Lewis
structure), we can simply predict the
overall geometry of the molecules.

 Lewis theory says that these regions of

electron groups should repel each other
This idea can then be extended to
predict the shapes of molecules
the position of atoms surrounding a
central atom will be determined by
where the bonding electron groups
are
the positions of the electron groups
will be determined by trying to
minimize repulsions between them

125

VSEPR Theory
The geometric arrangement of electron pairs around a
central atom by minimize the electrostatic repulsion
between electron pairs.
Electron groups around the central atom of a molecule will
be most stable when they are separated as far apart as
possible we call this valence shell electron pair
repulsion theory (VSEPR)
The resulting geometric arrangement will allow us to predict
the shapes and bond angles in the molecule
VSEPR formula: ABaEb
A = central atom; B = surrounding atoms
E = lone pairs on central atom; a, b = integers (1,2,3)

Electron Groups
The Lewis structure predicts the number of
valence electron pairs around the central atom(s)
Each lone pair of electrons constitutes one
electron group on a central atom
Each bonding pair constitutes one electron group
on a central atom
regardless of whether it is single, double, or
triple

O N O

there are three electron

groups on N
three lone pair
one single bond
one double bond

Valence shell electron pair repulsion

(VSEPR) model:
Predict the geometry of the molecule from the
electrostatic repulsions between the electron
(bonding and nonbonding) pairs.
# of atoms
bonded to
Class
central
atom

AB2

# lone
pairs on
central
atom

Arrangement Molecular
of electron Geometry
pairs

linear

linear
B

128

VSEPR
# of atoms
bonded to
central
Class
atom

AB2
AB3

2
3

# lone
pairs on
central
atom

Arrangement
of electron Molecular
Geometry
pairs

linear

linear

trigonal
planar

trigonal
planar

129

Boron Trifluoride

130

VSEPR
# of atoms
bonded to
Class
central
atom

AB2

# lone
pairs on
central
atom

Arrangement Molecular
of electron Geometry
pairs

linear

linear
trigonal
planar

AB3

trigonal
planar

AB4

tetrahedral

tetrahedral

131

Methane

132

VSEPR
# of atoms
bonded to
central
Class
atom

AB2

# lone
pairs on
central
atom

Arrangement Molecular
of electron Geometry
pairs

linear

linear
trigonal
planar

AB3

trigonal
planar

AB4

tetrahedral

AB5

trigonal
bipyramidal

tetrahedral
trigonal
bipyramidal

133

Phosphorus Pentachloride

134

VSEPR
# of atoms
bonded to
central
Class
atom

AB2

# lone
pairs on
central
atom

Arrangement
of electron Molecular
Geometry
pairs

linear

linear
trigonal
planar
tetrahedral

AB3

trigonal
planar

AB4

tetrahedral

AB5

AB6

trigonal
bipyramidal
octahedral

trigonal
bipyramidal
octahedral

135

Sulfur Hexafluoride

136

137

lone-pair vs. lone-pair lone-pair vs. bonding- bonding-pair vs. bonding>

> pair repulsion
pair repulsion
repulsion
138

VSEPR
# of atoms
bonded to
Class
central
atom

# lone
pairs on
central
atom

AB3

AB2E

Arrangement Molecular
of electron Geometry
pairs

trigonal
planar
trigonal
planar

trigonal
planar

bent

139

VSEPR
# of atoms
bonded to
central
atom
Class

AB4

AB3E

# lone
pairs on
central
atom

Arrangement
of electron
Molecular
pairs
Geometry
tetrahedral

tetrahedral

tetrahedral
trigonal
pyramidal

140

VSEPR
# of atoms
bonded to
central
atom
Class

AB4

# lone
pairs on
central
atom

Arrangement
of electron Molecular
pairs
Geometry

tetrahedral

tetrahedral
trigonal
pyramidal

bent

AB3E

tetrahedral

AB2E2

tetrahedral

141

VSEPR
# of atoms
bonded to
central
atom
Class

# lone
pairs on
central
atom

AB5

AB4E

Arrangement
of electron Molecular
Geometry
pairs
trigonal
bipyramidal

trigonal
bipyramidal

trigonal
bipyramidal

distorted
tetrahedron

142

# of atoms
bonded to
central
Class
atom

AB5

AB4E
AB3E2

4
3

# lone
pairs on
central
atom

1
2

Arrangement
of electron Molecular
pairs
Geometry
trigonal
bipyramidal
trigonal
bipyramidal
trigonal
bipyramidal

trigonal
bipyramidal
distorted
tetrahedron

T-shaped

143

# of atoms
bonded to
central
Class
atom

# lone
pairs on
central
atom

Arrangement
of electron Molecular
Geometry
pairs

AB5

AB4E

trigonal
bipyramidal

AB3E2

trigonal
bipyramidal

AB2E3

trigonal
bipyramidal

trigonal
bipyramidal

trigonal
bipyramidal
distorted
tetrahedron
T-shaped
linear

144

VSEPR
# of atoms
bonded to
central
Class
atom

AB6
AB5E

6
5

# lone
pairs on
central
atom

Arrangement
of electron Molecular
pairs
Geometry

octahedral

octahedral

octahedral

square
pyramidal

145

# of atoms
bonded to
central
Class
atom

AB6
AB5E
AB4E2

6
5
4

# lone
pairs on
central
atom

Arrangement
Molecular
of electron
Geometry
pairs

octahedral

octahedral

octahedral

square
pyramidal

octahedral

square
planar

146

147

Predicting Molecular
Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the
central atom and number of atoms
bonded to the central atom.
3. Use VSEPR to predict the geometry of
the molecule.

149

Example 1
Use the VSEPR model to predict the geometry
of the following molecules and ions:
(a) AsH3
(b) OF2

(c)
(d)
(e) C2H4

Example 1
Strategy The sequence of steps in
determining molecular geometry is as follows:

Solution
(a) The Lewis structure of AsH3 is

There are four electron pairs around the

central atom; therefore, the electron pair
arrangement is tetrahedral

Example 1
Recall that the geometry of a molecule is determined
only by the arrangement of atoms (in this case the As
and H atoms). Thus, removing the lone pair leaves us
with three bonding pairs and a trigonal pyramidal
geometry, like NH3. We cannot predict the HAsH
angle accurately, but we know that it is less than
109.5 because the repulsion of the bonding electron
pairs in the AsH bonds by the lone pair on As is
greater than the repulsion between the bonding pairs.
(b) The Lewis structure of OF2 is

There are four electron pairs around the central atom;

therefore, the electron pair arrangement is tetrahedral.

Example 1
Recall that the geometry of a molecule is determined only
by the arrangement of atoms (in this case the O and F
atoms). Thus, removing the two lone pairs leaves us with
two bonding pairs and a bent geometry, like H2O. We
cannot predict the FOF angle accurately, but we know that it
must be less than 109.5 because the repulsion of the
bonding electron pairs in the OF bonds by the lone pairs
on O is greater than the repulsion between the bonding
pairs.
(c) The Lewis structure of

is

Example 1
There are four electron pairs around the central atom;
therefore, the electron pair arrangement is tetrahedral.
Because there are no lone pairs present, the
arrangement of the bonding pairs is the same as the
electron pair arrangement. Therefore,
has a
tetrahedral geometry and the ClAlCl angles are all
109.5.
(d) The Lewis structure of

is

There are five electron pairs around the central I atom;

therefore, the electron pair arrangement is trigonal
bipyramidal. Of the five electron pairs, three are lone
pairs and two are bonding pairs.

Example 1
Recall that the lone pairs preferentially occupy the
equatorial positions in a trigonal bipyramid. Thus,
removing the lone pairs leaves us with a linear geometry
for, that is, all three I atoms lie in a straight line.
(e) The Lewis structure of C2H4 is

The C=C bond is treated as though it were a single bond

in the VSEPR model. Because there are three electron
pairs around each C atom and there are no lone pairs
present, the arrangement around each C atom has a
trigonal planar shape like BF3, discussed earlier.

Example 1
Thus, the predicted bond angles in C2H4 are all 120.

Comment
(1) The ion is one of the few structures for which the
bond angle (180) can be predicted accurately even
though the central atom contains lone pairs.
(2) In C2H4, all six atoms lie in the same plane. The overall
planar geometry is not predicted by the VSEPR model, but
we will see why the molecule prefers to be planar later. In
reality, the angles are close, but not equal, to 120
because the bonds are not all equivalent.

CHECKPOINT 7
Predict the geometries of the following species using the
VSEPR method:
a) PCl3
b) H2O
c) CHCl3
d) ClF3
e) TeCl4

trigonal pyramidal
bent shape
Tetrahedral
t-shape
seesaw

CHECKPOINT 8
Which of the following species are tetrahedral?
SiCl4, SeF4, XeF4, Cl4, CdCl42-

Answer: SiCl4 Cl4 and CdCl42-

Dipole Moments and Polar

Molecules
Dipole moment, m, is a
measure of bond polarity

a dipole is a material with a + and

end
it is directly proportional to the size
of the partial charges and to the
distance between the charges

Generally, the more electrons

two atoms share and the larger
the atoms are, the larger the
dipole moment
A dipole arrow
is used
to the polarity of a bond

electron poor
region

electron rich
region

d+

d-

m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m
* Note to students: You will not be
tested on DP calculation

Behavior of Polar Molecules

field off

field on
160

3.3 Covalent Bond

Molecular Geometry and Polarity

For a molecule to be polar it must

1. have polar bonds

electronegativity difference theory

2. have an unsymmetrical shape and an overall DP

vector addition

Polarity affects the intermolecular forces of

attraction
therefore boiling points and solubilities

Nonbonding pairs affect molecular geometry and

also molecular polarity

3.3 Covalent Bond

Molecule Polarity

The HCl bond is polar. The bonding electrons

are pulled toward the Cl end of the molecule. The
net result is a polar molecule.

3.3 Covalent Bond

Molecule Polarity

The OC bond is polar. The bonding electrons are

pulled equally toward both O ends of the molecule. The 2
dipole cancell out each other. The net result is a nonpolar
molecule.

3.3 Covalent Bond

Molecule Polarity

The HO bond is polar. Both sets of bonding electrons are pulled

toward the O end of the molecule. A net dipole moment (dotted dipole
arrow) appears. The net result is a polar molecule.

3.3 Covalent Bond

Predicting Polarity of Molecules

1. Draw the Lewis structure and determine the

molecular geometry
2. Determine whether the bonds in the molecule
are polar or non-polar
3. Determine whether the polar bonds add
together to give a net dipole moment

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

Predict whether NH3 is a polar molecule

2. Determine if the bonds are

polar
a) Find electronegativity
difference EN
b) if the bonds are not polar,
we can stop here and
declare the molecule will be
nonpolar

ENN = 3.0
ENH = 2.1
3.0 2.1 = 0.9
therefore the bonds
are polar covalent

Predict whether NH3 is a polar molecule

3) Determine whether

the polar bonds add

together to give a
net dipole moment
a) vector addition
b) generally, asymmetric
shapes result in
uncompensated
polarities and a net
dipole moment

The HN bond is polar. All

the sets of bonding
electrons are pulled toward
the N end of the molecule.
The net result is a polar
molecule.

Bond moments and resultant dipole moments

in NH3 and NF3.

169

170

Example 2
Predict whether each of the following
molecules has a dipole moment:
(a) BrCl
(b) BF3 (trigonal planar)
(c) CH2Cl2 (tetrahedral)

Example 2
Strategy
Keep in mind that the dipole moment of a
molecule depends on both the difference in
electronegativities of the elements present and
its geometry.
A molecule can have polar bonds (if the
bonded atoms have different
electronegativities), but it may not possess a
dipole moment if it has a highly symmetrical
geometry.

Example 2
Solution
(a) Because bromine chloride is diatomic, it has a
linear geometry. Chlorine is more
electronegative than bromine. so BrCl is polar
with chlorine at the negative end

Thus, the molecule does have a dipole moment.

In fact, all diatomic molecules containing
different elements possess a dipole moment.

Example 2
(b) Because fluorine is more electronegative than
boron, each BF bond in BF3 (boron trifluoride) is
polar and the three bond moments are equal.
However, the symmetry of a trigonal planar shape
means that the three bond moments exactly cancel
one another:
B-F

An analogy is an object that is pulled in the

directions shown by the three bond moments. If the
forces are equal, the object will not move.
Consequently, BF3 has no dipole moment; it is a
nonpolar molecule.

Example 2
(c) The Lewis structure of CH2Cl2 (methylene
chloride) is

This molecule is similar to CH4 in that it has

an overall tetrahedral shape. However,
because not all the bonds are identical,
there are three different bond angles: HCH,
HCCl, and ClCCl. These bond angles are
close to, but not equal to, 109.5.

Example 2
Because chlorine is more electronegative than
carbon, which is more electronegative than
hydrogen, the bond moments do not cancel and
the molecule possesses a dipole moment:

Thus, CH2Cl2 is a polar molecule.

Example 3
Explain why CO2 is nonpolar, but OCS is polar.

Ans: In CO2 the two bond moments point in

opposite directions and are of equal
magnitude. Therefore, they cancel. In OCS,
even though the two bond moments point in
opposite directions, they are not of the same
magnitude and do not cancel.

CHECKPOINT 9
List the following molecules in order of
decreasing dipole moment: H2O, HF, CO2

Answer: HF, H2O,CO2