Chapter 09

Lecture
Outline
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Chapter 9

Models of Chemical Bonding

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Models of Chemical Bonding

9.1 Atomic Properties and Chemical Bonds
9.2 The Ionic Bonding Model
9.3 The Covalent Bonding Model
9.4 Bond Energy and Chemical Change
9.5 Between the Extremes:
Electronegativity and Bond Polarity

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Figure 9.1

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A comparison of metals and nonmetals.

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.

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Figure 9.2

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Three models of chemical bonding.

Figure 9.3

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Gradations in bond type among Period 3

(black type) and Group 4A (red type) elements.

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

or N

or

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or

Lewis Symbols and Bonding

For a metal, the total number of dots in the Lewis symbol
is the number of electrons the atom loses to form a cation.
For a nonmetal, the number of unpaired dots equals
- the number of electrons the atom gains to form an anion
- or the number it shares to form covalent bonds.
The octet rule states that when atoms bond, they lose,
gain, or share electrons to attain a filled outer level of 8
electrons (or 2, for H and Li).

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Figure 9.4
Lewis electron-dot symbols for elements in Periods 2 and 3.

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The Ionic Bonding Model

An ionic bond is formed when a metal transfers electrons
to a nonmetal to form ions, which attract each other to
give a solid compound.
The total number of electrons lost by the metal atom(s)
equals the total number of electrons gained by the
nonmetal atoms.

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Figure 9.5 Three ways to depict electron transfer in the formation

of Li+ and F-.
Electron configurations

Li+ 1s2 + F-

Li 1s22s1 + F 1s22p5

1s22s22p6

Orbital diagrams

Li

1s

2s

2p

1s

2s

2p

Li+

F-

1s

2s

2p

1s

2s

2p

Lewis electron-dot symbols

Li

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Li

Sample Problem 9.1

Depicting Ion Formation

PROBLEM: 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.
PLAN: Draw orbital diagrams and Lewis symbols for Na and O
atoms. To attain filled outer levels, Na loses one electron and
O gains two. Two Na atoms are needed for each O atom so
that the number of electrons lost equals the number of
electrons gained.
SOLUTION:

Na

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2Na+

2+ O

Na

Sample Problem 9.1

Na

3s

Na

3p

2s

3s

3p

2Na+ + O2-

2s

2p

The formula is Na2O

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2p

Figure 9.6

Na(s)

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The exothermic formation of sodium bromide.

Br2(l)

NaBr(l)

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.

Coloumbs Law
Electrostatic energy
Electrostatic energy

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charge A x charge B
distance
cation charge x anion charge
cation radius + anion radius

Holattice

Periodic Trends in Lattice Energy

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.

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Figure 9.7

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Trends in lattice energy.

Properties of Ionic Compounds

Ionic compounds tend to be hard, rigid, and brittle, with
high melting points.
Ionic compounds do not conduct electricity in the solid
state.
In the solid state, the ions are fixed in place in the lattice and do
not move.

Ionic compounds conduct electricity when melted or

dissolved.
In the liquid state or in solution, the ions are free to move and
carry a current.

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Figure 9.8

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Why ionic compounds crack.

Figure 9.9

Solid ionic
compound

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Electrical conductance and ion mobility.

Molten ionic
compound

Ionic compound
dissolved in water

Table 9.1 Melting and Boiling Points of Some Ionic Compounds

Compound

bp (C)

CsBr

636

1300

NaI

661

1304

MgCl2

714

1412

KBr

734

1435

CaCl2

782

>1600

NaCl

801

1413

LiF

845

1676

KF

858

1505

2852

3600

MgO

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mp (C)

Figure 9.10

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Covalent bond formation in H2.

Figure 9.11

Distribution of electron density in H2.

At some distance (bond length),

attractions balance repulsions.

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Electron density is high around

and between the nuclei.

Bonding Pairs and Lone Pairs

Atoms share electrons to achieve a full outer level of
electrons. The shared electrons are called a shared pair
or bonding pair.
The shared pair is represented as a pair of dots or a line:

H H

or

HH

An outer-level electron pair that is not involved in

bonding is called a lone pair, or unshared pair.

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or

FF

F F

Properties of a Covalent Bond

The bond order is the number of electron pairs being
shared by a given pair of atoms.
A single bond consists of one bonding pair and has a bond order of 1.

The bond energy (BE) is the energy needed to

overcome the attraction between the nuclei and the
shared electrons. The stronger the bond the higher the
bond energy.
The bond length is the distance between the nuclei of
the bonded atoms.

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Trends in bond order, energy, and length

For a given pair of atoms, a higher bond order results in a
shorter bond length and higher bond energy.
For a given pair of atoms, a shorter bond is a stronger bond.
Bond length increases down a group in the periodic table
and decreases across the period.
Bond energy shows the opposite trend.

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Table 9.2 Average Bond Energies (kJ/mol) and Bond Lengths (pm)

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Table 9.3 The Relation of Bond Order, Bond Length,

and Bond Energy

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Figure 9.12
Internuclear distance
(bond length)

Bond length and covalent radius.

Covalent
radius

Internuclear distance
(bond length)

72 pm

Internuclear distance
(bond length)

Covalent
radius
100 pm

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Covalent
radius
114 pm

Internuclear distance
(bond length)

Covalent
radius
133 pm

Sample Problem 9.2

Comparing Bond Length and Bond Strength

PROBLEM: Using the periodic table, but not Tables 9.2 or 9.3, rank
the bonds in each set in order of decreasing bond length
and decreasing bond strength:
(a) SF, SBr, SCl

(b) C=O, CO, CO

PLAN: (a) S is singly bonded to three different halogen atoms, so the

bond order is the same. Bond length increases and bond
strength decreases as the atomic radius of the halogen
increases.
(b) The same two atoms are bonded in each case, but the
bond orders differ. Bond strength increases and bond
length decreases as bond order increases.

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Sample Problem 9.2

SOLUTION:
(a) Atomic size increases going down a group, so F < Cl < Br.
Bond length: SBr > SCl > SF
Bond strength: SF > SCl > SBr
(b) By ranking the bond orders, we get
Bond length: CO > C=O > CO
Bond strength: CO > C=O > CO

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Figure 9.13
Strong forces within molecules and weak forces between them.

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Figure 9.14

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Covalent bonds of network covalent solids:

quartz and diamond.

Figure 9.15

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The infrared (IR) spectra of 2-butanol (green) and

diethyl ether (red).

Bond Energies and Horxn

The heat released or absorbed during a chemical change
is due to differences between the bond energies of
reactants and products.
Hrxn = Hreactant bonds broken+ Hproduct bonds formed

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Figure 9.16

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Using bond energies to calculate Hrxn for

HF formation.

Figure 9.17

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Using bond energies to calculate Hrxn for the

combustion of methane.

Sample Problem 9.3

Using Bond Energies to Calculate Hrxn

PROBLEM: Calculate Hrxn for the chlorination of methane to form

chloroform.

bonds broken
H positive
PLAN:

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bonds formed
H negative

All the reactant bonds break, and all the product bonds form.
Find the bond energies in Table 9.2 and substitute the two
sums, with correct signs, into Equation 9.2.

Sample Problem 9.3

SOLUTION:
For bonds broken:
4 x C-H = (4 mol)(413 kJ/mol) = 1652 kJ
3 x Cl-Cl = (3 mol)(243 kJ/mol) = 729 kJ
Hbonds broken = 2381 kJ
For bonds formed:
3 x C-Cl = (3 mol)(-339 kJ/mol) = -1017 kJ
1 x C-H = (1 mol)(-413 kJ/mol) = -413 kJ
3 x H-Cl = (3 mol)(-427 kJ/mol) = -1281 kJ
Hbonds formed = -2711 kJ
Hreaction = Hbonds broken + H bonds formed
= 2381 kJ + (-2711 kJ) = - 330 kJ

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Electronegativity and Bond Polarity

A covalent bond in which the shared electron pair is not
shared equally, but remains closer to one atom than the
other, is a polar covalent bond.
The ability of an atom in a covalent bond to attract the
shared electron pair is called its electronegativity.
Unequal sharing of electrons causes the more
electronegative atom of the bond to be partially negative
and the less electronegative atom to be partially positive.

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Figure 9.18

Bonding between the models.

Polar covalent bonds are much

more common than either pure
ionic or pure covalent bonds.

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Figure 9.19

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The Pauling electronegativity (EN) scale.

Trends in Electronegativity
The most electronegative element is fluorine.
In general electronegativity decreases down a group
as atomic size increases.
In general electronegativity increases across a
period as atomic size decreases.
Nonmetals are more electronegative than metals.

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Electronegativity and Oxidation Number

Electronegativities can be used to assign oxidation numbers:
The more electronegative atom is assigned all the
shared electrons.
The less electronegative atom is assigned none of the
shared electrons.
Each atom in a bond is assigned all of its unshared
electrons.
O.N. = # of valence e- (# of shared e- + # of unshared e-)

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Example:
Cl is more electronegative than H, so for Cl:
valence e- = 7
shared e=2
unshared e- = 6
O.N.
= 7 (2 + 6) = -1
H is less electronegative than Cl, so for H:
valence e- = 1
shared e= 0 (all shared e- assigned to Cl)
unshared e- = 0
O.N.
= 1 (0 + 0) = +1
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Depicting Polar Bonds

The unequal sharing of electrons can be depicted by a
polar arrow. The head of the arrow points to the more
electronegative element.

A polar bond can also be marked using + and - symbols.

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Figure 9.20

Electron density distributions in H2, F2, and HF.

In HF, the electron density shifts from H to F.

The HF bond has partial ionic character.

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Figure 9.21

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EN ranges for classifying the partial ionic

character of bonds.

Figure 9.22

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Percent ionic character as a function of EN.

Sample Problem 9.4

Determining Bond Polarity from EN Values

PROBLEM: (a) Use a polar arrow to indicate the polarity of each

bond: NH, FN, ICl.
(b) Rank the following bonds in order of increasing
polarity: HN, HO, HC.
PLAN: (a) We use Figure 9.21 to find the EN values for each
element. The polar arrow points toward the more
electronegative element.
(b) The greater the EN between the atoms, the more polar
the bond.
SOLUTION: (a) The EN values are:
N = 3.0, H = 2.1; F = 4.0; I = 2.5, Cl = 3.0
NH

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FN

ICl

Sample Problem 9.4

(b) The EN values are:
N = 3.0, H = 2.1; O = 3.5; C = 2.5
EN for HN = 3.0 2.1 = 0.9
EN for HO = 3.5 2.1 = 1.4
EN for HC = 2.5 2.1 = 0.4
H-C < H-N < H-O

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Figure 9.23

Properties of the Period 3 chlorides.

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As EN decreases, melting point and electrical conductivity decrease because

the bond type changes from ionic to polar covalent to nonpolar covalent.

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