Chapter 9

Models of Chemical Bonding

9-1
 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 Between the Extremes: Electronegativity and Bond Polarity

9.5 An Introduction to Metallic Bonding

9-2
 Figure 9.1

A general comparison of metals and

non-metals

9-3
 Types of Chemical Bonding

1. Metal with non-metal

electron transfer and ionic bonding

2. Non-metal with non-metal

electron sharing and covalent bonding

(localized)

3. Metal with metal

electron pooling and metallic bonding

(delocalized)

9-4
 The three models of chemical bonding

Figure 9.2

9-5
 Lewis Electron-Dot Symbols

For Main Group elements:

The group number gives the number of valence electrons.

Place one dot per valence electron on each of the four sides
of the element symbol.

Pair the dots (electrons) until all of the valence electrons are
used.

Example:

Nitrogen (N) is in Group 5A and therefore has 5 valence electrons.

. . .
:

:N . . N. . N: . N.
. . .

:
9-6
 Lewis electron-dot symbols for elements in Periods 2 and 3

Figure 9.3

9-7
 General Rules

For a metal, the total number of dots equals the maximum number
of electrons it loses to form a cation.

For a non-metal, the number of unpaired dots equals the number

of electrons that become paired either through electron gain or
electron sharing. The number of unpaired dots equals either the
negative charge of the anion an atom forms or the number of
covalent bonds it forms.

9-8
 The Ionic Bonding Model

Involves the transfer of electrons from metal to non-metal to form

ions that come together in a solid ionic compound

The Octet Rule

When atoms bond, they lose, gain or share electrons to attain a filled
outer shell of eight (or two) electrons

In ionic bonding, the total number of electrons lost by the metal atoms
equals the total number of electrons gained by the non-metal atoms.

9-9
 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.
PLAN: Draw orbital diagrams for the atoms and then move electrons to
make filled outer levels. It can be seen that two sodiums are
needed for each oxygen.

SOLUTION:

Na O 2-
2s 2p
3s 3p O

2s 2p 2 Na+
Na
Na

:
3s 3p + : O: 2Na+ + :O : 2-
Na

:
.
.

9-10
Figure 9.4
Three ways to represent the formation of Li+ and F-
through electron transfer

1. Electron configurations

Li 1s22s1 + F 1s22s22p5 Li+ 1s2 + F- 1s22s22p6

2. Orbital diagrams

Li+
Li
1s 2s 2p
1s 2s 2p

+ F + F-
1s 2s 2p 1s 2s 2p

3. Lewis electron-dot symbols

.

:
Li . + :F: Li+ + : F: -

:
:

9-11
 Ionic Bonding and Lattice Energy

The electron transfer process is an endothermic process, but ionic compound

formation is an exothermic process.

Li(g) Li+ + e- IE1 = 520 kJ

F(g) + e- F-(g) EA = -328 kJ

Li(g) + F(g) Li+(g) + F-(g) IE1 + EA = 192 kJ

But ∆Hfo for solid LiF = -617 kJ/mol!

Li+(g) + F-(g) LiF(g) ∆Ho = -755 kJ

(an exothermic process due to the attraction of
oppositely charged ions)

9-12
 Even more energy is released when the gaseous ions coalesce
into a crystalline solid. Thus….

Li+(g) + F-(g) LiF(s) ∆Holattice of LiF = lattice energy = -1050 kJ

The lattice energy is the enthalpy change that occurs when gaseous
ions coalesce into an ionic solid.

How do we measure lattice energy experimentally? Use

Hess’s law in a Born-Haber cycle

9-13
 Figure 9.6 The Born-Haber cycle for lithium fluoride

9-14
 Working the Numbers

STEP 1: Enthalpy of Li atomization = 161 kJ

STEP 2: 1/2 the bond energy of F2(g)= 0.5(159 kJ) = 79.5 kJ

STEP 3: IE1 for Li(g) = 520 kJ

STEP 4: EA of F(g) = -328 kJ

The enthalpy change for the overall process, ∆Hfo, = -617 kJ

Only the lattice energy is unknown, and it is equal to the enthalpy

change of the overall process minus the sum of the above four
steps = -1050 kJ

9-15
 Central Point

Ionic solids exist only because the lattice energy drives the
energetically unfavorable electron transfer.

9-16
 Periodic Trends in Lattice Energy

Coulomb’s Law
charge A x charge B
electrostatic force 
distance2

But energy = force x distance. Therefore,

charge A x charge B
electrostatic energy 
distance

cation charge x anion charge

electrostatic energy  Holattice
cation radius + anion radius

9-17
 Trends in lattice energy

Figure 9.7

9-18
 Effect of Ionic Charge on Lattice Energy

Compare LiF and MgO: Li+ and Mg2+ have similar radii, and
F- and O2- have similar radii.

∆Holattice (LiF) = -1050 kJ/mol ∆Holattice (MgO) = -3923 kJ/mol

The nearly four-fold larger value for MgO reflects the difference in
the product of the charges (12 vs 22) in the numerator of the
electrostatic energy equation (monovalent vs divalent ions).

9-19
 Does the ionic model explain the
properties of ionic compounds?

9-20
 Electrostatic forces and
the reason ionic Figure 9.8
compounds crack

9-21
 Electrical
Conductance and
Ion Mobility

Figure 9.9
Solid ionic Molten ionic Ionic compound
compound compound dissolved in water
9-22
 Table 9.1 Melting and Boiling Points of Some Ionic Compounds

Compound mp (oC) bp (oC)

CsBr 636 1300

NaI 661 1304
MgCl2 714 1412
KBr 734 1435
CaCl2 782 >1600
NaCl 801 1413
LiF 845 1676
KF 858 1505
MgO 2852 3600

9-23
 Vaporizing an
ionic compound

Figure 9.10

9-24
 The Covalent Bonding Model

Each atom in a covalent bond “counts” the shared electrons

as belonging entirely to itself.

An electron pair that is part of an atom’s valence shell but not

involved in bonding is called a lone pair, or unshared pair.

Bond order: the number of electron pairs being shared between

any two bonded atoms

single bond (H2) - bond order of 1

double bond (H2C=CH2) - bond order of 2
triple bond (N2) - bond order of 3

9-25
Covalent bond
formation in H2

Figure 9.11

9-26
 The attractive and repulsive
forces in covalent bonding

Figure 9.12

9-27
 Properties of Covalent Bonds

Bond energy (bond enthalpy or bond strength): the energy required

to overcome the mutual attraction between the bonded nuclei and
the shared electrons.

Bond breakage is an endothermic process; bond energy is always

positive.

Bond formation is an exothermic process.

9-28
 Bond Length

For a given pair of atoms, a higher bond order results in a

shorter bond length and a higher bond energy.

A shorter bond is a stronger bond.

9-29
9-30
9-31
 Bond length and covalent radius
internuclear distance covalent internuclear distance covalent
(bond length) radius (bond length) radius

internuclear distance covalent internuclear distance covalent

(bond length) radius (bond length) radius

Figure 9.13
9-32
9-33
 SAMPLE PROBLEM 9.2 Comparing Bond Length and Bond Strength

PROBLEM: Using the periodic table, rank the bonds in each set in order of
decreasing bond length and bond strength:

(a) S - F, S - Br, S - Cl (b) C = O, C - O, C O

PLAN: (a) Bond order =1 for all and sulfur is bonded to halogens; bond
length should increase and bond strength should decrease with
increasing atomic radius. (b) Similar atoms (C) are bonded but
bond order changes; bond length decreases as bond order
increases, and bond strength increases as bond order increases.

SOLUTION:
(a) Atomic size increases (b) Using bond orders we get:
moving down a group.

Bond length: S - Br > S - Cl > S - F Bond length: C - O > C = O > C O

Bond strength: S - F > S - Cl > S - Br Bond strength: C O>C=O>C-O

9-34
 Properties of Covalent Compounds

Weak forces between molecules, not the strong covalent

bonds within each molecule, are responsible for the
physical properties of covalent compounds.

Covalent compounds have relatively low melting and boiling

points.

Most covalent compounds are poor electrical conductors.

9-35
Strong forces within molecules, weak forces between them

Figure 9.14 Strong covalent bonding forces within molecules

Weak intermolecular forces between molecules

9-36
 Network Covalent Solids

No separate molecules; held together by covalent bonds that

extend throughout the sample

quartz: melts at 1550 oC.

diamond: melts at 3550 oC.

These examples illustrate the strength of covalent bonds.

9-37
 Covalent bonds of network covalent solids

Figure 9.15

9-38
 The Concept of Electronegativity (EN)

Defined as the relative ability of a bonded atom to attract

shared electrons (not the same as EA)

Bond energy of H2 = 432 kJ/mol

Bond energy of F2 = 159 kJ/mol
Bond energy of HF = 565 kJ/mol, not 296 kJ/mol

The stronger-than-expected HF bond is due to unequal

sharing of electrons, with F bearing a partial negative
charge and H bearing a partial positive charge. The
attraction between the partial charges strengthens the
bond.

9-39
 The Pauling electronegativity (EN) scale

Figure 9.16
9-40
 Trends in Electronegativity

In general, electronegativity is inversely related to

atomic size.

For main-group elements, EN generally increases up

a group and across a period.

Non-metals are more electronegative than metals.

The least electronegative (most electropositive) non-

radioactive element is Cs (lower left-hand corner of
the Periodic Table).

9-41
 Electronegativity and atomic size

Figure 9.17
9-42
 Electronegativity and Oxidation Number

(a) The more electronegative atom in a bond is assigned

all of the shared electrons; the less electronegative atom is
assigned none of the shared electrons.

(b) Each atom in a bond is assigned all of its unshared

electrons.

(c) The oxidation number is given by:

O.N. = # valence e- - (# shared e- + # unshared e-)

e.g.: HCl: Cl more electronegative than H; has 7 valence

electrons; has an O.N. of 7 - 8 = -1
H has 1 valence electron; has an O.N. of 1 - 0 = +1

9-43
 Polar Covalent Bonds and Bond Polarity

Covalent bonds involving atoms with different electronegativities:

generate partial (+) and (-) charges; defined as polar covalent
bonds (e.g., HCl)

Polar covalent bonds: depicted by a polar arrow ( ) that

points toward the negative pole

H2 and F2: examples of nonpolar covalent bonds

9-44
 SAMPLE PROBLEM 9.3 Determining Bond Polarity from EN Values

PROBLEM: (a) Use a polar arrow to indicate the polarity of each bond:
N-H, F-N, I-Cl.
(b) Rank the following bonds in order of increasing polarity:
H-N, H-O, H-C.

PLAN: (a) Use Figure 9.16 to find EN values; the arrow should point
toward the negative end.

(b) EN increases across a period.

SOLUTION: (a) The EN of N = 3.0, H = 2.1, F = 4.0, I = 2.5, Cl = 3.0

N-H F-N I - Cl

(b) The order of increasing EN is C < N < O; all have an EN

larger than that of H.

H-C < H-N < H-O

9-45
 Partial Ionic Character of Polar Covalent Bonds

Related directly to the electronegativity difference (∆EN) between

the bonded atoms

The greater the ∆EN, the larger the partial charges and the higher
the partial ionic character (PIC).

Thus LiF has more PIC than HF; HF has more PIC than F2.

9-46
 3.0

2.0
EN

Boundary ranges for

classifying the ionic
character of chemical
bonds

Figure 9.18 0.0

9-47
 Percent ionic character as a function of
electronegativity difference (EN)

Figure 9.19
9-48
 Charge density of
the LiF molecule
(an ionic compound)

Li F

No bond has 100%

ionic character; electron
sharing occurs to some extent

Figure 9.20

9-49
 Ionic-To-Covalent Bonding Continuum Across a Period

Consider bonding between a metal and non-metal in Period 3

NaCl, MgCl2, AlCl3, SiCl4, PCl3, S2Cl2, and Cl2

Increasing covalent character (decreasing ionic character)

from NaCl to Cl2

Underlying factor: As ∆EN becomes smaller, the bond becomes

more covalent.

9-50
 Figure 9.21

Properties of the Period 3 chlorides

9-51
 Metallic Bonding

The electron-sea model: all metal atoms in the sample

contribute their valence electrons to form an “electron
sea” that is delocalized throughout the substance

The metal atoms are not held in place as rigidly as are

the ions of an ionic solid.

9-52
 Table 9.5 Melting and Boiling Points of Some Metals

element mp (oC) bp (oC)

lithium (Li) 180 1347

tin (Sn) 232 2623

aluminum (Al) 660 2467

barium (Ba) 727 1850

silver (Ag) 961 2155

copper (Cu) 1083 2570

uranium (U) 1130 3930

9-53
 Melting points of the Group 1A and Group 2A elements

Figure 9.23

9-54
 The reason metals deform metal is deformed

Figure 9.24

9-55
 Tools of the Laboratory

Infrared Spectroscopy
Figure B9.1

Some vibrational modes in general diatomic and triatomic molecules

9-56
 Tools of the Laboratory

Infrared
Spectroscopy

Some vibrational
modes in general
diatomic and triatomic
molecules

Figure B9.1

9-57
 Tools of the Laboratory Infrared Spectroscopy

Some vibrational modes

in general diatomic and
triatomic molecules.

Figure B9.1

9-58
 Tools of the Laboratory

Figure B9.2

The infrared (IR) spectrum of acrylonitrile

9-59