Chapter 9 Ionic and Covalent Bonding PDF

Chapter 9
Ionic and
Covalent Bonding
Contents and Concepts
Ionic Bonds
Molten salts and aqueous solutions of salts are
electrically conducting. This conductivity results
from the motion of ions in the liquids. It suggests
the possibility that ions exist in certain solids, held
together by the attraction of ions of opposite
charges.
1. Describing Ionic Bonds

2. Electron Configurations of Ions
3. Ionic Radii
Copyright Cengage Learning. All rights reserved. 9|2
Covalent Bonds
Not all bonds can be ionic. Hydrogen, H2, is a clear
example in which there is a strong bond between
two like atoms. The bonding in the hydrogen
molecule is covalent. A covalent bond forms
between atoms by the sharing of a pair of
electrons.
4. Describing Covalent Bonds
5. Polar Covalent Bonds; Electronegativity
6. Writing Lewis Electron-Dot Formulas
7. Delocalized Bonding: Resonance
8. Exceptions to the Octet Rule
9. Formal Charge and Lewis Formulas
10. Bond Length and Bond Order
11. Bond Energy
Learning Objectives
Ionic Bonds
1. Describing Ionic Bonds
a. Define ionic bond.
b. Explain the Lewis electron-dot symbol of an
atom.
c. Describe the energetics of ionic bonding.
d. Define lattice energy.
e. Describe the BornHaber cycle to obtain a
lattice energy from thermodynamic data.
f. Describe some general properties of ionic
substances.
2. Electron Configurations of Ions
a. State the three categories of monatomic
ions of main-group elements.
b. Write the electron configuration and Lewis
symbol for a main-group ion.
c. Note the polyatomic ions given earlier in
Table 2.5.
d. Note the formation of +2 and +3 transition-
metal ions.
e. Write the electron configurations of
transition-metal ions.

3. Ionic Radii
a. Define ionic radius.
b. Define isoelectronic ions.
c. Use periodic trends to obtain relative ionic
radii.

Covalent Bonds
4. Describing Covalent Bonds
a. Describe the formation of a covalent bond
between two atoms.
b. Define Lewis electron-dot formula.
c. Define bonding pair and lone (nonbonding)
pair of electrons.
d. Define coordinate covalent bond.
e. State the octet rule.
f. Define single, double, and triple bond.

5. Polar Covalent Bonds; Electronegativity
a. Define polar covalent bond.
b. Define electronegativity.
c. State the general periodic trends in
electronegativity.
d. Use electronegativity to obtain relative bond
polarity.
6. Writing Lewis Electron-Dot Formulas

a. Write Lewis formulas having single bonds.
b. Write Lewis formulas having multiple
bonds.
c. Write Lewis formulas for ionic species.
7. Delocalized Bonding: Resonance
a. Define localized bonding.
b. Define resonance description.
c. Write resonance forms.
8. Exceptions to the Octet Rule

a. Write Lewis formulas (exceptions to the
octet rule).
b. Note exceptions to the octet rule in Group
IIA and Group IIIA.

9. Formal Charge and Lewis Formulas
a. Define formal charge.
b. State the rules for obtaining the formal
charge.
c. State two rules useful in writing Lewis
formulas.
d. Use formal charges to determine the best
Lewis formula.
Copyright Cengage Learning. All rights reserved. 9 | 10

10. Bond Length and Bond Order
a. Define bond length (bond distance).
b. Define covalent radii.
c. Define bond order.
d. Explain how bond order and bond length
are related.
11. Bond Energy

a. Define bond energy.
b. Estimate DH from bond energies.

A chemical bond is a strong attractive force that
exists between certain atoms in a substance.
There are three types of chemical bonds:

Ionic bonds
Covalent bonds
Metallic bonds

An ionic bond is a chemical bond formed by the
electrostatic attraction between positive and
negative ions.

An ionic bond forms when one or more electrons
are transferred from the valence shell of one atom
to the valence shell of another atom.
Na ([Ne]3s1) + Cl ([Ne]3s23p5)
Na+ ([Ne]) + Cl ([Ne]3s23p6)
The atom that transferred the electron(s) becomes

a cation.
The atom that gained the electron(s) becomes an
anion.

A Lewis electron-dot symbol is a notation in
which the electrons in the valence shell of an atom
or ion are represented by dots placed around the
chemical symbol of the element.
Note: Dots are placed one to a side, until all four

sides are occupied.

Table 9.1 illustrates the Lewis electron-dot
symbols for second- and third-period atoms.

Represent the transfer of electrons in
? forming calcium oxide, CaO, from

atoms.
2
Ca + O Ca2+ + [O ]

Lets look next at the energy involved in forming
ionic compounds.
The energy to remove an electron is the

ionization energy.
The energy to add an electron is the electron

affinity.

The combination of ionization energy and electron
affinity is still endothermic; the process requires
energy.
However, when the two ions bond, more than

enough energy is released, making the overall
process exothermic.

The lattice energy is the change in energy that
occurs when an ionic solid is separated into gas-
phase ions.
It is very difficult to measure lattice energy directly.

It can be found, however, by using the energy
changes for steps that give the same result.

For example, to find the lattice energy for NaCl, we
can use the following steps.

The process of finding the lattice energy indirectly
from other thermochemical reactions is called the
BornHaber cycle.

Ionic substances are typically high-melting solids.
There are two factors that affect the strength of the
ionic bond. They are given by Coulombs law:
kQ1Q2
F
r
The higher the ionic charge, the stronger the force;
the smaller the ion, the stronger the force.

Based on this relationship, we can predict the
relative melting points of NaCl and MgO.
The charge on the ions of MgO is double the

charge on the ions of NaCl. Because the charge is
double, the force will be four times stronger.
The size of Na+ is larger than that of Mg2+; the size

of Cl- is larger than that of O2-. Because the
distance between Mg2+ and O2- is smaller than the
distance between Na+ and Cl-, the force between
Mg2+ and O2- will be greater.
Based on the higher charge and the smaller
distance for MgO, its melting point MgO should be
significantly higher than the melting point of NaCl.
The actual melting point of NaCl is 801C; the

melting point of MgO is 2800C.

When we examine the electron configuration of
main-group ions, we find that each element gains
or loses electrons to attain a noble-gas
configuration.

Give the electron configuration and the
? Lewis symbol for the chloride ion, Cl-.
For chlorine, Cl, Z = 17, so the Cl- ion has 18

electrons. The electron configuration for Cl- is
1s2 2s2 2p6 3s2 3p6

The Lewis symbol for Cl [ ]
is Cl

Group IIIA to VA metals often exhibit two different
ionic charges: one that is equal to the group
number and one that is 2 less than the group
number.
The higher charge is due to the loss of both the s

subshell electrons and the p subshells electron(s).
The lower charge is due to the loss of only the p
subshell electron(s).
For example, in Group IVA, tin and lead each form

both +4 and +2 ions. In Group VA, bismuth forms
+5 and +3 ions.

Polyatomic ions are atoms held together by
covalent bonds as a group and that, as a group,
have gained or lost one or more electron.

Transition metals form several ions.
The atoms generally lose the ns electrons before

losing the (n 1)d electrons.
As a result, most transition metals form the +2 ion.

Give the electron configurations of Mn
? and Mn2+.
Manganese, Z = 25, has 25 electrons. Its electron

configuration is
1s2 2s2 2p6 3s2 3p6 3d5 4s2
Mn2+ has 23 electrons. When ionized, Mn loses

the 4s electrons first; the electron configuration for
Mn2+ is
1s2 2s2 2p6 3s2 3p6 3d5
Concept Check 9.1
The following are electron configurations for some
ions. Which ones would you expect to see in
chemical compounds? State the concept or rule you
used to decide for or against any ion.
a. Fe2+ [Ar]3d 44s2 b. N2 [He]2s22p5 c. Zn2+ [Ar]3d10
d. Na2+ [He]2s2p5 e. Ca2+ [Ne]3s23p6

a. Fe2+: [Ar]3d44s2
No. The 4s2 electrons would be lost before the
3d electrons.
b. N2-: [He]2s22p5
No. Nitrogen will gain three electrons to fill the
shell, forming N3-.
c. Zn2+: [Ar]3d10
Yes!
d. Na2+: [He]2s22p5
No. Sodium will lose only its one valence
electron, forming Na+.
e. Ca2+: [Ne]3s23p6
Yes!
Ionic radius is a measure of the size of the
spherical region around the nucleus of an ion
within which the electrons are most likely to be
found. While ionic radius, like atomic radius, can
be somewhat arbitrary, it can be measured in ionic
compounds.

A cation
is always
smaller
than its
neutral
atom.
An anion
is always
larger than
its neutral
atom.
The term isoelectronic refers to different species
having the same number and configuration of
electrons.
For example, Ne, Na+, and F- are isoelectronic.
Ionic radius for an isoelectronic series decreases

with increasing atomic number.

Using the periodic table only, arrange
? the following ions in order of increasing

ionic radius: Br-, Se2-, Sr2+.
34 35 These ions are

Se Br isoelectronic,
38 so their size decreases
Sr with increasing atomic
number:
Sr2+ < Br- < Se2-

A covalent bond is a chemical bond formed by
sharing a pair of electrons.

To consider how a covalent bond forms, we can
monitor the energy of two isolated hydrogen atoms
as they move closer together.
The energy decreasesfirst gradually, and then

more steeplyto a minimum. As the atoms
continue to move closer, it increases dramatically.
The distance between the atoms when energy is at

a minimum is called the bond length.
This is illustrated on the following graph, from right

to left.
As the hydrogen atoms move closer together, the
electron of each atom is attracted to both its own
nucleus and the nucleus of the second atom. The
electron probability distribution illustrates this
relationship.

A formula using dots to represent valence
electrons is called a Lewis electron-dot formula.
An electron pair is represented by two dots.
A electron pair that is between two atoms is a

bonding pair. It can also be represented by one
line for each bonding pair.
Electron pairs that are not bonding are

nonbonding, or lone pair electrons.

A coordinate covalent bond is formed when both
electrons of the bond are donated by one atom.
H H +
H+ + NH H NH
H H
The two electrons forming the bond with the

hydrogen on the left were both donated by the
nitrogen. Once shared, they are indistinguishable
from the other NH bonds.

In forming covalent bonds, atoms tend toward
having a full eight electrons in their valence shell.
This tendency is called the octet rule.
Hydrogen is an exception to the octet rule: it has

two electrons in its valence shell (a duet).

A single bond is a covalent bond in which one
pair of electrons is shared by two atoms.
A double bond is a covalent bond in which two

pairs of electrons are shared by two atoms.
A triple bond is a covalent bond in which three

pairs of electrons are shared by two atoms.
Double bonds form primarily with C, N, and O.

Triple bonds form primarily with C and N.

A polar covalent bond (or polar bond) is a
covalent bond in which the bonding electrons
spend more time near one atom than near the
other atom.
Electronegativity, X, is a measure of the ability of

an atom in a molecule to draw bonding electrons
to itself. Electronegativity is related to ionization
energy and electron affinity.

Electronegativity increases from left to right and
from bottom to top in the periodic table. F, O, N,
and Cl have the highest electronegativity values.
The difference in electronegativity between the two
atoms in a bond is a rough measure of bond
polarity.
When the difference is very large, an ionic bond

forms. When the difference is large, the bond is
polar. When the difference is small, the bond is
nonpolar.

Using electronegativities, arrange the
? following bonds in order by increasing

polarity: CN, NaF, OH.
For CN, the difference is 3.0 (N) 2.5 (C) = 0.5.
For NaF, the difference is

4.0 (F) 0.9 (Na) = 3.1.
For OH, the difference is 3.5 (O) 2.1 (H) = 1.4.
Bond polarities: CN < OH < NaF

Writing Lewis Electron-Dot Formulas
1. Calculate the number of valence electrons.
2. Write the skeleton structure of the molecule or
ion.
3. Distribute electrons to the atoms surrounding
the central atom or atoms to satisfy the octet
rule.
4. Distribute the remaining electrons as pairs to
the central atom or atoms.

Write the electron dot formulas for the
? following:
a. OF2
b. NF3
c. NH2OH, hydroxylamine

Count the valence electrons in OF2:
O 1(6)
F 2(7) F O F
20 valence electrons
O is the central atom (it is less electronegative).

Now, we distribute the remaining 16 electrons,
beginning with the outer atoms. The last four
electrons go on O.

Count the valence electrons in NF3:
N 1(5)
F N F
F 3(7)
26 valence electrons F
N is the central atom (it is less electronegative).

Now, we distribute the remaining 20 electrons,
beginning with the outer atoms. The last two
electrons go on N.

Count the electrons in NH2OH:
N 1(5)
H N O H
H 3(1)
O 1(6) H
N is the central atom. Now, we distribute the

remaining six electrons, beginning with the outer
atoms. The last two electrons go on N.

? Write electron-dot formulas for the
following:
a. CO2
b. HCN

Count the electrons in CO2:
C 1(4)
O 2(6) C
O O
C is the central atom. Now, we distribute the
remaining 12 electrons, beginning with the outer
atoms.
Carbon does not have an octet, so two of the lone
pairs shift to become a bonding pair, forming
double bonds.

Count the electrons in HCN:
H 1(1)
C 1(4)
N 1(5) H C N
C is the central atom. The remaining electrons go

on N.
Carbon does not have an octet, so two of the lone
pairs shift to become a bonding pair, forming a
triple bond.

Phosphorus pentachloride exists in
? solid state as the ionic compound

[PCl4]+[PCl6]-; it exists in the gas phase
as the PCl5 molecule. Write the Lewis
formula of the PCl4+ ion.

Count the valence electrons in PCl4+:
P 1(5) Cl +
Cl 4(7)
1 Cl P Cl
Cl
P is the central atom. The remaining 24 nonbonding

electrons are placed on Cl atoms. Add square
brackets with the charge around the ion.
Delocalized bonding is a type of bonding in which
a bonding pair of electrons is spread over a
number of atoms rather than being localized
between two atoms.

A single electron-dot diagram cannot properly
describe delocalized bonding. Using the
resonance description, the electron structure of a
molecule or ion having delocalized bonding is
given by writing all possible electron-dot formulas.
They are connected with a double-headed arrow.

Draw the resonance formulas of the
? acetate ion, CH3COO-.

CH3COO-
Valence electrons: 2(4) + 3(1) + 2(6) + 1 = 24
C is the central atom.
A double bond is needed between CO.
There are two equivalent places for it, so two
resonance structures are required.
H - H -
O O
H C C H C C
O O
H H
Some molecules have electron-dot structures that
do not satisfy the octet rule. Some have an odd
number of electrons, such as NO. Other molecules
either have too few or too many electrons around
the central atom.

Elements that have too few electrons are in
Groups IIA and IIIA. Be, B, and Al exhibit too few
electrons around the central atom.
F F F F
F Be F B Al
F F

There are many more examples of central atoms
with more than an octet. Because elements of the
third period and beyond have a d subshell, they
can expand their valence electron configurations.
S, P, Cl (as a central atom), and other elements in
period 3 are examples of atoms in this situation.
Elements in the second period, having only s and

p subshells, are unable to do this.

Give the Lewis formula of the IF5
? molecule.

Count the valence electrons in IF5:
I 1(7)
F
F 5(7)
F
F
I
F
F
I is the central atom. Thirty-two electrons remain;

they first complete F octets. The remaining
electrons go on I.

The formal charge on an atom in the Lewis formula
is the hypothetical charge you obtain by assuming
that bonding electrons are equally shared between
bonded atoms and that the electrons of each lone
pair belong completely to one atom.

Formal charge = valence electrons on free atom
(number of electrons in bonds)
(number of lone-pair electrons)
The sum of the formal charges on the atoms

equals the charge on the formula.

Formal charges can help to determine the most
likely electron-dot formula using three rules:
1. Whenever you can write several Lewis formulas
for a molecule, choose the one having the
lowest magnitudes of formal charges.
2. When two proposed Lewis formulas have the
same magnitudes of formal charges, choose the
one having the negative formal charge on the
more electronegative atom.
3. When possible, choose Lewis formulas that do
not have like charges on adjacent atoms.

Compare the formal charges for the
? following electron-dot formulas of CO2.

O C O O C O
Formal charge = group number (number of bond

pairs) (number of nonbonding electrons)
For the left structure: For the right structure:
C: 440=0 C: 440=0
O: 624=0 O: 6 1 6 = 1
O: 6 3 2 = +1
The left structure is better.
Bond length (or bond distance) is the distance
between nuclei in a bond.
Bond order is, defined in terms of the Lewis

formula, the number of pairs of electrons in a
bond.
Bond length decreases as bond order increases.

Consider the propylene molecule:
? H
C C
H
C H
134 pm H 150 pm
H H
One of the carboncarbon bonds has a length of

150 pm; the other 134 pm. Identify each bond with
a bond length.
The shorter bond is the double bond;

the longer bond is the single bond.
Bond energy is the average enthalpy change for
breaking the AB bond in a molecule in the gas
phase. Bond energy is a measure of bond
strength: the larger the bond energy, the stronger
the bond.

Bond energies can be used to estimate the
enthalpy change, DH, for a reaction. To do so, we
imagine the reaction in two steps: breaking bonds
and forming new bonds.
DH = sum of the bond energies for bonds broken

sum of the bond energies for bonds formed
When DH is negative, heat is released. When DH

is positive, heat is absorbed.

Estimate the enthalpy change for the
? H
following reaction, using bond energies:
H
H H
C C + Cl2 H C C H
H H
Cl Cl
Bonds Broken: Bonds Formed:
1 C=C 602 kJ 1 CC 346 kJ
1 ClCl 240 kJ 2 CCl 654 kJ
Absorbed 842 kJ Released 1000 kJ
DH = 842 kJ 1000 kJ
DH = 158 kJ

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Chapter 9

1. Describing Ionic Bonds

Copyright Cengage Learning. All rights reserved. 9|5

Copyright Cengage Learning. All rights reserved. 9|6

Copyright Cengage Learning. All rights reserved. 9|7

6. Writing Lewis Electron-Dot Formulas

8. Exceptions to the Octet Rule

Copyright Cengage Learning. All rights reserved. 9|9

Copyright Cengage Learning. All rights reserved. 9 | 10

11. Bond Energy

Copyright Cengage Learning. All rights reserved. 9 | 11

There are three types of chemical bonds:

Copyright Cengage Learning. All rights reserved. 9 | 12

Copyright Cengage Learning. All rights reserved. 9 | 13

The atom that transferred the electron(s) becomes

Copyright Cengage Learning. All rights reserved. 9 | 14

Note: Dots are placed one to a side, until all four

Copyright Cengage Learning. All rights reserved. 9 | 15

Copyright Cengage Learning. All rights reserved. 9 | 16

? forming calcium oxide, CaO, from

Copyright Cengage Learning. All rights reserved. 9 | 17

The energy to remove an electron is the

The energy to add an electron is the electron

Copyright Cengage Learning. All rights reserved. 9 | 18

However, when the two ions bond, more than

Copyright Cengage Learning. All rights reserved. 9 | 19

It is very difficult to measure lattice energy directly.

Copyright Cengage Learning. All rights reserved. 9 | 20

Copyright Cengage Learning. All rights reserved. 9 | 21

Copyright Cengage Learning. All rights reserved. 9 | 22

Copyright Cengage Learning. All rights reserved. 9 | 23

The charge on the ions of MgO is double the

The size of Na+ is larger than that of Mg2+; the size

The actual melting point of NaCl is 801C; the

Copyright Cengage Learning. All rights reserved. 9 | 25

Copyright Cengage Learning. All rights reserved. 9 | 26

? Lewis symbol for the chloride ion, Cl-.

For chlorine, Cl, Z = 17, so the Cl- ion has 18

Copyright Cengage Learning. All rights reserved. 9 | 27

The higher charge is due to the loss of both the s

For example, in Group IVA, tin and lead each form

Copyright Cengage Learning. All rights reserved. 9 | 28

Copyright Cengage Learning. All rights reserved. 9 | 29

The atoms generally lose the ns electrons before

As a result, most transition metals form the +2 ion.

Copyright Cengage Learning. All rights reserved. 9 | 30

Manganese, Z = 25, has 25 electrons. Its electron

Mn2+ has 23 electrons. When ionized, Mn loses

Copyright Cengage Learning. All rights reserved. 9 | 32

Copyright Cengage Learning. All rights reserved. 9 | 34

For example, Ne, Na+, and F- are isoelectronic.

Ionic radius for an isoelectronic series decreases

Copyright Cengage Learning. All rights reserved. 9 | 36

? the following ions in order of increasing

34 35 These ions are

Copyright Cengage Learning. All rights reserved. 9 | 37

Copyright Cengage Learning. All rights reserved. 9 | 38

The energy decreasesfirst gradually, and then

The distance between the atoms when energy is at

This is illustrated on the following graph, from right

Copyright Cengage Learning. All rights reserved. 9 | 41

An electron pair is represented by two dots.

A electron pair that is between two atoms is a