9

Chemical Bonding 1: Basic Concepts

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

9.1 Introduction: Types of Chemical Bonds

9.1.1 Types of chemical bonds

The nature and type of a chemical bond are determined primarily by the valence electrons (those
in the outermost shell of an atom) shared or transferred between bonded atoms. According to
Lewis Theory, a chemical bond is formed when the bonding atoms share or transfer electrons to
achieve a stable electronic configuration.
An ionic bond is formed if electrons are completely transferred, as in the case of a reaction
between a metal and a nonmetal. On the other hand, a covalent bond is formed if electrons
are shared, such as between two nonmetals with similar electronegativities. There are two other
variations of covalent bonding. The first is a polar covalent bond, which is a bond between
two nonmetal atoms that have significantly different electronegativities and therefore share the
bonding pair unequally. The other, a dative covalent bond (also called a coordinate bond), is a
covalent bond in which one of the atoms provides both of the shared electrons. Finally, metallic
bonding involves the sharing of valence electrons among all the atoms of a metal or metal alloy.

9.2 Lewis Dot Symbols

A Lewis dot symbol (or Lewis structure) is used to describe valence electron configurations of
atoms and monatomic ions, and can be helpful in determining how bonds are formed. It consists
of the chemical symbol of the element, with dots for each valence electron, placed one at a time
around the four sides of the symbol. It is generally written only for main group or representative
elements. The number of valence electrons for these elements is equal to the group number.
Representative examples are

Li Be B C N O F Ne

Note that elements in the same group have the same number of valence electrons and therefore
similar Lewis dot symbols.

Chemistry in Quantitative Language: Fundamentals of General Chemistry Calculations. Second Edition.

Christopher O. Oriakhi, Oxford University Press. © Christopher O. Oriakhi 2021.
DOI: 10.1093/oso/9780198867784.003.0009
82 Chemistry in Quantitative Language

Lewis dot symbols can be written for ions just as they are for atoms. The only difference is that
cations have fewer electrons than the neutral atoms, while anions have more. Also, the Lewis dot
symbol includes square brackets and the charge on the ion. Anions have eight dots (a full octet)
surrounding them, but for cations the dots are omitted because they have no valence electrons.
Thus, Lewis dot symbols for sulfur and aluminum ions would be written as:

2– 3+
S Al

Example 9.1

Write the Lewis dot symbols for (a) Al (b) Ca2+ (c) P (d) O2−

Solution

First write the symbol of the atom or ion. Then determine the valence electrons available and
draw them around the atom. Show the ion charge as a superscript outside square brackets.
Remember that cations have no valence electrons and so are shown with no dots.
2+ 2–
(a) Al (b) Ca (c) P (d) O

9.2.1 Octet rule

The octet rule states that atoms will gain, lose, or share electrons until they are surrounded by
eight valence electrons, with the ns2 np6 electronic configuration of noble gases. This gives them
the remarkable stability associated with the noble gases. For example, in the formation of ionic
KF, K loses an electron to achieve the electronic configuration of argon while F gains an electron
to attain the electronic configuration of neon.

–
K + F K+ F

[Ar]4s1 [He]2s22p5 [Ar] [Ne]

9.2.2 Duet rule

Atoms with low atomic numbers that have fewer electrons than needed to provide an octet for
every atom follow the duet rule. They gain, lose, or share electrons until they are surrounded by
two electrons. For example, during bond formation, elements like H, He, and Li gain, lose, or
share electrons to form a duet.
 Chemical Bonding 1: Basic Concepts 83

9.3 Ionic Bonding: Formation of Ionic Compounds

An ionic compound is formed when a metal reacts with a nonmetal. In the reaction, cations and
anions are formed by electron transfer from metals to nonmetals. These oppositely charged ions
become bound together as an ionic solid via electrostatic interactions. Consider the formation of
sodium chloride (NaCl) as an example. Sodium reacts violently with chlorine gas to form sodium
chloride. The reaction is exothermic, releasing a large amount of heat.
◦
Na (s) + 1/2Cl2 (g) −→ NaCl (s) Hf = −410.9 kJ

In this reaction the sodium atom loses an electron to become Na+ , and the chlorine gains the
electron to become Cl– . Consequently both Na+ and Cl– acquire an octet of electrons. The
ions then aggregate by virtue of electrostatic interactions to form solid NaCl. In this crystalline
solid, each Na+ ion is surrounded by six Cl– ions and each Cl– ion is surrounded by six Na+
ions. This arrangement repeats itself numerous times to yield a regular array or crystal structure
of NaCl.

9.3.1 Lattice energies and the strength of the ionic bond

Energy is required to form ionic bonds. This energy and hence the stability of the compound
comes largely from the coulomb or electrostatic attraction between oppositely charged ions
within the ionic solid. The strength of the electrostatic attraction or the ionic bond is measured by
the lattice energy of the compound. The lattice energy or lattice enthalpy (H lattice ) is defined as
the energy released when one mole of a crystalline ionic compound is formed from its free,
gaseous elements. For the ionic solid MX, the lattice energy is the enthalpy change for the
reaction

Mn+ (g) + Xn− (g) −→ MX(s) Hlattice

For example, the formation of crystalline NaCl solid is highly exothermic as shown by the large
negative value of the lattice energy.

Na+ (g) + Cl− (g) −→ NaCl (s) Hlattice = −788 kJ

For the convention used here, where the free gaseous ions combine to form an ionic solid, the
lattice energies will be exothermic (negative values). Note that some textbooks adopt a different
convention that defines lattice energy as the energy required (endothermic process) to separate
one mole of ionic solid into its component gaseous ions and therefore with positive H lattice
values.
The lattice energy of an ionic solid cannot be measured directly because it is experimentally
difficult to isolate gaseous ions. However, the energy value can be estimated using the Born–
Haber cycle. This is treated in detail in Chapter 20.
84 Chemistry in Quantitative Language

9.3.2 Calculating lattice energies of ionic solids

The lattice energy of an ionic solid can be calculated by using a modified form of Coulomb’s
law (the point charge model). However, the calculated values are generally higher than the
experimentally measured lattice energies.
 
Q1 Q2 −19 Q1 Q2
Hlattice = k = 2.31 × 10 J· nm
d d
Here, U is the lattice energy; Q1 and Q2 are charges on the ions; d is the interionic distance (the
sum of the radii of the positive and negative ions) and k is a constant equal to 1/4πo or 2.31 ×
10−19 J.nm (o is the permittivity of the vacuum).
The lattice energy of an ionic solid depends on:
• The magnitude of the ionic charges
• The radius or size of the ions
• The distance between charges

Large lattice energy is indicative of a tightly bound solid due to a stronger interaction between
the constituent ions.
Note that lattice energy increases both as the ionic charge increases and as the ionic size
decreases (smaller ions are closer together and interact more strongly).

Example 9.2

Account for the following trend in lattice energy:

Metal oxide Lattice energy (kJ/mol)

BeO −4293
MgO −3795
CaO −3414
SrO −3217
BaO −3029

Solution

Trends in lattice energies of ionic compounds can be explained mainly by considering both
the charge on the ions and the ionic radius. All these metal oxides are in group 2A of
the periodic table, so the metal ions all have a charge of +2 (and of course the oxygen is
always −2). Further, the O2− ion is the same size in all the compounds, so the lattice energy
depends on the radius of the positive ion, which increases from Be2+ to Ba2+ . In other words,
the Be2+ is closer to the O2− than the Ba2+ is, and so can interact more strongly, and hence
will have greater lattice energy.

Example 9.3

What is the lattice energy in kJ/mol of the ionic bond between a sodium ion and a chloride
ion? The ionic radii of Na+ and Cl− are 186 pm and 181 pm, respectively.
 Chemical Bonding 1: Basic Concepts 85

Solution

Given:
 
QCl − = −1 the Cl− ion’s charge
 
QNa + = +1 the charge of the Na+ ion
NA = 6.022 × 1023 ion pairs mol−1

1. Compute the distance (d) between the nuclei of Na+ and Cl− and express it in nm to use
the simplified equation for lattice energy.
   
d = Na+ ionic radius + Cl− ionic radius
= 186pm + 181pm = 367 pm or 0.367 nm

2. Calculate the lattice energy in J using the modified coulombic attraction equation:
 
−19 Q1 Q2
Hlattice = 2.31 × 10 J· nm
d
 
+1 × −1
= 2.31 × 10−19 J· nm
0.367 nm
= −6.29 × 10−19 J

3. Convert 6.29 × 10−19 J to kJ/mol using NA :

   
6.022 × 1023 ion pairs −6.29 × 10−19 J
Hlattice = ×
1 mol ion pairs

= −3.77 × 105 J/mol or − 377 kJ/mol

9.3.3 Lewis structure of ionic compounds

Ionic or electrovalent bonds form by the complete transfer of electrons from one atom to
another. This results in charged ions which are attracted to each other by electrostatic forces.
This attraction is called ionic bonding, and the compounds formed are called ionic compounds.
Generally, these bonds form between metals and nonmetals. Examples of ionic compounds
include LiBr, Na2 S, CaO, MgCl2 , and HBr. Lewis dot symbols can be used to illustrate the
formation of cations and anions as shown by the following examples:

–
Na + Cl Na+ Cl

[Ne]3s1 [Ne]3s23p5 [Ne] [Ar]

2–
Ca + O Ca2+ O

[Ar]4s2 [He]2s22p4 [Ar] [Ne

86 Chemistry in Quantitative Language

Example 9.4

Use Lewis dot symbols, electronic configurations, and the octet rule to show why aluminum
and oxygen can form the ionic compound Al2 S3 .

Solution

S 2–
Al Al3+ S
2–
+ S + S
or Al2S3
Al S 2–
Al3+ S

[Ne]3s23p1 [Ne]3s23p4 [Ne] [Ar]

9.4 Covalent Bonding: Lewis Structures for Molecules

Covalent bonding involves the donation and sharing of two valence electrons between two atoms
in a molecule to attain a stable electronic configuration. This type of bonding is most common
between nonmetals. The Lewis structure for a covalent bond uses a line to represent the bond
itself (that is, the pair of electrons), with any unshared electrons shown as ‘lone pairs’ of dots.
Covalent bonds can be:

Single: one pair of electrons is shared between two atoms, as in H2 and F2 :

H + H H H or H H

F + F F F or F F

Double: two pairs of electrons are shared by two atoms, as in O2 and CO2 :

O O and O C O

Triple: three pairs of electrons are shared by two atoms, as in a nitrogen molecule:

N N

9.5 Covalent Bonding: Writing Lewis Structures

The Lewis structure is an electron-dot representation of the bonding relationship between atoms
in a molecule or polyatomic ion. Note that the Lewis structure only describes the bonding, but
by itself says nothing about the shape of the molecule.
 Chemical Bonding 1: Basic Concepts 87

9.5.1 Rules for writing Lewis structures

1. Determine the total number of valence electrons from all atoms. For anions, add one
electron for each net negative charge. For cations, subtract one electron for each net
positive charge.
2. Draw the skeletal structure for the molecule or ion and connect bonded atoms with an
electron pair bond or a dash.
3. Calculate the number of electrons that remain after forming initial single bonds. Do this
by subtracting the number of electrons needed to form single bonds from the total valence
electrons.
4. Complete the octets of all the atoms bonded to the central atom (except H, He, Li, which
follow the duet rule) by adding lone pairs of electrons.
5. Place any remaining electrons as lone pairs around the central atom(s) even if doing so
leads to more than an octet of electrons. Some elements do violate the octet rule (this is
discussed later).You have finished when all the valence electrons are used up.
6. If there are not enough electrons to form an octet around the central atom at this point, a
multiple bond may be involved. Form a double or triple bond by moving one or more lone
pairs from a terminal atom to a region between it and the central atom.

Example 9.5

Write the Lewis structures of (a) CO3 2− (b) NH3 (c) SiH4 .

Solution

Steps CO3 2− NH3 SiH4

1. Calculate total valence electrons. 4 + 3(6) + 2 = 24 5 + 3(1) = 8 4 + 4(1) = 8
2. Draw skeletal structure. H
O H N H H Si H
O C O H H
3. Calculate remaining electrons. 24 – 6 = 18 8–6=2 8–8=0

4. Distribute the remaining electrons H

first to terminal atoms to achieve O H Si H
H N H
octet structures.
O C O H H
5. Place remaining electrons on cen- There are not enough electrons to None None
tral atom (if any). complete the octet on the central
atom. Multiple bonding needed.
6. Make a double bond between O 2– N/A N/A
and C by moving a lone pair from O
one of the oxygen atoms. All the
O C O
atoms now have complete octets.

Example 9.6

Write the Lewis structures of (a) NH4 + (b) PO4 3− (c) HClO4 .
88 Chemistry in Quantitative Language

Solution

Steps NH4 + PO4 3− HClO4

1. Calculate total valence electrons. 5 + 4(1) −1 = 8 5 + 4(6) + 3 = 32 1 + 7 + 4(6) = 32
2. Draw skeletal structures. O O
H
H N+ H O P O H O Cl O

H O O
3. Calculate remaining electrons. 8–8=0 32 – 8 = 24 32 – 10 = 22
4. Distribute remaining electrons to 3–
achieve octet structures.
O
O
H O P O
H N H
+ H O Cl O
O
H O
5. Place remaining electrons(if any) None None None
on central atom.

9.6 Resonance and Formal Charge

9.6.1 Resonance
A molecule or polyatomic ion is said to show resonance when more than one Lewis structure
can be drawn to correctly describe its valence electron structure. These possible Lewis structures
are called resonance structures. Resonance structures, therefore, are two or more structures with
the same arrangement of atoms, but a different arrangement of electrons. Most often this occurs
in structures with double bonds next to single bonds. One resonance form can be converted to
another by simply moving lone pairs to bonding positions, and vice-versa. For example, consider
SO3 , an intermediate in the production of sulfuric acid. The three Lewis structures below are all
valid; they have the same arrangement of atoms and same energy, and differ only in the position
of the double bond.
O O O
S S S
O O O O O O

Resonance forms are not real bonding depictions. The actual molecule is a hybrid or an average
of the contributing resonance forms. In a resonance hybrid, electrons are said to be “delocalized”,
and their density is “spread” over a few adjacent atoms.

9.6.2 Rules for writing resonance structures

1. All contributing resonance structures must be correct or valid Lewis structures.
2. Atoms should be left where they are! Only electrons can be moved.
3. Only nonbonding electrons (lone pairs or radicals), or those in double or triple bonds, can
readily participate in resonance. Therefore, lone pairs on oxygen, halogens, nitrogen, etc.,
as well as those on anions, can participate in resonance.
 Chemical Bonding 1: Basic Concepts 89

4. The total number of electrons does not change.

5. The number of electron pairs must be the same across all contributing structural forms.
6. A double-headed arrow (↔) is placed between resonance structures.
7. The more reasonable resonance form(s) are those that minimize formal charges (as in
Section 9.6.3), minimize formal charge separations, and avoid placing like formal charges
on adjacent atoms. These will contribute most strongly to the overall description of the
molecule.

Example 9.7

Write all the acceptable resonance (Lewis) structures for the nitrate ion, NO3 − .
Solution

Follow all the steps for writing Lewis structures. Then apply the rules for writing resonance
structures.

Steps NO3 −
1. Calculate total valence electrons. 5 + 3(6) + 1 = 24
2. Draw skeletal structure. O

O N O
3. Calculate remaining electrons. 24 – 6 = 18
4. Distribute remaining electrons to
O
achieve octet structures. In doing
so the octet is satisfied on the O N O
three oxygen atoms but not on the
central N atom.
5. Place remaining electrons (if any) None
on central atom.
6. Make a double bond between O
O O
and N by moving a lone pair from
one of the oxygen atoms. O N O O N O

7. We find three Lewis structures

– – –
that can satisfy the octet rule, so O O O
the nitrate ion shows resonance. O N O O N O O N O

9.6.3 Formal charge

The formal charge assigned to an atom in a molecule or ion is the charge the atom would have if
all electrons were shared equally. This helps determine which of several possible Lewis structures
is most correct. It can be calculated using the following formula:
Formal charge (FC) = [# of valence electrons (V)] – [electrons in lone pairs (LP) + 1/2 the
number of shared pair electrons (SP)]:

FC = V − [LP + 1/2 (SP)]

90 Chemistry in Quantitative Language

9.6.4 Rules for assigning formal charge to an atom in a molecule

1. Draw the best Lewis structure for the molecule or ion.
2. Determine the number of valence electrons for the free atom.
3. Determine the number of lone pair electrons on the atom on the structure.
4. Determine the number of bonded or shared electrons.
5. Determine and assign the formal charge, using:

FC = V − [LP + 1/2 (SP)]

6. Check that the formal charges for all atoms add up to the total charge on the molecule
or ion.
7. The structure with the smallest formal charges is the most preferred structure.

9.6.5 Using formal charge to determine molecular structure

The following guidelines involving formal charge can be helpful in deciding which of the possible
Lewis structures is most stable or has the least energy.

1. A molecular structure in which the formal charge on each atom is zero is the best, and is
preferable to one in which some formal charges are not zero.
2. If the Lewis structure must have nonzero formal charges, the arrangement with the smallest
nonzero formal charges is preferable.
3. The Lewis structure with negative charge on the more electronegative atoms is preferable.
4. Structures with adjacent formal charges that are zero or of opposite sign are preferable.
5. Formal charges other than +1, 0, or −1 are uncommon except for metals.

Example 9.8

Calculate the formal charge on each atom in the resonance forms of N2 O. Which of the
resonance structures best represents the actual bonding pattern in this molecule?

Solution

Calculating formal charge for the resonance structures of N2 O

Lewis structure
N N O N N O N N O

Number of valence electrons 5 5 6 5 5 6 5 5 6

Number of lone pair electrons 6 0 2 4 0 4 2 0 6
Number of bonded electrons 2 8 6 4 8 4 6 8 2
FC = V – [LP + ½(SP)] −2 +1 +1 −1 +1 0 0 +1 −1
N N O
The preferable resonance form
 Chemical Bonding 1: Basic Concepts 91

Example 9.9

The following are three possible Lewis structures for carbon disulfide:

S C S S C S S C S

(a) Assign formal charges to the atoms in each structure.

(b) Which resonance form is preferred?

Solution

The Lewis structure is already provided. Use the valence electrons, lone pairs, and shared
pair information to determine the FC in the three structures. Finally, use the rules discussed
earlier to determine the preferred resonance form.

Calculating Formal Charge for the Resonance Structure of CS2

Lewis structure
S C S S C S S C S

Lewis structure 6 4 6 6 4 6 6 4 6
Number of lone pair electrons 4 0 4 2 0 6 6 0 2
Number of bonded electrons 4 8 4 6 8 2 2 8 6
FC = V – [LP + ½(SP)] 0 0 0 −1 0 −1 −1 0 +1
The preferable resonance form
S C S

9.7 Exceptions to the Octet Rule

While most molecules and ions follow the octet rule, some have too few electrons, and others
have too many. Thus, we have three general exceptions to the octet rule.

1. Expanded valence shells (hypervalent compounds): molecules such as PCl5 , SF6 , and
XeF4 have expanded valence shells in which one or more atoms possess more than eight
electrons. Central atoms from periods 3 and later of the periodic table can expand their
valence shells by utilizing empty d orbitals.
2. Electron-deficient molecules: atoms such as Be and B do not have enough elec-
trons to satisfy the octet rule, regardless of what other atoms they might be combined
with.
3. Odd-electron molecules: molecules such as NO (eleven total valence electrons) and NO2
(seventeen total valence electrons), with an odd number of electrons, do not obey the octet
92 Chemistry in Quantitative Language

rule. For example, the Lewis structures for NO and NO2 show only seven electrons around
the nitrogen atom.

N
N O and
O O

Example 9.10

The inorganic salt lithium hexafluorophosphate (LiPF6 ) is widely used industrially in the
manufacture of electrolyte for rechargeable lithium ion batteries, because of its high solubility
in nonaqueous, polar solvents such as ethylene carbonate and dimethyl carbonate. Draw the
Lewis structure for the hexafluorophosphate ion, PF6 − .

Solution

Steps PF6 −
1. Calculate total valence electrons. 5 + 6(7) + 1 = 48
2. Draw skeletal structure. –
F
F F
P
F F
F

3. Calculate remaining electrons after using twelve to form single bonds. 48 – 12 = 36

4. Distribute remaining electrons to achieve octets. P is the central atom in the F –
ion and has 12 valence electrons around it, which is four more than needed for F F
an octet.
P
F F
F

5. Place remaining electrons on central atom (if any). None left.

Example 9.11

Xenon oxyfluoride, XeOF4, is a colorless volatile liquid. It is generally prepared by the

controlled hydrolysis of XeF6 :

XeF6 + H2 O −→ XeOF4 + 2HF

Write the Lewis structures for the reactant XeF6 and the product XeOF4 , and give the number
of electrons in the expanded octet of each molecule.
 Chemical Bonding 1: Basic Concepts 93

Solution

Steps XeF6 XeOF4

1. Calculate total valence electrons. 8 + 6(7) = 50 8 + 6 + 4(7) = 42
2. Draw skeletal structure. F
F F O
Xe
F F F Xe F
F F F
3. Calculate remaining electrons after using twelve to form 50 –12 = 38 42 – 10 = 32
single bonds.
4. Distribute remaining electrons to achieve octets on
terminal atoms.
F
F F O
Xe
F F F Xe F
F F F
5. Place remaining two electrons on Xe in both cases.
F
F F O
Xe
F F F Xe F
F F F

9.8 Polar Covalent Bonds: Bond Polarity and Electronegativity

Electronegativity is a measure of the ability of an atom in a molecule to attract electrons.

The difference in the electronegativities of two atoms determines the bond type and, conse-
quently, the physical and chemical properties of materials they are part of. Figure 9.1 gives the
electronegativity of elements in the periodic table (Pauling’s scale).
Most chemical bonds fall somewhere between ionic (in which one atom has completely
donated electrons to another) and covalent (in which both atoms share electrons equally). Bond
polarity is a measure of how equally electrons or charge in a bond are shared between two atoms.
The polarity of a bond increases with increasing differences in electronegativity between the two
atoms. For example, Cl2 (Cl—Cl) is nonpolar, while HCl (H—Cl) is polar.
Most bonds have at least some polar character, with one end being partially positive (δ+) and
the other partially negative (δ−).

9.8.1 Determining polarity of a molecule

Molecules containing covalently bonded atoms may be polar or nonpolar. Two key factors
influence whether a molecule will be polar overall:
94 Chemistry in Quantitative Language

Increasing Electronegativity

H He
Increasing Electronegativity

2.1 1.5
Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.0 3.5 4.0 1.5
Na Mg Al Mg P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0 1.5
K Ca Sc Tl V Cr Mn Pe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.5 1.9 1.9 1.9 1.6 1.6 1.8 2.0 2.4 2.8 3.0
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5 2.6
Cs Ba Ls Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.9 1.9 2.0 2.2 2.4
Rb Ra Ac
0.8 0.9 1.1

Figure 9.1 Electronegativity of elements (Pauling scale).

Table 9.1 Electronegativity differences and bond types

Electronegativity
Difference (χ ) Bond Type Example
χ < 0.4 Nonpolar Covalent F—F, χ = 0
0.4 < χ < 2.0 Polar Covalent H—Cl, χ = 0.9
χ > 2.0 Ionic Na—F, χ = 3.1

1. The polarity of individual bonds in the molecule. For a molecule to be polar, it must have
at least one polar bond or lone pair.
2. The shape and symmetry of the molecule. If the molecule is symmetrical, it will be
nonpolar. A molecule will have overall polarity if the polar bonds are oriented in space
such that their dipoles do not offset each other. Diatomic molecules are an exception to
this, as the polarity of the molecule is essentially the same as the polarity of the bond.

Use Table 9.1 as a guide. If all the bonds are in the noncovalent range, the molecule will be
nonpolar regardless of the shape. On the other hand, if the bond type is in the ionic range, take
the bond as polar in judging the polarity of the molecule.
As we discuss in Chapter 10, the VSEPR Theory can predict the shape and bond angle in a
molecule and tell if a molecule polar or non-polar overall. The following shapes are symmetrical
if all the ligands or terminal atoms bonded to a central atom are the same:

• Linear
• Trigonal planar
• Tetrahedral
• Trigonal bipyramidal
• Octahedral
• Square planar

In summary, a molecule is

1. Nonpolar if it has only nonpolar covalent bonds.

2. Nonpolar if it has polar covalent bonds, but the shape is symmetrical. Polarity is cancelled
by symmetry.
3. Polar if it has polar covalent bonds and its shape is not symmetrical.
 Chemical Bonding 1: Basic Concepts 95

Example 9.12

In each of the following pairs, identify the more polar bond and indicate the negative and
positive poles.
(a) C—F and C—N
(b) Li—Br and Li—F
(c) P—Cl and B—O
(d) Si—O and Ca—Cl

Solution

Use the following steps to answer this question:

1. Calculate the electronegativity difference (χ ) between the bonded atoms using the
values for each element in Figure 9.1.
2. Determine the relative polarities of the bonds using the guidelines in Table 9.1. Recall
that for

χ ≤ 0.4 Bond is nonpolar covalent

0.4 < χ < 2.0 Bond is polar covalent
χ > 2.0 Bond is ionic

4. Indicate the negative and the positive polarity based on your results.

Bond χ Relative Polarity

(a) C—F 4.0 – 2.5 = 1.5 C—F > C—N
C—N 3.0 – 2.5 = 0.5
(b) Li—Br 2.8 – 1.0 = 1.8 Li—F > Li—Br
Li—F 4.0 – 1.0 = 3.0
(c) P—Cl 3.0 – 2.1 = 0.9 B—O > P—Cl
B—O 3.5 – 2.0 = 1.5
(d) Si—O 3.5 – 1.8 = 1.7 Ca—Cl > Si—O
Ca—Cl 3.0 – 1.0 = 2.0

Example 9.13

Determine whether the bonds in each of the following compounds are covalent or ionic.
(a) H2
(b) H2 O
(c) CaO
(d) LiF

Solution

Use Figure 9.1 to obtain the electronegativity difference and Table 9.1 to determine the
bond type.
96 Chemistry in Quantitative Language

Compound H2 HCl CaO LiF

Electronegativity difference, χ 2.1 − 2.1 = 0 3.0 − 2.1 = 0.9 3.5 − 1.0 = 2.5 4.0 − 1.0 = 3.0
Bond type Covalent Covalent Ionic Ionic

9.8.2 Dipole moment and percent ionic character

The dipole moment is a measure of the polarity of the molecule and occurs as a result of charge
separation due to differences in electronegativity. A larger difference in electronegativity results
in a larger dipole moment. The distance between the separated charges is also a deciding factor
in the size of the dipole moment.

9.8.3 Dipole moment (μ)

When two atoms with equal but opposite charges, Q, separated by a distance r, share bonding
electrons unequally, the result is a bond dipole.
Q+ Q–

By definition, the dipole moment, μ, is the product of the magnitude of the separated charge and
the distance of the separation, i.e.
μ = Q×r

The unit of the dipole moment is the Debye (D). 1D = 3.34 × 10−30 coulomb-meters (C.m). For
molecules, charge is usually measured in units of the electronic charge e, 1.60 × 10−19 C, and
distance in Å. For example, if two charges, +1 and −1(in units of e), are separated by 1.00 Å,
the resulting dipole moment is
  
   10−10 m 1D
μ = Q × r = 1.60 × 10−19 C 1.00Å = 4.79D
1Å 3.34 × 10−30 C.m

Example 9.14

The bond length of HF (g) is 0.92 Å.

(a) If the charges on H and F were +1 and −1, respectively, what would be the resultant
dipole moment, in D?
(b) The experimentally measured dipole moment of gaseous HF is 1.82 D. What magnitude
of charge on the H and F atoms, in units of e, would lead to this dipole moment?
Solution

(a) The charge on each atom is the electronic charge, e: 1.60 × 10−19 C. The separation is
0.92 Å. By analogy to the calculation above, the dipole moment is
  
 −19
  10−10 m 1D
μ = Q × r = 1.60 × 10 C 0.92Å = 4.41D
1Å 3.34 × 10−30 C.m
 Chemical Bonding 1: Basic Concepts 97

(b) Given that the dipole moment, μ, is 1.82 D, and that the charge separation distance r is
0.92 Å, we want to calculate the value of Q:
μ
From μ = Q × r, we get Q =
r
⎛  ⎞
3.34 × 10−30 C−m
⎜ (1.82D) ⎟
μ ⎜ 1.0D ⎟
Q= =⎜ ⎜  −10  ⎟ = 6.61 × 10−20 C
⎟
r ⎝   10 m ⎠
0.92Å
1.0Å

Convert 6.607 ×10−20 C to units of e as follows:

 
  1e
Charge in e units = 6.61 × 10−20 C = 0.413e
1.60 × 10−19 C
Therefore, the separated charge in HF, based on the experimental dipole moment, is:
0.413+ 0.413−
0.413 + 0.413 − or H − F

9.8.4 Percent ionic character of a covalent polar bond

Generally, both bond polarity and ionic character increase with an increasing difference in
electronegativity. One method for determining the percentage ionic character of chemical bonds
is to measure dipole moments. Percent ionic character (I) of a bond is given by
μobs
I= × 100
μionic
where I is the percent ionic character, μobs is the actual or observed dipole moment, and μionic
is the calculated dipole moment assuming a completely ionic bond (100%). (Note that no actual
bonds have 100% ionic character.)

Example 9.15

Given that the bond length in HI is 1.61Å and the measured dipole moment is 0.44 D, what
is the percent ionic character of the HI bond?

Solution

First calculate the μionic assuming HI is 100% ionic:

    
−19
 10−10 m 1D
μ = Q × r = 1.60 × 10 C 1.61Å = 7.71D
1Å 3.34 × 10−80 C.m
Next, calculate the percent ionic character knowing that μobs is 0.44 D.
μobs 0.44D
I= × 100 = × 100 = 5.71%
μionic 7.71D
98 Chemistry in Quantitative Language

9.9 Problems

1. Draw the Lewis symbols for each of the following elements using the periodic table as a
guide.
(a) Rb (b) Mg (c) Si (d) As (e) Se
2. Write Lewis symbols for the following ions.
(a) B3+ (b) Mg2+ (c) N3− (d) Cl−
3. Considering the Lewis symbols for Be, Mg, Ca, and Sr, what generalization can be made
about the Lewis structures for elements within the same group of the periodic table?
4. Use Lewis dot structures, electronic configurations and the octet rule to illustrate the
formation of the following ionic compounds.
(a) MgO (b) K2 O (c) CaF2 (d) Li3 N
5. Use Lewis dot structures, electronic configurations and the octet rule to illustrate the
formation of the following ionic compounds.
(a) Li2 S (b) AlCl3 (c) Ca3 N2 (d) B2 O3
6. Boron nitride (BN), often called white graphene, has remarkable physical and mechanical
properties and finds industrial application as dry lubricant, thermocouple protection
sheath, crucible material, and coating for reactor vessels. Show the formation of BN
using Lewis symbols.
7. Illustrate the formation of SiBr4 from Si and Br atoms using Lewis symbols and Lewis
structures.
8. Which of the following ionic compounds would have the higher lattice energy?
(a) MgF2 vs MgI2 (b) CsI vs CaO (c) CaS vs CaTe (d) RbF vs SrO
9. Without any calculation, arrange the following in order of increasing lattice energy:
LiF, KF, BeO, MgO, CaO. Explain your rationale.
10. Account for the trend in lattice energies:

Metal oxide Lattice energy (kJ/mol)

BeH2 −3205
MgH2 −2791
CaH2 −2410
SrH2 −2250
BaH2 −2121

11. Calculate the lattice energy in kJ/mol of the ionic bond between a calcium ion and an
oxygen ion. The ionic radii of Ca2+ and O2− are 100 pm and 140 pm, respectively.
12. Estimate the lattice energy between a pair of beryllium and sulfide ions. The ionic radii
of Be2+ and S2− are 27 pm and 184 pm, respectively.
13. Give the number of valence electrons in Cs, Mg, Ga, and Cl.
14. How many valence electrons are in each of the following?
(a) HCN (b) CIO−4 (c) IF+
6 (d) XeF6
 Chemical Bonding 1: Basic Concepts 99

15. Calculate the total number of valence electrons in each of the following.
(a) CCL4 (b) PH+ 4 (c) H3 PO4 (d) SO2−4
16. On the basis of Lewis theory, determine the compounds formed between:
(a) Ca and Se (b) Ba and Br (c) Mg and N (d) B and O
17. Write the Lewis structures for each of the following molecules.
(a) NF3 (b) H2 O2 (c) GeCl4 (d) N2 F2
18. Write the Lewis structures for the following organic compounds.
(a) Methanol (CH3 OH)
(b) Methylamine (CH3 NH2 )
(c) Formic acid (HCOOH)
(d) Dimethyl ether (CH3 OCH3 )
19. The decomposition of potassium chlorate (KClO3 ) is commonly used in the laboratory
preparation of oxygen as well as in oxygen generators aboard aircraft.

2KClO3 (s) −→ 2KCl (s) + 3O2 (g)

Draw the Lewis structure for ClO3 − .

20. Draw all possible resonance structures for each molecule or ion.
(a) O3 (b) SO2 (c) SCN− (d) NO− 3
21. Draw all possible resonance structures for each molecule or ion.
(a) N2 O (N is the central atom in all structures) (b) CO2 (c) N2 O2 (d) CH3 SO−
3
22. Sodium azide (NaN3 ) is used to generate nitrogen gas to inflate airbags upon impact.
The impact triggers the following reaction:

2NaN3 (s) −→ 2Na (s) + 3 N2 (g)

Draw the Lewis structure of the azide ion (N3 − ) showing all resonance forms.
23. The sulfate ion, SO4 2− , is observed to have four equal S—O bond lengths that are shorter
than a single bond. Write the Lewis structures to account for this observation.
24. The phosphate ion, PO4 3− , contains a central phosphorus atom bonded to four oxygen
atoms. The four P—O bond lengths are observed to be equivalent and are at 109.5o . Write
the various resonance structures which contribute to bonding in the phosphate ion.
25. The following structure is one of the four possible resonance structures for the BF3
molecule:

F+
B
F F

Draw the Lewis structures for the other three resonance forms.
26. Draw resonance structures that obey the octet rule and calculate the formal charge on
each atom in the following molecules or ions.
(a) NO−2 (b) SO2 (c) NO+ (d) CH3 NCO
100 Chemistry in Quantitative Language

27. What is the formal charge on each atom in the following Lewis structures?
(a) (b)
O O
H
H O S O H H C C

O H Cl
(c)
O (d)
H H
O
H S H H N+ C N
C C
H H O
H H H H

28. Draw a Lewis structure for nitric acid, HNO3 , and show all possible resonance forms.
Use formal charge to determine the most important form contributing to the structure.
29. Carbon dioxide is used in many industrial applications as a supercritical fluid. For
example, it is a good solvent, and it is also used for decaffeinating coffee and tea.
Draw three Lewis structures for CO2 and use formal charge to decide the most preferred
structure.
30. Borazine, B3 N3 H6 , which is often referred to as ‘inorganic benzene’, is isoelectronic
with benzene and has a planar six-member ring structure of alternating B and N atoms.

H B H
N N

B B
H N H

(a) Draw all reasonable resonance forms for the molecule (Hint: Include those in which
the octet rule is violated.)
(b) Calculate the formal charges on the atoms in each of the resonance forms.
31. Draw all possible resonance structures for the urea molecule shown below, minimizing
formal charges. Which of these forms is preferred in terms of formal charge?
O

C
H2N NH2
 Chemical Bonding 1: Basic Concepts 101

32. Draw Lewis structures for each of the following molecules or ions. Where necessary use
expended octets.
(a) BrF5 (b) AsF−6 (c) IF+
6 (d) XeO4
33. Which bond of the following pairs is the more polar, based on the electronegativity values
given in Figure 9.1?
(a) H—F or H—Cl (b) H—H or C—O (c) B—N or C—F
(d) H—H or H—F (d) O—C or O—N
34. Which bond of the following pairs has more ionic character, according to the electroneg-
ativity values given in Figure 9.1?
(a) Li—F or Li—Cl (b) K—O or K—N (c) Na—S or Na—P
(d) Li—N or Na—N (e) K—Cl or Ca—Cl
35. Classify the following bonds as ionic, non-polar, or polar.
(a) Boron—Nitrogen (b) Rubidium—Fluorine (c) Sulfur—Sulfur
(d) Hydrogen—Iodine
36. Which of the following molecules has a net dipole moment?
(a) HF (b) SO2 (c) CO2 (d) Br2
37. Which of the following molecules has a net dipole moment?
(a) SF6 (b) H2 S (c) BF3 (d) NH3
38. Determine the percent ionic character of CO if the observed dipole moment is 0.110 D
and the C—O interatomic distance is 113 pm. (Note: q = 1.6 × 10−19 C; 1 D = 3.34 ×
10−30 C.m)
39. In the gas phase, the dipole moment of KBr was measured to be 10.41D (3.473 × 10−29
C.m). If the K—Br interatomic distance is 282 pm, calculate:
(a) The theoretical dipole moment
(b) The percent ionic character
(c) The approximate charge distribution on the molecule.
40. The gas phase measured dipole moment and interatomic distance of BrF molecule are
1.29 D and 178 pm, respectively. What are
(a) The theoretical dipole moment
(b) The percent ionic character
(c) Approximate charge distribution on the molecule.