2.

2.3 Covalent Bonding

Ionic compounds, as you have just learned, contain many ions arranged in a
three-dimensional structure. But not all compounds are brittle ionic solids with
high melting points. Some, such as paraffin wax, are solids at SATP but have rel-
atively low melting points. Others are liquids or gases, such as water and carbon
dioxide. In what way do these substances differ from ionic compounds? Can we
explain these differences with atomic theory? The answer is yes, but first we
should look at their formulas.
We have written the formulas of ionic compounds as simplest formula
ratios. The compound NaCl includes sodium and chloride ions in a 1:1 ratio. We
could build a crystal from 8 ions of each element, or 8 million of each and it
would form the same structure and would have the same properties. There is
only one ionic compound of sodium and chloride ions, and that compound
always contains a 1:1 ratio of the two ions.
This is not true of the bonding of nonmetals with each other. For example,
consider the simplest ratio formula CH. If carbon and hydrogen formed an ionic
compound with this ratio, we would expect that any structure in which these ele-
ments were in this ratio would have the same properties. However, this is not the
case. Using a mass spectrometer and combustion analysis we can demonstrate
that there are several compounds that have this simplest ratio formula. The gas
acetylene (ethyne), C2H2(g), and the liquid benzene, C6H6(l), both have the sim-
plest ratio formula CH, but they are otherwise much different in their physical
and chemical properties. Simplest ratio formulas indicate only the relative num- Figure 1
bers of atoms in a molecular compound; they give no information about the The pair of shared electrons between the
actual number of atoms or the arrangement of those atoms in a molecule. To dis- nuclei of two hydrogen atoms results in a
tinguish among molecular compounds, we need to represent them with formulas covalent bond.
that describe the molecules that make them up.
Molecules can be classified by the number of atoms that they contain.
Molecules that contain only two atoms, such as carbon monoxide, CO, are called
diatomic molecules. If they contain more than two atoms, such as ammonia, diatomic molecule: a molecule consisting
NH3, they are called polyatomic molecules. of two atoms of the same or different elements
Some elements also exist as molecules. Hydrogen and oxygen are examples
of elements composed of diatomic molecules. Sulfur, S8, and phosphorus, P4, are polyatomic molecule: a molecule con-
polyatomic molecules. sisting of more than two atoms of the same
or different elements
Formation of Covalent Bonds
You already know that hydrogen can form a cation (H+) by losing a valence elec-
tron, or it can form an anion (H–) by gaining an electron and filling its electron
shell. However, two hydrogen atoms can each obtain a stable filled energy level
by sharing a pair of electrons. (Remember that the first energy level can only con-
tain two electrons.) The covalent bond that results arises from the simultaneous covalent bond: the attractive force
attraction of two nuclei for a shared pair of electrons (Figure 1). between two atoms that results when
We can use the model of the Lewis symbol, or electron dot diagram, to com- electrons are shared by the atoms; a type
of chemical bond
municate the theory of covalent bonding. When an electron dot diagram is used
to represent covalent bonding, we adapt it slightly and call it a Lewis structure Lewis structure: a representation of
(because it illustrates the structure of the molecule). A Lewis structure shows the covalent bonding based on Lewis symbols;
valence electrons surrounding each of the component atoms as dots, with the shared electron pairs are shown as lines
exception of the electrons that are shared: These shared electrons are represented and lone pairs as dots
by a dash. In effect, this dash represents a covalent bond.
Cl Cl Cl Cl

Chemical Bonding 75

lone pair: a pair of valence electrons not
involved in bonding
octet rule: a generalization stating that,
when atoms combine, the covalent bonds are
formed between them in such a way that
each atom achieves eight valence electrons
(two in the case of hydrogen)
structural formula: a representation of
the number, types, and arrangement of atoms
in a molecule, with dashes representing
covalent bonds
bonding capacity: the number of elec-
trons lost, gained, or shared by an atom
when it bonds chemically
76 Chapter 2
According to the Lewis structure for a chlorine molecule, each Cl atom has
three pairs of electrons that are not involved in the formation of a covalent bond.
Each pair is referred to as a lone pair. There is one shared pair of electrons
between the atoms.
Many elements will form bonds that result in a full valence shell for each
atom, so that each atom has the electron structure of an atom of a noble gas
when the shared electrons are included. In other words, it has a stable octet. This
generalization is referred to as the octet rule. There are many exceptions to this
rule, but you will not be learning about these in this course.
Sample Problem 1
Draw Lewis symbols for the reaction of two bromine atoms and a Lewis struc-
ture for the resulting bromine molecule.
Solution
Br Br Br Br
This method of representing molecules can be further simplified by not
indicating lone pairs. This representation is referred to as a structural formula.
The structural formula for chlorine would be ClCl, and for bromine BrBr. As
you can see, they are easier to write, and are quite similar to the chemical for-
mulas, Cl2 and Br2.
Each pair of shared electrons results in a single bond. Elements that need
only one more electron to complete their outer shell or energy level tend to form
single bonds. Hydrogen and chlorine are typical examples.
Elements in Group 16 are two electrons short of a full outer shell. How, then,
can they form covalent bonds with each other and still achieve a stable state? The
answer is simple, though not necessarily obvious: They form a double bond, with
each pair of atoms sharing two pairs of electrons between them. Oxygen and
carbon dioxide are examples of molecules that include double bonds. The double
bond is represented, in a Lewis structure and structural formula, as a double dash.
Sample Problem 2
(a) Draw the Lewis structure for a molecule of oxygen.
(b) Give the structural formula for the molecule.
Solution
(a) O + O O O
(b) O O
Can you predict how atoms of nitrogen, which require three electrons each
to achieve a stable octet, might form N2? The two atoms form a triple bond by
sharing three electron pairs.
N N N N
The structural formula for a molecule of nitrogen is
N N
The number of covalent bonds (shared electron pairs) that an atom can form
is known as its bonding capacity (Table 1). Each atom of nitrogen, we have just
 2.3

learned, shares three electron pairs, so it has a bonding capacity of three. What is
the bonding capacity of oxygen? It always shares two electron pairs, so has a
bonding capacity of two. It is easy to find the bonding capacity of any element by
looking at the Lewis structure of a molecule containing that element: The number
of dashes associated with the element is the same as the bonding capacity.

Table 1: Bonding Capacities of Some Common Atoms

Atom Number of Number of Bonding capacity
valence electrons bonding electrons
carbon 4 4 4
nitrogen 5 3 3
oxygen 6 2 2
halogens 7 1 1
hydrogen 1 1 1

So far, we have looked at molecules of elements. Because the atoms are the
same, each has the same bonding capacity and each contributes the same
number of electrons to the covalent bond. The molecules of compounds, how-
ever, consist of atoms of two or more different elements, often with different
bonding capacities. How do we decide on their arrangement, when we draw
structural formulas? The central position in the arrangement is often occupied
by the element with the highest bonding capacity. Carbon and nitrogen, for
instance, are commonly at the centre of a structural formula. Electronegativity is
another means of deciding upon the central atom. When there is a choice of
atoms for the central position in the molecule, choose the least electronegative
element. Hydrogen is never the central atom since it can only form a single cova-
lent bond. Halides and oxygen are also usually not the central atom.
There are exceptions to these generalizations, but they meet our needs in
most cases.

Sample Problem 3
(a) Draw a Lewis structure for a molecule of carbon dioxide.
(b) Give the structural formula for the molecule.

Solution
(a) O + C + O O C O
(b) O C O

Practice
Understanding Concepts
1. Draw a Lewis structure and write the molecular formula for each of
the following:
(a) F2(g)
(b) H2O(l)
(c) CH4(g)
(d) PCl3(s)
(e) H2S(g)
(f) SiO2(s)

Chemical Bonding 77

polyatomic ion: a covalently bonded
group of atoms with an overall charge
coordinate covalent bond: a covalent
bond in which both of the shared electrons
come from the same atom
78 Chapter 2
Coordinate Covalent Bonds
Many substances contain a combination of covalent and ionic bonding. Consider
the compound ammonium chloride, NH4Cl. This white, crystalline solid dis-
solves rapidly in water and is an electrolyte—it dissociates to form a cation and
an anion. It has many of the properties of an ionic compound, but it is composed
only of nonmetals. We explain the properties of ammonium chloride by
describing it as an ionic compound composed of a chloride ion, Cl–, and a poly-
atomic ion, ammonium, NH4+. The bond holding the chloride and ammonium
ions together is ionic, but the bonds within the polyatomic ammonium ion are
covalent. There are several polyatomic ions, including NH4+, SO42– (sulphate),
and CO32–(carbonate), all of which are covalently bonded groups of atoms car-
rying an overall charge.
How does this arrangement fit with our description of covalent bonds?
Molecules that are composed of two or more different elements can sometimes
form covalent bonds where both of the electrons making up the bond are pro-
vided by the same atom. This type of bond is called a coordinate covalent bond.
Consider the formation of the ammonium ion from the regular covalent mole-
cule ammonia, NH3, and a hydrogen ion, H+. The hydrogen ion does not bring
any electrons with it. To achieve a complete outer shell it can borrow two elec-
trons from the atom with which it bonds.
To explain this bond, we can draw Lewis structures. First, we must establish
the Lewis structure for ammonia. We can arrange the atoms with nitrogen
(which has the highest bonding capacity) at the centre, showing the five valence
electrons of nitrogen and the one valence electron of each of the three hydrogen
atoms.
H N H
H
We can show the pairs of shared electrons (covalent bonds) between adjacent
nitrogen and hydrogen atoms as dashes.
H N H
H
Notice the lone pair of electrons in this structure. A hydrogen ion, which has
no electrons of its own, can bond to the ammonia molecule by sharing this
unbonded pair of electrons. This is the coordinate covalent bond.
H H
H N H H N H
H H
Once the hydrogen ion is bonded, there is no way to tell which of the hydro-
gens was the ion. Each of the four hydrogen atoms in the structure are equiva-
lent: The positive charge is not really associated with any particular hydrogen
atom. To indicate this, square brackets are placed around the entire ammonium
ion and the positive charge is written outside the bracket.
 2.3

The Strength of Covalent Bonds

Covalent bonds are strong. A large amount of energy is needed to separate the
atoms that make up molecules. For this reason, molecules tend to be stable at rel-
atively high temperatures: They do not easily decompose upon heating.
The stronger the bonds within the molecule, the greater the energy required
to separate them. The strength of a bond between two atoms increases as the
number of electron pairs in the bond increases. Therefore, triple bonds are
stronger than double bonds, which are stronger than single bonds between the
same two atoms. (a) O
S
O O
SUMMARY Drawing Lewis Structures and Structural
Formulas for Molecular Compounds (b) 3(6) + 6 = 24
1. Arrange the symbols of the elements of the compound as you would O S
expect the atoms to be arranged in the compound. The element with the (c) O
highest bonding capacity is generally written in the central position S
(Figure 2(a)). O O
2. Add up the number of valence electrons available in each of the atoms
(Figure 2(b)). If the structure is a polyatomic ion, add one electron for (d)
O
each unit of negative charge, or subtract one for each unit of positive S
charge. O O
3. Place one pair of electrons between each adjacent pair of elements
(e) Sulfur atom has an
(forming single covalent bonds) (Figure 2(c)).
incomplete octet.
4. Place pairs of the remaining valence electrons as lone pairs on the periph-
eral atoms (not the central atom) (Figure 2(d)). O O
5. If octets are not complete, move lone pairs into bonding position between S S
those atoms and the central atom until all octets are complete O O O O
(Figure 2(e)).
(f) SO3 includes two coordinate
6. If the peripheral atoms all have complete octets and there are pairs of elec-
covalent bonds.
trons remaining, place these electrons as lone pairs on the central atom.
7. Count the number of bonds between the central atom and the peripheral O
atoms. If this number exceeds the bonding capacity of the central atom,
S
one or more of the bonds is coordinate covalent. To identify which ones,
O
try removing the peripheral atoms one at a time. If you can do this and
leave the central structure with complete octets, you have identified coordi- O
nate covalent bonds (Figure 2(f)).
(g) O
8. To give the structural formula, remove the dots representing the lone pairs
and replace bond dots with dashes (Figure 2(g)). S
9. If you are representing a polyatomic ion, place brackets around the entire O O
structure and write the charge outside the brackets. Figure 2

Practice
Understanding Concepts
2. Draw Lewis structures and structural formulas for each of the fol-
lowing molecules:
(a) H2(g) (d) NF3(g)
(b) O3(g) (e) N2H2(g)
(c) OF2(g) (f) P2H4(g)

Chemical Bonding 79

intramolecular force: the attractive
force between atoms and ions within a com-
pound
intermolecular force: the attractive
force between molecules
80 Chapter 2
3. Draw Lewis structures and structural formulas for each of the fol-
lowing polyatomic ions:
3–
(a) PO4(aq) –
(c) BrO3(aq)
–
(b) OH(aq) –
(d) ClO4(aq)
4. Which of the Lewis structures in questions 2 and 3 include coordinate
covalent bonds?
Explaining the Properties of Molecular Compounds
You are familiar with many molecular compounds: propane, C3H8(g), for the bar-
becue, water, H2O(l), in your bathtub, and sugar, C12H22O11(s), for your coffee. As
you can see, their physical properties vary greatly. In contrast to ionic com-
pounds, which are all solids at SATP, molecular compounds may be solids, liq-
uids, or gases (Table 2).
Table 2: Comparison of Ionic and Molecular Solids
Properties Ionic Molecular
melting point high low
electrical conductivity
in the solid state no conductivity no conductivity
in the liquid state conductivity no conductivity
consistency of solid hard, brittle soft, waxy or flexible
Examples sodium chloride iodine
copper(II) sulfate phosphorus
We have discussed the forces that bond atoms and ions together within a
compound, the intramolecular forces (“intra” means within). These are suffi-
cient to explain the existence of ionic and molecular compounds, and to explain
many of the properties of ionic compounds, but they aren’t sufficient to explain
the physical state of molecular compounds. Why is water a liquid at SATP and a
solid at STP? Why isn’t it a gas at all temperatures? Something, some force, must
hold the molecules together in the solid and liquid states.
Forces between molecules are called intermolecular forces (“inter” means
between). The evidence indicates that these forces are strong enough to cause
molecules to arrange themselves in an orderly fashion to form a lattice structure
(similar to that of ionic solids). Both solid water and solid carbon dioxide (dry
ice) show such structures when examined by crystallography (Figure 3).
However, intermolecular forces must be weak compared to covalent bonds. We
can deduce this from the observation that it is much easier to melt a molecular
solid than it is to cause the same substance to decompose. When water is heated
from –4°C to 104°C it changes state from a solid, to a liquid, and then to a gas,
but it does not decompose to oxygen and hydrogen. The energy added in the
form of heat is sufficient to overcome the intermolecular forces between the mol-
ecules, but not the covalent bonds between the atoms. Adding a relatively small
amount of heat will cause a solid molecular compound to change state from a
solid to a liquid, and then to a gas, but it takes much more energy to break the
covalent bonds between the atoms in the compound.
Later in this chapter, you will learn more about intermolecular forces and
how they affect the properties of substances.
 2.3

Practice
Understanding Concepts
5. Distinguish between bonding electrons and lone pairs.
6. Are the following pairs of atoms more likely to form ionic or covalent
bonds?
(a) sulfur and oxygen
(b) iodine and iodine
(c) calcium and chlorine
(d) potassium and bromine
7. (a) List six examples of molecular elements and compounds and six
examples of ionic compounds.
(b) Compare the two lists, referring to bond types to explain the con-
trasting physical properties.
8. (a) How does the bonding capacity of nitrogen differ from that of Figure 3
chlorine? The molecules in solid carbon dioxide, CO2,
(b) Give a theoretical explanation for your answer to (a). form a crystal lattice.
9. How are coordinate covalent bonds similar to covalent bonds? How
are they different?
10. (a) Use an electron dot diagram to explain the formula for nitrogen, N2.
(b) Draw the Lewis structure for nitrogen.
(c) Nitrogen is a fairly inert (unreactive) gas. Explain this, referring to
the bonds involved.
11. Illustrate the formation of each of the following molecular com-
pounds, using electron dot diagrams and Lewis structures:
(a) HCl (c) H2S
(b) NH3 (d) CO2
12. Use the octet rule to develop a table that lists the bonding capacities
for carbon, nitrogen, oxygen, hydrogen, fluorine, chlorine, bromine,
and iodine.
13. Use bonding capacities (Table 1, page 77) to draw the structural for-
mula of each of the following molecules.
(a) O2
(b) Br2
(c) H2O2
(d) C2H4
(e) HCN
(f) C2H5OH
(g) CH3OCH3
(h) CH3NH2
14. (a) Illustrate the structure of a hydronium ion (H3O+) by drawing its
Lewis structure.
(b) Name the bonds within the hydronium ion.
(c) What kinds of bonds is this ion likely to form with other entities?
15. Is it correct for the structural formula of H2S to be written as H—H—S?
Explain, using a diagram.

Chemical Bonding 81
 Section 2.3 Questions
Understanding Concepts
1. Compound A is formed when the element with atomic number 3
combines with the element of atomic number 9. Compound B is
formed when the element with atomic number 7 combines with
the element of atomic number 9.
(a) Compare the properties of compounds A and B.
(b) What types of compounds are A and B? Give reasons for
your answer.
(c) Clearly show the structure of each compound formed, using
electron dot diagrams and Lewis structures.
2. Oxygen forms ionic bonds with aluminum to form bauxite (or
aluminum oxide). However, oxygen forms covalent bonds with
carbon to form carbon dioxide. Use the concepts of electronega-
tivity and periodic trends to explain these differences in bonding.
3. An alkali metal M reacts with a halogen X to form a compound
with the formula MX.
(a) Would this compound have ionic or covalent bonds? Explain.
(b) Predict the physical properties of the compound MX.
4. The compound NaCl and the element Cl2 are both held together
by chemical bonds.
(a) Classify each substance as either an ionic or a covalent com-
pound.
(b) Explain, in terms of chemical bonds and attractive forces,
why NaCl is a solid at SATP while Cl2 is a gas at SATP.
5. Using only oxygen and sulfur atoms, create as many compounds
as you can and draw Lewis diagrams for each. Which of the com-
pounds contain only multiple bonds?

Applying Inquiry Skills

6. Design an experiment to test your classification of compounds A
and B in question 1.
7. Design an experiment to test your predictions of the physical
properties of the compound MX in question 3.

(a)

2.4 Electronegativity, Polar Bonds,

and Polar Molecules
Why are some molecular substances solid, some liquid, and some gaseous at
SATP? Why do different liquids have different boiling points? Why can water
(b) striders walk across the surface of a pond without falling in? Believe it or not, all
these phenomena depend on the bonds and forces between molecules.

Polar Covalent Bonds

So far, we have discussed models for two types of chemical bonding: ionic and
covalent. However, when a chemical bond is formed, it is not always exclusively
Figure 1
one or the other.
Electron densities of the bonding electrons in When electrons are shared between two atoms, a covalent bond results.
two covalent molecules When the atoms are identical, such as in a chlorine molecule, the electrons are
(a) Cl2 shared equally (Figure 1(a)). However, this is not the case for a compound like
(b) HCl hydrogen chloride, where electrons are shared between two different elements. In

82 Chapter 2