CHEM1907/8

Lecture 8. Chemical Bonding

Ionic Bonding

Chemical Bonding
Learning Objectives

(Silberberg; 9.1-9.4)

Understand ionic and covalent bonding

Predict which type of bond might occur between atoms
Understand the nature of single and double bonds

Lewis Structures
Learning Objectives

(Silberberg; 10.1)

Draw Lewis structures of neutral complexes

Draw Lewis structures of charged complexes
Draw resonance structures

Covalent Bonding When two non-metals form a

compound, the bonding is very different.
Consider the formation of H2.
Initially each H-atom sees
the electron of the other
atom. Each atom wants
the electron so an attraction
occurs
As the distance between
the atoms decreases, each
atom finds it cannot totally
remove the other electron
and electron-electron
repulsion and nuclear-nuclear repulsion become important
Therefore, there is a specific distance at which the energy is
minimized. This distance is called the bond length of a covalent
bond.

Chemical Compounds and Bonds

What dictates whether two atoms will form
an ionic or a covalent bond?

Metals tend to lose electrons to form

cations and non-metals gain electrons to form anions: each
trying to gain a closed shell. Ionic bonding occurs between these
cations and anions; the overall energy involved in the process is
composed of three phenomena: the electron transfer, the
electrostatic interaction and the lattice energy.
The electron transfer is usually endothermic:
(requiring the input of energy)
E = +192 kJ mol1
Li(g) + F(g) Li+(g) + F(g);
Once formed, the electrostatic attraction between the cations
and anions (Coulombs Law) yields energy (exothermic).
Li(g) + F(g) Li+(g) + F(g) this is 755 kJ mol1

If there is a large difference in the electronegativities of

the atoms, (eg sodium chloride) an ionic bond will form.
If there is a small difference in the electronegativities of
the atoms (eg methane), a covalent bond will form.

Ionic solids:
are hard, crystalline, brittle and have a high melting point;
do not conduct electricity as a solid (the electrons are held too
tightly); and
do conduct electricity as a molten liquid, or in solution, when
ions are released to carry the current.
The structure of an ionic compound is a three-dimensional lattice
(e.g., cubic, tetrahedral, octahedral).
The actual structure depends on the radii of the ions and the
stoichiometry.

The coalescing of gaseous ions into a solid is defined by the lattice energy;
its magnitude (exothermic) dictates the strength of the ionic attraction and
properties (e.g., melting point, hardness, solubility).
Li(g) + F(g) LiF(s) lattice energy = 1050 kJ mol1

Trends in Covalent Bonding

Covalent Bond Lengths

In a covalent bond, an electron from each atom is shared,

that is, covalent bonds involve electron pairs. In this way, both
atoms think they have a filled shell.
Some atoms can share more than one pair of electrons at a
time. Such sharing results in a double bond (for sharing two
electron pairs) or a triple bond (for sharing three pairs)
Pairs of electrons in the valence shell of an atom, but which
do not take part in bonding (i.e. are not shared) are called a
lone pair or non-bonding pair of electrons.
If a bond is formed between two different atoms, the electron
pair of the bond will be attracted towards the atom with the
higher electronegativity (EN). This results in the atom with
the higher EN having a partial negative charge and the bond
is termed polar.

Chemical Compounds and Bonds

If there is a large difference in the electronegativities of the
atoms, (eg sodium chloride) an ionic bond will form.
C
Cl

DIFFERENCES IN ELECTRONEGATIVITY

Lecture Slides (26/03/03)

Characteristics of Ionic Compounds

2.55
3.16

Na
H

0.93
2.20

The electronegativity of chlorine pulls the single valence electron

from sodium to form a Cl ion and a Na+ ion.

There is a broad inverse correlation between the strength

of a bond and its length
Bond

Energy
(kJ/mol)

Length
(pm)

HH
CH
ClCl
BrBr

432
413
239
193

74
109
199
228

CO
C=O
CO

358
745
1070

187
123
113

CC

347

154

C=C
CC

614
839

134
121

CN

305

147

C=N
CN

615
891

127
115

Formation of a Covalent Bond

If there is a small difference in the electronegativities of the
atoms (eg methane), a covalent bond will form.
A covalent bond is classified as either a
non-polar covalent bond
or a polar covalent bond

where E 0 to 0.5
where E 0.5 to 2.0

Formation of an ionic bond

Properties of ionic and covalent compounds

Where the difference between the electronegativity of two atoms is

large an ionic bond is formed.

Boiling points. Boiling points of ionic compounds are much

higher than those of covalent compounds

ionic bond

where E 2.0-4.0

Ionic bonds are formed between metals and non-metals

Covalent bonds are formed between non-metals

Conducting an electric current. Unlike covalent compounds,

solutions of ionic compounds are able to conduct an electric
current

We have seen that sharing a pair of electrons between two

atoms results in a stable covalent bond. To develop a model of
bonding lets localise the electron pairs (not really true, but part
of our model) and designate them as either bonding or lone
pairs.
Experimentally, stable covalent compounds are formed when
each atom has a noble gas-like electron configuration. For the
most common elements in the first three rows of the periodic
table, this means that there are 8 valence electrons in the noble
gas structure, hence we call this the octet rule (except H which
wants only 2 valence electrons).
In our model (called valence bond theory) we try and
give every atom what they want: a complete octet of
electrons to determine the bonding in the molecule

Drawing Lewis Structures

Formation of Li+F . Electron Transfer

The Octet Rule and Lewis structures

Lewis Structures (Silberberg Ch. 10.1)

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

Li
Li [He]2s

Only the valence electrons appear in a Lewis structure

The line joining two atoms represents a pair of electrons
shared between two atoms
H
H
Single bond - two shared electrons; one line.

1s

2s

Li+F

F [He]2s 2p5

2p

1s 2s

2p

Li 1s2 (or [He])

Double bond - four shared electrons; two lines.

H

+
1

C C

1s 2s

Triple bond - six shared electrons; three lines.

F 2s22p6 (or [Ne])

1s 2s
2p

2p

Dots placed next to an atom represent nonbonding electrons

Resonance Structures

CClF3

Place the atoms relative to each other. Place the least electronegative atom in the centre (ie the atom with the lowest group
number and the highest period number relative to the other atoms)

1.

Sometimes there is more than one way to draw the molecule.

Which is correct? Often none: the molecule is really an average
of all the structures.

2. # valence electrons:
4 + (4 7) = 32

Determine the total number of valence electrons. For polyatomic

ions add one e for each negative charge of the ion or subtract
one e for each positive charge
Draw a single bond from each surrounding atom to the central
atom and subtract two valence electrons for each bond

4.

3.

Distribute the remaining electrons in pairs so that each atom has

eight electrons (or two for H). Begin by placing lone pairs on the
surrounding (more electronegative) atoms to give each an octet.
If a central atom still does not have an octet, change a lone pair
from one of the surrounding atoms into a bonding pair to the
central atom to make a multiple bond.

Electrons left:
32 (4 2) = 24

What is the Likely Structure of NCO?

Formal Charges

Formal Charge and Oxidation Number

What if the structures are not identical?

Formal charge (used to examine resonance structures) is not the

same as oxidation number (used to monitor redox reactions):

There is a method called formal charges that can be used.

To assign formal charges to an atom, work out the number of
valence electrons the atom started with. Then subtract the
number of electrons it owns completely in the compound (lone
pairs are completely owned, bonding pairs are half owned).
To work out which resonance structure is favoured, assign
formal charges to each atom. The structure with minimum
formal charge is favoured.
If two or more have the same formal charge, then both
structures will probably contribute to the final structure,
however, if one atom is more electronegative than another, the
structure with a negative charge on the more electronegative
atom will be preferred.

(A)

In determining formal charge, the bonding electrons are assigned

equally to the bonded atoms (as if the bonding were nonpolar
covalent), so each atom receives half of them:
FC =

(No

of valence

e)

[(No

of shared

No

of unshared

e)]

In determining oxidation number, the bonding electrons are

assigned completely to the more electronegative atom (as if the
bonding were ionic):
ON = (No of valence e) [(No of shared e + No of unshared e)]
e.g., Determine the formal charge and the oxidation number of O in water

(B)

(C)

[
[
[

(
2)

(
1)

(0)

(0)

(+1)

]
]

(0)

(0)

(0)

(
1)

Note the the sum of

the formal charge
on each atom equals
the charge of the
overall polyatomic ion

Structures (B) & (C) are reasonable; (C) may contribute most
(O will be happier accommodating ve charge, compared to N)