Unit 03 – Chemical Bonding

By : Achini Shehara
Types of chemical bonding

Ionic bonding is the electrostatic attraction between

positive and negative ions in an ionic crystal lattice.

Covalent bonds are formed when the outer electrons of

two atoms are shared.

The ionic or covalent bonds formed are usually very

strong – it takes a lot of energy to break them. There is
also a third form of strong bonding: metallic bonding.
The forces between molecules are called intermolecular
forces. There are several types of intermolecular force:

■■ Van der Waals’ forces (also called ‘dispersion forces’ and

‘temporary dipole–induced dipole forces’)

■■ Permanent dipole–dipole forces

■■ Hydrogen bonds
Ionic bonding

How are ions formed?

One way of forming ions is for atoms to gain or lose one or

more electrons.
■■ Positive ions are formed when an atom loses one or more
electrons. Metal atoms usually lose electrons and form
positive ions.
■■ Negative ions are formed when an atom gains one or
more electrons. Non-metal atoms usually gain electrons
and form negative ions.

The strong force of attraction between the positive and

negative ions in the ionic crystal lattice results in an ionic
bond. An ionic bond is sometimes called an electrovalent
bond
Dot-and-cross diagrams
A dot-and-cross diagram shows:

■■ the outer electron shells only

■■ that the charge of the ion is spread evenly, by
using square brackets
■■ the charge on each ion, written at the top right-
hand corner of the square brackets
Covalent bonding

Single covalent bonds

When two non-metal atoms combine, they share one,
or more, pairs of electrons. A shared pair of electrons
is called a single covalent bond, or a bond pair. A single
covalent bond is represented by a single line between the
atoms: for example, Cl-Cl
When drawing the arrangement of electrons in a
molecule we:

■■ use a ‘dot’ for electrons from one of the atoms and a

‘cross’ for the electrons from the other atom

■■ if there are more than two types of atom we can use

additional symbols such as a small circle or a small
triangle

■■ we draw the outer electrons in pairs, to emphasise

the number of bond pairs and the number of lone pairs.
There are some cases in which the electrons around
a central atom may not have a noble gas configuration.

For example:
■■ boron trifluoride, BF3, has only six electrons around
the boron atom; we say that the boron atom is ‘electron
deficient’
■■ sulfur hexafluoride, SF6, has twelve electrons around
the central sulfur atom; we say that the sulfur atom has an
‘expanded octet’
Multiple covalent bonds

Some atoms can bond together by sharing two pairs of

electrons. We call this a double covalent bond. A double
covalent bond is represented by a double line between
the atoms: for example, O O.
Atoms can also bond together by sharing three pairs
of electrons. We call this a triple covalent bond.
Co-ordinate bonding
(dative covalent bonding)

A co-ordinate bond (or dative covalent bond) is formed

when one atom provides both the electrons needed for a
covalent bond.

For dative covalent bonding we need:

■■ one atom having a lone pair of electrons

■■ a second atom having an unfilled orbital to accept the
lone pair; in other words, an electron-deficient compound.
Bond length and bond energy

In general, double bonds are shorter than single bonds.

This is because double bonds have a greater quantity of

negative charge between the two atomic nuclei.

The greater force of attraction between the electrons and

the nuclei pulls the atoms closer together. This results in a
stronger bond.

We measure the strength of a bond by its bond energy.

Nitrogen is unreactive because it has a triple bond, N N. It
takes a lot of energy to break the nitrogen atoms apart;
the bond energy required is 994 kJ mol–1.

Oxygen is much more reactive. Although it has a double

bond, it only takes 496 kJ to break a mole of O=O bonds.
Shapes of molecules
Electron-pair repulsion theory

Because all electrons have the same (negative) charge, they

repel each other when they are close together. So, a pair of
electrons in the bonds surrounding the central atom in a
molecule will repel other electron pairs. This repulsion forces
the pairs of electrons apart until the repulsive forces are
minimised.

The shape and bond angles of a covalently bonded

molecule depend on:

■■ the number of pairs of electrons around each atom

■■ whether these pairs are lone pairs or bonding pairs.
Lone pairs of electrons have a more concentrated electron
charge cloud than bonding pairs of electrons. Their
cloud charges are wider and slightly closer to the nucleus
of the central atom. This results in a different amount
of repulsion between different types of electron pairs.

The order of repulsion is lone pair–lone pair (most

repulsion) > lone pair–bond pair > bond pair–bond pair
(least repulsion).
The differences in electron-pair repulsion determine the
shape and bond angles in a molecule.
Note that in drawing three-dimensional diagrams, the
triangular ‘wedge’ is the bond coming towards you and the
dashed black line is the bond going away from you.
■■ Methane has four bonding pairs of electrons surrounding the
central carbon atom. The equal repulsive forces of each bonding
pair of electrons results in a tetrahedral structure with all H C H
bond angles being 109.5°.
In ammonia and water, the tetrahedral arrangement of the
electron pairs around the central atom becomes distorted

■■ Ammonia has three bonding pairs of electrons and one lone

pair. As lone pair–bond pair repulsion is greater than bond pair–
bond pair repulsion, the bonding pairs of electrons are pushed
closer together. This gives the ammonia molecule a triangular
pyramidal shape. The H N H bond angle is about 107°.

■■ Water has two bonding pairs of electrons and two lone

pairs. The greatest electron pair repulsion is between the
two lone pairs. This results in the bonds being pushed even
closer together. The shape of the water molecule is a nonlinear V
shape. The H O H bond angle is 104.5°.
Boron trifluoride

Boron trifluoride is an electron-deficient molecule. It

has only six electrons in its outer shell. The three bonding
pairs of electrons repel each other equally, so the
F –B-F bond angles are 120° . We describe
the shape of the molecule as trigonal planar. ‘Trigonal’
means ‘having three angles’.
Carbon dioxide

Carbon dioxide has two carbon–oxygen double bonds

and no lone pairs. The four electrons in each double bond
repel other electrons in a similar way to the two electrons
in a single bond. So, the O C O bond angle is 180°. We
describe the shape of the carbon dioxide molecule as linear.
Phosphorus pentafluoride

Phosphorus pentafluoride has five bonding pairs of

electrons and no lone pairs. The repulsion between the
electron pairs results in the most stable structure being
a trigonal bipyramid. Three of the fluorine atoms lie in the
same plane as the phosphorus atom. The bond angles FPF
within this plane are 120°. Two of the fluorine atoms lie above
and below this plane at 90° to it
Sulfur hexafluoride

Sulfur hexafluoride has six bonding pairs of electrons and

no lone pairs. The equal repulsion between the electron pairs
results in the structure shown. All F – S- F bond angles are 90°.
We describe the shape as octahedral.
Metallic bonding
What is a metallic bond?
In a metal, the atoms are packed closely together in a regular
arrangement called a lattice. Metal atoms in a lattice tend to
lose their outer shell electrons and become positive ions. The
outer shell electrons occupy new energy levels and are free to
move throughout the metal lattice.
We call these electrons delocalised electrons (mobile
electrons).

Delocalised electrons are electrons that are not associated with

any one particular atom or bond. Metallic bonding is strong.

This is because the ions are held together by the strong

electrostatic attraction between their positive charges and the
negative charges of the delocalised electrons.
This electrostatic attraction acts in all directions. The
strength of metallic bonding increases with:

■■ increasing positive charge on the ions in the metal

lattice
■■ decreasing size of metal ions in the lattice
■■ increasing number of mobile electrons per atom.
Metallic bonding and the properties of metals

Most metals have high melting points and high boiling

points

It takes a lot of energy to weaken the strong attractive

forces between the metal ions and the delocalised
electrons.

These attractive forces can only be overcome at high

temperatures.
Metals conduct electricity

When a voltage is applied to a piece of metal, an electric

current flows in it because the delocalised electrons
(mobile electrons) are free to move.

Metallic bonding is the only type of bonding that allows us to

predict reliably that a solid will conduct electricity. Covalent
solids cannot conduct electricity because none of their
electrons are free to move, although graphite is an exception
to this. Ionic solids cannot conduct because neither their
electrons nor their ions are free to move.
Metals conduct heat

The conduction of heat is partly due to the movement of the

delocalised electrons and partly due to the vibrations passed
on from one metal ion to the next.
Intermolecular forces

The forces within molecules due to covalent bonding are

strong. However, the forces between molecules are much
weaker. We call these forces intermolecular forces.
There are three types of intermolecular force:

■■ van der Waals’ forces (which are also called dispersion

forces and temporary dipole–induced dipole forces)
■■ permanent dipole–dipole forces
■■ hydrogen bonding.
In order to understand how intermolecular forces
work, we first have to know about electronegativity and
bond polarity.
Electronegativity

Electronegativity is the ability of a particular atom, which

is covalently bonded to another atom, to attract the bond
pair of electrons towards itself.
The greater the value of the electronegativity, the greater
the power of an atom to attract the electrons in a
covalent bond towards itself. For Groups 1 to 17 the
pattern of electronegativity is:
■■ electronegativity increases across a period from
Group 1 to Group 17
■■ electronegativity increases up each group.
This means that fluorine is the most electronegative
element.

For the most electronegative elements, the order of

electronegativity is:

increasing electronegativity
Br < Cl < N < O < F
Polarity in molecules

When the electronegativity values of the two atoms

forming a covalent bond are the same, the pair of electrons
is equally shared. We say that the covalent bond is non-
polar. For example, hydrogen (H2), chlorine (Cl2) and
bromine (Br2) are non-polar molecules.

When a covalent bond is formed between two atoms

having different electronegativity values, the more
electronegative atom attracts the pair of electrons in the
bond towards it.
As a result:
■■ the centre of positive charge does not coincide with the
centre of negative charge
■■ we say that the electron distribution is asymmetric
■■ the two atoms are partially charged
■■ we show
– the less electronegative atom with the partial charge δ+
(‘delta positive’)
– the more electronegative atom with the partial charge
δ– (‘delta negative’)
■■ we say that the bond is polar (or that it has a dipole).
Polarity and chemical reactivity

Bond polarity influences chemical reactivity. For example,

both nitrogen, N N, and carbon monoxide, C O, have
triple bonds requiring a similar amount of energy to
break them.

Nitrogen is a non-polar molecule and is fairly

unreactive. But carbon monoxide is a polar molecule, and
this explains its reactivity with oxygen and its use as a
reducing agent.
Van der Waals’ forces
Bromine is a non-polar molecule that is liquid at
room temperature.

The weak forces of attraction are keeping the bromine

molecules together at room temperature.

These very weak forces of attraction are called van der

Waals’ forces.

van der Waals’ forces exist between all atoms or molecules.

So, how do van der Waals’ forces arise?
The electron charge clouds in a non-polar molecule (or atom) are
constantly moving.

It often happens that more of the charge cloud is on one side of

the molecule than the other.

This means that one end of the molecule has, for a short moment,
more negative charge than the other.

A temporary dipole is set up. This dipole can set up

(induce) a dipole on neighbouring molecules.

As a result of this, there are forces of attraction between the δ+

end of the dipole in one molecule and the δ– end of the dipole
in a neighbouring molecule.
These dipoles are always temporary because the electrons
clouds are always moving. van der Waals’ forces are sometimes
called temporary dipole–induced dipole forces.

van der Waals’ forces increase with

■■ increasing number of electrons (and protons) in the
molecule
■■ increasing the number of contact points between the
molecules – contact points are places where the molecules
come close together.
Permanent dipole – dipole forces

In some molecules the dipole is permanent. These

molecules are called polar molecules.

The forces between two molecules having permanent

dipoles are called permanent dipole – dipole forces.

The attractive force between the δ+ charge on one

molecule and the δ- charge on a neighbouring molecule
causes a weak attractive force between the molecules
Hydrogen bonding

Hydrogen bonding is the strongest type of intermolecular

force. For hydrogen bonding to occur between two
molecules we need:

■■ one molecule having a hydrogen atom covalently bonded

to F, O or N (the three most electronegative atoms)

■■ a second molecule having a F, O or N atom with an

available lone pair of electrons.
The average number of hydrogen bonds formed per
molecule depends on:

■■ the number of hydrogen atoms attached to F, O or N in

the molecule
■■ the number of lone pairs present on the F, O or N.
Bonding and physical properties
Physical state at room temperature and pressure

Ionic compounds
Ionic compounds are solids at room temperature and pressure.
This is because:
■■ there are strong electrostatic forces (ionic bonds) holding
the positive and negative ions together
■■ the ions are regularly arranged in a lattice,
with the oppositely charged ions close to each other

Metals
Metals, apart from mercury, are solids. Most metals have high
melting points, high boiling points and high enthalpy changes of
vaporisation. This is because it takes a lot of energy to overcome
the strong attractive forces between the positive ions and the
‘sea’ of delocalised electrons
Covalent compounds

Covalently bonded substances with a simple molecular structure,

for example water and ammonia, are usually liquids or gases. This
is because the forces between the molecules are weak. It does
not take much energy to overcome these intermolecular forces,
so these substances have low melting points, low boiling points
and low enthalpy changes of vaporisation compared with ionic
compounds.

Some substances that have covalently bonded molecules may be

solids at room temperature, for example iodine and poly(ethene).
These are usually molecules where the van der Waals’ forces are
considerable. However, the melting points of these substances
are still fairly low compared with ionic compounds or most
metals.
Solubility
Ionic compounds
Most ionic compounds are soluble in water. This is because water
molecules are polar and they are attracted to the ions on the
surface of the ionic solid. These attractions are called ion–dipole
attractions.
Metals
Metals do not dissolve in water. However, some metals, for
example sodium and calcium, react with water.
Covalent compounds
Covalently bonded substances with a simple molecular
structure fall into two groups.
■■ Those that are insoluble in water. Most covalently bonded
molecules are non-polar. Water molecules are not attracted to
them, so they are insoluble. An example is iodine.
■■ Those that are soluble in water. Small molecules that can
form hydrogen bonds with water are generally soluble. An
example is ethanol, C2H5OH.
Electrical conductivity
Ionic compounds
Ionic compounds do not conduct electricity when in the solid
state. This is because the ions are fixed in the lattice and can only
vibrate around a fixed point. When molten, an ionic compound
conducts electricity because the ions are mobile.

Metals
Metals conduct electricity both when solid and when molten. This
is because the delocalised electrons are mobile.

Covalent compounds
Covalently bonded substances with a simple molecular
structure do not conduct electricity. This is because they have
neither ions nor electrons that are mobile.