Forces between atoms, ions and molecules

Covalent bonds
A covalent bond is formed by a shared pair of electrons. The two electrons are localized
between the nuclei of the bonded atoms, and the electrostatic attraction between the
negatively-charged bonding electrons and the positively-charged nuclei holds the atoms
together strongly.
Covalent dot-and-cross diagrams are used to show covalent bonds, usually between nonmetal atoms. A single covalent bond is found, for example, in a chlorine molecule:
Cl Cl

Note that drawing the shells is optional. We could equally well draw:

Atoms can also share two electrons each to form two covalent bonds between them (a
double covalent bond), for example in an oxygen molecule:
O=O

Rarely a triple covalent bond may be formed between two atoms (examples:
H-CC-H and NN). A quadruple covalent bond would require too many negatively
charged electrons in the same space between the two atoms, and does not occur instead
atoms with valency 4 often form giant covalent lattices.
Expanded Octet:
Although it is usual for bonding to result in an electron arrangement isoelectronic with a
noble gas, there are a number of atoms that can accept more than a full shell as a result
of covalent bond formation. While atoms of elements in the second period never have more
than 8 electrons in their outer shell, those in period 3 and subsequent periods often do
this is called having an expanded octet.
Examples:

SF6 sulphur hexafluoride

XeF4 xenon tetrafluoride

Page 1

Incomplete outer shells

In other cases, covalent bond formation increases the number of electrons around an atom,
but not all the way to a filled shell.

Example:

BH3

borine

Check your understanding:

Draw dot-cross diagrams for
i) NH3, ii) CO2, iii) BF3, iv) SCl2
Lone pairs
The two unbonded atoms in the N atoms outer shell in ammonia are
not just two random electrons, but a non-bonding pair of electrons
called a LONE PAIR. Youll also find two lone pairs on each of the
O-atoms of O2. These lone pairs are important they can get
involved in reactions, and they help determine the shape of
molecules.
a lone pair
Dative covalent bonds
In some situations, one atom may contribute both electrons to form the covalent bond. The
bond formed is in all respects identical to a normal covalent bond, and is called a DATIVE
covalent bond.
A dative covalent bond can be formed where one atom has a lone pair of electrons
available to donate, and another atom has a vacancy for two electrons in its outer shell.
e.g.

The ammonium ion, formed by the reaction of an ammonia molecule

with an H+ ion (acid):
NH3(g) + H+(aq) NH4+(aq)

H
H

N:

H+

H
|
N
|
H

+
H

This is possible because the N has a lone pair to donate and the H+ ion has an empty n=1
shell able to accept the two electrons.
Check your understanding:
v) Draw a dot-cross diagram for the ion H3O+

Page 2

Dative bonds can also form part of a set of double or triple bonds.
The bonding in CO is :

C=O
You will always be able to tell a dative covalent bond in a dot cross diagram because both
electrons in the intersection of shells will be the same symbol (i.e. from the same atom).
Check your understanding:
Ozone and sulphur trioxide also have dative bonds. See if you can draw a dot-cross
diagram for vi) O3 and vii) SO3. Note that sulphur in SO3 has an expanded octet.

Ionic Bonds
An ionic bond is the strong electrostatic attraction between oppositely-charged ions.
Ionic dot-and-cross diagrams are used to show bonds between positive and negative ions.

show the outer shell only unless asked otherwise

draw each ion in square brackets, and add the charge to the bracket
use the element symbol to represent the nucleus
either show empty outer shell or filled ex-inner shell

e.g.

Check your understanding:

Draw dot-cross diagrams for
viii) lithium oxide
ix) aluminium fluoride
Bonding in substances containing compound ions
Some positive or negative ions contain more than one type of atom we call these
compound ions e.g. SO42- or NH4+. The bonding INSIDE these compound ions is
covalent, but these ions form ionic bonds with other ions.

Page 3

Metals forming covalent bonds to non-metals

We dont just see pure ionic and pure covalent bonding there are degrees in between.
Ionic and covalent are simply two extremes with all possibilities in between.
Dont be thrown if you see a metal atom involved in covalent bonding especially metals
like Al, Pb or Sn. This is the exception, however, and would be indicated by properties
which would be inconsistent with ionic bonding e.g. SnCl4 is a red liquid at room temp (i.e.
has a low melting and boiling point) so its bonding is not ionic.

Metallic bonds
Metallic bonds are the strong electrostatic
attractions between the positively-charged metal
ions and the negatively charged delocalized
electrons.
A dot-and-cross diagram is not needed to
represent metallic bonding: the generic labeled
diagram shown here suffices.

Note that the strength of the metallic bond (and hence how high the melting and boiling
point is) depends on how highly charged the metal ion is, and how many electrons it has
donated to the sea of delocalized electrons. e.g. Al has a higher melting point than Na.

Intermolecular Forces
There are three types of intermolecular forces that hold molecules (i.e. substances with
simple molecular structures and covalent bonding, as opposed to giant ionic structures,
giant covalent structures or metallic structures) together. The strength of the intermolecular
forces is reflected in the melting and boiling points the stronger the intermolecular forces,
the more energy required to overcome them, and the higher the melting and boiling points.
The intermolecular forces are:
1) Induced dipole-dipole interactions, also called London forces*
2) Permanent dipole-dipole interactions*
3) Hydrogen Bonding
* be aware that induced dipole-dipole interactions and permanent dipole-dipole interactions
are collectively referred to as Van der Waals forces.
To understand intermolecular forces, we are going to need to understand what dipoles are:
A dipole is a separation of positive and negative charges. The simplest example of this is a
pair of electric charges of equal magnitude but opposite sign, separated by a small
distance. The negative end of one dipole will attract the positive end of another dipole and
vice versa, in a similar way to more familiar magnetic dipoles.

Page 4

Induced dipole-dipole interactions (London forces)

If there were no forces between molecules, it would take no energy to separate them.
Everything would be a gas, and the melting and boiling points would be absolute zero
(0 Kelvin, equal to -273C).
In reality even the noble gases, which are found as individual atoms, show variation in
melting and boiling points.
Evidence:
Rn
Xe
energy to vaporize
(kJ mol-1)

Ar
He

Kr

Ne
40
80
number of electrons

We conclude that the more electrons present, the stronger the London forces. Generally
this means the bigger the atom/molecule the stronger the London forces.
Induced dipole-dipole interactions arise because electrons are always moving (quickly,
randomly within the space defined as their orbitals). At any moment in time it is possible for
more electrons to lie on one side of the nucleus than the other. When this happens an
instantaneous dipole occurs, with the nucleus the positive end of the dipole and the
unbalanced electrons the negative end.
This instantaneous dipole produces an induced dipole in neighboring atoms or molecules
which are hence attracted.
They are the weakest type of attraction between molecules, but all molecules (including
monatomic molecules) have them.
Application:
Predict the trend in boiling points for the alkane homologous series.
The boiling points of the alkanes will increase with increasing number of carbon atoms. As
the size of the molecule increases, so does the number of electrons in the molecule, and
hence so does the strength of the London forces. The stronger these forces, the more
energy will be required to overcome them and the higher the boiling points will be.
Isoelectronic molecules
These are molecules having the same number of electrons as each other, for example
isomers. Because London forces are short-range forces, they get stronger the closer the
molecules become. This means that differences how close molecules can get to one
another and how they pack together will affect their melting and boiling points.
Page 5

We consider these factors in terms of area of surface contact (NOT the same as surface
area!). The straighter and more linear a molecule is, the more of its surface area can be
adjacent to another molecule, conversely the more spherical it is, the less of its surface
area can be in contact with an adjacent molecule:
small area
of surface
contact

large area
of surface
contact

The more branched a molecule becomes, the smaller its area of surface contact, and
hence the weaker the London forces will be and the lower the melting and boiling points
compared to a molecule with the same number of electrons, which is more linear.
e.g.

pentane boils at 36C

2,2-dimethylpropane boils at 10C

H

H H H H H

H H C H H

H C C C C C H

H C

H H H H H

C H

H H C H H
H

Check your understanding:

Arrange the following groups of substances in order, highest boiling point first.
x) Ne, He, Ar
xi) chloromethane, fluoromethane, bromomethane

Permanent Dipole-Dipole Interactions

Polar molecules exhibit an additional form of intermolecular force, known as permanent
dipole-dipole interactions. Evidence for polar molecules being attracted to an electrostatic
charge when non-polar molecules are not comes from the deflection of flowing polar
molecules by a charged plastic rod.
A polar molecule is one which has a dipole locked into the molecule because of the
distribution of charge between the bonded atoms. To understand how polar molecules give
rise to permanent dipole-dipole intermolecular forces, we need to understand what gives a
molecule a permanent dipole:
Electronegativity and Polar Bonds
If both nuclei attract the bonding electrons equally, they occupy the space between the
nuclei, and we have a perfect covalent bond e.g. Cl2 which is a non-polar bond.
Bonding pair

Cl

Cl

If one bonded atom attracts the bonding electrons more strongly than the other, because it
is more electronegative, than we have a polar bond the electrons spend more time
closer to the atom they are more attracted to: e.g. H2O, HCl, NH3
Page 6

Cl

The symbols + and - mean a partial positive and a partial negative charge not as much
as H+ or Cl- would be. We say that the bond has a dipole, and is therefore a polar bond.

Definition:

Electronegativity is the ability of a bonded atom to attract the electrons in

a covalent bond.

The more electronegative an atom is, the more it attracts the bonding electrons. It is
therefore the DIFFERENCE in electronegativity between the two atoms in the bond which
determines how polar the bond will be. Ionic and covalent are just the two extremes, with
polar covalent bonds in between.
small difference/no difference
moderate difference
very large difference

pure covalent bond

polar (covalent) bond
ionic bond

e.g.
e.g.
e.g.

C-H
C-Cl
NaCl

We need to know how electronegative each of the atoms is in the bond to work out how
polarized the bond will be, and what the resulting properties of the molecule will be.
Trends in electronegativity:
The top three most electronegative elements are F > O > N
Electronegativity increases across a period from Group 1 to Group 7 (not 8!)
Electronegativity decreases going down a group as atomic radius increases
The electronegativity of hydrogen is lower than most non metals and higher than
most metals.
The electronegativity of carbon and hydrogen is approximately the same so C-H
bonds are essentially non-polar.
e.g.
Potassium has an electronegativity of 0.8 while fluorine has an electronegativity of
4.0 so there is a very large difference in electronegativity. In potassium fluoride the
bonding electrons essentially reside on the fluorine atom, so the bonding is ionic with
very little covalent character.
Hydrogen has an electronegativity of 2.1 while oxygen has an electronegativity of
3.5 so there is a moderate difference in electronegativity. In water the bonds are
covalent but the bonding electrons are attracted more towards the oxygen atom, so
the bonds are polar.
Carbon has an electronegativity of 2.5 while hydrogen has an electronegativity of
2.1 so there is very little difference. The bonds in methane are covalent and the
electrons are evenly shared between C and H atoms, so the bonds are non-polar.

Page 7

Molecules with permanent dipoles (polar molecules)

We can use electronegativity to work out which bonds are polarized in a molecule. Whether
the molecule has a permanent dipole then depends on whether the dipoles in the polar
bonds balance each other out, given the 3-D shape of the molecule:
H
H C H

CH4 no polar bonds; no permanent dipole, not a polar molecule

H
F
F C F
F

CH2O polar bond between C=O, C-H bonds not polar; has a permanent
dipole; is a polar molecule

O
H

CF4 has polar bonds, but symmetrically arranged; no permanent dipole; not
a polar molecule

So molecules with polar bonds are not necessarily polar molecules, but polar molecules
arise from unsymmetrical polar bonds. Consider CO and H2O as simple examples. H2O has
an overall dipole but CO2 does not.

Attraction between polar molecules

Polar molecules tend to have their permanent dipoles aligned, because the negative end of
one permanent dipole attracts the positive end of the dipole in an adjacent molecule. This
attraction is the permanent dipole-dipole interaction: a second intermolecular force in
addition to London forces. Polar molecules therefore have higher melting and boiling
points than similar non-polar molecules.
Evidence:
N2
O2
NO

m.p.(K)
63
55
110

non-polar molecule
non-polar molecule
polar molecule

Check your understanding:

Consider the series of molecules CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4
xii) Which of these contains polar bonds ?
xiii) Which of these molecules is polar ?
xiv) Explain why the ammonium ion contains polar bonds but has no overall dipole

Page 8

xv) Arrange the following groups of substances in order, highest boiling point first.
1)

H H H H
H C C C C H

2)
H

H H H H

3)
H

C
H

H H H H
H C C C C H

4)

Cl H H H

H
H

H
H

H
C

H
H C C C H
H
H
Cl

What is the main type of interaction between molecules in:

xvi) butanone
xvii) pentene
xviii) Explain why pentane has a b.p. of 36C while 2-methylbutane has a b.p. of 28C

Hydrogen Bonding
is not bonding in the normal sense but an intermolecular force. It is the strongest of all
the intermolecular forces and results in some unexpected properties in substances that
have it. A lot of biochemical systems/living systems depend on hydrogen bonding.
Evidence:

x
40

energy to vaporize
(kJ mol-1)

H2O

due to H-bonds
x
20

x
H 2S

H2Te

x
H2Se

no. of electrons
When do we get hydrogen bonds ?
Hydrogen bonds are a special case of permanent dipole-dipole interactions. They occur
between the lone pair on a very electronegative atom and a hydrogen atom which is +
because it is bonded to a very electronegative atom.
Rules for when hydrogen bonding occurs between two molecules:
One molecule has a H-atom which is very highly positively polarized
The other molecule has one of the very electronegative atoms fluorine, oxygen or
nitrogen; and this atom has a lone pair available.
BOTH OF THESE CRITERIA MUST BE MET TO GET A HYDROGEN BOND
e.g.

NH3
SiH4
HF
HCl
CH2O

has hydrogen bonding

no hydrogen bonding
has hydrogen bonding
no hydrogen bonding
no hydrogen bonding (H is bonded to C, so not +)
Page 9

Drawing a hydrogen bond:

Draw the two molecules, show lone pairs
Label the + and - atoms
Show a H-bond from lone pair to + H atom
Make hydrogen bond angle 180

+
H

+
-

:O:
H

180

+
H
:O:
-

As they are much stronger than the other types of intermolecular forces, substances with
hydrogen bonding require much more energy to break the hydrogen bonds, and therefore
have much higher melting and boiling points than similar molecules without hydrogen
bonding.
Comparing the extent of hydrogen bonding:
If we have two different compounds both of which are capable of forming hydrogen bonds,
we can determine which will have the strongest hydrogen bonding. (This will be reflected in
that compound having a higher melting and boiling point).
i)
ii)

The more electronegative the - atom is, the stronger the hydrogen bond it forms
will be.
The more hydrogen bonds a molecule can form (count the available lone pairs on
the electronegative - atoms), the stronger the hydrogen bonding will be.

e.g. H2O has stronger hydrogen bonding than NH3, because i) oxygen is more
electronegative than nitrogen so the hydrogen bonds are stronger and ii) oxygen has two
lone pairs so can form two hydrogen bonds whereas nitrogen has one lone pair and can
only form one hydrogen bond. The hydrogen bonds in water take more energy to
overcome than in ammonia, so water has a higher melting and boiling point than ammonia.
Check your understanding:
xix) Draw a diagram to illustrate the hydrogen bonding in ammonia
xx)
Place the following molecules into order of increasing boiling point: CH3OH, CH4,
CH2O
xxi) Compare the intermolecular forces in ammonia, NH3, and hydrazine, N2H4, and
suggest which will have the highest boiling point.

Page 10

Answers to 'Check your Understanding' questions simple molecules

Draw dot-cross diagrams for
i) PH3

iii) BF3

ii) CS2

iv)

SCl2

v) Dot-cross diagram for H3O+

Dot-cross diagram for:

vi) O3

Dot-cross diagrams for

viii) lithium oxide

vii) SO3

xi) aluminium fluoride

Arrange the following groups of substances in order, highest boiling point first.
x) Ar, Ne, He because London forces increase with increasing number of electrons in the
atoms
xi) fluoromethane, chloromethane, bromomethane because London forces increase with
increasing number of electrons in the halogen atom
Page 11

Consider the series of molecules CH4, CH3Cl, CH2Cl2, CHCl3 and CCl4
xii) Which of these contains polar bonds ?
Ans: all except CH4
xiii) Which of these molecules is polar ?
Ans: CH3Cl, CH2Cl2, and CHCl3
xiv) Explain why the ammonium ion contains polar bonds but has no overall dipole
Ans: N and H have different electronegativities so the bonds are polar. The tetrahedral
shape of the ammonium ion means that the dipoles are balanced symmetrically around the
ions, so there is no overall dipole.
xv)Arrange the following groups of substances in order, highest boiling point first.
1) CH3-CH2-CH2-CH3
2) CH3-C(CH3)2-H
3) CH3-CH2-CH2-CH2Cl
4) CH3-C(CH3)2-Cl
Ans: 3
4
1
2

Permanent dipole-dipole, stronger London forces (linear shape)

Permanent dipole-dipole, weaker London forces (less area of surface contact)
No permanent dipole-dipole, stronger London forces (linear shape)
No permanent dipole-dipole, weaker London forces (less area of surface
contact)

What is the main type of interaction between molecules in

xvi) butanone
Ans: permanent dipole-dipole (C=O is a polar bond)
xvii) pentene
Ans: London forces (no polar bonds)
xviii) Explain why pentane has a b.p. of 36C while 2-methylbutane has a b.p. of 28C:
Ans: These are isoelectronic molecules. Pentane molecules are unbranched, less
spherical there is more area of surface contact and hence stronger London forces
compared to branched 2-methylbutane.
Check your understanding:
xix) Your diagram should show at least TWO ammonia molecules with:
i)
+ on each H atom and - on each N atom
ii)
a lone pair on each N atom
iii)
a hydrogen bond (shaded lines) between the H of one molecule and
the lone pair on the N atom of another molecule.
xx)

Lowest:
Highest:

CH4
CH2O
CH3OH

only London forces

London forces and permanent dipole-dipole
London forces, permanent dipole-dipole and
hydrogen bonding.

Page 12

xxi)

Hydrazine has a higher boiling point than ammonia. Both have hydrogen bonding
(and permanent dipole-dipole, and London forces) but hydrazine can form more
hydrogen bonds because it has two N atoms each with a lone pair available, while
ammonia only has one.

Page 13