Intermolecular Forces

Intermolecular forces are very important and play a big part in the properties of small covalent
molecules, in particular, boiling points.

this section is only for small covalent compounds such as O2, Cl2, CH4, C2H6, H2, H2O, NH3 etc. Do not
talk about intermolecular forces with ionic, metallic or giant covalent networks.

Before we get into the intermolecular forces, you need to know what electronegativity is first.

Electronegativity

a measure of how well an atom can attract electrons towards itself in a covalent bond

fluorine is the most electronegative element.

For example, in a Br-Br bond, the two electrons would be sitting 50/50 between the two atoms:

The two Br atoms are identical and therefore have the same electronegativity,
so the electrons are evenly spaced between the atoms. This is classed as a non-
polar bond.

Polar Bonds

Lets now look at a H-Cl bond:

Chlorine is more electronegative than hydrogen so it pulls the electrons in the

bond towards itself. You can see that the electrons are not split 50/50 between
the atoms anymore.

This is what we call a polar bond.

The + and - symbols are written above the H and Cl atoms to show partial charges. These charges show
that the electrons are not evenly distributed between the atoms so there a charge there, just not as
strong as a full or + charge.

This + and - that is set up is also known as a dipole.

Intermolecular Forces
Imagine that you have a small covalent molecule. In one mole there are 6 x 1023 molecules.

Between all these molecules there are weak forces, which is where the word intermolecular comes from.
It is these forces that hold all the molecules together.

There are three types of intermolecular forces that you need to know about:

London Forces (weakest force)

Permanent dipole-dipole

Hydrogen Bonds (strongest force)

London Forces

All covalent molecules have London forces. For non-polar molecules such as Cl2 or the alkanes, these are
the only forces that they have.

When talking about how London forces arise, you must talk about electrons.

The theory:

1. electrons move within electron clouds. At some point there will be more electrons on one side of an
electron cloud than the other, which sets up a + and - charge; the temporary dipole.

2. this dipole influences another nearby molecule and induces a similar dipole in it. The resulting
positive/negative attraction between the molecules is the London force.

3. the dipoles are temporary as the electrons are constantly moving, so it is a continuous cycle of the
dipoles forming and breaking.
Boiling Points
The more London forces forces that there are, then the higher the boiling point. So, if a molecule has a
higher molecular weight, such as I2 versus Cl2, then it will have more electrons and therefore more
London forces and a higher boiling point.

get into the habit of finishing answers with the phrase: therefore takes more energy to break the
forces as a lot of students assume it and miss the final mark.

Hydrocarbons

Again looking only a London forces. Two important factors: chain length and branching

1. chain length: hexane has a higher boiling point than butane as it has a longer chain and therefore more
electrons. More electrons = more London forces.

2. branching: if you compare two alkanes of the same molecular weight, and one of them is branched,
then the branched alkane will have a lower boiling point. This because the carbon chains are pushed
further apart and the forces between them are therefore weaker.

Sometimes they might say smaller surface area or less contact points. It all just means less London forces.

CH3CH2CH2CH2CH2CH3 higher boiling point than

Dipole/Dipole or Permanent Dipole

These forces are for molecules with a polar covalent bond such as H-Cl. The attraction between the +
and - is the intermolecular force, shown by the dashed line:

The dipoles are permanent as the + and - charges are always like
this due to electronegativity differences between the atoms.
Dipole/dipole forces are stronger than London forces.

Questions often compare the boiling points of things like Cl2 with H-Cl, which is to do with the
different types of force i.e. London forces versus dipole/dipole. You could also compare things like H-
Cl and H-Br. In this case, you need to talk about H-Br having more London forces as H-Br has a higher
molecular weight.

Hydrogen Bonding
Hydrogen bonding is similar to permanent dipole but specifically for N-H, O-H and F-H bonds. N, O and F
are the three most electronegative elements, which makes the bonds very polar and results in much
stronger intermolecular forces.
Common molecules to look at are NH3 and H2O.

The diagram below shows the hydrogen bonding in water, shown by the dashed line:

the O-H-O bond angle should be drawn as 180 degrees.

A typical question is to show you a diagram like the one below and to explain the trend. H2O is much
higher than expected and doesnt follow the trend. This is due to hydrogen bonding. The other molecules
are just down to London forces and size.

if they ask about H2O versus H-F. Water has the higher boiling point as each water molecule can form
two hydrogen bonds due to the two lone pairs on the oxygen. Fluorine is more electronegative than
oxygen but it can only form one hydrogen bond.

Generally, when doing boiling point questions, ask yourself:

Do the molecules have the same forces or different?

If different then which is stronger?

If the same, then size and London forces is usually the answer.
But.Br2 versus NH3

Br2 has the higher boiling point. Confused?

The natural reaction is to think that ammonia will have the higher boiling point as it has hydrogen
bonding and bromine doesnt. But they are very different in size; ammonia is much smaller than
bromine.

In this case, due to bromines size:

the sum of all the London forces were greater than the strength of the hydrogen bond in ammonia

So dont automatically think that a hydrogen bond always equals stronger.

Solubility
Covalent

Intermolecular forces also explain the differences in solubility for simple covalent compounds.

like dissolves in like

Like dissolves in like means that generally, polar molecules such as ethanol will dissolve in polar solvents
like H2O. And non-polar molecules e.g. halogens, alkanes dissolve in non-polar solvents like hexane.

When any molecule dissolves, think of it as bond making and bond breaking.

Intermolecular forces have to be broken in the molecule to be dissolved and the solvent. Then the
molecule has to form intermolecular forces with the solvent. If the intermolecular forces formed are
stronger than the forces broken then it will dissolve.

Generally, to dissolve in water the compound needs to be able to hydrogen bond to it, which gets asked a
lot in exams.

Non-polar molecules cant form hydrogen bonds with water and therefore cant dissolve in it. But for
example, in hexane non-polar molecules can form London forces and will dissolve.

Ionic solubility

I know that this is a simple covalent orientated topic but the specification also mentions ionic compounds
dissolving.

The most important point.do not talk about intermolecular forces here.

Its quite similar to the theory above. Generally, most ionic compounds will dissolve in water. Ionic
compounds are extremely polar i.e they have a full + and charge.
Two steps:

1. lattice breaks: the ionic lattice must break i.e. the bonds break.

2. hydration: the + and ions are surrounded by water molecules, which is called hydration i.e.
attraction between + on water and ion and - on water and + ion.

So similar to the simple covalent theory you can think of it as bond breaking (lattice breaking) and bond
making (hydration).

But please do not talk about intermolecular forces with ionic compounds! Ever..ever