Chemguide: Core Chemistry 14 - 16

Intermolecular forces

This page introduces the intermolecular forces which

exist between individual molecules and help them stick
together in liquids and solids.

I am assuming that you have read the page on

electronegativity and polar bonds.

What is an intermolecular force?

Intermolecular forces are also known as intermolecular

attractions. I tend to use the two terms interchangeably -
they mean the same thing.

Intermolecular forces are forces between molecules, in

the same way that an intercontinental missile can fly
between continents, or an interaction is something
happening between, for example, two or more people.

That is quite different from the forces which hold

molecules together. If you heat water, H2O, and turn it
into steam, you are breaking the forces between the
water molecules, but you aren't breaking the covalent
bonds within each water molecule.

If you heat solid iodine, I2, it turns to iodine vapour - so

you have overcome all the intermolecular forces holding
the molecules close to each other, but you still have I2
molecules in the vapour. You haven't done anything to
the covalent bonds holding the atoms together.

This is really important - intermolecular forces are forces

between one molecule and its neighbour(s). The covalent
bonds within the molecule are a quite separate issue.

The origin of intermolecular forces

Intermolecular attractions in polar molecules

Suppose you have a simple molecule like hydrogen

chloride, HCl. The hydrogen and chlorine are held
together by a covalent bond, but chlorine is more
electronegative than hydrogen, so the bonding pair is
pulled slightly towards the chlorine end of the bond.

The molecule is polar - one end is slightly positive and

the other is slightly negative because of the uneven
distribution of the electrons.

If two HCl molecules come close enough together, there

is an attraction between the positive end of one and the
negative end of the other. There is an intermolecular
attraction.

These are usually described as van der Waals dipole-

dipole attractions - often just as dipole-dipole
attractions.

At ordinary temperatures, when HCl is a gas, the

molecules are moving around fast enough that this weak
attraction isn't strong enough to hold them together.

But at lower temperatures, where the molecules aren't

moving so fast, eventually the intermolecular forces will
be strong enough to hold the particles in, first of all, a
liquid and, at even lower temperatures, in a solid.

Intermolecular attractions in non-polar molecules -

temporary fluctuating dipoles

Note: This next bit is copied directly from Chemguide's

advanced chemistry pages. You probably won't need to know
this in any detail at 14-16 year old level. But it isn't very
difficult, and is interesting.

Attractions are electrical in nature. In a symmetrical

molecule like hydrogen, however, there doesn't seem to
be any electrical distortion to produce positive or
negative parts. But that's only true on average.

The lozenge-shaped diagram represents a small

symmetrical molecule - H2, perhaps, or Br2. The even
shading shows that on average there is no electrical
distortion.

But the electrons are mobile, and at any one instant they
might find themselves towards one end of the molecule,
making that end δ-. The other end will be temporarily
short of electrons and so becomes δ+.

An instant later the electrons may well have moved up to

the other end, reversing the polarity of the molecule.

This constant "sloshing around" of the electrons in the

molecule causes rapidly fluctuating dipoles even in the
most symmetrical molecule. It even happens in noble
gases, like helium, which consist of single uncombined
atoms.

If both the helium electrons happen to be on one side of

the atom at the same time, the nucleus is no longer
properly covered by electrons for that instant.

How temporary dipoles give rise to intermolecular

attractions

I'm going to use the same lozenge-shaped diagram now

to represent any molecule which could, in fact, be a
much more complicated shape. Shape does matter, but
keeping the shape simple makes it a lot easier to both
draw the diagrams and understand what is going on.

Imagine a molecule which has a temporary polarity being

approached by one which happens to be entirely non-
polar just at that moment. (A pretty unlikely event, but it
makes the diagrams much easier to draw! In reality, one
of the molecules is likely to have a greater polarity than
the other at that time - and so will be the dominant one.)

As the right hand molecule approaches, its electrons will

tend to be attracted by the slightly positive end of the left
hand one.

This sets up an induced dipole in the approaching

molecule, which is orientated in such a way that the δ+
end of one is attracted to the δ- end of the other.

An instant later the electrons in the left hand molecule

may well have moved up the other end. In doing so, they
will repel the electrons in the right hand one.

The polarity of both molecules reverses, but you still

have δ+ attracting δ-. As long as the molecules stay
close to each other the polarities will continue to fluctuate
in synchronisation so that the attraction is always
maintained.

There is no reason why this has to be restricted to two

molecules. As long as the molecules are close together
this synchronised movement of the electrons can occur
over huge numbers of molecules.

This diagram shows how a whole lattice of molecules

could be held together in a solid using these temporary
fluctuating dipoles. An instant later, of course, you would
have to draw a quite different arrangement of the
distribution of the electrons as they shifted around - but
always in synchronisation.

These attractions due to temporary fluctuating dipoles

are properly known as van der Waals dispersion forces
or just as dispersion forces, and that is what I will call
them as a matter of routine.

Hydrogen bonding

You can't do a survey of intermolecular forces without

mentioning hydrogen bonds. These are really important
attractions, although you won't meet them much at this
level. They are, for example, the attractions which hold
the two strands of DNA together.

Hydrogen bonds occur in compounds where a hydrogen

atom is covalently bound to one of the very
electronegative atoms, nitrogen, oxygen and fluorine.
Two simple examples are water, H2O, and ammonia
NH3.

The oxygen and nitrogen attract the bonding pairs quite

closely to themselves, and so there is quite a strong
dipole on each bond, especially in the water case.
Oxygen is more electronegative than nitrogen.

But this isn't just another attraction between polar

molecules - it is stronger than that. The hydrogen atoms
are so strongly attracted to the lone pairs on nearby
water molecules, that there is almost the beginning of a
covalent bond being formed.

It isn't really a covalent bond, but it is nevertheless quite

a powerful attraction. This attraction between a fairly
positive hydrogen atom and a lone pair on a very
electronegative nearby atom is called a hydrogen bond.

Summing it all up

There are various forms of intermolecular attractions:

Attractions involving temporary fluctuating dipoles.

Attractions involving permanent dipoles.

Attractions involving hydrogen bonds.

You mustn't assume that these are alternatives. More

than one of these maybe present in the same substance,
and they just reinforce each other.

For example, in water, there are fluctuating dipoles as

well as permanent dipoles as well as hydrogen bonds.
This all adds up to amazingly strong intermolecular
attractions given the size of the molecule.

On the other hand, butane, a gas used as a fuel, hasn't

got an overall dipole on the molecule, and doesn't have
any hydrogen atoms attached to a very electronegative
atom. The only attractive forces between the molecules
are fluctuating dipoles.

As a result, butane is a gas with a boiling point of -0.5°C,

but water, with its larger intermolecular attractions is a
liquid with a boiling point of 100°C.

Finally

As far as exams at this 14-16 year old level are

concerned, you can almost certainly forget about most of
this page. There are one or two cases where you will
need information from this in another context. I will point
you back to here when that happens.

Where would you like to go now?

To the atomic structure and bonding menu . . .

To the Chemistry 14-16 menu . . .

To Chemguide Main Menu . . .

© Jim Clark 2019