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1 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
Note: If you have come straight to this page from a search engine, it would
make sense to read my page about van der Waals forces before you go on.
If you are an A level (or equivalent) student, the information on that page is
what you will need for exam purposes. This current page is essentially a
discussion document to try to get a bit closer to the truth.
18-10-2014 21:45
2 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
about Debye forces: "The contribution to the total bonding from this
effect is also very small."
about dispersion forces: "Dispersion forces usually make by far the
biggest contribution to van der Waals bonding"
That is then followed by a table showing percentage contributions of the
three types of van der Waals forces for a few simple molecules. Three of
these are non-polar molecules where the contribution due to the dispersion
forces is unsurprisingly 100%. The other two are simple polar molecules,
carbon monoxide and hydrogen chloride. Because of the way it is bonded,
carbon monoxide has only got a very small permanent dipole.
molecule
dipoledipole
forces
Debye
forces
dispersion
forces
CO
0.005
0.08
100
HCl
15
81
The hydrogen chloride figures are particularly surprising. HCl has polar
molecules, and yet most of the intermolecular forces are due to dispersion
forces.
18-10-2014 21:45
3 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
The first column of data shows the dipole moments of the various
molecules. The second one is a measure of the polarisability of the various
molecules. This is a measure of how easy it is for the electrons to move
around in the molecule in response to an external electric field - from a
neighbouring dipole, for example. (Ignore the third column - it is a term used
in the calculation of total intermolecular forces.)
Apart from water, and perhaps ethanol, in all the other cases, the London
(dispersion) forces make by far the greatest contribution to the overall
intermolecular bonding. Notice that the dispersion forces are less important
in the molecules which are least polarisable - like water. We'll look at that
again in a moment.
Note: If you want to see this table in its original context, this link will take
you to the Google Books source. If you are interested in how these figures
are derived, you could go back through the previous pages in the book.
Unfortunately several pages just before this aren't available from Google.
The maths of this defeats me, but I have no reason to suppose that it is
wrong.
18-10-2014 21:45
4 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
Many sources state simply that dispersion forces are weak, and give values
for the energy needed to break them. The student who brought this to my
attention told me that his teachers were quoting dispersion forces as having
a strength of less than 4 kJ/mole. That's typical of the sort of values you can
find on the web.
This is completely misleading! The size of the dispersion forces is governed
by the size and shape of the molecule. You cannot quote a single value as if
it was typical of all dispersion forces.
If you think about tiny molecules like helium or hydrogen, then the
dispersion forces will indeed by very weak. You haven't got many electrons
to move around, and very little distance over which to move them.
But look at the following sequence of moderately sized molecules. These
are all non-polar, and so dispersion forces are the only intermolecular
attractions.
If you haven't come across the structure of benzene yet, don't worry about it.
Each corner of every hexagon has a carbon atom. The corners with only two
lines going away from them also have a hydrogen atom attached. The
circles in the centre of the hexagons show delocalised electrons - electrons
not firmly attached to a particular atom.
Notice that every time you attach another hexagon, the boiling point goes up
by about 140C. By the time you have got to anthracene, the boiling point is
quite high. Since this is due only to the dispersion forces between the
molecules, those dispersion forces must be strong.
I have actually chosen these particular examples because they are
non-polar, the delocalised electrons make them very polarisable to give
temporary dipoles, and the molecules are flat so that they can lie closely
together. The polarisability and the fact that the molecules can lie closely
together help to make the dispersion forces strong.
But it isn't very difficult to find examples of non-polar molecular compounds
with fairly high boiling points, and therefore strong dispersion forces. A more
familiar example comes from the fractional distillation of crude oil.
Crude oil is a mixture of hydrocarbons of all sizes and shapes. These are
non-polar molecules which would be held in the liquid by dispersion forces,
and they range from gases to liquids with boiling points over 400C. There
will be a wide range of strengths of the dispersion forces, from the relatively
18-10-2014 21:45
5 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
Having shown that dispersion forces aren't necessarily weak (in fact, can be
quite strong), let's now look at the relative importance of dipole-dipole
interactions and dispersion forces.
Both molecules have identical numbers of electrons, and the size of the two
molecules is much the same. That means that you might expect the
dispersion forces in both molecules to be similar (but see below).
Fluorine is the most electronegative element, and therefore the carbonfluorine bond is going to be very polar. However, even given the large
permanent polarity of the molecule, the boiling point has only been
increased by 10.2 K.
Look at it like this. If there were no intermolecular forces at all between
molecules, everything would boil at a temperature fractionally above zero K.
(Not actually at zero K - there has to be a little bit of energy to enable
movement.) In ethane, the dispersion forces are strong enough that the
boiling point has been increased to 184.5 K.
Now add the effect of the permanent dipole-dipole interactions to that. The
only extra difference the dipole-dipole attraction has made is to increase the
boiling point by a further 10.2 K. That is a negligible effect compared with
the effect of the dispersion forces. You cannot say that dipole-dipole
interactions are stronger than dispersion forces.
Part of the problem with this example is that fluorine is so electronegative
that electrons in the carbon-fluorine bond are pulled very firmly towards the
fluorine atom. That makes the molecule much less polarisable, and so
reduces the size of the dispersion forces which depend on temporary
movement of electrons in the molecules.
18-10-2014 21:45
6 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
So there are two effects operating in opposite directions. The polarity of the
carbon-fluorine bond is adding dipole-dipole attractions, while at the same
time, the more tightly held electrons are reducing the effect of the dispersion
forces.
The two boiling points are almost the same. That means that the gain in
dipole-dipole attractions is roughly cancelled out by the loss of dispersion
forces.
To find out how much effect the addition of the fluorine had on the dispersion
forces, I looked at what happened if you lengthened the chain to which the
fluorine is attached.
In organic chemistry, the effect of putting a very electronegative element in a
chain falls off quite quickly along the chain. If the fluorine was having a
major effect on the dispersion forces, then there should be a falling-off of
that effect as the chain length grows. Is there?
fluoride
B.Pt
(K)
alkane
B.Pt
(K)
CH3F
194.7 CH3CH3
184.5
CH3CH2F
235.9 CH3CH2CH3
231
CH3CH2CH2F
270.5 CH3CH2CH2CH3
272.6
CH3CH2CH2CH2F
305.7 CH3CH2CH2CH2CH3
309.2
CH3CH2CH2CH2CH2F
336
CH3CH2CH2CH2CH2CH2F 365
CH3CH2CH2CH2CH2CH3
342.1
CH3CH2CH2CH2CH2CH2CH3 371.5
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7 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
chloride
B.Pt
(K)
alkane
B.Pt
(K)
CH3Cl
249.2 CH3CH2CH3
231
CH3CH2Cl
285.5 CH3CH2CH2CH3
272.6
CH3CH2CH2Cl
319.6 CH3CH2CH2CH2CH3
309.2
CH3CH2CH2CH2Cl
351.5 CH3CH2CH2CH2CH2CH3
342.1
CH3CH2CH2CH2CH2Cl 381
CH3CH2CH2CH2CH2CH2CH3 371.5
Notice that, again, there isn't all that much difference in boiling points
between the members of each horizontal pair. The polar molecule has a
18-10-2014 21:45
8 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
slightly higher boiling point than the non-polar one, but not by very much.
The increase in intermolecular attractions due to the additional dipole-dipole
interactions is almost negligible compared with the effect of the dispersion
forces.
Molecules with a permanent dipole do usually have a higher boiling point
than similarly sized non-polar molecules, but that is because they have
dipole-dipole forces as well as dispersion forces. As we have seen, the extra
dipole-dipole interactions don't actually add all that much to the boiling point.
In conclusion
This is just a selection of molecules that I have looked at, but I have decided
it is too boring to keep on making the same point over and over. If you are
interested, you can easily do this yourself - just try to keep the molecules
you are comparing as similar as possible in terms of their shape and length
and the number of electrons they contain.
Two other series that are worth a look are alcohols, and carbonyl
compounds (containing carbon - oxygen double bonds), particularly
aldehydes so that the carbonyl group is on the end of a chain.
If you believe that hydrogen bonding (in alcohols) is a particularly strong
form of intermolecular bonding, doing this for alcohols will upset you!
Just as a taster, in the table from the book further up this page, t-butanol is
mentioned as having a contribution from dispersion forces of 67.2%. The
modern name for t-butanol is 2-methylpropan-2-ol. If you remove the -OH
group and replace it with a methyl group you get 2,2-dimethylpropane. Both
of these molecules have the same shape and number of electrons.
The alkane boils at 282.6 K; the alcohol at 355.4 K. Dispersion forces can
be thought of as contributing 282.6 to the boiling point; all the other dipole
forces, including hydrogen bonding, an additional 72.8. Which is the major
force holding these alcohol molecules in the liquid? It is the dispersion
forces!
Finally, then . . .
Dispersion forces have very variable strengths depending on the size,
shape and polarisability of the molecules. Describing them as weak is
wrong. They can be anything from very weak to quite strong
depending on the shape and size of the molecule.
For most molecules, including those which can hydrogen bond,
dispersion forces contribute the most to the overall intermolecular
bonding. Describing dispersion forces as the weakest kind of
intermolecular force is wrong.
18-10-2014 21:45
9 of 9
http://www.chemguide.co.uk/atoms/bonding/vdwstrengths.html#top
18-10-2014 21:45