What are van der Waals forces?

I'm having trouble understanding the difference between hydrogen

bonding and London forces. I know that hydrogen bonding only Vocabulary
occurs with hydrogen but what is the difference in their actual
bonding? dipole-dipole force
Beau 12/02/99 dipole moment
Molecules can attract each other at moderate distances and hydrogen bonding
repel each other at close range. The attractive forces are
collectively called "van der Waals forces". Van der Waals intermolecular force
forces are much weaker than chemical bonds, and random London force
thermal motion around room temperature can usually overcome van der Waals force
or disrupt them.

Intermolecular forces are feeble; but without them, life as we know it would be
impossible. Water would not condense from vapor into solid or liquid forms if its
molecules didn't attract each other. Intermolecular forces are responsible for many
properties of molecular compounds, including crystal structures (e. g. the shapes of
snowflakes), melting points, boiling points, heats of fusion and vaporization, surface
tension, and densities. Intermolecular forces pin gigantic molecules like enzymes,
proteins, and DNA into the shapes required for biological activity.

Van der Waals' forces include all intermolecular forces that act between electrically
neutral molecules. Several special cases occur.

Permanent forces occur when the interacting

molecules contain groups or regions that are
permanently electron-rich or electron poor. For
example, the animation at right shows short range
forces acting between molecules of gaseous HCl.
The electron-rich region (on the chlorine atom) is
colored red; the electron-poor hydrogen atom is
shown in blue. Notice that the molecules align when
they pass close to each other because the positive
end of one molecule is attracted to the negative end
of the other. The yellow glow indicates the formation
of a weak intermolecular attraction during a close
encounter. Notice that a molecule's momentum is
often strong enough to overcome the attraction and prevent it from being captured in a
cluster of other molecules.

When the the molecule has a distinctly positive end and a negative end, the permanent
force is referred to as a dipole-dipole attraction. Weaker (but still noticeable) permanent
forces can act between any molecules with polar bonds. For example, the oxygen atoms
in CO2 are electron-rich, while the carbon atom in the center is electron poor, so the
oxygen atom of one CO2 can be attracted to the carbon of another during very close
encounters.
Hydrogen bonds are abnormally strong dipole-dipole attractions that involve molecules
with -OH, -NH, or FH groups. Hydrogen atoms are very small (with an atomic radius of
about 37 pm, they're smaller than any other atom but helium). When a bonded
electronegative atom (oxygen, nitrogen, or fluorine) pulls electrons away from the
hydrogen atom, the positive charge that results is tightly concentrated. The hydrogen is
intensely attracted to small, electron-rich O, N, and F atoms on other molecules. (Larger
electron-rich groups and atoms (like -Cl, for example) will also attract the hydrogen, but
because their electrons aren't as tightly concentrated, the resulting dipole-dipole
attraction is too weak to be considered a "real" hydrogen bond.) Hydrogen bonds are
essential for building biological systems: they're strong enough to bind biomolecules
together but weak enough to be broken, when necessary, at the temperatures that
typically exist inside living cells.

A polar molecule can also induce a temporary dipole in a nonpolar molecule. The
electron cloud around a nonpolar molecule responds almost instantaneously to the
presence of a dipole, so this "dipole-induced dipole" force isn't as orientation-dependent
as the dipole-dipole interaction.

Transitory forces arise when electron clouds

oscillate in step on two molecules at close
range. Bond vibrations in molecules may
produce the oscillations or they may be
triggered by random, instantaneous pile-ups of
electrons in atoms. The electron-rich and
electron-poor regions on the molecule may not
persist for more that 10-14 or 10-15 seconds, but
if they can polarize the electron distribution on an adjacent molecule, electron clouds on
the two molecules may begin to oscillate cooperatively with each other. The dipoles are
transitory but aligned, and a net attractive force pulls the molecules together. At closer
range, the oscillation becomes even more effective.

In the animation at left, the electrons in H2 molecules are oscillating in time to produce a
tiny crystal of solid hydrogen. The electron-rich (red) ends are aligned with electron-poor
(blue) ends through nearly all of the cycle. The arrows show the direction of the transitory
dipole moment during the oscillation.

Transitory forces are sometimes called "London forces" in honor of their discoverer.
Since all molecules have electron clouds that can oscillate, London forces always
contribute to intermolecular attractions. However, they are usually weaker than the
permanent forces that they are usually only invoked to explain intermolecular forces
between nonpolar molecules or noble gas atoms. However, molecules with large, diffuse
electron clouds (like polyatomic anions or molecules containing multiple bonds) can have
London forces that are at least as strong as permanent forces are.

More electrons in a molecule or atom means potentially larger electron imbalances and
so stronger London forces. This nicely explains the periodic trend in boiling points for the
noble gases; Ne boils at a much lower temperature than Xe because, having fewer
electrons, its London forces are more easily overcome by thermal motion. It also explains
why high-molecular weight nonpolar compounds tend to be solids or liquids while light
nonpolar compounds tend to gases; high molecular weight generally means more
electrons and more powerful London attractions.
 Author: Fred Senese senese@antoine.frostburg.edu

Sign up for a free monthly

newsletter describing updates,
new features, and changes
on this site.

Subscribe Details

General Chemistry Online! What are van der Waals forces?

Copyright © 1997-2005 by Fred Senese

Comments & questions to fsenese@frostburg.edu
Last Revised 07/3