Intermolecular Forces

Water is the only substance we often as a solid, a liquid, and a gas. At low
temperatures, it is a solid in which the individual molecules are locked into a rigid
structure. As we raise the temperature, the average kinetic energy of the molecules
increases, which increases the rate at which these molecules move.

There are three ways in which a water molecule move: (1) vibration, (2) rotation, and
(3) translation. Water molecules vibrate when H--O bonds are stretched or
bent. Rotation involves the motion of a molecule around its center of
gravity. Translation literally means to change from one place to another. It therefore
describes the motion of molecules through space.

The covalent bonds between the hydrogen and oxygen atoms in a water molecule are
called intramolecular bonds. (The prefix intra- comes from the Latin stem meaning
"within or inside.

The bonds between the neighboring water molecules in ice are called intermolecular
bonds, from the Latin stem meaning "between." (This far more common prefix is
used in words such as interface, intercollegiate, and international.)

The intramolecular bonds that hold the atoms in H2O molecules together are almost
25 times as strong as the intermolecular bonds between water molecules. (It takes 464
kJ/mol to break the H--O bonds within a water molecule and only 19 kJ/mol to break
the bonds between water molecules.)

All three modes of motion disrupt the bonds between water molecules. As the system
becomes warmer, the thermal energy of the water molecules eventually becomes too
large to allow these molecules to be locked into the rigid structure of ice. At this point,
the solid melts to form a liquid in which intermolecular bonds are constantly broken
and reformed as the molecules move through the liquid. Eventually, the thermal
energy of the water molecules becomes so large that they move too rapidly to form
intermolecular bonds and the liquid boils to form a gas in which each particle moves
more or less randomly through space.

The difference between solids and liquids, or liquids and gases, is therefore based on a
competition between the strength of intermolecular bonds and the thermal energy of
the system. At a given temperature, substances that contain strong intermolecular
bonds are more likely to be solids. For a given intermolecular bond strength, the
higher the temperature, the more likely the substance will be a gas.

The van der Waals equation is used today to give a better fit to the experimental data
of real gases than can be obtained with the ideal gas equation. But that wasn't van der
Waals's goal. He was trying to develop a model that would explain the behavior of
liquids by including terms that reflected the size of the atoms or molecules in the
liquid and the strength of the bonds between these atoms or molecules. The weak
intermolecular bonds in liquids and solids are therefore often called van der Waals
forces. These forces can be divided into three categories: (1) dipole-dipole, (2) dipole-
induced dipole, and (3) induced dipole-induced dipole.

Dipole-Dipole Forces

Many molecules contain bonds that fall between the extremes of ionic and covalent
bonds. The difference between the electronegativities of the atoms in these molecules
is large enough that the electrons aren't shared equally, and yet small enough that the
electrons aren't drawn exclusively to one of the atoms to form positive and negative
ions. The bonds in these molecules are said to be polar, because they have positive
and negative ends, or poles, and the molecules are often said to have a dipole moment.

HCl molecules, for example, have a dipole moment because the hydrogen atom has a
slight positive charge and the chlorine atom has a slight negative charge. Because of
the force of attraction between oppositely charged particles, there is a small dipole-
dipole force of attraction between adjacent HCl molecules.

The dipole-dipole interaction in HCl is relatively weak; only 3.3 kJ/mol. (The
covalent bonds between the hydrogen and chlorine atoms in HCl are 130 times as
strong.) The force of attraction between HCl molecules is so small that hydrogen
chloride boils at -85.0oC.

Dipole-Induced Dipole Forces

What would happen if we mixed HCl with argon, which has no dipole moment? The
electrons on an argon atom are distributed homogeneously around the nucleus of the
atom. But these electrons are in constant motion. When an argon atom comes close to
a polar HCl molecule, the electrons can shift to one side of the nucleus to produce a
very small dipole moment that lasts for only an instant.

By distorting the distribution of electrons around the argon atom, the polar HCl
molecule induces a small dipole moment on this atom, which creates a weak dipole-
induced dipole force of attraction between the HCl molecule and the Ar atom. This
force is very weak, with a bond energy of about 1 kJ/mol.

Induced Dipole-Induced Dipole Forces

Neither dipole-dipole nor dipole-induced forces can explain the fact that helium
becomes a liquid at temperatures below 4.2 K. By itself, a helium atom is perfectly
symmetrical. But movement of the electrons around the nuclei of a pair of
neighboring helium atoms can become synchronized so that each atom simultaneously
obtains an induced dipole moment.

These fluctuations in electron density occur constantly, creating an induced dipole-

induced dipole force of attraction between pairs of atoms. As might be expected, this
force is relatively weak in helium -- only 0.076 kJ/mol. But atoms or molecules
become more polarizable as they become larger because there are more electrons to be
polarized. It has been argued that the primary force of attraction between molecules in
solid I2 and in frozen CCl4 is induced dipole-induced dipole attraction.