Intermolecular Forces

Introduction

Dipole Dipol Dipole Induced

e Forces
Dipole Forces

Induced Dipole
Induced Dipole Forces

Introduction
Water is the only substance we routinely encounter 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.
To understand the effect of this motion, we need to differentiate between intramolecular and
intermolecular bonds. 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." Thus, intramural sports match teams from the same institution.) 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 kinetic theory assumes that there is no force of attraction between the particles in a gas. If this
assumption were correct, gases would never condense to form liquids and solids at low temperatures.
In 1873 the Dutch physicist Johannes van der Waals derived an equation that not only included the
force of attraction between gas particles but also corrected for the fact that the volume of these particles
becomes a significant fraction of the total volume of the gas at high pressures.
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.

Intermolecular Forces
Skills to develop
Classify intermolecular forces as ionic, covalent, London dispersion, dipole-dipole, or
hydrogen bonding.
Explain properties of material in terms of type of intermolecular forces.
Predict the properties of a substance based on the dominate intermolecular force.

Intermolecular Forces
Forces binding atoms in a molecule are due to chemical bonding. The energy required to break a bond
is called the bond-energy. For example the average bond-energy for O-H bonds in water is 463 kJ/mol.
On average, 463 kJ is required to break 6.023x1023 O-H bonds, or 926 kJ to convert 1.0 mole of water
into 1.0 mol of O and 2.0 mol of H atoms. A space filling model of water molecule is shown here.

The forces holding molecules together are generally called intermolecular forces. The energy required
to break molecules apart is much smaller than a typical bond-energy, but intermolecular forces play
important roles in determining the properties of a substances. Intermolecular forces are particularly
important in terms how molecules interact and form biological organisms or even life. This link gives
an excellent introduction to the interactions between molecules.

Classifying Intermolecular Forces

In general, intermolecular forces can be divided into several categories. The four prominent types are:
1. Strong ionic attraction
Recall lattice energy and its relations to properties of solid. The more ionic, the higher the
lattice energy. Examine the following list and see if you can explain the observed values by way
of ionic attraction:
LiF, 1036; LiI, 737; KF, 821; MgF2, 2957 kJ/mol.
2. Intermediate dipole-dipole forces
Substances whose molecules have dipole moment have higher melting point or boiling point
than those of similar molecular mass, but their molecules have no dipole moment.
3. Weak London dispersion forces or van der Waal's force These forces alway operate in any
substance. The force arisen from induced dipole and the interaction is weaker than the dipoledipole interaction. In general, the heavier the molecule, the stronger the van der Waal's force of
interaction. For example, the boiling points of inert gases increase as their atomic masses
increases due to stronger Landon dispersion interactions.
4. Hydrogen bond
Certain substances such as H2O, HF, NH3 form hydrogen bonds, and the formation of which
affects properties (mp, bp, solubility) of substance. Other compounds containing OH and NH2
groups also form hydrogen bonds. Molecules of many organic compounds such as alcohols,
acids, amines, and aminoacids contain these groups, and thus hydrogen bonding plays a
important role in biological science.
5. Covalent bonding
Covalent is really intramolecular force rather than intermolecular force. It is mentioned here,
because some solids are formed due to covalent bonding. For example, in diamond, silicon,
quartz etc., the all atoms in the entire crystal are linked together by covalent bonding. These
solids are hard, brittle, and have high melting points. Covalent bonding holds atoms tighter than
ionic attraction.
6. Metallic bonding
Forces between atom in metallic solids belong to another category. Valence electrons in metals
are rampant. They are not restricted to certain atoms or bonds. Rather they run freely in the
entire solid, providing good conductivity for heat and electric energy. These behaviour of
electrons give special properties such as ductility and mechanical strength to metals.
The division into types is for convenience in their discussion. Of course all types can be present
simultaneously for many substances. Usually, intermolecular forces are discussed together with The
States of Matter, which is linked to a well illustrated web-site.
Intermolecular forces also play important roles in solutions, a discussion of which is given in
Hydration, solvation in water. A summary of the interactions is illustrated in the following diagram: