CHAPTER 4

Intermolecular
Forces. Liquids
and Solids
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 1. The Kinetic Molecular Theory of Liquids and Solids
 According to the Kinetic Energy theory of matter, Gas, liquid and solids consists of molecules in constant motion, these
molecules have K.E.

 In gases, the distances between molecules are In a liquid, the molecules are so close together that
so great at (25°C and 1 atm), there is no there is very little empty space. Thus, liquids are
appreciable interaction between the molecules. much more difficult to compress than gases, and
they are also much denser under normal conditions.
Gases can be readily compressed. The lack of
strong forces between molecules also allows a Molecules in a liquid are held together by one or
gas to expand to fill the volume of its container. more types of attractive forces.

Furthermore, the large amount of empty space The molecules can, however, move past one another
explains why gases have very low densities under freely, and so a liquid can flow, can be poured, and
normal conditions. assumes the shape of its container.

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 In a solid, molecules are held rigidly in position with virtually
no freedom of motion.

There is even less empty space in a solid than in a liquid. Thus,

solids are almost incompressible and possess definite shape
and volume.

the density of the solid form is higher than that of the liquid
form for a given substance. It is not uncommon for two states
of a substance to coexist.
Particles in Solids, Liquids, and Gases
Table 1. Characteristic Properties of Gases, Liquids, and Solids

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Elements that occur naturally as Gases, Liquids, and Solids at 25°C and 1 atm

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1.1. Kinetic Theory and Temperature
All particles have energy, and the energy varies depending on the temperature the sample of matter is in, which
determines if the substance is a solid, liquid, or gas. Solid particles have the least amount of energy, and gas particles have
the greatest amount of energy.

• The temperature of a substance is a measure of the average kinetic energy of the particles. A change in phase may
occur when the energy of the particles is changed.

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Example. 1
Choose the correct answer:

1. which has the highest average kinetic enery at 500K

a.N2
b.CH4
c.CO2
d. They all have same average Kinetic Energy

2. if C02 is at 500k, N2 is at 700K and CH4 is at 300K which one has the highest KE
a.CO2
b.CH4
c.N2

3. What is the average kinetic energy of N2 gas at 25 °C

KE=3/2 KT
3.716j=J/mol
The average kinetic energy is not dependant on the identity of the gas but on the Temperature

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 1.2. Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
In contrast to intermolecular forces, intramolecular forces hold atoms together
in a molecule. (Chemical bonding.) Intramolecular forces stabilize individual
molecules, whereas intermolecular forces are primarily responsible for the bulk
properties of matter (for example, melting point and boiling point).

As the temperature of a gas drops, the average kinetic energy of its molecules
decreases. Eventually, at a sufficiently low temperature, the molecules no longer
have enough energy to break away from the attraction of neighboring
molecules. At this point, the molecules aggregate to form small drops of liquid.
This transition from the gaseous to the liquid phase is known as condensation.

Generally, intermolecular forces are much weaker than intramolecular forces.

Much less energy is usually required to evaporate a liquid than to break the
bonds in the molecules of the liquid.
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  To discuss the properties of condensed matter, we must understand the different types of
intermolecular forces.

1. Dipole-dipole, dipole-induced dipole, and dispersion forces make up what chemists commonly refer to
as Van der Waals forces.

2. On the other hand, Ions and dipoles are attracted to one another by electrostatic forces called ion-
dipole forces, which are not van der Waals forces.

3. Hydrogen bonding is a particularly strong type of dipole-dipole interaction. Because only a few elements
can participate in hydrogen bond formation, it is treated as a separate category.

 Depending on the phase of a substance, the nature of chemical bonds, and the types of elements present,
more than one type of interaction may contribute to the total attraction between molecules,

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1.2.1. Ion-Dipole Forces
Coulomb’s law also explains ion-dipole forces, which attract an ion (either a cation or an anion) and a polar
molecule to each other. The strength of this interaction depends on the charge and size of the ion and on
the magnitude of the dipole moment and size of the molecule.
The charges on cations are generally more concentrated, because cations are usually smaller than anions.
Therefore, a cation interacts more strongly with dipoles than does an anion having a charge of the same
magnitude. Hydration, is one example of ion-dipole interaction.

(a) Interaction of a water molecule with a Na+ ion and a Mg 2+ ion.

(b) In aqueous solutions, metal ions are usually surrounded by six
water molecules in an octahedral arrangement .

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 1.2.2.Dipole-Dipole Forces
Dipole-dipole forces are attractive forces between polar molecules, that is, between molecules that possess dipole
moments. Their origin is electrostatic, and they can be understood in terms of Coulomb’s law. The larger the dipole
moment, the greater the force. In liquids, polar molecules are not held as rigidly as in a solid, but they tend to align in
a way that, on average, maximizes the attractive interaction.

Molecules that have a permanent

dipole moment tend to align with
opposite polarities in the solid phase for
maximum attractive information.

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1.2.3 Induced dipole
What attractive interaction occurs in nonpolar substances?
If we place an ion or a polar molecule near an atom (or a nonpolar molecule), the electron
distribution of the atom (or molecule) is distorted by the force exerted by the ion or the
polar molecule, resulting in a kind of dipole.

The dipole in the atom (or nonpolar molecule) is said to be an induced dipole because the
separation of positive and negative charges in the atom(or nonpolar molecule) is due to
the proximity of an ion or a polar molecule.

The attractive interaction between an ion and the induced dipole is called ion-induced (a) Spherical charge distribution in a
dipole interaction, and the attractive interaction between a polar molecule and the helium atom. (b) Distortion caused by the
induced dipole is called dipole-induced dipole interaction. approach of a cation. (c) Distortion
caused by the approach of a dipole.

Generally, the larger the number of electrons and the more diffuse the electron cloud in
the atom or molecule, the greater its polarizability.
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 1.2.4. Dispersion Forces
• In a helium atom the electrons are moving at some
distance from the nucleus. At any instant it is likely that
the atom has a dipole moment created by the
specific positions of the electrons. This dipole
moment is called an instantaneous dipole because it
lasts for just a tiny fraction of a second. In the next
instant the electrons are in different locations and the
atom has a new instantaneous dipole, and so on.

• At the next moment, a different instantaneous dipole can create temporary dipoles in the surrounding He
atoms. The important point is that this kind of interaction produces dispersion forces, attractive forces that
arise as a result of temporary dipoles induced in atoms or molecules.

• The magnitude of this attractive interaction is directly proportional to the polarizability of the atom or
molecule.

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• Dispersion forces, which are also called London forces, usually increase with molar mass because molecules
with larger molar mass tend to have more electrons, and dispersion forces increase in strength with the
number of electrons.

 As expected, the melting point increases as the number of electrons in the

molecule increases.

 Because these are all nonpolar molecules, the only attractive intermolecular
forces present are the dispersion forces.

Melting points of similar substances that

consist of nonpolar molecules.

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1.2.5. The Hydrogen Bond
Is a strong type of intermolecular attraction, which is a special type of dipole-dipole interaction between
the hydrogen atom in a polar bond, such as N-H, O-H, or F-H, and an electronegative O, N, or F atom.
The average energy of a hydrogen bond is quite large for a dipole-dipole interaction (up to 40 kJ/mol).
Thus, hydrogen bonds have a powerful effect on the structures and properties of many compounds.

HCOOH forms hydrogen bonds

with two H2O molecules.

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 Hydrogen bonding in water, ammonia, and hydrogen fluoride. Solid lines represent covalent bonds, and dotted lines
represent hydrogen bonds.

 The strength of a hydrogen bond is determined by the coulombic interaction between the lone-pair electrons of
the electronegative atom and the hydrogen nucleus.

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 o The boiling point of HF is lower than that
of water because each H2O takes part in
three intermolecular hydrogen bonds.
Therefore, the forces holding the
molecules together are stronger in H2O
than in HF.

Boiling points of the hydrogen compounds of Groups 4A, 5A, 6A, and 7A elements

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 The intermolecular forces discussed so far are all attractive in nature. Keep in mind, though, that
molecules also exert repulsive forces on one another. Thus, when two molecules approach each other,
the repulsion between the electrons and between the nuclei in the molecules comes into play.

 This is the reason that liquids and solids are so hard to compress. In these phases, the molecules are
already in close contact with one another, and so they greatly resist being compressed further.

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 Example .2
What type(s) of intermolecular forces exist between the following pairs: (a) HBr and H2S, (b) Cl 2 and CBr4, (c) I2 and NO3-,
(d) NH3 and C6H6?
Strategy

Classify the species into three categories: ionic, polar (possessing a dipole moment), and nonpolar. Keep in mind that
dispersion forces exist between all species.

Solution Therefore, the intermolecular

forces present are dipole-
(a) Both HBr and H2S are polar molecules dipole forces, as well as
dispersion forces.

(b) Both Cl2 and CBr4 are nonpolar, so there are

only dispersion forces between these molecules.

(c) I2 is a homonuclear diatomic molecule and therefore nonpolar, so the forces between it and the ion NO3 - are ion-induced
dipole forces and dispersion forces.

(d) NH3 is polar, and C6H6 is nonpolar. The forces are dipole-induced dipole forces and dispersion forces.
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 2. Liquid pahse and its properties
Intermolecular forces give rise to a number of structural features and properties of
liquids.
2.1. Surface Tension
Molecules within a liquid are pulled in all directions by intermolecular forces. However,
molecules at the surface are pulled downward and sideways by other molecules, but not
upward away from the surface. These intermolecular attractions tend to pull the
molecules into the liquid and cause the surface to tighten like an elastic film.

• A measure of the elastic force in the surface of a liquid is surface tension.

The surface tension is the amount of energy required to stretch or increase the surface of a
liquid by a unit area (for example, by 1cm2).

• Liquids that have strong intermolecular forces also have high surface tensions. Thus,
because of hydrogen bonding, water has a considerably greater surface tension than
most other liquids

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 • An example of surface tension is capillary action. water rising spontaneously in a capillary tube.
A thin film of water adheres to the wall of the glass tube. The surface tension of water causes this film to contract, and as it
does, it pulls the water up the tube. Two types of forces bring about capillary action.

One is cohesion, which is the intermolecular attraction between like molecules (in this case, the water molecules).
The second force, called adhesion, is an attraction between unlike molecules, such as those in water and in the sides of a
glass

 (a) When adhesion is greater than cohesion, the liquid (a

water) rises in the capillary tube.

 (b) When cohesion is greater than adhesion, (b) as it is for

mercury, a depression of the liquid in the capillary tube results.

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 2.2. Viscosity
 Viscosity is a measure of a fluid’s resistance to flow.

• The greater the viscosity, the more slowly the liquid flows.
• The viscosity of a liquid usually decreases as temperature increases; thus, hot molasses flows much faster than cold
molasses.
• Liquids that have strong intermolecular forces have higher viscosities than those that have weak intermolecular
forces . Water has a higher viscosity than many other liquids because of its ability to form hydrogen bonds.

Example
like water, glycerol can form hydrogen bonds. Each
glycerol molecule has three -OH groups that can
participate in hydrogen bonding with other glycerol
molecules.

Glycerol is a clear, odorless,

liquid used to make explosives,
ink, and lubricants.

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Table.1 Viscosity of some common liquid

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 Example. 2
• Why does the viscosity of a liquid decrease with increasing temperature?

 When a liquid is heated, the kinetic energy of its molecules increases, and the intermolecular attraction becomes
weaker. Hence, the viscosity of a liquid decreases with increase in its temperature.

• Why is ice less dense than water?

 When ice is formed it forms more hydrogen bonds with other water molecules to
form hexagonal lattice structures. In the middle of the hexagons there is a lot of
empty space. Ice takes up more space than water. Lower density

 When ice melts, a number of water molecules have enough kinetic energy to break
free of the intermolecular hydrogen bonds. These molecules become trapped in the
cavities of the three-dimensional structure. As a result, there are more molecules per
unit volume in liquid water than in ice. Higher density

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