LIQUIDS AND INTERMOLECULAR FORCES

A Molecular Comparison of Gases, Liquids and Solids

Some Characteristics of Gases, Liquids and Solids and the Microscopic Explanation for the Behavior
gas
assumes the shape and volume
of its container
particles can move past one
another

liquid
assumes the shape of the part of
the container which it occupies
particles can move/slide past one
another

solid
retains a fixed volume and shape
rigid - particles locked into place

compressible
lots of free space between
particles
flows easily
particles can move past one
another

not easily compressible

little free space between particles

not easily compressible

little free space between particles

flows easily
particles can move/slide past one
another

does not flow easily

rigid - particles cannot move/slide
past one another

Intermolecular Forces
Dispersion Forces
The London dispersion force is the weakest intermolecular force. The London dispersion force is a temporary
attractive force that results when the electrons in two adjacent atoms occupy positions that make the atoms form
temporary dipoles. This force is sometimes called an induced dipole-induced dipole attraction. London forces are
the attractive forces that cause nonpolar substances to condense to liquids and to freeze into solids when the
temperature is lowered sufficiently.
Because of the constant motion of the electrons, an atom or molecule can develop a temporary (instantaneous)
dipole when its electrons are distributed unsymmetrically about the nucleus.
A second atom or molecule, in turn, can be distorted by the appearance of the dipole in the first atom or molecule
(because electrons repel one another) which leads to an electrostatic attraction between the two atoms or
molecules.

Dispersion forces are present between any two molecules (even polar molecules) when they are almost touching.
Molecular Size

Dispersion forces are present between all molecules, whether they are polar or nonpolar.
Larger and heavier atoms and molecules exhibit stronger dispersion forces than smaller and
lighter ones.
In a larger atom or molecule, the valence electrons are, on average, farther from the nuclei than in
a smaller atom or molecule. They are less tightly held and can more easily form temporary
dipoles.
The ease with which the electron distribution around an atom or molecule can be distorted is
called the polarizability.

Dispersion forces tend to be:

stronger between molecules that are easily polarized.

weaker between molecules that are not easily polarized.

Hydrogen Bond
Molecules with hydrogen atoms bonded to electronegative atoms such as O, N, and F (and to a much lesser extent
Cl and S) tend to exhibit unusually strong intermolecular interactions
Hydrogen bond formation requires both a hydrogen
bond donor and a hydrogen bond acceptor
Example of a Hydrogen bond
The most common example is the water dimer
it is called such because it is made up of two or more
water molecules which are connected by hydrogen bonds

Considering CH3OH, C2H6, Xe, and (CH3)3N, which can form hydrogen bonds with themselves? Draw the
hydrogen-bonded structures.
Strategy:
A.

Identify the compounds with a hydrogen atom attached to O, N, or F.

These are likely to be able to act as hydrogen bond donors.
B.
Of the compounds that can act as hydrogen bond donors, identify those
that also contain lone pairs of electrons, which allow them to be hydrogen bond
acceptors. If a substance is both a hydrogen donor and a hydrogen bond
acceptor, draw a structure showing the hydrogen bonding.
Solution:
A Of the species listed, xenon (Xe), ethane (C 2H6), and trimethylamine
[(CH3)3N] do not contain a hydrogen atom attached to O, N, or F; hence they
cannot act as hydrogen bond donors.
B The one compound that can act as a hydrogen bond donor, methanol
(CH3OH), contains both a hydrogen atom attached to O (making it a hydrogen bond donor) and two lone pairs of
electrons on O (making it a hydrogen bond acceptor); methanol can thus form hydrogen bonds by acting as either
a hydrogen bond donor or a hydrogen bond acceptor. The hydrogen-bonded structure of methanol is as follows:

Ion-Dipole force
An ion-dipole force is an attractive force that results from the electrostatic attraction between an ion and a neutral
molecule that has a dipole.

Most commonly found in solutions. Especially important for

solutions of ionic compounds in polar liquids.

A positive ion (cation) attracts the partially negative end of a

molecule.

A negative ion (anion) attracts the partially positive end of a

neutral polar molecule.

Properties of Liquids
Viscosity

neutral polar

is a type of bulk property defined as a liquids resistance to flow. When the intermolecular forces of
attraction are strong within a liquid, there is a larger viscosity. An example of this phenomenon is imagining a
race between two liquids down a windshield. Which would you expect to roll down the windshield faster honey or
water? Obviously from experience one would expect water to easily speed right past the honey, a fact that reveals
honey has a much higher viscosity than water.
Surface tension
is the energy, or work, required to increase the surface area of a liquid due to intermolecular. Since these
intermolecular forces vary depending on the nature of the liquid (e.g. water vs. gasoline) or solutes in the liquid
(e.g. surfactants like detergent), each solution exhibits differing surface tension properties.

Phase change
- a change from one state (solid or liquid or gas) to another without a change in chemical composition
Types of Phase changes

Freezing
Melting
Condensation
Vaporization
Deposition
Sublimation
Recombination
Ionization

Energy Changes Accompanying Phase Changes

Each phase change is accompanied by a change in the energy of the system. Whenever a phase change involves
going to a less ordered state, energy must be supplied to overcome intermolecular forces. Thus, energy is required
to melt a solid. The attractive forces that hold particles in fixed positions in the solid must be overcome to form
the liquid. Likewise, vaporization requires energy. The attractive forces that hold particles close to each other in
the liquid must be overcome to form the gas. Sublimation also requires energy. As the strengths of the
intermolecular forces increase, the amounts of energy required to cause a phase change also increase.

Heating Curves
Suppose we heat a sample of ice that is initially at
-25C and 1 atm pressure. What happens? The
addition of heat causes the temperature of the ice to
increase. As long as the temperature is below 0C,
the sample remains frozen. When the temperature
reaches 0C, the ice begins to melt. Because melting
is an endothermic process, the heat we add at 0C is
used to convert ice to water, and the temperature
remains constant until all the ice has melted. Once
we reach this point, the further addition of heat
causes the temperature of the liquid water to
increase.
We can plot the processes described as a heating curve, which is a graph of the temperature of the system versus
the amount of heat added. Figure 11.18 shows a heating curve for heating ice at -25C to steam at 125C under a
constant pressure of 1 atm. Heating the ice from -25C to 0C is represented by the line segment AB in Figure

above, while the conversion of ice at 0C to water at 0C leads to the horizontal segment BC. Adding additional
heat increases the temperature of the water until the temperature reaches 100C (segment CD). The heat is then
used to convert water to steam at a constant temperature of 100C (segment DE). Once all the water has been
converted to steam, the steam is heated to its final temperature of 125C (segment EF).

Critical Temperature
Gases can be converted to liquids by compressing the gas at a suitable temperature.
Gases become more difficult to liquefy as the temperature increases because the kinetic energies of the particles
that make up the gas also increase.
The critical temperature of a substance is the temperature at and above which vapor of the substance cannot be
liquefied, no matter how much pressure is applied.

substance
NH3
O2
CO2
H2O

critical temperature (oC)

132
-119
31.2
374

Critical Pressure
The critical pressure of a substance is the pressure required to liquefy a
gas at its critical temperature. Some examples are shown below.
substance

critical pressure (atm)

NH3
O2
CO2
H2O

111.5
49.7
73.0
217.7

Vapor Pressure

The vapor pressure of a substance is the pressure at which

its gaseous (vapor) phase is in equilibrium with its liquid or
solid phase. It is a measure of the tendency of molecules
and atomsto escape from a liquid or solid.
At atmospheric pressures, when a liquid's vapor pressure
increases with increasing temperatures to the point at which
it equals the atmospheric pressure, the liquid has reached its
boiling point, namely, the temperature at which the liquid
changes its state from a liquid to a gas throughout its bulk.
That temperature is very commonly referred to as the
liquid'snormal boiling point.
Not surprisingly, a liquid's normal boiling point will be at a
lower temperature the greater is the tendency of its
molecules to escape from the liquid, namely, the higher is its
vapor pressure. In other words, the higher is the vapor
pressure of a liquid, the higher is the volatility and the lower
is the normal boiling point of the liquid. The adjacent vapor
pressure chart graphs the dependency of vapor pressure upon temperature for a variety of liquids [5] and also
confirms that liquids with higher vapor pressures have lower normal boiling points.
For example, at any given temperature, methyl chloride (CH 3Cl) has the highest vapor pressure of any of the
liquids graphed in the chart. It also has the lowest normal boiling point (26 C), which is where its vapor
pressure curve (the blue line) intersects the horizontal pressure line of one atmosphere (atm) of absolute vapor
pressure.
In terms of intermolecular forces, the boiling point represents the temperature at which the liquid molecules
possess enough kinetic energy to overcome the various intermolecular attractions binding the molecules to each
other within the liquid. Therefore the boiling point is also an indicator of the strength of those attractive forces.
The higher the intermolecular attractive forces are, the more difficult it is for molecules to escape from the liquid
and hence the lower is the vapor pressure of the liquid. The lower the vapor pressure of the liquid, the higher the
temperature must be to initiate boiling. Thus, the higher the intermolecular attractive forces are, the higher is the
normal boiling point.

Phase Diagram of water

Phase Diagram of Carbon Dioxide

Liquid Crystals
Liquid crystal materials generally have several common characteristics. Among these
are a rod-like molecular structure, rigidness of the long axis, and strong dipoles and/or
easily polarizable substituents.

The distinguishing characteristic of the liquid crystalline state is the tendency of the
molecules (mesogens) to point along a common axis, called the director. This is in
contrast to molecules in the liquid phase, which have no intrinsic order. In the solid state,
molecules are highly ordered and have little translational freedom. The characteristic
orientational order of the liquid crystal state is between the traditional solid and liquid
phases and this is the origin of the term mesogenic state, used synonymously with liquid
crystal state. Note the average alignment of the molecules for each phase in the following
diagram.
Types of Liquid Crystals

Two main types of liquid crystals

Nematic the phase of a liquid crystal characterized by arrangement of the long
axes of the molecules in parallel lines but not layers
Smectic the phase of a liquid crystal characterized by arrangement of
molecules in layers with the long molecular axes in a given layer being parallel to
one another and those of other layers and perpendicular or slightly inclined to the
plane of the layer

o Smectic A Does not have positional order within layers

o Smecitc C - Has positional order within layers