Lecture Presentation
Chapter 11
Liquids and
Intermolecular
Forces
James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education, Inc.
States of Matter
The fundamental
difference between states
of matter is the strength of
the intermolecular forces
of attraction.
Stronger forces bring
molecules closer together.
Solids and liquids are
referred to as the
condensed phases.
Intermolecular
Forces
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Differences in the
States of Matter
Intermolecular
Forces
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Which State of Matter?
• The answer to this
question largely
relies on the
balance between the
kinetic energies of
the particles.
interparticle energies
of attraction.
Intermolecular
Forces
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Intermolecular Forces
• The attractions between molecules are not nearly as
strong as the intramolecular attractions (bonds) that
hold compounds together.
• Many physical properties reflect intermolecular
forces, like boiling points, melting points, viscosity,
surface tension, and capillary action. Intermolecular
Forces
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Types of Intermolecular Force
• Weakest to strongest forces:
dispersion forces (or London dispersion
forces)
dipole–dipole forces
hydrogen bonding (a special dipole–dipole
force)
ion–dipole forces
o Note: The first two types are also referred
to collectively as van der Waals forces.
Intermolecular
Forces
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Dispersion Forces
• The figure below shows how a nonpolar particle
(in this case a helium atom) can be temporarily
polarized to allow dispersion force to form.
• The tendency of an electron cloud to distort is
called its polarizability.
Intermolecular
Forces
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Factors Which Affect Amount of
Dispersion Force in a Molecule
• number of electrons in an
atom (more electrons,
more dispersion force)
• size of atom or
molecule/molecular
weight
• shape of molecules with
similar masses (more
compact, less dispersion
force) Intermolecular
Forces
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Polarizability & Boiling Point
• If something is easier
to polarize, it has a
higher boiling point.
• Remember: This
means less
intermolecular force
(smaller molecule:
lower molecular
weight, fewer
electrons). Intermolecular
Forces
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Dipole–Dipole Interactions
• Polar molecules have a more positive
and a more negative end–a dipole (two
poles, δ+ and δ−).
• The oppositely charged ends attract
each other.
Intermolecular
Forces
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Dipole–Dipole Interactions
For molecules of approximately equal mass
and size, the more polar the molecule, the
higher its boiling point. Intermolecular
Forces
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Which Have a Greater Effect:
Dipole–Dipole Interactions or
Dispersion Forces?
• If two molecules are of comparable size
and shape, dipole–dipole interactions
will likely be the dominating force.
• If one molecule is much larger than
another, dispersion forces will likely
determine its physical properties.
Intermolecular
Forces
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What Does This Graph Show Us?
• In a group, the period
3/4/5 elements have
higher boiling points
as the group member
gets larger.
• What happens with
the period 2
elements? For group
4A, the trend is
continued. What about
for the other groups? Intermolecular
Forces
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Hydrogen Bonding
• The dipole–dipole interactions
experienced when H is
bonded to N, O, or F are
unusually strong.
• We call these interactions
hydrogen bonds.
• A hydrogen bond is an
attraction between a hydrogen
atom attached to a highly
electronegative atom and a
nearby small electronegative
atom in another molecule or Intermolecular
chemical group. Forces
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What Forms Hydrogen Bonds?
• Hydrogen bonding arises in part from the
high electronegativity of nitrogen, oxygen,
and fluorine.
• These atoms interact with a nearly bare
nucleus (which contains one proton).
Intermolecular
Forces
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Ion–Dipole Interactions
• Ion–dipole interactions are found in solutions of ions.
• The strength of these forces is what makes it
possible for ionic substances to dissolve in polar
solvents.
Intermolecular
Forces
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Summarizing Intermolecular Forces
Intermolecular
Forces
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Liquid Properties Affected by
Intermolecular Forces
• boiling point (previously discussed) and
melting point
• viscosity
• surface tension
• capillary action
Intermolecular
Forces
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Viscosity
• Resistance of a liquid to flow is called
viscosity.
• It is related to the ease with which
molecules can move past each other.
• Viscosity increases with stronger
intermolecular forces and decreases
with higher temperature.
Intermolecular
Forces
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Surface Tension
• Water acts as if it
has a “skin” on it
due to extra inward
forces on its
surface. Those
forces are called the
surface tension.
Intermolecular
Forces
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Cohesion and Adhesion
• Intermolecular forces that bind similar
molecules to one another are called
cohesive forces.
• Intermolecular forces that bind a
substance to a surface are called
adhesive forces.
• These forces are important in capillary
action.
Intermolecular
Forces
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Capillary Action
• The rise of liquids up
narrow tubes is called
capillary action.
• Adhesive forces attract
the liquid to the wall of
the tube.
• Cohesive forces attract
the liquid to itself.
• Water has stronger
adhesive forces with glass;
mercury has stronger
Intermolecular
cohesive forces with itself. Forces
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Phase Changes
• Conversion from one
state of matter to
another is called a
phase change.
• Energy is either added
or released in a phase
change.
• Phase changes:
melting/freezing,
vaporizing/condensing,
subliming/depositing.
Intermolecular
Forces
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Energy Change & Change of State
• The heat of fusion is the energy required to change
a solid at its melting point to a liquid.
• The heat of vaporization is the energy required to
change a liquid at its boiling point to a gas.
• The heat of sublimation is the energy required to
change a solid directly to a gas.
Intermolecular
Forces
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Heating Curves
• A plot of temperature vs.
heat added is called a
heating curve.
• Within a phase, heat is
the product of specific
heat, sample mass, and
temperature change.
• The temperature of the
substance does not rise
during a phase change.
• For the phase changes, the product of mass Intermolecular
Forces
and the heat of fusion of vaporization is heat.
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Critical temperature and critical pressure
• Gas liquefies at some point when P is applied.
• 100°C, 760 torr
110°C, 1065 torr
374°C, 1.65x105 torr
Above this temperature, no amount of pressure can cause a distinct
liquid phase to form. Instead, as P increases, the gas becomes more
compressed.
- The highest T at which a distinct liquid phase can form is called
critical temperature.
- The critical pressure is the pressure required to bring about
liquefaction at this critical temperature.
- When the temperature exceeds the critical temperature and the
pressure exceeds the critical presssure, the liquid and gas
phases are indistinguishable from each other, and the substance
is in a state called a supercritical fluid. A supercritical fluid
expands to fill its container (like a gas) but the molecules are still
Intermolecular
quite closely packed (like a liquid). Forces
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Supercritical Fluids
• Gases liquefies when pressure is
applied.
• The temperature beyond which a
gas cannot be compressed is
called its critical temperature.
The pressure needed to
compress the liquid at critical
temperature is
called critical pressure.
• The state beyond this
temperature is called a
supercritical fluid.
Intermolecular
Forces
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Vapor Pressure
• At any temperature,
some liquid molecules
have enough energy to
escape the surface and
become a gas.
• As the temperature
rises, the fraction of
molecules that have
enough energy to break
free increases.
Intermolecular
Forces
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Vapor Pressure
• As more molecules
escape the liquid,
the pressure they
exert increases.
• The liquid and vapor
reach a state of
dynamic equilibrium:
liquid molecules
evaporate and vapor
molecules condense
at the same rate.
Intermolecular
Forces
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Vapor Pressure
• The boiling point of
a liquid is the
temperature at which
its vapor pressure
equals atmospheric
pressure.
• The normal boiling
point is the
temperature at which
its vapor pressure is
760 torr.
Intermolecular
Forces
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Vapor Pressure
• The natural log of the
vapor pressure of a liquid
is inversely proportional to
its temperature.
• This relationship is
quantified in the
Clausius–Clapeyron
equation.
Intermolecular
Forces
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Practice – Which of the following
is the most volatile?
a) water
b) TiCl4
c) ether
d) ethanol
e) acetone
Intermolecular
Forces
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 32
Practice – Which of the following
has the strongest Intermolecular
attractions?
a) water
b) TiCl4
c) ether
d) ethanol
e) acetone
Intermolecular
Forces
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 33
Practice – Which of the following
has the highest normal boiling
point?
a) water
b) TiCl4
c) ether
d) ethanol
e) acetone
Intermolecular
Forces
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 34
Phase Diagram
• A phase diagram is a graph of pressure vs.
temperature for a substance. It shows
– melting, boiling, and sublimation points at different
pressures.
– the triple point and critical point.
Intermolecular
Forces
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Phase Diagram of Water
• Note the high critical
temperature and critical
pressure.
– These are due to the
strong van der Waals
forces between water
molecules.
Intermolecular
Forces
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Phase Diagram of Water
• Unusual feature for water:
The slope of the solid–
liquid line is negative.
This means that as the
pressure is increased, the
melting point decreases.
Intermolecular
Forces
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Phase Diagram of Carbon Dioxide
• Unusual features for
carbon dioxide:
cannot exist in the
liquid state at
pressures below
5.11 atm (triple point)
CO2 sublimes at
normal pressures.
Intermolecular
Forces
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Practice – Consider the phase diagram of CO2
shown. What phase(s) is/are present at each of the
following conditions?
• 20.0 °C, 72.9 atm liquid
• −56.7 °C, 5.1 atm solid, liquid, gas
• 10.0 °C, 1.0 atm gas
• −78.5 °C, 1.0 atm solid, gas
• 50.0 °C, 80.0 atm scf
Intermolecular
Forces
Tro: Chemistry:
© 2015 PearsonAEducation,
Molecular Inc. Approach, 2/e 39
Liquid Crystals
• Some substances do not go directly from the
solid state to the liquid state.
• In this intermediate state, liquid crystals have
some traits of solids and some of liquids.
• Molecules in liquid crystals have some degree
of order.
Intermolecular
Forces
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Liquid
Crystals
• In nematic liquid
crystals, molecules
are only ordered in
one dimension, along the long axis.
• In smectic liquid crystals, molecules are
ordered in two dimensions, along the long axis
and in layers.
• In cholesteryic liquid crystals, nematic-like
crystals are layered at angles to each other. Intermolecular
Forces
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Substances that form liquid crystals are often composed of rod-
shaped molecules that are somewhat rigid. In the liquid phase,
these molecules are oriented randomly. In the
liquid crystalline phase, by contrast, the molecules are arranged
in specific patterns
Depending on the nature of the ordering, liquid crystals
are classified as nematic, smectic A, smectic C, or cholesteric.
Intermolecular
Forces
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In a nematic liquid crystal, the molecules are aligned
so that their long axes tend to point in the same
direction but the ends are not aligned with one another.
In smectic A and smectic C liquid crystals, the
molecules maintain the long-axis alignment seen in
nematic crystals, but in addition they pack into layers.
Intermolecular
Forces
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• The lengths of liquid crystals are much greater than their
widths.
• The double bonds, including those in the benzene rings,
add rigidity to the molecules, and the rings, Because
they are flat, help the molecules stack with one another.
• The polar —CH O and —COOH groups give rise to
3
dipole–dipole interactions and promote alignment of the
• molecules. Thus, the molecules order themselves quite
naturally along their long axes.
• They can, however, rotate around their axes and slide
parallel to one another.
• In smectic liquid crystals, the intermolecular forces
(dispersion forces, dipole–dipole attractions, and
hydrogen bonding) limit the ability of the molecules to
slide past one another. Intermolecular
Forces
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In a cholesteric liquid crystal, the molecules are
arranged in layers, with their long axes parallel to the
other molecules within the same layer. Upon moving
from one layer to the
next, the orientation of the molecules rotates by a fixed
angle, resulting in a spiral pattern. These liquid
crystals are so named because many derivatives of
cholesterol adopt this structure
Intermolecular
Forces
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