Chapter 11 Intermolecular

Forces, Liquids, and Solids

Sections 11.1 - 11.3

Homework
Read pages 443-454
Pg 476 #1, 2, 3, 9, 10, 13, 15, 16, 17, 23, 25, 29, 31
 States of Matter
The fundamental difference between states of
matter is the distance between particles.
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 States of Matter
Because in the solid and liquid states
particles are closer together, we refer to them
as condensed phases.
The States of Matter
• The state a substance is
in at a particular
temperature and
pressure depends on
two antagonistic entities:

 The kinetic energy of the

particles
 The strength of the
attractions between the
particles
 Intermolecular Forces

The attractions between molecules are not

nearly as strong as the intramolecular
attractions that hold compounds together.
 Intermolecular Forces

They are, however, strong enough to control

physical properties such as boiling and
melting points, vapor pressures, and
viscosities.
 Intermolecular Forces

These intermolecular forces as a group are

referred to as van der Waals forces.
 van der Waals Forces

• Dipole-dipole interactions
• Hydrogen bonding
• London dispersion forces
 Ion-Dipole Interactions
• A fourth type of force, ion-dipole interactions
are an important force in solutions of ions.
• The strength of these forces are what make it
possible for ionic substances to dissolve in
polar solvents.
Dipole-Dipole Interactions
• Molecules that have
permanent dipoles are
attracted to each other.
 The positive end of one is
attracted to the negative
end of the other and vice-
versa.
 These forces are only
important when the
molecules are close to
each other.
 Dipole-Dipole Interactions

The more polar the molecule, the higher

is its boiling point.
 London Dispersion Forces

While the electrons in the 1s orbital of helium

would repel each other (and, therefore, tend
to stay far away from each other), it does
happen that they occasionally wind up on the
same side of the atom.
 London Dispersion Forces

At that instant, then, the helium atom is polar,

with an excess of electrons on the left side
and a shortage on the right side.
 London Dispersion Forces

Another helium nearby, then, would have a

dipole induced in it, as the electrons on the
left side of helium atom 2 repel the electrons
in the cloud on helium atom 1.
 London Dispersion Forces

London dispersion forces, or dispersion

forces, are attractions between an
instantaneous dipole and an induced dipole.
 London Dispersion Forces

• These forces are present in all molecules,

whether they are polar or nonpolar.
• The tendency of an electron cloud to distort in
this way is called polarizability.
Factors Affecting London Forces

• The shape of the molecule

affects the strength of dispersion
forces: long, skinny molecules
(like n-pentane tend to have
stronger dispersion forces than
short, fat ones (like neopentane).
• This is due to the increased
surface area in n-pentane.
Factors Affecting London Forces

• The strength of dispersion forces tends to

increase with increased molecular weight.
• Larger atoms have larger electron clouds,
which are easier to polarize.
PRACTICE EXERCISE
Of Br2, Ne, HCl, HBr, and N2, which is likely
to have (a) the largest intermolecular
dispersion forces, (b) the largest dipole-
dipole attractive forces?

Answers: (a) Br2 (largest molecular weight), (b)

HCl (largest polarity)
 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.
How Do We Explain This?

• The nonpolar series

(SnH4 to CH4) follow
the expected trend.
• The polar series
follows the trend
from H2Te through
H2S, but water is
quite an anomaly.
 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.
 Hydrogen Bonding
Hydrogen bonding
arises in part from the
high electronegativity
of nitrogen, oxygen,
and fluorine.

Also, when hydrogen is bonded to one of those

very electronegative elements, the hydrogen
nucleus is exposed.
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PRACTICE EXERCISE
In which of the following substances is
significant hydrogen bonding possible:
methylene chloride (CH2Cl2) phosphine
(PH3) hydrogen peroxide (HOOH), or
acetone (CH3COCH3)?

Answer: HOOH
Summarizing Intermolecular Forces
PRACTICE EXERCISE
(a) Identify the intermolecular forces
present in the following substances, and (b)
select the substance with the highest boiling
point: CH3CH3, CH3OH, and CH3CH2OH.

Answers: (a) CH3CH3 has only dispersion forces,

whereas the other two substances have both
dispersion forces and hydrogen bonds; (b)
CH3CH2OH
Intermolecular Forces Affect
Many Physical Properties

The strength of the

attractions between
particles can greatly
affect the properties
of a substance or
solution.
 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.
Surface Tension
Surface tension
results from the net
inward force
experienced by the
molecules on the
surface of a liquid.
 Chapter 11 Intermolecular
Forces, Liquids, and Solids
Sections 11.4 - 11.6

Homework
Read pages 455-464
Pg 477 #4, 5, 6, 35, 37, 39, 43, 45, 49, 51, 53, 55
 Bellwork-Intermolecular forces

List the following compounds in order of

increasing intermolecular forces.
HCOOH CH3COOH CH3(CH2)10COOH CH4 CH3CH3
formic acid acetic acid lauric acid methane ethane

Which compound should have the highest

boiling point?
Which compound is most likely a gas at room
temp?
Which compound should flow the slowest?
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Phase Changes
 Energy Changes Associated
with Changes of State

• Heat of Fusion: Energy required to change a

solid at its melting point to a liquid.
 Energy Changes Associated
with Changes of State

• Heat of Vaporization: Energy required to

change a liquid at its boiling point to a gas.
Energy Changes Associated
with Changes of State
• The heat added to the
system at the melting and
boiling points goes into
pulling the molecules
farther apart from each
other.
• The temperature of the
substance does not rise
during the phase change.
PRACTICE EXERCISE
What is the enthalpy change during the process
in which 100.0 g of water at 50.0°C is cooled to
ice at –30.0°C?
The specific heats of ice, water, and steam are
2.09 J/g-K, 4.18 J/g-K and 1.84 J/g-K, respectively.

For H2O,
∆ Hfus = 6.01 kJ/mol
∆Hvap = 40.67 kJ/mol.

Answer: –20.9 kJ – 33.4 kJ – 6.27 kJ = –60.6 kJ

 Vapor Pressure
• At any temperature, some molecules in a
liquid have enough energy to escape.
• As the temperature rises, the fraction of
molecules that have enough energy to
escape increases.
Vapor Pressure

As more molecules
escape the liquid,
the pressure they
exert increases.
Vapor Pressure

The liquid and vapor

reach a state of
dynamic equilibrium:
liquid molecules
evaporate and vapor
molecules condense
at the same rate.
 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.
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PRACTICE EXERCISE

Estimate the boiling

point of diethyl ether
under an external
pressure of 0.80 atm.
At what external
pressure will ethanol
have a boiling point of
60°C?
Answer: 27 °C, about 340 torr (0.45 atm)
 Phase Diagrams
Phase diagrams display the state of a
substance at various pressures and
temperatures and the places where equilibria
exist between phases.
 Phase Diagrams
• The AB line is the liquid-vapor interface.
• It starts at the triple point (A), the point at
which all three states are in equilibrium.
 Phase Diagrams
It ends at the critical point (B); above this
critical temperature and critical pressure the
liquid and vapor are indistinguishable from
each other.
 Phase Diagrams
Each point along this line is the boiling point
of the substance at that pressure.
 Phase Diagrams
• The AD line is the interface between liquid
and solid.
• The melting point at each pressure can be
found along this line.
 Phase Diagrams
• Below A the substance cannot exist in the
liquid state.
• Along the AC line the solid and gas phases
are in equilibrium; the sublimation point at
each pressure is along this line.
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.
Phase Diagram of Water

• The slope of the solid–

liquid line is negative.
 This means that as the
pressure is increased at a
temperature just below the
melting point, water goes
from a solid to a liquid.
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Describe any changes in the phases present
when the system is (a) kept at 0°C while the
pressure is increased from that at point 1 to that
at point 5 (vertical line), (b) kept at 1.00 atm
while the temperature is
increased from that at
point 6 to that at point 9.

Figure 11.28 Phase diagram of

H2O.
Phase Diagram of Carbon Dioxide

Carbon dioxide
cannot exist in the
liquid state at
pressures below
5.11 atm; CO2
sublimes at normal
pressures.
Phase Diagram of Carbon Dioxide

The low critical

temperature and
critical pressure for
CO2 make
supercritical CO2 a
good solvent for
extracting nonpolar
substances (such as
caffeine).
Chapter 11 Intermolecular
Forces, Liquids, and Solids
Sections 11.7 & 11.8

Homework
Read pages 464- 476
Pg 477 #7, 57, 59, 71, 73, 75, 77, 79
BELLWORK
Describe what happens when the following
changes are made in a CO2 sample initially at
1 atm and –60ºC:
(a) Pressure increases
at constant temperature
to 60 atm.
(b)Temperature
increases from –60ºC to
–20ºC at constant
60 atm pressure.
 Solids
• We can think of solids
as falling into two
groups:

 Crystalline—particles
are in highly ordered
arrangement.
 All ionic solids are
crystals at room temp (&
much higher temps too!)
Solids
 Amorphous—no particular
order in the arrangement of
particles.
 Can be from-
• Mix of molecules that do not fit
together well
• Large molecules with shapes
that don’t stack well
• Molecules that were cooled to
quickly to form a crystal.
Intermolecular
Forces
Crystalline solids melt at a specific temperature
BECAUSE their internal structure is regular.
The intermolecular forces holding the solid
particles in position are identical so they are
overcome at the same temp.

Intermolecular
Forces
Crystalline solids melt at a specific temperature
BECAUSE their internal structure is regular.
The intermolecular forces holding the solid
particles in position are identical so they are
overcome at the same temp.

Amorphous ones tend to melt over a temperature

range BECAUSE their internal structure is
varied.
Intermolecular attractions vary throughoutIntermolecular
the
solid because particles are positioned Forces

differently throughout the solid.

Attractions in Ionic Crystals
In ionic crystals, ions
pack themselves so as
to maximize the
attractions and
minimize repulsions
between the ions.
Crystalline Solids
Because of the
order in a crystal,
we can focus on the
repeating pattern of
arrangement called
the unit cell.
 Crystalline Solids

There are several types of basic

arrangements in crystals, such as the ones
shown above.
 Crystalline Solids

We can determine
the empirical
formula of an ionic
solid by determining
how many ions of
each element fall
within the unit cell.
 Ionic Solids
What are the empirical formulas for these
compounds?
(a) Green: chlorine; Gray: cesium
(b) Yellow: sulfur; Gray: zinc
(c) Green: calcium; Gray: fluorine

(a) (b) (c)

CsCl ZnS CaF2
Intermolecular
Forces
2 = one whole atom
& eight 1/8 atoms

Intermolecular
Forces
There are two ways to define the unit cell

NaCl unit cell

representing
appropriate ion
sizes
Intermolecular
Forces
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are needed to see this picture.

Intermolecular
Forces
The coordination number tells the
number of particles surrounding a
particular particle in a crystal.
For ionic compounds & alloys there
can be multiple coordination
numbers.

Intermolecular
Forces
The coordination number tells the
number of particles surrounding a
particular particle in a crystal.
For ionic compounds & alloys there
can be multiple coordination
numbers.

Intermolecular
Forces
The coordination number tells the
number of particles surrounding a
particular particle in a crystal.
For ionic compounds & alloys there
can be multiple coordination
numbers.

Intermolecular
Forces
Types of Bonding in Crystalline Solids
 Covalent-Network and
Molecular Solids

• Diamonds are an example of a covalent-

network solid in which atoms are covalently
bonded to each other.
 They tend to be hard and have high melting
points.
 Covalent-Network and
Molecular Solids

• Graphite is an example of a molecular solid in

which atoms are held together with van der
Waals forces.
 They tend to be softer and have lower melting
points. CONDUCTS electricity
Intermolecular
Forces
C6H6

Intermolecular
Forces
 Metallic Solids
• Metals are not
covalently bonded, but
the attractions between
atoms are too strong to
be van der Waals
forces.
• In metals, valence
electrons are
delocalized throughout
the solid.