Chapter 9:

The Liquid and Solid

States
Professor Sadia Ameen
Department of Bio-Convergence Sciences, Jeonbuk National
University, Advanced Science Campus, 56212, Republic of Korea

E-mail: sadiaameen@jbnu.ac.kr
 Questions for Consideration
1. How do the properties of liquids and solids
differ, and what happens when substances
undergo a change of state?
2. Why do atoms or molecules hold together
as liquids or solids instead of existing only
as gases?
3. What are some unique properties of
liquids?
4. How do atoms or ions fit together to make
solids, and how does their arrangement
affect their properties?
10-2
 Chapter 9 Topics:

1. Changes of State
2. Intermolecular Forces
3. Properties of Liquids
4. Properties of Solids

10-3
 9.1 Changes of State
Solids, Liquids, and Gases: How do they differ?

Figure 10.4

10-4
General Properties of the States of Matter

10-5
 Physical State of a Substance
Figure 10.5

© Jim Birk

Water exists in all three physical states

Aluminum melts above 2467oC. under normal conditions.

10-6
 Changes of State
 Transitions between these states
 Also called phase changes
 6 main phase changes:
 Evaporation (also called vaporization)
 Condensation
 Freezing
 Melting (also called fusion)
 Sublimation
 Deposition
10-7
 Liquid-Gas Phase Changes
 Evaporation, or vaporization
 Evaporation occurs because some surface liquid
molecules have high enough kinetic energy to escape
to the gas phase.
 Heat is required to maintain the temperature
needed for evaporation.
 Endothermic

Figure 10.7

Figure 10.8
10-8
 Liquid-Gas Phase Changes
 Condensation
 Transition from a gas to a liquid
 Occurs when gas particles cannot escape the
container and thus, come into contact with a
liquid
 An exothermic process (energy is released)
 The reverse of evaporation
Figure 10.7

10-9
 Equilibrium
 Equilibrium is a state in which opposing processes
occur at equal rates.
 An equilibrium is designated by a double arrow,
such as:
vaporization
liquid ↔ gas
condensation

 In the above equilibrium, the rates of evaporation

and condensation are equal.
 The gas produced by evaporation exerts a
pressure on the liquid below it.

10-10
 Liquid-Vapor Equilibrium
 A liquid placed in a closed container will
evaporate only until an equilibrium is reached.
liquid ↔ gas
 The pressure exerted by the vapor at equilibrium
is the vapor pressure. Figure 10.9

10-11
 Vapor pressure depends on
molecular structure and temperature.
Figure 10.10

10-12
 Boiling Point
 Boiling occurs when the vapor pressure equals the external
pressure of the atmosphere.
 The temperature at which vapor pressure equals the
external pressure of the atmosphere is the boiling point.
 If the external pressure is exactly 1 atm, the boiling
temperature is called the normal boiling point.

Figure 10.10

10-13
Homework: Vapor Pressure Curves
 Consider the vapor
pressure curve for
propane to the left,
which is used as a fuel
in barbeque grills.
 What is the normal
boiling point for
propane? What is its
boiling point at 0.40
atm?

Figure from p. 380

10-14
Homework Solution: Vapor Pressure
Curves
 What is the normal boiling
point for propane?
The normal boiling point is
found at a pressure of 1.0
atm. At this pressure, the
boiling is about -41°C.
 What is its boiling point at
0.40 atm?
At 0.40 atm, the boiling
point is about -60°C.
Figure from p. 380

10-15
 Liquid-Solid Phase Changes
 The temperature at which the liquid and solid
states coexist in equilibrium is called the freezing
point or the melting point.
Solid ↔ liquid

10-16
© Jim Birk
 Liquid-Solid Phase Changes

 Freezing
 The average kinetic energy of a liquid
decreases when it is cooled.
 If the average kinetic energy becomes low
enough, then the molecules become fixed in
position in the solid state.
 Freezing is the conversion of a liquid into a
solid.

10-17
 Melting
 Melting
 Phase change from solid to liquid
 Reverse of freezing
 Also called fusion
 Melting point
 Same temperature as freezing point

10-18
 Melting
 When ice melts, the
water molecules stay
intact but flow past
one another.
 When the ionic
compound NaCl melts,
ionic bonds are broken
and ions flow freely.

Figure 10.12

10-19
 Liquid-Solid Phase Changes
 Freezing point (or melting point)
 The temperature at which the freezing of a liquid
into a solid state occurs
 As with boiling temperature, the two states are
in equilibrium with one another.
melting
solid ↔ liquid
freezing

 Normal freezing point

 The temperature when the freezing equilibrium
is achieved under a pressure of 1 atm.

10-20
 Solid-Gas Phase Changes
 Under certain conditions, substances can go
directly from the solid state to the gas state:
sublimation. CO2 and I2 do this under normal
conditions.

Figure 10.13

10-21
 Solid-Gas Phase Changes
 Deposition
 Can go directly from gas to solid without
passing through the liquid state
 Reverse of sublimation

10-22
 Homework : Changes in the State of
Matter
 Identify the process shown in the
following diagram:
Diagram from Practice Problem 10.2

Figure from p. 382

10-23
Homework Solution: Changes in the
State of Matter

Figure from p. 382

 In the starting material, there is a large distance

between particles, so we can identify it as a gas. In
the ending material, the particles are closely spaced
and not random, and thus it is a solid. The gas-to-
solid transition is called deposition.

10-24
Cooling and Heating
Curves
 Show the phase changes
of a substance as heat is
removed or added at
constant pressure

A. Cooling Curve
 Heat is removed to cause
phase changes.
B. Heating Curve
 Heat is added to cause
phase changes.

Figure 10.14

10-25
Cooling Curve

Figure 10.14
10-26
 Heating Curve
 Notice that
temperature remains
constant during a
phase change, even
though heat is being
added.

Figure 10.14
10-27
 Homework: Cooling and Heating
Curves
 The diagram to the
top right represents
the physical states
of a substance.
Identify where each
state would Figure from p. 383
predominate on the Figure from p. 384

heating curve given

to the right.

10-28
Homework Solution: Cooling and
Heating Curves

Figure 10.14

10-29
 Energy Changes
 Each change of state takes place at constant
temperature
 Any phase change is accompanied by an
energy change
 For temperature changes, the following equation is
used:
q = mC∆T
 The change in energy for each change of state is
called the heat of that process (q).
 Molar heat of fusion
 Energy required to melt 1 mole of a substance
 Molar heat of vaporization
 Energy required to evaporate 1 mole of a
substance 10-30
 Homework : Energy for Phase Changes
 Calculate the heat required to boil 125 g
of water at 100.0°C. The molar heat of
vaporization of water is 4.07 × 104 J/mol.

Figure from p. 386

10-31
 Homework Solution: Energy for Phase
Changes
Because the heat of vaporization is in units of J/mol,
and since J is the desired unit for heat, we only need
cancel out moles. To do this, we need to convert
grams of water into moles of water using water’s
molar mass, then multiply by the heat of
vaporization to find Joules:
1 mol H 2 O 4.07 × 104 J
125 g H 2 O × × = 2.82 × 105 J
18.01 g H 2 O 1 mol H 2 O

10-32
 9.2 Intermolecular Forces

 Why is CO2 a gas at room temperature and

H2O a liquid?
 Why do liquids have different boiling points?
 What causes molecules to stick together
when in the liquid state?
 Attractive forces, called intermolecular
forces, exist between molecules.

10-33
 Intermolecular Forces

 Three types of intermolecular forces:

 London dispersion forces
 Dipole-dipole forces
 Hydrogen bonding

10-34
Intermolecular Forces

10-35
 London Dispersion Forces
 London dispersion forces
exist in all substances.
 It is the only
intermolecular force
present in nonpolar
substances.
 London dispersion forces
are a result of temporary
electron cloud distortions
and temporary polarity
(dipoles).
Figure 10.15 10-36
 London Dispersion Forces
Figure 10.16

 The larger the electron

cloud, the more it can
be distorted.
 The larger the molecule,
the stronger the
London dispersion
forces.

Cl2 Br2 I2
Figure 10.15
10-37
 Liquid Crystals
 Long, very large
molecules can be held
together by London
forces.

Figure 10.17

10-38
Homework : London Dispersion Forces

 For each pair, determine which has

the stronger London dispersion
forces.

1. He or Kr Kr
2. HCl or HBr HBr
3. CH4 or C2H6 C2H6

10-39
 Homework : London Dispersion Forces
 Which has stronger London dispersion
forces, CH4 or SiH4?

10-40
 Homework Solution: London Dispersion
Forces
 Which has stronger London dispersion forces,
CH4 or SiH4?
Since silicon is larger than carbon, SiH4
interactions are stronger than CH4
interactions. The larger the electron cloud,
the easier it is to distort it, resulting in larger
London dispersion forces.

10-41
 London Dispersion Forces
 Relative boiling
points tell us about
intermolecular
force strength.
 The stronger the
forces, the higher
the temperature
needed to
overcome them.

Figure 10.19

10-42
Boiling Points of Hydrocarbons

10-43
 Dipole-Dipole Forces
 Dipole-dipole forces exist between polar
molecules.
 A polar molecule has a positive and negative
end, so it is considered a dipole.
 SO2 is polar so it experiences dipole-dipole
forces in the liquid state, in addition to London
dispersion forces.

Figure 10.18

10-44
 Homework : Dipole-Dipole Forces

 Which of the following molecules experience

dipole-dipole forces?
Figure from p. 324

SO2 CH2Cl2 PCl3 BF3

Yes Yes Yes No
10-45
 Homework : Dipole-Dipole Forces
 Which of the following molecules
experience dipole-dipole forces?
1. SCl2
2. CO
3. NH3
4. CCl4

10-46
 Homework Solutions: Dipole-Dipole
Forces
 Which of the following molecules experience dipole-
dipole forces?
1. SCl2
SCl2 has polar bonds and a bent structure, so there is an
overall molecular dipole pointing towards the lone pairs on
S. This molecule experiences dipole-dipole forces.
2. CO
The bond in CO is polar, so the molecule is polar.
Therefore, the molecule experiences dipole-dipole forces.

10-47
 Homework Solutions: Dipole-Dipole
Forces
 Which of the following molecules experience
dipole-dipole forces?
3. NH3
NH3 has polar bonds and a trigonal pyramidal
structure. Therefore, an overall molecular dipole
points toward the lone pair on N. This molecule
experiences dipole-dipole forces.
4. CCl4
CCl4 has a tetrahedral structure. Since all the
atoms around the central atom are the same, CCl4
is a nonpolar molecule. This molecule does NOT
experience dipole-dipole forces.
10-48
Homework : Dipole-Dipole Forces

 Which is more polar? HCl or HBr?

 Which has the stronger dipole-dipole forces?

 The boiling point of HBr is higher than HCl.

 How can we explain this?

10-49
Homework Solutions: Dipole-Dipole Forces
 Which is more polar? HCl or HBr?
 HCl is more polar because of a greater difference in
electronegativity.
 Which has the stronger dipole-dipole forces?
 HCl has the stronger dipole-dipole forces.
 Explain why the boiling point of HBr is higher than
HCl.
 Although HCl has stronger dipole-dipole forces, the
stronger London dispersion forces for the larger HBr
cause the total intermolecular forces for HBr to be
greater than for HCl. With molecules of very
different molar mass, London dispersion forces
become the more important intermolecular force.
10-50
Boiling Points Figure 10.20

10-51
 Hydrogen Bonding
 The irregularity in boiling point trends in Figure
10.20 is due to a particularly strong dipole-dipole
force called hydrogen bonding.
 Hydrogen bonding occurs between molecules that
contain hydrogen covalently bonded to either
nitrogen, oxygen, or fluorine:
N-H, O-H, or F-H
 Hydrogen bonding causes boiling points to be
much higher than expected.
 An important force in living systems, where it
stabilizes molecular shapes

10-52
 Hydrogen Bonding
(shown by the dotted lines)

Figure 10.21

10-53
Hydrogen bonding is the strong force that
holds together the DNA double helix.

Figure 10.22 10-54

 Hydrogen Bonding
 Hydrogen bonding in H2O Figure 10.24

causes ice to be less dense

than the liquid state.

© Jim Birk
© Jim Birk

10-55
Homework : Hydrogen Bonding

 Which of the following hydrogen-bond in

the pure liquid state?
1. CH3NH2 Yes
2. NF3 No
3. CH3-O-CH3 No
4. CH3CH2OH Yes
5. HCl No

10-56
 Homework : Hydrogen Bonding
 Identify the molecules from the following
list that experience hydrogen bonding in
the pure liquid state:
N(CH3)3, CH3CO2H, and HOCl

10-57
Homework Solutions: Hydrogen Bonding
 Identify the molecules from the following list that
experience hydrogen bonding in the pure liquid state:
N(CH3)3, CH3CO2H, and HOCl.
 CH3CO2H and HOCl experience hydrogen bonding
because the hydrogen atoms in these molecules are
bonded to oxygen, a small, highly electronegative
element.
 In N(CH3)3 the hydrogen atoms are bonded to
carbon, which has a relatively similar
electronegativity. Therefore, N(CH3)3 does not
experience hydrogen bonding.
10-58
Summary of Intermolecular Forces

Figure 10.23

10-59
Trends in Intermolecular Force Strength
 When determining which substance has the
stronger total intermolecular forces or the
higher boiling point, follow the following
guidelines:
1. First look to see if the substance can hydrogen
bond. If so it likely has the strongest
intermolecular forces. (e.g., HF > HCl)
2. If you are comparing two molecules of very
different molar masses, London dispersion
forces are more important. (e.g., HBr > HCl)
3. If you are comparing two molecules of very
similar molar masses, dipole-dipole forces are
more important. (e.g., CO > N2)

10-60
 Homework : Trends in Intermolecular
Forces
 Consider the substances CO and HF. Which
has the stronger intermolecular forces?
Which has the higher melting point? Boiling
point?

10-61
 Homework Solutions: Trends in
Intermolecular Forces
 Consider the substances CO and HF. Which has the
stronger intermolecular forces? Which has the
higher melting point? Boiling point?

HF has the stronger intermolecular forces because it

experiences hydrogen bonding, whereas CO only
experiences dipole-dipole forces. Higher
temperatures are required to overcome the stronger
intermolecular forces of HF, therefore it will have the
higher melting and boiling points.

10-62
Homework : Trends in Boiling Point

 Which of the following should

have the highest boiling point?
1. CH3OH or CH3SH CH3OH
2. I2 or SO2 I2
3. CO or N2 CO

10-63
 9.3 Properties of Liquids

 Vapor Pressure
 Density
 Viscosity
 Surface tension
 Capillary action

10-64
 Properties of Liquids

 Are related to the distance

between particles and to
intermolecular forces.
 Particles in a liquid are
much closer together than
the particles in a gas.
 Liquid particles are not
fixed, as they are in a solid. © Jim Birk

10-65
Trends in Vapor Pressure

Figure 10.10

10-66
Trends in Vapor Pressure

10-67
 Homework : Trends in Vapor Pressure
 Which of the following should have
the highest vapor pressure (at a given
temperature)? CH SH 3
CH3OH has stronger intermolecular forces due
to hydrogen bonding, so it will have a lower

1. CH3OH or CH3SH vapor pressure than CH3SH

SO2
2. I2 or SO2 The vapor pressure of the simple substances
depends on molecular weight, (If there is no
3. CO or N2 intermolecular bonds)! The more molecular weight
- the lower vapor pressure

N2
Nitrogen gas is symmetrical and exhibits
dispersion forces. In addition, nitrogen gas is
10-68
non-polar.
 Density
 Remember:
mass
d = Figure 10.24

volume
 Densities of the states of matter
are related to the distance between
particles
 Most substances are denser as
solids than as liquids because their
molecules or atoms are closer
together
 Water is an exception in that ice is
less dense than liquid water
© Jim Birk

10-69
 Viscosity
Viscosity - resistance to flow
 Generally the viscosity of a
liquid is low. Figure 10.5

 Values depend on size and

intermolecular force strength.
 Large molecules get tangled in
each other to increase viscosity.

10-70
 Surface Tension
 Surface tension causes a
liquid to try to minimize
Figure 10.27
its surface area.
 Surface molecules have
fewer molecules to
interact with than the
inner molecules.

10-71
 Surface Tension
 Surface tension is the Figure 10.27
amount of work required to
increase the surface area of
Figure 10.27
a liquid by a unit amount.
 Surface tension causes a
liquid surface to behave
like a stretched membrane.
 The greater the
intermolecular forces in a
liquid, the greater the
surface tension.
 Surface tension decreases
as temperature increases.
10-72
 Meniscus
 A meniscus is either a concave or convex curved
surface of a liquid produced by intermolecular
forces.
 A concave surface occurs when the intermolecular forces
between the liquid and the glass are greater than the
intermolecular forces among the liquid molecules.
 A convex surface occurs when the intermolecular forces
between the liquid and the glass are less than the
intermolecular forces among the liquid molecules.
Figure 10.30

10-73
 9.4 Properties of Solids
 The particles in the
solid state are held
together in specific
positions – there is no
translational motion.
© Jim Birk

 Crystalline solids are

well ordered.
 Amorphous solids lack
regular form.
10-74
Amorphous and Crystalline Solids
 Amorphous solid
 Occurs when the temperature of a liquid drops
rapidly, resulting in the particles solidifying in
a partially disordered state
 Particles are somewhat randomly arranged.
 Lacks regular form
 Crystalline solid
 Occurs when a liquid solidifies slowly, allowing
the array of particles to become well ordered
 Most solids are of this type.
 Results in the symmetrical arrangement of
planar faces

10-75
 Crystals and Crystal Lattices

 A crystalline solid is composed of a

repeating, 3-dimensional array of particles.
 The pattern formed is called a crystal lattice.
 Atoms, molecules, or ions pack together
efficiently to maximize attractive forces and
bonding interactions.

10-76
Gold Atoms in 2 Dimensions
(Close Packing)

Figure 10.32

10-77
Close-Packing in Nature and Commerce

© Jim Birk Wasp Nest Pineapple Fly Eye

Golf Ball Bubble Wrap Chicken Wire

10-78
Close Packing in 3 Dimensions

Figure 10.34

10-79
 Types of Crystalline Solids
(See Table 10.3)
 Metallic
 Pure metals and alloys; composed of atoms
 Metallic bonding
 Ionic
 Ionic compounds; composed of ions
 Ionic bonding
 Molecular
 Molecular compounds or nonmetal elements; composed
of molecules or atoms
 Intermolecular forces
 Network
 Molecular compounds or nonmetal elements;
 All atoms are connected by covalent bonds
10-80
Classification of Solids

10-81
 Homework : Types of Crystalline Solids

 A crystalline solid is very hard, does not

conduct electricity when solid or when
melted, and has a high melting point.
What type of solid is it?

10-82
 Homework Solution: Types of Crystalline
Solids
 A crystalline solid is very hard, does not
conduct electricity when solid or when melted,
and has a high melting point. What type of
solid is it?
This solid is a network solid. Network solids
are the only crystalline solids that have high
melting points, are very hard, and have the
possibility of nonconductors.

10-83
 Metallic Solids
 Are ductile and
malleable
 Valence electrons
move freely through
all parts of a metal.
 Attractions between
atoms of a metal are
delocalized, and
therefore it is easy to
move atoms by Figure 10.35

applying force.
10-84
 Alloys
 Form when a metal is mixed with one or more
additional metallic or nonmetallic elements
 Have properties different from those of their
parent elements

Figure 10.36
10-85
 Ionic Solids
 Contain cations and
anions arranged in
crystalline solids
 Electrostatic forces (ionic
bonds) hold together ionic
crystals.
 High melting points
 Hard and brittle
 Solids are not electrical
conductors, but melted or
dissolved, they become
good conductors. Figure 10.37

10-86
Ionic Solids

Figure 10.37

10-87
 Superconductors
 Offer no resistance to the conduction of electrical current
 Repel magnetic fields
 Although the nature of superconductors is not entirely
understood, the crystal structure of the solid material does
play a role
 Often formed from silicon and/or other metalloids

Figure 10.38
Figure 10.39 10-88
 Molecular Solids
 Intermolecular forces between molecules hold
a molecular solid together
 Nonpolar solids are held together by London
dispersion forces
 Form soft crystals with low melting points
 Electrical insulators
 Poor conductors of heat
 Polar solids are held together by London
dispersion forces and dipole-dipole forces
 Typically harder than nonpolar solids
 Low to moderate melting points
 Electrical insulators (no ions)
10-89
 Network Solids
 Consists of a giant molecule
that forms the entire crystal
 Formed by metalloids or
carbon
 Strong covalent bonds
connect the atoms in a
network solid
 Poor electrical conductors
 High melting points
 Very hard
 Have very stable, three– Figure 10.41
dimensional structures
 Many have a diamond
structure, or some derivative
of it
10-90
 Network Solids
The Diamond Form of Carbon

Chapter 2 opening photo Figure 10.41

10-91
Network Solid in 2 Dimensions
Graphite Form of Carbon

Figure 10.43

© Jim Birk
10-92
 Homework : Types of Solids

 Predict the type of solid for each:

a) CO2 sublimes at -78.4oC Molecular

b) Br2 mp = -7.2oC Molecular
c) C (diamond) mp = 3550oC Network
d) MgO mp = 2800oC Ionic

10-93
 Homework : Structures of Solids
 Identify the type of solid shown by the
following molecular-level image. What
types of forces hold the particles together
in this solid?

10-94
Figure from p. 408
Homework Solution: Structures of Solids
 This diagram shows a molecular solid.
Since it is made of nitrogen molecules
exclusively, it is nonpolar and is therefore
held together by weak London forces.
Figure from p. 408

10-95
Thank you