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Liquids and Solids
Chapter 10
Copyright©2000 by Houghton Mifflin 1

A phase is a homogeneous part of the system in
contact with other parts of the system but
separated from them by a well-defined boundary.
2 Phases
Solid phase - ice
Liquid phase - water

Schematic representations of the
three states of matter.

Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
“Measure” of intermolecular force

Generally,
boiling point
intermolecular
melting point
forces are much
weaker than
∆ vap
H
forces. ∆ fus
H
Forces between (rather than within)
molecules.
Ô dipole-dipole attraction: molecules with

dipoles orient themselves so that “+” and
“−” ends of the dipoles are close to each
other.
which hydrogen is bonded to a highly

Dipole-Dipole Forces
Attractive forces between polar molecules
Orientation of Polar Molecules in a Solid

(a)The electrostatic
interaction of two
(b) The interaction

of many dipoles in

(a) The polar water molecule.
molecules.

Why is the hydrogen bond considered a
“special” dipole-dipole interaction?
Why this sudden increase?
Decreasing molar mass

Decreasing boiling point
The boiling point represents the
magnitude and type of bonding

Ion-Dipole Forces
Attractive forces between an ion and a polar molecule
Ion-Dipole Interaction

London Dispersion Forces
4
relatively weak forces that exist among noble
gas atoms and nonpolar molecules (Ar,
8 18
4 caused by instantaneous dipole, in which

electron distribution becomes asymmetrical.
the ease with which electron “cloud” of an
4

(a) An
instantaneous
occur on atom A,
creating an
dipole. This
dipole creates an
on neighboring
atom B.
molecules such
as H2 also can
develop
induced dipoles. Copyright©2000 by Houghton Mifflin 14

Dispersion Forces Continued
Polarizability is the ease with which the electron distribution

in the atom or molecule can be distorted.
Polarizability increases with:

• greater number of electrons
• more diffuse electron cloud
Dispersion
forces usually
increase with

What type(s) of intermolecular forces exist between
each of the following molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces.
S
O
SO2 O
SO 2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules.
Properties of Liquids
Surface tension is the amount of energy required to stretch
or increase the surface of a liquid by a unit area.
Or
The resistance to an increase in its surface area (polar molecules).
Strong
intermolecular
High
surface

A molecule in the interior of a liquid is attracted by the
molecules surrounding it, whereas a molecule at the
surface of a liquid is attracted only by molecules below
it and on each side.

More Properties of Liquids
Capillary Action: Spontaneous rising of a
liquid in a narrow tube.
Nonpolar liquid
mercury forms a
meniscus in a
glass tube, whereas
polar water forms a
meniscus.
Cohesion is the intermolecular attraction between like molecules
Adhesion is an attraction between unlike molecules
Adhesion
Cohesion

Viscosity is a measure of a fluid’s resistance to flow.
Strong
intermolecular
High
viscosity

Types of Solids
Crystalline Solids: highly regular
(NaCl), pyrite (FeS2 )].
Amorphous solids: considerable disorder in

their structures (glass).

An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.
A glass is an optically transparent fusion product of inorganic

materials that has cooled to a rigid state without crystallizing
Crystalline Non-crystalline
quartzCopyright©2000 quartz
(SiO2 ) by Houghton Mifflin
glass 23
A crystalline solid possesses rigid and long-range order. In a
crystalline solid, atoms, molecules or ions occupy specific
An amorphous solid does not possess a well-defined

arrangement and long-range molecular order.
A unit cell is the basic (smallest) repeating structural unit of a

crystalline solid.
lattice At lattice points:

point • Atoms
• Molecules
• Ions

Unit Cell Unit cells in 3 dimensions
Shared by 8 Shared by 2
unit cells cells
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)

Three cubic
unit cells
corresponding
lattices.

3
RELATIONSHIP BETWEEN ATOMIC RADIUS AND EDGE

LENGTH IN THREE DIFFERENT UNIT CELLS
c = 4r b = 4r
l = 2r 2 2 2 2 2 2
c2 = l2 + b2 (4r)2 = 2l 2
2 2 2 2
c = l √3 = 4r l = r√8
l = 4r/√3
3
RELATIONSHIP BETWEEN ATOMIC RADIUS AND EDGE
LENGTH IN THREE DIFFERENT UNIT CELLS
Simple Body-centered Face-centered
c = 4r b = 4r
s = 2r 2 2 2 2 2 2
c2 = s2 + b2 (4r)2 = 2s2
2 2 2 2
c = s√3 = 4r s = r√8
s = 4r/√3
Analysis of crystal structure using X-Ray Diffraction

Extra distance = BC + CD = 2d sinθ = nλ (Bragg Equation)
Bragg Equation
Used for analysis of crystal structures.
nλ = 2d sin θ
d = distance between atoms

n = an integer

X rays of wavelength 0.154 nm are diffracted from a
crystal at an angle of 14.170. Assuming that n = 1,
crystal?
nλ = 2d sin θ n=1 θ = 14.170 λ = 0.154 nm = 154 pm
n 1 x 154 pm
d= λ = 2 x sin14.17 = 77.0 pm
2sinθ

11.5
Types of Crystalline Solids
Ionic Solid: contains ions at the points of the

lattice that describe the structure of the solid
(NaCl).
Molecular Solid: discrete covalently bonded

molecules at each of its lattice points (sucrose,

Types of Crystals
Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Poor conductor of heat and electricity
CsCl ZnS CaF2

Types of Crystals
Atomic Crystals
• Lattice points occupied by atoms
• Held together by covalent bonds

carbon
atoms

diamond graphite
Packing in Metals
Model: Packing uniform, hard spheres to

best use available space. This is called
closest packing. Each atom has 12 nearest
4
hexagonal closest packed (“aba”)
4
cubic closest packed (“abc”)

The closest packing arrangement of uniform spheres, (a) aba
packing (b) abc packing.

When spheres are closest packed so that the spheres in the third
layer are directly over those in the first layer (aba), the unit cell is

When spheres are packed in the abc arrangement, the unit cell is
face-centered cubic.

The indicated
sphere has 12
neighbors.

When silver crystallizes, it forms face-centered cubic
cells. The unit cell edge length is 409 pm. Calculate
m V = a3 = (409 pm) 3 = 6.83 x 10-23 cm3

d=
V
4 atoms/unit cell in a face-centered cubic cell
107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10-22
g
mole Ag 6.022 x 1023 atoms
m 7.17 x 10-22 g
d= = = 10.5 g/cm3
V -23 3

Types of Crystals
Molecular Crystals
• Lattice points occupied by molecules
• Held together by intermolecular forces

Types of Crystals
Metallic Crystals
• Lattice points occupied by metal atoms
• Held together by metallic bonds
• Good conductors of heat and electricity

Cross Section of a Metallic Crystal
nucleus &
inner shell e-
mobile “sea”
-

Examples of three types of crystalline
solids (a) An atomic solid. (b) An ionic

Types of Crystals

Bonding Models for Metals
Electron Sea Model: A regular array of

metals in a “sea” of electrons.
Band (Molecular Orbital) Model: Electrons

assumed to travel around metal crystal in
metal atoms.

The electron sea model for metals postulates a regular array of
cations in a "sea" of valence electrons.
electron.
valence electrons.

The molecular
orbital energy
levels produced
when various
numbers of
interact.

(left) A representation of the energy levels
(bands) in a magnesium crystal.
vapor.

Metal Alloys
Substances that have a mixture of elements and

properties.
1. Substitutional Alloy: some metal atoms

replaced by others of similar size.

Metal Alloys
(continued)
2. Interstitial Alloy: Interstices (holes) in

closest packed metal structure are
steel = iron + carbon

3. : Alloy steels contain a mix
of substitutional (carbon) and

Two types
substitutional
(b) interstitial

Network Solids
Composed of strong directional covalent

bonds that are best viewed as a “giant
molecule”.
4
brittle
4
carbon, silicon-based
graphite, diamond, ceramics, glass

The structures of
diamond and
graphite. In each
case only a small
part of the entire

Partial representation of the molecular orbital
energies in (a) diamond and (b) a typical metal.

The p orbitals (a) perpendicular to the plane of
the carbon ring system in graphite can combine

Graphite consists of layers of
carbon atoms.

Computer-generated model of
silica.

(top) The structure
of quartz (empirical
Quartz contains
chains of SiO4
that share oxygen

atoms.

Semiconductors
A substance in which some electrons can

cross the band gap.
4 Conductivityis enhanced by doping with

group 3a or group 5a elements.

(a) A silicon crystal
doped with arsenic,
valence electron than

silicon.
doped with boron,

which has one less
electron than silicon.
Energy-level diagrams for (a) an n-type
semiconductor and (b) a p-type

The p-n
junction
involves the
p-type and
an n-type

Molecular Solids
• Discrete molecular units at each lattice position

e.g. ice, solid CO
2 , 8S , 4P .
• Covalent bond within molecule while weak
e.g. Ice (Hydrogen bond), CO2 , P 4, S 8(LD) very
• As the size of the molecule increases, the LD

become large causing many substances to be
solids at 25
0
C.
A “steaming” piece of dry ice
2

(a) Sulfur crystals (yellow) contain S 8molecules. (b) White phosphorus (containing P 4
molecules) is so reactive with the oxygen in air that it must be stored under water.

Ionic Solids
• Ionic solids are stable, high melting point and held

together by strong electrostatic forces
• Structure of most binary ionic solids (NaCl) can

be explained by the closest packing of spheres
– Anion (large ion) packed in one of the closest packing
(hcp or ccp)

The holes that exist
among closest packed
trigonal hole formed by

three spheres in a given
(b) The tetrahedral hole

formed when a sphere
by three spheres in an
adjacent layer.
formed by six spheres in

two adjacent layers.
(a) The location (X) of a tetrahedral hole in the face-centered
cubic unit cell. (b) One of the tetrahedral holes. (c) The unit cell
2-
ions (yellow) are closest packed with the
Zn2+ ions (red) in alternating tetrahedral holes.

(a) The locations
(gray X) the
holes in the
cubic
unit cell.
the unit cell for solid

NaCl.
Vapor Pressure
. . . is the pressure of the vapor present at

equilibrium.
the intermolecular forces in the liquid.
Volatile liquids have high vapor pressures.

Behavior of a liquid in a closed
container.

The equilibrium vapor pressure is the vapor pressure
measured when a dynamic equilibrium exists between
H2O (l) H2O (g)
Dynamic Equilibrium
Rate of Rate of
condensation
= evaporation

Before At
Evaporation Equilibrium
(a) The vapor pressure of a liquid can be measured easily using a
simple barometer of the type shown here. (b) The three liquids,
2 5 2 5 2
different vapor pressures.

(a) The vapor pressure of water, ethanol, and diethyl ether as a
vap ) versus 1/T (Kelvin

Molar heat of vaporization ( H ) is the energy required to
∆ vap
Clausius-Clapeyron Equation
Hvap P = (equilibrium) vapor pressure
ln P = - ∆ +C T = temperature (K)
RT
R = gas constant (8.314 J/K•mol)

PT1 Hvap 1 1
ln P = ∆
T2 T2 T1

The boiling point is the temperature at which the
(equilibrium) vapor pressure of a liquid is equal to the
external pressure.
The normal boiling point is the temperature at which a liquid

boils when the external pressure is 1 atm.

Melting Point
Molecules break loose from lattice points and

solid changes to liquid. (Temperature is constant
as melting occurs.)

H2O (s) H2O (l)
The melting point of a solid
Sublimation
or the freezing point of a
which the solid and liquid
Freezing
Melting
phases coexist in equilibrium

11.8
Molar heat of fusion ( H ) is the energy required to melt
∆ fus
1 mole of a solid substance.

The supercooling of water. The

H2O (s) H2O (g)
Sublimation
Deposition
Molar heat of sublimation
sub) is the energy required
∆
Hsub = Hfus + H vap

∆ ∆ ∆
( Hess’s Law)

Phase Diagram
Represents phases as a function of temperature

and pressure.
vapor can not be liquefied.
the critical temperature.
(for water, T c = 374°C and 218 atm).

The phase diagram for water.

The critical temperature (Tc ) is the temperature above which
the gas cannot be made to liquefy, no matter how great the
The critical pressure

(Pc) is the minimum
applied to bring about

liquefaction at the
critical temperature.

Diagrams of various heating experiments on
samples of water in a closed system.
Negative Slope

The phase diagram for
carbon dioxide.
Positive Slope

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Liquids and Solids

Copyright©2000 by Houghton Mifflin 1

Solid phase - ice

Liquid phase - water

Copyright©2000 by Houghton Mifflin 2

Copyright©2000 by Houghton Mifflin 3

“Measure” of intermolecular force

Ô dipole-dipole attraction: molecules with

which hydrogen is bonded to a highly

Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

Copyright©2000 by Houghton Mifflin 7

(b) The interaction

Copyright©2000 by Houghton Mifflin 8

Copyright©2000 by Houghton Mifflin 9

Decreasing molar mass

Copyright©2000 by Houghton Mifflin 11

Attractive forces between an ion and a polar molecule

Copyright©2000 by Houghton Mifflin 12

4 caused by instantaneous dipole, in which

Copyright©2000 by Houghton Mifflin 13

induced dipoles. Copyright©2000 by Houghton Mifflin 14

Polarizability is the ease with which the electron distribution

Polarizability increases with:

Copyright©2000 by Houghton Mifflin 15

Copyright©2000 by Houghton Mifflin 17

Copyright©2000 by Houghton Mifflin 18

Cohesion is the intermolecular attraction between like molecules

Adhesion is an attraction between unlike molecules

Copyright©2000 by Houghton Mifflin 20

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

Copyright©2000 by Houghton Mifflin 21

Crystalline Solids: highly regular

(NaCl), pyrite (FeS2 )].

Amorphous solids: considerable disorder in

Copyright©2000 by Houghton Mifflin 22

A glass is an optically transparent fusion product of inorganic

An amorphous solid does not possess a well-defined

A unit cell is the basic (smallest) repeating structural unit of a

lattice At lattice points:

Copyright©2000 by Houghton Mifflin 24

Copyright©2000 by Houghton Mifflin 29

Copyright©2000 by Houghton Mifflin 30

RELATIONSHIP BETWEEN ATOMIC RADIUS AND EDGE

Simple Body-centered Face-centered

Copyright©2000 by Houghton Mifflin 33

Used for analysis of crystal structures.

d = distance between atoms

Copyright©2000 by Houghton Mifflin 35

nλ = 2d sin θ n=1 θ = 14.170 λ = 0.154 nm = 154 pm

Copyright©2000 by Houghton Mifflin 36

Ionic Solid: contains ions at the points of the

Molecular Solid: discrete covalently bonded

Copyright©2000 by Houghton Mifflin 37

• Poor conductor of heat and electricity

CsCl ZnS CaF2

• Poor conductor of heat and electricity

Copyright©2000 by Houghton Mifflin 39

Model: Packing uniform, hard spheres to

Copyright©2000 by Houghton Mifflin 40

Copyright©2000 by Houghton Mifflin 41

Copyright©2000 by Houghton Mifflin 42

Copyright©2000 by Houghton Mifflin 43