CHAPTER 13

LIQUIDS AND SOLIDS

1
Chapter Goals
1. Kinetic-Molecular Description of Liquids and Solids
2. Intermolecular Attractions and Phase Changes
The Liquid State
3. Viscosity
4. Surface Tension
5. Capillary Action
6. Evaporation
7. Vapor Pressure
8. Boiling Points and Distillation
9. Heat Transfer Involving Liquids

2
Chapter Goals
The Solid State
10. Melting Point
11. Heat Transfer Involving Solids
12. Sublimation and the Vapor Pressure of Solids
13. Phase Diagrams (P versus T)
14. Amorphous Solids and Crystalline Solids
15. Structures of Crystals
16. Bonding in Solids
17. Band Theory of Metals
18. Synthesis Question

3
Kinetic-Molecular Description
of Liquids and Solids
Solids and liquids are condensed states.
The atoms, ions, or molecules in solids and
liquids are much closer to one another than in
gases.
Solids and liquids are highly incompressible.

Liquids and gases are fluids.

They easily flow.
The intermolecular attractions in liquids
and solids are strong.
4
Kinetic-Molecular Description
of Liquids and Solids
Schematicrepresentation of the three
common states of matter.

gas
liquid solid
cool cool

heat heat

5
Kinetic-Molecular Description of
Liquids and Solids
Ifwe compare the strengths of interactions
among particles and the degree of ordering
of particles, we see that
Gases< Liquids < Solids
Miscible liquids are soluble in each other.
Examples of miscible liquids:
Water dissolves in alcohol.
Gasoline dissolves in motor oil.

6
Kinetic-Molecular Description of
Liquids and Solids
Immiscible liquids are insoluble in each
other.
Two examples of immiscible liquids:
Water does not dissolve in oil.
Water does not dissolve in cyclohexane.

7
Intermolecular Attractions and
Phase Changes
There are four important intermolecular attractions.
This list is from strongest attraction to the weakest
attraction.
1. Ion-ion interactions
The force of attraction between two oppositely
charged ions is governed by Coulombs law.

F
q q
-

2
d
-
q and q are the ion charges.
d is the distance between the ions.
8
Intermolecular Attractions and
Phase Changes
Coulombs law determines:
1. The melting and boiling points of ionic
compounds.
2. The solubility of ionic compounds.
Example 13-1: Arrange the following ionic
compounds in the expected order of
increasing melting and boiling points.
NaF, CaO, CaF2
You do it!
What important points must you consider?

9
Intermolecular Attractions and
Phase Changes

+ - 2+ 2+ 2-
Na F Ca F2 Ca O

10
Intermolecular Attractions and
Phase Changes
2. Hydrogen bonding
Consider H2O a very polar molecule.

11
Intermolecular Attractions and
Phase Changes
3. Dipole-dipole interactions
Consider BrF a polar molecule.

12
Intermolecular Attractions and
Phase Changes
4. London Forces are very weak.
They are the weakest of the intermolecular
forces.
This is the only attractive force in nonpolar
molecules.
Consider Ar as an isolated atom.

13
Intermolecular Attractions and
Phase Changes
In a group of Ar atoms the temporary
dipole in one atom induces other atomic
dipoles.

14
Intermolecular Attractions and
Phase Changes
Similar
effects occur in a group of I2
molecules.
The effect is shown in this movie.

15
The Liquid State

Viscosity
Viscosity is the resistance to flow.
For example, compare how water pours out
of a glass compared to molasses, syrup or
honey.
Oilfor your car is bought based on this
property.
10W30 or 5W30 describes the viscosity of
the oil at high and low temperatures.

16
The Liquid State

An example of viscosity of two liquids.

17
The Liquid State

Surface Tension
Surface tension is a measure of the
unequal attractions that occur at the
surface of a liquid.
The molecules at the surface are
attracted unevenly.

18
The Liquid State

Capillary Action
Capillary action is the ability of a liquid to
rise (or fall) in a glass tube or other
container

19
The Liquid State

Cohesive forces are the forces that hold

liquids together.
Adhesive forces are the forces between
a liquid and another surface.
Capillary rise implies that the:
Adhesive forces > cohesive forces
Capillary fall implies that the:
Cohesive forces > adhesive forces

20
The Liquid State
Water exhibits a capillary rise.
Mercury exhibits a capillary
fall.

Water Mercury

21
The Liquid State
Capillary action also affects the meniscus of liquids.

22
The Liquid State

Evaporation
Evaporation is the
process in which
molecules escape
from the surface
of a liquid and
become a gas.
Evaporation is
temperature
dependent.

23
The Liquid State
Vapor Pressure
Vapor pressure is the pressure exerted by a liquids
vapor on its surface at equilibrium.
Vapor Pressure (torr) and boiling point for three liquids
at different temperatures.
0oC 20oC 30oC normal boiling point
diethyl ether 185 442 647 36oC
ethanol 12 44 74 78oC
water 5 18 32 100oC
What are the intermolecular forces in each of these compounds?

You do it!

24
The Liquid State
Vapor Pressure as a function of temperature.

25
The Liquid State

Boiling Points and Distillation

The boiling point is the temperature at
which the liquids vapor pressure is
equal to the applied pressure.
The normal boiling point is the boiling
point when the pressure is exactly 1 atm.

26
The Liquid State

Distillation
Distillation is a process in which a
mixture or solution is separated into its
components on the basis of the
differences in boiling points of the
components.
Distillation is another vapor pressure
phenomenon.

27
The Liquid State
Heat Transfer Involving Liquids
From Chapter 1
q = m C T
Example 13-2: How much heat is
released by 2.00 x 102 g of H2O as it cools
from 85.0oC to 40.0oC? The specific heat
of water is 4.184 J/goC.
You do it!
28
The Liquid State

? J 2.00 10 2 g(4.184 J
g o
C
)(85. 0 40 .0 o
C)
? J 3.76 10 4 J 37.6 kJ

29
The Liquid State
Molar heat capacity is the amount of heat
required to raise the temperature of one
mole of a substance 1.00 oC.
Example 13-3: The molar heat capacity of
ethyl alcohol, C2H5OH, is 113 J/moloC. How
much heat is required to raise the T of 125
g of ethyl alcohol from 20.0oC to 30.0oC?
1 mol C2H5OH = 46.0 g
You do it!

30
The Liquid State

1 mol C 2 H 5OH
? mol = 125 g 2.72 mol C 2 H 5OH
46.0 g C 2 H 5OH

? J = 2.72 mol

113 J
mol C
o 30.0 20.0 o
C 3.07 kJ

31
The Liquid State
The calculations we have done up to now tell us the energy
changes as long as the substance remains in a single phase.
Next, we must address the energy associated with phase
changes.
For example, solid to liquid or liquid to gas and the reverse.
Heat of Vaporization is the amount of heat required to change
1.00 g of a liquid substance to a gas at constant temperature.
Heat of vaporization has units of J/g.
Heat of Condensation is the reverse of heat of vaporization,
phase change from gas to liquid.
2260 J
1.00 g H 2 O ( ) at 100.0 C -2260

o
J 1.00 g H 2 O (g) at 100.0o C

32
The Liquid State
Molar heat of vaporization or Hvap
The Hvap is the amount of heat required to change 1.00
mole of a liquid to a gas at constant temperature.
Hvap has units of J/mol.
Molar heat of condensation
The reverse of molar heat of vaporization is the heat of
condensation.

40.7 kJ
1.00 mol H 2 O ( ) at 100.0 C -40.7 kJ 1.00 mol H 2 O (g) at 100.0o C
o

33
The Liquid State

34
The Liquid State

Example 13-4: How many joules of energy

must be absorbed by 5.00 x 102 g of H2O at
50.0oC to convert it to steam at 120oC?
The molar heat of vaporization of water is
40.7 kJ/mol and the molar heat capacities
of liquid water and steam are 75.3 J/mol oC
and 36.4 J/mol oC, respectively.
You do it!

35
The Liquid State
1 mol H 2 O
? mol = 500 g H 2 O 27.8 mol H 2 O
18 g H 2 O
1st let's calculate the heat required to warm water from 50 to 100 o C

? J = 27.8 mol
75.3 J
mol o C

100.0 50.0 o
C 105
. 10 5
J

Next, lets calculate the energy required to boil the water.

40.7 103 J
? J = 27.8 mol . 105 J
1131
mol
Finally, lets calculate the heat required
to heat steam from 100 to 120oC.
? J = 27.8 mol

36.4 J
mol o C
120.0 -100.0 o

C 0.20 10 5
J

36
The Liquid State
The total amount of energy for this process is
the sum of the 3 pieces we have calculated

105
. 10 J 1131
5
. 10 J 0.20 10 J
5 5

5 3
12.56 10 J or 1.26 10 kJ

37
The Liquid State

Example 13-5: If 45.0 g of steam at

140oC is slowly bubbled into 450 g of
water at 50.0oC in an insulated container,
can all the steam be condensed?
You do it!

38
The Liquid State
1 mol 1 mol
45.0 g steam 2.50 mol 450 g water 25.0 mol
18 g steam 18 g
(1) Calculate the amount of heat required to condense the steam.
2.50 mol 36.4 J
o
mol C
140.0 -100.0 C 2.50 mol 40.7
o kJ
mol 105. kJ
(2) Calculate the amount of heat available in the liquid water.
25.0 mol 75.3 J
o
mol C
(100.0 - 50.0 o
C) 94.1 kJ
Amount of heat to condense all of the steam is 105 kJ.
Amount of heat that the liquid water can absorb is 94.1 kJ.
Thus all of the steam cannot be condensed.

39
The Liquid State

Clausius-Clapeyron equation
determine vapor pressure of a liquid at a new T
determine what T we must heat something to get a

specified vapor pressure

way to determine Hvap if we know pressure at 2 Ts

P2 H vap 1 1
ln
P1 R T1 T2
40
The Liquid State

InDenver the normal atmospheric pressure is

630 torr. At what temperature does water boil in
Denver?
P2 H vap 1 1
ln
P1 R T1 T2
630 torr 40.7 103 J mol 1 1
ln
760 torr 8.314 J K mol 373 K T2
1
ln 0.829 4895 0.002681
T2
41
The Liquid State
0188
. 1
0.002681
4895 T2
5 1
383
. 10 0.002681
T2
5 1
383
. 10 0.002681
T2
1
0.00272
T2
T2 368 K or 95o C 42
The Liquid State

Boiling Points of Various Kinds of Liquids

Gas MW BP(oC)
He 4 -269
Ne 20 -246
Ar 40 -186
Kr 84 -153
Xe 131 -107
Rn 222 -62
43
The Liquid State

44
The Liquid State

o
Compound MW(amu) B.P.( C)
CH4 16 -161
C2 H6 30 -88
C3 H8 44 -42
n-C4H10 58 -0.6
n-C5H12 72 +36
45
The Liquid State

46
The Liquid State

o
Compound MW(amu) B.P.( C)
HF 20 19.5
HCl 37 - 85.0
HBr 81 - 67.0
HI 128 - 34.0

47
The Liquid State

48
The Liquid State
o
Compound MW(amu) B.P.( C)
H 2O 18 100
H 2S 34 - 61
H 2Se 81 - 42
H 2 Te 130 -2

49
The Liquid State

50
The Liquid State

Atthe molecular level what happens

when a species boils?

51
The Liquid State

Example 13-6: Arrange the following

substances in order of increasing boiling
points.
C2H6, NH3, Ar, NaCl, AsH3
You do it!
Ar < C2H6 < AsH3 < NH3 < NaCl
nonpolar nonpolar polar very polar ionic
London London dipole-dipole H-bonding ion-ion

52
The Solid State

Normal Melting Point

The normal melting point is the
temperature at which the solid melts
(liquid and solid in equilibrium) at exactly
1.00 atm of pressure.
The melting point increases as the
strength of the intermolecular attractions
increase.

53
The Solid State

Which requires more energy?

NaCl
NaCl s
or
H O
H 2O s 2

What experimental proof do you have?

54
Heat Transfer Involving Solids

Heat of Fusion
Heat of fusion is the amount of heat
required to melt one gram of a solid at its
melting point at constant temperature.
334 J
1.00 g H 2 O (s) at 0 C -334
o J 1.00 g H 2 O ( ) at 0o C

Heat of crystallization is the reverse of

the heat of fusion.

55
Heat Transfer Involving Solids

Molar heat of fusion or Hfusion

The molar heat of fusion is the amount
of heat required to melt a mole of a
substance at its melting point.
The molar heat of crystallization is the
reverse of molar heat of fusion
6012 J
1.00 mole H 2 O (s) at 0 C -6012
o J 1.00 mole H 2 O ( ) at 0o C

56
Heat Transfer Involving Solids
Here is a summary of the heats of
transformation for water.
40.7 kJ
1.00 mol H 2 O ( ) at 100.0 C -40.7 kJ 1.00 mol H 2 O (g) at 100.0 o C
o

6012 J
1.00 mole H 2 O (s) at 0 C -6012
o
J 1.00 mole H 2 O ( ) at 0o C

57
Heat Transfer Involving Solids

Example 11-7: Calculate the amount of

heat required to convert 150.0 g of ice at
-10.0oC to water at 40.0oC.
specific heat of ice is 2.09 J/goC
you do it

58
Heat Transfer Involving Solids

J
? J = (150.0 g)(2.09 o )(10 o C) = 3.14 103 J
g C
J
? J = (150.0 g)(334 ) = 5.01 10 4 J
g
J o 4
? J = (150.0 g)(4.18 o )(40 C) = 2.51 10 J
g C
4
7.83 10 J
59
Sublimation and the Vapor
Pressure of Solids
Sublimation
In the sublimation process the solid
transforms directly to the vapor phase
without passing through the liquid
phase.
Solid CO2 or dry ice does this well.

solid condensati
on sublimation
gas
60
Phase Diagrams (P versus T)
Phase diagrams are a convenient way to display
all of the different phase transitions of a
substance.
This is the phase diagram for water.

61
Phase Diagrams (P versus T)
Compare waters phase diagram to
carbon dioxides phase diagram.

62
Amorphous Solids and
Crystalline Solids
Amorphous solids do not have a well ordered
molecular structure.
Examples of amorphous solids include waxes,
glasses, asphalt.
Crystalline solids have well defined structures
that consist of extended array of repeating
units called unit cells.
cells
Crystalline solids display X-ray diffraction patterns
which reflect the molecular structure.
The Bragg equation, detailed in the textbook,
describes how an X-ray diffraction pattern can be
used to determine the interatomic distances in
crystals.
63
Structure of Crystals
Unit cells are the smallest repeating unit of a
crystal.
As an analogy, bricks are repeating units for
buildings.
There are seven basic crystal systems.

64
Structure of Crystals
We shall look at the
three variations of the
cubic crystal system.
Simple cubic unit cells.
The balls represent the
positions of atoms, ions,
or molecules in a simple
cubic unit cell.

65
Structure of Crystals

Ina simple cubic unit

cell each atom, ion, or
molecule at a corner is
shared by 8 unit cells
Thus 1 unit cell contains
8(1/8) = 1 atom, ion, or
molecule.

66
Structure of Crystals
Body centered cubic (bcc) has an
additional atom, ion, or molecule
in the center of the unit cell.
On a body centered cubic unit cell
there are 8 corners + 1 particle in
center of cell.
1 bcc unit cell
contains 8(1/8) + 1 = 2 particles.

67
Structure of Crystals

A face centered cubic

(fcc) unit cell has a
cubic unit cell structure
with an extra atom, ion,
or molecule in each
face.

68
Structure of Crystals
A facecentered cubic unit cell has 8
corners and 6 faces.
1 fcc unit cell contains
8(1/8) + 6(1/2) = 4 particles.

69
Bonding in Solids
Molecular Solids have molecules in each
of the positions of the unit cell.
Molecular solids have low melting points,
are volatile, and are electrical insulators.
Examples of molecular solids inlude:
water, sugar, carbon dioxide, benzene

70
Bonding in Solids
Covalent Solids have atoms that are
covalently bonded to one another
Some examples of covalent solids are:
Diamond, graphite, SiO2 (sand), SiC

71
Bonding in Solids
Ionic Solids have ions that occupy the
positions in the unit cell.
Examples of ionic solids include:
CsCl, NaCl, ZnS

72
Bonding in Solids

Metallic Solids may be thought of as

positively charged nuclei surrounded by
a sea of electrons.
The positive ions occupy the crystal
lattice positions.
Examples of metallic solids include:
Na, Li, Au, Ag, ..

73
Bonding in Solids
Variationsin Melting Points for Molecular Solids
What are the intermolecular forces in each solid?

Compound Melting Point (oC)

ice 0.0
ammonia -77.7
benzene, C6H6 5.5
napthalene, C10H8 80.6
benzoic acid, C6H5CO2H 122.4

74
Bonding in Solids
Variations in Melting Points for Covalent Solids
Substance Melting Point (oC)
sand, SiO2 1713
carborundum, SiC ~2700
diamond >3550
graphite 3652-3697

75
Bonding in Solids
Variations in Melting Points for Ionic Solids
Compound Melting Point (oC)
LiF 842
LiCl 614
LiBr 547
LiI 450
CaF2 1360
CaCl2 772
CaBr2 730
CaI2 740

76
Bonding in Solids
Variations in Melting Points for Metallic Solids
Metal Melting Point (oC)
Na 98
Pb 328
Al 660
Cu 1083
Fe 1535
W 3410

77
Bonding in Solids

Example 13-8. A group IVA element with

a density of 11.35 g/cm3 crystallizes in a
face-centered cubic lattice whose unit
cell edge length is 4.95 . Calculate the
elements atomic weight. What is the
atomic radius of this element?

78
Bonding in Solids
Face centered cubic unit cells have 4 atoms,
ions, or molecules per unit cell.
Problem solution pathway:
1. Determine the volume of a single unit cell.
2. Use the density to determine the mass of a single
unit cell.
3. Determine the mass of one atom in a unit cell.
4. Determine the mass of 1 mole of these atoms

79
Bonding in Solids
1. Determine the volume of a single unit cell.
0 0
1 A 10 cm thus 4.95 A 4.95 10 -8 cm
-8

Face centered cubic unit cells are cubic so V 3

4.95 10 -8
cm 3
1.21 10 - 22 cm 3

2. Use the density to determine the mass of a unit cell.

1.2110 - 22
cm
3 11.35 g
3
1.38 10 - 21 g
cm one unit cell

80
Bonding in Solids

3. Determine the mass of one atom in the unit

cell.
Because face centered cubic has 4 atoms per unit cell
the mass of one atom can be determined in this fashion.
1.38 10 -21 g unit cell
3.44 10 22 g
4 atoms unit cell atom

4. Determine the mass of one mole of these atoms.

3.44 10 22 g
atom
6.022 10 23 atoms
mole
207 g/mole

81
Bonding in Solids
To determine an atomic radius requires
some geometry.
For simple cubic unit cells:
The edge length = 2 radii

82
Bonding in Solids
For face-centered cubic unit cells:
The face diagonal = 2 x edge length.
The diagonal length = 4 radii.

83
Bonding in Solids

For body-centered cubic unit cells:

The body diagonal = 3 x edge length.
The diagonal length = 4 radii.

84
Bonding in Solids
Determine the diagonal length then divide by 4
to get the atomic radius.

diagonal = -8
2 4.95 10 cm
-8
7.00 10 cm
-8
radius = 7.00 10 cm 175
. 10 -8
cm
4

85
Band Theory of Metals
Sodiums3s orbitals can interact to
produce overlapping orbitals

86
Band Theory of Metals
The 3s orbitals can also overlap with unfilled 3p orbitals

87
Band Theory of Metals
Insulators
have a large gap between the s
and p bands.
Gap is called the forbidden zone.
zone
Semiconductors have a small gap between
the bands.

88
Synthesis Question
Maxwell House Coffee Company decaffeinates
its coffee beans using an extractor that is 7.0
feet in diameter and 70.0 feet long.
Supercritical carbon dioxide at a pressure of
300.0 atm and temperature of 100.0 oC is
passed through the stainless steel extractor.
The extraction vessel contains 100,000
pounds of coffee beans soaked in water until
they have a water content of 50%.

89
Synthesis Question
This process removes 90% of the caffeine in a
single pass of the beans through the extractor.
Carbon dioxide that has passed over the
coffee is then directed into a water column that
washes the caffeine from the supercritical CO2.
How many moles of carbon dioxide are
present in the extractor?

90
Synthesis Question

Diameter of vessel (7.0 ft)(30.48 cm/ft) 213.4 cm

Radius of vessel 213.4 cm/2 106.7 cm
Length of vessel (70.0 ft)(30.48 cm/ft) 2134 cm
Volume of vessel r 2 h (3.1416)(106.7cm) 2 (2134cm)
(7.633 107 cm 3 )(1 mL/cm3 )(1 L/1000 mL)
7.633 10 4 L

91
Synthesis Question

PV nRT
300 atm 7.633 10 L
4
n PV
RT 0.08206 L atm mol K 373 K
n 748,000 mol of CO 2

92
Group Question

How many CO2 molecules are there in

1.0 cm3 of the Maxwell House Coffee
Company extractor? How many more
CO2 molecules are there in a cm3 of the
supercritical fluid in the Maxwell House
extractor than in a mole of CO2 at STP?

93
End of Chapter 13
Our understanding
of Band Theory was
a major
breakthrough in
semiconductor
knowledge.
Why computers
work!

94