13 Liquids and Solids

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
• Schematic representation of the three
common states of matter.

5
Kinetic-Molecular Description of
Liquids and Solids
• If we 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 Coulomb’s law.

-
q q
F 2
d
-
q and q are the ion charges.
d is the distance between th e ions.
8
 Intermolecular Attractions and
Phase Changes
• Coulomb’s law determines:
1. The melting and boiling points of ionic
compounds.
• Multiple charged ion have high melting and boiling
point
• Ions of similar charges, smaller ions result in
stronger attraction
2. The solubility of ionic compounds.

9
Intermolecular Attractions and
Phase Changes
• Example 13-1: Arrange the following
ionic compounds in the expected order of
increasing melting and boiling points.
NaF, CaO, CaF2

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

10
Intermolecular Attractions and
Phase Changes

2. Dipole-dipole interactions

Interaction of the positive end, d+, of a

polar molecule with the negative end, d-,
of another polar molecule

11
Intermolecular Attractions
Illustrate the predominant intermolecular
force between AsCl3 and OF2.

12
Dipole-dipole interaction
between AsCl3 and OF2
+

As
Cl
- Cl +
Cl -
- O
F F
- -
+
or O
F F
+ - -
As
Cl
- Cl
Cl - 13
-
Intermolecular Attractions
Illustrate the predominant intermolecular
force between CH3OH and HF.

14
Intermolecular Attractions and
Phase Changes
2. Dipole-dipole interactions
– Consider BrF a polar molecule.

15
Intermolecular Attractions and
Phase Changes
3. Hydrogen bonding
– Consider H2O a very polar molecule.

16
Hydrogen bonding between HF and
CH3OH.
- +

F H
H

C H
H O +
-
H
or H

C - H -
H O +

H F

H+ 17
 Intermolecular forces associated
with dimethyl ether, CH3OCH3.
H
H + H H H
+ C + H
- H C H
H C H
O - +
H H +
O H C -
H + H
O C H C O C
H C
- +
H
O- H
+
H
H H H+ H+ H
H
dipole-dipole hydrogen bonding

18
Intermolecular Attractions and
Phase Changes

19
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.

20
Intermolecular Attractions and
Phase Changes
• In a group of Ar atoms the temporary
dipole in one atom induces other atomic
dipoles.

21
Intermolecular Attractions and
Phase Changes
• Similar effects occur in a group of I2
molecules.
The effect is shown in this movie.

22
 Summary of London Forces
Consider what happens when two Ar
atoms approach each other.

- - - - -
e
- + e
-
e- e -e -e
e- e +
-
-e -e
e - - e +- e-
- e- e +
-+ -+
e e e e e

23
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.

24
The Liquid State
• Oil for your car is bought based on this
property.
– 10W30 or 5W30 describes the viscosity of
the oil at high and low temperatures.
• Increasing the size and surface area of
molecules, generally increases the viscosity.

25
The Liquid State
• An example of viscosity of two liquids.

• Ostwald Viscometer

26
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.

27
The Liquid State
• Floating paper clip demonstration of
surface tension.

28
The Liquid State
Capillary Action
• Capillary action is the ability of a liquid to
rise (or fall) in a glass tube or other
container

29
The Liquid State
• Cohesive forces are the forces that hold
liquids together.
• Adhesive forces are the forces between a
liquid and a solid surface surface.
– Capillary rise implies that the:
• Adhesive forces > cohesive forces
– Capillary fall implies that the:
• Cohesive forces > adhesive forces

30
The Liquid State
• Water exhibits a capillary rise.
 Mercury exhibits a capillary
fall.

Water Mercury

31
The Liquid State
• Capillary action also affects the meniscus of liquids.

32
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.

33
The Liquid State
• This is an animation of evaporation

34
The Liquid State
Vapor Pressure
• Vapor pressure is the pressure exerted by a
liquid’s vapor on its surface at equilibrium.

35
• Vapor Pressure (torr) and boiling point for three
liquids at different temperatures.
0 oC 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?

36
The Liquid State
Vapor Pressure as a function of temperature.

37
The Liquid State
Boiling Points and Distillation
• The boiling point is the temperature at
which the liquid’s vapor pressure is equal
to the applied pressure.
• The normal boiling point is the boiling
point when the pressure is exactly 1 atm.

38
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.
39
The Liquid State
Heat Transfer Involving Liquids
• From Chapter 1
q = mC 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!
40
The Liquid State
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!

41
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.

42
The Liquid State
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!

43
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 2O( ) at 100.0o C -2260 J
1.00 g H 2O(g) at 100.0o C

44
 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.
DHvap has units of J/mol.
Molar heat of condensation
• The reverse of molar heat of vaporization is the
heat of condensation.
40.7 kJ
o
1.00 mol H 2O(  ) at 100.0 C - 40.7 kJ
1.00 mol H 2O(g) at 100.0o C

45
The Liquid State

46
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!

47
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!

48
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
T’s

P2 H vap 1 1
ln
P1 R T1 T2
49
The Liquid State

• In Denver 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
50
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 51
The Liquid State
• Boiling Points of Various Kinds of Liquids

52
The Liquid State
• Summary

53
The Liquid State
Example 13-6: Arrange the following substances in
order of increasing boiling points.
C2H6, NH3, Ar, NaCl, AsH3
You do it!

54
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.

55
The Solid State
• Which requires more energy?

NaCl s NaCl 

or
H 2O s H 2O 

 What experimental proof do you have?

56
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
o
1.00 g H 2O(s) at 0 C -334 J
1.00 g H 2O(  ) at 0o C

• Heat of crystallization is the reverse of

the heat of fusion.
57
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
o
1.00 mole H 2O(s) at 0 C -6012 J
1.00 mole H 2O(  ) at 0o C

58
 Heat Transfer Involving Solids
• Here is a summary of the heats of
transformation for water.
40.7 kJ
o
1.00 mol H 2O(  ) at 100.0 C - 40.7 kJ
1.00 mol H 2O(g) at 100.0o C
6012 J
o
1.00 mole H 2O(s) at 0 C -6012 J
1.00 mole H 2O(  ) at 0o C

59
Heat Transfer Involving Solids
Example 13-7: 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

60
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.

sublimation
solid condensation
gas
61
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.

62
Phase Diagrams (P versus T)
• Compare water’s phase diagram to
carbon dioxide’s phase diagram.

63
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.
– 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.
64
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.

65
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.

66
Structure of Crystals
• In a 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.

67
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.

68
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.

69
Structure of Crystals
• A face centered cubic unit cell has 8
corners and 6 faces.
– 1 fcc unit cell contains
• 8(1/8) + 6(1/2) = 4 particles.

70
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 include:
– water, sugar, carbon dioxide, benzene

71
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

72
Bonding in Solids
• Ionic Solids have ions that occupy the
positions in the unit cell.
• Examples of ionic solids include:
– CsCl, NaCl, ZnS

73
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, ……..

74
Bonding in Solids
• Characteristics of Type of Solids

75
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 Å.
Calculate the element’s atomic weight. What is
the atomic radius of this element?

76
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

77
Bonding in Solids
1. Determine the volume of a single unit cell.
0 0
-8
1A 10 cm thus 4.95 A 4.95 10-8 cm
Face centered cubic unit cells are cubic so V 3
3
4.95 10-8 cm 1.21 10-22 cm 3

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

- 22 3 11.35 g - 21 g
1.21 10 cm 1.38 10
cm 3 one unit cell

78
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 22 g
3.44 10
4 atoms unit cell atom

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

3.44 10 22 g 6.022 1023 atoms 207 g/mole

atom mole

79
Bonding in Solids
• To determine an atomic radius requires
some geometry.
• For simple cubic unit cells:
– The edge length = 2 radii

80
 Bonding in Solids
• For face-centered cubic unit cells:
– The face diagonal = 2 x edge length.
– The diagonal length = 4 radii.

81
Bonding in Solids
• For body-centered cubic unit cells:
– The body diagonal = 3 x edge length.
– The diagonal length = 4 radii.

82
Bonding in Solids
• Determine the diagonal length then divide by 4
to get the atomic radius.
-8
diagonal = 2 4.95 10 cm
-8
7.00 10 cm
-8
radius = 7.00 10 cm 4 175
. 10 cm -8

83
Band Theory of Metals
• Sodium’s 3s orbitals can interact to
produce overlapping orbitals

84
Band Theory of Metals
• The 3s orbitals can also overlap with unfilled
3p orbitals

85
Band Theory of Metals
• Insulators have a large gap between the s
and p bands.
– Gap is called the forbidden zone.
• Semiconductors have a small gap between
the bands.

86
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 100.0oC 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%.

87
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?

88
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?

89
13 Liquids and Solids