Summerpp 13

Copyright 2000 by Harcourt, Inc. All rights reserved.
1
CHAPTER 13
Liquids and Solids
Copyright 2000 by Harcourt, Inc
Requests for permission to make copies of any part of the
work should be mailed to:Permissions Department,
Harcourt Inc, 6277 Sea Harbor Drive,
Orlando, Florida 32887-6777
2
Chapter Goals
Kinetic-Molecular Description of Liquids & Solids
Intermolecular Attractions & Phase Changes
Properties of Liquids
Viscosity, Surface Tension, Capillary Action
Evaporation, Vapor Pressure,
Boiling Points & Distillation, Heat transfer
Properties of Solids
Melting Points, Heat Transfer
Sublimation & Vapor Pressure
Phase Diagrams, Amorphous & Crystalline Solids
Crystal Structures, Bonding in Solids, Band Theory
Synthesis Question
3
Kinetic-Molecular Description of
Liquids & Solids
Solids & liquids are condensed states
atoms, ions, molecules are close to one another
highly incompressible
Liquids & gases are fluids
easily flow
I ntermolecular attractions in liquids &
solids are strong
4
Liquids & Solids
heat
gas
liquid solid
cool cool
heat
5
Liquids & Solids
strengths of interactions among particles &
degree of ordering of particles
Gases< Liquids < Solids
Miscible liquids diffuse into one another
they are soluble in each other
for example:
water/alcohol
gasoline/motor oil
6
Liquids & Solids
I mmiscible liquids do not diffuse into each
other
they are insoluble in each other
for example:
water/oil
water/cyclohexane
7
Intermolecular Attractions and
Phase Changes
Ion-ion interactions
force of attraction between two oppositely
charged ions is determined by Coulombs law

( )( )
F
q q
d
+ -
2

8
Phase Changes
energy of attraction between two ions is given
by:
( )( )
( )( )
E = F d =
q q
d
d
=
q q
d
+ -
2
+ -

9
Phase Changes
Coulombs law & the attraction energy
determine:
melting & boiling points of ionic compounds
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, CaF
2
you do it
What important points must you consider?
11
Phase Changes
Dipole-dipole interactions
consider NH
3
a very polar molecule
12
Phase Changes
Hydrogen bonding
consider H
2
O
13
Phase Changes
14
Phase Changes
London Forces
very weak
only attractive force in nonpolar molecules
consider Ar
isolated atom
15
Phase Changes
Group of Ar molecules
temporary dipole induces other dipoles
16
The Liquid State
Viscosity - resistance to flow
water vs. molasses
you buy oil for your car based on this property
Ostwald viscometer used to measure this
property
17
The Liquid State
Surface Tension - measure of the unequal
attractions that occur at the surface of a
liquid
molecules at surface are attracted unevenly
water bugs
floating razor blades
18
The Liquid State
Capillary Action - ability of a liquid to rise
(or fall) in a glass tube
cohesive forces - hold liquids together
adhesive forces - forces between a liquid
and another surface
capillary rise implies adhesive > cohesive
capillary fall implies cohesive > adhesive
19
The Liquid State
Capillary Action
water mercury

20
The Liquid State

Evaporation
process in which molecules escape from the surface
of a liquid
T dependent
21
The Liquid State
Evaporation
22
The Liquid State
Vapor Pressure
pressure exerted by a liquids vapor on its surface
at equilibrium
Vap. Press. (torr) for 3 Liquids Norm. B.P.
0
o
C 20
o
C 30
o
C
diethyl ether 185 442 647 36
o
C
ethanol 12 44 74 78
o
C
water 5 18 32 100
o
C
23
The Liquid State
Vapor Pressure
24
The Liquid State
Boiling Points & Distillation
boiling point is temperature at which the
liquids vapor pressure is equal to applied
pressure
normal boiling point is boiling point @ 1 atm
distillation is a method we use to separate
mixtures of liquids based on their
differences in boiling points
25
The Liquid State
Distillation
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.
26
The Liquid State
Heat Transfer Involving Liquids
from Chapter 1

Example 13-2: How much heat is released by 200
g of H
2
O as it cools from 85.0
o
C to 40.0
o
C?
The specific heat of water is 4.184 J/g
o
C.
you do it
q = m C T A
28
The Liquid State
molar heat capacity - amount of heat required
to raise the T of one mole of a substance one
degree C
Example 13-3: The molar heat capacity of
ethyl alcohol, C
2
H
5
OH, is 113 J/mol
o
C. How
much heat is required to raise the T of 125 g
of ethyl alcohol from 20.0
o
C to 30.0
o
C?
1 mol C
2
H
5
OH = 46.0 g
you do it
30
The Liquid State
energy associated with changes of state
heat of vaporization
amount of heat required to change 1 g of a
liquid substance to a gas at constant T
units of J/g
heat of condensation
reverse of heat of vaporization
1.00 g HO @ 100 C 1.00 g HO @ 100 C
2 (l)
o
-2260 J
+2260 J
2 (g)
o

31
The Liquid State
molar heat of vaporization or AH
vap

amount of heat required to change 1 mol of a
liquid to a gas at constant T
units of J/mol
molar heat of condensation
reverse of molar heat of vaporization
1.00 mol HO @ 100 C 1.00 mol HO @ 100 C
2 (l)
o
-40.7 kJ
+40.7 kJ
2 (g)
o

32
The Liquid State
33
The Liquid State
Example 13-4: How many joules of energy
must be absorbed by 500 g of H
2
O at 50.0
o
C
to convert it to steam at 120
o
C? 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
o
C and 36.4 J/mol
o
C, respectively.
34
The Liquid State
( )
( )
? .
.
. . .
mol = 500 g H O
1 mol H O
g H O
mol H O
1st let's calculate the heat required to warm water from 50 to 100 C
? J = 27.8 mol
J
mol C
C J
2
2
2
2
o
o
o
=
|
\
|
.
|
=
18
278
753
1000 500 105 10
5
35
The Liquid State
2nd lets calculate the energy required to boil the water

( )
? J = 27.8 mol
J
mol
J
407 10
1131 10
3
5
.
.
|
\
|
.
|
=
36
The Liquid State
2nd lets calculate the energy required to boil the water

3rd lets calculate the heat required to heat steam from
100 to 120
o
C
( )
? J = 27.8 mol
J
mol
J
407 10
1131 10
3
5
.
.
|
\
|
.
|
=
( )
( )
? J = 27.8 mol
J
mol C
120.0 -100.0 C J
o
o
36 4
0 20 10
5
.
.
|
\
|
.
|
=
37
The Liquid State
total amount of energy for this process is the sum of
the 3 pieces we have calculated
( ) ( ) ( )
105 10 1131 10 0 20 10
1256 10
5 5 5
5
. . .
.
+ + =

J J J
J or 1.26 10 kJ
3
38
The Liquid State
Example 13-5: If 45.0 g of steam at 140
o
C
is slowly bubbled into 450 g of water at
50.0
o
C in an insulated container, can all the
steam be condensed?
you do it
42
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 AH
vap
if we know pressure at 2 Ts
ln
P
P
H
R T T
2
1
vap
1 2
|
\
|
.
|
=
|
\
|
.
|
A
1 1
43
The Liquid State
In Denver the normal atmospheric pressure is 630
torr. At what temperature does water boil in
Denver?
( )
ln
P
P
H
R T T
torr
760 torr

8.314 K T
T
2
1
vap
1 2
J
mol
J
K mol 2
2
|
\
|
.
|
=
|
\
|
.
|
|
\
|
.
|
=

|
\
|
.
|
=
|
\
|
.
|
A
1 1
630 40 7 10 1
373
1
0829 4895 0 002681
1
3
ln
.
ln . .
44
The Liquid State
=
|
\
|
.
|
=
|
\
|
.
|
=
=
=
0188
4895
0 002681
1
383 10 0 002681
1
383 10 0 002681
1
0 00272
1
368
5
5
.
.
. .
. .
.
T
T
T
T
T K or 95 C
2
2
2
2
2
o
45
The Liquid State
Boiling Points of Various Kinds of Liquids
Gas MW BP(
o
C)
He 4 -269
Ne 20 -246
Ar 40 -186
Kr 84 -153
Xe 131 -107
Rn 222 -62
46
The Liquid State
-300
-250
-200
-150
-100
-50
0
4 20 40 84 131 222
BP
MW
47
The Liquid State
Compound MW(amu) B.P.(
o
C)
CH
4
16 -161
C
2
H
6
30 -88
C
3
H
8
44 -42
n-C
4
H
10
58 -0.6
n-C
5
H
12
72 +36
48
The Liquid State
-200
-150
-100
-50
0
50
16 30 44 58 72
BP
MW
49
The Liquid State
Compound MW(amu) B.P.( C)
HF 20 19.5
HCl 37 -85.0
HBr 81 -67.0
HI 128 -34.0
o
50
The Liquid State
-100
-80
-60
-40
-20
0
20
40
20 37 81 128
BP
MW
HF
HCl
HBr
HI
51
The Liquid State
Compound MW(amu) B.P.( C)
H O 18 100
H S 34 - 61
H Se 81 - 42
H Te 130 - 2
o
2
2
2
2
52
The Liquid State
-80
-60
-40
-20
0
20
40
60
80
100
120
18 34 81 130
BP
MW
H
2
O
H
2
S
H
2
Se
H
2
Te
53
The Liquid State
Example 13-6: Arrange the following
substances in order of increasing boiling
points.
C
2
H
6
, NH
3
, Ar, NaCl, AsH
3

you do it
55
The Solid State
Normal Melting Point
T at which the solid melts (liquid and solid in
equilibrium) at 1 atm of pressure
melting point increases as intermolecular
attractions increase
56
Heat Transfer Involving Solids
heat of fusion
amount of heat required to melt one gram of a
solid at its melting point at constant T

heat of crystallization
reverse of heat of fusion
1.00 g H O (s) @ 0 C 1.00 g H O (l) @ 0 C
2
o
J
2
o

334
57
molar heat of fusion
amount of heat required to melt a mole of a
substance at its melting point
molar heat of crystallization
reverse of molar heat of fusion
AH
fusion
AH
crystallization
1.00 mol H O (s) @ 0 C 1.00 mol H O (l) @ 0 C
2
o J
2
o

6012
58
Summary of heats of transformation of water
1.00 g H O (s) @ 0 C 1.00 g H O (l) @ 0 C
2
o
J
2
o

334
1.00 g HO @ 100 C 1.00 g HO @ 100 C
2 (l)
o
-2260 J
+2260 J
2 (g)
o

59
Example 11-7: Calculate the amount of heat
required to convert 150.0 g of ice at -10.0
o
C
to water at 40.0
o
C.
specific heat of ice is 2.09 J/g
o
C
you do it
61
of Solids
Sublimation
solid transforms directly to vapor
solid CO
2
or dry ice
solid gas
deposition
sublimation

62
Phase Diagrams (P vs T)
convenient way to display all of the different
phases of a substance
phase
diagram for
water
63
Phase Diagrams (P vs T)
phase
diagram
for
carbon
dioxide
64
Amorphous & Crystalline Solids
Amorphous solids do not have a well
ordered structure
paraffin, glasses
Crystalline solids have well defined
structures that consist of extended array of
repeating units
give X-ray difraction patterns
see Bragg equation in book
65
Structure of Crystals
unit cell - smallest repeating unit of a
crystal
bricks are repeating units for buildings
7 basic crystal systems
66
Simple
cubic
67
Simple cubic
each particle at a corner is shared by 8 unit cells
1 unit cell contains 8(1/8) = 1 particle
68
Body centered cubic (bcc)
8 corners + 1 particle in center of cell
1 unit cell contains 8(1/8) + 1 = 2 particles
69
Face
centered
cubic
(fcc)
70
Face centered cubic (fcc)
8 corners + 6 faces
1 unit cell contains 8(1/8) + 6(1/2) = 4 particles
71
Bonding in Solids
Molecular Solids
molecules occupy unit cells
low melting points,volatile & insulators
examples:
water, sugar, carbon dioxide, benzene
72
Bonding in Solids
Covalent Solids
atoms that are covalently bonded to one another
examples:
SiO
2
(sand), diamond, graphite, SiC
73
Bonding in Solids
Ionic Solids
ions occupy the unit cell
examples:
CsCl, NaCl, ZnS
74
Bonding in Solids
Metallic Solids
positively charged nuclei surrounded by a sea
of electrons
positive ions occupy lattice positions
examples:
Na, Li, Au, Ag, ..
75
Bonding in Solids
Variations in Melting Points
Molecular Solids
Compound Melting Point (
o
C)
ice 0
ammonia -77.7
benzene, C
6
H
6
5.5
napthalene, C
10
H
8
80.6
benzoic acid, C
6
H
5
CO
2
H 122.4
76
Bonding in Solids
Covalent Solids
Substance
sand, SiO
2
carborundum, SiC
diamond
graphite
Melting Point (
o
C)
1713
~2700
>3550
3652-3697

77
Bonding in Solids
Ionic Solids
Compound
LiF
LiCl
LiBr
LiI
CaF
2
CaCl
2
CaBr
2
CaI
2
Melting Point (
o
C)
842
614
547
450
1360
772
730
740
78
Bonding in Solids
Metallic Solids
Metal
Na
Pb
Al
Cu
Fe
W
Melting Point (
o
C)
98
328
660
1083
1535
3410
79
Unit Cell Problem
A group IVA element with a density of
11.35 g/cm
3
crystallizes in a face-
centered cubic lattice whose unit cell
edge length is 4.95 A. Calculate the
elements atomic weight. What is the
atomic radius of this element?
80
Unit Cell Problem
fcc has 4 atoms per unit cell
determine the volume of a single unit cell
( )
1
A
= 10 cm 4.95
A
10 cm
fcc has cubic dimensions so V = l
10 cm cm
0
-8
0
-8
3
-8 3
=
=

495
495 121 10
3
22
.
. .
81
Unit Cell Problem
use density to determine the mass of a unit cell
determine the mass of one atom in a unit cell
( )( )
121 10 1135 138 10
138 10
4
344 10
22 21
21
22
. . .
.
.
=
cm g/ cm g/ unit cell
in fcc there are 4 atoms per unit cell
thus the mass of one atom is
g
g/ atom
3 3
82
Unit Cell Problem
determine the mass of 1 mole of these atoms
( )( )
344 10 6022 10 2072
22 23
. . . =
g/ atom atoms / mole g/ mole

Pb has a molar mass of 207.2 g/ mol
83
Unit Cell Problem
determine the radius of a Pb atom requires some
geometry from high school
notice there are 4 radii on the diagonal
84
Unit Cell Problem
determine the diagonal length then divide by 4 to
get atomic radius
( )
diagonal = 2 4.95 10 cm
10 cm
radius =
10 cm
4
10 cm
-8
-8
-8
-8
=
700
700
175
.
.
.
85
Band Theory of Metals
Nas 3s orbitals can interact to produce
overlapping orbitals
86
Can also overlap with unfilled 3p orbitals
87
Insulators have a large gap - forbidden zone
Semiconductors have a small gap
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
0
C 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 CO
2
. How many moles of
carbon dioxide are present in the extractor?
90
Synthesis Question
L 10 7.633
mL) L/1000 )(1 mL/cm )(1 cm 10 (7.633
(2134cm) 06.7cm) (3.1416)(1 h r vessel of Volume
cm 2134 cm/ft) ft)(30.48 (70.0 vessel of Length
cm 106.7 cm/2 213.4 vessel of Radius
cm 213.4 cm/ft) ft)(30.48 (7.0 vessel of Diameter
4
3 3 7
2 2
=
=
= =
= =
= =
= =
t
91
Synthesis Question
( )( )
( )( )
2
K mol
atm L
4
CO of mol 748,000 n
K 373 0.08206
L 10 7.633 atm 300
RT
PV
n
nRT PV
=
= =
=
92
Group Question
How many CO
2
molecules are there in 1.0
cm
3
of the Maxwell House Coffee Company
extractor? How many more CO
2
molecules
are there in a cm
3
of the supercritical fluid
in the Maxwell House extractor than in a
mole of CO
2
at STP?
93
Chapter Goals
Kinetic-Molecular Description of Liquids &
Solids
Intermolecular Attractions & Phase Changes
Properties of Liquids
Viscosity, Surface Tension, Capillary Action
Evaporation, Vapor Pressure,
Boiling Points & Distillation, Heat transfer
Properties of Solids
Melting Points, Heat Transfer
Phase Diagrams, Amorphous & Crystalline Solids
Crystal Structures, Bonding in Solids, Band
Theory
94
End of Chapter 13
Our understanding of
Band Theory was a
major breakthrough
in semiconductor
knowledge.
Why computers
work!

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Copyright 2000 by Harcourt, Inc. All rights reserved.

Copyright 2000 by Harcourt, Inc. All rights reserved.

Copyright 2000 by Harcourt, Inc. All rights reserved.

Copyright 2000 by Harcourt, Inc. All rights reserved.

Copyright 2000 by Harcourt, Inc. All rights reserved.

Copyright 2000 by Harcourt, Inc. All rights reserved.

g/ atom atoms / mole g/ mole

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