12-1

Lecture PowerPoint
Chemistry
The Molecular Nature of
Matter and Change
Fifth Edition
Martin S. Silberberg
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
12-2
Chapter 12
Intermolecular Forces:
Liquids, Solids, and Phase Changes
12-3
Intermolecular Forces:
Liquids, Solids, and Phase Changes
12.1 An Overview of Physical States and Phase Changes
12.2 Quantitative Aspects of Phase Changes
12.3 Types of Intermolecular Forces
12.4 Properties of the Liquid State
12.5 The Uniqueness of Water
12.6 The Solid State: Structure, Properties, and Bonding
12.7 Advanced Materials
12-4
Phase Changes
solid liquid gas
melting
freezing
vaporizing
condensing
sublimination
endothermic
exothermic
12-5
Table 12.1
A Macroscopic Comparison of Gases, Liquids, and Solids
State Shape and Volume Compressibility Ability to Flow
Gas Conforms to shape and volume
of container
high high
Liquid Conforms to shape of container;
volume limited by surface
very low moderate
Solid Maintains its own shape and
volume
almost none almost none
12-6
Figure 12.1
Heats of vaporization and fusion for several common substances.
12-7
Figure 12.2 Phase changes and their enthalpy changes.
12-8
Figure 12.3
A cooling curve for the conversion of gaseous water to ice.
12-9
Within a phase, a change in heat is accompanied by a change in
temperature which is associated with a change in average E
k
as
the most probable speed of the molecules changes.
Quantitative Aspects of Phase Changes
During a phase change, a change in heat occurs at a constant
temperature, which is associated with a change in E
p
, as the
average distance between molecules changes.
q = (amount)(molar heat capacity)(AT)
q = (amount)(enthalpy of phase change)
12-10
Sample Problem 12.1 Finding the Heat of a Phase Change Depicted by
Molecular Scenes
SOLUTION:
PROBLEM: These molecular scenes represent a phase change of water. Select
data from the previous text discussion to find the heat (in kJ) lost or
gained when 24.3 g of H
2
O undergoes this change.
PLAN: The scenes show a disorderly, condensed phase (liquid) changing to
separate molecules (gas) and represent the vaporization of water. Three
endothermic stages: (1) heating liquid 85.0 to 100.
o
C, (2) liquid to gas at
100.
o
C, and (3) heating gas 100. to 117
o
C.
mol H
2
O = 24.3 g H
2
O x
mol H
2
O
18.02 g H
2
O
= 1.35 mol H
2
O
q = n x C
water(l)
x AT = (1.35 mol)(75.4 J/mol
o
C)(100. 85.0
o
C) = 1527 J = 1.53 kJ
q = n x C
water(g)
x AT = (1.35 mol)(33.1 J/mol
o
C)(117 100.
o
C) = 759.6 J = 0.760 kJ
q = n(AH
o
vap
) = (1.35 mol)(40.7 kJ/mol) = 54.9 kJ
q
total
= 1.53 + 54.9 + 0.760 kJ = 57.2 kJ
12-11
Figure 12.4 Liquid-gas equilibrium.
12-12
Figure 12.5
The effect of temperature on the distribution of
molecular speed in a liquid.
12-13
ATTRACTIVE FORCES
electrostatic in nature
Intramolecular forces bonding forces
These forces exist within each molecule.
They influence the chemical properties of the substance.
Intermolecular forces nonbonding forces
These forces exist between molecules.
They influence the physical properties of the substance.
12-14
Figure 12.6 Figure 12.7
Vapor pressure as a function
of temperature and
intermolecular forces.
A linear plot of the
relationship between vapor
pressure and temperature

.
12-15
The Clausius-Clapeyron Equation
C
T R
H
P +
|
.
|

\
|
A 1 -
= ln
vap
|
|
.
|

\
|

A
1 2
vap
1
2
1 1 -
= ln
T T R
H
P
P
12-16
Sample Problem 12.2 Using the Clausius-Clapeyron Equation
SOLUTION:
PROBLEM: The vapor pressure of ethanol is 115 torr at 34.9
o
C. If AH
vap
of
ethanol is 40.5 kJ/mol, calculate the temperature (in
o
C) when
the vapor pressure is 760 torr.
PLAN: We are given 4 of the 5 variables in the Clausius-Clapeyron
equation. Substitute and solve for T
2
.
|
|
.
|

\
|

A
1 2
vap
1
2
1 1 -
= ln
T T R
H
P
P
34.9
o
C + 273.15 = 308.0 K
ln
760 torr
115 torr
=
- 40.5 x10
3
J/mol
8.314 J/molK
1
T
2

1
308.0 K

T
2
= 350. K 273.15 = 77C
12-17
Figure 12.8 Iodine subliming.
iodine solid
iodine vapor
iodine solid
test tube with ice
12-18
Figure 12.9
Phase diagrams for CO
2
and H
2
O.
CO
2

H
2
O
12-19
bond length
covalent radius
van der Waals distance
van der Waals radius
Figure 12.10
Covalent and van der Waals radii.
12-20
Figure 12.11
Periodic trends in covalent and van der Waals radii (in pm).
12-21
12-22
Figure 12.12 Polar molecules and dipole-dipole forces.
solid
liquid
12-23
Figure 12.13 Dipole moment and boiling point.
12-24
(Intramolecular) Forces
12-25
THE HYDROGEN BOND
a dipole-dipole intermolecular force
The elements which are so electronegative are N, O, and F.
A hydrogen bond may occur when an H atom in a molecule,
bound to small highly electronegative atom with lone pairs of
electrons, is attracted to the lone pairs in another molecule.
..
F
..
.
.

..
H O
..
N
.
.

F H
.
.

..
..
O
..
.
.

..
N H
hydrogen bond
donor
hydrogen bond
acceptor
hydrogen bond
acceptor
hydrogen bond
donor
hydrogen bond
donor
hydrogen bond
acceptor
12-26
Figure 12.14 Hydrogen bonding and boiling point.
12-27
Sample Problem 12.3 Drawing Hydrogen Bonds Between Molecules
of a Substance
SOLUTION:
PROBLEM: Which of the following substances exhibits H bonding? For
those that do, draw two molecules of the substance with the H
bond(s) between them.
C
2
H
6
(a) CH
3
OH (b)
CH
3
C NH
2
O
(c)
PLAN: Find molecules in which H is bonded to N, O, or F. Draw H
bonds in the format B: HA.
(a) C
2
H
6
has no H bonding sites.
(c)
(b)
C O H
H
H
H
C O H
H
H
H
CH
3
C N
O
H
H
CH
3
C N
O
H
H
C H
3
C
N
O
H
H
C H
3
O
N
O
H
H
12-28
Polarizability and Charged-Induced Dipole Forces
distortion of an electron cloud
Polarizability increases down a group
size increases and the larger electron clouds are further
from the nucleus
Polarizability decreases left to right across a period
increasing Z
eff
shrinks atomic size and holds the electrons
more tightly
Cations are less polarizable than their parent atom
because they are smaller.
Anions are more polarizable than their parent atom
because they are larger.
12-29
Figure 12.15 Dispersion forces among nonpolar particles.
separated
Ar
molecules
instantaneous
dipoles
12-30
Figure 12.16
Molar mass and boiling point.
12-31
Figure 12.17 Molecular shape and boiling point.
more points for
dispersion
forces to act
fewer points for
dispersion
forces to act
12-32
Figure 12.18
Summary diagram for analyzing the intermolecular forces in a sample.
INTERACTING PARTICLES
(atoms, molecules, ions)
ions only
IONIC BONDING
(Section 9.2)
ion + polar molecule
ION-DIPOLE FORCES
ions present ions not present
polar molecules only
DIPOLE-DIPOLE
FORCES
HYDROGEN
BONDING
polar + nonpolar
molecules
DIPOLE-
INDUCED DIPOLE
FORCES
nonpolar
molecules only
DISPERSION
FORCES only
DISPERSION FORCES ALSO PRESENT
H bonded to
N, O, or F
12-33
Sample Problem 12.4 Predicting the Types of Intermolecular Force
PROBLEM: For each pair of substances, identify the dominant
intermolecular force(s) in each substance, and select the
substance with the higher boiling point.
(a) MgCl
2
or PCl
3

(b) CH
3
NH
2
or CH
3
F
(c) CH
3
OH or CH
3
CH
2
OH
(d) Hexane (CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
)
or 2,2-dimethylbutane
CH
3
CCH
2
CH
3
CH
3
CH
3
PLAN: Use the formula, structure, Table 12.2 (button) and Figure 12.18.
Bonding forces are stronger than nonbonding (intermolecular) forces.
Hydrogen bonding is a strong type of dipole-dipole force.
Dispersion forces are decisive when the difference is molar mass or
molecular shape.
12-34
SOLUTION:
Sample Problem 12.4 Predicting the Types of Intermolecular Force
(a) Mg
2+
and Cl

are held together by ionic bonds while PCl

3
is covalently
bonded and the molecules are held together by dipole-dipole interactions. Ionic
bonds are stronger than dipole interactions and so MgCl
2
has the higher boiling
point.
(b) CH
3
NH
2
and CH
3
F are both covalent compounds and have bonds which are
polar. The dipole in CH
3
NH
2
can H bond while that in CH
3
F cannot. Therefore
CH
3
NH
2
has the stronger interactions and the higher boiling point.
(c) Both CH
3
OH and CH
3
CH
2
OH can H bond but CH
3
CH
2
OH has more CH for
more dispersion force interaction. Therefore CH
3
CH
2
OH has the higher boiling
point.
(d) Hexane and 2,2-dimethylbutane are both nonpolar with only dispersion
forces to hold the molecules together. Hexane has the larger surface area,
thereby the greater dispersion forces and the higher boiling point.
12-35
Figure 12.19 The molecular basis of surface tension.
hydrogen bonding
occurs in three
dimensions
hydrogen bonding
occurs across the surface
and below the surface
the net vector
for attractive
forces is downward
12-36
Table 12.3 Surface Tension and Forces Between Particles
Substance Formula
Surface Tension
(J/m
2
) at 20
0
C Major Force(s)
diethyl ether
ethanol
butanol
water
mercury
dipole-dipole; dispersion
H bonding
H bonding; dispersion
H bonding
metallic bonding
1.7x10
-2

2.3x10
-2

2.5x10
-2

7.3x10
-2

48x10
-2

CH
3
CH
2
OCH
2
CH
3

CH
3
CH
2
OH
CH
3
CH
2
CH
2
CH
2
OH
H
2
O
Hg
12-37
Surface Tension in liquid Mercury (Hg)
12-38
Figure 12.20 Shape of water or mercury meniscus in glass.
12-39
Table 12.4 Viscosity of Water at Several Temperatures
Temperature (
o
C)
Viscosity
(Ns/m
2
)*
20
40
60
80
1.00x10
3

0.65x10
3

0.47x10
3

0.35x10
3

*The units of viscosity are Newton-seconds per square meter.
viscosityresistance to flow
12-40
Figure 12.21 The H-bonding ability of the water molecule
(forms a tetrahedral shape).
hydrogen bond donor
hydrogen bond acceptor
12-41
The Unique Nature of Water
great solvent properties due to polarity and
hydrogen bonding ability

exceptional high specific heat capacity

high surface tension and capillarity

density differences of liquid and solid states
12-42
Figure 12.22 The hexagonal structure of ice.
12-43
Figure 12.23 The expansion and contraction of water.
12-44
Figure 12.24
The macroscopic properties of water and their atomic
and molecular roots.
12-45
Figure 12.25 The striking beauty of crystalline solids.
12-46
portion of 3-D lattice
Figure 12.26 The crystal lattice and the unit cell.
lattice point
unit
cell
unit
cell
12-47
Figure 12.27 (1 of 3) The three cubic unit cells.
Simple Cubic
Coordination number = 6
Atoms/unit cell = 1/8 x 8 = 1
1/8 atom at
8 corners
12-48
Figure 12.27 (2 of 3) The three cubic unit cells.
Body-centered
Cubic
Coordination number = 8
1/8 atom at
8 corners
1 atom at
center
Atoms/unit cell = (1/8 x 8) + 1 = 2
12-49
Figure 12.27 (3 of 3) The three cubic unit cells.
Face-centered
Cubic
Coordination number = 12
Atoms/unit cell = (1/8 x 8) + (1/2 x 6) = 4
1/8 atom at
8 corners
1/2 atom at
6 faces
12-50
Figure 12.28 Packing identical spheres.
simple cubic
(52% packing efficiency)
body-centered cubic
(68% packing efficiency)
12-51
hexagonal
unit cell
Figure 12.28 (continued)
closest packing of first
and second layers
layer a
layer a
layer b
layer c
hexagonal
closest
packing
cubic closest
packing
abab (74%)
abcabc (74%)
expanded
side views
face-centered
unit cell
12-52
Figure 12.29 Edge length and atomic (ionic) radius in
the three cubic unit cells.
12-53
Sample Problem 12.5 Determining Atomic Radius from Crystal Structure
PROBLEM: The crystal structure of copper adopts cubic closest packing
and the edge length of the unit cell is 361.5 pm What is the
atomic radius of copper?
PLAN: Copper has a face-centered cubic unit cell with edge length A = 361.5
pm see Figure 12.29C. The diagonal of the cells face is 4r and the
Pythagorean theorem can be used to solve for r.
SOLUTION: 2 2
= C B A +
pm pm A 2 . 511 ) 5 . 361 ( 2 2 C
2 2
= = =
C = 4r r = C/4 = 511.2 pm/4 = 127.8 pm
12-54
Figure 12.30 Figure 12.31
Cubic closest packing for
frozen argon.
Cubic closest packing
of frozen methane.
12-55
Table 12.5 Characteristics of the Major Types of Crystalline Solids
Particle(s)
Interparticle
Forces
Physical
Properties
Examples (mp,
o
C)
Atomic
Molecular
Ionic
Metallic
Network
Covalent
Group 8A(18)
[Ne(-249) to Rn(-71)]
Molecules
Positive &
negative ions
Atoms
Atoms
Soft, very low mp, poor
thermal & electrical
conductors
Dispersion Atoms
Dispersion,
dipole-dipole,
H bonds
Fairly soft, low to moderate
mp, poor thermal &
electrical conductors
Nonpolar: O
2
[-219],
C
4
H
10
[-138], Cl
2
[-101],
C
6
H
14
[-95], P
4
[44.1]
Polar: SO
2
[-73],CHCl
3
[-64], HNO
3
[-42], H
2
O
[0.0], CH
3
COOH[17]
Covalent bond
Metallic bond
Ion-ion
attraction
Very hard, very high mp,
usually poor thermal and
electrical conductors
Soft to hard, low to very
high mp, excellent thermal
and electrical conductors,
malleable and ductile
Hard & brittle, high mp,
good thermal & electrical
conductors when molten
NaCl [801]
CaF
2
[1423]
MgO [2852]
Na [97.8]
Zn [420]
Fe [1535]
SiO
2
(quartz) [1610]
C (diamond) [~4000]
Type
12-56
Figure 12.32 The sodium chloride structure.
expanded view
space-filling
12-57
Figure 12.33 The zinc blende structure.
zinc sulfide (ZnS)
12-58
Figure 12.34 The fluorite (CaF
2
) structure.
12-59
Figure 12.35 Crystal structures of metals.
cubic closest packing hexagonal closest packing
12-60
12-61
Figure 12.36 Crystalline and amorphous silicon dioxide.
12-62
Figure 12.37 The band of molecular orbitals in lithium metal.
12-63
Figure 12.38
Electrical conductivity in a conductor, semiconductor, and insulator.
conductor semiconductor insulator
12-64
Figure 12.39
The levitating power of a superconducting oxide.
rare earth magnet
superconducting ceramic disk
liquid nitrogen
12-65
Figure 12.40
Crystal structures and band
representations of doped
semiconductors.
12-66
Forward bias
Reverse bias
p-n junction
Figure 12.41 The p-n junction.
12-67
Figure 12.42
Structures of two typical molecules that
form liquid crystal phases.
12-68
Figure 12.43 The three common types of liquid crystal phases.
nematic smectic cholesteric
12-69
Figure 12.45
Schematic of a liquid
crystal display (LCD).
12-70
Figure 12.44 Liquid crystals in biological systems.
nematic arrays of
tobacco mosaic virus particles
actin and myosin protein
filaments in voluntary muscle cells
12-71
Table 12.7 Some Uses of Modern Ceramics and Ceramic Mixtures
Ceramic Applications
SiC, Si
3
N
4
, TiB
2
, Al
2
O
3
Whiskers (fibers) to strengthen Al and other ceramics
Si
3
N
4
Car engine parts; turbine rotors for turbo cars;
electronic sensor units
Si
3
N
4
, BN, Al
2
O
3
Supports or layering materials (as insulators) in
electronic microchips
SiC, Si
3
N
4
, TiB
2
, ZrO
2
,
Al
2
O
3
, BN
ZrO
2
, Al
2
O
3

Cutting tools, edge sharpeners (as coatings and
whole devices), scissors, surgical tools, industrial
diamond
BN, SiC Armor-plating reinforcement fibers (as in Kevlar
composites)
Surgical implants (hip and knee joints)
12-72
Figure 12.46
Expanded view of the atom arrangements in some
modern ceramic materials.
SiC
silicon
carbide
BN
cubic boron
nitride
(borazon)
YBa
2
Cu
3
O
7

high
temperature
superconductor
12-73
Table 12.8 Molar Masses of Some Common Polymers
Name M
polymer
(g/mol) n Uses
Acrylates 2 x10
5
2 x10
3
Rugs, carpets
Polyamide (nylons) 1.5 x10
4
1.2 x10
2
Tires, fishing line
Polycarbonate 1 x10
5
4 x10
2
Compact discs
Polyethylene 3 x10
5
1 x10
4
Grocery bags
Polyethylene (ultra-
high molecular weight)
5 x10
6
2 x10
5
Hip joints
Poly(ethylene
terephthalate)
2 x10
4
1 x10
2
Soda bottles
Polystyrene 3 x10
5
3 x10
3
Packing; coffee cups
Poly(vinyl chloride) 1 x10
5

1.5 x10
3

Plumbing
12-74
Figure 12.47
The random-coil shape of a polymer chain.
12-75
Figure 12.48
The semicrystallinity of a polymer chain.
12-76
Figure 12.49
The viscosity of a polymer in solution.
12-77
Table 12.9 Some Common Elastomers
Name T
g
(
o
C)*
*Glass transition temperature
Uses
Poly (dimethyl siloxane) -123
-106
-65
-43
Polybutadiene
Polyisoprene
Polychloroprene (neoprene)
Breast implants
Rubber bands
Surgical gloves
Footwear, medical tubing
12-78
Figure 12.50
The colors of quantum dots.
12-79
Figure 12.51 The magnetic behavior of a ferrofluid.
12-80
Figure 12.52 Driving a nanocar.
12-81
Figure B12.1
Diffraction of x-rays by crystal planes.
Tools of the Laboratory
12-82
Figure B12.2
Formation of an x-ray diffraction pattern of the
protein hemoglobin.
Tools of the Laboratory
12-83
Tools of the Laboratory
Figure B12.3
Scanning tunneling micrographs.
Gold surface
Cesium atoms on gallium
arsenide surface