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Chapter 12 Power Point 5e HP
Chapter 12 Power Point 5e HP
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