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Chapter 12
Intermolecular Forces:

Liquids, Solids, and Phase Changes

12-1

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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

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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.

12-3

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Phase Changes

exothermic

sublimination
vaporizing

melting

solid

liquid

freezing
endothermic

12-4

gas

condensing

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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

12-5

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Figure12.1

Heats of vaporization and fusion for several common substances.

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Figure12.2

12-7

Phase changes and their enthalpy changes.

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Figure12.3

A cooling curve for the conversion of gaseous water to ice.

12-8

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Quantitative Aspects of Phase Changes

Within a phase, a change in heat is accompanied by a change in


temperature which is associated with a change in average Ek as the
most probable speed of the molecules changes.

q = (amount)(molar heat capacity)(T)


During a phase change, a change in heat occurs at a constant
temperature, which is associated with a change in Ep, as the
average distance between molecules changes.

q = (amount)(enthalpy of phase change)

12-9

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Figure12.4

12-10

Liquid-gas equilibrium.

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Figure12.5

12-11

The effect of temperature on the distribution of


molecular speed in a liquid.

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Figure12.6

Vapor pressure as a function of


temperature and intermolecular forces.

12-12

Figure12.7

A linear plot of vapor


pressure- temperature
relationship.

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The Clausius-Clapeyron Equation

ln P =

-Hvap 1
C
R T

P2
-Hvap 1 1
ln
=

R T2 T
P1
1

12-13

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SAMPLE PROBLEM 12.1

The vapor pressure of ethanol is 115 torr at 34.90C. If Hvap of


ethanol is 40.5 kJ/mol, calculate the temperature (in 0C) when
the vapor pressure is 760 torr.

PROBLEM:

PLAN:

Using the Clausius-Clapeyron Equation

We are given 4 of the 5 variables in the Clausius-Clapeyron


equation. Substitute and solve for T2.

SOLUTION:

P2
-Hvap 1 1
ln
=

P1
R T2 T1

760 torr
ln
115 torr

-40.5 x103 J/mol


8.314 J/mol*K

T2 = 350K = 770C

12-14

34.90C = 308.0K
1
1
T2
308K

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Figure12.8

Phase diagrams for CO2 and H2O.

CO2

12-15

H 2O

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Figure12.9

Covalent and van der Waals radii.

van der Waals distance

bond length
covalent radius

van der Waals radius

12-16

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Figure12.10

Periodic trends in covalent and van der Waals radii (in pm).

12-17

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12-18

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12-19

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Figure12.11

Polar molecules and dipole-dipole forces.


solid

liquid

12-20

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THE HYDROGEN BOND


a dipole-dipole intermolecular force
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.
The elements which are so electronegative are N, O, and F.

hydrogen bond
acceptor

..
O

..
O
..

..

..

..
F
..

hydrogen bond
donor

hydrogen bond
acceptor

hydrogen bond
acceptor

12-21

..

..

..
F
..

hydrogen bond
donor

..
N
hydrogen bond
donor

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Figure12.12

12-22

Dipole moment and boiling point.

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SAMPLE PROBLEM 12.2


PROBLEM:

Which of the following substances exhibits H bonding? For


those that do, draw two molecules of the substance with the H
bonds between them.
O
(a)

PLAN:

12-23

C2 H6

(b) CH3OH

(c)

CH3C NH2

Find molecules in which H is bonded to N, O or F. Draw H


bonds in the format -B:
H-A-.

SOLUTION:
(b)

Drawing Hydrogen Bonds Between Molecules


of a Substance

(a) C2H6 has no H bonding sites.

H
H C O H
H
H
H O C H
H

(c)

H
O

H N CH3C CH C
3
N H
O
CH3C N H

H N
CH3C

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Figure12.13

12-24

Hydrogen bonding and boiling point.

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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 Zeff 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.

12-25

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Figure12.14

Dispersion forces among nonpolar molecules.

separated
Cl2
molecules

12-26

instantaneous
dipoles

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Figure12.15

Molar mass and boiling point.

12-27

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Figure12.16 Molecular shape and boiling point.

fewer points for


dispersion
forces to act
more points for
dispersion
forces to act

12-28

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SAMPLE PROBLEM 12.3


PROBLEM:

Predicting the Type and Relative Strength of


Intermolecular Forces

For each pair of substances, identify the dominant


intermolecular forces in each substance, and select the
substance with the higher boiling point.
(a) MgCl2 or PCl3
(b) CH3NH2 or CH3F
(c) CH3OH or CH3CH2OH

PLAN:

CH3

(d) Hexane (CH3CH2CH2CH2CH2CH3)


CH3CCH2CH3
or 2,2-dimethylbutane
CH3
Use the formula, structure and Table 2.2 (button).

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.

12-29

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SAMPLE PROBLEM 12.3


continued

Predicting the Type and Relative Strength of


Intermolecular Forces

SOLUTION:
(a) Mg2+ and Cl- are held together by ionic bonds while PCl3 is covalently bonded
and the molecules are held together by dipole-dipole interactions. Ionic bonds
are stronger than dipole interactions and so MgCl2 has the higher boiling point.
(b) CH3NH2 and CH3F are both covalent compounds and have bonds which are
polar. The dipole in CH3NH2 can H bond while that in CH3F cannot. Therefore
CH3NH2 has the stronger interactions and the higher boiling point.
(c) Both CH3OH and CH3CH2OH can H bond but CH3CH2OH has more CH for
more dispersion force interaction. Therefore CH3CH2OH 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.

12-30

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Figure 12.17

Summary diagram for analyzing the intermolecular forces in a sample.


INTERACTING PARTICLES
(atoms, molecules, ions)
ions present
ions only
IONIC BONDING
(Section 9.2)

ions not present


polar molecules only
DIPOLE-DIPOLE
FORCES

ion + polar molecule


ION-DIPOLE FORCES

H bonded to
N, O, or F

HYDROGEN
BONDING

nonpolar
molecules only
DISPERSION
FORCES only
polar + nonpolar
molecules
DIPOLEINDUCED DIPOLE
FORCES

DISPERSION FORCES ALSO PRESENT

12-31

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Figure12.18

The molecular basis of surface tension.

hydrogen bonding
occurs across the surface
and below the surface

hydrogen bonding
occurs in three
dimensions

12-32

the net vector


for attractive
forces is downward

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Table 12.3

Surface Tension and Forces Between Particles


Surface Tension

Substance

Formula

(J/m2) at 200C

diethyl ether

CH3CH2OCH2CH3

1.7x10-2

dipole-dipole; dispersion

ethanol

CH3CH2OH

2.3x10-2

H bonding

butanol

CH3CH2CH2CH2OH

2.5x10-2

H bonding; dispersion

water

H2 O

7.3x10-2

H bonding

mercury

Hg

48x10-2

metallic bonding

12-33

Major Force(s)

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Figure12.19

Shape of water or mercury meniscus in glass.

capillarity

stronger
cohesive forces

adhesive forces

H 2O

12-34

Hg

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Table 12.4 Viscosity of Water at Several Temperatures


viscosity - resistance to flow
Temperature(0C)

Viscosity
(N*s/m2)*

20

1.00x10-3

40

0.65x10-3

60

0.47x10-3

80

0.35x10-3

*The units of viscosity are newton-seconds per square meter.

12-35

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Figure12.20

The H-bonding ability of the water molecule.

hydrogen bond donor

hydrogen bond acceptor

12-36

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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

12-37

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Figure12.21

12-38

The hexagonal structure of ice.

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Figure12.22

12-39

The striking beauty of crystalline solids.

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Figure12.23

The crystal lattice and the unit cell.

lattice point

unit
cell

unit
cell

portion of a 3-D lattice

12-40

portion of a 2-D lattice

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Figure12.24(1of3)

The three cubic unit cells.

Simple Cubic

1/8 atom at
8 corners

Atoms/unit cell = 1/8 * 8 = 1


coordination number = 6

12-41

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Figure12.24(2of3)

The three cubic unit cells.

Body-centered
Cubic
1/8 atom at
8 corners
1 atom at
center
Atoms/unit cell = (1/8*8) + 1 = 2
coordination number = 8

12-42

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Figure12.24(3of3)

The three cubic unit cells.

Face-centered
Cubic
1/8 atom at
8 corners
1/2 atom at
6 faces

coordination number = 12

12-43

Atoms/unit cell = (1/8*8)+(1/2*6) = 4

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Figure12.26

Packing of spheres.

simple cubic
(52% packing efficiency)
body-centered cubic
(68% packing efficiency)

12-44

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Figure12.26(continued)

layer a
layer b

hexagonal
closest
packing

layer a

cubicclosest
packing

layer c

closest packing of first


and second layers
abab (74%)

12-45

hexagonal
unit cell

expanded
side views

abcabc (74%)

face-centered
unit cell

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12-46

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12-47

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12-48

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SAMPLE PROBLEM 12.4 Determining Atomic Radius from Crystal Structure


PROBLEM:

PLAN:

Barium is the largest nonradioactive alkaline earth metal. It has


a body-centered cubic unit cell and a density of 3.62 g/cm3.
What is the atomic radius of barium?
(Volume of a sphere: V = 4/3r3)

We can use the density and molar mass to find the volume of 1 mol of
Ba. Since 68%(for a body-centered cubic) of the unit cell contains
atomic material, dividing by Avogadros number will give us the volume
of one atom of Ba. Using the volume of a sphere, the radius can be
calculated.

density of Ba (g/cm3)

radius of a Ba atom

reciprocal divided by M
volume of 1 mol Ba metal

V = 4/3r3
volume of 1 Ba atom

multiply by packing efficiency


volume of 1 mol Ba atoms

12-49

divide by Avogadros number

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SAMPLE PROBLEM 12.4 Determining Atomic Radius from Crystal Structure


continued
SOLUTION:
Volume of Ba metal =
37.9 cm3/mol Ba
26 cm3
mol Ba atoms

3.62 g
x 0.68

137.3 g Ba
mol Ba

= 37.9 cm3/mol Ba

= 26 cm3/mol Ba atoms

mol Ba atoms
6.022x1023 atoms

= 4.3x10-23 cm3/atom

-23
3
3V
3(4.3x10
cm
) = 2.2 x 10-8cm
r =3
3
4
4 x 3.14

r = 3V/4
3

12-50

1 cm3

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12-51

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Figure12.27

Diffraction of x-rays by crystal planes.

12-52

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Figure12.28

Formation of an x-ray diffraction pattern of the


protein hemoglobin.

12-53

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Figure12.29

Cubic closest packing for


frozen argon.

12-54

Figure12.30

Cubic closest packing


of frozen methane.

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Table 12.5
Particles
Atomic

Atoms

Molecular Molecules

Characteristics of the Major Types of Crystalline Solids


Interparticle
Forces
Dispersion

Dispersion,
dipole-dipole,
H bonds

Physical
Behavior
Soft, very low mp, poor
thermal & electrical
conductors
Fairly soft, low to moderate
mp, poor thermal &
electrical conductors

Ionic

Positive & Ion-ion


negative ions attraction

Hard & brittle, high mp,


good thermal & electrical
conductors when molten

Metallic

Atoms

Metallic bond

Soft to hard, low to very


high mp, excellent thermal
and electrical conductors,
malleable and ductile

Network

Atoms

Covalent bond Very hard, very high mp,


usually poor thermal and
electrical conductors

12-55

Examples (mp,0C)
Group 8A(18)
[Ne-249 to Rn-71]
Nonpolar - O2[-219],
C4H10[-138], Cl2
[-101], C6H14[-95]
Polar - SO2[-73],
CHCl3[-64], HNO3[42], H2O[0.0]
NaCl [801]
CaF2 [1423]
MgO [2852]
Na [97.8]
Zn [420]
Fe [1535]

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Figure12.31

The sodium chloride structure.

expanded view

12-56

space-filling

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Figure12.32

cubic closest packing

12-57

Crystal structures of metals.

hexagonal closest packing

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12-58

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Figure12.33 Crystalline and amorphous silicon dioxide.

12-59

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Figure12.35

12-60

The band of molecular orbitals in lithium metal.

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Figure12.36

Electrical conductivity in a conductor, semiconductor, and insulator.

conductor

insulator

semiconductor

12-61

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Figure 12.37

The levitating power of a superconducting oxide.

rare earth magnet

superconducting ceramic disk


liquid nitrogen

12-62