1

Chapter 11

Intermolecular Forces,
Liquids, and Solids
2
CONTENTS
11.1 Introduction: A Molecular Comparison

11.2 Types of Intermolecular Forces :
11.2.1 Ion-dipole forces
11.2.2 Dipole-dipole forces
11.2.3 Hydrogen bonding
11.2.4 London dispersion forces
11.2.5 Comparison between forces

11.3 Properties of Liquids
11.3.1 Viscosity and surface tension

3
11.4 Phase Change
11.4.1 Energy changes accompanying phase
change
11.4.2 Cooling curve
11.4.3 Critical temperature and pressure

11.5 Vapour pressure

11.6 Phase diagram
11.6.1 Phase diagram of CO
2
11.6.2 Phase diagram of water
4
11.7 Structure of solids
11.7.1 Crystalline and amorphous solids
11.7.2 Unit cell - PC, FCC & BCC structure

11.8 Bonding in Solids
11.8.1 Molecular solids
11.8.2 Covalent-network solids
11.8.3 Ionic and metallic solids
5
Learning Outcomes
Able to differentiate the 4 main intermolecular
forces (IMF)
Able to relate IMF of a compound to the boiling
point, surface tension, viscosity and vapor
pressure
Able to use phase diagram in problem solving
Able to use knowledge on unit cell of an element
to calculate molar mass, density, radius etc.
6
11.1 Introduction: A Molecular Comparison
Solid - Liquid - Gas
7
Solid - Liquid - Gas
State Gas Liquid Solid
Volume Assumes vol. &
shape of
container
Assumes shape
of the portion of
container but
not volume

Retain its own
shape &
volume
Compressibili
ty
Compressible Virtually
incompressible

Virtually
incompressible
Diffusion Occurs rapidly Occurs slowly

Extremely low
Flow Readily Readily

Does not flow

8
11.2 Intermolecular Forces
The attraction between molecules is an
intermolecular force.
Intermolecular forces are much weaker than
ionic or covalent bonds.
When a substance melts or boils, intermolecular
forces are broken.
When a substance condenses, intermolecular
forces are formed.
Boiling points/melting points indicate the strength
of intermolecular forces.
9
11.2 Types of Intermolecular Forces
Ion-dipole force

Dipole-dipole force

Hydrogen bonding

London-Dispersion force
o+ o+ o- o-
o+ o-
+
A - H :B -
10
11.2.1 Ion-Dipole Forces
Exists between ions and the partial charge on
the end of polar molecules/dipole
Important for solutions of ionic compounds in
polar liquids
E.g.: NaCl in water
Magnitude of attraction increases:
charge of the ion increases
magnitude of dipole moment increase
Ionic bonding > Ion-dipole > Dipole-dipole

11
Ion-Dipole Forces
+
-
+
+
+
+
+
+ +
+
-
-
-
-
-
-
-
-
12
11.2.2 Dipole-dipole Forces


Exists between neutral polar molecules
The partially positive end of one molecule attracts the
partially negative end of another.

Weaker than ion-dipole forces

E.g.: CO---CO


C
O
C
C
C
C
O
O
O
O
13
Dipole-dipole Forces
+
+
+
+
+
+
+
+
-
-
-
-
-
-
-
-
Attractions
are greater
than
repulsion, so
the
molecules
feel a net
attraction to
each other
14
Dipole-dipole Forces
For molecules of approximately equal mass
and size, strength of attraction increases
with increasing polarity
Mass
(amu)
Dipole
moment ()
Boiling point
(K)
CH
3
CH
2
CH
3
44 0.1 231
CH
3
OCH
3
46 1.3 248
CH
3
CHO 44 3.9 294

15
Dipole-dipole Forces
For molecules of comparable polarity,
those with smaller molecular volumes
generally experience higher dipole-dipole
attractive forces.
16
11.2.3 Hydrogen Bonding
Special type of intermolecular attraction.
Hydrogen bonding is a special case of dipole-
dipole interactions.
H-bonding requires:
H bonded to a small electronegative element (most
important for compounds of F, O, and N)
An unshared electron pair on a nearby small
electronegative ion or atoms (usually F, O, or N on
another molecule)
17
11.2.3 Hydrogen Bonding
E.g.:




Ion-dipole > Hydrogen bonding > Dipole-dipole
O H
H
O H
H
N H
H
O H
H
H
18
Hydrogen Bonding
Hydrogen
bond
19
Hydrogen Bonding
Hydrogen bonding is important in :
Stabilising the structure of protein
Folding of protein molecules
Survival of aquatic in frozen lake
Ice is less dense than water
Ice floats so forms an insulating layer on top of
lakes or river. Therefore, aquatic life can
survive in winter.

20
11.2.4 London Dispersion Forces


What intermolecular forces exist between
nonpolar molecules in liquid and solid state ?
Dipole-dipole attractions cannot exist between
non-polar atoms or molecules
Non-polar molecules do not have permanent
dipoles but all nonpolar substances can be
liquefied
Therefore, there must exist some kind of
attractive interactions between the particles
21
Two schematic presentations of the
instantaneous dipoles on two adjacent helium
atoms, showing the electrostatic attraction
between them
London Dispersion Forces
22
London Dispersion Forces
In a collection of helium atoms, the average
distribution of electrons about each nucleus is
spherically symmetrical

The atoms are nonpolar and posses no
permanent dipole moment
23
London Dispersion Forces
In any atom or molecule, electrons constantly
moving
The nucleus of one molecule (or atom) attracts
the electrons of the adjacent molecule (or
atom).
For an instant, the electron clouds become
distorted.
In that instant a dipole id formed (called an
instantaneous dipole)
24
London Dispersion Forces
One instantaneous dipole can induce another
instantaneous dipole in ad adjacent molecule
(or atom).
These two temporary dipoles attract each
other.
The attraction is called London-dispersion
force (LDF) , or simply a dispersion force.
LDF is the weakest of all intermolecular forces.
LDF exist between all molecules (polar or
nonpolar)
25
London Dispersion Forces (LDF)
What affects the strength of a dispersion force?
Molecules must be very close together for
these attractive forces to occur.
POLARIZABILITY is the ease with which an
electron distribution can be deformed.
The larger the molecule, the more polarize it is.
LDF increase as molecular weight increases.
LDF depend on the shape of the molecule.
26
London Dispersion Forces
Factors affecting London dispersion force :
1. Molecular weight
increase in mol. wt. (increase in atomic radii)
results in increase number of electrons
the larger the molecule, the farther its electron
from the nuclei, the greater its polarizability
greater polarizability, the greater the strength of
London dispersion force
27
London Dispersion Forces
E.g. : Noble gases . As go down the
periodic table, mol. wt. increase
(atomic radii increase) , resulting
greater boiling point
Substance Mol. Wt (amu) Boiling point (K)
He 4.0 4.6
Ne 20.2 27.3
Ar 39.9 87.5
Kr 83.8 120.9
Xe 131.3 166.1
28
London Dispersion Forces
Factors affecting London dispersion force
2. Shape of molecule
greater the surface area available
for contact, greater the dispersion
force
e.g.: straight chain molecule
>branched chain molecule
Neopentane
(bp=282.7K)
N-pentane
(bp=309.4K)
29
11.2.5 Comparison between Forces
LDF are found in all substances.
Their strength depends on molecular shapes
and molecular weights.
Dipole-dipole forces add to the effect of LDF.
They are found only in polar molecules.
Ion-dipole interactions are stronger than H-
bonding.
30
11.2.5 Comparison between Forces
H-bonding is a special case of dipole-
dipole interactions.
It is the strongest of intermolecular forces
involving neutral species.
H-bonding is most important for H
compounds of N, O, and F.
31
If ions are involved, ion-dipole (if a dipole
is present) and ionic bonding are
possible.
Ion-dipole interactions are stronger than H-
bonding.
Ordinary ionic or covalent bonds are
much stronger than these interactions!
11.2.5 Comparison between Forces
32
33
11.3 Properties of Liquids
11.3.1 VISCOSITY
Viscosity - resistance of liquid to flow.
Liquid flows by sliding molecules over
each other.
The stronger the intermolecular
forces, the higher the viscosity.
Viscosity usually decreases with an
increase in temperature.
34
11.3.2 SURFACE TENSION
bulk molecules (those in liquid) are equally
attracted to their neighbours
surface molecules are only attracted
inwards to the bulk molecules
therefore surface molecules are packed
more closely than bulk molecules
Surface tension - amount of energy required to
increase the surface area of a liquid by a unit
amount.
Properties of Liquids
35
Explaining Surface Tension
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11_16
Surface
36
SURFACE TENSION (CONT..)

Strong intermolecular forces cause higher
surface tension.
Water has a high surface tension (H-
bonding)
Hg(l) has even higher surface tension (there
are very strong metallic bonds between Hg
atoms)
Properties of Liquids
37
SURFACE TENSION (CONT..)

Cohesive forces
Intermolecular forces that bind molecules to
one another
Adhesive forces
Intermolecular forces that bind molecules to
a surface
Properties of Liquids
38
Properties of Liquids
To illustrate this:
Meniscus - the shape of the liquid surface
if adhesive forces > than cohesive forces -
the liquid is attracted to its container,
meniscus is U-shaped (e.g. water in glass)
if cohesive forces > than adhesive forces -
meniscus curved downwards (e.g. Hg in glass)

Capillary action the rise of liquids up very narrow
tubes.
The liquid climbs until adhesive and cohesive forces
are balanced by gravity.
39
Liquid Levels in Capillaries: Capillary Rise
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11-19A
11_19a
40
11.4 Phase Changes
A phase change occurs when the matter is
transformed from one physical state to another

During phase change temperature remains constant
Sublimation : Solid Gas
Vaporization : Liquid Gas
Melting or Fusion : Solid Liquid
Deposition : Gas Solid
Condensation : Gas Liquid
Freezing : Liquid Solid
41

During phase change, the energy change of the
system are as given below
Sublimation AH
SUB
> 0 (Endothermic)
Vaporisation AH
VAP
> 0 (Endothermic)
Melting OR Fusion AH
FUS
> 0 (Endothermic)
Deposition AH
DEP
< 0 (Exothermic)
Condensation AH
CON
< 0 (Exothermic)
Freezing AH
FREEZ
< 0 (Exothermic)

11.4.1 Energy changes accompanying phase changes
Phase Changes
42


The amount of energy required to cause a phase
change increases as the strength of the intermolecular
forces increases

Generally heat of fusion is less than heat of
vaporisation
Less energy is needed to allow particles to move
past one another than to separate them totally

Steam can cause severe burns, when it comes in
contact with skin because condensation (exothermic)
11.4.1 Energy changes
accompanying phase changes
43


+
- -
11.4.2 Cooling curve

-Cooling curve for the conversion of gaseous water to ice.
44


+
- -
11.4.2 Cooling curve

-Supercooling:
When a liquid is
cooled below its
freezing point
and it still
remains a liquid.

45
11.4.3 Critical Temperature and
Pressure

Gas can be liquefied by compressing them at a suitable T
As temperature increases, gas become more difficult to liquefy
because of the increasing kinetic energy

For every substance, there exist a temperature above which the
gas cannot be liquefied, regardless of the pressure

CRITICAL TEMPERATURE (T
C
) - the highest temperature at
which a substance can exist as a liquid (using pressure)

CRITICAL PRESSURE (P
C
) - the pressure required to bring
about liquefaction at T
C

The greater the intermolecular forces, the easier it is to liquefy a
substance, thus the higher the T
C
of the substance.
46
11.5 Vapour Pressure

What is vapor pressure ?
We place a quantity of ethanol ( b.p. 78.3C @ 1 atm)
in an evacuated container

some of the molecules on the surface of the liquid have
enough energy to escape the attraction of the bulk
liquid

these molecules moves into the gaseous phase
as the number of molecules in the gas phase
increases, some of the gas phase molecules struck the
surface and returns to the liquid

47
Measurement of the Vapour Pressure of Water
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11-4
48

It will reach a condition where the rate at which molecules
return to the liquid is equal to the rate they escape from the
liquid.
At this condition ;
the number of molecules in the gas phase reaches a
steady state
pressure of the vapor remains constant
dynamic equilibrium is attained between the rate of
condensation and rate of evaporation
pressure of the vapor remains constant (vapor pressure)
Vapour Pressure
49
Vapour pressure of a liquid is
defined as the pressure exerted by its
vapor when the liquid and the vapor
state are in dynamic equilibrium
(Dynamic equilibrium is a condition in
which two opposing processes occur
simultaneously at equal rates.)
Vapour Pressure
50


Liquids boil when the external pressure at the
liquid surface equals the vapour pressure.
The normal boiling point is the boiling point at 760
mmHg (1 atm).
The temperature of the boiling point increases as
the external pressure increases.
Two ways to get a liquid to boil:
Increase temperature or decrease pressure.
Vapour Pressure and Boiling
Point
51


Under appropriate condition, equilibrium can exist
between:
liquid - gas
solid - liquid
solid - gas

We can summarise these conditions as phase
diagram

Phase diagram - a plot of pressure vs. temperature
summarizing all equilibria between phases.
11.6 Phase Diagram
52
53


(Explanation for Figure)
A-B = vapor pressure curve, represent equilibrium
between liquid and gas phase
Vapor pressure curve ends at the critical point
A = triple point (temp. & pressure at which all three
phases are in equilibrium
A-D = change in melting point with increasing pressure
The solid is denser than liquid. An increase in
pressure will result in more compact solid phase i.e.
higher temperature are required to melt a solid in high
pressure
Phase Diagram
54
11.6.1 Phase Diagrams for Carbon
Dioxide
Notice that the solid-
liquid equilibrium
(melting point) line of
CO
2
follows the normal
behaviour i.e. its melting
point increases with
increasing temperature.
For solid CO
2
to exist as
liquid the pressure must
exceed 5.11 atm
CO
2
does not melt, but
sublimes at 1 atm
55
11.6.2 Phase Diagram for Water
The melting point of
water decreases with
increasing pressure
Liquid form is more
compact than its solid
form
56
Objectives:
Distinguish between crystalline and amorphous
solids
Determine the net contents in a cubic unit cell
calculate the density of a substance
Predict the types of solids
Molecular solid
Covalent-Network solid
Ionic or metallic solid
11.7 Structure of Solids
57
11.7.1
CRYSTALLINE SOLIDS
Well-ordered ,definite arrangement of
molecules, atoms or ions
Have highly regular shape, repeating in three
dimensional patterns
Tend to melt at specific temperature
Have narrow range of intermolecular forces
E.g. : NaCl, Cu
Structure of Solids
58
11.7.1
AMORPHOUS
Molecules, atoms or ions do not have orderly
arrangement
Lack of well-defined faces and shape
Tend to melt over a range of temperature
Amorphous solids have variable intermolecular
forces
E.g. : rubber, glass
Structure of Solids
59
11.7.2 UNIT CELLS
Crystalline solids have ordered, repeating
structure.
The smallest repeating unit in a crystal is called
a UNIT CELL.
Unit cell - the smallest unit with all the
symmetry of the entire crystal.
The 3-D stacking of unit cells is the crystal
lattice CRYSTAL LATTICE.
Structure of Solids
60

Cubic

Tetragonal

Orthorhombic

Rhombohedral

Monoclinic

Triclinic

Hexagonal
Types of unit cells
61
There are 3 types of a cubic unit cell

Primitive cubic (PC)
atoms are at the corners of a simple cube
I.e. each atom shared by 8 unit cells



Cubic Cell
62
Cubic Cell
Body-centred cubic (BCC)
atoms at the corners of a cube plus one in the
centre of the cube body
corner atoms shared by 8 unit cells, centre
atom completely enclosed in one unit cell
63
Face-centred cubic (FCC)
atoms at the corners of a cube plus one atom in
the centre of each cube face
corner atoms shared by 8 unit cells, face atoms
shared by 2 unit cells
Cubic Cell
64
Fraction of an Atom at Various
Positions in the Unit Cell
Position

Fraction

Centre

1

Face

1/2

Corner

1/8

65
EXERCISE 1 - Determine the
number of atoms per unit cell
How many atoms are there in the face-centred
cubic unit cell?
Solution
FCC has 6 faces and 8 corners
6 faces 1/2 atom = 3 atoms
face
8 corners 1/8 atom = 1 atom
corner

Total = 4 atoms
66
To determine the net content in a cubic unit cell
1. calculate the atomic radius
2. density
The relationship between the edge length (a) and
radius (r) of atoms in
Simple/primitive cubic cell a = 2r
Body-centred cubic cell

Face-centred cubic cell


Net content in a cubic unit cell
r
3
4
a=
r 8 r
2
4
a = =
67
Exercise 2
Find the density (g/cm
3
) for oFe given that it
has BCC (Body-centred Cubic) unit cell and the
following data:

Edge of unit cell = 2.86
Fe molar mass = 55.85 g/mol
N
A
= 6.022 x 10
23
atoms/mol

68
Volume of Unit Cell = (2.86 )
3
(1 cm/10
8
)
3

= 2.34 10
-23
cm
3

mass/unit cell = 55.85g/mole 2 atoms
6.022 10
23
atoms/mole
= 1.85 10
-22
g

Density = Mass/Volume = 7.91 g/cm
3
Answer to Exercise 2
69
Answer:

Density = 7.95 g/cm
3
Volume = (2.86 10
-10
m)
3
= 2.34 10
-29
m
3


Mass = density volume

= 7.95 g 2.34 x 10
-29
m
3
(100cm)
3

cm
3
1m
3
= 1.86 10
-22
g per unit cell
Exercise 3
Using Fe as BCC, calculate the mass of one Fe atom
given density 7.95 g/cm
3
and edge, a is 2.86 .
70


Because Fe is a body-centred cubic cell, there are two
Fe atoms in the cell, therefore:

Mass of one Fe atom = (1.86 x 10
-22
g) / 2
= 9.30 x 10
-23
g

Using the molar mass to calculate the mass of one
Fe atom, you find the agreement is good:

Answer to Exercise 3 (cont)
atom Fe g
atoms Fe
Fe mol
Fe mol
Fe g
/ 10 277 . 9
10 02 . 6
1
1
85 . 55
23
23

71
Gold (Au) crystallizes in a cubic close-packed (CCP
or FCC) and has a density of 19.3 g/cm
3
. Calculate
the atomic radius of gold.

Answer
Step1
each unit cell has 8 corners and 6 faces = 4 atoms
m = 4atom 197.0 g Au 1mol of Au
I unit cell 1 mol Au 6.022 X 10
23
atom
= 1.31 X 10
-21
g/unit cell
Exercise 4
72
Step2
Volume can be calculated from density:
V = mass/density = 1.31 10
-21
g = 6.79 10
-23
cm
3
19.3 g/cm
3

Convert to picometer, pm unit


Answer
3 7
3
12
3
2
3 23
10 79 . 6
10 1
1
1
10 1
10 79 . 6
pm V
m
pm
cm
m
cm V
=
|
.
|

\
|

|
|
.
|

\
|

=

73

Step3 Step 4
a = V
1/3
a = 8
1/2
r
= (6.79 X 10
7
pm
3
)
1/3
r = a/ 8
1/2

= 408 pm = 408 / 8
1/2

= 144 pm
Answer
74
Close Packing of Spheres
Molecular crystals are formed by close packing
molecules
A crystal is built up by placing close packed layers of
spheres on top of each other
The most efficient arrangement is a layer of equal
sized spheres, each surrounded by 6 others in the
layer
Solids have maximum intermolecular forces due to
efficient packing
There is only one place for the second layers and
two choices for the third layers
75
There are 2 types of close packing (Based on third
layer)
Hexagonal Close Packing (HCP)
ABAB
Hexagonal

Close Packing of Spheres
76
Close Packing of Spheres
Cubical Close
Packing (CCP)
ABCABC
Or also known as
Face-centred
Cubic (FCC)
77
The number of particles immediately
surrounding a particle in the crystal is known
as Co-ordinate number (CN)

In the case of CCP and HCP, sphere has 12
equidistant nearest neighbor (6 in one plane
and 3 each in above and below the plane.
Therefore the CN is 12 for HCP and CCP)
Close Packing of Spheres
78
79
The melting point and hardness depends on
arrangement of particles
attraction forces between them

We can classify solids according to types of
forces (4 types)


11.8 Bonding in Solids
80
Bonding in Solids
Molecular (formed from atoms or molecules)
usually soft with low melting point and conductivity

Covalent network (formed from atoms)
very hard with very high melting point and poor conductor

Ionic (formed from ions)
hard, brittle, high melting point and poor conductivity

Metallic (formed from metal atoms)
soft or hard with high melting point, good conductivity
and ductile)
81
Intermolecular forces

Dipole-dipole, London dispersion and H-bonds.
Weak intermolecular forces give rise to low
melting point.
Efficient packing of molecules is important
(since they are not regular spheres)
E.g. : Benzene (m.p 5C & b.p 80C)
Toluene (m.p -95C & b.p 111C)
11.8.1 Molecular Solids
82
E.g. : Benzene VS Toluene
Benzene
m.p 5C, b.p 80C
Symmetrical planar
molecule packed
efficiently in solid
form - high melting
point
IMF in liquid state
lower than toluene
Toluene
m.p -95C, b.p 111C
Lower symmetry,
prevents from packing
efficiently
Intermolecular forces
depend on close
contact - not effective
IMF in liquid state larger
than benzene
Molecular Solids
83
Atoms are held together in large networks or chain by
covalent bonds
Covalent bonds are stronger than intermolecular forces
E.g. Diamond & Graphite
Diamond
Each carbon atom is bonded to 4 other carbon atom
Graphite
The carbon atoms are arranged in layers of inter-
connected hexagonal rings
The layers are held by dispersion forces
Readily slide past one another
11.8.2 Covalent-Network
Solids
84
Structures of Diamond and Graphite
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85
Ions are held together by ionic bonds
The strength of ionic solids depends on the charges of the
ions
NaCl ---> Na
+
Cl
-
---> has m.p. of 801C
MgO ----> Mg
2+
O
2-
----> has m.p. of 2852C

The structure adopted by ionic solids depends largely on
the charges and relative sizes of the ions
E.g.: NaCl (Na
+
has CN of 6 and surrounded by 6
Cl) whereas CsCl (Cs is surrounded by 8 Cl
-
atoms)
increase in CN results in increase in structure
11.8.3 Ionic Solids
86
Metallic solids have metal atoms in the HCP
and FCC or BCC arrangements

The bonding is due to valence electrons that
are delocalized throughout the entire solid
the metal nuclei floats in a sea of
electrons
11.8.4 Metallic Solids
87
Metallic Solids
Hardness and melting point depends on strength of
bonding
Bonding strength increases with increase in
bonding electrons
e.g. Na (one valence electron- m.pt= 97.5C)
Cr (6 valence electrons - m.pt = 1890c)

Mobility of electron explains why electrons are
good conductor of heat and electricity
88



END of CHAPTER