Intermolecular Forces and

Liquids and Solids

Chapter 11
1
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Chapter Outline
A phase is a homogeneous part of the system in contact with
other parts of the system but separated from them by a well-
defined boundary.

A phase is one of the forms in which matter can exist, such

as solid, liquid, or a gas.

3 Phases
Solid phase - ice

Liquid phase – water

Water vapor-atmosphere

2
The main difference between phase of matter and state of
matter can be given as:

phase of matter explains uniform chemical and physical

properties of matter

state of matter explains the form of matter at a given

temperature and a pressure
States of Matter
 intRA vs. intER molecular forces
Intramolecular forces are the forces within a molecule or ionic
compound

Intermolecular forces are the attractive forces between molecules

or ions

Intramolecular forces

Intermolecular forces
 Intramolecular vs Intermolecular
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
• 41 kJ to vaporize 1 mole of water (inter)

Strenght of
Intramolecular bonds > intermolecular forces

Chemical process Physical process

“Measure” of intramolecular force “Measure” of intermolecular force
boiling point
melting point
Hvap
Hfus
Hsub 3
 Types of Intermolecular Forces
Intermolecular Model Basis of Energy Example
Force Attraction (kJ/mol)
 Intermolecular Forces

Dipole-Dipole Forces

Attractive forces between polar molecules

HCl is a polar molecule Electronegativity difference between atoms

(H and Cl)

9
 Intermolecular Forces
Ion-Dipole Forces
Attractive forces between an ion and a polar molecule

 The strength of this interaction depends on the charge and size of the
ion and on the magnitude of the dipole moment and size of the polar
molecule.

1
0
Interaction Between Water and Cations
(Hydration)

in solution
1
2
 Intermolecular Forces
What attractive interaction occurs in nonpolar substances?
Dispersion Forces
Attractive forces that arise as a result of temporary dipoles induced in
atoms or molecules
Induced dipole is the separation of positive and negative charges in the
atom (or nonpolar molecule) due to the promixity of an ion or a polar
molecule.
a nonpolar molecule (no dipole moment)

ion-induced dipole interaction

dipole-induced dipole interaction 7

Induced Dipoles Interacting With Each Other

1
5
 Intermolecular Forces
Polarizability is the tendency of an electron cloud to distort
in the atom or molecule.

Polarizability increases with:

• greater number of electrons
• more diffuse electron cloud

1
6
 Dispersion Forces (London Forces)

dispersion forces, attractive forces that arise as a result of temporary

dipoles induced in atoms or molecules

 Dispersion forces usually increase

with molar mass.

 Dispersion forces usually increase

with the number of electrons.
Example 11.1
What type(s) of intermolecular forces exist between the
following pairs?

(a) HBr and H2S

dipole-dipole forces

(a) Cl2 and CBr4

dispersion forces (London forces)

Example 11.1
What type(s) of intermolecular forces exist between the
following pairs?

c) I2 and

d) NH3 and C6H6

(a) I2 and
Example 11.1
(b) NH3 and C6H6

Strategy Classify the species into three categories: ionic,

polar (possessing a dipole moment), and nonpolar. Keep in
mind that dispersion forces exist between all species.

Solution
(a) Both HBr and H2S are polar molecules. Therefore, the
intermolecular forces present are dipole-dipole forces, as
well as dispersion forces.

(b) Both Cl2 and CBr4 are nonpolar, so there are only dispersion
forces between these molecules.
Example 11.1
(c) I2 is a homonuclear diatomic molecule and therefore
nonpolar, so the forces between it and the ion are
ion-induced dipole forces and dispersion forces.

(d) NH3 is polar, and C6H6 is nonpolar. The forces are dipole-
induced dipole forces and dispersion forces.
 Intermolecular Forces
Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction between
the hydrogen atom in a polar N-H, O-H, or F-H bond and an
electronegative O, N, or F atom.

23
 Hydrogen Bond

HCOOH and water

24
Is this hydrogen bonding?
Why Hydrogen Bonding is effective
and strong?
• F, O, & N are extremely small and very electronegative
atoms.

• Hydrogen atoms are very small and have no inner core

of electrons, therefore, the positive side of the bond
dipole has the concentrated charge of the partially
exposed, nearly bare proton of the nucleus.

…in other words, the atoms have a large difference in

electronegativity and their nuclei can get really close.
Why is the hydrogen bond considered a “special”
dipole-dipole interaction?

Decreasing molar mass

Decreasing boiling point

27
Example 11.2
Which of the following can form hydrogen bonds with water?

CH3OCH3 ✓

CH4

F- ✓

HCOOH ✓

Na+
Example 11.2
Strategy A species can form hydrogen bonds with water if it
contains one of the three electronegative elements (F, O, or N)
or it has a H atom bonded to one of these three elements.

Solution There are no electronegative elements (F, O, or N) in

either CH4 or Na+. Therefore, only CH3OCH3, F2, and HCOOH
can form hydrogen bonds with water.
Summarizing Intermolecular Forces
 Properties of Liquids
Surface tension is the amount of energy required to stretch or
increase the surface of a liquid by a unit area (J m-2).

Strong High
intermolecular surface
forces tension

Water molecules minimize surface

31
A small round bead on a nonpolar surface
 Properties of Liquids
Cappillary action, The rise of liquids up narrow tubes

Cohesion is the intermolecular attraction between like molecules

Adhesion is an attraction between unlike molecules
Water : adhesive forces with glass are greater than cohesive forces

Mercury: Cohesive forces with glass are greater than adhesive forces.

Adhesion

Cohesion mercury

water
32
 Properties of Liquids
Viscosity is a measure of a fluid’s resistance to flow.

Strong
intermolecular
forces

High
Water = less Viscosity
viscosity
syrup = high Viscosity
Larger molecules stronger IM

34
 The expression “slow as molasses in January” owes its truth to another
physical property of liquids called viscosity

not fast at all.

The viscosity of a liquid usually decreases as temperature increases;

thus, hot molasses flows much faster than cold molasses.

 Substances composed of longer

molecules tend to have larger viscosities
due to the increased contact of
molecules across layers of flow.
3-D Structure of Water

22
 Water has a maximum density at 4 celcius degree,
because on heating ice, the
hygrogen bonds break Maximum Density
progressively and the molecules 40C dice(0oC)=0.92g/cm3
start packing in more closely in Density of Water
the vacant spaces.

Lowest volume

Highest density

Left: Ice cubes float on water.

Right: Solid benzene sinks to
the bottom of liquid benzene.
The extra hydrogen bonds that occur when water freezes increase the
space between molecules, causing a decrease in overall density.
 Solids
Solids can be divided into two categories: amorphous and crystalline solids

An amorphous solid does not possess a well-defined arrangement and long-

range molecular order. (plastics, rubber etc.)

A crystalline solid possesses rigid and long-range order; its atoms, molecules,
or ions occupy specific positions. (quartz, diamond, NaCl etc.)
 The structures of crystals, however, must be described through
three-dimensional patterns

A unit cell is the basic repeating structural unit of a crystalline solid.

lattice
point At lattice points:
• Atoms
• Molecules
• Ions

Unit Cell Unit cells in 3 dimensions 23

Seven Basic Unit Cells

42
Packing Spheres
Arrangement of Identical Spheres in a Simple Cubic Cell

Top view of one layer of spheres Definition of a simple cubic cell

4 contact with spheres in its own layer
One contact with the sphere above
Eight corner in a cube
One contact with the sphere below
One complete sphere
Coordination number: 6
inside a simple cubic cell
43
The coordination number: the number of atoms surrounding an atom in a crystal lattice
 Three Types of Cubic Unit Cells

(Scc) (Bcc) (Fcc)

Coordination number: 6 Coordination number: 8 Coordination number: 12
Arrangement of Identical Spheres in a Body-Centered
Cubic Cell

45
 A Corner Atom, an Edge-Centered Atom and
a Face-Centered Atom

Shared by 8 Shared by 4 Shared by 2

unit cells unit cells
unit cells

46
 Number of Atoms Per Unit Cell

1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell

(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
47
 Relation Between Edge Length and Atomic Radius

r
r

a= edge length 48
r= Radius of atoms in the scc,bcc and fcc
Example 11.3

Gold (Au) crystallizes in a cubic close-packed structure (the

face-centered cubic unit cell) and has a density of 19.3 g/cm3.

Calculate the atomic radius of gold in picometers.

a= edge length
r= Radius of atoms in fcc
There are 4 atoms in fcc
1 mol Au= 197 gr
Example 11.3
Strategy We want to calculate the radius of a gold atom.

For a face-centered cubic unit cell, the relationship between

radius (r) and edge length (a), according to Figure 11.22,
is .

Therefore, to determine r of a Au atom, we need to find a. The

volume of a cube is . Thus, if we can
determine the volume of the unit cell, we can calculate a. We
are given the density in the problem.
Example 11.3
The sequence of steps is summarized as follows:

Solution
Step 1: We know the density, so in order to determine the
volume, we find the mass of the unit cell. Each unit cell
has eight corners and six faces. The total number of
atoms within such a cell, according to Figure 11.19, is
Example 11.3
The mass of a unit cell in grams is

From the definition of density (d = m/V), we calculate the

volume of the unit cell as follows:
Example 11.3
Step 2: Because volume is length cubed, we take the cubic
root of the volume of the unit cell to obtain the edge
length (a) of the cell

Step 3: From Figure 11.22 we see that the radius of an Au

sphere (r) is related to the edge length by
Example 11.3
Therefore,

= 144 pm
An Arrangement for Obtaining the X-ray Diffraction Pattern
of a Crystal

56
 Bragg Equation Determination of crystal structure
by X-ray diffraction

 Used to determine the interatomic spacings.

n = 2d sin 
n = integer order of the diffraction
= wavelength of the X rays, (Ǻ)
d = distance separating the atoms (Ǻ)
 = angle of incidence and reflection
Example 11.4
X rays of wavelength 0.154 nm strike an aluminum crystal; the
rays are reflected at an angle of 19.3°.

Assuming that n = 1, calculate the spacing between the planes

of aluminum atoms (in pm) that is responsible for this angle of
reflection.

The conversion factor is obtained from 1 nm = 1000 pm.

2d sin = n
Example 11.4
Strategy This is an application of Equation (11.1).

Solution Converting the wavelength to picometers and using

the angle of reflection (19.3°), we write
Example:

The first order diffraction of x-rays from crystal planes separated

by 2.81 Ǻ occurs at 11.8°. What is the wavelength of the x-ray

n = 2d sin 
n = 1 (first order)
d = 2.81 Ǻ
 = 11.8°
λ=?

λ = 24.14 °
Types of Crystals

61
Four types of solids

62
 Types of Crystals
Ionic Crystals

• Lattice points occupied by cations and anions

• Held together by electrostatic attraction
• Hard, brittle
• High melting point
• Poor conductor of electricity in solid form, good
conductors in solution

43
CsCl ZnS CaF2
Example 11.5
How many Na+ and Cl− ions are in each NaCl unit cell?
Example 11.5
Solution NaCl has a structure based on a face-centered cubic
lattice. One whole Na+ ion is at the center of the unit cell, and
there are twelve Na+ ions at the edges. Because each edge
Na+ ion is shared by four unit cells, the total number of Na+ ions
is 1 + (12 × ¼) = 4.

Similarly, there are six Cl− ions at the face centers and eight Cl−
ions at the corners. Each face-centered ion is shared by two
unit cells, and each corner ion is shared by eight unit cells, so
the total number of Cl− ions is (6 × ½) + (8 × 1/8) = 4. Thus,
there are four Na+ ions and four Cl− ions in each NaCl unit cell.

Check This result agrees with sodium chloride’s empirical

formula.
Example 11.6

The edge length of the NaCl unit cell is 564 pm. What is the
density of NaCl in g/cm3?
Example 11.6
Strategy
To calculate the density, we need to know the mass of the unit
cell. The volume can be calculated from the given edge length
because V = a3. How many Na+ and Cl− ions are in a unit cell?
What is the total mass in amu? What are the conversion
factors between amu and g and between pm and cm?

Solution
From Example 11.5 we see that there are four Na+ ions and
four Cl− ions in each unit cell. So the total mass (in amu) of a
unit cell is

mass = 4(22.99 amu + 35.45 amu) = 233.8 amu

Example 11.6
Converting amu to grams, we write

The volume of the unit cell is V = a3 = (564 pm)3. Converting

pm3 to cm3, the volume is given by

Finally, from the definition of density

= 2.16 g/cm3
 Types of Crystals
Covalent Crystals

• Lattice points occupied by atoms

• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity

carbon London forces

atoms (between layers)

50
diamond graphite
 Types of Crystals
Molecular Crystals

• Lattice points occupied by molecules

• Held together by intermolecular forces
• Soft, low melting point
• Poor conductor of heat and electricity

70
Solid CH4
 Types of Crystals
Metallic Crystals

• Lattice points occupied by metal atoms

• Held together by metallic bonds
• Soft to hard, low to high melting point
• Good conductors of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-

mobile “sea”
of e-

71
Crystal Structures of Metals

72
 Phase Changes
Least
Order
Phase changes, transformations from one
phase to another, occur when energy
(usually in the form of heat) is added or
removed.

Physical change

Changes in molecular order

Greatest
Order
 Energy content is responsible for the phase change.
 Energy is either added or released in a phase change.

 Phase changes that require the

addition of energy are called
endothermic changes

 Phase changes that release

energy are called as
exothermic change
 Vaporization
 At any given temperature, a certain number of the molecules in a
liquid possess sufficient kinetic energy to escape from the surface.

This process is called evaporation, or vaporization.

 Vaporization is an endothermic
process ( it requires heat).

Energy is required to overcome

intermolecular forces to turn from
liquid to gas
 Measurement of Vapor Pressure
 When a liquid evaporates, its gaseous molecules exert a vapor pressure.

Before At
Evaporation Equilibrium
77
 Liquid-Vapor Equilibrium
The equilibrium vapor pressure is the vapor pressure
measured when a dynamic equilibrium exists between
condensation and evaporation

H2O (l) H2O (g)

Dynamic Equilibrium
Rate of Rate of
condensation
= evaporation

 Equilibrium vapor pressure is the maximum

vapor pressure a liquid exerts at a given
temperature and that it is constant at
78
 Vapor Pressure Versus Temperature

 Vapor pressure changes with temperature

 The vapor pressure of water is 17.5 mmHg at 20oC, but it rises to

760 mmHg at 100 o C
Vapor pressure curve

The increase in vapor pressure with temperature for three liquids.

Molar heat of vaporization (Hvap) is the energy required to
vaporize 1 mole of a liquid at its boiling point (J/mol).
Clausius-Clapeyron Equation
Hvap P = (equilibrium) vapor pressure
ln P = - +C T = temperature (K)
RT
R = gas constant (8.314 J/K•mol)

81
Alternate Forms of the Clausius-Clapeyron Equation

At two temperatures

or

82
Example 11.7
Diethyl ether is a volatile, highly flammable organic liquid that is
used mainly as a solvent.

The vapor pressure of diethyl ether is 401 mmHg at 18°C.

Calculate its vapor pressure at 32°C.
Example 11.7
Strategy We are given the vapor pressure of diethyl ether at
one temperature and asked to find the pressure at another
temperature. Therefore, we need Equation (11.5).

Solution Table 11.6 tells us that Hvap = 26.0 kJ/mol. The data
are

From Equation (11.5) we have

Example 11.7
Taking the antilog of both sides (see Appendix 4), we obtain

Hence
P2 = 656 mmHg

Check We expect the vapor pressure to be greater at the

higher temperature. Therefore, the answer is reasonable.
The boiling point is the temperature at which the
(equilibrium) vapor pressure of a liquid is equal to the
external pressure.

The normal boiling point is the temperature at which a liquid

boils when the external pressure is 1 atm.

86
 The critical temperature (Tc) is the temperature above which
the gas cannot be made to liquefy, no matter how great the
applied pressure.

The critical pressure (Pc) is the minimum pressure that must

be applied to bring about liquefaction at the critical temperature.

If the room temperature is above Tc, If the room temperature is below Tc,
the gas cannot be liquified the gas can be liquified 87
 The Critical Phenomenon of SF6

T < Tc T > Tc T ~ Tc T < Tc

88
Solid-Liquid Equilibrium

The melting point of a solid or

the freezing point of a liquid
is the temperature at which the
solid and liquid phases coexist
in equilibrium.

H2O (s) H2O (l)

69
Molar heat of fusion ( Hfus) is the energy required to melt 1
mole of a solid substance at its freezing point.

90
 Heating Curve

Phase change

Phase change

91
 Solid-Gas Equilibrium

H2O (s) H2O (g)

Molar heat of sublimation

(Hsub) is the energy required
to sublime 1 mole of a solid.

Hsub = Hfus + Hvap

( Hess’s Law)

72
Example 11.8
Calculate the amount of energy (in kilojoules) needed to heat
346 g of liquid water from 0°C to 182°C.

Assume that the specific heat of water is 4.184 J/g · °C

over the entire liquid range and that the specific heat of steam
is 1.99 J/g · °C.
Example 11.8
Strategy The heat change (q) at each stage is given by
q = mst (see p. 247), where m is the mass of water, s is the
specific heat, and t is the temperature change.

If there is a phase change, such as vaporization, then q is given

by nHvap, where n is the number of moles of water.

Solution The calculation can be broken down in three steps.

Step 1: Heating water from 0°C to 100°C

Using Equation (6.12) we write
Example 11.8
Step 2: Evaporating 346 g of water at 100°C (a phase change)
In Table 11.6 we see Hvap = 40.79 kJ/mol for water, so

Step 3: Heating steam from 100°C to 182°C

Example 11.8
The overall energy required is given by

Check All the qs have a positive sign, which is consistent with

the fact that heat is absorbed to raise the temperature from 0°C
to 182°C. Also, as expected, much more heat is absorbed
during the phase transition.
 A phase diagram summarizes the conditions at which a substance
exists as a solid, liquid, or gas.
Triple point = three phase are in equilibrium with each other
at the same time

1 atm

Boiling Point Melting Point Critical point

 Phase Diagram of Water

374.4oC,
217.7 atm

Boiling Point Melting Point Critical point

Phase Diagram of Carbon At 1 atm
Dioxide CO2 (s) CO2 (g)

99
Effect of Increase in Pressure on the Melting Point
of Ice and the Boiling Point of Water

10
0
 Supercritical Fluids (SCF)
 Supercritical fluid is a state of a substance at a temperature and
pressure above its critical point
End of the Chapter