Chapter 11

Intermolecular Forces & the Physical Properties

of Liquids and Solids

Chemistry
Fourth Edition

By Julia Burdge
 Intermolecular Forces and the
CHAPTER 11 Physical Properties of Liquids
and Solids

11.1 Intermolecular Forces

11.2 Properties of Liquids
11.6 Phase Changes
11.7 Phase Diagrams

2
 11.1 Intermolecular Forces

Topics
Dipole-Dipole Interactions
Hydrogen Bonding
Dispersion Forces
Ion-Dipole Interactions

Learning Objectives
• Recognize and describe the forces that hold the molecules (or atoms
or ions) together in substances.

3
 11.1 States of Matter and Intermolecular
Forces
The attractive forces that hold particles together in the
condensed phases are called intermolecular forces.
The magnitude of intermolecular forces is what determines
whether the particles that make up a substance are a gas,
liquid, or solid.

4
11.1 States of Matter and Intermolecular Forces
How different are the states of matter at particulate level ?

Attraction
between
Intermolecular forces hold liquids
particles
and solids together

REAL GAS
NOT ideal PV = nRT

Gas vs. Liquid Liquid vs. Solid

Closer packing in Similar Volume
liquid phase

condensation Condensation
Comparable
higher attraction
intermolecular
forces
forces
5
11.1 States of Matter and Intermolecular Forces
How important are intermolecular forces?

 NOT chemical bonds, rather chemical interactions.

 Result from coulombic attraction/repulsion between charged or neutral species
 Depend on:
“charge” “polarity” “molar mass”
(ions vs. neutrals) (molecular shape, dipoles) (how big a substance is)

 Govern/affect the following physical properties or changes of matter:

solid
Phase Change
Diagram
gas
Vaporization  Gas
Temperature

Condensation

liquid
Melting  Liquid
Freezing
Protein
Solid
DNA
HEAT energy

Phase change properties Solubility Molecular structure6

11.1 Intermolecular Forces
Comparison with covalent bonding forces

20 to 30 kJ/mol

ΔHdissociation (H-Cl) = 432 kJ/mol

Intermolecular forces are much weaker than the bonds that make up
molecular compounds and result from the interaction between partial charges
7
11.1 Intermolecular Forces

We will begin our discussion of intermolecular forces with the

attractive forces that act between atoms or molecules in a
pure substance.

These forces are known collectively as van der Waals forces,

and they include dipole-dipole interactions, including
hydrogen bonding and dispersion forces.

8
11.1 Intermolecular Forces
What are the different types of intermolecular forces?
van der Waals forces

ion-dipole dipole-dipole

Hydrogen bonding Keesom forces

Induced dipole-induced dipole dipole-induced dipole

London dispersion Debye forces

9
11.1 Intermolecular Forces – Molecular Polarity

Recall the concept of

Dipoles / Molecular polarity & VSEPR
See Chapter 8

10
11.1 Intermolecular Forces – Molecular Polarity

Electronegativity Ability of an atom to draw electrons to itself.

(dimensionless)… The relative Δ𝝌 for two atoms is defined on the basis of bond dissociation energies.

11
11.1 Intermolecular Forces – Molecular Polarity
Relative Electronegativity Scale for Elements

Linus Pauling
(1901-1994)

 F (halogen) has the largest electronegativity (χ = 4.0)

 Cs (alkali metal) has the smallest electronegativity (χ ∼ 0.7)
 χ increases from left to right across a period and bottom−up in a group
 Metals, 0.7 < χ < 2.0 Metalloids, χ ∼ 2.0 Nonmetals > 2.0 12
11.1 Intermolecular Forces – Molecular Polarity
In a polar molecule, the e- density accumulates toward the most electronegative atom,
giving rise to opposite partial charges (δ− and δ+) and a dipole moment.

Dipole Moment μ … Extent to which polar molecules line up with an electric field.

Dipole moment arrow pointed towards

the most electronegative atom

13
11.1 Intermolecular Forces – Molecular Polarity
Any deviations from symmetry yield a polar molecule.
A = central atom ; X = terminal atom ; E = lone Electron pair
Family Bond Angle Spatial Molecular Lone pair substitutions
(e-pair geometry) Geometry

AX2 180º --
Linear

AX3 120º (AX2E)

Trigonal Planar Bent

AX4 109.5º (AX3E) (AX2E2)

Tetrahedral Trigonal pyramidal Bent

90º
(Axial - Equatorial)
AX5 120º
(AX4E) (AX3E2) (AX2E3)
(Equatorial-Equatorial)
Trigonal Bi-pyramidal Seesaw T-Shaped Linear

AX6 90º (AX5E) (AX4E2)

Octahedral Square pyramidal Square planar 14

11.1 Intermolecular Forces – Molecular Polarity

Linear & Bent Molecules (AX2)

O
O C O
H H

Symmetrical arrangement around the central atom Symmetrical arrangement the central atom
Opposite dipole-moments, Σ μ vectors = 0 D Σ μ vectors ≠ 0 D

NON POLAR POLAR

15
11.1 Intermolecular Forces – Molecular Polarity

Trigonal Planar & Pyramidal Molecules (AX3)

F O

B C
H N
H
F F Cl Cl H

Σ μ vectors = 0 D Σ μ vectors ≠ 0 D Σ μ vectors ≠ 0 D

NON POLAR POLAR POLAR

16
11.1 Intermolecular Forces – Molecular Polarity

Tetrahedral Molecules (AX4)

NON POLAR POLAR POLAR POLAR NON POLAR

AXn will not be polar, regardless of whether the A—X bonds are polar, if
 all the terminal atoms (or groups), X, are identical
 all the X atoms (or groups) are arranged symmetrically around the central atom, A.

17
11.1 Intermolecular Forces – Molecular Polarity

18
11.1 Intermolecular Forces

Dipole-Dipole Interactions
Dipole-dipole interactions are attractive
forces that act between polar molecules.

Cl — X Cl — X

TABLE 11.1 Dipole Moments and Boiling Points of Compounds with Similar
Molecular Masses
Compound Structural Formula Dipole Moment (D) Boiling Point (°C)
Propane 0.1 -42
Dimethyl ether 1.3 -25
Methyl chloride 1.9 -24
Acetaldehyde 2.7 + 21
Acetonitrile 2.9 + 82

For similar molar masses, the boiling point increases () with the molecular
polarity (due to higher dipole-dipole forces of attraction). 19
11.1 Intermolecular Forces

Hydrogen Bonding
Hydrogen bonding is a special type
of dipole-dipole interaction.

But, whereas dipole-dipole interactions act between any polar

molecules, hydrogen bonding occurs only in molecules that
contain H bonded to a small, highly electronegative atom,
such as N, O, or F .

20
11.1 Intermolecular Forces
Hydrogen Bonding
Effect of hydrogen bonding forces on the “Boiling Point”

 Increasing polarity
18 g/mol
 Stronger hydrogen bonding

20 g/mol

17 g/mol

Water has an unusually

high BP for its small
16 g/mol
Molecular Weight !!!

21
 11.1 Intermolecular Forces

Dipole – induced dipole (or Debye forces)

At any given point in time a molecule may have a nonuniform
distribution of electron density, giving it a fleeting, temporary dipole—
called an instantaneous dipole.

H H
O O O O
H H
Non Polar
Polar
PERMANENT dipole INDUCED or
instantaneous dipole

An instantaneous dipole in one molecule can also induce dipoles in

neighboring molecules.
22
11.1 Intermolecular Forces

Induced dipole – induced dipole (or London dispersion forces)

The momentary attractions between nuclei

and the electrons in neighboring molecules
lead to induced (momentary) dipoles.

The larger the electronic cloud, the easier the

polarizability.

Br—Br Br—Br

Non Polar Non Polar INDUCED dipole INDUCED dipole

The Intermolecular attraction via
the correlation of electrons in
motion  Lowers the energy and
Leads to a stabilized system 23
11.1 Intermolecular Forces

London Dispersion Forces

The magnitude of dispersion forces depends on how easily the
electrons in a molecule can be polarized.

Why Br2 and I2 are not gases as Cl2 and F2 ?

Why Br2 is liquid, while I2 is solid at room T°C ?

Br2 I2

Liquid / Solid Halogens

Br2 (BP = 58.8 °C) I2 (BP = 185 °C)

 I2 has higher Molecular Weight and more electrons in cloud than Br2
 Larger Size  easier distortion & greater polarizability by London Dispersion Forces
 Higher intermolecular forces  Larger energy to break attraction  higher Boiling Point
24
SAMPLE PROBLEM 11.1
What kind(s) of intermolecular forces exist in
(a)
(b)
(c)
(d)

Strategy
Draw Lewis dot structures and apply VSEPR theory to
determine whether each molecule is polar or nonpolar.

[Link]

Copyright © McGraw-Hill Education. All rights reserved. No reproduction or distribution without the prior written consent of McGraw-Hill Education. 25
 11.1 Intermolecular Forces

Ion-Dipole Interactions
Ion-dipole interactions are Coulombic attractions between
ions (either positive or negative) and polar molecules.

26
11.1 Overview of Coulombic Forces

Forces (F) felt by two charges depend on:

(i) magnitude of the charges
(ii) distance (d) between them

𝑭 =− 𝒌 ¿ ¿
Proportionality constant
Charge on the cation
Charge on the anion
elementary charge on an electron
e = 1.602 × 10-19 C
Inter-atomic distance
H2O (0 ºC) – molecular
Melting Point NaCl (801 ºC) - ionic
MgO (2800 ºC) - ionic 27
 11.1 Intermolecular Forces

Ion-Dipole Interactions
Ion-dipole interactions are Coulombic attractions between
ions (either positive or negative) and polar molecules.

The magnitude of ion-dipole interactions

depends on the charge and the size of
the ion, and on the dipole moment and
size of the polar molecule.

28
11.2 Properties of Liquids

Topics
Surface Tension
Viscosity
Vapor Pressure

Learning Objectives
• Recognize and describe the forces that hold the molecules (or atoms
or ions) together in substances.
• Explain the physical properties that arise because of these forces.
29
11.2 Properties of Liquids

Surface Tension
A quantitative measure of the
elastic force in the surface of a liquid
is the surface tension, the amount of
energy required to stretch or increase
the surface of a liquid by a unit area (e.g., by ).

A liquid with strong intermolecular forces has a high surface

tension.

30
11.2 Properties of Liquids
Surface Tension of water
Net INWARD forces of
Surface species are not attraction

completely surrounded by
other water molecules

Bulk species (interior ones) are

fully surrounded by water
molecules

SURFACE TENSION — the energy required to

break the surface of a liquid by a unit area.

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11.2 Properties of Liquids

Surface Tension
An illustration of surface tension is the meniscus, the curved
surface of a liquid contained in a narrow tube.

Material: Glass cylinder

water mercury

32
11.2 Properties of Liquids
Surface Tension – capillary action

Surface tension is responsible for capillary action, in

which water is pulled up into a narrow glass cylinder.

Two types of forces bring about capillary action.

One is cohesion, the attractions between like
molecules (i.e., water molecules).
UPWARD
The other is adhesion, the attractions between unlike Force
molecules (i.e., water and the glass wall molecules). (Surface tension)

DOWNWARD
Force
(Gravitation)

33
 11.2 Properties of Liquids
Viscosity
Another property determined by the magnitude of intermolecular
forces in a liquid is viscosity ). It is a measure of a fluid’s resistance to
flow.

The higher the viscosity, the more slowly a liquid flows.

Liquids with strong intermolecular forces have higher viscosities than

those with weaker forces.
34
11.2 Properties of Liquids

Vapor Pressure
Another property depending on the magnitude of intermolecular forces in a
liquid is the vapor pressure (or saturation vapor pressure).
It is the pressure exerted by a pure substance, at a given temperature, in a
closed system containing the vapor and a condensed phase of the substance
(e.g. liquid), both being in thermodynamic equilibrium.

35
 11.2 Properties of Liquids

Vapor Pressure

T1
T2

T1

T2 > T1
The Vapor pressure increases with temperature.
Substances that have high vapor pressures at
room temperature are said to be volatile.

36
 11.2 Properties of Liquids

Vapor Pressure

T1 T2

∆ 𝐻 vap
ln 𝑃 =− +𝐶 Clausius-Clapeyron equation
𝑅𝑇
The relation provides an estimation of the vapor pressure of a
liquid at any given temperature.
37
11.2 Properties of Liquids

Slope:
The Temperature Dependence of
∆ 𝐻 vap
Vapor Pressure goes as: −
𝑅
∆ 𝐻 vap
ln 𝑃 =− +𝐶
𝑅𝑇

A plot of lnPvap vs. yields a

∆ 𝐻 vap
−
slope of: y-intercept
𝑅 =C
∆vapH is the molar heat of vaporization

(Vaporization is an endothermic process) 38

11.2 Properties of Liquids

Vapor Pressure
Clausius-Clapeyron Equation

( )
𝑃 1 ∆ 𝐻 vap 1 1
ln = −
𝑃2 𝑅 𝑇2 𝑇1 39
 SAMPLE PROBLEM
11.7
The vapor pressure of diethyl ether is 401 mmHg at ,
and its molar heat of vaporization is . Calculate its
vapor pressure at .

Setup

40
 SAMPLE PROBLEM
11.7
Solution

41
11.6 Phase Changes

Topics
Liquid-Vapor Phase Transition
Solid-Liquid Phase Transition
Solid-Vapor Phase Transition

Learning Objectives
• Recognize and describe the forces that hold the molecules (or atoms
or ions) together in substances.
• Explain the physical properties that arise because of these forces.
• Correlate the phase changes with the type and magnitude of
intermolecular forces. 42
11.6 Phase Changes

Liquid-Vapor Phase Transition

A phase is a homogeneous part of a system that is separated
from the rest of the system by a well-defined boundary.

When a substance goes from one phase to another phase, we

say that it has undergone a phase change.

Phase changes in a system are generally caused by the

addition or removal of energy, usually in the form of heat.

43
11.6 Phase Changes

Liquid-Vapor Phase Transition

Example Phase Change
Freezing of water Exothermic
Evaporation (or vaporization) of water Endothermic
Melting (fusion) of ice Endothermic
Condensation of water vapor Exothermic
Sublimation of dry ice Endothermic

44
11.6 Phase Changes

Liquid-Vapor Phase Transition

45
11.6 Phase Changes

Liquid-Vapor Phase Transition

The boiling point of a substance is defined as the
temperature at which its vapor pressure equals the external,
atmospheric pressure.

The temperature at which the vapor pressure of a liquid is

equal to 1 atm is called the normal boiling point.

46
 11.6 Phase Changes

Liquid-Vapor Phase Transition

Because the boiling point is defined in terms of the vapor
pressure of the liquid, the boiling point is related to the molar
heat of vaporization the amount of heat required to vaporize
a mole of substance at its boiling point.

47
11.6 Phase Changes

Liquid-Vapor Phase Transition

TABLE 11.6 Molar Heats of Vaporization for Selected Liquids
Substance Boiling Point (oC ) ΔHvap (kJ/mol)
Argon -186 6.3
Benzene 80.1 31.0
Ethanol 78.3 39.3
Diethyl ether 34.6 26.0
Mercury 357 59.0
Methane -164 9.2
Water 100 40.79

48
11.6 Phase Changes

Liquid-Vapor Phase Transition

Every substance has a critical temperature above which its
gas phase cannot be liquefied, no matter how great the
applied pressure.

Critical pressure is the minimum pressure that must be

applied to liquefy a substance at its critical temperature.

A fluid at a temperature and pressure that exceed and ,

respectively, is called a supercritical fluid.

49
11.6 Phase Changes

Liquid-Vapor Phase Transition

A fluid at a temperature and pressure that exceed and ,
respectively, is called a supercritical fluid.

[Link]
50
11.6 Phase Changes

Liquid-Vapor Phase Transition

TABLE 11.7 Critical Temperatures and Critical Pressures of Selected Substances
Substance T C ( oC) Pc (atm)
Ammonia 132.4 111.5
Argon -122.2 6.3
Benzene 288.9 47.9
Carbon dioxide 31.0 73.0
Ethanol 243 63.0
Diethyl ether 192.6 35.6
Mercury 1462 1036
Methane -83.0 45.6
Molecular hydrogen -239.9 12.8
Molecular nitrogen -147.1 33.5

51
11.6 Phase Changes

Solid-Liquid Phase Transition

The transformation of liquid to solid is called freezing, and the
reverse process is called melting, or fusion.

The melting point of a solid or the freezing point of a liquid is

the temperature at which solid and liquid phases coexist in
equilibrium.

The normal melting (or freezing) point of a substance is the

temperature at which it melts (or freezes) at 1 atm.

52
11.6 Phase Changes

Solid-Liquid Phase Transition

The molar heat of fusion is the energy, usually expressed in
kJ/mol, required to melt 1 mole of a solid.

TABLE 11.8 Molar Heats of Fusion for Selected Substances

Substance Melting Point (°C) ΔHfus (kJ/mol)
Argon -190 1.3
Benzene 5.5 10.9
Ethanol -117.3 7.61
Diethyl ether -116.2 6.90
Mercury -39 23.4
Methane -183 0.84
Water 0 6.01

53
11.6 Phase Changes

Solid-Liquid Phase Transition

54
11.6 Phase Changes

Solid-Vapor Phase Transition

Sublimation is the process by which
molecules go directly from the solid
phase to the vapor phase.

The reverse process, in which

molecules go directly from the vapor
phase to the solid phase, is called
deposition.
© The McGraw-Hill Companies,
Inc./Ken Karp, photographer

55
11.6 Phase Changes

Solid-Vapor Phase Transition

The molar enthalpy of sublimation of a substance is the
energy, usually expressed in kilojoules, required to sublime 1
mole of a solid.

(Hess’ Law)

56
 SAMPLE PROBLEM
11.7
(b) Calculate the amount of heat deposited on the skin of a
person burned by 1.00 g of steam at . (See sample problem
11.7)

57
 SAMPLE PROBLEM
11.7
Solution
(b)

Most of the burning occurs when the steam condenses to

liquid.
58
11.7 Phase Diagrams

Topics
Phase Diagrams

Learning Objectives
• Recognize and describe the forces that hold the molecules (or atoms
or ions) together in substances.
• Explain the physical properties that arise because of these forces.
• Correlate the phase changes with the type and magnitude of
intermolecular forces. 59
11.7 Phase Diagrams

Phase Diagrams
A phase diagram summarizes the conditions (temperature
and pressure) at which a substance exists as a solid, liquid, or
gas.

60
11.7 Phase Diagrams

Phase Diagrams
Heating solid initially at and 1 atm (point 1) causes it to
sublime when it reaches (point 2). At , increasing the pressure
from 1 atm (point 3) to about 70 atm (point 4) will cause to
condense to a liquid.

61
11.7 Phase Diagrams

Phase Diagrams
The Unusual Phase Diagram of Water

62
11.7 Phase Diagrams

The Unusual Phase Diagram of Water

• In water’s diagram, the slope of the line between the solid and liquid
states is negative rather than positive. The reason is that water is an
unusual substance in that its solid state is less dense than the liquid
state. Ice floats in liquid water.

• Therefore, a pressure change has the opposite effect on those two

phases. If ice is relatively near its melting point, it can be changed into
liquid water by the application of pressure. The water molecules are
actually closer together in the liquid phase than they are in the solid
phase.

• For water, the critical pressure is very high, 217.75 atm. The critical
point is the intersection point of the critical temperature and the
critical pressure.
63
 SAMPLE PROBLEM
11.7
Using the following phase diagram,

(a) determine the normal boiling point and the normal

melting point of the substance,

(b) determine the physical state of the substance at 2 atm and

, and

(c) determine the pressure and temperature that correspond

to the triple point of the substance.

64
SAMPLE PROBLEM
11.7

65
 SAMPLE PROBLEM
11.7
Solution
(a) The normal boiling and melting points are 140°C and
205°C, respectively.

66
 SAMPLE PROBLEM
11.7
Solution
(b) At 2 atm and 110°C the substance is a solid.

67
 SAMPLE PROBLEM
11.7
Solution
(c) The triple point occurs at 0.8 atm and 115°C.

68