Intermolecular Forces and

Liquids and Solids

 Intermolecular forces
• There are 2 types of attraction in molecules: intramolecular
bonds & intermolecular forces

• We have already looked at intramolecular bonds (ionic,

covalent, polar covalent, metallic)
• Intermolecular forces (IMF) have to do with the attraction between
molecules (versus the attraction between atoms in a
molecule, metal, or compound)

• The three IMFs are: 1) H-bonding, 2) dipole - dipole, 3) Iom-dipole

and 4) London Dispersion forces (in order of decreasing
strength)
Intermolecular forces are attractive forces between molecules.
(Example: water molecule to water molecule)
Intramolecular forces hold atoms together within in a molecule.
(Example: H to O bond within a water molecule).

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

Generally, intermolecular forces are

much weaker than intramolecular
forces.

11.2
 Intermolecular Forces

1. London Forces (a.k.a. Dispersion Forces) Weakest

2. Dipole-Dipole Interactions
3. Ion-Dipole Interactions
-(Salt dissolving in solution; Na+ and Cl- )

4. Hydrogen Bonding (STRONGEST)

 Intermolecular Forces

Dipole-Dipole Forces 6

Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

 Ion-Dipole Forces

Attractive forces between an ion and a polar molecule

Ion-Dipole Interaction

The larger the charge the stronger the force

11.2
Olmsted Williams Fig 10-34

A molecular picture showing the ion-dipole

Interaction that helps a solid ionic crystal dissolve
in water. The arrows indicate ion-dipole interactions.
London Dispersion forces (LDF)
• London forces (also called van der Waal forces) are
due to small dipoles that exist in non-polar molecules

• The resulting tiny dipoles cause attractions between

atoms/molecules (the greater the mass, the greater
the London forces)
 The Hydrogen Bond
STRONGEST
INTERMOLECULAR
FORCE
http://chemmovies.unl.edu/ChemAnime/HYBOND/HYBONDD.html
Animation
Hydrogen - bonding
• H-bonding is a special type of dipole - dipole
attraction that is very strong

• It occurs when F, O, or N are bonded to H

• They are given a special name (H-bonding)

because compounds containing these forces
are important in biological systems
• A hydrogen bond is an intermolecular
bond.

• A hydrogen bond is formed between

polar molecules that contain hydrogen
covalently bonded to a small, highly
electronegative atom: F, O, N.

F—H
O—H
N—H
• it will be attracted to another F, O, or N,
on another molecule.

• A dipole-dipole bond bond will be

formed between the two molecules
which is called a hydrogen bond.
hydrogen
bond
covalent
bond
covalent
bond
Gases: The average kinetic energy of the
gas molecules is much larger than the
average energy of the attractions between 14
them.
Liquids: the intermolecular attractive forces
are strong enough to hold the molecules
close together, but without much order.
Solids: the intermolecular attractive forces
are strong enough to lock molecules in place
(high order).
 Properties of Liquids

Surface tension is the amount of energy required to stretch

15
or increase the surface of a liquid by a unit area.

Strong
intermolecular
forces

High
surface
tension
 Properties of Liquids

Cohesion is the intermolecular attraction between like molecules

16

Adhesion is an attraction between unlike molecules

Adhesion

Cohesion
 Properties of Liquids

Viscosity is a measure of a fluid’s resistance to flow. 17

Strong
intermolecular
forces

High
viscosity
18
A crystalline solid possesses rigid and long-range order. In a
crystalline solid, atoms, molecules or ions occupy specific
(predictable) positions. 19

An amorphous solid does not possess a well-defined

arrangement and long-range molecular order.

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
 Types of Crystals
Ionic Crystals
• Lattice points occupied by cations and anions 20

• Held together by electrostatic attraction

• Hard, brittle, high melting point
• Poor conductor of heat and electricity

CsCl ZnS CaF2

Cesuim chloride Zinc sulphide Calcium fluoride
 Types of Crystals
Covalent Crystals
• Lattice points occupied by atoms 21

• Held together by covalent bonds

• Hard, high melting point
• Poor conductor of heat and electricity
carbon
atoms

diamond graphite
 Types of Crystals
Molecular Crystals
• Lattice points occupied by molecules 22

• Held together by intermolecular forces

• Soft, low melting point

• Poor conductor of heat and electricity

water benzene
 Types of Crystals
Metallic Crystals
• Lattice points occupied by metal atoms 23

• 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-
The equilibrium vapor pressure is the vapor pressure
measured when a dynamic equilibrium exists between
condensation and evaporation 24

H2O (l) H2O (g)

Dynamic Equilibrium
Rate of Rate of
condensation
= evaporation
 Measurement of Vapor Pressure

25

Before At
Evaporation Equilibrium
 Solid-Liquid Equilibrium

26

H2O (s) H2O (l)

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
The boiling point is the temperature at which the
(equilibrium) vapor pressure of a liquid is equal to the
external pressure. 27

The normal boiling point is the temperature at which a liquid

boils when the external pressure is 1 atm.
 The critical temperature (Tc) is the temperature above which
the gas cannot be made to liquefy, no matter how great the
applied pressure. 28

The critical pressure

(Pc) is the minimum
pressure that must be
applied to bring about
liquefaction at the
critical temperature.
Summary
• The bigger the IMF’s, the more energy it takes to overcome
them . . . . . . thus

• The bigger the IMF’s, the higher the melting and boiling point

• Bonds are stronger than IMF’s, so the melting and boiling

points of covalent network solids (i.e.. diamond), ionic
compounds (i.e.. salts), and metals (i.e.. iron) are much higher
than molecular substances (i.e.. water)
IMF
1. Intramolecular are stronger.

2. A covalent bond is 100x stronger.

3. The molecules gather together as liquids or solids

at low temperatures.

4. London forces
• Are present in all compounds
• Can occur between atoms or molecules
• Are transient in nature (dipole-dipole are more permanent).
• London forces are weaker
5. a) O2 would be lower because it is smaller in mass.
London attractions are smaller and consequently
lower melting/boiling points.

b) O2 because it has only London forces. NO has a

is polar, giving it small dipoles.

6. C8H18 would have the higher melting/boiling point.

This is a result of the stronger London forces

7. a large difference in electronegativity and the small

sizes of (FON) atoms.