Intermolecular

Forces
and
Liquids and
Solids 1
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.

2 Phases
Solid phase - ice
Liquid phase - water

2
• The state a substance is in at
a particular temperature and
pressure depends on two
antagonistic entities:
– The kinetic energy of the
particles.
– The strength of the
attractions between the
particles.

3
Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a 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)
“Measure” of intermolecular force
boiling point
Generally, intermolecular
melting point
forces are much weaker than DHvap
intramolecular forces. DHfus
4
DHsub
Intermolecular Forces

The attractions between molecules are not nearly as

strong as the intramolecular attractions that hold
compounds together.
These intermolecular attractions are, however, strong
enough to control physical properties, such as boiling
and melting points, vapor pressures, and viscosities.
These intermolecular forces as a group are referred
to as van der Waals forces.
Intermolecular Forces
Dipole-Dipole Forces
Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

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Dipole–Dipole Interactions
– The positive end of one is attracted to the negative end of the
other, and vice versa.
– These forces are only important when the molecules are close
to each other.
The more polar the molecule, the
higher its boiling point.
Ion-Dipole Forces
Attractive forces between an ion and a polar
molecule

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Ion–Dipole Interactions
• The strength of these forces is what makes it possible for
ionic substances to dissolve in polar solvents.
 Induced Dipoles Interacting With Each Other
Dipole-induced
dipole bonds are
those electric bonds
that exist between a
molecule with a
permanent dipole
moment and a
molecule in which a
temporary dipole
moment has been
induced (by the other
molecule)
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Dispersion Forces
Attractive forces that arise as a result of temporary dipoles
induced in atoms or molecules

ion-induced dipole interaction dipole-induced dipole interaction

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Dispersion Forces Continued
Polarizability is the ease with which the electron distribution in
the atom or molecule can be distorted.

Polarizability increases with:

• greater number of electrons
• more diffuse electron cloud

Dispersion forces usually

increase with molar mass.

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London Dispersion Forces
While the electrons in
the 1s orbital of
helium would repel
each other (and,
therefore, tend to stay
far away from each
other), it does happen
that they occasionally
wind up on the same
side of the atom.
At that instant, then, the
helium atom is polar,
with an excess of
electrons on the left side
and a shortage on the
right side.
Another helium atom
nearby, then, would
have a dipole induced
in it, as the electrons
on the left side of
helium atom 2 repel
the electrons in the
cloud on helium atom
1.
London dispersion
forces, or dispersion
forces, are
attractions between
an instantaneous
dipole and an
induced dipole.
• These forces are
present in all
molecules, whether
they are polar or
nonpolar.
• The tendency of an
electron cloud to
distort in this way is
called
polarizability.
Factors Affecting London Forces
• The shape of the molecule affects
the strength of dispersion forces:
long, skinny molecules (like n-
pentane) tend to have stronger
dispersion forces than short, fat
ones (like neopentane).
• This is due to the increased surface
area in n-pentane.
Factors Affecting London Forces
• The strength of
dispersion forces tends
to increase with
increased molecular
weight.
• Larger atoms have
larger electron clouds
that are easier to
polarize.
 Which Have a Greater Effect?
Dipole–Dipole Interactions or Dispersion Forces

• If two molecules are of comparable size and shape, dipole–

dipole interactions will likely be the dominating force.
• If one molecule is much larger than another, dispersion
forces will likely determine its physical properties.
What type(s) of intermolecular forces exist
between each of the following molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are also
dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces.

S
SO2
SO2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules.
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How Do We Explain This?
• The nonpolar series
(SnH4 to CH4)
follow the expected
trend.
• The polar series
follow the trend
until you get to the
smallest molecules
in each group.
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.

A H…B or A H…A
A & B are N, O, or F

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Hydrogen Bonding

• The dipole–dipole
interactions experienced
when H is bonded to N, O,
or F are unusually strong.
 Hydrogen Bond

HCOOH and water 29

Hydrogen Bonding
• Hydrogen bonding
arises in part from
the high
electronegativity of
nitrogen, oxygen,
and fluorine.

Also, when hydrogen is bonded to one

of those very electronegative elements,
the hydrogen nucleus is exposed.
 True or False ? Why?
For molecules with similar molecular
weights, the dispersion
forces become stronger as the
molecules become
more polarizable.

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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.

Strong
intermolecular
forces

High
surface
tension

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Surface tension
results from the
net inward force
experienced by
the molecules on
the surface of a
liquid.
Properties of Liquids
Cohesion is the intermolecular attraction between like
molecules
Adhesion is an attraction between unlike molecules
Adhesion

Cohesion

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Properties of Liquids
Viscosity is a measure of a fluid’s resistance to flow.
Strong
intermolecular
forces

High
viscosity

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• Resistance of a liquid to
flow is called viscosity.
• It is related to the ease
with which molecules
can move past each
other.
• Viscosity increases with
stronger intermolecular
forces and decreases
with higher
temperature.
3-D Structure of Water Water is a Unique Substance

Maximum Density
40C

Density of Water

Ice is less dense than water

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3-D Structure of Water

Density of Water

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Crystal Structure
A crystalline solid possesses rigid and long-range order. In a crystalline solid,
atoms, molecules or ions occupy specific (predictable) positions.
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 At lattice points:

point • Atoms
• Molecules
• Ions

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Unit Cell Unit cells in 3 dimensions
Seven Basic Unit Cells

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Three Types of Cubic Unit Cells

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 Arrangement of Identical Spheres in a Simple Cubic Cell

The coordination number is defined as the number of atoms (or ions)

surrounding an atom (or ion) in a crystal lattice. 44
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)
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Relation Between Edge Length and Atomic Radius

48
When silver crystallizes, it forms face-centered cubic cells. The unit cell
edge length is 409 pm. Calculate the density of silver.

m V = a3 = (409 pm)3 = 6.83 x 10-23 cm3

d=
V
4 atoms/unit cell in a face-centered cubic cell

107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10 -22 g
mole Ag 6.022 x 1023 atoms

m 7.17 x 10-22 g 3
d= = = 10.5 g/cm
V 6.83 x 10-23 cm3

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Metallic iron crystallizes in a cubic
lattice. The unit cell edge length is 287
pm. The density of iron is 7.87 g/cm . 3

How many iron atoms are within a unit

cell?
52
Europium crystallizes in a body-
centered cubic lattice (the Eu atoms
occupy only the lattice points). The
density of Eu is 5.26 g/cm . 3

Calculate the unit cell edge length in

pm.
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 Types of Crystals
The structures and properties of crystals, such as melting point, density, and hardness, are
determined by the kinds of forces that hold the particles together. We can classify any crystal
as one of four types: ionic, covalent, molecular, or metallic.
Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity

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CsCl ZnS CaF2
How many Na+and Cl-
ions are in each NaCl unit
cell?

55
Thus, there are four Na+ ions and four Cl- ions in each
NaCl unit cell. This result agrees with sodium chloride’s
empirical formula.
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Most ionic crystals have high melting points, an
indication of the strong cohesive forces holding the ions
together. A measure of the stability of ionic crystals is the
lattice ; the higher the lattice energy, the more stable the
compound. These solids do not conduct electricity
because the ions are fixed in position. However, in the
molten state (that is, when melted) or dissolved in water,
the ions are free to move and the resulting liquid is
electrically conducting.

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 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
atoms

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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

water benzene

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 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-

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