Chapter 11

Intermolecular Forces, Liquids, and Solids

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 States of Matter
• The fundamental difference between states of matter is the distance between
particles.
• Intermolecular forces – the forces that exist between molecules
– Responsible for most of the physical properties of liquids and solids
• Because in the solid and liquid states particles are closer together, we refer to
them as condensed phases.

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 States of Matter
• The fundamental difference between states of matter is the distance between
particles.
• Intermolecular forces – the forces that exist between molecules
– Responsible for most of the physical properties of liquids and solids
• Because in the solid and liquid states particles are closer together, we refer to
them as condensed phases.

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 The States of Matter
Which physical state a substance is in (at a given temp & pressure) depends on the
balance between:
1. the kinetic energy of the particles
• Keeps the particles moving
2. the strength of the attractions between the particles (intermolecular forces)
• Keeps the particles together

Average KE is higher than

attractive intermolecular forces

Attractive intermolecular forces

are strong enough to hold
particles together but not strong
enough to keep them from
moving past one another

Attractive intermolecular forces

are strong enough to hold
particles together and lock them
in place
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 Intermolecular Forces

• The attractions between molecules are not nearly as

strong as the intramolecular attractions (like ionic or
covalent bonds) that hold compounds together.
• But they are strong enough to control physical
properties such as boiling and melting points, vapor
pressures, and viscosities. 5
 Intermolecular Forces
• Ion-dipole forces
• Dipole-dipole forces van der Waals forces
• London dispersion forces
• Hydrogen bonding

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 Ion-Dipole Interactions
• Ion-dipole interactions – exist between an ion and
the partial charge on the end of a polar molecule
– important in solutions of ions.
– The strength of these forces are what make it possible for
ionic substances to dissolve in polar solvents.

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Dipole-Dipole Forces
• Molecules that have
permanent dipoles
(meaning the dipoles are
always there) are attracted
to each other.
– Dipole-dipole forces - 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.
• Weaker than ion-dipole forces
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 Dipole-Dipole Forces

• The strength of intermolecular attractions increases

with increasing polarity
– The more polar the molecule, the higher is its boiling
point.

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 London Dispersion Forces

• Attractive forces exist between nonpolar atoms and molecules, even

though there is no dipole moment.
• Ex:
– Electrons in the 1s orbital of helium repel each other
– So they tend to stay far away from each other
– But it occasionally happens that the 2 electrons wind up on the same side of
the atom.
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 London Dispersion Forces

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.
– This is called an instantaneous dipole

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 London Dispersion Forces

Another helium 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.
– This is called an induced dipole
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 London Dispersion Forces

London dispersion forces, or dispersion forces,

are attractions between an instantaneous dipole
and an induced dipole.

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 London Dispersion Forces

• The strength of the dispersion forces depends on

the polarizability of the atoms or molecules
– Polarizability - the ease of an electron cloud to be
distorted to induce a momentary dipole
• Measure of “squashiness”
• The more polarizable, the larger dispersion forces

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 Factors Affecting London Forces
• Size:
– Larger atoms have larger electron clouds which are
easier to polarize.
– So the strength of dispersion forces tends to increase
with increased molecular weight.
• Ex: boiling points increase with increasing molecular weight

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Factors Affecting London Forces

• Shape of the molecule

– 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.

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Comparing Dipole-Dipole & Dispersion Forces

• Dispersion forces are present in all molecules, whether

they are polar or nonpolar.
– So which force has greater effect? Dipole-Dipole Interactions or
Dispersion Forces

1. Dipole-dipole interactions will likely determine the

physical properties if two molecules are of comparable
size and shape
2. Dispersion forces will likely determine its physical
properties if one molecule is much larger than another

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Hydrogen Bonding: First, an Example

• Boiling point curves:

The nonpolar series
(SnH4 to CH4) follows
the expected trend.
• The polar series
follows the trend from
H2Te through H2S, but
water is quite an
anomaly.

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 Hydrogen Bonding
• Hydrogen bond –attraction between the
hydrogen atom in a polar bond
(particularly an H—F, H—O, or H—N bond)
and nonbonding electron pair on a nearby
small electronegative ion or atom (usually
an F, O, or N atom in another molecule)
– Special case of dipole-dipole attraction
– Unusually strong
• In general, stronger than other intermolecular forces
• But still weaker than chemical bonds
• Account for high boiling and melting points, high
heats of vaporization in water and other substances
with hydrogen bonding
• Play major roles in protein and DNA function

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 Hydrogen Bonding
• Explains why ice floats!
• Ice is less dense than liquid
water (not the normal trend
for solids)
• This is because of hydrogen
bonding in water: causes the
solid to assume a more open,
ordered arrangement

• Hydrogen bonding arises in part from the high electronegativity of nitrogen,

oxygen, and fluorine.
H N H O H F
• When hydrogen is bonded to one of those very electronegative elements, the 20
hydrogen nucleus is exposed.
 Summarizing Intermolecular Forces
• Dispersion forces are found in all molecules (increase with increasing molecular weight and depend on
shape)
• Dipole-dipole forces add to the effect of dispersion forces and are found in polar molecules
• Hydrogen bonds required H atoms bonded to F, O, or N and also add to effect of dispersion forces; they
tend to be stronger than other intermolecular forces
• None of intermolecular attractions are as strong as ionic or covalent bonds
• All of these attractions are additive – so the more attractions between 2 molecules, the harder they are to
separate

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 Examples
• Identify the intermolecular attractions present
in the following substances and circle the
substance with the highest boiling point:
CH3CH3, CH3OH, CH3CH2OH

• List the substances BaCl2, H2, CO, HF, and Ne in

order of increasing boiling points.
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 Examples
• Identify the intermolecular attractions present
in the following substances and circle the
substance with the highest boiling point:
CH3CH3, CH3OH, CH3CH2OH
Dispersion forces only Dispersion forces, dipole-dipole forces, and hydrogen bonds

• List the substances BaCl2, H2, CO, HF, and Ne in

order of increasing boiling points.
H2 < Ne < CO < HF < BaCl2
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Intermolecular Forces Affect Many
Physical Properties

The strength of the

attractions between
particles can greatly
affect the properties
of a substance or
solution.

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 Viscosity
• Viscosity - resistance of a liquid
to flow
– The greater the viscosity, the
slower the liquid flows
• It is related to the ease with
which molecules can move
past each other
– Therefore, it’s related to
attractive intermolecular forces
and molecular structure (ie if
they get tangled easily)
• Viscosity
– increases with increasing
molecular weight
– decreases with higher
temperature

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Surface Tension
• Surface tension – energy
required to increase the surface
area of a liquid by a unit amount
• Results from the net inward force
experienced by the molecules on
the surface of a liquid
– A molecule in the interior is
attracted equally in all directions
– But a molecule at the surface is
only attracted to others below or
beside it
– Result: molecules are pulled
inward, away from the surface
– Therefore, surface area is reduced
• that’s why water beads up or forms
drops

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Other Terms Involving Intermolecular Forces
Adhesive forces are
• Cohesive forces stronger than
cohesive forces
– Bind similar molecules to each other
• Ex: hydrogen bonding in water
• Adhesive forces H2O Hg

– Bind a substance to another surface

• Ex: Water adheres to glass surfaces,
creating a U-shaped meniscus
• Capillary action Cohesive forces are
– Rise of liquids up very narrow tubes stronger than
adhesive forces
– Caused by both adhesive and cohesive
forces

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Phase Changes (Changes of State)

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 Energy Changes Associated with Changes
of State

• Energy is added to a solid to cause the molecules to be able to

start moving past one another, when it becomes a liquid
• The process of melting is also sometimes called fusion (which
seems backward)
• The heat of fusion ΔHfus is the energy required to change a
solid at its melting point to a liquid.
– Ex: When we put ice in our drinks, the ice melts, requiring energy
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(heat) from the surroundings, the drink. After removing heat from
 Energy Changes Associated with Changes
of State
ΔHvap is usually much larger
than ΔHfus because
essentially all
intermolecular attractions
must be overcome to form
a gas, whereas some
remain in a liquid

• The gas-phase molecules over a liquid exert a pressure called vapor pressure
• As temperature increases, vapor pressure increases (because more
molecules are entering the gas phase) until it equals the external pressure
over the liquid (then the liquid boils)
• The heat of vaporization ΔHvap is the energy required to change a liquid at
its boiling point to a gas
– Example: Your body regulates its temperature using this. When you sweat, the
moisture evaporates, requiring energy (heat from your body). Removing heat from
your body cools you off 30
 Energy Changes Associated with Changes
of State

ΔHsub of mercury

• Sublimation –when molecules of a solid are

transformed directly into the gaseous state
• The heat of sublimation ΔHsub is the energy required to
change a solid to a gas
– It equals the sum of ΔHvap and ΔHfus
– Ex: Dry ice (solid CO2 sublimes) 31
 Phase Changes
• Endothermic:
− Melting
− Boiling
− Sublimation
• Exothermic:
– Condensation
– Freezing
– Deposition

• The following pairs are equal in magnitude, but opposite in sign to

each other
– heat of vaporization (positive), heat of condensation (negative)
– heat of fusion (positive), heat of freezing (negative)
– heat of sublimation (positive), heat of deposition (negative) 32
Energy Changes Associated with Changes
of State
• The temperature of the
substance does not rise during
a phase change
– This is because the heat added
to the system at the melting and
boiling points goes into pulling
the molecules farther apart from
each other, until the whole
sample has changed phases
– So the heat during the phase
change is not used to change the
temperature of the system until
after the phase change is over
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Energy Changes Associated with Changes
of State
• Heating curve – a graph of the
temperature of the system versus
the amount of heat added
• Recall: the amount of heat, q,
needed to raise temp of a
substance:

q = Cs  m  T

where,
Cs is specific heat of substance,
m is mass of substance,
ΔT is temp change 34
 Example
Calculate the enthalpy change upon converting 1.00 mol of ice at -25 °C to
water vapor (steam) at 125 °C under a constant pressure of 1 atm. The
specific heats of ice, water, and steam are 2.04 J/g-K, 4.18 J/g-K, and 1.84
J/g-K, respectively. For H2O, ΔHfus = 6.01 kJ/mol and ΔHvap = 40.67 kJ/mol.

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 Example
Calculate the enthalpy change upon converting 1.00 mol of ice at -25 °C to
water vapor (steam) at 125 °C under a constant pressure of 1 atm. The
specific heats of ice, water, and steam are 2.04 J/g-K, 4.18 J/g-K, and 1.84
J/g-K, respectively. For H2O, ΔHfus = 6.01 kJ/mol and ΔHvap = 40.67 kJ/mol.
Answer: 0.91 kJ + 6.01 kJ + 7.52 kJ + 40.7 kJ + 0.83 kJ = 56.0 kJ

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 Critical Temperature and Pressure
• A gas normally liquefies at some temperature when pressure
is applied to it
– Example:
• Water vapor at 100 °C: if we increase pressure to 760 torr, liquid water will
form
• Water vapor at 110 °C: now we have to increase pressure to 1075 torr to
form liquid water
• Water vapor at 374 °C: liquid phase only forms at 1.655 x 105 torr
• Above this temperature, no amount of pressure will cause a distinct liquid
phase to form
• Critical temperature – the highest temperature at which a
distinct liquid phase can form
• Critical pressure – the pressure required to bring about
liquefaction at the the critical temperature 37
Vapor Pressure
• At any temperature,
some molecules in a
liquid have enough
energy to escape.
• As the temperature rises,
the number of molecules
that have enough energy
to escape increases.
• As more molecules
escape the liquid, the
pressure they exert
increases.
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 Vapor Pressure

• The liquid and vapor reach a

state of dynamic equilibrium:
liquid molecules evaporate
and vapor molecules
condense at the same rate.
– (dynamic equilibrium or just
equilibrium – condition in which
two opposing processes are
occurring simultaneously at
Note: Liquids in open containers eventually dry equal rate)
because there is no equilibrium occurring. • Vapor pressure – the pressure
As molecules evaporate, they spread out and
are rarely recaptured by the liquid. exerted by a vapor when the
liquid and vapor states are in
dynamic equilibrium
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 Vapor Pressure
• Only the fastest molecules of the liquid have
sufficient kinetic energy to escape the liquid and
enter vapor phase (shaded areas)
• The higher the temp, the larger is the fraction of
molecules with energy to escape

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 Vapor Pressure
• Boiling point of a liquid is
the temperature at which it’s
vapor pressure equals the
external pressure acting on
the surface of the liquid
– Then bubbles start forming in
the liquid
• Normal boiling point – the
boiling point of a liquid at 1
atm of pressure

• Liquids that evaporate

readily are said to be volatile Four substances that differ greatly in volatility:
as temp increases, vapor pressure increases
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 Phase Diagrams
• Phase diagrams display the state of a substance at various pressures and
temperatures and the places where equilibria exist between phases
– Allow us to predict the phase of a substance that is stable at any given
temperature and pressure
– Temperature and pressure are the axes
– It contains 3 curves: each represents the conditions of temp and pressure at
which the various phases can coexist at equilibrium

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 Phase Diagrams
• The circled line is the liquid-vapor interface.
– It starts at the triple point (T), the ONLY point at which all three states are in
equilibrium.
– It ends at the critical point (C), which is the critical temperature and critical pressure of
the substance
• above this point, the liquid and vapor are indistinguishable from each other
• the state of the substance is then called a supercritical fluid
– Each point along this line is the boiling point of the substance at that pressure.

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 Phase Diagrams
• The circled line is the liquid-solid interface.
– Each point along this line is the melting point of the substance at
that pressure.
• Note: the melting point and the freezing point of a substance are identical
• Normal melting point – the melting point at 1 atm

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 Phase Diagrams
• Along the circled line the solid and gas phases are
in equilibrium
– Below the triple point the substance cannot exist in the
liquid state.
– The sublimation point at each pressure is along this line.

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Phase Diagram of Water
• Note the high critical
temperature and critical
pressure.
– These are due to the strong van
der Waals forces between water
molecules.
• The slope of the solid-liquid
line is negative (atypical)
– The melting point decreases with
increasing pressure
– Water is among the very few
substances whose liquid form is
more compact than its solid form
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Phase Diagram of Carbon Dioxide

• Triple point for CO2 is

even higher
– Carbon dioxide cannot
exist in the liquid state
at pressures below
5.11 atm
– So CO2 sublimes at
normal pressures

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We can think of solids as
falling into two groups:
Solids
– Crystalline - particles are
in highly ordered
arrangement.
• Melts at a certain temp
– Amorphous - there is no
particular order in the
arrangement of particles
• Melts over a range of
temperatures

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 OMIT rest of Chapter 11
• Section 11.7: OMIT from “Unit Cells” onward
• Section 11.8: OMIT whole section

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