9/15/2023

Chapter 11
Liquids
and
Intermolecular Forces

Chapter 11 – Intermolecular Forces

Why does ice float?

How does a water bug

Why does rubbing stay on the surface?
alcohol make skin
feel cool?
Why is dry ice “dry”?

What do the numbers

mean on a bottle of
motor oil?
All of these questions can be answered with
an understanding of how molecules and
other particles interact with one another.

Chapter 11 – Intermolecular Forces

What are intermolecular forces (IMFs)?

11.1 Molecular Comparison of Gases, Liquids, & Solids
11.2 Intermolecular Forces

How do IMFs explain properties of liquids?

11.3 Select Properties of Liquids

How do IMFs explain phase changes?

11.4 Phase Changes
11.5 Vapor Pressure
11.6 Phase Diagrams
11.7 Liquid Crystals

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Gases, Liquids, & Solids

A Molecular Comparison

Gases: Liquids: Solids:

rapidly moving, somewhere in- regular array of
widely-spaced between, but with closely-spaced,
particles. some special fixed particles.
properties

11.1 – Gases Liquids, and Solids

Compare three halogens all at room temperature:

What is the fundamental difference between phases of matter?

Distance between particles!

11.1 – Gases Liquids, and Solids

In gases, the kinetic energy of the

Intermolecular attractions
particles allow them to overcome the
result in condensed phases
intermolecular forces (recall KMT –
(liquids and solids).
negligible attractions for gases).

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11.1 – Gases Liquids, and Solids

Phase is determined by:
potential kinetic

The potential energy, in the form of _______________

attractive forces
between particles, tends to draw particles together.
The kinetic energy associated with ______________
movement
tends to disperse particles.

>> energies of attraction

• Gas: Kinetic energies ____ Cl2 (g)

• Liquid: Kinetic energies ____

~ energies of attraction Br2 (l)

<< energies of attraction

• Solid: Kinetic energies ____ I2 (s)

Concept Check Solids, Liquids, Gases

Determine if the following statements best describe a solid,
liquid, gas, or more than one phase.
Possible Answers:
• compressible
• condensed phases
• does not flow
Solid Liquid • does not expand to fill its container
• flows readily
• expands to fill its container
• KE similar to energies of inter-
particle attraction
• KE << energies of inter-particle
Gas Solid AND Liquid attraction
• KE >> energies of inter-particle
attraction
• particles are closely packed in an
orderly array
Liquid AND Gas • particles are closely packed but
randomly oriented
• particles are far apart
• retains its own shape
• virtually incompressible

11.2 Intermolecular Forces

Part 1

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11.2 Intermolecular Forces

Intermolecular Forces (IMFs) are attractive forces between
molecules.
• Weaker than intramolecular forces (covalent, ionic, or
metallic bonds)
• Represented by dotted lines

Strong intramolecular
attraction (covalent bond)
431 kJ/mol

Weak intermolecular attraction

16 kJ/mol

11.2 Intermolecular Forces

Intramolecular Forces Intermolecular Forces

• Found within a molecule • Found between molecules
• Covalent, ionic, or metallic • Dispersion, dipole-dipole, or
bond hydrogen bonding forces
• Relatively strong • Relatively weak

11.2 Intermolecular Forces

Intermolecular forces (IMFs) are attractive forces between

molecules.
• Many physical properties reflect the strength of intermolecular
forces, like boiling points, melting points, viscosity, surface
tension and capillary action.

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11.2 Intermolecular Forces

Intermolecular forces (IMFs) are much more important in the

properties of liquids and solids, but can also affect properties
of gases (van der Waal’s equation).

𝒏𝑹𝑻 𝒏𝟐 𝒂
𝑷
𝑽 𝒏𝒃 𝑽𝟐

Look at the correction factor, a, for real gases when

comparing the noble gases. The increase in the value of a
is due to greater dispersion forces as the size of atoms
increases.

11.2 Intermolecular Forces

Three types of intermolecular forces (IMF) can exist between

electrically neutral molecules:
1. London dispersion forces
2. Dipole-dipole forces van der Walls forces

3. Hydrogen bonding

An additional intermolecular force which is important in solutions:

4. Ion-dipole forces

All IM forces are electrostatic attractions between

positive and negative species.

11.2 Intermolecular Forces

Dispersion Forces
Dispersion forces (London dispersion forces) arise from temporary
electron cloud distortions which cause temporary polarity (induced
dipoles).

• Dispersion forces exist between all particles.

• Dispersion forces are the only attractions present in atoms and
non-polar molecules.

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11.2 Intermolecular Forces

Dispersion Forces
Dispersion forces (London dispersion forces) arise from temporary
electron cloud distortions which cause temporary polarity (induced
dipoles).

• Instantaneous dipole-
induced dipoles
• The only IMF present in
nonpolar substances.
• Exists in ALL substances
because all substances
have electrons.

11.2 Intermolecular Forces

Dispersion Forces

Larger electron clouds are more

polarizable (distort easily).

The larger the molecule, the

stronger the dispersion forces.
Increasing molecule size

11.2 Intermolecular Forces

Dispersion Forces

As particle size increases This explains why at room

IMF strength between temp:
molecules increases • Cl2 is a gas
• Br2 is a liquid
Boiling point increases
• I2 is a solid

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Concept Check Dispersion Forces

For each pair, which has the stronger dispersion forces?

• He or Kr
• HCl or HBr
• CH4 or C2H6
• Br2 or Ar
• n-pentane (C5H12) or neopentane (C5H12)

11.2 Intermolecular Forces

Dispersion Forces

The shape of the molecule impacts the strength of dispersion

forces:
n-pentane Stronger neopentane
dispersion
forces

Long, unbranched Compact, branched

Large area of Small area of

intermolecular contact intermolecular contact
bp = 309 K bp = 283 K

11.2 Intermolecular Forces

Dipole-Dipole Interactions
SO2
Dipole-dipole interactions
are IMFs that exist between polar
molecules.

Repulsive dipole-dipole
interaction (blue)

The positive pole of one polar

molecule attracts the
negative pole of another.
• Repulsions also occur
• Molecules align to
maximize attractions
CH3CN Attractive dipole-
dipole interaction (red)

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11.2 Intermolecular Forces

Dipole-Dipole Interactions
How do I identify and compare dipole-dipole forces?
 Requires knowledge and understanding of molecular geometry.
That’s right – you’re not done with Lewis structures and VSEPR yet!

 For molecules of approximately equal mass, size, and shape,

the more polar the molecule, the stronger its IMFs.

11.2 Intermolecular Forces

Dipole-Dipole Forces

Which will have the greater effect, dipole-dipole interactions

or dispersion forces?

If two molecules are of If one molecule is much larger

comparable size and shape, than another, dispersion forces
dipole-dipole interactions will likely determine its physical
will likely be the dominating properties.
force.

Concept Check Dipole-Dipole Interactions

Which of the following compounds will experience
dipole-dipole interactions in the liquid state?

O2 HF CO CO2 CCl4 CH3OH

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Concept Check LDF vs. DDI

Rank the following molecules from strongest IMF to
weakest IMF.

MW μ
Molecule Rank?
(g/mol) (Debye)
SiH4 32.1 0
H2S 34.1 1.43
PH3 34.0 0.96
SO3 80.1 0

11.2 Intermolecular Forces

Part 2

11.2 Intermolecular Forces

Hydrogen Bonding

Boiling point generally increases

What’s happening here? with increasing molar mass.

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11.2 Intermolecular Forces

Hydrogen Bonding

Hydrogen bonding occurs between molecules that contain

hydrogen covalently bonded to fluorine, oxygen, or nitrogen.

• Unusually strong form of

dipole-dipole attraction.
• Much weaker than
covalent/ionic/metallic
bonding, but stronger than
most other IMFs.

11.2 Intermolecular Forces

Hydrogen Bonding

Hydrogen Bonding occurs when: 1

• Molecule 1: H is covalently 2
bonded to F, O, or N (to
initiate the H-bond)
• Molecule 2: F, O, or N must
have one or more lone pair
(to accept the H-bond)

Concept Check Hydrogen Bonding

Which of the following molecules participate in
hydrogen bonding when in a pure liquid state?

CH3NH2 CH3OCH3

NF3 CH3CH2OH

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11.2 Intermolecular Forces

Hydrogen Bonding in Water

Molecule MM IMF Boiling Point

H2O 18 hydrogen bonding 100°C
N2 28 dispersion -196°C
CCl4 154 dispersion 88°C
CHCl3 119 dipole-dipole 61°C
NH3 17 hydrogen bonding -33°C
HF 20 hydrogen bonding 20°C
CH3OH 32 hydrogen bonding 65°C
Water is a very small molecule with an
unexpectedly high boiling point. WHY?

11.2 Intermolecular Forces

Hydrogen Bonding in Water
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

hydrogen bond donor

1 2

hydrogen bond acceptor

3 4

Each H2O molecule can form four H bonds to other molecules!

11.2 Intermolecular Forces

Hydrogen Bonding in Water
The water molecules in ice are fixed into
an open tetrahedral arrangement as a
result of hydrogen bonding.

This open structure in ice makes it

less dense than liquid water.

What would happen when a lake freezes if ice were more dense
than water?

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11.2 Intermolecular Forces

Hydrogen Bonding in Water

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

11.2 Intermolecular Forces

Hydrogen Bonding

Hydrogen bonding occurs

between small molecules,
but is also critical in the
structure of macromolecules.

Hydrogen bonding is critical to the

structure of DNA and proteins.

11.2 Intermolecular Forces

Ion-Dipole Forces

Ion-dipole interactions occur between

an ion and a polar molecule.
• Important in aqueous solutions
• Strength of these forces makes it
possible for ionic substances to
dissolve in polar solvents… more
in Ch. 13!

Ion-dipole forces are typically the

strongest IMF.

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11.2 Intermolecular Forces

Comparing IMFs Ranking Strength of IMFs:
1. Substances capable of H-
bonding usually have
stronger total IMFs.
2. When comparing two
substances that differ in
molar mass by more than a
few units, dispersion forces
dominate.
3. If you are comparing two
molecules of very similar
molar mass, dipole-dipole
interactions will dominate.

Concept Check Predominant IMF

Match each molecule to its predominant
intermolecular force.

• HF (aq)

• C6H6 (l)

• CH3Cl (g)

• KCl (aq)

Concept Check All IMFs

What is/are all the intermolecular forces (IMFs) present
among molecules of liquid hydrogen cyanide (HCN)?
Choose one or all that apply.

dispersion forces

 dipole-dipole interactions

 hydrogen bonding

 ion-dipole interactions

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11.3 & 8.5 Select Properties of Liquids

11.3 & 8.5 Select Properties of Liquids

In addition to boiling point and melting point, there are some
unique properties of liquids that we can attribute to the strength
of intermolecular forces:

 Viscosity
 Surface tension
 Capillary action
 Heats of vaporization & fusion (11.4)
 Vapor pressure (11.5)

11.3 & 8.5 Select Properties of Liquids

Viscosity

Viscosity is defined as the

resistance to flow; a measure of
the rate at which molecules
“slide” past one another

• Viscosity values are proportional to

IM forces and particle size

• As IMF ↑, viscosity ↑

• As temp ↑, viscosity ↓

[Link]

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11.3 & 8.5 Select Properties of Liquids

Surface Tension

Surface tension is the energy required

to increase the surface area of a liquid
by a given amount.
• In order to move to the surface to
increase the surface area,
molecules must overcome IMFs.
• Molecules at the surface are more
tightly packed.

11.3 & 8.5 Select Properties of Liquids

Surface Tension

As IMF ↑, surface tension ↑

Why does mercury “bead”

better than water?

11.3 & 8.5 Select Properties of Liquids

Capillary Action

Capillary action is the phenomena

of water (or aqueous solution)
rising up a small diameter glass
tube. It is a result of the
competing attraction of
• Adhesive forces of water
molecules (polar) to glass
(also polar)
̶ increases surface area Liquid climbs the tube until
• Cohesive forces (surface gravity balances the combined
tension) of water adhesive and cohesive forces.
molecules to each other
̶ decreases surface area

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11.3 & 8.5 Select Properties of Liquids

Capillary Action
concave convex

11.3 & 8.5 Select Properties of Liquids

Phase Changes

IMFs determine the temperature

at which substances undergo
phase changes.

11.3 & 8.5 Select Properties of Liquids

Vapor Pressure

In a closed container, a liquid and

its vapor will reach a state of
dynamic equilibrium
(rate of evaporation = rate of
condensation).

The vapor pressure is the pressure,

at a specific temperature, caused
by gas atoms/molecules in
equilibrium with the liquid state in
a closed vessel.

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11.3 & 8.5 Select Properties of Liquids

Vapor Pressure

Vapor pressure results from

particles in the liquid phase that
have enough kinetic energy to
overcome the attractive forces
between molecules and escape
into the gas phase.

A liquid with a high VP (would

easily evaporate) is volatile.

• As IMF ↑, vapor pressure ↓

• As temp ↑, vapor pressure ↑

11.3 & 8.5 Select Properties of Liquids

Vapor Pressure

The boiling point of a liquid is

defined as the temperature at
which the vapor pressure of the
liquid is equal to the atmospheric
pressure.

The normal boiling point is the

temperature at which the vapor
pressure is 1 atm (760 torr)

Boiling point increases with

increasing IMFs because
vapor pressure decreases.

11.3 & 8.5 Select Properties of Liquids

Summary

Viscosity: stronger IMF, higher viscosity

Surface Tension: stronger IMF, increased surface tension

Capillary Action: stronger IMF, decreased capillary action

Vapor Pressure: stronger IMF, lower vapor pressure

Boiling point: IMF, higher BP

Melting point: stronger IMF, higher MP

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Concept Check VP and BP

a. Which substance has the

strongest IM forces?

b. What is the normal

boiling point of ethanol?

c. What is the boiling point

of water at 600 torr?

d. What is the vapor pressure

of diethyl ether at 20°C?

Concept Check IMFs and Physical Properties

Large intermolecular forces (IMFs) in a substance
are manifested by ___________.
Choose one or all that apply.

high viscosity
 high surface tension
 low vapor pressure
 high boiling point

Concept Check Strengths of IMFs and BP

Rank the following molecules from the highest boiling point
to the lowest boiling point.
Hint: Consider the structures of each compound to determine the predominant IMF.

Molar Dipole
Molecule Mass Moment
(g/mol) (D)
pentane 72 0.055
2,2-dimethylpropane 72 0
1-pentanol 88 1.70
3-pentanol 88 1.64

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11.4 Phase Changes

11.6 Phase Diagrams

11.4 Phase Changes

Phase Changes occur when energy is added to or removed

from a substance.
IMFs determine the temperature
at which substances undergo
phase changes.

11.4 Phase Changes

When heat (q) is added to a substance, KE increases.
• This can raise the temperature OR change the phase of the
substance:

Heat of Vaporization (ΔHvap)

• Heat required to evaporate 1 mol of liquid at constant T
• Energy used to overcome IMFs during evaporation
• Generally reported at boiling T
• For water, ΔHvap = 40.7 kJ/mol

Heat of Fusion (ΔHfus)

• Heat required to melt 1 mol of liquid at constant T
• Energy used to overcome IMFs during melting
• Generally reported at melting T
• For water, ΔHvap = 6.01 kJ/mol

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11.4 Phase Changes

q = (amount)(H of phase change)

q = n x Hfus or vap

11.4 Phase Changes

Heating Curve

Energy change within

a single phase
q = m x c x T

q = n x Hfus q = n x Hvap
Energy change during a phase change

11.4 Phase Changes

Heating Curve

Example:
What is the change in energy (in kJ)
when 25.0 g of water is heated from
-25°C to 75? °C

There are 3 stages involved in this process:

1) heating of the solid to its melting point (q1)
2) the phase change from solid to liquid (q2)
3) heating the liquid to the final temperature (q3)
q1 q2 q3
𝒒𝒕𝒐𝒕𝒂𝒍 𝒎𝒄𝜟𝑻 𝒊𝒄𝒆 𝒏𝜟𝑯𝒇𝒖𝒔 𝒎𝒄𝜟𝑻 𝒘𝒂𝒕𝒆𝒓
Hint: The specific heat of ice is 2.03 J/(g·K) and water is 4.184 J/(g·K).
ΔHfus is 6.01 kJ/mol

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11.4 Phase Changes

Heating Curve
Example:
What is the change in energy (in kJ)
when 25.0 g of water is heated from
-25°C to 75? °C
q1 q2 q3
𝒒𝒕𝒐𝒕𝒂𝒍 𝒎𝒄𝜟𝑻 𝒊𝒄𝒆 𝒏𝜟𝑯𝒇𝒖𝒔 𝒎𝒄𝜟𝑻 𝒘𝒂𝒕𝒆𝒓

𝐽
𝑞 25.0 𝑔 2.03 0°𝐶 25°𝐶 1269 𝐽
𝑔
Some equations to review:
1 𝑚𝑜𝑙 𝐽 𝒒 𝒎𝑪∆𝑻 𝒒 𝒏∆𝑯
𝑞 25.0 𝑔𝑥 6010 8347 𝐽
18.0 𝑔 𝑚𝑜𝑙
𝐽
𝑞 25.0 𝑔 4.184 75°𝐶 0°𝐶 7845 𝐽
𝑔

𝑞 1269 𝐽 8347 𝐽 7845 𝐽 17,461 𝐽 𝟏𝟕. 𝟓 𝒌𝑱

11.4 Phase Diagrams

Phase Diagram: plot of pressure vs. temperature summarizing
all phases and equilibria between phases.
Given a T and P, a phase diagram tells us which phase will exist.
LINES: equilibrium between two phases
AREAS: only one phase is stable

11.4 Phase Diagrams

The melting curve (blue line) represents the phase boundary
(equilibrium) between solid and liquid.
• Marks melting point (MP) of a substance at a given pressure
• As P increases, MP increases if solid is more dense than liquid
(exception H20)

Normal melting point:

MP at 1 atm

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11.4 Phase Diagrams

The Vapor-pressure curve (red line) represents the phase boundary
(equilibrium) between liquid and gas.
• Marks boiling point (BP) of a substance at a given pressure
• As pressure increases, the temperature required to boil increases

Normal boiling point:

BP at 1 atm

11.4 Phase Diagrams

The liquid–vapor interface starts at the triple point (T), at which all
three states are in equilibrium, and ends at the critical point (C),
above which the liquid and vapor are indistinguishable from each
other.
Critical T: Highest T at which a distinct liquid phase can form
Critical P: P required to bring about liquification at critical T

Critical
temperature and
pressure for the
gas is the minimum
temperature when
the gas cannot be
condensed to
liquid by any
pressure.

11.4 Phase Diagrams

The Sublimation curve (green line) represents the phase boundary
(equilibrium)between solid and gas.
• Marks sublimation point T of a substance at a given pressure
• Below the triple point, substance cannot exist in liquid phase

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Concept Check Phase Diagrams

On the phase diagram of nitrogen shown below, click on the
pressure-temperature region where nitrogen exists as a gas.

11.4 Phase Diagrams

H2O CO2

• High critical T and P • CO2 cannot exist as liquid

̶ Strong IMFs below P=5.11 atm
• Negative slope of melting curve • CO2 sublimes at normal P
̶ MP decreases with increasing P
̶ Liquid form more dense

Concept Check CH4 Phase Diagram

Consider the phase diagram
for methane (CH4):

What phase is methane at 0.10 atm

and -220°C?

What point is the triple point?

What is the normal boiling point?

What is the normal freezing point?

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End of Chapter 11

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