Lecture Presentation

Chapter 11

Liquids and
Intermolecular
Forces

John D. Bookstaver
St. Charles Community College
Cottleville, MO
© 2012 Pearson Education, Inc.
 States of Matter
The fundamental difference between states of
matter is the distance between particles.

Intermolecular
Forces
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 States of Matter

Because in the solid

and liquid states
particles are closer
together, we refer to
them as condensed
phases.

Intermolecular
Forces
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The States of Matter
• 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.
Intermolecular
Forces
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 Intermolecular Forces

The attractions between molecules are not

nearly as strong as the intramolecular
attractions that hold compounds together.
Intermolecular
Forces
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 Intermolecular Forces

These intermolecular attractions are,

however, strong enough to control physical
properties, such as boiling and melting points,
vapor pressures, and viscosities. Intermolecular
Forces
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 Intermolecular Forces

These intermolecular forces as a group are

referred to as van der Waals forces.

Intermolecular
Forces
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 van der Waals Forces

• Dipole–dipole interactions
• Hydrogen bonding
• London dispersion forces

Intermolecular
Forces
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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.
Intermolecular
Forces
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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.

Intermolecular
Forces
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London Dispersion Forces

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.
Intermolecular
Forces
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London Dispersion Forces

London dispersion
forces, or
dispersion forces,
are attractions
between an
instantaneous dipole
and an induced
dipole.

Intermolecular
Forces
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 London Dispersion Forces
• 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.
Intermolecular
Forces
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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.

Intermolecular
Forces
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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.
Intermolecular
Forces
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 Dipole–Dipole Interactions
• Molecules that have permanent dipoles are
attracted to each other.
– 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.

Intermolecular
Forces
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 Dipole–Dipole Interactions

The more polar the molecule, the higher

its boiling point. Intermolecular
Forces
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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.

Intermolecular
Forces
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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.

Intermolecular
Forces
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 Hydrogen Bonding

• The dipole–dipole
interactions experienced
when H is bonded to N, O,
or F are unusually strong.
• We call these interactions
hydrogen bonds.

Intermolecular
Forces
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 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. Intermolecular
Forces
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 Ion–Dipole Interactions
• Ion–dipole interactions (a fourth type of force)
are important in solutions of ions.
• The strength of these forces is what makes it
possible for ionic substances to dissolve in
polar solvents.

Intermolecular
Forces
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Summarizing Intermolecular Forces

Intermolecular
Forces
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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.

Intermolecular
Forces
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Sample Exercise 11.1 Identifying Substances That Can Form
Hydrogen Bonds
In which of these substances is hydrogen bonding likely to play an important role in determining
physical properties: methane (CH4), hydrazine (H2NNH2), methyl fluoride (CH3F),
hydrogen sulfide (H2S)?

Solution
The foregoing criteria eliminate CH4 and H2S, which do not contain H bonded to N, O, or F. They also
eliminate CH3F, whose Lewis structure shows a central C atom surrounded by three H atoms and an F atom.
(Carbon always forms four bonds, whereas hydrogen and fluorine form one each.) Because the molecule
contains a C − F bond and not a H − F bond, it does not form hydrogen bonds. In H2NNH2, however, we find
N − H bonds, and the Lewis structure shows a nonbonding pair of electrons on each N atom, telling us
hydrogen bonds can exist between the molecules:

Practice Exercise
In which of these substances is significant hydrogen bonding possible: methylene chloride (CH 2Cl2), phosphine
(PH3), hydrogen peroxide (HOOH), acetone (CH3COCH3)?
Answer: HOOH

Intermolecular
Forces
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Sample Exercise 11.2 Predicting Types and Relative Strengths of
Intermolecular Attractions
List the substances BaCl2, H2, CO, HF, and Ne in order of increasing boiling point.

Solution
Solve The attractive forces are stronger for ionic substances than for molecular ones, so BaCl 2 should have
the highest boiling point. The intermolecular forces of the remaining substances depend on molecular weight,
polarity, and hydrogen bonding. The molecular weights are H2 (2), CO (28), HF (20), and Ne (20). The
boiling point of H2 should be the lowest because it is nonpolar and has the lowest molecular weight. The
molecular weights of CO, HF, and Ne are similar. Because HF can hydrogen bond, however, it should have
the highest boiling point of the three. Next is CO, which is slightly polar and has the highest molecular
weight. Finally, Ne, which is nonpolar, should have the lowest boiling point of these three. The predicted
order of boiling points is, therefore,
H2 < Ne < CO < HF < BaCl2
Check The boiling points reported in the literature are H2 (20 K), Ne (27 K), CO (83 K), HF (293 K), and
BaCl2 (1813 K)—in agreement with our predictions.

Practice Exercise
(a) Identify the intermolecular attractions present in the following substances, and (b) select the substance with the
highest boiling point: CH3CH3, CH3OH, and CH3CH2OH.

Answers: (a) CH3CH3 has only dispersion forces, whereas the other two substances have both dispersion forces
and hydrogen bonds, (b) CH3CH2OH
Intermolecular
Forces
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 Viscosity
• 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.
Intermolecular
Forces
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Surface Tension

Surface tension
results from the net
inward force
experienced by the
molecules on the
surface of a liquid.

Intermolecular
Forces
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Phase Changes

Intermolecular
Forces
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Energy Changes Associated
with Changes of State

The heat of fusion is the energy required to

change a solid at its melting point to a liquid.Intermolecular
Forces
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Energy Changes Associated
with Changes of State

The heat of vaporization is defined as the

energy required to change a liquid at its Intermolecular
boiling point to a gas. Forces
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 Energy Changes Associated
with Changes of State

The heat of sublimation is defined as the energy

required to change a solid directly to a gas. Intermolecular
Forces
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Energy Changes Associated
with Changes of State
• The heat added to the
system at the melting
and boiling points goes
into pulling the
molecules farther apart
from each other.
• The temperature of the
substance does not rise
during a phase change.
Intermolecular
Forces
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Sample Exercise 11.3 Calculating H for Temperature and Phase
Changes
Calculate the enthalpy change upon converting 1.00 mol of ice at −25 C to steam at 125 C under a constant
pressure of 1 atm. The specific heats of ice, liquid water, and steam are 2.03 J/g-K, 4.18 J/g-K, and 1.84 J/g-K,
respectively. For H2O, Hfus = 6.01 kJ/mol and Hvap = 40.67 kJ/mol.

Solution
AB: Heating ice from 0 oC to 25 oC

H(A→B) = (1.00)(18.0)(2.03 J/g-K)(25 K) = 914 J = 0.91 kJ

BC: Melting of ice at 0 oC
H(B→C) = (1.00 mol)(6.01 kJ/mol) = 6.01 kJ
CD: Heating liquid water from 0 to 100 oC

H (C→D)= (1.00)(18.0)(4.18)(100) = 7520 J = 7.52 kJ

DE: evaporation of water at 100 oC

H(D→E) = (1.00 mol)(40.67 kJ/mol) = 40.7 kJ

EF: Heating of steam from 100 to 125 oC

H(E→F) = (1.00)(18.0)(1.84 J/g-K)(25 K) = 830 J = 0.83 kJ

H = 0.91 kJ + 6.01 kJ + 7.52 kJ + 40.7 kJ + 0.83 kJ = 56.0 kJ

Intermolecular
Forces
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 Vapor Pressure
• At any temperature some molecules in a liquid have
enough energy to break free.
• As the temperature rises, the fraction of molecules
that have enough energy to break free increases.

Intermolecular
Forces
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Vapor Pressure

As more molecules
escape the liquid,
the pressure they
exert increases.

Intermolecular
Forces
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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.

Intermolecular
Forces
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 Vapor Pressure
• The boiling point of
a liquid is the
temperature at which
its vapor pressure
equals atmospheric
pressure.
• The normal boiling
point is the
temperature at which
its vapor pressure is
760 torr.
Intermolecular
Forces
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Vapor Pressure

The natural log of the

vapor pressure of a
liquid is inversely
proportional to its
temperature.

Intermolecular
Forces
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Vapor Pressure

This relationship is
quantified in the
Clausius–Clapeyron
equation:

ln P = −Hvap/RT + C,

where C is a constant.
Intermolecular
Forces
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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.

Intermolecular
Forces
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Sample Exercise 11.4 Relating Boiling Point to Vapor Pressure
Use Figure 11.25 to estimate the boiling point of diethyl ether under an
external pressure of 0.80 atm.

Solution
Analyze We are asked to read a graph of vapor pressure versus temperature to determine the boiling point of
a substance at a particular pressure. The boiling point is the temperature at which the vapor pressure is equal
to the external pressure.
Plan We need to convert 0.80 atm to torr because that is the pressure scale on the graph. We estimate the
location of that pressure on the graph, move horizontally to the vapor pressure curve, and then drop vertically
from the curve to estimate the temperature.

Intermolecular
Forces
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 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.

Intermolecular
Forces
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