Ch.

11: Liquids and

Intermolecular Forces

Learning goals and key skills:

 Identify the intermolecular attractive interactions (dispersion, dipole-dipole, hydrogen bonding,

ion-dipole) that exist between molecules or ions based on their composition and molecular
structure and be able to compare the relative strengths of these intermolecular forces
 Explain the concept of polarizability and how it relates to dispersion forces
 Explain the concepts of viscosity and surface tension in liquids
 Know the names of various changes of state for a pure substance
Interpret heating curves and be able to calculate quantities related to temperature and
enthalpies of phase changes
 Define critical pressure, critical temperature, vapor pressure, normal boiling point, normal
melting point, critical point, and triple point
 Be able to interpret and sketch phase diagrams. Explain how water’s phase diagram differs
from most other substances, and why.
Understand how the molecular arrangements characteristic or nematic, smectic, and
choloesteric liquid crystals differ from ordinary liquids and from each other. Be able to recognize
the features of molecules that favor formation of liquid crystalline phases.

Gases

In gases the
particles/molecules are far
apart and the
intermolecular forces
between them are weak.

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 ... vs liquids and solids

In liquids and solids this

is not true. Instead we
must consider the
intermolecular forces,
i.e., the forces that exist
between atoms and
molecules.

Strength of intermolecular attractions

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 States of Matter
The fundamental difference between states
of matter is the distance between particles.

Because in the solid and liquid states

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

The States of Matter

The state a substance is in at a particular

temperature and pressure depends on:
– The kinetic energy of the particles
– The strength of the attractions between the
particles

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Intermolecular Forces

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 Intermolecular Forces
•ion-dipole
•hydrogen bonding

•dipole-dipole van der Waals

•dispersion forces (London) forces

The strength of these intermolecular forces is directly

related to the melting/boiling points, enthalpy of fusion,
enthalpy of vaporization, and solubility of the substances.

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 Dispersion forces

These induced dipoles lead to intermolecular attractions. This

is how nonpolar gas molecules (e.g. He, N2, etc.) can liquefy.
The ease with which the electron distribution in a molecule is
distorted is called its polarizability.

London dispersion forces

Dispersion forces tend to increase with
increasing molecular weight.

MW Boiling Pt.
(g/mol) (K)
F2 38 85
Cl2 71 239
Br2 160 332
I2 254 458

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Factors Affecting Dispersion Forces

• The shape of the

molecule affects the
dispersion forces:
long, thin molecules
(like n-pentane tend to
have stronger
dispersion forces than
short, round ones (like
neopentane).
• This is due to the
increased surface area
in n-pentane.

Polar Covalent Bonds and

Electronegativity
Although atoms often form
compounds by sharing
electrons, the electrons are
not always shared equally.

Electronegativity is
the ability of atoms
in a molecule to
attract electrons to
itself.

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 Dipole-Dipole Forces

Dipole-Dipole
Forces
Influence of dipole-dipole forces is seen
in the boiling points of simple molecules.
MW (g/mol) Boiling Pt (K)
N2 28 77
CO 28 81
Br2 160 332
ICl 162 370

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 Dipole-Dipole Forces
Dipole-dipole forces increase with increasing
polarity (dipole moments).
MW Dipole Boiling
(g/mol) Moment, μ (D) Pt (K)
CH3CH2CH3 44 0.1 231
CH3OCH3 46 1.3 248
CH3CHO 44 2.7 294
CH3CN 41 3.9 355

Hydrogen Bonding
A special form of dipole-dipole attraction,
which enhances dipole-dipole attractions.

H-bonding is strongest when X and Y are

N, O, or F

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 Boiling Points of Simple Hydrogen-Containing Compounds

Base-Pairing through H-Bonds

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 Double helix
of DNA

Portion of a
DNA chain

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 ••
water
-
Ion-dipole forces O dipole
••

H
H +

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 Intermolecular Forces Summary

Ionic bonding Ions

Ion charge, dipole
Ion-dipole
Increasing Strength

moment
Very polar H-X bond
Hydrogen bonding and lone pair of e-
(X = N, O, F)
Dipole-dipole Dipole moment
Dispersion forces
(Induced dipole- polarizability
induced dipole) only

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 “Like dissolves like”

Polar molecules are more likely to

dissolve in a polar solvent, and
nonpolar molecules are more likely
to dissolve in a nonpolar solvent.

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 Liquids

• molecules close together

→ appreciable intermolecular forces
• liquids are almost incompressible
• molecules are in constant motion
• finite volume, but indefinite shape

Viscosity
The resistance of liquids to flow
Increases with stronger intermolecular forces and
decreases with increasing temperature.

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 Surface Tension

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

Cohesive and adhesive forces

Cohesive forces
- between the liquid
molecules
Adhesive forces
- between the liquid
molecules and another
substance

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 Properties of liquids
Viscosity – the resistance of liquids to flow;
“the thickness”
Surface tension – energy required to break
through the surface or to disrupt a liquid drop
and make the drop spread out like a film.
Cohesive forces – forces between liquid
molecules
Adhesive forces – forces between liquid
molecules and another substance
Capillary action – the rise of liquids up
narrow tubes and other surfaces

Phase changes

Changes of state involve energy (at constant T)

Ice + (heat of fusion) → water

Water + (heat of vaporization) → steam

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 Phase changes

Energy changes associated

with changes of state

For water DHfus = 6.01 kJ/mol or 334 J/g

DHvap = 40.67 kJ/mol or 2258 J/g

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Heating/Cooling Curve for Water

Heating/Cooling Curve for Water

The total heat is the sum of each step qtotal = ∑ qi

The ice is heated qice = sicemΔT

The ice melts to water qfus = ΔHfusm

The water is heated qwater = swatermΔT

The water evaporates to steam qvap = ΔHvapm

The steam is heated qsteam = ssteammΔT

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 Example: Heating curve problem
Determine the amount of heat (in kJ) required to heat
500. g of ice from -50.0 °C to steam at 200. °C.

sice = 2.09 J/gK qice, -50.0 to 0 °C = +52 250 J

DHfus = 334 J/g qfus, ice to water = +167 000 J
swater = 4.184 J/gK qwater, 0 to 100 °C = +209 200 J
DHvap = 2258 J/g qvap, water to steam = +1 129 000 J
ssteam=1.84 J/gK
qsteam, 100 to 200. °C = +92 000 J
qtotal = 1 650 000 J = 1650 kJ

Note that most of the heat is used to convert water into steam.

Example: Heating curve problem

Determine the amount of heat (in kJ) required to
convert 42.0 g of ethanol from -155 °C to 78 °C.
ethanol (C2H5OH) melts at -114 C and boils at 78 °C.
The enthalpy of fusion of ethanol is 5.02 kJ/mol and
the enthalpy of vaporization is 38.56 kJ/mol. The
specific heats of solid and liquid ethanol are 0.97 J/gK
and 2.3 J/gK, respectively.

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 Critical Temperature: The highest temperature at which a distinct
liquid phase can form
Critical Pressure: Pressure required to bring about liquefaction at this
critical temperature.

Supercritical Fluid: Above this critical point, we have a supercritical fluid

where the density is similar to a liquid and the viscosity is similar to a gas.

Vapor Pressure

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 Temperature effects on the
distribution of energy in a liquid

E needed to
evaporate liquid

Liquids that evaporate

rapidly are volatile

Vapor pressure curves

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 Equilibrium Vapor Pressure &
the Clausius-Clapeyron Equation
• Clausius-Clapeyron
equation — used to find
heat of vaporization, ∆Hvap.
• The logarithm of the vapor
pressure P is proportional
to ∆Hvap and to 1/T.
• ln P = –(∆Hvap/RT) + C
P  DH vap 1 1
ln  2      
 P1  R  T2 T1 

Clausius-Clapeyron Equation

Liquid bromine has a vapor pressure of

400. torr at 41.0 °C and a normal boiling
point of 58.2 °C. Calculate the heat of
vaporization of bromine (in kJ/mol).

P  DH vap 1 1
ln  2      
 P1  R  T2 T1 

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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.

Normal Phase Diagram: CO2

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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.

Info from P-T phase diagrams

From a (pressure-temperature) phase diagram we can find:

• the normal melting point

• the normal boiling point
• the triple point
• whether the liquid is more or less dense than the solid

• the vapor pressure curve

• the sublimation pressure curve

• the critical temperature (Tc) and critical pressure (Pc)

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Liquid Crystals

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 Liquid Crystals
• Rod-shaped and contain double or triple bond near the middle
• Polar groups create a dipole moment and promote alignment

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