Chemistry: A Molecular Approach

Fifth Edition

Chapter 12
Liquids, Solids, and
Intermolecular Forces

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Intermolecular Forces
• Intermolecular attractive forces exist among all particles that
make up matter.
• The very existence of condensed states (solid, liquid), or gas
—depends on the magnitude of intermolecular forces among
the constituent particles relative to the amount of thermal
energy in the sample.

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Three States of Water (1 of 2)
Notice that the densities of ice and liquid water are much
larger than the density of steam.
Notice that the densities and molar volumes of ice and liquid
water are much closer to each other than to steam.
Notice that the density of ice is lower than the density of
liquid water. This is not the norm but is vital to the
development of life as we know it.

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Three States of Water (2 of 2)
Density (g )
Temperature
ram

grams per cubic centimeter, at 1

Phase (°C )elsius

g / cm , at 1 atm
3
atmosphere
Molar Volume Molecular View
3 H 2 O molecules are
5.90 times 10 to spread far apart
4
Gas (steam) 100 5.90  10fourth
the negative 30.6 L iters

power

H 2 O molecules are
crowded close together but
able to move
Liquid (water) 20 0.998 18.0 m L
illi iters

H 2 O molecules are
packed closely together
roughly in a grid

Solid (ice) 0 0.917 19.6 m L

illi iters

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Properties of the Three States of Matter
Strength of Intermolecular Forces
State Density Shape Volume (Relative to Thermal Energy)
Gas Low Indefinite Indefinite Weak
Liquid High Indefinite Definite Moderate
Solid High Definite Definite Strong

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Liquids
• The particles in a liquid are
closely packed, but they have
some ability to move around.
• The close packing results in
liquids being incompressible.
• But the ability of the particles to
move allows liquids to take the
shape of their container and to
flow. However, they don’t have
enough freedom to escape or
expand to fill the container.

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Gases (1 of 2)
• In the gas state, the particles have
complete freedom of motion and are
not held together.
• The particles are constantly flying
around, bumping into each other and
the container.
• There is a large amount of space
between the particles compared to
the size of the particles.
– Therefore, the molar volume of
the gas state of a material is
much larger than the molar
volume of the solid or liquid
states.
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Gases (2 of 2)
• Gases are compressible
because there is a lot of
empty space, so the particles
can be squeezed closer
together.
• Because the particles are not
held in close contact and are
moving freely, gases expand
to fill and take the shape of
their container.

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Compressibility

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Solids (1 of 2)

• The particles in a solid are packed close together and are fixed in
position, though they may vibrate.
• The close packing of the particles results in solids being
incompressible.
• The inability of the particles to move around results in solids retaining
their shape and volume when placed in a new container and prevents
the solid from flowing.

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Solids (2 of 2)
• Some solids have their particles arranged in an orderly
geometric pattern; we call these crystalline solids.
– Salt and diamonds
• Other solids have particles that do not show a regular
geometric pattern over a long range; we call these
amorphous solids.
– Plastic and glass

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Phase Changes (1 of 2)
• Changing the material’s state requires changing the amount of
kinetic energy the particles have or limiting their freedom.
• Solids melt and liquids boil when heated.
• Transition between liquid and solid can also be induced by
changing pressure.
• Gases can be condensed by decreasing the temperature
and/or increasing the pressure.
– Pressure can be increased by decreasing the gas volume.
– Reducing the volume reduces the amount of translational
freedom the particles have.

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Phase Changes (2 of 2)

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Conceptual Connection 12.2 (1 of 2)
This molecular diagram shows a sample of liquid water:

Which of the diagrams below best depicts the vapor emitted

from a pot of boiling water?

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Intermolecular Forces
• The structure of particles determines the strength of the
intermolecular forces that hold the substance together.
• The particles are attracted to each other by electrostatic forces.
• The intermolecular forces determine the state of the substance.
• The strength of the attractive forces varies depending on the
kind(s) of particles.
• The stronger the attractive forces among the particles, the more
they resist moving.
– However, no material completely lacks particle motion.

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Intermolecular Attractions
• The strength of the attractions among the particles of a
substance determines its state.
• At room temperature, moderate to strong attractive forces
result in materials being solids or liquids.
• The stronger the attractive forces are, the higher will be the
boiling point of the liquid and the melting point of the solid.
– Other factors also influence the melting point.

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Why Are Molecules Attracted to Each
Other?
• Intermolecular attractions are due to attractive forces between opposite
charges.
– + ion to − ion
– + end of polar molecule to − end of polar molecule
▪ H-bonding especially strong
– Even nonpolar molecules will have temporary charges.

• Larger charge = stronger attraction

• Farther distance = weaker attraction

• However, these attractive forces are small

relative to the bonding forces among atoms.
– Generally smaller charges
– Generally over much larger distances

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Kinds of Attractive Forces
• Temporary polarity in the molecules due to unequal
electron distribution leads to attractions called
dispersion forces.
• Permanent polarity in the molecules due to their
structure leads to attractive forces called dipole–dipole
attractions.
• An especially strong dipole–dipole attraction results
when H is attached to an extremely electronegative
atom. These are called hydrogen bonds.

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Dispersion Forces
• Fluctuations in the electron distribution in atoms and molecules
result in a temporary dipole.
– Region with excess electron density has partial (–) charge.
– Region with depleted electron density has partial (+) charge.
• The attractive forces caused by these temporary dipoles are
called dispersion forces.
– AKA London forces
• All molecules and atoms will have them.
• As a temporary dipole is established in one molecule, it induces
a dipole in all the surrounding molecules.

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Dispersion Force (1 of 2)

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Dispersion Force (2 of 2)

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Size of the Instantaneous Dipole
• The magnitude of the instantaneous dipole depends on
several factors.
• Polarizability of the electrons
– Volume of the electron cloud
– Larger molar mass = more electrons = larger electron
cloud = increased polarizability = stronger attractions
• Shape of the molecule
– More surface-to-surface contact = larger induced
dipole = stronger attraction

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Effect of Molecular Size on Size of
Dispersion Force (1 of 2)
The noble gases are all
nonpolar atomic elements.
The stronger the attractive
forces among the molecules,
the higher the boiling point
will be.

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Effect of Molecular Size on Size of
Dispersion Force (2 of 2)
• As the molar mass increases, the number of electrons
increases. Therefore, the strength of the dispersion forces
increases.
• The stronger the attractive forces among the molecules,
the higher the boiling point will be.

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Effect of Molecular Shape on Size of
Dispersion Force

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Boiling Points of n-Alkanes

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Conceptual Connection 12.3 (2 of 2)
Which halogen has the highest boiling point?

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Dipole–Dipole Force
• Polar molecules have a permanent dipole.
– Bond polarity and shape
– Dipole moment
– The always-present induced dipole
• The permanent dipole adds to the attractive forces among
the molecules, raising the boiling and melting points
relative to nonpolar molecules of similar size and shape.

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Dipole-Dipole Interaction

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Trends in the Strength of Intermolecular
Attraction
• The stronger the attractions among the atoms or
molecules, the more energy it will take to separate them.
• Boiling a liquid requires that we add enough energy to
overcome all the attractions among the particles.
– However, not breaking the covalent bonds
• The higher the normal boiling point of the liquid, the
stronger the intermolecular attractive forces.

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Effect of Dipole–Dipole Attraction on
Boiling and Melting Points

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Dipole Moment and Boiling Point

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Attractive Forces and Solubility
• Solubility depends, in part, on the attractive forces of the solute and
solvent molecules.
– Like dissolves like.
– Miscible liquids will always dissolve in each other.
• Polar substances dissolve in polar solvents.
– Hydrophilic groups = OH, CHO, C  O, COOH, NH2 , Cl
• Nonpolar molecules dissolve in nonpolar solvents.
– Hydrophobic groups = C  H, C  C
• Many molecules have both hydrophilic and hydrophobic parts; solubility
in water becomes a competition between the attraction of the polar
groups for the water and the attraction of the nonpolar groups for their
own kind.

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Immiscible Liquids
Pentane, C5H12, is a nonpolar molecule.
Water is a polar molecule.
The attractive forces among the water molecules are much
stronger than their attractions for the pentane molecules.
The result is that the liquids are immiscible.

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Example 12.1 Dipole–Dipole Forces
Which molecules have dipole–dipole forces?

a. CO2 b. CH2Cl2 c. CH4

Solution
A molecule has dipole–dipole forces if it is polar. To determine if a molecule is polar: (1) determine if the
molecule contains polar bonds (Section 10.6); and (2) determine if the polar bonds add together to form a net
dipole moment (Section 11.5).

a. CO2
1. Since the electronegativity of carbon is 2.5 and that of oxygen is 3.5 (see Figure 10.8), CO 2 has polar
bonds.
2. The geometry of CO2 is linear. Consequently, the dipoles of the polar bonds cancel, so the molecule is not
polar and does not have dipole–dipole forces.

b. CH2Cl2
1. The electronegativity of C is 2.5, that of H is 2.1, and that of Cl is 3.0. Consequently, CH 2Cl2 has two polar
bonds (C—Cl) and two bonds that are nearly nonpolar (C—H).
2. The geometry of CH2Cl2 is tetrahedral. Because the C—Cl bonds and the C—H bonds are different, their
dipoles do not cancel but sum to a net dipole moment. The molecule is polar and has dipole–dipole
forces.
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Example 12.1 Dipole–Dipole Forces Continued

c. CH4
1. The electronegativity of C is 2.5 and that of hydrogen is 2.1, so the C—H bonds are nearly nonpolar.
2. In addition, since the geometry of the molecule is tetrahedral, any slight polarities that the bonds might have
cancel. CH4 is therefore nonpolar and does not have dipole–dipole forces.

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Example 12.1 Dipole–Dipole Forces
Continued

For Practice 12.1

Which molecules have dipole–dipole forces?
a. CI4 b. CH3Cl c. HCl

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Hydrogen Bonding (1 of 3)
• When a small, very electronegative atom is bonded to
hydrogen, it strongly pulls the bonding electrons toward it.
– O  H, N  H, or F  H
• Because hydrogen has no other electrons, when its
electron is pulled away, the nucleus becomes de-
shielded, exposing the H proton.
• The exposed proton acts as a very strong center of
positive charge, attracting all the electron clouds from
neighboring molecules.

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Hydrogen Bonding (2 of 3)

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Hydrogen Bonding in Water and
Ethanol

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Hydrogen Bonding (3 of 3)
• Hydrogen bonds are very strong intermolecular attractive
forces.
– Stronger than dipole–dipole or dispersion forces
• Substances that can hydrogen bond will have higher
boiling points and melting points than similar substances
that cannot.
• But, hydrogen bonds are not nearly as strong as chemical
bonds.
– 2–5% the strength of covalent bonds

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Effect of Hydrogen Bonding on Boiling
Point

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Boiling Points of Group 4A and 6A
Compounds
HF, H2O, and NH3 have hydrogen bonds.
Therefore, they have higher boiling points
than would be expected from the general
trends.

For nonpolar molecules, such as the

hydrides of group 4, the intermolecular
attractions are due to dispersion forces.
Therefore, they increase down the column,
causing the boiling point to increase.

Polar molecules, such as the hydrides of

groups 5–7, have both dispersion forces
and dipole–dipole attractions. Therefore,
they have higher boiling points than the
corresponding group 4 molecules.

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Ion–Dipole Forces
• In a mixture, ions from an ionic compound are attracted to
the dipole of polar molecules.
• The strength of the ion–dipole attraction is one of the main
factors that determines the solubility of ionic compounds in
water.

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Summary (1 of 2)
• Dispersion forces are the weakest of the intermolecular
forces.
• Dispersion forces are present in all molecules and atoms.
• The magnitude of the dispersion forces increases with
molar mass.
• Polar molecules also have dipole–dipole attractive forces.

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Summary (2 of 2)
• Hydrogen bonds are the strongest of the intermolecular
attractive forces a pure substance can have.
• Hydrogen bonds will be present when a molecule has H
directly bonded to either O, N, or F atoms.
– The only example of H bonded to F is HF.
• Ion–dipole attractions are present in mixtures of ionic
compounds with polar molecules.
• Ion–dipole attractions are the strongest intermolecular
attraction.
• Ion–dipole attractions are especially important in aqueous
solutions of ionic compounds.

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Type and Relative Strength of
Intermolecular Forces

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Conceptual Connection 12.5 (1 of 2)
Which substance has the highest boiling point?
a. CH3OH
b. CO
c. N2

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Surface Tension (1 of 3)
• Surface tension is a
property of liquids that
results from the tendency
of liquids to minimize their
surface area.
• To minimize their surface
area, liquids form drops
that are spherical.
– As long as there is no
gravity

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Surface Tension (2 of 3)
• The layer of molecules on the
surface behaves differently than
the interior because the cohesive
forces on the surface molecules
have a net pull into the liquid
interior.
• The surface layer acts like an
elastic skin, allowing you to “float”
a paper clip even though steel is
denser than water.

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Surface Tension (3 of 3)
• Because they have fewer neighbors to attract them, the surface
molecules are less stable than those in the interior.
– Have a higher potential energy
• The surface tension of a liquid is the energy required to increase
the surface area a given amount.
– Surface tension of H2O  72.8 mJ/m2
▪ At room temperature
– Surface tension of C6H6  28 mJ/m2

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Factors Affecting Surface Tension
• The stronger the intermolecular attractive forces, the
higher the surface tension will be.
• Raising the temperature of a liquid reduces its surface
tension.
– Raising the temperature of the liquid increases the
average kinetic energy of the molecules.
– The increased molecular motion makes it easier to
stretch the surface.

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Viscosity
• Viscosity is the resistance of a liquid to flow.
– 1 poise = 1 P = 1 g/cm ×s
– Often given in centipoise, c P
▪ H 2 O = 1 cP at room temperature

• Larger intermolecular attractions = higher viscosity

Hydrocarbon Molar Mass (g /mol )

ram e Formula Viscosity (cP)
n-Pentane 72.15 C H 3 C H 2 C H 2C H 2C H 3 0.240

n-Hexane 86.17 CH3CH2CH2CH2CH2CH3 0.326

n-Heptane 100.2 C H 3C H 2C H 2C H 2C H 2 C H2 C H 3 0.409

n-Octane 114.2 C H 3 C H 2 C H 2C H 2C H 2 C H 2 C H 2 C H 3 0.542

n-Nonane 128.3 C H 3 C H 2 C H 2C H 2C H 2 C H 2 C H 2 C H 2 C H 3 0.711

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Factors Affecting Viscosity (1 of 2)
• The stronger the intermolecular attractive forces, the
higher the liquid’s viscosity will be.
• The more spherical the molecular shape, the lower the
viscosity will be.
– Molecules roll more easily.
– Less surface-to-surface contact lowers attractions.

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Factors Affecting Viscosity (2 of 2)
• Raising the temperature of a liquid reduces its viscosity.
– Raising the temperature of the liquid increases the
average kinetic energy of the molecules.
– The increased molecular motion makes it easier to
overcome the intermolecular attractions and flow.

Temperature (°C )
elsius Viscosity (cP)
20 1.002

40 0.653

60 0.467

80 0.355

100 0.281

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Capillary Action (1 of 2)
• Capillary action is the ability of a liquid to flow up a thin tube
against the influence of gravity.
– The narrower the tube, the higher the liquid rises.
• Capillary action is the result of two forces working in
conjunction, the cohesive and adhesive forces.
– Cohesive forces hold the liquid molecules together.
– Adhesive forces attract the outer liquid molecules to the
tube’s surface.

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Capillary Action (2 of 2)
• The adhesive forces pull the
surface liquid up the side of
the tube, and the cohesive
forces pull the interior liquid
with it.
• The liquid rises up the tube
until the force of gravity
counteracts the capillary
action forces.
• The narrower the tube
diameter, the higher the liquid
will rise up the tube.
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Meniscus
• The curving of the liquid surface in a
thin tube is due to the competition
between adhesive and cohesive
forces.
• The meniscus of water is concave in a
glass tube because its adhesion to the
glass is stronger than its cohesion for
itself.
• The meniscus of mercury is convex in
a glass tube because its cohesion for
itself is stronger than its adhesion for
the glass.
– Metallic bonds are stronger than
intermolecular attractions.
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The Molecular Dance
• Molecules in a liquid are constantly in motion.
– Vibrational with limited rotational and translational
• The average kinetic energy is proportional to the
temperature.
• However, some molecules have more kinetic energy than
the average, and others have less.

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Vaporization
• If these high-energy
molecules are at the
surface, they may have
enough energy to
overcome the attractive
forces.
– Therefore, the larger
the surface area, the
faster the rate of
evaporation.
• This will allow them to
escape the liquid and
become a vapor.

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Distribution of Thermal Energy
• Only a small fraction of the molecules in a liquid have enough
energy to escape.
• But, as the temperature increases, the fraction of the molecules
with “escape energy” increases.
• The higher the temperature, the faster the rate of evaporation.

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Condensation
• Some molecules of the vapor will lose energy through
molecular collisions.
• The result will be that some of the molecules will get
captured back into the liquid when they collide with it.
• Also, some may stick and gather together to form droplets
of liquid, particularly on surrounding surfaces.
• We call this process condensation.

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Evaporation Versus Condensation
• Vaporization and condensation are opposite processes.
• In an open container, the vapor molecules generally spread
out faster than they can condense.
• The net result is that the rate of vaporization is greater than
the rate of condensation, and there is a net loss of liquid.
• However, in a closed container, the vapor is not allowed to
spread out indefinitely.
• The net result in a closed container is that at some time the
rates of vaporization and condensation will be equal.

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Effect of Intermolecular Forces on
Evaporation and Condensation
• The weaker the attractive forces among molecules, the less energy
they will need to vaporize.
• Also, weaker attractive forces means that more energy will need to be
removed from the vapor molecules before they can condense.
• The net result will be more molecules in the vapor phase and a liquid
that evaporates faster; the weaker the attractive forces, the faster
the rate of evaporation.
• Liquids that evaporate easily are said to be volatile.
– For example, gasoline, fingernail polish remover
• Liquids that do not evaporate easily are called nonvolatile.
– For example, motor oil

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Summarizing the Process of
Vaporization
• The rate of vaporization increases with increasing
temperature.
• The rate of vaporization increases with increasing surface
area.
• The rate of vaporization increases with decreasing
strength of intermolecular forces.

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Energetics of Vaporization
• When the high-energy molecules are lost from the
liquid, it lowers the average kinetic energy.
• If energy is not drawn back into the liquid, its
temperature will decrease; therefore, vaporization is
an endothermic process.
– Condensation is an exothermic process.
• Vaporization requires input of energy to overcome the
attractions among molecules.

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Heat of Vaporization
• The amount of heat energy required to vaporize one mole of the
liquid is called the heat of vaporization, ΔHvap.
– Sometimes called the enthalpy of vaporization
• It is always endothermic; therefore, ΔHvap is +.
• It is somewhat temperature dependent.
• ΔHcondensation = −ΔHvaporization
Chemical Normal Boiling 𝚫Hvap (k J ,mol)
ilo oule 𝚫Hvap (k J ,mol)
ilo oule

Liquid Formula Point (°C )

elsius at Boiling Point at 25 °C elsius

Water H2 O 100 40.7 40.7

Isopropyl alcohol C3 H8O 82.3 39.9 45.4

Acetone C3 H6O 56.1 29.1 31.0

Diethyl ether C4H10O 34.6 26.5 27.1

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Example 12.3 Using the Heat of Vaporization in Calculations
Calculate the mass of water (in g) that can be vaporized at its boiling point with 155 kJ of heat.

Sort
You are given a certain amount of heat in kilojoules and asked to find the mass of water that can be vaporized.
Given: 155 kJ
Find: g H2O

Strategize
The heat of vaporization gives the relationship between heat absorbed and moles of water vaporized. Begin with
the given amount of heat (in kJ) and convert to moles of water that can be vaporized. Then use the molar mass as a
conversion factor to convert from moles of water to mass of water.

Conceptual Plan

Relationships Used
ΔHvap = 40.7 kJ/mol (at 100 °C)
18.02 g H2O = 1 mol H2O

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Example 12.3 Using the Heat of Vaporization in Calculations
Continued

Solve
Follow the conceptual plan to solve the problem.

Solution

For Practice 12.3

Calculate the amount of heat (in kJ) required to vaporize 2.58 kg of water at its boiling point.

For Practice 12.3

Suppose that 0.48 g of water at 25 °C condenses on the surface of a 55-g block of aluminum that is initially 25 °C. If
the heat released during condensation goes only toward heating the metal, what is the final temperature (in °C) of the
metal block? (The specific heat capacity of aluminum is 0.903 J/g °C.)

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Dynamic Equilibrium (1 of 4)
• In a closed container, once the rates of vaporization and
condensation are equal, the total amount of vapor and
liquid will not change.
• Evaporation and condensation are still occurring, but
because they are opposite processes, there is no net gain
or loss of either vapor or liquid.

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Dynamic Equilibrium (2 of 4)

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Dynamic Equilibrium (3 of 4)
• When two opposite processes reach the same rate so that
there is no gain or loss of material, we call it a dynamic
equilibrium.
– This does not mean there are equal amounts of vapor
and liquid; it means that they are changing by equal
amounts.

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Vapor Pressure
• The pressure exerted by a vapor when it is in dynamic
equilibrium with its liquid is called the vapor pressure.
– Remember using Dalton’s law of partial pressures to
account for the pressure of the water vapor when collecting
gases by water displacement?
• The weaker the attractive forces among the molecules, the more
molecules will be in the vapor.
• Therefore, the weaker the attractive forces, the higher the
vapor pressure.
– The higher the vapor pressure, the more volatile the liquid.

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Temperature Dependence of Vapor
Pressure
• Increasing the temperature increases the number of
molecules able to escape the liquid.
• The net result is that as the temperature increases, the
vapor pressure increases.
• Small changes in temperature can make big changes in
vapor pressure.
– The rate of change in vapor pressure depends on the
strength of the intermolecular forces.

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Vapor Pressure Curves

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Boiling Point (1 of 2)

• When the temperature of a liquid reaches a point where its vapor

pressure is the same as the external pressure, vapor bubbles can form
anywhere in the liquid, not just on the surface.
• This phenomenon is what is called boiling, and the temperature at
which the vapor pressure equals external pressure is the boiling point.
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Boiling Point (2 of 2)
• The normal boiling point is the temperature at which the vapor
pressure of the liquid = 1 atm.
• The lower the external pressure, the lower the boiling point of the
liquid.
Approximate
Approximate Boiling Point of
Location Elevation (f t)
ee Pressure (atm)* Water (°C )
elsius

Mount Everest, Tibet (highest mountain 29,029 0.32 78

peak on Earth)
Denali (formerly Mount McKinley), Alaska 20,310 0.46 83
(highest mountain peak in North America)
Mount Whitney, California (highest mountain 14,505 0.60 87
peak in 48 contiguous U.S. states)
Denver, Colorado (mile high city) 5,280 0.83 94
Boston, Massachusetts (sea level) 20 1.0 100

*The atmospheric pressure in each of these locations is subject to weather conditions and
can vary significantly from these values.

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Heating Curve of a Liquid
• As you heat a liquid, its
temperature increases linearly
until it reaches the boiling point.
– q = mass × Cs × ΔT
• Once the temperature reaches
the boiling point, all the added
heat goes into boiling the liquid;
the temperature stays constant.
• Once all the liquid has been
turned into gas, the temperature
can again start to rise.

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Conceptual Connection 12.8 (2 of 2)
Use Figure 12.28 to estimate the boiling point of water at an
external pressure of 200 torr.

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Clausius–Clapeyron Equation
• The logarithm of the vapor pressure versus inverse absolute
temperature is a linear function.
• A graph of ln(Pvap) versus 1/T is a straight line.
• The slope of the line is ΔHvap/8.314 J/mol ×K.
– Units for ΔHvap are J /mol.
oule e

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Clausius–Clapeyron Equation: Two-
Point Form
• The equation below can be used with just two measurements of
vapor pressure and temperature.
– However, it generally gives less precise results.
▪ Fewer data points will not give as precise an average
because there is less averaging out of the errors, as with
any other sets of measurements.
• It can also be used to predict the vapor pressure if you know the
heat of vaporization and the normal boiling point.
– Remember, the vapor pressure at the normal boiling point is
760 torr.

P2  ΔHvap 1 1
ln   Clausius-Clapeyron equation (two-point form)
P1 R T2 T1

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Example 12.5 Using the Two-Point Form of the Clausius–Clapeyron
Equation to Predict the Vapor Pressure at a Given
Temperature
Methanol has a normal boiling point of 64.6 °C and a heat of vaporization (ΔHvap) of 35.2 kJ/mol. What is
the vapor pressure of methanol at 12.0 °C?
Sort
You are given the normal boiling point of methanol (the temperature at which the vapor pressure is 760 mmHg)
and the heat of vaporization. You are asked to find the vapor pressure at a specified temperature that is also given.
Given: T1(°C) = 64.6 °C
P1 = 760 torr
ΔHvap = 35.2 kJ/mol
T2(°C) = 12.0 °C
Find: P2

Strategize
The conceptual plan is essentially the Clausius–Clapeyron equation, which relates the given and find quantities.

Conceptual Plan

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Example 12.5 Using the Two-Point Form of the Clausius–Clapeyron
Equation to Predict the Vapor Pressure at a Given
Temperature
Continued

Solve
First, convert T1 and T2 from °C to K.

Solution

Then, substitute the required values into the

Clausius–Clapeyron equation and solve for P2.

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Example 12.5 Using the Two-Point Form of the Clausius–Clapeyron
Equation to Predict the Vapor Pressure at a Given
Temperature
Continued
In order to isolate P2, you must take the inverse natural logarithm (or inv ln) of ln(P2/P1). Remember that inv ln (ln
x) = x.

Check
The units of the answer are correct. The magnitude of the answer makes sense because vapor pressure should be
significantly lower at the lower temperature.

For Practice 12.5

Propane has a normal boiling point of –42.0 °C and a heat of vaporization (ΔHvap) of 19.04 kJ/mol. What is the
vapor pressure of propane at 25.0 °C?

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Supercritical Fluid
• As a liquid is heated in a sealed container, more vapor collects,
causing the pressure inside the container to rise, the density of the
vapor to increase, and the density of the liquid to decrease.
• At some temperature, the meniscus between the liquid and vapor
disappears, and the states commingle to form a supercritical fluid.
• Supercritical fluids have properties of both gas and liquid states.

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The Critical Point
• The temperature required to produce a supercritical fluid is
called the critical temperature.
• The pressure at the critical temperature is called the
critical pressure.
• At the critical temperature or higher temperatures, the gas
cannot be condensed to a liquid, no matter how high the
pressure gets.

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Sublimation and Deposition
• Molecules in a solid have thermal energy that allows them to vibrate.
• Surface molecules with sufficient energy may break free from the
surface and become a gas; this process is called sublimation.
• The capturing of vapor molecules into a solid is called deposition.
• The solid and vapor phases exist in dynamic equilibrium in a closed
container at temperatures below the melting point.
– Therefore, molecular solids have a vapor pressure.

sublimation

solid  gas
deposition

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Sublimation

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Fusion (Melting)
• As a solid is heated, its temperature rises, and the
molecules vibrate more vigorously.
• Once the temperature reaches the melting point, the
molecules have sufficient energy to overcome some of the
attractions that hold them in position, and the solid melts
(or fuses).
• The opposite of melting is freezing.

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Heating Curve of a Solid
• As you heat a solid, its temperature
increases linearly until it reaches the
melting point.
– q = mass × Cs × ΔT

• Once the temperature reaches the melting

point, all the added heat goes into melting
the solid.
– The temperature stays constant.
• Once all the solid has been turned into
liquid, the temperature can again start to
rise.
– Ice/water will always have a
temperature of 0 °C at 1 atm.
elsius

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Energetics of Melting
• When the high-energy molecules are lost from the
solid, it lowers the average kinetic energy.
• If energy is not drawn back into the solid, its
temperature will decrease; therefore, melting is an
endothermic process, and freezing is an exothermic
process.
• Melting requires input of energy to overcome the
attractions among molecules.

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Heat of Fusion (1 of 2)
• The amount of heat energy required to melt one mole of the solid is
called the heat of fusion, ΔHfus.
– Sometimes called the enthalpy of fusion

• It is always endothermic; therefore, ΔHfus is +.

• It is somewhat temperature dependent.

• ΔHcrystallization = −ΔHfusion

• Generally much less than ΔHvap.

• ΔHsublimation = ΔHfusion + ΔHvaporization

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Heat of Fusion (2 of 2)

Liquid Chemical Formula Melting Point (°C ) elsius 𝚫Hfus (k J /mol )

ilo oule e

Water H2 O 0.00 6.02

Isopropyl alcohol C3 H 8 O −89.5 5.37
Acetone C3 H 6 O −94.8 5.69
Diethyl ether C4H10O −116.3 7.27

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Heats of Fusion and Vaporization

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Heating Curve of Water

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Segment 1
• Heating 1.00 mole of ice at −25.0 °C up to the melting
elsius

point, 0.0 °Celsius

• q = mass × Cs × ΔT
– Mass of 1.00 mole of ice = 18.0 g rams

– Cs = 2.09 J/mol ×°C

 J 
q  18.0 g    2.09   0.0°C   25.0°C 
 g  °C 
q  941 J  0.941 kJ

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Segment 2
• Melting 1.00 mole of ice at the melting point, 0.0 °C elsius

• q  n ×D Hfus
– n = 1.00 mole of ice
– ΔHfus = 6.02 k J /mol
ilo oules e

 kJ 
q  1.00 mol    6.02 
 mol 
q  6.02 kJ

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Segment 3
• Heating 1.00 mole of water at 0.0 °C up to the boiling
elsius

point, 100.0 °C elsius

• q = mass × Cs × ΔT
– Mass of 1.00 mole of water = 18.0 g rams

– Cs = 2.09 J/mol ×°C

 J 
q  18.0 g   4.18   100.0°C  0.0°C 
 g  °C 
q  7.52  103  7.52 kJ

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Segment 4
• Boiling 1.00 mole of water at the boiling point, 100.0 °C elsius

• q  n ×D Hvap
– n = 1.00 moles of ice
– ΔHfus = 40.7 k J /mol
ilo oules e

 kJ 
q  1.00 mol    40.7 
 mol 
q  40.7 kJ

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Segment 5
• Heating 1.00 mole of steam at 100.0 °C up to 125.0 °Celsius elsius

• q = mass × Cs × ΔT
– Mass of 1.00 mole of water = 18.0 g rams

– Cs = 2.01 J/mol ×°C

 J 
q  18.0 g   2.01   125.0°C  100.0°C 
 g  °C 
q  904 J  0.904 kJ

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Phase Diagrams
• Phase diagrams describe the different states and state changes that
occur at various temperature/pressure conditions.
• Regions represent states.
• Lines represent state changes.
– The liquid/gas line is the vapor pressure curve.
– Both states coexist.
– The critical point is the farthest point on the vapor pressure curve.
• Triple point is the temperature-pressure condition where all three states
coexist.
• For most substances, the freezing point increases as pressure increases.

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Phase Diagram of Water

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Navigation within a Phase Diagram

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Phase Diagrams for Other Substances

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Water: An Extraordinary Substance (1 of 2)
• Water is a liquid at room temperature.
– Most molecular substances with similar molar masses
are gases at room temperature.
▪ For example, NH3, CH4
– This is due to H bonding among molecules.
• Water is an excellent solvent, dissolving many ionic and
polar molecular substances.
– It has a large dipole moment.
– Even many small nonpolar molecules have some
solubility in water.
▪ For example, O2, CO2
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Water: An Extraordinary Substance (2 of 2)
• Water has a very high specific heat for a molecular
substance.
– Moderating effect on coastal climates
• Water expands when it freezes at a pressure of 1 atm.
– About 9%
– Making ice less dense than liquid water

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Boiling Points of Main-Group Hydrides
• The hydrogen bonds present in water result in a relatively
high boiling point.

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