General Chemistry CHM115

The Molecular Nature of Matter and Change

Fall semester 2020

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 Chapter 12

Intermolecular Forces:
Liquids, Solids, and Phase Changes

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 Intermolecular Forces:
Liquids, Solids, and Phase Changes

12.1 An Overview of Physical States and Phase Changes

12.2 Quantitative Aspects of Phase Changes

12.3 Types of Intermolecular Forces

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 Intermolecular Forces:
Liquids, Solids, and Phase Changes

12.1 An Overview of Physical States and Phase Changes

12.2 Quantitative Aspects of Phase Changes

12.3 Types of Intermolecular Forces

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 Attractive Forces

Intramolecular or bonding forces are found within a

molecule. The chemical behavior of each phase of matter is
the same because the same constituent particle is present in
each case.
H2O molecules are present whether the substance is in the solid, liquid,
or gas phase.

Intermolecular or nonbonding forces are found between

molecules. The physical behavior of each phase of matter is
different because the strength of these forces differs from
state to state.

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 Table 12.1 A Macroscopic Comparison of Gases, Liquids,
and Solids

State Shape and Volume Compressibility Ability to Flow

Gas Conforms to shape and High High

volume of container

Liquid Conforms to shape of Very low Moderate

container; volume limited by
surface

Solid Maintains its own shape and Almost none Almost none
volume

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 Kinetic Molecular View of the Three States

Attractive Forces vs. Properties

Kinetic Energy

Gas Attractive forces are weak Particles are far apart. A gas
relative to kinetic energy. has no fixed shape or volume.

Liquid Attractive forces are stronger A liquid can flow and change
because particles have less shape, but has a fixed volume.
kinetic energy.

Solid Attractions dominate motion. A solid has a fixed shape and

Particles are fixed in place volume.
relative to each other.

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 Phase Changes

sublimation

melting (fusion) vaporization

endothermic

solid liquid gas

exothermic condensation
freezing

deposition

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 Figure 12.1 Two familiar phase changes.

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 Figure 12.3 Phase changes and their enthalpy changes.

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 Intermolecular Forces:
Liquids, Solids, and Phase Changes

12.1 An Overview of Physical States and Phase Changes

12.2 Quantitative Aspects of Phase Changes

12.3 Types of Intermolecular Forces

12.6 The Solid State: Structure, Properties, and Bonding

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 Quantitative Aspects of Phase Changes

Within a phase, heat flow is accompanied by a change

in temperature, since the average kinetic energy Ek of
the particles changes.

q = (amount) x (molar heat capacity) x DT

During a phase change, heat flow occurs at constant

temperature, as the average distance between particles
changes.

q = (amount)(DH of phase change)

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 Figure 12.4 A cooling curve for the conversion of gaseous water
to ice.
T

ΔT

q
T=Constant
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 Sample Problem 12.1 Finding the Heat of a Phase Change
Depicted by Molecular Scenes

PROBLEM: The scenes below represent a phase change of water.

Select data from the previous text discussion to find the heat
(in kJ) released or absorbed when 24.3 g of H2O undergoes
this change.

PLAN: The scenes show a disorderly, condensed phase at 85.0ºC

changing to separate particles at 117ºC. A liquid is becoming a
gas, so these scenes show vaporization. We must identify the
number of stages in the process and calculate the heat absorbed
in each.

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 Sample Problem 12.1

SOLUTION:
There are 3 stages involved in this process:
1) heating of the liquid to its boiling point
2) the phase change from liquid to gas
3) heating the gas to the final temperature

1 mol H2O
mol H2O = 24.3 g H2O x = 1.35 mol H2O
18.02 g H2O

For Stage 1:
q = n x Cm,water(l) x DT Cm,water(l)= 75.4 J/mol∙ºC

= (1.35 mol)(75.4 J/mol∙ºC)(100. – 85.0ºC)

= 1527 J = 1.53 kJ

12-15 Molar capacity heat (Cm in J/mol.ºC)

 For Stage 1:
q = m x Cwater(l) x DT Cwater(l)= 4.186 J/g∙ºC

= (24.3 g)(4.186 J/g∙ºC)(100. – 85.0ºC)

= 1527 J = 1.53 kJ

Specific capacity heat (C in J/g.ºC)

Example of Water (liquid):

Specific capacity heat Molar capacity heat

(C in J/g.ºC) (Cm in J/mol.ºC)
x M(Water)=18 g/mol
4.186 75.4
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 Sample Problem 12.1

For Stage 2: DHºvap= 40.7 kJ/mol

q = n x (DHºvap) = (1.35 mol)(40.7 kJ/mol) = 54.9 kJ

For Stage 3:
Cm,water(g)= 33.1 J/mol∙ºC
q = n x Cm,water(g) x DT

= (1.35 mol)(33.1 J/mol∙ºC)(117 – 100.ºC)

= 759.6 J = 0.760 kJ
Or

q = m x Cwater(g) x DT Cwater(g)= 1.99 J/g∙ºC

= (24.3 g)x(1.99 J/g∙ºC)(117 – 100.ºC)

= 759.6 J = 0.760 kJ

qtotal = 1.53 + 54.9 + 0.760 kJ = 57.2 kJ

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 Effect of P and T on Physical State
Figure 12.10 Phase diagram for CO2.

At the critical point, the

densities of the liquid and
gas phases become equal.

At the triple point, all three

phases are in equilibrium.

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 Figure 12.11 Phase diagram for H2O.

A
E F

C D

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 Sample Problem 12.3 Using a Phase Diagram to Predict Phase
Changes
PROBLEM:
Consider the phase diagram for carbon. Describe the phases and changes
that a sample of carbon undergoes during the following processes:
(a) The sample is heated at 102 bar (99 atm) from 1000 K to 5000 K.
(b) The sample is then compressed at 5000 K to 106 bar (990,000 atm).

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 Sample Problem 12.3 Using a Phase Diagram to Predict Phase
Changes

PLAN: We have to describe the phase changes due to heating at

constant pressure (102 bar) and then due to compressing at
constant temperature (5000 K).

(a) Using the phase diagram, we find the starting conditions (102 bar and
1000 K), label it point a, and draw a horizontal line to reach the ending
conditions (102 bar and 5000 K), noting any phase-transition curves
crossed.
(b) Then, labeling the new starting conditions point b (102 bar and 5000
K), we draw a vertical line to the ending pressure (106 bar) and note any
phase-transition curves crossed.

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 Sample Problem 12.3

SOLUTION:
(a) At 102 bar and 1000 K, the sample is in the form of graphite. As it is
heated the sample sublimes (at around 4400 K) and exists as carbon
vapor.
sublimation
Carbon(solid) Carbon(vapor)
Endothermic

(b) As the vapor is compressed at 5000 K, it first condenses to liquid carbon

(at around 300 bar), and then solidifies to diamond (at around 3 x 105 bar).
Condensation Freezing
Carbon(Vapor) Carbon(liquid) Carbon(solid)
Exothermic Exothermic diamond

CHECK: (a) From the phase diagram, the first triple point occurs above 102
bar, so graphite would vaporize before it liquefies.
(b) The liquid would solidify to diamond because graphite no longer exists
at 5000 K under any pressure.
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 Intermolecular Forces:
Liquids, Solids, and Phase Changes

12.1 An Overview of Physical States and Phase Changes

12.2 Quantitative Aspects of Phase Changes

12.3 Types of Intermolecular Forces

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 The Nature of Intermolecular Forces

Intermolecular forces arise from the attraction between

molecules with partial charges, or between ions and
molecules.

Intermolecular forces are relatively weak compared to

bonding forces because they involve smaller charges that
are farther apart.

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 Table 12.2 Comparison of Bonding and Nonbonding
(Intermolecular) Forces

(Intramolecular)

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 Table 12.2 Comparison of Bonding and Nonbonding
(Intermolecular) Forces (continued)

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 Figure 12.13 Polar molecules and dipole-dipole forces.

solid

liquid

The positive pole of one

polar molecule attracts the
negative pole of another.

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 Figure 12.14 Dipole moment and boiling point.

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 The Hydrogen Bond

Hydrogen bonding is possible for molecules that have a

hydrogen atom covalently bonded to a small, highly
electronegative atom with lone electron pairs, specifically
N, O, or F.

An intermolecular hydrogen bond is the attraction

between the H atom of one molecule and a lone pair of
the N, O, or F atom of another molecule.

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 Figure 12.15 Hydrogen bonding and boiling point.

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 Sample Problem 12.3 Drawing Hydrogen Bonds Between
Molecules of a Substance
PROBLEM: Which of the following substances exhibits H bonding?
For any that do, draw the H bonds between two of its
molecules.
(a) C2H6 (b) CH3OH (c)

PLAN: If the molecule does not contain N, O, or F it cannot form H

bonds. If it contains any of these atoms covalently bonded to H,
we draw two molecules in the pattern –B:----H–A.

SOLUTION:

(a) C2H6 has no N, O, or F, so no H-bonds can form.

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 Sample Problem 12.3

(b) CH3OH contains a covalent bond between O and H. It can form

H bonds between its molecules:

(c) can form H bonds at two sites:

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