Objectives: Chapter 11.1 – 11.

6
• Understand phase changes and related terms (sublimation, vaporization, fusion, condensation, fusion,
deposition, dynamic equilibrium, endothermic, exothermic). Draw and evaluate phase diagrams.
• Identify interparticle forces in atoms, compounds, and mixtures (dispersion, dipole-dipole, H-bonding, ion dipole,
ion-induced dipole, dipole-induced dipole)
• Using molecular structures, interparticle forces, and temperature to predict trends in physical properties (boiling
and melting points, vapour pressure, viscosity, solubility, surface tension, enthalpy of vaporization, enthalpy of
fusion, polarizability) for liquids, solids, gases, and solutions.
• Classify extended structures as ionic, network covalent (amorphous), network covalent (crystalline) or metallic
• Classify cubic unit cells (simple cubic, face-centred cubic, body-centred cubic) and closest packing sequences
(hcp and ccp). Identify the tetrahedral and octahedral sites in a fcc lattice. Memorize the structures of rocksalt
and antifluorite.
• Use crystal lattice systems to determine coordination number, formula units, density, atomic radius, molar mass,
and packing efficiency.
• Dr. Mar and Dr. McDermott Problem Set 7: all questions and Problem Set 8: 1 – 7a. Quiz 8: 2 – 6

© Department of Chemistry, University of Alberta (2025) 1

Phase Changes

 The behaviour of a real gas deviates from ideality

when attractive forces between gas particles become
significant. When these forces are strong enough,
the gas may condense to a liquid.
 Many substances consist of discrete molecules.
What happens when water undergoes a change in
state:

▪ The intramolecular (“bonding”) forces are intact, but intermolecular (“nonbonding”) forces are
disrupted or formed
© Department of Chemistry, University of Alberta (2025) 2
 Phase Changes
vaporization condensation
 The occurrence of a phase change depends on
the interplay between these interparticle
forces and the KE of the moving particles.
sublimation deposition

 When a substance changes its state, it absorbs

or releases energy. What are the names of the
processes shown in the figure? Fusion or Freezing
melting

On going s → l → g, energy is absorbed. (Why?) On going g → l → s, energy is released. (Why?)

© Department of Chemistry, University of Alberta (2025) 3

Phase Changes
 The magnitude of H° for a change in state reflects the strength of
interparticle forces. Consider the three substances below:
H°fus (kJ/mol) H°vap (kJ/mol)
H 2O 6.0 40.7
CH3CH2OH 5.0 38.6
Ar 1.3 6.3

 Why is H°fus << H°vap, in general, for all substances?

 Why are H°fus and H°vap both quite large for H2O?

© Department of Chemistry, University of Alberta (2025) 4

Equilibrium Nature of Phase Changes

 In open systems, phase changes are not reversible. In closed

systems, phase changes are reversible equilibrium processes.
Liquid-Gas Equilibria
 Consider what happens when we start with a closed container of
liquid with a vacuum above.
 Near the surface, some particles have enough KE to escape into
the gas phase. Now some gas particles may eventually
recondense into the liquid phase.
 When the rate of vaporization matches the rate of condensation, a
dynamic equilibrium (l ⇄ g) is established. As long as there is
some liquid present, the pressure reaches a constant value called
the vapour pressure of the liquid.

© Department of Chemistry, University of Alberta (2025) 5

Vapour Pressure
 The vapour pressure depends only on the type of liquid (not the amount) and the
temperature.

© Department of Chemistry, University of Alberta (2025) 6

Vapour Pressure

 Higher temperature increases the vapour pressure.

 Substances with weaker interparticle forces in the liquid have higher vapour pressures.

 Which has the higher vapour pressure, water or diethyl ether, (CH3CH2)2O?

© Department of Chemistry, University of Alberta (2025) 7

 Vapour Pressure
 When a liquid is heated in an open
container, there is a temperature
where the vapour pressure equals
the external pressure; we say that
boiling occurs. The normal boiling
point is the temperature at which
the vapour pressure is 1 atm.

 At what temperature does water

boil in Edmonton?

© Department of Chemistry, University of Alberta (2025) 8

Equilibrium Nature of Phase Changes

Solid-Liquid Equilibria
 As temperature rises, particles in a solid vibrate until they have enough KE to
slip from their regular positions and become randomly arranged, so that
melting begins. The reverse process of freezing also happens until a dynamic
equilibrium (s ⇄ l) is reached at the melting point.
 Because liquids and solids are nearly incompressible, pressure has little effect
on melting points.

Solid-Gas Equilibria
 Instead of melting, a solid may sublime directly to a gas if interparticle forces
are too weak to keep particles together when they leave the solid. A similar
equilibrium (s ⇄ g) is established.

© Department of Chemistry, University of Alberta (2025) 9

Phase Diagrams

 Watch these demos that show the physical behaviour of carbon dioxide at different
temperatures and pressures.
 Sublimation of dry ice: [Link]

 Liquid carbon dioxide: [Link]

 Supercritical carbon dioxide: [Link]

 Supercritical fluids – if a liquid is heated in a closed container, the density of the liquid
will decrease. Simultaneously the density of the gas will increase. Eventually the liquid
and gas will have the same density and a supercritical fluid has formed. At this point,
the boundary between phases will disappear.

© Department of Chemistry, University of Alberta (2025) 10

Phase Diagrams  Regions indicate which one phase is stable at
 Phase diagrams depict which phase is most stable at
given T and p. What conditions of p, T (low vs.
different conditions of temperature and pressure.
high) are solids, liquids, or gases found?
Consider the phase diagram for carbon dioxide.

Phase diagram for CO2

 Lines indicate which two phases coexist in

equilibrium. Note that the s ⇄ l equilibrium line
has a positive slope for CO2 — which phase is
denser, solid or liquid?

 The critical point (pc, Tc) is where the l ⇄ g line

terminates. Above p c, Tc, the vapour cannot be
liquified — this state is called a supercritical fluid.
 The triple point occurs when all 3 phases coexist in
equilibrium. For CO2, where is the triple point? Can
liquid CO2 be stable under normal atmospheric
conditions?

© Department of Chemistry, University of Alberta (2025) 11

Phase Diagrams
 Phase diagrams depict which phase is most stable at
different conditions of temperature and pressure.
Consider the phase diagram for carbon dioxide.
 Regions indicate which one phase is stable at
given T and p.

 Lines indicate which two phases coexist in

equilibrium.

 The critical point (pc, Tc) is where the l ⇄ g line

p (atm)

terminates. Above p c, Tc, the vapour cannot be

liquified — this state is called a supercritical fluid.

 The triple point occurs when all 3 phases coexist in

equilibrium.

T (C)
© Department of Chemistry, University of Alberta (2025) 12
 Phase Diagrams
 Draw the phase diagram for water, given the information:

 normal mp: ____________ triple point: 0.0098 ºC, 0.0060 atm

normal bp: _____________ critical point: 374 ºC, 218 atm
p (atm)

T (C)
© Department of Chemistry, University of Alberta (2025) 13
Example
Answer the following questions:
Phase diagram for H2O 1. Can H2O (g) be stable at –10ºC?

2. What phase is stable above 374ºC?

3. At 0 ºC, which phase is denser, solid or liquid?

4. Describe what you observe when:

a. Pressure is fixed at 1.0 atm, and heat is added.

b. Temperature is fixed at –10 ºC, and pressure is applied.

Phase diagrams only indicate which phase is most thermodynamically stable. It is possible for other phases
to exist (under metastable conditions).
© Department of Chemistry, University of Alberta (2025) 14
Interparticle Forces
 Interparticle forces influence only the physical (not chemical) properties of a substance.
Their strengths are reflected in:
 mp, bp
 heats of fusion, vaporization
 surface tension, viscosity
 solubility
 But be careful! Not all substances are molecular! There are no “molecules” in:
 simple ionic solids
 extended network solids
 The entities in a substance can thus be atoms, ions, or molecules.
 Interparticle forces, such as those responsible for the (n2a/V2) term in the van der Waals
equation, are also called van der Waals forces. These “nonbonding forces” tend to be quite
weak compared to chemical bonding forces.
 Interparticle forces are primarily based on electrostatic attractions between opposite charges
q1 q2
(F ∝ ).
r2

© Department of Chemistry, University of Alberta (2025) 15

Types of Chemical Forces: Bonding
Bonding forces are stronger than interparticle forces because larger charges are interacting, and they are
closer together.
Force Model Basis of Attraction Energy (kJ/mol) Example

Ionic Cation-anion 400–4000

Covalent Nuclei—shared e− pair 150–1100

Cations—delocalized
Metallic 75–1000
electrons

© Department of Chemistry, University of Alberta (2025) 16

Types of Interparticle Forces: Ion-Dipole & Dipole-dipole

 Ion−dipole forces arise between ions and nearby

polar molecules.

 Dipole−dipole forces occur between polar

molecules, with dipoles aligned to maximize
attractions

© Department of Chemistry, University of Alberta (2025) 17

Types of Interparticle Forces: Hydrogen Bonding

 Hydrogen bonding forces are a special kind of dipole-dipole force that may occur between
molecules that have an H atom bonded to a small, highly electronegative atom (N, O, F)

 Why is this force particularly strong for these types of molecules?

© Department of Chemistry, University of Alberta (2025) 18

Example
 Account for the anomaly for H2O in the  (Silberberg sample problem 11.3) Which
trend of bp: of these substances exhibit H-bonding?
 C2H6, CH3OH, CH3CONH2

© Department of Chemistry, University of Alberta (2025) 19

Types of Interparticle Forces: Induced Dipoles

 Attractions can also occur with nonpolar

molecules. Although they have no dipole
moment, an induced dipole may be temporarily
produced through momentary shifts in electron
density

© Department of Chemistry, University of Alberta (2025) 20

Types of Interparticle Forces: Induced Dipoles
 Ion−induced dipole forces occur between ions and nonpolar molecules.

 Dipole−induced dipole forces occur between polar and nonpolar molecules.

 Instantaneous dipole−induced dipole (or dispersion) forces occur between nonpolar molecules (or
single atoms).

© Department of Chemistry, University of Alberta (2025) 21

Polarizability

 Forces involving interactions with induced dipoles depend on a molecular property

called polarizability, which refers to the ease with which the electron cloud can be
distorted to create a charge separation.

 Polarizability increases with greater number of electrons and larger molecular size. In
some instances, large molecules with high molar mass may experience quite substantial
dispersion forces.

 For atoms: polarizability increases down a group because the elements become bigger, and a
larger electron cloud is easier to distort. Polarizability decreases across a period as the electrons
are held more tightly (great Zeff).
 For ions: anions are more polarizable than cations.

© Department of Chemistry, University of Alberta (2025) 22

Types of Chemical Forces: Nonbonding (Interparticle)
Force Model Basis of Attraction Energy (kJ/mol) Example
Ion-dipole Ion charge—dipole charge 40–600

Hydrogen bond Polar bond to H—dipole 10–40

charge
Dipole-dipole Dipole charges 5–25

Ion–induced dipole Ion charge—polarizable e− 3–15

cloud
Dipole–induced dipole Dipole charge—polarizable 2–10
e− cloud
Induced dipole–induced Polarizable e− clouds 0.05–40
dipole (dispersion or
London)

© Department of Chemistry, University of Alberta (2025) 23

Example
 Predict the trend in bp for Cl2, Br2, I2.

© Department of Chemistry, University of Alberta (2025) 24

Example
 Explain the trend in bp for N2 (77 K), NO (121 K), and O2 (90 K).

© Department of Chemistry, University of Alberta (2025) 25

 Determining the dominant interparticle forces present in a substance

ions molecules atoms

only ions ions and polar ions and nonpolar only polar polar and non- only nonpolar
molecules molecules molecules polar molecules molecules or atoms

ionic ion–dipole ion–induced dipole–dipole dipole–induced induced dipole–

bonding forces dipole forces forces dipole forces induced dipole forces

H-bonding

▪ Determine the dominant interparticle force for the following substances:

SO2(g) NaCl(s) KBr(aq) H2O(l) NO(g) N2(g) I2(s) (NH4)3PO4 dissolved in CO2(l)
HCl(l) NH3(g) Ar(g) NH4NO3(s) HF(g) CCl4(l) dilute NO(g) in N2(g)
© Department of Chemistry, University of Alberta (2025) 26
 Determining the dominant interparticle forces present in a substance

ions molecules atoms

only ions ions and polar ions and nonpolar only polar polar and non- only nonpolar
molecules molecules molecules polar molecules molecules or atoms

ionic ion–dipole ion–induced dipole–dipole dipole–induced induced dipole–

bonding forces dipole forces forces dipole forces induced dipole forces

NaCl, KBr(aq) (NH4)3PO4 in CO2 SO2, NO, HCl NO in N2 N2, I2, Ar, CCl4
NH4NO3

H-bonding
NH3, H2O, HF

▪ Determine the dominant interparticle force for the following substances:

SO2(g) NaCl(s) KBr(aq) H2O(l) NO(g) N2(g) I2(s) (NH4)3PO4 dissolved in CO2(l)
HCl(l) NH3(g) Ar(g) NH4NO3(s) HF(g) CCl4(l) dilute NO(g) in N2(g)
© Department of Chemistry, University of Alberta (2025) 27
Extra example
 Which liquid has the highest boiling point, CH3NH2 or CH3F?

 Which compound has the lowest vapour pressure, CH3OH or CH3CH2CH2OH?

© Department of Chemistry, University of Alberta (2025) 28

Liquids

 Liquids have a definite volume, but are not confined to the shape of the container.
 They are poorly understood, resembling gases (random particle motion) and solids (tightly
packed particles).
 Their properties depend on the strengths of interparticle forces

© Department of Chemistry, University of Alberta (2025) 29

Liquid Properties: Surface Tension
 Surface tension refers to the resistance of a liquid to increase
its surface area.
 Surface tension is properly defined as the energy required to
increase the surface area, and is measured in units of J/m 2.
 Why do liquids tend to form spherical droplets? Consider the
forces acting on a particle at the surface vs. in the interior.

 High surface tension implies strong interparticle forces. Which

has higher surface tension, CH3CH2OH or H2O?

© Department of Chemistry, University of Alberta (2025) 30

 Liquid Properties: Viscosity

 Viscosity refers to the resistance of a liquid to flow. High viscosity

(as in honey and motor oil) implies strong IM forces

© Department of Chemistry, University of Alberta (2025) 31

Solubility

 A solution is a homogeneous mixture in which the solute (minor component) is dissolved in the
solvent (major component). Solubility rules are complicated, but in general, a good guideline is
“like dissolves like.” Consider the competition between the following forces:

solute-solute forces

solvent-solvent forces solute-solvent forces

© Department of Chemistry, University of Alberta (2025) 32

 Fig 12.1 Types of interparticle
forces in solutions.

The forces are listed

in order of decreasing strength (kJ/mol),
©2021 McGraw Hill 33
Examples

 octane in water  cocaine in water

 How can we increase the solubility of

cocaine in water?
 sodium chloride in water

© Department of Chemistry, University of Alberta (2025) 34

Solids
 Solids have a definite volume and shape. The particles are tightly packed and hardly
move.
 Solids can be:

crystalline amorphous

Ordered arrangements (has a pattern) No long-range order/pattern

We focus on crystalline solids.

© Department of Chemistry, University of Alberta (2025) 35
Types of Crystalline Solids: Discrete (molecular) Structures
Structural model Dominant
Type Physical properties Examples
(Structural particles) interparticle forces

Soft
Non-polar Ar(s) MP –189oC
Low mp
CH4(s) MP –182oC
Poor thermal and
Atomic/ CO2(s) sublimes –78oC
electrical conductors
Molecular

Polar
Hydrogen- Fairly soft
H2O(s) MP 0oC
bonded
Low to moderate mp
CHCl3(s) MP –64oC
Poor thermal and
Molecular electrical conductors

© Department of Chemistry, University of Alberta (2025) 36

Types of Crystalline Solids: Extended Structures
Structural model
Type Dominant forces Physical properties Examples
(Structural particles)
Hard and brittle
High mp CsCl(s) 645oC
Ionic Good thermal and (when MgO(s) 2800oC
molten) electrical conductors

Very hard C(diamond) >3500oC

Very high mp
Covalent SiO2(quartz) 1600oC
Usually poor thermal and
network electrical conductors C(graphite), Si, SiC, BN

Soft to hard
Usually high mp
Lustrous Fe(s) 1500oC
Metallic Ductile, malleable W(s) 3400oC
Excellent thermal and
electrical conductors

© Department of Chemistry, University of Alberta (2025) 37

Structures of Crystals
 A crystal is composed of particles packed in an orderly three-dimensional array called
the crystal structure
 The lattice consists of all points with identical surroundings in a crystal structure. There is no
way to tell if you’ve moved from one lattice point to another lattice point.
 The unit cell is the smallest portion of the crystal that, when stacked together repeatedly,
without gaps, can reproduce the entire crystal


A lattice point can be anywhere in the crystal. We always
choose lattice points that correspond to the centre of atoms.

Unit cells can take multiple shapes. We will study cubic unit
cells.

A lattice is imaginary. The crystal structure is what is real.

© Department of Chemistry, University of Alberta (2025) 38
Unit cells

 The highly symmetrical external shapes of crystals suggests a regular ordered

arrangement of atoms. There are a very large number of atoms, so we need a compact
way to describe their arrangement. We do this by defining a unit cell.
 Here is a simplified 2D example of a unit cell. Choose a point, then highlight nearby
identical points. Choose 4 points that form the smallest unit cell.

What is the unit cell?

Several choices are possible. The usual convention is to choose
the one that indicates all of the symmetry present in the lattice
(beyond the scope of this course).

© Department of Chemistry, University of Alberta (2025) Complete lesson on Structures of Crystals 39

Unit Cell Types

 There are 7 systems and 14 types of unit cells

that occur in nature.
 Every crystalline solid can be classified by one of
these types of unit cells.
 We will focus on cubic lattices
 although keep in mind that there are also other
types of lattices with lower symmetry not
described in introductory textbooks

© Department of Chemistry, University of Alberta (2025) 40

Cubic Lattices (see Unit Cell Video on eClass to help visualize these)

 In a primitive (“simple”) cubic lattice, the lattice points lie at the corners of a cubic unit
cell.

 In a body-centered cubic lattice, the lattice points lie at the corners and centre of a cubic
unit cell.

 In a face-centered cubic lattice, the lattice points lie at the corners and faces of a cubic
unit cell.

© Department of Chemistry, University of Alberta (2025) 41

Cubic Lattices How many atoms per unit cell?
 Atoms located at boundaries of a unit cell are shared with adjacent
unit cells, so count only the portions that lie within the given unit cell.

 What fraction of each atom contributes to the contents of the unit cell?

 How many corners, faces, and edges does a cube have?

© Department of Chemistry, University of Alberta (2025) 42

Simple Cubic
Centers of 8 identical particles define the corners of a cube

Atoms are SHARED with other cells

Coordination number = # particles that are equidistant nearest neighbors to a

reference point

Counting atoms:
1/8 of each atom at the corners belongs to the unit cell → 1 atom per unit cell

© Department of Chemistry, University of Alberta (2025) 43

Body-Centered Cubic
8 identical particles at the corners of the cube
1 additional particle at the center of the cube

The nearest neighbor to a corner is located at the center of the cube (not another corner)
OR
The nearest neighbor to the center particle is at the corners

Counting atoms:
1/8 of each atom at the corners belongs to the unit cell
1 atom in the center →
© Department of Chemistry, University of Alberta (2025) 44
Face-Centered Cubic
8 identical particles at the corners of the cube
6 additional particles at each face of the cube
0 particles in the center

The nearest neighbor to a corner is located at the face of the cube (not another corner)

Counting atoms:
1/8 of each atom at the corners belongs to the unit cell
½ of each atom at the face
© Department of Chemistry, University of Alberta (2025) 45
Examples Label as SC, FCC, BCC, or none

C60
Cu Fe

© Department of Chemistry, University of Alberta (2025) 46

Examples

 What are the formulas and lattices of these solids? Hint: Only one type of atom/ion are
considered. Corners are always lattice points, so only consider the atoms/ions found at
corners.

Cs
O

Cl Re

© Department of Chemistry, University of Alberta (2025) 47

Example
 The structure of Cu(s) has atoms at points of an fcc lattice. The density of Cu(s) is 8.93
g/cm3.
a. Calculate the length of a unit cell edge (in Å).
Strategy: type of unit cell → number of atoms → mol → mass → volume → length

© Department of Chemistry, University of Alberta (2025) 48

Example (cont’d)
b. Calculate the radius of a Cu atom
length → radius (formula depends on unit cell type)

© Department of Chemistry, University of Alberta (2025) 49

Radius Calculations
These diagrams help you figure out the trigonometry.

50
© Department of Chemistry, University of Alberta (2025)
Try @ Home
The crystal structure of MgO is similar to that of NaCl (shown below). The ionic radius of
Mg2+ is 72 pm and that of O2— is 140 pm.
a. Determine the number of formula units in the unit cell
b. Determine the edge and volume of the unit cell
c. Determine the density of MgO

© Department of Chemistry, University of Alberta (2025) 51

Structures of Metallic Solids

© Department of Chemistry, University of Alberta (2025) 52

Structures of Metallic Solids

 Because metallic bonding is nondirectional (“sea of electrons”), the atoms pack tightly to fill space.
If atoms are rigid and non-interacting, the most efficient packing of equal-sized spheres in 2D
gives a closest-packed layer.

 There remain interstitial spaces (or voids or holes) between the spheres, having roughly triangular
shape.

© Department of Chemistry, University of Alberta (2025) 53

Stacking Sequences The unit cell video on eClass is a great visual aid
 In 3D, these closest-packed layers can be arranged in different stacking sequences.

Hexagonal Closest Packing (hcp)

arrangement

ABAB

Primitive hexagonal cubic cell

74% packing efficiency

© Department of Chemistry, University of Alberta (2025) 54

Stacking Sequences The unit cell video on eClass is a great visual aid
 In 3D, these closest-packed layers can be arranged in different stacking sequences.

Cubic Closest Packing (ccp)

arrangement

ABCABC

fcc

74% packing efficiency

‘
© Department of Chemistry, University of Alberta (2025) 55
Structures of Ionic Solids
 Ionic bonding (based on electrostatic forces) is also non-directional, but the structures
now contain two types of spheres:
 larger anions are often found in close-packing arrangements

 smaller cations are found in holes (“interstices”)

Octahedral sites are sandwiched Tetrahedral sites are sandwiched

between three spheres of one layer and between three spheres of one layer and
three spheres of another layer. one sphere of another layer.

© Department of Chemistry, University of Alberta (2025) 56

Structures of Ionic Solids

 Suppose anions are placed at points of an fcc lattice. Locate the octahedral and
tetrahedral sites:

© Department of Chemistry, University of Alberta (2025) 57

Structures of Ionic Solids
 Two common structure types for ionic solids are derived by placing cations in
octahedral or tetrahedral sites within a ccp arrangement of anions.
NaCl-type (rocksalt) Li2O-type (antifluorite)

 There are many other possibilities of arrangements of anions and cations that lead to
the structures of other ionic solids.
© Department of Chemistry, University of Alberta (2025) 58
 Example
 Zinc selenide (with the structure shown) has a density of 5.42 g/cm 3.
a. What is the formula?

b. Calculate the length of a unit cell edge (in Å).

© Department of Chemistry, University of Alberta (2025) 59