Chapter 11

Intermolecular Attractions
and the Properties of Liquids
and Solids
Chemistry, 7th Edition
International Student Version
Brady/Jespersen/Hyslop

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved.

Intermolecular Forces
 Important differences between gases,
solids, and liquids:
 Gases
 Expand to fill their container
 Liquids
 Retain volume, but not shape
 Solids
 Retain volume and shape

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 1

1
 Intermolecular Forces
 Physical state of molecule depends on
 Average kinetic energy of particles
 Recall KE  Tave
 Intermolecular Forces
 Energy of Inter-particle attraction
 Physical properties of gases, liquids
and solids determined by
 How tightly molecules are packed together
 Strength of attractions between
molecules

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 2

Intermolecular Attractions
 Converting gas  liquid or solid
 Molecules must get closer together
 Cool or compress
 Converting liquid or solid  gas
 Requires molecules to move farther apart
 Heat or reduce pressure
 As T decreases, kinetic energy of molecules
decreases
 At certain T, molecules don’t have enough
energy to break away from one another’s
attraction

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 3

2
 Inter vs. Intra-Molecular Forces
 Intramolecular forces
 Covalent bonds within molecule
 Strong
 Hbond (HCl) = 431 kJ/mol
 Intermolecular forces
 Attraction forces between molecules
 Weak
 Hvaporization (HCl) = 16 kJ/mol
Covalent Bond (strong) Intermolecular attraction (weak)

Cl H Cl H

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 4

Electronegativity Review
Electronegativity: Measure of attractive force
that one atom in a covalent bond has for
electrons of the bond

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 5

3
 Bond Dipoles
 Two atoms with different electronegativity
values share electrons unequally
 Electron density is uneven
 Higher charge concentration around more
electronegative atom
H F
 Bond dipoles
 Indicated with delta (δ) notation  
 Indicates partial charge has arisen

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 6

Net Dipoles
 Symmetrical molecules
 Even if they have polar bonds
 Are non-polar because bond dipoles cancel
 Asymmetrical molecules
 Are polar because bond dipoles do not cancel
 These molecules have permanent, net dipoles
 Molecular dipoles
 Cause molecules to interact
 Decreased distance between molecules increases
amount of interaction

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 7

4
 Intermolecular Forces
 When substance melts or boils
 Intermolecular forces are broken
 Not covalent bonds
 Responsible for non-ideal behavior of gases
 Responsible for existence of condensed
states of matter
 Responsible for bulk properties of matter
 Boiling points and melting points
 Reflect strength of intermolecular forces

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 8

Three Important Types of

Intermolecular Forces

1. Dipole-dipole forces
 Hydrogen bonds
2. London dispersion forces
3. Ion-dipole forces
 Ion-induced dipole forces

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 9

5
 Dipole-Dipole Attractions
 Occur only between polar +  + 
molecules
 Possess dipole moments
 Molecules need to be  +  +
close together
 Polar molecules tend to
align their partial charges +  + 
 Positive to negative
 As dipole moment
increases, intermolecular
force increases
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 10

Dipole-Dipole Attractions
 Tumbling molecules
 Mixture of attractive and repulsive dipole-dipole
forces
 Attractions (- -) are maintained longer than
repulsions(- -)
 Get net attraction
 ~1–4% of covalent bond

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 11

6
 Dipole-Dipole Attractions
 Interactions between net dipoles in polar
molecules
 About 1–4% as strong as a covalent bond
 Decrease as molecular distance increases
 Dipole-dipole forces increase with
increasing polarity

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 12

Hydrogen Bonds
 Special type of dipole-dipole Interaction
 Very strong dipole-dipole attraction
 ~10% of a covalent bond
 Occurs between H and highly electronegative atom
(O, N, or F)
 H—F, H—O, and H—N bonds very polar
 Electrons are drawn away from H, so high partial charges
 H only has one electron, so +H presents almost bare
proton
 –X almost full –1 charge
 Element’s small size, means high charge density
 Positive end of one can get very close to negative end of
another
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 13

7
 Examples of Hydrogen Bonding
H O H O H F H O
H H H
H
H N H O
H H
H H H
H N H N H H F H N
H H H O H N H
H H

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 14

Hydrogen Bonding in Water

 Responsible for expansion of water as it freezes

 Hydrogen bonding produces strong attractions in
liquid
 Hydrogen bonding (dotted lines) between
water molecules in ice form tetrahedral
configuration
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 15

8
 London Forces
 When atoms near one another,
their valence electrons interact
 Repulsion causes electron clouds
in each to distort and polarize
 Instantaneous dipoles result from
this distortion
 Effect enhanced with increased
volume of electron cloud size
 Effect diminished by increased
distance between particles and
compact arrangement of atoms

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 16

London Forces
 Instantaneous dipole-induced dipole
attractions
 London Forces
 Dispersion forces
 Operate between all molecules
 Neutral or net charged
 Nonpolar or polar

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 17

9
 London Dispersion Forces
 Ease with which dipole moments can be
induced and thus London Forces depend
on
1. Polarizability of electron cloud
2. Points of attraction
 Number atoms
 Molecular shape (compact or
elongated)

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 18

Your Turn!
Which of the following is the weakest of all
intermolecular forces?
A. Hydrogen-bonds
B. London dispersion forces
C. Dipole-dipole attractions
D. Ion-dipole attractions
E. Ion-Ion attractions

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 19

10
 Polarizability
 Ease with which the electron
cloud can be distorted
 Larger molecules often more
polarizable
 Larger number of less tightly
held electrons
 Magnitude of resulting partial
charge is larger
 Larger electron cloud

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 20

Table 11.1 Boiling Points of Halogens

and Noble Gases
Larger molecules have stronger London forces
and thus higher boiling points.

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 21

11
 Number of Atoms in Molecule
 London forces depend on number atoms in
molecule
 Boiling point of hydrocarbons demonstrates this
trend

Formula BP at 1 atm, C Formula BP at 1 atm, C

CH4 –161.5 C5H12 36.1
C2H6 –88.6 C6H14 68.7
C3H8 –42.1 : :
C4H10 –0.5 C22H46 327

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 22

How Intermolecular Forces

Determine Physical Properties

Hexane, C6H14 Propane, C3H8

BP 68.7 °C BP –42.1 °C
 More sites (marked with *) along its chain where
attraction to other molecules can occur
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 23

12
 Molecular Shape
 Increased surface area available for contact =
increased London forces
 London dispersion forces between spherical
molecules are lower than chain-like molecules
 More compact molecules
 Hydrogen atoms not as free to interact with
hydrogen atoms on other molecules
 Less compact molecules
 Hydrogen atoms have more chance to
interact with hydrogen atoms on other
molecules
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 24

Physical Origin of Shape Effect

 Small area for  Larger area for
interaction interaction

More compact – lower BP Less compact – higher BP

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 25

13
 Your Turn!
List all intermolecular forces for CH3CH2OH.

A. Hydrogen-bonds
B. Hydrogen-bonds, dipole-dipole attractions,
London dispersion forces
C. Dipole-dipole attractions
D. London dispersion forces
E. London dispersion forces, dipole-dipole
attractions

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 26

Your Turn!
In the liquid state, which species has the
strongest intermolecular forces, CH4, Cl2, O2 or
HF?
A. CH4
B. Cl2
C. O2
D. HF

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 27

14
 Your Turn!
What is the strongest type of intermolecular
force in CHCl3?
A. ion-dipole
B. dipole-dipole
C. dispersion
D. Hydrogen bonding
E. None of the above

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 28

Your Turn!
Which of the following has dispersion forces as
its strongest intermolecular force?
A. CH4
B. CO2
C. O2
D. All of the above

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 29

15
 Ion-Dipole Attractions
 Attractions between ion and charged end of
polar molecules
 Attractions can be quite strong as ions have full
charges

(a) Negative ends of water dipoles surround cation

(b) Positive ends of water dipoles surround anion
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 30

Ex. Ion-Dipole Attractions: AlCl3·6H2O

 Attractions between ion and polar molecules
 Positive charge of Al3+ ion
attracts partial negative
charges – on O of water
molecules
 Ion-dipole attractions hold
water molecules to metal
ion in hydrate
 Water molecules are found
at vertices of octahedron
around aluminum ion

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 31

16
 Ion-Induced Dipole Attractions
 Attractions between ion and dipole it induces
on neighboring molecules
 Depends on
 Ion charge and
 Polarizability of its neighbor
 Attractions can be quite strong as ion charge is
constant, unlike instantaneous dipoles of ordinary
London forces
 E.g., I– and Benzene

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 32

Summary of Intermolecular
Attractions
Dipole-dipole
 Occur between neutral molecules with permanent
dipoles
 About 1–4% of covalent bond
 Mid range in terms of intermolecular forces
Hydrogen bonding
 Special type of dipole-dipole interaction
 Occur when molecules contain N—H,
H—F and O—H bonds
 About 10% of a covalent bond

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 33

17
 Summary of Intermolecular
Attractions
London dispersion
 Present in all substances
 Weakest intermolecular force
 Weak, but can add up to large net attractions
Ion-dipole
 Occur when ions interact with polar molecules
 Strongest intermolecular attraction
Ion-induced dipole
 Occur when ion induces dipole on neighboring particle
 Depend on ion charge and polarizability of its neighbor

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 34

Using Intermolecular Forces

 Often can predict physical properties (like BP,
MP and many others) by comparing strengths
of intermolecular attractions
 Ion-Dipole Strongest
 Hydrogen Bonding
 Dipole-Dipole
 London Forces Weakest
 Larger, longer, and therefore heavier molecules
often have stronger intermolecular forces
 Smaller, more compact, lighter molecules have
generally weaker intermolecular forces
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 35

18
 Physical Properties that Depend on
How Tightly Molecules Pack
 Compressibility
 Measure of ability of substance to be forced into
smaller volume
 Determined by strength of intermolecular forces
 Gases highly compressible
 Molecules far apart
 Weak intermolecular forces
 Solids and liquids nearly incompressible
 Molecules very close together
 Stronger intermolecular forces

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 36

Diffusion
 Movement that
spreads one gas
though another gas
to occupy space
uniformly
 Spontaneous
intermingling of
molecules of one gas
with molecules of
another gas
 Occurs more rapidly in gases than in liquids
 Hardly at all in solids
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 37

19
 Diffusion  In Gases
 Molecules travel long
distances between
collisions
 Diffusion rapid
 In Liquids
 Molecules closer
 Encounter more collisions
 Takes a long time to move
from place to place
 In Solids
 Diffusion close to zero at
room temperature
 Will increase at high
temperature

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 38

Intermolecular Forces Determine

Strength of Many Physical Properties
 Retention of volume and shape
 Solids retain both volume and shape
 Strongest intermolecular attractions
 Molecules closest
 Liquids retain volume, but not shape
 Attractions intermediate
 Gases, expand to fill their containers
 Weakest intermolecular attractions
 Molecules farthest apart

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 39

20
 Intermolecular Forces and
Temperature
 Decrease with increasing temperature
 Increasing kinetic energy overcomes attractive
forces
 If allowed to expand, increasing temperature
increases distance between gas particles and
decreases attractive forces

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 40

Surface Tension
Why does H2O bead up on a freshly waxed car
instead of forming a layer?

 Inside body of liquid

 Intermolecular forces are
the same in all directions
 Molecules at surface
 Potential energy increases
when removing neighbors
 Molecules move together
to reduce surface area and
potential energy

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 41

21
 Surface Tension
 Causes a liquid to
take the shape (a  Wax = nonpolar
sphere) that  H2O = polar
minimizes its surface  Water beads in order
area to reduce potential
 Molecules at surface energy by reducing
have higher potential surface area
energy than those in
bulk of liquid and
move to reduce the
potential energy

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 42

Surface Tension
 Liquids containing
molecules with strong
 Surface tension
intermolecular forces have
increases as
high surface tension intermolecular
 Allows us to fill glass above forces increase
rim  Surface tension
 Gives surface rounded decreases as
appearance temperature
increases
 Surface acts as “skin” that lets
water pile up
 Surface resists expansion and
pushes back

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 43

22
 Wetting
 Ability of liquid to spread
across surface to form
thin film
 Greater similarity in
attractive forces between
liquid and surface, yields
greater wetting effect
 Occurs only if
intermolecular attractive
force between surface
and liquid about as
strong as within liquid
itself
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 44

Wetting
Ex. H2O wets clean glass surface as it forms
H–bonds to SiO2 surface
 Does not wet greasy glass, because grease is
nonpolar and water is very polar
 Only London forces
 Forms beads instead
Surfactants
 Added to detergents to lower surface tension of H2O
 Now water can spread out on greasy glass

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 45

23
 Surfactants (Detergents)
 Substances that have both polar and non-polar
characteristics
 Long chain hydrocarbons with polar tail
O

O Na+
O
S
O O Na+
O
 Nonpolar end dissolves in nonpolar grease
 Polar end dissolves in polar H2O
 Thus increasing solubility of grease in water

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 46

Viscosity
 Resistance to flow
 Measure of fluid’s resistance to flow or
changing form
 Related to intermolecular attractive forces
 Also called internal friction
 Depends on intermolecular attractions

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 47

24
 Viscosity
 Viscosity decreases when temperature
increases
 Most people associate liquids with viscosity
 Syrup more viscous than water
 Gases have viscosity
 Respond almost instantly to form-changing forces
 Solids, such as rocks and glass have viscosity
 Normally respond very slowly to forces acting to
change their shape

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 48

Effect of Intermolecular Forces on

Viscosity

Acetone Ethylene glycol

 Polar molecule  Polar molecule
 Hydrogen-bonding
 Dipole-dipole and
 Dipole-dipole and
 London forces
 London forces

Which is more viscous?

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 49

25
 Your Turn!
For each pair given, which is more viscous?

CH3CH2CH2CH2OH or CH3CH2CH2CHO
C6H14 or C12H26
NH3(l ) or PH3(l )

A. CH3CH2CH2CH2OH C6H14 NH3(l )

B. CH3CH2CH2CH2OH C12H26 NH3(l )
C. CH3CH2CH2CHO C6H14 PH3(l )
D. CH3CH2CH2CHO C12H26 NH3(l )
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 50

Solubility
 “Like dissolves like”
 To dissolve polar substance, use polar solvent
 To dissolve nonpolar substance, use nonpolar
solvent
 Compare relative polarity
 Similar polarity means greater ability to dissolve
in each other
 Differing polarity means that they don’t dissolve,
they are insoluble
 Surfactants
 Both polar and non-polar characteristics
 Used to increase solubility
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 51

26
 Your Turn!
Which of the following are not expected to be
soluble in water?
A. HF
B. CH4
C. CH3OH
D. All are soluble

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 52

Your Turn!
What type of intermolecular attraction causes
KI to dissolve in water?
A. Hydrogen bonding
B. dipole-dipole
C. dispersion
D. ion-dipole
E. None of the above

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 53

27
 Phase Changes
 Changes of physical state
 Deal with motion of molecules
 As temperature changes
 Matter will undergo phase changes
 Liquid  Gas
 Evaporation, vaporization
 As heat is added, H2O, forms steam or water
vapor
 Requires energy or source of heat

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 54

Phase Changes
 Solid  Gas
 Sublimation
 Ice cubes in freezer, leave in long enough disappear
 Endothermic
 Gas  Liquid
 Condensation
 Dew is H2O vapor condensing onto cooler ground
 Exothermic
 Often limits lower night time temperature

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 55

28
 Rate of Evaporation
 Depends on
 Temperature
 Surface area
 Strength of
intermolecular
attractions
 Molecules that escape
from liquid have larger
than minimum escape
KE
 When they leave
 Average KE of
remaining molecules
is less and so T lower
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 56

Effect of Temperature on Evaporation

Rate
 For given liquid
 Rate of evaporation per
unit surface area
increases as T
increases
 Why?
 At higher T, total
fraction of molecules
with KE large enough
to escape is larger
 Result: rate of
evaporation is larger
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 57

29
 Kinetic Energy Distribution in Two
Different Liquids
A B

 Smaller  Larger intermolecular

intermolecular forces forces
 Lower KE required to  Higher KE required to
escape liquid escape liquid
 A evaporates faster  B evaporates slower
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 58

Changes Of State Involve Equilibria

 Fraction of molecules in condensed state is
higher when intermolecular attractions are
higher
 Intermolecular attractions must be
overcome to separate the particles, while
separated particles are simultaneously
attracted to one another
condensed separated
phase phase

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 59

30
 Before System Reaches
Equilibrium
 Liquid is placed in empty,
closed, container
 Begins to evaporate
 Once in gas phase
 Molecules can condense by
 Striking surface of liquid
and giving up some kinetic
energy

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 60

System At Equilibrium

 Rate of evaporation =
rate of condensation
 Occurs in closed
systems where
molecules cannot
escape

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 61

31
 Similar Equilibria Reached in
Melting
Melting Point (mp)
 Solid begins to change
into liquid as heat added
 Dynamic equilibria
exists between solid and
liquid states
 Melting (red arrows) and
freezing (black arrows)
occur at same rate
 As long as no heat added or
removed from equilibrium
mixture
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 62

Equilibria Reached in
Sublimation
At equilibrium
 Molecules sublime
from solid at same
rate as molecules
condense from vapor

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 63

32
 Phase Changes
Gas

Vaporization Condensation
Energy of System

Sublimation
Deposition
Liquid
Melting
Freezing
or Fusion

Solid
 Exothermic, releases heat
 Endothermic, absorbs heat
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 64

Energy Changes Accompanying

Phase Changes
 All phase changes are possible under the right
conditions
 Following sequence is endothermic
heat solid  melt  heat liquid  boil  heat gas

 Following sequence is exothermic

cool gas  condense  cool liquid  freeze  cool solid

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 65

33
 Heating Curve
 Heat added at constant rate

 Horizontal lines
 Phase changes
 Melting point
 Boiling point

 Diagonal lines
 Heating of solid, liquid or gas

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 66

Cooling Curve
 Heat removed at constant rate
 Horizontal lines
 Phase changes
 Melting point
 Boiling point

 Diagonal lines
 Cooling of solid,
liquid or gas

 Supercooling
 Temperature of liquid dips below its freezing point

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 67

34
 Enthalpy Of Phase Changes
Endothermic Phase Changes
1. Must add heat
2. Energy entering system (+)
Sublimation: Hsub > 0
Vaporization: Hvap > 0
Melting or Fusion: Hfus > 0
Exothermic Phase Changes
1. Must give off heat
2. Energy leaving system (–)
Deposition: H < 0 = –Hsub
Condensation: H < 0 = –Hvap
Freezing: H < 0 = –Hfus
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 68

Phase Changes
 As T changes, matter undergoes phase
changes
 Phase Change
 Transformation from one phase to another
 Liquid-Vapor Equilibrium
 Molecules in liquid
 Not in rigid lattice
 In constant motion
 Denser than gas, so more collisions
 Some have enough kinetic energy to
escape, some don’t
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 69

35
1

Liquid-Vapor Equilibrium
 At any given T,
 Average kinetic
energy of molecules is
constant
 But particles have a
distribution of kinetic
energies
 Certain number of
molecules have
enough KE to escape
surface
 As T increases, average KE increases and number
molecules with enough KE to escape increases
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 70

Vapor Pressure
 Pressure molecules exert when they evaporate or
escape into gas (vapor) phase
 Pressure of gas when liquid or solid is at
equilibrium with its gas phase
 Increasing temperature increases vapor pressure
because vaporization is endothermic
 liquid + heat of vaporization ↔ gas
Equilibrium Vapor Pressure
 VP once dynamic equilibrium reached
 Usually referred to as simply vapor pressure

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 71

36
Slide 71

1 Nick, please check to ensure that the art placed is the correct image that you requested. thanks

Jennifer
THis is correct
Nick Kingsley; 14/02/2014
 Measuring Vapor Pressure

To measure pressures inside vessels, a manometer

is used.

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 72

Vapor Pressure Diagram

 Variation of vapor
pressure with T
 Ether
 Volatile
 High vapor pressure
near RT
 Propylene glycol
 Non-volatile
 Low vapor pressure
RT = 25 C near RT

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 73

37
 Effect of Volume on VP
A. Initial V
 Liquid – vapor
equilibrium exists
B. Increase V
 Pressure decreases
 Rate of
condensation
decreases
C. More liquid
evaporates
 New equilibrium
established

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 74

Do Solids Have Vapor Pressures?

 Yes
 At given temperature
 Some solid particles have enough KE to escape
into vapor phase
 When vapor particles collide with surface
 They can be captured
 Equilibrium vapor pressure of solid
 Pressure of vapor in equilibrium with solid

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 75

38
 Boiling Point (bp)

 T at which vapor pressure of liquid =

atmospheric pressure.
 Bp increases as strength of intermolecular
forces increase

Normal Boiling Point

 T at which vapor pressure of liquid = 1 atm

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 76

Effects of Hydrogen Bonding

 Boiling points of
hydrogen compounds
of elements of Groups
4A, 5A, 6A, and 7A.
 Boiling points of
molecules with
hydrogen bonding are
much higher than
expected

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 77

39
 Your Turn!
Which of the following will affect the boiling
point of a substance?
A. Polarizability
B. Intermolecular attractions
C. The external pressure on the material
D. All of these
E. None of these

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 78

Your Turn!
Which of the following substances will have
the highest boiling point?
A. LiCl
B. Cl2
C. HCl
D. CO2
E. Not enough information to tell

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 79

40
 Your Turn!
Which of the following substances will have
the highest boiling point?
A) F2
B) Cl2
C) I2
D) Br2
E) Not enough information to tell

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 80

Energies of Phase Changes

 Expressed per mole
 Molar heat of fusion (Hfus)
 Heat absorbed by one mole of solid when it melts to give
liquid at constantT and P
 Molar heat of vaporization (Hvap )
 Heat absorbed when one mole of liquid is changed to one
mole of vapor at constant T and P
 Molar heat of sublimation (Hsub )
 Heat absorbed by one mole of solid when it sublimes to
give one mole of vapor at constant T and P
 All of these quantities tend to increase with
increasing intermolecular forces

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 81

41
 Your Turn!
How much heat, in J, is required to convert 10.00
g of ice at -10.00 °C to water at
50.00 °C?
Specific heat (J/g °C ): ice, 2.108, water, 4.184
Enthalpy of fusion = 6.010 kJ/mol
A. 5483 J 2.108 J 10 K
10.00 g H 2O  210.8 J
B. 5638 J gK 1
C. 2304 J 10.00 g H 2O
1 mol 6010 J
 3335 J
18.02 g H 2 O 1 mole
D. 2364 J
4.184 J 50 K
E. 62,400 J 10.00 g H 2 O  2092 J
gK 1
210.8 J + 3335 J + 2092 J = 5638 J
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 82

Your Turn!
How much energy is required to vaporize 12.00 g
of NH3 ΔHvap is 21.70 kJ/mol?
A. 4435 kJ
B. 32.47 kJ
C. 30.79 kJ 12.00 g NH 3
1 mol 21.70 kJ
 15.29 kJ
17.03 g NH 3 1 mol
D. 9.42 kJ
E. 15.29 kJ

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 83

42
 Phase Diagrams
 Show the effects of both pressure and temperature
on phase changes
 Boundaries between phases indicate equilibrium
 Triple point:
 The temperature and pressure at which s, l, and g are all
at equilibrium
 Critical point:
 The temperature and pressure at which a gas can no
longer be condensed
 TC = temperature at critical point
 PC = pressure at critical point

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 84

Phase Diagram  X axis – temperature

 Y axis – pressure
 As P increases
(T constant), solid most
likely
 More compact
E
 As T increases
(P constant), gas most
likely
 Higher energy
F  Each point = T and P
 B = 0.01 °C, 4.58 torr
 E = 100 °C, 760 torr
 F = –10 °C, 2.15 torr
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 85

43
 Phase Diagram of Water
 AB = vapor pressure
curve for ice
 BD = vapor pressure
curve for liquid water
 BC = melting point line
 B = triple point: T and P
where all three phases
are in equilibrium
 D = critical point
 T and P above which
liquid does not exist

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 86

Case Study: An Ice Necklace

 A cube of ice may be suspended on a

string simply by pressing the string into the
ice cube. As the string is pressed onto the
surface, it becomes embedded into the ice.
 Why does this happen?

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 87

44
 Phase Diagram – CO2
 Now line between
solid and liquid
slants to right
 More typical
 Where is triple
point?
 Where is critical
point?

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 88

Supercritical Fluid
 Substance with temperature above its critical
temperature (TC) and density near its liquid
density
 Have unique properties that make them
excellent solvents
 Values of TC tend to increase with increased
intermolecular attractions between particles

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 89

45
 Le Chatelier’s Principle
 Equilibria are often disturbed or upset
 When dynamic equilibrium of system is upset
by a disturbance
 System responds in direction that tends to
counteract disturbance and, if possible, restore
equilibrium
 Position of equilibrium
 Used to refer to relative amounts of substance on
each side of double (equilibrium) arrows

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 90

Liquid Vapor Equilibrium

Liquid + Heat  Vapor
 Increasing T
 Increases amount of vapor
 Decreases amount of liquid
 Equilibrium has shifted
 Shifted to the right
 More vapor is produced at expense of liquid
 Temperature-pressure relationships can be
represented using a phase diagram

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 91

46
 Your Turn!
At 89 °C and 760 mmHg,
what physical state is
present?
A. Solid
B. Liquid
C. Gas
D. Supercritical fluid
E. Not enough
information is given

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 92

Measuring Hvap
 Clausius-Clapeyron equation
 Measure pressure at various temperatures, then
plot
 Hvap 1
ln P    C
T
 R 
 Two point form of Clausius-Clapeyron equation
 Measure pressure at two temperatures and solve
equation
P1 Hvap 1 1
ln    
P2 R  T 2 T1 

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 93

47
 Learning Check
The vapor pressure of diethyl ether is 401 mm Hg at
18.00 °C, and its molar heat of vaporization is 26
kJ/mol. Calculate its vapor pressure at 32.00 °C.

P1 Hvap 1 1  T = 273.15 + 18 = 291.15 K

ln     1
P2 R T 2 T1  T2 = 273.15 + 32 = 305.15 K
P1 2.6  104 J/mol  1 1 
ln   -   0.4928
P2 8.314 J/(K  mol)  305.15 K 291.15 K 
P1 P1
 e  0.4928  0.6109  P2
P2 0.6109
401 mm Hg
P2   6.6  102 mm Hg
0.6109
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 94

Your Turn!
Determine the enthalpy of vaporization, in
kJ/mol, for benzene, using the following vapor
pressure data.
T = 60.6 °C; P = 400. mmHg
T = 80.1 °C; P = 760. mmHg
A. 32.2 kJ/mol
B. 14.0 kJ/mol
C. –32.4 kJ/mol
D. 0.32 kJ/mol
E. –14.0 kJ/mol
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 95

48
 Your Turn! - Solution

Hvap  1 1 
P1
ln    
P2 R T2 T1 
400 mm Hg Hvap  1 1 
ln    
760 mm Hg J  353.1 K 333.6 K 
8.314
K mol
Hvap  32,235 J/mol or 32.2 kJ/mol

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 96

Types of Solids
 Crystalline Solids
 Solids with highly regular arrangements of
components
 Amorphous Solids
 Solids with considerable disorder in their
structures

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 97

49
 Crystal Structures Have Regular
Patterns
 Lattice
 Many repeats of unit cell
 Regular, highly
symmetrical system
 Three (3) dimensional
system of points
designating positions of
components
 Atoms
 Ions
 Molecules
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 98

Crystalline Solids
 Unit Cell
 Smallest
segment that
repeats regularly
 Smallest
repeating unit of
lattice
 Two-
dimensional unit
cells

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 99

50
 Three Types Of 3-D Unit Cells
 Simple cubic
 Has one host atom at each corner
 Edge length a = 2r
 Where r is radius of atom or ion
 Body-centered cubic (BCC)
 Has one atom at each corner and one in
center 4r
 Edge length a 
3
 Face-centered cubic (FCC)
 Has one atom centered in each face, and
one at each corner
 Edge length a  4r / 2
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 100

Close Packing of Spheres

1st layer 2nd layer

 Most efficient arrangement of spheres in two

dimensions
 Each sphere has 6 nearest neighbors
 Second layer with atoms in holes on the first
layer
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 101

51
Two Ways to Put on Third Layer
JY2

Cubic lattice: 3-dimensional arrays

1. Directly above 2. Above holes in first

spheres in first layer
layer  Remaining holes not
covered by second layer

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 102

3-D Simple Cubic Lattice

Unit Cell

Portion of lattice— Space filling

open view model
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 103

52
Slide 103

JY2 Nick, please check that the art now placed is correct, thanks.
Yee, Jennifer; 11/10/2013
 Other Cubic Lattices
Face Centered Body Centered
Cubic Cubic

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 104

Ionic Solids
Lattices of alternating charges
 Want cations next to anions
 Maximizes electrostatic attractive forces
 Minimizes electrostatic repulsions
 Based on one of three basic lattices:
 Simple cubic
 Face centered cubic
 Body centered cubic

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 105

53
 Common Ionic Solids
Rock salt or NaCl
 Face centered cubic lattice of Cl– ions (green)
 Na+ ions (blue) in all octahedral holes

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 106

Other Common Ionic Solids

Cesium Zinc Sulfide, Calcium

Chloride, CsCl ZnS Fluoride, CaF2

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 107

54
 Spaces In Ionic Solids Are Filled
With Counter Ions
 In NaCl
 Cl– ions form face-
centered cubic unit
cell
 Smaller Na+ ions fill
spaces between Cl–
ions
 Count atoms in unit
cell
 Have 6 of each or
1:1 Na+:Cl– ratio
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 108

Counting Atoms per Unit Cell

 Four types of sites in unit cell
 Central or body position – atom is completely contained
in one unit cell
 Face site – atom on face shared by two unit cells
 Edge site – atom on edge shared by four unit cells
 Corner site – atom on corner shared by eight unit cells

Site Counts as Shared by X unit cells

Body 1 1
Face 1/2 2
Edge 1/4 4
Corner 1/8 8
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 109

55
 Example: NaCl
Edge Corner
Face

Site # of Na+ # of Cl–

Body 1 0
Face 0 6  1 2   3
Edge 12  1 4   3 0
Center Corner 0 8  1 8   1
Total 4 4

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 110

Learning Check:
Determine the number of each type of ion in
the unit cell.

1:1 4:4 4:8

CsCl ZnS CaF2

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 111

56
 Some Factors Affecting
Crystalline Structure
 Size of atoms or ions involved
 Stoichiometry of salt
 Materials involved
 Some substances do not form crystalline solids

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 112

Amorphous Solids (Glass)

 Have little order, thus referred to as “super
cooled liquids”
 Edges are not clean, but ragged due to the lack
of order

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 113

57
 X-Ray Crystallography
 X rays are passed through
crystalline solid
 Some x rays are
absorbed, most re-emitted
in all directions
 Some emissions by atoms
are in phase, others out of
phase
 Emission is recorded on
film
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 114

X-ray Diffraction

Experimental Setup Diffraction Pattern

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 115

58
 Interpreting Diffraction Data
 As x rays hit atoms
in lattice they are
deflected
 Angles of
deflections related
to lattice spacing
 So we can
estimate atomic
and ionic radii
from distance data
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 116

Interpreting Diffraction Data

Bragg Equation
 nλ=2d sinθ
 n = integer (1, 2, …)
  = wavelength of
X rays
 d = interplane
spacing in crystal
  = angle of
incidence and angle
of reflectance of
X rays to various
crystal planes

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 117

59
 Example: Diffraction Data
The diffraction pattern of copper metal was
measured with X-ray radiation of wavelength
of 131.5 pm. The first order (n = 1) Bragg
diffraction peak was found at an angle θ of
50.5°. Calculate the spacing between the
diffracting planes in the copper metal.

n = 2d sin 
1(131.5 pm) = 2 × d × sin(50.5)
d = 283 pm
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 118

Example: Using Diffraction Data

X-ray diffraction measurements reveal that
copper crystallizes with a face-centered cubic
lattice in which the unit cell length is 362 pm.
What is the radius of a copper atom expressed
in picometers?

This is basically a geometry problem.

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 119

60
Ex. Using Diffraction Data (cont.)
Pythagorean theorem: a2 + b2 = c2
Where a = b = 362 pm sides and c = diagonal
2a2 = c2 and c  2a 2  2a
diagonal  2  (362 pm)  512 pm
diagonal = 4  rCu = 512 pm
rCu = 128 pm

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 120

Learning Check
Silver packs together in a faced center cubic
fashion. The interplanar distance, d,
corresponds to the length of a side of the unit
cell, and is 407 pm. What is the radius of a
silver atom?
a  2 2r
407 pm  2 2r
a
r = 53.6 pm

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 121

61
Ionic Crystals (e.g. NaCl, NaNO3)
 Have cations and anions at lattice sites
 Are relatively hard
 Have high melting points
 Are brittle
 Have strong attractive forces between ions
 Do not conduct electricity in their solid
states
 Conduct electricity well when molten

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 122

Your Turn!
Yitterbium crystallizes with a face centered
cubic lattice. The atomic radius of yitterbium is
175 pm. Determine the unit cell length.
A. 495 pm
B. 700 pm
C. 350 pm
D. 990 pm
E. 247 pm

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 123

62
 Your Turn! - Solution

diagonal of cube = 4r where r = atomic radius

diagonal of cube = 2 a where a = side of cube
4r 4 x 175 pm
a=   495 pm
2 2

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 124

Covalent Crystals
 Lattice positions occupied by atoms that are
covalently bonded to other atoms at
neighboring lattice sites
 Also called network solids
 Interlocking network of covalent bonds extending
all directions
 Covalent crystals tend to
 Be very hard
 Have very high melting points
 Have strong attractions between covalently
bonded atoms
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 125

63
 Ex. Covalent (Network) Solid
 Diamond (all C)
 Shown
 SiO2 silicon oxide
 Alternating Si and O
 Basis of glass and quartz
 Silicon carbide (SiC)

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 126

Metallic Crystals
 Simplest models
 Lattice positions of metallic
crystal occupied by positive
ions
 Cations surrounded by “cloud”
of electrons
 Formed by valence electrons
 Extends throughout entire solid

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 127

64
 Metallic Crystals
 Conduct heat and electricity
 By their movement, electrons transmit kinetic
energy rapidly through solid
 Have the luster characteristically associated
with metals
 When light shines on metal
 Loosely held electrons vibrate easily
 Re-emit light with essentially same frequency
and intensity

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 128

Learning Check:
Classify the following in terms of most likely type of solid.

Substance ionic molecular covalent metallic

X: Pulverizes when struck;
non-conductive of heat
and electricity 
Y: White crystalline solid
that conducts electrical
current when molten or

dissolved
Z: Shiny, conductive,
malleable with high
melting temperature


Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 129

65
 Your Turn!
Molecular crystals can contain all of the listed
attraction forces except:
A. Dipole-dipole attractions
B. Electrostatic forces
C. London forces
D. Hydrogen bonding

Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved. 130

66