Chapter 11

Intermolecular Attractions and

the Properties of Liquids and
Solids
Chemistry: The Molecular Nature of
Matter, 7E

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

Covalent Bond (strong) Intermolecular attraction (weak)

Cl H Cl H

2
Physical States of Matter
• Gases
Expand to fill their container

– Liquids
Retain volume, but not shape

– Solids
Retain volume and shape

3
 Factors affecting Physical state of
matter

Physical state of molecule depends on

2. Intermolecular Forces
1. Average kinetic energy • Energy of Inter-particle
of particles attraction
• KEave  T

• Physical properties of gases, liquids and

solids determined by
How tightly molecules are packed together
Strength of attractions between molecules
4
 Intermolecular Attractions
Gas  liquid or solid Liquid or solid  gas
Molecules must get closer Requires molecules to move
together farther apart
(Cool or compress) (Heat or reduce pressure)

Effect of Temperature
― As T decreases, kinetic energy of molecules
decreases
― Molecules don’t have enough energy to break
away from one another’s attraction until reaches
certain T

5
 Review: Electronegativity

Electronegativity: Measure of attractive

force that one atom in a covalent bond has
for electrons of the bond

6
 Bond Dipoles
• Two atoms with different
electronegativity values share electrons
unequally
• Electron density is uneven
– Higher charge concentration around more
electronegative atom
• Bond dipoles
– Indicated with delta (δ) notation
– Indicates partial charge has arisen

7
 Net Dipoles
Symmetrical molecules = non polar
– (Even if they have polar bonds)
– Are non-polar because bond dipoles cancel

Asymmetrical molecules = polar

– Are polar because bond dipoles do not cancel
– These molecules have permanent, net dipoles

So, molecular dipoles

– Cause molecules to interact
– Decreased distance between molecules increases
amount of interaction (↓ ↑) 8
 Intermolecular Forces
• When substance melts or boils
― Intermolecular forces are broken

Intermolecular forces are responsible

for:
• Non-ideal behavior of gases
• Existence of condensed states of
matter ( liquid and solid )
• Bulk properties of matter
― Boiling points and melting points
(Reflect strength of intermolecular forces)
9
 Three Important Types of
Intermolecular Forces
1. Dipole-dipole forces
― Hydrogen bonds
2. Ion-dipole forces
― Ion-induced dipole forces
3. London dispersion forces

10
 I- Dipole-Dipole Attractions
• Occur only between polar +  + 
molecules

Molecules need to be  +  +
close together

• Polar molecules tend to +  + 

align their partial charges
(Positive to negative )

11
 Dipole-Dipole Attractions

 Decrease as molecular distance increases

(↓↑)
 Increase as dipole moment increases (↑↑)
 Increase with increasing polarity (↑↑)
 About 1–4% as strong as a covalent bond

+  + 

12
 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

13
 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

14
 Hydrogen Bonds

― 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
― Positive end of one can get very close to
negative end of another

11-15
 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

16
 II- London Forces
• Operate between all molecules
― Neutral or net charged ― Nonpolar or polar

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
17
 Factors affecting formation of
instantaneous dipole
Effect enhanced with Effect decreased or
increased volume of electron almost diminished by
cloud size (↑↑) increased distance between
particles and compact
arrangement of atoms
(↓↑)

+  + 

11-18
 London Dispersion Forces
London Forces depend on:
1. Polarizability of 2. Points of attraction
electron cloud a) Number atoms
b) Molecular shape (compact
or elongated)

19
 1- Polarizability

 Ease with which the electron

cloud can be distorted
― Larger molecules often more
polarizable

Larger number of Larger Magnitude of

less tightly held electron resulting partial
electrons cloud charge is larger

20
 Table 11.1 Boiling Points of Halogens and Noble
Gases

Larger molecules have stronger London forces and

thus higher boiling points.

21
 2a. Number of Atoms in Molecule
• London forces depend on number atoms in
molecule
• Boiling point of hydrocarbons demonstrates this
trend
(increase no of atoms, increase no of bond, increase
temp to break, increase BP)
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

22
 Explanation

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
23
 2b- 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 Less compact molecules

Hydrogen atoms not as free to Hydrogen atoms have more
interact with hydrogen atoms chance to interact with hydrogen
on other molecules atoms on other molecules (more
(less London forces) London forces)

24
 Explanation
More compact – lower BP Less compact – higher BP
• Small area for interaction • Larger area for interaction

25
 III- Ion-Dipole Attractions
• Attractions between ion and charged end
of polar molecules
― quite strong as ions have full charges

(a) Negative ends of water dipoles surround cation

(b) Positive ends of water dipoles surround anion
26
 Ex. Ion-Dipole Attractions: AlCl3·6H2O
Attractions between ion (Al3+) and polar molecules (O)
→ 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
27
 Ion-Induced Dipole Attractions
• Special type of Ion-Dipole Attractions.
• Attraction between ion and non polar molecule
• Attractions between ion and dipole it induces on
neighboring molecules depends on:
1. Ion charge /size (charge density)
2. 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
F2+ and Oxygen

28
Summary of Intermolecular Attractions

1- 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
29
 Summary of Intermolecular Attractions

2- London dispersion
– Present in all substances
– Weakest intermolecular force
– Weak, but can add up to large net attractions
3- 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
30
What kind of intermolecular forces
are present
Compound Type of bond
Compounds with H- bonds Hydrogen –bonds
e.g., HF Dipole-dipole attractions
London forces
Polar Compounds Dipole-dipole attractions
e.g., PCl3, SO2 London forces
Non-Polar Compounds London forces
e.g., SF6
When ions are present
 Ion with polar molecule Ion-Dipole attractions
 Ion with non-polar Ion-induced dipole attractions
molecule
 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

32
 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

33
 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

34
 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

35
 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

36
 Using Intermolecular Forces
• Can predict physical properties (like BP, MP and
many others) by comparing strengths of
intermolecular attractions
• Ion-Dipole Strongest
• Dipole-Dipole
― Hydrogen Bonding
• London Forces Weakest

 Larger, longer, and therefore heavier molecules often have

stronger intermolecular forces
 Smaller, more compact, lighter molecules have generally
weaker intermolecular forces 37
 Physical properties affected by
Intermolecular forces
1. Compressibility
2. Diffusion
3. Retention of volume and shape
4. Surface tension
5. Wettability
6. Viscosity or internal friction
7. Solubility

11-38
 1- Compressibility
– It is a Physical Property that depend on
how tightly molecules pack
– Measure of ability of substance to be
forced into smaller volume

Determined by strength of intermolecular forces

Gases Solids and liquids

― Molecules far apart ― Molecules very close

― Weak intermolecular together
forces ― Stronger intermolecular
forces
Therefore, highly compressible Therefore, nearly incompressible
39
 2- Diffusion
• Movement that
spreads one gas
though another gas
to occupy space
uniformly
(Spontaneous
intermingling of molecules
) ― Occurs more rapidly in gases than in liquids
― Hardly at all in solids

40
 Diffusion

In Gases In Liquids In Solids

• Molecules travel • Molecules closer • Diffusion close to
long distances • Encounter more zero at room
between collisions collisions temperature
• Diffusion rapid • Takes a shorter time • Diffusion will
to move from place to increase at high
place temperature

41
3- Retention of volume and shape

Gases Liquids Solids

Expand to fill their Retain volume, Retain both
containers but not shape volume and shape
• Weakest • Attractions • Strongest
intermolecular intermediate intermolecular
attractions attractions
• Molecules • Molecules
farthest apart closest

42
Effect of Temperature on Intermolecular forces

• Intermolecular forces decrease with increasing

temperature (↓↑) why ??

― Increase temperature, increase kinetic energy

overcomes attractive forces

― If allowed to expand (open container), increasing

temperature increases distance between gas particles
and decreases attractive forces

43
 4- Surface Tension
Why does H2O bead up on a freshly waxed car instead
of forming a layer? Forms a sphere

• 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

44
 Surface Tension
• Causes a liquid to take the shape (a sphere)
that minimizes its surface area

Wax = nonpolar H2O = polar

Water beads in order to reduce potential energy

by reducing surface area

45
 Surface Tension
• Liquids containing molecules with strong
intermolecular forces have high surface
tension
Surface tension increases as intermolecular forces increase
Surface tension decreases as temperature increases

– Allows us to fill glass above rim

― Gives surface rounded appearance
― Surface acts as “skin” that lets water pile up
― Surface resists expansion and pushes back
46
 5- Wetting
• Ability of liquid to
spread across surface →
to form thin film

• Occurs only if:

intermolecular
attractive force
between surface and
liquid = strong as
within liquid itself Greater similarity in attractive
forces between liquid and
surface →greater wetting
effect
47
 Wetting
Example:
H2O wets clean glass surface as it forms
H–bonds to SiO2 surface
– Does not wet greasy glass, Why ??
Because grease is nonpolar and water is very polar
 Only London forces
 Forms beads instead
To increase wetting: add surfactants
– Surfactants ( detergents) lower surface tension
of H2O
Now water can spread out on greasy glass
48
 Surfactants (Detergents)
• Substances that have both polar and non-polar
characteristics
 Long chain hydrocarbons with polar tail
O

O Na +
O Polar end dissolves in
polar H2O
S
O O Na+
O
Nonpolar end dissolves in nonpolar grease

Thus increasing solubility of grease in water

49
Part 2
 Physical properties affected by
Intermolecular forces
1. Compressibility
2. Diffusion
3. Retention of volume and shape
4. Surface tension
5. Wettability
6. Viscosity or internal friction
7. Solubility

11-51
 6- Viscosity or Internal friction

• Measure of fluid’s resistance to flow or changing

form
• Related to intermolecular attractive forces
• Viscosity decreases when temperature increases
(↓↑)
52
 Viscosity
• 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

53
Effect of Intermolecular Forces on
Viscosity

Acetone Ethylene glycol

Polar molecule Polar molecule
―Dipole-dipole ―Hydrogen-bonding
―London forces ―Dipole-dipole
―London forces

Which is more viscous?

54
 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 )

55
 7- 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

56
 Surfactants
― Both polar and non-polar characteristics
― Used to increase solubility

O Na+

11-57
 Your Turn!
Which of the following are not expected to be
soluble in water?
A. HF
B. CH4
C. CH3OH
D. All are soluble

58
 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

59
 Phase Changes
• Physical States: Solid, liquid and gas
Changes of physical state: Deal with motion of
molecules
• As temperature changes  matter will
undergo phase changes

60
 I- Liquid  Gas
 Evaporation, vaporization
 As heat is added, H2O, forms steam or water vapor
 Endothermic (requires energy or source of heat)
II- Solid  Gas
 Sublimation
 Ice cubes in freezer, leave in long enough disappear
 Endothermic ( needs heat)
III- Gas  Liquid
 Condensation
 Dew is H2O vapor condensing onto cooler ground
 Exothermic
 Often limits lower night time temperature
61
 Rate of Evaporation (Liquid  Gas)
Depends on
1. Temperature (↑↑)
2. Surface area (↑↑)
3. Strength of intermolecular attractions (↑↓)
• KE of molecules that escape from liquid have >
minimum escape KE
― When they leave → Average KE of remaining molecules is
less and so T lower

62
 Effect of Temperature on Evaporation Rate
– Rate of evaporation of liquid 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

63
 Kinetic Energy Distribution in Two
Different Liquids

A B

• Smaller • Larger intermolecular

intermolecular forces forces
• Lower KE required • Higher KE required to
to escape liquid escape liquid
• A evaporates faster • B evaporates slower
64
Changes Of State Involve Equilibria

condensed separated
phase phase
When intermolecular To separate the particles
attractions are higher Intermolecular attractions
→ Fraction of molecules must be overcome,
in condensed state is * Separated particles are
higher simultaneously attracted to
one another

Separated

Condensed
65
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 +
giving up some kinetic
energy

66
 System At Equilibrium
Rate of evaporation =Rate of condensation

Occurs in closed systems

where molecules cannot
escape

67
 Equilibrium in Melting
Melting Point (mp): Solid → liquid (as heat added)

Dynamic equilibria
• Exists between solid and liquid states
• As long as no heat added or
removed from equilibrium mixture
• Rate of Melting =Rate of Freezing

68
 Equilibrium in Sublimation
Sublimation: Solid → gas (as heat added)

At equilibrium
• Molecules sublime from
solid at same rate as
molecules condense from
vapor
• Rate of sublimation =Rate
of deposition
69
 Liquid-Vapor Equilibrium
Molecules in liquid

– Not in rigid lattice but In constant motion At any given T

– Denser than gas, so more collisions

– Some have enough kinetic energy to escape, some don’t

As T increases
― Average KE increases
― Number molecules with enough KE to
escape increases
 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
Solid + heat of sublimation↔
gas

VP once dynamic equilibrium reached

71
Usually referred to as simply vapor pressure
 Measuring Vapor Pressure
To measure pressures inside vessels, a
manometer is used.

72
 Vapor Pressure Diagram
Variation of vapor pressure with T
• Ether
– Volatile
– High vapor pressure
near RT
– Low intermolecular F
Lower
Higher – Low boiling point
• Propylene glycol
– Non-volatile
– Low vapor pressure
RT = 25 C near RT
– High intermolecular F
RT: Room Temperature – High boiling point 73
Variation of vapor pressure with volume

A. Initial V B. Increase V C. More liquid

– Liquid – vapor – Pressure decreases evaporates
equilibrium – Rate of condensation – New equilibrium
exists decreases established

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
75
 Boiling Point (bp)
• T at which vapor pressure of liquid =
atmospheric pressure (1 atm)
• Bp increases as strength of intermolecular
forces increase

76
Effects of Hydrogen Bonding

Groups 4A, 5A, 6A, and 7A:

• B.P are much higher than
expected
• As hydrogen bond increase
Boiling points increase

Remember factors affecting

London forces

77
 Relationships
• High vapor pressure → low intermolecular forces
→ high rate of evaporation → low boiling point

• Low vapor pressure → high intermolecular

forces → low rate of evaporation → high boiling
point
 Heating Curve
Heat added at constant rate

4 Horizontal lines (2-4)

3
 No temperature change
2  Phase changes
1  Melting point
 Boiling point

Diagonal lines ( 1-3-5)

 Temperature increase (Heating of solid, liquid or gas)
79
 Cooling Curve
Heat removed at constant rate

1 Horizontal lines (2-4)

2
 No temperature
3
change
 Phase changes
 Freezing point
4 5

Supercooling
Diagonal lines (1-3-5) Temperature of liquid
 Temperature decrease dips below its freezing
 Cooling of solid, liquid or gas point
80
 Phase Changes

• As T changes, matter undergoes phase

changes

• Phase Change
• Transformation from one phase to another

81
 All phase changes
Phase Changes are possible under
the right conditions

Gas

Vaporization Condensation
Energy of System

Sublimation
Deposition
Liquid
Melting Freezing
or Fusion

Solid
Exothermic, releases heat gas  condense  cool liquid  freeze
 cool solid
Endothermic, absorbs heat solid  melt  heat liquid  boil  heat
82 ga
 Energies of Phase Changes
Expressed per mole All of these quantities tend to increase
with increasing intermolecular forces

• Molar heat of fusion (Hfus)

– Heat absorbed by one mole of solid when it melts to give
liquid at constant T 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
83
 Enthalpy Of Phase Changes
Endothermic Changes Exothermic Changes
1. Must add heat 1. Must give off heat
2. Energy entering system (+) 2. Energy leaving system (–)
Sublimation: Hsub > 0 Deposition: H < 0 = –Hsub
Vaporization: Hvap > 0 Condensation: H < 0 = –Hvap
Melting or Fusion: Hfus > 0 Freezing: H < 0 = –Hfus

Sublimation: Solid to gas Deposition: gas to solid

Vaporization: liquid to gas Condensation: gas to liquid
Melting: solid to liquid Freezing: liquid to solid

84
 Energy Change Calculation
• When temperature changes: q=m s ∆t
• When phase change (temperature is not
changing):
q= n Hsub q =m Hsub
q = n Hvap q =m Hvap
q = n Hfus q =m Hfus
We use according to unit of Hfus in the problem
(Kj/mole or Kj/gm ) ?
For Multi phase Change Problems
Heating Curve
Note: all qs have postive charge ( heat added)

q4=m∆Hvap
Temperature

q3=ms∆t
q2=m∆H fus
q1=ms∆t

Heated added
q total =q1+q2+q3
For Multi phase Change Problems
Cooling Curve
Note: all qs have negative charge ( heat removed)

q1=ms∆t
Temperature

q2=m∆H vap
q3=ms∆t

q4=m∆Hfus

Heated removed

q total =q1+q2+q3
 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

88
 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

89
 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

90
 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 qIce: mc (t2-t1)

A. 5483 J 2.108 J 10 K
10.00 g H 2 O = 210.8 J
B. 5638 J gK 1 Solid to liquid

C. 2304 J 1 mol 6010 J

10.00 g H 2 O = 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 q mc (t2-t1)
liquid:

gK 1
210.8 J + 3335 J + 2092 J = 5638 J
91
 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
1 mol 21.70 kJ
12.00 g NH 3 = 15.29 kJ
C. 30.79 kJ 17.03 g NH 3 1 mol
D. 9.42 kJ
E. 15.29 kJ

92
 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 93
Phase Diagram pressure and temperature on
phase changes

• X axis – temperature
Melting
• Y axis – pressure
i l in g • As P increases
B o E (T constant), solid most
likely [More compact]
• As T increases
(P constant), gas most
likely [Higher energy]
F
• Each point = T and P
B: Triple point – B = 0.01 °C, 4.58 torr
E: Boiling point – E = 100 °C, 760 torr
F: Freezing point – F = 0 °C, 760 torr
D: Critical point 94
 Phase Diagram of Water

• AB = vapor pressure curve for ice

Vaporization • BD = vapor pressure curve for
liquid water
• BC = melting point line
Condensation

Sublimation

Deposition

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 95
 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?
• The ice cube can absorb
the heat from the liquid
water in the string and still
remain at or below the
freezing point.
• The water in the string
freezes, sticking the string
to the ice 96
Phase Diagram – CO2
• Now line between
solid and liquid slants
to right

• More typical
• Where is triple
point?
• Where is critical
point?

97
 Supercritical Fluid
• Substance with:
– Temperature above its critical temperature (TC)
– 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

98
 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

99
 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
100
 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

101
 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 
102
 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  T1 = 273.15 + 18 = 291.15 K
ln    
P2 R T 2 T1  T2 = 273.15 + 32 = 305.15 K
P1 2.6 ´ 10 4 J/mol æ 1 1 ö
ln = çç - ÷=- 0.4928
÷
P2 8.314 J/(K ×mol) è305.15 K 291.15 K ø
P1 P1
 e  0.4928  0.6109  P2
P2 0.6109
401 mm Hg
P2 = 2
=6.6 ´ 10 mm Hg
0.6109 103
 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
104
 Your Turn! - Solution

P1 D Hvap æ 1 1 ö
ln = ç - ÷
P2 R ç T
è 2 T ÷
1ø

400 mm Hg DHvap æ 1 1 ö
ln = ç
ç - ÷
÷
760 mm Hg J è353.1 K 333.6 K ø
8.314
K mol
DHvap =32,235 J/mol or 32.2 kJ/mol

105