Chapter 11

Liquids, Solids, and Materials

Johannes D. van der Waals

1837-1923.* Fritz London 1900-1954.
Studied intermolecular forces Studied intermolecular
in VPT relationships in induced-dipole interactions.
liquids and gases. 1
 Gases, Liquids and Solids
High temperatures
Low temperatures

Kinetic Energy

2
Attractive Intermolecular Forces
 Ionic Forces
Ion-Ion Ion-Dipole

+ - +
- + -
+ - +
NaCl dissolved
in water
e.g. NaCl(s)
Ion-ion forces are very strong
and produce high boiling
points and melting points.
e.g. NaCl(aq)
Ions form strong intermolecular forces
with the polar molecule water.

From now on we will concentrate on covalent molecules 3

 Intermolecular Interactions
Non-Polar Molecules: 1. Dispersion (Disp) Forces

Polar Molecules: 1. Dispersion (Disp) Forces

2. Dipole-Dipole (DD) Forces

Molecules with 1. Dispersion (Disp) Forces

F-H, O-H, N-H 2. Dipole-Dipole (DD) Forces
Bonds: 3. Hydrogen Bonding (HB) Forces

4
 London Dispersion Forces
(aka van der Waals Forces)
The electrons on one atom are attracted to
the nucleus on a neighboring atom.

This creates an “instantaneous” (i.e. temporary)

dipole on the first atom.

The instantaneous dipole on the first atom

then induces an instantaneous dipole on the
second atom.

The two induced dipoles attract each other.

London Dispersion Forces are proportional to a molecule’s polarizability,

which is the ease with which the electron cloud can be deformed.
The polarizability, is approximately proportional to the number of electrons
in the molecule. 5
 Noble Gases
Element MW # e- Tbp
[amu] [K]
He 4.0 2 4
Ne 20.2 10 27
Ar 39.9 18 87
Kr 83.9 36 121
Xe 131.3 54 166

The noble gases are spherical, non-polar atoms.

As the molecule (atom) increases in size, the boiling

point increases (vapor pressure decreases).

6
 London Dispersion Forces
London Dispersion Force  # e-
London Dispersion Force  MW

Tbp is a good measure of the strength of intermolecular forces.

A higher Tbp indicates stronger intermolecular forces.

Compd. MW # e- Tbp Compd. MW # e- Tbp

Dispersion Forces
[amu] [ oC ] [amu] [ oC ]

Increasing
F2 38 18 -188 CH4 16 10 -161
Cl2 71 34 -34 C 2 H6 30 18 -88
Br2 160 70 +59 C 3 H8 44 26 -42
I2 254 106 +184 n-C4H10 58 34 0

7
Dispersion forces also depend upon the molecular shape.
Pentane: C5H12 - MW = 72 amu

n-pentane neopentane
Tbp = 36oC Tbp = 9oC
H2
H3C CH 3
H3C C CH 3
C
C C
H2 H2 H3C CH 3

Large Small
Contact Area Contact Area
(Surface Area) (Surface Area)

8
Dipole-Dipole Forces
In liquids of polar molecules, oppositely
charged ends of the molecules tend to
attract each other, causing partial alignment.

For molecules of roughly equal MW’s

(i.e. with similar Dispersion Forces),
the molecule with the higher dipole moment
will have a higher boiling point due to greater
Dipole-Dipole forces.

9
Consider this….
Propane Acetonitrile
CH3CH2CH3 CH3CN
H H
H C H
H
C C
H C C N
H H H
H H

0  = 3.9 Debye (D)

No Dipole Moment Large Dipole Moment

MW = 44 amu MW = 41 amu
Tbp = -42 oC Tbp = +82 oC

Why is the boiling point of acetonitrile so much

higher than the boiling point of propane???
Dipole-Dipole Forces 10
 Hydrogen Bonding
F-H Bonds:
H F H F
H-F
H bonding:
O
O-H Bonds:
between H
H H and a very
e.g. H2O , CH3OH electronegative
O

H H
atom
N-H Bonds:
N
H
e.g. NH3, CH3NH2 H
H

N
H
H
H
11
Compd. MW # e-  Tbp
[amu] [D] [oC ]
F-F 38 18 0 -188
H-Cl 36 18 1.1 -85
H-F 20 10 1.8 +20 Why so high??

+ - + -
H F H F

Hydrogen Bond

12
Hydrogen Bonding
Compd. MW # e- Tbp
[amu] [oC ]
H2S 34 18 -60
H2O 18 10 +100

PH3 34 18 -88
NH3 17 10 -33

13
 Highest Lowest
BP BP

CH3CH2OH HOCH2CH2OH CH3OCH3 CH3CH2CH3

MW=74 MW=62 MW=46 MW=44
Disp Disp Disp Disp
DD DD DD
HB

Ethyl alcohol - Ethylene glycol - Ether - Propane -

a liquid with a viscous liquid; a very a gas used
slightly lower keeps radiator fluid volatile for charcoal
bp than water from boiling over Liquid Grills
(78°) in your car (35°) (- 42°)
(198°)

14
 Vapor Pressure
H2O H O H O H2O
2 2
H2OH O
Vap. Press. 2
H2O H2O
(H2O) H2O
H2O H2O H2O

liquid water

15
 Vapor Pressure Rises with Temperature
Vapor Pressure

Temperature

At higher temperatures, more molecules have

sufficient energy to escape from the liquid.

16
 The Boiling Point
The boiling point of a liquid is the temperature at which
its vapor pressure is equal to the external pressure.

The “normal” boiling point is the temperature at which

the vapor pressure of the liquid is equal to 760 torr (1 atm.)

17
 The Critical Temperature
H 2O
T Vap. Press. Tc = Critical Temperature
[oC] [atm]
Highest temperature at which
25 0.03 substance can be liquified.
100 1
150 5 Pc = Critical Pressure
250 40 Pressure required to liquify
300 100 substance at Tc
374 218
375 
Tc = 374 oC
Pc = 218 atm
18
The Critical Temperature
Substance Tc Pc
Helium -268 oC 2.3 atm
Oxygen -119 50
Ethane 32 48
Propane 97 42
Freon (CCl2F2) 112 40
Water 374 218

19
 Phase Diagrams
1. Why can’t you ice skate in Red Lake, Minnesota
in February?

to
St. Paul

2. Why does carbon dioxide sublime, whereas

water first melts and then vaporizes?

20
 Phase Diagram of H2O

Solid Liquid Vapor

Pressure (atm)

0 100
Temperature (oC) 21
 Phase Diagram of H2O
C

Solid Liquid Vapor

Pressure (atm)

AB: Liquid-Vapor Equilibrium

AC: Solid-Liquid Equilibrium
4.6
A AD: Solid-Vapor Equilibrium
torr
A: Triple Point
Solid-Liquid-Vapor
B: Critical Point
D

0.01
Temperature (oC)
22
 Pressure dependence of Tbp

Liquid  Vapor
Pressure (atm)

Liquid Vapor
d(liq) >> d(vap)
2
V(liq) << V(vap)

Increased pressure shifts

1
equilibrium in direction
of lower volume.
100 120
Temperature (oC)

23
 Pressure dependence of Tmp
in H2O

120 Solid (ice)  Liquid

Pressure (atm)

d(ice) < d(liq)

Solid Liquid
V(ice) > V(liq)

Increased pressure shifts

1
equilibrium in direction
of lower volume.
-20 0 Application to
Temperature (oC) ice skating

24
 Phase Diagram of H2O
Melting point decreases with Pressure

Solid Liquid Vapor

Pressure (atm)

P1 Melting + Vaporization

4.6
torr

P2 Sublimation

0.01
Temperature (oC) 25
Phase Diagram of “Normal” Substances
Melting point increases with Pressure

Solid Liquid Vapor

Pressure (atm)

P1 Melting + Vaporization

5.1 CO2
P2 Sublimation

-56
Temperature (oC) 26
 Pressure dependence of Tmp
in “normal” substances
100 Solid  Liquid
Pressure (atm)

d(sol) > d(liq)

Solid Liquid
V(sol) < V(liq)

Increased pressure shifts

1
equilibrium in direction
of lower volume.
Tmpo Tmp
Temperature (oC)
27
 Phase Transitions
Gas

Vaporization Condensation
Enthalpy

Sublimation Deposition

Liquid

Melting Freezing

Solid
28
 Energy Changes of Phase Transitions
Melting (Fusion)
Hfus = Hliq - Hsol
= 6.01 kJ/mol (for H2O)
ENDOTHERMIC
Enthalpy

Freezing (Crystallization)
Hcrys = Hsol - Hliq
Liquid
= -6.01 kJ/mol (for H2O)
EXOTHERMIC
Melting Freezing

Solid
29
 Energy Changes of Phase Transitions
Gas

Vaporization
Hvap = Hgas - Hliq
Vaporization Condensation
= 40.7 kJ/mol (for H2O)
Enthalpy

ENDOTHERMIC

Condensation
Liquid Hcond = Hliq - Hgas
= -40.7 kJ/mol (for H2O)
EXOTHERMIC

30
 Heating Curves

5
Temperature (oC)

4
Tbp

1. Heating solid
3
2. Melting solid to liquid
Tmp 2 3. Heating liquid
4. Vaporizing liquid to gas
1
5. Heating gas

Heat Added (Joules)

31
Quantitative considerations of heating curves
For water:
Hfus= 6.0 kJ/mol Heat capacities:
Cs(sol)= 2.09 J/g-oC
Hvap= 40.7 kJ/mol
Cs(liq)= 4.18 J/g-oC
Tmp= 0 oC
Cs(gas)= 1.84 J/g-oC
Tbp = 100 oC

To heat 18 g of H2O from -40o to 140oC:

18 x 2.09 x 40 = 1.5 kJ (heating the ice)
1.0 x 6.01 = 6.0 kJ (melting the ice)
18 x 4.18 x 100 = 7.5 kJ (heating the water)
1.0 x 40.7 = 40.7 kJ (boiling the water)
18 x 1.84 x 40 = 1.3 kJ (heating the steam)
32
 Properties of Liquids
Viscosity
Viscosity is the resistance of a liquid to flowing.

High viscosity liquids (e.g. molasses, motor oil) flow slowly.

Low viscosity liquids (e.g. water, gasoline) flow quickly.

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 Properties of Liquids
Surface Tension
Surface tension is a measure of the strength
of intermolecular attractions which pull on
molecules at the surface of a liquid.

It is because of its high surface tension that

water tends to “bead” up on a waxy surface.

That’s because a sphere gives the minimum ratio

of surface area to volume.

The high surface tension of water also causes molecules on

the surface to pack very closely together. This is why some
insects can “walk on water”.
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 Structure of Solids
Crystalline Solid Amorphous Solid
Ordered arrangement of atoms Irregular (disordered)
(or molecules) in 3-dimensional arrangement of atoms
structure, called a lattice (or molecules)

e.g. Quartz (SiO2) e.g. Silica Glass (SiO2)

35
 The Crystalline Lattice

Lattice: Three Dimensional array of points representing

the centers of each atom in the crystal.

Lattice Point: Point corresponding to atom center

Unit Cell: Parallelopiped corresponding to minimum

unit which can be used to replicate crystal

36
 Bonding in Solids
There are four classifications of solids, depending
on the type of bonds that are present.

• Covalent-Network Solids

• Ionic Solids

• Metallic Solids

• Molecular Solids

37
 Covalent-Network Solids
Form of particles: Atoms connected in network of covalent bonds

Forces between particles: Covalent bonds

Properties: Very Hard

Very high melting point
Usually poor thermal and electrical conductivity

Examples: Diamond (C), Quartz (SiO2)

Diamond
Each carbon is connected to
4 others by a covalent bond

38
 Ionic Solids
Form of particles: Positive and negative ions

Forces between particles: Electrostatic attractions

Properties: Hard and Brittle

High melting point
Poor thermal and electrical conductivity

Examples: All typical salts. e.g. NaCl, Ca(NO3)3, MgBr2

+ - +
- + -
+ - +

39
 Metallic Solids
Form of particles: Atoms
Forces between particles: Metallic Bonds (due to
delocalized valence electrons)
Properties: Soft to very hard
Low to very high melting point
Excellent thermal and electrical conductivity
Malleable and Ductile
Examples: All metals. e.g. Cu, Fe, Sn, Au, Ag

Bonding due to delocalized valence

electrons (shown in blue)

Strength of bonding varies between

different metals, resulting in wide
range of physical properties
40
 Molecular Solids
Form of particles: Atoms or molecules

Forces between particles: Dispersion

Dipole-Dipole (if molecules are polar)
Hydrogen Bonds (if O-H, N-H, F-H)
Properties: Fairly soft
Moderately low melting point (usually <200 oC)
Poor thermal and electrical conductivity

Examples: Argon , CH4, CO2,

C6H12O6 (sucrose), H2O

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