Intermolecular Forces and
Liquids and Solids
Chapter 11
A phase is a homogeneous part of the system in contact with
other parts of the system but separated from them by a well-
defined boundary.
2 Phases
Solid phase - ice
Liquid phase - water
2
Phase Changes
Least
Order
Greatest 3
Order
Intermolecular Forces
• are in general much weaker than
intramolecular forces (aka: bonds).
intermolecular forces are generally
less than 15% as strong as ionic or
covalent bonds
Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
Generally, intermolecular forces are much weaker than
intramolecular forces.
5
What are Intermolecular Forces?
• Ion-dipole (strongest)
• hydrogen bonding
• dipole-dipole
• dispersion (weakest)
Intermolecular Forces
Ion-Dipole Forces
Attractive forces between an ion and a polar molecule
Ion-Dipole Interaction
7
Intermolecular Forces
Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction
between they hydrogen atom in a polar N-H, O-H, or F-H bond
and an electronegative O, N, or F atom.
A H…B or A H…A
A & B are N, O, or F
8
Why is the hydrogen bond considered a “special”
dipole-dipole interaction?
Decreasing molar mass
Decreasing boiling point
9
Example 11.2
Which of the following can form hydrogen bonds with water?
CH3OCH3
CH4
F2
HCOOH
Na+
Example 11.2
Strategy A species can form hydrogen bonds with water if it
contains one of the three electronegative elements (F, O, or N)
or it has a H atom bonded to one of these three elements.
Solution There are no electronegative elements (F, O, or N) in
either CH4 or Na+. Therefore, only CH3OCH3, F2, and HCOOH
can form hydrogen bonds with water.
Example 11.2
Check Note that HCOOH (formic acid) can form hydrogen
bonds with water in two different ways.
HCOOH forms hydrogen
bonds
with two H2O molecules.
Intermolecular Forces
Dipole-Dipole Forces
Attractive forces between polar molecules
Orientation of Polar Molecules in a Solid
13
Intermolecular Forces
Dispersion Forces
Attractive forces that arise as a result of temporary
dipoles induced in atoms or molecules
ion-induced dipole interaction
dipole-induced dipole interaction 14
Intermolecular Forces
Dispersion Forces Continued
Polarizability is the ease with which the electron distribution
in the atom or molecule can be distorted.
Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud
Dispersion forces usually
increase with molar mass.
15
What type(s) of intermolecular forces exist between each of the
following molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces.
S
SO2
SO2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules. 16
Example 11.1
What type(s) of intermolecular forces exist between the
following pairs?
(a) HBr and H2S
(b) Cl2 and CBr4
(c) I2 and
(d) NH3 and C6H6
Example 11.1
Strategy Classify the species into three categories: ionic,
polar (possessing a dipole moment), and nonpolar. Keep in
mind that dispersion forces exist between all species.
Solution
(a) Both HBr and H2S are polar molecules. Therefore, the
intermolecular forces present are dipole-dipole forces, as
well as dispersion forces.
(b) Both Cl2 and CBr4 are nonpolar, so there are only dispersion
forces between these molecules.
Example 11.1
(c) I2 is a homonuclear diatomic molecule and therefore
nonpolar, so the forces between it and the ion are
ion-induced dipole forces and dispersion forces.
(d) NH3 is polar, and C6H6 is nonpolar. The forces are dipole-
induced dipole forces and dispersion forces.
Properties of Liquids
Surface tension is the amount of energy required to stretch
or increase the surface of a liquid by a unit area.
Strong
intermolecular
forces
High
surface
tension
20
Properties of Liquids
Cohesion is the intermolecular attraction between like molecules
Adhesion is an attraction between unlike molecules
Adhesion
Cohesion
21
Properties of Liquids
Viscosity is a measure of a fluid’s resistance to flow.
Strong
intermolecular
forces
High
viscosity
22
A crystalline solid possesses rigid and long-range order. In a
crystalline solid, atoms, molecules or ions occupy specific
(predictable) positions.
An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.
A unit cell is the basic repeating structural unit of a crystalline
solid.
lattice
point At lattice points:
• Atoms
• Molecules
• Ions
Unit Cell Unit cells in 3 dimensions 23
Seven Basic Unit Cells
24
Three Types of Cubic Unit Cells
25
Arrangement of Identical Spheres in a Simple Cubic Cell
26
Arrangement of Identical Spheres in a Body-Centered
Cubic Cell
27
A Corner Atom, a Edge-Centered Atom and a
Face-Centered Atom
Shared by 4 Shared by 2
Shared by 8
unit cells unit cells
unit cells
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Number of Atoms Per Unit Cell
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
29
When silver crystallizes, it forms face-centered cubic cells. The
unit cell edge length is 409 pm. Calculate the density of silver.
m
d= V = a3 = (409 pm)3 = 6.83 x 10-23 cm3
V
4 atoms/unit cell in a face-centered cubic cell
107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10-22 g
mole Ag 6.022 x 1023 atoms
m 7.17 x 10-22 g 3
d= = = 10.5 g/cm
V 6.83 x 10-23 cm3
30
Example 11.3
Gold (Au) crystallizes in a cubic close-packed structure (the
face-centered cubic unit cell) and has a density of 19.3 g/cm3.
Calculate the atomic radius of gold in picometers.
Example 11.3
Strategy We want to calculate the radius of a gold atom.
For a face-centered cubic unit cell, the relationship between
radius (r) and edge length (a), according to Figure 11.22,
is .
Therefore, to determine r of a Au atom, we need to find a. The
volume of a cube is . Thus, if we can
determine the volume of the unit cell, we can calculate a. We
are given the density in the problem.
Example 11.3
The sequence of steps is summarized as follows:
Solution
Step 1: We know the density, so in order to determine the
volume, we find the mass of the unit cell. Each unit cell
has eight corners and six faces. The total number of
atoms within such a cell, according to Figure 11.19, is
Example 11.3
The mass of a unit cell in grams is
From the definition of density (d = m/V), we calculate the
volume of the unit cell as follows:
Example 11.3
Step 2: Because volume is length cubed, we take the cubic
root of the volume of the unit cell to obtain the edge
length (a) of the cell
Step 3: From Figure 11.22 we see that the radius of an Au
sphere (r) is related to the edge length by
Example 11.3
Therefore,
= 144 pm
Reflection of X rays from Two Layers of Atoms.
Extra distance = BC + CD = 2d sinq = nl (Bragg Equation)
37
X rays of wavelength 0.154 nm are diffracted from a crystal at an
angle of 14.17o. Assuming that n = 1, what is the distance (in pm)
between layers in the crystal?
nl = 2d sin q n=1 q = 14.17o l = 0.154 nm = 154 pm
nl 1 x 154 pm
d= = = 314.0 pm
2sinq 2 x sin14.17
38
Types of Crystals
Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity
CsCl ZnS CaF2
39
Types of Crystals
Covalent Crystals
• Lattice points occupied by atoms
• Held together by covalent bonds
• Hard, high melting point
• Poor conductor of heat and electricity
carbon
atoms
40
diamond graphite
Types of Crystals
Molecular Crystals
• Lattice points occupied by molecules
• Held together by intermolecular forces
• Soft, low melting point
• Poor conductor of heat and electricity
water benzene
41
Types of Crystals
Metallic Crystals
• Lattice points occupied by metal atoms
• Held together by metallic bonds
• Soft to hard, low to high melting point
• Good conductors of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-
mobile “sea”
of e-
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Types of Crystals
43
An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.
A glass is an optically transparent fusion product of inorganic
materials that has cooled to a rigid state without crystallizing
Crystalline Non-crystalline
44
quartz (SiO2) quartz glass
The equilibrium vapor pressure is the vapor pressure
measured when a dynamic equilibrium exists between
condensation and evaporation
H2O (l) H2O (g)
Dynamic Equilibrium
Rate of Rate of
condensation
= evaporation
45
Measurement of Vapor Pressure
Before At
Evaporation Equilibrium
46
Molar heat of vaporization (DHvap) is the energy required to
vaporize 1 mole of a liquid at its boiling point.
Clausius-Clapeyron Equation
DHvap P = (equilibrium) vapor pressure
ln P = - +C
RT T = temperature (K)
R = gas constant (8.314 J/K•mol)
Vapor Pressure Versus Temperature
47
Alternate Forms of the Clausius-Clapeyron Equation
At two temperatures
or
48
Example 11.7
Diethyl ether [(C2H5)2O] is a volatile, highly flammable organic
liquid that is used mainly as a solvent.
The vapor pressure of diethyl ether is 401 mmHg at 18°C.
Calculate its vapor pressure at 32°C.
Example 11.7
Strategy We are given the vapor pressure of diethyl ether at
one temperature and asked to find the pressure at another
temperature. Therefore, we need Equation (11.5).
Solution Table 11.6 tells us that DHvap = 26.0 kJ/mol. The data
are
From Equation (11.5) we have
Example 11.7
Taking the antilog of both sides (see Appendix 4), we obtain
Hence
P2 = 656 mmHg
Check We expect the vapor pressure to be greater at the
higher temperature. Therefore, the answer is reasonable.
Solid-Liquid Equilibrium
H2O (s) H2O (l)
The melting point of a solid
or the freezing point of a
liquid is the temperature at
which the solid and liquid
phases coexist in equilibrium
52
The boiling point is the temperature at which the
(equilibrium) vapor pressure of a liquid is equal to the
external pressure.
The normal boiling point is the temperature at which a liquid
boils when the external pressure is 1 atm.
53
The critical temperature (Tc) is the temperature above which
the gas cannot be made to liquefy, no matter how great the
applied pressure.
The critical pressure
(Pc) is the minimum
pressure that must be
applied to bring about
liquefaction at the
critical temperature.
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Heating Curve
55
Solid-Gas Equilibrium
H2O (s) H2O (g)
Molar heat of sublimation
(DHsub) is the energy required
to sublime 1 mole of a solid.
DHsub = DHfus + DHvap
( Hess’s Law)
56
Example 11.8
Calculate the amount of energy (in kilojoules) needed to heat
346 g of liquid water from 0°C to 182°C.
Assume that the specific heat of water is 4.184 J/g · °C
over the entire liquid range and that the specific heat of steam
is 1.99 J/g · °C.
Example 11.8
Strategy The heat change (q) at each stage is given by
q = msDt (see p. 247), where m is the mass of water, s is the
specific heat, and Dt is the temperature change.
If there is a phase change, such as vaporization, then q is given
by nDHvap, where n is the number of moles of water.
Solution The calculation can be broken down in three steps.
Step 1: Heating water from 0°C to 100°C
Using Equation (6.12) we write
Example 11.8
Step 2: Evaporating 346 g of water at 100°C (a phase change)
In Table 11.6 we see DHvap = 40.79 kJ/mol for water, so
Step 3: Heating steam from 100°C to 182°C
Example 11.8
The overall energy required is given by
Check All the qs have a positive sign, which is consistent with
the fact that heat is absorbed to raise the temperature from 0°C
to 182°C. Also, as expected, much more heat is absorbed
during the phase transition.
A phase diagram summarizes the conditions at which a
substance exists as a solid, liquid, or gas.
Phase Diagram of Water
61
Phase Diagram of Carbon At 1 atm
Dioxide CO2 (s) CO2 (g)
62
Effect of Increase in Pressure on the Melting Point
of Ice and the Boiling Point of Water
63
Chemistry In Action: Liquid Crystals
64
