Chapter 12

Intermolecular Forces:

Liquids, Solids, and Phase Changes

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 Intermolecular Forces:
Liquids, Solids, and Phase Changes

12.1 An Overview of Physical States and Phase Changes

12.2 Quantitative Aspects of Phase Changes

12.3 Types of Intermolecular Forces

12.4 Properties of the Liquid State

12.5 The Uniqueness of Water

12.6 The Solid State: Structure, Properties, and Bonding

State the type of bonding- ionic, covalent
or metallic- you would expect in each

• 1. CsF 2. 1-pentanol
State the type of bonding- ionic, covalent
or metallic- you would expect in each

3. Silver (Ag) 4. Ethane ( C2H6)

ATTRACTIVE FORCES

electrostatic in nature

Intramolecular forces bonding forces

These forces exist within each molecule and hold atoms

together within a molecule
They influence the chemical properties of the substance.

Intermolecular forces nonbonding forces

These forces exist between molecules.

They influence the physical properties of the substance.
 Intermolecular force vs
Intramolecular force
Figure 1 Figure 2
Types of Intramolecular Forces
 Figure 12.17

Summary diagram for analyzing the intermolecular forces in a sample.

INTERACTING PARTICLES
(atoms, molecules, ions)
ions present ions not present

ions only polar molecules only nonpolar

IONIC BONDING DIPOLE-DIPOLE molecules only
(Section 9.2) FORCES DISPERSION
FORCES only
ion + polar molecule H bonded to
N, O, or F
ION-DIPOLE FORCES polar + nonpolar
molecules
HYDROGEN DIPOLE-
BONDING INDUCED DIPOLE
FORCES

DISPERSION FORCES ALSO PRESENT

 Dipole-dipole forces

These forces occur when the partially positively

charged part of a molecule interacts with the
partially negatively charged part of the
neighboring molecule. This type of force is
strongest in polar covalent compounds.
 London Dispersion Force

Is a temporary attractive force that results when

the electrons in two adjacent atoms occupy
position positions that make atoms form
temporary dipole moments induced in
ordinarily nonpolar molecules.
Weakest among intermolcular forces.
 THE HYDROGEN BOND

a dipole-dipole intermolecular force

A hydrogen bond may occur when an H atom in a molecule,

bound to small highly electronegative atom with lone pairs of
electrons, is attracted to the lone pairs in another molecule.

The elements which are so electronegative are N, O, and F.

hydrogen bond hydrogen bond
donor acceptor
.. .. ..
..
F H O O H N

..
..
..

..
hydrogen bond hydrogen bond
acceptor .. donor
N H F
..
..

..
hydrogen bond hydrogen bond
acceptor donor
 Polar vs non-polar compounds
A molecule will be non-polar if:
• all of the terminal atoms are the same
• all of the atoms are symmetrically arranged around the
central atom
• the terminal atoms have the same charges

A molecule will be polar if:

• one or more terminal atoms differ from each other
• the terminal atoms are not symmetrically arranged
• the molecule have one slightly positive and one slightly
negative
SAMPLE PROBLEM 12.3 Predicting the Type and Relative Strength of
Intermolecular Forces
PROBLEM: For each pair of substances, identify the dominant
intermolecular forces in each substance, and select the
substance with the higher boiling point.
(a) MgCl2 or PCl3
(b) CH3NH2 or CH3F

(c) CH3OH or CH3CH2OH

(d) Hexane (CH3CH2CH2CH2CH2CH3)
or 2,2-dimethylbutane

PLAN: Use the formula, structure and Table 2.2 (button).

• Bonding forces are stronger than nonbonding(intermolecular) forces.

• Hydrogen bonding is a strong type of dipole-dipole force.
• Dispersion forces are decisive when the difference is molar mass or
molecular shape.
 SAMPLE PROBLEM 12.3 Predicting the Type and Relative Strength of
Intermolecular Forces
continued

SOLUTION:
(a) Mg2+ and Cl- are held together by ionic bonds while PCl3 is covalently
bonded and the molecules are held together by dipole-dipole interactions. Ionic
bonds are stronger than dipole interactions and so MgCl2 has the higher boiling
point.
(b) CH3NH2 and CH3F are both covalent compounds and have bonds which are
polar. The dipole in CH3NH2 can H bond while that in CH3F cannot. Therefore
CH3NH2 has the stronger interactions and the higher boiling point.
(c) Both CH3OH and CH3CH2OH can H bond but CH3CH2OH has more CH for
more dispersion force interaction. Therefore CH3CH2OH has the higher boiling
point.
(d) Hexane and 2,2-dimethylbutane are both nonpolar with only dispersion
forces to hold the molecules together. Hexane has the larger surface area,
thereby the greater dispersion forces and the higher boiling point.
 Identify what type of
intermolecular forces in each
1. SO2
substance
2. HBr
3. CH3CH3
4. CF4
5. CH3CH2CH2CH2CH2CH2OH
Table 12.1

A Macroscopic Comparison of Gases, Liquids, and Solids

State Shape and Volume Compressibility Ability to Flow

Gas Conforms to shape and volume high high

of container

Liquid Conforms to shape of container; very low moderate

volume limited by surface

Solid Maintains its own shape and almost none almost none
volume
Phase Changes
exothermic
sublimination

melting vaporizing

solid liquid gas

freezing condensing

endothermic
 Boiling point
• Temperature of the substance when its vapor
pressure equals the pressure exerted in on the
surface of the liquid

• Normal boiling point is the temperature at

which liquid boils in an open container at
normal atmospheric pressure
 Heat of Vaporization
• energy absorbed when 1 kg of a liquid vaporizes at its normal
boiling point

• Joule (J) -SI unit of energy required to lift a 1-kg mass 1 meter
against the force of gravity

• 2.26 x 106 J is the energy needed to move molecules in 1 kg of

water far enough apart that they form water vapor

• Heat of vaporization of water = 2.26 x 106 J/kg

 Heat of Fusion
• The energy released as 1 kg of a substance
solidifies at its freezing point

• Heat of fusion of water = 3.34 x 105 J/kg

Figure 12.1

Heats of vaporization and fusion for several common substances.

Figure 12.2 Phase changes and their enthalpy changes.
 Sample Problem

12.15 p356) From the data below, calculate

the total heat (in J) needed to convert 22.0 g
of ice at
-60C to liquid water at 0.50C: mp at 1 atm, 00C
�Hfus = 6.02 kJ/ mol; Cliq = 4.21 J/g 0C
Csolid = 2.09 J/g 0C
Given:
mass of ice = 22g Cliq = 4.21
J/g 0C
temp of ice = -60C Csolid = 2.09
J/g 0C
melting point = 00C
temp of solid = 0.50C
�Hfus = 6.02 kJ/ mol (1 mol/18g) (1000J/1kJ �
Hfus=334.44 J/g

Req’d: Qt
Sol’n:
Heat involve to change the temp from -60C to
00 C
q1 = mCsolidΔT
q1 = 22 g ( 2.09 J/g0C) (0-(-6))0C = 275.88J
Heat involve to change the phase from solid to liquid
q2 = m �Hfus= 22 g ( 334.44 J/g) = 7357.68 J
Heat involve to increase the temp from 00C to 0.50C
q3 = mCliqΔT = 22 g (4.21 J/g 0C)(0.5-0)0C = 46.31J
qt = q1 + q2 + q3
qt= 275.88J + 7357.68 J + 46.31J = 7679.87 J
Figure 12.3
A cooling curve for the conversion of gaseous water to ice.
 Quantitative Aspects of Phase Changes

Within a phase, a change in heat is accompanied by a change in

temperature ( sensible heat) which is associated with a change in
average Ek as the most probable speed of the molecules changes.

q = (amount)(molar heat capacity)(ΔT)

During a phase change, a change in heat ( latent heat) occurs at a

constant temperature, which is associated with a change in Ep, as
the average distance between molecules changes.

q = (amount)(enthalpy of phase change)

Clausius-Clapeyron Equation

- allows us to estimate the vapor

pressure at another temperature
if the vapor pressure is known at
some temperature and the
enthalpy of vaporization is known
Clausius-Clapeyron Equation
P2  H vap 1 1
ln  (  )
P1 R T2 T1

• Where:
• P1 - vapor pressure at T1
• P2 = vapor pressure at T2
• ΔHvap = enthalpy of vaporization of a
given gas
• T1 - initial temperature
• T2 - final temperature of a gas
SAMPLE PROBLEM 12.1 Using the Clausius-Clapeyron Equation

PROBLEM: The vapor pressure of ethanol is 115 torr at 34.90C. If ΔHvap of

ethanol is 40.5 kJ/mol, calculate the temperature (in 0C) when
the vapor pressure is 760 torr.

PLAN: We are given 4 of the 5 variables in the Clausius-Clapeyron

equation. Substitute and solve for T2.

SOLUTION:
34.90C = 308.0K

760 torr -40.5 x103 J/mol 1 1

ln = -
115 torr 8.314 J/mol*K T2 308K

T2 = 350K = 770C
Figure 12.8 Phase diagrams for CO2 and H2O.

CO2 H2O
 Properties of Fluids

Surface Tension- the

measure of the elastic
force in the surface of
a liquid. It is the
amount of energy
required to stretch or
increase the surface of
a liquid by a unit area.
Figure 12.18 The molecular basis of surface tension.

hydrogen bonding
occurs across the surface
and below the surface
the net vector
for attractive
forces is downward

hydrogen bonding
occurs in three
dimensions
Table 12.3 Surface Tension and Forces Between Particles

Surface Tension
Substance Formula (J/m2) at 200C Major Force(s)

diethyl ether CH3CH2OCH2CH3 1.7x10-2 dipole-dipole; dispersion

ethanol CH3CH2OH 2.3x10-2 H bonding

butanol CH3CH2CH2CH2OH 2.5x10-2 H bonding; dispersion

water H2O 7.3x10-2 H bonding

mercury Hg 48x10-2 metallic bonding

 Capillary action

The tendency of a adhesive forces

liquid to rise in a
narrow tubes or to be
drawn into small
openings.
adhesion-
cohesion- molecular stronger attraction between
attraction by which cohesive forces unlike molecules
the particles of a
body are united
throughout the mass
Table 12.4 Viscosity of Water at Several Temperatures

viscosity - resistance to flow

Viscosity
Temperature(0C) (N*s/m2)*

20 1.00x10-3

40 0.65x10-3

60 0.47x10-3

80 0.35x10-3

*The units of viscosity are newton-seconds per square meter.

Vapor pressure- the equilibrium pressure of a vapor
above its liquid; that is, the pressure exerted by the
vapor above the surface of the liquid in a closed
container.
Boiling point- the temperature at which a liquid
boils. The boiling point of a liquid when the
external pressure is 1 atm is called the normal
boiling point
Figure 12.20 The H-bonding ability of the water molecule.

hydrogen bond donor

hydrogen bond acceptor

The Unique Nature of Water

• great solvent properties due to polarity and

hydrogen bonding ability

• exceptional high specific heat capacity

• high surface tension and capillarity

• density differences of liquid and solid

states
Figure 12.21 The hexagonal structure of ice.
 Two types of Solids

Crystalline solids- are solid material whose

components arranged in fixed geometric patterns
or lattices. ex. ice, NaCl, copper sulfate, diamond

Amorphous solids- are solids that form no

regular patter such as plastic, rubber, glass and
coal
Figure 12.33 Crystalline and amorphous silicon dioxide.
Figure 12.22 The striking beauty of crystalline solids.
• Crystal lattice- the regular repeating structure
of a crystalline solid

• Unit cell- the smallest sub unit of a crystal

lattice that can be repeated over and over to
make the entire crystal
 Figure 12.23 The crystal lattice and the unit cell.
lattice point unit
cell

unit
cell

portion of a 3-D lattice portion of a 2-D lattice

Figure 12.24 (1 of 3) The three cubic unit cells.

Simple Cubic

1/8 atom at
8 corners

Atoms/unit cell = 1/8 * 8 = 1

coordination number = 6
Figure 12.24 (2 of 3) The three cubic unit cells.

Body-centered
Cubic

1/8 atom at
8 corners

1 atom at
center

Atoms/unit cell = (1/8*8) + 1 = 2

coordination number = 8
Figure 12.24 (3 of 3) The three cubic unit cells.

Face-centered
Cubic

1/8 atom at
8 corners

1/2 atom at
6 faces

Atoms/unit cell = (1/8*8)+(1/2*6) = 4

coordination number = 12
Figure 12.26 Packing of spheres.

simple cubic
(52% packing efficiency)

body-centered cubic
(68% packing efficiency)
 Table 12.5 Characteristics of the Major Types of Crystalline Solids
Interparticle Physical
Particles Forces Behavior Examples (mp,0C)

Atomic Atoms Dispersion Soft, very low mp, poor Group 8A(18)
thermal & electrical [Ne-249 to Rn-71]
conductors
Molecular Molecules Dispersion, Fairly soft, low to moderate Nonpolar - O2[-219],
dipole-dipole, mp, poor thermal & C4H10[-138], Cl2
H bonds electrical conductors [-101], C6H14[-95]
Polar - SO2[-73],
CHCl3[-64], HNO3[-
42], H2O[0.0]
Ionic Positive & Ion-ion Hard & brittle, high mp, NaCl [801]
negative ions attraction good thermal & electrical CaF2 [1423]
conductors when molten MgO [2852]
Metallic Atoms Metallic bond Soft to hard, low to very Na [97.8]
high mp, excellent thermal Zn [420]
and electrical conductors,
Fe [1535]
malleable and ductile
Network Atoms Covalent bond Very hard, very high mp,
usually poor thermal and
electrical conductors
Figure 12.31 The sodium chloride structure.

expanded view space-filling

Figure 12.32 Crystal structures of metals.

cubic closest packing hexagonal closest packing