Chapter 12

Intermolecular
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 12.1 Intermolecular Forces
• Intermolecular forces are the attractive forces
holding particles together in the condensed
(liquid and solid) phases of matter
• Result from coulombic attractions
– Dependent on the magnitude of the charge
– Dependent on distance between charges
• Weaker than forces of ionic bonding
• Involve partial charges

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The Three Phases of Matter

condensed phases

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 Types of Intermolecular Forces
• van der Waals forces –between atoms
and molecules of pure substances
– Dipole-dipole interactions – attractive forces
between polar molecules
– Hydrogen bonding – attractive force in polar
molecules containing a H atom bonded to a
small, highly electronegative element (N, O
and F)
– (London) Dispersion forces – attractive
forces arising from instantaneous dipoles and
induced dipoles

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Arrangement of Polar Molecules in a Liquid
and a Solid.

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• Intermolecular forces determine certain
physical properties.

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Hydrogen Bonds Between HF Molecules

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Effect of Molar Mass and Hydrogen Bonding
on Boiling Points

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 Instantaneous and Induced Dipoles

Magnitude depends on the ability to be polarized which

is greater for larger molecules.
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Polarization and Molar Mass

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What kind(s) of intermolecular forces exist in

CH2ClCH2COOH(l)

Cl H O
H C C C O H
H H
dispersion forces
dipole-dipole interactions
hydrogen bonding
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•Ion-dipole Interactions
– Occur in mixtures of ionic and polar
species
– Coulombic attraction between ions and
polar molecules
– Dependent upon
• Size and charge of ion
• Dipole moment of the molecule
• Size of the molecule
– Can also be repulsive
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 12.2 Properties of Liquids
• Surface Tension – a quantitative measure of the
elastic force at the surface of a liquid

• Manifestations
– Formation of a mensicus
– Capillary action which
results from a combination of
• Cohesion (attractions between
like molecules, cohesive forces)
• Adhesion (attractions between
unlike molecules, adhesive forces)
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Effect of Surface Tension

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Intermolecular Forces: Surface
versus Interior of a Liquid

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 Cohesion and Adhesion

Water Mercury
Adhesion > Cohesion Cohesion > Adhesion
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• Viscosity – a measure of a fluid’s
resistance to flow
– Units: N.s/m2
– The higher the viscosity the greater the
resistance to flow
– Varies inversely with temperature
– Stronger intermolecular forces produce
higher viscosities

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 Glycerol – high viscocity
due to
• Three hydrogen bonding
sites
• Molecular shape
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• Vapor Pressure of a Liquid
– Depends on the magnitude of intermolecular
forces
– Temperature dependent

T1<T2
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• Equilibrium Vapor Pressure – a dynamic
state

− Evaporation (vaporization) – liquid

molecules escape into the gas phase
− Condensation – gas molecules return to
the liquid phase
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Comparison of Rates of Evaporation and
Condensation at Constant Temperature

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Effect of Temperature and Intermolecular Forces
on Vapor Pressure

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• Clausius-Clapeyron Equation – linear relation
between temperature and vapor pressure

where R = 8.314 J/K . mol

− At two temperatures, T1 and T2:

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An unknown compound exhibits a vapor pressure of
255 mmHg at 25.5oC and 434 mmHg at 48.8oC.
What is DHvap of this substance?

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 T1  25.5 C  273.15  298.65 K
o

T2  48.8o C  273.15  321.95 K

P1 DH vap  1 1
ln    
P2 R  T2 T1 

255 mmHg DHvap  1 1 

ln    
434 mmHg 8.314J/K  mol  321.95 K 298.65 K 

DH vap
 0.53178 
8.314J/K  mol
3.1061x103  3.3484x103 
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 0.53178 
DH vap
8.314J/K  mol
 2.423x10 4
K 1 
(0.53178)(8.314J/K  mol)
 DH vap
 2.423x10 4 K 1

4
1.82 x 10 J/mol  DH vap
18.2 kJ/mol  DH vap
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 12.3 Crystal Structure
• Crystalline solid – possesses rigid and
long-range order
• Lattice structure – arrangement of
particles in a crystalline solid
– Depends on nature of particles
– Depends on size of particles
• Stability depends on type of force between
particles (ionic or covalent bonds and/or
intermolecular forces)
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unit cell – basic repeating structural unit of
a crystalline solid
lattice point – each atom ion or molecule in
a unit cell

single unit cell 3-D array of unit cells

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Seven Types of Unit Cells

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Coordination number – number of atoms
(particles) surrounding an atom in a crystal
lattice
• Indicates how tightly atoms pack
• Larger coordination numbers indicate
tighter packing

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• Types of cubic unit cells
– simple or primitive (scc)
– body-centered (bcc)
– face-centered (fcc)

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Alternate Perspective of bcc Arrangement

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 Sharing of Atoms by Adjacent Unit Cells

corner atom edge atom face atom

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•Allocation of atoms among unit cells
− corner atoms – 1/8 atom within unit cell
− face atoms – 1/2 atom within unit cell
− body atoms – 1 atom within unit cell

• Number of atoms per unit cell

– scc: 1 atom
– bcc: 2 atoms
– fcc: 4 atoms

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• Closest Packing – most efficient way to
arrange atoms in a crystal
– hexagonal closest packed (ABA)
– cubic closest packed (ABC)

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 Closest Packing and Cubic Unit Cells

hexagonal

cubic

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fcc 36
Geometric Relationships

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When silver crystallizes, it forms face-
centered cubic cells. The unit cell edge
o
length is 4.087A . Calculate the density of
silver.

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Mass of unit cell

4 atoms 107.9 amu 1g

m    7.167 1022 g
unit cell atom 6.022 1023 amu

Volume of unit cell

 1m 100 cm
a  4.087 A  
  4.087 10 8 cm
10 1m
110 A
3
 8
V  a  4.087 10 cm  6.827 10 3  23
cm3

Density of unit cell

m 7.167 1022 g/unit cell 3
d   10.5 g/cm
V 6.827 10 23 cm3 /unit cell
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• X-ray diffraction utilizes the scattering of
X-rays and the resulting scattering patterns
to deduce arrangement of particles

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− Bragg equation

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 12.4 Types of Crystals
• Ionic Crystals
– Composed of anions and cations
– Held together by coulombic forces
– Anions generally are bigger than cations
– Size and relative number of each ion
determines the crystal structure

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Unit cell of NaCl as Defined by Cl− or Na+

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Examples of Ionic Crystal Lattices

CsCl ZnS CaF2

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How many of each ion are contained within
a unit cell of CaF2?

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 Ca2+

F−

Ca2+
8 corner ions x 1/8= 1 ion
6 face ions x ½ = 3 ions
4 ions of Ca2+
F−
8 body ions x 1 = 8 ions of F−

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• Covalent crystals
– Held together by covalent bonds

diamond graphite
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• Molecular crystals
– Lattice points occupied by molecules
– Held together by intermolecular forces

water

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• Metallic crystals
– Lattice points occupied by atoms
– Generally bcc, fcc, hexagonal closest packed
– Very dense
– Bonding arises from delocalized electrons

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 12.5 Amorphous Solids
• Lack regular arrangement of atoms
• Glass is a familiar and important
amorphous solid
– Transparent fusion of inorganic materials
– Chief component SiO2
– Behaves more as a liquid than a solid

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Comparison of crystalline quartz and amorphous
quartz glass

crystalline amorphous

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 12.6 Phase Changes
• Phase – homogenous part of a system
that is separated from the rest of the
system by a well-defined boundary
• Phase change – transition from one
phase to another
– Caused by the removal or addition of
energy
– Energy involved is usually in the form of
heat
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The Six Possible Phase Changes

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• Liquid-Vapor Phase Transition
– Boiling point – the temperature at which the
vapor pressure of liquid equals atmospheric
pressure
– Molar heat of vaporization (DHvap) – the
amount of heat required to vaporize one mole
of a substance at its boiling point usually in
kJ/mol
– Dependent on the strength of intermolecular
forces
– Condensation – opposite of vaporization

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• Critical temperature (Tc) – the
temperature above which a gas cannot be
liquified by application of pressure
• Critical pressure (Pc) – the pressure that
must be applied to liquefy a gas at Tc.
• Supercritical fluid – the fluid that exists
above Tc and Pc.

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• Solid-Liquid Phase Transition
– Freezing – transformation of liquid to solid
– Melting (fusion) – opposite of freezing
– Melting point of solid (or freezing point of
liquid) – temperature at which the solid and
liquid phases coexist in equilibrium
• Dynamic equilibrium in which the forward
and reverse processes are occurring at the
same rate
– Molar heat of fusion (DHfus) – energy to melt
one mole of a solid usually in kJ/mol

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Typical Heating Curve

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• Solid-Vapor Phase Transition
– Sublimation – process by which
molecules go directly from the solid
phase to the vapor phase
– Deposition – reverse of sublimation
– Molar heat of sublimation (DHsub) –
energy required to sublime one mole of
solid usually in kJ/mol

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Heating Curve for Water

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Calculate the amount of energy (in kJ)
required to convert 125 g of ice at 10.0oC
to liquid water at the normal boiling point.
Assume that the specific heat of ice is
2.050 J/goC.

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Energy to warm ice from 10oC to 0oC
DT  0.0o C  (10.0o C)  10.0o C

2.050 J o 3
q  msDT  125 g  o
 10.0 C  2.563  10 kJ
g C
3 kJ
2.563 10 J  3
 2.563 kJ
1 10 J
Energy to melt ice at 0oC
mol
125 g   6.937 mol
18.02 g
6.01 kJ
q  nDH vap  6.937 mol   4.169 101 kJ
mol
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 Energy to warm water from 0.0oC to 100.0oC
DT  100.0o C  0.0o C  100.0o C
4.184 J o 4
q  msDT  125 g  o
 100.0 C  5.230  10 J
g C
4 1 kJ 1
5.230 10 J  3
 5.230  10 kJ
1 10 J

Total energy required

1 1
2.563 kJ  (4.169 10 kJ)  (5.230 10 kJ)  96.6kJ

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 12.7 Phase Diagrams
• Phase diagram – summarizes the
conditions (temperature and pressure) at
which a substance exists as a solid, liquid
or gas
– Divided into three regions (solid, liquid, gas)
– Phase boundary line – line separating any
two regions
– Triple point – the point at which all three
phase boundary lines meet
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Phase Diagram of CO2

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Heating CO2 Starting at 100oc and 1 atm

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Phase Diagram of H2O

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What is a) the normal* melting point, b) the normal*
boiling point and c) the physical state of the substance
at 2.0 atm and 110o C?

*normal – measured at 1.00 atm

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normal melting point normal boiling point
~135oC Copyright McGraw-Hill 2009
~200oC 72
solid physical state
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 Key Points
• Intermolecular forces
– Dipole-dipole interactions
– Hydrogen bonding
– (London) dispersion forces
• Properties of liquids
– Surface tension
– Viscosity
– Vapor pressure
• Clausius-Clapeyron equation
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• Crystal structure
– Unit cells
• Lattice point
– Packing spheres
• Coordination number
• Cubic unit cells
– Closest Packing
• Types of crystals
– Ionic
– Covalent
– Molecular
– Metallic
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• Amorphous solids
• Phase changes
– Liquid-vapor transitions
• Boiling point
• Heat of vaporization
• Critical temperature and pressure
– Solid-liquid transitions
• Melting point
• Heat of fusion
• Phase diagrams

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