KI1101-2012-KD Lec07 IntermolecularAttractions

Chapter 12:
Intermolecular Attractions
and the Properties of Liquids
and Solids
Personal
Use
Only
Chemistry: The Molecular Nature
of Matter, 6E
Jespersen/Brady/Hyslop
Chemistry, Stucture and Reactivity, Bodner
Personal Use Only
Chapter 12 Intermolecular Forces

Important differences between gases,
solids, and liquids:
Gases
Expand to fill their container
Personal Use Only

Liquids
Retain volume, but not shape
Solids
Retain volume and shape
Chemistry: The Molecular Nature of Matter, 6E
Chapter 12 Intermolecular Forces

Physical State of molecule depends on
Average kinetic energy of particles
Recall KE Tave
Intermolecular Forces
Energy of Inter-particle attraction
Personal Use Only

Physical Properties of Gases, Liquids
and Solids determined by
How tightly molecules are packed together
Strength of attractions between
molecules
Intermolecular Attractions
Converting gas liquid or solid
Molecules must get closer together
Cool or compress
Converting liquid or solid gas
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Requires molecules to move farther apart
Heat or reduce pressure
As T, Kinetic Energy of molecules

At certain T, molecules dont have
enough energy to break away from one
anothers attraction
Inter vs. Intra-Molecular Forces

Intramolecular forces
Covalent bonds within molecule
Strong
Hbond (HCl) = 431 kJ/mol
Intermolecular forces
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Attraction forces between molecules
Weak
Hvaporization (HCl) = 16 kJ/mol
Intermolecular attraction (weak)
Covalent Bond (strong)
Cl
H
Cl
Electronegativity Review
Electronegativity: Measure of attractive
force that one atom in a covalent bond has
for electrons of the bond
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Bond Dipoles
Two atoms with different electronegativity
values share electrons unequally
Electron density is uneven
Higher charge concentration around more
electronegative atom
H
F
Personal Use Only
Bond dipoles
Indicated with delta () notation

Indicates partial charge has arisen
Net Dipoles
Symmetrical molecules
Even if they have polar bonds
Are non-polar because bond dipoles cancel
Asymmetrical molecules
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Are polar because bond dipoles do not cancel
These molecules have permanent, net dipoles
Molecular dipoles
Cause molecules to interact

Decreased distance between molecules increases
amount of interaction
When substance melts or boils
Intermolecular forces are broken

Not covalent bonds
Responsible for non-ideal behavior of

gases
Responsible for existence of condensed
states of matter
Responsible for bulk properties of matter
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Boiling Points and Melting Points

Reflect strength of intermolecular forces
10
Three Important Types of

1. Dipole-dipole forces
Hydrogen bonds
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2. London dispersion forces
3. Ion-dipole forces
Ion-induced dipole forces
11
I. Dipole-dipole Attractions
Occur only between polar
molecules
Possess dipole moments
Molecules need to be
close together
Polar molecules tend to
align their partial charges
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+ to
As dipole moment ,
intermolecular force
12
I. Dipole-dipole Attractions
Tumbling molecules
Mixture of attractive and
repulsive dipole-dipole
forces
Attractions (- -) greater
than repulsions(- -)
Get net attraction
~ 1% of covalent bond
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13
Dipole - Dipole Attractions

Interactions between net dipoles in polar
molecules
About 1% as strong as a covalent bond
Decrease as molecular distance increases
Drops off as 1/d3 (d = distance between
dipoles)
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Dipole-dipole forces with polarity
14
Hydrogen Bonds
Special type of Dipole-Dipole Interaction
Very strong dipole-dipole attraction
~40 kJ/mol
Occurs between H and highly electronegative atom

(O, N, or F)
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HF, HO, and HN bonds very polar
e s lie closer to X than to H, so high partial charges

H only has 1 e, so +H presents almost bare proton
X almost full 1 charge
Elements small size, means high charge density

Positive end of one can get very close to negative end of
another
15
Examples of Hydrogen Bonding

H
Personal Use Only

H
N
H
H
H
O
H
N
H
16
Effects of Hydrogen Bonding

Boiling points of H
compounds of
elements of Groups
IVA, VA, VIA, and
VIIA.
Boiling points of
molecules with H
bonding are higher
than expected.
Dont follow rule that
BP as MM
(London forces )
Boiling Point (C)
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17
Hydrogen Bonding in Water
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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
18
II. London Dispersion Forces
Intermolecular forces between

nonpolar molecules
Two neutral molecules (atoms)
can affect each other
Electrostatic
attraction
e
2+
2+
e
Nucleus of 1 molecule (atom)

He atom 1
attracts es of adjacent molecule
(atom)
Electron cloud distorts
Temporary or instantaneous
dipole forms
One instantaneous dipole can
induce another in adjacent molecule
(atom)
Results in net attractive force
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He atom 2
19
London Forces
When atoms near one another,
their valence electrons interact
Repulsion causes electron clouds
in each to distort and polarize
Instantaneous, induced
dipoles result from this
distortion
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Effect enhanced with increased
particle mass
Effect diminished by increased
distance between particles
20
London Dispersion Forces
Instantaneous dipole-induced dipole

attractions

London forces
Dispersion forces
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Decrease as 1/d6 (d = distance between

molecules)
Operate between all molecules
Neutral or net charged

Nonpolar or polar
21
Ease with which dipole moments can be

induced and thus London Dispersion
Forces depends on
1. Polarizability
2. Molecular size
Number atoms
Molecular mass
1. Molecular Shape
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22
1. Polarizability
Ease with which electron
distribution in neutral atom
(or molecule) can be distorted
Larger molecules = more polarizable
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Larger number of e s greater ease of
distorting electron cloud
Magnitude of resulting partial charge is larger
London Forces as MM
More e, less tightly held
London Forces as electron cloud volume

Depends on size of atoms
23
Your Turn!
List all intermolecular forces for CH3CH2OH.
A. H-bonding
B. H-bonding, Dipole-Dipole, London
C. Dipole-Dipole
D. London
E. London, H-bonding
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24
Table 12.1 Boiling Points of Halogens

and Noble Gases
Larger molecules have stronger London forces
and thus higher boiling points.
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25
2. Number of Atoms in Molecule

London forces depend on number atoms in
molecule
Boiling point of hydrocarbons demonstrates this
trend
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Formula BP at 1 atm, C Formula BP at 1 atm, C
CH4
C5H12
36.1
161.5
C2H6
88.6
C6H14
68.7
C3H8
42.1
C4H10
0.5
C22H46
327
26
How Intermolecular Forces

Determine Physical Properties
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Hexane, C6H14
Propane, C3H8
BP 68.7oC
BP 42.1oC
More sites (marked with *) along its chain where
attraction to other molecules can occur
27
3. 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
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Hs not as free to interact with Hs on other
molecules
Less compact molecules
Hs have more chance to interact with Hs
on other molecules
28
Physical Origin of Shape Effect

Small area for
interaction
Larger area for

interaction
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More compact lower BP
Less compact higher BP
29
Your Turn!
Which species has a higher boiling point, Cl 2 or
HCl; F2 or HF ?
A. HCl; F2
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B. Cl2; F2
C. HCl; HF
D. Cl2 ; HF
30
III. Ion-dipole Attractions

Attractions between ion and charged end of
polar molecules
Attractions can be quite strong as ions have full
charges
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(a) Negative ends of water dipoles surround cation
(b) Positive ends of water dipoles surround anion
31
Ex. Ion-dipole Attractions AlCl36H2O

Attractions between ion and polar molecules
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
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Water molecules are found
at vertices of octahedron
around aluminum ion
32
Ion-induced Dipole Attractions

Attractions between ion and dipole it induces
on neighboring molecules
Depends on
Ion charge and
Polarizability of its neighbor
Attractions can be quite strong as ion charge does
NOT flicker on and off like instantaneous dipoles of
ordinary London forces
Ex. I and Benzene
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33
Summary of Intermolecular
Attractions
Dipole-dipole
occur between neutral molecules with permanent
dipoles;
about 1% - 5% of covalent bond
Mid range in terms of intermolecular forces
Hydrogen bonding
Special type of dipole-dipole interaction
Occur when molecules contain NH,
HF and OH bonds
About 5% to 10% of a covalent bond
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34
Summary of Intermolecular
Attractions
London dispersion
Present in all substances
Weakest intermolecular forces
Weak, but can lead to large net attractions
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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
35
Using Intermolecular Forces

Often can predict physical properties (like BP
and MP) by comparing strengths of
intermolecular attractions
Strongest
Ion-Dipole
Hydrogen Bonding
Dipole-Dipole
Weakest
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Larger, longer, heavier molecules have stronger
IMFs
Smaller, more compact, lighter molecules have
weaker IMFs
36
Learning Check
Identify the kinds of intermolecular forces present
in the following compounds
Rank them in order of increasing boiling point:
H2S, CH3OH, CBr4, and Ne
H
Br
Ne
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S
dipoledipole
H
H
Br
Hydrogen
bonding
Br
Br
London
forces
London
forces
MM=20.2
MM=331.6
CH3OH >H2S > CBr4 > Ne

37
Physical Properties that Depend on

How Tightly Molecules Pack
Compressibility
Measure of ability of substance to be forced into
smaller volume
Determined by strength of intermolecular forces
Gases highly compressible
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Molecules far apart
Weak intermolecular forces
Solids and liquids nearly incompressible

Molecules very close together
Stronger intermolecular forces
38
Intermolecular Forces Determine

Strength of Many Physical Properties
Retention of Volume and Shape
Solids keep both volume and shape
Strongest intermolecular attractions
Molecules closest
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Gases, keep nothing
Weakest intermolecular attractions

Molecules farthest apart
Liquids keep volume, but not shape

Attractions intermediate
39
Diffusion
Movement that
spreads one gas
though another gas to
occupy space
uniformly
Spontaneous
intermingling of
molecules of one gas
with molecules of
another gas
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Occurs more rapidly in gases than in liquids
Hardly at all in solids
40
Diffusion
In Gases
Molecules travel long
distances between
collisions
Diffusion rapid
In Liquids
Molecules closer
Encounter more
collisions
Takes a long time to
move from place to
place
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In Solids
Diffusion nonexistent at
room temp
Will at high Temp
41
Surface Tension
Why does H2O bead up
on a freshly waxed car
instead of forming a
layer?
Inside body of liquid
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Intermolecular forces in
all directions
Molecules at surface
IMF only pull down and
to side
Fewer attractions, so
free to expand in
direction with no forces
42
Surface Tension
Tendency of liquid
to take shape that
minimizes surface
area
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Molecules at surface
have higher potential
energy than those in
bulk of liquid
Energy required to
expand or increase
surface by unit area
Wax = nonpolar
H2O = polar
Water beads as wants
to maximize
attractions
43
Surface Tension
Liquids containing
molecules with strong
intermolecular forces have
high surface tension
Allows us to fill glass above
rim
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Gives surface rounded
appearance
Surface acts as skin that lets
water pile up
Surface resists expansion and
pushes back
Surface Tension
as IMF
Surface Tension
as IMF
44
Wetting
Ability of liquid to spread
across surface to form
thin film
Greater similarity in
attractive forces
between liquid and
surface, yields greater
wetting effect
Occurs only if
intermolecular attractive
force between surface
and liquid about as
strong as within liquid
itself
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45
Wetting
Ex. H2O wets clean glass surface as it forms H
bonds to SiO2 surface
Does not wet greasy glass, as grease interacts
weakly with water
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Only London dispersion forces
Forms bead instead
Surfactants
Added to detergents to lower surface tension of H2O

Now water can get better access to surface to be
cleaned
46
Surfactants
Substances that have polar and non-polar

characteristics
Long chain hydrocarbons with polar tail
O
O Na+
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O
O Na+
Nonpolar end interacts with grease

Polar end interacts with H2O
Thus increasing solubility of grease in water
47
Viscosity
Resistance to flow
Measure of fluids
resistance to flow or
changing form
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Larger molecules collide
and interact more
often, impeding their
flow
www.chemistryexplained.com
Also called internal friction

Depends on intermolecular attractions
Molecular shape
48
Viscosity
Viscosity when Temperature
Most people associate liquids with viscosity
Molasses more viscous than water
Gases have viscosity
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Respond almost instantly to form-changing forces
Solids, such as rocks
Normally respond very slowly to forces acting to

change their shape
For same size molecules, viscosity

increases as strength of Intermolecular
Forces increases
49
Effect of Intermolecular Forces on

Viscosity
Personal Use Only

Acetone
Polar molecule
Ethylene glycol
Polar molecule
Hydrogen-bonding
Dipole-dipole and
London forces
Dipole-dipole and
London forces
Which is more viscous??

50
Your Turn!
For each pair given, which is more viscose ?
CH3CH2CH2CH2OH, CH3CH2CH2CHO;
C6H14, C12H26; NH3(l ), PH3(l )
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A. CH3CH2CH2CH2OH; C6H14; NH3(l )
B. CH3CH2CH2CH2OH; C12H26; NH3(l )

C. CH3CH2CH2CHO; C6H14; PH3(l )
D. CH3CH2CH2CHO; C12H26; NH3(l )
E. CH3CH2CH2CH2OH; C12H26; PH3(l )
51
Solubility
Like dissolves like
To dissolve polar substance, use polar solvent
To dissolve nonpolar substance, use nonpolar
solvent
Compare relative polarity of two substances
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Similar polarity means greater ability to interact
with each other
Differing polarity means that they dont interact;
move past each other
Surfactants
Both polar and non-polar characteristics
Used to increase solubility
52
Your Turn!
Which of the following are not expected
to be soluble in water?
A. HF
B. CH4
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C. CH3OH
D. All are soluble
53
Phase Changes
Changes of physical state
Deal with motion of molecules
As temperature changes
Matter will undergo phase changes
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Liquid Gas
Evaporation
As heat H2O, forms steam or water vapor
Requires energy or source of heat to occur
54
Phase Changes
Solid Gas
Sublimation
Ice cubes in freezer, leave in long enough disappear
Endothermic
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Gas Liquid
Cooling or Condensation
Dew is H2O vapor condensing onto cooler ground
Exothermic
55
Rate of Evaporation
Depends on
Temperature
Surface area
Strength of
intermolecular
attractions
Molecules that escape
from liquid have larger
than average KEs
When they leave
Average KE of
remaining molecules
is less
T lower
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56
Effect of Temperature on Evaporation

Rate
For given liquid
Rate of evaporation per
unit surface area as
T
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Why?
At higher T, total
fraction of molecules
with KE large enough to
escape is larger
Result: rate of
evaporation is larger
57
Kinetic Energy Distribution in Two

Different Liquids
A
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Smaller IMFs
Lower KE required to
escape liquid
A evaporates faster
Larger IMFs
Higher KE required
to escape liquid
B evaporates slower
58
Changes Of State Involve Equilibria

Fraction of molecules in condensed state is
higher when intermolecular attractions are
higher
Intermolecular attractions must be overcome
to separate the particles, while separated
particles are simultaneously attracted to one
another
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condensed
phase
separated
phase
59
Before System Reaches

Equilibrium
Liquid is placed in
empty container
Begins to evaporate
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Once in gas phase
Molecules can
condense by
Striking surface of liquid
and giving up some
kinetic energy
60
System At Equilibrium
Rate of evaporation =
rate of condensation
Can occur in system
where molecules are
constrained to remain
close to liquid surface
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61
Similar Equilibria Reached in

Melting
Melting Point (mp)
Solid begins to change

into liquid as heat added
Dynamic Equilibria
exists between solid and
liquid states
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Melting (red arrows) and
freezing (black arrows)
occur at same rate
As long as no heat added or
removed from equilibrium
mixture
62
Equilibria Reached in
Sublimation
At equilibrium
Molecules evaporate
from solid at same
rate as molecules
condense from vapor
Molecules sublime
and condense on
crystal at same rate
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63
Phase Changes
Gas
Energy of System
Vaporization
Condensation
Sublimation
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Deposition
Liquid
Melting
or Fusion
Freezing
Solid
Exothermic, releases heat
Endothermic, absorbs heat
64
Energy Changes Accompanying

Phase Changes
All phase changes are possible under the
right conditions
Following sequence is endothermic
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heat solid melt heat liquid boil heat gas
Following sequence is exothermic

cool gas condense cool liquid freeze cool
solid
65
H Accompanying Phase Changes

Endothermic Phase Changes
1. Must Add Heat
2. Energy entering system (+)
Sublimation: Hsub > 0
Vaporization: Hvap > 0
Melting or Fusion: Hfus > 0
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Exothermic Phase Changes
1. Must Give Off Heat
2. Energy leaving system ()
Deposition: H < 0 = Hsub
Condensation: H < 0 = Hvap
Freezing: H < 0 = Hfus
66
Phase Changes
As T changes, matter undergoes phase
changes
Phase Change
Transformation from one phase to another
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Liquid-Vapor Equilibrium
Molecules in liquid
Not in rigid lattice
In constant motion
Denser than gas, so more collisions
Some have enough kinetic energy to
escape, some dont
67
Liquid-Vapor Equilibrium
At any given T,
Fraction of molecules
Average Kinetic
Energy of molecules
is constant
But have distribution
KEs of particles
Certain number of
molecules have
enough KE to escape
surface
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Kinetic Energy
Process is Evaporation or Vaporization

As T , Avg. KE and number molecules
with enough KE to escape
68
Vapor Pressure (VP)

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 conversion is endothermic
liquid + heat of vaporization gas
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Equilibrium Vapor Pressure
VP once dynamic equilibrium reached
Usually referred to as simply vapor pressure
69
Measuring Vapor Pressure
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To measure pressures inside vessels, a manometer is
used.
70
Vapor Pressure Diagram

Variation of
vapor pressure
with T
Ether
Volatile
High vapor
pressure near RT
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Propylene
glycol
RT = 25 C
Non-volatile
Low vapor
pressure near RT
71
Effect of Volume on VP
A. Initial V
Liquid vapor
equilibrium exists
A. V
P
Rate of
condensation
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A. More liquid
evaporates
New equilibrium
established
72
Measuring Hvap
Clausis-Clayperon Equation
Measure P at various Ts, then plot
Hvap
ln P
R
1
C
T
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Two point form of Clausis-Clayperon Equation
Measure P at two Ts and solve equation
P1 Hvap
ln
P2
R
1
1

T 2 T1
73
Learning Check
The vapor pressure of diethyl ether is 401 mmHg at
18C, and its molar heat of vaporization is 26
kJ/mol. Calculate its vapor pressure at 32C.
P1 Hvap
ln
P2
R
1
1 T1 = 273.15 + 18 = 291.15K

T 2 T1 T2 = 273.15 + 32 = 305.15K
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P1
2.6 10 4 J / mol
1
1
ln
0.4928
P2 8.314 J /(K mol ) 305.15K 291.15K
P1
P1
e 0.4928 0.6109
P2
P2
0.6109
401mmHg
P2
6.6 102 mmHg
0.6109
74
Your Turn!
Determine the enthalpy of vaporization, in
kJ/mol, for benzene, using the following
vapor pressure data. T = 60.6 C; P = 400 torr
T = 80.1 C; P = 760 torr
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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
75
Your Turn! - Solution

P1 DHvap
ln =
P2
R
1 1
-
T 2 T1
DHvap
400mm Hg
1
1
ln
=
J
760mm Hg
353.1 K 333.6 K
8.314
K mol
DHvap = 32, 235 J/mol or 32.2 kJ/mol
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76
Do Solids Have Vapor Pressures?

Yes
At given T
Some solid particles have enough KE so escape
into vapor phase
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When vapor particles collide with surface
they can be captured
Equilibrium vapor pressure of solid

P of vapor in equilibrium with solid
77
Boiling Point (bp)

T at which vapor pressure of liquid =
atmospheric pressure.
Bp as strength of IMF
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Normal boiling point
T at which vapor pressure = 1 atm
78
Effects of Hydrogen Bonding

Boiling points of H
compounds of elements
of Groups IVA, VA, VIA,
and VIIA.
Boiling points of
molecules with H
bonding are higher
than expected
Dont follow rule that
BP as MM (London
forces )
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79
Your Turn!
Which of the following will affect the boiling
point of a substance?
A.Molecular mass of the material
B.Intermolecular attractions
C.The external pressure on the material
D.All of these
E.None of these
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80
Heating Curve
Heat added at constant rate
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Horizontal lines
Phase changes
Melting point
Boiling point
Diagonal lines
Heating of solid, liquid or gas
81
Cooling Curve
Heat removed at constant rate
Horizontal lines
Phase changes
Melting point
Boiling point
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Diagonal lines
Cooling of solid,
liquid or gas
Supercooling
T of liquid dips below its freezing point
82
Your Turn!
How much heat, in J, is required to convert
10.00 g of ice at -10.00 oC to water at
50.00 oC ?
Specific heat (J/g K): ice, 2.108, water, 1.487
Enthalpy of fusion = 6.010 kJ/mol54
A. 5483 J
B. 5643 J
C. 2304 J
D. 2364 J
E. 62,400 J
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83
Energies of Phase Changes

Expressed per mole
Molar heat of fusion (Hfus)
heat absorbed by 1 mole of solid when it melts to give
liquid at same T and P
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Molar heat of vaporization (Hvap )
heat absorbed when 1 mole of liquid is changed to 1 mole

of vapor at constant T and P
Molar heat of sublimation (Hsub )

Heat absorbed by 1 mole of solid when it sublimes to give
1 mole of vapor at constant T and P
All of these quantities tend to with ing

intermolecular forces
84
Le Chateliers 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
Personal Use Only

Position of equilibrium
used to refer to relative amounts of substance on

each side of double (equilibrium) arrows
85
Liquid Vapor Equilibrium

Liquid + Heat Vapor
ing T
s amount of vapor
s amount of liquid
Equilibrium has shifted
Personal Use Only

= right shift
more vapor is produced at expense of liquid
Temperature-pressure relationships can be

represented using a phase diagram
86
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
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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
87
Phase Diagram
X axis = temperature
Y axis = pressure
As P (T const), solid
most likely
More compact
E As T (P const), gas
Personal Use Only

most likely
Higher energy
Each point = T and P
B = 0.01C, 4.58 torr

E = 100C, 760 torr
F = 10C, 2.15 torr
88
Phase Diagram of Water

AB = vapor pressure
curve for ice
BD = vapor pressure
curve for liquid water
BC = melting point line
B = triple point = T
where all 3 phases in
equilibrium
D = critical point
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T and P above which
liquid does not exist
89
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?
Personal Use Only

90
Phase Diagram CO2

Now line
between solid
and liquid
slants to right
More typical
Where is Triple
point?
Where is
Critical point?
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91
Supercritical Fluid
Substance with temperature above its critical
temperature (TC) and density near its liquid
density
Have unique properties that make them
excellent solvents
Values of TC tend to with increased
intermolecular attractions between particles
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92
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
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93
Types of Solids
Crystalline Solids
Solids with highly regular arrangements of
components
Amorphous Solids
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Solids with considerable disorder in their
structures
94
Crystalline Solids
Unit Cell
Smallest
segment that
repeats regularly
Smallest
repeating unit of
lattice
2-Dimensional
Unit Cells
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95
Crystal Structures Have Regular

Patterns
Lattice
Many repeats of unit cell
Regular, highly
symmetrical system
Three (3) dimensional
system of points
designating positions of
components
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Atoms
Ions
Molecules
96
Three Types Of 3-D Unit Cells

Simple cubic
Has one host atom at each corner
Edge length a = 2r
where r is radius of atom or ion
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Body-centered cubic (BCC)
Has one atom at each corner and one in

center
4r
Edge length a
Face-centered cubic (FCC)

Has one atom centered in each face, and
one at each corner
Edge length
a 2 2r
97
Close Packing of Spheres

Most efficient arrangement of spheres in 2-D
Each sphere has 6 nearest neighbors
Square lattice: 2-dimensional arrays
2nd layer
1st layer
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98
Two Ways to Put on 3rd Layer

Cubic lattice: 3-dimensional arrays
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1. Directly above
spheres in 1st layer
2. Above holes in 1st layer

Remaining holes not
covered by 2nd layer
99
3-D Simple Cubic Lattice

Unit Cell
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Portion of lattice
open view
Space filling
model
100
Other Cubic Lattices

Face Centered
Cubic
Body Centered
Cubic
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101
Ionic Solids
Lattices of Alternating charges
Want cations next to anions
Maximizes electrostatic attractive forces
Minimizes electrostatic repulsions
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Based on one of three basic lattices:
Simple cubic
Face centered cubic
Body centered cubic
102
Common Ionic Solids

Rock salt or NaCl
Face centered cubic lattice of Cl ions (green)
Na+ ions (blue) in all octahedral holes
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103
Other Common Ionic Solids
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Cesium
Chloride, CsCl
Zinc Sulfide,
ZnS
Calcium
Fluoride, CaF2
104
Spaces In Ionic Solids Are Filled

With Counter Ions
In NaCl
Cl ions form facecentered cubic unit

cell
Smaller Na+ ions fill
spaces between Cl
ions
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Count atoms in unit
cell
Have 6 of each or
1:1 Na+:Cl ratio
105
Counting Atoms per Unit Cell

4 types of sites in unit cell
Central or body position atom is completely contained
in one unit cell
Face site atom on face shared by two unit cells
Edge site atom on edge shared by four unit cells
Corner site atom on corner shared by eight unit cells
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Site
Counts as Shared by X unit cells
Body
Face
1/2
Edge
1/4
Corner
1/8
106
Example: NaCl
Face
Edge
Corner
Site
# of Cl
6 1 2 3
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12 1 4 3
8 18 1
Center
Body
1
Face
0
Edge
107
Learning Check:
Determine the number of each type of ion in
the unit cell.
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1:1
CsCl
4:4
ZnS
4:8
CaF2
108
Some Factors Affecting

Crystalline Structure
Size of atoms or ions involved
Stoichiometry of salt
Materials involved
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Some substances do not form crystalline solids
109
Amorphous Solids (Glass)

Have little order, thus referred to as super
cooled liquids
Edges are not clean, but ragged due to the lack
of order
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110
X-Ray Crystallography
X-rays are passed through
crystalline solid
Some x-rays are absorbed,
most re-emitted in all
directions
Some emissions by atoms
are in phase, others out of
phase
Emission is recorded on film
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111
X-ray Diffraction
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Experimental Setup
Diffraction Pattern
112
Interpreting Diffraction Data

As x-rays hit
atoms in lattice
they are deflected
Angles of
deflections related
to lattice spacing
So we can
estimate atomic
and ionic radii
from distance data
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113
Interpreting Diffraction Data

Bragg Equation
n=2dsin
n = integer (1, 2, )
= wavelength of
Xrays
d = interplane
spacing in crystal
= angle of
incidence and angle
of reflectance of
Xrays to various
crystal planes
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114
Ex. 2 Diffraction Data

The diffraction pattern of copper metal was
measured with x-ray radiation of wavelength
of 1.315 . The first order (n=1) Bragg
diffraction peak was found at an angle theta of
50.5 degrees. Calculate the spacing between
the diffracting planes in the copper metal.
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n = 2dsin
1(1.315 )=2dsin(50.5)
d = 2.83
115
Ex 3. Using Diffraction data

X-ray diffraction measurements reveal that
copper crystallizes with a face-centered cubic
lattice in which the unit cell length is 3.62 .
What is the radius of a copper atom expressed
in angstroms and in picometers?
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This is basically a geometry problem.
116
Ex.3 (cont)
Pythagorean theorem: a2 + b2 = c2
Where a = b = 3.62 sides and c = diagonal
2a2 = c2
and
c 2a 2 2a
diagonal 2 (3.62A) 5.12A
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diagonal = 4 rCu = 5.12
rCu = 1.28
Now convert to pm
Recall 1 = 1 1010 m
and 1 pm = 1 1012 m
1 10 10 m
1pm
1.28A
128pm
12
A
1 10 m
117
Learning Check
Silver packs together in a faced center cubic
fashion. The interplanar distance, d,
corresponds to the length of a side of the unit
cell, and is 4.07 angstroms. What is the radius
of a silver atom?
a 2 2rOnly
Personal Use
a
4.07 A 2 2r
r = 0.536
118
Ionic Crystals (ex. NaCl, NaNO3)

Have cations and anions at lattice sites
Are relatively hard
Have high melting points
Are brittle
Have strong attractive forces between ions
Do not conduct electricity in their solid
states
Conduct electricity well when molten
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119
Sample Homework Problem

Potassium chloride crystallizes with the rock
salt structure. When bathed in X-rays, the
layers of atoms corresponding to the
surfaces of the unit cell produce a diffracted
beam of X-rays (=154 pm) at an angle of
6.97. From this, calculate the density
(g/cm3).
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120
Your Turn!
Yitterbium crystallizes with a face centered
cubic lattice. The atomic radius of Yitterbium
is 175 pm. Determine the unit cell length.
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A. 495 pm
B. 700 pm
C. 350 pm
D. 990 pm
E. 247 pm
121
Your Turn! - Solution

diagonal of cube = 4r where r = atomic radius
diagonal of cube = 2 a where a = side of cube
4r
4 x 175 pm
a=
=
= 495 pm
2
2
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122
Covalent Crystals
Lattice positions occupied by atoms that are
covalently bonded to other atoms at
neighboring lattice sites
Also called network solids
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Interlocking network of covalent bonds extending
all directions
Covalent crystals tend to
be very hard
have very high melting points
have strong attractions between
covalently bonded atoms
123
Ex. Covalent (Network) Solid

Diamond (all C)
shown
SiO2 silicon oxide
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Alternating Si and O
Basis of glass and quartz
Silicon carbide (SiC)
124
Metallic Crystals
Simplest models
Lattice positions of metallic
crystal occupied by positive
ions
Cations surrounded by cloud
of electrons
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formed by valence electrons
extends throughout entire solid
125
Metallic Crystals
Conduct heat and electricity
By their movement, electrons transmit kinetic
energy rapidly through solid
Have the luster characteristically associated

with metals
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When light shines on metal
Loosely held electrons vibrate easily
Re-emit light with essentially same frequency
and intensity
126
Learning Check:
Classify the following in terms of most likely type of solid.
Substance
ionic molecular covalent metallic
X: pulverizes when struck;

non-conductive of heat
and electricity
Y: White crystalline solid
that conducts electrical
current when molten or
dissolved
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Z: shiny, conductive,
malleable with high
melting temperature
127
Your Turn!
Molecular crystals can contain all of the listed
attraction forces except:
A. Dipole-dipole attractions
B. Electrostatic forces
C. London forces
D. Hydrogen bonding
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128

KI1101-2012-KD Lec07 IntermolecularAttractions

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Chapter 12:

Chemistry, Stucture and Reactivity, Bodner

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Chapter 12 Intermolecular Forces

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Retain volume, but not shape

Chemistry: The Molecular Nature of Matter, 6E

Chapter 12 Intermolecular Forces

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Chemistry: The Molecular Nature of Matter, 6E

Converting liquid or solid gas

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As T, Kinetic Energy of molecules

Chemistry: The Molecular Nature of Matter, 6E

Inter vs. Intra-Molecular Forces

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Chemistry: The Molecular Nature of Matter, 6E

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Chemistry: The Molecular Nature of Matter, 6E

Indicated with delta () notation

Chemistry: The Molecular Nature of Matter, 6E

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Cause molecules to interact

Chemistry: The Molecular Nature of Matter, 6E

When substance melts or boils

Intermolecular forces are broken

Responsible for non-ideal behavior of

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Boiling Points and Melting Points

Chemistry: The Molecular Nature of Matter, 6E

Three Important Types of

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Chemistry: The Molecular Nature of Matter, 6E

Possess dipole moments

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Chemistry: The Molecular Nature of Matter, 6E

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Chemistry: The Molecular Nature of Matter, 6E

Dipole - Dipole Attractions

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Chemistry: The Molecular Nature of Matter, 6E

Occurs between H and highly electronegative atom

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e s lie closer to X than to H, so high partial charges

Elements small size, means high charge density

Chemistry: The Molecular Nature of Matter, 6E

Examples of Hydrogen Bonding

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Chemistry: The Molecular Nature of Matter, 6E

Effects of Hydrogen Bonding

Boiling Point (C)

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Chemistry: The Molecular Nature of Matter, 6E

Hydrogen Bonding in Water

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Chemistry: The Molecular Nature of Matter, 6E

II. London Dispersion Forces

Intermolecular forces between

Nucleus of 1 molecule (atom)

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Chemistry: The Molecular Nature of Matter, 6E

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Chemistry: The Molecular Nature of Matter, 6E