4:07 General Chemistry I

Chapter 12 - Liquids, Solids, &

Intermolecular Forces
Condensed Phases
Phase Changes
H
Fall 2011
Ground Sound.
Intermolecular Interactions
Dispersion Forces
Dipole-Dipole
Hydrogen Bonding

Please do not exit the room between 4:10 and 4:20

unless you are seated in the back of the room.
Please do not exit the room between 4:10 and 4:20
unless you are seated in the back of the room.
Boiling Point
The Boiling Point is the temperature at which the
vapor pressure of the liquid is the same as the
atmospheric pressure.
The normal boiling point is the temperature required for
the vapor pressure of the liquid to be equal to 1 atm.
The boiling point depends on the atmospheric
pressure .
The temperature of boiling water on the top of a mountain
will be less than boiling water at sea level.
3
Distribution of Thermal Energy
Temperature (K) average kinetic energy
T
boil =
boiling pt T = Temp P = Pressure (Force/A on liq)
f
escape
fraction molecules in liq w/ energy to overcome P
T < T
boil
, f
escape
small
As T, f
escape
(molecules with escape energy) .
T = T
boil
, f
escape
large; molecular escape energy = P;
molecules escape rapidly.
Vapor pressure = external pressure.
How do intermolecular forces vs thermal energy set macroscopic properties?
Dispersion
Dipole-Dipole
Hydrogen Bonding
Energetics:
H
vap
, H
fus
...
Surface Tension
Viscosity
Phase Changes
Fusion (sl)
Sublimation (sg)
Intermolecular
Forces
Intermolecular
Forces
Macroscopic
Properties
Melting (sl)
Freezing (ls)
Boiling
Sublimation (sg)
Water is Weird.
Liquids
Solids
Gases
Crystals
Molecular
Ionic
Atomic
2009, Prentice-Hall, Inc.
Phase Changes
Or
Fusion
Phase Transitions of Solids: Melting,
Freezing, Sublimation
Crossing the lines
http://boomeria.org/chemlectures/textass2/fig17-9.jpg
Sublimation
Melting
(Fusion)
Freezing
4:07 General Chemistry I
Melting, Freezing, Sublimation
Get one thing straight......
americanrhetoric.com; thegreenhead.com
I am not melting!
I am dissolving!
I am not melting!
I am dissolving!
Temperature and Melting
On heating a solid, its temperature
increases until it reaches its melting
point.
Once the solid starts to melt, the
temperature remains the same until it
all turns to a liquid.
Above melting
pt - Heat, T
Solid, below melting
pt - Heat, T
At melting pt
Heat, T = 0 (l g)
Sublimation
Sublimation, a physical
change, occurs when solid
form changes directly to
gaseous form.
No transit through the liquid form.
Like melting, sublimation is
endothermic.
Energetics of Melting and Freezing
Melting is endothermic (Input energy to
system, as per experience.).
H
2
O(s) H
2
O(l) H > 0 at 0
o
C
Absorbs heat from surroundings (experience?)
As heat flows out of the surroundings, it
causes the surroundings to cool.
As heat flows out of a drink into ice cubes
(causing them to melt), the liquid gets cooler.
Freezing is exothermic.
H
2
O(l) H
2
O(s) H < 0 at 0
o
C
Releases heat into its surroundings
As heat flows into the surroundings, it
causes the surroundings to warm.
Think of the back of the refrigerator
Refrigerator where heat is pumped out into the
surroundings
Heat of Fusion
The heat of fusion (AH
fus
) is the amount of heat
needed to melt one mole of a solid.
Because freezing is the same but reverse process
of melting, the amount of energy transferred is the
same with a sign change.
AH
freeze
= -AH
fus
In general, AH
vap
> AH
fus
because vaporization
requires freeing molecules of all intermolecular
attractive forces.
ice cube 1
in/side ~ 1 mole
H
2
O
Energetics of Melting & Freezing
Melting endothermic
H
2
O
(s)
H
2
O
(l)
H = +6.02 kJ/mol at 0
o
C
Freezing exothermic
H
2
O
(l)
H
2
O
(s)
H = -6.02 kJ/mol at 0
o
C
AH
freeze
= -AH
fus
Liquid
Chemical
formula
Melting
point, C
AH
fusion
,
(kJ/mol)
Water H
2
O 0.00 6.02
Isopropyl alcohol C
3
H
7
OH -89.5 5.37
Acetone C
3
H
6
O -94.8 5.69
Diethyl ether C
4
H
10
O -116.3 7.27
Lower T
melt
higher AH
fusion
add more energy: s l
Both consistent w higher
intermolecular forces
4:07 General Chemistry I
Example: Calculate the mass of ice that is
melted with 237 kJ of heat.
Because the given amount of heat is almost 40x the AH
vap
,
the amount of water makes sense, ~40x18.
1 mol H
2
O = 6.02 kJ, 1 mol = 18.02 g
237 kJ
g H
2
O
Check:
Solution:
Solution Map:
Relationships:
Given:
Find:
kJ 6.02
mol 1
O H g 09 7
mol 1
g 8.02 1
kJ 6.02
O H mol 1
kJ 37 2
2
2
=
kJ mol H
2
O g H
2
O
mol 1
g 02 . 18
14
Example: How much heat energy, in kJ, is required to
melt 87 g of acetone, C
3
H
6
O, (MM 58.08)?
Because the given mass is more than one mole, the
answer being greater than AH
vap
makes sense.
1 mol C
3
H
6
O = 5.69 kJ at -94.8 C, 1 mol = 58.08 g
87 g C
3
H
6
O
kJ
Check:
Solution:
Solution Map:
Relationships:
Given:
Find:
g 58.08
mol 1
kJ .5 8
O H C mol 1
kJ .69 5
g 58.08
O H C mol 1
O H C g 7 8
6 3
6 3
6 3
=
g C
3
H
6
O mol C
3
H
6
O kJ
mol 1
kJ .69 5
Calculation from H
fus
(Fusion is melting.)
A bath containing 120. g of solid diethyl ether is
used to cool a reaction vessel. How much
energy is needed to melt the solid, starting at the
melting point?
C
4
H
10
O
(s)
C
4
H
10
O
(l)
H
fus
= +7.27 kJ/mol at -116.3
o
C
Chemical
Reaction
Moles
Mass
Volume
H
fus
120. g C
4
H
10
O x 1 mol C
4
H
10
O x 7.27 kJ = 208 kJ
506.5 g 1 mol C
4
H
10
O
16
Heating Curve of Water (-25 to 125

C)
2009, Prentice-Hall, Inc.
Phase Changes
Or
Fusion
C
h
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a
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F
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)
m
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Intermolecular
Forces
Intermolecular
Forces
Macroscopic
Properties
4:07 General Chemistry I
How do intermolecular forces vs thermal energy set macroscopic properties?
Dispersion
Dipole-Dipole
Hydrogen Bonding
Energetics:
H
vap
, H
fus
...
Surface Tension
Viscosity
Phase Changes
Evaporation
Condensation
Intermolecular
Forces
Intermolecular
Forces
Macroscopic
Properties
Melting
Freezing
Boiling
Sublimation
Water is Weird.
Liquids
Solids
Gases
Crystals
Molecular
Ionic
Atomic
Intermolecular Forces
Intermolecular Forces: Attractions between
molecules that hold them together. These forces
depend on the distribution of electronic charge and
often depend on the shape of the molecule and the
atoms that form it.
Important ideas:
Like charges repel
Unlike charges attract
The closer the charges the stronger the interaction
The higher the charge the stronger the interaction
#1 Dispersion Forces
Also known as London forces or instantaneous dipoles.
Caused by distortions in the electron cloud of one molecule
inducing distortion in the electron cloud on another.
Distortions in the electron cloud lead to a temporary dipole.
The temporary dipoles lead to attractions between
moleculesdispersion forces.
All molecules have attractions caused by dispersion forces.
Strength of the Dispersion Force
Depends on how easily electrons move (polarize)
With more electrons, farther from the nuclei, larger
dipoles are induced.
Dispersion force increase with larger molecules.
Noble Gas Molar Mass
(g/mol)
Boiling Point
(K)
He 4.00 4.2
Ne 20.18 27
Ar 39.95 87
Kr 83.80 120
Xe 131.29 165


Stronger attraction
leads to higher boiling
points.
Here, dispersion forces.
23
Boiling Points of n-Alkanes
Relationship Between Dispersion Force and
Molecular Size
-300
-250
-200
-150
-100
-50
0
50
100
150
200
250
1 2 3 4 5 6
Period
B
o
ilin
g
P
o
in
t
,
C
BP, Noble Gas
BP, Halogens
BP, XH4
Intermolecular
interactions of
dispersion
forces
increase with
molecular
size.
Examples: All these molecules are non-polar. In each
pair, identify the species with the highest boiling point.
CH
4
or C
3
H
8
BF
3
or BCl
3
CO
2
or CS
2
In each case, larger
molecule, higher molar mass
has higher boiling point.
Dispersion forces are the
only means of interaction for
nonpolar molecules.
Intermolecular
interactions of
dispersion forces
increase with
molecular size.
4:07 General Chemistry I
#2 Permanent Dipoles + Dipole-Dipole Attraction
Permanent dipoles
occur when electro-
negative atoms are
bonded in a asymmetric
arrangements.
Polar molecules
Molecular dipole
(debyes, D)
Dipole-Dipole
intermolecular attraction
is o
-
o
+.
Molar Mass
(g/mol)
Boiling
Point, C
Dipole
size, D
CH
3
CH
2
CH
3
44 -42 0
CH
3
-O-CH
3
46 -24 1.3
CH
3
- CH=O 44 20.2 2.7
CH
3
-CN 41 81.6 3.9

Polarity &
Dipole-to-Dipole Attraction
Stronger attraction leads to
higher boiling points.
Here, dipole dipole attraction.
T
boil
strength
intermolecular
interaction
CS
2
Nonpolar bonds = nonpolar molecule.
CH
2
F
2
Polar bonds and asymmetrical = polar molecule.
CF
4
Polar bonds and symmetrical shape = nonpolar molecule.
Examples: Do DipoleDipole Attractive Forces Exist
S C S
-- --
-
-
-
-
(EN C= 2.5, F = 4, H = 2.1, S = 2.5)
C
H
H
F
F
C
F
F
F
F
No dipole-dipole attraction
Dipole-dipole attraction
No dipole-dipole attraction
Attractive Forces
+ - + - + - + -
+
+
+
+
_
_
_
_
Dispersion forcesAll molecules.
Dipole-to-dipole forcesPolar molecules.
Therefore, the strength of attraction is stronger between
polar molecules than between non-polar molecules of the
same size.
#3 Hydrogen Bonding
Molecules that contain OH, NH, or
HF groups have particularly strong
intermolecular attractions.
Manifest properties include:
Unusually high melting & boiling points.
Unusually high solubility in water.
This attraction involves H and is
called a hydrogen bond.
Hydrogen bonding
super dipole dipole force
Mine.
(electron)
Hydrogen Bonding What Happens?
Very electronegative atom bonded to H pull
bonding electrons toward it strongly.
Because H has only a duet of electrons in its
bonds, the loss electrons to the electronegative
atom deshields the nucleus.
This exposes the proton (o
+
).
The exposed proton (o
+
) acts is a very strong
center of positive charge that attracts the electron
clouds of all neighboring molecules.
4:07 General Chemistry I
Properties and H-Bonding
Name Formula
Molar
mass
(g/mol)
Structure
Boiling
point,
C
Melting
point,
C
Solubility
in water
Ethane C
2
H
6
30.0 -88 -172 Immiscible
Ethanol CH
4
O 32.0 64.7 -97.8 Miscible
H C
H
H
C H
H
H
H C
H
H
O H
Stronger attraction leads to higher boiling points and
melting points. It enables solubility in hydrogen bonding
solvent, water.
Here, hydrogen bonds.
able to H bond
not able to H bond
H-Bonds vs. Chemical Bonds
Hydrogen bonds are not chemical bonds.
Hydrogen bonds are attractive forces between
molecules.
Chemical bonds are attractive forces that make
molecules through shared electrons of atoms.
Relationship Between H-Bonding and
Intermolecular Attraction
-200
-150
-100
-50
0
50
100
150
1 2 3 4 5
Period
B
o
i
l
i
n
g

P
o
i
n
t
,

C
BP, HX
BP, H2X
BP, H3X
BP, XH4
CH
4
NH3
HF
H
2
O
SiH4
GeH4
SnH4
H2S
H2Se
H2Te
Mine.
(electron)
34
Ion-Dipole Attraction
In a mixture, ions from an ionic compound are
attracted to the dipole of polar molecules
The strength of the ion-dipole attraction is one of
the main factors that determines the solubility of
ionic compounds in water
Types of Intermolecular Forces
Type of
force
Relative
strength Present in Example
Dispersion
force
Weak, but
increases
with molar
mass
All atoms
and
molecules
H
2
Dipole
Dipole force
Moderate
Only polar
molecules
HCl
Hydrogen
Bond
Strong
Molecules
having H
bonded to
F, O, or N
HF
36
Range
short
Medium
Ion-ion
longest
4:07 General Chemistry I
Measures of Intermolecular Energies
Weak but
numerous
Evidence for Ranking of Attractive Forces
Ionic compounds require large amounts of
energy to break apart ionic bonds.
Dipole-Dipole forces require intermediate
amounts of energy to break apart.
Dispersion forces are weak interactions and
very little energy is needed to change state.
Vaporization-
from liquid to gas
Fusion-
from solid to liquid
Attractive Forces and Properties
Like dissolves like.
Miscible = Liquids that do not separate, no
matter what the proportions.
Polar molecules dissolve in polar
solvents.
Water, alcohol, CH
2
Cl
2
Molecules with O or N higher solubility in H
2
O
due to H-bonding with H
2
O
Non-polar molecules dissolve in non-
polar solvents.
Ligroin (hexane), toluene, CCl
4
If molecule has both polar and non-polar
parts, then hydrophilic-hydrophobic
competition.
Soaps, detergents
Immiscible liquids
2009, Prentice-Hall, Inc.
Summary Intermolecular Forces
How do intermolecular forces vs thermal energy set macroscopic properties?
Dispersion
Dipole-Dipole
Hydrogen Bonding
Energetics:
H
vap
, H
fus
...
Surface Tension
Viscosity
Phase Changes
Evaporation
Condensation
Intermolecular
Forces
Intermolecular
Forces
Macroscopic
Properties
Melting
Freezing
Boiling
Sublimation
Water is Weird.
Liquids
Solids
Gases
Crystals
Molecular
Ionic
Atomic
Types of Crystalline Solids
4:07 General Chemistry I
Crystalline Solids
Dispersion,
dipole-dipole,
or H-bonding
Electrostatic forces
between cations & anions
that arrange in geometric
pattern (crystal lattice)
to maximize attractions.
covalent
bonds,
dispersion, or
metallic
bonds
High H
fus
:
electrostatic
forces strong
Low H
fus
:
intermolecular
forces weak
Varied H
fus
:
intermolecular
forces vary
w/ bond
Examples: Classify each crystalline solid as
molecular, ionic, or atomic.
H
2
O(s) molecular.
Si(s) atomic.
C
12
H
22
O
11
(s) molecular.
CaF
2
(s) ionic.
Sc(NO
3
)
3
(s) ionic.
Atomic Solids
Covalent bonds
are strong
H
fus
high.
Covalent bonds
directional
hard materials.
Common elements
include C, Si, & B.
(e.g., SiO
2
& SiC)
Dispersion forces
are very weak
H
fus
very low
All noble gases
form nonbonding
atomic solids.
Metallic
bonds vary
in strength,
as does
H
fus
.
Metals from
Group 1A, 2A, 3A, &
transition metals
(Group Bs)
Metallic Atomic Solids
Metallic Bonds
Metal atoms release some of their electrons to
be shared by all the atoms in the crystal.
Metallic bond is attraction of metal cations for
mobile electrons.
An islands of cations in a sea of electrons
Metallic Properties set by metallic bonds.
Luster, malleability, ductility, and electrical &
thermal conductivities related to the electron
mobility in the solid.
Metallic bond strength varies with cation charge
and size.
And so, AH
fusion
varies
PracticeDecide if Each of the Following Atomic
Solids Is Covalent, Metallic, or Nonbonding.
diamond covalent.
neon nonbonding.
iron metallic.
Substances w/ Both Bonding & Nonbonding Attractions
Some substances have chains or layers of
bonded atoms that are then attracted by
dispersion forces.
Chain substances include grey selenium, polymeric
SO
3
, and asbestos.
Layer substances include graphite, black phosphorus,
and mica.
4:07 General Chemistry I
Water is Weird.
Water is found in all three states on
Earth.
As a liquid, it is the most common
solvent found in nature.
Without water, life as we know it
could not exist.
The search for extraterrestrial life starts
with the search for water.
Water is Weird.
Liquid at room temperature.
Most molecular substances that have a molar mass
(18.02 g/mol) similar to waters are gaseous.
Relatively high boiling point.
Expands as it freezes.
Most substances contract as they freeze.
Causes ice to be less dense than liquid water.
High dipole moment makes water highly polar.
Hints for a Successful Friday, 4 Nov
MC-12 is due Friday, 4 Nov (no prep)
Start Ch 13 on Friday
Skim Ch 13 and gaze upon its homework.
MC-13 due W, 9 Nov (no MC-13 prep)
Intermolecular
Forces
Intermolecular
Forces
Macroscopic
Properties
E
x
a
m

3

i
s

i
n

1
.
5

w
e
e
k
s
.