Chem Chapter11 LEC

Chapter 11
Liquids,
Solids, and
Intermolecular
Forces
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Tro, Chemistry: A Molecular Approach 2
Comparisons of the
States of Matter
the solid and liquid states have a much higher density
than the gas state
therefore the molar volume of the solid and liquid states is
much smaller than the gas state
the solid and liquid states have similar densities
generally the solid state is a little denser
notable exception: ice is less dense than liquid water
the molecules in the solid and liquid state are in close
contact with each other, while the molecules in a gas
are far apart
Freedom of Motion
the molecules in a gas have complete freedom of
motion
their kinetic energy overcomes the attractive forces between
the molecules
the molecules in a solid are locked in place, they
cannot move around
though they do vibrate, they dont have enough kinetic
energy to overcome the attractive forces
the molecules in a liquid have limited freedom they
can move around a little within the structure of the
liquid
they have enough kinetic energy to overcome some of the
attractive forces, but not enough to escape each other
Properties of the 3 Phases of Matter
Fixed = keeps shape when placed in a container
Indefinite = takes the shape of the container
State Shape Volume
Compressible
Flow
Strength of
I ntermolecular
Attractions
Solid Fixed Fixed No No very strong
Liquid Indef. Fixed No Yes moderate
Gas Indef. Indef. Yes Yes very weak

Kinetic - Molecular Theory
the properties of solids, liquids, and gases can be
explained based on the kinetic energy of the
molecules and the attractive forces between
molecules
kinetic energy tries to give molecules freedom of
motion
degrees of freedom = translational, rotational,
vibrational
attractive forces try to keep the molecules together
kinetic energy depends only on the temperature
KE = 1.5 kT
Gas Structure
Gas molecules are rapidly
moving in random straight
lines and free from sticking
to each other.
Explaining the Properties of Solids
the particles in a solid are packed close
together and are fixed in position
though they may vibrate
the close packing of the particles results in
solids being incompressible
the inability of the particles to move around
results in solids retaining their shape and
volume when placed in a new container; and
prevents the particles from flowing
Solids
some solids have their particles
arranged in an orderly geometric
pattern we call these crystalline
solids
salt and diamonds
other solids have particles that do not
show a regular geometric pattern over
a long range we call these
amorphous solids
plastic and glass
Explaining the Properties of Liquids
they have higher densities than gases
because the molecules are in close contact
they have an indefinite shape because the
limited freedom of the molecules allows
them to move around enough to get to the
container walls
but they have a definite volume because
the limit on their freedom keeps them
from escaping the rest of the molecules

Compressibility
Phase Changes
Why are molecules attracted to
each other?
intermolecular attractions are due to attractive forces between
opposite charges
+ ion to - ion
+ end of polar molecule to - end of polar molecule
H-bonding especially strong
even nonpolar molecules will have temporary charges
larger the charge = stronger attraction
longer the distance = weaker attraction
however, these attractive forces are small relative to the
bonding forces between atoms
generally smaller charges
generally over much larger distances
Trends in the Strength of
Intermolecular Attraction?
the stronger the attractions between the atoms or
molecules, the more energy it will take to separate
them
boiling a liquid requires we add enough energy to
overcome the attractions between the molecules or
atoms
the higher the normal boiling point of the liquid, the
stronger the intermolecular attractive forces
Attractive Forces
+ - + -
+ - + -
+
+
+
+
_
_
_
_
+
+
+ + +
+
+
-
-
- - -
-
-
+
+
+
+
+
-
-
-
-
-
Dispersion Forces
fluctuations in the electron distribution in atoms and
molecules result in a temporary dipole
region with excess electron density has partial () charge
region with depleted electron density has partial (+) charge
the attractive forces caused by these temporary dipoles
are called dispersion forces
aka London Forces
all molecules and atoms will have them
as a temporary dipole is established in one molecule, it
induces a dipole in all the surrounding molecules
Dispersion Force
Size of the Induced Dipole
the magnitude of the induced dipole depends on
several factors
polarizability of the electrons
volume of the electron cloud
larger molar mass = more electrons = larger
electron cloud = increased polarizability =
stronger attractions
shape of the molecule
more surface-to-surface contact = larger
induced dipole = stronger attraction
Effect of Molecular Size
on Size of Dispersion Force
Noble Gases are all
nonpolar atomic
elements.
As the molar mass
increases, the number
of electrons increase.
Therefore the strength
of the dispersion
forces increases.
The stronger the
attractive forces
between the molecules,
the higher the boiling
point will be.
Relationship between Induced Dipole and Molecular Size
-300
-250
-200
-150
-100
-50
0
50
100
150
200
250
1 2 3 4 5 6
Period
B
o
i
l
i
n
g

P
o
i
n
t
,

C
BP, Noble Gas
BP, Halogens
BP, XH4
Name Molar Mass BP, C MP, C Density, g/mL
Methane 16 -162 -183 0.47
Ethane 30 -89 -183 0.57
Propane 44 -42 -188 0.5
Butane 58 0 -138 0.58
Pentane 72 36 -130 0.56
Hexane 86 69 -95 0.66
Heptane 100 98 -91 0.68
Octane 114 126 -57 0.7
Nonane 128 151 -54 0.72
Decane 142 174 -30 0.74
Undecane 156 196 -26 0.75
Dodecane 170 216 -10 0.76
Tridecane 184 235 -5 0.76
Tetradecane 198 254 6 0.77
Pentadecane 212 271 10 0.79
Hexadecane 226 287 18 0.77
Properties of Straight Chain Alkanes
Non-Polar Molecules
Boiling Points of n-Alkanes
n-Alkane Boiling & Melting Points
-300
-200
-100
0
100
200
300
400
500
0 100 200 300 400 500
Molar Mass
T
e
m
p
e
r
a
t
u
r
e
,

C
BP, n-alkane
MP, n-alkane
Effect of Molecular Shape
on Size of Dispersion Force
Alkane Boiling Points
-20
0
20
40
60
80
100
120
140
58 72 86 100 114
Mol ar Mass
T
e
m
p
e
r
a
t
u
r
e
,

C
n-alkanes
iso-alkanes
Alkane Boiling Points
branched chains
have lower BPs
than straight
chains
the straight chain
isomers have
more surface-to-
surface contact
Practice Choose the Substance in Each Pair with
the Highest Boiling Point
a) CH
4
CH
3
CH
2
CH
2
CH
3
b) CH
3
CH
2
CH=CHCH
2
CH
3
cyclohexane
C
C
C
C
H
H H
H H
H H
H
H
H
C
H
H
H
H
C
C
C
C
H
H
H
H
H
H
C
C
H
H H
H
H
H
H
H
H
H
H
H
C
C
H
H
H
C
C
H
C
H
H
C
a) CH
4
CH
3
CH
2
CH
2
CH
3
b) CH
3
CH
2
CH=CHCH
2
CH
3
cyclohexane
both molecules
are nonpolar
larger molar
mass
both molecules are
nonpolar
flat molecule larger
surface-to-surface
contact
C
C
C
C
H
H H
H H
H H
H
H
H
C
H
H
H
H
C
C
C
C
H
H
H
H
H
H
C
C
H
H H
H
H
H
H
H
H
H
H
H
C
C
H
H
H
C
C
H
C
H
H
C
Dipole-Dipole Attractions
polar molecules have a permanent dipole
because of bond polarity and shape
dipole moment
as well as the always present induced dipole
the permanent dipole adds to the attractive forces
between the molecules
raising the boiling and melting points relative to nonpolar
molecules of similar size and shape
Effect of Dipole-Dipole Attraction on
Boiling and Melting Points
30
Molar
Mass
Boiling
Point
Dipole
Size
CH
3
CH
2
CH
3
44.09 -42C 0.08 D
CH
3
-O-CH
3
46.07 -24C 1.30 D
CH
3
- CH=O 44.05 20.2C 2.69 D
CH
3
-CN
41.05 81.6C 3.92 D

or
a) CH
2
FCH
2
F CH
3
CHF
2
b)
C C
H
H
H
H
F
F
C C
H
H
H
F
H
F
or
more polar
polar
nonpolar
a) CH
2
FCH
2
F CH
3
CHF
2
b)
C C
H
H
H
H
F
F
C C
H
H
H
F
H
F
Attractive Forces and Solubility
Solubility depends on the attractive forces of solute
and solvent molecules
Like dissolves Like
miscible liquids will always dissolve in each other
polar substance dissolve in polar solvents
hydrophilic groups = OH, CHO, C=O, COOH, NH
2
,
Cl
nonpolar molecules dissolve in nonpolar solvents
hydrophobic groups = C-H, C-C
Many molecules have both hydrophilic and
hydrophobic parts - solubility becomes competition
between parts
Immiscible Liquids
Polar Solvents
Water
Dichloromethane
(methylene chloride)
Ethanol
(ethyl alcohol)
Nonpolar Solvents
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
n-hexane
C H
C H
C
H
CH
CH
C
CH
3
toluene
C
Cl
Cl
Cl
Cl
carbon tetrachloride
Hydrogen Bonding
When a very electronegative atom is bonded to
hydrogen, it strongly pulls the bonding electrons
toward it
O-H, N-H, or F-H
Since hydrogen has no other electrons, when it
loses the electrons, the nucleus becomes
deshielded
exposing the H proton
The exposed proton acts as a very strong center
of positive charge, attracting all the electron
clouds from neighboring molecules
H-Bonding
HF
H-Bonding in Water
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

P
o
i
n
t
,

C
BP, HX
BP, H2X
BP, H3X
BP, XH4
CH
4
NH
3
HF
H
2
O
SiH
4
GeH
4
SnH
4
H
2
S
H
2
Se
H
2
Te
Practice Choose the substance in each pair that
is a liquid at room temperature (the other is a gas)
a) CH
3
OH CH
3
CHF
2
b) CH
3
-O-CH
2
CH
3
CH
3
CH
2
CH
2
NH
2

is a liquid at room temperature (the other is a gas)
a) CH
3
OH CH
3
CHF
2
b) CH
3
-O-CH
2
CH
3
CH
3
CH
2
CH
2
NH
2

can H-bond
can H-bond
is more soluble in water
a) CH
3
OH CH
3
CHF
2
b) CH
3
CH
2
CH
2
CH
3
CH
3
Cl
is more soluble in water
a) CH
3
OH CH
3
CHF
2
b) CH
3
CH
2
CH
2
CH
3
CH
3
Cl
can H-bond with H
2
O
more polar
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
Summary
Dispersion forces are the weakest of the
intermolecular attractions.
Dispersion forces are present in all molecules
and atoms.
The magnitude of the dispersion forces
increases with molar mass
Polar molecules also have dipole-dipole
attractive forces
Summary (contd)
Hydrogen bonds are the strongest of the intermolecular
attractive forces
a pure substance can have
Hydrogen bonds will be present when a molecule has
H directly bonded to either O , N, or F atoms
only example of H bonded to F is HF
Ion-dipole attractions are present in mixtures of ionic
compounds with polar molecules.
Ion-dipole attractions are the strongest intermolecular
attraction
Ion-dipole attractions are especially important in
aqueous solutions of ionic compounds
Liquids
properties &
structure
50
Surface Tension
surface tension is a property of liquids that results from
the tendency of liquids to minimize their surface area
in order to minimize their surface area, liquids form
drops that are spherical
as long as there is no gravity
the layer of molecules on the surface behave differently
than the interior
because the cohesive forces on the surface molecules have a
net pull into the liquid interior
the surface layer acts like an elastic skin
Surface Tension
because they have fewer neighbors
to attract them, the surface
molecules are less stable than those
in the interior
have a higher potential energy
the surface tension of a liquid is the
energy required to increase the
surface area a given amount
at room temp, surface tension of H
2
O
= 72.8 mJ/m
2

Factors Affecting Surface Tension
the stronger the intermolecular attractive forces,
the higher the surface tension will be
raising the temperature of a liquid reduces its
surface tension
raising the temperature of the liquid increases the
average kinetic energy of the molecules
the increased molecular motion makes it easier to
stretch the surface
Surface Tension of Water vs. Temperature
50
55
60
65
70
75
80
-20 0 20 40 60 80 100 120
Temperature, C
S
u
r
f
a
c
e

T
e
n
s
i
o
n
,

m
J
/
m
2
Viscosity
viscosity is the resistance of a liquid to flow
1 poise = 1 P = 1 g/cms
often given in centipoise, cP
larger intermolecular attractions = larger viscosity
higher temperature = lower viscosity
Viscosity of Water vs. Temperature
0
0.2
0.4
0.6
0.8
1
1.2
0 20 40 60 80 100 120
Temperature, deg C
V
i
s
c
o
s
i
t
y
,

c
P
Capillary Action
capillary action is the ability of a liquid to
flow up a thin tube against the influence of
gravity
the narrower the tube, the higher the liquid rises
capillary action is the result of the two forces
working in conjunction, the cohesive and
adhesive forces
cohesive forces attract the molecules together
adhesive forces attract the molecules on the edge
to the tubes surface
Capillary Action
the adhesive forces pull the surface liquid up the
side of the tube, while the cohesive forces pull
the interior liquid with it
the liquid rises up the tube until the force of
gravity counteracts the capillary action forces

Meniscus
the curving of the liquid surface in a thin
tube is due to the competition between
adhesive and cohesive forces
the meniscus of water is concave in a
glass tube because its adhesion to the
glass is stronger than its cohesion for
itself
the meniscus of mercury is convex in a
glass tube because its cohesion for itself
is stronger than its adhesion for the glass
metallic bonds stronger than intermolecular
attractions
Vaporization
molecules in the liquid are constantly
in motion
the average kinetic energy is
proportional to the temperature
however, some molecules have more
kinetic energy than the average
if these molecules are at the surface,
they may have enough energy to
overcome the attractive forces
therefore the larger the surface area,
the faster the rate of evaporation
this will allow them to escape the
liquid and become a vapor
Distribution of Thermal Energy
only a small fraction of the molecules in a liquid have enough
energy to escape
but, as the temperature increases, the fraction of the molecules
with escape energy increases
the higher the temperature, the faster the rate of evaporation
Condensation
some molecules of the vapor will lose energy
through molecular collisions
the result will be that some of the molecules will
get captured back into the liquid when they
collide with it
also some may stick and gather together to form
droplets of liquid
particularly on surrounding surfaces
we call this process condensation
Evaporation vs. Condensation
vaporization and condensation are opposite processes
in an open container, the vapor molecules generally
spread out faster than they can condense
the net result is that the rate of vaporization is greater
than the rate of condensation, and there is a net loss of
liquid
however, in a closed container, the vapor is not allowed
to spread out indefinitely
the net result in a closed container is that at some time
the rates of vaporization and condensation will be equal
Effect of Intermolecular Attraction on
Evaporation and Condensation
the weaker the attractive forces between molecules, the
less energy they will need to vaporize
also, weaker attractive forces means that more energy
will need to be removed from the vapor molecules
before they can condense
the net result will be more molecules in the vapor
phase, and a liquid that evaporates faster the weaker
the attractive forces, the faster the rate of
evaporation
liquids that evaporate easily are said to be volatile
e.g., gasoline, fingernail polish remover
liquids that do not evaporate easily are called nonvolatile
e.g., motor oil
Energetics of Vaporization
when the high energy molecules are lost from
the liquid, it lowers the average kinetic energy
if energy is not drawn back into the liquid, its
temperature will decrease therefore,
vaporization is an endothermic process
and condensation is an exothermic process
vaporization requires input of energy to
overcome the attractions between molecules
Heat of Vaporization
the amount of heat energy required to vaporize one mole
of the liquid is called the Heat of Vaporization, AH
vap

sometimes called the enthalpy of vaporization
always endothermic, therefore AH
vap
is +
somewhat temperature dependent
- AH
condensation
= -AH
vaporization

Example 11.3 Calculate the mass of water that
can be vaporized with 155 kJ of heat at 100C
since the given amount of heat is almost 4x the AH
vap
,
the amount of water makes sense

1 mol H
2
O = 40.7 kJ, 1 mol = 18.02 g

155 kJ
g H
2
O
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
kJ 40.7
mol 1
O H g 8.6 6
mol 1
g 8.02 1
kJ 40.7
O H mol 1
kJ 55 1
2
2
=
kJ mol H
2
O g H
2
O
mol 1
g 02 . 18
Dynamic Equilibrium
in a closed container, once the rates of vaporization and
condensation are equal, the total amount of vapor and
liquid will not change
evaporation and condensation are still occurring, but
because they are opposite processes, there is no net
gain or loss or either vapor or liquid
when two opposite processes reach the same rate so
that there is no gain or loss of material, we call it a
dynamic equilibrium
this does not mean there are equal amounts of vapor and
liquid it means that they are changing by equal amounts
Dynamic Equilibrium
Vapor Pressure
the pressure exerted by the vapor when it is in dynamic
equilibrium with its liquid is called the vapor pressure
remember using Daltons Law of Partial Pressures to account
for the pressure of the water vapor when collecting gases by
water displacement?
the weaker the attractive forces between the molecules,
the more molecules will be in the vapor
therefore, the weaker the attractive forces, the
higher the vapor pressure
the higher the vapor pressure, the more volatile the liquid
Vapor-Liquid Dynamic Equilibrium
if the volume of the chamber is increased, that will decrease the
pressure of the vapor inside
at that point, there are fewer vapor molecules in a given volume, causing
the rate of condensation to slow
eventually enough liquid evaporates so that the rates of the
condensation increases to the point where it is once again as fast
as evaporation
equilibrium is reestablished
at this point, the vapor pressure will be the same as it was before
Dynamic Equilibrium
a system in dynamic equilibrium can respond to
changes in the conditions
when conditions change, the system shifts its
position to relieve or reduce the effects of the
change
Vapor Pressure vs. Temperature
increasing the temperature increases the number
of molecules able to escape the liquid
the net result is that as the temperature
increases, the vapor pressure increases
small changes in temperature can make big
changes in vapor pressure
the rate of growth depends on strength of the
intermolecular forces
Vapor Pressure Curves
Temperature vs Vapor Pressure
0
100
200
300
400
500
600
700
800
900
1000
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Temperature, C
V
a
p
o
r

P
r
e
s
s
u
r
e
,

m
m
H
g
water
TiCl4
chlorof orm
ether
ethanol
acetone
760 mmHg
normal BP
100C
BP Ethanol at 500 mmHg
68.1C
Boiling Point
when the temperature of a liquid reaches a point
where its vapor pressure is the same as the
external pressure, vapor bubbles can form
anywhere in the liquid
not just on the surface
this phenomenon is what is called boiling and
the temperature required to have the vapor
pressure = external pressure is the boiling point
Boiling Point
the normal boiling point is the temperature at
which the vapor pressure of the liquid = 1 atm
the lower the external pressure, the lower the boiling
point of the liquid
Heating Curve of a Liquid
as you heat a liquid, its
temperature increases
linearly until it reaches the
boiling point
q = mass x C
s
x AT
once the temperature
reaches the boiling point, all
the added heat goes into
boiling the liquid the
temperature stays constant
once all the liquid has been
turned into gas, the
temperature can again start
to rise
Clausius-Clapeyron Equation
the graph of vapor pressure vs. temperature is an
exponential growth curve
RT
H
vap
vap
P
A
- = e |
the logarithm of the vapor pressure vs.
inverse absolute temperature is a linear function
) ( ln
T
1
R
H
) ln(P
RT
H
) ( ln ) ln(P
ln ) ( ln ) ln(P
ln ) ln(P
vap
vap
vap
vap
RT
H
vap
RT
H
vap
vap
vap
|
|
|
|
+
|
|
.
|
\
|
A
=
|
|
.
|
\
|
A
+ =
|
|
.
|
\
|
+ =
|
|
.
|
\
|
- =
A
A
e
e
the slope of the line x 8.314 J/molK = AH
vap
in J/mol
Example 11.4 Determine the AH
vap
of
dichloromethane given the vapor pressure vs.
temperature data
enter the data into a spreadsheet and calculate the
inverse of the absolute temperature and natural log of
the vapor pressure
Temperature,
K
Vapor Pressure,
torr
Inverse Temperature,
K
-1

ln(Vapor
Pressure)
200 0.8 0.00500 -0.2
220 4.5 0.00455 1.5
240 21 0.00417 3.0
260 71 0.00385 4.3
280 197 0.00357 5.3
300 391 0.00333 6.0
79
vap
of
temperature data
graph the inverse of the absolute temperature vs. the
natural log of the vapor pressure
Clausius-Clapeyron Plot for Dichloromethane
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
Inv. Temperature K
-1
l
n
(
v
a
p
o
r

p
r
e
s
s
u
r
e
)
80
vap
of
temperature data
add a trendline, making sure the display equation on
chart option is checked off
y = -3776.7x + 18.719
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
Inv. Temperature K
-1
l
n
(
v
a
p
o
r

p
r
e
s
s
u
r
e
)
81
vap
of
temperature data
determine the slope of the line
-3776.7 3800 K
y = -3776.7x + 18.719
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
Inv. Temperature K
-1
l
n
(
v
a
p
o
r

p
r
e
s
s
u
r
e
)
82
vap
of
temperature data
use the slope of the line to determine the heat of
vaporization
-3776.7 3800 K
mol
kJ
mol
J 4
vap
K mol
J
vap
vap
6 . 31 10 16 . 3 H
314 . 8
H -
K 3800
R
H -
slope
= = A
A
=
A
=
-
Clausius-Clapeyron Equation
2-Point Form
the equation below can be used with just two measurements of
vapor pressure and temperature
however, it generally gives less accurate results
fewer data points will not give as accurate an average because there is less
averaging out of the errors
as with any other sets of measurements
can also be used to predict the vapor pressure if you know the
heat of vaporization and the normal boiling point
remember: the vapor pressure at the normal boiling point is 760 torr
|
|
.
|
\
|

A
=
|
|
.
|
\
|
1 2
vap
1
2
T
1
T
1
R
H
P
P
ln
K 2 . 285 15 . 273 0 . 12 T
K 8 . 337 15 . 273 6 . 64 T
2
1
= + =
= + =
|
.
|
\
|

=
|
|
.
|
\
|
-
K 337.8
1
K 285.2
1
8.314
10 2 . 35
P
P
ln
K mol
J
mol
J 3
1
2
Example 11.5 Calculate the vapor pressure of
methanol at 12.0C
the units are correct, the size makes sense since the
vapor pressure is lower at lower temperatures
T
1
= BP = 64.6C, P
1
= 760 torr, AH
vap
= 35.2 kJ/mol,
T
2
= 12.0C
P
2
, torr
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
P
1
, T
1
, AH
vap
P
2

|
|
.
|
\
|

A
=
|
|
.
|
\
|
1 2
vap
1
2
T
1
T
1
R
H
P
P
ln
T(K) = T(C) + 273.15
T
1
= BP = 337.8 K, P
1
= 760 torr, AH
vap
= 35.2 kJ/mol,
T
2
= 285.2 K
P
2
, torr
|
|
.
|
\
|

A
=
|
|
.
|
\
|
1 2
vap
1
2
T
1
T
1
R
H
P
P
ln
torr 4 . 75 P
0993 . 0
torr 760
P
2
31 . 2
2
=
= =

e
31 . 2
P
P
ln
1
2
=
|
|
.
|
\
|
Supercritical Fluid
as a liquid is heated in a sealed container, more vapor collects
causing the pressure inside the container to rise
and the density of the vapor to increase
and the density of the liquid to decrease
at some temperature, the meniscus between the liquid and vapor
disappears and the states commingle to form a supercritical
fluid
supercritical fluid have properties of both gas and liquid states
The Critical Point
the temperature required to produce a
supercritical fluid is called the critical
temperature
the pressure at the critical temperature is called
the critical pressure
at the critical temperature or higher
temperatures, the gas cannot be condensed to a
liquid, no matter how high the pressure gets
Sublimation and Deposition
molecules in the solid have thermal energy that allows
them to vibrate
surface molecules with sufficient energy may break
free from the surface and become a gas this process is
called sublimation
the capturing of vapor molecules into a solid is called
deposition
the solid and vapor phases exist in dynamic equilibrium
in a closed container
at temperatures below the melting point
therefore, molecular solids have a vapor pressure
solid gas
sublimation
deposition
Sublimation
Melting = Fusion
as a solid is heated, its temperature rises and the
molecules vibrate more vigorously
once the temperature reaches the melting point,
the molecules have sufficient energy to
overcome some of the attractions that hold them
in position and the solid melts (or fuses)
the opposite of melting is freezing

Heating Curve of a Solid
as you heat a solid, its
temperature increases linearly
until it reaches the melting point
q = mass x C
s
x AT
once the temperature reaches the
melting point, all the added heat
goes into melting the solid the
temperature stays constant
once all the solid has been turned
into liquid, the temperature can
again start to rise
ice/water will always have a
temperature of 0C
at 1 atm
Energetics of Melting
when the high energy molecules are lost from
the solid, it lowers the average kinetic energy
if energy is not drawn back into the solid its
temperature will decrease therefore, melting
is an endothermic process
and freezing is an exothermic process
melting requires input of energy to overcome
the attractions between molecules
92
Heat of Fusion
the amount of heat energy required to melt one mole of the solid is
called the Heat of Fusion, AH
fus

sometimes called the enthalpy of fusion
always endothermic, therefore AH
fus
is +
somewhat temperature dependent
- AH
crystallization
= -AH
fusion
- generally much less than AH
vap

- AH
sublimation
= AH
fusion
+ AH
vaporization

Heats of Fusion and Vaporization
94
Heating Curve of Water
Segment 1
heating 1.00 mole of ice at -25.0C up to the melting
point, 0.0C
q = mass x C
s
x AT
mass of 1.00 mole of ice = 18.0 g
C
s
= 2.09 J/molC
( ) ( ) ( ) ( )
kJ 0.941 J 941
C 25.0 C 0.0 09 . 2 g 0 . 18
C g
J
= =
=
-
q
q
Segment 2
melting 1.00 mole of ice at the melting point, 0.0C
q = nAH
fus

n = 1.00 mole of ice
AH
fus
= 6.02 kJ/mol
( ) ( )
kJ 6.02
02 . 6 mol 1.00
mol
kJ
=
=
q
q
Segment 3
heating 1.00 mole of water at 0.0C up to the boiling
point, 100.0C
q = mass x C
s
x AT
mass of 1.00 mole of water = 18.0 g
C
s
= 2.09 J/molC
( ) ( ) ( ) ( )
kJ 52 . 7 J 10 52 . 7
C .0 0 C 100.0 18 . 4 g 0 . 18
3
C g
J
= =
=
-
q
q
Segment 4
boiling 1.00 mole of water at the boiling point, 100.0C
q = nAH
vap

n = 1.00 mole of ice
AH
fus
= 40.7 kJ/mol
( ) ( )
kJ 7 . 0 4
7 . 40 mol 1.00
mol
kJ
=
=
q
q
Segment 5
heating 1.00 mole of steam at 100.0C up to 125.0C
q = mass x C
s
x AT
mass of 1.00 mole of water = 18.0 g
C
s
= 2.01 J/molC
( ) ( ) ( ) ( )
kJ 904 . 0 J 904
C .0 100 C 125.0 01 . 2 g 0 . 18
C g
J
= =
=
-
q
q
Phase Diagrams
describe the different states and state changes that
occur at various temperature - pressure conditions
areas represent states
lines represent state changes
liquid/gas line is vapor pressure curve
both states exist simultaneously
critical point is the furthest point on the vapor pressure
curve
triple point is the temperature/pressure condition
where all three states exist simultaneously
for most substances, freezing point increases as
pressure increases
101
Phase Diagrams
P
r
e
s
s
u
r
e

Temperature
vaporization
condensation
critical
point
triple
point
Solid
Liquid
Gas
1 atm
normal
melting pt.
normal
boiling pt.
Fusion Curve
Vapor Pressure
Curve
Sublimation
Curve
melting
freezing
sublimation
deposition
Phase Diagram of Water
0
5000
10000
15000
20000
25000
-50 0 50 100 150 200 250 300 350 400 450
Temperature, (C)
P
r
e
s
s
u
r
e
,

(
k
P
a
)
104
Phase Diagram of Water
Temperature
P
r
e
s
s
u
r
e

critical
point
374.1C
217.7 atm
triple
point
Ice
Water
Steam
1 atm
normal
boiling pt.
100C
normal
melting pt.
0C
0.01C
0.006 atm
Morphic Forms of Ice
107
Phase Diagram of CO
2
P
r
e
s
s
u
r
e

Temperature
critical
point
31.0C
72.9 atm
triple
point
Solid
Liquid
Gas
1 atm
-56.7C
5.1 atm
normal
sublimation pt.
-78.5C
Water An Extraordinary Substance
water is a liquid at room temperature
most molecular substances with small molar masses are gases at room
temperature
due to H-bonding between molecules
water is an excellent solvent dissolving many ionic and polar
molecular substances
because of its large dipole moment
even many small nonpolar molecules have solubility in water
e.g., O
2
, CO
2

water has a very high specific heat for a molecular substance
moderating effect on coastal climates
water expands when it freezes
at a pressure of 1 atm
about 9%
making ice less dense than liquid water

Solids
properties &
structure
Determining Crystal Structure
crystalline solids have a very regular geometric
arrangement of their particles
the arrangement of the particles and distances between
them is determined by x-ray diffraction
in this technique, a crystal is struck by beams of x-rays,
which then are reflected
the wavelength is adjusted to result in an interference
pattern at which point the wavelength is an integral
multiple of the distances between the particles
X-ray Crystallography
Braggs Law
when the interference between x-rays is constructive,
the distance between the two paths (a) is an integral
multiple of the wavelength
n=2a
the angle of reflection is therefore related to the
distance (d) between two layers of particles
sinu = a/d
combining equations and rearranging we get an
equation called Braggs Law
u
sin 2 -
-
=
n
d
Example 11.6 An x-ray beam at =154 pm striking an
iron crystal results in the angle of reflection u = 32.6.
Assuming n = 1, calculate the distance between layers
the units are correct, the size makes sense since the
iron atom has an atomic radius of 140 pm
n = 1, u = 32.6, = 154 pm
d, pm
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
n, u, d
u
sin 2 -
-
=
n
d
( )( )
( ) ( ) ( )
pm 143
6 . 32 sin 2
pm 154 1
sin 2
=
= =
-
-
u
n
d
Crystal Lattice
when allowed to cool slowly, the particles in a
liquid will arrange themselves to give the
maximum attractive forces
therefore minimize the energy
the result will generally be a crystalline solid
the arrangement of the particles in a crystalline
solid is called the crystal lattice
the smallest unit that shows the pattern of
arrangement for all the particles is called the
unit cell

Unit Cells
unit cells are 3-dimensional,
usually containing 2 or 3 layers of particles
unit cells are repeated over and over to give the macroscopic
crystal structure of the solid
starting anywhere within the crystal results in the same unit cell
each particle in the unit cell is called a lattice point
lattice planes are planes connecting equivalent points in unit
cells throughout the lattice
118
7 Unit Cells
Cubic
a = b = c
all 90
a
b
c
Tetragonal
a = c < b
all 90
a
b
c
Orthorhombic
a = b = c
all 90
a
b
c
Monoclinic
a = b = c
2 faces 90
a
b
c
Hexagonal
a = c < b
2 faces 90
1 face 120
c
a
b
Rhombohedral
a = b = c
no 90
a
b
c
Triclinic
a = b = c
no 90
Unit Cells
the number of other particles each particle is in contact
with is called its coordination number
for ions, it is the number of oppositely charged ions an ion is
in contact with
higher coordination number means more interaction,
therefore stronger attractive forces holding the crystal
together
the packing efficiency is the percentage of volume in
the unit cell occupied by particles
the higher the coordination number, the more efficiently the
particles are packing together

Cubic Unit Cells
all 90 angles between corners of the unit cell
the length of all the edges are equal
if the unit cell is made of spherical particles
of each corner particle is within the cube
of each particle on a face is within the cube
of each particle on an edge is within the cube
( )
3
3

3
4
Sphere a of Volume
length edge Cube a of Volume
r = -
= -
Simple Cubic
Cubic Unit Cells -
Simple Cubic
8 particles, one at each corner
of a cube
1/8
th
of each particle lies in the
unit cell
each particle part of 8 cells
1 particle in each unit cell
8 corners x 1/8
edge of unit cell = twice the
radius
coordination number of 6
2r
Body-Centered Cubic
Cubic Unit Cells -
Body-Centered Cubic
9 particles, one at each corner of
a cube + one in center
1/8
th
of each corner particle lies
in the unit cell
2 particles in each unit cell
8 corners x 1/8 + 1 center
edge of unit cell = (4/\ 3) times
the radius of the particle
3
4r
Face-Centered Cubic
Cubic Unit Cells -
Face-Centered Cubic
14 particles, one at each corner of a
cube + one in center of each face
1/8
th
of each corner particle + 1/2
of face particle lies in the unit cell
4 particles in each unit cell
8 corners x 1/8 + 6 faces x 1/2
edge of unit cell = 2\ 2 times the
radius of the particle
2 2r
fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 10
23
atoms
cm 10 43 . 1
m 10
cm 1
pm 1
m 10
pm 43 1
8
2 -
-12
=
g 10 792 . 1
mol 1
g 982 . 26
atoms 10 6.022
mol 1
Al atoms 4
22
23

=
Example 11.7 Calculate the density of Al if it

crystallizes in a fcc and has a radius of 143 pm
the accepted density of Al at 20C is 2.71 g/cm
3
, so the
answer makes sense
face-centered cubic, r = 143 pm
density, g/cm
3

Check:
Solution:
Concept
Plan:

Relation-
ships:
Given:
Find:
1 cm = 10
2
m, 1 pm = 10
-12
m
l r V mass fcc
d m, V
# atoms x mass 1 atom
V = l
3
, l = 2r2, d = m/V
d = m/V
l = 2r2 V = l
3

face-centered cubic, r = 1.43 x 10
-8
cm, m = 1.792 x 10
-22
g
density, g/cm
3
cm 10 5 4 4.0 cm)(1.414) 10 43 . 1 ( 2 2 2
-8 8
= = =

r l
( )
3 23
3
8 3
cm 10 618 . 6
cm 10 045 . 4
=
= = l V
3
cm
g
3 23
22
71 . 2
cm 10 618 . 6
g 10 792 . 1
=

= =

V
m
d
Closest-Packed Structures
First Layer
with spheres, it is more efficient to offset each
row in the gaps of the previous row than to line-
up rows and columns
Second Layer
the second layer atoms can sit directly over the
atoms in the first called an AA pattern
or the second layer can sit over the holes in the
first called an AB pattern
Third Layer with Offset 2
nd
Layer
the third layer atoms can align directly over the
atoms in the first called an ABA pattern
or the third layer can sit over the uncovered
holes in the first called an ABC pattern
Hexagonal Closest-Packed
Cubic Closest-Packed
Face-Centered Cubic
Hexagonal Closest-Packed Structures
Cubic Closest-Packed Structures
Classifying Crystalline Solids
classified by the kinds of units found
sub-classified by the kinds of attractive forces holding
the units together
molecular solids are solids whose composite units are
molecules
ionic solids are solids whose composite units are ions
atomic solids are solids whose composite units are
atoms
nonbonding atomic solids are held together by dispersion
forces
metallic atomic solids are held together by metallic bonds
network covalent atomic solids are held together by
covalent bonds
Molecular Solids
the lattice site are occupied by molecules
the molecules are held together by
intermolecular attractive forces
dispersion forces, dipole attractions, and H-bonds
because the attractive forces are weak, they tend
to have low melting point
generally < 300C
Ionic Solids
Attractive Forces
held together by attractions between opposite charges
nondirectional
therefore every cation attracts all anions around it, and vice versa
the coordination number represents the number of close cation-
anion interactions in the crystal
the higher the coordination number, the more stable the solid
lowers the potential energy of the solid
the coordination number depends on the relative sizes of the
cations and anions
generally, anions are larger than cations
the number of anions that can surround the cation limited by the size of
the cation
the closer in size the ions are, the higher the coordination number is
Ionic Crystals
CsCl
coordination number = 8
Cs
+
= 167 pm
Cl
= 181 pm
NaCl
Na
+
= 97 pm
Cl
= 181 pm
Lattice Holes
Simple Cubic
Hole
Octahedral
Hole
Tetrahedral
Hole
Lattice Holes
in hexagonal closest packed or cubic closest
packed lattices there are 8 tetrahedral holes
and 4 octahedral holes per unit cell
in simple cubic there is 1 hole per unit cell
number and type of holes occupied
determines formula (empirical) of salt
= Octahedral
= Tetrahedral
Cesium Chloride Structures
of each Cl

(184 pm) inside
the unit cell
whole Cs
+
(167 pm) inside the
unit cell
cubic hole = hole in simple cubic
arrangement of Cl
ions

Cs:Cl = 1: (8 x ), therefore the
formula is CsCl
Rock Salt Structures
Cl
ions (181 pm) in a face-centered

cubic arrangement
of each corner Cl

inside the unit cell
of each face Cl

each Na
+
(97 pm) in holes between Cl

octahedral holes
1 in center of unit cell
of each edge Na
+
Na:Cl = ( x 12) + 1: ( x 8) + ( x 6)
= 4:4 = 1:1,
therefore the formula is NaCl
Zinc Blende Structures
S
2
cubic arrangement
of each corner S
2
of each face S
2
each Zn
2+
(74 pm) in holes between S
2

tetrahedral holes
1 whole in the holes
Zn:S = (4 x 1) : ( x 8) + ( x 6) = 4:4
= 1:1,
therefore the formula is ZnS
Fluorite Structures
Ca
2+
cubic arrangement
of each corner Ca
2+
of each face Ca
2+
each F
(133 pm) in holes between Ca

2+

tetrahedral holes
1 whole in all the holes
Ca:F = ( x 8) + ( x 6): (8 x 1) = 4:8
= 1:2,
therefore the formula is CaF
2

fluorite structure common for 1:2 ratio
usually get the antifluorite structure
when the cation:anion ratio is 2:1
the anions occupy the lattice sites and the
cations occupy the tetrahedral holes
Nonbonding Atomic Solids
noble gases in solid form
solid held together by weak dispersion forces
very low melting
tend to arrange atoms in closest-packed
structure
either hexagonal cp or cubic cp
maximizes attractive forces and minimizes energy
Metallic Atomic Solids
solid held together by metallic bonds
strength varies with sizes and charges of cations
coulombic attractions
melting point varies
mostly closest packed arrangements of the
lattice points
cations

Metallic Structure
Metallic Bonding
metal atoms release their valence electrons
metal cation islands fixed in a sea of
mobile electrons
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
+ + + + + + + + +
+ + + + + + + + +
+ + + + + + + + +
Crystal Structure of Metals at Room Temperature
= body-centered cubic
= hexagonal closest
packed
= other
= cubic cp, face-centered
= diamond
Network Covalent Solids
atoms attached to its nearest neighbors by covalent
bonds
because of the directionality of the covalent bonds,
these do not tend to form closest-packed arrangements
in the crystal
because of the strength of the covalent bonds, these
have very high melting points
generally > 1000C
dimensionality of the network affects other physical
properties
The Diamond Structure:
a 3-Dimensional Network
the carbon atoms in a diamond each have 4
covalent bonds to surrounding atoms
sp
3

tetrahedral geometry
this effectively makes each crystal one giant
molecule held together by covalent bonds
you can follow a path of covalent bonds from any
atom to every other atom
Properties of Diamond
very high melting, ~3800C
need to overcome some covalent bonds
very rigid
due to the directionality of the covalent bonds
very hard
due to the strong covalent bonds holding the
atoms in position
used as abrasives
electrical insulator
thermal conductor
best known
chemically very nonreactive
The Graphite Structure:
a 2-Dimensional Network
in graphite, the carbon atoms in a sheet are covalently
bonded together
forming 6-member flat rings fused together
similar to benzene
bond length = 142 pm
sp
2

each C has 3 sigma and 1 pi bond
trigonal-planar geometry
each sheet a giant molecule
the sheets are then stacked and held together by
dispersion forces
sheets are 341 pm apart
Properties of Graphite
hexagonal crystals
high melting, ~3800C
need to overcome some covalent bonding
slippery feel
because there are only dispersion forces holding
the sheets together, they can slide past each other
glide planes
lubricants
electrical conductor
parallel to sheets
thermal insulator
chemically very nonreactive
Silicates
~90% of earths crust
extended arrays of SiO
sometimes with Al substituted for Si aluminosilicates
glass is the amorphous form

Quartz
3-dimensional array of Si covalently bonded to 4 O
tetrahedral
melts at ~1600C
very hard
Micas
minerals that are mainly 2-dimensional arrays of
Si bonded to O
hexagonal arrangement of atoms
sheets
chemically stable
thermal and electrical insulator
Band Theory
the structures of metals and covalent network
solids result in every atoms orbitals being
shared by the entire structure
for large numbers of atoms, this results in a
large number of molecular orbitals that have
approximately the same energy, we call this an
energy band
Band Theory
when 2 atomic orbitals combine they produce
both a bonding and an antibonding molecular
orbital
when many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals
the band of bonding molecular orbitals is called
the valence band
the band of antibonding molecular orbitals is
called the conduction band
Molecular orbitals of polylithium
Band Gap
at absolute zero, all the electrons will occupy the
valence band
as the temperature rises, some of the electrons
may acquire enough energy to jump to the
conduction band
the difference in energy between the valence
band and conduction band is called the band gap
the larger the band gap, the fewer electrons there are
with enough energy to make the jump
Types of Band Gaps and
Conductivity
Band Gap and Conductivity
the more electrons at any one time that a substance has in the
conduction band, the better conductor of electricity it is
if the band gap is ~0, then the electrons will be almost as likely
to be in the conduction band as the valence band and the
material will be a conductor
metals
the conductivity of a metal decreases with temperature
if the band gap is small, then a significant number of the
electrons will be in the conduction band at normal temperatures
and the material will be a semiconductor
graphite
the conductivity of a semiconductor increases with temperature
if the band gap is large, then effectively no electrons will be in
the conduction band at normal temperatures and the material
will be an insulator
Doping Semiconductors
doping is adding impurities to the semiconductors
crystal to increase its conductivity
goal is to increase the number of electrons in the
conduction band
n-type semiconductors do not have enough electrons
themselves to add to the conduction band, so they are
doped by adding electron rich impurities
p-type semiconductors are doped with an electron
deficient impurity, resulting in electron holes in the
valence band. Electrons can jump between these holes
in the valence band, allowing conduction of electricity
Diodes
when a p-type semiconductor adjoins an n-type
semiconductor, the result is an p-n junction
electricity can flow across the p-n junction in
only one direction this is called a diode
this also allows the accumulation of electrical
energy called an amplifier

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Chapter 11

Example 11.7 Calculate the density of Al if it

ions (181 pm) in a face-centered

(133 pm) in holes between Ca

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