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Chapter 11

States of Matter:
Gases, Liquids and Solids
Chem 108, Spring, 2013 Chapter 11
Gases are compressible fluids.
-Fill out the container they occupy.
Liquids are relatively incompressible fluids.
-Fill out the lower part of the container they occupy.
Solids are nearly incompressible and rigid.
-Retain their shape regardless of container.
Gases, Liquids and Solids
Kinetic Molecular Theory
At constant pressure, the state of matter
depends largely on two competing factors
the amount of thermal energy the particles
possess, making the particles move apart from
one another
the strength of attraction between the particles,
making the particles condense
(thermal energy related to kinetic energy of a gas:
KE = (3/2)RT for ideal gas)
Chem 108, Spring, 2013 Chapter 11
Kinetic Molecular Theory
These two factors are in competition with one
another
Low temperature: thermal energy low compared
to attraction matter is in condensed state (liquid
or solid)
High temperature: thermal energy high compared
to attraction matter is in gaseous state

Chem 108, Spring, 2013 Chapter 11
States and Degrees of Freedom
The molecules in a gaseous state have
complete freedom of motion
thermal energy overcomes the attractive forces
between molecules
The molecules in a solid state are locked in
place
molecules dont have enough thermal energy to
overcome the attractive forces
Chem 108, Spring, 2013 Chapter 11
States and Degrees of Freedom
The molecules in a liquid state have limited
freedom
they have enough kinetic energy to overcome
some of the attractive forces, but not enough to
escape each other and form a gas
Chem 108, Spring, 2013 Chapter 11
Phase Changes
Increasing thermal energy (i.e., heating) of a
substance can cause a change of state
Decreasing thermal energy (i.e., cooling) of a
substance can cause a change of state
Six possible phase changes:
Chem 108, Spring, 2013 Chapter 11
Chem 108, Spring, 2013 Chapter 11
Phase changes
Phase Changes
Effect of pressure opposite effect of
temperature
increase pressure, more intermolecular
interactions, more likely to condense
increase pressure can induce phase changes:
freezing, condensation, deposition
decrease pressure can induce phase changes:
melting (fusion), vaporization, sublimation
notable exception: water
Chem 108, Spring, 2013 Chapter 11
Chem 108, Spring, 2013 Chapter 11
Phase Changes
Intermolecular Forces
Intermolecular forces are electrostatic, and
are described by Coulombs Law:



q
1
and q
2
are charges, r is distance between
charges
Opposite charges attract, like charges repel
Chem 108, Spring, 2013 Chapter 11
2
2 1 2 1
4
1

4
1
r
q q
F
r
q q
E
o o
tcc tcc
= =
Intermolecular Forces
Molecules can have more or fewer electrons
than protons
more electrons: anions
fewer electrons: cations
Molecules can also have partial charges
electronegativity difference between two atoms of
a bond
Opposite charges on molecules will give
attractive intermolecular force
Chem 108, Spring, 2013 Chapter 11
Intermolecular Forces
Example: H
2
CO (formaldehyde)
electronegativity difference (O = 3.44, C = 2.55, H:
2.20)
polar bonds; partial charges; polar molecule
(molecule has dipole moment)
partial negative charge on one H
2
CO attracted to
partial positive charge on another H
2
CO molecule
Chem 108, Spring, 2013 Chapter 11
http://en.wikipedia.org/wiki/Electronegativity
Intermolecular Forces
CO
2

electronegativity difference ( O = 3.44, C = 2.55)
polar bonds; partial charges; non-polar molecule
(molecule does not have dipole moment)
Chem 108, Spring, 2013 Chapter 11
Intermolecular Forces
Four intermolecular forces
In decreasing strength,

ion-dipole
hydrogen bond
dipole-dipole
London dispersion force
Chem 108, Spring, 2013 Chapter 11
Ion-Dipole Interaction
Cations and anions have full
positive or negative charge
Ionic charges attracted to
partial opposite charge on
another molecule that has a
dipole
Chem 108, Spring, 2013 Chapter 11
Dipole-Dipole Interaction
Interaction of two molecules that have dipole
moments
opposite ends of dipole align
Example: CH
3
COCH
3
(acetone)
Chem 108, Spring, 2013 Chapter 11
Hydrogen Bonding
Dipole-dipole interaction when polar bond is
HO, HF, or HN
Example: water
Chem 108, Spring, 2013 Chapter 11
Hydrogen Bonding
Water, glycerol, methanol have unusually low
vapor pressures and unusually high boiling
points because of hydrogen bonding

London Dispersion Forces
Quantum mechanical effect due to
correlated motion of electrons
Used to explain attractive forces between
non-polar molecules
Qualitative explanation: instantaneous
dipole on one molecule induces dipole on
another molecule
Chem 108, Spring, 2013 Chapter 11
London Dispersion Forces
Chem 108, Spring, 2013 Chapter 11
Ion-Induced Dipole
Dipole-Induced Dipole
Ion or dipole induces a
dipole on an otherwise
nonpolar molecule
Chem 108, Spring, 2013 Chapter 11
http://martine.people.cofc.edu/111Lectweek14.htm
van der Waals Forces
Loosely,
collection of attractive forces that hold molecules
together
or
collection of attractive and repulsive forces
or
dipole-dipole, London dispersion, and hydrogen
bonding forces
or
dipole-dipole, London dispersion
Chem 108, Spring, 2013 Chapter 11
Magnitude of Intermolecular Forces
force energy (kJ/mol)
ion-dipole 40 600
hydrogen bond 4 50
dipole-dipole 5 20
London dispersion 0.1 40
covalent bond 150 1000
ionic bond 500 3000
Chem 108, Spring, 2013 Chapter 11
Identification of Intermolecular Forces
Determine type of molecules (ion, polar, non-polar)
ions and polar molecules?
ion-dipole intermolecular force
ions and non-polar molecules?
ion-induced dipole intermolecular force
OH, NH, FH bonds?
hydrogen bonding
polar molecules?
dipole-dipole intermolecular force
polar and non-polar molecules?
dipole-induced dipole intermolecular force
dispersion forces always present
Chem 108, Spring, 2013 Chapter 11
Chem 108, Spring, 2013 Chapter 11
You Cant Believe Everything You Read
From Wikipedia,
London dispersion forces are weak
intermolecular forces that arise from the
interactive forces between instantaneous [dipoles]
in molecules without permanent [dipole]
moments.
Evaluate this statement
http://en.wikipedia.org/wiki/Van_der_Waals_force
Intermolecular Force and Physical
Properties of Liquids and Solutions
Increase intermolecular force,
increase boiling point
decrease vapor pressure
increase melting point
increase surface tension
increase viscosity
Trends In Intermolecular Forces
Hydration energies (kJ/mol)
Li+ 520
Na+ 406
K+ 322
Rb+ 297
Cs+ 276
ion-dipole force increases with charge
density
Chem 108, Spring, 2013 Chapter 11
http://www.science.uwaterloo.ca/~cchieh/cact/applychem/hydration.html
Trends in Intermolecular Forces
dispersion forces
increase with
polarizability of
electrons
(polarizability is ability of
electrons to be polarized,
or pushed around)
Chem 108, Spring, 2013 Chapter 11
Trends in Intermolecular Forces
dispersion forces increase with increasing
surface area
Chem 108, Spring, 2013 Chapter 11
Trends in Intermolecular Forces

dispersion
forces
increase
with polarity
Chem 108, Spring, 2013 Chapter 11
Trends in
Intermolecular
Forces

something
special
about
hydrogen
bonding
Chem 108, Spring, 2013 Chapter 11
Hydrogen Bonding in DNA
Chem 108, Spring, 2013 Chapter 11
Hydrogen bonding
responsible for DNA double
helix structure
four nucleobases in DNA (C,
G, T, A)
T and A, and C and G, are
paired by hydrogen bonding
Hydrogen Bonding in DNA
Base pairing in DNA allows replication
Chem 108, Spring, 2013 Chapter 11
Chem 108, Spring, 2013 Chapter 11
Example
Choose compound with the higher boiling point

CH
4
CH
3
CH
2
CH
2
CH
3





CH
3
CH
2
CH=CHCH
2
CH
3
cyclohexane
Chem 108, Spring, 2013 Chapter 11
Example
Choose the compound with the higher boiling point

a) CH
2
FCH
2
F CH
3
CHF
2




b)

Chem 108, Spring, 2013 Chapter 11
Identify the intermolecular forces that
you would expect for each of the
following substances:
a. O
2

b. H
2
O

c. CHBr
3

Example
a. Nonpolar molecule: London dispersion forces
b. Polar molecule with OH bond: London
dispersion forces, hydrogen bonding (dipole-
dipole forces)
c. Polar molecule: London forces, dipole-dipole
forces
Chem 108, Spring, 2013 Chapter 11
Energy required to increase surface area
Molecules at surface higher energy
Minimize surface minimize energy
sphere: minimal surface area/volume
Surface Tension
Chem 108, Spring, 2013 Chapter 11
Factors Affecting Surface Tension
Increase intermolecular attractive forces,
increase surface tension
Increase temperature, decrease 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
Chem 108, Spring, 2013 Chapter 11
Water has high surface tension
large attractive intermolecular force because of
hydrogen bonding
objects float on water because it takes energy to
break the water surface
Surface Tension
Chem 108, Spring, 2013 Chapter 11
Viscosity is a measure of
resistance to flow
In the figure, steel balls
were dropped into the
glycerol and the water at
the same time.
glycerol is more viscous
than water
Viscosity
glycerol water
Chem 108, Spring, 2013 Chapter 11
Factors Affecting Viscosity
Increase intermolecular force, increase
viscosity
Increase temperature, decrease viscosity
For a given solvent viscosity, spherical solutes
will move faster than non-spherical solutes
Chem 108, Spring, 2013 Chapter 11
Capillary Action
Capillary action: liquid rises in narrow-bore tube
Capillary action is the result of two forces
working in conjunction, the cohesive and
adhesive forces
cohesive forces hold the liquid molecules together
adhesive forces attract the outer liquid molecules to
the tubes surface
Capillary Action
Capillary action: rise (or fall) of liquid in narrow-bore
tube
Two competing factors
attractive forces between liquid and wall of tube
attractive forces between molecules of liquid
http://en.wikipedia.org/wiki/Capillary_action
Liquid-wall forces dominate: liquid
rises in tube, forms concave
meniscus eg water
Liquid-liquid forces dominate:
liquid falls in tube, forms convex
meniscus eg mercury
Capillary Action
The water is attracted to the glass, so a thin
film moves up the surface of the glass. This
action expands the surface area, so the water
column rises to counteract the increase in
surface area. The process then repeats itself,
until surface tension forces equate to gravity.
Chem 108, Spring, 2013 Chapter 11
Equilibrium
Equilibrium
At equilibrium, vapor pressure does not
change
Dynamic equilibrium:
rate at which molecules vaporize is equal to rate
at which molecules condense
Equilibrium covered more thoroughly in
chapter 14
Chem 108, Spring, 2013 Chapter 11
Vapor pressure: equilibrium partial pressure
of the vapor over the liquid
Increase intermolecular force, decrease vapor
pressure
Increase temperature, increase vapor pressure
Vapor Pressure
Chem 108, Spring, 2013 Chapter 11
Boiling point: temperature at which the vapor
pressure is equal to the pressure above the
liquid
normal boiling point: boiling point when external
pressure is 1 atm
Increase pressure, increase boiling point
Increase intermolecular force, increase boiling
point
Boiling Point
Chem 108, Spring, 2013 Chapter 11
Boiling Point
Clausius-Clapeyron Equation
Quantitative relation between temperature
and vapor pressure





Plot of lnP versus 1/T is linear with slope equal
to -AH/R
|
|
.
|

\
|

|
|
.
|

\
|
A
=
+
|
|
.
|

\
|
A
=
=
A
1 2 1
2
1 1
ln
ln
1
ln
T T R
H
P
P
T R
H
P
e P
vap
vap
RT H
vap
|
|
Example
The vapor pressure of diethyl ether is 439.8
mmHg at 20.0C. The enthalpy of vaporization
of ether is 29.2 kJ/mol. What is the vapor
pressure, in atm, of ether at 34.0C?
What is the normal boiling point of ether?
Example
Phase diagram for water
Chem 108, Spring, 2013 Chapter 11
Heating Curve
Heating Curve
In a single phase, heat going into system
increases temperature of system
At phase transition, heat going into system
changes phase of system without increase in
temperature
Example: how does a rice cooker know when
to turn off?
Enthalpy of Phase Transitions
Enthalpy of fusion: enthalpy change when a
substance melts
enthalpy of fusion of water at 0
o
C
H
2
O(s) H
2
O(l) AH
fus
= 6.01 kJ/mol
Enthalpy of freezing: enthalpy change when a
substance freezes
enthalpy of freezing of water at 0
o
C
H
2
O(l) H
2
O(s) AH
freeze
= 6.01 kJ/mol
Enthalpy of Phase Transitions
Similar definitions for enthalpy of other phase
transitions
enthalpy of vaporization of water at 100
o
C, 1 atm:
H
2
O(l) H
2
O(g) AH
vap
= 40.7 kJ/mol
Large AH
vap
gives water good evaporative
cooling properties
Why would it hurt more to put your hand in
100
o
C steam than in 100
o
C liquid water? (Do
not try this at home.)
Enthalpy of Phase Transitions
Enthalpy of
vaporization
greater than
enthalpy of
fusion
takes more
energy to break
free from liquid
than from solid
Heating Curve
Calculate heat transferred during heating

heat solid

melt solid

heat liquid

vaporize liquid

heat gas
T mC T C q
S
A = A =
T mC T C q
S
A = A =
T mC T C q
S
A = A =
fus
H n q A =
vap
H n q A =
Example
One 25.0 g ice cube at 0.0
o
C is placed in 100
mL water at 25
o
C. What is the final
temperature, in
o
C, of the water when all the
ice has melted? The enthalpy of fusion of
water is 6.01 kJ/mol. The specific heat
capacity of water is 4.184 J/g K.
Chem 108, Spring, 2013 Chapter 11
The fuel requirements of some homes are supplied
by propane gas, C
3
H
8
, which is contained as a liquid
in steel cylinders. If a home uses 2.40 kg of propane
in an average day, how much heat must be
absorbed by the propane cylinder each day to
evaporate the liquid propane, forming the gas that
is subsequently burned? The heat of vaporization of
propane is 16.9 kJ/mol.
Example
Phase Diagrams
Phase of a pure substance depends on
temperature and pressure
Experimental: set temperature and pressure,
then measure phase of substance at
equilibrium
Phase diagram is graphical display of
dependence of phase on temperature and
pressure
Phase Diagram of CO
2

Phase Diagram of Water
Structure of Ice
Phase Diagram of Carbon
http://lbruno.home.cern.ch/lbruno/documents/Bibliography/LHC_Note_78.pdf
Phase Diagram of Sulfur
Phase Boundaries and Triple Point
Lines in phase diagram represent temperature
and pressure values at which two phases
coexist
Triple point: temperature and pressure at
which three phases coexist
Chem 108, Spring, 2013 Chapter 11
Heat liquid + vapor in sealed container
At critical point, two phases coalesce into one;
supercritical fluid
Critical Point
Would the cooking time for an egg at the top of
a 14,000 foot mountain be shorter or longer
that at sea level.
Example
Solids
Two types: crystalline or amorphous
glass: amorphous solid formed by rapid cooling
Solids
Crystal Lattice
Ordered arrangement of atoms in solid
Unit cell: smallest unit of crystal that can be
used to generate macroscopic crystal
Coordination number: number of atoms in
con
Seven crystal classes, fourteen Bravais lattices
Bravais Lattices
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/lecture1/lec1.html
Unit Cells
Coordination number: number of other
particles each particle is in contact with for
ions, it is the number of oppositely charged
ions an ion is in contact with
higher coordination number, stronger attractive
forces holding the crystal together
Packing efficiency: fraction of volume in the
unit cell occupied by particles
the higher the coordination number, the more
efficiently the particles are packing together
Chem 108, Spring, 2013 Chapter 11
Cubic Unit Cells
Focus on cubic crystal class
Unit cell is a cube
angles between crystal axes = 90
o

edge lengths equal
Three cubic unit cells
simple cubic
face-centered cubic
body-centered cubic
Ref: Ebbing and Gammon. 9
th
ed.
Cubic Unit Cells
Chem 108, Spring, 2013 Chapter 11
Simple Cubic Unit Cell
1 atoms/unit cell
2r = a
Chem 108, Spring, 2013 Chapter 11
Body Centered Cubic Unit Cell
2 atoms/unit cell
4r = \3 a
Chem 108, Spring, 2013 Chapter 11
Face Centered Cubic Unit Cell
4 atoms/unit cell
4r = \2 a
Chem 108, Spring, 2013 Chapter 11
Example
Lithium crystallizes as a body-centered cubic
crystal, with unit cell edge length 350.9 pm.
Calculate the radius of the lithium atom
When silver crystallizes, it forms face-centered
cubic cells. The unit cell edge length is 409
pm. Calculate the density, in g/mL, of silver.
Example
Example
Calculate the molar mass of platinum from the
data in the picture below.
Example
What is the packing efficiency of a body-
centered cubic crystal?
Chem 108, Spring, 2013 Chapter 11
Classifying Crystalline Solids
Molecular solids consists of atoms or molecules. It is held
together by intermolecular forces.
Ionic solids consist of cations and anions. It is held together by
ionic bonds, the electrical attractions between oppositely
charged particles.
Atomic solids are solids whose composite particles are atoms
nonbonding atomic solids are held together by dispersion forces
metallic atomic solids consists of the positive cores of metal
atoms held together by metallic bonding, a sea of delocalized
electrons.
network covalent atomic consists of atoms held together in large
chains or networks by covalent bonds.
Molecular Solids
Carbon dioxide
Chem 108, Spring, 2013 Chapter 11
Ionic Solids
Chem 108, Spring, 2013 Chapter 11
Nonbonding Atomic Solids
Solid argon
http://www.webelements.com/argon/crystal_structure.html
Covalent Network Solid
Diamond
Chem 108, Spring, 2013 Chapter 11
Graphite
Covalent Network Solid
Constructive and Destructive Interference
of Waves

X-Ray Diffraction

Chem 108, Spring, 2013 Chapter 11
X-Ray Diffraction
In phase
(constructive
interference)
http://www.eserc.stonybrook.edu/projectjava/bragg/
out of phase
(destructive
interference)
u sin 2d n =
Example
X rays of wavelength 0.154 nm are diffracted
from a crystal at an angle of 14.170. Assuming
that n = 1, what is the distance (in pm)
between layers in the crystal?

Chem 108, Spring, 2013 Chapter 11
Band Theory
When two 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.
Chem 108, Spring, 2013 Chapter 11
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
Chem 108, Spring, 2013 Chapter 11
Band Gap
Chem 108, Spring, 2013 Chapter 11
Doping Semiconductors
Doping adds impurities to semiconductor crystal to
increase its conductivity to increase number of
electrons in the conduction band
n-type semiconductors are doped by adding
electron-rich impurities
add arsenic to silicon
p-type semiconductors are doped by adding
electron-deficient impurities
add gallium to silicon
forms holes in the valence band.
Chem 108, Spring, 2013 Chapter 11
Diodes
n-p junction formed when p-type
semiconductor adjoins an n-type
semiconductor
Electricity can flow across the p-n junction in
only one direction
called diode
Diodes
Diode: current flows one way
n-type
p-type
battery
+
-
n-type
p-type
battery
-
+
No current Current
Diode