Chapter 08

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Chapter Objectives
Larry Brown
Tom Holme
Describe the structures of graphite and diamond and explain

how their properties arise from their structures.
www.cengage.com/chemistry/brown
Describe the arrangement of atoms in the common cubic

crystal lattices and calculate the packing efficiency for a
lattice.
Chapter 8
Molecules and Materials
Use band theory to describe bonding in solids.

Draw band diagrams for metals, insulators, and
semiconductors (including n- and p-type materials).
Okan Esentrk METU Chemistry Dept.

Jacqueline Bennett SUNY Oneonta
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Chapter Objectives
Chapter Objectives
Identify a material as a metal, insulator, or semiconductor

from its band diagram.
Describe the growth of polymers through addition and

condensation reactions and predict which of these processes
is likely to be important for a given monomer.
Explain how the electrical properties of metals, insulators, and

semiconductors are related to their chemical bonding.
Describe the connection between polymer properties and

molecular structure.
Identify the types of intermolecular forces likely to be most

important for a particular substance.
Explain the connection between intermolecular forces and
properties such as boiling point and vapor pressure.
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Carbon
Carbon
There are three forms of the element carbon;

Graphite, diamond, and fullerenes.
Graphite and diamond have been known for a long time.

Fullerenes were discovered in 1985 in the form of C60.
C60 was named buckminsterfullerene due to its resemblance to
geodesic domes popularized by the architect Buckminster.
Tensile strength significantly

higher than steel.
Nanotubes grown with a
metallic element enclosed
within them show promise as
wires that are one molecule
wide.
Carbon has long been used as material in important applications.
Nanotubes are a type of fullerene

that have remarkable properties.
Diamond is used in drill bits and jewelry.

Graphite is used in pencils, as a lubricant, and as a composite
material.
Applications for fullerenes and nanotubes are still being explored.
Most recently discovered form of

carbon.
Carbon
Practice - What property of carbon nanotubes might
lead to interesting engineering applications?
1. Resistance to
reactions
2. Tensile strength
3. Elasticity
Phase diagrams are maps

showing in which state or
phase a compound or
element will be most stable
at a given combination of
pressure and temperature.
The state or phase of a
compound can be
manipulated by changing
the temperature and
pressure of the
compound.
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Phase Diagrams
Phase Diagrams
The AB line is the liquid-vapor interface.
It starts at the triple point (A), the point at which all
three states are in equilibrium.
Each point along this line is the boiling point of the
substance at that pressure.
Phase diagrams display the state of a

substance at various pressures and
temperatures and the places where equilibria
exist between phases.
Phase Diagrams
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Supercritical Fluid
AB line ends at the critical point (B); above this critical

temperature and critical pressure the liquid and vapor
are indistinguishable from each other.
As a liquid is heated in a sealed container, more vapor

collects, causing the pressure inside the container to rise
critical temperature: is the highest T at which a substance can exist as

a liquid
critical pressure: is the pressure required for liquefaction at the critical
temperature
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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 fluids have properties of both gas and liquid
states
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Phase Diagrams
The AD line is the interface between liquid and solid.
The melting point at each pressure can be found along this line.
Below A the substance cannot exist in the liquid state.
Along the AC line the solid and gas phases are in equilibrium;
the sublimation point at each pressure is along this line.
Phase Diagram of Water
Note the high critical

temperature and critical
pressure:
These are due to the

intermolecular forces between
water molecules.
The slope of the solidliquid

line is negative.
This means that as the pressure

is increased at a temperature just
below the melting point, water
goes from a solid to a liquid.
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Phase Diagram of Carbon Dioxide

Practice Consider the phase diagram of CO2 shown. What phase(s)
is/are present at each of the following conditions?
Carbon dioxide cannot exist in the

liquid state at pressures below 5.11
atm; CO2 sublimes at normal
pressures.
20.0 C, 72.9 atm liquid
56.7 C, 5.1 atm solid, liquid, gas
The low critical temperature and

critical pressure for CO2 make
supercritical CO2 a good solvent for
extracting nonpolar substances
(such as caffeine).
10.0 C, 1.0 atm
78.5 C, 1.0 atm solid, gas
50.0 C, 80.0 atm scf
gas
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Condensed Phases - Solids
Atoms or molecules arrange themselves into two types of

solids.
Packing efficiency in crystalline solids is the percentage of

space occupied by a given arrangement.
Crystalline solids: atoms or

molecules assume a regular,
repeating geometric
arrangement.
The less empty space in the packing of atoms or

molecules in a solid, the higher the packing efficiency.
The higher the packing efficiency, the higher the density of
a solid.
Amorphous solids: atoms or

molecules assume a random
arrangement.
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Packing of atoms into solids can be modeled with marbles.

Large gaps between aligned rows indicates a lower
packing efficiency, 76%.
Smaller gaps between offset rows indicates a higher
packing efficiency, 91%.
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Two ways to maximize packing

efficiency.
The second layer of atoms

will stack offset to the first
layer of atoms to give about
74% packing efficiency.
The third layer can stack

directly above the atoms in
the first layer - hexagonal
close-packing (hcp).
The third layer an stack

directly above the hollows in
the first layer - cubic closepacking (ccp).
(ccp)
(hcp).
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A unit cell, repeating pattern of arrangement, is the smallest collection

of atoms that displays all the features of the crystal structure.
Three types of cubic unit cells

- simple cubic (sc) containing 1/8 each of 8 corner atoms,
- body-centered cubic (bcc) containing one additional atom within
- face-centered cubic (fcc) with an additional 1/2 each of 6 atoms along
the faces.
Practice - How much does each atom at

the corner of a cubic unit cell contribute
to that unit cell?
1.
2.
3.
4.
1 atom
1/ atom
4
1/ atom
8
1/
12 atom
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7 Unit Cells
Calculation of Packing Efficiency

c
c
b
Cubic
a=b=c
all 90
To determine the number of complete atoms per unit cell:
b
a
Tetragonal
a=c<b
all 90
1
1
(# face-center atoms) + (# corner atoms) = 4
2
8
1
bcc = (# body-center atoms) + (# corner atoms) = 2
8
1
sc = (# corner atoms) = 1
8
fcc =
a
Hexagonal
a=c<b
2 faces 90
1 face 120
Monoclinic
abc
2 faces 90
Orthorhombic
abc
all 90
c
b
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b
b
a
Rhombohedral
a=b=c
no 90
To find the total volume occupied by atoms:

r is the radius.
a
Triclinic
abc
no 90
total volume occupied by atoms = # atoms in unit cell r 3

3
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Calculation of Packing Efficiency
Example Problem 8.1
To find the volume of the unit cell in terms of radius:
Show that the packing efficiency of the face-centered cubic

structure is 74%.
V = a 3 (where a is the edge length of the unit cell)
( )
afcc = 2 2 r;
abcc =
4
r;
3
asc = 2r
To calculate packing efficiency:

Packing efficiency =
volume of atoms in unit cell

100
total volume of atoms in unit cell
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Coordination number is the number of atoms immediately adjacent to any

given atom.
Simple cubic has a coordination number of 6.
Body-centered cubic has a coordination number of 8.
Close-packed structures have a coordination number of 12.
As coordination numbers increase, each atom in the lattice

interacts with more neighbor atoms.
The attractive forces for these interactions hold the crystal
together.
Simple Cubic
fcc
bcc
CN = 6
CN = 12
CN = 8
Close-packed structure, with a coordination number of 12,

is one of the most common crystal structures.
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Practice - In the two-dimensional square packing
shown, what is the coordination number?
1.
2.
3.
4.
2
4
6
8
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The Crystal Structure of NaCl
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4 Cl- anion per unit cell (8*1/8 + 6*1/2)

4 Na+ cation per unit cell (12*1/4 + 1)
1:1 ratio then formula is NaCl
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Practice - What are the empirical formulas for
these compounds?
(a) Green: chlorine; Gray: cesium
(b) Yellow: sulfur; Gray: zinc
(c) Green: calcium; Gray: fluorine
(a)
(b)
CsCl
ZnS
(c)
CaF2
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The properties of a solid are related to its crystal structure.
Each carbon atom in diamond is covalently bonded to four
neighboring atoms.
Diamond is an inordinately hard material.
The carbon atoms in graphite are covalently bonded into
flat sheets.
Preferred crystal lattice for the solid phase of each element.

There is no discern-able pattern as to which crystal structure is most
likely for any particular metal.
Graphite sheets can slide past each other.

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Bonding in Solids: Metals, Insulators, and Semiconductors
The carbon atoms in diamond

are joined by covalent bonds in a
tetrahedral geometry.
The large number of covalent
bonds in diamond explains
the inordinately high strength
of diamond.
The carbon atoms in graphite are
bonded together in sheets.
The graphite sheets are held
together by much weaker
forces.
Properties of metals can be explained by bonding in metals.

Metals are:
Malleable - worked into useful shapes or foils.
Ductile - pulled into wires
Good conductors of heat and electricity.
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Models of Metallic Bonding
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The bonding in metals cannot be explained in terms of ionic or covalent

bonding.
There is little electronegativity difference from element to element so

metals and alloys do not form ionic bonds.
The outermost subshells are not filled, so a large number of covalent

bonds would be needed to satisfy the octet rule.
The sea of electrons model is the first and simplest qualitative explanation
of metallic bonding.
The valence electrons are delocalized and move freely throughout the
solid.
Explains malleability, ductility, and conductivity properties of metals.

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When a force is applied to a metal, the positively charged

cores respond to the stress, deforming the metal.
The free flow of electrons maintains the bonding throughout
the process.
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Band theory is a quantitative model of bonding in solids.
The wave functions of the valence electrons interact with each other.
Bonding molecular orbitals result from constructive interference.
Antibonding molecular orbitals result from destructive interference.
Energies of the molecular orbitals are related to the energy of

the original atomic orbitals.
Bonding molecular orbitals are lower energy.
Antibonding molecular orbitals are higher energy.
The number of molecular orbitals formed equals the number of atomic

orbitals involved.
For every bonding molecular orbital formed, one antibonding

molecular orbital is also formed.
For odd number of bonding atoms, a nonbonding molecular orbital is

formed.
The molecular orbitals formed belong to the entire set of atoms.

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Li2 Molecular Orbital Diagram

Valance electrons
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Band Theory and Conductivity
As the number of atoms

increases, the number of
bonding and antibonding
molecular orbitals increases.
The energy spacing

between molecular orbitals
decreases.
For large numbers of

atoms, the energy levels
merge to form a
continuous band of
allowed energies.
Electrons fill the lowest energy band first.

The energy difference between the filled and empty bands
determines the electrical properties of the bulk material.
The band populated by valence electrons is the valence band.
The empty band above the valence band is the conduction
band.
The energy difference between the valence and conduction
band is the band gap.
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Band Theory and Conductivity
Practice - Which of these band diagrams is consistent with

diamond being an insulator?
Current flows when electrons move from the valence band to the
conduction band.
Conductors have small band gaps. A very small amount of energy is

required to move electrons to the conduction band.
Insulators have large band gaps. A large amount of energy is

required to move electrons to the conduction band.
Semiconductors have band gap intermediate of conductors and

insulators.
1.
2.
3.
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A
B
C
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Practice
Practice
What is the key difference between metallic bonding (in
the sea of electrons model) and ionic bonding (as
described in Chapter 7) that explains why metals conduct
electricity and ionic solids do not?
How many electrons per atom are delocalized in the sea

of electrons model for the following metals? +
(a) iron; (b) vanadium; and (c) silver.
ANS: Unlike metallic bonding, ionic bonding does not

produce free electrons in the solid phase. Those free
electrons in metallic bonding can conduct current, but
without the free electrons, ionic solid will not conduct
electricity.
a) iron = 8
b) vanadium = 5
c) silver = 11
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Semiconductors
Semiconductors
Electrical conductivity of semiconductors can be modified via

doping.
n-type semiconductors
The extra valence electron fills the donor level, which is
just below the conduction band.
Little energy is required to promote the donor level
electron to the conduction band.
p-type semiconductors
The lack of valence electrons creates an acceptor level,
just above the valence band.
Little energy is required to promote a valence band
electron to the acceptor level.
The vacancies in the valence band are referred to as
holes.
Doping - adding trace amounts of an element to a

substance to modify its properties.
n-type: prepared by doping with a valence electron rich
element; negative
p-type: prepared by doping with a valence electron
deficient element; positive
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Semiconductors
Semiconductors
Formation of n-type doped silicon.
Doping with phosphorus introduces an extra valence electron.
The extra electron fills the donor level, which lies close to the
conduction band.
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Example Problem 8.2
Formation of a p-type doped silicon.
The dopant has fewer than 4 valence electrons.
An acceptor level slightly higher than the valence band is created.
Aluminum is a common p-type dopant.
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Practice
Which kind of material (n- or p-type) would result if pure

germanium was doped with:
Is an n-type semiconductor actually

negatively charged?
gallium
ANS: No, the dopant provides an extra

electron, but the dopant also has an
extra proton.
arsenic
phosphorus
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Semiconductors
Intermolecular Forces
A p-n junction can be

constructed from p-type and ntype material.
The flow of electrons across

the junction is easily regulated
by applying voltage.
Current flows across the

junction when the negative pole
of a battery is connected to the
n-type material.
Current does not flow across

the junction when the negative
pole is connected to the p-type
material.
Important in solid state

electronics.
A p-n junction can act as a

simple switch when the correct
voltage polarity is applied.
Intermolecular forces - the attractive and repulsive forces

between molecules.
The attractive and repulsive intermolecular forces are
weak in comparison to bonding forces.
Intermolecular forces are largely responsible for
determining the structure and properties of condensed
phases.
The principle of minimization of energy applies here as
well.
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Type of intermolecular forces

Ion-dipole forces
Dipole-dipole forces
van der Waals
Forces
London dispersion forces
(among neutral
Hydrogen bonding
molecules)
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Dispersion Forces
Dispersion Forces
Dispersion forces are common to all molecules.
An instantaneous dipole occurs when a fluctuation in electron

density for an atom or molecule produces a dipole.
Also called London forces.

Instantaneous dipoles are short-lived and constantly
forming and disappearing.
Also referred to as instantaneous dipole-induced dipole

forces.
An induced dipole is created when an external electric field

forces a dipole to exist.
Dipoles exist for two oppositely charged points separated

by some distance.
A permanent dipole or an instantaneous dipole is the

source of the external electric field.
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Dispersion Forces
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Dispersion Forces
Individual dispersion forces are very weak.
The sum of dispersion forces over an Avogadros number
of atoms results in a significant amount of energy.
Dispersion forces hold many liquids and solids together.
The strength of a dispersion force can be estimated from the
polarizability of a molecule.
Polarizability is a measure of how susceptible a molecules
electron density is to perturbation by external electric
fields.
Large molecules are more polarizable than smaller
molecules and experience stronger dispersion forces.
An external electric field distorts the electron density around

an atom or dipole, inducing a dipole.
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Factors Affecting London Forces
Factors Affecting London Forces
The shape of the molecule

affects the strength of dispersion
forces: long, skinny molecules
(like n-pentane) tend to have
stronger dispersion forces than
short, fat ones (like neopentane).
This is due to the increased
surface area in n-pentane.
The strength of dispersion forces tends to increase

with increased molecular weight.
Larger atoms have larger electron clouds, which are
easier to polarize.
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Practice
66
Dipole-Dipole Forces
Why are dispersion forces attractive?
Dipole-dipole forces are the attractive and repulsive forces for

molecules with a permanent dipole.
ANS: Dispersion or London forces

are the result of instantaneous
dipoles. While their lifetimes are very
short, these dipoles will attract one
another just as opposite charges or
permanent dipoles would.
The charge at the poles of a dipole is seldom more than a

fraction of the charge on an electron, making these forces
weaker than a chemical bond.
Molecules with larger dipoles have stronger dipole-dipole
forces.
Dipole-dipole forces are typically stronger than dispersion
forces.
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Dipole-Dipole Forces
Dipole-Dipole Interactions
Dipole-dipole forces
for 50 polar
molecules.
At any given time,
the number of
attractive
interactions is
greater than the
number of
repulsive
interactions.
The more polar the molecule, the higher is its boiling

point (stronger dipole-dipole interactions).
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How Do We Explain This?
Which Have a Greater Effect:

Dipole-Dipole or Dispersion Forces?
If two molecules are of comparable size and shape, dipoledipole interactions will likely be the dominating force.
If one molecule is much larger than another, dispersion forces
will likely determine its physical properties.
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The nonpolar series

(SnH4 to CH4) follow
the expected trend.
The polar series
follows the trend
from H2Te through
H2S, but water is
quite an anomaly.
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Hydrogen Bonding
Hydrogen Bonding
Hydrogen bonding
arises in part from the
high electronegativity
of nitrogen, oxygen,
and fluorine.
Hydrogen bonds are a special case of dipoledipole forces.

Hydrogen bonds are especially strong
compared to dipole-dipole forces.
Hydrogen bonds occur only in compounds
containing hydrogen covalently bonded to
the highly electronegative elements F, O,
or N.
The strong dipole created in these
types of covalent bonds creates a
strong dipole-dipole interaction with
similar bonds.
Also, when hydrogen is bonded to one of those

very electronegative elements, the hydrogen
nucleus is exposed.
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Summarizing Intermolecular Forces
Intermolecular forces are weak compared to the average
covalent bond.
The large number of intermolecular forces make
intermolecular forces a key factor in determining the bulk
properties of materials.
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Example Problem 8.3
Which type(s) of intermolecular forces need to be overcome

to convert each of the following liquids to gases?
CH4
CH3F
CH3OH
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Carbon atoms within a graphite sheet held together by

covalent bonds.
Intermolecular forces hold graphite sheets together.
Condensed Phases - Liquids
Vapor Pressure
Liquids are also a condensed phase.
Vapor pressure - the gas phase pressure of a substance in

dynamic equilibrium with the pure liquid in a pure substance.
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Particles in condensed phases are in constant contact.

Vapor pressure is a characteristic property of a particular
substance at a particular temperature.
Every particle in a solid vibrates around a fixed position.

Every particle in a liquid is free to constantly move with
respect to other particles.
As more molecules
escape the liquid, the
pressure they exert
increases.
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Vapor Pressure
Vapor Pressure
There is a distribution of kinetic energies for liquids at a given

temperature.
Liquid molecules at the surface of the liquid with sufficient
kinetic energy will pass into the gas phase.
Vapor pressure increases with temperature.
To measure the vapor pressure of a solid or a liquid, the

system must reach equilibrium.
The equilibrium is a dynamic equilibrium.
The rate of evaporation equals the rate of condensation.
The amount of gas and liquid does not appear to change.
Liquids with strong intermolecular forces have lower vapor

pressures.
Liquids with high vapor pressures are described as volatile.
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Boiling Point
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Boiling Point
The boiling point of a liquid is the temperature at which its

vapor pressure equals atmospheric pressure.
Normal boiling point - temperature where the vapor pressure
of a liquid equals to 1 atm (760 torr).
The stronger the intermolecular forces in a liquid, the lower
the vapor pressure, thus, the higher the boiling temperature.
Vapor pressures at 295 K

for various substances.
Substances with weaker
attractive forces have higher
vapor pressures and lower
normal boiling points.
At lower atmospheric
pressure, such as in
mountainous regions,
observed boiling points are
lower.
Weaker the attractive forces,

the higher the vapor pressure,
hence more volatile the liquid.
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Changing the Containers Volume

Disturbs the Equilibrium
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
Initially, the rate of

vaporization and
condensation are equal
and the system is in
dynamic equilibrium
When the volume is

increased, the rate of
vaporization becomes
faster than the rate of
condensation
When the volume is

decreased, the rate of
vaporization becomes
slower than the rate of
condensation
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Practice
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Practice Which of the following

is the most volatile?
a)
b)
c)
d)
e)
What makes a chemical compound

volatile?
ANS: A high vapor pressure due to
weak attractive forces.
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water
TiCl4
ether
ethanol
acetone
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has the strongest Intermolecular
attractions?

has the highest normal boiling
point?
a)
b)
c)
d)
e)
a)
b)
c)
d)
e)
water
TiCl4
ether
ethanol
acetone
water
TiCl4
ether
ethanol
acetone
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ClausiusClapeyron Equation
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The logarithm of the vapor pressure vs. inverse
absolute temperature is a linear function
The graph of vapor pressure vs. temperature is an

exponential growth curve
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2-Point Form
A graph of ln(Pvap) vs. 1/T is a straight line
y=
The equation below can be used with just two

measurements of vapor pressure and temperature
It can also be used to predict the vapor pressure if
you know the heat of vaporization and the normal
boiling point
x+ b
remember: the vapor pressure at the normal boiling

point is 760 torr
The slope of the line x 8.314 J/molK = Hvap (J/mol)
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a) The weaker the intermolecular forces, the higher

the vapor pressure, the more volatile the compound.
Order of increasing volatility is the order of
decreasing strength of intermolecular forces.
a) No effect
b) No effect
c) Decreases with increasing intermolecular attractive
forces
d) Increases with inc. T b/c average kinetic energy
increases
e) Decreases with incresing density. Mass increase also
means increase in dispersion forces. Same as c.
Strong player is the dispersion forces (molar mass).

CBr4 < CHBr3 < CH2Br2 < CH2Cl2<CH3Cl < CH4
b) Reverse order for boiling points.
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Surface Tension
Surface Tension
Surface tension is
the result of
molecules at the
surface of a liquid
experiencing
fewer
intermolecular
forces than liquid
molecules inside
the bulk liquid.
Surface tension results from

the net inward force
experienced by the molecules
on the surface of a liquid.
Surface tension is the

amount of energy
required to increase the
surface areas by a unit
amount.
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Surface Tension
Surface Tension
Liquid molecules at the surface of a liquid experience fewer

attractive forces than the molecules in the bulk material.
The interaction between a liquid and the surface of a solid

depends on two types of attractive forces.
Surface tension is a liquids response to the imbalance in

attractive forces and the tendency to minimize energy.
Liquids form spherical shapes.
Spherical shapes have the greatest volumes with the least
amount of surface area.
Stronger attractive forces result in greater surface tension.
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Cohesion forces are liquid-liquid interactions.

Adhesion forces are liquid-solid interactions.
The relative strengths of the two forces dictate the shape
of a liquids meniscus.
Strong adhesion forces and weaker cohesion forces
result in a concave meniscus.
Weak adhesion forces and stronger cohesion forces
result in a convex meniscus.
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Surface Tension
Surface Tension
The concave meniscus
for water results from
stronger adhesive forces.
The convex meniscus for
mercury (shown in the
figure) results from
stronger cohesive forces.
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1
Factors Affecting Surface Tension
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2
Viscosity
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
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3
Resistance of a liquid
to flow is called
viscosity.
It is related to the ease
with which molecules
can move past each
other.
Viscosity increases
with stronger
intermolecular forces
and decreases with
higher temperature.
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Surface Tension and Viscosity
Factors Affecting Viscosity

The stronger the intermolecular attractive forces, the
higher the liquids viscosity will be
The more spherical the molecular shape, the lower the
viscosity will be
molecules roll more easily
less surface-to-surface contact lowers attractions
The stronger the intermolecular attractive forces, the higher

the surface tension and viscosity will be
Raising the temperature of a liquid reduces its surface
tension and its viscosity
Raising the temperature of a liquid reduces its

viscosity
raising the temperature of the liquid increases the average
kinetic energy of the molecules
the increased molecular motion makes it easier to overcome
the intermolecular attractions and flow
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5
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6
Polymers
A substance that has a low boiling point
will also have a low value for which
property?
Polymers are giant molecules constructed by sequentially

stringing together smaller molecules called monomers.
Physical properties of polymers can be adjusted by
modifying the monomers used, reaction types, and
catalysts used to prepare the polymer.
1. Surface tension
Monomers containing one or more double bonds undergo free

radical addition reactions to form addition polymers.
2. Vapor pressure
Addition polymerization occurs through initiation,

propagation, and termination steps.
3. Volatility
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Addition Polymers
Addition Polymers
Initiation: a free radical (species with an unpaired electron) is

produced.
Initiators, such as an
organic peroxide, produce
free radicals upon heating.
Propagation: the free radical attacks the double bond of the

monomer to break the double bond, leaving a single bond; a
new free radical containing the monomer results.
The free radical propagates itself by reacting with more
monomers.
Each propagation step adds

another monomer to the
chain.
Termination occurs when
two radicals combine and
polymer chain growth ends.
Termination: a free radical reacts with another free radical.

Also called chain termination.
Termination is a random event, not all polymer chains will
have the same length.
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9
11
0
Addition Polymers
Addition Polymers
The distribution of polymer lengths and molar masses are

described in terms of degree of polymerization.
Polymer properties can be tailored.

Choose appropriate monomer.
Average number of repeating units in the polymer.

Modify degree of polymerization.
Degree of polymerization =
molar mass of polymer

molar mass of monomer
Control the linking of monomers.
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2
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Addition Polymers
Addition Polymers
The choice of propylene gives rise to different types of

polypropylene.
Isotactic - all methyl groups are arranged on the same side of

the polymer chain.
Polypropylene resembles ethylene, but one H has been

replaced with a methyl (-CH3) group.
Syndiotactic - methyl groups alternate systematically from one

side of the polymer chain to the other.
The methyl group attaches to the carbon backbone in

three different ways.
Atactic - methyl groups are arranged randomly along the

polymer chain.
Arrangement of methyl groups impacts the properties of the
polymer.
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3
Addition Polymers
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4
Condensation Polymers
Monomers can link together
in different ways.
Isotactic
Syndotactic
Atactic
Isotactic and syndiotactic
polymers generally lead
to more predictable and
controllable properties.
11
5
Condensation
polymers are
formed when
functional
groups on the
monomers
react, linking
the monomers
together and
producing water
or another small
molecule.
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Example Problem 8.4
Copolymers
Each of the following monomers or pairs of monomers can

undergo condensation polymerization reactions. Draw the
structures showing the repeat units and linkages in each of
the resulting polymers.
Copolymers are made up of more than one type of monomer.

Nylon and Dacron are examples.
The order in which the monomers are arranged impacts
the properties of a polymer.
OH
Alternating copolymers - monomers arranged in a regular,

alternating series.
Block copolymer - regions where a single monomer is
repeated, interspersed with other regions where a different
monomer is repeated.
Random copolymers - monomers are arranged randomly
Graft copolymer - monomers of different polymers are
branched from a backbone of a different polymer.
H 2N
O
O
H 2N
OH
O
H 2N
NH 2
HO
OH
11
7
Copolymers
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8
Physical Properties
The four types of copolymers.
Thermoplastic polymers melt or deform on heating.

Thermosetting polymers maintain their shape and strength
when heated.
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Polymers and Additives
The Invention of New Materials
Additives are added to polymers to modify polymer properties.
New materials are created through a systematic approach

and good fortune.
Pigment to impart color.
Fullerenes were discovered as an unusual result from an

experiment with small atom clusters.
Plasticizers to increase flexibility.

High temperature superconductivity was discovered using
the heat-and-beat method of synthesis.
Antistatic agents, fillers, fire retardants, and light and heat

stabilizers.
Conducting polymers can be designed with a polymer

backbone of alternating single and double bonds.
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1
12
2
The Invention of New Materials
Poly(acetylene), a prototypical example of a conducting

polymer.
Conductivity arises from the alternating single and double
bonds.
Conductivity can be enhanced via doping.
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31

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Describe the structures of graphite and diamond and explain

Describe the arrangement of atoms in the common cubic

Use band theory to describe bonding in solids.

Okan Esentrk METU Chemistry Dept.

Identify a material as a metal, insulator, or semiconductor

Describe the growth of polymers through addition and

Explain how the electrical properties of metals, insulators, and

Describe the connection between polymer properties and

Identify the types of intermolecular forces likely to be most

There are three forms of the element carbon;

Graphite and diamond have been known for a long time.

Tensile strength significantly

Carbon has long been used as material in important applications.

Nanotubes are a type of fullerene

Diamond is used in drill bits and jewelry.

Most recently discovered form of

Phase diagrams are maps

Phase diagrams display the state of a

AB line ends at the critical point (B); above this critical

As a liquid is heated in a sealed container, more vapor

critical temperature: is the highest T at which a substance can exist as

and the density of the vapor to increase

At some temperature, the meniscus between the liquid and

The AD line is the interface between liquid and solid.

Below A the substance cannot exist in the liquid state.

Phase Diagram of Water

Note the high critical

These are due to the

The slope of the solidliquid

This means that as the pressure

Phase Diagram of Carbon Dioxide

Carbon dioxide cannot exist in the

20.0 C, 72.9 atm liquid

56.7 C, 5.1 atm solid, liquid, gas

The low critical temperature and

10.0 C, 1.0 atm

78.5 C, 1.0 atm solid, gas

50.0 C, 80.0 atm scf

Condensed Phases - Solids

Condensed Phases - Solids

Atoms or molecules arrange themselves into two types of

Packing efficiency in crystalline solids is the percentage of

Crystalline solids: atoms or

The less empty space in the packing of atoms or

Amorphous solids: atoms or

Condensed Phases - Solids

Condensed Phases - Solids

Packing of atoms into solids can be modeled with marbles.

Two ways to maximize packing

The second layer of atoms

The third layer can stack

The third layer an stack

Condensed Phases - Solids

A unit cell, repeating pattern of arrangement, is the smallest collection

Three types of cubic unit cells

Practice - How much does each atom at

Calculation of Packing Efficiency

To determine the number of complete atoms per unit cell:

To find the total volume occupied by atoms:

total volume occupied by atoms = # atoms in unit cell r 3

Calculation of Packing Efficiency

Example Problem 8.1

To find the volume of the unit cell in terms of radius:

4 Cl- anion per unit cell (81/8 + 61/2)