Larry Brown

Tom Holme

www.cengage.com/chemistry/brown

Chapter 8
Molecules and Materials

Jacqueline Bennett • SUNY Oneonta

Chapter Objectives
• Describe the structures of graphite and diamond and explain
how their properties arise from their structures.

• Describe the arrangement of atoms in the common cubic

crystal lattices and calculate the packing efficiency for a
lattice.

• Use band theory to describe bonding in solids.

• Draw band diagrams for metals, insulators, and

semiconductors (including n- and p-type materials).

2
Chapter Objectives
• Identify a material as a metal, insulator, or semiconductor
from its band diagram.

• Explain how the electrical properties of metals, insulators, and

semiconductors are related to their chemical bonding.

• 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.

3
Chapter Objectives
• 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.

• Describe the connection between polymer properties and

molecular structure.

4
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.
5
Carbon
• Carbon has long been used as material in important
applications.

• 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.

6
Carbon
• 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.

7
Carbon
• Nanotubes are a type of fullerene
that have remarkable properties.

• Tensile strength significantly

higher than steel.

• Nanotubes grown with a

metallic element enclosed
within them show promise as
wires that are one molecule
wide.

• Most recently discovered form of

carbon.

8
Condensed Phases - Solids
• Atoms or molecules arrange themselves into two types of
solids.

• Crystalline solids: atoms or molecules assume a regular,

repeating geometric arrangement.

• Amorphous solids: atoms or molecules assume a random

arrangement.

9
Condensed Phases - Solids
• Packing efficiency in crystalline solids is the percentage of
space occupied by a given 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.

10
Condensed Phases - Solids

• 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%.
11
Condensed Phases - Solids
• 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
close-packing (ccp). ccp hcp 12
Condensed Phases - Solids
• A unit cell 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, and
face-centered cubic (fcc) with an additional 1/2 each of 6
atoms along the faces.

13
Cubic Unit Cells

14
Calculation of Packing Efficiency

• To determine the number of complete atoms per unit cell:

1 1
fcc = (# face-center atoms)  (# corner atoms)  4
2 8
1
bcc = (# body-center atoms)  (# corner atoms)  2
8
1
sc  (# corner atoms)  1
8

• To find the total volume occupied by atoms:

• r is the radius.
 4 3
total volume occupied by atoms  # atoms in unit cell    r 
3 
15
Calculation of Packing Efficiency

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

V  a 3 (where a is the edge length of the unit cell)

 
afcc  2 2 r; abcc 
4
3
r; asc  2r

• To calculate packing efficiency:

volume of atoms in unit cell

Packing efficiency   100
total volume of atoms in unit cell

16
Example Problem 8.1
• Show that the packing efficiency of the face-centered cubic
structure is 74%.

17
Condensed Phases - Solids
• 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.

18
Condensed Phases - Solids
• As coordination numbers increase, each atom in the lattice
interacts with more neighbor atoms.

• The attractive forces for these interactions hold the crystal

together.

• Close-packed structure, with a coordination number of 12,

is one of the most common crystal structures.

19
Condensed Phases - Solids

• 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. 20
Condensed Phases - Solids
• 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.

• Graphite sheets can slide past each other.

21
Condensed Phases - Solids
• 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.

22
Bonding in Solids: Metals, Insulators, and Semiconductors

• 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.

23
Models of Metallic Bonding
• 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.

24
Models of Metallic Bonding
• 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.

25
Models of Metallic Bonding

• 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.
26
Models of Metallic Bonding
• 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.

27
Models of Metallic Bonding
• 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

28
Models of Metallic Bonding
• 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.

29
Models of Metallic Bonding
• 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.
30
Band Theory and Conductivity
• 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.

31
Band Theory and Conductivity
• 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.

32
Band Theory and Conductivity

• Band gap diagrams of a conductor, semiconductor, and

insulator.
33
Semiconductors
• Electrical conductivity of semiconductors can be modified via
doping.

• 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”

34
Semiconductors
• 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.
35
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.
36
Semiconductors

• 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. 37
Example Problem 8.2
• Which kind of material (n- or p-type) would result if pure
germanium was doped with:

• gallium

• arsenic

• phosphorus

38
Semiconductors
• A p-n junction can be constructed from p-type and n-type
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.

39
Semiconductors

• A p-n junction
can act as a
simple switch
when the
correct voltage
polarity is
applied.

40
Intermolecular Forces
• 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.
41
Dispersion Forces
• Dispersion forces are common to all molecules.

• Also called London forces.

• Also referred to as instantaneous dipole-induced dipole

forces.

• Dipoles exist for two oppositely charged points separated

by some distance.

42
Dispersion Forces
• An instantaneous dipole occurs when a fluctuation in electron
density for an atom or molecule produces a dipole.

• Instantaneous dipoles are short-lived and constantly

forming and disappearing.

• An induced dipole is created when an external electric field

forces a dipole to exist.

• A permanent dipole or an instantaneous dipole is the

source of the external electric field.

43
Dispersion Forces

• An external electric field distorts the electron density around

an atom or dipole, inducing a dipole.
44
Dispersion Forces
• Individual dispersion forces are very weak.

• The sum of dispersion forces over an Avogadro’s 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 molecule’s
electron density is to perturbation by external electric
fields.
• Large molecules are more polarizable than smaller
molecules and experience stronger dispersion forces.
45
Dipole-Dipole Forces
• Dipole-dipole forces are the attractive and repulsive forces for
molecules with a permanent dipole.

• 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.

46
Dipole-Dipole Forces

• Dipole-dipole forces
for 50 polar
molecules.

• At any given time,

the number of
attractive
interactions is
greater than the
number of
repulsive
interactions.

47
Hydrogen Bonding
• Hydrogen bonds are a special case of dipole-dipole 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.

48
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.

49
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

50
Intermolecular Forces

• Carbon atoms within a graphite sheet held together by

covalent bonds.
• Intermolecular forces hold graphite sheets together.
51
Condensed Phases - Liquids
• Liquids are also a condensed phase.

• Particles in condensed phases are in constant contact.

• 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.

52
Vapor Pressure
• Vapor pressure - the gas phase pressure of a substance in
dynamic equilibrium with the pure liquid in a pure substance.

• Vapor pressure is a characteristic property of a particular

substance at a particular temperature.

53
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.

• Liquids with strong intermolecular forces have lower
vapor pressures.
• Liquids with high vapor pressures are described as
volatile.

54
Vapor Pressure
• 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.

55
Boiling Point
• Normal boiling point - temperature where the vapor pressure
of a liquid equals atmospheric pressure.
• The stronger the intermolecular forces in a liquid, the lower
the vapor pressure, thus, the higher the boiling temperature.

56
Boiling Point
• 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.
57
Surface Tension
• Liquid molecules at the surface of a liquid experience fewer
attractive forces than the molecules in the bulk material.

• Surface tension is a liquid’s 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.

58
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.

59
Surface Tension
• The interaction between a liquid and the surface of a solid
depends on two types of attractive forces.

• Cohesion forces are liquid-liquid interactions.

• Adhesion forces are liquid-solid interactions.
• The relative strengths of the two forces dictate the shape
of a liquid’s 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.

60
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.

61
Polymers
• THIS SECTION AND REST IS NOT INCLUDED

62