SOLID STRUCTURES

1. CLASSIFICATION OF SOLIDS
Polymers contain long chains of atoms, where the
atoms within a given chain are connected by covalent
bonds and adjacent chains held to one another largely
by weaker intermolecular forces.

Nanomaterials are solids in which the dimensions of

individual crystals have been reduced to the order of
1–100 nm.
2. STRUCTURES OF SOLIDS
Crystalline and Amorphous Solids

Solids in which atoms are

arranged in an orderly
repeating pattern are called
crystalline solids.

Amorphous solids lack

the order found in
crystalline solids.
Unit Cells and Crystal Lattices

Unit cell: a relatively small repeating unit in a crystalline solid, that

is made up of a unique arrangement of atoms and embodies the
structure of the solid.
(a) the size and shape of the unit cell and
(b) the locations of atoms within the unit cell.

The geometrical pattern of points on which the unit cells are

arranged is called a crystal lattice.

a two- dimensional array

of lattice points

The positions of the lattice

points are defined by the
lattice vectors a and b.
The four two-dimensional lattices. The unit cell for each lattice is shaded.
In three dimensions, a lattice is defined by three lattice vectors a, b, and c
If we place a lattice point at each corner of
a unit cell, we get a primitive lattice.

A body-centered cubic lattice has one

lattice point at the center of the unit cell
in addition to the lattice points at the
eight corners.

A face-centered cubic lattice has one

lattice point at the center of each of the
six faces of the unit cell in addition to
the lattice points at the eight corners.
Filling the Unit Cell

In most crystals the atoms are not exactly coincident with the lattice
points. Instead, a group of atoms, called a motif, is associated with
each lattice point. The unit cell contains a specific motif of atoms, and
the crystal structure is built up by repeating the unit cell over and over.

Two-dimensional structure of graphene built up from a single unit cell.

X-Ray Diffraction By Crystals
3. METALLIC SOLIDS
Metallic bonding, results from the fact that the valence electrons
are delocalized throughout the entire solid.

“malleable”

“ductile”

high thermal conductivity

high electrical conductivity
The Structures of Metallic Solids

polonium iron, aluminum,

chromium, lead,
sodium， copper,
tungsten. silver, gold
(1／8) × 8 = 1 atom (1／8) × 8 = 1 atom (1／8) × 8 = 1 atom
1 ＋ 1 ＝ 2 atoms (1／2) × 6 = 3 atoms
1 ＋ 3 ＝ 4 atoms
Close Packing
SAMPLE EXERCISE： Calculating Packing Efficiency

It is not possible to pack spheres together without leaving some void

spaces between the spheres. Packing efficiency is the fraction of
space in a crystal that is actually occupied by atoms. Determine the
packing efficiency of a face-centered cubic metal.

Solve： A face-centered cubic metal has four atoms per unit cell.
Therefore, the volume occupied by the atoms is

For a face-centered cubic metal the

atoms touch along the diagonal of a
face of the unit cell:
Therefore, a diagonal across a face of the unit cell is equal to 4 times
the atomic radius, r. Using simple trigonometry, and the identity
，we can show that

Finally, we calculate the packing efficiency by dividing the volume

occupied by atoms by the volume of the cubic unit cell, a3:
PRACTICE EXERCISE

Determine the packing efficiency by calculating the

fraction of space occupied by atoms in a
body-centered cubic metal.

Answer: 0.68 or 68%

 Alloys
An alloy is a material that contains more than one element and has
the characteristic properties of a metal.
 Alloys

substitutional interstitial heterogeneous intermetallic

alloys（替代 alloys（填 alloys（多相合金） compounds（金
式合金） 隙式合金） 属间化合物）

Substitutional and interstitial alloys are both homogeneous mixtures in

which components are dispersed randomly and uniformly.

Solids that form homogeneous mixtures are called solid solutions.

When atoms of the solute in a solid solution occupy positions normally

occupied by a solvent atom, we have a substitutional alloy.

When the solute atoms occupy interstitial positions in the “holes”

between solvent atoms, we have an interstitial alloy
The distribution of solute and solvent atoms in a substitutional
alloy and an interstitial alloy. Both types of alloys are solid
solutions and, therefore, homogeneous mixtures.
Mild steels < 0.2% C
For example: steel
Medium steels 0.2–0.6% C
High-carbon steel, 0.6–1.5% C
Stainless steel: 0.4% C, 18% Cr, and 1% Ni
In a heterogeneous alloy the components are not dispersed uniformly.

Microscopic view of the structure of the heterogeneous

alloy pearlite.
The dark regions are body-centered cubic iron metal, and the
lighter regions are cementite, Fe3C.
 Intermetallic compounds are compounds rather than mixtures.

a major superconductor, permanent

component of magnets
jet aircraft
engines
Three examples of intermetallic compounds.
14-karat red gold, a substitutional alloy
marked with a red dot
4. METALLIC BONDING
Electron-Sea Model

A simple model that

accounts for some of the
most important
characteristics of metals
is the electron-sea
model, which pictures
the metal as an array of
metal cations in a “sea”
of valence electrons.
Molecular-Orbital Model
5. IONIC SOLIDS
Ionic solids are held together by the electrostatic attraction between
cations and anions—ionic bonds.

NaCl +1, -1 801 °C

MgO +2, -2 2852 °C.
Structures of Ionic Solids
There are a number of factors that influence the structure of ionic
solids, but two of the most important are the relative sizes of the ions
and the stoichiometry.

Remember that, in ionic crystals, ions of opposite charge touch each other
but ions of the same charge should not touch.
How many cations are there per unit cell for each of these structures?
How many anions per unit cell?
Sample Exercise：Calculating the Empirical Formula
and Density of an Ionic Solid
6. MOLECULAR SOLIDS
Molecular solids consist of atoms or molecules held together by
dipole–dipole forces, dispersion forces, and/or hydrogen bonds.

soft and low melting points

7. COVALENT-NETWORK
SOLIDS
Covalent-network solids consist of atoms held together in large
networks by covalent bonds.

harder and higher melting points

Semiconductors
 elemental semiconductors（contain only
one type of atom ）
semiconductors
compound semiconductors,（contain two
or more elements）
Sample Exercise：Qualitative Comparison of Semiconductor
Band Gaps
Will GaP have a larger or smaller band gap than ZnS? Will it have
a larger or smaller band gap than GaN?
Solve Gallium is in the fourth period and group 3A. Phosphorus is
in the third period and group 5A. Zinc and sulfur are in the same
periods as gallium and phosphorus, respectively. However, zinc, in
group 2B, is one element to the left of gallium; sulfur in group 6A is
one ele- ment to the right of phosphorus. Thus, we would expect
the electronegativity difference to be larger for ZnS, which should
result in ZnS having a larger band gap than GaP.
For both GaP and GaN the more electropositive element is gallium.
So we need only compare the positions of the more
electronegative elements, P and N. Nitrogen is located above
phosphorus in group 5A. Therefore, based on increased orbital
overlap, we would expect GaN to have a larger band gap than GaP.
Check External references show that the band gap of GaP is 2.26
eV, ZnS is 3.6 eV, and GaN is 3.4 eV.
Semiconductor Doping

The electrical conductivity of a semiconductor is influenced by the

presence of small numbers of impurity atoms. The process of
adding controlled amounts of impurity atoms to a material is
known as doping.

The doped material is called an n-type semiconductor, n signifying

that the number of negatively charged electrons in the conduction
band has increased.

It is also possible to dope semiconductors with atoms that have

fewer valence electrons than the host material. A material like this
is called p-type semiconductor, p signifying that the number of
positive holes in the material has increased.
The addition of small amounts of impurities (doping) to a
semiconductor changes the electronic properties of the material.
Solid－State Lighting

light-emitting diodes (LEDs)

8. POLYMERIC SOLIDS
In 1827 Jons Jakob Berzelius coined the word polymer (from the
Greek polys, “many,” and meros, “parts”) to denote molecular sub-
stances of high molecular weight formed by the polymerization
(joining together) of monomers, molecules with low molecular
weight.

Plastics are materials that can be formed into various shapes,

usually by the application of heat and pressure.
Thermoplastic materials can be reshaped.
A thermosetting plastic is shaped through irreversible chemical
processes and, therefore, cannot be reshaped readily.
An elastomer is a material that exhibits rubbery or elastic behavior.
Making Polymers

ethylene polyethylene
This type of polymerization, in which monomers are coupled
through their multiple bonds, is called addition polymerization.(加
成聚合反应）
 A second general reaction used to synthesize commercially
important polymers is condensation polymerization（缩聚反应）.

The formation of the copolymer nylon 6,6.

Polymers formed from two different monomers are called copolymers.
Recycling Plastics
Structure and Physical Properties of Polymers

“flexible”
“macromolecules (large molecules)”
“amorphous (noncrystalline)”

The extent of such ordering is indicated by

the degree of crystallinity of the polymer.

Polymers can be made stiffer by introducing

chemical bonds between chains. Forming
bonds between chains is called cross-linking
Interaction between polymer Cross-linking of polymer
chains. In the circled regions, chains. The cross-linking
the forces that operate groups (red) constrain the
between adjacent segments of relative motions of the polymer
the chains lead to ordering chains, making the material
analogous to the ordering in harder and less flexible than
crystals, though less regular. when the cross-links are not
present.
Vulcanization of natural
rubber. (a) Formation of
polymeric natural rubber from
the monomer isoprene. (b)
Adding sulfur to rubber
creates sulfur- atom links
between chains. These links
form as the carbon-carbon
double bonds in the natural
rubber polymer open up.
9. NANOMATERIALS
Nanomaterials— materials that have dimensions on the 1–100-nm
scale—are under intense investigation in research laboratories around
the world.

Semiconductors on the Nanoscale

Cd3P2 powders with

different particle sizes.
The arrows indicate
decreasing particle size
and a corresponding
increase in the band gap
energy.
Photoluminescence. When illuminated with ultraviolet light,
these solutions, each containing nanoparticles of the
semiconductor CdSe, emit light that corresponds to their
respective band gap energies. The light emitted depends on
the size of the CdSe nanoparticles.
Metals on the Nanoscale
Fullerenes, Carbon Nanotubes, and Graphene

Buckminsterfullerene C60. The molecule has a highly

symmetric structure in which the 60 carbon atoms sit at the
vertices of a truncated icosahedron. The bottom view shows only
the bonds between carbon atoms.
Atomic models of carbon nanotubes. Left: “Armchair”
nanotube, which shows metallic behavior. Right: “Zigzag”
nanotube, which can be either semiconducting or metallic,
depending on tube diameter.
A portion of a two-dimensional graphene sheet.