Ch.

13 The Chemistry of Solids

13.1 Crystal Lattices and Unit Cells
In gases and liquids, molecules move continually and randomly, but in solids they
cant change their relative positions and so a regular repeating pattern within the structure is a
characteristic of most solids
Properties of Solids
molecules, atoms, or ions locked into a crystal lattice
particles are CLOSE together
these exhibit strong intermolecular forces
highly ordered, rigid, incompressible
Crystal Lattices
unit cells are the smallest repeating internal unit that has the
symmetry characteristic of the solid
Cubic Unit cells
there are 7 basic
crystal systems, but we will only be concerned with
the cubic form

All
angles are 90 degrees

All
sides are equal length

of each atom on a corner is

within the cube
of each atom on a face
is within the cube
of each atom on a side
is within the cube
Unit cells are important because (1) a # of
metals, ionic solids, and intermetallic cpds crystallize in cubic unit cells and (2) it
is relatively easy to do calculations with these unit cells. So we can easily
calculate the volume if given the cell edge (a) because a3 is the volume of the
cube
We shall look at the three variations of the
cubic crystal system (simple or primitive, body-centered, face-centered)
Simple or primitive
the balls
represent the positions of atoms, ion, or molecule in a simple
cubic unit cell
each
atom, ion, or molecule at a corner is shared by 8 unit cells
(8[]=1 atom / cell)
Body-Centered Cubic
has an
additional atom, ion, or molecule in the center of the unit cell
On a
body-centered cubic unit cell there are 8 corners + 1 particle in
the center

c
ontains 2 particles

Face Centered Cubic

has a
cubic unit cell structure with an extra atom, ion, or molecule in
each face


8
corners + 6 faces= 4 atoms / unit cell

# of atoms/Unit cells

vol

radius

Simple cubic

1 atom/unit cell

Cell edge = 2 atomic radii

a3

a/ 2 = r

Body-centered

2 atoms/unit cells

3 x a = 4 atomic radii

a3

a3/ 4 = r

Face-centered

4 atoms/unit cell

2 x a = 4 atomic radii

a3

a2/4= r

13.2 Structures and Formulas of Ionic Solids

 CsCl
Ionic Solids have ions that occupy the positions in the unit cell
Octahedral Holes: Na + are said to be in octahedral holes because surrounded
by 6 Cl- and makes an 8 sided crystal

Tetrahedral holes: ion surrounded by 4 oppositely charged ions

13.3 Bonding in Metals and Semiconductors

Molecular Orbital theory was introduced in ch 9 to rationalize covalent bonding in
molecules
MO theory can also be used to describe metallic bonding
metals can be thought of as a supermolecule
metallic bonding is described as delocalized: the electrons are associated with all
the atoms in the crystal are not associated with specific bonded
atoms
this theory of metallic bonding is called bond
theory
Bonding in Metals and Semiconductors
An energy level diagram
shows the bonding and antibonding molecular orbitals
blending together into a band of molecular orbitals
Band Theory
Fermi level: highest filled level
at OK

 Molecular orbitals are constructed from the valence orbitals on

each atom and are delocalized over all the atoms. When sufficient energy is added,
electrons are excited to the conduction band.
Band of energy levels in a metal is essentially continuous that

is the energy gap between levels are extremely small. So electron can move to higher
energy state (absorb energy) then can emit a photon to return electron to original level.
This rapid and efficient absorption and emission of light make polished metal surfaces be
reflective and shiny
Metals are shiny (lustrous), malleable, and ductile
Semiconductors
Band gap: a barrier to the promotion of electrons to a higher
energy level
GROUP 4A: orbitals of valence band are completely filled, but
the conduction band is empty
Intrinsic semiconductors: naturally occurring property of the
pure material
Extrinsic semiconductors: conductivity of material is changed
by adding/doping the material with a different element
p-type: positive holes are created
n-type: negative holes are created
13.4 Bonding in Ionic Compounds:Lattice Energy
Reminder: Ionic compounds have high melting points because ion-ion
interactions are so strong
Lattice Energy
Ionic cpds held together by
extensive attractions between ions of opposite charge
and repulsion between ions of like charges(Coulombs
law)
Dissolution of Solids in Liquids
The energy released when a mole of formula units of a solid is
formed from its constituent ions in the gas phase is called the crystal lattice energy

the crystal lattice energy is a measure of the attractive forces in

a solid

the crystal lattice energy increases as the charge density

increases (ionic charge/radius)
always negative
more negative = more strong attractions
Calculating a Lattice Enthalpy from Thermodynamic Data
Hesss law
13.5 The Solid State: Other Types of Solid Materials
Solids can be classified on the basis of the bonds that hold the atoms or
molecules together
molecular

network (covalent)
ionic
metallic

Molecular

characterized by relatively strong intramolecular bonds

between the atoms that form the molecules
the intermolecular forces between these molecule are much
weaker than the bonds
because the intermolecular forces are relatively weak,
molecular solids are often soft with low melting points
Network Solids (Covalent)
conventional chemical bonds hold the chemical subunits
together
the bonding between chemical subunits is identical to that
within the subunits resulting in a continuous network of chemical bonds
3 examples are diamond, graphite, and quartz
cannot detect discrete molecules
composed of a 3D array of covalently bonded atoms
most are hard and rigid and have high mp and bp
Ionic Solids
salts that are held together by the strong force of attraction
between ions of opposite charge
because this force of attraction depends of the square of the
distance between the positive and negative charges, the strength of the bond depends on
the radii of the ions that form the solid
as these ions become larger, the bond becomes weaker
Metallic Solids
metal atoms dont have enough electrons to fill their valence
shells by sharing electrons with their immediate neighbors
electrons in the valence shell are therefore shared by many
atoms instead of just two
in effect, the valence electrons are delocalized over many
many atoms. because these electrons arent tightly bound to individual atoms, they are
free to migrate through the metal, as a result, metals are good conductors
Amorphous Solids
do not have a regular structure
glass; melt over a range of temperature and breaks into
randomly shaped pieces
13.6 Phase Changes Involving Solids
Melting: Solid Liquid
the melting point of a solid is the temperature at which the
lattice collapses into a liquid. Like any phase change, melting requires energy (enthalpy of
fusion)
Trends:
Mp increases within a series of related
molecules as the size and mass increases
nonpolar substances that form molecular
solids have low mp. ionic have higher due to strong ion-ion intermolecular forces
Sublimation: Conversion of Solid to Vapor
solid vapor without passing through
the liquid phase
13.7 Phase Diagrams
Used to show the relationship between phases of matter and the P and T
Phase diagrams only apply to closed systems
Triple point: the condition at which all phases coexist
P vs T: displays all of the different phase transitions of a substance
Triple point: one point at which all 3 phases of a substance
solid, liquid, gas can coexist at equilibrium

 Critical T: is the T above which a gas cannot be liquefied, i.e.

the T above which the liquid and gas do not exist as distinct phases
Critical P: is the P required to liquefy a gas at its critical T
Critical point: is the combination of critical T and critical P
Supercritical fluid: a substance at a T above its critical T