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Chapter 7
Crystalline Solid State
• Many more “molecules” in the solid state.
– We will focus on crystalline solids composed of
atoms or ions.
• Unit cell – structural component that, when
repeated in all directions, results in a
macroscopic (observable) crystal.
– 14 possible crystal structures (Bravais lattices)
– Discuss positions of atoms in the unit cell.
The Cubic Unit Cell (or
Primitive)
• 1 atom per unit cell (how?).
• What is the coordination number? Volume
occupied?
• Let’s calculate the length of the edge. What
size of sphere would fit into the hole?
The Body-Centered Cubic
• How many atoms per unit cell?
• What is the length of the edge? This is a
more complicated systems than the simple
cubic.
Close-Packed Structures
• How many atoms is each atom surrounded by in
the same plane?
• What is the coordination number?
• Hexagonal close packing (hcp) – discuss the third
layer (ABA).
• Cubic close packing (ccp) or face-centered cubic
(fcc) – discuss the third layer (ABC).
• Two tetrahedral holes and one octahedral hole per
atom. Can you see them?
Close-Packed Structures
• The hcp has hexagonal prisms sharing vertical
faces (Figure).
– How many atoms per unit cell in the hcp structure?
– What is the length of the cell edge?
• The unit cell for the ccp or fcc is harder to see.
– Need four close-packed layers to complete the cube.
– What is the length of the cell edge?
• In both close-packed structures, 74.1% of the total
volume is occupied.
Ionic Crystals
• The tetrahedral and octahedral holes can
have varying occupancies.
• Holes are generally filled by smaller ions.
– Tetrahedral holes
– Octahedral holes
• NaCl structure
Metallic Crystals
• Most crystalize in bcc, ccp, and hcp structures.
• Hard sphere model does not work well.
– Depends on electronic structure.
• Properties
– Conductivity
– Dislocations
Diamond
• Each carbon atom is bonded tetrahedrally to
four nearest neighbors (Figure).
– Essentially the same strength in all directions.
Structures of Binary Compounds
• Close-packed structures are generally defined by
the larger ions (usually anions). The oppositely-
charged ions occupy the holes.
• Two important factors in considering the
structure
– Radius ratio (r+/r-)
– Relative number of combining cations and anions.
NaCl Crystal Structure
• Face-centered cubes of
both ions offset by a
half a unit cell in one
direction.
• Many alkali metals have
this same geometry.
• What is the coordination
number (nearest
neighbor)?
CsCl Crystal Structure
• Chloride ions form
simple cubes with cesium
ions in the center (Figure
7-7).
• The cesium ion is able to
fit in to center hole.
How?
• Other crystal structures.
TiO2 (the rutile structure)
• Distorted TiO6
octahedra.
– Ti has a C.N. of 6,
octahedral coordination
– O has a C.N. of 3
Rationalization of Structure of
Crystalline Solids
• Predicting coordination number from radius
ratio (r+/r-).
– A hard sphere treatment of the ions.
– Treats bonding as purely ionic.
– Simply, as as the M+ ratio increases, more
anions can pack around it.
• Table 7-1.
Let’s look at a few (NaCl, CaF2, and CaCl2).
Thermodynamics of Ionic Crystal
Formation
• A compound tends to adopt the crystal structure
corresponding to lowest Gibbs energy.
M+(g) + X-(g) MX(s)
G = H - TS (standard state), 2nd term can be
ignored
• Lattice enthalpy
MX(s) M+(g) + X-(g) HL (standard molar
enthalpy change)
Currently, we are interested in lattice formation.
The Born-Haber Cycle
• A special
thermodynamic cycle
that includes lattice
formation as one step.
• The cycle has to sum up
to zero if written
appropriately.
• Write down values for
KCl.
The Born-Haber Cycle
• Calculate the lattice enthalpy for MgBr2.
• A discrepancy between this value and the
real value may indicate the degree of
covalent character.
– We have assumed Coulombic interactions
between ions.
– The actual values for KCl and MgBr2 are 701
and 2406 kJ/mol (versus 720 and 2451).
Lattice Enthalpy Calculations
• Considering only Coulombic contributions
– The electrostatic potential energy between each pair.
z A z B e2
U
r0 4o
zA, zB = ionic charges in electron units
r0 = distance between ion centers
e = electronic charge
4o = permittivity of a vacuum
e2/ 4o = 2.307 10-28 J m
Calculation would be performed on each cation/anion pair
(nearest neighbor).
Lattice Enthalpy Calculations
• A more accurate equation depicts the Coulombic
interactions over the entire crystal.
NAe2 z A z B
U
4o r0
NA = Avogadro’s constant
A = Madelung’s constant, value specific to a crystal type (in
table). This is a sum of all the geometric factors carried
out until the interaction become infinitesimal.
Lattice Enthalpy Calculations
• Repulsions between ions in close proximity term.
r0
U N A C'e
C’ = constant (will cancel out when finding the minimum)
= compressibility constant, ~ 30 pm
• Combining terms
r0
NAe 2
zAzB
U A N A C' e
4o r0
Lattice Enthalpy Calculations
• Finding the minimum
energy
– dU/dr0 = O
N A z A z Be 2
U 1 A
4o r0 r0
• Helps to describe
bonding/reactivity in
solids.
Conductivity of Solids Versus
Temperature
• Metals – decrease with
temperature.
• Semiconductors – increase
with temperature.
• Insulators – increase with
temperature (if
measurable).
Semiconductor Types
• Intrinsic semiconductors –
pure material having
semiconductive properties.
• Doped semiconductors –
semiconductors that are
fabricated by adding a small
amount of another element
with energy levels close to
the pure state material.
– n-type semiconductors
– p-type semiconductors (look at
figure)
Semiconductors
• Fermi-level (semiconductor) – the energy at
which an electron is equally likely to be in
each of two levels (Figure).
• Effects of dopants on the Fermi level.
– n-type and p-type.
Diodes (creating p-n junctions)
• Migration of electrons from the n-type
material to the p-type material.
– Equilibrium is established due to charge transfer.
• Application of a negative potential to the n-
type material and a positive potential to the p-
type material.
– Discuss (Figure 7-16).
Superconductivity
• No resistance to flow of electrons.
– Currents started in a loop will continue to flow
indefinitely.
• Type I superconductors – expel all magnetic fields
below a critical temperature, Tc (Meisner effect).
• Type II superconductors – below a critical
temperature exclude all magnetic fields
completely. Between this temperature and a
second critical temperature, they allow partial
penetration by the magnetic field.
– Levitation experiment works well.
Theory of Superconducting
• Cooper pair theory
– Bardeen, Cooper, and
Schrieffer
– Electrons travel through the
material in pairs.
– The formation and
propagation of these pairs is
assisted by small vibrations
in the lattice.
• discuss
YBa2Cu3O7 High-Temperature
Superconductors
• Discovered in 1987
and has a Tc of 93 K.
– N2(l) can be used
• Type II
superconductor.
• Difficult to work
with.
• Possesses copper
oxide planes and
chains.
Bonding in Solid State Structures
• The hard-sphere model is too simplistic.
– Deviations are observed in ion sizes.
– Sharing of electrons (or transfer back to the
cation) can vary depending upon the
polarizability.
• LiI versus NaCl (which structure would exhibit
more covalent character?)
Bonding in TiO2
• The crystal has a rutile
structure.
– Each titanium has ___ nearest
neighbors and each oxygen
atom has ___ nearest
neighbors.
• There is no effective O···O
or Ti···Ti interactions (only
Ti···O interactions). Why?
• The structure consists of
TiO6 fragments (discuss).
Bonding in TiO2