Solid State Chemistry

Chem 331

Dr. Bailey
Stratton 219
x3286
cbailey@wells.edu
Koloman Moser

Wall decorations in the Sala del Reposo, Alhambra.

Mauritis C. Escher

Introduction to the Solid State

There are ~20,000,000 known chemical substances.
~95% are molecular (predominantly containing C).
~4% are inorganic molecular.
~1% are non-molecular extended structures (e.g. solid salts
and most elements).

Single Element Packing

Square Lattice

first layer

Simple Cubic Lattice

Packing used by e.g.
Po.

second layer
(directly above
first)

Single Element Packing

Square Lattice
BCC Lattice Packing
used by e.g. Li, K, V,
Fe, W, etc.

first layer
second layer
(sitting in
indentations)
third layer
(directly above
first)

Single Element Packing

Closest Packed Lattice
Two types of indentations
A. Directly over first layer.
B. Over first layer indentation.

first layer
second layer
(over any
indentation)

So, two different places to start third layer!

A
B

A
B

Single Element Packing

Closest Packed Lattice
Two types of indentations
A. Directly over first layer.
B. Over first layer indentation.

first layer
second layer
(over any
indentation)

So, two different places to start third layer!

IF directly over A, get ABAB packing, also known as hexagonal closest packed (hcp).
Used by Mg, Ca, Co, Zn, etc.

Single Element Packing

Closest Packed Lattice
Two types of indentations
A. Directly over first layer.
B. Over first layer indentation.

first layer
second layer
(over any
indentation)

So, two different places to start third layer!

IF third layer directly over B, get ABCABC packing, also known as face centered cubic (fcc).
Used by Al, Cu, Ni, Ag, Au etc.

Lattice Packing

Elemental Cu and Ni each uses fcc packing and both have very
similar lattice parameters (e.g. internuclear distances).
If we heat the two elements to melting and then mix together
and cool slowly, the fcc packing is retained, but with a random
placement of the two elements.
Known as a solid solution alloy.

Lattice Packing

Elemental Cu and Au each uses fcc packing but have very

different lattice parameters (Au >> Cu).
Upon reaction (melt and cool) yields a specifically ordered
arrangement = an intermetallic compound, which may not
conform to oxidation state rules.

Binary Compounds (MX)

Which elements do we need to be concerned about?
ignore noble gases; no known extended structures.
ignore radioactive elements.
this leaves about 80 elements of possible interest.

mathematically, this results in ~3,160 possible binary elemental

combinations (not taking into account various stoichiometries, AB,
AB2, A2.3B3, etcetera).
90% of known binary compounds have simple stoichiometries:
MX, MX2, MX3, M3X5, etcetera.
For MX there are 20 common structure types (well look at 3).
For MX2 there are 26 common structure types (well look at 2).
Each of these structural types can be thought of as starting from
single element packing lattices.

Most Common MX Structures

NaCl structure
Na+ in fcc lattice
Cl- in Oh holes

CsCl structure
Cl- in simple cubic lattice
Cs+ in cubic hole

Zinc blende (ZnS) structure

S-2 in fcc lattice
Zn+2 in alternating Td holes

Most Common MX2 Structures

Fluorite (CaF2) structure

Ca+2 in fcc lattice
F- in all Td holes
Rutile (TiO2) structure
Ti+2 in body centered cubic lattice
Oxygens in lower symmetry array.

Ternary Compounds (ABC)

82,160 potential combinations; ~20,000 known.
~700 structural types known (so far and growing fast); very few
examples of each type.
Synthesis: grind together and heat Li2O and MoO3, for example.
Reacts before melting.
Forms one of three compounds, depending on ratio on mixing:
1 Li2O : 1 MoO3 Li2MoO4
1 Li2O : 4 MoO3 Li2Mo4O13
2 Li2O : 5 MoO3 Li4Mo5O17

100%yield
100%yield
100%yield

If react with other ratios, get mixtures of these 3 plus startting

material.
If use Na2O instead of Li2O, get entirely different compounds.

Pseudoternary Compounds.
Both sodium chloride and silver chloride utilize NaCl structure.
If react (melt and re-cool) non-stoichiometric amounts, get
solid solution of NaCl structure type, but with random
occupation of Na/Ag sites.
(1-x) NaCl + xAgCl Na1-xAgxCl
Called pseudoternary because it contains 3 types of elements, but
still adopts binary-type structure.

Future? Why Do We Care?

Consider superconductors (a metal that, when cooled to a low
enough temperature, Tc, will carry a charge with no resistance).

best single element superconductor is Nb, Tc = 9 K.

best binary superconductor is Nb3Ge, Tc 20 K.
best ternary superconductor is La2CuO4, Tc 40 K.
best quarternary superconductor is Ba2YCu3O4, Tc 92 K; above N2(l).
best superconductor is Tl2Ba2Ga2Cu3O10, Tc 135 K.

to extrapolate out to room temperature, would need 8 elements, which

means 2.90 x 1010 possible combinations before stoichiometry!
what are the most complicated compounds in nature (max # cations in
different crystallographic environments)?
Asbecaite: Cu3TiAs6Be2Si2O30
Mordite: LaSrNa3ZnSi6O17

Synthesis of Non-Molecular Solids

Typically start with powdered reactants, mix together, press together, heat,
and then let cool (aka shake and bake).
See West Ch 9 for specifics of many methods.
By convention, high temp 800oC; low temp 200-600oC.

Dont want material to react with container, so common to use fused quartz
(up to 1200oC), but do use other materials.
Often start with oxides that are stable in air.
3CuO + 2BaO2 + Y(OH)3
mix well and press into a pellet; heat in aluminum oxide container 920oC
for 24 hours.
yields YBa2Cu3O6, which when reacted with 3/2H2O + 5/2O2 and
annealed below 500oC in O2 produces YBa2Cu3O4 (superconductor).

Nucleation and Diffusion

These solid state reactions occur in two steps: first nucleation, where product
forms within a few nm of where the reactants contact one another, then
product growth through diffusion.
The reason the material is pressed is to get points of contact (on the
molecular scale) as the reaction only occurs when contact occurs.
Very little is known about nucleation, but diffusion is reasonably well
understood.
d D t time
diffusion
distance

diffusion
constant

Different atoms diffuse at different rates, but typically D ~ 10-10 to 10-12

cm2/sec at 2/3Tm (in K).
Therefore, it would take ~320 years to move 1cm in a solid. But, they ARE
moving! Atomic scale on order of .
Atoms can also diffuse (migrate) in crystalline solids because of defects (more
later).

Melting Points
Compounds may melt congruently (Tm) , with a single melting
point. Changes from solid to liquid of same composition.
e.g. H2O(s) H2O(l); all elements melt congruently.
Some compounds melt incongruently (Tin), decomposing on
heating to components with different composition.
e.g. solid solid and liquid of different composition.
e.g. YBa2Cu3O4 melts incongruently.