Crystalline Solid State

(Part B)

Joyce Tan, M.Sc.

Department of Chemistry
An amorphous solid does not possess a well-defined
arrangement and long-range molecular order.
A glass is an optically transparent fusion product of inorganic
materials that has cooled to a rigid state without crystallizing

Crystalline Non-crystalline
quartz (SiO2) quartz glass
 Structure of Crystals
 Unit cells are the smallest repeating unit of a crystal.
 As an analogy, bricks are repeating units for buildings.
 There are seven basic crystal systems.
 Structure of Crystals
 We shall look at the three
variations of the cubic crystal
system.
 Simple cubic unit cells.
 The balls represent the positions
of atoms, ions, or molecules in a
simple cubic unit cell.
 Structure of Crystals
 Body centered cubic (bcc)
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 center of cell.
 1 bcc unit cell
 contains 8(1/8) + 1 =

2 particles.
 Structure of Crystals

 A face centered cubic

(fcc) unit cell has a cubic
unit cell structure with an
extra atom, ion, or
molecule in each face.
 Structure of Crystals
 A face centered cubic unit cell has 8 corners and 6 faces.
 1 fcc unit cell contains
 8(1/8) + 6(1/2) = 4 particles.
2 Kinds of Closed-packed Structures
48% void 32% void 26% void
not close-packed close-packed
Ionic Solids have ions that occupy the positions in the unit
cell. Examples of ionic solids include: CsCl, NaCl, ZnS
Types of Crystals
Ionic Crystals
• Lattice points occupied by cations and anions
• Held together by electrostatic attraction
• Hard, brittle, high melting point
• Poor conductor of heat and electricity

CsCl ZnS CaF2

 Bonding in Solids
 Variations in Melting Points for Ionic Solids
 Compound Melting Point (oC)
LiF 842
LiCl 614
LiBr 547
LiI 450
CaF2 1360
CaCl2 772
CaBr2 730
CaI2 740
Covalent Crystals
• Lattice points occupied by atoms
• Held together by covalent bonds in an extensive 3-D network
• Hard, high melting point (>1500C)
• Poor conductor of heat and electricity
carbon
atoms

diamond graphite
 Covalent Solids have atoms that are covalently bonded
to one another
 Some examples of covalent solids are:
 Diamond, graphite, SiO (sand), SiC
2
Crystal structure of quartz
Talc, Mg3(OH)2Si4O10
 Bonding in Solids
 Variations in Melting Points for Covalent Solids
Substance Melting Point (oC)
sand, SiO2 1713
carborundum, SiC ~2700
diamond >3550
graphite 3652-3697
Molecular Crystals
• Lattice points occupied by molecules
• Held together by van der Waals forces and/or H-bonding
• Soft, low melting point (<100C)
• Poor conductor of heat and electricity
• SO2, I2, P4 and S8
CO2 Benzene
 Bonding in Solids

 Variations in Melting Points for Molecular Solids

 What are the intermolecular forces in each solid?
 Compound Melting Point (oC)
ice 0.0
ammonia -77.7
benzene, C6H6 5.5
napthalene, C10H8 80.6
benzoic acid, C6H5CO2H 122.4
Metallic Crystals
• Lattice points occupied by metal atoms (bcc,fcc or hcp)
• Held together by metallic bonds
• Soft to hard, low to high melting point
• Good conductors of heat and electricity
Cross Section of a Metallic Crystal
nucleus &
inner shell e-

mobile “sea”
of e-
 Bonding in Solids
 Variations in Melting Points for Metallic Solids
Metal Melting Point (oC)
Na 98
Pb 328
Al 660
Cu 1083
Fe 1535
W 3410
Diagram of 4 types of substances
 Holes in Closed Packed Spheres

Octahedral hole

Octahedral hole Tetrahedral hole

Holes in Closed Packed Spheres
Face Centred Cubic (FCC) unit cell with all tetrahedral holes filled
Tetrahedral holes are Tetrahedral holes are filled
half filled by Zn2+ – ZnS by F-– CaF2 (1:2)
(1:1)
The ions occupying tetrahedral holes in a face centred cube (FCC) are all
contained within that unit cell. Each face centred cube contains 8
tetrahedral holes, one in each corner of the cube
Ionic (and other) structures may be derived from the
occupation of interstitial sites in close-packed
arrangements.
CCP S2- with Zn2+ in half Tetrahedral holes (only T+ {or T-} filled)
Lattice: fcc
4ZnS in unit cell
Motif: S at (0,0,0); Zn at (1/4,1/4,1/4)
Coordination: 4:4 (tetrahedral)
Cation and anion sites are topologically identical
STRUCTURES DERIVED FROM HEXAGONAL
CLOSE PACKING

HCP S2- with Zn2+ in half Tetrahedral

holes (only T+ {or T-} filled)
Lattice: Hexagonal - P
a = b, c Å Ã(8/3)a
Motif: 2S at (0,0,0) & (2/3,1/3,1/2); 2Zn
at (2/3,1/3,1/8) & (0,0,5/8)
2ZnS in unit cell
Coordination: 4:4 (tetrahedral)
Comparison of Wurtzite and Zinc Blende
Radius Ratios and Coordination Numbers

R+/R- 0.225  0.414  0.732 

Coordination tetrahedral octahedral cubic
& number 4 6 8

Typical CsCl ,
ZnS NaCl
structure CaF2
Chemistry In Action: High-Temperature Superconductors
 Band Theory of Metals
 Sodium’s 3s orbitals can interact to produce
overlapping orbitals
 Band Theory of Metals
 The 3s orbitals can also overlap with unfilled 3p orbitals
 Band Theory of Metals
 Insulators have a large gap between the s and p bands.
 Gap is called the forbidden zone.
zone
 Semiconductors have a small gap between the bands.
Fig. 13-36, p. 490
p. 487
Chemistry in Use, p. 489
p. 490